Inhomogeneity of block copolymers at the interface of an immiscible polymer blend

NASA Astrophysics Data System (ADS)

Ryu, Ji Ho; Kim, YongJoo; Lee, Won Bo

2018-04-01

We present the effects of structure and stiffness of block copolymers on the interfacial properties of an immiscible homopolymer blend. Diblock and two-arm grafted copolymers with variation in stiffness are modeled using coarse-grained molecular dynamics to compare the compatibilization efficiency, i.e., reduction of interfacial tension. Overall, grafted copolymers are located more compactly at the interface and show better compatibilization efficiency than diblock copolymers. In addition, an increase in the stiffness for one of the blocks of the diblock copolymers causes unusual inhomogeneous interfacial coverage due to bundle formation. However, an increase in the stiffness for one of blocks of the grafted copolymers prevents the bundle formation due to the branched chain. As a result, homogeneous interfacial coverage of homopolymer blends is realized with significant reduction of interfacial tension which makes grafted copolymer a better candidate for the compatibilizer of immiscible homopolymer blend.

Synthesis and Characterization of Comb and Centipede Multigraft Copolymers P nBA- g-PS with High Molecular Weight Using Miniemulsion Polymerization

DOE PAGES

Wang, Wenwen; Wang, Weiyu; Lu, Xinyi; ...

2014-10-23

For this study, comb and centipede multigraft copolymers, poly(n-butyl acrylate)-g-polystyrene (PnBA-g-PS) with PnBA backbones and PS side chains, were synthesized via high-vacuum anionic polymerization and miniemulsion polymerization. Single-tailed and double-tailed PS macromonomers were synthesized by anionic polymerization and Steglich esterification. Subsequently, the copolymerization of each macromonomer and nBA was carried out in miniemulsion, and multigraft copolymers were obtained. The latex particles of multigraft copolymers were characterized using dynamic light scattering. The molecular weights of macromonomers and multigraft copolymers were analyzed by size exclusion chromatography. Moreover, the molecular weights and structures of macromonomers were investigated by matrix-assisted laser desorption/ionization time-of-flight massmore » spectrometry and 1H nuclear magnetic resonance spectroscopy. The weight contents of PS in comb and centipede multigraft copolymers were calculated by 1H nuclear magnetic resonance spectroscopy. The thermal properties of multigraft copolymers were characterized by thermogravimetric analysis and differential scanning calorimetry. The microphase separation of multigraft copolymers was observed by atomic force microscopy and transmission electronic microscopy. Rheological measurements showed that comb and centipede multigraft copolymers have elastic properties when the weight content of PS side chains is 26–32 wt %. Centipede multigraft copolymers possess better elastic properties than comb multigraft copolymers with the similar weight content of PS. In conclusion, these findings are similar to previous results on poly(isoprene-g-polystyrene) comb and centipede copolymers made by anionic polymerization.« less

Hemicellulose block copolymers made from woods for wide-range directed self-assembly lithography enabling wider range of applicable patterning size

NASA Astrophysics Data System (ADS)

Morita, Kazuyo; Yamamoto, Kimiko

2017-03-01

Xylan, one of hemicellulose family, block copolymer was newly developed for wide-range directed self-assembly lithography (DSA). Xylan is higher hydrophilic material because of having many hydroxy groups in one molecule. It means that xylan block copolymer has a possibility of high-chi block copolymer. Generally, DSA is focused on microphase separation for smaller size with high-chi block copolymer and not well known for larger size. In this study, xylan block copolymer was confirmed enabling wider range of patterning size, from smaller size to larger size. The key of xylan block copolymer is a new molecular structure of block copolymer and sugar chain control technology. Sugar content is the important parameter for not only micro-phase separation property but also line edge roughness (LER) and defects. Based on the sugar control technology, wide-range (hp 8.3nm to 26nm L/S and CD 10nm to 51nm hole) DSA patterning was demonstrated. Additionally it was confirmed that xylan block copolymer is suitable for sequential infiltration synthesis (SIS) process.

Bicomponent Block Copolymers Derived from One or More Random Copolymers as an Alternative Route to Controllable Phase Behavior

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ashraf, Arman R.; Ryan, Justin J.; Satkowski, Michael M.

Block copolymers have been extensively studied due to their ability to spontaneously self-organize into a wide variety of morphologies that are valuable in energy-, medical- and conservation-related (nano)technologies. While the phase behavior of bicomponent diblock and triblock copolymers is conventionally governed by temperature and individual block masses, we demonstrate that their phase behavior can alternatively be controlled through the use of blocks with random monomer sequencing. Block random copolymers (BRCs), i.e., diblock copolymers wherein one or both blocks is a random copolymer comprised of A and B repeat units, have been synthesized, and their phase behavior, expressed in terms ofmore » the order-disorder transition (ODT), has been investigated. Our results establish that, depending on the block composition contrast and molecular weight, BRCs can microphase-separate. We also report that the predicted ODT can be generated at relatively constant molecular weight and temperature with these new soft materials. This sequence-controlled synthetic strategy is extended to thermoplastic elastomeric triblock copolymers differing in chemistry and possessing a random-copolymer midblock.« less

Crystalline imide/arylene ether copolymers

NASA Technical Reports Server (NTRS)

Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor); Bass, Robert G. (Inventor)

1995-01-01

Crystalline imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly)arylene ethers) in polar aprotic solvents and chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The block copolymers of the invention have one glass transition temperature or two, depending on the particular structure and/or the compatibility of the block units. Most of these crystalline block copolymers for tough, solvent resistant films with high tensile properties. While all of the copolymers produced by the present invention are crystalline, testing reveals that copolymers with longer imide blocks or higher imide content have increased crystallinity.

Diffusion of copolymers composed of monomers with drastically different friction factors in copolymer/homopolymer blends

DOE PAGES

Duranty, Edward R.; Baschnagel, Jörg; Dadmun, Mark

2017-02-07

Copolymers are commonly used as interface modifiers that allow for the compatibilization of polymer components in a blend. For copolymers to function as a compatibilizer, they must diffuse through the matrix of the blend to the interface between the two blend components. The diffusivity of a copolymer in a blend matrix therefore becomes important in determining good candidates for use as compatibilizers. In this paper, coarse-grained Monte Carlo simulations using the bond fluctuation model modified with an overlap penalty have been developed to study the diffusive behavior of PS/PMMA random copolymers in a PMMA homopolymer blend. The simulations vary themore » connectivity between different monomers, the thermodynamic interactions between the monomers which manifest within a chain, and between copolymer and homopolymer matrix and define the monomer friction coefficient of each component independently, allowing for the determination of the combined effect of these parameters on copolymer chain diffusion. Finally, the results of this work indicate that PS-r-PMMA copolymer diffusion is not linearly dependent on the copolymer composition on a logarithmic scale, but its diffusion is a balance of the kinetics governed by the dominant motion of the faster styrene monomers and thermodynamics, which are governed by the concentration of styrene monomer within a given monomer’s local volume.« less

Amphiphilic block copolymer membrane for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Wang, Fei; Sylvia, James M.; Jacob, Monsy M.; Peramunage, Dharmasena

2013-11-01

An amphiphilic block copolymer comprised of hydrophobic polyaryletherketone (PAEK) and hydrophilic sulfonated polyaryletherketone (SPAEK) blocks has been synthesized and characterized. A membrane prepared from the block copolymer is used as the separator in a single cell vanadium redox flow battery (VRB). The proton conductivity, mechanical property, VO2+ permeability and single VRB cell performance of this block copolymer membrane are investigated and compared to Nafion™ 117. The block copolymer membrane showed significantly improved vanadium ion selectivity, higher mechanical strength and lower conductivity than Nafion™ 117. The VRB containing the block copolymer membrane exhibits higher coulombic efficiency and similar energy efficiency compared to a VRB using Nafion™ 117. The better vanadium ion selectivity of the block copolymer membrane has led to a much smaller capacity loss during 50 charge-discharge cycles for the VRB.

Studies on novel radiopaque methyl methacrylate: glycidyl methacrylate based polymer for biomedical applications.

PubMed

Dawlee, S; Jayakrishnan, A; Jayabalan, M

2009-12-01

A new class of radiopaque copolymer using methyl methacrylate (MMA) and glycidyl methacrylate (GMA) monomers was synthesized and characterized. The copolymer was made radiopaque by the epoxide ring opening of GMA using the catalyst o-phenylenediamine and the subsequent covalent attachment of elemental iodine. The copolymer was characterized by Fourier transform infrared (FTIR) spectra, energy dispersive X-ray analysis using environmental scanning electron microscope (EDAX), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). X-ray visibility of the copolymer was checked by X-radiography. Blood compatibility and cytotoxicity of the newly synthesized copolymer were also evaluated. The iodinated copolymer was thermally stable, blood compatible, non-cytotoxic, and highly radiopaque. The presence of bulky iodine group created a new copolymer with modified properties for potential use in biomedical applications.

Periodic nanostructures from self assembled wedge-type block-copolymers

DOEpatents

Xia, Yan; Sveinbjornsson, Benjamin R.; Grubbs, Robert H.; Weitekamp, Raymond; Miyake, Garret M.; Piunova, Victoria; Daeffler, Christopher Scot

2015-06-02

The invention provides a class of wedge-type block copolymers having a plurality of chemically different blocks, at least a portion of which incorporates a wedge group-containing block providing useful properties. For example, use of one or more wedge group-containing blocks in some block copolymers of the invention significantly inhibits chain entanglement and, thus, the present block copolymers materials provide a class of polymer materials capable of efficient molecular self-assembly to generate a range of structures, such as periodic nanostructures and microstructures. Materials of the present invention include copolymers having one or more wedge group-containing blocks, and optionally for some applications copolymers also incorporating one or more polymer side group-containing blocks. The present invention also provides useful methods of making and using wedge-type block copolymers.

Method of producing nanopatterned articles, and articles produced thereby

DOEpatents

Russell, Thomas P; Park, Soojin; Xu, Ting

2013-11-12

A nanopatterned surface is prepared by forming a block copolymer film on a miscut crystalline substrate, annealing the block copolymer film, then reconstructing the surface of the annealed block copolymer film. The method creates a well-ordered array of voids in the block copolymer film that is maintained over a large area. The nanopatterned block copolymer films can be used ina variety of different applications, including the fabrication of high density data storage media.

40 CFR 721.10213 - Polyether polyester copolymer phosphate (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Polyether polyester copolymer... Specific Chemical Substances § 721.10213 Polyether polyester copolymer phosphate (generic). (a) Chemical... as polyether polyester copolymer phosphate (PMN P-09-253) is subject to reporting under this section...

21 CFR 177.1480 - Nitrile rubber modified acrylonitrile-methyl acrylate copolymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Nitrile rubber modified acrylonitrile-methyl... Nitrile rubber modified acrylonitrile-methyl acrylate copolymers. Nitrile rubber modified acrylonitrile... rubber modified acrylonitrile-methyl acrylate copolymers consist of basic copolymers produced by the...

40 CFR 721.10519 - Perfluoroalkyl acrylate copolymer (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... as perfluoroalkyl acrylate copolymer (PMN P-11-63) is subject to reporting under this section for the... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Perfluoroalkyl acrylate copolymer... Specific Chemical Substances § 721.10519 Perfluoroalkyl acrylate copolymer (generic). (a) Chemical...

40 CFR 721.10519 - Perfluoroalkyl acrylate copolymer (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... as perfluoroalkyl acrylate copolymer (PMN P-11-63) is subject to reporting under this section for the... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Perfluoroalkyl acrylate copolymer... Specific Chemical Substances § 721.10519 Perfluoroalkyl acrylate copolymer (generic). (a) Chemical...

40 CFR 721.336 - Perfluoroalkylethyl acrylate copolymer (generic name).

Code of Federal Regulations, 2011 CFR

2011-07-01

... as a perfluoroalkylethyl acrylate copolymer (PMN P-94-241) is subject to reporting under this section... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Perfluoroalkylethyl acrylate copolymer... Specific Chemical Substances § 721.336 Perfluoroalkylethyl acrylate copolymer (generic name). (a) Chemical...

40 CFR 721.336 - Perfluoroalkylethyl acrylate copolymer (generic name).

Code of Federal Regulations, 2013 CFR

2013-07-01

... as a perfluoroalkylethyl acrylate copolymer (PMN P-94-241) is subject to reporting under this section... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Perfluoroalkylethyl acrylate copolymer... Specific Chemical Substances § 721.336 Perfluoroalkylethyl acrylate copolymer (generic name). (a) Chemical...

40 CFR 721.336 - Perfluoroalkylethyl acrylate copolymer (generic name).

Code of Federal Regulations, 2014 CFR

2014-07-01

... as a perfluoroalkylethyl acrylate copolymer (PMN P-94-241) is subject to reporting under this section... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Perfluoroalkylethyl acrylate copolymer... Specific Chemical Substances § 721.336 Perfluoroalkylethyl acrylate copolymer (generic name). (a) Chemical...

40 CFR 721.336 - Perfluoroalkylethyl acrylate copolymer (generic name).

Code of Federal Regulations, 2012 CFR

2012-07-01

... as a perfluoroalkylethyl acrylate copolymer (PMN P-94-241) is subject to reporting under this section... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Perfluoroalkylethyl acrylate copolymer... Specific Chemical Substances § 721.336 Perfluoroalkylethyl acrylate copolymer (generic name). (a) Chemical...

Synthesis of biodegradable and electroactive multiblock polylactide and aniline pentamer copolymer for tissue engineering applications.

PubMed

Huang, Lihong; Zhuang, Xiuli; Hu, Jun; Lang, Le; Zhang, Peibiao; Wang, Yu; Chen, Xuesi; Wei, Yen; Jing, Xiabin

2008-03-01

To obtain one biodegradable and electroactive polymer as the scaffold for tissue engineering, the multiblock copolymer PLAAP was designed and synthesized with the condensation polymerization of hydroxyl-capped poly( l-lactide) (PLA) and carboxyl-capped aniline pentamer (AP). The PLAAP copolymer exhibited excellent electroactivity, solubility, and biodegradability. At the same time, as one scaffold material, PLAAP copolymer possesses certain mechanical properties with the tensile strength of 3 MPa, tensile Young 's modulus of 32 MPa, and breaking elongation rate of 95%. We systematically studied the compatibility of PLAAP copolymer in vitro and proved that the electroactive PLAAP copolymer was innocuous, biocompatible, and helpful for the adhesion and proliferation of rat C6 cells. Moreover, the PLAAP copolymer stimulated by electrical signals was demonstrated as accelerating the differentiation of rat neuronal pheochromocytoma PC-12 cells. This biodegradable and electroactive PLAAP copolymer thus possessed the properties in favor of the long-time application in vivo as nerve repair scaffold materials in tissue engineering.

21 CFR 172.775 - Methacrylic acid-divinylbenzene copolymer.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Methacrylic acid-divinylbenzene copolymer. 172.775... HUMAN CONSUMPTION Other Specific Usage Additives § 172.775 Methacrylic acid-divinylbenzene copolymer. Methacrylic acid-divinylbenzene copolymer may be safely used in food in accordance with the following...

21 CFR 172.775 - Methacrylic acid-divinylbenzene copolymer.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Methacrylic acid-divinylbenzene copolymer. 172.775... HUMAN CONSUMPTION Other Specific Usage Additives § 172.775 Methacrylic acid-divinylbenzene copolymer. Methacrylic acid-divinylbenzene copolymer may be safely used in food in accordance with the following...

Method of producing nanopatterned articles, and articles produced thereby

DOEpatents

Russell, Thomas P; Park, Soojin; Xu, Ting

2015-04-28

A nanopatterned surface is prepared by forming a block copolymer film on a miscut crystalline substrate, annealing the block copolymer film, then reconstructing the surface of the annealed block copolymer film The method creates a well-ordered array of voids in the block copolymer film that is maintained over a large area. The nanopatterned block copolymer films can be used in a variety of different applications, including the fabrication of high density data storage media.

Oxygen plasma resistant phosphine oxide containing imide/arylene copolymers

NASA Technical Reports Server (NTRS)

Jensen, Brian J.

1993-01-01

A series of oxygen plasma resistant imide/arylene ether copolymers were prepared by reacting anhydride-terminated poly(amide acids) and amine-terminated polyarylene ethers containing phosphine oxide units. Inherent viscosities for these copolymers ranged from 0.42 to 0.80 dL/g. After curing, the resulting copolymers had glass transition temperatures ranging from 224 C to 228 C. Solution cast films of the block copolymers were tough and flexible with tensile strength, tensile moduli, and elongation at break up to 16.1 ksi, 439 ksi, and 23 percent, respectively at 25 C and 9.1 ksi, 308 ksi and 97 percent, respectively at 150 C. The copolymers show a significant improvement in resistance to oxygen plasma when compared to the commercial polyimide Kapton. The imide/arylene ether copolymers containing phosphine oxide units are suitable as coatings, films, adhesives, and composite matrices.

Counteranion-Mediated Intrinsic Healing of Poly(ionic liquid) Copolymers.

PubMed

Guo, Panlong; Zhang, Houyu; Liu, Xiaokong; Sun, Junqi

2018-01-17

Fabrication of self-healing/healable materials using reversible interactions that are governed by their inherent chemical features is highly desirable because it avoids the introduction of extra groups that may present negative effects on their functions. The present study exploits the inherently featured electrostatic interactions of the ion pairs in polymeric ionic liquids (PILs) as the driving force to fabricate healable PIL copolymers. The healable PIL copolymers are fabricated through the copolymerization of the IL monomers with ethyl acrylate followed by the replacement of Br - counteranions with bulkier ones such as bis(trifluoromethanesulfonyl)imide (TFSI - ). Without modifying the chemical structures of the PIL moieties, the healing performance of the as-prepared PIL copolymers can be effectively mediated by their counteranions. The PIL copolymers that do not possess healability when paired with Br - counteranions become healable after exchanging the Br - counteranions with larger-sized ones (e.g., TFSI - ). The PIL copolymers paired with bulky counteranions exhibit enhanced chain mobility and highly reversible ion-pair interactions, which facilitate the healing process. The PIL copolymers paired with TFSI - anions can completely heal the damage/cut upon heating at 55 °C for 7.5 h. Meanwhile, the counteranions with larger sizes not only benefit the healing performance of the PIL copolymers but also enhance their ion conductivity. The ion conductivity of the PIL copolymers paired with TFSI - is an order of magnitude higher than that of the PIL copolymers paired with Br - . Therefore, the as-prepared healable PIL copolymers are potentially useful as solid electrolytes in PIL-based energy devices to improve their safety and reliability.

21 CFR 177.1020 - Acrylonitrile/butadiene/sty-rene co-polymer.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylonitrile/butadiene/sty-rene co-polymer. 177... SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances.../butadiene/sty-rene co-polymer. Acrylonitrile/butadiene/styrene copolymer identified in this section may be...

21 CFR 177.1020 - Acrylonitrile/butadiene/sty-rene co-polymer.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Acrylonitrile/butadiene/sty-rene co-polymer. 177... SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances.../butadiene/sty-rene co-polymer. Acrylonitrile/butadiene/styrene copolymer identified in this section may be...

21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

Code of Federal Regulations, 2011 CFR

2011-04-01

... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified as... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Cross-linked polyacrylate copolymers. 177.1211... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1211 Cross-linked polyacrylate...

21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified as... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Cross-linked polyacrylate copolymers. 177.1211... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1211 Cross-linked polyacrylate...

21 CFR 177.1020 - Acrylonitrile/butadiene/sty-rene co-polymer.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Acrylonitrile/butadiene/sty-rene co-polymer. 177... SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances.../butadiene/sty-rene co-polymer. Acrylonitrile/butadiene/styrene copolymer identified in this section may be...

21 CFR 177.1020 - Acrylonitrile/butadiene/sty-rene co-polymer.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Acrylonitrile/butadiene/sty-rene co-polymer. 177... SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances.../butadiene/sty-rene co-polymer. Acrylonitrile/butadiene/styrene copolymer identified in this section may be...

76 FR 42613 - National Emission Standards for Hazardous Air Pollutants for Polyvinyl Chloride and Copolymers...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-07-19

... National Emission Standards for Hazardous Air Pollutants for Polyvinyl Chloride and Copolymers Production... Polyvinyl Chloride and Copolymers Production is being extended for 14 days. DATES: Comments. The public... for the May 20, 2011, Proposed Polyvinyl Chloride and Copolymers Production Rule, the EPA is extending...

40 CFR 721.10419 - Tetrafluoroethylene chlorotrifluoroethylene copolymer (generic) (P-11-561).

Code of Federal Regulations, 2013 CFR

2013-07-01

... chlorotrifluoroethylene copolymer (generic) (P-11-561). 721.10419 Section 721.10419 Protection of Environment... chlorotrifluoroethylene copolymer (generic) (P-11-561). (a) Chemical substance and significant new uses subject to... copolymer (PMN P-11-561) is subject to reporting under this section for the significant new uses described...

40 CFR 721.10419 - Tetrafluoroethylene chlorotrifluoroethylene copolymer (generic) (P-11-561).

Code of Federal Regulations, 2012 CFR

2012-07-01

... chlorotrifluoroethylene copolymer (generic) (P-11-561). 721.10419 Section 721.10419 Protection of Environment... chlorotrifluoroethylene copolymer (generic) (P-11-561). (a) Chemical substance and significant new uses subject to... copolymer (PMN P-11-561) is subject to reporting under this section for the significant new uses described...

40 CFR 721.10419 - Tetrafluoroethylene chlorotrifluoroethylene copolymer (generic) (P-11-561).

Code of Federal Regulations, 2014 CFR

2014-07-01

... chlorotrifluoroethylene copolymer (generic) (P-11-561). 721.10419 Section 721.10419 Protection of Environment... chlorotrifluoroethylene copolymer (generic) (P-11-561). (a) Chemical substance and significant new uses subject to... copolymer (PMN P-11-561) is subject to reporting under this section for the significant new uses described...

21 CFR 177.1060 - n-Alkylglutarimide/acrylic copolymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true n-Alkylglutarimide/acrylic copolymers. 177.1060... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1060 n-Alkylglutarimide/acrylic copolymers. n-Alkylglutarimide/acrylic copolymers identified in this section may be safely used as articles...

21 CFR 177.1350 - Ethylene-vinyl acetate copolymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-vinyl acetate copolymers. 177.1350 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1350 Ethylene-vinyl acetate copolymers. Ethylene-vinyl acetate copolymers may be safely used as articles or components of articles...

21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-acrylic acid copolymers. 177.1310 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1310 Ethylene-acrylic acid copolymers. The ethylene-acrylic acid copolymers identified in paragraph (a) of this section may be safely...

21 CFR 177.1312 - Ethylene-carbon monoxide copolymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-carbon monoxide copolymers. 177.1312... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1312 Ethylene-carbon monoxide copolymers. The ethylene-carbon monoxide copolymers identified in paragraph (a) of this section may be safely...

21 CFR 177.1320 - Ethylene-ethyl acrylate copolymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-ethyl acrylate copolymers. 177.1320... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1320 Ethylene-ethyl acrylate copolymers. Ethylene-ethyl acrylate copolymers may be safely used to produce packaging materials, containers...

Self-assembly of block copolymers on topographically patterned polymeric substrates

DOEpatents

Russell, Thomas P.; Park, Soojin; Lee, Dong Hyun; Xu, Ting

2016-05-10

Highly-ordered block copolymer films are prepared by a method that includes forming a polymeric replica of a topographically patterned crystalline surface, forming a block copolymer film on the topographically patterned surface of the polymeric replica, and annealing the block copolymer film. The resulting structures can be used in a variety of different applications, including the fabrication of high density data storage media. The ability to use flexible polymers to form the polymeric replica facilitates industrial-scale processes utilizing the highly-ordered block copolymer films.

Protein based Block Copolymers

PubMed Central

Rabotyagova, Olena S.; Cebe, Peggy; Kaplan, David L.

2011-01-01

Advances in genetic engineering have led to the synthesis of protein-based block copolymers with control of chemistry and molecular weight, resulting in unique physical and biological properties. The benefits from incorporating peptide blocks into copolymer designs arise from the fundamental properties of proteins to adopt ordered conformations and to undergo self-assembly, providing control over structure formation at various length scales when compared to conventional block copolymers. This review covers the synthesis, structure, assembly, properties, and applications of protein-based block copolymers. PMID:21235251

Effect of Temperature on Electrical Conductivity of Guaiacol-Guanidine Hydrochloride-Formaldehyde Copolymer Resin

NASA Astrophysics Data System (ADS)

Kukade, S. D.; Bawankar, S. V.

2018-02-01

The purpose of the present paper is to report temperature dependence of electrical conductivity on Guaiacol-guanidine hydrochloride-formaldehyde copolymer resin. By using a microwave irradiation technique, various ratios of copolymer resin were synthesized from the reacting monomers, i.e., guaiacol, guanidine hydrochloride and formaldehyde. The characterization of the copolymer resins has been fulfilled by spectral methods viz. ultraviolet visible (UV visible), infrared and proton nuclear magnetic spectroscopy (1H-NMR). The solid state direct current electrical conductivity of synthesized copolymer resins has been measured as a function of temperature. The electrical conductivity values of all the copolymers have been found in the range of a semiconductor.

Branched Rod-Coil Polyimide-Poly(Alkylene Oxide) Copolymers and Electrolyte Compositions

NASA Technical Reports Server (NTRS)

Meador, Maryann B. (Inventor); Tigelaar, Dean M. (Inventor)

2014-01-01

Crosslinked polyimide-poly(alkylene oxide) copolymers capable of holding large volumes of liquid while maintaining good dimensional stability. Copolymers are derived at ambient temperatures from amine endcapped amic-acid oligomers subsequently imidized in solution at increased temperatures, followed by reaction with trifunctional compounds in the presence of various additives. Films of these copolymers hold over four times their weight at room temperature of liquids such as ionic liquids (RTIL) and/or carbonate solvents. These rod-coil polyimide copolymers are used to prepare polymeric electrolytes by adding to the copolymers various amounts of compounds such as ionic liquids (RTIL), lithium trifluoromethane-sulfonimide (LiTFSi) or other lithium salts, and alumina.

Polymer scaffold degradation control via chemical control

DOEpatents

Hedberg-Dirk, Elizabeth L.; Dirk, Shawn; Cicotte, Kirsten

2016-01-05

A variety of polymers and copolymers suitable for use as biologically compatible constructs and, as a non-limiting specific example, in the formation of degradable tissue scaffolds as well methods for synthesizing these polymers and copolymers are described. The polymers and copolymers have degradation rates that are substantially faster than those of previously described polymers suitable for the same uses. Copolymers having a synthesis route which enables one to fine tune the degradation rate by selecting the specific stoichiometry of the monomers in the resulting copolymer are also described. The disclosure also provides a novel synthesis route for maleoyl chloride which yields monomers suitable for use in the copolymer synthesis methods described herein.

Multidimensional chromatographic techniques for hydrophilic copolymers II. Analysis of poly(ethylene glycol)-poly(vinyl acetate) graft copolymers.

PubMed

Knecht, Daniela; Rittig, Frank; Lange, Ronald F M; Pasch, Harald

2006-10-13

A large variety of hydrophilic copolymers is applied in different fields of chemical industry including bio, pharma and pharmaceutical applications. For example, poly(ethylene glycol)-poly(vinyl alcohol) graft copolymers that are used as tablet coatings are responsible for the controlled release of the active compounds. These copolymers are produced by grafting of vinyl acetate onto polyethylene glycol (PEG) and subsequent hydrolysis of the poly(ethylene glycol)-poly(vinyl acetate) graft copolymers. The poly(ethylene glycol)-poly(vinyl acetate) copolymers are distributed with regard to molar mass and chemical composition. In addition, they frequently contain the homopolymers polyethylene glycol and polyvinyl acetate. The comprehensive analysis of such complex systems requires hyphenated analytical techniques, including two-dimensional liquid chromatography and combined LC and nuclear magnetic resonance spectroscopy. The development and application of these techniques are discussed in the present paper.

Improved block copolymer domain dispersity on chemical patterns via homopolymer-blending and molecular transfer printing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Guoliang; Nealey, Paul F.

Herein we have investigated the domain width distributions of block copolymers and their ternary blends after directed assembly on chemically patterned surfaces with and without density multiplication. On chemical patterns with density multiplication, the width of the interpolated block copolymer domains was bimodal. Once blended with the corresponding homopolymers, the block copolymers exhibited unimodal distributions of domain width due to the redistribution of homopolymers in the block copolymer domains. When the block copolymers were blended with hydroxyl-terminated homopolymers, the homopolymers with functional end-groups healed the chemical patterns and facilitated the formation of nanostructures with further improved domain width distributions. Lastly,more » it is demonstrated that the block copolymers achieved the most improved domain width distributions when directed to assemble without density multiplication on one-to-one chemical patterns generated by molecular transfer printing.« less

40 CFR 180.1162 - Acrylate polymers and copolymers; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Acrylate polymers and copolymers... RESIDUES IN FOOD Exemptions From Tolerances § 180.1162 Acrylate polymers and copolymers; exemption from the requirement of a tolerance. (a) Acrylate polymers and copolymers are exempt from the requirement of a...

40 CFR 180.1162 - Acrylate polymers and copolymers; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Acrylate polymers and copolymers... RESIDUES IN FOOD Exemptions From Tolerances § 180.1162 Acrylate polymers and copolymers; exemption from the requirement of a tolerance. (a) Acrylate polymers and copolymers are exempt from the requirement of a...

40 CFR 180.1162 - Acrylate polymers and copolymers; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Acrylate polymers and copolymers... RESIDUES IN FOOD Exemptions From Tolerances § 180.1162 Acrylate polymers and copolymers; exemption from the requirement of a tolerance. (a) Acrylate polymers and copolymers are exempt from the requirement of a...

40 CFR 180.1162 - Acrylate polymers and copolymers; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Acrylate polymers and copolymers... RESIDUES IN FOOD Exemptions From Tolerances § 180.1162 Acrylate polymers and copolymers; exemption from the requirement of a tolerance. (a) Acrylate polymers and copolymers are exempt from the requirement of a...

21 CFR 177.1960 - Vinyl chloride-hexene-1 copolymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Vinyl chloride-hexene-1 copolymers. 177.1960... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1960 Vinyl chloride-hexene-1 copolymers. The vinyl chloride-hexene-1 copolymers identified in paragraph (a) of this section or as...

21 CFR 177.1340 - Ethylene-methyl acrylate copolymer resins.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-methyl acrylate copolymer resins. 177.1340... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1340 Ethylene-methyl acrylate copolymer resins. Ethylene-methyl acrylate copolymer resins may be safely used as articles or components of...

21 CFR 177.1360 - Ethylene-vinyl acetate-vinyl alcohol copolymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-vinyl acetate-vinyl alcohol copolymers... for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1360 Ethylene-vinyl acetate-vinyl alcohol copolymers. Ethylene-vinyl acetate-vinyl alcohol copolymers (CAS Reg. No. 26221-27-2...

pH-sensitive methacrylic copolymers and the production thereof

DOEpatents

Mallapragada, Surya K.; Anderson, Brian C.; Bloom, Paul D.; Sheares Ashby, Valerie V.

2006-02-14

The present invention provides novel multi-functional methacrylic copolymers that exhibit cationic pH-sensitive behavior as well as good water solubility under acidic conditions. The copolymers are constructed from tertiary amine methacrylates and poly(ethylene glycol) containing methacrylates. The copolymers are useful as gene vectors, pharmaceutical carriers, and in protein separation applications.

pH-sensitive methacrylic copolymers and the production thereof

DOEpatents

Mallapragada, Surya K.; Anderson, Brian C.; Bloom, Paul D.; Sheares Ashby, Valerie V.

2007-01-09

The present invention provides novel multi-functional methacrylic copolymers that exhibit cationic pH-sensitive behavior as well as good water solubility under acidic conditions. The copolymers are constructed from tertiary amine methacrylates and poly(ethylene glycol) containing methacrylates. The copolymers are useful as gene vectors, pharmaceutical carriers, and in protein separation applications.

The Synthesis and Structural Characterization of Graft Copolymers Composed of γ-PGA Backbone and Oligoesters Pendant Chains

NASA Astrophysics Data System (ADS)

Kwiecień, Iwona; Radecka, Iza; Kowalczuk, Marek; Jelonek, Katarzyna; Orchel, Arkadiusz; Adamus, Grażyna

2017-10-01

The novel copolymers composed of poly-γ-glutamic acid (γ-PGA) and oligoesters have been developed. The structures of the obtained copolymers including variety of end groups were determined at the molecular level with the aid of electrospray ionization multistage mass spectrometry (ESI-MSn). The fragmentation experiment performed for the selected sodium adducts of the copolymers confirmed that the developed methods lead to the formation of graft copolymers composed of poly-γ-glutamic acid (γ-PGA) backbone and oligoesters pendant chains. Moreover, it was established that fragmentation of selected sodium adducts of graft copolymers proceeded via random breakage of amide bonds along the backbone and ester bonds of the oligoesters pendant chains. Considering potential applications of the synthesized copolymers in the area of biomaterials, the hydrolytic degradation under laboratory conditions and in vitro cytotoxicity tests were performed. The ESI-MSn technique applied in this study has been proven to be a useful tool in structural studies of novel graft copolymers as well as their degradation products. [Figure not available: see fulltext.

Sorption of Aromatic Compounds with Copolymer Sorbent Materials Containing β-Cyclodextrin.

PubMed

Wilson, Lee D; Mohamed, Mohamed H; Berhaut, Christopher L

2011-08-29

Urethane copolymer sorbent materials that incorporate β-cyclodextrin (CD) have been prepared and their sorption properties with chlorinated aromatic compounds (i.e., pentachlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid) have been evaluated. The sorption properties of granular activated carbon (GAC) were similarly compared in aqueous solution at variable pH conditions. The sorbents displayed variable BET surface areas as follows: MDI-X copolymers (< 10¹ m²/g), CDI-X copolymers (< 10¹ m²/g), and granular activated carbon (GAC ~10³ m²/g). The sorption capacities for the copolymers sorbents are listed in descending order, as follows: GAC > CDI-3 copolymer ≈ MDI-3 copolymer. The sorption capacity for the aromatic adsorbates with each sorbent are listed in descending order, as follows: 2,4-dichlorophenol > 2,4-dichlorophenoxy acetic acid > pentachlorophenol. In general, the differences in the sorption properties of the copolymer sorbents with the chlorinated organics were related to the following factors: (i) surface area of the sorbent; (ii) CD content and accessibility; and (iii) and the chemical nature of the sorbent material.

Sorption of Aromatic Compounds with Copolymer Sorbent Materials Containing β-Cyclodextrin

PubMed Central

Wilson, Lee D.; Mohamed, Mohamed H.; Berhaut, Christopher L.

2011-01-01

Urethane copolymer sorbent materials that incorporate β-cyclodextrin (CD) have been prepared and their sorption properties with chlorinated aromatic compounds (i.e., pentachlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid) have been evaluated. The sorption properties of granular activated carbon (GAC) were similarly compared in aqueous solution at variable pH conditions. The sorbents displayed variable BET surface areas as follows: MDI-X copolymers (< 101 m2/g), CDI-X copolymers (< 101 m2/g), and granular activated carbon (GAC ~103 m2/g). The sorption capacities for the copolymers sorbents are listed in descending order, as follows: GAC > CDI-3 copolymer ≈ MDI-3 copolymer. The sorption capacity for the aromatic adsorbates with each sorbent are listed in descending order, as follows: 2,4-dichlorophenol > 2,4-dichlorophenoxy acetic acid > pentachlorophenol. In general, the differences in the sorption properties of the copolymer sorbents with the chlorinated organics were related to the following factors: (i) surface area of the sorbent; (ii) CD content and accessibility; and (iii) and the chemical nature of the sorbent material. PMID:28824156

Self-assembly of model graft copolymers of agarose and weak polyelectrolyte-based amphiphilic diblock copolymers: controlled drug release and degradation.

PubMed

Muppalla, Ravikumar; Jewrajka, Suresh K; Prasad, Kamalesh

2013-06-01

Polysaccharide-based copolymers are promising biomaterials due to their biocompatibility and biodegradability. For potential biomedical applications the copolymer as a whole and all the degraded species must be biocompatible and easily removable from the system. In this regards, new model pH-responsive seaweed agarose (Agr) grafted with weak polyelectrolyte-based well-defined amphiphilic block copolymers ca. poly[(methyl methacrylate)-b-(2-dimethylamino)ethyl methacrylate)] (PMMA-b-PDMA) were designed and synthesized to study the self-assembly, degradation, and in vitro hydrophobic/hydrophilic drug release behavior. The graft copolymer solutions display extremely low critical micelle concentration (CMC) and form pH responsive stable micelles. The degradation study of the graft copolymer reveals that the entire degraded components are well soluble/dispersible in water due to formation of mixed micelles. The micelles are also strongly adsorbed on the mica surface owing to electrostatic interaction. One application of the graft copolymer micelles is that it can entrap both hydrophilic and poorly water soluble hydrophobic drugs effectively and exhibit slow release kinetics. The release kinetics of both the hydrophilic and poorly water soluble hydrophobic drugs change with pH as well as with the composition of the graft copolymer. Copyright © 2012 Wiley Periodicals, Inc.

Surface Chemistry of a Microcoated Energetic Material, Pentaerythritoltetranitrate (PETN)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Worley, C.M.; Vannet, M.D.; Ball, G.L.

1987-01-01

A microcoating technique was used to apply a polymer to an energetic explosive material. The explosive was pentaerythritoltetranitrate (PETN), and the coating was a copolymer consisting of vinylchloride/trifluorochloroethylene in a 1.5/1.0 molecular ratio. X-ray photoelectron spectroscopy (XPS) and ion scattering spectroscopy (ISS) were used to study the surface and interfacial chemistry of PETN powders and pellets made from compressed powders having either 0.5 or 20 wt% coating. Two simple models were used to discuss the nature of the copolymer film on the PETN. Model I shows the copolymer completely coating PETN; Model II depicts the copolymer as only partially coveringmore » PETN. Model II was applicable in explaining the 0.5 and 20 wt% microcoating of powders, as well as the 0.5 wt% coated pellets. However, the pellets with 20 wt% coating showed the copolymer to completely coat PETN (Model I), suggesting copolymer redistribution during pelletization. XPS and ISS results showed the copolymer film to be thin. An XPS expression modified to accommodate ISS data was developed for the calculation of the average copolymer thickness of PETN. The thicknesses were determined to be 10 {angstrom} and 6 {angstrom} for 0.5 wt% coated PETN powders and pellets, respectively. Bonding between the copolymer and PETN was concluded to be mechanical.« less

Directed self assembly of block copolymers using chemical patterns with sidewall guiding lines, backfilled with random copolymer brushes.

PubMed

Pandav, Gunja; Durand, William J; Ellison, Christopher J; Willson, C Grant; Ganesan, Venkat

2015-12-21

Recently, alignment of block copolymer domains has been achieved using a topographically patterned substrate with a sidewall preferential to one of the blocks. This strategy has been suggested as an option to overcome the patterning resolution challenges facing chemoepitaxy strategies, which utilize chemical stripes with a width of about half the period of block copolymer to orient the equilibrium morphologies. In this work, single chain in mean field simulation methodology was used to study the self assembly of symmetric block copolymers on topographically patterned substrates with sidewall interactions. Random copolymer brushes grafted to the background region (space between patterns) were modeled explicitly. The effects of changes in pattern width, film thicknesses and strength of sidewall interaction on the resulting morphologies were examined and the conditions which led to perpendicular morphologies required for lithographic applications were identified. A number of density multiplication schemes were studied in order to gauge the efficiency with which the sidewall pattern can guide the self assembly of block copolymers. The results indicate that such a patterning technique can potentially utilize pattern widths of the order of one-two times the period of block copolymer and still be able to guide ordering of the block copolymer domains up to 8X density multiplication.

Preparation of dual-stimuli-responsive liposomes using methacrylate-based copolymers with pH and temperature sensitivities for precisely controlled release.

PubMed

Sugimoto, Takumi; Yamazaki, Naoko; Hayashi, Takaaki; Yuba, Eiji; Harada, Atsushi; Kotaka, Aki; Shinde, Chiharu; Kumei, Takayuki; Sumida, Yasushi; Fukushima, Mitsuhiro; Munekata, Yuki; Maruyama, Keiichi; Kono, Kenji

2017-07-01

Dual-signal-sensitive copolymers were synthesized by copolymerization of methoxy diethylene glycol methacrylate, methacrylic acid, and lauroxy tetraethylene glycol methacrylate, which respectively provide temperature sensitivity, pH sensitivity, and anchoring to liposome surfaces. These novel copolymers, with water solubility that differs depending on temperature and pH, are soluble in water under neutral pH and low-temperature conditions, but they become water-insoluble and form aggregates under acidic pH and high-temperature conditions. Liposomes modified with these copolymers exhibited enhanced content release at weakly acidic pH with increasing temperature, although no temperature-dependent content release was observed in neutral conditions. Interaction between the copolymers and the lipid monolayer at the air-water interface revealed that the copolymer chains penetrate more deeply into the monolayer with increasing temperature at acidic pH than at neutral pH, where the penetration of copolymer chains was moderate and temperature-independent at neutral pH. Interaction of the copolymer-modified liposomes with HeLa cells demonstrated that the copolymer-modified liposomes were adsorbed quickly and efficiently onto the cell surface and that they were internalized more gradually than the unmodified liposomes through endocytosis. Furthermore, the copolymer-modified liposomes enhanced the content release in endosomes with increasing temperature, but no such temperature-dependent enhancement of content release was observed for unmodified liposomes. Copyright © 2017 Elsevier B.V. All rights reserved.

Assessment of new biocompatible poly(N-(morpholino)ethyl methacrylate)-based copolymers by transfection of immortalized keratinocytes.

PubMed

Van Overstraeten-Schlögel, Nancy; Shim, Yong-Ho; Tevel, Virginie; Piel, Géraldine; Piette, Jacques; Dubois, Philippe; Raes, Martine

2012-02-01

Skin carcinomas are among the most commonly diagnosed tumors in the world. In this study, we investigated the transfection of immortalized keratinocytes, used as an in vitro model for skin carcinoma, using the antisense technology and poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA)-based copolymers. In order to improve the transfection efficiency of the classic PDMAEMA polymers, copolymers were synthesized including a poly(N-morpholino)ethylmethacrylate) (PMEMA) moiety for an improved proton-sponge effect, intended to favour the release of the oligonucleotide from the acidic endosome. These copolymers were synthesized either statistically (with alternating PDMAEMA and PMEMA fragments) or in blocks (one PDMAEMA block followed by one PMEMA block). MTT assays were performed using the PDMAEMA-PMEMA copolymers and revealed no significant cytotoxicity of these polymers at an N/P ratio of 7.3. Using fluorescent oligonucleotides and analyzing transfection efficiency by flow cytometry, we noticed no significant differences between the two kinds of copolymers. However copolymers with a higher DMAEMA content and a higher Mn were also those displaying the highest vectorization efficiency. Confocal microscopy showed that these copolymers induced a fine granular distribution of the transfected antisense oligonucleotides inside the cells. We also assessed the functionality of the transfected antisense oligonucleotide by transfecting immortalized GFP expressing keratinocytes with a GFP antisense oligonucleotide using these copolymers. A significant silencing was achieved with a PDMAEMA-PMEMA in block copolymer (Mn=41,000, 89 % PDMAEMA). Together, these results suggest that PDMAEMA-PMEMA copolymers combining low toxicity, vectorization and proton sponge properties, can be efficiently used to transfect immortalized keratinocytes and so open new perspectives in the therapy of skin carcinomas as well as of other skin diseases of genetic or immunological origin. © 2012 Informa Healthcare USA, Inc.

All-Atom Molecular Dynamics-Based Analysis of Membrane-Stabilizing Copolymer Interactions with Lipid Bilayers Probed under Constant Surface Tensions.

PubMed

Houang, Evelyne M; Bates, Frank S; Sham, Yuk Y; Metzger, Joseph M

2017-11-30

An all-atom phospholipid bilayer and triblock copolymer model was developed for molecular dynamics (MD) studies. These were performed to investigate the mechanism of interaction between membrane-stabilizing triblock copolymer P188 and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC) lipid bilayers under applied lateral surface tension (γ) to model membrane mechanical stress. Results showed that P188 insertion is driven by the hydrophobic poly(propylene oxide) (PPO) core and dependent on bilayer area per lipid. Moreover, insertion of P188 increased the bilayer's resistance to mechanical rupture, as observed by a significant increase in the absolute lateral pressure required to disrupt the bilayer. To further investigate the specific chemical features of P188 underlying membrane stabilizer function, a series of MD simulations with triblock copolymers of the same class as P188 but of varying chemical composition and sizes were performed. Results showed that triblock copolymer insertion into the lipid bilayer is dependent on overall copolymer hydrophobicity, with higher copolymer hydrophobicity requiring a reduced bilayer area per lipid ratio for insertion. Further analysis revealed that the effect of copolymer insertion on membrane mechanical integrity was also dependent on hydrophobicity. Here, P188 insertion significantly increased the absolute apparent lateral pressure required to rupture the POPC bilayer, thereby protecting the membrane against mechanical stress. In marked contrast, highly hydrophobic copolymers decreased the lateral pressure necessary for membrane rupture and thus rendering the membrane significantly more susceptible to mechanical stress. These new in silico findings align with recent experimental findings using synthetic lipid bilayers and in muscle cells in vitro and mouse models in vivo. Collectively, these data underscore the importance of PEO-PPO-PEO copolymer chemical composition in copolymer-based muscle membrane stabilization in vitro and in vivo. All-atom modeling with MD simulations holds promise for investigating novel copolymers with enhanced membrane interacting properties.

Copolymers of poly(3-thiopheneacetic acid) with poly(3-hexylthiophene) as hole-transporting material for interfacially engineered perovskite solar cell by modulating band positions for higher efficiency.

PubMed

Shit, Arnab; Chal, Pousali; Nandi, Arun K

2018-06-13

In order to tune the band positions of the hole-transporting material (HTM) in an interfacially engineered perovskite solar cell (PSC), random copolymers of poly(3-thiopheneacetic acid) and poly(3-hexylthiophene) (P3TAA-co-P3HT) with different compositions were produced by oxidative polymerization. The copolymers were characterized using 1H NMR, FTIR, and UV-vis spectroscopy and gel permeation chromatography. Here, ZnO nanoparticles were used as the electron-transporting material (ETM) and methylammonium lead iodide (MAPbI3) perovskite was used as the light-absorbing material to form an FTO/ZnO/MAPbI3/copolymer/Ag device, of which the power conversion efficiency (PCE) was found to be dependent on the copolymer composition and reached a maximum (∼10%) at a P3TAA content of 43 mol% in the copolymer (P3). The band gaps of the copolymers as determined from UV-vis spectroscopy and cyclic voltammetry exhibit a staggered-gap hetero-interface configuration in which the HOMO and LUMO of P3 closely match those of MAPbI3 and give rise to the maximum PCE. Time-resolved photoluminescence spectra of MAPbI3/HTM samples indicate that charge transfer across the perovskite/copolymer interface was faster with a reduced recombination rate for a P3 sample. The electrochemical impedance spectra (EIS) of the PSCs exhibit Nyquist plots with two semicircles, which correspond to an equivalent circuit consisting of two parallel R-C and R-CPE circuits connected in series. Analysis of the data indicates that the effective electron lifetime was longest for the P3 copolymer, which indicates that the charge recombination was lower than that in the components and other copolymers. The copolymers exhibited an intermediate stability with respect to their components, and amongst the copolymers P3 exhibited the highest stability.

Controlling sub-microdomain structure in microphase-ordered block copolymers and their nanocomposites

NASA Astrophysics Data System (ADS)

Bowman, Michelle Kathleen

Block copolymers exhibit a wealth of morphologies that continue to find ubiquitous use in a diverse variety of mature and emergent (nano)technologies, such as photonic crystals, integrated circuits, pharmaceutical encapsulents, fuel cells and separation membranes. While numerous studies have explored the effects of molecular confinement on such copolymers, relatively few have examined the sub-microdomain structure that develops upon modification of copolymer molecular architecture or physical incorporation of nanoscale objects. This work will address two relevant topics in this vein: (i) bidisperse brushes formed by single block copolymer molecules and (ii) copolymer nanocomposites formed by addition of molecular or nanoscale additives. In the first case, an isomorphic series of asymmetric poly(styrene-b -isoprene-b-styrene) (S1IS2) triblock copolymers of systematically varied chain length has been synthesized from a parent SI diblock copolymer. Small-angle x-ray scattering, coupled with dynamic rheology and self-consistent field theory (SCFT), reveals that the progressively grown S2 block initially resides in the I-rich matrix and effectively reduces the copolymer incompatibility until a critical length is reached. At this length, the S2 block co-locates with the S1 block so that the two blocks generate a bidisperse brush (insofar as the S1 and S2 lengths differ). This single-molecule analog to binary block copolymer blends affords unique opportunities for materials design at sub-microdomain length scales and provides insight into the transition from diblock to triblock copolymer (and thermoplastic elastomeric nature). In the second case, I explore the distribution of molecular and nanoscale additives in microphase-ordered block copolymers and demonstrate via SCFT that an interfacial excess, which depends strongly on additive concentration, selectivity and relative size, develops. These predictions are in agreement with experimental findings. Moreover, using a poly(styrene-b-methyl methacrylate) (SM) diblock copolymer with an order-disorder transition temperature (TODT) of 186°C, we find that the addition of clustered and discrete nanoparticles of varying size and surface selectivity can cause T ODT to generally decrease, but occasionally increase. Also experimenting with a poly(styrene-b-isoprene) (SI) diblock copolymer with an TODT of 116°C, we find that the addition of smaller nanoparticles at small volume fractions effect the TODT more profoundly. The latter unexpected results are likewise predicted by SCFT and provide a unique strategy by which to improve the nanostructure stability of block copolymers by physical means.

Water-soluble graft copolymers of starch-acrylamide and uses therefor

DOEpatents

Butler, George B.; Hogen-Esch, Thieo E.; Meister, John J.; Pledger, Jr., Huey

1983-08-23

Graft copolymers having starch as the central chain with grafted side chains of acrylamide or acrylamide-acrylic acid, and a process for preparation of such copolymers in the presence of Ce.sup.+4 or other redox initiators. These copolymers are employed in preparing highly viscous aqueous solutions that are particularly useful in oil recovery from subterranean wells.

Light-emitting block copolymers composition, process and use

DOEpatents

Ferraris, John P.; Gutierrez, Jose J.

2006-11-14

Generally, and in one form, the present invention is a composition of light-emitting block copolymer. In another form, the present invention is a process producing a light-emitting block copolymers that intends polymerizing a first di(halo-methyl) aromatic monomer compound in the presence of an anionic initiator and a base to form a polymer and contacting a second di(halo-methyl) aromatic monomer compound with the polymer to form a homopolymer or block copolymer wherein the block copolymer is a diblock, triblock, or star polymer. In yet another form, the present invention is an electroluminescent device comprising a light-emitting block copolymer, wherein the electroluminescent device is to be used in the manufacturing of optical and electrical devices.

Poly(ortho-phenylenediamine-co-aniline) based copolymer with improved capacitance

NASA Astrophysics Data System (ADS)

Olmedo-Martínez, Jorge L.; Farías-Mancilla, Bárbara I.; Vega-Rios, Alejandro; Zaragoza-Contreras, E. Armando

2017-10-01

A poly(ortho-phenylenediamine-co-aniline) copolymer is synthesized via the oxidative route, using a 1:1 M ratio of aniline to ortho-phenylenediamine (oPDA) and ammonium persulfate as the oxidizing agent. Infrared spectroscopy indicates that the copolymer contains the functional groups typically present in polyaniline and poly(ortho-phenylenediamine); whereas UV-vis-NIR spectroscopy shows that the copolymer adopts a phenazine-type structure. Cyclic voltammetry evidences the copolymer synthesis, as a redox peak at -65 mV, different from those exhibited by polyaniline (160 mV and 600 mV) or poly(o-phenylenediamine) (-240 mV) is observed. Finally, electrochemical impedance spectroscopy and the charge/discharge test provide support to propose the copolymer application in electrodes for supercapacitors.

Pilot scale production of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) biopolymers with high molecular weight and elastomeric properties.

PubMed

Huong, Kai-Hee; Azuraini, Mat Junoh; Aziz, Nursolehah Abdul; Amirul, Al-Ashraf Abdullah

2017-07-01

Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [(P(3HB-co-4HB)] copolymer receives attention as next generation biomaterial in medical application. However, the exploitation of the copolymer is still constrained since such copolymer has not yet successfully been performed in industrial scale production. In this work, we intended to establish pilot production system of the copolymer retaining the copolymer quality which has recently discovered to have novel characteristic from lab scale fermentation. An increase of agitation speed has significantly improved the copolymer accumulation efficiency by minimizing the utilization of substrates towards cell growth components. This is evidenced by a drastic increase of PHA content from 28 wt% to 63 wt% and PHA concentration from 3.1 g/L to 6.5 g/L but accompanied by the reduction of residual biomass from 8.0 g/L to 3.8 g/L. Besides, fermentations at lower agitation and aeration have resulted in reduced molecular weight and mechanical strength of the copolymer, suggesting the role of sufficient oxygen supply efficiency in improving the properties of the resulting copolymers. The K L a-based scale-up fermentation was performed successfully in maintaining the yield and the quality of the copolymers produced without a drastic fluctuation. This suggests that the scale-up based on the K L a values supported the fermentation system of P(3HB-co-4HB) copolymer production in single-stage using mixed-substrate cultivation strategy. Copyright © 2017 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Biocompatible, Biodegradable, and Electroactive Polyurethane-Urea Elastomers with Tunable Hydrophilicity for Skeletal Muscle Tissue Engineering.

PubMed

Chen, Jing; Dong, Ruonan; Ge, Juan; Guo, Baolin; Ma, Peter X

2015-12-30

It remains a challenge to develop electroactive and elastic biomaterials to mimic the elasticity of soft tissue and to regulate the cell behavior during tissue regeneration. We designed and synthesized a series of novel electroactive and biodegradable polyurethane-urea (PUU) copolymers with elastomeric property by combining the properties of polyurethanes and conducting polymers. The electroactive PUU copolymers were synthesized from amine capped aniline trimer (ACAT), dimethylol propionic acid (DMPA), polylactide, and hexamethylene diisocyanate. The electroactivity of the PUU copolymers were studied by UV-vis spectroscopy and cyclic voltammetry. Elasticity and Young's modulus were tailored by the polylactide segment length and ACAT content. Hydrophilicity of the copolymer films was tuned by changing DMPA content and doping of the copolymer. Cytotoxicity of the PUU copolymers was evaluated by mouse C2C12 myoblast cells. The myogenic differentiation of C2C12 myoblasts on copolymer films was also studied by analyzing the morphology of myotubes and relative gene expression during myogenic differentiation. The chemical structure, thermal properties, surface morphology, and processability of the PUU copolymers were characterized by NMR, FT-IR, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and solubility testing, respectively. Those biodegradable electroactive elastic PUU copolymers are promising materials for repair of soft tissues such as skeletal muscle, cardiac muscle, and nerve.

A mathematical model for regulating monomer composition of the microbially synthesized polyhydroxyalkanoate copolymers.

PubMed

Xu, Jun; Guo, Baohua; Zhang, Zengmin; Wu, Qiong; Zhou, Quan; Chen, Jinchun; Chen, Guoqiang; Li, Guodong

2005-06-30

A mathematical model is proposed for predicting the copolymer composition of the microbially synthesized polyhydroxyalkanoate (PHA) copolymers. Based on the biochemical reactions involved in the precursor formation and polymerization pathways, the model correlates the copolymer composition with the cultivation conditions, the enzyme levels and selectivity, and the metabolic pathways. It suggests the following points: (1) in the case of a sole carbon source, the copolymer composition depends mainly on the topology of the metabolic pathways and the selectivity of both the enzymes involved in the precursor formation and the polymerization route; (2) the copolymer composition can be varied in a wide range via alteration of the flux ratio of different types of monomers channeled from two or more independent and simultaneous pathways; (3) the enzymes which should be over-expressed or inhibited to obtain the desired copolymer composition can be predicted. For example, inhibition of the beta-oxidation pathway will increase the content of the monomer units with longer chain length. To test the model, various experiments were envisaged by varying cultivation time, concentration and chain length of the sole carbon source, and molar ratio of the cosubstrates. The predictions from the model agree well with the experimental results. Therefore, the proposed model will be useful in predicting the PHA copolymer composition under different biochemical reaction conditions. In other words, it can provide a guide for the synthesis of desired PHA copolymers.

Water-soluble graft copolymers of starch-acrylamide and uses therefor

DOEpatents

Butler, G.B.; Hogen-Esch, T.E.; Meister, J.J.; Pledger, H. Jr.

1983-08-23

Graft copolymers having starch as the central chain with grafted side chains of acrylamide or acrylamide-acrylic acid, and a process for preparation of such copolymers in the presence of Ce[sup +4] or other redox initiators are disclosed. These copolymers are employed in preparing highly viscous aqueous solutions that are particularly useful in oil recovery from subterranean wells. 2 figs.

Microphase separation in random multiblock copolymers

NASA Astrophysics Data System (ADS)

Govorun, E. N.; Chertovich, A. V.

2017-01-01

Microphase separation in random multiblock copolymers is studied with the mean-field theory assuming that long blocks of a copolymer are strongly segregated, whereas short blocks are able to penetrate into "alien" domains and exchange between the domains and interfacial layer. A bidisperse copolymer with blocks of only two sizes (long and short) is considered as a model of multiblock copolymers with high polydispersity in the block size. Short blocks of the copolymer play an important role in the microphase separation. First, their penetration into the "alien" domains leads to the formation of joint long blocks in their own domains. Second, short blocks localized at the interface considerably change the interfacial tension. The possibility of penetration of short blocks into the "alien" domains is controlled by the product χ Nsh (χ is the Flory-Huggins interaction parameter and Nsh is the short block length). At not very large χ Nsh , the domain size is larger than that for a regular copolymer consisting of the same long blocks as in the considered random copolymer. At a fixed mean block size, the domain size grows with an increase in the block size dispersity, the rate of the growth being dependent of the more detailed parameters of the block size distribution.

Highχ block copolymers for directed self-assembly patterning without the need for topcoat or solvent annealing

NASA Astrophysics Data System (ADS)

Xu, Kui; Hockey, Mary Ann; Calderas, Eric; Guerrero, Douglas; Sweat, Daniel; Fiehler, Jeffrey

2017-03-01

High-χ block copolymers for directed self-assembly (DSA) patterning that do not need topcoat or solvent annealing have been developed. A variety of functionalities have been successfully added into the block copolymers, such as balanced surface energy between the polymer blocks, outstandingly high χ, tunable glass transition temperature (Tg), and selective crosslinking. Perpendicular orientation control, as desired for patterning, of the block copolymers can be simply achieved by thermal annealing due to the equal surface energy of the polymer blocks at the annealing temperatures, which allows avoiding solvent annealing or top-coat. The χ value can be tuned up to achieve L0 as low as 8-10 nm for lamellar-structured block copolymers and hole/pillar size as small as 5-6 nm for cylinder-structured block copolymers. The Tg of the block copolymers can be tuned to improve the kinetics of thermal annealing by enhancing the polymer chain mobility. Block-selective crosslinking facilitates the pattern transfer by mitigating pattern collapse during wet etching and improving oxygen plasma etching selectivity between the polymer blocks. This paper provides an introductory review of our high-χ block copolymer materials with various functionalities for achieving improved DSA performance.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duranty, Edward R.; Baschnagel, Jörg; Dadmun, Mark

Copolymers are commonly used as interface modifiers that allow for the compatibilization of polymer components in a blend. For copolymers to function as a compatibilizer, they must diffuse through the matrix of the blend to the interface between the two blend components. The diffusivity of a copolymer in a blend matrix therefore becomes important in determining good candidates for use as compatibilizers. In this paper, coarse-grained Monte Carlo simulations using the bond fluctuation model modified with an overlap penalty have been developed to study the diffusive behavior of PS/PMMA random copolymers in a PMMA homopolymer blend. The simulations vary themore » connectivity between different monomers, the thermodynamic interactions between the monomers which manifest within a chain, and between copolymer and homopolymer matrix and define the monomer friction coefficient of each component independently, allowing for the determination of the combined effect of these parameters on copolymer chain diffusion. Finally, the results of this work indicate that PS-r-PMMA copolymer diffusion is not linearly dependent on the copolymer composition on a logarithmic scale, but its diffusion is a balance of the kinetics governed by the dominant motion of the faster styrene monomers and thermodynamics, which are governed by the concentration of styrene monomer within a given monomer’s local volume.« less

Thermo- and pH-Responsive Copolymers Bearing Cholic Acid and Oligo(ethylene glycol) Pendants: Self-Assembly and pH-Controlled Release.

PubMed

Jia, Yong-Guang; Zhu, X X

2015-11-11

A family of block and random copolymers of norbornene derivatives bearing cholic acid and oligo(ethylene glycol) pendants were prepared in the presence of Grubbs' catalyst. The phase transition temperature of the copolymers in aqueous solutions may be tuned by the variation of comonomer ratios and pH values. Both types of copolymers formed micellar nanostructures with a hydrophilic poly(ethylene glycol) shell and a hydrophobic core containing cholic acid residues. The micellar size increased gradually with increasing pH due to the deprotonation of the carboxylic acid groups. These micelles were capable of encapsulating hydrophobic compounds such as Nile Red (NR). A higher hydrophobicity/hydrophilicity ratio in both copolymers resulted in a higher loading capacity for NR. With similar molecular weights and monomer compositions, the block copolymers showed a higher loading capacity for NR than the random copolymers. The NR-loaded micelles exhibited a pH-triggered release behavior. At pH 7.4 within 96 h, the micelles formed by the block and random of copolymers released 56 and 97% NR, respectively. Therefore, these micelles may have promise for use as therapeutic nanocarriers in drug delivery systems.

Mesoscopic Simulations of Adsorption and Association of PEO-PPO-PEO Triblock Copolymers on a Hydrophobic Surface: From Mushroom Hemisphere to Rectangle Brush.

PubMed

Song, Xianyu; Zhao, Shuangliang; Fang, Shenwen; Ma, Yongzhang; Duan, Ming

2016-11-08

The dissipative particle dynamics (DPD) method is used to investigate the adsorption behavior of PEO-PPO-PEO triblock copolymers at the liquid/solid interface. The effect of molecular architecture on the self-assembled monolayer adsorption of PEO-PPO-PEO triblock copolymers on hydrophobic surfaces is elucidated by the adsorption process, film properties, and adsorption morphologies. The adsorption thicknesses on hydrophobic surfaces and the diffusion coefficient as well as the aggregation number of Pluronic copolymers in aqueous solution observed in our simulations agree well with previous experimental and numerical observations. The radial distribution function revealed that the ability of self-assembly on hydrophobic surfaces is P123 > P84 > L64 > P105 > F127, which increased with the EO ratio of the Pluronic copolymers. Moreover, the shape parameter and the degree of anisotropy increase with increasing molecular weight and mole ratio of PO of the Pluronic copolymers. Depending on the conformation of different Pluronic copolymers, the morphology transition of three regimes on hydrophobic surfaces is present: mushroom or hemisphere, progressively semiellipsoid, and rectangle brush regimes induced by decreasing molecular weight and mole ratio of EO of Pluronic copolymers.

Tribological Behavior of Aqueous Copolymer Lubricant in Mixed Lubrication Regime.

PubMed

Ta, Thi D; Tieu, A Kiet; Zhu, Hongtao; Zhu, Qiang; Kosasih, Prabouno B; Zhang, Jie; Deng, Guanyu

2016-03-02

Although a number of experiments have been attempted to investigate the lubrication of aqueous copolymer lubricant, which is applied widely in metalworking operations, a comprehensive theoretical investigation at atomistic level is still lacking. This study addresses the influence of loading pressure and copolymer concentration on the structural properties and tribological performance of aqueous copolymer solution of poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) (PPO-PEO-PPO) at mixed lubrication using a molecular dynamic (MD) simulation. An effective interfacial potential, which has been derived from density functional theory (DFT) calculations, was employed for the interactions between the fluid's molecules and iron surface. The simulation results have indicated that the triblock copolymer is physisorption on iron surface. Under confinement by iron surfaces, the copolymer molecules form lamellar structure in aqueous solution and behave differently from its bulk state. The lubrication performance of aqueous copolymer lubricant increases with concentration, but the friction reduction is insignificant at high loading pressure. Additionally, the plastic deformation of asperity is dependent on both copolymer concentration and loading pressure, and the wear behavior shows a linear dependence of friction force on the number of transferred atoms between contacting asperities.

Synthesis and characterization of poly(L-alanine)-block-poly(ethylene glycol) monomethyl ether as amphiphilic biodegradable co-polymers.

PubMed

Zhang, Guolin; Ma, Jianbiao; Li, Yanhong; Wang, Yinong

2003-01-01

Di-block co-polymers of poly(L-alanine) with poly(ethylene glycol) monomethyl ether (MPEG) were synthesized as amphiphilic biodegradable co-polymers. The ring-opening polymerization of N-carboxy-L-alanine anhydride (NCA) in dichloromethane was initiated by amino-terminated poly(ethylene glycol) monomethyl ether (MPEG-NH2, M(n) = 2000) to afford poly(L-alanine)-block-MPEG. The weight ratio of two blocks in the co-polymers could be altered by adjusting the feeding ratio of NCA to MPEG-NH2. Their chemical structures were characterized on the basis of infrared spectrometry and nuclear magnetic resonance. According to circular dichroism measurement, the poly(L-alanine) chain on the co-polymers in an aqueous medium had a alpha-helix conformation. Two melting points from MPEG block and poly(L-alanine), respectively, could be observed in differential scanning calorimetry curves of the co-polymers, suggesting that a micro-domain phase separation appeared in their bulky states. The co-polymers could take up some water and the capacity was dependent on the ratio of poly(L-alanine) block to MPEG. Such co-polymers might be useful in drug-delivery systems and other biomedical applications.

The Origin of Hierarchical Structure Formation in Highly Grafted Symmetric Supramolecular Double-Comb Diblock Copolymers.

PubMed

Hofman, Anton H; Reza, Mehedi; Ruokolainen, Janne; Ten Brinke, Gerrit; Loos, Katja

2017-09-01

Involving supramolecular chemistry in self-assembling block copolymer systems enables design of complex macromolecular architectures that, in turn, could lead to complex phase behavior. It is an elegant route, as complicated and sensitive synthesis techniques can be avoided. Highly grafted double-comb diblock copolymers based on symmetric double hydrogen bond accepting poly(4-vinylpyridine)-block-poly(N-acryloylpiperidine) diblock copolymers and donating 3-nonadecylphenol amphiphiles are realized and studied systematically by changing the molecular weight of the copolymer. Double perpendicular lamellae-in-lamellae are formed in all complexes, independent of the copolymer molecular weight. Temperature-resolved measurements demonstrate that the supramolecular nature and ability to crystallize are responsible for the formation of such multiblock-like structures. Because of these driving forces and severe plasticization of the complexes in the liquid crystalline state, this supramolecular approach can be useful for steering self-assembly of both low- and high-molecular-weight block copolymer systems. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase Behavior of Neat Triblock Copolymers and Copolymer/Homopolymer Blends Near Network Phase Windows

DOE Office of Scientific and Technical Information (OSTI.GOV)

M Tureau; L Rong; B Hsiao

The phase behavior of poly(isoprene-b-styrene-b-methyl methacrylate) (ISM) copolymers near the styrene-rich network phase window was examined through the use of neat triblock copolymers and copolymer/homopolymer blends. Both end-block and middle-block blending protocols were employed using poly(isoprene) (PI), poly(methyl methacrylate) (PMMA), and poly(styrene) (PS) homopolymers. Blended specimens exhibited phase transformations to well-ordered nanostructures (at homopolymer loadings up to 26 vol % of the total blend volume). Morphological consistency between neat and blended specimens was established at various locations in the ISM phase space. Copolymer/homopolymer blending permitted the refinement of lamellar, hexagonally packed cylinder, and disordered melt phase boundaries as well asmore » the identification of double gyroid (Q{sup 230}), alternating gyroid (Q{sup 214}), and orthorhombic (O{sup 70}) network regimes. Additionally, the experimental phase diagram exhibited similar trends to those found in a theoretical ABC triblock copolymer phase diagram with symmetric interactions and statistical segments lengths generated by Tyler et al.« less

Interaction chromatography for characterization and large-scale fractionation of chemically heterogeneous copolymers

NASA Astrophysics Data System (ADS)

Han, Junwon

The remarkable development of polymer synthesis techniques to make complex polymers with controlled chain architectures has inevitably demanded the advancement of polymer characterization tools to analyze the molecular dispersity in polymeric materials beyond size exclusion chromatography (SEC). In particular, man-made synthetic copolymers that consist of more than one monomer type are disperse mixtures of polymer chains that have distributions in terms of both chemical heterogeneity and chain length (molar mass). While the molecular weight distribution has been quite reliably estimated by the SEC, it is still challenging to properly characterize the chemical composition distribution in the copolymers. Here, I have developed and applied adsorption-based interaction chromatography (IC) techniques as a promising tool to characterize and fractionate polystyrene-based block, random and branched copolymers in terms of their chemical heterogeneity. The first part of this thesis is focused on the adsorption-desorption based purification of PS-b-PMMA diblock copolymers using nanoporous silica. The liquid chromatography analysis and large scale purification are discussed for the PS-b-PMMA block copolymers that have been synthesized by sequential anionic polymerization. SEC and IC are compared to critically analyze the contents of PS homopolymers in the as-synthesized block copolymers. In addition, I have developed an IC technique to provide faster and more reliable information on the chemical heterogeneity in the as-synthesized block copolymers. Finally, a large scale (multi-gram) separation technique is developed to obtain "homopolymer-free" block copolymers via a simple chromatographic filtration technique. By taking advantage of the large specific surface area of nanoporous silica (≈300m 2/g), large scale purification of neat PS-b-PMMA has successfully been achieved by controlling adsorption and desorption of the block copolymers on the silica gel surface using a gravity column. The second part of this thesis is focused on the liquid chromatography analysis and fractionation of RAFT-polymerized PS-b -PMMA diblock copolymers and AFM studies. In this study, PS- b-PMMA block copolymers were synthesized by a RAFT free radical polymerization process---the PMMA block with a phenyldithiobenzoate end group was synthesized first. The contents of unreacted PS and PMMA homopolymers in as-synthesized PS-b-PMMA block copolymers were quantitatively analyzed by solvent gradient interaction chromatography (SGIC) technique employing bare silica and C18-bonded silica columns, respectively. In addition, by 2-dimensional large-scale IC fractionation method, atomic force microscopy (AFM) study of these fractionated samples revealed various morphologies with respect to the chemical composition of each fraction. The third part of this thesis is to analyze random copolymers with tunable monomer sequence distributions using interaction chromatography. Here, IC was used for characterizing the composition and monomer sequence distribution in statistical copolymers of poly(styrene-co-4-bromostyrene) (PBrxS). The PBrS copolymers were synthesized by the bromination of monodisperse polystyrenes; the degree of bromination (x) and the sequence distribution were adjusted by varying the bromination time and the solvent quality, respectively. Both normal-phase (bare silica) and reversed-phase (C18-bonded silica) columns were used at different combinations of solvents and non-solvents to monitor the content of the 4-bromostyrene units in the copolymer and their average monomer sequence distribution. The fourth part of this thesis is to analyze and fractionate highly branched polymers such as dendronized polymers and star-shaped homo and copolymers. I have developed an interaction chromatography technique to separate polymers with nonlinear chain architecture. Specifically, the IC technique has been used to separate dendronized polymers and PS-based highly branched copolymers and to ultimately obtain well-defined dendronized or branched copolymers with a low polydispersity. The effects of excess arm-polymers on (1) the micellar self-assembly of dendronized polymers and (2) the regularity of the pore morphology in the low-k applications by the sol-gel process have been studied.

40 CFR 414.40 - Applicability; description of the thermoplastic resins subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... *Ethylene-Methacrylic Acid Copolymers *Ethylene-Vinyl Acetate Copolymers *Fatty Acid Resins *Fluorocarbon..., Acrylates (Latex) *PVC Copolymers, Ethylene-Vinyl Chloride *Rosin Derivative Resins *Rosin Modified Resins...

Flame-retardant copolymers of dialkyl (meth)acryloyloxyalkyl phosphate or dialkyl (meth)acryloyloxyalkyl phosphonate monomers and polymer foams based made therefrom

DOEpatents

Qi, Yudong; Li, Yan; Bunker, Shana P.; Costeux, Stephane; Morgan, Ted A.

2017-12-12

Polymer foam bodies are made from phosphorus-containing thermoplastic random copolymers of a dialkyl (meth)acryloyloxyalkyl phosph(on)ate. Foam bodies made from these copolymers exhibit increased limiting oxygen indices and surprisingly have good properties. In certain embodiments, the phosphorus-containing thermoplastic copolymer is blended with one or more other polymers and formed into nanofoams.

Reversible geling co-polymer and method of making

DOEpatents

Gutowska, Anna

2005-12-27

The present invention is a thereapeutic agent carrier having a thermally reversible gel or geling copolymer that is a linear random copolymer of an [meth-]acrylamide derivative and a hydrophilic comonomer, wherein the linear random copolymer is in the form of a plurality of linear chains having a plurality of molecular weights greater than or equal to a minimum geling molecular weight cutoff and a therapeutic agent.

Melt structure and self-nucleation of ethylene copolymers

NASA Astrophysics Data System (ADS)

Alamo, Rufina G.

A strong memory effect of crystallization has been observed in melts of random ethylene copolymers well above the equilibrium melting temperature. These studies have been carried out by DSC, x-ray, TEM and optical microscopy on a large number of model, narrow, and broad copolymers with different comonomer types and contents. Melt memory is correlated with self-seeds that increase the crystallization rate of ethylene copolymers. The seeds are associated with molten ethylene sequences from the initial crystals that remain in close proximity and lower the nucleation barrier. Diffusion of all sequences to a randomized melt state is a slow process, restricted by topological chain constraints (loops, knots, and other entanglements) that build in the intercrystalline region during crystallization. Self-seeds dissolve above a critical melt temperature that demarcates homogeneity of the copolymer melt. There is a critical threshold level of crystallinity to observe the effect of melt memory on crystallization rate, thus supporting the correlation between melt memory and the change in melt structure during copolymer crystallization. Unlike binary blends, commercial ethylene-1-alkene copolymers with a range in inter-chain comonomer composition between 1 and about 15 mol % display an inversion of the crystallization rate in a range of melt temperatures where narrow copolymers show a continuous acceleration of the rate. With decreasing the initial melt temperature, broadly distributed copolymers show enhanced crystallization followed by a decrease of crystallization rate. The inversion demarcates the onset of liquid-liquid phase separation (LLPS) and a reduction of self-nuclei due to the strong thermodynamic drive for molecular segregation inside the binodal. The strong effect of melt memory on crystallization rate can be used to identify liquid-liquid phase separation in broadly distributed copolymers, and offers strategies to control the state of copolymer melts in ways of technological relevance for melt processing of LLDPE and other random olefin copolymers. References: B. O. Reid, et al., Macromolecules 46, 6485-6497, 2013 H. Gao, et al., Macromolecules 46, 6498-6506, 2013 A. Mamun et al., Macromolecules 47, 7958-7970, 2014 X. Chen et al., Macromol. Chem. Phys. 216, 1220 -1226, 2015 M. Ren et al., Macromol. Symp. 356, 131-141, 2015 Work supported by the NSF (DMR1105129).

Cathepsin S-cleavable, multi-block HPMA copolymers for improved SPECT/CT imaging of pancreatic cancer.

PubMed

Fan, Wei; Shi, Wen; Zhang, Wenting; Jia, Yinnong; Zhou, Zhengyuan; Brusnahan, Susan K; Garrison, Jered C

2016-10-01

This work continues our efforts to improve the diagnostic and radiotherapeutic effectiveness of nanomedicine platforms by developing approaches to reduce the non-target accumulation of these agents. Herein, we developed multi-block HPMA copolymers with backbones that are susceptible to cleavage by cathepsin S, a protease that is abundantly expressed in tissues of the mononuclear phagocyte system (MPS). Specifically, a bis-thiol terminated HPMA telechelic copolymer containing 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Three maleimide modified linkers with different sequences, including cathepsin S degradable oligopeptide, scramble oligopeptide and oligo ethylene glycol, were subsequently synthesized and used for the extension of the HPMA copolymers by thiol-maleimide click chemistry. All multi-block HPMA copolymers could be labeled by (177)Lu with high labeling efficiency and exhibited high serum stability. In vitro cleavage studies demonstrated highly selective and efficient cathepsin S mediated cleavage of the cathepsin S-susceptible multi-block HPMA copolymer. A modified multi-block HPMA copolymer series capable of Förster Resonance Energy Transfer (FRET) was utilized to investigate the rate of cleavage of the multi-block HPMA copolymers in monocyte-derived macrophages. Confocal imaging and flow cytometry studies revealed substantially higher rates of cleavage for the multi-block HPMA copolymers containing the cathepsin S-susceptible linker. The efficacy of the cathepsin S-cleavable multi-block HPMA copolymer was further examined using an in vivo model of pancreatic ductal adenocarcinoma. Based on the biodistribution and SPECT/CT studies, the copolymer extended with the cathepsin S susceptible linker exhibited significantly faster clearance and lower non-target retention without compromising tumor targeting. Overall, these results indicate that exploitation of the cathepsin S activity in MPS tissues can be utilized to substantially lower non-target accumulation, suggesting this is a promising approach for the development of diagnostic and radiotherapeutic nanomedicine platforms. Copyright © 2016 Elsevier Ltd. All rights reserved.

Lignin poly(lactic acid) copolymers

DOEpatents

Olsson, Johan Vilhelm; Chung, Yi-Lin; Li, Russell Jingxian; Waymouth, Robert; Sattely, Elizabeth; Billington, Sarah; Frank, Curtis W.

2017-02-14

Provided herein are graft co-polymers of lignin and poly(lactic acid) (lignin-g-PLA copolymer), thermoset and thermoplastic polymers including them, methods of preparing these polymers, and articles of manufacture including such polymers.

Synthesis and characterization of POSS-(PAA)8 star copolymers and GICs for dental applications.

PubMed

Zelmer, Christina; Wang, David K; Keen, Imelda; Hill, David J T; Symons, Anne L; Walsh, Laurence J; Rasoul, Firas

2016-04-01

To investigate the application of a new type of multiarm polymer resins in the formulation of Glass Ionic Cements. A series of star copolymers of t-butyl acrylate has been prepared by ATRP using a multiarm POSS-Br8 initiator. The resulting POSS-co-t-butyl acrylate star copolymers with eight arms were subsequently hydrolysed by trifluoroacetic acid to produce the corresponding POSS-co-acrylic acid star copolymers. All of the copolymers have been characterized by (1)H and (13)C NMR and FTIR spectroscopies and TGA/DSC. The as-prepared star copolymers were mixed with the glass powder from Fuji IX GP to produce the GIC samples for compression testing. The new type of multiarm polymer resins have been shown to have narrow molecular weight distributions and thermal properties of the acrylic acid copolymers are similar to that of poly(acrylic acid), with a two stage degradation profile involving transitions at ≈140°C and 250°C, corresponding to anhydride formation and loss of carbon dioxide, respectively. In aqueous solution the POSS-co-acrylic acid copolymers form aggregates with ≈33nm dimensions. When aqueous solutions of POSS-(PAA)8 are mixed with a glass powder, a rigid glass ionomer cement, GIC, is formed with a maximum compressive stress significantly greater than that for a linear PAA GIC of a comparable polymer molecular weight. Therefore, these POSS-(PAA)8 copolymers demonstrate the potential for the application of well characterized star copolymers in the future development of new GICs as dental materials. Copyright © 2016 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

PAA-PAMPS copolymers as an efficient tool to control CaCO3 scale formation.

PubMed

Dietzsch, Michael; Barz, Matthias; Schüler, Timo; Klassen, Stefanie; Schreiber, Martin; Susewind, Moritz; Loges, Niklas; Lang, Michael; Hellmann, Nadja; Fritz, Monika; Fischer, Karl; Theato, Patrick; Kühnle, Angelika; Schmidt, Manfred; Zentel, Rudolf; Tremel, Wolfgang

2013-03-05

Scale formation, the deposition of certain minerals such as CaCO3, MgCO3, and CaSO4·2H2O in industrial facilities and household devices, leads to reduced efficiency or severe damage. Therefore, incrustation is a major problem in everyday life. In recent years, double hydrophilic block copolymers (DHBCs) have been the focus of interest in academia with regard to their antiscaling potential. In this work, we synthesized well-defined blocklike PAA-PAMPS copolymers consisting of acrylic acid (AA) and 2-acrylamido-2-methyl-propane sulfonate (AMPS) units in a one-step reaction by RAFT polymerization. The derived copolymers had dispersities of 1.3 and below. The copolymers have then been investigated in detail regarding their impact on the different stages of the crystallization process of CaCO3. Ca(2+) complexation, the first step of a precipitation process, and polyelectrolyte stability in aqueous solution have been investigated by potentiometric measurements, isothermal titration calorimetry (ITC), and dynamic light scattering (DLS). A weak Ca(2+) induced copolymer aggregation without concomitant precipitation was observed. Nucleation, early particle growth, and colloidal stability have been monitored in situ with DLS. The copolymers retard or even completely suppress nucleation, most probably by complexation of solution aggregates. In addition, they stabilize existing CaCO3 particles in the nanometer regime. In situ AFM was used as a tool to verify the coordination of the copolymer to the calcite (104) crystal surface and to estimate its potential as a growth inhibitor in a supersaturated CaCO3 environment. All investigated copolymers instantly stopped further crystal growth. The carboxylate richest copolymer as the most promising antiscaling candidate proved its enormous potential in scale inhibition as well in an industrial-filming test (Fresenius standard method).

21 CFR 177.1060 - n-Alkylglutarimide/acrylic copolymers.

Code of Federal Regulations, 2011 CFR

2011-04-01

.../acrylic copolymers are copolymers obtained by reaction of substances permitted by § 177.1010(a) (1), (2... solvent or solvents characterizing the type of food and under the conditions of time and temperature...

Patterning by area selective oxidation

DOEpatents

Nam, Chang-Yong; Kamcev, Jovan; Black, Charles T.; Grubbs, Robert

2015-12-29

Technologies are described for methods for producing a pattern of a material on a substrate. The methods may comprise receiving a patterned block copolymer on a substrate. The patterned block copolymer may include a first polymer block domain and a second polymer block domain. The method may comprise exposing the patterned block copolymer to a light effective to oxidize the first polymer block domain in the patterned block copolymer. The method may comprise applying a precursor to the block copolymer. The precursor may infuse into the oxidized first polymer block domain and generate the material. The method may comprise applying a removal agent to the block copolymer. The removal agent may be effective to remove the first polymer block domain and the second polymer block domain from the substrate, and may not be effective to remove the material in the oxidized first polymer block domain.

Crafting threads of diblock copolymer micelles via flow-enabled self-assembly.

PubMed

Li, Bo; Han, Wei; Jiang, Beibei; Lin, Zhiqun

2014-03-25

Hierarchically assembled amphiphilic diblock copolymer micelles were exquisitely crafted over large areas by capitalizing on two concurrent self-assembling processes at different length scales, namely, the periodic threads composed of a monolayer or a bilayer of diblock copolymer micelles precisely positioned by flow-enabled self-assembly (FESA) on the microscopic scale and the self-assembly of amphiphilic diblock copolymer micelles into ordered arrays within an individual thread on the nanometer scale. A minimum spacing between two adjacent threads λmin was observed. A model was proposed to rationalize the relationship between the thread width and λmin. Such FESA of diblock copolymer micelles is remarkably controllable and easy to implement. It opens up possibilities for lithography-free positioning and patterning of diblock copolymer micelles for various applications in template fabrication of periodic inorganic nanostructures, nanoelectronics, optoelectronics, magnetic devices, and biotechnology.

Preparation of cashew gum-based flocculants by microwave- and ultrasound-assisted methods.

PubMed

Klein, Jalma Maria; de Lima, Vanessa Silva; da Feira, José Manoel Couto; Camassola, Marli; Brandalise, Rosmary Nichele; Forte, Maria Madalena de Camargo

2018-02-01

In this work, copolymers based on cashew gum (CG) grafted with polyacrylamide (PAM) were synthesized by microwave- and ultrasound-assisted methods, using potassium persulfate as an initiator in aqueous medium. The graft copolymers were characterized by Fourier-transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and thermogravimetric analysis. The efficiency of the graft copolymers (CG-g-PAM) in flocculation of a kaolin suspension was studied. Results indicated that the graft copolymers synthesized by ultrasound energy had better flocculation properties than the ones synthesized by the microwave-assisted method. The biodegradability of the graft copolymers was tested by inoculation with the basidiomycete Trametes villosa in liquid medium. The higher formation of biomass than that observed with the commercial flocculant Flonex-9045 indicated that the graft copolymer was accessible to enzymatic attack. Copyright © 2017 Elsevier B.V. All rights reserved.

Molecular Interaction Control in Diblock Copolymer Blends and Multiblock Copolymers with Opposite Phase Behaviors

NASA Astrophysics Data System (ADS)

Cho, Junhan

2014-03-01

Here we show how to control molecular interactions via mixing AB and AC diblock copolymers, where one copolymer exhibits upper order-disorder transition and the other does lower disorder-order transition. Linear ABC triblock copolymers possessing both barotropic and baroplastic pairs are also taken into account. A recently developed random-phase approximation (RPA) theory and the self-consistent field theory (SCFT) for general compressible mixtures are used to analyze stability criteria and morphologies for the given systems. It is demonstrated that the copolymer systems can yield a variety of phase behaviors in their temperature and pressure dependence upon proper mixing conditions and compositions, which is caused by the delicate force fields generated in the systems. We acknowledge the financial support from National Research Foundation of Korea and Center for Photofunctional Energy Materials.

Pulsed recording of anisotropy and holographic polarization gratings in azo-polymethacrylates with different molecular architectures

NASA Astrophysics Data System (ADS)

Forcén, Patricia; Oriol, Luis; Sánchez, Carlos; Alcalá, Rafael; Jankova, Katja; Hvilsted, Søren

2008-06-01

Recording of anisotropy and holographic polarization gratings using 532nm, 4ns light pulses has been carried out in thin films of polymers with the same azobenzene content (20wt%) and different molecular architectures. Random and block copolymers comprising azobenzene and methylmethacrylate (MMA) moieties as well as statistical terpolymers with azobenzene, biphenyl, and MMA units have been compared in terms of recording sensitivity and stability upon pulsed excitation. Photoinduced anisotropy just after the pulse was significantly higher in the case of the block copolymers than in the two statistical copolymers. The stability of the recorded anisotropy has also been studied. While a stationary value of the photoinduced anisotropy (approximately 50% of the initial photoinduced value) is reached for the block copolymer, photoinduced anisotropy almost vanished after a few hours in the statistical copolymers. Polarization holographic gratings have been registered using two orthogonally circularly polarized light beams. The results are qualitatively similar to those of photoinduced anisotropy, that is, stability of the registered grating and larger values of diffraction efficiency for the block copolymer as compared with the random copolymers. The recording of holographic gratings with submicron period in films several microns thick, showing both polarization and angular selectivity, has also been demonstrated. Block copolymers showed a lamellar block nanosegregated morphology. The interaction among azo chromophores within the nanosegregated azo blocks seems to be the reason for the stability and the photoresponse enhancement in the block copolymer as compared with the statistical ones.

Biodegradable copolymers carrying cell-adhesion peptide sequences.

PubMed

Proks, Vladimír; Machová, Lud'ka; Popelka, Stepán; Rypácek, Frantisek

2003-01-01

Amphiphilic block copolymers are used to create bioactive surfaces on biodegradable polymer scaffolds for tissue engineering. Cell-selective biomaterials can be prepared using copolymers containing peptide sequences derived from extracellular-matrix proteins (ECM). Here we discuss alternative ways for preparation of amphiphilic block copolymers composed of hydrophobic polylactide (PLA) and hydrophilic poly(ethylene oxide) (PEO) blocks with cell-adhesion peptide sequences. Copolymers PLA-b-PEO were prepared by a living polymerisation of lactide in dioxane with tin(II)2-ethylhexanoate as a catalyst. The following approaches for incorporation of peptides into copolymers were elaborated. (a) First, a side-chain protected Gly-Arg-Gly-Asp-Ser-Gly (GRGDSG) peptide was prepared by solid-phase peptide synthesis (SPPS) and then coupled with delta-hydroxy-Z-amino-PEO in solution. In the second step, the PLA block was grafted to it via a controlled polymerisation of lactide initiated by the hydroxy end-groups of PEO in the side-chain-protected GRGDSG-PEO. Deprotection of the peptide yielded a GRGDSG-b-PEO-b-PLA copolymer, with the peptide attached through its C-end. (b) A protected GRGDSG peptide was built up on a polymer resin and coupled with Z-carboxy-PEO using a solid-phase approach. After cleavage of the delta-hydroxy-PEO-GRGDSG copolymer from the resin, polymerisation of lactide followed by deprotection of the peptide yielded a PLA-b-PEO-b-GRGDSG block copolymer, in which the peptide is linked through its N-terminus.

Imide/arylene ether copolymers

NASA Technical Reports Server (NTRS)

Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor); Bass, Robert G. (Inventor)

1992-01-01

Imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly(arylene ethers) in polar aprotic solvents and by chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The resulting block copolymers have one glass transition temperature or two, depending upon the particular structure and/or the compatibility of the block units. Most of these block copolymers form tough, solvent resistant films with high tensile properties.

Physical Aging Studies of Styrene-Butadiene and Carbonate-Siloxane Block Copolymers

DTIC Science & Technology

1979-11-19

Carbonate-Siloxane Block Copolymers, ,-- by Martin Tant Garth . D D C Prepared for Publication r - r-on n[? in the JAN Journal of Applied Polymer Science B...revereie ifI nocesy and Identify by black mumibo,) Polymer glasses Non equilibrium glasses Stress relaxation Block copolymers 20. AOSTRACT (Continwaon...copolymers in material applications. -2- Introduction The physical aging phenomenon in glassy polymers has drawn considerable interest within the

A semiflexible alternating copolymer chain adsorption on a flat and a fluctuating surface.

PubMed

Mishra, Pramod Kumar

2010-04-21

A lattice model of a directed self-avoiding walk is used to investigate adsorption properties of a semiflexible alternating copolymer chain on an impenetrable flat and fluctuating surface in two (square, hexagonal and rectangular lattice) and three dimensions (cubic lattice). In the cubic lattice case the surface is two-dimensional impenetrable flat and in two dimensions the surface is a fluctuating impenetrable line (hexagonal lattice) and also flat impenetrable line (square and rectangular lattice). Walks of the copolymer chains are directed perpendicular to the plane of the surface and at a suitable value of monomer surface attraction, the copolymer chain gets adsorbed on the surface. To calculate the exact value of the monomer surface attraction, the directed walk model has been solved analytically using the generating function method to discuss results when one type of monomer of the copolymer chain has attractive, repulsive or no interaction with the surface. Results obtained in the flat surface case show that, for a stiffer copolymer chain, adsorption transition occurs at a smaller value of monomer surface attraction than a flexible copolymer chain while in the case of a fluctuating surface, the adsorption transition point is independent of bending energy of the copolymer chain. These features are similar to that of a semiflexible homopolymer chain adsorption.

Synthesis and Characterization of Fluorescently Labeled Diblock Copolymers for Location-Specific Measurements of The Glass Transition Temperature

NASA Astrophysics Data System (ADS)

Christie, Dane; Register, Richard; Priestley, Rodney

Interfaces play a determinant role in the size dependence of the glass transition temperature (Tg) of polymers confined to nanometric length scales. Interfaces are intrinsic in diblock copolymers, which, depending on their molecular weight and composition, are periodically nanostructured in the bulk. As a result diblock copolymers are model systems for characterizing the effect of interfaces on Tg in bulk nanostructured materials. Investigating the effect of intrinsic interfaces on Tg in diblock copolymers has remained unexplored due to their small periodic length scale. By selectively incorporating trace amounts of a fluorescent probe into a diblock copolymer, Tg can be characterized relative to the diblock copolymer's intrinsic interface using fluorescence spectroscopy. Here, pyrene is selectively incorporated into the poly(methyl methacrylate) (PMMA) block of lamellar forming diblock copolymers of poly(butyl- b-methyl methacrylate) (PBMA-PMMA). Preliminary results show a correlation of Tg as measured by fluorescence with the onset of Tg as measured by calorimetry in labeled homopolymers of PMMA. This result is consistent with previous characterizations of Tg using fluorescence spectroscopy. In selectively labeled diblock copolymers Tg is found to vary systematically depending on the distance of the probe from the PBMA-PMMA interface. We acknowledge funding from the Princeton Center for Complex Materials, a MRSEC supported by NSF Grant DMR 1420541.

MesoDyn simulation study on the phase morphologies of Miktoarm PEO-b-PMMA copolymer doped by nanoparticles

NASA Astrophysics Data System (ADS)

Mu, Dan; Li, Jian-Quan; Feng, Sheng-Yu

2013-03-01

The compatibility of six groups of 12 miktoarm poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) copolymers is studied at 270, 298 and 400 K via mesoscopic modeling. The values of the order parameters depend on both the architectures of the block copolymers and the simulation temperature, while the tendency to change of the order parameters at low temperature, such as 270 and 298 K, is nearly the same. However, the values of order parameters of the copolymer in the same group are the same at high temperature, i.e. 400 K. Obviously, temperature has a more obvious effect on long and PEO-rich chains. A study of plain copolymers doped with nanoparticles shows that the microscopic phase is influenced by not only the properties of the nanoparticles, such as the size, number and density, but also the composition and architecture of copolymers. Increasing the size and the number of the nanoparticles used as a dopant plays the most significant role on determining the phase morphologies of the copolymers at lower and higher temperature, respectively. In paricular, the 23141 and 23241-type copolymers, which are both of PEO-rich composition, presents microscopic phase separation as perforated lamallae phase morphologies at 400 K, alternated with PEO and PMMA components.

Polyamide copolymers having 2,5-furan dicarboxamide units

DOEpatents

Chisholm, Bret Ja; Samanta, Satyabrata

2017-09-19

Polyamide copolymers, and methods of making and using polyamide copolymers, having 2,5-furan dicarboxamide units are disclosed herein. Such polymers can be useful for engineering thermoplastics having advantageous physical and/or chemical properties.

Synthesis and characterization of novel polymers from non-petroleum sources for use in enhanced oil recovery. Progress report, July 1,1981-June 30, 1982. [Starch-g-polyacrylamide; polysaccharides and acrylamides; Schardinger-. beta. -dextrin and acrylamide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Butler, G.B.; Hogen-Esch, T.E.

1982-01-01

Annual progress reports are presented for the following tasks: (1) synthesis and structural characterization of polysaccharide-based graft copolymers for use in tertiary oil recovery; (2) determination of physical properties of the polymers and their solutions, and screening of the polymers to determine their utility in oil recovery. Over the past year synthesis and characterization studies have continued in the following five areas: (1) starch-g-polyacrylamide (ST-g-PAM) copolymers; (2) graft copolymers of other polysaccharides (gum arabic, yellow dextrin, pectin, okra polysaccharide, and guar gum) and acrylamides; (3) a naturally occurring polysaccharide extracted from okra (Akro); (4) graft copolymers of Schardinger-..beta..-dextrin and acrylamidemore » (SD-g-PAM); (5) chemical degradation of ST-g-PAM and SD-g-PAM copolymers. For physical properties studies, the following areas were investigated: (1) characterization of copolymers by ultracentrifugation, size exclusion chromatography and nucleophore membrane filtration; (2) rheological studies on copolymers; and (3) statistical analysis of variables in graft copolymerization. (ATT)« less

Interactions of poly(tert-butyl acrylate)-poly(styrene) diblock copolymers with lipids at the air-water interface.

PubMed

Mudgil, Poonam; Dennis, Gary R; Millar, Thomas J

2006-08-29

Diblock copolymers with hydrophilic poly(tert-butyl acrylate) (PtBA) and hydrophobic poly(styrene) (PS) blocks were synthesized with a view to use them as a surfactant in tear film for increasing the ocular comfort in dry eye syndrome. Interactions of six PtBA-PS copolymers with four important lipids found in the tear film, namely cholesterol, cholesteryl palmitate, dipalmitoyl phosphatidylcholine, and phosphatidylinositol, were studied at the air-water interface using a Langmuir trough. Thermodynamics of mixing of the copolymers and the lipids in the mixed monolayers was determined by calculating excess free energy of mixing. The diblock copolymers showed repulsive interactions with cholesteol and cholesteryl palmitate, near neutral interactions with dipalmitoyl phosphatidylcholine, and attractive interactions with phosphatidylinositol. The lipids interacted with the PS component of the copolymer. The results indicate that a copolymer with a small hydrophilic group and a big hydrophobic group can be a likely candidate for forming stable interactions with the lipids present in the tear film and hence increase the ocular comfort.

Adsorption of non-ionic ABC triblock copolymers: Surface modification of TiO2 suspensions in aqueous and non-aqueous medium

NASA Astrophysics Data System (ADS)

Lerch, Jean-Philippe; Atanase, Leonard Ionut; Riess, Gérard

2017-10-01

A series of non-ionic ABC triblock copolymers, such as poly(butadiene)-b-poly(2-vinylpyrridine)-b-poly(ethylene oxide) (PB-P2VP-PEO) were synthesized by sequential anionic polymerizations. For these copolymers comprising an organo-soluble PB and a water-soluble PEO block, their P2VP middle block has been selected for its anchoring capacity on solid surfaces. The adsorption isotherms on TiO2 were obtained in heptane and in aqueous medium, as selective solvents. In both of these cases, the P2VP middle block provides the surface anchoring, whereas PB and PEO sequences are acting as stabilizing moieties in heptane and water respectively. By extension to ABC triblock copolymers of the scaling theory developed for diblock copolymers, the density of adsorbed chains could be correlated with the molecular characteristics of the PB-P2VP-PEO triblock copolymers. From a practical point a view, it could be demonstrated that these copolymers are efficient dispersing agents for the TiO2 pigments in both aqueous and non-aqueous medium.

New thiol-responsive mono-cleavable block copolymer micelles labeled with single disulfides.

PubMed

Sourkohi, Behnoush Khorsand; Schmidt, Rolf; Oh, Jung Kwon

2011-10-18

Thiol-responsive symmetric triblock copolymers having single disulfide linkages in the middle blocks (called mono-cleavable block copolymers, ss-ABP(2)) were synthesized by atom transfer radical polymerization in the presence of a disulfide-labeled difunctional Br-initiator. These brush-like triblock copolymers consist of a hydrophobic polyacrylate block having pendent oligo(propylene oxide) and a hydrophilic polymethacrylate block having pendent oligo(ethylene oxide). Gel permeation chromatography and (1)H NMR results confirmed the synthesis of well-defined mono-cleavable block copolymers and revealed that polymerizations were well controlled. Because of amphiphilic nature, these copolymers self-assembled to form colloidally stable micelles above critical micellar concentration of 0.032 mg · mL(-1). In response to reductive reactions, disulfides in thiol-responsive micelles were cleaved. Atomic force microscopy and dynamic light scattering analysis suggested that the cleavage of disulfides caused dissociation of micelles to smaller-sized assembled structures in water. Moreover, in a biomedical perspective, the mono-cleavable block copolymer micelles are not cytotoxic and thus biocompatible. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

NASA Astrophysics Data System (ADS)

Hoarfrost, Megan Lane

Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there is incredible freedom in designing the block copolymer architecture in order to optimize the mechanical and other properties of the membrane without sacrificing conductivity. The derived scaling relationships are shown to be general for many block copolymer and ionic liquid chemistries. In certain cases, the mechanism of ion conduction in the ionic liquid is affected by block copolymer nanoconfinement. The introduction of excess neutral imidazole to [Im][TFSI] leads to enhanced proton conductivity as well as a high H+ transference number due to facilitated proton hopping between imidazole molecules. We show that there is increased proton hopping when the nonstoichiometric ionic liquid is confined to lamellar block copolymer nanodomains, which we hypothesize is due to changes in the hydrogen bond structure of the ionic liquid under confinement. This, in combination with unique ion aggregation behavior, leads to a lower activation energy for macroscopic ion transport compared to that in a corresponding homopolymer/ionic liquid mixture. Through this work, we further the understanding of the relationship between membrane composition, structure, and ion transport. The findings presented herein portend the rational design of nanostructured membranes having improved mechanical properties and conductivity.

Polyarylether composition and membrane

DOEpatents

Hung, Joyce; Brunelle, Daniel Joseph; Harmon, Marianne Elisabeth; Moore, David Roger; Stone, Joshua James; Zhou, Hongyi; Suriano, Joseph Anthony

2010-11-09

A composition including a polyarylether copolymer is provided. The copolymer includes a polyarylether backbone; and a sulfonated oligomeric group bonded to the polyarylether suitable for use as a cation conducting membrane. Method of bonding a sulfonated oligomeric group to the polyarylether backbone to form a polyarylether copolymer. The membrane may be formed from the polyarylether copolymer composition. The chain length of the sulfonated oligomeric group may be controlled to affect or control the ion conductivity of the membrane.

Supramolecular block copolymers by kinetically controlled co-self-assembly of planar and core-twisted perylene bisimides

PubMed Central

Görl, Daniel; Zhang, Xin; Stepanenko, Vladimir; Würthner, Frank

2015-01-01

New synthetic methodologies for the formation of block copolymers have revolutionized polymer science within the last two decades. However, the formation of supramolecular block copolymers composed of alternating sequences of larger block segments has not been realized yet. Here we show by transmission electron microscopy (TEM), 2D NMR and optical spectroscopy that two different perylene bisimide dyes bearing either a flat (A) or a twisted (B) core self-assemble in water into supramolecular block copolymers with an alternating sequence of (AmBB)n. The highly defined ultralong nanowire structure of these supramolecular copolymers is entirely different from those formed upon self-assembly of the individual counterparts, that is, stiff nanorods (A) and irregular nanoworms (B), respectively. Our studies further reveal that the as-formed supramolecular block copolymer constitutes a kinetic self-assembly product that transforms into thermodynamically more stable self-sorted homopolymers upon heating. PMID:25959777

Fabrication routes for one-dimensional nanostructures via block copolymers

NASA Astrophysics Data System (ADS)

Tharmavaram, Maithri; Rawtani, Deepak; Pandey, Gaurav

2017-05-01

Nanotechnology is the field which deals with fabrication of materials with dimensions in the nanometer range by manipulating atoms and molecules. Various synthesis routes exist for the one, two and three dimensional nanostructures. Recent advancements in nanotechnology have enabled the usage of block copolymers for the synthesis of such nanostructures. Block copolymers are versatile polymers with unique properties and come in many types and shapes. Their properties are highly dependent on the blocks of the copolymers, thus allowing easy tunability of its properties. This review briefly focusses on the use of block copolymers for synthesizing one-dimensional nanostructures especially nanowires, nanorods, nanoribbons and nanofibers. Template based, lithographic, and solution based approaches are common approaches in the synthesis of nanowires, nanorods, nanoribbons, and nanofibers. Synthesis of metal, metal oxides, metal oxalates, polymer, and graphene one dimensional nanostructures using block copolymers have been discussed as well.

Effect of molecular structure of aniline-formaldehyde copolymers on corrosion inhibition of mild steel in hydrochloric acid solution.

PubMed

Zhang, Yan; Nie, Mengyan; Wang, Xiutong; Zhu, Yukun; Shi, Fuhua; Yu, Jianqiang; Hou, Baorong

2015-05-30

Aniline-formaldehyde copolymers with different molecular structures have been prepared and investigated for the purpose of corrosion control of mild steel in hydrochloric acid. The copolymers were synthesized by a condensation polymerization process with different ratios of aniline to formaldehyde in acidic precursor solutions. The corrosion inhibition efficiency of as-synthesized copolymers for Q235 mild steel was investigated in 1.0 mol L(-1) hydrochloric acid solution by weight loss measurement, potentiodynamic polarization, and electrochemical impedance spectroscopy, respectively. All the results demonstrate that as-prepared aniline-formaldehyde copolymers are efficient mixed-type corrosion inhibitors for mild steels in hydrochloric acid. The corrosion inhibition mechanism is discussed in terms of the role of molecular structure on adsorption of the copolymers onto the steel surface in acid solution. Copyright © 2015. Published by Elsevier B.V.

Simultaneous determination of the styrene unit content and assessment of molecular weight of triblock copolymers in adhesives by a size exclusion chromatography method.

PubMed

Wang, Mingfang; Wang, Yuerong; Luo, Pei; Zhang, Hongyang; Zhang, Min; Hu, Ping

2017-10-01

The content of styrene units in nonhydrogenated and hydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers significantly influences product performance. A size exclusion chromatography method was developed to determine the average styrene content of triblock copolymers blended with tackifier in adhesives. A complete separation of the triblock copolymer from the other additives was realized with size exclusion chromatography. The peak area ratio of the UV and refraction index signals of the copolymers at the same effective elution volume was correlated to the average styrene unit content using nuclear magnetic resonance spectroscopy with commercial copolymers as standards. The obtained calibration curves showed good linearity for both the hydrogenated and nonhydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers (r = 0.974 for styrene contents of 19.3-46.3% for nonhydrogenated ones and r = 0.970 for the styrene contents of 23-58.2% for hydrogenated ones). For copolymer blends, the developed method provided more accurate average styrene unit contents than nuclear magnetic resonance spectroscopy provided. These results were validated using two known copolymer blends consisting of either styrene-isoprene-styrene or hydrogenated styrene-butadiene-styrene and a hydrocarbon tackifying resin as well as an unknown adhesive with styrene-butadiene-styrene and an aromatic tackifying resin. The methodology can be readily applied to styrene-containing polymers in blends such as poly(acrylonitrile-butadiene styrene). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microbial production of polyhydroxyalkanoate block copolymer by recombinant Pseudomonas putida.

PubMed

Li, Shi Yan; Dong, Cui Ling; Wang, Shen Yu; Ye, Hai Mu; Chen, Guo-Qiang

2011-04-01

Polyhydroxyalkanoate (PHA) synthesis genes phaPCJ(Ac) cloned from Aeromonas caviae were transformed into Pseudomonas putida KTOY06ΔC, a mutant of P. putida KT2442, resulting in the ability of the recombinant P. putida KTOY06ΔC (phaPCJ(A.c)) to produce a short-chain-length and medium-chain-length PHA block copolymer consisting of poly-3-hydroxybutyrate (PHB) as one block and random copolymer of 3-hydroxyvalerate (3HV) and 3-hydroxyheptanoate (3HHp) as another block. The novel block polymer was studied by differential scanning calorimetry (DSC), nuclear magnetic resonance, and rheology measurements. DSC studies showed the polymer to possess two glass transition temperatures (T(g)), one melting temperature (T(m)) and one cool crystallization temperature (T(c)). Rheology studies clearly indicated a polymer chain re-arrangement in the copolymer; these studies confirmed the polymer to be a block copolymer, with over 70 mol% homopolymer (PHB) of 3-hydroxybutyrate (3HB) as one block and around 30 mol% random copolymers of 3HV and 3HHp as the second block. The block copolymer was shown to have the highest tensile strength and Young's modulus compared with a random copolymer with similar ratio and a blend of homopolymers PHB and PHVHHp with similar ratio. Compared with other commercially available PHA including PHB, PHBV, PHBHHx, and P3HB4HB, the short-chain- and medium-chain-length block copolymer PHB-b-PHVHHp showed differences in terms of mechanical properties and should draw more attentions from the PHA research community. © Springer-Verlag 2010

New Polytetrahydrofuran Graft Copolymers.

DTIC Science & Technology

1979-03-15

chioroprene) , chiorobutyl - ~~~~~ rubber , bromobutyl rubber , chlorinated EPDM , chlorinated poly(buta— diene) and chlorinated butadiene styrene copolymer...bromobutyl rubber , which after dehalogenation is unstable with respect to conjugated dienes, the yields of graft copolymer are low. With poly(chloroprerte

Synthesis and Adsorption Properties of 4-Vinylpyridine and Styrene Copolymer In Situ Immobilized on Silica Surface

NASA Astrophysics Data System (ADS)

Yanovska, E. S.; Vretik, L. O.; Nikolaeva, O. A.; Polonska, Y.; Sternik, D.; Kichkiruk, O. Yu.

2017-03-01

Copolymer of 4-vinylpyridine with styrene was in situ immobilized on silica gel surface via the heterogeneous radical polymerization. Anchorage of the copolymer on the surface layer was confirmed by IR spectroscopy. The quantity of copolymer on the silica gel surface was evaluated as 25.73 wt.% by TG and DSC-MS analysis. "Islet" location of polymer layer on the silica surface was confirmed by the scanning electron microscopy. A high adsorption activity of silica gel with immobilized copolymer towards microquantitatives of Cu(II), Cd(II), Pb(II), Fe(III), and Ni(II) ions in steady state conditions as well as of Ni(II) ions in dynamic regime was found.

Synthesis and Adsorption Properties of 4-Vinylpyridine and Styrene Copolymer In Situ Immobilized on Silica Surface.

PubMed

Yanovska, E S; Vretik, L O; Nikolaeva, O A; Polonska, Y; Sternik, D; Kichkiruk, O Yu

2017-12-01

Copolymer of 4-vinylpyridine with styrene was in situ immobilized on silica gel surface via the heterogeneous radical polymerization. Anchorage of the copolymer on the surface layer was confirmed by IR spectroscopy. The quantity of copolymer on the silica gel surface was evaluated as 25.73 wt.% by TG and DSC-MS analysis. "Islet" location of polymer layer on the silica surface was confirmed by the scanning electron microscopy. A high adsorption activity of silica gel with immobilized copolymer towards microquantitatives of Cu(II), Cd(II), Pb(II), Fe(III), and Ni(II) ions in steady state conditions as well as of Ni(II) ions in dynamic regime was found.

Backbone degradable multiblock N-(2-hydroxypropyl)methacrylamide copolymer conjugates via reversible addition-fragmentation chain transfer polymerization and thiol-ene coupling reaction.

PubMed

Pan, Huaizhong; Yang, Jiyuan; Kopecková, Pavla; Kopecek, Jindrich

2011-01-10

Telechelic water-soluble HPMA copolymers and HPMA copolymer-doxorubicin (DOX) conjugates have been synthesized by RAFT polymerization mediated by a new bifunctional chain transfer agent (CTA) that contains an enzymatically degradable oligopeptide sequence. Postpolymerization aminolysis followed by chain extension with a bis-maleimide resulted in linear high molecular weight multiblock HPMA copolymer conjugates. These polymers are enzymatically degradable; in addition to releasing the drug (DOX), the degradation of the polymer backbone resulted in products with molecular weights similar to the starting material and below the renal threshold. The new multiblock HPMA copolymers hold potential as new carriers of anticancer drugs.

Thermodynamics of Surfactants, Block Copolymers and Their Mixtures in Water: The Role of the Isothermal Calorimetry

PubMed Central

De Lisi, Rosario; Milioto, Stefania; Muratore, Nicola

2009-01-01

The thermodynamics of conventional surfactants, block copolymers and their mixtures in water was described to the light of the enthalpy function. The two methodologies, i.e. the van’t Hoff approach and the isothermal calorimetry, used to determine the enthalpy of micellization of pure surfactants and block copolymers were described. The van’t Hoff method was critically discussed. The aqueous copolymer+surfactant mixtures were analyzed by means of the isothermal titration calorimetry and the enthalpy of transfer of the copolymer from the water to the aqueous surfactant solutions. Thermodynamic models were presented to show the procedure to extract straightforward molecular insights from the bulk properties. PMID:19742173

Synthesis, characterization and hydrolytic degradation study of polyetheresteramide copolymers based on epsilon-caprolactone, 6-aminocaproic acid, and poly(ethylene glycol).

PubMed

Liu, CaiBing; Qian, ZhiYong; Jia, WenJuan; Huang, MeiJuan; Chao, GuoTao; Gong, ChangYang; Deng, HongXin; Wen, YanJun; Yang, JinLiang; Gou, MaLing; Tu, MingJing

2007-10-01

In this paper, a new kind of biodegradable aliphatic polyetheresteramide copolymers (PEEA) based on epsilon-caprolactone, 6-aminocaproic acid, and poly(ethylene glycol) (PEG) were synthesized by melt polymerization method. The obtained copolymers were characterized by 1H-NMR. The thermal properties of PEEA copolymers were studied by DSC and TGA/DTA under nitrogen atmosphere. The water absorption and hydrolytic degradation behavior was also studied in detail. With the increase in PEG content or the decrease in caprolactone content, the water absorption of the copolymers increased accordingly. For the hydrolytic degradation behavior, with the increase in PEG content or caprolactone content, the degradation rate increased then.

Generation of Synthetic Copolymer Libraries by Combinatorial Assembly on Nucleic Acid Templates.

PubMed

Kong, Dehui; Yeung, Wayland; Hili, Ryan

2016-07-11

Recent advances in nucleic acid-templated copolymerization have expanded the scope of sequence-controlled synthetic copolymers beyond the molecular architectures witnessed in nature. This has enabled the power of molecular evolution to be applied to synthetic copolymer libraries to evolve molecular function ranging from molecular recognition to catalysis. This Review seeks to summarize different approaches available to generate sequence-defined monodispersed synthetic copolymer libraries using nucleic acid-templated polymerization. Key concepts and principles governing nucleic acid-templated polymerization, as well as the fidelity of various copolymerization technologies, will be described. The Review will focus on methods that enable the combinatorial generation of copolymer libraries and their molecular evolution for desired function.

Nanopatterned articles produced using surface-reconstructed block copolymer films

DOEpatents

Russell, Thomas P.; Park, Soojin; Wang, Jia-Yu; Kim, Bokyung

2016-06-07

Nanopatterned surfaces are prepared by a method that includes forming a block copolymer film on a substrate, annealing and surface reconstructing the block copolymer film to create an array of cylindrical voids, depositing a metal on the surface-reconstructed block copolymer film, and heating the metal-coated block copolymer film to redistribute at least some of the metal into the cylindrical voids. When very thin metal layers and low heating temperatures are used, metal nanodots can be formed. When thicker metal layers and higher heating temperatures are used, the resulting metal structure includes nanoring-shaped voids. The nanopatterned surfaces can be transferred to the underlying substrates via etching, or used to prepare nanodot- or nanoring-decorated substrate surfaces.

Amphiphilic graft copolymers from end-functionalized starches: synthesis, characterization, thin film preparation, and small molecule loading.

PubMed

Ryno, Lisa M; Reese, Cassandra; Tolan, McKenzie; O'Brien, Jeffrey; Short, Gabriel; Sorriano, Gerardo; Nettleton, Jason; Fulton, Kayleen; Iovine, Peter M

2014-08-11

End-functionalized macromolecular starch reagents, prepared by reductive amination, were grafted onto a urethane-linked polyester-based backbone using copper-catalyzed azide-alkyne cycloaddition (CuAAC) chemistry to produce novel amphiphilic hybrid graft copolymers. These copolymers represent the first examples of materials where the pendant chains derived from starch biopolymers have been incorporated into a host polymer by a grafting-to approach. The graft copolymers were prepared in good yields (63-90%) with high grafting efficiencies (66-98%). Rigorous quantitative spectroscopic analyses of both the macromolecular building blocks and the final graft copolymers provide a comprehensive analytical toolbox for deciphering the reaction chemistry. Due to the modular nature of both the urethane-linked polyester synthesis and the postpolymerization modification, the starch content of these novel hybrid graft copolymers was easily tuned from 28-53% (w/w). The uptake of two low molecular weight guest molecules into the hybrid polymer thin films was also studied. It was found that binding of 1-naphthol and pterostilbene correlated linearly with amount of starch present in the hybrid polymer. The newly synthesized graft copolymers were highly processable and thermally stable, therefore, opening up significant opportunities in film and coating applications. These results represent a proof-of-concept system for not only the construction of starch-containing copolymers, but also the loading of these novel polymeric materials with active agents.

Real-time monitoring of anticancer drug release with highly fluorescent star-conjugated copolymer as a drug carrier.

PubMed

Qiu, Feng; Wang, Dali; Zhu, Qi; Zhu, Lijuan; Tong, Gangsheng; Lu, Yunfeng; Yan, Deyue; Zhu, Xinyuan

2014-04-14

Chemotherapy is one of the major systemic treatments for cancer, in which the drug release kinetics is a key factor for drug delivery. In the present work, a versatile fluorescence-based real-time monitoring system for intracellular drug release has been developed. First, two kinds of star-conjugated copolymers with different connections (e.g., pH-responsive acylhydrazone and stable ether) between a hyperbranched conjugated polymer (HCP) core and many linear poly(ethylene glycol) (PEG) arms were synthesized. Owing to the amphiphilic three-dimensional architecture, the star-conjugated copolymers could self-assemble into multimicelle aggregates from unimolecular micelles with excellent emission performance in the aqueous medium. When doxorubicin (DOX) as a model drug was encapsulated into copolymer micelles, the emission of star-conjugated copolymer and DOX was quenched. In vitro biological studies revealed that fluorescent intensities of both star-conjugated copolymer and DOX were activated when the drug was released from copolymeric micelles, resulting in the enhanced cellular proliferation inhibition against cancer cells. Importantly, pH-responsive feature of the star-conjugated copolymer with acylhydrazone linkage exhibited accelerated DOX release at a mildly acidic environment, because of the fast breakage of acylhydrazone in endosome or lysosome of tumor cells. Such fluorescent star-conjugated copolymers may open up new perspectives to real-time study of drug release kinetics of polymeric drug delivery systems for cancer therapy.

Graft copolymers of ethyl methacrylate on waxy maize starch derivatives as novel excipients for matrix tablets: physicochemical and technological characterisation.

PubMed

Marinich, J A; Ferrero, C; Jiménez-Castellanos, M R

2009-05-01

Nowadays, graft copolymers are being used as an interesting option when developing a direct compression excipient for controlled release matrix tablets. New graft copolymers of ethyl methacrylate (EMA) on waxy maize starch (MS) and hydroxypropylstarch (MHS) were synthesised by free radical polymerization and alternatively dried in a vacuum oven (OD) or freeze-dried (FD). This paper evaluates the performance of these new macromolecules and discusses the effect of the carbohydrate nature and drying process on their physicochemical and technological properties. Grafting of EMA on the carbohydrate backbone was confirmed by IR and NMR spectroscopy, and the grafting yields revealed that graft copolymers present mainly a hydrophobic character. The graft copolymerization also leads to more amorphous materials with larger particle size and lower apparent density and water content than carbohydrates (MS, MHS). All the products show a lack of flow, except MHSEMA derivatives. MSEMA copolymers underwent much plastic flow and less elastic recovery than MHSEMA copolymers. Concerning the effect of drying method, FD derivatives were characterised by higher plastic deformation and less elasticity than OD derivatives. Tablets obtained from graft copolymers showed higher crushing strength and disintegration time than tablets obtained from raw starches. This behaviour suggests that these copolymers could be used as excipients in matrix tablets obtained by direct compression and with a potential use in controlled release.

Morphological studies on block copolymer modified PA 6 blends

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poindl, M., E-mail: marcus.poindl@ikt.uni-stuttgart.de, E-mail: christian.bonten@ikt.uni-stuttgart.de; Bonten, C., E-mail: marcus.poindl@ikt.uni-stuttgart.de, E-mail: christian.bonten@ikt.uni-stuttgart.de

Recent studies show that compounding polyamide 6 (PA 6) with a PA 6 polyether block copolymers made by reaction injection molding (RIM) or continuous anionic polymerization in a reactive extrusion process (REX) result in blends with high impact strength and high stiffness compared to conventional rubber blends. In this paper, different high impact PA 6 blends were prepared using a twin screw extruder. The different impact modifiers were an ethylene propylene copolymer, a PA PA 6 polyether block copolymer made by reaction injection molding and one made by reactive extrusion. To ensure good particle matrix bonding, the ethylene propylene copolymermore » was grafted with maleic anhydride (EPR-g-MA). Due to the molecular structure of the two block copolymers, a coupling agent was not necessary. The block copolymers are semi-crystalline and partially cross-linked in contrast to commonly used amorphous rubbers which are usually uncured. The combination of different analysis methods like atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) gave a detailed view in the structure of the blends. Due to the partial cross-linking, the particles of the block copolymers in the blends are not spherical like the ones of ethylene propylene copolymer. The differences in molecular structure, miscibility and grafting of the impact modifiers result in different mechanical properties and different blend morphologies.« less

Surface functionalization of carbon nanotubes by direct encapsulation with varying dosages of amphiphilic block copolymers

NASA Astrophysics Data System (ADS)

Yao, Xueping; Li, Jie; Kong, Liang; Wang, Yong

2015-08-01

Encapsulation of carbon nanotubes (CNTs) by amphiphilic block copolymers is an efficient way to stabilize CNTs in solvents. However, the appropriate dosages of copolymers and the assembled structures are difficult to predict and control because of the insufficient understanding on the encapsulation process. We encapsulate multiwalled CNTs with polystyrene-block-poly (4-vinyl pyridine) (PS-b-P4VP) by directly mixing them in acetic acid under sonication. The copolymer forms a lamellar structure along the surface of CNTs with the PS blocks anchoring on the tube wall and the P4VP blocks exposed to the outside. The encapsulated CNTs achieve good dispersibility in polar solvents over long periods. To increase our understanding of the encapsulation process we investigate the assembled structures and stability of copolymer/CNTs mixtures with changing mass ratios. Stable dispersions are obtained at high mass ratios between the copolymer and CNTs, i.e. 2 or 3, with the presence of free spherical micelles. Transmission electron microscopy and thermal gravimetric analysis determine that the threshold for the complete coverage of CNTs by the copolymer occurs at the mass ratio of 1.5. The coated copolymer layer activates the surface of CNTs, enabling further functionalization of CNTs. For instance, atomic layer deposition of TiO2 produces conformal thin layers on the encapsulated CNTs while isolated TiO2 bumps are produced on the pristine, inert CNTs.

Adsorption of Poly(ethylene oxide)-Poly(lactide) Copolymers. Effects of Composition and Degradation.

PubMed

Muller, Dries; Carlsson, Fredrik; Malmsten, Martin

2001-04-01

The effect of chemical degradation of two diblock copolymers of poly(ethylene oxide) (E) and poly(lactide) (L), E(39)L(5) and E(39)L(20), on their adsorption at silica and methylated silica was investigated with in situ ellipsometry. Steric stablization of polystyrene dispersions was investigated in relation to degradation. Hydrolysis of the poly(lactide) block of the copolymers was followed at different temperatures and pH by using HPLC to measure the occurrence of lactic acid in solution. The block copolymers were quite stable in pH-unadjusted solution at low temperature, whereas degradation was facilitated by increasing temperature or lowering of the pH. Lower degradation rates of E(39)L(20) where observed at low temperature in comparison with those of E(39)L(5), whereas the degradation rates of the copolymers were quantitatively similar at high temperature. The adsorption of the copolymers at methylated silica substrates decreased with increasing degree of degradation due to the reduction in the ability of hydrophobic block to anchor the copolymer layer at the surface. At silica the adsorption initially increased with increasing degradation, particularly for E(39)L(20) due to deposition of aggregates onto the surface. After extensive degradation the adsorption of the copolymers at both silica and methylated silica resembled that of the corresponding poly(ethylene oxide) homopolymer. Overall, it was found that the eventual reduction in adsorption occurred at a lower degree of degradation for E(39)L(5) than for E(39)L(20). Mean-field calculations showed a reduced anchoring for the block copolymers with decreasing poly(lactide) block length at hydrophobic surfaces. In accordance with this finding, it was observed that polystyrene dispersions were stabilized by E(39)L(20) or E(39)L(5) in a way that depended on both the lactide block length and the degree of degradation. Upon degradation of the hydrophobic block, stabilization of the polystyrene dispersions was maintained initially, but eventually degradation resulted in destabilization. The average residual copolymer concentration required for stabilization of the polystyrene dispersions was much higher than the corresponding concentration of intact copolymer required for stabilization. Copyright 2001 Academic Press.

40 CFR 721.10527 - Perfluoroalkylethyl methacrylate copolymer (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... as perfluoroalkylethyl methacrylate copolymer (PMN P-11-646) is subject to reporting under this... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Perfluoroalkylethyl methacrylate... Specific Chemical Substances § 721.10527 Perfluoroalkylethyl methacrylate copolymer (generic). (a) Chemical...

40 CFR 721.10527 - Perfluoroalkylethyl methacrylate copolymer (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... as perfluoroalkylethyl methacrylate copolymer (PMN P-11-646) is subject to reporting under this... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Perfluoroalkylethyl methacrylate... Specific Chemical Substances § 721.10527 Perfluoroalkylethyl methacrylate copolymer (generic). (a) Chemical...

40 CFR 721.10619 - Perfluoroalkylethyl methacrylate copolymer (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... as perfluoroalkylethyl methacrylate copolymer (PMN P-11-653) is subject to reporting under this... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Perfluoroalkylethyl methacrylate... Specific Chemical Substances § 721.10619 Perfluoroalkylethyl methacrylate copolymer (generic). (a) Chemical...

40 CFR 721.10619 - Perfluoroalkylethyl methacrylate copolymer (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... as perfluoroalkylethyl methacrylate copolymer (PMN P-11-653) is subject to reporting under this... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Perfluoroalkylethyl methacrylate... Specific Chemical Substances § 721.10619 Perfluoroalkylethyl methacrylate copolymer (generic). (a) Chemical...

The effect of copolymers on the interfaces in incompatible homopolymers blend: Molecular dynamics study

NASA Astrophysics Data System (ADS)

Ryu, Jiho; Lee, Won Bo

2015-03-01

Using molecular dynamics simulations the effect of copolymers as compatibilizer for reducing interfacial tension and enhancement of interfacial adhesion at the interface of thermodynamic unfavorable homopolymers blend is studied with block- and graft-copolymers. We have calculated local pressure tensor of system along the axis perpendicular to interface, varying bending potential energy of one part, which consist of just one kind of beads, of copolymer chain to examine the effect of stiffness of surfactin molecules. Here we consider symmetric diblock copolymer (f =1/2) having 1/2 N make of beads of type A and the other part made of beads of type B, and graft copolymer having backbone linear chain consist of 1/2 N beads of type of A and branched with two side-chain consist of 1/4 N beads of type B. All simulations were performed under the constant NPT ensemble at T* =1, ρ* ~0.85. Also we studied changes of effect of copolymers with increasing pairwise repulsive interaction potential between two beads of types A and B while homopolymers chain length are fixed, N =30. Chemical and Biomolecular Engineering, Sogang University, Seoul, South Korea.

Novel Pentablock Copolymers as Thermosensitive Self-Assembling Micelles for Ocular Drug Delivery

PubMed Central

Alami-Milani, Mitra; Zakeri-Milani, Parvin; Valizadeh, Hadi; Salehi, Roya; Salatin, Sara; Naderinia, Ali; Jelvehgari, Mitra

2017-01-01

Many studies have focused on how drugs are formulated in the sol state at room temperature leading to the formation of in situ gel at eye temperature to provide a controlled drug release. Stimuli-responsive block copolymer hydrogels possess several advantages including uncomplicated drug formulation and ease of application, no organic solvent, protective environment for drugs, site-specificity, prolonged and localized drug delivery, lower systemic toxicity, and capability to deliver both hydrophobic and hydrophilic drugs. Self-assembling block copolymers (such as diblock, triblock, and pentablock copolymers) with large solubility variation between hydrophilic and hydrophobic segments are capable of making temperature-dependent micellar assembles, and with further increase in the temperature, of jellifying due to micellar aggregation. In general, molecular weight, hydrophobicity, and block arrangement have a significant effect on polymer crystallinity, micelle size, and in vitro drug release profile. The limitations of creature triblock copolymers as initial burst release can be largely avoided using micelles made of pentablock copolymers. Moreover, formulations based on pentablock copolymers can sustain drug release for a longer time. The present study aims to provide a concise overview of the initial and recent progresses in the design of hydrogel-based ocular drug delivery systems. PMID:28507933

Proteins detection by polymer optical fibers sensitised with overlayers of block and random copolymers

NASA Astrophysics Data System (ADS)

El Sachat, Alexandros; Meristoudi, Anastasia; Markos, Christos; Pispas, Stergios; Riziotis, Christos

2014-03-01

A low cost and low complexity optical detection method of proteins is presented by employing a detection scheme based on electrostatic interactions, and implemented by sensitization of a polymer optical fibers' (POF) surface by thin overlayers of properly designed sensitive copolymer materials with predesigned charges. This method enables the fast detection of proteins having opposite charge to the overlayer, and also the effective discrimination of differently charged proteins like lysozyme (LYS) and bovine serum albumin (BSA). As sensitive materials the block and the random copolymers of the same monomers were employed, namely the block copolymer poly(styrene-b-2vinylpyridine) (PS-b- P2VP) and the corresponding random copolymer poly(styrene-r-2vinylpyridine) (PS-r-P2VP), of similar composition and molecular weights. Results show systematically different response between the block and the random copolymers, although of the same order of magnitude, drawing thus important conclusions on their applications' techno-economic aspects given that they have significantly different associated manufacturing method and costs. The use of the POF platform, in combination with those adaptable copolymer sensing materials could lead to efficient low cost bio-detection schemes.

Use of amphiphilic triblock copolymers for enhancing removal efficiency of organic pollutant from contaminated media

NASA Astrophysics Data System (ADS)

Lee, Jun Hyup; Lee, Byungsun; Son, Intae; Kim, Jae Hong; Kim, Chunho; Yoo, Ji Yong; Wu, Jong-Pyo; Kim, Younguk

2015-11-01

We have studied amphiphilic triblock copolymers poly(ethylene glycol)- b-poly(propylene glycol)- b-poly(ethylene glycol) (PEG- b-PPG- b-PEG) and poly(propylene glycol)- b-poly(ethylene glycol)- b-poly(propylene glycol) (PPG- b-PEG- b-PPG) as possible substitutes for sodium dodecyl sulfate as anionic surfactants for the removal of hydrophobic contaminants. The triblock copolymers were compared with sodium dodecyl sulfate in terms of their abilities to remove toluene as hydrophobic contaminant in fuel, and the effects of polymer structure, PEG content, and concentration were studied. The PEG- b-PPG- b-PEG copolymer containing two hydrophilic PEG blocks was more effective for the removal of hydrophobic contaminant at extremely high concentration. We also measured the removal capabilities of the triblock copolymers having various PEG contents and confirmed that removal capability was greatest at 10% PEG content regardless of polymer structure. As with sodium dodecyl sulfate, the removal efficiency of a copolymer has a positive correlation with its concentration. Finally, we proposed the amphiphilic triblock copolymer of PPG- b-PEG- b-PPG bearing 10% PEG content that proved to be the most effective substitute for sodium dodecyl sulfate.

Drug release from and hydrolytic degradation of a poly(ethylene glycol) grafted poly(3-hydroxyoctanoate).

PubMed

Kim, Hyung Woo; Chung, Chung Wook; Hwang, Sung Joo; Rhee, Young Ha

2005-07-01

Monoacrylate-poly(ethylene glycol)-grafted poly(3-hydroxyoctanoate) (PEGMA-g-PHO) copolymers were synthesized to develop a swelling-controlled release delivery system for ibuprofen as a model drug. The in vitro hydrolytic degradation of and the drug release from a film made of the PEGMA-g-PHO copolymer were carried out in a phosphate buffer saline (pH 7.4) medium. The hydrolytic degradation of the copolymer was strongly dependent on the degree of grafting (DG) of the PEGMA group. The degradation rate of the copolymer films in vitro increased with increasing DG of the PEGMA group on the PHO chain. The copolymer films showed a controlled delivery of ibuprofen to the medium in periods of time that depend on the composition, hydrophilic/hydrophobic characteristics, initial drug loading amount and film thickness of the graft copolymer support. The drug release rate from the grafted copolymer films was faster than the rate of weight loss of the films themselves. In particular, a combination of the low DG of the PEGMA group in the PHO chains with the low ibuprofen solubility in water led to long-term constant release from these matrices in vitro.

Non-immunogenic, hydrophilic/cationic block copolymers and uses thereof

DOEpatents

Scales, Charles W.; Huang, Faqing; McCormick, Charles L.

2010-05-18

The present invention provides novel non-immunogenic, hydrophilic/cationic block copolymers comprising a neutral-hydrophilic polymer and a cationic polymer, wherein both polymers have well-defined chain-end functionality. A representative example of such a block copolymer comprises poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA) and poly(N-[3-(dimethylamino)propyl]methacrylamide) (PDMAPMA). Also provided is a synthesis method thereof in aqueous media via reversible addition fragmentation chain transfer (RAFT) polymerization. Further provided are uses of these block copolymers as drug delivery vehicles and protection agents.

Salt-Induced Block Copolymer Micelles as Nanoreactors for the Formation of CdS Nanoparticles

DTIC Science & Technology

2001-11-01

or corona of micelles is presented. Poly(styrene-block-2-vinylpyridine) ( PS - b - P2VP ) and cadmium ions form aggregates of single micelles, called...ratio and block copolymer concentration in THF etc. EXPERIMENTAL DETAILS The synthesis of the PS - b - P2VP block copolymer was performed using sequential...nanoparticles: PS - b - P2VP block copolymer was dissolved in THF at different concentrations under vigorous stirring for 1 hour. Cd(Ac)2.2H 20 dissolved in a

Injectible bodily prosthetics employing methacrylic copolymer gels

DOEpatents

Mallapragada, Surya K.; Anderson, Brian C.

2007-02-27

The present invention provides novel block copolymers as structural supplements for injectible bodily prosthetics employed in medical or cosmetic procedures. The invention also includes the use of such block copolymers as nucleus pulposus replacement materials for the treatment of degenerative disc disorders and spinal injuries. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol) methyl ether polymer.

A Research Project on the Emulsifying and Homogenizing Properties of Block Copolymers in Polymer Blends.

DTIC Science & Technology

1987-06-15

Chain C.V. Berney Scattering in Heterogeneous P. Kofinas Block Copolymers R.E. Cohen 18. SANS Studies of the Configu- C.V. Berney rations of Single...Studies of the Configuratins C.V. Berney Single Chains in Heterogeneous Block P. Cheng Copolymers, J. Materials Research, P. Dofinas in press (1987) R.E...Cohen 2. A Reexamination of the Configurations C.V. Berney of Single-Chain Scattering in Hetero- P. Kofinas geneous Block Copolymers, R.E. Cohen

Influence of water-insoluble nonionic copolymer E(6)P(39)E(6) on the microstructure and self-aggregation dynamics of aqueous SDS solution-NMR and SANS investigations.

PubMed

Prameela, G K S; Phani Kumar, B V N; Aswal, V K; Mandal, Asit Baran

2013-10-28

The influence of water-insoluble nonionic triblock copolymer PEO-PPO-PEO [poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)] i.e., E6P39E6 with molecular weight 2800, on the microstructure and self-aggregation dynamics of anionic surfactant sodium dodecylsulfate (SDS) in aqueous solution (D2O) were investigated using high resolution nuclear magnetic resonance (NMR) and small-angle neutron scattering (SANS) measurements. Variable concentration and temperature proton ((1)H), carbon ((13)C) NMR chemical shifts, (1)H self-diffusion coefficients, (1)H spin-lattice and spin-spin relaxation rates data indicate that the higher hydrophobic nature of copolymer significantly influenced aggregation characteristics of SDS. The salient features of the NMR investigations include (i) the onset of mixed micelles at lower SDS concentrations (<3 mM) relative to the copolymer-free case and their evolution into SDS free micelles at higher SDS concentrations (~30 mM), (ii) disintegration of copolymer-SDS mixed aggregate at moderate SDS concentrations (~10 mM) and still binding of a copolymer with SDS and (iii) preferential localization of the copolymer occurred at the SDS micelle surface. SANS investigations indicate prolate ellipsoidal shaped mixed aggregates with an increase in SDS aggregation number, while a contrasting behavior in the copolymer aggregation is observed. The aggregation features of SDS and the copolymer, the sizes of mixed aggregates and the degree of counterion dissociation (α) extracted from SANS data analysis corroborate reasonably well with those of (1)H NMR self-diffusion and sodium ((23)Na) spin-lattice relaxation data.

Degradable ketal-based block copolymer nanoparticles for anticancer drug delivery: a systematic evaluation.

PubMed

Louage, Benoit; Zhang, Qilu; Vanparijs, Nane; Voorhaar, Lenny; Vande Casteele, Sofie; Shi, Yang; Hennink, Wim E; Van Bocxlaer, Jan; Hoogenboom, Richard; De Geest, Bruno G

2015-01-12

Low solubility of potent (anticancer) drugs is a major driving force for the development of noncytotoxic, stimuli-responsive nanocarriers, including systems based on amphiphilic block copolymers. In this regard, we investigated the potential of block copolymers based on 2-hydroxyethyl acrylate (HEA) and the acid-sensitive ketal-containing monomer (2,2-dimethyl-1,3-dioxolane-4-yl)methyl acrylate (DMDMA) to form responsive drug nanocarriers. Block copolymers were successfully synthesized by sequential reversible addition-fragmentation chain transfer (RAFT) polymerization, in which we combined a hydrophilic poly(HEA)x block with a (responsive) hydrophobic poly(HEAm-co-DMDMAn)y copolymer block. The DMDMA content of the hydrophobic block was systematically varied to investigate the influence of polymer design on physicochemical properties and in vitro biological performance. We found that a DMDMA content higher than 11 mol % is required for self-assembly behavior in aqueous medium. All particles showed colloidal stability in PBS at 37 °C for at least 4 days, with sizes ranging from 23 to 338 nm, proportional to the block copolymer DMDMA content. Under acidic conditions, the nanoparticles decomposed into soluble unimers, of which the decomposition rate was inversely proportional to the block copolymer DMDMA content. Flow cytometry and confocal microscopy showed dose-dependent, active in vitro cellular uptake of the particles loaded with hydrophobic octadecyl rhodamine B chloride (R18). The block copolymers showed no intrinsic in vitro cytotoxicity, while loaded with paclitaxel (PTX), a significant decrease in cell viability was observed comparable or better than the two commercial PTX nanoformulations Abraxane and Genexol-PM at equal PTX dose. This systematic approach evaluated and showed the potential of these block copolymers as nanocarriers for hydrophobic drugs.

Polybenzimidazole block copolymers for fuel cell: synthesis and studies of block length effects on nanophase separation, mechanical properties, and proton conductivity of PEM.

PubMed

Maity, Sudhangshu; Jana, Tushar

2014-05-14

A series of meta-polybenzimidazole-block-para-polybenzimidazole (m-PBI-b-p-PBI), segmented block copolymers of PBI, were synthesized with various structural motifs and block lengths by condensing the diamine terminated meta-PBI (m-PBI-Am) and acid terminated para-PBI (p-PBI-Ac) oligomers. NMR studies and existence of two distinct glass transition temperatures (Tg), obtained from dynamical mechanical analysis (DMA) results, unequivocally confirmed the formation of block copolymer structure through the current polymerization methodology. Appropriate and careful selection of oligomers chain length enabled us to tailor the block length of block copolymers and also to make varieties of structural motifs. Increasingly distinct Tg peaks with higher block length of segmented block structure attributed the decrease in phase mixing between the meta-PBI and para-PBI blocks, which in turn resulted into nanophase segregated domains. The proton conductivities of proton exchange membrane (PEM) developed from phosphoric acid (PA) doped block copolymer membranes were found to be increasing substantially with increasing block length of copolymers even though PA loading of these membranes did not alter appreciably with varying block length. For example when molecular weight (Mn) of blocks were increased from 1000 to 5500 then the proton conductivities at 160 °C of resulting copolymers increased from 0.05 to 0.11 S/cm. Higher block length induced nanophase separation between the blocks by creating less morphological barrier within the block which facilitated the movement of the proton in the block and hence resulting higher proton conductivity of the PEM. The structural varieties also influenced the phase separation and proton conductivity. In comparison to meta-para random copolymers reported earlier, the current meta-para segmented block copolymers were found to be more suitable for PBI-based PEM.

Imidazolium-based Block Copolymers as Solid-State Separators for Alkaline Fuel Cells and Lithium Ion Batteries

NASA Astrophysics Data System (ADS)

Nykaza, Jacob Richard

In this study, polymerized ionic liquid (PIL) diblock copolymers were explored as solid-state polymer separators as an anion exchange membrane (AEM) for alkaline fuel cells AFCs and as a solid polymer electrolyte (SPE) for lithium-ion batteries. Polymerized ionic liquid (PIL) block copolymers are a distinct set of block copolymers that combine the properties of both ionic liquids (e.g., high conductivity, high electrochemical stability) and block copolymers (e.g., self-assembly into various nanostructures), which provides the opportunity to design highly conductive robust solid-state electrolytes that can be tuned for various applications including AFCs and lithium-ion batteries via simple anion exchange. A series of bromide conducting PIL diblock copolymers with an undecyl alkyl side chain between the polymer backbone and the imidazolium moiety were first synthesized at various compositions comprising of a PIL component and a non-ionic component. Synthesis was achieved by post-functionalization from its non-ionic precursor PIL diblock copolymer, which was synthesized via the reverse addition fragmentation chain transfer (RAFT) technique. This PIL diblock copolymer with long alkyl side chains resulted in flexible, transparent films with high mechanical strength and high bromide ion conductivity. The conductivity of the PIL diblock copolymer was three times higher than its analogous PIL homopolymer and an order of magnitude higher than a similar PIL diblock copolymer with shorter alkyl side chain length, which was due to the microphase separated morphology, more specifically, water/ion clusters within the PIL microdomains in the hydrated state. Due to the high conductivity and mechanical robustness of this novel PIL block copolymer, its application as both the ionomer and AEM in an AFC was investigated via anion exchange to hydroxide (OH-), where a maximum power density of 29.3 mW cm-1 (60 °C with H2/O2 at 25 psig (172 kPa) backpressure) was achieved. Rotating disk electrode (RDE) experiments determined the interfacial resistance imposed during cell assembly between the AEM, catalyst, and ionomer was a factor in fuel cell performance. Further RDE studies investigated the electrochemical stability of the PIL block copolymer ionomer under applied potentials, where it was determined that potential cycling increased the degradation compared to constant voltage or open circuit voltage studies. The PIL diblock copolymer was then anion exchanged to the bis(trifluoromethane)sulfonamide (TFSI-) anion form and imbibed with a lithium salt and ionic liquid solution for use as a SPE in lithium-ion batteries resulting in a maximum discharge capacity of 112 mAh g-1 at 0.1 C with a Coulombic efficiency greater than 94% over 100 cycles. PIL block copolymers have promising mechanical properties and transport properties (i.e., ion conductivity) in both the hydrated (hydrophilic anions; Br-, OH-) and dry (hydrophobic anions; TFSI-) states resulting in highly conductive, chemically/thermally stable, and mechanically robust solid-state polymer separators for use as AEMs in AFCs and as SPEs in lithium-ion batteries.

Dynamical self-arrest in symmetric and asymmetric diblock copolymer melts using a replica approach within a local theory.

PubMed

Wu, Sangwook

2009-03-01

We investigate dynamical self-arrest in a diblock copolymer melt using a replica approach within a self-consistent local method based on dynamical mean-field theory (DMFT). The local replica approach effectively predicts (chiN)_{A} for dynamical self-arrest in a block copolymer melt for symmetric and asymmetric cases. We discuss the competition of the cubic and quartic interactions in the Landau free energy for a block copolymer melt in stabilizing a glassy state depending on the chain length. Our local replica theory provides a universal value for the dynamical self-arrest in block copolymer melts with (chiN)_{A} approximately 10.5+64N;{-3/10} for the symmetric case.

Nanopatterned articles produced using reconstructed block copolymer films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Russell, Thomas P.; Park, Soojin; Wang;, Jia-Yu

Nanopatterned surfaces are prepared by a method that includes forming a block copolymer film on a substrate, annealing and surface reconstructing the block copolymer film to create an array of cylindrical voids, depositing a metal on the surface-reconstructed block copolymer film, and heating the metal-coated block copolymer film to redistribute at least some of the metal into the cylindrical voids. When very thin metal layers and low heating temperatures are used, metal nanodots can be formed. When thicker metal layers and higher heating temperatures are used, the resulting metal structure includes nanoring-shaped voids. The nanopatterned surfaces can be transferred tomore » the underlying substrates via etching, or used to prepare nanodot- or nanoring-decorated substrate surfaces.« less

Method of producing nanopatterned articles using surface-reconstructed block copolymer films

DOEpatents

Russell, Thomas P; Park, Soojin; Wang, Jia-Yu; Kim, Bokyung

2013-08-27

Nanopatterned surfaces are prepared by a method that includes forming a block copolymer film on a substrate, annealing and surface reconstructing the block copolymer film to create an array of cylindrical voids, depositing a metal on the surface-reconstructed block copolymer film, and heating the metal-coated block copolymer film to redistribute at least some of the metal into the cylindrical voids. When very thin metal layers and low heating temperatures are used, metal nanodots can be formed. When thicker metal layers and higher heating temperatures are used, the resulting metal structure includes nanoring-shaped voids. The nanopatterned surfaces can be transferred to the underlying substrates via etching, or used to prepare nanodot- or nanoring-decorated substrate surfaces.

The influence of chain rigidity and the degree of sulfonation on the morphology of block copolymers as nano reactor

NASA Astrophysics Data System (ADS)

Hong, K.; Zhang, X.

2005-03-01

Polyelectrolyte block copolymer was used to form an ordered domain of ionic block as a ``nanoreactor'' due to its ability to bind oppositely charged metal ion, Zn^2+, Fe^2+ etc. The purpose of our research is to investigate the controllability of the size and morphology of domains (inorganic nano particles) by changing backbone stiffness, the charge density and the volume fraction of ionic block. Poly(styrene sulfonate) (PSS), which backbone is flexible, and poly(cyclohexadiene sulfonate) (PCHDS), which backbone is ``semiflexible'', were used as ionic blocks. We synthesized PtBS-PSS and PS-PCHDS with various degree of sulfonation and the volume fraction. Zinc oxide (ZnO) nano particles successfully formed in the ionic domain of microphase separated block copolymers. We used SANS to characterize the morphology of block copolymers and TEM for block copolymer containing ZnO nano particles. Our experimental results show that the chemistry of ``sulfonation'' of block copolymers can be successfully used to synthesize nano composite materials.

Microwave based synthesis and spectral characterization of thermo-sensitive poly(N,N-diethylacrylamide) grafted pectin copolymer.

PubMed

Işıklan, Nuran; Tokmak, Şeyma

2018-07-01

The functionalization of polysaccharides with synthetic polymers has attracted great attention owing to its application in many industrial fields. The aim of this work was to study the impact of pectin functionalization with N,N-diethylacrylamide (DEAAm). Pectin was modified via microwave-induced graft copolymerization of DEAAm using ceric ammonium nitrate (CAN) and N,N,N',N'-tetramethylethylenediamine (TEMED). FTIR, 13 C NMR, DSC/TGA, XRD, and SEM techniques were used to verify the structure of graft copolymers. Various reaction conditions such as microwave irradiation time, temperature, microwave power, monomer, initiator, and TEMED concentrations were investigated to get a maximum grafting yield of 192%. Lower critical solution temperatures (LCST) of graft copolymers were determined by UV spectroscopy. Graft copolymers were found to be thermo-sensitive, with LCST of 31°C and high thermal resistance. Biocompatibility test of copolymers showed that copolymers were not cytotoxic to L929 fibroblasts cells and can be used as a biomaterial. Copyright © 2018 Elsevier B.V. All rights reserved.

Synthesis of Novel μ-Star Copolymers with Poly(N-Octyl Benzamide) and Poly(ε-Caprolactone) Miktoarms through Chain-Growth Condensation Polymerization, Styrenics-Assisted Atom Transfer Radical Coupling, and Ring-Opening Polymerization.

PubMed

Huang, Chih-Feng; Aimi, Junko; Lai, Kuan-Yu

2017-02-01

Star copolymers are known to phase separate on the nanoscale, providing useful self-assembled morphologies. In this study, the authors investigate synthesis and assembly behavior of miktoarm star (μ-star) copolymers. The authors employ a new strategy for the synthesis of unprecedented μ-star copolymers presenting poly(N-octyl benzamide) (PBA) and poly(ε-caprolactone) (PCL) arms: a combination of chain-growth condensation polymerization, styrenics-assisted atom transfer radical coupling, and ring-opening polymerization. Gel permeation chromatography, mass-analyzed laser desorption/ionization mass spectrometry, and 1 H NMR spectroscopy reveal the successful synthesis of a well-defined (PBA 11 ) 2 -(PCL 15 ) 4 μ-star copolymer (M n ,NMR ≈ 12 620; Đ = 1.22). Preliminary examination of the PBA 2 PCL 4 μ-star copolymer reveals assembled nanofibers having a uniform diameter of ≈20 nm. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stimulus sensitive gel with radioisotope and methods of making

DOEpatents

Weller, Richard E.; Lind, Michael A.; Fisher, Darrell R.; Gutowska, Anna; Campbell, Allison A.

2005-03-22

The present invention is a thermally reversible stimulus-sensitive gel or gelling copolymer radioisotope carrier that is a linear random copolymer of an [meth-]acrylamide derivative and a hydrophilic comonomer, wherein the linear random copolymer is in the form of a plurality of linear chains having a plurality of molecular weights greater than or equal to a minimum gelling molecular weight cutoff. Addition of a biodegradable backbone and/or a therapeutic agent imparts further utility. The method of the present invention for making a thermally reversible stimulus-sensitive gelling copolymer radionuclcide carrier has the steps of: (a) mixing a stimulus-sensitive reversible gelling copolymer with an aqueous solvent as a stimulus-sensitive reversible gelling solution; and (b) mixing a radioisotope with said stimulus-sensitive reversible gelling solution as said radioisotope carrier. The gel is enhanced by either combining it with a biodegradable backbone and/or a therapeutic agent in a gelling solution made by mixing the copolymer with an aqueous solvent.

Stimulus sensitive gel with radioisotope and methods of making

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weller, Richard E; Lind, Michael A; Fisher, Darrell R

2001-10-02

The present invention is a thermally reversible stimulus-sensitive gel or gelling copolymer radioisotope carrier that is a linear random copolymer of an [meth]acrylamide derivative and a hydrophilic comonomer, wherein the linear random copolymer is in the form of a plurality of linear chains having a plurality of molecular weights greater than or equal to a minimum gelling molecular weight cutoff. Addition of a biodegradable backbone and/or a therapeutic agent imparts further utility. The method of the present invention for making a thermally reversible stimulus-sensitive gelling copolymer radionuclcide carrier has the steps of: (a) mixing a stimulus-sensitive reversible gelling copolymer withmore » an aqueous solvent as a stimulus-sensitive reversible gelling solution; and (b) mixing a radioisotope with said stimulus-sensitive reversible gelling solution as said radioisotope carrier. The gel is enhanced by either combining it with a biodegradable backbone and/or a therapeutic agent in a gelling solution made by mixing the copolymer with an aqueous solvent.« less

Nafion as Cosurfactant: Solubilization of Nafion in Water in the Presence of Pluronics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kelarakis, Antonios; Giannelis, Emmanuel P.

2011-01-18

Incorporation of Nafion to aqueous solutions of Pluronics adversely impacts micellization due to extensive Nafion/copolymer interactions. Light scattering and zeta potential measurements provide evidence for the formation of sizable and stable Nafion/copolymer complexes, in expense of the neat copolymer micelles. At high copolymer concentrations, the overall interaction diagram of Nafion/copolymer reflects the competitive action of the release of packing constraints due to micellar destabilization induced by Nafion on one hand and the gelator nature of the Nafion on the other. Measurements using a quartz crystal microbalance (QCM-D) show that aqueous solutions of Pluronics (even at very low concentration) can dissolvemore » the Nafion coating on the crystal resonator, while typical low molecular weight ionic surfactants fail to induce similar effects. These studies demonstrate that complexation with this class of copolymers is a facile route to impart dispersibility to Nafion in aqueous environments that otherwise can be achieved through tedious and harsh treatments.« less

Molecular and morphological characterization of midblock-sulfonated styrenic triblock copolymers

DOE PAGES

Mineart, Kenneth P.; Ryan, Justin J.; Lee, Byeongdu; ...

2017-01-11

Midblock-sulfonated triblock copolymers afford a desirable opportunity to generate network-forming amphiphilic materials that are suitable for use in a wide range of emerging technologies as fuel-cell, water-desalination, ion-exchange, photovoltaic, or electroactive membranes. Employing a previously reported synthetic strategy wherein poly( p- tert-butylstyrene) remains unreactive, we have selectively sulfonated the styrenic midblock of a poly( p- tert-butylstyrene- b-styrene- b- p- tert- butylstyrene) (TST) triblock copolymer to different extents. Comparison of the resulting sulfonated copolymers with results from our prior study provides favorable quantitative agreement and suggests that a shortened reaction time is advantageous. An ongoing challenge regarding the morphological development ofmore » charged block copolymers is the competition between microphase separation of the incompatible blocks and physical cross-linking of ionic clusters, with the latter often hindering the former. Here, we expose the sulfonated TST copolymers to solvent-vapor annealing to promote nanostructural refinement. Furthermore, the effect of such annealing on morphological characteristics, as well as on molecular free volume, is explored.« less

Synthesis, characterization and antimicrobial activity of biodegradable conducting polypyrrole-graft-chitosan copolymer

NASA Astrophysics Data System (ADS)

Cabuk, Mehmet; Alan, Yusuf; Yavuz, Mustafa; Unal, Halil Ibrahim

2014-11-01

In this study, polypyrrole-graft-chitosan (PPy-g-CS) copolymer was chemically synthesized and its structural and morphological properties characterized by FTIR, UV-vis, SEM, XRD, TGA and zeta-potential techniques. The results revealed that there were strong interactions between PPy and CS chains. The electrical conductivity of CS increased to semiconducting range by grafting. The crystallinity and thermal stability of PPy-g-CS copolymer improved when compared to CS. The copolymer was tested against various bacterial and fungal strains at various concentrations and results obtained were compared with the reference antibiotics. The results indicated that the antibacterial activity of PPy-g-CS copolymer was stronger than CS and PPy alone. The antibacterial activity of the PPy-g-CS copolymer observed to increase with rising concentration, and showed stronger activity against bacteria than Penicillin (10 mg), Rifampicin (5 mg) and Trimethoprim (25 mg), whereas showed equipotent activity with Amikacin (30 mg) and Erythromycin (15 mg) antibiotics.

Customization of copolymers to optimize selectivity and yield in polymer-driven antibody purification processes.

PubMed

Capito, Florian; Skudas, Romas; Stanislawski, Bernd; Kolmar, Harald

2013-01-01

This manuscript describes customization of copolymers to be used for polymer-driven protein purification in bioprocessing. To understand how copolymer customization can be used for fine-tuning, precipitation behavior was analyzed for five target antibodies (mAbs) and BSA as model impurity protein, at ionic strength similar to undiluted cell culture fluid. In contrast to the use of standardized homopolymers, customized copolymers, composed of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and 4-(acryloylamino)benzoic acid (ABZ), exhibited antibody precipitation yields exceeding 90%. Additionally, copolymer average molecular weight (Mw ) was varied and its influence on precipitation yield and contaminant coprecipitation was investigated. Results revealed copolymer composition as the major driving force for precipitation selectivity, which was also dependent on protein hydrophobicity. By adjusting ABZ content and Mw of the precipitant for each of the mAbs, conditions were found that allowed for high precipitation yield and selectivity. These findings may open up new avenues for using polymers in antibody purification processes. © 2013 American Institute of Chemical Engineers.

Microstructure synthesis control of biological polyhydroxyalkanoates with mass spectrometry

NASA Astrophysics Data System (ADS)

Pederson, Erik Norman

Polyhydroxyalkanoates (PHA's) are a class of biologically produced polymers, or plastic, that is synthesized by various microorganisms. PHA's are made from biorenewable resources and are fully biodegradable and biocompatible, making them an environmentally friendly green polymer. A method of incorporating polymer microstructure into the PHA synthesized in Ralstonia eutropha was developed. These microstructures were synthesized with polyhydroxybutyrate (PHB) and poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) as the polymer domains. To synthesize the PHB V copolymer, the additional presence of valerate was required. To control valerate substrate additions to the bioreactor, an off-gas mass spectrometry (MS) feedback control system was developed. Important process information including the cell physiology, growth kinetics, and product formation kinetics in the bioreactor was obtained with MS and used to control microstructure synthesis. The two polymer microstructures synthesized were core-shell granules and block copolymers. Block copolymers control the structure of the individual polymer chains while core-shell granules control the organization of many polymer chains. Both these microstructures result in properties unattainable by blending the two polymers together. The core-shell structures were synthesized with controlled domain thickness based on a developed model. Different block copolymers compositions were synthesized by varying the switching time of the substrate pulses responsible for block copolymer synthesis. The block copolymers were tested to determine their chemical properties and cast into films to determine the materials properties. These block copolymer films possessed new properties not achieved by copolymers or blends of the two polymers.

Applying thermosettable zwitterionic copolymers as general fouling-resistant and thermal-tolerant biomaterial interfaces.

PubMed

Chou, Ying-Nien; Chang, Yung; Wen, Ten-Chin

2015-05-20

We introduced a thermosettable zwitterionic copolymer to design a high temperature tolerance biomaterial as a general antifouling polymer interface. The original synthetic fouling-resistant copolymer, poly(vinylpyrrolidone)-co-poly(sulfobetaine methacrylate) (poly(VP-co-SBMA)), is both thermal-tolerant and fouling-resistant, and the antifouling stability of copolymer coated interfaces can be effectively controlled by regulating the VP/SBMA composition ratio. We studied poly(VP-co-SBMA) copolymer gels and networks with a focus on their general resistance to protein, cell, and bacterial bioadhesion, as influenced by the thermosetting process. Interestingly, we found that the shape of the poly(VP-co-SBMA) copolymer material can be set at a high annealing temperature of 200 °C while maintaining good antifouling properties. However, while the zwitterionic PSBMA polymer gels were bioinert as expected, control of the fouling resistance of the PSBMA polymer networks was lost in the high temperature annealing process. A poly(VP-co-SBMA) copolymer network composed of PSBMA segments at 32 mol % showed reduced fibrinogen adsorption, tissue cell adhesion, and bacterial attachment, but a relatively higher PSBMA content of 61 mol % was required to optimize resistance to platelet adhesion and erythrocyte attachment to confer hemocompatibility to human blood. We suggest that poly(VP-co-SBMA) copolymers capable of retaining stable fouling resistance after high temperature shaping have a potential application as thermosettable materials in a bioinert interface for medical devices, such as the thermosettable coating on a stainless steel blood-compatible metal stent investigated in this study.

Preparation of novel alkaline pH-responsive copolymers for the formation of recyclable aqueous two-phase systems and their application in the extraction of lincomycin.

PubMed

Liu, Jiali; Cao, Xuejun

2016-02-01

Aqueous two-phase systems have potential industrial application in bioseparation and biocatalysis engineering; however, their practical application is limited primarily because the copolymers involved in the formation of aqueous two-phase systems cannot be recovered. In this study, two novel alkaline pH-responsive copolymers were synthesized and examined for the extraction of lincomycin. The two copolymers could form a novel alkaline aqueous two-phase systems when their concentrations were both 6% w/w and the pH was 8.4(±0.1)-8.7(±0.1). One copolymer was synthesized using acrylic acid, 2-(dimethylamino)ethyl methacrylate, and butyl methacrylate as monomers. Moreover, 98.8% of the copolymer could be recovered by adjusting the solution pH to its isoelectric point (pH 6.29). The other copolymer was synthesized using the monomers methacrylic acid, 2-(dimethylamino)ethyl methacrylate, and methyl methacrylate. In this case, 96.7% of the copolymer could be recovered by adjusting the solution pH to 7.19. The optimal partition coefficient of lincomycin was 0.17 at 30°C in the presence of 10 mM KBr and 5.5 at 40°C in the presence of 80 mM Ti(SO4)2 using the novel alkaline aqueous two-phase systems. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of nanoparticles on the compatibility of PEO-PMMA block copolymers.

PubMed

Mu, Dan; Li, Jian-Quan; Li, Wei-Dong; Wang, Song

2011-12-01

The compatibility of six kinds of designed poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) copolymers was studied at 270, 298 and 400 K via mesoscopic modeling. The values of the order parameters depended on both the structures of the block copolymers and the simulation temperature, while the values of the order parameters of the long chains were higher than those of the short ones; temperature had a more obvious effect on long chains than on the short ones. Plain copolymers doped with poly(ethylene oxide) (PEO) or poly(methyl methacrylate) (PMMA) homopolymer showed different order parameter values. When a triblock copolymer had the same component at both ends and was doped with one of its component polymers as a homopolymer (such as A5B6A5 doped with B6 or A5 homopolymer), the value of its order parameter depended on the simulation temperature. The highest order parameter values were observed for A5B6A5 doped with B6 at 400 K and for A5B6A5 doped with A5 at 270 K. A study of copolymers doped with nanoparticles showed that the mesoscopic phase was influenced by not only the properties of the nanoparticles, such as the size and density, but also the compositions of the copolymers. Increasing the size of the nanoparticles used as a dopant had the most significant effect on the phase morphologies of the copolymers.

Imide/arylene ether block copolymers

NASA Technical Reports Server (NTRS)

Jensen, B. J.; Hergenrother, P. M.; Bass, R. G.

1991-01-01

Two series of imide/arylene either block copolymers were prepared using an arylene ether block and either an amorphous or semi-crystalline imide block. The resulting copolymers were characterized and selected physical and mechanical properties were determined. These results, as well as comparisons to the homopolymer properties, are discussed.

78 FR 15947 - Agency Information Collection Activities; Submission to OMB for Review and Approval; Comment...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-13

... Chloride and Copolymer Production, Primary Copper Smelting, Secondary Copper Smelting, and Primary... www.regulations.gov . Title: NESHAP for Area Sources: Polyvinyl Chloride and Copolymer Production.... Respondents/Affected Entities: Owners or operators of polyvinyl chloride and copolymer, primary copper smelter...

21 CFR 177.1315 - Ethylene-1, 4-cyclohexylene dimethylene terephthalate copolymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-1, 4-cyclohexylene dimethylene... Ethylene-1, 4-cyclohexylene dimethylene terephthalate copolymers. Ethylene-1, 4-cyclohexylene dimethylene... purposes of this section, ethylene-1,4-cyclohexylene dimethylene terephthalate copolymers (1,4-benzene...

Sustainable Elastomers from Renewable Biomass.

PubMed

Wang, Zhongkai; Yuan, Liang; Tang, Chuanbing

2017-07-18

Sustainable elastomers have undergone explosive growth in recent years, partly due to the resurgence of biobased materials prepared from renewable natural resources. However, mounting challenges still prevail: How can the chemical compositions and macromolecular architectures of sustainable polymers be controlled and broadened? How can their processability and recyclability be enabled? How can they compete with petroleum-based counterparts in both cost and performance? Molecular-biomass-derived polymers, such as polymyrcene, polymenthide, and poly(ε-decalactone), have been employed for constructing thermoplastic elastomers (TPEs). Plant oils are widely used for fabricating thermoset elastomers. We use abundant biomass, such as plant oils, cellulose, rosin acids, and lignin, to develop elastomers covering a wide range of structure-property relationships in the hope of delivering better performance. In this Account, recent progress in preparing monomers and TPEs from biomass is first reviewed. ABA triblock copolymer TPEs were obtained with a soft middle block containing a soybean-oil-based monomer and hard outer blocks containing styrene. In addition, a combination of biobased monomers from rosin acids and soybean oil was formulated to prepare triblock copolymer TPEs. Together with the above-mentioned approaches based on block copolymers, multigraft copolymers with a soft backbone and rigid side chains are recognized as the first-generation and second-generation TPEs, respectively. It has been recently demonstrated that multigraft copolymers with a rigid backbone and elastic side chains can also be used as a novel architecture of TPEs. Natural polymers, such as cellulose and lignin, are utilized as a stiff, macromolecular backbone. Cellulose/lignin graft copolymers with side chains containing a copolymer of methyl methacrylate and butyl acrylate exhibited excellent elastic properties. Cellulose graft copolymers with biomass-derived polymers as side chains were further explored to enhance the overall sustainability. Isoprene polymers were grafted from a cellulosic backbone to afford Cell-g-polyisoprene copolymers. Via cross-linking of these graft copolymers, human-skin-mimic elastomers and high resilient elastomers with a well-defined network structure were achieved. The mechanical properties of these resilient elastomers could be finely controlled by tuning the cellulose content. As isoprene can be produced by engineering of microorganisms, these elastomers could be a renewable alternative to petroleum products. In summary, triblock copolymer and graft copolymer TPEs with biomass components, skin-mimic elastomers, high resilient biobased elastomers, and engineering of macromolecular architectures for elastomers are discussed. These approaches and design provide us knowledge on the potential to make sustainable elastomers for various applications to compete with petroleum-based counterparts.

Block Copolymers: Synthesis and Applications in Nanotechnology

NASA Astrophysics Data System (ADS)

Lou, Qin

This study is focused on the synthesis and study of (block) copolymers using reversible deactivation radical polymerizations (RDRPs), including atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization. In particular, two primary areas of study are undertaken: (1) a proof-of-concept application of lithographic block copolymers, and (2) the mechanistic study of the deposition of titania into block copolymer templates for the production of well-ordered titania nanostructures. Block copolymers have the ability to undergo microphase separation, with an average size of each microphase ranging from tens to hundreds of nanometers. As such, block copolymers have been widely considered for nanotechnological applications over the past two decades. The development of materials for various nanotechnologies has become an increasingly studied area as improvements in many applications, such as those found in the semiconductor and photovoltaic industries are constantly being sought. Significant growth in developments of new synthetic methods ( i.e. RDRPs) has allowed the production of block copolymers with molecular (and sometimes atomic) definition. In turn, this has greatly expanded the use of block copolymers in nanotechnology. Herein, we describe the synthesis of statistical and block copolymers of 193 nm photolithography methacrylate and acrylate resist monomers with norbornyl and adamantyl moieties using RAFT polymerization.. For these resist (block) copolymers, the phase separation behaviors were examined by atomic force microscopy (AFM). End groups were removed from the polymers to avoid complications during the photolithography since RAFT end groups absorb visible light. Poly(glycidyl methacrylate-block-polystyrene) (PGMA-b-PS) was synthesize by ATRP and demonstrated that this block copolymer acts as both a lithographic UV (365 nm) photoresist and a self-assembly material. The PGMA segments can undergo cationic ring-opening crosslinking and can act as a negative-tone photoresist. The PGMA-b-PS thin films were also studied for phase separation with ˜25 nm patterns using transmission electron microscopy (TEM). Poly(styrene-block-4-vinyl pyridine) (PS-b-P4VP) block copolymer thin films are shown to form perpendicular cylinder phase separated structures, and these may be used to template the formation of ordered titania nanostructures with sub-50 nm diameters on either silicon or indium tin oxide (ITO) substrates. A study of the mechanism of TiO2 formation within the P4VP cylinder phase was developed and tested. It was found that the titania nanostructure morphology is affected by pH and deposition temperatures, and successful deposition required the cross-linking of the P4VP phase in order to obtain individual nanostructures.

21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

Code of Federal Regulations, 2011 CFR

2011-04-01

... this section are not applicable to ethylene-acrylic acid copolymers used in food-packaging adhesives... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Ethylene-acrylic acid copolymers. 177.1310 Section 177.1310 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES...

76 FR 30604 - National Emission Standards for Hazardous Air Pollutants for Polyvinyl Chloride and Copolymers...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-05-26

... National Emission Standards for Hazardous Air Pollutants for Polyvinyl Chloride and Copolymers Production... Standards for Hazardous Air Pollutants for Polyvinyl Chloride and Copolymers Production. The EPA is... present oral testimony at the public hearing, please contact Ms. Teresa Clemons, U.S. Environmental...

Properties of starch-polyglutamic acid (PGA) graft copolymer prepared by microwave irradiation - Fourier transform infrared spectroscopy (FTIR) and rheology studies

USDA-ARS?s Scientific Manuscript database

The rheological properties of waxy starch-'-polygutamic acid (PGA) graft copolymers were investigated. Grafting was confirmed by FTIR spectroscopy. The starch-PGA copolymers absorbed water and formed gels, which exhibited concentration-dependent viscoelastic solid properties. Higher starch-PGA conce...

21 CFR 175.365 - Vinylidene chloride copolymer coatings for polycarbonate film.

Code of Federal Regulations, 2010 CFR

2010-04-01

... polycarbonate film. 175.365 Section 175.365 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH... chloride copolymer coatings for polycarbonate film. Vinylidene chloride copolymer coatings identified in this section and applied on polycarbonate film may be safely used as food-contact surfaces, in...

Rheological properties of reactive extrusion modified waxy starch and waxy starch-polyacrylamide copolymer gels

USDA-ARS?s Scientific Manuscript database

The rheological properties of modified waxy starch and waxy starch-polyacrylamide graft copolymers prepared by reactive extrusion were investigated. Both materials can absorb huge amount of water and form gels. The modified waxy starch and waxy starch-polyacrylamide graft copolymer gels all exhibite...

21 CFR 177.1020 - Acrylonitrile/butadiene/sty-rene co-polymer.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Acrylonitrile/butadiene/sty-rene co-polymer. 177... SERVICES (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1020 Acrylonitrile/butadiene/sty-rene co-polymer. Acrylonitrile...

Master curve captures the effect of domain morphology on ethanol pervaporation through block copolymer membranes

USDA-ARS?s Scientific Manuscript database

We report on the effect of changing nanoscale morphology on pervaporation of ethanol/water mixtures through block copolymer membranes. Experiments were conducted using polystyrene-b-polybutadiene-b-polystyrene (SBS) copolymers with polybutadiene (PB) as the ethanol transporting block, using an 8 wt%...

21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

Code of Federal Regulations, 2014 CFR

2014-04-01

... applicable to ethylene-acrylic acid copolymers used in food-packaging adhesives complying with § 175.105 of... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Ethylene-acrylic acid copolymers. 177.1310 Section 177.1310 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES...

21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

Code of Federal Regulations, 2013 CFR

2013-04-01

... this section are not applicable to ethylene-acrylic acid copolymers used in food-packaging adhesives... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Ethylene-acrylic acid copolymers. 177.1310 Section 177.1310 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES...

21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

Code of Federal Regulations, 2012 CFR

2012-04-01

... this section are not applicable to ethylene-acrylic acid copolymers used in food-packaging adhesives... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Ethylene-acrylic acid copolymers. 177.1310 Section 177.1310 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES...

Imide/arylene ether copolymers with pendent trifluoromethyl groups

NASA Technical Reports Server (NTRS)

Jensen, Brian J.; Havens, Stephen J.

1992-01-01

A series of imide/arylene ether block copolymers were prepared using an arylene ether block containing a hexafluoroisopropylidene group and an imide block containing a hexafluoroisopropylidene and a trifluoromethyl group in the polymer backbone. The copolymers were characterized and mechanical properties were determined and compared to the homopolymers.

Electrically conductive doped block copolymer of polyacetylene and polyisoprene

DOEpatents

Aldissi, Mahmoud

1985-01-01

An electrically conductive block copolymer of polyisoprene and polyacetyl and a method of making the same are disclosed. The polymer is prepared by first polymerizing isoprene with n-butyllithium in a toluene solution to form an active isoprenyllithium polymer. The active polymer is reacted with an equimolar amount of titanium butoxide and subsequently exposed to gaseous acetylene. A block copolymer of polyisoprene and polyacetylene is formed. The copolymer is soluble in common solvents and may be doped with I.sub.2 to give it an electrical conductivity in the metallic regime.

High aspect ratio sub-15 nm silicon trenches from block copolymer templates.

PubMed

Gu, Xiaodan; Liu, Zuwei; Gunkel, Ilja; Chourou, S T; Hong, Sung Woo; Olynick, Deirdre L; Russell, Thomas P

2012-11-08

High-aspect-ratio sub-15-nm silicon trenches are fabricated directly from plasma etching of a block copolymer mask. A novel method that combines a block copolymer reconstruction process and reactive ion etching is used to make the polymer mask. Silicon trenches are characterized by various methods and used as a master for subsequent imprinting of different materials. Silicon nanoholes are generated from a block copolymer with cylindrical microdomains oriented normal to the surface. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inducing Order from Disordered Copolymers: On Demand Generation of Triblock Morphologies Including Networks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tureau, Maëva S.; Kuan, Wei-Fan; Rong, Lixia

Disordered block copolymers are generally impractical in nanopatterning applications due to their inability to self-assemble into well-defined nanostructures. However, inducing order in low molecular weight disordered systems permits the design of periodic structures with smaller characteristic sizes. Here, we have induced nanoscale phase separation from disordered triblock copolymer melts to form well-ordered lamellae, hexagonally packed cylinders, and a triply periodic gyroid network structure, using a copolymer/homopolymer blending approach, which incorporates constituent homopolymers into selective block domains. This versatile blending approach allows one to precisely target multiple nanostructures from a single disordered material and can be applied to a wide varietymore » of triblock copolymer systems for nanotemplating and nanoscale separation applications requiring nanoscale feature sizes and/or high areal feature densities.« less

Synthesis and Characterization of Itaconic Anhydride and Stearyl Methacrylate Copolymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shang, S.; Huang, S; Weiss, R

The free-radical copolymerization and the properties of comb-like copolymers derived from renewable resources, itaconic anhydride (ITA) and stearyl methacrylate (SM), are described. The ITA-SM copolymers were nearly random with a slight alternating tendency. The copolymers exhibited a nanophase-separated morphology, with the stearate side-chains forming a bilayer, semi-crystalline structure. The melting point (Tm) of the side-chains and the crystallinity decreased with increasing ITA concentration. The crystalline side-chains suppressed molecular motion of the main chain, so that a glass transition temperature (Tg) was not resolved unless the ITA concentration was sufficiently high so that Tg > Tm. The softening point and modulusmore » of the copolymers increased with the increasing ITA concentration, but the thermal stability decreased.« less

HPMA copolymers: Origins, early developments, present, and future☆

PubMed Central

Kopeček, Jindřich; Kopečková, Pavla

2010-01-01

The overview covers the discovery of N-(2-hydroxypropyl)methacrylamide (HPMA) copolymers, initial studies on their synthesis, evaluation of biological properties, and explorations of their potential as carriers of biologically active compounds in general and anticancer drugs in particular. The focus is on the research in the authors’ laboratory – the development of macromolecular therapeutics for the treatment of cancer and musculoskeletal diseases. In addition, the evaluation of HPMA (co)polymers as building blocks of mod and new biomaterials is presented: the utilization of semitelechelic poly(HPMA) and HPMA copolymers for the modification of biomaterial and protein surfaces and the design of hybrid block and graft HPMA copolymers that self-assemble into smart hydrogels. Finally, suggestions for the design of second-generation macromolecular therapeutics are portrayed. PMID:19919846

Synthesis of Cis, syndiotactic A -alt-B Copolymers from Two Enantiomerically Pure Trans -2,3-Disubstituted-5,6-Norbornenes

DOE PAGES

Jang, Eun Sil; John, Jeremy M.; Schrock, Richard R.

2016-09-06

Cis,syndiotactic A-alt-B copolymers, where A and B are two enantiomerically pure trans-2,3-disubstituted-5,6-norbornenes with “opposite” chiralities, can be prepared with stereogenic-at-metal initiators of the type M(NR)(CHR')(OR”)(pyrrolide). Formation of a high percentage of alternating AB copolymer linkages relies on an inversion of chirality at the metal with each propagating step and a relatively fast formation of an AB sequence as a consequence of a preferred diastereomeric relationship between the chirality at the metal and the chirality of the monomer. Finally, this approach to formation of an alternating AB copolymer contrasts dramatically with the principle of forming AB copolymers from achiral monomers andmore » catalysts.« less

Nano-network with dual temperature and pH responsiveness based on copolymers of 2-hydroxyethyl methacrylate with 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]-undecane

NASA Astrophysics Data System (ADS)

Chiriac, Aurica P.; Nita, Loredana E.; Nistor, Manuela T.

2011-12-01

This study refers to the synthesis of a nano-network with dual temperature and pH responsiveness based on the 2-hydroxyethyl methacrylate (HEMA) copolymers with a comonomer with spiroacetal moiety and crosslinking capacity, namely 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]-undecane (U). The copolymers were synthesized by radical emulsion polymerization, using 4,4'-azobis(cyanopentanoic acid) as initiator, in the presence of sodium lauryl sulfate as tensioactive agent and poly(vinyl alcohol) as protective colloid. Three copolymer variants were taken into study resulted from the different ratio between the comonomers (HEMA/U), which was about 98/2, 95/5, and 90/10, respectively. The copolymers were characterized by FTIR and thermal analysis. The copolymers sensitivity was evidenced by studying the evolution of the hydrodynamic radius and zeta potential of the polymeric particles as a function of pH. Thus, the particles size increases with the comonomer amount, from 193 nm in case of the homopolymer up to 253 nm for the copolymer with maximum content of the comonomer (10%). The increase of the particle hydrodynamic radius with the growth of temperature was also put into evidence.

A facile synthesis of poly(aniline-co-o-bromoaniline) copolymer: Characterization and application as semiconducting material

NASA Astrophysics Data System (ADS)

Mahudeswaran, A.; Vivekanandan, J.; Vijayanand, P. S.; Kojima, T.; Kato, S.

2016-01-01

Poly(aniline-co-o-bromoaniline) (p(an-co-o-BrAn)) copolymer has been synthesized using chemical oxidation method in the hydrochloric acid medium. Copolymerization of aniline with o-bromoaniline of different compositions, such as 1:1, 1:2, 2:1, 1:3 and 3:1 molar ratios were prepared. The synthesized copolymer is soluble in polar solvents like dimethyl sulphoxide (DMSO), dimethyl formamide (DMF), Tetrahydrofuran (THF) and 1-methyl 2-pyrrolidone (NMP). The copolymer is analyzed by various characterization techniques, such as FTIR, UV-Visible (UV-Vis) spectroscopy, X-ray diffraction (XRD), conductivity, Differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). FTIR spectrum confirms the characteristic peaks of the copolymer containing benzenoid and quinoid ring stretching. UV spectrum reveals the formation of π-π∗ transition and n-π∗ transition between the energy levels. XRD peaks reveal that the copolymer possesses amorphous nature. Morphological study reveals that the agglomerated particles form globular structure and size of the each particle is about 100 nm. The electrical conductivity of the copolymers is found in the range of 10-5Scm-1. These organic semiconductor materials can be used to fabricate thinner and cheaper environmental friendly optoelectronic devices that will replace the conventional inorganic semiconductors.

Anomalistic Self-Assembled Phase Behavior of Block Copolymer Blended with Organic Derivative Depending on Temperature

DOE PAGES

Kim, Tae-Hwan; Kim, Eunhye; Do, Changwoo; ...

2016-08-16

Amphiphilic Pluronic block copolymers have attracted great attention in a broad spectrum of potential applications due to the excellent phase behaviors in an aqueous solution, and many efforts have been made to investigate their phase behaviors under various external conditions. With a variety of external conditions, however, the closed looplike phase behaviors of a Pluronic block copolymer in an aqueous solution have not been reported yet. Herein, we report the closed looplike (CLL) phase behavior of a Pluronic P65 triblock copolymer blended with an organic derivative, 5-methylsalicylic acid (5mS), in aqueous solution, which is very unique for block copolymers. Asmore » the 5mS concentration increases, the isotropic to ordered phase or back to isotropic phase transition temperature is decreased while the number of closed loops is increased to two. To the best of our knowledge, this is the first demonstration of a CLL phase transition of a Pluronic block copolymer in an aqueous solution, which is readily applicable to optical devices such as optical sensors or optoelectronics, and nanotemplates for a highly ordered superlattice. Additionally, this provides new insight into the understanding on the phase behavior of a Pluronic block copolymer blended with additives.« less

Comparing blends and blocks: Synthesis of partially fluorinated diblock polythiophene copolymers to investigate the thermal stability of optical and morphological properties

PubMed Central

Boufflet, Pierre; Wood, Sebastian; Wade, Jessica; Fei, Zhuping; Kim, Ji-Seon

2016-01-01

Summary The microstructure of the active blend layer has been shown to be a critically important factor in the performance of organic solar devices. Block copolymers provide a potentially interesting avenue for controlling this active layer microstructure in solar cell blends. Here we explore the impact of backbone fluorination in block copolymers of poly(3-octyl-4-fluorothiophene)s and poly(3-octylthiophene) (F-P3OT-b-P3OT). Two block co-polymers with varying block lengths were prepared via sequential monomer addition under Kumada catalyst transfer polymerisation (KCTP) conditions. We compare the behavior of the block copolymer to that of the corresponding homopolymer blends. In both types of system, we find the fluorinated segments tend to dominate the UV–visible absorption and molecular vibrational spectral features, as well as the thermal behavior. In the block copolymer case, non-fluorinated segments appear to slightly frustrate the aggregation of the more fluorinated block. However, in situ temperature dependent Raman spectroscopy shows that the intramolecular order is more thermally stable in the block copolymer than in the corresponding blend, suggesting that such materials may be interesting for enhanced thermal stability of organic photovoltaic active layers based on similar systems. PMID:27829922

Drug-conjugated PLA-PEG-PLA copolymers: a novel approach for controlled delivery of hydrophilic drugs by micelle formation.

PubMed

Danafar, H; Rostamizadeh, K; Davaran, S; Hamidi, M

2017-12-01

A conjugate of the antihypertensive drug, lisinopril, with triblock poly(lactic acid)-poly(ethylene glycol)-poly(lactic acid) (PLA-PEG-PLA) copolymer was synthesized by the reaction of PLA-PEG-PLA copolymer with lisinopril in the presence of dicyclohexylcarbodiimide and dimethylaminopyridine. The conjugated copolymer was characterized in vitro by hydrogen nuclear magnetic resonance (HNMR), Fourier transform infrared (FTIR), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC) techniques. Then, the lisinopril conjugated PLA-PEG-PLA were self-assembled into micelles in aqueous solution. The resulting micelles were characterized further by various techniques such as dynamic light scattering (DLS) and atomic force microscopy (AFM). The results revealed that the micelles formed by the lisinopril-conjugated PLA-PEG-PLA have spherical structure with the average size of 162 nm. The release behavior of conjugated copolymer, micelles and micelles physically loaded by lisinopril were compared in different media. In vitro release study showed that in contrast to physically loaded micelles, the release rate of micelles consisted of the conjugated copolymer was dependent on pH of media where it was higher at lower pH compared to the neutral medium. Another feature of the conjugated micelles was their more sustained release profile compared to the lisinopril-conjugated copolymer and physically loaded micelles.

Evaluation of molecular volume change of block copolymer depending on temperature: A SANS study

DOE PAGES

Kim, Tae-Hwan; Do, Changwoo; Han, Young-Soo

2017-12-24

Amphiphilic Pluronic triblock copolymers form various self-assembled structures such as sphere, cylinder, lamellae and so on, depending on temperature, leading to the increase of hydrophobicity of block copolymers. However, the effective molecular volume change of the block copolymer has not been fully exploited yet, when temperature increases. Here in this paper, we have investigated the effective molecular volume change of the block copolymer upon heating by using the contrast variation small angle neutron scattering. The scattering length densities (SLDs) of the block copolymer were experimentally obtained from the neutron scattering contrast variation method between the solvent and the block copolymermore » at varying temperature. Even though the SLD, which is the intrinsic property of the material, should not be changed by temperature elevation, it was dependent on temperature, indicating that the molecular volume is changed. Therefore, we obtained the increase rate of the molecular volume change of the block copolymer (the effective molecular volume change) from the comparison of the calculated SLD and the standard SLD, which is evaluated by plotting the SANS intensity at the first order Bragg peak as the function of temperature at each volume fraction of D 2O and H 2O that is about 25.5%–51.3% depending on temperature.« less

Evaluation of molecular volume change of block copolymer depending on temperature: A SANS study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Tae-Hwan; Do, Changwoo; Han, Young-Soo

Amphiphilic Pluronic triblock copolymers form various self-assembled structures such as sphere, cylinder, lamellae and so on, depending on temperature, leading to the increase of hydrophobicity of block copolymers. However, the effective molecular volume change of the block copolymer has not been fully exploited yet, when temperature increases. Here in this paper, we have investigated the effective molecular volume change of the block copolymer upon heating by using the contrast variation small angle neutron scattering. The scattering length densities (SLDs) of the block copolymer were experimentally obtained from the neutron scattering contrast variation method between the solvent and the block copolymermore » at varying temperature. Even though the SLD, which is the intrinsic property of the material, should not be changed by temperature elevation, it was dependent on temperature, indicating that the molecular volume is changed. Therefore, we obtained the increase rate of the molecular volume change of the block copolymer (the effective molecular volume change) from the comparison of the calculated SLD and the standard SLD, which is evaluated by plotting the SANS intensity at the first order Bragg peak as the function of temperature at each volume fraction of D 2O and H 2O that is about 25.5%–51.3% depending on temperature.« less

Influence of chain microstructure on thermodegradative behavior of furfuryl methacrylate-N-vinylpyrrolidone random copolymers by thermogravimetry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peniche, C.; Zaldivar, D.; Bulay, A.

1993-12-20

The thermal behavior of random copolymers of furfuryl methacrylate (F) and N-vinyl-pyrrolidone (P) was studied by means of dynamic thermogravimetric analysis (TGA) in the range 100--600 C. The dynamic experiments show that these copolymers exhibit two degradation steps in the intervals 260--320 C and 350--520 C, respectively. The normalized weight loss in the low temperature interval increases as the mole fraction of F in the copolymer m[sub F] increases, whereas an inverted trend in the high temperature interval is observed. The apparent activation energy E[sub a] of the first degradation step for copolymers prepared with different composition, was obtained accordingmore » to the treatment suggested by Broido. A plot of the values of E[sub a] versus the F dead molar fraction in the copolymer chains m[sub FF] gave a straight line that indicates that there is a direct relationship between the thermogravimetric behavior of these systems and their corresponding microstructure, that is, the distribution of comonomeric units along the copolymers chains. The first decomposition step was also studied by isothermal TGA and a good linearity for the variation of the weight loss percentage [Delta]W versus m[sub F] at least during the first 30 min of treatment was obtained.« less

High-Tg Polynorbornene-Based Block and Random Copolymers for Butanol Pervaporation Membranes

NASA Astrophysics Data System (ADS)

Register, Richard A.; Kim, Dong-Gyun; Takigawa, Tamami; Kashino, Tomomasa; Burtovyy, Oleksandr; Bell, Andrew

Vinyl addition polymers of substituted norbornene (NB) monomers possess desirably high glass transition temperatures (Tg); however, until very recently, the lack of an applicable living polymerization chemistry has precluded the synthesis of such polymers with controlled architecture, or copolymers with controlled sequence distribution. We have recently synthesized block and random copolymers of NB monomers bearing hydroxyhexafluoroisopropyl and n-butyl substituents (HFANB and BuNB) via living vinyl addition polymerization with Pd-based catalysts. Both series of polymers were cast into the selective skin layers of thin film composite (TFC) membranes, and these organophilic membranes investigated for the isolation of n-butanol from dilute aqueous solution (model fermentation broth) via pervaporation. The block copolymers show well-defined microphase-separated morphologies, both in bulk and as the selective skin layers on TFC membranes, while the random copolymers are homogeneous. Both block and random vinyl addition copolymers are effective as n-butanol pervaporation membranes, with the block copolymers showing a better flux-selectivity balance. While polyHFANB has much higher permeability and n-butanol selectivity than polyBuNB, incorporating BuNB units into the polymer (in either a block or random sequence) limits the swelling of the polyHFANB and thereby improves the n-butanol pervaporation selectivity.

New self-assembly strategies for next generation lithography

NASA Astrophysics Data System (ADS)

Schwartz, Evan L.; Bosworth, Joan K.; Paik, Marvin Y.; Ober, Christopher K.

2010-04-01

Future demands of the semiconductor industry call for robust patterning strategies for critical dimensions below twenty nanometers. The self assembly of block copolymers stands out as a promising, potentially lower cost alternative to other technologies such as e-beam or nanoimprint lithography. One approach is to use block copolymers that can be lithographically patterned by incorporating a negative-tone photoresist as the majority (matrix) phase of the block copolymer, paired with photoacid generator and a crosslinker moiety. In this system, poly(α-methylstyrene-block-hydroxystyrene)(PαMS-b-PHOST), the block copolymer is spin-coated as a thin film, processed to a desired microdomain orientation with long-range order, and then photopatterned. Therefore, selfassembly of the block copolymer only occurs in select areas due to the crosslinking of the matrix phase, and the minority phase polymer can be removed to produce a nanoporous template. Using bulk TEM analysis, we demonstrate how the critical dimension of this block copolymer is shown to scale with polymer molecular weight using a simple power law relation. Enthalpic interactions such as hydrogen bonding are used to blend inorganic additives in order to enhance the etch resistance of the PHOST block. We demonstrate how lithographically patternable block copolymers might fit in to future processing strategies to produce etch-resistant self-assembled features at length scales impossible with conventional lithography.

Chirality plays critical roles in enhancing the aqueous solubility of nocathiacin I by block copolymer micelles.

PubMed

Feng, Kun; Wang, Shuzhen; Ma, Hairong; Chen, Yijun

2013-01-01

Although drug solubilization by block copolymer micelles has been extensively studied, the rationale behind the choice of appropriate block copolymer micelles for various poorly water-soluble drugs has been of relatively less concern. The objective of this study was to use methoxy-poly(ethylene glycol)-polylactate micelles (MPEG-PLA) to solubilize glycosylated antibiotic nocathiacin I and to compare the effects of chirality on the enhancement of aqueous solubility. Nocathiacin I-loaded MPEG-PLA micelles with opposite optical property in PLA were synthesized and characterized. The drug release profile, micelle stability and preliminary safety properties of MPEG-PLA micelles were evaluated. Meanwhile, three other poorly water-soluble chiral compound-loaded micelles were also prepared and compared.  The aqueous solubility of nocathiacin I was greatly enhanced by both L- and D-copolymers, with the degree of enhancement appearing to depend on the chirality of the copolymers. Comparison of different chiral compounds confirmed the trend that aqueous solubility of chiral compounds can be more effectively enhanced by block copolymer micelles with specific stereochemical configuration. The present study introduced chiral concept on the selection and preparation of block copolymer micelles for the enhancement of aqueous solubility of poorly water-soluble drugs. © 2012 The Authors. JPP © 2012 Royal Pharmaceutical Society.

Anomalistic Self-Assembled Phase Behavior of Block Copolymer Blended with Organic Derivative Depending on Temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Tae-Hwan; Kim, Eunhye; Do, Changwoo

Amphiphilic Pluronic block copolymers have attracted great attention in a broad spectrum of potential applications due to the excellent phase behaviors in an aqueous solution, and many efforts have been made to investigate their phase behaviors under various external conditions. With a variety of external conditions, however, the closed looplike phase behaviors of a Pluronic block copolymer in an aqueous solution have not been reported yet. Herein, we report the closed looplike (CLL) phase behavior of a Pluronic P65 triblock copolymer blended with an organic derivative, 5-methylsalicylic acid (5mS), in aqueous solution, which is very unique for block copolymers. Asmore » the 5mS concentration increases, the isotropic to ordered phase or back to isotropic phase transition temperature is decreased while the number of closed loops is increased to two. To the best of our knowledge, this is the first demonstration of a CLL phase transition of a Pluronic block copolymer in an aqueous solution, which is readily applicable to optical devices such as optical sensors or optoelectronics, and nanotemplates for a highly ordered superlattice. Additionally, this provides new insight into the understanding on the phase behavior of a Pluronic block copolymer blended with additives.« less

Novel Self-Assembling Amino Acid-Derived Block Copolymer with Changeable Polymer Backbone Structure.

PubMed

Koga, Tomoyuki; Aso, Eri; Higashi, Nobuyuki

2016-11-29

Block copolymers have attracted much attention as potentially interesting building blocks for the development of novel nanostructured materials in recent years. Herein, we report a new type of self-assembling block copolymer with changeable polymer backbone structure, poly(Fmoc-Ser) ester -b-PSt, which was synthesized by combining the polycondensation of 9-fluorenylmethoxycarbonyl-serine (Fmoc-Ser) with the reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene (St). This block copolymer showed the direct conversion of the backbone structure from polyester to polypeptide through a multi O,N-acyl migration triggered by base-induced deprotection of Fmoc groups in organic solvent. Such polymer-to-polymer conversion was found to occur quantitatively without decrease in degree of polymerization and to cause a drastic change in self-assembling property of the block copolymer. On the basis of several morphological analyses using FTIR spectroscopy, atomic force, and transmission and scanning electron microscopies, the resulting peptide block copolymer was found to self-assemble into a vesicle-like hollow nanosphere with relatively uniform diameter of ca. 300 nm in toluene. In this case, the peptide block generated from polyester formed β-sheet structure, indicating the self-assembly via peptide-guided route. We believe the findings presented in this study offer a new concept for the development of self-assembling block copolymer system.

Patterning at the 10 nanometer length scale using a strongly segregating block copolymer thin film and vapor phase infiltration of inorganic precursors

NASA Astrophysics Data System (ADS)

Choi, Jonathan W.; Li, Zhaodong; Black, Charles T.; Sweat, Daniel P.; Wang, Xudong; Gopalan, Padma

2016-06-01

In this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order-disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns and registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. We conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes.In this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order-disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns and registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. We conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01409g

Controlled self-assembly of conjugated rod-coil block copolymers for applications in organic optoelectronics

NASA Astrophysics Data System (ADS)

Tao, Yuefei

Organic electronics are of great interest in manufacturing light weight, mechanical flexible, and inexpensive large area devices. While significant improvements have been made over the last several years and it is now clear that morphology on the lengthscale of exciton diffusion (10nm) is of crucial importance, a clear relationship between structure and device properties has not emerged. This lack of understanding largely emerges from an inability to control morphology on this lengthscale. This thesis will center around an approach, based on block copolymer self-assembly, to generate equilibrium nanostructures on the 10 nm lengthscale of exciton diffusion and study their effects on device performance. Self-assembly of semiconducting block copolymers is complicated by the non-classical chain shape of conjugated polymers. Unlike classical polymers, the chains do not assume a Gaussian coil shape which is stretched near block copolymer interfaces, instead the chains are elongated and liquid crystalline. Previous work has demonstrated how these new molecular interactions and shapes control the phase diagram of so-called rod-coil block copolymers. Here, we will focus on controlling domain size, orientation, and chemical structure. While domain size can be controlled directly through molecular weight, this requires significant additional synthesis of domain size is to be varied. Here, the domain size is controlled by blending homopolymers into a self-assembling rod-coil block copolymer. When coil-like blocks are incorporated, the domains swell, as expected. When rod-like blocks are incorporated, they interdigitate with the rods of the block copolymers. This results in an increase in interfacial area which forces the coils to rearrange and an overall decrease in domain size with increasing rod content. Control over lamellar orientation is crucial in order to design and control charge transport pathways and exciton recombination or separation interfaces. While numerous techniques have been demonstrated for classical block copolymers, the pi conjugation in the rod blocks allow for additional control mechanisms. Liquid crystals are traditionally aligned in magnetic fields. Here, it is demonstrated that if the rod-like blocks are aligned unidirectionally, the block copolymer interfaces follow to create macroscopic alignment of the nanostructures. Organic Light Emitting Diodes (OLEDs) are generally composed of electron transporting and hole transporting moieties to balance charge recombination. Here, a new multifunctional bipolar rod-coil block copolymer containing the hole transporting and electron transporting materials is synthesized. Self-assembly of this new block copolymer results in 15nm lamellae oriented in grains both parallel and perpendicula to the anode. The self-assembled block copolymer shows superior device performance to controls consisting of a luminescent, analogous homopolymer, and a blend of the two component homopolymers. The effects of the morphologies and chemical structure on photovoltaics is explored with a rod-coil block copolymer, (poly(3-hexylthiophene-b-acrylic perylene)). By varying the kinetics of self-assembly through processing, the block copolymer can be disordered, ordered with only short range registry between the nanodomains, or with long-range order. The short range ordered samples showed the best device performance suggesting that the connectivity that is a biproduct of poor order is beneficial for device performance.

Direct quantification of molar masses of copolymers by online liquid chromatography under critical conditions-nuclear magnetic resonance and size exclusion chromatography-nuclear magnetic resonance.

PubMed

Hehn, Mathias; Wagner, Thomas; Hiller, Wolf

2014-01-07

Online LCCC-NMR and SEC-NMR are compared regarding the determination of molar masses of block copolymers. Two different direct referencing methods are particularly demonstrated in LCCC-NMR for a detailed characterization of diblock copolymers and their co-monomers. First, an intramolecular reference group was used for the direct determination of block lengths and molar masses. For the first time, it was shown that LCCC-NMR can be used for an accurate determination of Mw and Mn of copolymers. These data were in perfect agreement with SEC-NMR measurements using the same intramolecular referencing method. In contrast, the determination of molar masses with common relative methods based on calibrations with homopolymers delivered inaccurate results for all investigated diblock copolymers due to different hydrodynamic volumes of the diblock copolymer compared to their homopolymers. The intramolecular referencing method provided detailed insights in the co-monomer behavior during the chromatographic separation of LCCC. Especially, accurate chain lengths and chemical compositions of the "invisible" and "visible" blocks were quantified during the elution under critical conditions and provided new aspects to the concept of critical conditions. Second, an external reference NMR signal was used to directly determine concentrations and molar masses of the block copolymers from the chromatographic elution profile. Consequently, the intensity axes of the resulting chromatograms were converted to molar amounts and masses, allowing for determination of the amount of polymer chains with respect to elution volume, the evaluation of the limiting magnitude of concentration for LCCC-NMR, and determination of the molar masses of copolymers.

Molecular Dynamics Study of Polystyrene-b-poly(ethylene oxide) Asymmetric Diblock Copolymer Systems.

PubMed

Dobies, M; Makrocka-Rydzyk, M; Jenczyk, J; Jarek, M; Spontak, R J; Jurga, S

2017-09-12

Two polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymers differing in molecular mass (49 and 78 kDa) but possessing the same PEO cylindrical morphology are examined to elucidate their molecular dynamics. Of particular interest here is the molecular motion of the PEO blocks involved in the rigid amorphous fraction (RAF). An analysis of complementary thermal calorimetry and X-ray scattering data confirms the presence of microphase-separated morphology as well as semicrystalline structure in each copolymer. Molecular motion within the copolymer systems is monitored by dielectric and nuclear magnetic resonance spectroscopies. The results reported herein reveal the existence of two local Arrhenius-type processes attributed to the noncooperative local motion of PEO segments involved in fully amorphous and rigid amorphous PEO microphases. In both systems, two structural relaxations governed by glass-transition phenomena are identified and assigned to cooperative segmental motion in the fully amorphous phase (the α process) and the RAF (the α c process). We measure the temperature dependence of the dynamics associated with all of the processes mentioned above and propose that these local processes are associated with corresponding cooperative segmental motion in both copolymer systems. In marked contrast to the thermal activation of the α process as discerned in both copolymers, the α c process appears to be a sensitive probe of the copolymer nanostructure. That is, the copolymer with shorter PEO blocks exhibits more highly restricted cooperative dynamics of PEO segments in the RAF, which can be explained in terms of the greater constraint imposed by the glassy PS matrix on the PEO blocks comprising smaller cylindrical microdomains.

Prediction of the solubility of cucurbitacin drugs in self-associating poly(ethylene oxide)-b-poly(alpha-benzyl carboxylate epsilon-caprolactone) block copolymer with different tacticities using molecular dynamics simulation.

PubMed

Patel, Sarthak K; Lavasanifar, Afsaneh; Choi, Phillip

2010-01-01

Molecular dynamics (MD) simulation was used to investigate the solubility of two hydrophobic drugs Cucurbitacin B (CuB) and Cucurbitacin I (CuI) in poly(ethylene oxide)-b-poly(alpha-benzyl carboxylate epsilon-caprolactone) (PEO-b-PBCL) block copolymers with different tacticities. In particular, di-block copolymer with three different tacticities viz. PEO-b-iPBCL, PEO-b-sPBCL, and PEO-b-aPBCL were used. The solubility was quantified by calculating the corresponding Flory-Huggins interaction parameters (chi) using random binary mixture models with 10wt% of drug. The tacticity of the di-block copolymer was found to influence significantly the solubility of two drugs in it. In particular, based on MD simulation results, only PEO-b-sPBCL exhibited solubility while the other two did not. Given the fact that the drugs were shown to be soluble in PEO-b-PBCL experimentally, it is predicted that the tacticity of the di-block copolymer synthesized in experiment is syndiotactic. This predication matches well with the dominant ring opening polymerization of cyclic lactones to syndiotactic polymers by stannous octoate as catalyst used to prepare PEO-b-PBCL block copolymers in our previous experiments. The simulation results showed that the solubility of the drugs in PEO-b-sPBCL is attributed to the favorable intra-molecular interaction of the di-block copolymer and favorable intermolecular interaction between the di-block copolymer and the drugs. Radial distribution function analysis provides useful insights into the nature and type of the intermolecular interactions.

Biocompatible Polysiloxane-Containing Diblock Copolymer PEO-b-PγMPS for Coating Magnetic Nanoparticles

PubMed Central

Chen, Hongwei; Wu, Xinying; Duan, Hongwei; Wang, Y. Andrew; Wang, Liya; Zhang, Minming; Mao, Hui

2009-01-01

We report a biocompatible polysiloxane containing amphiphilic diblock copolymer, poly(ethylene oxide)-block-poly(γ-methacryloxypropyltrimethoxysilane) (PEO-b-PγMPS), for coating and stabilizing nanoparticles for biomedical applications. Such amphiphilic diblock copolymer which comprises both a hydrophobic segment with “surface anchoring moiety” (silane group) and a hydrophilic segment with PEO (Mn=5000 g/mol) was obtained by the reversible addition fragmentation chain transfer (RAFT) polymerization using the PEO macromolecular chain transfer agent. When used for coating paramagnetic iron oxide nanoparticles (IONPs), copolymers were mixed with hydrophobic oleic acid coated core size uniformed IONPs (D=13 nm) in co-solvent tetrahydrofuran. After being aged over a period of time, resulting monodispersed IONPs can be transferred into aqueous medium. With proper PγMPS block length (Mn=10,000 g/mol), polysiloxane containing diblock copolymers formed a thin layer of coating (~3 nm) around monocrystalline nanoparticles as measured by transmission electron microscopy (TEM). Magnetic resonance imaging (MRI) experiments showed excellent T2 weighted contrast effect from coated IONPs with a transverse relaxivity r2=98.6 mM−1s−1 (at 1.5 Tesla). Such thin coating layer has little effect on the relaxivity when compared to that of IONPs coated with conventional amphiphilic copolymer. Polysiloxane containing diblock copolymer coated IONPs are stable without aggregation or binding to proteins in serum when incubated for 24 h in culture medium containing 10% serum. Furthermore, much lower level of intracellular uptake by macrophage cells was observed with polysiloxane containing diblock copolymers coated IONPs, suggesting the reduction of non-specific cell uptakes and antibiofouling effect. PMID:20161520

Synthesis of Diblock copolymer poly-3-hydroxybutyrate -block-poly-3-hydroxyhexanoate [PHB-b-PHHx] by a β-oxidation weakened Pseudomonas putida KT2442.

PubMed

Tripathi, Lakshmi; Wu, Lin-Ping; Chen, Jinchun; Chen, Guo-Qiang

2012-04-05

Block polyhydroxyalkanoates (PHA) were reported to be resistant against polymer aging that negatively affects polymer properties. Recently, more and more attempts have been directed to make PHA block copolymers. Diblock copolymers PHB-b-PHHx consisting of poly-3-hydroxybutyrate (PHB) block covalently bonded with poly-3-hydroxyhexanoate (PHHx) block were for the first time produced successfully by a recombinant Pseudomonas putida KT2442 with its β-oxidation cycle deleted to its maximum. The chloroform extracted polymers were characterized by nuclear magnetic resonance (NMR), thermo- and mechanical analysis. NMR confirmed the existence of diblock copolymers consisting of 58 mol% PHB as the short chain length block with 42 mol% PHHx as the medium chain length block. The block copolymers had two glass transition temperatures (Tg) at 2.7°C and -16.4°C, one melting temperature (Tm) at 172.1°C and one cool crystallization temperature (Tc) at 69.1°C as revealed by differential scanning calorimetry (DSC), respectively. This is the first microbial short-chain-length (scl) and medium-chain-length (mcl) PHA block copolymer reported. It is possible to produce PHA block copolymers of various kinds using the recombinant Pseudomonas putida KT2442 with its β-oxidation cycle deleted to its maximum. In comparison to a random copolymer poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (P(HB-co-HHx)) and a blend sample of PHB and PHHx, the PHB-b-PHHx showed improved structural related mechanical properties.

21 CFR 177.1340 - Ethylene-methyl acrylate copolymer resins.

Code of Federal Regulations, 2011 CFR

2011-04-01

... ethylene-methyl acrylate copolymer resins used in food-packaging adhesives complying with § 175.105 of this... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Ethylene-methyl acrylate copolymer resins. 177.1340 Section 177.1340 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN...

Dimensionally Stable Ether-Containing Polyimide Copolymers

NASA Technical Reports Server (NTRS)

Fay, Catharine C. (Inventor); St.Clair, Anne K. (Inventor)

1999-01-01

Novel polyimide copolymers containing ether linkages were prepared by the reaction of an equimolar amount of dianhydride and a combination of diamines. The polyimide copolymers described herein possess the unique features of low moisture uptake, dimensional stability, good mechanical properties, and moderate glass transition temperatures. These materials have potential application as encapsulants and interlayer dielectrics.

21 CFR 177.1340 - Ethylene-methyl acrylate copolymer resins.

Code of Federal Regulations, 2013 CFR

2013-04-01

... ethylene-methyl acrylate copolymer resins used in food-packaging adhesives complying with § 175.105 of this... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Ethylene-methyl acrylate copolymer resins. 177.1340 Section 177.1340 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN...

21 CFR 177.1340 - Ethylene-methyl acrylate copolymer resins.

Code of Federal Regulations, 2012 CFR

2012-04-01

... ethylene-methyl acrylate copolymer resins used in food-packaging adhesives complying with § 175.105 of this... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Ethylene-methyl acrylate copolymer resins. 177.1340 Section 177.1340 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN...

Polyether/Polyester Graft Copolymers

NASA Technical Reports Server (NTRS)

Bell, Vernon L., Jr.; Wakelyn, N.; Stoakley, D. M.; Proctor, K. M.

1986-01-01

Higher solvent resistance achieved along with lower melting temperature. New technique provides method of preparing copolymers with polypivalolactone segments grafted onto poly (2,6-dimethyl-phenylene oxide) backbone. Process makes strong materials with improved solvent resistance and crystalline, thermally-reversible crosslinks. Resulting graft copolymers easier to fabricate into useful articles, including thin films, sheets, fibers, foams, laminates, and moldings.

21 CFR 172.808 - Copolymer condensates of ethylene oxide and propylene oxide.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Copolymer condensates of ethylene oxide and... ethylene oxide and propylene oxide. Copolymer condensates of ethylene oxide and propylene oxide may be... percent aqueous solution. (2) α-Hydro-omega-hydroxy-poly (oxy-ethylene)poly(oxypropylene)-(53-59 moles...

Slip-spring model of entangled rod-coil block copolymers

NASA Astrophysics Data System (ADS)

Wang, Muzhou; Likhtman, Alexei E.; Olsen, Bradley D.

2015-03-01

Understanding the dynamics of rod-coil block copolymers is important for optimal design of functional nanostructured materials for organic electronics and biomaterials. Recently, we proposed a reptation theory of entangled rod-coil block copolymers, predicting the relaxation mechanisms of activated reptation and arm retraction that slow rod-coil dynamics relative to coil and rod homopolymers, respectively. In this work, we introduce a coarse-grained slip-spring model of rod-coil block copolymers to further explore these mechanisms. First, parameters of the coarse-grained model are tuned to match previous molecular dynamics simulation results for coils, rods, and block copolymers. For activated reptation, rod-coil copolymers are shown to disfavor configurations where the rod occupies curved portions of the entanglement tube of randomly varying curvature created by the coil ends. The effect of these barriers on diffusion is quantitatively captured by considering one-dimensional motion along an entanglement tube with a rough free energy potential. Finally, we analyze the crossover between the two mechanisms. The resulting dynamics from both mechanisms acting in combination is faster than from each one individually.

Synthesis and characterization of theranostic poly(HPMA)-c(RGDyK)-DOTA-64Cu copolymer targeting tumor angiogenesis: tumor localization visualized by positron emission tomography.

PubMed

Yuan, Jianchao; Zhang, Haiyuan; Kaur, Harpreet; Oupicky, David; Peng, Fangyu

2013-05-01

Poly(HPMA)-c(RGDyK)-DOTA-64Cu copolymers were synthesized and characterized for tumor localization in vivo as a theranostic scaffold for cancer imaging and anticancer drug delivery targeting tumor angiogenesis. Tumor localization of the poly(HPMA)-c(RGDyK)-DOTA-64Cu copolymers was visualized in mice bearing human prostate cancer xenografts by positron emission tomography (PET) using a microPET scanner. PET quantitative analysis demonstrated that tumor 64Cu radioactivity (2.75 ± 0.34 %ID/g) in tumor-bearing mice 3 hours following intravenous injection of the poly(HPMA)-c(RGDyK)-DOTA-64Cu copolymers was significantly higher than the tumor 64Cu radioactivity (1.29 ± 0.26 %ID/g) in tumor-bearing mice injected with the nontargeted poly(HPMA)-DOTA-64Cu copolymers (p = .004). The poly(HPMA)-c(RGDyK)-DOTA-64Cu copolymers hold potential as a theranostic scaffold for cancer imaging and radiochemotherapy of prostate cancer targeting tumor angiogenesis by noninvasive tracking with PET.

Rapid Ordering in "Wet Brush" Block Copolymer/Homopolymer Ternary Blends.

PubMed

Doerk, Gregory S; Yager, Kevin G

2017-12-26

The ubiquitous presence of thermodynamically unfavored but kinetically trapped topological defects in nanopatterns formed via self-assembly of block copolymer thin films may prevent their use for many envisioned applications. Here, we demonstrate that lamellae patterns formed by symmetric polystyrene-block-poly(methyl methacrylate) diblock copolymers self-assemble and order extremely rapidly when the diblock copolymers are blended with low molecular weight homopolymers of the constituent blocks. Being in the "wet brush" regime, the homopolymers uniformly distribute within their respective self-assembled microdomains, preventing increases in domain widths. An order-of-magnitude increase in topological grain size in blends over the neat (unblended) diblock copolymer is achieved within minutes of thermal annealing as a result of the significantly higher power law exponent for ordering kinetics in the blends. Moreover, the blends are demonstrated to be capable of rapid and robust domain alignment within micrometer-scale trenches, in contrast to the corresponding neat diblock copolymer. These results can be attributed to the lowering of energy barriers associated with domain boundaries by bringing the system closer to an order-disorder transition through low molecular weight homopolymer blending.

Stabilizing Various Bicontinuous Morphologies via Polydispersity of Diblock Copolymers

NASA Astrophysics Data System (ADS)

Lai, Chi To; Shi, An-Chang

Diblock copolymers are macromolecules composed of two chemically distinct homopolymers covalently bound end-to-end. The ability to self-assembly into a wide variety of ordered periodic structures, as means of minimizing the free energy, is their most well-studied property. There are many factors affecting the observed equilibrium morphology, one of which is polydispersity. The phase behaviour of polydispersed diblock copolymers is more rich, and diverse when compared to their monodispersed counterpart. The rich behaviour of polydispersed diblock copolymers provides an opportunity to engineer novel morphologies which are not available in monodispersed systems. Using the self-consistent field theory (SCFT), we explore the possibility of exploiting polydispersity of diblock copolymers in binary mixtures to stabilize the various bicontinuous phases, such as the double-diamond morphology. Specifically, solutions of the SCFT equations corresponding to different bicontinuous phases are obtained numerically for binary mixtures of diblock copolymers. The relative stability of the different ordered phases is examined by comparing their free energy. From the study, we determine optimal sets of parameters that stabilize the double-diamond or other exotic morphologies.

Separation of Poly(styrene-block-t-butyl methacrylate) Copolymers by Various Liquid Chromatography Techniques

PubMed Central

Šmigovec Ljubič, Tina; Pahovnik, David; Žigon, Majda; Žagar, Ema

2012-01-01

The separation of a mixture of three poly(styrene-block-t-butyl methacrylate) copolymers (PS-b-PtBMA), consisting of polystyrene (PS) blocks of similar length and t-butyl methacrylate (PtBMA) blocks of different lengths, was performed using various chromatographic techniques, that is, a gradient liquid chromatography on reversed-phase (C18 and C8) and normal-phase columns, a liquid chromatography under critical conditions for polystyrene as well as a fully automated two-dimensional liquid chromatography that separates block copolymers by chemical composition in the first dimension and by molar mass in the second dimension. The results show that a partial separation of the mixture of PS-b-PtBMA copolymers can be achieved only by gradient liquid chromatography on reversed-phase columns. The coelution of the two block copolymers is ascribed to a much shorter PtBMA block length, compared to the PS block, as well as a small difference in the length of the PtBMA block in two of these copolymers, which was confirmed by SEC-MALS and NMR spectroscopy. PMID:22489207

Polymeric micelles based on poly(methacrylic acid) block-containing copolymers with different membrane destabilizing properties for cellular drug delivery.

PubMed

Mebarek, Naila; Aubert-Pouëssel, Anne; Gérardin, Corine; Vicente, Rita; Devoisselle, Jean-Marie; Bégu, Sylvie

2013-10-01

Poly(methacrylic acid)-b-poly(ethylene oxide) are double hydrophilic block copolymers, which are able to form micelles by complexation with a counter-polycation, such as poly-l-lysine. A study was carried out on the ability of the copolymers to interact with model membranes as a function of their molecular weights and as a function of pH. Different behaviors were observed: high molecular weight copolymers respect the membrane integrity, whereas low molecular weight copolymers with a well-chosen asymmetry degree can induce a membrane alteration. Hence by choosing the appropriate molecular weight, micelles with distinct membrane interaction behaviors can be obtained leading to different intracellular traffics with or without endosomal escape, making them interesting tools for cell engineering. Especially micelles constituted of low molecular weight copolymers could exhibit the endosomal escape property, which opens vast therapeutic applications. Moreover micelles possess a homogeneous nanometric size and show variable properties of disassembly at acidic pH, of stability in physiological conditions, and finally of cyto-tolerance. Copyright © 2013 Elsevier B.V. All rights reserved.

Micellar Packing in Aqueous Solutions of As-Received and Pure Pluronic Block Copolymers

NASA Astrophysics Data System (ADS)

Ryu, Chang; Park, Han Jin

2013-03-01

Pluronic block copolymers (Pluronics) are produced on a commercial scale to enable wide range of novel applications from emulsification and colloidal stabilization as nonionic surfactants. While the Pluronic block copolymers offer the advantages of being readily available for such applications, it contains non-micellizable low molecular weight (MW) impurities that would interfere with the self-assembly and micellar packing of PEO-PPO-PEO triblock copolymers in aqueous solutions. The impacts of the low MW impurities will be discussed on the micellar packing of Pluronics F108 and F127 solutions, which form BCC and FCC. While as-received Pluronic samples typically contain about 20 wt.% low MW impurities, we were able to reduce the impurity level to less than 2 wt.% using our large scale purification technique. Comparative studies on small angle x-ray scattering (SAXS) experiments on as-received and purified Pluronics solutions revealed that the contents of triblock copolymers in solutions essentially governs the inter-micellar distance of Pluronic cubic structures. A universal relationship between triblock copolymer concentration and SAXS-based domain spacing has been finally discussed. Funding from Agency for Defense Development, Korea.

Selective molecular annealing: in situ small angle X-ray scattering study of microwave-assisted annealing of block copolymers.

PubMed

Toolan, Daniel T W; Adlington, Kevin; Isakova, Anna; Kalamiotis, Alexis; Mokarian-Tabari, Parvaneh; Dimitrakis, Georgios; Dodds, Christopher; Arnold, Thomas; Terrill, Nick J; Bras, Wim; Hermida Merino, Daniel; Topham, Paul D; Irvine, Derek J; Howse, Jonathan R

2017-08-09

Microwave annealing has emerged as an alternative to traditional thermal annealing approaches for optimising block copolymer self-assembly. A novel sample environment enabling small angle X-ray scattering to be performed in situ during microwave annealing is demonstrated, which has enabled, for the first time, the direct study of the effects of microwave annealing upon the self-assembly behavior of a model, commercial triblock copolymer system [polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene]. Results show that the block copolymer is a poor microwave absorber, resulting in no change in the block copolymer morphology upon application of microwave energy. The block copolymer species may only indirectly interact with the microwave energy when a small molecule microwave-interactive species [diethylene glycol dibenzoate (DEGDB)] is incorporated directly into the polymer matrix. Then significant morphological development is observed at DEGDB loadings ≥6 wt%. Through spatial localisation of the microwave-interactive species, we demonstrate targeted annealing of specific regions of a multi-component system, opening routes for the development of "smart" manufacturing methodologies.

Cooperation of Amphiphilicity and Crystallization for Regulating the Self-Assembly of Poly(ethylene glycol)-block-poly(lactic acid) Copolymers.

PubMed

Wang, Zhen; Cao, Yuanyuan; Song, Jiaqi; Xie, Zhigang; Wang, Yapei

2016-09-20

Tuning the amphiphilicity of block copolymers has been extensively exploited to manipulate the morphological transition of aggregates. The introduction of crystallizable moieties into the amphiphilic copolymers also offers increasing possibilities for regulating self-assembled structures. In this work, we demonstrate a detailed investigation of the self-assembly behavior of amphiphilic poly(ethylene glycol)-block-poly(l-lactic acid) (PEG-b-PLLA) diblock copolymers with the assistance of a common solvent in aqueous solution. With a given length of the PEG block, the molecular weight of the PLA block has great effect on the morphologies of self-assembled nanoaggregates as a result of varying molecular amphiphilicity and polymer crystallization. Common solvents including N,N-dimethylformamide, dioxane, and tetrahydrofuran involved in the early stage of self-assembly led to the change in chain configuration, which further influences the self-assembly of block copolymers. This study expanded the scope of PLA-based copolymers and proposed a possible mechanism of the sphere-to-lozenge and platelet-to-cylinder morphological transitions.

Dynamic photoinduced realignment processes in photoresponsive block copolymer films: effects of the chain length and block copolymer architecture.

PubMed

Sano, Masami; Shan, Feng; Hara, Mitsuo; Nagano, Shusaku; Shinohara, Yuya; Amemiya, Yoshiyuki; Seki, Takahiro

2015-08-07

A series of block copolymers composed of an amorphous poly(butyl methacrylate) (PBMA) block connected with an azobenzene (Az)-containing liquid crystalline (PAz) block were synthesized by changing the chain length and polymer architecture. With these block copolymer films, the dynamic realignment process of microphase separated (MPS) cylinder arrays of PBMA in the PAz matrix induced by irradiation with linearly polarized light was studied by UV-visible absorption spectroscopy, and time-resolved grazing incidence small angle X-ray scattering (GI-SAXS) measurements using a synchrotron beam. Unexpectedly, the change in the chain length hardly affected the realignment rate. In contrast, the architecture of the AB-type diblock or the ABA-type triblock essentially altered the realignment feature. The strongly cooperative motion with an induction period before realignment was characteristic only for the diblock copolymer series, and the LPL-induced alignment change immediately started for triblock copolymers and the PAz homopolymer. Additionally, a marked acceleration in the photoinduced dynamic motions was unveiled in comparison with a thermal randomization process.

Controlling block copolymer phase behavior using ionic surfactant

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ray, D.; Aswal, V. K.

2016-05-23

The phase behavior of poly(ethylene oxide)-poly(propylene oxide-poly(ethylene oxide) PEO-PPO-PEO triblock copolymer [P85 (EO{sub 26}PO{sub 39}EO{sub 26})] in presence of anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solution as a function of temperature has been studied using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations (1 wt%) of block copolymer and surfactants. Each of the individual components (block copolymer and surfactant) and the nanoparticle–surfactant mixed system have been examined at varying temperature. The block copolymer P85 forms spherical micelles at room temperature whereas shows sphere-to-rod like micelle transition at highermore » temperatures. On the other hand, SDS surfactant forms ellipsoidal micelles over a wide temperature range. Interestingly, it is found that phase behavior of mixed micellar system (P85 + SDS) as a function of temperature is drastically different from that of P85, giving the control over the temperature-dependent phase behavior of block copolymers.« less

Phase transition of LB films of mixed diblock copolymer at the air/water interface

NASA Astrophysics Data System (ADS)

Seo, Y. S.; Kim, K. S.; Samuilov, V.; Rafailovich, M. H.; Sokolov, J.; Lammertink, Rob G. H.; Vancso, G. J.

2000-03-01

We have studied the morphology of Langmuir blodgett films at the air/water interface of mixed diblock copolymer films. Solutions of poly(styrene-b-ferrocenyldimethylsilane) and PS-b-P2VP mixed in a ratio of 20/80 in chloroform were spread at the air/water interface. The morphology of the films was studied with AFM as a function of the surface pressure and the diblock copolymer molecular weight. The results show that the two diblock copolymers can be induced to mix at the air/water interface with increasing surface pressure. A reversible transition from spherical to cylindrical morphologies is induced in the mixture which can not be observed in films formed of the two components separately. The effective surface phase diagram as a function of block copolymer composition and pressure will be presented.

Toxicological assessment of Anionic Methacrylate Copolymer: I. Characterization, bioavailability and genotoxicity.

PubMed

Eisele, Johanna; Haynes, Geoff; Kreuzer, Knut; Hall, Caroline

2016-12-01

Anionic Methacrylate Copolymer (AMC) is a fully polymerized copolymer used in the pharmaceutical industry as an enteric/delayed-release coating to permit the pH-dependent release of active ingredients in the gastrointestinal tract from oral dosage forms. This function is of potential use for food supplements. Oral administration of radiolabeled copolymer to rats resulted in the detection of chemically unchanged copolymer in the feces, with negligible absorption (<0.1%). AMC is therefore determined not to be bioavailable. Within a genotoxicity test battery AMC did not show any evidence of genotoxicity in bacteria and mammalian cells. Furthermore, no genotoxic effects occurred in vivo within a micronucleus test. There would therefore appear to be no safety concerns under intended conditions of oral use for the discussed toxicological endpoints. Copyright © 2016 Elsevier Inc. All rights reserved.

Synthesis and characterization of functional acrylic copolymers via RAFT mini-emulsion polymerization

NASA Astrophysics Data System (ADS)

Yılmaz, Onur; Özkan, ćiǧdem Kılıçarislan; Yılmaz, Catalina N.; Yorgancıoǧlu, Ali; Özgünay, Hasan; Karavana, Hüseyin Ata

2017-12-01

Copolymers bearing reactive functional groups with controlled molecular weights are of importance since they can be used in many fields such as composites, coatings, membranes, catalysis, biology, optoelectronics, pharmaceuticals, etc. In the present study low molecular weight copolymers based on butyl acrylate (BA) and methyl methacrylate (MMA) in combination with reactive functional monomers of vinyl trietoxysilane (VTES), 3-trimetoxysilylpropyl methacrylate (TMSPMA) and glycidyl methacrylate (GMA) were synthesized via RAFT mini-emulsion technique using 2-cyano 2-propyldodecyldithiocarbonate as CTA agent. The results showed that the average molecular weights of copolymers were close to the theoretical values. On the other hand, PDI values were found to be higher than conventional RAFT polymers. The particle sizes of the latexes were small with very homogenous distributions and good stability. FTIR, H-NMR and TGA results verified the success of copolymer syntheses.

PEO-PPO-PEO Tri-Block Copolymers for Gene Delivery Applications in Human Regenerative Medicine—An Overview

PubMed Central

Cucchiarini, Magali

2018-01-01

Lineal (poloxamers or Pluronic®) or X-shaped (poloxamines or Tetronic®) amphiphilic tri-block copolymers of poly(ethylene oxide) and poly(propylene oxide) (PEO-PPO-PEO) have been broadly explored for controlled drug delivery in different regenerative medicine approaches. The ability of these copolymers to self-assemble as micelles and to undergo sol-to-gel transitions upon heating has endowed the denomination of “smart” or “intelligent” systems. The use of PEO-PPO-PEO copolymers as gene delivery systems is a powerful emerging strategy to improve the performance of classical gene transfer vectors. This review summarizes the state of art of the application of PEO-PPO-PEO copolymers in both nonviral and viral gene transfer approaches and their potential as gene delivery systems in different regenerative medicine approaches. PMID:29518011

Let there be light: photo-cross-linked block copolymer nanoparticles.

PubMed

Roy, Debashish; Sumerlin, Brent S

2014-01-01

Polymeric nanoparticles are prepared by selectively cross-linking a photo-sensitive dimethylmaleimide-containing block of a diblock copolymer via UV irradiation. A well-defined photo-cross-linkable block copolymer is prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization of a dimethylmaleimide-functional acrylamido monomer containing photoreactive pendant groups with a poly(N,N-dimethylacrylamide) (PDMA) macro-chain transfer agent. The resulting amphiphilic block copolymers form micelles in water with a hydrophilic PDMA shell and a hydrophobic photo-cross-linkable dimethylmaleimide-containing core. UV irradiation results in photodimerization of the dimethylmaleimide groups within the micelle cores to yield core-cross-linked aggregates. Alternatively, UV irradiation of homogeneous solutions of the block copolymer in a non-selective solvent leads to in situ nanoparticle formation. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-aggregation of cationically modified poly(ε-caprolactone)2-co-poly(ethylene glycol) copolymers: Effect of cationic grafting ligand and poly(ε-caprolactone) chain length.

PubMed

Charoongchit, Pimchanok; Suksiriworapong, Jiraphong; Sripha, Kittisak; Mao, Shirui; Sapin-Minet, Anne; Maincent, Philippe; Junyaprasert, Varaporn Buraphacheep

2017-03-01

Cationic copolymers have been attractive to investigate due to their potential to complexation with anionic drugs and expected to use in the pharmaceutical application. In this study, the modified poly(ε-caprolactone) 2 -co-poly(ethylene glycol) copolymers (P(CL) 2 -PEG) were successfully synthesized by click reaction. The amount of small molecular cationic ligand, propargyltrimethyl ammonium iodide, was varied and grafted onto various mole ratios of P(CL) to PEG. The effects of P(CL) chain length and amount of the grafting cationic ligand on physicochemical properties of polymers and particles were studied. The number-average molecular weights of the copolymers grafted with cationic ligand were found ranging between 10,000 and 23,000g/mol as investigated by NMR. From DSC study, the results showed that the grafting ligand affected thermal behaviors of the copolymers by increasing the glass transition temperature and decreasing the melting temperature of the copolymers. Furthermore, these cationic copolymers could self-aggregate with their critical aggregation concentration depending on mole ratios of hydrophilic to hydrophobic portions. The particles containing higher amounts of the cationic ligand tended to aggregate in both acidic and basic pH environment and at high salt concentration. Additionally, particle size, size distribution (PdI), and morphology of self-assembling particles varied depending on P(CL) chain length and the amount of the grafting cationic ligand. The synthesized cationic copolymer showed a capability to encapsulate a high negatively charged drug, enoxaparin, with an encapsulation efficiency of 87%. After drug incorporation, the particles substantially changed in size, shape, PdI, and zeta potential to become more suitable for drug delivery. These cationic copolymers with flexible properties will be the candidate for further development as carriers for the delivery of negatively charged drugs. Copyright © 2016. Published by Elsevier B.V.

Understanding Melt-Memory of Commercial Polyolefins

NASA Astrophysics Data System (ADS)

Alamo, Rufina

Self-nucleation (SN) or controlling self-generated seeds in a polymer melt is an avenue to increase the rate of solidification of semicrystalline polymers of commercial relevance. Self-nuclei are remains in the melt of the segmental self-assembly to form polymer crystallites providing a path to enhance primary crystal nucleation. SN has been extensively studied in homopolymers such as iPP. Recently, a strong memory effect of crystallization has been observed in melts of random ethylene copolymers well above the equilibrium melting temperature. The melt memory is associated with clusters or seeds that remain in the melt from the copolymer's sequence length partitioning. Cooling from progressively lower self-seeded melt temperatures, ethylene copolymers with a broad inter-chain comonomer composition (1 - 15 mol%) display first the expected accelerated crystallization, followed by a decrease in the rate in a range of melt temperatures where narrow copolymers show a continuous acceleration of the rate. This unusual inversion of the crystallization rate was postulated to arise from the onset of liquid-liquid phase separation (LLPS) between comonomer-rich and comonomer-poor components of the broad copolymer. The UCST type phase diagram of these commercial copolymers has been documented via SANS using a blend of components, some deuterated, to reproduce the broad distribution. Furthermore, the components that contribute to LLPS have been identified by the crystallization behavior of molar mass fractions. The influence of long chain branching on the topology of copolymer melts has been analyzed using model 3-arm stars hydrogenated polybutadienes. The effect of melt viscosity on strength of melt memory is also evident when SN data of random ethylene copolymers are compared with those of propylene-ethylene copolymers. The strong dependence of melt viscosity on melt memory, and a critical threshold crystallinity level to observe the effect of melt memory on crystallization rate, support the kinetic nature of the SN phenomenon. Support from NSF, DMR-1105129 and DMR-1607786 is gratefully acknowledged.

Electrically conductive doped block copolymer of polyacetylene and polyisoprene. [Soluble in organic solvents

DOEpatents

Aldissi, M.

1984-06-27

An electrically conductive block copolymer of polyisoprene and polyacetylene and a method of making the same are disclosed. The polymer is prepared by first polymerizing isoprene with n-butyllithium in a toluene solution to form an active isoprenyllithium polymer. The active polymer is reacted with an equimolar amount of titanium butoxide and subsequently exposed to gaseous acetylene. A block copolymer of polyisoprene and polyacetylene is formed. The copolymer is soluble in common solvents and may be doped with I/sub 2/ to give it an electrical conductivity in the metallic regime.

Electric-Field-Induced Alignment of Block Copolymer/Nanoparticle Blends

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liedel, Clemens; Schindler, Kerstin; Pavan, Mariela J.

External electric fi elds readily align birefringent block-copolymer mesophases. In this study the effect of gold nanoparticles on the electric-fi eld-induced alignment of a lamellae-forming polystyrene- block -poly(2-vinylpyridine) copolymer is assessed. Nanoparticles are homogeneously dispersed in the styrenic phase and promote the quantitative alignment of lamellar domains by substantially lowering the critical field strength above which alignment proceeds. The results suggest that the electric-fi eldassisted alignment of nanostructured block copolymer/nanoparticle composites may offer a simple way to greatly mitigate structural and orientational defects of such fi lms under benign experimental conditions.

Characterization of 1:1 Random Copolymers Obtained from 6-, 7-, 11-, and 12-Carbon Amino Acids.

DTIC Science & Technology

1993-10-22

Random Copolymers Obtained From 6-, 7-, 11-, and 12-Carbon Amino Acids by C. G. Johnson and L. J. Mathias 0 T .... Prepared for Publication r. t in the...NOOOG4-f-j- From 6-, 7-, 11-, and 12-Carbon Amino Acids 1225 ~~~ :: V Co~de 413m(iUK C. G Johnson, and Lo J. Mathias ś RFORMING ORGANIZA7,iCN ;fAMjjS...distribution is unlimited. Copolymers were prepared from the title amino acids by rr ilt condensation under dry nitrogen. The resulting copolymers were

Preparation and infrared/raman classification of 630 spectroscopically encoded styrene copolymers.

PubMed

Fenniri, Hicham; Chun, Sangki; Terreau, Owen; Bravo-Vasquez, Juan-Pablo

2008-01-01

The barcoded resins (BCRs) were introduced recently as a platform for encoded combinatorial chemistry. One of the main challenges yet to be overcome is the demonstration that a large number of BCRs could be generated and classified with high confidence. Here, we describe the synthesis and classification of 630 polystyrene-based copolymers prepared from the combinatorial association of 15 spectroscopically active styrene monomers. Each of the 630 copolymers displayed a unique vibrational fingerprint (infrared and Raman), which was converted into a spectral vector. To each of the 630 copolymers, a vector of the known (reference) composition was assigned. Unknown (prediction) vectors were decoded using multivariate data analysis. From the inner product of the reference and prediction vectors, a correlation map comparing 396 900 copolymer pairs (630 x 630) was generated. In 100% of the cases, the highest correlation was obtained for polymer pairs in which the reference and prediction vectors correspond to copolymers prepared from identical styrene monomers, thus demonstrating the high reliability of this encoding strategy. We have also established that the spectroscopic barcodes generated from the Raman and infrared spectra are independent of the copolymers' morphology (beaded versus bulk polymers). Besides the demonstration of the generality of the polymer barcoding strategy, the analytical methods developed here could in principle be extended to the investigation of the composition and purity of any other synthetic polymer and biopolymer library, or even scaffold-based combinatorial libraries.

Label-Free LSPR Detection of Trace Lead(II) Ions in Drinking Water by Synthetic Poly(mPD-co-ASA) Nanoparticles on Gold Nanoislands.

PubMed

Qiu, Guangyu; Ng, Siu Pang; Liang, Xiongyi; Ding, Ning; Chen, Xiangfeng; Wu, Chi-Man Lawrence

2017-02-07

Using self-assembly gold nanoislands (SAM-AuNIs) functionalized by poly(m-phenylenediamine-co-aniline-2-sulfonic acid) (poly(mPD-co-ASA)) copolymer nanoparticles as specific receptors, a highly sensitive localized surface plasmon resonance (LSPR) optochemical sensor is demonstrated for detection of trace lead cation (Pb(II)) in drinking water. The copolymer receptor is optimized in three aspects: (1) mole ratio of mPD:ASA monomers, (2) size of copolymer nanoparticles, and (3) surface density of the copolymer. It is shown that the 95:5 (mPD:ASA mole ratio) copolymer with size less than 100 nm exhibits the best Pb(II)-sensing performance, and the 200 times diluted standard copolymer solution contributes to the most effective functionalization protocol. The resulting poly(mPD-co-ASA)-functionalized LSPR sensor attains the detection limit to 0.011 ppb toward Pb(II) in drinking water, and the linear dynamic range covers 0.011 to 5000 ppb (i.e., 6 orders of magnitude). In addition, the sensing system exhibits robust selectivity to Pb(II) in the presence of other metallic cations as well as common anions. The proposed functional copolymer functionalized on AuNIs is found to provide excellent Pb(II)-sensing performance using simple LSPR instrumentation for rapid drinking-water inspection.

Widely Tunable Morphologies in Block Copolymer Thin Films Through Solvent Vapor Annealing Using Mixtures of Selective Solvents

PubMed Central

Chavis, Michelle A.; Smilgies, Detlef-M.; Wiesner, Ulrich B.; Ober, Christopher K.

2015-01-01

Thin films of block copolymers are extremely attractive for nanofabrication because of their ability to form uniform and periodic nanoscale structures by microphase separation. One shortcoming of this approach is that to date the design of a desired equilibrium structure requires synthesis of a block copolymer de novo within the corresponding volume ratio of the blocks. In this work, we investigated solvent vapor annealing in supported thin films of poly(2-hydroxyethyl methacrylate)-block-poly(methyl methacrylate) [PHEMA-b-PMMA] by means of grazing incidence small angle X–ray scattering (GISAXS). A spin-coated thin film of lamellar block copolymer was solvent vapor annealed to induce microphase separation and improve the long-range order of the self-assembled pattern. Annealing in a mixture of solvent vapors using a controlled volume ratio of solvents (methanol, MeOH, and tetrahydrofuran, THF), which are chosen to be preferential for each block, enabled selective formation of ordered lamellae, gyroid, hexagonal or spherical morphologies from a single block copolymer with a fixed volume fraction. The selected microstructure was then kinetically trapped in the dry film by rapid drying. To our knowledge, this paper describes the first reported case where in-situ methods are used to study the transition of block copolymer films from one initial disordered morphology to four different ordered morphologies, covering much of the theoretical diblock copolymer phase diagram. PMID:26819574

Hairy and Slippery Polyoxazoline-Based Copolymers on Model and Cartilage Surfaces.

PubMed

Morgese, Giulia; Ramakrishna, Shivaprakash N; Simic, Rok; Zenobi-Wong, Marcy; Benetti, Edmondo M

2018-02-12

Comb-like polymers presenting a hydroxybenzaldehyde (HBA)-functionalized poly(glutamic acid) (PGA) backbone and poly(2-methyl-2-oxazoline) (PMOXA) side chains chemisorb on aminolized substrates, including cartilage surfaces, forming layers that reduce protein contamination and provide lubrication. The structure, physicochemical, biopassive, and tribological properties of PGA-PMOXA-HBA films are finely determined by the copolymer architecture, its reactivity toward the surface, i.e. PMOXA side-chain crowding and HBA density, and by the copolymer solution concentration during assembly. Highly reactive species with low PMOXA content form inhomogeneous layers due to the limited possibility of surface rearrangements by strongly anchored copolymers, just partially protecting the functionalized surface from protein contamination and providing a relatively weak lubrication on cartilage. Biopassivity and lubrication can be improved by increasing copolymer concentration during assembly, leading to a progressive saturation of surface defects across the films. In a different way, less reactive copolymers presenting high PMOXA side-chain densities form uniform, biopassive, and lubricious films, both on model aminolized silicon oxide surfaces, as well as on cartilage substrates. When assembled at low concentrations these copolymers adopt a "lying down" conformation, i.e. adhering via their backbones onto the substrates, while at high concentrations they undergo a conformational transition, assuming a more densely packed, "standing up" structure, where they stretch perpendicularly from the substrate. This specific arrangement reduces protein contamination and improves lubrication both on model as well as on cartilage surfaces.

Highly Efficient One-Pot Synthesis of COS-Based Block Copolymers by Using Organic Lewis Pairs.

PubMed

Yang, Jia-Liang; Cao, Xiao-Han; Zhang, Cheng-Jian; Wu, Hai-Lin; Zhang, Xing-Hong

2018-01-31

A one-pot synthesis of block copolymer with regioregular poly(monothiocarbonate) block is described via metal-free catalysis. Lewis bases such as guanidine, quaternary onium salts, and Lewis acid triethyl borane (TEB) were equivalently combined and used as the catalysts. By using polyethylene glycol (PEG) as the macromolecular chain transfer agent (CTA), narrow polydispersity block copolymers were obtained from the copolymerization of carbonyl sulfide (COS) and propylene oxide (PO). The block copolymers had a poly(monothiocarbonate) block with perfect alternating degree and regioregularity. Unexpectedly, the addition of CTA to COS/PO copolymerization system could dramatically improve the turnover frequency (TOF) of PO (up to 240 h -1 ), higher than that of the copolymerization without CTA. In addition, the conversion of CTA could be up to 100% in most cases, as revealed by ¹H NMR spectra. Of consequence, the number-average molecular weights ( M n s) of the resultant block copolymers could be regulated by varying the feed ratio of CTA to PO. Oxygen-sulfur exchange reaction (O/S ER), which can generate randomly distributed thiocarbonate and carbonate units, was effectively suppressed in all of the cases in the presence of CTA, even at 80 °C. This work presents a versatile method for synthesizing sulfur-containing block copolymers through a metal-free route, providing an array of new block copolymers.

Polystyrene/wood composites and hydrophobic wood coatings from water-based hydrophilic-hydrophobic block copolymers

Treesearch

Marja-Leena Kosonen; Bo Wang; Gerard T. Caneba; Douglas J. Gardner; Tim G. Rials

2000-01-01

The combination of synthetic thermoplastic polymers and wood is normally problematic because wood surfaces are hydrophilic while typical thermoplastic polymers are hydrophobic. A possible solution is to use block copolymer coupling agents. In this work we show the use of a potentially useful synthetic method of producing hydrophilic-hydrophobic block copolymers as...

21 CFR 177.1570 - Poly-1-butene resins and butene/ethylene copolymers.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Poly-1-butene resins and butene/ethylene... Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1570 Poly-1-butene resins and butene/ethylene copolymers. The poly-1-butene resins and butene/ethylene copolymers...

Effect of nanoscale morphology on selective ethanol transport through block copolymer membranes

USDA-ARS?s Scientific Manuscript database

We report on the effect of block copolymer domain size on transport of liquid mixtures through the membranes by presenting pervaporation data of an 8 wt% ethanol/water mixture through A-B-A and B-A-B triblock copolymer membranes. The A-block was chosen to facilitate ethanol transport while the B-blo...

Highly Conductive Anion Exchange Block Copolymers

DTIC Science & Technology

We are developing a comprehensive fundamental understanding of the interplay between transport and morphology in newly synthesized hydroxide...conducting block copolymers. We are synthesizing hydroxide conducting block copolymers of various (1) morphology types, (2) ionic concentrations, and (3...ionic domain sizes. We are carefully characterizing the morphology and transport properties using both conventional and new advanced in situ techniques

Highly crosslinked silicon polymers for gas chromatography columns

NASA Technical Reports Server (NTRS)

Shen, Thomas C. (Inventor)

1994-01-01

A new highly crosslinked silicone polymer particle for gas chromatography application and a process for synthesizing such copolymer are described. The new copolymer comprises vinyltriethoxysilane and octadecyltrichlorosilane. The copolymer has a high degree of crosslinking and a cool balance of polar to nonpolar sites in the porous silicon polymer assuring fast separation of compounds of variable polarity.

DISPERSION POLYMERIZATION OF STYRENE IN SUPERCRITICAL CARBON DIOXIDE UTILIZING RANDOM COPOLYMERS INCLUDING FLUORINATED ACRYLATE FOR PREPARING MICRON-SIZE POLYSTYRENE PARTICLES. (R826115)

EPA Science Inventory

The dispersion polymerization of styrene in supercritical CO₂ utilizing CO₂-philic random copolymers was investigated. The resulting high yield of polystyrene particles in the micron-size range was formed using various random copolymers as stabilizers. The p...

Negative Electrode For An Alkaline Cell

DOEpatents

Coco, Isabelle; Cocciantelli, Jean-Michel; Villenave, Jean-Jacques

1998-07-14

The present invention concerns a negative electrode for an alkaline cell, comprising a current collector supporting a paste containing an electrochemically active material and a binder, characterized in that said binder is a polymer containing hydrophilic and hydrophobic groups, said polymer being selected from an acrylic homopolymer, copolymer and terpolymer, an unsaturated organic acid copolymer and an unsaturated acid anhydride copolymer.

Fabrication of supramolecular star-shaped amphiphilic copolymers for ROS-triggered drug release.

PubMed

Zuo, Cai; Peng, Jinlei; Cong, Yong; Dai, Xianyin; Zhang, Xiaolong; Zhao, Sijie; Zhang, Xianshuo; Ma, Liwei; Wang, Baoyan; Wei, Hua

2018-03-15

Star-shaped copolymers with branched structures can form unimolecular micelles with better stability than the micelles self-assembled from conventional linear copolymers. However, the synthesis of star-shaped copolymers with precisely controlled degree of branching (DB) suffers from complicated sequential polymerizations and multi-step purification procedures, as well as repeated optimizations of polymer compositions. The use of a supramolecular host-guest pair as the block junction would significantly simplify the preparation. Moreover, the star-shaped copolymer-based unimolecular micelle provides an elegant solution to the tradeoff between extracellular stability and intracellular high therapeutic efficacy if the association/dissociation of the supramolecular host-guest joint can be triggered by the biologically relevant stimuli. For this purpose, in this study, a panel of supramolecular star-shaped amphiphilic block copolymers with 9, 12, and 18 arms were designed and fabricated by host-guest complexations between the ring-opening polymerization (ROP)-synthesized star-shaped poly(ε-caprolactone) (PCL) with 3, 4, and 6 arms end-capped with ferrocene (Fc) (PCL-Fc) and the atom transfer radical polymerization (ATRP)-produced 3-arm poly(oligo ethylene glycol) methacrylates (POEGMA) with different degrees of polymerization (DPs) of 24, 30, 47 initiated by β-cyclodextrin (β-CD) (3Br-β-CD-POEGMA). The effect of DB and polymer composition on the self-assembled properties of the five star-shaped copolymers was investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM), and fluorescence spectrometery. Interestingly, the micelles self-assembled from 12-arm star-shaped copolymers exhibited greater stability than the 9- and 18-arm formulations. The potential of the resulting supramolecular star-shaped amphiphilic copolymers as drug carriers was evaluated by an in vitro drug release study, which confirmed the ROS-triggered accelerated drug release from the doxorubicin (DOX)-loaded supramolecular star-shaped micelles due to the oxidation-induced dissociation of β-CD/Fc pair and the consequent loss of the colloidal stability of the star-shaped micelles. Studies of the delivery efficacy by an in vitro cytotoxicity study further indicated that higher DBs and longer hydrophilic arm compromised the therapeutic efficacy of the DOX-loaded supramolecular star-shaped micelles, resulting in significantly reduced cytotoxicity, as measured by increased IC 50 value. Overall, our results revealed that the screening of hydrophilic block by DB and MW for an optimized star-shaped copolymer should balance the stability versus therapeutic efficacy tradeoff for a comprehensive consideration. Therefore, the 12-arm star-shaped copolymer with POEGMA 30 is the best formulation tested. Copyright © 2017 Elsevier Inc. All rights reserved.

Constructing a molecular theory of self-assembly: Interplay of ideas from surfactants and block copolymers.

PubMed

Nagarajan, Ramanathan

2017-06-01

Low molecular weight surfactants and high molecular weight block copolymers display analogous self-assembly behavior in solutions and at interfaces, generating nanoscale structures of different shapes. Understanding the link between the molecular structure of these amphiphiles and their self-assembly behavior has been the goal of theoretical studies. Despite the analogies between surfactants and block copolymers, models predicting their self-assembly behavior have evolved independent of one another, each overlooking the molecular feature considered critical to the other. In this review, we focus on the interplay of ideas pertaining to surfactants and block copolymers in three areas of self-assembly. First, we show how improved free energy models have evolved by applying ideas from surfactants to block copolymers and vice versa, giving rise to a unitary theoretical framework and better predictive capabilities for both classes of amphiphiles. Second we show that even though molecular packing arguments are often used to explain aggregate shape transitions resulting from self-assembly, the molecular packing considerations are more relevant in the case of surfactants whereas free energy criteria are relevant for block copolymers. Third, we show that even though the surfactant and block copolymer aggregates are small nanostructures, the size differences between them is significant enough to make the interfacial effects control the solubilization of molecules in surfactant micelles while the bulk interactions control the solubilization in block copolymer micelles. Finally, we conclude by identifying recent theoretical progress in adapting the micelle model to a wide variety of self-assembly phenomena and the challenges to modeling posed by emerging novel classes of amphiphiles with complex biological, inorganic or nanoparticle moieties. Published by Elsevier B.V.

PCL-PDMS-PCL copolymer-based microspheres mediate cardiovascular differentiation from embryonic stem cells

NASA Astrophysics Data System (ADS)

Song, Liqing

Poly-epsilon-caprolactone (PCL) based copolymers have received much attention as drug or growth factor delivery carriers and tissue engineering scaffolds due to their biocompatibility, biodegradability, and tunable biophysical properties. Copolymers of PCL and polydimethylsiloxane (PDMS) also have shape memory behaviors and can be made into thermoresponsive shape memory polymers for various biomedical applications such as smart sutures and vascular stents. However, the influence of biophysical properties of PCL-PDMS-PCL copolymers on stem cell lineage commitment is not well understood. In this study, PDMS was used as soft segments of varying length to tailor the biophysical properties of PCL-based co-polymers. While low elastic modulus (<10 kPa) of the tri-block copolymer PCL-PDMS-PCL affected cardiovascular differentiation of embryonic stem cells, the range of 60-100 MPa PCL-PDMS-PCL showed little influence on the differentiation. Then different size (30-140 mum) of microspheres were fabricated from PCL-PDMS-PCL copolymers and incorporated within embryoid bodies (EBs). Mesoderm differentiation was induced using bone morphogenetic protein (BMP)-4 for cardiovascular differentiation. Differential expressions of mesoderm progenitor marker KDR and vascular markers CD31 and VE-cadherin were observed for the cells differentiated from EBs incorporated with microspheres of different size, while little difference was observed for cardiac marker alpha-actinin expression. Small size of microspheres (30 mum) resulted in higher expression of KDR while medium size of microspheres (94 mum) resulted in higher CD31 and VE-cadherin expression. This study indicated that the biophysical properties of PCL-based copolymers impacted stem cell lineage commitment, which should be considered for drug delivery and tissue engineering applications.

Phase Structure and Properties of a Biodegradable Block Copolymer Coalesced from It's Crystalline Inclusion Compound Formed with alpha-Cyclodextrin

NASA Astrophysics Data System (ADS)

Shuai, Xintao; Wei, Min; Probeni, Francis; Bullions, Todd A.; Shin, I. Daniel; Tonelli, Alan E.

2002-03-01

A well-defined biodegradable block copolymer of poly(epsilon caprolactone) (PCL) and poly(L-lactic acid) (PLLA) was synthesized and characterized and then included as a guest in an inclusion compound (IC) formed with the host alpha-cyclodextrin (CD). The PCL-b-PLLA block copolymer was subsequently coalesced from it's CD-IC crystals by either treatment with hot water (50 C) or an aqueous amylase solution at 25 C. The coalesced PCL-b-PLLA was examined by FTIR, DSC, TGA, and WAXD and was found to be much more homogeneosly organized, with much less segregation and crystallinity of the PCL and PLLA microphases. The morpholgy, crystallization kinetics, thermal behavior, and biodegradability of the coalesced PCL-b-PLLA block copolymer was studied by comparison to similar observations made on as-synthesized PCL-b-PLLA, PCL and PLLA homopolymers, and their solution-cast blend. The PCL and PLLA blocks are found to be more intimately mixed, with less phase segregation, in the coalesced diblock copolymer, and this leads to homogeneous bulk crystallization, which is not observed for the as-synthesized diblock copolymer. The coalesced PCL-b-PLLA was also found to be more quickly biodegraded (lipase from Rhizopus arrhizus)than the as-synthesized PCL-b-PLLA or the physical blend of PCL and PLLA homopolymers. Overall, the coalescence of the inherently phase segregated diblock copolymer PCL-b-PLLA results in a small amount of compact, chain-extended PCL and PLLA crystals embedded in an amorphous phase, largely consisting of well-mixed PCL and PLLA blocks. Thus, we have demonstrated that it is possible to control the morpholgy of a biodegradable diblock copolymer, thereby significantly modifying it's properties, by coalescence from it's CD-IC crystals.

Differences in the adsorption behaviour of poly(ethylene oxide) copolymers onto model polystyrene nanoparticles assessed by isothermal titration microcalorimetry correspond to the biological differences.

PubMed

Stolnik, S; Heald, C R; Garnett, M G; Illum, L; Davis, S S

2005-01-01

The adsorption behaviour of a tetrafunctional copolymer of poly (ethylene oxide)-poly (propylene oxide) ethylene diamine (commercially available as Poloxamine 908) and a diblock copolymer of poly (lactic acid)-poly (ethylene oxide) (PLA/PEG 2:5) onto a model colloidal drug carrier (156 nm sized polystyrene latex) is described. The adsorption isotherm, hydrodynamic thickness of the adsorbed layers and enthalpy of the adsorption were assessed. The close similarity in the conformation of the poly (ethylene oxide) (PEO) chains (molecular weight 5,000 Da) in the adsorbed layers of these two copolymers was demonstrated by combining the adsorption data with the adsorbed layer thickness data. In contrast, the results from isothermal titration microcalorimetry indicated a distinct difference in the interaction of the copolymers with the polystyrene colloid surface. Poloxamine 908 adsorption to polystyrene nanoparticles is dominated by an endothermic heat effect, whereas, PLA/PEG 2:5 adsorption is entirely an exothermic process. This difference in adsorption behaviour could provide an explanation for differences in the biodistribution of Poloxamine 908 and PLA/PEG 2:5 coated polystyrene nanoparticles observed in previous studies. A comparison with the interaction enthalpy for several other PEO-containing copolymers onto the same polystyrene colloid was made. The results demonstrate the importance of the nature of the anchoring moiety on the interaction of the adsorbing copolymer with the colloid surface. An endothermic contribution is found when an adsorbing molecule contains a poly (propylene oxide) (PPO) moiety (e.g. Poloxamine 908), whilst the adsorption is exothermic (i.e. enthalpy driven) for PEO copolymers with polylactide (PLA/PEG 2:5) or alkyl moieties.

Molecular origin of photovoltaic performance in donor- block-acceptor all-conjugated block copolymers

DOE PAGES

Smith, Kendall A.; Lin, Yen -Hao; Mok, Jorge W.; ...

2015-11-03

All-conjugated block copolymers may be an effective route to self-assembled photovoltaic devices, but we lack basic information on the relationship between molecular characteristics and photovoltaic performance. Here, we synthesize a library of poly(3-hexylthiophene) (P3HT) block poly((9,9-dialkylfluorene)-2,7-diyl-alt-[4,7-bis(alkylthiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (PFTBT) donor- block-acceptor all-conjugated block copolymers and carry out a comprehensive study of processing conditions, crystallinity, domain sizes, and side-chain structure on photovoltaic device performance. We find that all block copolymers studied exhibit an out-of-plane crystal orientation after deposition, and on thermal annealing at high temperatures the crystal orientation flips to an in-plane orientation. By varying processing conditions on polymer photovoltaic devices, we showmore » that the crystal orientation has only a modest effect (15-20%) on photovoltaic performance. The addition of side-chains to the PFTBT block is found to decrease photovoltaic power conversion efficiencies by at least an order of magnitude. Through grazing-incidence X-ray measurements we find that the addition of side-chains to the PFTBT acceptor block results in weak segregation and small (< 10 nm) block copolymer self-assembled donor and acceptor domains. This work is the most comprehensive to date on all-conjugated block copolymer systems and suggests that photovoltaic performance of block copolymers depends strongly on the miscibility of donor and acceptor blocks, which impacts donor and acceptor domain sizes and purity. Lastly, strategies for improving the device performance of block copolymer photovoltaics should seek to increase segregation between donor and acceptor polymer domains.« less

Solid-state NMR characterization of copolymers of nylon 11 and nylon 12.

PubMed

Johnson, C G; Mathias, L J

1997-05-01

Solid-state 13C and 15N NMR spectroscopy, in conjunction with differential scanning calorimetry, wide-angle X-ray diffraction and infrared spectroscopy, were used to characterize a series of nylon 11 and 12 copolymers with mole percentages of nylon 12 monomer of 0, 15, 35, 50, 65, 85, and 100%. Monotonic melting point (Tm) and heat of fusion depressions were observed for the copolymer series with the 65 mol% nylon 12 copolymer having the lowest apparent crystallinity and Tm at 148 degrees C. Solid-state 15N NMR spectra showed a smooth shift of the main peak position for the as-prepared copolymers from 84 ppm for the alpha-form of pure nylon 11 to 89 ppm for the gamma-form of pure nylon 12. Similar behavior was seen for FTIR amide V and VI modes which are also sensitive to the alpha- and gamma-crystal forms. 13C NMR T1 measurements showed that the overall most mobile sample was the 65:35 copolymer. The amide group of the 1:1 copolymer was labelled using 15N-labelled amino acids available through the Gabriel synthesis; an annealed, solution-cast film of this sample showed a T1N value of 349 s, similar to values seen for annealed nylon 11 and nylon 12 homopolymers. The WAXS pattern for the 65 mol% nylon 12 sample showed a sharp peak at 2 theta = 21.3, overlapping a broad peak centered at 2 theta = 21.0. These are consistent with the values seen for gamma-form nylon 12. The 1:1 copolymer (15N labelled) was shown to be polymorphic, like the homopolymers after specific treatments, with a gamma-like phase formed upon solvent casting, and an alpha-like phase dominating for as-polymerized material and precipitated flakes.

Assessment of PLGA-PEG-PLGA Copolymer Hydrogel for Sustained Drug Delivery in the Ear

PubMed Central

Feng, Liang; Ward, Jonette A.; Li, S. Kevin; Tolia, Gaurav; Hao, Jinsong; Choo, Daniel I.

2014-01-01

Temperature sensitive copolymer systems were previously studied using modified diffusion cells in vitro for intratympanic injection, and the PLGA-PEG-PLGA copolymer systems were found to provide sustained drug delivery for several days. The objectives of the present study were to assess the safety of PLGA-PEG-PLGA copolymers in intratympanic injection in guinea pigs in vivo and to determine the effects of additives glycerol and poloxamer in PLGA-PEG-PLGA upon drug release in the diffusion cells in vitro for sustained inner ear drug delivery. In the experiments, the safety of PLGA-PEG-PLGA copolymers to inner ear was evaluated using auditory brainstem response (ABR). The effects of the additives upon drug release from PLGA-PEG-PLGA hydrogel were investigated in the modified Franz diffusion cells in vitro with cidofovir as the model drug. The phase transition temperatures of the PLGA-PEG-PLGA copolymers in the presence of the additives were also determined. In the ABR safety study, the PLGA-PEG-PLGA copolymer alone did not affect hearing when delivered at 0.05-mL dose but caused hearing loss after 0.1-mL injection. In the drug release study, the incorporation of the bioadhesive additive, poloxamer, in the PLGA-PEG-PLGA formulations was found to decrease the rate of drug release whereas the increase in the concentration of the humectant additive, glycerol, provided the opposite effect. In summary, the PLGA-PEG-PLGA copolymer did not show toxicity to the inner ear at the 0.05-mL dose and could provide sustained release that could be controlled by using the additives for inner ear applications. PMID:24438444

Injectable biodegradable temperature-responsive PLGA-PEG-PLGA copolymers: synthesis and effect of copolymer composition on the drug release from the copolymer-based hydrogels.

PubMed

Qiao, Mingxi; Chen, Dawei; Ma, Xichen; Liu, Yanjun

2005-04-27

Injectable biodegradable temperature-responsive poly(DL-lactide-co-glycolide-b-ethylene glycol-b-DL-lactide-co-glycolide) (PLGA-PEG-PLGA) triblock copolymers with DL-lactide/glycolide molar ratio ranging from 6/1 to 15/l were synthesized from monomers of DL-lactide, glycolide and polyethylene glycol and characterized by 1H NMR. The resulting copolymers are soluble in water to form free flowing fluid at room temperature but become hydrogels at body temperature. The hydrophobicity of the copolymer increased with the increasing of DL-lactide/glycolide molar ratio. In vitro dissolution studies with two different hydrophobic drugs (5-fluorouracil and indomethacin) were performed to study the effect of DL-lactide/glycolide molar ratio on drug release and to elucidate drug release mechanism. The release mechanism for hydrophilic 5-fluorouracil was diffusion-controlled, while hydrophobic indomethacin showed an biphasic profile comprising of an initial diffusion-controlled stage followed by the hydrogel erosion-dominated stage. The effect of DL-lactide/glycolide molar ratio on drug release seemed to be dependent on the drug release mechanism. It has less effect on the drug release during the diffusion-controlled stage, but significantly affected drug release during the hydrogel erosion-controlled stage. Compared with ReGel system, the synthesized copolymers showed a higher gelation temperature and longer period of drug release. The copolymers can solubilize the hydrophobic indomethacin and the solubility (13.7 mg/ml) was increased 3425-fold compared to that in water (4 microg/ml, 25 degrees C). Two methods of physical mixing method and solvent evaporation method were used for drug solubilization and the latter method showed higher solubilization efficiency.

Poly(trimethylene carbonate)/Poly(malic acid) Amphiphilic Diblock Copolymers as Biocompatible Nanoparticles.

PubMed

Barouti, Ghislaine; Khalil, Ali; Orione, Clement; Jarnouen, Kathleen; Cammas-Marion, Sandrine; Loyer, Pascal; Guillaume, Sophie M

2016-02-18

Amphiphilic polycarbonate-poly(hydroxyalkanoate) diblock copolymers, namely, poly(trimethylene carbonate) (PTMC)-b-poly(β-malic acid) (PMLA), are reported for the first time. The synthetic strategy relies on commercially available catalysts and initiator. The controlled ring-opening polymerization (ROP) of trimethylene carbonate (TMC) catalyzed by the organic guanidine base 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), associated with iPrOH as an initiator, provided iPrO-PTMC-OH, which served as a macroinitiator in the controlled ROP of benzyl β-malolactonate (MLABe) catalyzed by the neodymium triflate salt (Nd(OTf)3). The resulting hydrophobic iPrO-PTMC-b-PMLABe-OH copolymers were then hydrogenolyzed into the parent iPrO-PTMC-b-PMLA-OH copolymers. A range of well-defined copolymers, featuring different sizes of segments (Mn,NMR up to 9300 g mol(-1) ; ÐM =1.28-1.40), were thus isolated in gram quantities, as evidenced by NMR spectroscopy, size exclusion chromatography, thermogravimetric analysis, differential scanning calorimetry, and contact angle analyses. Subsequently, PTMC-b-PMLA copolymers with different hydrophilic weight fractions (11-75 %) self-assembled in phosphate-buffered saline upon nanoprecipitation into well-defined nano-objects with Dh =61-176 nm, a polydispersity index <0.25, and a negative surface charge, as characterized by dynamic light scattering and zeta-potential analyses. In addition, these nanoparticles demonstrated no significant effect on cell viability at low concentrations, and a very low cytotoxicity at high concentrations only for PTMC-b-PMLA copolymers exhibiting hydrophilic fractions over 47 %, thus illustrating the potential of these copolymers as promising nanoparticles. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aggregate morphologies of amphiphilic ABC triblock copolymer in dilute solution using self-consistent field theory.

PubMed

Wang, Rong; Tang, Ping; Qiu, Feng; Yang, Yuliang

2005-09-15

The complex microstructures of amphiphilic ABC linear triblock copolymers in which one of the end blocks is relatively short and hydrophilic, and the other two blocks B and C are hydrophobic in a dilute solution, have been investigated by the real-space implementation of self-consistent field theory (SCFT) in two dimensions (2D). In contrast to diblock copolymers in solution, the aggregation of triblock copolymers are more complicated due to the presence of the second hydrophobic blocks and, hence, big ranges of parameter space controlling the morphology. By tailoring the hydrophobic degree and its difference between the blocks B and C, the various shapes of vesicles, circlelike and linelike micelles possibly corresponding to spherelike, and rodlike micelles in 3D, and especially, peanutlike micelles not found in diblock copolymers are observed. The transition from vesicles to circlelike micelles occurs with increasing the hydrophobicity of the blocks B and C, while the transition from circlelike micelles to linelike micelles or from the mixture of micelles and vesicles to the long linelike micelles takes place when the repulsive interaction of the end hydrophobic block C is stronger than that of the middle hydrophobic block B. Furthermore, it is favorable for dispersion of the block copolymer in the solvent into aggregates when the repulsion of the solvent to the end hydrophobic block is larger than that of the solvent to the middle hydrophobic block. Especially when the bulk block copolymers are in a weak segregation regime, the competition between the microphase separation and macrophase separation exists and the large compound micelle-like aggregates are found due to the macrophase separation with increasing the hydrophobic degree of blocks B and C, which is absent in diblock copolymer solution. The simulation results successfully reproduce the existing experimental ones.

Random and Block Sulfonated Polyaramides as Advanced Proton Exchange Membranes

DOE PAGES

Kinsinger, Corey L.; Liu, Yuan; Liu, Feilong; ...

2015-10-09

We present here the experimental and computational characterization of two novel copolyaramide proton exchange membranes (PEMs) with higher conductivity than Nafion at relatively high temperatures, good mechanical properties, high thermal stability, and the capability to operate in low humidity conditions. The random and block copolyaramide PEMs are found to possess different ion exchange capacities (IEC) in addition to subtle structural and morphological differences, which impact the stability and conductivity of the membranes. SAXS patterns indicate the ionomer peak for the dry block copolymer resides at q = 0.1 Å –1, which increases in amplitude when initially hydrated to 25% relativemore » humidity, but then decrease in amplitude with additional hydration. This pattern is hypothesized to signal the transport of water into the polymer matrix resulting in a reduced degree of phase separation. Coupled to these morphological changes, the enhanced proton transport characteristics and structural/mechanical stability for the block copolymer are hypothesized to be primarily due to the ordered structure of ionic clusters that create connected proton transport pathways while reducing swelling upon hydration. Interestingly, the random copolymer did not possess an ionomer peak at any of the hydration levels investigated, indicating a lack of any significant ionomer structure. The random copolymer also demonstrated higher proton conductivity than the block copolymer, which is opposite to the trend normally seen in polymer membranes. However, it has reduced structural/mechanical stability as compared to the block copolymer. In conclusion, this reduction in stability is due to the random morphology formed by entanglements of polymer chains and the adverse swelling characteristics upon hydration. Therefore, the block copolymer with its enhanced proton conductivity characteristics, as compared to Nafion, and favorable structural/mechanical stability, as compared to the random copolymer, represents a viable alternative to current proton exchange membranes.« less

Thermosensitive mPEG-b-PA-g-PNIPAM comb block copolymer micelles: effect of hydrophilic chain length and camptothecin release behavior.

PubMed

Yang, Xiao-Li; Luo, Yan-Ling; Xu, Feng; Chen, Ya-Shao

2014-02-01

Block copolymer micelles are extensively used as drug controlled release carriers, showing promising application prospects. The comb or brush copolymers are especially of great interest, whose densely-grafted side chains may be important for tuning the physicochemical properties and conformation in selective solvents, even in vitro drug release. The purpose of this work was to synthesize novel block copolymer combs via atom transfer radical polymerization, to evaluate its physicochemical features in solution, to improve drug release behavior and to enhance the bioavailablity, and to decrease cytotoxicity. The physicochemical properties of the copolymer micelles were examined by modulating the composition and the molecular weights of the building blocks. A dialysis method was used to load hydrophobic camptothecin (CPT), and the CPT release and stability were detected by UV-vis spectroscopy and high-performance liquid chromatography, and the cytotoxicity was evaluated by MTT assays. The copolymers could self-assemble into well-defined spherical core-shell micelle aggregates in aqueous solution, and showed thermo-induced micellization behavior, and the critical micelle concentration was 2.96-27.64 mg L(-1). The micelles were narrow-size-distribution, with hydrodynamic diameters about 128-193 nm, depending on the chain length of methoxy polyethylene glycol (mPEG) blocks and poly(N-isopropylacrylamide) (PNIPAM) graft chains or/and compositional ratios of mPEG to PNIPAM. The copolymer micelles could stably and effectively load CPT but avoid toxicity and side-effects, and exhibited thermo-dependent controlled and targeted drug release behavior. The copolymer micelles were safe, stable and effective, and could potentially be employed as CPT controlled release carriers.

A pH- and temperature-responsive bioresorbable injectable hydrogel based on polypeptide block copolymers for the sustained delivery of proteins in vivo.

PubMed

Turabee, Md Hasan; Thambi, Thavasyappan; Duong, Huu Thuy Trang; Jeong, Ji Hoon; Lee, Doo Sung

2018-02-27

Sustained delivery of protein therapeutics is limited owing to the fragile nature of proteins. Despite its great potential, delivery of proteins without any loss of bioactivity remains a challenge in the use of protein therapeutics in the clinic. To surmount this shortcoming, we report a pH- and temperature-responsive in situ-forming injectable hydrogel based on comb-type polypeptide block copolymers for the controlled delivery of proteins. Polypeptide block copolymers, composed of hydrophilic polyethylene glycol (PEG), temperature-responsive poly(γ-benzyl-l-glutamate) (PBLG), and pH-responsive oligo(sulfamethazine) (OSM), exhibit pH- and temperature-induced sol-to-gel transition behavior in aqueous solutions. Polypeptide block copolymers were synthesized by combining N-carboxyanhydride-based ring-opening polymerization and post-functionalization of the chain-end using N-hydroxy succinimide ester activated OSM. The physical properties of polypeptide-based hydrogels were tuned by varying the composition of temperature- and pH-responsive PBLG and OSM in block copolymers. Polypeptide block copolymers were non-toxic to human embryonic kidney cells at high concentrations (2000 μg mL -1 ). Subcutaneous administration of polypeptide block copolymer sols formed viscoelastic gel instantly at the back of Sprague-Dawley (SD) rats. The in vivo gels exhibited sustained degradation and were found to be bioresorbable in 6 weeks without any noticeable inflammation at the injection site. Anionic characteristics of hydrogels allow efficient loading of a cationic model protein, lysozyme, through electrostatic interaction. Lysozyme-loaded polypeptide block copolymer sols readily formed a viscoelastic gel in vivo and sustained lysozyme release for at least a week. Overall, the results demonstrate an elegant approach to control the release of certain charged proteins and open a myriad of therapeutic possibilities in protein therapeutics.

Molecular origin of photovoltaic performance in donor- block-acceptor all-conjugated block copolymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Kendall A.; Lin, Yen -Hao; Mok, Jorge W.

All-conjugated block copolymers may be an effective route to self-assembled photovoltaic devices, but we lack basic information on the relationship between molecular characteristics and photovoltaic performance. Here, we synthesize a library of poly(3-hexylthiophene) (P3HT) block poly((9,9-dialkylfluorene)-2,7-diyl-alt-[4,7-bis(alkylthiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (PFTBT) donor- block-acceptor all-conjugated block copolymers and carry out a comprehensive study of processing conditions, crystallinity, domain sizes, and side-chain structure on photovoltaic device performance. We find that all block copolymers studied exhibit an out-of-plane crystal orientation after deposition, and on thermal annealing at high temperatures the crystal orientation flips to an in-plane orientation. By varying processing conditions on polymer photovoltaic devices, we showmore » that the crystal orientation has only a modest effect (15-20%) on photovoltaic performance. The addition of side-chains to the PFTBT block is found to decrease photovoltaic power conversion efficiencies by at least an order of magnitude. Through grazing-incidence X-ray measurements we find that the addition of side-chains to the PFTBT acceptor block results in weak segregation and small (< 10 nm) block copolymer self-assembled donor and acceptor domains. This work is the most comprehensive to date on all-conjugated block copolymer systems and suggests that photovoltaic performance of block copolymers depends strongly on the miscibility of donor and acceptor blocks, which impacts donor and acceptor domain sizes and purity. Lastly, strategies for improving the device performance of block copolymer photovoltaics should seek to increase segregation between donor and acceptor polymer domains.« less

Controlled disulfonated poly(arylene ether sulfone) multiblock copolymers for direct methanol fuel cells.

PubMed

Li, Qing; Chen, Yu; Rowlett, Jarrett R; McGrath, James E; Mack, Nathan H; Kim, Yu Seung

2014-04-23

Structure-property-performance relationships of disulfonated poly(arylene ether sulfone) multiblock copolymer membranes were investigated for their use in direct methanol fuel cell (DMFC) applications. Multiple series of reactive polysulfone, polyketone, and polynitrile hydrophobic block segments having different block lengths and molecular composition were synthesized and reacted with a disulfonated poly(arylene ether sulfone) hydrophilic block segment by a coupling reaction. Large-scale morphological order of the multiblock copolymers evolved with the increase of block size that gave notable influence on mechanical toughness, water uptake, and proton/methanol transport. Chemical structural changes of the hydrophobic blocks through polar group, fluorination, and bisphenol type allowed further control of the specific properties. DMFC performance was analyzed to elicit the impact of structural variations of the multiblock copolymers. Finally, DMFC performances of selected multiblock copolymers were compared against that of the industrial standard Nafion in the DMFC system.

Nonlinear optical measurements of conducting copolymers of aniline under CW laser excitation

NASA Astrophysics Data System (ADS)

Pramodini, S.; Poornesh, P.

2015-08-01

Synthesis and measurements of third-order optical nonlinearity and optical limiting of conducting copolymers of aniline are presented. Single beam z-scan technique was employed for the nonlinear optical studies. Continuous wave He-Ne laser operating at 633 nm was used as the source of excitation. Copolymer samples exhibited reverse saturable absorption (RSA) process. The nonlinear refraction studies depict that the copolymers exhibit self-defocusing property. The estimated values of βeff, n2 and χ(3) were found to be of the order of 10-2 cm/W, 10-5 esu and 10-7 esu respectively. Self-diffraction rings were observed due to refractive index change when exposed to the laser beam. A good optical limiting and clamping of power of ∼0.9 mW and ∼0.05 mW was observed. Therefore, copolymers of aniline emerge as a potential candidate for photonic device applications.

Effect of matrix chemical heterogeneity on effective filler interactions in model polymer nanocomposites

NASA Astrophysics Data System (ADS)

Hall, Lisa; Schweizer, Kenneth

2010-03-01

The microscopic Polymer Reference Interaction Site Model theory has been applied to spherical and rodlike fillers dissolved in three types of chemically heterogeneous polymer melts: alternating AB copolymer, random AB copolymers, and an equimolar blend of two homopolymers. In each case, one monomer species adsorbs more strongly on the filler mimicking a specific attraction, while all inter-monomer potentials are hard core which precludes macrophase or microphase separation. Qualitative differences in the filler potential-of-mean force are predicted relative to the homopolymer case. The adsorbed bound layer for alternating copolymers exhibits a spatial moduluation or layering effect but is otherwise similar to that of the homopolymer system. Random copolymers and the polymer blend mediate a novel strong, long-range bridging interaction between fillers at moderate to high adsorption strengths. The bridging strength is a non-monotonic function of random copolymer composition, reflecting subtle competing enthalpic and entropic considerations.

Design, synthesis, and characterization of lightly sulfonated multigraft acrylate-based copolymer superelastomers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Misichronis, Konstantinos; Wang, Weiyu; Cheng, Shiwang

2018-01-29

Multigraft copolymer superelastomers consisting of a poly(n-butyl acrylate) backbone and polystyrene side chains were synthesized and the viscoelastic properties of the non-sulfonated and sulfonated final materials were investigated using extensional rheology (SER3). The non-linear viscoelastic experiments revealed significantly increased true stresses (up to 10 times higher) after sulfonating only 2–3% of the copolymer while the materials maintained high elongation (<700%). The linear viscoelastic experiments showed that the storage and loss modulus are increased by sulfonation and that the copolymers can be readily tuned and further improved by increasing the number of branching points and the molecular weight of the backbone.more » Here, in this way, we show that by tuning not only the molecular characteristics of the multigraft copolymers but also their architecture and chemical interaction, we can acquire thermoplastic superelastomer materials with desired viscoelastic properties.« less

Arbitrary lattice symmetries via block copolymer nanomeshes

PubMed Central

Majewski, Pawel W.; Rahman, Atikur; Black, Charles T.; Yager, Kevin G.

2015-01-01

Self-assembly of block copolymers is a powerful motif for spontaneously forming well-defined nanostructures over macroscopic areas. Yet, the inherent energy minimization criteria of self-assembly give rise to a limited library of structures; diblock copolymers naturally form spheres on a cubic lattice, hexagonally packed cylinders and alternating lamellae. Here, we demonstrate multicomponent nanomeshes with any desired lattice symmetry. We exploit photothermal annealing to rapidly order and align block copolymer phases over macroscopic areas, combined with conversion of the self-assembled organic phase into inorganic replicas. Repeated photothermal processing independently aligns successive layers, providing full control of the size, symmetry and composition of the nanoscale unit cell. We construct a variety of symmetries, most of which are not natively formed by block copolymers, including squares, rhombuses, rectangles and triangles. In fact, we demonstrate all possible two-dimensional Bravais lattices. Finally, we elucidate the influence of nanostructure on the electrical and optical properties of nanomeshes. PMID:26100566

Synthesis, characterization, and rheological studies of model water-soluble graft copolymers for application in enhanced oil recovery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, L.S.

1982-12-01

Model water-soluble graft copolymers have been synthesized with acrylamide as the major grafting monomer and dextran as the substrate in order to define more clearly the structural parameters that are important in enhanced oil recovery applications. The structures of the model graft copolymer samples were studied by aqueous size exclusion chromatography, viscometry, elemental analysis, and selective hydrolysis of the graft copolymer backbone. The grafting systems with selected grafting monomers included Fe(II)/H/sub 2/O/sub 2/ with acrylamide, and Ce(IV)/HNO/sub 3/ with acrylamide, acrylamide/2-acrylamido-2-meth propane sulfonic acid, or acrylamide/diacetone acrylamide. The viscosity and pseudoplasticity of the resulting graft copolymers were affected by bothmore » total molecular weight and length of grafted chains; however, the latter was apparently more important when behavior was compared to linear counterparts.« less

Effects of PEO-PPO-PEO Triblock Copolymers on Phospholipid Membrane Integrity under Osmotic Stress

PubMed Central

Wang, Jia-Yu; Chin, Jaemin; Marks, Jeremy D.; Lee, Ka Yee C.

2010-01-01

The effects of PEO-PPO-PEO triblock copolymers, mainly Poloxamer 188, on phospholipid membrane integrity under osmotic gradients were explored using giant unilamellar vesicles (GUVs). Fluorescence leakage assays showed two opposing effects of P188 on the structural integrity of GUVs depending on the duration of their incubation time. A two-state transition mechanism of interaction between the triblock copolymers and the phospholipid membrane is proposed: an adsorption (I) and an insertion (II) state. While the triblock copolymer in state I acts to moderately retard the leakage, their insertion in state II perturbs the lipid packing, thus increasing the membrane permeability. Our results suggest that the biomedical application of PEO-PPO-PEO triblock copolymers, either as cell membrane resealing agents or as accelerators for drug delivery, is directed by the delicate balance between these two states. PMID:20666423

Synthesis and morphology of hydroxyapatite/polyethylene oxide nanocomposites with block copolymer compatibilized interfaces

NASA Astrophysics Data System (ADS)

Lee, Ji Hoon; Shofner, Meisha

2012-02-01

In order to exploit the promise of polymer nanocomposites, special consideration should be given to component interfaces during synthesis and processing. Previous results from this group have shown that nanoparticles clustered into larger structures consistent with their native shape when the polymer matrix crystallinity was high. Therefore in this research, the nanoparticles are disguised from a highly-crystalline polymer matrix by cloaking them with a matrix-compatible block copolymer. Specifically, spherical and needle-shaped hydroxyapatite nanoparticles were synthesized using a block copolymer templating method. The block copolymer used, polyethylene oxide-b-polymethacrylic acid, remained on the nanoparticle surface following synthesis with the polyethylene oxide block exposed. These nanoparticles were subsequently added to a polyethylene oxide matrix using solution processing. Characterization of the nanocomposites indicated that the copolymer coating prevented the nanoparticles from assembling into ordered clusters and that the matrix crystallinity was decreased at a nanoparticle spacing of approximately 100 nm.

Addition of poly (propylene glycol) to multiblock copolymer to optimize siRNA delivery.

PubMed

Dai, Zhi; Arévalo, Maria T; Li, Junwei; Zeng, Mingtao

2014-01-01

Previous studies have examined different strategies for siRNA delivery with varying degrees of success. These include use of viral vectors, cationic liposomes, and polymers. Several copolymers were designed and synthesized based on blocks of poly(ethylene glycol) PEG, poly(propylene glycol) PPG, and poly(l-lysine). These were designated as P1, P2, and P3. We studied the copolymer self-assembly, siRNA binding, particle size, surface potential, architecture of the complexes, and siRNA delivery. Silencing of GFP using copolymer P3 to deliver GFP-specific siRNA to Neuro-2a cells expressing GFP was almost as effective as using Lipofectamine 2000, with minimal cytotoxicity. Thus, we have provided a new copolymer platform for siRNA delivery that we can continue to modify for improved delivery of siRNA in vitro and eventually in vivo.

Cyclic Multiblock Copolymers via Combination of Iterative Cu(0)-Mediated Radical Polymerization and Cu(I)-Catalyzed Azide-Alkyne Cycloaddition Reaction.

PubMed

Xiao, Lifen; Zhu, Wen; Chen, Jiqiang; Zhang, Ke

2017-02-01

Cyclic multiblock polymers with high-order blocks are synthesized via the combination of single-electron transfer living radical polymerization (SET-LRP) and copper-catalyzed azide-alkyne cycloaddition (CuAAC). The linear α,ω-telechelic multiblock copolymer is prepared via SET-LRP by sequential addition of different monomers. The SET-LRP approach allows well control of the block length and sequence as A-B-C-D-E, etc. The CuAAC is then performed to intramolecularly couple the azide and alkyne end groups of the linear copolymer and produce the corresponding cyclic copolymer. The block sequence and the cyclic topology of the resultant cyclic copolymer are confirmed by the characterization of 1 H nuclear magnetic resonance spectroscopy, gel permeation chromatography, Fourier transform infrared spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, self-assembly, and drug-loading capacity of well-defined cyclodextrin-centered drug-conjugated amphiphilic A(14)B(7) Miktoarm star copolymers based on poly(epsilon-caprolactone) and poly(ethylene glycol).

PubMed

Gou, Peng-Fei; Zhu, Wei-Pu; Shen, Zhi-Quan

2010-04-12

Novel drug-conjugated amphiphilic A(14)B(7) miktoarm star copolymers composed of 14 poly(epsilon-caprolactone) (PCL) arms and 7 poly(ethylene glycol) (PEG) arms with beta-cyclodextrin (beta-CD) as core moiety were synthesized by the combination of controlled ring-opening polymerization (CROP) and "click" chemistry. (1)H NMR, FT-IR, and SEC-MALLS analyses confirmed the well-defined A(14)B(7) miktoarm star architecture. These amphiphilic miktoarm star copolymers could self-assemble into multimorphological aggregates in aqueous solution, which were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). Moreover, the drug-loading efficiency and drug-encapsulation efficiency of the drug-conjugated miktoarm star copolymers were higher than those of the corresponding non-drug-conjugated miktoarm star copolymers.

Influence of Chirality in Ordered Block Copolymer Phases

NASA Astrophysics Data System (ADS)

Prasad, Ishan; Grason, Gregory

2015-03-01

Block copolymers are known to assemble into rich spectrum of ordered phases, with many complex phases driven by asymmetry in copolymer architecture. Despite decades of study, the influence of intrinsic chirality on equilibrium mesophase assembly of block copolymers is not well understood and largely unexplored. Self-consistent field theory has played a major role in prediction of physical properties of polymeric systems. Only recently, a polar orientational self-consistent field (oSCF) approach was adopted to model chiral BCP having a thermodynamic preference for cholesteric ordering in chiral segments. We implement oSCF theory for chiral nematic copolymers, where segment orientations are characterized by quadrupolar chiral interactions, and focus our study on the thermodynamic stability of bi-continuous network morphologies, and the transfer of molecular chirality to mesoscale chirality of networks. Unique photonic properties observed in butterfly wings have been attributed to presence of chiral single-gyroid networks, this has made it an attractive target for chiral metamaterial design.

Synthesis of ethylene-propylene rubber graft copolymers by borane approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chung, T.C.; Janvikul, W.; Bernard, R.

1994-01-01

This paper describes a new method to prepare graft copolymers which have an EP rubber backbone and several free radical polymerized polymers grafted thereto. The process involves hydroboration of commercial EPDM rubbers, such as poly(ethylene-co-propylene-co-1,4-hexadiene) and poly(ethylene-co-propylene-co-5-ethylidene-2-norbornene), with 9-borabicyclononane (9-BBN). The resulting secondary alkyl-9-BBN moieties in the EPDM copolymer were then exposed to oxygen in the presence of free radical polymerizable monomers. Under certain conditions, the selective autoxidation reaction of secondary alkyl-9-BBN took place to create desirable polymeric radicals which can in situ initiate free radical polymerization. High graft efficiency was observed with controllable copolymer compositions. The graft copolymer ofmore » EP-g-PMMA is used to show the chemistry as well as some of the physical properties.« less

Molecular Design of Sulfonated Triblock Copolymer Permselective Membranes

DTIC Science & Technology

2008-07-03

factors governing sorption and permeability ofphosphoorganic agents in PEM made of sulfonated triblock copolymers of styrene and lower olefins by means...membrane morphology at environmental conditions, and the membrane sorption and transport properties with respect to water and nerve gas simulant...and chemical factors governing sorption and permeability of phosphoorganic agents in PEM made of sulfonated triblock copolymers of styrene and lower

Characteristics of immobilized aminoacylase from Aspergillus oryzae on macroporous copolymers.

PubMed

He, B L; Jiang, P; Qiu, Y B

1990-01-01

Aminoacylase from Aspergillus oryzae was adsorbed on functionallized macroporous copolymers where the enzyme showed excellent catalyzing activity and operation stability. Various factors which effect the activity of the immobilized aminoacylase such as temperature, pH and ionic strength were investigated. The continuous operation of the enzyme immobilized on macroporous copolymers was compared with that of the enzyme immobilized on DEAE-Sephadex.

Method for making block siloxane copolymers

DOEpatents

Butler, N.L.; Jessop, E.S.; Kolb, J.R.

1981-02-25

A method for synthesizing block polysiloxane copolymers is disclosed. Diorganoscyclosiloxanes and an end-blocking compound are interacted in the presence of a ring opening polymerization catalyst, producing a blocked prepolymer. The prepolymer is then interacted with a silanediol, resulting in condensation polymerization of the prepolymers. A second end-blocking compound is subsequently introduced to end-cap the polymers and copolymers formed from the condensation polymerization.

Method for making block siloxane copolymers

DOEpatents

Butler, Nora; Jessop, Edward S.; Kolb, John R.

1982-01-01

A method for synthesizing block polysiloxane copolymers. Diorganoscyclosiloxanes and an end-blocking compound are interacted in the presence of a ring opening polymerization catalyst, producing a blocked prepolymer. The prepolymer is then interacted with a silanediol, resulting in condensation polymerization of the prepolymers. A second end-blocking compound is subsequently introduced to end-cap the polymers and copolymers formed from the condensation polymerization.

[Antiviral and immunostimulating effect of maleic anhydride copolymers in experimental neuroviral infections].

PubMed

Davydova, A A; Stotskaia, L L; Berezina, L K; Osipova, L V; Barinskiĭ, I F

1986-01-01

The virus-inhibiting and immunostimulating activity of Soviet preparations, maleic anhydride copolymers, was demonstrated in alpha-, flavi-, and bunyavirus infections. Positive results were obtained in subcutaneous and intraperitoneal inoculations of the preparations used in prophylactic and therapeutic-prophylactic schedules. Stimulation of vaccination immunity was observed after combined use of copolymers and the vaccine against Eastern equine encephalomyelitis.

21 CFR 177.1050 - Acrylonitrile/styrene copoly-mer modified with butadiene/styrene elastomer.

Code of Federal Regulations, 2013 CFR

2013-04-01

... chapter as Type VI-B under conditions for use E, F, or G described in table 2 of § 176.170(c) of this... copol-ymer is extracted with 250 milliliters spectral grade n-heptane at reflux temperature for 2 hours. (e) Accelerated extraction end test. The modified copolymer shall yield acrylonitrile monomer not in...

21 CFR 177.1050 - Acrylonitrile/styrene copoly-mer modified with butadiene/styrene elastomer.

Code of Federal Regulations, 2011 CFR

2011-04-01

... chapter as Type VI-B under conditions for use E, F, or G described in table 2 of § 176.170(c) of this... copol-ymer is extracted with 250 milliliters spectral grade n-heptane at reflux temperature for 2 hours. (e) Accelerated extraction end test. The modified copolymer shall yield acrylonitrile monomer not in...

21 CFR 177.1050 - Acrylonitrile/styrene copoly-mer modified with butadiene/styrene elastomer.

Code of Federal Regulations, 2012 CFR

2012-04-01

... chapter as Type VI-B under conditions for use E, F, or G described in table 2 of § 176.170(c) of this... copol-ymer is extracted with 250 milliliters spectral grade n-heptane at reflux temperature for 2 hours. (e) Accelerated extraction end test. The modified copolymer shall yield acrylonitrile monomer not in...

Block Copolymer Membranes for Biofuel Purification

NASA Astrophysics Data System (ADS)

Evren Ozcam, Ali; Balsara, Nitash

2012-02-01

Purification of biofuels such as ethanol is a matter of considerable concern as they are produced in complex multicomponent fermentation broths. Our objective is to design pervaporation membranes for concentrating ethanol from dilute aqueous mixtures. Polystyrene-b-polydimethylsiloxane-b-polystyrene block copolymers were synthesized by anionic polymerization. The polydimethylsiloxane domains provide ethanol-transporting pathways, while the polystyrene domains provide structural integrity for the membrane. The morphology of the membranes is governed by the composition of the block copolymer while the size of the domains is governed by the molecular weight of the block copolymer. Pervaporation data as a function of these two parameters will be presented.

Radical-initiated controlled synthesis of homo- and copolymers based on acrylonitrile

NASA Astrophysics Data System (ADS)

Grishin, D. F.; Grishin, I. D.

2015-07-01

Data on the controlled synthesis of polyacrylonitrile and acrylonitrile copolymers with other (meth)acrylic and vinyl monomers upon radical initiation and metal complex catalysis are analyzed. Primary attention is given to the use of metal complexes for the synthesis of acrylonitrile-based (co)polymers with defined molecular weight and polydispersity in living mode by atom transfer radical polymerization. The prospects for using known methods of controlled synthesis of macromolecules for the preparation of acrylonitrile homo- and copolymers as carbon fibre precursors are estimated. The major array of published data analyzed in the review refers to the last decade. The bibliography includes 175 references.

Ultrahigh-Density Nanowire Arrays Grown in Self-Assembled Diblock Copolymer Templates

NASA Astrophysics Data System (ADS)

Thurn-Albrecht, T.; Schotter, J.; Kästle, G. A.; Emley, N.; Shibauchi, T.; Krusin-Elbaum, L.; Guarini, K.; Black, C. T.; Tuominen, M. T.; Russell, T. P.

2000-12-01

We show a simple, robust, chemical route to the fabrication of ultrahigh-density arrays of nanopores with high aspect ratios using the equilibrium self-assembled morphology of asymmetric diblock copolymers. The dimensions and lateral density of the array are determined by segmental interactions and the copolymer molecular weight. Through direct current electrodeposition, we fabricated vertical arrays of nanowires with densities in excess of 1.9 × 1011 wires per square centimeter. We found markedly enhanced coercivities with ferromagnetic cobalt nanowires that point toward a route to ultrahigh-density storage media. The copolymer approach described is practical, parallel, compatible with current lithographic processes, and amenable to multilayered device fabrication.

Oligosaccharide/silicon-containing block copolymers with 5 nm features for lithographic applications.

PubMed

Cushen, Julia D; Otsuka, Issei; Bates, Christopher M; Halila, Sami; Fort, Sébastien; Rochas, Cyrille; Easley, Jeffrey A; Rausch, Erica L; Thio, Anthony; Borsali, Redouane; Willson, C Grant; Ellison, Christopher J

2012-04-24

Block copolymers demonstrate potential for use in next-generation lithography due to their ability to self-assemble into well-ordered periodic arrays on the 3-100 nm length scale. The successful lithographic application of block copolymers relies on three critical conditions being met: high Flory-Huggins interaction parameters (χ), which enable formation of <10 nm features, etch selectivity between blocks for facile pattern transfer, and thin film self-assembly control. The present paper describes the synthesis and self-assembly of block copolymers composed of naturally derived oligosaccharides coupled to a silicon-containing polystyrene derivative synthesized by activators regenerated by electron transfer atom transfer radical polymerization. The block copolymers have a large χ and a low degree of polymerization (N) enabling formation of 5 nm feature diameters, incorporate silicon in one block for oxygen reactive ion etch contrast, and exhibit bulk and thin film self-assembly of hexagonally packed cylinders facilitated by a combination of spin coating and solvent annealing techniques. As observed by small angle X-ray scattering and atomic force microscopy, these materials exhibit some of the smallest block copolymer features in the bulk and in thin films reported to date.

Synthesis of biocompatible poly(ɛ-caprolactone)- block-poly(propylene adipate) copolymers appropriate for drug nanoencapsulation in the form of core-shell nanoparticles

PubMed Central

Nanaki, Stavroula G; Pantopoulos, Kostas; Bikiaris, Dimitrios N

2011-01-01

Poly(propylene adipate)-block-poly(ɛ-caprolactone) copolymers were synthesized using a combination of polycondensation and ring-opening polymerization of ɛ-caprolactone in the presence of poly(propylene adipate). Gel permeation chromatography was used for molecular weight determination, whereas hydrogen-1 nuclear magnetic resonance and carbon-13 nuclear magnetic resonance spectroscopy were employed for copolymer characterization and composition evaluation. The copolymers were found to be block while their composition was similar to the feeding ratio. They formed semicrystalline structures, while only poly(ɛ-caprolactone) formed crystals, as shown by wide angle X-ray diffraction. Differential scanning calorimetry data suggest that the melting point and heat of fusion of copolymers decreased by increasing the poly(propylene adipate) amount. The synthesized polymers exhibited low cytotoxicity and were used to encapsulate desferrioxamine, an iron-chelating drug. The desferrioxamine nanoparticles were self-assembled into core shell structures, had mean particle size <250 nm, and the drug remained in crystalline form. Further studies revealed that the dissolution rate was mainly related to the melting temperature, as well as to the degree of crystallinity of copolymers. PMID:22162656

Probing the Effect of Molecular Nonuniformity in Directed Self-Assembly of Diblock Copolymers in Nanoconfined Space.

PubMed

Pitet, Louis M; Alexander-Moonen, Els; Peeters, Emiel; Druzhinina, Tamara S; Wuister, Sander F; Lynd, Nathaniel A; Meijer, E W

2015-10-27

Various complex self-assembled morphologies of lamellar- and cylinder-forming block copolymers comprising poly(dimethylsiloxane)-b-polylactide (PDMS-b-PLA) confined in cylindrical channels were generated. Combining top-down lithography with bottom-up block copolymer self-assembly grants access to morphologies that are otherwise inaccessible with the bulk materials. Channel diameter (D) was systematically varied with four diblock copolymers having different compositions and bulk domain spacing (L0), corresponding to a range of frustration ratios (D/L0 from 2 to 4). Excessive packing frustration imposed by the channels leads to contorted domains. The resulting morphologies depend strongly on both D/L0 and copolymer composition. Under several circumstances, mixtures of complex morphologies were observed, which hypothetically arise from the severe sensitivity to D/L0 combined with the inherent compositional/molar mass dispersities associated with the nonuniform synthetic materials and silicon templates. Stochastic calculations offer compelling support for the hypothesis, and tractable pathways toward solving this apparent conundrum are proposed. The materials hold great promise for next-generation nanofabrication to address several emerging technologies, offering significantly enhanced versatility to basic diblock copolymers as templates for fabricating complex nanoscale objects.

Selective adsorption of Pb (II) ions by amylopectin-g-poly (acrylamide-co-acrylic acid): A bio-degradable graft copolymer.

PubMed

Sasmal, Dinabandhu; Maity, Jayanta; Kolya, Haradhan; Tripathy, Tridib

2017-04-01

Amylopectin-g-poly (acrylamide-co-acrylic acid) [AP-g-poly (AM-co-AA)] was synthesised in water medium by using potassium perdisulphate as an initiator. The graft copolymer was characterized by molecular weight determination by size exclusion chromatography (SEC), fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) spectroscopy, scanning electron microscope (SEM) studies, thermal analysis, measurement of neutralisation equivalent and biodegradation studies. The graft copolymer was used for Pb (II) ion removal from aqueous solution. The Pb (II) ion removal capacity of the graft copolymer was also compared with another laboratory developed graft copolymer Amylopectin-g-poly (acrylamide) (AP-g-PAM). Both the graft copolymers were also used for the competitive metal ions removal with Pb (II)/Cd (II), Pb (II)/Zn (II), Pb (II)/Ni (II), Pb (II)/Cu (II) pairs separately under similar conditions. AP-g-poly (AM-co-AA) showed better Pb (II) ion adsorbing power over AP-g-PAM and also much selective towards Pb (II) ions. The adsorption follows a second order rate equation and Langmuir isotherm model. Copyright © 2017 Elsevier B.V. All rights reserved.

Rapid Ordering in “Wet Brush” Block Copolymer/Homopolymer Ternary Blends

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doerk, Gregory S.; Yager, Kevin G.

The ubiquitous presence of thermodynamically unfavored but kinetically trapped topological defects in nanopatterns formed via self-assembly of block copolymer thin films may prevent their use for many envisioned applications. Here, we demonstrate that lamellae patterns formed by symmetric polystyrene-block-poly(methyl methacrylate) diblock copolymers self-assemble and order extremely rapidly when the diblock copolymers are blended with low molecular weight homopolymers of the constituent blocks. Being in the “wet brush” regime, the homopolymers uniformly distribute within their respective self-assembled microdomains, preventing increases in domain widths. An order-of-magnitude increase in topological grain size in blends over the neat (unblended) diblock copolymer is achieved withinmore » minutes of thermal annealing as a result of the significantly higher power law exponent for ordering kinetics in the blends. Moreover, the blends are demonstrated to be capable of rapid and robust domain alignment within micrometer-scale trenches, in contrast to the corresponding neat diblock copolymer. Furthermore, these results can be attributed to the lowering of energy barriers associated with domain boundaries by bringing the system closer to an order–disorder transition through low molecular weight homopolymer blending.« less

Sustainable thermoplastic elastomers derived from cellulose, fatty acid and furfural via ATRP and click chemistry.

PubMed

Yu, Juan; Lu, Chuanwei; Wang, Chunpeng; Wang, Jifu; Fan, Yimin; Chu, Fuxiang

2017-11-15

Cellulose-based thermoplastic elastomers (TPEs) have attracted considerable attention because of their rigid backbone, good mechanical properties, renewable nature and abundance. In the present study, sustainable TPEs based on ethyl cellulose (EC), fatty acid and furfural were generated by the combination of ATRP and "click chemistry". To fabricate sustainable TPEs with higher toughness, a range of polymers, including mono random-copolymer poly(tetrahydrofurfuryl methacrylate-co-lauryl methacrylate) (P(THFMA-co-LMA), dual polymer side chains PTHFMA and PLMA, and mono-block copolymer PTHFMA-b-PLMA, were designed as side chains to fabricate EC brush copolymers with random, dual or block side chain architectures using the "grafting from" and "grafting onto" methods. The multi-armed structures, chemical compositions and phase separation of these EC brush copolymers were confirmed by FT-IR, 1 H NMR, GPC, DSC, TEM and SEM. Overall, three types of EC brush copolymers all exhibited the desired mechanical properties of TPEs. In addition, the EC brush copolymers with dual/block side chain architectures showed higher tensile strength than that of the random polymers with similar compositions. Copyright © 2017. Published by Elsevier Ltd.

Patterning at the 10 nanometer length scale using a strongly segregating block copolymer thin film and vapor phase infiltration of inorganic precursors

DOE PAGES

Choi, Jonathan W.; Li, Zhaodong; Black, Charles T.; ...

2016-05-04

Here in this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order–disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns andmore » registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. Lastly, we conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes.« less

Patterning at the 10 nanometer length scale using a strongly segregating block copolymer thin film and vapor phase infiltration of inorganic precursors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Jonathan W.; Li, Zhaodong; Black, Charles T.

Here in this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order–disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns andmore » registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. Lastly, we conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes.« less

Tunable Encapsulation Structure of Block Copolymer Coated Single-Walled Carbon Nanotubes in Aqueous Solution

DOE PAGES

Han, Youngkyu; Ahn, Suk-Kyun; Zhang, Zhe; ...

2015-05-15

The nano-sized and shape-tunable molecular building blocks can provide great opportunities for the fabrication of precisely controlled nanostructures. In this work, we have fabricated a molecular building block of single-walled carbon nanotubes (SWNTs) coated by PPO-PEO-PPO block copolymers whose encapsulation structure can be controlled via temperature or addition of small molecules. The structure and optical properties of SWNT-block copolymers have been investigated by small angle neutron scattering (SANS), ultraviolet-visible (UV-vis) spectroscopy, atomic force microscopy (AFM), and molecular dynamics (MD) simulation. The structure of the hydrated block copolymer layer surrounding SWNT can be controlled reversibly by varying temperature as well asmore » by irreversibly adding 5-methylsalicylic acid (5MS). Increasing hydrophobicity of the polymers with temperature and strong tendency of 5MS to interact with both block copolymers and orbitals of the SWNTs are likely to be responsible for the significant structural change of the block copolymer encapsulation layer, from loose corona shell to tightly encapsulating compact shell. These result shows an efficient and simple way to fabricate and manipulate carbon-based nano building blocks in aqueous systems with tunable structure.« less

Rapid Ordering in “Wet Brush” Block Copolymer/Homopolymer Ternary Blends

DOE PAGES

Doerk, Gregory S.; Yager, Kevin G.

2017-12-01

The ubiquitous presence of thermodynamically unfavored but kinetically trapped topological defects in nanopatterns formed via self-assembly of block copolymer thin films may prevent their use for many envisioned applications. Here, we demonstrate that lamellae patterns formed by symmetric polystyrene-block-poly(methyl methacrylate) diblock copolymers self-assemble and order extremely rapidly when the diblock copolymers are blended with low molecular weight homopolymers of the constituent blocks. Being in the “wet brush” regime, the homopolymers uniformly distribute within their respective self-assembled microdomains, preventing increases in domain widths. An order-of-magnitude increase in topological grain size in blends over the neat (unblended) diblock copolymer is achieved withinmore » minutes of thermal annealing as a result of the significantly higher power law exponent for ordering kinetics in the blends. Moreover, the blends are demonstrated to be capable of rapid and robust domain alignment within micrometer-scale trenches, in contrast to the corresponding neat diblock copolymer. Furthermore, these results can be attributed to the lowering of energy barriers associated with domain boundaries by bringing the system closer to an order–disorder transition through low molecular weight homopolymer blending.« less

Synthesis of biocompatible poly(ɛ-caprolactone)- block-poly(propylene adipate) copolymers appropriate for drug nanoencapsulation in the form of core-shell nanoparticles.

PubMed

Nanaki, Stavroula G; Pantopoulos, Kostas; Bikiaris, Dimitrios N

2011-01-01

Poly(propylene adipate)-block-poly(ɛ-caprolactone) copolymers were synthesized using a combination of polycondensation and ring-opening polymerization of ɛ-caprolactone in the presence of poly(propylene adipate). Gel permeation chromatography was used for molecular weight determination, whereas hydrogen-1 nuclear magnetic resonance and carbon-13 nuclear magnetic resonance spectroscopy were employed for copolymer characterization and composition evaluation. The copolymers were found to be block while their composition was similar to the feeding ratio. They formed semicrystalline structures, while only poly(ɛ-caprolactone) formed crystals, as shown by wide angle X-ray diffraction. Differential scanning calorimetry data suggest that the melting point and heat of fusion of copolymers decreased by increasing the poly(propylene adipate) amount. The synthesized polymers exhibited low cytotoxicity and were used to encapsulate desferrioxamine, an iron-chelating drug. The desferrioxamine nanoparticles were self-assembled into core shell structures, had mean particle size <250 nm, and the drug remained in crystalline form. Further studies revealed that the dissolution rate was mainly related to the melting temperature, as well as to the degree of crystallinity of copolymers.

Antibacterial activity, thermal stability and ab initio study of copolymer containing sulfobetaine and carboxybetaine groups

NASA Astrophysics Data System (ADS)

Tarannum, Nazia; Singh, Meenakshi; Yadav, Anil K.

2017-10-01

Here, we have explored the antibacterial activity, thermal stability and theoretical study of two copolymers that contain sulfobetaine and carboetaine moiety. Copolymers were synthesized based on Schiff base chemistry with generation of zwitterionic centres by nucleophilic addition of sultone/lactone. To predict and confirm the molecular structure of zwitterionic polyelectrolyte molecule, the theoretical study of structural features and other thermodynamic characteristics of copolymer constituents was obtained by ab initio calculations. Various parameters such as geometry optimization, energy calculations, frequency calculations and intrinsic reaction coefficient (IRC) are simulated using Hartree Fock (HF) method. The geometry optimizations are analyzed at HF/3-21 G default level of theory. The vibrational frequency is calculated via density functional theory (DFT)/B3LYP 6-31G*(d) level whose values are in accord with the experimental observed frequency. Both copolymers have been successfully assessed for antibacterial activity against Staphylococcus aureus and Pseudomonas aeuroginosa bacterial strains by disc diffusion method. The antibacterial study helped in evaluating zone of inhibition, minimum inhibitory concentration and minimum bactericidal concentration. Sulfobetaine copolymer is found to be more effective in curtailing the infection caused by bacteria as compared to carbobetaine.

Probing charge transfer complex states in organic solar cells using photocurrent spectroscopy

NASA Astrophysics Data System (ADS)

Moghe, Dhanashree; Adil, Danish; Kanimozhi, Catherine; Dutta, Gitesh; Patil, Satish; Guha, Suchismita

2013-03-01

Diketopyrrolopyrrole (DPP) containing copolymers-fullerene blends have gained a lot of interest in organic optoelectronics with a great potential in organic photovoltaics (OPVs). The interfacial charge transfer complex (CTC) states formed in donor-acceptor blended OPVs play a major role in the overall efficiency of the device. We investigate the spectral photocurrent characteristics of five DPP based copolymers; two of them being benzothiadiazole and carbazole -based statistical copolymers of DPP. These systems provide a wide range of bandgap energies ranging from ~ 1.4 to 1.7 eV. We use Fourier transform photocurrent spectroscopy (FTPS) and monochromatic photocurrent (PC) to identify the CTC states in these DPP copolymer -fullerene blends. The stability of the CTC state is found to be dependent on the band gap energy difference between the donor copolymer and the acceptor. We support our inferences from theoretical results obtained using density-functional theory (DFT) and time-dependent DFT for two DPP based copolymers The theoretical calculations reveal a higher contribution of the CTC states to the lowest excited state in the phenyl-based DPP monomer, which has a larger bandgap energy compared to the thiophene-based DPP system, in the presence of a fullerene molecule.

Nanostructures and surface hydrophobicity of self-assembled thermosets involving epoxy resin and poly(2,2,2-trifluoroethyl acrylate)-block-poly(ethylene oxide) amphiphilic diblock copolymer.

PubMed

Yi, Fangping; Zheng, Sixun; Liu, Tianxi

2009-02-19

Poly(2,2,2-trifluoroethyl acrylate)-block-poly(ethylene oxide) (PTFEA-b-PEO) amphiphilic diblock copolymer was synthesized via the reversible addition-fragmentation transfer polymerization of 2,2,2-triffluroethyl acrylate with dithiobenzoyl-terminated poly(ethylene oxide) as a chain-transfer agent. The amphiphilic diblock copolymer was incorporated into epoxy resin to prepare the nanostructured epoxy thermosets. The nanostructures were investigated by means of atomic force microscopy, small-angle X-ray scattering, and dynamic mechanical analysis. In terms of the miscibility of the subchains of the block copolymer with epoxy after and before curing reaction, it is judged that the formation of the nanostructures follows the mechanism of self-assembly. The static contact angle measurements indicate that the nanostructured thermosets containing PTFEA-b-PEO diblock copolymer displayed a significant enhancement in surface hydrophobicity as well as a reduction in surface free energy. The improvement in surface properties was ascribed to the enrichment of the fluorine-containing subchain (i.e., PTFEA block) of the amphiphilic diblock copolymer on the surface of the nanostructured thermosets, which was evidenced by surface atomic force microscopy and energy-dispersive X-ray spectroscopy.

Naproxen conjugated mPEG-PCL micelles for dual triggered drug delivery.

PubMed

Karami, Zahra; Sadighian, Somayeh; Rostamizadeh, Kobra; Parsa, Maliheh; Rezaee, Saeed

2016-04-01

A conjugate of the NSAIDs drug, naproxen, with diblock methoxy poly(ethylene glycol)-poly(ε-caprolactone) (mPEG-PCL) copolymer was synthesized by the reaction of copolymer with naproxen in the presence of dicyclohexylcarbodiimide and dimethylaminopyridine. The naproxen conjugated copolymers were characterized with different techniques including (1)HNMR, FTIR, and DSC. The naproxen conjugated mPEG-PCL copolymers were self-assembled into micelles in aqueous solution. The TEM analysis revealed that the micelles had the average size of about 80 nm. The release behavior of conjugated copolymer was investigated in two different media with the pH values of 7.4 and 5.2. In vitro release study showed that the drug release rate was dependant on pH as it was higher at lower pH compared to neutral pH. Another feature of the conjugated micelles was a more sustained release profile compared to the conjugated copolymer. The kinetic of the drug release from naproxen conjugated micelles under different values of pH was also investigated by different kinetic models such as first-order, Makoid-Banakar, Weibull, Logistic, and Gompertz. Copyright © 2015 Elsevier B.V. All rights reserved.

Defining donor and acceptor strength in conjugated copolymers

NASA Astrophysics Data System (ADS)

Hedström, Svante; Wang, Ergang; Persson, Petter

2017-03-01

The progress in efficiency of organic photovoltaic devices is largely driven by the development of new donor-acceptor (D-A) copolymers. The number of possible D-A combinations escalates rapidly with the ever-increasing number of donor and acceptor units, and the design process often involves a trial-and-error approach. We here present a computationally efficient methodology for the prediction of optical and electronic properties of D-A copolymers based on density functional theory calculations of donor- and acceptor-only homopolymers. Ten donors and eight acceptors are studied, as well as all of their 80 D-A copolymer combinations, showing absorption energies of 1.3-2.3 eV, and absorption strengths varying by up to a factor of 2.5. Focus lies on exhibited trends in frontier orbital energies, optical band gaps, and absorption intensities, as well as their relation to the molecular structure. Based on the results, we define the concept of donor and acceptor strength, and calculate this quantity for all investigated units. The light-harvesting capabilities of the 80 D-A copolymers were also assessed. This gives a valuable theoretical guideline to the design of D-A copolymers with the potential to reduce the synthesis efforts in the development of new polymers.

Facile synthesis of main-chain degradable block copolymers for performance enhanced dismantlable adhesion.

PubMed

Sato, Eriko; Hagihara, Takashi; Matsumoto, Akikazu

2012-04-01

Block copolymers consisting of readily degradable polyperoxides and non-degradable vinyl polymers as the block segments were successfully synthesized by reversible chain transfer catalyzed polymerization, which is one of living radical polymerization techniques. The block copolymers showed characteristic morphology and wettability being different from the polymer blends. When block copolymers containing polyperoxide and polymethacrylate blocks were heated below 150 °C, the polyperoxide blocks were completely degraded and the polymethacrylate blocks were recovered without degradation. Block copolymers containing a poly(2-ethylhexyl methacrylate) block were then investigated as a dismantlable adhesion material, which requires adequate bonding strength during use and easy debonding on demand. Among the several block copolymers, the one consisting of poly(2-ethylhexyl methacrylate) and polyperoxide from methyl sorbate (PPMS) (M(n) = 4900) exhibited good performance as a pressure-sensitive adhesive (PSA). After heating the test specimens in a temperature range from 60 to 100 °C, PSA performance, which was evaluated by 180° peel strength and shear holding power measurements, was significantly diminished. Especially, after heating at 100 °C for 1 h, spontaneous debonding of some test specimens was observed because of the evolution of volatile acetaldehyde from PPMS.

Highly conductive side chain block copolymer anion exchange membranes.

PubMed

Wang, Lizhu; Hickner, Michael A

2016-06-28

Block copolymers based on poly(styrene) having pendent trimethyl styrenylbutyl ammonium (with four carbon ring-ionic group alkyl linkers) or benzyltrimethyl ammonium groups with a methylene bridge between the ring and ionic group were synthesized by reversible addition-fragmentation radical (RAFT) polymerization as anion exchange membranes (AEMs). The C4 side chain polymer showed a 17% increase in Cl(-) conductivity of 33.7 mS cm(-1) compared to the benzyltrimethyl ammonium sample (28.9 mS cm(-1)) under the same conditions (IEC = 3.20 meq. g(-1), hydration number, λ = ∼7.0, cast from DMF/1-propanol (v/v = 3 : 1), relative humidity = 95%). As confirmed by small angle X-ray scattering (SAXS), the side chain block copolymers with tethered ammonium cations showed well-defined lamellar morphologies and a significant reduction in interdomain spacing compared to benzyltrimethyl ammonium containing block copolymers. The chemical stabilities of the block copolymers were evaluated under severe, accelerated conditions, and degradation was observed by (1)H NMR. The block copolymer with C4 side chain trimethyl styrenylbutyl ammonium motifs displayed slightly improved stability compared to that of a benzyltrimethyl ammonium-based AEM at 80 °C in 1 M NaOD aqueous solution for 30 days.

The promise of a specially-designed graft copolymer of acrylic acid onto cellulose as selective sorbent for heavy metal ions.

PubMed

Essawy, Hisham A; Mohamed, Magdy F; Ammar, Nabila S; Ibrahim, Hanan S

2017-10-01

A specially-designed graft copolymer of acrylic acid onto in-situ formed cellulose-fulvate hybrid showed privileged tendency for uptake of Pb(II) during competitive removal from a mixture containing Cd(II) and Ni(II) within 5min at pH 5. This novel trend is attributed mainly to the crowded high content of coordinating centers within the designed graft copolymer along with the acquired superabsorbency. This provides an outstanding tool to separate some metal ions selectively from mixtures containing multiple ions on kinetic basis. Thus, the designed graft copolymer structure exhibited superior efficiency that reached ∼95% for sole removal of Pb(II). Kinetic modeling for Pb(II) individual removal showed excellent fitting with a pseudo second-order model. Intraparticle diffusion model on the other hand ensured governance of boundary layer effect over diffusion during the removal process due to the superabsorbency feature of the graft copolymer. The experimental findings were described with models such as Freundlich, Langmuir, and Dubinin-Radushkevich. The Langmuir and Freundlich models showed convenience with the adsorption isotherm of Pb(II) onto the developed graft copolymer. Copyright © 2017 Elsevier B.V. All rights reserved.

Phase behavior of block copolymers in compressed carbon dioxide and as single domain-layer, nanolithographic etch resists for sub-10 nm pattern transfer

NASA Astrophysics Data System (ADS)

Chandler, Curran Matthew

Diblock copolymers have many interesting properties, which first and foremost include their ability to self-assemble into various ordered, regularly spaced domains with nanometer-scale feature sizes. The work in this dissertation can be logically divided into two parts -- the first and the majority of this work describes the phase behavior of certain block copolymer systems, and the second discusses real applications possible with block copolymer templates. Many compressible fluids have solvent-like properties dependent on fluid pressure and can be used as processing aids similar to liquid solvents. Here, compressed CO2 was shown to swell several thin homopolymer films, including polystyrene and polyisoprene, as measured by high pressure ellipsometry at elevated temperatures and pressures. The ellipsometric technique was modified to produce accurate data at these conditions through a custom pressure vessel design. The order-disorder transition (ODT) temperatures of several poly(styrene-bisoprene) diblock copolymers were also investigated by static birefringence when dilated with compressed CO2. Sorption of CO2 in each copolymer resulted in significant depressions of the ODT temperature as a function of fluid pressure, and the data above was used to estimate the quantitative amount of solvent in each of the diblock copolymers. These depressions were not shown to follow dilution approximation, and showed interesting, exaggerated scaling of the ODT at near-bulk polymer concentrations. The phase behavior of block copolymer surfactants was studied when blended with polymer or small molecule additives capable of selective hydrogen bonds. This work used small angle X-ray scattering (SAXS) to identify several low molecular weight systems with strong phase separation and ordered domains as small as 2--3 nanometers upon blending. One blend of a commercially-available surfactant with a small molecule additive was further developed and showed promise as a thin-film pattern transfer template. In this scenario, block copolymer thin films on domain thick with self-assembled feature sizes of only 6--7 nm were used as plasma etch resists. Here the block copolymer's pattern was successfully transferred into the underlying SiO2 substrate using CF4--based reactive ion etching. The result was a parallel, cylindrical nanostructure etched into SiO2.

RAFT-synthesized Graft Copolymers that Enhance pH-dependent Membrane Destabilization and Protein Circulation Times

PubMed Central

Crownover, Emily; Duvall, Craig L.; Convertine, Anthony; Hoffman, Allan S.; Stayton, Patrick S.

2012-01-01

Here we describe a new graft copolymer architecture of poly(propylacrylic acid) (polyPAA) that displays potent pH-dependent, membrane-destabilizing activity and in addition is shown to enhance protein blood circulation kinetics. PolyPAA containing a single telechelic alkyne functionality was prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization with an alkyne-functional chain transfer agent (CTA) and coupled to RAFT polymerized poly(azidopropyl methacrylate) (polyAPMA) through azide-alkyne [3+2] Huisgen cycloaddition. The graft copolymers become membrane destabilizing at endosomal pH values and are active at significantly lower concentrations than the linear polyPAA. A biotin terminated polyPAA graft copolymer was prepared by grafting PAA onto polyAPMA polymerized with a biotin functional RAFT CTA. The blood circulation time and biodistribution of tritium labeled avidin conjugated to the polyPAA graft copolymer was characterized along with a clinically utilized 40 kDa branched polyethylene glycol (PEG) also possessing biotin functionalization. The linear and graft polyPAA increase the area under the curve (AUC) over avidin alone by 9 and 12 times, respectively. Furthermore, polyPAA graft copolymer conjugates accumulated in tumor tissue significantly more than the linear polyPAA and the branched PEG conjugates. The collective data presented in this report indicate that the polyPAA graft copolymers exhibit robust pH-dependent, membrane-destabilizing activity, low cytotoxicity and significantly enhance blood circulation time and tumor accumulation. PMID:21699931

Methotrexate-Loaded Four-Arm Star Amphiphilic Block Copolymer Elicits CD8+ T Cell Response against a Highly Aggressive and Metastatic Experimental Lymphoma.

PubMed

Hira, Sumit Kumar; Ramesh, Kalyan; Gupta, Uttam; Mitra, Kheyanath; Misra, Nira; Ray, Biswajit; Manna, Partha Pratim

2015-09-16

We have synthesized a well-defined four-arm star amphiphilic block copolymer [poly(DLLA)-b-poly(NVP)]4 [star-(PDLLA-b-PNVP)4] that consists of D,L-lactide (DLLA) and N-vinylpyrrolidone (NVP) via the combination of ring-opening polymerization (ROP) and xanthate-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization. Synthesis of the polymer was verified by 1H NMR spectroscopy and gel permeation chromatography (GPC). The amphiphilic four-arm star block copolymer forms spherical micelles in water as demonstrated by transmission electron microscopy (TEM) and 1H NMR spectroscopy. Pyrene acts as a probe to ascertain the critical micellar concentration (cmc) by using fluorescence spectroscopy. Methotrexate (MTX)-loaded polymeric micelles of star-(PDLLA15-b-PNVP10)4 amphiphilic block copolymer were prepared and characterized by fluorescence and TEM studies. Star-(PDLLA15-b-PNVP10)4 copolymer was found to be significantly effective with respect to inhibition of proliferation and lysis of human and murine lymphoma cells. The amphiphilic block copolymer causes cell death in parental and MTX-resistant Dalton lymphoma (DL) and Raji cells. The formulation does not cause hemolysis in red blood cells and is tolerant to lymphocytes compared to free MTX. Therapy with MTX-loaded star-(PDLLA15-b-PNVP10)4 amphiphilic block copolymer micelles prolongs the life span of animals with neoplasia by reducing the tumor load, preventing metastasis and augmenting CD8+ T cell-mediated adaptive immune responses.

Micelles of enzymatically synthesized PEG-poly(amine-co-ester) block copolymers as pH-responsive nanocarriers for docetaxel delivery.

PubMed

Zhang, Xiaofang; Liu, Bo; Yang, Zhe; Zhang, Chao; Li, Hao; Luo, Xingen; Luo, Huiyan; Gao, Di; Jiang, Qing; Liu, Jie; Jiang, Zhaozhong

2014-03-01

A series of PEGylated poly(amine-co-ester) terpolymers were successfully synthesized in one step via lipase-catalyzed copolymerization of ω-pentadecalactone (PDL), diethyl sebacate (DES), and N-methyldiethanolamine (MDEA) comonomers in the presence of poly(ethylene glycol) methyl ether as a chain-terminating agent. The resultant amphiphilic poly(ethylene glycol)-poly(PDL-co-MDEA-co-sebacate) (PEG-PPMS) block copolymers consisted of hydrophilic PEG chain segments and hydrophobic random PPMS chain segments, which self-assembled in aqueous medium to form stable, nanosized micelles at physiological pH of 7.4. Upon decreasing the medium pH from 7.4 to 5.0, the copolymer micelles swell significantly due to protonation of the amino groups in the micelle PPMS cores. Correspondingly, docetaxel (DTX)-encapsulated PEG2K-PPMS copolymer micelles showed gradual sustained drug release at pH of 7.4, but remarkably accelerated DTX release at acidic pH of 5.0. The drug-loaded micelle particles were readily internalized by SK-BR-3 cancer cells and, compared to free DTX drug, DTX-loaded micelles of the copolymers with optimal compositions exhibited enhanced potency against the cells. Biodegradable PEG-PPMS copolymer micelles represent a new type of promising, pH-responsive nanocarriers for anticancer drug delivery, and the drug release rate from the micelles can be systematically controlled by both pH and the copolymer composition. Copyright © 2013 Elsevier B.V. All rights reserved.

Efficient encapsulation of proteins with random copolymers.

PubMed

Nguyen, Trung Dac; Qiao, Baofu; Olvera de la Cruz, Monica

2018-06-12

Membraneless organelles are aggregates of disordered proteins that form spontaneously to promote specific cellular functions in vivo. The possibility of synthesizing membraneless organelles out of cells will therefore enable fabrication of protein-based materials with functions inherent to biological matter. Since random copolymers contain various compositions and sequences of solvophobic and solvophilic groups, they are expected to function in nonbiological media similarly to a set of disordered proteins in membraneless organelles. Interestingly, the internal environment of these organelles has been noted to behave more like an organic solvent than like water. Therefore, an adsorbed layer of random copolymers that mimics the function of disordered proteins could, in principle, protect and enhance the proteins' enzymatic activity even in organic solvents, which are ideal when the products and/or the reactants have limited solubility in aqueous media. Here, we demonstrate via multiscale simulations that random copolymers efficiently incorporate proteins into different solvents with the potential to optimize their enzymatic activity. We investigate the key factors that govern the ability of random copolymers to encapsulate proteins, including the adsorption energy, copolymer average composition, and solvent selectivity. The adsorbed polymer chains have remarkably similar sequences, indicating that the proteins are able to select certain sequences that best reduce their exposure to the solvent. We also find that the protein surface coverage decreases when the fluctuation in the average distance between the protein adsorption sites increases. The results herein set the stage for computational design of random copolymers for stabilizing and delivering proteins across multiple media.

One-step synthesis and self-assembly behavior of thermo-responsive star-shaped β-cyclodextrin-(P(MEO2MA- co-PEGMA))21 copolymers

NASA Astrophysics Data System (ADS)

Wei, Lulu; Lu, Beibei; Li, Lei; Wu, Jianning; Liu, Zhiyong; Guo, Xuhong

2017-09-01

A novel β-cyclodextrin-poly(2-(2-methoxyethoxy)ethyl methacrylate)- co-poly(ethylene glycol) methacrylate (abbreviated as: β-CD-(P(MEO2MA- co-PEGMA))21) was prepared by using the one-step strategy, and then the star-shaped copolymers were used in the atom transfer radical polymerization (ATRP). The structure of star-shaped β-CD-(P(MEO2MA- co-PEGMA))21 copolymers were studied by FTIR, 1H NMR and gel permeation chromatography (GPC). The star-shaped copolymers could self-assembled into micelles in aqueous solution owing to the outer amphiphilic β-CD as a core and the hydrophilic P(MEO2MA- co-PEGMA) segments as a shell. These thermo-responsive starshaped copolymers micelles exhibited lower critical solution temperature (LCST) in water, which could be finely tuned by changing the feed ratio of MEO2MA to PEGMA. The LCST of star-shaped β-CD-(P(MEO2MA- co-PEGMA))21 copolymer micelles were increased from 35°C to 58°C with the increasing content of PEGMA. The results were investigated by DLS and TEM. When the temperature was higher than corresponding LCSTs, the micelles started to associate and form spherical nanoparticles. Therefore, β-CD-(P(MEO2MA- co-PEGMA))21 star-shaped copolymer micelles could be potentially applied in nano-carrier, nano-reactor, smart materials and biomedical fields.

Doxorubicin-loaded micelles based on multiarm star-shaped PLGA-PEG block copolymers: influence of arm numbers on drug delivery.

PubMed

Ma, Guilei; Zhang, Chao; Zhang, Linhua; Sun, Hongfan; Song, Cunxian; Wang, Chun; Kong, Deling

2016-01-01

Star-shaped block copolymers based on poly(D,L-lactide-co-glycolide) (PLGA) and poly(ethylene glycol) (PEG) (st-PLGA-PEG) were synthesized with structural variation on arm numbers in order to investigate the relationship between the arm numbers of st-PLGA-PEG copolymers and their micelle properties. st-PLGA-PEG copolymers with arm numbers 3, 4 and 6 were synthesized by using different cores such as trimethylolpropane, pentaerythritol and dipentaerythritol, and were characterized by nuclear magnetic resonance and gel permeation chromatography. The critical micelle concentration decreased with increasing arm numbers in st-PLGA-PEG copolymers. The doxorubicin-loaded st-PLGA-PEG micelles were prepared by a modified nanoprecipitation method. Micellar properties such as particle size, drug loading content and in vitro drug release behavior were investigated as a function of the number of arms and compared with each other. The doxorubicin-loaded 4-arm PLGA-PEG micelles were found to have the highest cellular uptake efficiency and cytotoxicity compared with 3-arm PLGA-PEG micelles and 6-arm PLGA-PEG micelles. The results suggest that structural tailoring of arm numbers from st-PLGA-PEG copolymers could provide a new strategy for designing drug carriers of high efficiency. Structural tailoring of arm numbers from star shaped-PLGA-PEG copolymers (3-arm/4-arm/6-arm-PLGA-PEG) could provide a new strategy for designing drug carriers of high efficiency.

Comparison between hot-melt extrusion and spray-drying for manufacturing solid dispersions of the graft copolymer of ethylene glycol and vinylalcohol.

PubMed

Guns, Sandra; Dereymaker, Aswin; Kayaert, Pieterjan; Mathot, Vincent; Martens, Johan A; Van den Mooter, Guy

2011-03-01

To investigate the effect of the manufacturing method (spray-drying or hot-melt extrusion) on the kinetic miscibility of miconazole and the graft copolymer poly(ethyleneglycol-g-vinylalcohol). The effect of heat pre-treatment of solutions used for spray-drying and the use of spray-dried copolymer as excipient for hot-melt extrusion was investigated. The solid dispersions were prepared at different drug-polymer ratios and analyzed with modulated differential scanning calorimetry and X-ray powder diffraction. Miconazole either mixed with the PEG-fraction of the copolymer or crystallized in the same or a different polymorph as the starting material. The kinetic miscibility was higher for the solid dispersions obtained from solutions which were pre-heated compared to those spray-dried from solutions at ambient temperature. Hot-melt extrusion resulted in an even higher mixing capability. Here the use of the spray-dried copolymer did not show any benefit concerning the kinetic miscibility of the drug and copolymer, but it resulted in a remarkable decrease in the torque experienced by the extruder allowing extrusion at lower temperature and torque. The manufacturing method has an influence on the mixing capacity and phase behavior of solid dispersions. Heat pre-treatment of the solutions before spray-drying can result in a higher kinetic miscibility. Amorphization of the copolymer by spray-drying before using it as an excipient for hot-melt extrusion can be a manufacturing benefit.

Field-theoretic simulations of block copolymer nanocomposites in a constant interfacial tension ensemble.

PubMed

Koski, Jason P; Riggleman, Robert A

2017-04-28

Block copolymers, due to their ability to self-assemble into periodic structures with long range order, are appealing candidates to control the ordering of functionalized nanoparticles where it is well-accepted that the spatial distribution of nanoparticles in a polymer matrix dictates the resulting material properties. The large parameter space associated with block copolymer nanocomposites makes theory and simulation tools appealing to guide experiments and effectively isolate parameters of interest. We demonstrate a method for performing field-theoretic simulations in a constant volume-constant interfacial tension ensemble (nVγT) that enables the determination of the equilibrium properties of block copolymer nanocomposites, including when the composites are placed under tensile or compressive loads. Our approach is compatible with the complex Langevin simulation framework, which allows us to go beyond the mean-field approximation. We validate our approach by comparing our nVγT approach with free energy calculations to determine the ideal domain spacing and modulus of a symmetric block copolymer melt. We analyze the effect of numerical and thermodynamic parameters on the efficiency of the nVγT ensemble and subsequently use our method to investigate the ideal domain spacing, modulus, and nanoparticle distribution of a lamellar forming block copolymer nanocomposite. We find that the nanoparticle distribution is directly linked to the resultant domain spacing and is dependent on polymer chain density, nanoparticle size, and nanoparticle chemistry. Furthermore, placing the system under tension or compression can qualitatively alter the nanoparticle distribution within the block copolymer.

Synthesis and Characterization of Solution and Melt Processible Poly(Acrylonitrile-Co-Methyl Acrylate) Statistical Copolymers

NASA Astrophysics Data System (ADS)

Pisipati, Padmapriya

Polyacrylonitrile (PAN) and its copolymers are used in a wide variety of applications ranging from textiles to purification membranes, packaging material and carbon fiber precursors. High performance polyacrylonitrile copolymer fiber is the most dominant precursor for carbon fibers. Synthesis of very high molecular weight poly(acrylonitrile-co-methyl acrylate) copolymers with weight average molecular weights of at least 1.7 million g/mole were synthesized on a laboratory scale using low temperature, emulsion copolymerization in a closed pressure reactor. Single filaments were spun via hybrid dry-jet gel solution spinning. These very high molecular weight copolymers produced precursor fibers with tensile strengths averaging 954 MPa with an elastic modulus of 15.9 GPa (N = 296). The small filament diameters were approximately 5 im. Results indicated that the low filament diameter that was achieved with a high draw ratio, combined with the hybrid dry-jet gel spinning process lead to an exponential enhancement of the tensile properties of these fibers. Carbon fibers for polymer matrix composites are currently derived from polyacrylonitrile copolymer fiber precursors where solution spinning accounts for ˜40 % of the total fiber production cost. To expand carbon fiber applications into the automotive industry, the cost of the carbon fiber needs to be reduced from 8 to ˜3-5. In order to develop an alternative melt processing route several benign plasticizers have been investigated. A low temperature, persulfate-metabisulfite initiated emulsion copolymerization was developed to synthesize poly(acrylonitrile-co-methyl acrylate) copolymers with acrylonitrile contents between 91-96 wt% with a molecular weight range of 100-200 kg/mol. This method was designed for a potential industrial scale up. Furthermore, water was investigated as a potential melting point depressant for these copolymers. Twenty-five wt% water lead to a decrease in the Tm of a 93/7 wt/wt % poly(acrylonitrile-co-methyl acrylate) of Mw = 200 kg/mol to 160 0C as measured via DSC. Glycerin, ethylene glycol and glycerin/water combinations were investigated as potential plasticizers for high molecular weight (˜200,000 g/mol), high acrylonitrile (93-96 mole:mole %) content poly(acrylonitrile-co-methyl acrylate) statistical copolymers. Pure glycerin (25 wt %) induced crystallization followed by a reduced "Tm" of about 213 0C via DSC. However this composition did not melt process well. A lower M W (˜35 kg/mol) copolymer did extrude with no apparent degradation. Our hypothesis is that the hydroxyl groups in glycerin (or water) disrupt the strong dipole-dipole interactions between the chains enabling the copolymer endothermic transition (Tm) to be reduced and enable melting before the onset of degradation. Additionally high molecular weight (Mw = 200-230 kg/mol) poly(acrylonitrile-co-methyl acrylate) copolymers with lower acrylonitrile content (82-85 wt %) were synthesized via emulsion copolymerization and successfully melt pressed. These materials will be further investigated for their utility in packaging applications.

Poly(carbonate-imide) polymer

NASA Technical Reports Server (NTRS)

St. Clair, Terry L. (Inventor); Maudgal, Shubha (Inventor); Pratt, J. Richard (Inventor)

1987-01-01

A novel series of polymers and copolymers based on a polyimide backbone with the incorporation of carbonate moieties along the backbone. The process for preparing these polymers and copolymers is also disclosed as is a novel series of dinitrodiphenyl carbonates and diaminodiphenyl carbonates. The novel polymers and copolymers exhibit high temperature capability and because of the carbonate unit, many exhibit a high degree of order and/or crystallinity.

Poly (Carbonate-Mide) Polymer

NASA Technical Reports Server (NTRS)

St.clair, T. L. (Inventor); Maudgal, S. (Inventor); Pratt, J. R. (Inventor)

1986-01-01

A novel series of polymers and copolymers based on a polymide backbone with the incorporation of carbonate moieties along the backbone is presented. The preparation process for the polymers and copolymers is disclosed together with a novel series of dinitrodiphenyl carbonates and diaminodiphenyl carbonates. The novel polyners and copolymers exhibit high temperature capability and because of the carbonate unit, many exhibit a high degree of order and/or crystallinity.

Alkaline battery containing a separator of a cross-linked copolymer of vinyl alcohol and unsaturated carboxylic acid

NASA Technical Reports Server (NTRS)

Hsu, L. C.; Philipp, W. H.; Sheibley, D. W.; Gonzalez-Sanabria, O. D. (Inventor)

1985-01-01

A battery separator for an alkaline battery is described. The separator comprises a cross linked copolymer of vinyl alcohol units and unsaturated carboxylic acid units. The cross linked copolymer is insoluble in water, has excellent zincate diffusion and oxygen gas barrier properties and a low electrical resistivity. Cross linking with a polyaldehyde cross linking agent is preferred.

Synthesis and Testing of Polymers Susceptible to Degradation by Proteolytic Enzymes

DTIC Science & Technology

1975-05-01

diisocyanatohexane, was biodegraded by the enzymes urease and rennin and also by two fungi. The tensile strength was greater than 10,000 psi, with high...Copolymer Degradation by Urease Enzyme Copolymer Degradation by Rennin Enzyme Degradation of Modified Gelatins: Undrawn Bulk Material Degradation of...bacteria. Results with urease enzyme did indicate significant degradation, as shown by the following tables: Table 1. Copolymer Degradation by

Non-Invasive Nanodiagnostics of Cancer (NINOC)

DTIC Science & Technology

2010-04-01

tested. CONCLUSIONS Well-defined diblock copolymers of poly(ethylene glycol) and polymethacrylic acid (PEG-b-PMA) with aldehyde functionality were...treatment of cancer, tumor-specific targeting has been proposed using a variety of targeting moieties such as folic acid , transferrin, RGD-peptides...tert-butyl and PEG groups (Table 1). In order to obtain the final block copolymer 6, the hydrolysis of copolymer 5 was carried out in the acidic

Environmentally Compliant Thermoplastic Powder Coating, Phase 1

DTIC Science & Technology

1992-10-07

TPC flame sprayed application equipment and ethylene acrylic acid (EAA) and ethylene methacrylic acid (EMAA) copolymers thermoplastic powder...have worked closely with Dow Chemical to develop and optimize their systems using Dow "Envelon" ethylene acrylic acid (EAA) thermoplastic copolymers...provide on/off control. CFS recommends the use of Dow "Envelon" ethylene acrylic acid (EAA) copolymer thermoplastic powder with this unit. The CFS system

21 CFR 177.1480 - Nitrile rubber modified acrylonitrile-methyl acrylate copolymers.

Code of Federal Regulations, 2013 CFR

2013-04-01

...) Specifications. (i) Nitrogen content is in the range 16.5-19 percent as determined by Kjeldahl analysis. (ii... copolymers in the form of particles of a size that will pass through a U.S. standard sieve No. 6 and that will be held on a U.S. standard sieve No. 10: (i) Extracted copolymer not to exceed 2.0 parts per...

21 CFR 177.1480 - Nitrile rubber modified acrylonitrile-methyl acrylate copolymers.

Code of Federal Regulations, 2011 CFR

2011-04-01

...) Specifications. (i) Nitrogen content is in the range 16.5-19 percent as determined by Kjeldahl analysis. (ii... copolymers in the form of particles of a size that will pass through a U.S. standard sieve No. 6 and that will be held on a U.S. standard sieve No. 10: (i) Extracted copolymer not to exceed 2.0 parts per...

21 CFR 177.1480 - Nitrile rubber modified acrylonitrile-methyl acrylate copolymers.

Code of Federal Regulations, 2012 CFR

2012-04-01

...) Specifications. (i) Nitrogen content is in the range 16.5-19 percent as determined by Kjeldahl analysis. (ii... copolymers in the form of particles of a size that will pass through a U.S. standard sieve No. 6 and that will be held on a U.S. standard sieve No. 10: (i) Extracted copolymer not to exceed 2.0 parts per...

Biosynthesis of poly(3-hydroxybutyrateco-3-hydroxy-4-methylvalerate) by Strain Azotobacter chroococcum 7B

PubMed Central

Bonartsev, A.P.; Bonartseva, G. A.; Myshkina, V. L.; Voinova, V. V.; Mahina, T. K.; Zharkova, I. I.; Yakovlev, S. G.; Zernov, A. L.; Ivanova, E. V.; Akoulina, E. A.; Kuznetsova, E. S.; Zhuikov, V. A.; Alekseeva, S. G.; Podgorskii, V. V.; Bessonov, I. V.; Kopitsyna, M. N.; Morozov, A. S.; Milanovskiy, E. Y.; Tyugay, Z. N.; Bykova, G. S.; Kirpichnikov, M. P.; Shaitan, K. V.

2016-01-01

Production of novel polyhydroxyalkanoates (PHAs), biodegradable polymers for biomedical applications, and biomaterials based on them is a promising trend in modern bioengineering. We studied the ability of an effective strain-producer Azotobacter chroococcum 7B to synthesize not only poly(3-hydroxybutyrate) homopolymer (PHB) and its main copolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), but also a novel copolymer, poly(3-hydroxybutyrate-co-3-hydroxy-4-methylvalerate) (PHB4MV). For the biosynthesis of PHB copolymers, we used carboxylic acids as additional carbon sources and monomer precursors in the chain of synthesized copolymers. The main parameters of these polymers’ biosynthesis were determined: strain-producer biomass yield, polymer yield, molecular weight and monomer composition of the synthesized polymers, as well as the morphology of A. chroococcum 7B bacterial cells. The physico-chemical properties of the polymers were studied using nuclear magnetic resonance spectroscopy (NMR), differential scanning calorimetry (DSC), contact angle test, and other methods. In vitro biocompatibility of the obtained polymers was investigated using stromal cells isolated from the bone marrow of rats with the XTT cell viability test. The synthesis of the novel copolymer PHB4MV and its chemical composition were demonstrated by NMR spectroscopy: the addition of 4-methylvaleric acid to the culture medium resulted in incorporation of 3-hydroxy-4-methylvalerate (3H4MV) monomers into the PHB polymer chain (0.6 mol%). Despite the low molar content of 3H4MV in the obtained copolymer, its physico-chemical properties were significantly different from those of the PHB homopolymer: it has lower crystallinity and a higher contact angle, i.e. the physico-chemical properties of the PHB4MV copolymer containing only 0.6 mol% of 3H4MV corresponded to a PHBV copolymer with a molar content ranging from 2.5% to 7.8%. In vitro biocompatibility of the obtained PHB4MV copolymer, measured in the XTT test, was not statistically different from the cell growth of PHB and PHBV polymers, which make its use possible in biomedical research and development. PMID:27795846

Fabrication of biofunctional nanomaterials via Escherichia coli OmpF protein air/water interface insertion/integration with copolymeric amphiphiles.

PubMed

Ho, Dean; Chang, Stacy; Montemagno, Carlo D

2006-06-01

Fabrication of next-generation biologically active materials will involve the integration of proteins with synthetic membrane materials toward a wide spectrum of applications in nanoscale medicine, including high-throughput drug testing, energy conversion for powering medical devices, and bio-cloaking films for mimicry of cellular membrane surfaces toward the enhancement of implant biocompatibility. We have used ABA triblock copolymer membranes (PMOXA-PDMS-PMOXA) of varied thicknesses as platform materials for Langmuir film-based functionalization with the OmpF pore protein from Escherichia coli by fabricating monolayers of copolymer amphiphile-protein complexes on the air/water interface. Here we demonstrate that the ability for protein insertion at the air/water interface during device fabrication is dependent upon the initial surface coverage with the copolymer as well as copolymer thickness. Methacrylate-terminated block copolymer structures that were 4 nm (4METH) and 8 nm (8METH) in length were used as the protein reconstitution matrix, whereas a 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) lipid (~4 nm thickness) was used as a comparison to demonstrate the effects of copolymer length on protein integration capabilities. Wilhemy surface pressure measurements (mN/m) revealed a greater protein insertion in the 4METH and POPC structures compared with the 8METH structure, indicating that shorter copolymer chains possess enhanced biomimicry of natural lipid-based membranes. In addition, comparisons between the isothermal characteristics of the 4METH, 8METH, and POPC membranes reveal that phase transitions of the 4METH resemble a blend of the 8METH and POPC materials, indicating that the 4METH chain may possess hybrid properties of both copolymers and lipids. Furthermore, we have shown that following the deposition of the amphiphilic materials on the air/water interface, the OmpF can be deposited directly on top of the amphiphiles (surface addition), thus effectively further enhancing protein insertion because of the buoying effects of the membranes. These characteristics of Langmuir-Blodgett-based fabrication of copolymer-biomolecule hybrids represent a synthesis strategy for next-generation biomedical materials.

Simulation study on the effects of chemical structure and molecular size on the acceptor strength in poly(3-hexylthiophene)-based copolymer with alternating donor and acceptor for photovoltaic applications

NASA Astrophysics Data System (ADS)

Rassamesard, Areefen; Pengpan, Teparksorn

2017-02-01

This research assessed the effects of various chemical structures and molecular sizes on the simulated geometric parameters, electron structures, and spectroscopic properties of single-chain complex alternating donor-acceptor (D-A) monomers and copolymers that are intended for use as photoactive layer in a polymer solar cell by using Kohn-Sham density functional theory with B3LYP exchange-correlation functional. The 3-hexylthiophene (3HT) was selected for electron donor, while eight chemicals, namely thiazole (Z), thiadiazole (D), thienopyrazine (TP), thienothiadiazole (TD), benzothiadiazole (BT), thiadiazolothieno-pyrazine (TPD), oxadiazole (OXD) and 5-diphenyl-1,2,4-triazole (TAZ), were employed as electron acceptor functional groups. The torsional angle, bridge bond length, intramolecular charge transfer, energy levels, and molecular orbitals were analyzed. The simulation results reveal that the geometry and electron structure of donor-acceptor monomer and copolymer are significantly impacted by heterocyclic rings, heteroatoms, fused rings, degree of steric hindrance and coplanarity of the acceptor molecular structure. Planar conformation was obtained from the D copolymer, and a pseudo-planar structure with the TD copolymer. The TAZ acceptor exhibited strong steric hindrance due to its bulky structure and non-planarity of its structure. An analysis of the electron structures indicated that the degree of intramolecular electron-withdrawing capability had the rank order TAZ  <  Z  <  D  <  TPD  <  OXD  <  TP  <  BT  <  TD. The TD is indicated as the most effective acceptor among those that were simulated. However, the small energy gaps of TD as well as TPD copolymer indicate that these two copolymers can be used in transparent conducting materials. The copolymer based on BT acceptor exhibited good intramolecular charge transfer and absorbed at 656 nm wavelength which is close to the maximum flux of solar spectrum. Hence, the BT acceptor functional group provides a compromise in the characteristics of a donor-acceptor copolymer, useful in a polymeric candidate material for the photoactive layer in a polymer solar cell.

Doxorubicin-loaded micelles of reverse poly(butylene oxide)-poly(ethylene oxide)-poly(butylene oxide) block copolymers as efficient "active" chemotherapeutic agents.

PubMed

Cambón, A; Rey-Rico, A; Mistry, D; Brea, J; Loza, M I; Attwood, D; Barbosa, S; Alvarez-Lorenzo, C; Concheiro, A; Taboada, P; Mosquera, V

2013-03-10

Five reverse poly(butylene oxide)-poly(ethylene oxide)-poly(butylene oxide) block copolymers, BOnEOmBOn, with BO ranging from 8 to 21 units and EO from 90 to 411 were synthesized and evaluated as efficient chemotherapeutic drug delivery nanocarriers and inhibitors of the P-glycoprotein (P-gp) efflux pump in a multidrug resistant (MDR) cell line. The copolymers were obtained by reverse polymerization of poly(butylene oxide), which avoids transfer reaction and widening of the EO block distribution, commonly found in commercial poly(ethylene oxide)-poly(propylene oxide) block copolymers (poloxamers). BOnEOmBOn copolymers formed spherical micelles of 10-40 nm diameter at lower concentrations (one order of magnitude) than those of equivalent poloxamers. The influence of copolymer block lengths and BO/EO ratios on the solubilization capacity and protective environment for doxorubicin (DOXO) was investigated. Micelles showed drug loading capacity ranging from ca. 0.04% to 1.5%, more than 150 times the aqueous solubility of DOXO, and protected the cargo from hydrolysis for more than a month due to their greater colloidal stability in solution. Drug release profiles at various pHs, and the cytocompatibility and cytotoxicity of the DOXO-loaded micelles were assessed in vitro. DOXO loaded in the polymeric micelles accumulated more slowly inside the cells than free DOXO due to its sustained release. All copolymers were found to be cytocompatible, with viability extents larger than 95%. In addition, the cytotoxicity of DOXO-loaded micelles was higher than that observed for free drug solutions in a MDR ovarian NCI-ADR-RES cell line which overexpressed P-gp. The inhibition of the P-gp efflux pump by some BOnEOmBOn copolymers, similar to that measured for the common P-gp inhibitor verapamil, favored the retention of DOXO inside the cell increasing its cytotoxic activity. Therefore, poly(butylene oxide)-poly(ethylene oxide) block copolymers offer interesting features as cell response modifiers to complement their role as efficient nanocarriers for cancer chemotherapy. Copyright © 2013 Elsevier B.V. All rights reserved.

Aqueous self-assembly of poly(ethylene oxide)-block-poly(ε-caprolactone) (PEO-b-PCL) copolymers: disparate diblock copolymer compositions give rise to nano- and meso-scale bilayered vesicles

NASA Astrophysics Data System (ADS)

Qi, Wei; Ghoroghchian, P. Peter; Li, Guizhi; Hammer, Daniel A.; Therien, Michael J.

2013-10-01

Nanoparticles formed from diblock copolymers of FDA approved PEO and PCL have generated considerable interest as in vivo drug delivery vehicles. Herein, we report the synthesis of the most extensive family PEO-b-PCL copolymers that vary over the largest range of number-average molecular weights (Mn: 3.6-57k), PEO weight fractions (fPEO: 0.08-0.33), and PEO chain lengths (0.75-5.8k) reported to date. These polymers were synthesized in order to establish the full range of aqueous phase behaviours of these diblock copolymers and to specifically identify formulations that were able to generate bilayered vesicles (polymersomes). Cryogenic transmission electron microscopy (cryo-TEM) was utilized in order to visualize the morphology of these structures upon aqueous self-assembly of dry polymer films. Nanoscale polymersomes were formed from PEO-b-PCL copolymers over a wide range of PEO weight fractions (fPEO: 0.14-0.27) and PEO molecular weights (0.75-3.8k) after extrusion of aqueous suspensions. Comparative morphology diagrams, which describe the nature of self-assembled structures as a function of diblock copolymer molecular weight and PEO weight fraction, show that in contrast to micron-scale polymersomes, which form only from a limited range of PEO-b-PCL diblock copolymer compositions, a multiplicity of PEO-b-PCL diblock copolymer compositions are able to give rise to nanoscale vesicles. These data underscore that PEO-b-PCL compositions that spontaneously form micron-sized polymersomes, as well as those that have previously been reported to form polymersomes via a cosolvent fabrication system, provide only limited insights into the distribution of PEO-b-PCL diblocks that give rise to nanoscale vesicles. The broad range of polymersome-forming PEO-b-PCL compositions described herein suggest the ability to construct extensive families of nanoscale vesicles of varied bilayer thickness, providing the ability to tune the timescales of vesicle degradation and encapsulant release based on the intended in vivo application.Nanoparticles formed from diblock copolymers of FDA approved PEO and PCL have generated considerable interest as in vivo drug delivery vehicles. Herein, we report the synthesis of the most extensive family PEO-b-PCL copolymers that vary over the largest range of number-average molecular weights (Mn: 3.6-57k), PEO weight fractions (fPEO: 0.08-0.33), and PEO chain lengths (0.75-5.8k) reported to date. These polymers were synthesized in order to establish the full range of aqueous phase behaviours of these diblock copolymers and to specifically identify formulations that were able to generate bilayered vesicles (polymersomes). Cryogenic transmission electron microscopy (cryo-TEM) was utilized in order to visualize the morphology of these structures upon aqueous self-assembly of dry polymer films. Nanoscale polymersomes were formed from PEO-b-PCL copolymers over a wide range of PEO weight fractions (fPEO: 0.14-0.27) and PEO molecular weights (0.75-3.8k) after extrusion of aqueous suspensions. Comparative morphology diagrams, which describe the nature of self-assembled structures as a function of diblock copolymer molecular weight and PEO weight fraction, show that in contrast to micron-scale polymersomes, which form only from a limited range of PEO-b-PCL diblock copolymer compositions, a multiplicity of PEO-b-PCL diblock copolymer compositions are able to give rise to nanoscale vesicles. These data underscore that PEO-b-PCL compositions that spontaneously form micron-sized polymersomes, as well as those that have previously been reported to form polymersomes via a cosolvent fabrication system, provide only limited insights into the distribution of PEO-b-PCL diblocks that give rise to nanoscale vesicles. The broad range of polymersome-forming PEO-b-PCL compositions described herein suggest the ability to construct extensive families of nanoscale vesicles of varied bilayer thickness, providing the ability to tune the timescales of vesicle degradation and encapsulant release based on the intended in vivo application. Electronic supplementary information (ESI) available: Materials and methods, characterization data. See DOI: 10.1039/c3nr03250g

Structural Color for Additive Manufacturing: 3D-Printed Photonic Crystals from Block Copolymers.

PubMed

Boyle, Bret M; French, Tracy A; Pearson, Ryan M; McCarthy, Blaine G; Miyake, Garret M

2017-03-28

The incorporation of structural color into 3D printed parts is reported, presenting an alternative to the need for pigments or dyes for colored parts produced through additive manufacturing. Thermoplastic build materials composed of dendritic block copolymers were designed, synthesized, and used to additively manufacture plastic parts exhibiting structural color. The reflection properties of the photonic crystals arise from the periodic nanostructure formed through block copolymer self-assembly during polymer processing. The wavelength of reflected light could be tuned across the visible spectrum by synthetically controlling the block copolymer molecular weight and manufacture parts that reflected violet, green, or orange light with the capacity to serve as selective optical filters and light guides.

Mesostructured Block Copolymer Nanoparticles: Versatile Templates for Hybrid Inorganic/Organic Nanostructures

PubMed Central

Connal, Luke A.; Lynd, Nathaniel A.; Robb, Maxwell J.; See, Kimberly A.; Jang, Se Gyu; Spruell, Jason M.

2012-01-01

We present a versatile strategy to prepare a range of nanostructured poly(styrene)-block-poly(2-vinyl pyridine) copolymer particles with tunable interior morphology and controlled size by a simple solvent exchange procedure. A key feature of this strategy is the use of functional block copolymers incorporating reactive pyridyl moieties which allow the absorption of metal salts and other inorganic precursors to be directed. Upon reduction of the metal salts, well-defined hybrid metal nanoparticle arrays could be prepared, while the use of oxide precursors followed by calcination permits the synthesis of silica and titania particles. In both cases, ordered morphologies templated by the original block copolymer domains were obtained. PMID:23335837

Thermodynamics of strain-induced crystallization of random copolymers.

PubMed

Nie, Yijing; Gao, Huanhuan; Wu, Yixian; Hu, Wenbing

2014-01-14

Industrial semi-crystalline polymers contain various kinds of sequence defects, which behave like non-crystallizable comonomer units on random copolymers. We performed dynamic Monte Carlo simulations of strain-induced crystallization of random copolymers with various contents of comonomers at high temperatures. We observed that the onset strains of crystallization shift up with the increase of comonomer contents and temperatures. The behaviors can be predicted well by a combination of Flory's theories on the melting-point shifting-down of random copolymers and on the melting-point shifting-up of strain-induced crystallization. Our thermodynamic results are fundamentally important for us to understand the rubber strain-hardening, the plastic molding, the film stretching as well as the fiber spinning.

Ultrahigh-density nanowire arrays grown in self-assembled diblock copolymer templates.

PubMed

Thurn-Albrecht, T; Schotter, J; Kästle, G A; Emley, N; Shibauchi, T; Krusin-Elbaum, L; Guarini, K; Black, C T; Tuominen, M T; Russell, T P

2000-12-15

We show a simple, robust, chemical route to the fabrication of ultrahigh-density arrays of nanopores with high aspect ratios using the equilibrium self-assembled morphology of asymmetric diblock copolymers. The dimensions and lateral density of the array are determined by segmental interactions and the copolymer molecular weight. Through direct current electrodeposition, we fabricated vertical arrays of nanowires with densities in excess of 1.9 x 10(11) wires per square centimeter. We found markedly enhanced coercivities with ferromagnetic cobalt nanowires that point toward a route to ultrahigh-density storage media. The copolymer approach described is practical, parallel, compatible with current lithographic processes, and amenable to multilayered device fabrication.

Preparation and properties of immobilized pectinase onto the amphiphilic PS-b-PAA diblock copolymers.

PubMed

Lei, Zhongli; Bi, Shuxian

2007-01-30

Well-defined amphiphilic block copolymers poly(styrene-b-acrylic acid) (PS-b-PAA) with controlled block length were synthesized using atom transfer radical polymerization (ATRP). Pectinase enzyme was immobilized on the well-defined amphiphilic block copolymers PS-b-PAA. The carboxyl groups on the amphiphilic PS-b-PAA diblock copolymers present a very simple, mild, and time-saving process for enzyme immobilization. Various characteristics of immobilized pectinase such as the pH and temperature stability, thermal stability, and storage stability were valuated. Among them the pH optimum and temperature optimum of free and immobilized pectinase were found to be pH 6.0 and 65 degrees C.

Morphologies of precise polyethylene-based acid copolymers and ionomers

NASA Astrophysics Data System (ADS)

Buitrago, C. Francisco

Acid copolymers and ionomers are polymers that contain a small fraction of covalently bound acidic or ionic groups, respectively. For the specific case of polyethylene (PE), acid and ionic pendants enhance many of the physical properties such as toughness, adhesion and rheological properties. These improved properties result from microphase separated aggregates of the polar pendants in the non-polar PE matrix. Despite the widespread industrial use of these materials, rigorous chemical structure---morphology---property relationships remain elusive due to the inevitable structural heterogeneities in the historically-available acid copolymers and ionomers. Recently, precise acid copolymers and ionomers were successfully synthesized by acyclic diene metathesis (ADMET) polymerization. These precise materials are linear, high molecular weight PEs with pendant acid or ionic functional groups separated by a precisely controlled number of carbon atoms. The morphologies of nine precise acid copolymers and eleven precise ionomers were investigated by X-ray scattering, solid-state 13C nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). For comparison, the morphologies of linear PEs with pseudo-random placement of the pendant groups were also studied. Previous studies of precise copolymers with acrylic acid (AA) found that the microstructural precision produces a new morphology in which PE crystals drive the acid aggregates into layers perpendicular to the chain axes and presumably at the interface between crystalline and amorphous phases. In this dissertation, a second new morphology for acid copolymers is identified in which the aggregates arrange on cubic lattices. The fist report of a cubic morphology was observed at room and elevated temperatures for a copolymer functionalized with two phosphonic acid (PA) groups on every 21st carbon atom. The cubic lattice has been identified as face-centered cubic (FCC). Overall, three morphology types have been identified for precise acid copolymers and ionomers at room temperature: (1) liquid-like order of aggregates dispersed throughout an amorphous PE matrix, (2) one-dimensional long-range order of aggregates in layers coexisting with PE crystals, and (3) three-dimensional periodicity of aggregates in cubic lattices in a PE matrix featuring defective packing. The liquid-like morphology is a result of high content of acid or ionic substituents deterring PE crystallinity due to steric hindrance. The layered morphology occurs when the content of pendants is low and the PE segments are long enough to crystallize. The cubic morphologies occur in precise copolymers with geminal substitution of phosphonic acid (PA) groups and long, flexible PE segments. At temperatures above the thermal transitions of the PE matrix, all but one material present a liquid-like morphology. Those conditions are ideal to study the evolution of the interaggregate spacing (d*) in X-ray scattering as a function of PE segment length between pendants, pendant type and pendant architecture (specifically, mono or geminal substitution). Also at elevated temperatures, the morphologies of precise acrylic acid (AA) copolymers and ionomers were investigated further via atomistic molecular dynamics (MD) simulations. The simulations complement X-ray scattering by providing real space visualization of the aggregates, demonstrating the occurrence of isolated, string-like and even percolated aggregate structures. This is the first dissertation completely devoted to the morphology of precise acid copolymers and precise ionomers. The complete analysis of the morphologies in these novel materials provides new insights into the shapes of aggregates in acid copolymers and ionomers in general. A key aspect of this thesis is the complementary use of experimental and simulation methods to unlock a wealth of new understanding.

Graft copolymerization of ethylacrylate onto xanthan gum, using potassium peroxydisulfate as an initiator.

PubMed

Pandey, Sadanand; Mishra, Shivani B

2011-11-01

Graft copolymer of xanthan gum (XG) and ethylacrylate (EA) has been synthesized by free radical polymerization using potassium peroxydisulfate (KPS) as an initiator in an air atmosphere. The grafting parameters, i.e. grafting ratio and efficiency decrease with increase in concentration of xanthan gum from 0.050 mg/25 mL to 0.350 mg/25 mL, but these grafting parameters increase with increase in concentration of ethylacrylate from 9×10(-2) to 17×10(-2) ML(-1), and KPS from 15×10(-3) to 35×10(-3) ML(-1). The graft copolymer has been characterized by FTIR, XRD, TGA and SEM analysis. The grafted copolymer was also evaluated as efficient Zn(2+) metal binder. The grafted copolymer shows improvement in the stability, solubility as well as their sorbing capacity. Thus graft copolymer formed could find applications in metal ion removal and in drug delivery. Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of Stereochemistry on Directed Self-Assembly of Poly(styrene-b-lactide) Films on Chemical Patterns

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Xiao; Liu, Yadong; Wan, Lei

2016-03-15

We demonstrated here for the first time that the stereochemistry of polylactide (PLA) blocks affected the assembly behaviors of PS-b-PLA on chemical patterns. Two PS-b-PLA block copolymers, where the PLA block is either racemic (PDLLA) or left-handed (PLLA), were synthesized and directed to assemble on chemical patterns with a wide range of L-s/L-o. PS-b-PDLLA was stretched up to 70% on chemical patterns, while PS-b-PLLA was only stretched by 20%. The assembly behavior of PS-b-PDLLA was different from AB diblock copolymer, but similar to that of ABA triblock copolymer. The high stretchability might be attributed to the formation of stereocomplexes inmore » PDLLA blocks. Compared to ABA triblock copolymers, stereocomplexed diblock copolymers have much faster assembly kinetics. This observation provides a new concept to achieve large process windows by the introduction of specific interactions, for example, H-bonding, supramolecular interaction, and sterecomplexation, between polymer chains.« less

A novel acrylamide-free flocculant and its application for sludge dewatering.

PubMed

Lu, Lianghua; Pan, Zhida; Hao, Nan; Peng, Wenqing

2014-06-15

In the present research, copolymers of methyl acrylate (MA) with anionic or cationic monomers were synthesized via emulsion polymerization, and used as sludge dewatering aids in wastewater treatment. The copolymerization of different stoichiometry of two monomers afforded a variety of water soluble copolymers with charge densities ranging from 40% to 80%, which align with the charge density of current flocculant products. These copolymers resemble current commercial products, but provide a greener solution by eliminating acrylamide monomer, which is a suspected carcinogen. High molecular weight copolymers were achieved by applying powder-like synthesis process with intrinsic viscosity of final products as high as 12.98 dl/g for anionic flocculant and 10.74 dl/g for cationic flocculant. The copolymers of methyl acrylate and [2-(Acryloyloxy)ethyl]trimethylammonium chloride (AETAC) with 55% charge density exhibited comparable performance in clay settling test, real water jar test, and sludge dewatering, when compared to AM-based commercial product in the real wastewater treatment application. Copyright © 2014 Elsevier Ltd. All rights reserved.

Directed self-assembly of block copolymers for nanolithography: fabrication of isolated features and essential integrated circuit geometries.

PubMed

Stoykovich, Mark P; Kang, Huiman; Daoulas, Kostas Ch; Liu, Guoliang; Liu, Chi-Chun; de Pablo, Juan J; Müller, Marcus; Nealey, Paul F

2007-10-01

Self-assembling block copolymers are of interest for nanomanufacturing due to the ability to realize sub-100 nm dimensions, thermodynamic control over the size and uniformity and density of features, and inexpensive processing. The insertion point of these materials in the production of integrated circuits, however, is often conceptualized in the short term for niche applications using the dense periodic arrays of spots or lines that characterize bulk block copolymer morphologies, or in the long term for device layouts completely redesigned into periodic arrays. Here we show that the domain structure of block copolymers in thin films can be directed to assemble into nearly the complete set of essential dense and isolated patterns as currently defined by the semiconductor industry. These results suggest that block copolymer materials, with their intrinsically advantageous self-assembling properties, may be amenable for broad application in advanced lithography, including device layouts used in existing nanomanufacturing processes.

Resonant soft x-ray GISAXS on block copolymer films

NASA Astrophysics Data System (ADS)

Wang, Cheng; Araki, T.; Watts, B.; Ade, H.; Hexemer, A.; Park, S.; Russell, T. P.; Schlotter, W. F.; Stein, G. E.; Tang, C.; Kramer, E. J.

2008-03-01

Ordered block copolymer thin films may have important applications in modern device fabrication. Current characterization methods such as conventional GISAXS have fixed electron density contrast that can be overwhelmed by surface scattering. However, soft x-rays have longer wavelength, energy dependent contrast and tunable penetration, making resonant GISAXS a very promising tool for probing nanostructured polymer thin films. Our preliminary investigation was performed using PS-b-P2VP block copolymer films on beam-line 5-2 SSRL, and beam-line 6.3.2 at ALS, LBNL. The contrast/sensitivity of the scattering pattern varies significantly with photon energy close to the C K-edge (˜290 eV). Also, higher order peaks are readily observed, indicating hexagonal packing structure in the sample. Comparing to the hard x-ray GISAXS data of the same system, it is clear that resonant GISAXS has richer data and better resolution. Beyond the results on the A-B diblock copolymers, results on ABC block copolymers are especially interesting.

Screen-Printing of ZnO Nanostructures from Sol-Gel Solutions for Their Application in Dye-Sensitized Solar Cells.

PubMed

Sarkar, Kuhu; Braden, Erik V; Bonke, Shannon A; Bach, Udo; Müller-Buschbaum, Peter

2015-08-24

Diblock copolymers have been used in sol-gel synthesis to successfully tailor the nanoscale morphology of thin ZnO films. As the fabrication of several-micron-thick mesoporous films such as those required in dye-sensitized solar cells (DSSCs) was difficult with this approach, we exploited the benefits of diblock-copolymer-directed synthesis that made it compatible with screen printing. The simple conversion of the diblock copolymer ZnO precursor sol to a screen-printing paste was not possible as it resulted in poor film properties. To overcome this problem, an alternative route is proposed in which the diblock copolymer ZnO precursor sol is first blade coated and calcined, then converted to a screen-printing paste. This allows the benefits of diblock-copolymer-directed particle formation to be compatible with printing methods. The morphologies of the ZnO nanostructures were studied by SEM and correlated with the current density-voltage characteristics. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetic hydrogels from alkyne/cobalt carbonyl-functionalized ABA triblock copolymers

DOE PAGES

Jiang, Bingyin; Hom, Wendy L.; Chen, Xianyin; ...

2016-03-09

A series of alkyne-functionalized poly(4-(phenylethynyl)styrene)- block-poly(ethylene oxide)- block-poly(4-(phenylethynyl)styrene) (PPES-b-PEO-b-PPES) ABA triblock copolymers was synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. PES n[Co 2(CO) 6] x-EO 800-PES n[Co 2(CO) 6] x ABA triblock copolymer/cobalt adducts (10–67 wt % PEO) were subsequently prepared by reaction of the alkyne-functionalized PPES block with Co 2(CO) 8 and their phase behavior was studied by TEM. Heating triblock copolymer/cobalt carbonyl adducts at 120 °C led to cross-linking of the PPES/Co domains and the formation of magnetic cobalt nanoparticles within the PPES/Co domains. Magnetic hydrogels could be prepared by swelling the PEO domains of the cross-linkedmore » materials with water. Furthermore, swelling tests, rheological studies and actuation tests demonstrated that the water capacity and modulus of the hydrogels were dependent upon the composition of the block copolymer precursors.« less

PLA-PEG-PLA copolymer-based polymersomes as nanocarriers for delivery of hydrophilic and hydrophobic drugs: preparation and evaluation with atorvastatin and lisinopril.

PubMed

Danafar, H; Rostamizadeh, K; Davaran, S; Hamidi, M

2014-10-01

Tri-block poly(lactide)-poly(ethylene glycol)-poly(lactide) (PLA-PEG-PLA) copolymers were synthesized and used to prepare polymersomes loaded separately by the hydrophobic and hydrophilic model drugs, atorvastatin and lisinopril, respectively. The resulting nanostructures were characterized by various techniques such as FTIR, DSC, PCS and AFM. The polymersomes exhibited high encapsulation efficiencies of almost 78% and 70.8% for atorvastatin and lisinopril, respectively. Investigation on FTIR and DSC results revealed that such a high encapsulation efficiency is due to strong interaction between atorvastatin and the copolymer. The impact of drug/copolymer ratio and copolymer composition on drug-loading efficiency and drug release behavior were also studied. The results showed that in case of lisinopril, polymersomes exhibited a triphasic drug release, while for atorvastatin a biphasic release profile was obtained. Overall, the results indicated that PLA-PEG-PLA polymersomes can be considered as a promising carrier for both hydrophilic and hydrophobic drugs.

Kinetic control of block copolymer self-assembly into multicompartment and novel geometry nanoparticles

NASA Astrophysics Data System (ADS)

Chen, Yingchao; Wang, Xiaojun; Zhang, Ke; Wooley, Karen; Mays, Jimmy; Percec, Virgil; Pochan, Darrin

2012-02-01

Micelles with the segregation of hydrophobic blocks trapped in the same nanoparticle core have been produced through co-self-assembly of two block copolymers in THF/water dilute solution. The dissolution of two block copolymer sharing the same polyacrylic acid PAA blocks in THF undergoes consequent aggregation and phase separation through either slow water titration or quick water addition that triggers the micellar formation. The combination and comparison of the two water addition kinetic pathways are the keys of forming multicompartment structures at high water content. Importantly, the addition of organic diamine provides for acid-base complexation with the PAA side chains which, in turn, plays the key role of trapping unlike hydrophobic blocks from different block copolymers into one nanoparticle core. The kinetic control of solution assembly can be applied to other molecular systems such as dendrimers as well as other block copolymer molecules. Transmission electron microscopy, cryogenic transmission electron microscopy, light scattering have been applied to characterize the micelle structures.

Morphology and conductivity of PEO-based polymers having various end functional groups

NASA Astrophysics Data System (ADS)

Jung, Ha Young; Mandal, Prithwiraj; Park, Moon Jeong

Poly(ethylene oxide) (PEO)-based polymers have been considered most promising candidates of polymer electrolytes for lithium batteries owing to the high ionic conductivity of PEO/lithium salt complexes. This positive aspect prompted researchers to investigate PEO-containing block copolymers prepared by linking mechanically robust block to PEO covalently. Given that the microphase separation of block copolymers can affect both mechanical properties and ion transport properties, various strategies have been reported to tune the morphology of PEO-containing block copolymers. In the present study, we describe a simple means for modulating the morphologies of PEO-based block copolymers with an aim to improve ion transport properties. By varying terminal groups of PEO in block copolymers, the disordered morphology can be readily transformed into ordered lamellae or gyroid phases, depending on the type and number density of end group. In particular, the existence of terminal groups resulted in a large reduction in crystallinity of PEO chains and thereby increasing room temperature ionic conductivity.

Nature of Interactions between PEO-PPO-PEO Triblock Copolymers and Lipid Membranes: (I) The Effect of Polymer Hydrophobicity on Its Ability to Protect Liposomes from Peroxidation

PubMed Central

Wang, Jia-Yu; Marks, Jeremy; Lee, Ka Yee C.

2013-01-01

PEO-PPO-PEO triblock copolymers have opposing effects on lipid membrane integrity- they can behave either as membrane sealants or as membrane permeabilizers. To gain insights into their biomembrane activities, the fundamental interactions between a series of PEO-based polymers and phospholipid vesicles were investigated. Specifically, the effect of copolymer hydrophobicity on its ability to prevent liposomes from peroxidation was evaluated, and partitioning free energy and coefficient involved in the interactions were derived. Our results show that the high degree of hydrophilicity is a key feature of the copolymers that can effectively protect liposomes from peroxidation and the protective effect of the copolymers stems from their adsorption at the membrane surface without penetrating into the bilayer core. The origin of this protective effect induced by polymer absorption is attributed to the retardation of membrane hydration dynamics, which is further illustrated in the accompany study on dynamic nuclear polarization (DNP)-derived hydration dynamics1. PMID:22808900

Fast assembly of ordered block copolymer nanostructures through microwave annealing.

PubMed

Zhang, Xiaojiang; Harris, Kenneth D; Wu, Nathanael L Y; Murphy, Jeffrey N; Buriak, Jillian M

2010-11-23

Block copolymer self-assembly is an innovative technology capable of patterning technologically relevant substrates with nanoscale precision for a range of applications from integrated circuit fabrication to tissue interfacing, for example. In this article, we demonstrate a microwave-based method of rapidly inducing order in block copolymer structures. The technique involves the usage of a commercial microwave reactor to anneal block copolymer films in the presence of appropriate solvents, and we explore the effect of various parameters over the polymer assembly speed and defect density. The approach is applied to the commonly used poly(styrene)-b-poly(methyl methacrylate) (PS-b-PMMA) and poly(styrene)-b-poly(2-vinylpyridine) (PS-b-P2VP) families of block copolymers, and it is found that the substrate resistivity, solvent environment, and anneal temperature all critically influence the self-assembly process. For selected systems, highly ordered patterns were achieved in less than 3 min. In addition, we establish the compatibility of the technique with directed assembly by graphoepitaxy.

Polyether-polyester graft copolymer

NASA Technical Reports Server (NTRS)

Bell, Vernon L. (Inventor)

1987-01-01

Described is a polyether graft polymer having improved solvent resistance and crystalline thermally reversible crosslinks. The copolymer is prepared by a novel process of anionic copolymerization. These polymers exhibit good solvent resistance and are well suited for aircraft parts. Previous aromatic polyethers, also known as polyphenylene oxides, have certain deficiencies which detract from their usefulness. These commercial polymers are often soluble in common solvents including the halocarbon and aromatic hydrocarbon types of paint thinners and removers. This limitation prevents the use of these polyethers in structural articles requiring frequent painting. In addition, the most popular commercially available polyether is a very high melting plastic. This makes it considerably more difficult to fabricate finished parts from this material. These problems are solved by providing an aromatic polyether graft copolymer with improved solvent resistance and crystalline thermally reversible crosslinks. The graft copolymer is formed by converting the carboxyl groups of a carboxylated polyphenylene oxide polymer to ionic carbonyl groups in a suitable solvent, reacting pivalolactone with the dissolved polymer, and adding acid to the solution to produce the graft copolymer.

Study of the therapeutic benefit of cationic copolymer administration to vascular endothelium under mechanical stress

PubMed Central

Giantsos-Adams, Kristina; Lopez-Quintero, Veronica; Kopeckova, Pavla; Kopecek, Jindrich; Tarbell, John M.; Dull, Randal

2015-01-01

Pulmonary edema and the associated increases in vascular permeability continue to represent a significant clinical problem in the intensive care setting, with no current treatment modality other than supportive care and mechanical ventilation. Therapeutic compound(s) capable of attenuating changes in vascular barrier function would represent a significant advance in critical care medicine. We have previously reported the development of HPMA-based copolymers, targeted to endothelial glycocalyx that are able to enhance barrier function. In this work, we report the refinement of copolymer design and extend our physiological studies todemonstrate that the polymers: 1) reduce both shear stress and pressure-mediated increase in hydraulic conductivity, 2) reduce nitric oxide production in response to elevated hydrostatic pressure and, 3) reduce the capillary filtration coefficient (Kfc) in an isolated perfused mouse lung model. These copolymers represent an important tool for use in mechanotransduction research and a novel strategy for developing clinically useful copolymers for the treatment of vascular permeability. PMID:20932573

Highly Ordered Block Copolymer Templates for the Generation of Nanostructured Materials

NASA Astrophysics Data System (ADS)

Bhoje Gowd, E.; Nandan, Bhanu; Bigall, Nadja C.; Eychmuller, Alexander; Stamm, Manfred

2009-03-01

Among many different types of self-assembled materials, block copolymers have attracted immense interest for applications in nanotechnology. Block copolymer thin film can be used as a template for patterning of hard inorganic materials such as metal nanoparticles. In the present work, we demonstrate a new approach to fabricate highly ordered arrays of nanoscopic inorganic dots and wires using switchable block copolymer thin films. Various inorganic nanoparticles from a simple aqueous solution were directly deposited on the surface reconstructed block copolymer templates. The preferential interaction of the nanoparticles with one of the blocks is mainly responsible for the lateral distribution of the nanoparticles in addition to the capillary forces. Subsequent stabilization by UV-irradiation followed by pyrolysis in air at 450 ^oC removes the polymer to produce highly ordered metallic nanostructures. This method is highly versatile as the procedure used here is simple, eco-friendly and provides a facile approach to fabricate a broad range of nanoscaled architectures with tunable lateral spacing.

Polydiacetylene/triblock copolymer nanoblend applied as a sensor for micellar casein: A thermodynamic approach.

PubMed

de Souza, Luana Cypriano; de Paula Rezende, Jaqueline; Pires, Ana Clarissa dos Santos; da Silva, Luis Henrique Mendes; da Silva, Maria do Carmo Hespanhol; Castrillon, Elkin Dario Castellon; de Andrade, Nélio José

2016-04-15

Polydiacetylene (PDA) and triblock copolymer nanoblends were synthesized to detect micellar casein (MC), the main milk protein and an indicator of milk quality. UV-Vis spectrum showed that MC induced blue-to-red transition in nanoblends. When nanoblends and MC were separated by dialysis membrane colorimetric response (CR) was similar, whereas a remarkable CR reduction was noticed after addition of dialyzed-MC, suggesting that small molecules present in MC (salts) caused PDA color change. Interaction enthalpy variation between nanoblends and MC showed an abrupt increase that coincided with MC concentration when colorimetric transition occurred. Copolymer hydrophobic/hydrophilic balance and presence of other molecules in the system affected nanoblends CR. MC salts were found to interact with nanoblends leading to color changes. MC concentration, MC salt release, copolymer hydrophobic/hydrophilic balance, and presence of other molecules in the system affected responses of the sensors. These results contribute to future applications of PDA/copolymer nanosensors to dairy models. Copyright © 2015 Elsevier Ltd. All rights reserved.

Evaluation of Isoprene Chain Extension from PEO Macromolecular Chain Transfer Agents for the Preparation of Dual, Invertible Block Copolymer Nanoassemblies.

PubMed

Bartels, Jeremy W; Cauët, Solène I; Billings, Peter L; Lin, Lily Yun; Zhu, Jiahua; Fidge, Christopher; Pochan, Darrin J; Wooley, Karen L

2010-09-14

Two RAFT-capable PEO macro-CTAs, 2 and 5 kDa, were prepared and used for the polymerization of isoprene which yielded well-defined block copolymers of varied lengths and compositions. GPC analysis of the PEO macro-CTAs and block copolymers showed remaining unreacted PEO macro-CTA. Mathematical deconvolution of the GPC chromatograms allowed for the estimation of the blocking efficiency, about 50% for the 5 kDa PEO macro-CTA and 64% for the 2 kDa CTA. Self assembly of the block copolymers in both water and decane was investigated and the resulting regular and inverse assemblies, respectively, were analyzed with DLS, AFM, and TEM to ascertain their dimensions and properties. Assembly of PEO-b-PIp block copolymers in aqueous solution resulted in well-defined micelles of varying sizes while the assembly in hydrophobic, organic solvent resulted in the formation of different morphologies including large aggregates and well-defined cylindrical and spherical structures.

Two-Dimensional Liquid Chromatography Analysis of Polystyrene/Polybutadiene Block Copolymers.

PubMed

Lee, Sanghoon; Choi, Heejae; Chang, Taihyun; Staal, Bastiaan

2018-05-15

A detailed characterization of a commercial polystyrene/polybutadiene block copolymer material (Styrolux) was carried out using two-dimensional liquid chromatography (2D-LC). The Styrolux is prepared by statistical linking reaction of two different polystyrene- block-polybutadienyl anion precursors with a multivalent linking agent. Therefore, it is a mixture of a number of branched block copolymers different in molecular weight, composition, and chain architecture. While individual LC analysis, including size exclusion chromatography, interaction chromatography, or liquid chromatography at critical condition, is not good enough to resolve all the polymer species, 2D-LC separations coupling two chromatography methods were able to resolve all polymer species present in the sample; at least 13 block copolymer species and a homopolystyrene blended. Four different 2D-LC analyses combining a different pair of two LC methods provide their characteristic separation results. The separation characteristics of the 2D-LC separations are compared to elucidate the elution characteristics of the block copolymer species.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Wei; Goodwin, Andrew; Wang, Yangyang

All-acrylic multigraft copolymers made by a facile synthesis procedure exhibit elongation at break >1700% and strain recovery behavior far exceeding those of commercial acrylic and styrenic triblock copolymers.

Complexation of anionic copolymers of acrylamide and N-(2-hydroxypropyl)methacrylamide with aminoglycoside antibiotics

NASA Astrophysics Data System (ADS)

Solovskii, M. V.; Tarabukina, E. B.; Amirova, A. I.; Zakharova, N. V.; Smirnova, M. Yu.; Gavrilova, I. I.

2014-03-01

The complexation of aminoglycoside antibiotics neomycin, gentamicin, kanamycin, and amikacin in the form of free bases with carboxyl- and sulfo-containing copolymers of acrylamide and N-(2-hydroxypropyl)methacrylamide (HPMA) in water and water-salt solutions is studied by means of viscometry, equilibrium dialysis, potentiometric titration, and molecular hydrodynamics. Factors influencing the stability of formed copolymer-antibiotic complexes and determinations of their toxicity are established.

Flame resistant fibrous materials. [developed from chlorofluoropolymers

NASA Technical Reports Server (NTRS)

1973-01-01

Four chlorofluoropolymer systems were developed that satisfactorily met the criteria for classification as self-extinguishing. Three of these systems consisted of Halar (a copolymer of chlorotrifluoroethylene and ethylene) and tin-based flame retardants. The fourth system was a copolymer of chlorotrifluoroethylene and tetrafluoroethylene with no flame retardants added. Production of fibers from all four candidates, by melt extrusion, was demonstrated. Fibers produced from the chlorotrifluoroethylene tetrafluoroethylene copolymer showed the most promise.

A 6-month study of the effects of 0.3% triclosan/copolymer dentifrice on dental implants.

PubMed

Sreenivasan, Prem K; Vered, Yuval; Zini, Avi; Mann, Jonathan; Kolog, Hilla; Steinberg, Doron; Zambon, Joseph J; Haraszthy, Violet I; da Silva, Maike P; De Vizio, William

2011-01-01

Supportive therapy to maintain dental implants is increasingly important. This study examined the effect of a 0.3% triclosan/2% copolymer dentifrice on oral biofilms and gingival inflammation (GI) on dental implants and peri-implant tissues. One hundred and twenty adults with a dental implant and contra-lateral tooth were enrolled in this 6 month, double-blind, two-treatment, parallel group study. Sixty subjects were randomly assigned to a triclosan/copolymer dentifrice test group and 60 subjects to a fluoride dentifrice control group and instructed to brush twice daily for 6 months. At baseline, 3, and 6 months, a calibrated dentist assessed dental plaque, GI and collected supragingival dental plaque for microbiological analysis. Subjects in the triclosan/copolymer group demonstrated significantly lower levels of dental plaque, gingivitis, and bleeding on probing at 3 and 6 months at both the implant and contra-lateral tooth compared with the fluoride group (p<0.05). There were significantly fewer Gram-negative anaerobes in the triclosan/copolymer group (p<0.05) including >90% reductions in Aggregatibacter actinomycetemcomitans, Campylobacter rectus, Eubacterium saburreum, Fusobacterium nucleatum, Porphyromonas gingivalis, Prevotella melaninogenica, Solobacterium moorei, and Tannerella forsythia. Twice daily use of a triclosan/copolymer dentifrice may enhance dental implant maintenance by reducing dental plaque and GI. © 2010 John Wiley & Sons A/S.

Controlled Thermoresponsive Hydrogels by Stereocomplexed PLA-PEG-PLA Prepared via Hybrid Micelles of Pre-Mixed Copolymers with Different PEG Lengths

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abebe, Daniel G.; Fujiwara, Tomoko

2012-09-05

The stereocomplexed hydrogels derived from the micelle mixture of two enantiomeric triblock copolymers, PLLA-PEG-PLLA and PDLA-PEG-PDLA, reported in 2001 exhibited sol-to-gel transition at approximately body temperature upon heating. However, the showed poor storage modulus (ca. 1000 Pa) determined their insufficiency as injectable implant biomaterials for many applications. In this study, the mechanical property of these hydrogels was significantly improved by the modifications of molecular weights and micelle structure. Co-micelles composed of block copolymers with two sizes of PEG block length were shown to possess unique and dissimilar properties from the micelles composed of single-sized block copolymers. The stereomixture of PLA-PEG-PLAmore » comicelles showed a controllable sol-to-gel transition at a wide temperature range of 4 and 80 C. The sol-gel phase diagram displays a linear relationship of temperature versus copolymer composition; hence, a transition at body temperature can be readily achieved by adjusting the mixed copolymer ratio. The resulting thermoresponsive hydrogels exhibit a storage modulus notably higher (ca. 6000 Pa) than that of previously reported hydrogels. As a physical network solely governed by self-reorganization of micelles, followed by stereocomplexation, this unique system offers practical, safe, and simple implantable biomaterials.« less

Tuning the chromaticity of the emission color of the copolymers containing Eu(III), Tb(III), Be(II) ions based on colorimetric principle

NASA Astrophysics Data System (ADS)

Zhang, Aiqin; Yang, Yamin; Zhai, Guangmei; Jia, Husheng; Xu, Bingshe

2016-02-01

In this work, a method of tuning the chromaticity of the emission color of the copolymers containing Eu(III), Tb(III), Be(II) ions based on colorimetric principle was proposed. The technological route from coordination to copolymerization was employed to obtain the white light macromolecular phosphor. The three primary color monomers have been synthesized and their Commission Internationale de L'Eclairage (CIE) coordinates are respectively (0.540, 0.314), (0.231, 0.463), and (0.161, 0.054). The molar feed ratios of the three primary color monomers were calculated from the CIE coordinates based on colorimetric principle. Serial copolymers have been synthesized by free radical copolymerization of the three primary color monomers and methyl methacrylate. The quantum efficiency of the copolymers was higher than that of the complex monomers. The complexes were directly boned to the polymer chain, in which the energy transfer was reduced significantly compared to the doped-polymers. The experimental values of copolymers' CIE coordinates were located in the white light region in good agreement with theoretical values. The results indicate that the chromaticity of the emission color of the copolymers containing Eu(III), Tb(III), Be(II) ions could be tuned by theoretical calculation based on colorimetric principle.

Location-Specific Measurements of The Glass Transition Temperature in Fluorescently Labeled Diblock Copolymers

NASA Astrophysics Data System (ADS)

Christie, Dane; Register, Richard; Priestley, Rodney

Block copolymers can self-assemble into periodic structures containing a high internal surface area, nanoscale domain periods, and periodically varying composition profiles. Depending on their components, block copolymers may also exhibit variations in their dynamic properties e.g., glass transition temperature (Tg) across the domain period. Measuring the variation of Tg across the domain period of block copolymers has remained a significant challenge due to the nanometer length scale of the domain period. Here we use fluorescence spectroscopy and the selective incorporation of a pyrene-containing methacrylate monomer at various positions along the chain to characterize the distribution of glass transition temperatures across the domain period of an amorphous block copolymer. The pyrene-containing monomer location is determined from the monomer segment distribution calculated using self-consistent field theory. Our model system is a lamella-forming diblock copolymer of poly(butyl methacrylate - b- methyl methacrylate). We show that Tg is asymmetrically distributed across the interface; as the interface is approached, larger gradients in Tg exist in the hard PMMA-rich domain than in the soft PBMA-rich domain. By characterizing Tg of PBMA or PMMA interfacial segments, we show that polymer dynamics at the interface are heterogeneous; there is a 15 K difference in Tg measured between PBMA interfacial segments and PMMA interfacial segments.

In vitro evaluation of anticancer nanomedicines based on doxorubicin and amphiphilic Y-shaped copolymers

PubMed Central

Li, Di; Ding, Jian Xun; Tang, Zhao Hui; Sun, Hai; Zhuang, Xiu Li; Xu, Jing Zhe; Chen, Xue Si

2012-01-01

Four monomethoxy poly(ethylene glycol)-poly(L-lactide-co-glycolide)2 (mPEG-P( LA-co-GA)2) copolymers were synthesized by ring-opening polymerization of L-lactide and glycolide with double hydroxyl functionalized mPEG (mPEG-(OH)2) as macroinitiator and stannous octoate as catalyst. The copolymers self-assembled into nanoscale micellar/vesicular aggregations in phosphate buffer at pH 7.4. Doxorubicin (DOX), an anthracycline anticancer drug, was loaded into the micellar/vesicular nanoparticles, yielding micellar/vesicular nanomedicines. The in vitro release behaviors could be adjusted by content of hydrophobic polyester and pH of the release medium. In vitro cell experiments showed that the intracellular DOX release could be adjusted by content of P(LA-co-GA), and the nanomedicines displayed effective proliferation inhibition against Henrietta Lacks’s cells with different culture times. Hemolysis tests indicated that the copolymers were hemocompatible, and the presence of copolymers could reduce the hemolysis ratio of DOX significantly. These results suggested that the novel anticancer nanomedicines based on DOX and amphiphilic Y-shaped copolymers were attractive candidates as tumor tissular and intracellular targeting drug delivery systems in vivo, with enhanced stability during circulation and accelerated drug release at the target sites. PMID:22701317

Three-dimensional block copolymer nanostructures by the solvent-annealing-induced wetting in anodic aluminum oxide templates.

PubMed

Chu, Chiang-Jui; Chung, Pei-Yun; Chi, Mu-Huan; Kao, Yi-Huei; Chen, Jiun-Tai

2014-09-01

Block copolymers have been extensively studied over the last few decades because they can self-assemble into well-ordered nanoscale structures. The morphologies of block copolymers in confined geometries, however, are still not fully understood. In this work, the fabrication and morphologies of three-dimensional polystyrene-block-polydimethylsiloxane (PS-b-PDMS) nanostructures confined in the nanopores of anodic aluminum oxide (AAO) templates are studied. It is discovered that the block copolymers can wet the nanopores using a novel solvent-annealing-induced nanowetting in templates (SAINT) method. The unique advantage of this method is that the problem of thermal degradation can be avoided. In addition, the morphologies of PS-b-PDMS nanostructures can be controlled by changing the wetting conditions. Different solvents are used as the annealing solvent, including toluene, hexane, and a co-solvent of toluene and hexane. When the block copolymer wets the nanopores in toluene vapors, a perpendicular morphology is observed. When the block copolymer wets the nanopores in co-solvent vapors (toluene/hexane = 3:2), unusual circular and helical morphologies are obtained. These three-dimensional nanostructures can serve as naontemplates for refilling with other functional materials, such as Au, Ag, ZnO, and TiO2 . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Block copolymer micelles for controlled delivery of glycolytic enzyme inhibitors.

PubMed

Akter, Shanjida; Clem, Brian F; Lee, Hyun Jin; Chesney, Jason; Bae, Younsoo

2012-03-01

To develop block copolymer micelles as an aqueous dosage form for a potent glycolytic enzyme inhibitor, 3-(3-pyridinyl)-1-(4-pyridinyl)-2-propen-1-one (3PO). The micelles were prepared from poly(ethylene glycol)-poly(aspartate hydrazide) [PEG-p(HYD)] block copolymers to which 3PO was conjugated through an acid-labile hydrazone bond. The optimal micelle formulation was determined following the screening of block copolymer library modified with various aromatic and aliphatic pendant groups. Both physical drug entrapment and chemical drug conjugation methods were tested to maximize 3PO loading in the micelles during the screening. Particulate characterization showed that the PEG-p(HYD) block copolymers conjugated with 3PO (2.08∼2.21 wt.%) appeared the optimal polymer micelles. Block copolymer compositions greatly affected the micelle size, which was 38 nm and 259 nm when 5 kDa and 12 kDa PEG chains were used, respectively. 3PO release from the micelles was accelerated at pH 5.0, potentiating effective drug release in acidic tumor environments. The micelles retained biological activity of 3PO, inhibiting various cancer cells (Jurkat, He-La and LLC) in concentration ranges similar to free 3PO. A novel micelle formulation for controlled delivery of 3PO was successfully prepared.

Synthesis and characterization of arginine-glycine-aspartic peptides conjugated poly(lactic acid-co-L-lysine) diblock copolymer.

PubMed

Yu, Hui; Guo, Xiaojuan; Qi, Xueliang; Liu, Peifeng; Shen, Xinyuan; Duan, Yourong

2008-03-01

A biodegradable Copolymer of poly(lactic acid-co-lysine)(PLA-PLL) was synthesized by a modified method and novel Arginine-Glycine-Aspartic (RGD) peptides were chemical conjugated to the primary epsilon-amine groups of lysine components in four steps: I to prepare the monomer of 3-(Nepsilon-benzoxycarbonyl-L-lysine)-6-L-methyl-2,5-morpholinedione; II to prepare diblock copolymer poly(lactic acid-co-(Z)-L-lysine) (PLA-PLL(Z)) by ring-opening polymerization of monomer and L,L-lactide with stannous octoate as initiator; III to prepare diblock copolymer PLA-PLL by deprotected the copolymer PLA-PLL(Z) in HBr/HoAc solution; IV the reaction between RGD and the primary epsilon-amine groups of the PLA-PLL. The structure of PLA-PLL-RGD and its precursors were conformed by FTIR-Raman and 1H NMR. Low weight average molecular weight (9,200 g/mol) of the PLA-PLL was obtained and its PDI is 1.33 determined by GPC. The PLA-PLL contained 2.1 mol% lysine groups as determined by 1H NMR using the lysine protecting group's phenyl protons. Therefore, the novel RGD-grafted diblock copolymer is expected to find application in drug carriers for tumor therapy or non-viral DNA carriers for gene therapy.

On the role of methacrylic acid copolymers in the intracellular delivery of antisense oligonucleotides.

PubMed

Yessine, Marie-Andrée; Meier, Christian; Petereit, Hans-Ulrich; Leroux, Jean-Christophe

2006-05-01

The delivery of active biomacromolecules to the cytoplasm is a major challenge as it is generally hindered by the endosomal/lysosomal barrier. Synthetic titratable polyanions can overcome this barrier by destabilizing membrane bilayers at pH values typically found in endosomes. This study investigates how anionic polyelectrolytes can enhance the cytoplasmic delivery of an antisense oligonucleotide (ODN). Novel methacrylic acid (MAA) copolymers were examined for their pH-sensitive properties and ability to destabilize cell membranes in a pH-dependent manner. Ternary complex formulations prepared with the ODN, a cationic lipid and a MAA copolymer were systematically characterized with respect to their size, zeta potential, antisense activity, cytotoxicity and cellular uptake using the A549 human lung carcinoma cell line. The MAA copolymer substantially increased the activity of the antisense ODN in inhibiting the expression of protein kinase C-alpha. Uptake, cytotoxicity and antisense activity were strongly dependent on copolymer concentration. Metabolic inhibitors demonstrated that endocytosis was the major internalization pathway of the complexes, and that endosomal acidification was essential for ODN activity. Confocal microscopy analysis of cells incubated with fluorescently-labeled complexes revealed selective delivery of the ODN, but not of the copolymer, to the cytoplasm/nucleus. This study provides new insight into the mechanisms of intracellular delivery of macromolecular drugs, using synthetic anionic polyelectrolytes.

Pyrolytic carbon membranes containing silica: morphological approach on gas transport behavior

NASA Astrophysics Data System (ADS)

Park, Ho Bum; Lee, Sun Yong; Lee, Young Moo

2005-04-01

Pyrolytic carbon membrane containing silica (C-SiO 2) is a new-class material for gas separation, and in the present work we will deal with it in view of the morphological changes arising from the difference in the molecular structure of the polymeric precursors. The silica embedded carbon membranes were fabricated by a predetermined pyrolysis step using imide-siloxane copolymers (PISs) that was synthesized from benzophenone tetracarboxylic dianhydrides (BTDA), 4,4'-oxydianiline (ODA), and amine-terminated polydimethylsiloxane (PDMS). To induce different morphologies at the same chemical composition, the copolymers were prepared using one-step (preferentially a random segmented copolymer) sand two-step polymerization (a block segmented copolymer) methods. The polymeric precursors and their pyrolytic C-SiO 2 membranes were analyzed using thermal analysis, atomic force microscopy, and transmission electron microscopy, etc. It was found that the C-SiO 2 membrane derived from the random PIS copolymer showed a micro-structure containing small well-dispersed silica domains, whereas the C-SiO 2 membrane from the block PIS copolymer exhibited a micro-structure containing large silica domains in the continuous carbon matrix. Eventually, the gas transport through these C-SiO 2 membranes was significantly affected by the morphological changes of the polymeric precursors.

Brownian dynamics simulation of amphiphilic block copolymers with different tail lengths, comparison with theory and comicelles.

PubMed

Hafezi, Mohammad-Javad; Sharif, Farhad

2015-11-01

Study on the effect of amphiphilic copolymers structure on their self assembly is an interesting subject, with important applications in the area of drug delivery and biological system treatments. Brownian dynamics simulations were performed to study self-assembly of the linear amphiphilic block copolymers with the same hydrophilic head, but hydrophobic tails of different lengths. Critical micelle concentration (CMC), gyration radius distribution, micelle size distribution, density profiles of micelles, shape anisotropy, and dynamics of micellization were investigated as a function of tail length. Simulation results were compared with predictions from theory and simulation for mixed systems of block copolymers with long and short hydrophobic tail, reported in our previous work. Interestingly, the equilibrium structural and dynamic parameters of pure and mixed block copolymers were similarly dependant on the intrinsic/apparent hydrophobic block length. Log (CMC) was, however; proportional to the tail length and had a different behavior compared to the mixed system. The power law scaling relation of equilibrium structural parameters for amphiphilic block copolymers predicts the same dependence for similar hydrophobic tail lengths, but the power law prediction of CMC is different, which is due to its simplifying assumptions as discussed here. Copyright © 2015 Elsevier Inc. All rights reserved.

Mesoporous Polymer Frameworks from End-Reactive Bottlebrush Copolymers

DOE PAGES

Altay, Esra; Nykypanchuk, Dmytro; Rzayev, Javid

2017-08-07

Reticulated nanoporous materials generated by versatile molecular framework approaches are limited to pore dimensions on the scale of the utilized rigid molecular building blocks (<5 nm). The inherent flexibility of linear polymers precludes their utilization as long framework connectors for the extension of this strategy to larger length scales. We report a method for the fabrication of mesoporous frameworks by using bottlebrush copolymers with reactive end blocks serving as rigid macromolecular interconnectors with directional reactivity. End-reactive bottlebrush copolymers with pendant alkene functionalities were synthesized by a combination of controlled radical polymerization and polymer modification protocols. Ru-catalyzed cross-metathesis cross-linking of bottlebrushmore » copolymers with two reactive end blocks resulted in the formation of polymer frameworks where isolated cross-linked domains were interconnected with bottlebrush copolymer bridges. The resulting materials were characterized by a continuous network pore structure with average pore sizes of 9–50 nm, conveniently tunable by the length of the utilized bottlebrush copolymer building blocks. As a result, the materials fabrication strategy described in this work expands the length scale of molecular framework materials and provides access to mesoporous polymers with a molecularly tunable reticulated pore structure without the need for templating, sacrificial component etching, or supercritical fluid drying.« less

Synthesis and characterization of donor-acceptor copolymers carrying triphenylamine units for photovoltaic applications

NASA Astrophysics Data System (ADS)

Neumann, Katharina; Thelakkat, Mukundan

2012-09-01

The synthesis and analysis of solution processable polymers for organic solar cells is crucial for innovative solar cell technologies such as printing processes. In the field of donor materials for photovoltaic applications, polymers based on tetraphenylamine (TPA) are well known hole conducting materials. Here, we synthesized two conjugated TPA containing copolymers via Suzuki polycondensation. We investigated the tuning of the energy levels of the TPA based polymers by two different concepts. Firstly, we introduced an acceptor unit in the side chain. The main-chain of this copolymer was built from TPA units. The resulting copolymer 2-(4-((4'-((4-(2-ethylhexyloxy)phenyl)(paratolyl) amino)biphenyl-4-yl)(para-tolyl)amino)benzylidene) malononitrile P1 showed a broader absorption up to 550 nm. Secondly, we used a donor-acceptor concept by synthesizing a copolymer with alternating electron donating TPA and electron withdrawing Thieno[3,4-b]thiophene ester units. Consequently, the absorption maximum in the copolymer octyl-6-(4-((4-(2-ethylhexyloxy)phenyl)(p-tolyl)amino)phenyl)-4-methylthieno[3,4-b]thiophene-2-carboxylate P2 was red shifted to 580 nm. All three polymers showed high thermal stability. By UV-vis and Cyclic voltammetry measurements the optical and electrochemical properties of the polymers were analyzed.

Self-assembly of block copolymer micelles: synthesis via reversible addition-fragmentation chain transfer polymerization and aqueous solution properties.

PubMed

Mya, Khine Y; Lin, Esther M J; Gudipati, Chakravarthy S; Gose, Halima B A S; He, Chaobin

2010-07-22

Poly(hexafluorobutyl methacrylate) (PHFBMA) homopolymer was synthesized by reversible addition-fragmentation chain transfer (RAFT)-mediated living radical polymerization in the presence of cyano-2-propyl dithiobenzoate (CPDB) RAFT agent. A block copolymer of PHFBMA-poly(propylene glycol acrylate) (PHFBMA-b-PPGA) with dangling poly(propylene glycol) (PPG) side chains was then synthesized by using CPDB-terminated PHFBMA as a macro-RAFT agent. The amphiphilic properties and self-assembly of PHFBMA-b-PPGA block copolymer in aqueous solution were investigated by dynamic and static light scattering (DLS and SLS) studies, in combination with fluorescence spectroscopy and transmission electron microscopy (TEM). Although PPG shows moderately hydrophilic character, the formation of nanosize polymeric micelles was confirmed by fluorescence and TEM studies. The low value of the critical aggregation concentration exhibited that the tendency for the formation of copolymer aggregates in aqueous solution was very high due to the strong hydrophobicity of the PHFBMA(145)-b-PPGA(33) block copolymer. The combination of DLS and SLS measurements revealed the existence of micellar aggregates in aqueous solution with an association number of approximately 40 +/- 7 for block copolymer micelles. It was also found in TEM observation that there are 40-50 micelles accumulated into one aggregate and these micelles are loosely packed inside the aggregate.

Production and characterization of medium-chain-length polyhydroxyalkanoate copolymer from Arctic psychrotrophic bacterium Pseudomonas sp. PAMC 28620.

PubMed

Sathiyanarayanan, Ganesan; Bhatia, Shashi Kant; Song, Hun-Suk; Jeon, Jong-Min; Kim, Junyoung; Lee, Yoo Kyung; Kim, Yun-Gon; Yang, Yung-Hun

2017-04-01

Arctic psychrotrophic bacterium Pseudomonas sp. PAMC 28620 was found to produce a distinctive medium-chain-length polyhydroxyalkanoate (MCL-PHA) copolymer when grown on structurally unrelated carbon sources including glycerol. The maximum MCL-PHA copolymer yield was obtained about 52.18±4.12% from 7.95±0.66g/L of biomass at 144h of fermentation when 3% glycerol was used as sole carbon and energy source during the laboratory-scale bioreactor process. Characterization of the copolymer was carried out using fourier transform infrared spectroscopy (FTIR), gas chromatography-mass spectrometry (GC-MS), proton ( 1 H) and carbon ( 13 C) nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), differential scanning calorimeter (DSC) and thermo-gravimetric analysis (TGA). The copolymer produced by Pseudomonas sp. PAMC 28620 consisting of four PHA monomers and identified as 3-hydroxyoctanoate (3HO), 3-hydroxydecanoate (3HD), 3-hydroxydodecanoate (3HDD) and 3-hydroxytetradecanoate (3HTD). An average molecular weight of the copolymer was found approximately 30.244kDa with polydispersity index (PDI) value of 2.05. Thermal analysis showed the produced MCL-PHA copolymer to be low-crystalline (43.73%) polymer with great thermal stability, having the thermal decomposition temperature of 230°C-280°C, endothermic melting temperature (T m ) of 172.84°C, glass transition (T g ) temperature of 3.99°C, and apparent melting enthalpy fusion (ΔH m ) about 63.85Jg -1 . Copyright © 2017 Elsevier B.V. All rights reserved.

Responsive copolymers for enhanced petroleum recovery. Second annual report

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCormick, C.; Hester, R.

The authors describe second year efforts in synthesis, characterization, and rheology to develop polymers with significantly improved efficiency in mobility control and conformance. These advanced polymer systems would maintain high viscosities or behave as virtual gels under low shear conditions and at elevated electrolyte concentrations. At high fluid shear rates, associates would deaggregate yielding low viscosity solutions, reducing problems of shear degradation or face plugging during injection. Polymeric surfactants were also developed with potential for use in higher salt, higher temperature reservoirs for mobilization of entrapped oil. Chapters include: Ampholytic terpolymers of acrylamide with sodium 3-acrylamido-3-methylbutanoate and 2-acrylamido-2-methylpropanetrimethylammonium chloride; Hydrophilicmore » sulfobetaine copolymers of acrylamide and 3-(2-acrylamido-methylpropane-dimethylammonio)-1-propanesulfonate; Copolymerization of maleic anhydride and N-vinylformamide; Reactivity ratio of N-vinylformamide with acrylamide, sodium acrylate, and n-butyl acrylate; Effect of the distribution of the hydrophobic cationic monomer dimethyldodecyl(2-acrylamidoethyl)ammonium bromide on the solution behavior of associating acrylamide copolymers; Effect of surfactants on the solution properties of amphipathic copolymers of acrylamide and N,N-dimethyl-N-dodecyl-N-(2-acrylamidoethyl)ammonium bromide; Associative interactions and photophysical behavior of amphiphilic terpolymers prepared by modification of maleic anhydride/ethyl vinyl ether copolymers; Copolymer compositions of high-molecular-weight functional acrylamido water-soluble polymers using direct-polarization magic-angle spinning {sup 13}C NMR; Use of factorial experimental design in static and dynamic light scattering characterization of water soluble polymers; and Porous medium elongational rheometer studies of NaAMB/AM copolymer solutions.« less

Novel rubbers from cationic copolymerization of soybean oils and dicyclopentadiene. 1. Synthesis and characterization.

PubMed

Andjelkovic, Dejan D; Larock, Richard C

2006-03-01

Novel thermosetting copolymers, ranging from tough and ductile to very soft rubbers, have been prepared by the cationic copolymerization of regular (SOY) and 100% conjugated soybean oils (C(100)SOY) with dicyclopentadiene (DCP) catalyzed by Norway fish oil (NFO)-modified and SOY- and C(100)SOY-diluted boron trifluoride diethyl etherate (BFE). The gelation time of the reactions varies from 4 to 991 min at 110 degrees C. The yields of the bulk copolymers are essentially quantitative, while the yields of the cross-linked copolymers remaining after Soxhlet extraction with methylene chloride range from 69% to 88%, depending on the monomer stoichiometry and the catalyst used. (1)H NMR spectroscopy and Soxhlet extraction data indicate that these copolymers consist of a cross-linked soybean oil-DCP network plasticized by certain amounts of methylene chloride-soluble linear or less cross-linked soybean oil-DCP copolymers, unreacted oil, and some low molecular weight hydrolyzed oil. The molecular weights of these soluble fractions are in the range from 400 to 10,000 g/mol based on polystyrene standards. The bulk copolymers have glass transition temperatures ranging from -22.6 to 56.6 degrees C, while their tan delta peak values range from 0.7 to 1.2. Thermogravimetric analysis (TGA) indicates that these soybean oil-DCP copolymers are thermally stable below 200 degrees C, with 10% and 50% weight loss temperatures ranging from 280 to 372 degrees C and 470-554 degrees C, respectively. These properties suggest that these biobased thermosets may prove useful alternatives to current petroleum-based plastics and find widespread utility.

Poly(Acrylic Acid-b-Styrene) Amphiphilic Multiblock Copolymers as Building Blocks for the Assembly of Discrete Nanoparticles

PubMed Central

Greene, Anna C.; Zhu, Jiahua; Pochan, Darrin J.; Jia, Xinqiao; Kiick, Kristi L.

2011-01-01

In order to expand the utility of current polymeric micellar systems, we have developed amphiphilic multiblock copolymers containing alternating blocks of poly(acrylic acid) and poly(styrene). Heterotelechelic poly(tert-butyl acrylate-b-styrene) diblock copolymers containing an α-alkyne and an ω-azide were synthesized by atom transfer radical polymerization (ATRP), allowing control over the molecular weight while maintaining narrow polydispersity indices. The multiblock copolymers were constructed by copper-catalyzed azide-alkyne cycloaddition of azide-alkyne end functional diblock copolymers which were then characterized by 1H NMR, FT-IR and SEC. The tert-butyl moieties of the poly(tert-butyl acrylate-b-styrene) multiblock copolymers were easily removed to form the poly(acrylic acid-b-styrene) multiblock copolymer ((PAA-PS)9), which contained up to 9 diblock repeats. The amphiphilic multiblock (PAA-PS)9 (Mn = 73.3 kg/mol) was self-assembled by dissolution into tetrahydrofuran and extensive dialysis against deionized water for 4 days. The critical micelle concentration (CMC) for (PAA-PS)9 was determined by fluorescence spectroscopy using pyrene as a fluorescent probe and was found to be very low at 2 × 10-4 mg/mL. The (PAA-PS)9 multiblock was also analyzed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The hydrodynamic diameter of the particles was found to be 11 nm. Discrete spherical particles were observed by TEM with an average particle diameter of 14 nm. The poly(acrylic acid) periphery of the spherical particles should allow for future conjugation of biomolecules. PMID:21552373

Side-chain amino-acid-based pH-responsive self-assembled block copolymers for drug delivery and gene transfer.

PubMed

Kumar, Sonu; Acharya, Rituparna; Chatterji, Urmi; De, Priyadarsi

2013-12-10

Developing safe and effective nanocarriers for multitype of delivery system is advantageous for several kinds of successful biomedicinal therapy with the same carrier. In the present study, we have designed amino acid biomolecules derived hybrid block copolymers which can act as a promising vehicle for both drug delivery and gene transfer. Two representative natural chiral amino acid-containing (l-phenylalanine and l-alanine) vinyl monomers were polymerized via reversible addition-fragmentation chain transfer (RAFT) process in the presence of monomethoxy poly(ethylene glycol) based macro-chain transfer agents (mPEGn-CTA) for the synthesis of well-defined side-chain amino-acid-based amphiphilic block copolymers, monomethoxy poly(ethylene glycol)-b-poly(Boc-amino acid methacryloyloxyethyl ester) (mPEGn-b-P(Boc-AA-EMA)). The self-assembled micellar aggregation of these amphiphilic block copolymers were studied by fluorescence spectroscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM). Potential applications of these hybrid polymers as drug carrier have been demonstrated in vitro by encapsulation of nile red dye or doxorubicin drug into the core of the micellar nanoaggregates. Deprotection of side-chain Boc- groups in the amphiphilic block copolymers subsequently transformed them into double hydrophilic pH-responsive cationic block copolymers having primary amino groups in the side-chain terminal. The DNA binding ability of these cationic block copolymers were further investigated by using agarose gel retardation assay and AFM. The in vitro cytotoxicity assay demonstrated their biocompatible nature and these polymers can serve as "smart" materials for promising bioapplications.

Multi-armed poly(L-glutamic acid)-graft-oligoethylenimine copolymers as efficient nonviral gene delivery vectors.

PubMed

Chen, Lei; Tian, Huayu; Chen, Jie; Chen, Xuesi; Huang, Yubin; Jing, Xiabin

2010-01-01

The application of polyethylenimine (PEI) in gene delivery has been severely limited by significant cytotoxicity that results from a nondegradable methylene backbone and high cationic charge density. It is therefore necessary to develop novel biodegradable PEI derivates for low-toxic, highly efficient gene delivery. A series of novel cationic copolymers with various charge density were designed and synthesized by grafting different kinds of oligoethylenimine (OEI) onto a determinate multi-armed poly(L-glutamic acid) backbone. The molecular structures of multi-armed poly(L-glutamic acid)-graft-OEI (MP-g-OEI) copolymers were characterized using nuclear magnetic resonance, viscosimetry and gel permeation chromatography. Moreover, the MP-g-OEI/DNA complexes were measured by a gel retardation assay, dynamic light scattering and atomic force microscopy to determine DNA binding ability, particle size, zeta potential, complex formation and shape, respectively. MP-g-OEI copolymers were also evaluated in Chinese hamster ovary and human embryonic kidney-293 cells for their cytotoxicity and transfection efficiency. The particle sizes of MP-g-OEI/DNA complexes were in a range of 109.6-182.6 nm and the zeta potentials were in a range of 29.2-44.5 mV above the N/P ratio of 5. All the MP-g-OEI copolymers exhibited lower cytotoxicity and higher gene transfection efficiency than PEI25k in the absence and presence of serum with different cell lines. Importantly, the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay revealed that the cytotoxicity of MP-g-OEI copolymers varied with their molecular weight and charge density, and two of MP-g-OEI copolymers (OEI600-MP and OEI1800-MP) could achieve optimal transfection efficiency at a similar low N/P ratio as that for PEI25k. MP-g-OEI copolymers demonstrated considerable potential as nonviral vectors for gene therapy. Copyright 2009 John Wiley & Sons, Ltd.

Structure-directing star-shaped block copolymers: supramolecular vesicles for the delivery of anticancer drugs.

PubMed

Yang, Chuan; Liu, Shao Qiong; Venkataraman, Shrinivas; Gao, Shu Jun; Ke, Xiyu; Chia, Xin Tian; Hedrick, James L; Yang, Yi Yan

2015-06-28

Amphiphilic polycarbonate/PEG copolymer with a star-like architecture was designed to facilitate a unique supramolecular transformation of micelles to vesicles in aqueous solution for the efficient delivery of anticancer drugs. The star-shaped amphipilic block copolymer was synthesized by initiating the ring-opening polymerization of trimethylene carbonate (TMC) from methyl cholate through a combination of metal-free organo-catalytic living ring-opening polymerization and post-polymerization chain-end derivatization strategies. Subsequently, the self-assembly of the star-like polymer in aqueous solution into nanosized vesicles for anti-cancer drug delivery was studied. DOX was physically encapsulated into vesicles by dialysis and drug loading level was significant (22.5% in weight) for DOX. Importantly, DOX-loaded nanoparticles self-assembled from the star-like copolymer exhibited greater kinetic stability and higher DOX loading capacity than micelles prepared from cholesterol-initiated diblock analogue. The advantageous disparity is believed to be due to the transformation of micelles (diblock copolymer) to vesicles (star-like block copolymer) that possess greater core space for drug loading as well as the ability of such supramolecular structures to encapsulate DOX. DOX-loaded vesicles effectively inhibited the proliferation of 4T1, MDA-MB-231 and BT-474 cells, with IC50 values of 10, 1.5 and 1.0mg/L, respectively. DOX-loaded vesicles injected into 4T1 tumor-bearing mice exhibited enhanced accumulation in tumor tissue due to the enhanced permeation and retention (EPR) effect. Importantly, DOX-loaded vesicles demonstrated greater tumor growth inhibition than free DOX without causing significant body weight loss or cardiotoxicity. The unique ability of the star-like copolymer emanating from the methyl cholate core provided the requisite modification in the block copolymer interfacial curvature to generate vesicles of high loading capacity for DOX with significant kinetic stability that have potential for use as an anti-cancer drug delivery carrier for cancer therapy. Copyright © 2015 Elsevier B.V. All rights reserved.

Copolymères (carbazolylène-pyrrolylène) : synthèse par oxydation chimique et propriétés

NASA Astrophysics Data System (ADS)

Boucard, V.; Adès, D.; Siove, A.

1998-06-01

Conditions in which (carbazolylene-pyrrolylene) random copolymers could be synthetized directly by chemical oxidation by FeCl3 were studied. A substantial amount of soluble copolymers is obtained after work-up in the conditions corresponding to carbazole/pyrrole/2 FeCl3 molar proportions. An important fraction of polypyrrole was obtained beside a fraction of species soluble in ethanol (carbazole and dimer) and an other fraction of products soluble in water (pyrrole accompanied by the first terms of the oligomeric series). Soluble copolymers were characterized by means of SEC, NMR and UV-Visible spectroscopies. Cyclic voltammetry analysis disclosed that these copolymers exhibit both the carbazolic and the pyrrolic features. Les conditions dans lesquelles des copolymères statistiques (carbazo lylène-pyrrolylène) pouvaient être synthétisés directement par oxydation chimique par FeCl3 ont été étudiées. Des quantités substantielles de copolymères solubles en milieu organique sont obtenues par extraction lorsque les proportions molaires en réactifs carbazole/pyrrole/2 FeCl3 sont utilisées. Une fraction importante de polypyrrole est obtenue à côté d'une fraction d'espèces solubles dans l'éthanol (carbazole et son dimère) et d'une fraction de produits solubles dans l'eau (pyrrole et les premiers termes oligomères). Les copolymères solubles ont été caractérisés par CES, spectroscopies RMN et UV-Visible. L'analyse voltampérométrique de ces matériaux révèle qu'ils possèdent à la fois les caractéristiques des entités carbazolylènes et celles des entités pyrrolylènes.

Synthesis of carboxylic block copolymers via reversible addition fragmentation transfer polymerization for tooth erosion prevention.

PubMed

Lei, Y; Wang, T; Mitchell, J W; Qiu, J; Kilpatrick-Liverman, L

2014-12-01

Dental professionals are seeing a growing population of patients with visible signs of dental erosion. The approach currently being used to address the problem typically leverages the enamel protection benefits of fluoride. In this report, an alternative new block copolymer with a hydrophilic polyacrylic acid (PAA) block and a hydrophobic poly(methyl methacrylate) (PMMA) block was developed to similarly reduce the mineral loss from enamel under acidic conditions. This series of PMMA-b-PAA block copolymers was synthesized by reversible addition fragmentation transfer (RAFT) polymerization. Their structures were characterized by gel permeation chromatography (GPC) and (1)H nuclear magnetic resonance (NMR) spectra. The molar fractions of acrylic acid (AA) in the final block copolymer were finely controlled from 0.25 to 0.94, and the molecular weight (Mn) of PMMA-b-PAA was controlled from 10 kDa to 90 kDa. The binding capability of the block copolymer with hydroxyapatite (HAP) was investigated by ultraviolet-visible spectroscopy (UV-Vis) and Fourier transform infrared (FTIR) spectroscopy. FTIR spectra confirmed that the PMMA-b-PAA block copolymer could bind to HAP via bridging bidentate bonds. Both UV-Vis and FTIR spectra additionally indicated that a high polymer concentration and low solution pH favored the polymer binding to HAP. The erosion-preventing efficacy of the PMMA-b-PAA block copolymer in inhibiting HAP mineral loss was quantitatively evaluated by atomic absorption spectroscopy (AAS). Based on the results, polymer treatment reduced the amount of calcium released by 27% to 30% in comparison with the unprotected samples. Scanning electron microscope (SEM) observations indicated that PMMA-b-PAA polymer treatment protected enamel from acid erosion. This new amphiphilic block copolymer has significant potential to be integrated into dentifrices or mouthrinses as an alternative non-fluoride ingredient to reduce tooth erosion. © International & American Associations for Dental Research.

Synthesis of Carboxylic Block Copolymers via Reversible Addition Fragmentation Transfer Polymerization for Tooth Erosion Prevention

PubMed Central

Lei, Y.; Wang, T.; Mitchell, J.W.; Qiu, J.; Kilpatrick-Liverman, L.

2014-01-01

Dental professionals are seeing a growing population of patients with visible signs of dental erosion. The approach currently being used to address the problem typically leverages the enamel protection benefits of fluoride. In this report, an alternative new block copolymer with a hydrophilic polyacrylic acid (PAA) block and a hydrophobic poly(methyl methacrylate) (PMMA) block was developed to similarly reduce the mineral loss from enamel under acidic conditions. This series of PMMA-b-PAA block copolymers was synthesized by reversible addition fragmentation transfer (RAFT) polymerization. Their structures were characterized by gel permeation chromatography (GPC) and 1H nuclear magnetic resonance (NMR) spectra. The molar fractions of acrylic acid (AA) in the final block copolymer were finely controlled from 0.25 to 0.94, and the molecular weight (Mn) of PMMA-b-PAA was controlled from 10 kDa to 90 kDa. The binding capability of the block copolymer with hydroxyapatite (HAP) was investigated by ultraviolet–visible spectroscopy (UV-Vis) and Fourier transform infrared (FTIR) spectroscopy. FTIR spectra confirmed that the PMMA-b-PAA block copolymer could bind to HAP via bridging bidentate bonds. Both UV-Vis and FTIR spectra additionally indicated that a high polymer concentration and low solution pH favored the polymer binding to HAP. The erosion-preventing efficacy of the PMMA-b-PAA block copolymer in inhibiting HAP mineral loss was quantitatively evaluated by atomic absorption spectroscopy (AAS). Based on the results, polymer treatment reduced the amount of calcium released by 27% to 30% in comparison with the unprotected samples. Scanning electron microscope (SEM) observations indicated that PMMA-b-PAA polymer treatment protected enamel from acid erosion. This new amphiphilic block copolymer has significant potential to be integrated into dentifrices or mouthrinses as an alternative non-fluoride ingredient to reduce tooth erosion. PMID:25248611

"Non-equilibrium" block copolymer micelles with glassy cores: a predictive approach based on theory of equilibrium micelles.

PubMed

Nagarajan, Ramanathan

2015-07-01

Micelles generated in water from most amphiphilic block copolymers are widely recognized to be non-equilibrium structures. Typically, the micelles are prepared by a kinetic process, first allowing molecular scale dissolution of the block copolymer in a common solvent that likes both the blocks and then gradually replacing the common solvent by water to promote the hydrophobic blocks to aggregate and create the micelles. The non-equilibrium nature of the micelle originates from the fact that dynamic exchange between the block copolymer molecules in the micelle and the singly dispersed block copolymer molecules in water is suppressed, because of the glassy nature of the core forming polymer block and/or its very large hydrophobicity. Although most amphiphilic block copolymers generate such non-equilibrium micelles, no theoretical approach to a priori predict the micelle characteristics currently exists. In this work, we propose a predictive approach for non-equilibrium micelles with glassy cores by applying the equilibrium theory of micelles in two steps. In the first, we calculate the properties of micelles formed in the mixed solvent while true equilibrium prevails, until the micelle core becomes glassy. In the second step, we freeze the micelle aggregation number at this glassy state and calculate the corona dimension from the equilibrium theory of micelles. The condition when the micelle core becomes glassy is independently determined from a statistical thermodynamic treatment of diluent effect on polymer glass transition temperature. The predictions based on this "non-equilibrium" model compare reasonably well with experimental data for polystyrene-polyethylene oxide diblock copolymer, which is the most extensively studied system in the literature. In contrast, the application of the equilibrium model to describe such a system significantly overpredicts the micelle core and corona dimensions and the aggregation number. The non-equilibrium model suggests ways to obtain different micelle sizes for the same block copolymer, by the choices we can make of the common solvent and the mode of solvent substitution. Published by Elsevier Inc.

Self-oscillating AB diblock copolymer developed by post modification strategy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ueki, Takeshi, E-mail: ueki@cross.t.u-tokyo.ac.jp, E-mail: ryo@cross.t.u-tokyo.ac.jp; Onoda, Michika; Tamate, Ryota

We prepared AB diblock copolymer composed of hydrophilic poly(ethylene oxide) segment and self-oscillating polymer segment. In the latter segment, ruthenium tris(2,2′-bipyridine) (Ru(bpy){sub 3}), a catalyst of the Belousov-Zhabotinsky reaction, is introduced into the polymer architecture based on N-isopropylacrylamide (NIPAAm). The Ru(bpy){sub 3} was introduced into the polymer segment by two methods; (i) direct random copolymerization (DP) of NIPAAm and Ru(bpy){sub 3} vinyl monomer and (ii) post modification (PM) of Ru(bpy){sub 3} with random copolymer of NIPAAm and N-3-aminopropylmethacrylamide. For both the diblock copolymers, a bistable temperature region (the temperature range; ΔT{sub m}), where the block copolymer self-assembles into micelle atmore » reduced Ru(bpy){sub 3}{sup 2+} state whereas it breaks-up into individual polymer chain at oxidized Ru(bpy){sub 3}{sup 3+} state, monotonically extends as the composition of the Ru(bpy){sub 3} increases. The ΔT{sub m} of the block copolymer prepared by PM is larger than that by DP. The difference in ΔT{sub m} is rationalized from the statistical analysis of the arrangement of the Ru(bpy){sub 3} moiety along the self-oscillating segments. By using the PM method, the well-defined AB diblock copolymer having ΔT{sub m} (ca. 25 °C) large enough to cause stable self-oscillation can be prepared. The periodic structural transition of the diblock copolymer in a dilute solution ([Polymer] = 0.1 wt. %) is closely investigated in terms of the time-resolved dynamic light scattering technique at constant temperature in the bistable region. A macroscopic viscosity oscillation of a concentrated polymer solution (15 wt. %) coupled with the periodic microphase separation is also demonstrated.« less

Biocompatibility of a polyether urethane, polypropylene oxide, and a polyether polyester copolymer. A qualitative and quantitative study of three alloplastic tympanic membrane materials in the rat middle ear.

PubMed

Bakker, D; van Blitterswijk, C A; Hesseling, S C; Koerten, H K; Kuijpers, W; Grote, J J

1990-04-01

The biocompatibility of porous implants made of Estane 5714 F1 polyether urethane, polypropylene oxide, and a poly(ethylene oxide hydantoin) and poly(tetramethylene terephthalate) segmented polyether polyester copolymer (HPOE/PBT copolymer), which were selected as candidates for an alloplastic tympanic membrane, was assessed after implantation in rat middle ears for periods of up to 1 year. Implantation of the materials led to tissue reactions initially associated with the wound-healing process, whereas after 1 month not only the presence of macrophages and foreign-body giant cells surrounding the implant materials but also implant degradation were characteristic for a foreign-body reaction. Macrophages and foreign-body giant cells dominated the picture of the tissue surrounding polypropylene oxide. The altered morphology of these cells, the persistent infiltration of the implantation sites by exudate cells, and the premature death of five rats in the 1-year group suggest that polypropylene oxide degradation was accompanied by the release of toxic substances. Estane and copolymer degradation did not induce tissue responses reflecting implant toxicity, and tympanic membranes given these alloplasts showed a normal healing pattern. Inclusions in the cytoplasm of macrophages associated with degradation and phagocytosis of all of the polymers under study were found to contain iron, silicon, titanium, and aluminum. Growth of fibrous tissue and bone, the latter into Estane and HPOE/PBT copolymer implants, indicated appropriate implant fixation by tissue, although macrophages and foreign-body giant cells were present as well. Especially the fixation of copolymer by ingrowth of bone seems promising in terms of the amount of bone in the pores and the electron-dense bone/copolymer interface. The latter is indicative for bonding osteogenesis. The HPOE/PBT copolymer is a better candidate for alloplastic tympanic membrane than Estane, and the use of polypropylene oxide cannot be recommended.

High-performance polymer waveguide devices via low-cost direct photolithography process

NASA Astrophysics Data System (ADS)

Wang, Jianguo; Shustack, Paul J.; Garner, Sean M.

2002-09-01

All-optical networks provide unique opportunities for polymer waveguide devices because of their excellent mechanical, thermo-optic, and electro-optic properties. Polymer materials and components have been viewed as a viable solution for metropolitan and local area networks where high volume and low cost components are needed. In this paper, we present our recent progress on the design and development of photoresist-like highly fluorinated maleimide copolymers including waveguide fabrication and optical testing. We have developed and synthesized a series of thermally stable, (Tg>150 oC, Td>300 oC) highly fluorinated (>50%) maleimide copolymers by radical co-polymerization of halogenated maleimides with various halogenated co-monomers. A theoretical correlation between optical loss and different co-polymer structures has been quantitatively established from C-H overtone analysis. We studied this correlation through design and manipulation of the copolymer structure by changing the primary properties such as molecular weight, copolymer composition, copolymer sequence distribution, and variations of the side chain including photochemically functional side units. Detailed analysis has been obtained using various characterization methods such as (H, C13, F19) NMR, UV-NIR, FTIR, GPC and so forth. The co-polymers exhibit excellent solubility in ketone solvents and high quality thin films can be prepared by spin coating. The polymer films were found to have a refractive index range of 1.42-1.67 and optical loss in the range of 0.2 to 0.4 dB/cm at 1550nm depending on the composition as extrapolated from UV-NIR spectra. When glycidyl methacrylate is incorporated into the polymer backbone, the material behaves like a negative photoresist with the addition of cationic photoinitiator. The final crosslinked waveguides show excellent optical and thermal properties. The photolithographic processing of the highly fluorinated copolymer material was examined in detail using in-situ FTIR. The influence of various polymer

Modeling and self-assembly behavior of PEG-PLA-PEG triblock copolymers in aqueous solution

NASA Astrophysics Data System (ADS)

Wu, Xiaohan; Li, Suming; Coumes, Fanny; Darcos, Vincent; Lai Kee Him, Joséphine; Bron, Patrick

2013-09-01

A series of poly(ethylene glycol)-polylactide-poly(ethylene glycol) (PEG-PLA-PEG) triblock copolymers with symmetric or asymmetric chain structures were synthesized by combination of ring-opening polymerization and copper-catalyzed click chemistry. The resulting copolymers were used to prepare self-assembled aggregates by dialysis. Various architectures such as nanotubes, polymersomes and spherical micelles were observed from transmission electron microscopy (TEM), cryo-TEM and atomic force microscopy (AFM) measurements. The formation of diverse aggregates is explained by modeling from the angle of both geometry and thermodynamics. From the angle of geometry, a ``blob'' model based on the Daoud-Cotton model for star polymers is proposed to describe the aggregate structures and structural changes with copolymer composition and molar mass. In fact, the copolymer chains extend in aqueous medium to form single layer polymersomes to minimize the system's free energy if one of the two PEG blocks is short enough. The curvature of polymersomes is dependent on the chain structure of copolymers, especially on the length of PLA blocks. A constant branch number of aggregates (f) is thus required to preserve the morphology of polymersomes. Meanwhile, the aggregation number (Nagg) determined from the thermodynamics of self-assembly is roughly proportional to the total length of polymer chains. Comparing f to Nagg, the aggregates take the form of polymersomes if Nagg ~ f, and change to nanotubes if Nagg > f to conform to the limits from both curvature and aggregation number. The length of nanotubes is mainly determined by the difference between Nagg and f. However, the hollow structure becomes unstable when both PEG segments are too long, and the aggregates eventually collapse to yield spherical micelles. Therefore, this work gives new insights into the self-assembly behavior of PEG-PLA-PEG triblock copolymers in aqueous solution which present great interest for biomedical and pharmaceutical applications.A series of poly(ethylene glycol)-polylactide-poly(ethylene glycol) (PEG-PLA-PEG) triblock copolymers with symmetric or asymmetric chain structures were synthesized by combination of ring-opening polymerization and copper-catalyzed click chemistry. The resulting copolymers were used to prepare self-assembled aggregates by dialysis. Various architectures such as nanotubes, polymersomes and spherical micelles were observed from transmission electron microscopy (TEM), cryo-TEM and atomic force microscopy (AFM) measurements. The formation of diverse aggregates is explained by modeling from the angle of both geometry and thermodynamics. From the angle of geometry, a ``blob'' model based on the Daoud-Cotton model for star polymers is proposed to describe the aggregate structures and structural changes with copolymer composition and molar mass. In fact, the copolymer chains extend in aqueous medium to form single layer polymersomes to minimize the system's free energy if one of the two PEG blocks is short enough. The curvature of polymersomes is dependent on the chain structure of copolymers, especially on the length of PLA blocks. A constant branch number of aggregates (f) is thus required to preserve the morphology of polymersomes. Meanwhile, the aggregation number (Nagg) determined from the thermodynamics of self-assembly is roughly proportional to the total length of polymer chains. Comparing f to Nagg, the aggregates take the form of polymersomes if Nagg ~ f, and change to nanotubes if Nagg > f to conform to the limits from both curvature and aggregation number. The length of nanotubes is mainly determined by the difference between Nagg and f. However, the hollow structure becomes unstable when both PEG segments are too long, and the aggregates eventually collapse to yield spherical micelles. Therefore, this work gives new insights into the self-assembly behavior of PEG-PLA-PEG triblock copolymers in aqueous solution which present great interest for biomedical and pharmaceutical applications. Electronic supplementary information (ESI) available: 1H-NMR, DOSY, FTIR, and GPC measurements, methods and results of the copolymers in PEG-PLA-PEG synthesis. See DOI: 10.1039/c3nr02899b

High-Molecular Compounds (Selected Articles).

DTIC Science & Technology

1987-10-15

us ions The method of potentiometric titration in dimethylformamide was used to study the structure of macro molecular chain of copolymers based on...macromolecular chain we used the method of potential metric titration . The objects of the study uere alpha chloroacrylic acid (KO)K) in monomer...homopolymer, and copolymer (with methylmethacrylate) form 131. I e d* r. I%0 I 0 12 # z Curves of potential metric titration of solutions of copolymers of KjAK

Immobilization of polyphenol oxidase in conducting copolymers and determination of phenolic compounds in wines with enzyme electrodes.

PubMed

Kiralp, Senem; Toppare, Levent; Yağci, Yusuf

2003-11-01

Polyphenol oxidase (PPO) was immobilized in copolymers of thiophene functionalized menthyl monomer (MM) with pyrrole. Immobilization of enzyme was performed via entrapment in conducting copolymers during electrochemical polymerization of pyrrole. Maximum reaction rates, Michaelis-Menten constants and temperature, pH and operational stabilities of enzyme electrodes were investigated. Total amount of phenolic compounds in red wines of Turkey were analyzed by using these electrodes.

Photooxidative degradation of clear ultraviolet absorbing acrylic copolymer surfaces

NASA Technical Reports Server (NTRS)

Gupta, A.; Liang, R. H.; Vogl, O.; Pradellok, W.; Huston, A. L.; Scott, G. W.

1983-01-01

Photodegradation of copolymer of methyl methacrylate and 2(2'-hydroxy 5'vinyl-phenyl) 2H-benzotriazole has been investigated in order to determine the changes in the chemical composition of the surface of the copolymer on photooxidation. An electronic energy transfer mechanism has been postulated in order to interpret the observed photochemical changes in the polymer. Preliminary examination of the photophysical properties of the chromophore provides support for such a mechanism.

Palladium (Ii) Catalyzed Polymerization Of Norbornene And Acrylates

DOEpatents

Sen, Ayusman; Kacker, Smita; Hennis, April; Polley, Jennifer D.

2001-10-09

Homopolymers or copolymers of acrylates, homopolymers or copolymers of norbornenes, and copolymers of acrylates with norbornenes, may be prepared by contacting acrylate and/or norbornene monomer reactant under polymerization conditions and in the presence of a solvent with a catalyst system consisting essentially of a Pd(II) dimer component having the formula: where L is a monodentate phosphorus or nitrogen ligand, X is an anionic group, and R is an alkyl or aryl group.

Macroscopic Modeling of A3B15A3 Triblock Copolymers in B Solvent

DTIC Science & Technology

2010-11-01

matrix composed of the midblock (2). Some examples of TPEs are poly[styrene-butadiene-styrene] (SBS), poly[styrene- isoprene -styrene] (SIS), poly[styrene...92. 19. Hadziioannou, G.; Skoulios, A. Molecular Weight Dependence of Lamellar Structure in Styrene Isoprene Two- and Three-block Copolymers...Microphase Seperation in Styrene- Isoprene Block Copolymers. Macromolecules 1994, 27. 42. Mckay, K. W.; Gros, W. A.; Diehl, C. F. The Influence of

Rod-Coil Block Polyimide Copolymers

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B. (Inventor); Kinder, James D. (Inventor)

2005-01-01

This invention is a series of rod-coil block polyimide copolymers that are easy to fabricate into mechanically resilient films with acceptable ionic or protonic conductivity at a variety of temperatures. The copolymers consist of short-rigid polyimide rod segments alternating with polyether coil segments. The rods and coil segments can be linear, branched or mixtures of linear and branched segments. The highly incompatible rods and coil segments phase separate, providing nanoscale channels for ion conduction. The polyimide segments provide dimensional and mechanical stability and can be functionalized in a number of ways to provide specialized functions for a given application. These rod-coil black polyimide copolymers are particularly useful in the preparation of ion conductive membranes for use in the manufacture of fuel cells and lithium based polymer batteries.

Microbial Cometabolism and Polyhydroxyalkanoate Co-polymers.

PubMed

Ray, Subhasree; Kalia, Vipin Chandra

2017-03-01

Polyhydroxyalkanoate (PHAs) are natural, biodegradable biopolymers, which can be produced from renewable materials. PHAs have potential to replace petroleum derived plastics. Quite a few bacteria can produce PHA under nutritional stress. They generally produce homopolymers of butyrate i.e., polyhydroxybutyrate (PHB), as a storage material. The biochemical characteristics of PHB such as brittleness, low strength, low elasticity, etc. make these unsuitable for commercial applications. Co-polymers of PHA, have high commercial value as they overcome the limitations of PHBs. Co-polymers can be produced by supplementing the feed with volatile fatty acids or through hydrolysates of different biowastes. In this review, we have listed the potential bacterial candidates and the substrates, which can be co-metabolized to produce PHA co-polymers.

Humidity-Induced Phase Transitions in Ion-Containing Block Copolymer Membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Moon Jeong; Nedoma, Alisyn J.; Geissler, Phillip L.

2008-08-21

The phase behavior of ion-containing block copolymer membranes in equilibrium with humidified air is studied as a function of the relative humidity (RH) of the surrounding air, ion content of the copolymer, and temperature. Increasing RH at constant temperature results in both disorder-to-order and order-to-order transitions. In-situ small-angle neutron scattering experiments on the open block copolymer system, when combined with water uptake measurement, indicate that the disorder-to-order transition is driven by an increase in the partial molar entropy of the water molecules in the ordered phase relative to that in the disordered phase. This is in contrast to most systemsmore » wherein increasing entropy results in stabilization of the disordered phase.« less

ABC triblock copolymer vesicles with mesh-like morphology.

PubMed

Zhao, Wei; Chen, Dian; Hu, Yunxia; Grason, Gregory M; Russell, Thomas P

2011-01-25

Polymer vesicles made from poly(isoprene-b-styrene-b-2-vinyl pyridine) (PI-b-PS-b-P2VP) triblock copolymer confined within the nanopores of an anodic aluminum oxide (AAO) membrane are studied. It was found that these vesicles have well-defined, nanoscopic size, and complex microphase-separated hydrophobic membranes, comprised of the PS and PI blocks, while the coronas are formed by the P2VP block. Vesicle formation was tracked using both transmission and scanning electron microscopy. A mesh-like morphology formed in the membrane at a well-defined composition of the three blocks that can be tuned by changing the copolymer composition. The nanoscale confinement, copolymer composition, and subtle molecular interactions contribute to the generation of these vesicles with such unusual morphologies.

Preparation and characterization of the graft copolymer of chitosan with poly[rosin-(2-acryloyloxy)ethyl ester].

PubMed

Duan, Wengui; Chen, Chunhong; Jiang, Linbin; Li, Guang Hua

2008-09-05

Graft copolymerization of rosin-(2-acryloyloxy)ethyl ester (RAEE) onto chitosan (Cts) was carried out under microwave irradiation using potassium persulfate as an initiator. The structures, morphology, and thermal properties of the Cts graft copolymer (Cts-g-PRAEE) were characterized by means of FT-IR, XRD, SEM, and TG. Also, Cts and Cts-g-PRAEE copolymer were used as carriers of fenoprofen calcium (FC), and their controlled release behavior in artificial intestinal juice were studied. The results show that the rate of release of fenoprofen calcium from the carrier of Cts-g-PRAEE copolymer becomes very slower than that of Cts in artificial intestinal juice. Copyright © 2008. Published by Elsevier Ltd.

Ordered nanoscale domains by infiltration of block copolymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Darling, Seth B.; Elam, Jeffrey; Tseng, Yu-Chih

A method of preparing tunable inorganic patterned nanofeatures by infiltration of a block copolymer scaffold having a plurality of self-assembled periodic polymer microdomains. The method may be used sequential infiltration synthesis (SIS), related to atomic layer deposition (ALD). The method includes selecting a metal precursor that is configured to selectively react with the copolymer unit defining the microdomain but is substantially non-reactive with another polymer unit of the copolymer. A tunable inorganic features is selectively formed on the microdomain to form a hybrid organic/inorganic composite material of the metal precursor and a co-reactant. The organic component may be optionally removedmore » to obtain an inorganic features with patterned nanostructures defined by the configuration of the microdomain.« less

Design and Synthesis of Network-Forming Triblock Copolymers Using Tapered Block Interfaces

PubMed Central

Kuan, Wei-Fan; Roy, Raghunath; Rong, Lixia; Hsiao, Benjamin S.; Epps, Thomas H.

2012-01-01

We report a strategy for generating novel dual-tapered poly(isoprene-b-isoprene/styrene-b-styrene-b-styrene/methyl methacrylate-b-methyl methacrylate) [P(I-IS-S-SM-M)] triblock copolymers that combines anionic polymerization, atom transfer radical polymerization (ATRP), and Huisgen 1,3-dipolar cycloaddition click chemistry. The tapered interfaces between blocks were synthesized via a semi-batch feed using programmable syringe pumps. This strategy allows us to manipulate the transition region between copolymer blocks in triblock copolymers providing control over the interfacial interactions in our nanoscale phase-separated materials independent of molecular weight and block constituents. Additionally, we show the ability to retain a desirous and complex multiply-continuous network structure (alternating gyroid) in our dual-tapered triblock material. PMID:23066522

Poly(aryl ethers) and related polysiloxane copolymer molecular coatings: Preparation and radiation degradation

NASA Technical Reports Server (NTRS)

Mcgrath, J. E.

1982-01-01

The radiation degradation of poly(arylene ether sulfones) and related materials is studied. These basic studies are important both as a means to developing stronger, more stable matrix resins for composite materials, as well as to improve the data base in regard to chemical structure-physical property relationships. Thirty homo and copolymers were synthesized, at least partially characterized and, in several cases suitable film casting techniques were developed. Four samples were chosen for initial radiation degradation. Poly(dimethyl siloxane) soft bocks/segments can preferentially migrate to the surface of copolymer films. Since siloxanes are utilized as thermal control coatings, this form of 'molecular' coating is of interest. The chemistry for preparing such copolymers with any of the polymers described was demonstrated.

Tailoring magnetic properties of self-biased hexaferrites using an alternative copolymer of isobutylene and maleic anhydride

NASA Astrophysics Data System (ADS)

Wu, Chuanjian; Yu, Zhong; Sokolov, Alexander S.; Yu, Chengju; Sun, Ke; Jiang, Xiaona; Lan, Zhongwen; Harris, Vincent G.

2018-05-01

Discussed is a novel self-biased hexaferrite gelling system based on a nontoxic and water-soluble copolymer of isobutylene and maleic anhydride. This copolymer simultaneously acts as a dispersant and gelling agent, and recently received much attention from the ceramics community. Herein its effects on the rheological conditions throughout magnetic-field pressing, and consequently, orientation, density and magnetic properties of textured hexaferrites were investigated. Ka-band FMR linewidths were measured, and the crystalline anisotropy and porosity induced linewidth broadening were estimated according to Schlömann's theory. The copolymer allowed to reduce the friction between micron-sized magnetic particulates, resulting in higher density and degree of crystalline orientation, and lower FMR linewidth.

Nitroxide-mediated radical ring-opening copolymerization: chain-end investigation and block copolymer synthesis.

PubMed

Delplace, Vianney; Harrisson, Simon; Tardy, Antoine; Gigmes, Didier; Guillaneuf, Yohann; Nicolas, Julien

2014-02-01

Well-defined, degradable copolymers are successfully prepared by nitroxide-mediated radical ring opening polymerization (NMrROP) of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) or methyl methacrylate (MMA), a small amount of acrylonitrile (AN) and cyclic ketene acetals (CKAs) of different structures. Phosphorous nuclear magnetic resonance allows in-depth chain-end characterization and gives crucial insights into the nature of the copoly-mer terminal sequences and the living chain fractions. By using a small library of P(OEGMA-co-AN-co-CKA) and P(MMA-co-AN-co-CKA) as macroinitiators, chain extensions with styrene are performed to furnish (amphiphilic) block copolymers comprising a degradable segment. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copolymers of fluorinated polydienes and sulfonated polystyrene

DOEpatents

Mays, Jimmy W [Knoxville, TN; Gido, Samuel P [Hadley, MA; Huang, Tianzi [Knoxville, TN; Hong, Kunlun [Knoxville, TN

2009-11-17

Copolymers of fluorinated polydienes and sulfonated polystyrene and their use in fuel cell membranes, batteries, breathable chemical-biological protective materials, and templates for sol-gel polymerization.

Solid phase graft copolymerization of acrylic monomers onto thermoplastics and their use as blend compatibilizers

NASA Astrophysics Data System (ADS)

Subramanian, Srinivas

This research work is an extension of some of the earlier work done on the development of solid phase grafting technique to graft various monomers onto polymers as well as postulation of the usefulness of the graft copolymers thus synthesized. Polystyrene grafted with acrylic acid, previously developed in bench scale, was synthesized in pilot-plant scale batches. Process parameter studies on the grafting of acrylic acid onto polypropylene and developmental studies on the grafting of maleic anhydride onto polystyrene were also done. Polymers grafted with polar molecules such as maleic anhydride and acrylic acid have been used to compatibilize immiscible blends of polar and non-polar polymers. On the same note, the applicability of the solid phase graft copolymers as blend compatibilizers were investigated and their performance was compared to commercially available compatibilizers. Solid phase graft copolymerization process is a technique to synthesize graft copolymers. Some of its salient features are use of minimal solvent to conduct the reaction and easy equipment modification. It is a low pressure and low temperature process. This technique provides a viable alternative to the environmentally hazardous, and time consuming conventional process currently in use. Hence, development of this technique could be beneficial not only to the plastics industry, but also to mankind. Also, this technique provides a low-cost and extremely easy method to develop graft copolymers such as acrylic acid functionalized polymers that are rapidly gaining popularity as blend compatibilizers and polymer reinforcing agents. A study that proves the potential of these solid phase graft copolymers as good blend compatibilizers for industrially important immiscible polymers will develop interest in the industries about this grafting process. The free radical solid phase graft copolymerization process was carried in a modified Brabender-type mixer fitted with specially designed blades to promote efficient mixing of the polymer, initiator, monomer, and solvent. The grafting was qualitatively confirmed by means of a FTIR and quantitatively using titration. The polymer blends were synthesized in a single screw extruder. Rheological, morphological, thermal, mechanical, and molecular weight studies were done on these blends. The graft copolymers produced in larger batches had the same amount of graft content as those produced in smaller batches. This small success is a positive step towards the goal of commercializing this process. Grafting of acrylic acid onto polypropylene gave graft levels of 4 weight percent. However, the attempt to graft maleic anhydride onto polystyrene was not successful. The solid phase graft copolymers were successfully able to compatibilize the polymer blend systems studied (PS/PMMA, PS/nylon 6,6, PS/nylon 6, and PP/nylon 6). The properties of the blends compatibilized using the solid phase graft copolymers were comparable to and in some instances, better than those of the blends compatibilized with commercially available graft copolymers. The successful scale-up of the process, development of new graft copolymers and ability of copolymers to compatibilize blends augurs well for the solid phase grafting process.

Morphological and physical characterization of poly(styrene-isobutylene-styrene) block copolymers and ionomers thereof

NASA Astrophysics Data System (ADS)

Baugh, Daniel Webster, III

Poly(styrene-isobutylene-styrene) block copolymers made by living cationic polymerization using a difunctional initiator and the sequential monomer addition technique were analyzed using curve-resolution software in conjunction with high-resolution GPC. Fractional precipitation and selective solvent extraction were applied to a representative sample in order to confirm the identity of contaminating species. The latter were found to be low molecular weight polystyrene homopolymer, diblock copolymer, and higher molecular weight segmented block copolymers formed by intermolecular electrophilic aromatic substitution linking reactions occurring late in the polymerization of the styrene outer blocks. Solvent-cast films of poly(styrene-isobutylene-styrene) (PS-PIB-PS) block copolymers and block ionomers were analyzed using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Four block copolymer samples with center block molecular weights of 52,000 g/mol and PS volume fractions (o sbPS) ranging from 0.17 to 0.31 were studied. All samples exhibited hexagonally packed cylinders of PS within the PIB matrix. Cylinder spacing was in the range 32 to 36 nm for most samples, while cylinder diameters varied from 14 to 21 nm. Porod analysis of the scattering data indicated the presence of isolated phase mixing and sharp phase boundaries. PS-PIB-PS block copolymers and ionomers therefrom were analyzed using dynamic mechanical analysis (DMA) and tensile testing. The study encompassed five block copolymer samples with similar PIB center blocks with molecular weights of approx52,000 g/mol and PS weight fractions ranging from 0.127 to 0.337. Ionomers were prepared from two of these materials by lightly sulfonating the PS outer blocks. Sulfonation levels varied from 1.7 to 4.7 mol % and the sodium and potassium neutralized forms were compared to the parent block copolymers. Dynamic mechanical analysis (DMA) of the block copolymer films indicated the existence of a third phase attributed to PIB chains near the PS domain interface which experience reduced mobility due to their firm attachment to the hard PS domain. The relative amount of this phase decreased in samples with larger PS blocks, while the temperature of the associated transition increased. Tensile testing showed increased tensile strength but decreased elongation at break with larger PS blocks. DMA of the ionomers indicated improved dynamic modulus at temperatures above 100spcirc$C. Tensile testing of the ionomers indicated slight improvements in tensile strength with little loss in elongation at break. PS-PIB-PS block copolymer ionomer (BCP01, center block molecular weight = 53,000 g/mole; 25.5 wt % polystyrene, 4.7% sulfonation of phenyl units, 100% neutralized with KOH) was compounded with various organic and inorganic acid salts of 2-ethylhexyl-p-dimethyl aminobenzoate (ODAB) to explore the efficacy of these compounds as ionic plasticizers. (Abstract shortened by UMI.)

Determination of oligomeric chain length distributions at surfaces using ToF-SIMS: segregation effects and polymer properties

NASA Astrophysics Data System (ADS)

Gardella, Joseph A.; Mahoney, Christine M.

2004-06-01

While many XPS and SIMS studies of polymers have detected and quantified segregation of low surface energy blocks or components in copolymers and polymer blends [D. Briggs, in: D.R. Clarke, S. Suresh, I.M. Ward (Eds.), Surface Analysis of Polymers by XPS and Static SIMS, Cambridge University Press, Cambridge, 1998 (Chapter 5).], this paper reports ToF-SIMS studies of direct measurement of the segment length distribution at the surface of siloxane copolymers. These data allow insight into the segregation of particular portions of the oligomeric distribution; specifically, in this study, longer PDMS oligomers segregated at the expense of shorter PDMS chains. We have reported XPS analysis of competitive segregation effects for short PDMS chains [Macromolecules 35 (13) (2002) 5256]. In this study, a series of poly(ureaurethane)-poly(dimethylsiloxane) (PUU-PDMS) copolymers have been synthesized containing varying ratios of G-3 and G-9 (G- X describes the average segment length of the PDMS added), while maintaining a constant overall siloxane weight percentage (10, 30, and 60%). These copolymers were utilized as model systems to study the preferential segregation of certain siloxane segment lengths to the surface over others. ToF-SIMS analysis of PUU-PDMS copolymers has yielded high-mass range copolymer fragmentation patterns containing intact PDMS segments. For the first time, this information is utilized to determine PDMS segment length distributions at the copolymer surface as compared to the bulk. The results show that longer siloxane segment lengths are preferentially segregating to the surface over shorter chain lengths. These results also show the importance of ToF-SIMS and mass spectrometry in the development of new materials containing low molecular weight amino-propyl-terminated siloxanes.

Docetaxel-Loaded Self-Assembly Stearic Acid-Modified Bletilla striata Polysaccharide Micelles and Their Anticancer Effect: Preparation, Characterization, Cellular Uptake and In Vitro Evaluation.

PubMed

Guan, Qingxiang; Sun, Dandan; Zhang, Guangyuan; Sun, Cheng; Wang, Miao; Ji, Danyang; Yang, Wei

2016-12-02

Poorly soluble drugs have low bioavailability after oral administration, thereby hindering effective drug delivery. A novel drug-delivery system of docetaxel (DTX)-based stearic acid (SA)-modified Bletilla striata polysaccharides (BSPs) copolymers was successfully developed. Particle size, zeta potential, encapsulation efficiency (EE), and loading capacity (LC) were determined. The DTX release percentage in vitro was determined using high performance liquid chromatography (HPLC). The hemolysis and in vitro anticancer activity were studied. Cellular uptake and apoptotic rate were measured using flow cytometry assay. Particle size, zeta potential, EE and LC were 125.30 ± 1.89 nm, -26.92 ± 0.18 mV, 86.6% ± 0.17%, and 14.8% ± 0.13%, respectively. The anticancer activities of DTX-SA-BSPs copolymer micelles against HepG2, HeLa, SW480, and MCF-7 (83.7% ± 1.0%, 54.5% ± 4.2%, 48.5% ± 4.2%, and 59.8% ± 1.4%, respectively) were superior to that of docetaxel injection (39.2% ± 1.1%, 44.5% ± 5.3%, 38.5% ± 5.4%, and 49.8% ± 2.9%, respectively) at 0.5 μg/mL drug concentration. The DTX release percentage of DTX-SA-BSPs copolymer micelles and docetaxel injection were 66.93% ± 1.79% and 97.06% ± 1.56% in two days, respectively. Cellular uptake of DTX-FITC-SA-BSPs copolymer micelles in cells had a time-dependent relation. Apoptotic rate of DTX-SA-BSPs copolymer micelles and docetaxel injection were 73.48% and 69.64%, respectively. The SA-BSPs copolymer showed good hemocompatibility. Therefore, SA-BSPs copolymer can be used as a carrier for delivering hydrophobic drugs.

Poly-N-Isopropylacrylamide/acrylic Acid Copolymers for the Generation of Nanostructures at Mica Surfaces and as Hydrophobic Host Systems for the Porin MspA from Mycobacterium smegmatis.

PubMed

Gamage, Pubudu; Basel, Matthew T; Lovell, Kimberly; Pokhrel, Megh Raj; Battle, Deletria; Ito, Takashi; Pavlenok, Mikhail; Niederweis, Michael; Bossmann, Stefan H

2009-09-17

The work presented here aims at utilizing poly-N-isopropyl-acrylamide/acrylic acid copolymers to create nanostructured layers on mica surfaces by a simple spin-casting procedure. The average composition of the copolymers determined by elemental analysis correlates excellently with the feed composition indicating that the radical polymerization process is statistical. The resulting surfaces were characterized by Atomic Force Microscopy (magnetic AC-mode) at the copolymer/air interface. Postpolymerization modification of the acrylic acid functions with perfluoro-octyl-iodide decreased the tendency towards spontaneous formation of nanopores. Crosslinking of individual polymer chains permitted the generation of ultraflat layers, which hosted the mycobacterial channel protein MspA, without compromising its channel function. The comparison of copolymers of very similar chemical composition that have been prepared by living radical polymerization and classic radical polymerization indicated that differences in polydispersity played only a minor role when poly-N-isopropyl-acrylamide/acrylic acid copolymers were spincast, but a major role when copolymers featuring the strongly hydrophobic perfluoro-octyl-labels were used. The mean pore diameters were 23.8+/-4.4 nm for P[(NIPAM)(95.5)-co-(AA)(4.5)] (PDI (polydispersity index)=1.55) and 21.8+/-4.2 nm for P[(NIPAM)(95.3)-co-(AA)(4.7)] (PDI=1.25). The depth of the nanopores was approx. 4 nm. When depositing P[(NIPAM)(95)-co-(AA)(2.8)-AAC(8)F(17 2.2)] (PDI=1.29) on Mica, the resulting mean pore diameter was 35.8+/-7.1 nm, with a depth of only 2 nm.

Poly-N-Isopropylacrylamide/acrylic Acid Copolymers for the Generation of Nanostructures at Mica Surfaces and as Hydrophobic Host Systems for the Porin MspA from Mycobacterium smegmatis

PubMed Central

Gamage, Pubudu; Basel, Matthew T.; Lovell, Kimberly; Pokhrel, Megh Raj; Battle, Deletria; Ito, Takashi; Pavlenok, Mikhail; Niederweis, Michael

2009-01-01

The work presented here aims at utilizing poly-N-isopropyl-acrylamide/acrylic acid copolymers to create nanostructured layers on mica surfaces by a simple spin-casting procedure. The average composition of the copolymers determined by elemental analysis correlates excellently with the feed composition indicating that the radical polymerization process is statistical. The resulting surfaces were characterized by Atomic Force Microscopy (magnetic AC-mode) at the copolymer/air interface. Postpolymerization modification of the acrylic acid functions with perfluoro-octyl-iodide decreased the tendency towards spontaneous formation of nanopores. Crosslinking of individual polymer chains permitted the generation of ultraflat layers, which hosted the mycobacterial channel protein MspA, without compromising its channel function. The comparison of copolymers of very similar chemical composition that have been prepared by living radical polymerization and classic radical polymerization indicated that differences in polydispersity played only a minor role when poly-N-isopropyl-acrylamide/acrylic acid copolymers were spincast, but a major role when copolymers featuring the strongly hydrophobic perfluoro-octyl-labels were used. The mean pore diameters were 23.8±4.4 nm for P[(NIPAM)95.5-co-(AA)4.5] (PDI (polydispersity index)=1.55) and 21.8±4.2 nm for P[(NIPAM)95.3-co-(AA)4.7] (PDI=1.25). The depth of the nanopores was approx. 4 nm. When depositing P[(NIPAM)95-co-(AA)2.8-AAC8F17 2.2] (PDI=1.29) on Mica, the resulting mean pore diameter was 35.8±7.1 nm, with a depth of only 2 nm. PMID:20161351

Preparation, characterization, and in vitro activity evaluation of triblock copolymer-based polymersomes for drugs delivery

NASA Astrophysics Data System (ADS)

Besada, Lucas N.; Peruzzo, Pablo; Cortizo, Ana M.; Cortizo, M. Susana

2018-03-01

Polymersomes are polymer-based vesicles that form upon hydration of amphiphilic block copolymers and display high stability and durability, due to their mechanical and physical properties. They have hydrophilic reservoirs as well as thick hydrophobic membranes; allowing to encapsulate both water-soluble bioactive agent and hydrophobic drugs. In this study, poly ethylene glycol (PEG3350 and PEG6000) were used as hydrophilic part and poly(vinyl benzoate) (PVBz) as hydrophobic block to synthesize amphiphilic triblock copolymers (PVBz- b-PEG- b-PVBz). Different proportions of hydrophilic/hydrophobic part were assayed in order to obtain polymersomes by solvent injection method. For the synthesis of the copolymers, the initial block of PEG was derived to obtain a macroinitiator through a xanthate functional group (PEGX3 or PEGX6) and the polymerization of vinyl benzoate was carried out through reversible addition-fragmentation chain transfer polymerization (RAFT). The structure of PEGX and copolymers was confirmed by Infrared, 1H-NMR and UV-Vis spectrometry, while the average molecular weight (Mw) and polydispersity index (PI) were determined by size exclusion chromatography (SEC). The structures adopted by the copolymers in aqueous solution by self-assembly were investigated using transmission electron microscopy (TEM), dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS). Both techniques confirm that polymersomes were obtained for a fraction of hydrophilic block ( f) ≈ 35 ± 10%, with a diameter of 38.3 ± 0.3 nm or 22.5 ± 0.7 nm, as determined by TEM and according to the M w of the precursor block copolymer. In addition, we analyzed the possible cytotoxicity in view of its potential application as biomedical nanocarrier. The results suggest that polymersomes seem not induce cytotoxicity during the periods of time tested.

General and simple approach for control cage and cylindrical mesopores, and thermal/hydrothermal stable frameworks.

PubMed

El-Safty, Sherif A; Mizukami, Fujio; Hanaoka, Takaaki

2005-05-19

Highly ordered cage and cylindrical mesoporeous silica monoliths (HOM) with 2- and 3-dimensional (2D and 3D, respectively) structures, mesopore/micropore volumes, and thick-walled frameworks were successfully fabricated by instant direct templating of lyotropic phases of copolymer (EO(m)-PO(n)-EO(m)) surfactants. Large cage-like pores with uniform constriction sizes up to 10 nm and open cylindrical channel-like mesopores can be easily achieved by this simple and efficient synthesis design. Our results show that the cage-like pores could be fabricated at relatively lower copolymer concentrations used in the lyotropic phase domains at copolymer/TMOS ratios of 35 wt %. These ordered cage pore architectures underwent transition to open-cylindrical pores by increasing the copolymer concentration. High EO/PO block copolymers, in general, were crucially affected on the increase of the interior cavity sizes and on the stability of the cage mesopore characters. However, for F108 (EO(141)PO(44)EO(141)) systems, the fabrication of ordered and stable cage pore monoliths was achieved with significantly higher copolymer concentrations up to 90 wt %. Interestingly, the effective copolymer molecular nature was also observed in the ability to design various ordered mesophase geometries in large domain sizes. Our findings here show evidence that the synthetic strategy provides realistic control over a wide range of mesostructured phase geometries and their extended long-range ordering in the final replicas of the silica monolith frameworks. In addition, the HOM silica monoliths exhibited considerable structural stability against higher thermal temperature (up to 1000 degrees C) and longer hydrothermal treatment times under boiling water and steam. The remarkable structural findings of 3D frameworks, transparent monoliths, and micropores combined with large cage- and cylindrical-like mesopores are expected to find promising uses in materials chemistry.

Characterization of ultrahigh-molecular weight cationic polyacrylamide using frit-inlet asymmetrical flow field-flow fractionation and multi-angle light scattering.

PubMed

Woo, Sohee; Lee, Ju Yong; Choi, Woonjin; Moon, Myeong Hee

2016-01-15

In this study, frit inlet asymmetrical flow field-flow fractionation (FlFFF) with multi-angle light scattering (MALS) and differential refractive index (DRI) detection is utilized for size separation, determination of molecular weight (MW), and conformation of ultrahigh-MW (10(7)-10(9) g/mol) cationic polyacrylamides (C-PAMs), a class of water-soluble copolymers based on acrylamide and vinyl-type comonomers with quaternary ammonium cations that are widely used in wastewater treatment and in paper industries. Linear and branched C-PAM copolymers prepared in two different polymerization methods (solution and emulsion) from varying amounts of crosslinking agent and initiator were size fractionated by FlFFF with field-programming. It was found experimentally that the linear copolymers from both polymerization methods were less than 10(8) g/mol in MW with compact, nearly spherical structures, while the branched C-PAM copolymers from the emulsion polymerization showed a significant increase in average MW up to ∼ 10(9)g/mol, which was about 20-fold greater than those from the solution method, and the branched copolymers had more compact or shrunken conformations. While both linear and branched copolymers less than 10(8) g/mol MW were well resolved in an increasing order of MW (normal mode), it was noted that branched copolymers prepared through emulsion polymerization exhibited significantly larger MWs of 10(8-)10(9) g/mol and eluted in the steric/hyperlayer mode, in which the elution order is reversed in an extreme run condition (strong initial field strength followed by a fast field decay during programming). Copyright © 2015 Elsevier B.V. All rights reserved.

Novel degradable co-polymers of polypyrrole support cell proliferation and enhance neurite out-growth with electrical stimulation.

PubMed

Durgam, Hymavathi; Sapp, Shawn; Deister, Curt; Khaing, Zin; Chang, Emily; Luebben, Silvia; Schmidt, Christine E

2010-01-01

Synthetic polymers such as polypyrrole (PPy) are gaining significance in neural studies because of their conductive properties. We evaluated two novel biodegradable block co-polymers of PPy with poly(epsilon-caprolactone) (PCL) and poly(ethyl cyanoacrylate) (PECA) for nerve regeneration applications. PPy-PCL and PPy-PECA co-polymers can be processed from solvent-based colloidal dispersions and have essentially the same or greater conductivity (32 S/cm for PPy-PCL, 19 S/cm for PPy-PECA) compared to the PPy homo-polymer (22 S/cm). The PPy portions of the co-polymers permit electrical stimulation whereas the PCL or PECA blocks enable degradation by hydrolysis. For in vitro tests, films were prepared on polycarbonate sheets by air brushing layers of dispersions and pressing the films. We characterized the films for hydrolytic degradation, electrical conductivity, cell proliferation and neurite extension. The co-polymers were sufficient to carry out electrical stimulation of cells without the requirement of a metallic conductor underneath the co-polymer film. In vitro electrical stimulation of PPy-PCL significantly increased the number of PC12 cells bearing neurites compared to unstimulated PPy-PCL. For in vivo experiments, the PPy co-polymers were coated onto the inner walls of nerve guidance channels (NGCs) made of the commercially available non-conducting biodegradable polymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHB-HV). The NGCs were implanted in a 10 mm defect made in the sciatic nerve of rats, and harvested after 8 weeks. Histological staining showed axonal growth. The studies indicated that these new conducting degradable biomaterials have good biocompatibility and support proliferation and growth of PC12 cells in vitro (with and without electrical stimulation) and neurons in vivo (without electrical stimulation).

Microphase separation in thin films of lamellar forming polydisperse di-block copolymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W.

Despite the ubiquity of polydispersity in chain lengths of di-block copolymers, its effects on microphase separation in thin films have eluded a clear understanding. In this paper, we have studied effects of polydispersity on the microphase separation in thin films of lamellar forming di-block copolymers using self-consistent field theory (SCFT) and neutron reflectivity experiments. Di-block copolymers containing a polydisperse block of poly(glycidylmethacrylate) (PGMA) connected to a near-monodisperse block poly(2-vinyl-4,4-dimethyl-d 6 azlactone) (PVDMA-d 6) are considered in this work. Effects of chain length polydispersity, film thickness, substrate–monomer and monomer–monomer interactions on the microphase segregation are studied using SCFT. The theoretical studymore » reveals that in comparison to a film created with monodisperse di-block copolymers, an increase in polydispersity tends to decrease the number of lamellar strata that can be packed in a film of given thickness. This is a direct consequence of an increase in lamellar domain spacing with an increase in polydispersity index. Furthermore, it is shown that polydispersity induces conformational asymmetry and an increase in the polydispersity index leads to an increase in the effective Kuhn segment length of the polydisperse blocks. It is shown that the conformational asymmetry effects, which are entropic in origin and of increasing importance as film thickness decreases, drive the polydisperse blocks to the middle of the films despite favorable substrate interactions. These predictions are verified by results from neutron reflectivity experiments on thin films made from moderately polydisperse PGMA-PVDMA-d 6 di-block copolymer deposited on silicon substrates. In conclusion, results from SCFT are used to predict neutron reflectivity profiles, providing a facile and robust route to obtain useful physical insights into the structure of polydisperse diblock copolymers at interfaces.« less

Microphase separation in thin films of lamellar forming polydisperse di-block copolymers

DOE PAGES

Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W.; ...

2015-02-03

Despite the ubiquity of polydispersity in chain lengths of di-block copolymers, its effects on microphase separation in thin films have eluded a clear understanding. In this paper, we have studied effects of polydispersity on the microphase separation in thin films of lamellar forming di-block copolymers using self-consistent field theory (SCFT) and neutron reflectivity experiments. Di-block copolymers containing a polydisperse block of poly(glycidylmethacrylate) (PGMA) connected to a near-monodisperse block poly(2-vinyl-4,4-dimethyl-d 6 azlactone) (PVDMA-d 6) are considered in this work. Effects of chain length polydispersity, film thickness, substrate–monomer and monomer–monomer interactions on the microphase segregation are studied using SCFT. The theoretical studymore » reveals that in comparison to a film created with monodisperse di-block copolymers, an increase in polydispersity tends to decrease the number of lamellar strata that can be packed in a film of given thickness. This is a direct consequence of an increase in lamellar domain spacing with an increase in polydispersity index. Furthermore, it is shown that polydispersity induces conformational asymmetry and an increase in the polydispersity index leads to an increase in the effective Kuhn segment length of the polydisperse blocks. It is shown that the conformational asymmetry effects, which are entropic in origin and of increasing importance as film thickness decreases, drive the polydisperse blocks to the middle of the films despite favorable substrate interactions. These predictions are verified by results from neutron reflectivity experiments on thin films made from moderately polydisperse PGMA-PVDMA-d 6 di-block copolymer deposited on silicon substrates. In conclusion, results from SCFT are used to predict neutron reflectivity profiles, providing a facile and robust route to obtain useful physical insights into the structure of polydisperse diblock copolymers at interfaces.« less

Microphase separation in thin films of lamellar forming polydisperse di-block copolymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W.

Despite the ubiquity of polydispersity in chain lengths of di-block copolymers, its effects on microphase separation in thin films have eluded a clear understanding. In this work, we have studied effects of polydispersity on the microphase separation in thin films of lamellar forming di-block copolymers using self-consistent field theory (SCFT) and neutron reflectivity experiments. Di-block copolymers containing a polydisperse block of poly(glycidylmethacrylate) (PGMA) connected to a near-monodisperse block poly(2-vinyl-4,4-dimethyl-d6 azlactone) (PVDMA-d6) are considered in this work. Effects of chain length polydispersity, film thickness, substrate-monomer and monomer-monomer interactions on the microphase segregation are studied using SCFT. The theoretical study reveals thatmore » in comparison to a film created with monodisperse di-block copolymers, an increase in polydispersity tends to decrease the number of lamellar strata that can be packed in a film of given thickness. This is a direct consequence of an increase in lamellar domain spacing with an increase in polydispersity index. Furthermore, it is shown that polydispersity induces conformational asymmetry and an increase in the polydispersity index leads to an increase in the effective Kuhn segment length of the polydisperse blocks. It is shown that the conformational asymmetry effects, which are entropic in origin and of increasing importance as film thickness decreases, drive the polydisperse blocks to the middle of the films despite favorable substrate interactions. These predictions are verified by results from neutron reflectivity experiments on thin films made from moderately polydisperse PGMA-PVDMA-d6 di-block copolymer deposited on silicon substrates. Finally, results from SCFT are used to predict neutron reflectivity profiles, providing a facile and robust route to obtain useful physical insights into the structure of polydisperse diblock copolymers at interfaces.« less

Thin Film Assembly of Spider Silk-like Block Copolymers

DTIC Science & Technology

2011-01-01

Shipley, N. H.; Lewis, R. V. Int. J. Biol.Macromol. 1999, 24, 271. (c) Thiel, B. L.; Guess, K. B.; Viney, C. Biopolymers 1997, 41, 703. (13) Silk ...Film Assembly of Spider Silk -like Block Copolymers Sreevidhya T. Krishnaji,†,‡ Wenwen Huang,§ Olena Rabotyagova,†,‡ Eugenia Kharlampieva, ) Ikjun Choi...Received November 26, 2010 We report the self-assembly of monolayers of spider silk -like block copolymers. Langmuir isotherms were obtained for a series of

Responsive Copolymers for Enhanced Petroleum Recovery

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCormick, C.; Hester, R.

The objectives of this work was to: synthesize responsive copolymer systems; characterize molecular structure and solution behavior; measure rheological properties of aqueous fluids in fixed geometry flow profiles; and to tailor final polymer compositions for in situ rheology control under simulated conditions. This report focuses on the synthesis and characterization of novel stimuli responsive copolymers, the investigation of dilute polymer solutions in extensional flow and the design of a rheometer capable of measuring very dilute aqueous polymer solutions at low torque.

Effect of DEXTRAN-graft-POLYACRYLAMIDE Internal Structure on Flocculation Process Parameters

NASA Astrophysics Data System (ADS)

Bezugla, T.; Kutsevol, N.; Shyichuk, A.; Ziolkowska, D.

2008-08-01

Dextran-graft-Polyacrylamide copolymers (D-g-PAA) of brush-like architecture were tested as flocculation aids in the model kaolin suspensions. Due to expanded conformation the D-g-PAA copolymers are more effective flocculants than individual PAA with close molecular mass. The internal structure of D-g-PAA copolymers which is determined by number and length of grafted PAA chains, the distance between grafts, etc., has the significant influence on flocculation behavior of such polymers.

Control of Morphology of Crystallizable Polymer Mixtures via Manipulation of the Heterogeneous Melt

DTIC Science & Technology

1990-11-09

Distribution of Matrix Homopolymer C.V. Berney in Block Copolymers of Spherical P. Cheng Morphology R.E. Cohen 2. Distribution of Chain Ends Inside P. Cheng...the Polybutadiene Microspheres of SB C.V. Berney Diblock Copolymers R.E. Cohen 3. Spatial Organization of Homopolymer P. Cheng Chains Inside Spherical...Polybutadiene C.V. Berney Domains of SB Diblock Copolymers R.E. Cohen 4. Blends of Crystallizable Polybutadienes M. Marx R.E. Cohen 5. Synthesis and

Electrospinning of Poly (MMA-CO-Maa) Copolymers And Their Layered Silicate Nanocomposites For Improved Thermal Properties

DTIC Science & Technology

2004-12-01

7518. Ho, B.C., Lee, Y.D. and Chin, W.K., 1992: Thermal Degradation of Polymethacrylic Acid , J. Polym. Sci., Polymer Chemistry, 30, 2389-2397. Lee...AMSRD-ARL-WM-MD Aberdeen Proving Ground, MD 21005-5069 ABSTRACT Copolymers consisting of methyl methacrylate (MMA) and methacrylic acid (MAA...from solution of poly (MMA-co-MAA) copolymer (50/50 weight ratio of MMA and methacrylic acid , MAA) in dimethylformamide (DMF) and the corresponding

Synthesis and solution self-assembly of side-chain cobaltocenium-containing block copolymers.

PubMed

Ren, Lixia; Hardy, Christopher G; Tang, Chuanbing

2010-07-07

The synthesis of side-chain cobaltocenium-containing block copolymers and their self-assembly in solution was studied. Highly pure monocarboxycobaltocenium was prepared and subsequently attached to side chains of poly(tert-butyl acrylate)-block-poly(2-hydroxyethyl acrylate), yielding poly(tert-butyl acrylate)-block-poly(2-acryloyloxyethyl cobaltoceniumcarboxylate). The cobaltocenium block copolymers exhibited vesicle morphology in the mixture of acetone and water, while micelles of nanotubes were formed in the mixture of acetone and chloroform.

The One-Pot Directed Assembly of Cylinder-Forming Block Copolymer on Adjacent Chemical Patterns for Bimodal Patterning.

PubMed

Chang, Tzu-Hsuan; Xiong, Shisheng; Liu, Chi-Chun; Liu, Dong; Nealey, Paul F; Ma, Zhenqiang

2017-09-01

The direct self-assembly of cylinder-forming poly(styrene-block-methyl-methacrylate) (PS-b-PMMA) block copolymer is successfully assembled into two orientations, according to the underlying guiding pattern in different areas. Lying-down and perpendicular cylinders are formed, respectively, depending on the design of chemical pattern: sparse line/space pattern or hexagonal dot array. The first chemical pattern composed of prepatterned cross-linked polystyrene (XPS) line/space structure has a period (L S ) equal to twice the intercylinder period of the block copolymer (L 0 ). The PS-b-PMMA thin film on the prepared chemical template after thermal annealing forms a lying-down cylinder morphology when the width of the PS strips is less than the width of PS block in the PS-b-PMMA block copolymer. The morphology is only applicable at the discrete thickness of the PS-b-PMMA film. In addition to forming the lying-down cylinders directly on the XPS guiding pattern, the cylinder-forming block copolymer can also be assembled in a perpendicular way on the second guiding pattern (the hexagonal dot array). The block copolymer films are registered into two orientations in a single directed self-assembly process. The features of the assembled patterns are successfully transferred down to the silicon oxide substrate. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

MinC/MinD copolymers are not required for Min function

PubMed Central

Park, Kyung-Tae; Du, Shishen; Lutkenhaus, Joe

2015-01-01

Summary In Escherichia coli, precise placement of the cytokinetic Z ring at midcell requires the concerted action of the three Min proteins. MinD activates MinC, an inhibitor of FtsZ, at least in part, by recruiting it to the membrane and targeting it to the Z ring, while MinE stimulates the MinD ATPase inducing an oscillation that directs MinC/MinD activity away from midcell. Recently, MinC and MinD were shown to form copolymers of alternating dimers of MinC and MinD and it was suggested that these copolymers are the active form of MinC/MinD. Here, we use MinD mutants defective in binding MinC to generate heterodimers with wild type MinD that are unable to form MinC/MinD copolymers. Similarly, MinC mutants defective in binding to MinD were used to generate heterodimers with wild type MinC that are unable to form copolymers. Such heterodimers are active and in the case of MinC were shown to mediate spatial regulation of the Z ring demonstrating that MinC/MinD copolymer formation is not required. Our results are consistent with a model in which a membrane anchored MinC/MinD complex is targeted to the Z ring through the conserved carboxy tail of FtsZ leading to breakage of FtsZ filaments. PMID:26268537

Interpreting Neutron Reflectivity Profiles of Diblock Copolymer Nanocomposite Thin Films Using Hybrid Particle-Field Simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mahalik, Jyoti P.; Dugger, Jason W.; Sides, Scott W.

Mixtures of block copolymers and nanoparticles (block copolymer nanocomposites) are known to microphase separate into a plethora of microstructures, depending on the composition, length scale and nature of interactions among its different constituents. Theoretical and experimental works on this class of nanocomposites have already high-lighted intricate relations among chemical details of the polymers, nanoparticles, and various microstructures. Confining these nanocomposites in thin films yields an even larger array of structures, which are not normally observed in the bulk. In contrast to the bulk, exploring various microstructures in thin films by the experimental route remains a challenging task. Here in thismore » work, we construct a model for the thin films of lamellar forming diblock copolymers containing spherical nanoparticles based on a hybrid particle-field approach. The model is benchmarked by comparison with the depth profiles obtained from the neutron reflectivity experiments for symmetric poly(deuterated styrene-b-n butyl methacrylate) copolymers blended with spherical magnetite nanoparticles covered with hydrogenated poly(styrene) corona. We show that the model based on a hybrid particle-field approach provides details of the underlying microphase separation in the presence of the nanoparticles through a direct comparison to the neutron reflectivity data. This work benchmarks the application of the hybrid particle-field model to extract the interaction parameters for exploring different microstructures in thin films containing block copolymers and nanocomposites.« less

Contact Active Antimicrobial Coatings Prepared by Polymer Blending.

PubMed

Cuervo-Rodríguez, Rocío; López-Fabal, Fátima; Gómez-Garcés, José L; Muñoz-Bonilla, Alexandra; Fernández-García, Marta

2017-11-01

Herein, contact active antimicrobial films are prepared by simply blending cationic amphiphilic block copolymers with commercial polystyrene (PS). The copolymers are prepared by combining atom transfer radical polymerization and "click chemistry." A variety of copolymers are synthesized, and composed of a PS segment and an antimicrobial block bearing flexible side chain with thiazole and triazole groups, 4-(1-(2-(4-methylthiazol-5-yl)ethyl)-1H-1,2,3-triazol-4-yl) butyl methacrylate (TTBM). The length of the TTBM block is varied as well as the alkylating agent. Different films are prepared from N,N-dimethylformamide solution, containing variable PS-b-PTTBM/PS ratio: from 0 to 100 wt%. Remarkably, the blend films, especially those with 30 and 50 wt% of copolymers, exhibit excellent antimicrobial activities against Gram-positive, Gram-negative bacteria and fungi, even higher than films prepared exclusively from the cationic copolymers. Blends composed of 50 wt% of the copolymers present a more than 99.999% killing efficiency against the studied microorganisms. The better activity found in blends can be due to the higher roughness, which increases the surface area and consequently the contact with the microorganisms. These results demonstrate that the use of blends implies a reduction of the content of antimicrobial agent and also enhances the antimicrobial activity, providing new insights for the better designing of antimicrobial coatings. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heat Capacity of Spider Silk-like Block Copolymers

PubMed Central

Huang, Wenwen; Krishnaji, Sreevidhya; Hu, Xiao; Kaplan, David; Cebe, Peggy

2012-01-01

We synthesized and characterized a new family of di-block copolymers based on the amino acid sequences of Nephila clavipes major ampulate dragline spider silk, having the form HABn and HBAn (n=1–3), comprising an alanine-rich hydrophobic block, A, a glycine-rich hydrophilic block, B, and a histidine tag, H. The reversing heat capacities, Cp(T), for temperatures below and above the glass transition, Tg, were measured by temperature modulated differential scanning calorimetry. For the solid state, we then calculated the heat capacities of our novel block copolymers based on the vibrational motions of the constituent poly(amino acid)s, whose heat capacities are known or can be estimated from the ATHAS Data Bank. For the liquid state, the heat capacity was estimated by using the rotational and translational motions in the polymer chain. Excellent agreement was found between the measured and calculated values of the heat capacity, showing that this method can serve as a standard by which to assess the Cp for other biologically inspired block copolymers. The fraction of beta sheet crystallinity of spider silk block copolymers was also determined by using the predicted Cp, and was verified by wide angle X-ray diffraction and Fourier transform infrared spectroscopy. The glass transition temperatures of spider silk block copolymer were fitted by Kwei’s equation and the results indicate that attractive interaction exists between the A-block and B-block. PMID:23869111

Nanostructured DPA-MPC-DPA triblock copolymer gel for controlled drug release of ketoprofen and spironolactone.

PubMed

Azmy, Bahaa; Standen, Guy; Kristova, Petra; Flint, Andrew; Lewis, Andrew L; Salvage, Jonathan P

2017-08-01

Uncontrolled rapid release of drugs can reduce their therapeutic efficacy and cause undesirable toxicity; however, controlled release from reservoir materials helps overcome this issue. The aims of this study were to determine the release profiles of ketoprofen and spironolactone from a pH-responsive self-assembling DPA-MPC-DPA triblock copolymer gel and elucidate underlying physiochemical properties. Drug release profiles from DPA 50 -MPC 250 -DPA 50 gel (pH 7.5), over 32 h (37 °C), were determined using UV-Vis spectroscopy. Nanoparticle size was measured by dynamic light scattering (DLS) and critical micelle concentration (CMC) by pyrene fluorescence. Polymer gel viscosity was examined via rheology, nanoparticle morphology investigated using scanning transmission electron microscopy (STEM) and the gel matrix observed using cryo-scanning electron microscopy (Cryo-SEM). DPA 50 -MPC 250 -DPA 50 copolymer (15% w/v) formed a free-standing gel (pH 7.5) that controlled drug release relative to free drugs. The copolymer possessed a low CMC, nanoparticle size increased with copolymer concentration, and DLS data were consistent with STEM. The gel displayed thermostable viscosity at physiological temperatures, and the gel matrix was a nanostructured aggregation of smaller nanoparticles. The DPA 50 -MPC 250 -DPA 50 copolymer gel could be used as a drug delivery system to provide the controlled drug release of ketoprofen and spironolactone. © 2017 Royal Pharmaceutical Society.

Assessing the phytoavailability of arsenic and phosphorus to corn plant after the addition of an acrylic copolymer to polluted soils.

PubMed

Mansouri, Tahereh; Golchin, Ahmad; Kouhestani, Hossein

2017-08-13

Soil pollution by arsenic increases the potential risk of arsenic entrance into the food chain. The usefulness of maleic anhydride- styrene- acrylic acid copolymer on the mobility and phytoavailability of arsenic was evaluated. Treatments were the concentrations of acrylic copolymer (0, 0.05, 0.10, and 0.20% w/w) and the concentrations of soil total arsenic (0, 6, 12, 24, 48, and 96 mg kg -1 ). Sodium arsenate was added in appropriate amounts to subsamples of an uncontaminated soil to give contaminated soils with different levels of arsenic. The contaminated soils were subjected to a greenhouse experiment using corn as the test crop. The results showed that contamination of soil by arsenic increased the concentrations of soil available arsenic, root and aerial parts arsenic. By the use of acrylic copolymer, the concentration of available arsenic in the soil and the accumulation of arsenic in the root and aerial parts of the corn plant decreased but the dry weights of the root and aerial parts increased significantly. When the concentration of soil total arsenic was 96 mg kg -1 , the application of copolymer at the concentration of 0.20% w/w reduced the concentrations of arsenic in soil, root, and aerial parts by 62.53, 43.65, and 37.00% respectively, indicating that application of acrylic copolymer immobilized arsenic in soils.

Development of pH Sensitive Nanoparticles for Intestinal Drug Delivery Using Chemically Modified Guar Gum Co-Polymer.

PubMed

Varma, Vegesna Naga Sravan Kumar; Shivakumar, Hosakote Gurumalappa; Balamuralidhara, Veerna; Navya, Manne; Hani, Umme

2016-01-01

The aim of the research work was to chemically modify guargum (GG) as a pH sensitive co-polymer and formulating intestinal targeting ESO nanoparticles (NPs) using the synthesized co-polymer. Poly acrylamide-grafted-guar gum (PAAm-g-GG) co-polymer was synthesized by free radical polymerization. Chemical modification of PAAm-g-GG by alkaline hydrolysis results in formation of a pH-sensitive co-polymer. The effect of GG and acryl amide (AAm) on grafting was studied. Esomeprazole magnesium (ESO) loaded pH sensitive NPs were prepared by nano-emulsification polymer crosslinking method and characterized. Sixteen formulations were prepared and the concentration of process variables wasvaried to obtain nanoparticles of 200-600 nm. The NPs were found to be homogenous in size distribution. The encapsulation efficiency and drug loading ranged from 33.2% to 50.1% and 12.2% to 17.2% respectively. Particle size, encapsulation efficiency and drug loading increasedalong with co-polymer concentration. In-vitro release studies at pH 1.2 for 2 h, followed by pH 6.8 showed that environment pH significantly affected the drug release. SEM has shown that NPsare spherical with smooth surface. The pH sensitive PAAm-g-GGNPs resisted the initial release of the drug from the drug loaded NPs in acidic pH and delayed the release process to a longer period in alkaline environment.

Development of pH Sensitive Nanoparticles for Intestinal Drug Delivery Using Chemically Modified Guar Gum Co-Polymer

PubMed Central

Varma, Vegesna Naga Sravan Kumar; Shivakumar, Hosakote Gurumalappa; Balamuralidhara, Veerna; Navya, Manne; Hani, Umme

2016-01-01

The aim of the research work was to chemically modify guargum (GG) as a pH sensitive co-polymer and formulating intestinal targeting ESO nanoparticles (NPs) using the synthesized co-polymer. Poly acrylamide-grafted-guar gum (PAAm-g-GG) co-polymer was synthesized by free radical polymerization. Chemical modification of PAAm-g-GG by alkaline hydrolysis results in formation of a pH-sensitive co-polymer. The effect of GG and acryl amide (AAm) on grafting was studied. Esomeprazole magnesium (ESO) loaded pH sensitive NPs were prepared by nano-emulsification polymer crosslinking method and characterized. Sixteen formulations were prepared and the concentration of process variables wasvaried to obtain nanoparticles of 200-600 nm. The NPs were found to be homogenous in size distribution. The encapsulation efficiency and drug loading ranged from 33.2% to 50.1% and 12.2% to 17.2% respectively. Particle size, encapsulation efficiency and drug loading increasedalong with co-polymer concentration. In-vitro release studies at pH 1.2 for 2 h, followed by pH 6.8 showed that environment pH significantly affected the drug release. SEM has shown that NPsare spherical with smooth surface. The pH sensitive PAAm-g-GGNPs resisted the initial release of the drug from the drug loaded NPs in acidic pH and delayed the release process to a longer period in alkaline environment. PMID:27610149

Mixing a sol and a precipitate of block copolymers with different block ratios leads to an injectable hydrogel.

PubMed

Yu, Lin; Zhang, Zheng; Zhang, Huan; Ding, Jiandong

2009-06-08

A facile method to obtain a thermoreversible physical hydrogel was found by simply mixing an aqueous sol of a block copolymer with a precipitate of a similar copolymer but with a different block ratio. Two ABA-type triblock copolymers poly(D,L-lactic acid-co-glycolic acid)-B-poly(ethylene glycol)-B-poly(D,L-lactic acid-co-glycolic acid) (PLGA-PEG-PLGA) were synthesized. One sample in water was a sol in a broad temperature region, while the other in water was just a precipitate. The mixture of these two samples with a certain mix ratio underwent, however, a sol-to-gel-to-precipitate transition upon an increase of temperature. A dramatic tuning of the sol-gel transition temperature was conveniently achieved by merely varying mix ratio, even in the case of a similar molecular weight. Our study indicates that the balance of hydrophobicity and hydrophilicity within this sort of amphiphilic copolymers is critical to the inverse thermal gelation in water resulting from aggregation of micelles. The availability of encapsulation and sustained release of lysozyme, a model protein by the thermogelling systems was confirmed. This "mix" method provides a very convenient approach to design injectable thermogelling biomaterials with a broad adjustable window, and the novel copolymer mixture platform is potentially used in drug delivery and other biomedical applications.

New inorganic/organic copolymers (ORMOCER{reg_sign}s) for dental applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolter, H.; Storch, W.; Ott, H.

1994-12-31

Urethane and thioether (meth)acrylate alkoxysilanes have been used, as sol-gel precursors, for the preparation of a special family of inorganic/organic copolymers (ORMOCER{reg_sign}s). The basic silane type offers the following structural and synthetic possibilities for modifying the properties of the resulting copolymers: variation of the number of alkoxy groups, combination with other, different, sol-gel precursors, variation of the number of attached (meth)acrylate groups (1--5), and variation within the molecular segment (kind, structure and length) connecting the inorganic with the organic polymer structure. To achieve the additional organic polymer structure in the cured copolymer the use of different radically induced polymerization approachesmore » (UV-, visible light-, thermal- and redox induced) is possible. Taking the incorporation of fillers into account, the Young`s modulus of these copolymers is adjustable in a range of 1--17,000 MPa, and the thermal expansion coefficient in a range of 17--250{center_dot}10{sup {minus}6}{center_dot}K{sup {minus}1} (5--50 C). Other advantages are the low shrinkage (1--2,8 vol.-%), the high flexural strength (up to 160 MPa), and the high abrasion resistance. This new copolymer type seems to have significant potential for medical applications, especially as dental filling material to replace the currently used controversial amalgam fillings.« less

Interpreting Neutron Reflectivity Profiles of Diblock Copolymer Nanocomposite Thin Films Using Hybrid Particle-Field Simulations

DOE PAGES

Mahalik, Jyoti P.; Dugger, Jason W.; Sides, Scott W.; ...

2018-04-10

Mixtures of block copolymers and nanoparticles (block copolymer nanocomposites) are known to microphase separate into a plethora of microstructures, depending on the composition, length scale and nature of interactions among its different constituents. Theoretical and experimental works on this class of nanocomposites have already high-lighted intricate relations among chemical details of the polymers, nanoparticles, and various microstructures. Confining these nanocomposites in thin films yields an even larger array of structures, which are not normally observed in the bulk. In contrast to the bulk, exploring various microstructures in thin films by the experimental route remains a challenging task. Here in thismore » work, we construct a model for the thin films of lamellar forming diblock copolymers containing spherical nanoparticles based on a hybrid particle-field approach. The model is benchmarked by comparison with the depth profiles obtained from the neutron reflectivity experiments for symmetric poly(deuterated styrene-b-n butyl methacrylate) copolymers blended with spherical magnetite nanoparticles covered with hydrogenated poly(styrene) corona. We show that the model based on a hybrid particle-field approach provides details of the underlying microphase separation in the presence of the nanoparticles through a direct comparison to the neutron reflectivity data. This work benchmarks the application of the hybrid particle-field model to extract the interaction parameters for exploring different microstructures in thin films containing block copolymers and nanocomposites.« less

Brushed block copolymer micelles with pH-sensitive pendant groups for controlled drug delivery.

PubMed

Lee, Hyun Jin; Bae, Younsoo

2013-08-01

To investigate the effects of small aliphatic pendent groups conjugated through an acid-sensitive linker to the core of brushed block copolymer micelles on particle properties. The brushed block copolymers were synthesized by conjugating five types of 2-alkanone (2-butanone, 2-hexanone, 2-octanone, 2-decanone, and 2-dodecanone) through an acid-labile hydrazone linker to poly(ethylene glycol)-poly(aspartate hydrazide) block copolymers. Only block copolymers with 2-hexanone and 2-octanone (PEG-HEX and PEG-OCT) formed micelles with a clinically relevant size (< 50 nm in diameter), low critical micelle concentration (CMC, < 20 μM), and drug entrapment yields (approximately 5 wt.%). Both micelles degraded in aqueous solutions in a pH-dependent manner, while the degradation was accelerated in an acidic condition (pH 5.0) in comparison to pH 7.4. Despite these similar properties, PEG-OCT micelles controlled the entrapment and pH-dependent release of a hydrophobic drug most efficiently, without altering particle size, shape, and stability. The molecular weight of PEG (12 kDa vs 5 kDa) induced no change in pH-controlled drug release rates of PEG-OCT micelles. Acid-labile small aliphatic pendant groups are useful to control the entrapment and release of a hydrophobic drug physically entrapped in the core of brushed block copolymer micelles.

Dual-degradable disulfide-containing PEI–Pluronic/DNA polyplexes: transfection efficiency and balancing protection and DNA release

PubMed Central

Zhang, Lifen; Chen, Zhenzhen; Li, Yanfeng

2013-01-01

Polymeric gene-delivery vectors to achieve lack of toxicity and a balance between protection and DNA release remains a formidable challenge. Incorporating intracellular environment-responsive degradable bonds is an appreciable step toward developing safer transfection agents. In this study, novel, dual-degradable polycation copolymers (Pluronic-diacrylate [PA]–polyethyleneimine [PEI]–SS) were synthesized through the addition of low molecular weight (800 Da) PEI cross-linked with SS (PEI-SS) to PA. Three PA-PEI-SS copolymers (PA-PEI-SS1, 2, and 3) with different PEI-SS to Pluronic molar ratios were investigated and found to strongly condense plasmid DNA into positively charged nanoparticles with an average particle size of approximately 200 nm and to possess higher stability against DNase I digestion and sodium heparin. Disulfide and ester bonds of the copolymers were susceptible to intracellular redox conditions. In vitro experiments demonstrated that the PA-PEI-SS copolymers had significantly lower cytotoxicity and higher transfection efficiency in both BGC-823 and 293T cell lines than the controls of degradable PEI-SS and nondegradable 25 kDa PEI. Transfection activity was influenced by the PEI-SS content in the polymers and PA-PEI-SS1 showed the highest efficiency of the three copolymers. These studies suggest that these dual-degradable copolymers could be used as potential biocompatible gene delivery carriers. PMID:24109182

A new route to fabricate biocompatible hydrogels with controlled drug delivery behavior.

PubMed

Hu, Xiaohong; Gong, Xiao

2016-05-15

Hydrogels for drug delivery have attracted extensive interests since they can be used for biomaterials such as contact lenses. Here, we report that biocompatible hydrogels for contact lenses with controlled drug delivery behavior can be fabricated using copolymer hydrogels and Layer-by-Layer (LbL) surface modification technique. Methyl acrylic anhydride (MAA) modified β-cyclodextrin (β-CD) (MA-β-CD) was synthesized and copolymerized with hydroxyethyl methacrylate (HEMA) to form copolymer hydrogel. The introduction of second monomer of MA-β-CD would accelerate the polymerization of hydrogel, leading to increase of residual CC groups. The structure of copolymers was characterized by differential scanning calorimetry (DSC). Transparence, equilibrium swelling ratio and contact angle of copolymer hydrogel were also detailed discussed in the work. In vitro drug release results showed that copolymer hydrogel with higher MA-β-CD content exhibited a better drug loading capacity and drug release behaviors could be tuned by MA-β-CD/monomer ratio. Finally, alkynyl functional hyaluronic acid (HA-BP) and nitrine functional chitosan (CS-N3) were synthesized and covalently cross-linked to copolymer hydrogel surface using LbL technique through click chemistry. The successful LbL multilayers were confirmed by X-ray Photoelectron Spectroscopy (XPS). Resultsofcytotoxicityexperiment revealed that the hydrogels were biocompatible since they could support the growth of cells. Copyright © 2016 Elsevier Inc. All rights reserved.

Tuning the pore composition by two simultaneous interfacial self-assembly processes: breath figures and coffee stain.

PubMed

de León, Alberto S; del Campo, Adolfo; Fernández-García, Marta; Rodríguez-Hernández, Juan; Muñoz-Bonilla, Alexandra

2014-06-03

In the current paper, we prepared microstructured porous films by the breath figures approach using polymer blends consisting of polystyrene as the major component and an amphiphilic additive, either a synthetic block copolymer {two different polystyrene-b-poly[poly(ethylene glycol) methyl ether methacrylate] copolymers} or a series of commercial surfactants. Tetrahydrofuran was employed as the solvent. Confocal micro-Raman spectroscopy demonstrated the preferential location of the amphiphilic additives in the cavities of the film as a consequence of the breath figures mechanism. However, the distribution of the copolymer within the cavities varies depending upon the structure and, more precisely, the surface properties of the additives, leading to three different situations. First of all, the copolymer with a larger polystyrene segment, insoluble in the condensed water droplets, is homogeneously distributed along the whole surface of the cavities. On the contrary, when the copolymer is soluble in water (shorter polystyrene segment), it migrates inside the droplet and a coffee-stain phenomenon takes place during the water droplet evaporation, conducting to a ring-like deposition on the top edge of the cavities. Finally, when a water-soluble surfactant with high surface activity is used, the surfactant is solubilized inside the water droplets, which provokes a decrease on the surface tension and the coffee-ring effect is modified. In this situation, the copolymer covers the bottom of the pore.

Temperature-dependent optical properties of gold nanoparticles coated with a charged diblock copolymer and an uncharged triblock copolymer.

PubMed

Volden, Sondre; Kjøniksen, Anna-Lena; Zhu, Kaizheng; Genzer, Jan; Nyström, Bo; Glomm, Wilhelm R

2010-02-23

We demonstrate that the optical properties of gold nanoparticles can be used to detect and follow stimuli-induced changes in adsorbed macromolecules. Specifically, we investigate thermal response of anionic diblock and uncharged triblock copolymers based on poly(N-isopropylacrylamide) (PNIPAAM) blocks adsorbed onto gold nanoparticles and planar gold surfaces in a temperature range between 25 and 60 degrees C. By employing a palette of analytical probes, including UV-visible spectroscopy, dynamic light scattering, fluorescence, and quartz crystal microbalance with dissipation monitoring, we establish that while the anionic copolymer forms monolayers at both low and high temperature, the neutral copolymer adsorbs as a monolayer at low temperatures and forms multilayers above the cloud point (T(C)). Raising the temperature above T(C) severely affects the optical properties of the gold particle/polymer composites, expelling associated water and altering the immediate surroundings of the gold nanoparticles. This effect, stronger for the uncharged polymer, is related to the amount of polymer adsorbed on the surface, where a denser shell influences the surface plasmon band to a greater degree. This is corroborated with light scattering experiments, which reveal that flocculation of the neutral polymer-coated particles occurs at high temperatures. The flocculation behavior of the neutral copolymer on planar gold surfaces results in multilayer formation. The observed effects are discussed within the framework of the Mie-Drude theory.

Direct hierarchical assembly of nanoparticles

DOEpatents

Xu, Ting; Zhao, Yue; Thorkelsson, Kari

2014-07-22

The present invention provides hierarchical assemblies of a block copolymer, a bifunctional linking compound and a nanoparticle. The block copolymers form one micro-domain and the nanoparticles another micro-domain.

Entropic effects, shape, and size of mixed micelles formed by copolymers with complex architectures

NASA Astrophysics Data System (ADS)

Kalogirou, Andreas; Gergidis, Leonidas N.; Moultos, Othonas; Vlahos, Costas

2015-11-01

The entropic effects in the comicellization behavior of amphiphilic A B copolymers differing in the chain size of solvophilic A parts were studied by means of molecular dynamics simulations. In particular, mixtures of miktoarm star copolymers differing in the molecular weight of solvophilic arms were investigated. We found that the critical micelle concentration values show a positive deviation from the analytical predictions of the molecular theory of comicellization for chemically identical copolymers. This can be attributed to the effective interactions between copolymers originated from the arm size asymmetry. The effective interactions induce a very small decrease in the aggregation number of preferential micelles triggering the nonrandom mixing between the solvophilic moieties in the corona. Additionally, in order to specify how the chain architecture affects the size distribution and the shape of mixed micelles we studied star-shaped, H-shaped, and homo-linked-rings-linear mixtures. In the first case the individual constituents form micelles with preferential and wide aggregation numbers and in the latter case the individual constituents form wormlike and spherical micelles.

Entropic effects, shape, and size of mixed micelles formed by copolymers with complex architectures.

PubMed

Kalogirou, Andreas; Gergidis, Leonidas N; Moultos, Othonas; Vlahos, Costas

2015-11-01

The entropic effects in the comicellization behavior of amphiphilic AB copolymers differing in the chain size of solvophilic A parts were studied by means of molecular dynamics simulations. In particular, mixtures of miktoarm star copolymers differing in the molecular weight of solvophilic arms were investigated. We found that the critical micelle concentration values show a positive deviation from the analytical predictions of the molecular theory of comicellization for chemically identical copolymers. This can be attributed to the effective interactions between copolymers originated from the arm size asymmetry. The effective interactions induce a very small decrease in the aggregation number of preferential micelles triggering the nonrandom mixing between the solvophilic moieties in the corona. Additionally, in order to specify how the chain architecture affects the size distribution and the shape of mixed micelles we studied star-shaped, H-shaped, and homo-linked-rings-linear mixtures. In the first case the individual constituents form micelles with preferential and wide aggregation numbers and in the latter case the individual constituents form wormlike and spherical micelles.

Preparation and characterization of poly(acrylic acid)-hydroxyethyl cellulose graft copolymer.

PubMed

Abdel-Halim, E S

2012-10-01

Poly(acrylic acid) hydroxyethyl cellulose [poly(AA)-HEC] graft copolymer was prepared by polymerizing acrylic acid (AA) with hydroxyethyl cellulose (HEC) using potassium bromate/thiourea dioxide (KBrO(3)/TUD) as redox initiation system. The polymerization reaction was carried out under a variety of conditions including concentrations of AA, KBrO(3) and TUD, material to liquor ratio and polymerization temperature. The polymerization reaction was monitored by withdrawing samples from the reaction medium and measuring the total conversion. The rheological properties of the poly(AA)-HEC graft copolymer were investigated. The total conversion and rheological properties of the graft copolymer depended on the ratio of KBrO(3) to TUD and on acrylic acid concentration as well as temperature and material to liquor ratio. Optimum conditions of the graft copolymer preparation were 30 mmol KBrO(3) and 30 mmol TUD/100g HEC, 100% AA (based on weight of HEC), duration 2h at temperature 50 °C using a material to liquor ratio of 1:10. Copyright © 2012. Published by Elsevier Ltd.

Phase behaviors of supramolecular graft copolymers with reversible bonding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xu; Wang, Liquan, E-mail: jlin@ecust.edu.cn, E-mail: lq-wang@ecust.edu.cn; Jiang, Tao

2013-11-14

Phase behaviors of supramolecular graft copolymers with reversible bonding interactions were examined by the random-phase approximation and real-space implemented self-consistent field theory. The studied supramolecular graft copolymers consist of two different types of mutually incompatible yet reactive homopolymers, where one homopolymer (backbone) possesses multifunctional groups that allow second homopolymers (grafts) to be placed on. The calculations carried out show that the bonding strength exerts a pronounced effect on the phase behaviors of supramolecular graft copolymers. The length ratio of backbone to graft and the positions of functional groups along the backbone are also of importance to determine the phase behaviors.more » Phase diagrams were constructed at high bonding strength to illustrate this architectural dependence. It was found that the excess unbounded homopolymers swell the phase domains and shift the phase boundaries. The results were finally compared with the available experimental observations, and a well agreement is shown. The present work could, in principle, provide a general understanding of the phase behaviors of supramolecular graft copolymers with reversible bonding.« less

In-situ Polymerization of Polyaniline/Polypyrrole Copolymer using Different Techniques

NASA Astrophysics Data System (ADS)

Hammad, A. S.; Noby, H.; Elkady, M. F.; El-Shazly, A. H.

2018-01-01

The morphology and surface area of the poly(aniline-co-pyrrole) copolymer (PANPY) are important properties which improve the efficiency of the copolymer in various applications. In this investigation, different techniques were employed to produce PANPY in different morphologies. Aniline and pyrrole were used as monomers, and ammonium peroxydisulfate (APS) was used as an oxidizer with uniform molar ratio. Rapid mixing, drop-wise mixing, and supercritical carbon dioxide (ScCO2) polymerization techniques were appointed. The chemical structure, crystallinity, porosity, and morphology of the composite were distinguished by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Brunauer, Emmett and Teller (BET) analysis, and transmission electron microscopy (TEM) respectively. The characterization tests indicated that the polyaniline/polypyrrole copolymer was successfully prepared with different morphologies. Based on the obtained TEM, hollow nanospheres were formed using rapid mixing technique with acetic acid that have a diameter of 75 nm and thickness 26 nm approximately. Also, according to the XRD, the produced structures have a semi- crystalline structure. The synthesized copolymer with ScCO2-assisted polymerization technique showed improved surface area (38.1 m2/g) with HCl as dopant.

Sustainable Hydrogels Based on Lignin-Methacrylate Copolymers with Enhanced Water Retention and Tunable Material Properties.

PubMed

Rajan, Kalavathy; Mann, Jeffrey K; English, Eldon; Harper, David P; Carrier, Danielle Julie; Rials, Timothy G; Labbé, Nicole; Chmely, Stephen C

2018-04-12

Synthesizing lignin-based copolymers would valorize a major coproduct stream from pulp and paper mills and biorefineries as well as reduce the dependence on petrochemical-based consumer goods. In this study, we used organosolv lignin isolated from hybrid poplar ( Populus trichocarpa × P. deltoides) to generate lignin-containing methacrylate hydrogels. The copolymer hydrogels were synthesized by first grafting 2-hydroxyethyl methacrylate (HEMA) onto lignin (OSLH) via esterification and then by free radical polymerization of OSLH with excess HEMA. The copolymer hydrogels were prepared with different stoichiometric ratios of OSLH (e.g., 0, 10, 20, and 40 wt %) with respect to HEMA. Copolymerization with OSLH led to an increase in cross-linking density, which in turn enhanced the hydrogel's material properties; we report up to 39% improvement in water retention, 20% increase in thermostability, and up to a 3 order increase in magnitude of the storage modulus ( G'). The copolymer's properties, such as water retention and glass transition temperature, could be tuned by altering the percent functionalization of lignin OH groups and the ratio of OSLH to HEMA.

A novel voltammetric sensor for ascorbic acid based on molecularly imprinted poly(o-phenylenediamine-co-o-aminophenol).

PubMed

Kong, Yong; Shan, Xueling; Ma, Jianfeng; Chen, Meilan; Chen, Zhidong

2014-01-27

A molecularly imprinted copolymer, poly(o-phenylenediamine-co-o-aminophenol) (PoPDoAP), was prepared as a new ascorbic acid (AA) sensor. The copolymer was synthesized by incorporation of AA as template molecules during the electrochemical copolymerization of o-phenylenediamine and o-aminophenol, and complementary sites were formed after the copolymer was electrochemically reduced in ammonium aqueous solution. The molecularly imprinted copolymer sensor exhibited a high sensitivity and selectivity toward AA. Differential pulse voltammograms (DPVs) showed a linear concentration range of AA from 0.1 to 10 mM, and the detection limit was calculated to be 36.4 μM. Compared to conventional polyaniline-based AA sensors, the analytical performance of the imprinted copolymer sensor was improved due to the broadened usable pH range of PoPDoAP (from pH 1.0 to pH 8.0). The sensor also exhibited a good reproducibility and stability. And it has been successfully applied in the determination of AA in real samples, including vitamin C tablet and orange juices, with satisfactory results. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis of polycarbonate-r-polyethylene glycol copolymer for templated synthesis of mesoporous TiO2 films.

PubMed

Patel, Rajkumar; Kim, Jinkyu; Lee, Chang Soo; Kim, Jong Hak

2014-12-01

We synthesized a novel polycarbonate Z-r-polyethylene glycol (PCZ-r-PEG) copolymer by solution polycondensation. Successful synthesis of PCZ-r-PEG copolymer was confirmed by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (1H-NMR), gel permeation chromatography (GPC), and transmission electron microscopy (TEM). PCZ-r-PEG copolymer was used as a structure-directing agent for fabrication of mesoporous thin film containing a titanium dioxide (TiO2) layer. To control the porosity of the resultant inorganic layer, the ratio of titanium(IV) isopropoxide (TTIP) to PCZ-r-PEG copolymer was varied. The structure and porosity of the resulting mesoporous films were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses. Mesoporous TiO2 films fabricated on an F-doped tin oxide (FTO) surface were used as photoanodes for quasi-solid-state dye-sensitized solar cells (qssDSSCs). The highest efficiency achieved was 3.3% at 100 mW/cm2 for a film thickness of 750 nm, which is high considering the thickness of TiO2 film, indicating the importance of the structure-directing agent.

Fungal biodegradation of lignopolystyrene graft copolymers. [Pleurotus ostreatus; Phanerochaete chrysosporium; Trametes versicolor; Gloeophyllum trabeum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Milstein, O.; Gersonde, R.; Huttermann, A.

1992-10-01

White rot basidiomycetes were able to biodegrade styrene (1-phenylethene) graft copolymers of lignin containing different proportions of lignin and polystyrene (poly(1-phenylethylene)). The biodegradation tests were run on lignin-styrene copolymerization products which contained 10.3, 32.2, and 50.4{percent} (wt/wt) lignin. The polymer samples were incubated with the white rot fungi Pleurotus ostreatus, Phanerochaete chrysosporium, and Trametes versicolor and the brown rot fungus Gloeophyllum trabeum. White rot fungi degraded the plastic samples at a rate which increased with increasing lignin content in the copolymer sample. Both polystyrene and lignin components of the copolymer were readily degraded. Polystyrene pellets were not degradable in thesemore » tests. Degradation was verified for both incubated and control samples by weight loss, quantitative UV spectrophotometric analysis of both lignin and styrene residues, scanning electron microscopy of the plastic surface, and the presence of enzymes active in degradation during incubation. Brown rot fungus did not affect any of the plastics. White rot fungi produced and secreted oxidative enzymes associated with lignin degradation in liquid media during incubation with lignin-polystyrene copolymer.« less

Immobilization of Acidithiobacillus ferrooxidans on sulfonated microporous poly(styrene-divinylbenzene) copolymer with granulated activated carbon and its use in bio-oxidation of ferrous iron.

PubMed

Koseoglu-Imer, Derya Yuksel; Keskinler, Bulent

2013-01-01

The immobilization efficiencies of Acidithiobacillus ferrooxidans cells on different immobilization matrices were investigated for biooxidation of ferrous iron (Fe(2+)) to ferric iron (Fe(3+)). Six different matrices were used such as the polyurethane foam (PUF), granular activated carbon (GAC), raw poly(styrene-divinylbenzene) copolymer (rawSDVB), raw poly(styrene-divinylbenzene) copolymer with granular activated carbon (rawSDVB-GAC), sulfonated poly(styrene-divinylbenzene) copolymer (sulfSDVB) and sulfonated poly(styrene-divinylbenzene) copolymer with granular activated carbon (sulfSDVB-GAC). The sulfSDVB-GAC polymer showed the best performance for Fe(2+) biooxidation. It was used at packed-bed bioreactor and the kinetic parameters were obtained. The highest Fe(2+) biooxidation rate (R) was found to be 4.02 g/L h at the true dilution rate (Dt) of 2.47 1/h and hydraulic retention time (τ) of 0.4 h. The sulfSDVB-GAC polymer was used for the first time as immobilization material for A. ferrooxidans for Fe(2+) biooxidation. Copyright © 2012 Elsevier B.V. All rights reserved.

Synthesis and photooxidation of styrene copolymer bearing camphorquinone pendant groups

PubMed Central

Moszner, Norbert; Lukáč, Ivan

2012-01-01

Summary (±)-10-Methacryloyloxycamphorquinone (MCQ) was synthesized from (±)-10-camphorsulfonic acid either by a known seven-step synthetic route or by a novel, shorter five-step synthetic route. MCQ was copolymerized with styrene (S) and the photochemical behavior of the copolymer MCQ/S was compared with that of a formerly studied copolymer of styrene with monomers containing the benzil (BZ) moiety (another 1,2-dicarbonyl). Irradiation (λ > 380 nm) of aerated films of styrene copolymers with monomers containing the BZ moiety leads to the insertion of two oxygen atoms between the carbonyl groups of BZ and to the formation of benzoyl peroxide (BP) as pendant groups on the polymer backbone. An equivalent irradiation of MCQ/S led mainly to the insertion of only one oxygen atom between the carbonyl groups of camphorquinone (CQ) and to the formation of camphoric anhydride (11) covalently bound to the polymer backbone. While the decomposition of pendant BP groups formed in irradiated films of styrene copolymers with pendant BZ groups leads to crosslinking, only small molecular-weight changes in irradiated MCQ/S were observed. PMID:22509202

A thermosensitive hydrogel based on biodegradable amphiphilic poly(ethylene glycol) polycaprolactone poly(ethylene glycol) block copolymers

NASA Astrophysics Data System (ADS)

Gong, Chang Yang; Qian, Zhi Yong; Liu, Cai Bing; Juan Huang, Mei; Gu, Ying Chun; Wen, Yan Jun; Kan, Bing; Wang, Ke; Dai, Mei; Li, Xing Yi; Gou, Ma Ling; Tu, Ming Jing; Wei, Yu Quan

2007-06-01

A series of low molecular weight poly(ethylene glycol)-polycaprolactone-poly(ethylene glycol) (PEG-PCL-PEG) biodegradable block copolymers were successfully synthesized using isophorone diisocyanate (IPDI) as the coupling agent, and were characterized using 1H NMR and Fourier transform infrared spectroscopy. The aqueous solutions of the PEG-PCL-PEG copolymers displayed a special thermosensitive gel-sol transition when the concentration was above the corresponding critical gel concentration. Gel-sol phase diagrams were recorded using the test-tube-inversion method; they depended on the hydrophilic/hydrophobic balance in the macromolecular structure, as well as some other factors, including the heating history, volume, and the ageing time of the copolymer aqueous solutions and dissolution temperature of the copolymers. As a result, the gel-sol transition temperature range could be altered, which might be very useful for application in injectable drug delivery systems. This work was financially supported by the Chinese Key Basic Research Program (2004CB518800 and 2004CB518807), and the Sichuan Key Project of Science and Technology (06(05SG022-021-02)).

Asymmetric Membranes from Two Chemically Distinct Triblock Terpolymers Blended during Standard Membrane Fabrication.

PubMed

Li, Yuk Mun; Srinivasan, Divya; Vaidya, Parth; Gu, Yibei; Wiesner, Ulrich

2016-10-01

Deviating from the traditional formation of block copolymer derived isoporous membranes from one block copolymer chemistry, here asymmetric membranes with isoporous surface structure are derived from two chemically distinct block copolymers blended during standard membrane fabrication. As a first proof of principle, the fabrication of asymmetric membranes is reported, which are blended from two chemically distinct triblock terpolymers, poly(isoprene-b-styrene-b-(4-vinyl)pyridine) (ISV) and poly(isoprene-b-styrene-b-(dimethylamino)ethyl methacrylate) (ISA), differing in the pH-responsive hydrophilic segment. Using block copolymer self-assembly and nonsolvent induced phase separation process, pure and blended membranes are prepared by varying weight ratios of ISV to ISA. Pure and blended membranes exhibit a thin, selective layer of pores above a macroporous substructure. Observed permeabilities at varying pH values of blended membranes depend on relative triblock terpolymer composition. These results open a new direction for membrane fabrication through the use of mixtures of chemically distinct block copolymers enabling the tailoring of membrane surface chemistries and functionalities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Semicrystalline polyamide engineering thermoplastics based on the renewable monomer, 1,9-nonane diamine: Thermal properties and water absorption

DOE PAGES

Kugel, Alex; He, Jie; Samanta, Satyabrata; ...

2012-08-27

Here, a series of poly(1,9-nonamethylene adipamide-co-1,9-nonamethylene terephthalamide) copolymers were produced using melt polymerization and the thermal properties, crystal structure, and moisture uptake characterized. The results confirmed that the copolymers exhibit isomorphism. As expected, glass transition temperature and the apparent melting temperature increased with increasing terephthalmide content. Using the difference in the apparent melting temperature to the crystallization temperature as a measure of relative crystallization rate, it was observed that crystallization rate decreased as the terephthalamide content of the copolymer was increased from 0 to 50 mole percent but then sharply increased when increased beyond 50 mole percent. This behavior maymore » be the result of extensive inter- and intramolecular interactions in the melt associated with terephthalmide units in the polymer chain that nucleate crystallization upon cooling below the equilibrium melting temperature. Comparing the thermal properties of copolymers possessing an excess of terephthalmide units to the commodity polyamide Nylon 6,6, it is believed that these copolymers may have utility as partially renewable engineering thermoplastics.« less

Hydrogen Bonding-Mediated Microphase Separation during the Formation of Mesoporous Novolac-Type Phenolic Resin Templated by the Triblock Copolymer, PEO-b-PPO-b-PEO

PubMed Central

Chu, Wei-Cheng; Chiang, Shih-Fan; Li, Jheng-Guang; Kuo, Shiao-Wei

2013-01-01

After blending the triblock copolymer, poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (PEO-b-PPO-b-PEO) with novolac-type phenolic resin, Fourier transform infrared spectroscopy revealed that the ether groups of the PEO block were stronger hydrogen bond acceptors for the OH groups of phenolic resin than were the ether groups of the PPO block. Thermal curing with hexamethylenetetramine as the curing agent resulted in the triblock copolymer being incorporated into the phenolic resin, forming a nanostructure through a mechanism involving reaction-induced microphase separation. Mild pyrolysis conditions led to the removal of the PEO-b-PPO-b-PEO triblock copolymer and formation of mesoporous phenolic resin. This approach provided a variety of composition-dependent nanostructures, including disordered wormlike, body-centered-cubic spherical and disorder micelles. The regular mesoporous novolac-type phenolic resin was formed only at a phenolic content of 40–60 wt %, the result of an intriguing balance of hydrogen bonding interactions among the phenolic resin and the PEO and PPO segments of the triblock copolymer. PMID:28788378

Square and Rectangular Arrays from Directed Assembly of Sphere-forming Diblock Copolymers in Thin Films

NASA Astrophysics Data System (ADS)

Ji, Shengxiang; Nagpal, Umang; Liao, Wen; de Pablo, Juan; Nealey, Paul

2010-03-01

Patterns of square and rectangular arrays with nanoscale dimensions are scientifically and technologically important. Fabrication of square array patterns in thin films has been demonstrated by directed assembly of cylinder-forming diblock copolymers on chemically patterned substrates, supramolecular assembly of diblock copolymers, and self-assembly of triblock terpolymers. However, a macroscopic area of square array patterns with long-range order has not been achieved, and the fabrication of rectangular arrays has not been reported so far. Here we report a facile approach for fabricating patterns of square and rectangular arrays by directing the assembly of sphere-forming diblock copolymers on chemically patterned substrates. On stripe patterns, a square arrangement of half spheres, corresponding to the (100) plane of the body-centred cubic (BCC) lattice, formed on film surfaces. When the underlying pattern periods mismatched with the copolymer period, the square pattern could be stretched (up to ˜60%) or compressed (˜15%) to form rectangular arrays. Monte Carlo simulations have been further used to verify the experimental results and the 3-dimensional arrangements of spheres.

Ultrahigh Molecular Weight Linear Block Copolymers: Rapid Access by Reversible-Deactivation Radical Polymerization and Self- Assembly into Large Domain Nanostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mapas, Jose Kenneth D.; Thomay, Tim; Cartwright, Alexander N.

2016-05-05

Block copolymer (BCP) derived periodic nanostructures with domain sizes larger than 150 nm present a versatile platform for the fabrication of photonic materials. So far, the access to such materials has been limited to highly synthetically involved protocols. Herein, we report a simple, “user-friendly” method for the preparation of ultrahigh molecular weight linear poly(solketal methacrylate-b-styrene) block copolymers by a combination of Cu-wire-mediated ATRP and RAFT polymerizations. The synthesized copolymers with molecular weights up to 1.6 million g/mol and moderate dispersities readily assemble into highly ordered cylindrical or lamella microstructures with domain sizes as large as 292 nm, as determined bymore » ultra-small-angle x-ray scattering and scanning electron microscopy analyses. Solvent cast films of the synthesized block copolymers exhibit stop bands in the visible spectrum correlated to their domain spacings. The described method opens new avenues for facilitated fabrication and the advancement of fundamental understanding of BCP-derived photonic nanomaterials for a variety of applications.« less

Inverse design of bulk morphologies in block copolymers using particle swarm optimization

NASA Astrophysics Data System (ADS)

Khadilkar, Mihir; Delaney, Kris; Fredrickson, Glenn

Multiblock polymers are a versatile platform for creating a large range of nanostructured materials with novel morphologies and properties. However, achieving desired structures or property combinations is difficult due to a vast design space comprised of parameters including monomer species, block sequence, block molecular weights and dispersity, copolymer architecture, and binary interaction parameters. Navigating through such vast design spaces to achieve an optimal formulation for a target structure or property set requires an efficient global optimization tool wrapped around a forward simulation technique such as self-consistent field theory (SCFT). We report on such an inverse design strategy utilizing particle swarm optimization (PSO) as the global optimizer and SCFT as the forward prediction engine. To avoid metastable states in forward prediction, we utilize pseudo-spectral variable cell SCFT initiated from a library of defect free seeds of known block copolymer morphologies. We demonstrate that our approach allows for robust identification of block copolymers and copolymer alloys that self-assemble into a targeted structure, optimizing parameters such as block fractions, blend fractions, and Flory chi parameters.

Protein resistance of dextran and dextran-PEG copolymer films

PubMed Central

Kozak, Darby; Chen, Annie; Bax, Jacinda; Trau, Matt

2011-01-01

The protein resistance of dextran and dextran-poly(ethylene glycol) (PEG) copolymer films was examined on an organosilica particle-based assay support. Comb-branched dextran-PEG copolymer films were synthesized in a two step process using the organosilica particle as a solid synthetic support. Particles modified with increasing amounts (0.1-1.2 mg m−2) of three molecular weights (10 000, 66 900, 400 000 g mol−1) of dextran were found to form relatively poor protein-resistant films compared to dextran-PEG copolymers and previously studied PEG films. The efficacy of the antifouling polymer films was found to be dependent on the grafted amount and its composition, with PEG layers being the most efficient, followed by dextran-PEG copolymers, and dextran alone being the least efficient. Immunoglobulin gamma (IgG) adsorption decreased from ~ 5 to 0.5 mg m−2 with increasing amounts of grafted dextran, but bovine serum albumin (BSA) adsorption increased above monolayer coverage (to ~2 mg m−2) indicating ternary adsorption of the smaller protein within the dextran layer. PMID:21614699

Stimuli-responsive one-dimensional copolymer nanostructures fabricated by metallogel template polymerization and their adsorption of aspirin.

PubMed

Wen, Xing; Tang, Liming; Qiang, Lu

2014-06-14

pH responsive poly(N,N'-methylenebisacrylamide-co-4-vinylpyridine) (P(MBA-4VP)) one dimensional (1D) nanostructures have been prepared by metallogel template copolymerization, which was carried out in an Ag(i)-coordinated organogel with benzoyl peroxide (BPO) as the initiator. The product has been characterized using infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. The experimental results reveal that the gel fiber is a crucial template for polymerization. Due to the degradation of the template in copolymerization, nanofibers of metallogel were transcribed to copolymer nanowires. The introduction of co-monomer 4-vinylpyridine (4VP) imparts to the 1D copolymer nanostructures pH sensitivity and the possible use as an adsorption material of aspirin. Adsorbed 1D copolymer nanostructures could be regenerated using proton solvent, acid medium and salt solution. In addition, silver nanoparticle loaded copolymer nanowires have been produced from the reduction of silver ions instead of template removal, where silver ions act both as the template and as the nanoparticle growth substrate.

Ordered porous mesostructured materials from nanoparticle-block copolymer self-assembly

DOEpatents

Warren, Scott; Wiesner, Ulrich; DiSalvo, Jr., Francis J

2013-10-29

The invention provides mesostructured materials and methods of preparing mesostructured materials including metal-rich mesostructured nanoparticle-block copolymer hybrids, porous metal-nonmetal nanocomposite mesostructures, and ordered metal mesostructures with uniform pores. The nanoparticles can be metal, metal alloy, metal mixture, intermetallic, metal-carbon, metal-ceramic, semiconductor-carbon, semiconductor-ceramic, insulator-carbon or insulator-ceramic nanoparticles, or combinations thereof. A block copolymer/ligand-stabilized nanoparticle solution is cast, resulting in the formation of a metal-rich (or semiconductor-rich or insulator-rich) mesostructured nanoparticle-block copolymer hybrid. The hybrid is heated to an elevated temperature, resulting in the formation of an ordered porous nanocomposite mesostructure. A nonmetal component (e.g., carbon or ceramic) is then removed to produce an ordered mesostructure with ordered and large uniform pores.

Different copolymer films on ZnFeCo particles: Synthesis and anticorrosion properties

NASA Astrophysics Data System (ADS)

Ozyilmaz, A. Tuncay; Avsar, Busra; Ozyilmaz, Gul; Karahan, İ. Hakkı; Camurcu, Taskin; Colak, Fatma

2014-11-01

Zinc-iron-cobalt (ZnFeCo) particles were electrochemically deposited on carbon steel (CS) electrode applying current of 3 mA with chronopotentiometry technique. ZnFeCo particles had homogenous, smooth with prismatic structure. It was shown that the ZnFeCo particles exhibited important barrier effect on CS substrate. Poly(aniline-co-o-anisidine), poly(aniline-co-pyrrole), poly(aniline-co-N-methylpyrrole) and poly(o-anisidine-co-pyrrole) copolymer films were obtained on CS/ZnFeCo electrode. Evaluation of anticorrosion performance of copolymer coatings in 3.5% NaCl solution was investigated by using AC impedance spectroscopy (EIS) technique, anodic polarization and the Eocp-time curves. Copolymer films exhibited significant physical barrier behavior on ZnFeCo plated carbon steel, in longer exposure time.

A Theoretically Informed Model for the Rheology of Entangled Block Copolymer Nanocomposites

NASA Astrophysics Data System (ADS)

Su, Yongrui; Ramirez-Hernandez, Abelardo; Peters, Brandon; de Pablo, Juan J.

2014-03-01

The addition of nanoparticles to block copolymer systems has been shown to have important effects on their equilibrium structure and properties. Less is known about the non-equilibrium behavior of block polymer nanocomposites. A new particle-based, theoretically informed coarse-grained model for multicomponent nanocomposites is proposed to examine the effects of nanoparticles on the rheology of entangled block copolymer melts. Entanglements are treated at the two-molecule level, through slip-springs that couple the dynamics of neighboring pairs of chains. The inclusion of slip-springs changes the polymer dynamics from unentangled to entangled. The nanoparticles are functionalized with short polymer chains that can entangle with the copolymers. We study the nonlinear rheology of the resulting nanocomposites under shear flow with a dissipative particle dynamics (DPD) thermostat.

Double-bond-containing polyallene-based triblock copolymers via phenoxyallene and (meth)acrylate

NASA Astrophysics Data System (ADS)

Ding, Aishun; Lu, Guolin; Guo, Hao; Huang, Xiaoyu

2017-03-01

A series of ABA triblock copolymers, consisting of double-bond-containing poly(phenoxyallene) (PPOA), poly(methyl methacrylate) (PMMA), or poly(butyl acrylate) (PBA) segments, were synthesized by sequential free radical polymerization and atom transfer radical polymerization (ATRP). A new bifunctional initiator bearing azo and halogen-containing ATRP initiating groups was first prepared followed by initiating conventional free radical homopolymerization of phenoxyallene with cumulated double bond to give a PPOA-based macroinitiator with ATRP initiating groups at both ends. Next, PMMA-b-PPOA-b-PMMA and PBA-b-PPOA-b-PBA triblock copolymers were synthesized by ATRP of methyl methacrylate and n-butyl acrylate initiated by the PPOA-based macroinitiator through the site transformation strategy. These double-bond-containing triblock copolymers are stable under UV irradiation and free radical circumstances.

Copolymers For Capillary Gel Electrophoresis

DOEpatents

Liu, Changsheng; Li, Qingbo

2005-08-09

This invention relates to an electrophoresis separation medium having a gel matrix of at least one random, linear copolymer comprising a primary comonomer and at least one secondary comonomer, wherein the comonomers are randomly distributed along the copolymer chain. The primary comonomer is an acrylamide or an acrylamide derivative that provides the primary physical, chemical, and sieving properties of the gel matrix. The at least one secondary comonomer imparts an inherent physical, chemical, or sieving property to the copolymer chain. The primary and secondary comonomers are present in a ratio sufficient to induce desired properties that optimize electrophoresis performance. The invention also relates to a method of separating a mixture of biological molecules using this gel matrix, a method of preparing the novel electrophoresis separation medium, and a capillary tube filled with the electrophoresis separation medium.

Anionic polymerization of p-(2,2'-diphenylethyl)styrene and applications to graft copolymers.

PubMed

Huang, Minglu; Han, Bingyong; Lu, Jianmin; Yang, Wantai; Fu, Zhifeng

2017-01-01

Well-controlled anionic polymerization of an initiator-functionalized monomer, p -(2,2'-diphenylethyl)styrene (DPES), was achieved for the first time. The polymerization was performed in a mixed solvent of cyclohexane and tetrahydrofuran (THF) at 40 °C with n -BuLi as initiator. When the volume ratio of cyclohexane to THF was 20, the anionic polymerization of DPES showed living polymerization characteristics, and well-defined block copolymer PDPES- b -PS was successfully synthesized. Furthermore, radical polymerization of methyl methacrylate in the presence of PDPES effectively afforded a graft copolymer composed of a polystyrene backbone and poly(methyl methacrylate) branches. The designation of analogous monomers and polymers was of great significance to synthesize a variety of sophisticated copolymer and functionalize polymer materials.

Pattern interpolation in thin films of lamellar, symmetric copolymers on nano-patterned substrates

NASA Astrophysics Data System (ADS)

Detcheverry, Francois; Nagpal, Umang; Liu, Guoliang; Nealey, Paul; de Pablo, Juan

2009-03-01

A molecular model of block copolymer systems is used to conduct a systematic study of the morphologies that arise when thin films of symmetric, lamellar forming block copolymer materials are deposited on nanopatterned surfaces. Over 500 distinct cases are considered. It is found that, in general, three distinct morphologies can arise depending on the strength of the substrate-polymer interactions, the film thickness, and the period of the substrate pattern. The relative stability of those morphologies is determined by direct calculation of the free energy differences. The dynamic propensity of those morphologies to emerge is examined by careful analysis of simulated trajectories. The results of this systematic study are used to interpret recent experimental data for films of polystyrene-PMMA copolymers on chemically nanopatterned surfaces.

Poly(vinylidene fluoride-co-hexafluoropropylene)-graft-poly(dopamine methacrylamide) copolymers: A nonlinear dielectric material for high energy density storage

NASA Astrophysics Data System (ADS)

Rahimabady, Mojtaba; Qun Xu, Li; Arabnejad, Saeid; Yao, Kui; Lu, Li; Shim, Victor P. W.; Gee Neoh, Koon; Kang, En-Tang

2013-12-01

A nonlinear dielectric poly(vinylidene fluoride-co-hexafluoropropylene)-graft-poly(dopamine methacrylamide) [P(VDF-HFP)-g-PDMA] graft copolymer with ultra-high energy density of 33 J/cm3 was obtained by thermally initiated radical graft polymerization. It was observed that the dielectric constant of the graft copolymer films was 63% higher than that of P(VDF-HFP), with a large dielectric breakdown strength (>850 MV/m). Theoretical analyses and experimental measurements showed that the significant improvement in the electric polarization was attributed to the introduction of the highly polarizable hydroxyl groups in the PDMA side chains, and the large breakdown strength arose from the strong adhesion bonding of the catechol-containing graft copolymer to the metal electrode.

Utilization of Network-Forming Block Copolymers and Ionomers in the Development of Novel Nanostructures and Responsive Media

NASA Astrophysics Data System (ADS)

Mineart, Kenneth

Network forming block copolymers, i.e. thermoplastic elastomers (TPEs), are one of the highest commodity forms of block copolymers due to their competitive elasticity and extendability as well as their ability to be melt and solution processed. TPEs owe many of their advantages to a combination of hard and soft blocks. The soft blocks, which must be covalently bound at both ends to hard blocks, connect adjacent hard domains resulting in physically cross-linked systems. Herein, simulations and theory are used to provide a molecular-level depiction of the evolution from diblock copolymers, which do not contain the ability to form physical cross-links, to network forming triblock copolymers. In addition, systems with high interblock incompatibility that are within the diblock-to-triblock transition (i.e. having high molecular asymmetry) are identified to form three component (ABC triblock copolymer) phases from copolymer containing only two chemically distinct blocks. Following this work, which emphasizes the fundamental principle of TPEs, the dissertation shifts focus to physically- and chemically-modified triblock and pentablock copolymer TPEs. Recent progress has sought to broaden TPEs to include properties that are above and beyond their inherent mechanical benefits, including responsiveness to external stimuli. The first examples presented here consist of TPEs prepared in combination with amorphous hydrocarbon additives to yield TPE gels (TPEGs). The resulting TPEGs, which maintain the beneficial processing properties of TPEs, are subsequently molded into 1- and 2-D arrays of microchannels that are filled with liquid metal. The final devices exhibit strain-sensitive electrical conductivity to at least 600% strain, have tunable compliance (ease of stretching), and are fully recyclable. The substitution of the amorphous hydrocarbon component for crystalline analogues with melting points <100 °C yield TPE composites (TPECs). The TPECs gain the added capability of thermally-triggered shape-memory actuation, which results in a number of design possibilities including: (i) multiple-transition shape-memory in single a composite, (ii) complex actuation in laminates and, (iii) thermally-responsive electrical conductivity in microchannel-molded composites filled with liquid metal. These shape-memory TPECs can also be tuned to have different shape-memory response rates through the addition of an amorphous hydrocarbon tackifier, which serves to dilute the crystalline content without altering TPE concentration. The second set of functionalized TPEs examined are midblock-sulfonated block copolymers, which have substantial ion and water transport abilities, but are often restricted in thermal processability. The casting solvent-dependent morphology of a midblock sulfonated pentablock copolymer highlights the impact of solvent templating on resulting film domain structures. It is shown that film deposition from a miscible mixture of toluene and isopropanol (TIPA) leads to spherical sulfonated domains within a nonpolar matrix whereas deposition from neat tetrahydrofuran (THF) produces a combination of lamellar and hexagonally-pack cylinder nanostructures. These morphologies can both be converted to the anticipated equilibrium morphology, alternating lamellae, using THF vapor-annealing. Further, the morphology resulting from each solvent-casting approach impacts the rate and overall capacity at which films absorb water. Specifically, THF-cast copolymers swell faster and to a greater extent. However, some intrigue lies in the transformation of the TIPA-cast copolymer upon swelling, which yields disordered, but continuous, hydrophilic domains. The disordered morphology outperforms ordered analogues in solar simulation experiments indicating higher ion conductivity.

Block Copolymer Electrolytes: Thermodynamics, Ion Transport, and Use in Solid- State Lithium/Sulfur Cells

NASA Astrophysics Data System (ADS)

Teran, Alexander Andrew

Nanostructured block copolymer electrolytes containing an ion-conducting block and a modulus-strengthening block are of interest for applications in solid-state lithium metal batteries. These materials can self-assemble into well-defined microstructures, creating conducting channels that facilitate ion transport. The overall objective of this dissertation is to gain a better understanding of the behavior of salt-containing block copolymers, and evaluate their potential for use in solid-state lithium/sulfur batteries. Anionically synthesized polystyrene-b-poly(ethylene oxide) (SEO) copolymers doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were used as a model system. This thesis investigates the model system on several levels: from fundamental thermodynamic studies to bulk characterization and finally device assembly and testing. First, the thermodynamics of neat and salt-containing block copolymers was studied. The addition of salt to these materials is necessary to make them conductive, however even small amounts of salt can have significant effects on their phase behavior, and consequently their iontransport and mechanical properties. As a result, the effect of salt addition on block copolymer thermodynamics has been the subject of significant interest over the last decade. A comprehensive study of the thermodynamics of block copolymer/salt mixtures over a wide range of molecular weights, compositions, salt concentrations and temperatures was conducted. Next, the effect of molecular weight on ion transport in both homopolymer and copolymer electrolytes were studied over a wide range of chain lengths. Homopolymer electrolytes show an inverse relationship between conductivity and chain length, with a plateau in the infinite molecular weight limit. This is due to the presence of two mechanisms of ion conduction in homopolymers; the first mechanism is a result of the segmental motion of the chains surrounding the salt ions, 2 creating a liquid-like environment around the ion while the second mechanism of ion conduction is attributed to diffusion of the entire polymer chain with coordinated ions. Equilibrated block copolymer electrolytes exhibit a non-monotonic dependence on molecular weight, decreasing with increasing molecular weight in the small molecular weight limit before increasing when molecular weight exceeds about 10 kg mol-1. Conductivity in annealed electrolytes was shown to be affected by two competing factors: the glass transition temperature of the insulating polystyrene block and the width of the conducting poly(ethylene oxide) (PEO) channel. In the low molecular weight limit, all ions are in contact with both polystyrene (PS) and PEO segments. The intermixing between PS and PEO segments is restricted to an interfacial zone of width of about 5 nm. The fraction of ions affected by the interfacial zone decreases as the conducting channel width increases. Furthermore, the effect of thermal history on the conductivity of the block copolymer electrolytes was examined. Results suggest that long-range order impedes ion transport, and consequently decreases in conductivity of up to 80% were seen upon annealing. The effect of morphology on ion transport was studied by conducting simultaneous impedance and X-ray scattering experiments as the block copolymer electrolyte transitioned from an ordered lamellar structure to a disordered phase. The ionic conductivity increased discontinuously through the transition from order to disorder. A simple framework for quantifying the magnitude of the discontinuity was presented. Finally, block copolymer electrolytes were examined specifically for use in high energy density solid state lithium/sulfur batteries. Such materials have been shown to form a stable interface with lithium metal anodes, maintain intimate contact upon cycling, and have sufficiently high shear moduli to retard dendrite formation. Having previously satisfied the concerns associated with the lithium metal anode, the compatibility of the sulfur cathode was explored. The sulfur cathode presents many unique challenges, including the generation of soluble lithium polysulfides (Li2Sx, 2 ≤ x ≤ 8) during discharge. The solubility of such species in block copolymers and their effect on morphology was examined. The lithium polysulfides were found to exhibit similar solubility in the block copolymers as in typical organic electrolytes, however induced unusual and unexpected phase behavior in the block copolymers. Inspired by successful efforts to physically confine the soluble lithium polysulfides via nanostructured carbon-sulfur composites in the cathode, our nanostructured block copolymer electrolytes were employed in full electrochemical cells with a lithium metal anode and sulfur cathode. Different cathode compositions, electrolyte additives, and cell architectures were tested. Surprisingly, the polysulfides diffused readily from the cathode through the block copolymer electrolyte, and the normally robust SEO|Li metal interface was detrimentally affected their presence during cycling. The polysulfides appeared to change the mechanical properties of the electrolyte such that intimate contact with the lithium metal was lost. Several promising strategies to overcome this problem were investigated and offer exciting avenues for improvement for future researchers. (Abstract shortened by UMI.).

21 CFR 175.360 - Vinylidene chloride copolymer coatings for nylon film.

Code of Federal Regulations, 2011 CFR

2011-04-01

... vinylidene chloride copolymers produced by copolymerizing vinylidene chloride with methyl methacrylate and/or 2-sulfoethyl methacrylate, or with methyl methacrylate and/or 2-sulfoethyl methacrylate together...

21 CFR 175.360 - Vinylidene chloride copolymer coatings for nylon film.

Code of Federal Regulations, 2010 CFR

2010-04-01

... vinylidene chloride copolymers produced by copolymerizing vinylidene chloride with methyl methacrylate and/or 2-sulfoethyl methacrylate, or with methyl methacrylate and/or 2-sulfoethyl methacrylate together...

Encapsulant Material For Solar Cell Module And Laminated Glass Applications

DOEpatents

Hanoka, Jack I.; Klemchuk, Peter P.

2001-02-13

An encapsulant material includes a layer of metallocene polyethylene disposed between two layers of an acid copolymer of polyethylene. More specifically, the layer of metallocene polyethylene is disposed adjacent a rear surface of the first layer of the acid copolymer of polyethylene, and a second layer of the acid copolymer of polyethlene is disposed adjacent a rear surface of the layer of metallocene polyethylene. The encapsulant material can be used in solar cell module and laminated glass applications.

Co-polymer Films for Sensors

NASA Technical Reports Server (NTRS)

Ryan, Margaret A. (Inventor); Jewell, April D. (Inventor); Taylor, Charles (Inventor); Yen, Shiao-Pin S. (Inventor); Kisor, Adam (Inventor); Manatt, Kenneth S. (Inventor); Blanco, Mario (Inventor); Goddard, William A. (Inventor); Homer, Margie L. (Inventor); Shevade, Abhijit V. (Inventor)

2012-01-01

Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

Block copolymer adhesion promoters via ring-opening metathesis polymerization

DOEpatents

Kent, M.S.; Saunders, R.

1997-02-18

Coupling agents are disclosed based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization. 18 figs.

Tunable PhoXonic Band Gap Materials from Self-Assembly of Block Copolymers and Colloidal Nanocrystals (NBIT Phase II)

DTIC Science & Technology

2013-12-12

their application in sensors and as displays. We found that the thermochromic behavior of a lamellar block copolymer poly(styrene-b-2-vinylpyridine...the solution pH. The findings of this work provide the basis for understanding and controlling the properties of thermochromic block copolymers...by the glassy PS layers . The glassy layers completely constrain the lateral expansion of the P2VP gel block and the dislocation defect network that

Testing strong-segregation theory against self-consistent-field theory for block copolymer melts

NASA Astrophysics Data System (ADS)

Matsen, M. W.

2001-06-01

We introduce a highly efficient self-consistent-field theory (SCFT) method for examining the cylindrical and spherical block copolymer morphologies using a standard unit cell approximation (UCA). The method is used to calculate the classical diblock copolymer phase boundaries deep into the strong-segregation regime, where they can be compared with recent improvements to strong-segregation theory (SST). The comparison suggests a significant discrepancy between the two theories indicating that our understanding of strongly stretched polymer brushes is still incomplete.

Ion Conduction in Perfectly Aligned Block Copolymer-Ionic Liquid Mixtures

NASA Astrophysics Data System (ADS)

Choi, Jae-Hong; Elabd, Yossef A.; Winey, Karen I.

2011-03-01

Our earlier work to correlate the transport measurements in diblock copolymer-ionic liquid mixtures was limited by our bulk samples that have only partial alignment. Here, thin films with perfect alignment of lamellar microdomains from mixtures of a poly(methyl methacrylate- b -styrene) diblock copolymer and an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, have been studied. The morphologies will be characterized by cross-sectional transmission electron microscopy. Ion conduction will be presented within and through the thin film.

Drilling fluid containing a copolymer filtration control agent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Enright, D.P.; Lucas, J.M.; Perricone, A.C.

1981-10-06

The invention relates to an aqueous drilling fluid composition, a filtration control agent for utilization in said aqueous drilling fluid, and a method of forming a filter cake on the wall of a well for the reduction of filtrate from said drilling fluid, by utilization of a copolymer of: (1) a (Meth) acrylamido alkyl sulfonic acid or alkali metal salt thereof; and (2) a (Meth) acrylamide or n-alkyl (Meth) acrylamide. The copolymer may be cross-linked with a quaternary ammonium salt cross-linking agent.

Drilling fluid containing a copolymer filtration control agent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lucas, J. M.

1985-10-15

The invention relates to an aqueous drilling fluid composition, a filtration control agent for utilization in said aqueous drilling fluid, and a method of forming a filter cake on the wall of a well for the reduction of filtrate from said drilling fluid, by utilization of a copolymer of: a (meth) acrylamido alkyl sulfonic acid or alkali metal salt thereof; and N, N-dialkyl (meth) acrylamide. The copolymer may be cross-linked with N,N'-methylenebisacrylamide or other appropriate cross-linking agent.

Palladium (II) catalyized polymerization of norbornene and acrylates

DOEpatents

Sen, Ayusman; Kacker, Smita; Hennis, April; Polley, Jennifer D.

2000-08-29

Homopolymers or copolymers of acrylates, homopolymers or copolymers of norbornenes, and copolymers of acrylates with norbornenes, may be prepared by contacting acrylate and/or norbornene monomer reactant under polymerization conditions and in the presence of a solvent with a catalyst system consisting essentially of a Pd(II) dimer component having the formula: [(L)Pd(R)(X)].sub.2, where L is a monodentate phosphorus or nitrogen ligand, X is an anionic group, and R is an alkyl or aryl group.

Co-polymer films for sensors

NASA Technical Reports Server (NTRS)

Ryan, Margaret A. (Inventor); Homer, Margie L. (Inventor); Yen, Shiao-Pin S. (Inventor); Kisor, Adam (Inventor); Jewell, April D. (Inventor); Shevade, Abhijit V. (Inventor); Manatt, Kenneth S. (Inventor); Taylor, Charles (Inventor); Blanco, Mario (Inventor); Goddard, William A. (Inventor)

2010-01-01

Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

pH-sensitive methacrylic copolymer gels and the production thereof

DOEpatents

Mallapragada, Surya K [Ames, IA; Anderson, Brian C [Lake Bluff, IA

2007-05-15

The present invention provides novel gel forming methacrylic blocking copolymers that exhibit cationic pH-sensitive behavior as well as good water solubility. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol)methyl ether polymer. The polymers may be used for drug and gene delivery, protein separation, as structural supplements, and more.

Block copolymer adhesion promoters via ring-opening metathesis polymerization

DOEpatents

Kent, Michael S.; Saunders, Randall

1997-01-01

Coupling agents based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization.

Triblock copolymers based on ε-caprolactone and trimethylene carbonate for the 3D printing of tissue engineering scaffolds.

PubMed

Güney, Aysun; Malda, Jos; Dhert, Wouter J A; Grijpma, Dirk W

2017-05-09

Biodegradable PCL-b-PTMC-b-PCL triblock copolymers based on trimethylene carbonate (TMC) and ε-caprolactone (CL) were prepared and used in the 3D printing of tissue engineering scaffolds. Triblock copolymers of various molecular weights containing equal amounts of TMC and CL were prepared. These block copolymers combine the low glass transition temperature of amorphous PTMC (approximately -20°C) and the semi-crystallinity of PCL (glass transition approximately -60°C and melting temperature approximately 60°C). PCL-b-PTMC-b-PCL triblock copolymers were synthesized by sequential ring opening polymerization (ROP) of TMC and ε-CL. From these materials, films were prepared by solvent casting and porous structures were prepared by extrusion-based 3D printing. Films prepared from a polymer with a relatively high molecular weight of 62 kg/mol had a melting temperature of 58°C and showed tough and resilient behavior, with values of the elastic modulus, tensile strength and elongation at break of approximately 120 MPa, 16 MPa and 620%, respectively. Porous structures were prepared by 3D printing. Ethylene carbonate was used as a crystalizable and water-extractable solvent to prepare structures with microporous strands. Solutions, containing 25 wt% of the triblock copolymer, were extruded at 50°C then cooled at different temperatures. Slow cooling at room temperature resulted in pores with widths of 18 ± 6 μm and lengths of 221 ± 77 μm, rapid cooling with dry ice resulted in pores with widths of 13 ± 3 μm and lengths of 58 ± 12 μm. These PCL-b-PTMC-b-PCL triblock copolymers processed into porous structures at relatively low temperatures may find wide application as designed degradable tissue engineering scaffolds. In this preliminary study we prepared biodegradable triblock copolymers based on 1,3-trimethylene carbonate and ε-caprolactone and assessed their physical characteristics. Furthermore, we evaluated their potential as melt-processable thermoplastic elastomeric biomaterials in 3D printing of tissue engineering scaffolds.

High temperature polymers for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Einsla, Brian Russel

Novel proton exchange membranes (PEMs) were investigated that show potential for operating at higher temperatures in both direct methanol (DMFC) and H 2/air PEM fuel cells. The need for thermally stable polymers immediately suggests the possibility of heterocyclic polymers bearing appropriate ion conducting sites. Accordingly, monomers and random disulfonated poly(arylene ether) copolymers containing either naphthalimide, benzoxazole or benzimidazole moieties were synthesized via direct copolymerization. The ion exchange capacity (IEC) was varied by simply changing the ratio of disulfonated monomer to nonsulfonated monomer in the copolymerization step. Water uptake and proton conductivity of cast membranes increased with IEC. The water uptake of these heterocyclic copolymers was lower than that of comparable disulfonated poly(arylene ether) systems, which is a desirable improvement for PEMs. Membrane electrode assemblies were prepared and the initial fuel cell performance of the disulfonated polyimide and polybenzoxazole (PBO) copolymers was very promising at 80°C compared to the state-of-the-art PEM (NafionRTM); nevertheless these membranes became brittle under operating conditions. Several series of poly(arylene ether)s based on disodium-3,3'-disulfonate-4,4 '-dichlorodiphenylsulfone (S-DCDPS) and a benzimidazole-containing bisphenol were synthesized and afforded copolymers with enhanced stability. Selected properties of these membranes were compared to separately prepared miscible blends of disulfonated poly(arylene ether sulfone) copolymers and polybenzimidazole (PBI). Complexation of the sulfonic acid groups with the PBI structure reduced water swelling and proton conductivity. The enhanced proton conductivity of NafionRTM membranes has been proposed to be due to the aggregation of the highly acidic side-chain sulfonic acid sites to form ion channels. A series of side-chain sulfonated poly(arylene ether sulfone) copolymers based on methoxyhydroquinone was synthesized in order to investigate this possible advantage and to couple this with the excellent hydrolytic stability of poly(arylene ether)s. The methoxy groups were deprotected to afford reactive phenolic sites and nucleophilic substitution reactions with functional aryl sulfonates were used to prepare simple aryl or highly acidic fluorinated sulfonated copolymers. The proton conductivity and water sorption of the resulting copolymers increased with the ion exchange capacity, but changing the acidity of the sulfonic acid had no apparent effect.