Radiation induced graft copolymerization of methyl methacrylate onto chrome-tanned pig skins

NASA Astrophysics Data System (ADS)

Pietrucha, K.; Pȩkala, W.; Kroh, J.

Graft copolymerization of methyl methacrylate (MMA) onto chrome-tanned pig skins was carried out by the irradiation with 60Co ?-rays. The grafted polymethyl methacrylate (PMMA) chains were isolated by acid hydrolysis of the collagen backbone in order to characterize the graft copolymers. Proof of grafting was obtained through the detection of amino acid endgroups in the isolated grafts by reaction with ninhydrin. The grafting yield of MMA in aqueous emulsion was found to be higher than that for pure MMA and MMA in acetone. The degree of grafting increases with increasing monomer concentration in emulsion and reaches maximum at radiation dose ca 15 kGy. The yield of grafting is very high - ca 90% of monomer converts into copolymer and only 10% is converted into homopolymer. The present paper reports the physical properties of chrome-tanned pig skins after graft polymerization with MMA in emulsion. Modified leathers are more resistant against water absorption and abrasion in comparison with unmodified ones. They have more uniform structure over the whole surface, greater thickness and stiffness. The results reported seem to indicate that MMA may be used in the production of shoe upper and sole leathers. The mechanism of some of the processes occuring during radiation grafting of MMA in water emulsion on tanned leathers has been also suggested and discussed.

Gradient structure-induced temperature responsiveness in styrene/methyl methacrylate gradient copolymers micelles.

PubMed

Zheng, Chao; Huang, Haiying; He, Tianbai

2014-02-01

In this work, micelles are formed by gradient copolymer of styrene and methyl methacrylate in acetone-water mixture and their temperature responsiveness is investigated in a narrow range near room temperature. Three different kinds of structural transitions could be induced by temperature: unimers to micelle transition, shrinkage/stretching of micelles, and morphological transition from spherical micelles to vesicles. In addition, a model analysis on the interface of gradient copolymer micelle is made to better understand these phenomena. It is found that both position and composition of the interface could alter in response to the change in temperature. According to the experiments and model analysis, it is proposed that temperature responsiveness might be an intrinsic and universal property of gradient copolymer micelles, which only originates from the gradient structure. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design of polystyrene latex particles covered with polyoxometalate clusters via multiple covalent bonding

DOE PAGES

Chen, Xinyue; Li, Hui; Yin, Panchao; ...

2015-02-27

In this study, polyoxometalates (POMs) covalently functionalized with methyl methacrylate groups were applied as surfactants in the emulsion polymerization reaction of styrene. Due to the copolymerization of the methyl methacrylate groups and the styrene monomers, the polyoxometalate clusters are covalently grafted onto the surface of polystyrene latex nanoparticles. Finally, such latex particles are fully covered with catalytic POM clusters and might serve as quasi-homogeneous catalysts.

A silicone rubber based composites using n-octadecane/poly (styrene-methyl methacrylate) microcapsules as energy storage particle

NASA Astrophysics Data System (ADS)

Wu, W. L.; Chen, Z.

A phase-change energy-storage material, silicone rubber (SR) coated n-octadecane/poly (styrene-methyl methacrylate) (SR/OD/P(St-MMA)) microcapsule composites, was prepared by mixing SR and OD/P(St-MMA) microcapsules. The microcapsule content and silicone rubber coated method were investigated. The morphology and thermal properties of the composites were characterized by scanning electron microscopy (SEM), thermogravimetric analysis (TG), differential scanning calorimetry (DSC) and heat storage properties. The results showed that the thermal and mechanical properties of SR/OD/P(St-MMA) composites were excellent when the microcapsules were coated with room temperature vulcanized silicone rubber (RTVSR), of which content was 2 phr (per hundred rubber). The enthalpy value of the composites was 67.6 J g-1 and the composites were found to have good energy storage function.

Predominant 1,2-insertion of styrene in the Pd-catalyzed alternating copolymerization with carbon monoxide.

PubMed

Nozaki, K; Komaki, H; Kawashima, Y; Hiyama, T; Matsubara, T

2001-01-31

The regioselectivity of styrene insertion to an acyl-Pd bond was studied by NMR in (i) a stoichiomeric reaction and (ii) a copolymerization with CO. In the stoichiometric reaction of styrene with [(CH(3)CO)Pd(CH(3)CN)[(R,S)-BINAPHOS

Control of particle size by feed composition in the nanolatexes produced via monomer-starved semicontinuous emulsion copolymerization.

PubMed

Sajjadi, Shahriar

2015-05-01

Conventional batch and semicontinuous emulsion copolymerizations often produce large particles whose size cannot be easily correlated with the comonomer feed compositions, and are to some degree susceptible to composition drift. In contrast, we found that copolymer nanolatexes made via semicontinuous monomer-starved emulsion copolymerizations are featured with an average nanoparticle size being controlled by the feed composition, a high conversion achieved, and a high degree of particle composition uniformity. This was achieved because the rate of particle growth, during nucleation, was controlled by the rate of comonomer addition, and the copolymer composition, surfactant parking area on the particles, and nucleation efficiency determined by the comonomer feed composition. Two model systems, methyl methacrylate/styrene and vinyl acetate/butyl acrylate, with significant differences in water solubility were studied. Monomers were added to the aqueous solution of sodium dodecylsulfate and potassium persulfate at a low rate to achieve high instantaneous conversions. Copyright © 2015 Elsevier Inc. All rights reserved.

21 CFR 177.2000 - Vinylidene chloride/methyl acrylate/methyl methacrylate polymers.

Code of Federal Regulations, 2014 CFR

2014-04-01

... methacrylate polymers. 177.2000 Section 177.2000 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic.../methyl methacrylate polymers. The vinylidene chloride/methyl acrylate/methyl methacrylate polymers (CAS...

Synthesis, characterization, and morphology study of poly(acrylamide-co-acrylic acid)-grafted-poly(styrene-co-methyl methacrylate) "raspberry"-shape like structure microgels by pre-emulsified semi-batch emulsion polymerization.

PubMed

Ramli, Ros Azlinawati; Hashim, Shahrir; Laftah, Waham Ashaier

2013-02-01

A novel microgels were polymerized using styrene (St), methyl methacrylate (MMA), acrylamide (AAm), and acrylic acid (AAc) monomers in the presence of N,N'-methylenebisacrylamide (MBA) cross-linker. Pre-emulsified monomer was first prepared followed by polymerizing monomers using semi-batch emulsion polymerization. Fourier Transform Infrared Spectroscopy (FTIR) and (1)H Nuclear Magnetic Resonance (NMR) were used to determine the chemical structure and to indentify the related functional group. Grafting and cross-linking of poly(acrylamide-co-acrilic acid)-grafted-poly(styrene-co-methyl methacrylate) [poly(AAm-co-AAc)-g-poly(St-co-MMA)] microgels are approved by the disappearance of band at 1300 cm(-1), 1200 cm(-1) and 1163 cm(-1) of FTIR spectrum and the appearance of CH peaks at 5.5-5.7 ppm in (1)H NMR spectrum. Scanning Electron Microscope (SEM) images indicated that poly(St-co-MMA) particle was lobed morphology coated by cross-linked poly(AAm-co-AAc) shell. Furthermore, SEM results revealed that poly(AAm-co-AAc)-g-poly(St-co-MMA) is composite particle that consist of "raspberry"-shape like structure core. Internal structures of the microgels showed homogeneous network of pores, an extensive interconnection among pores, thicker pore walls, and open network structures. Water absorbency test indicated that the sample with particle size 0.43 μm had lower equilibrium water content, % than the sample with particle size 7.39 μm. Copyright © 2012 Elsevier Inc. All rights reserved.

Zirconium oxocluster/polymer hybrid nanoparticles prepared by photoactivated miniemulsion copolymerization

NASA Astrophysics Data System (ADS)

Benedetti, Cesare; Flouda, Paraskevi; Antonello, Alice; Rosenauer, Christine; Pérez-Pla, Francisco F.; Landfester, Katharina; Gross, Silvia; Muñoz-Espí, Rafael

2017-09-01

The photoactivated free radical miniemulsion copolymerization of methyl methacrylate (MMA) and the zirconium oxocluster Zr4O2(methacrylate)12 is used as an effective and fast preparation method for polymer/inorganic hybrid nanoparticles. The oxoclusters, covalently anchored to the polymer network, act as metal-organic cross-linkers, thus improving the thermomechanical properties of the resulting hybrid nanoparticles. Benzoin carbonyl organic compounds were used as photoinitiators. The obtained materials are compared in terms of cross-linking, effectiveness of cluster incorporation, and size distribution with the analogous nanoparticles produced by using conventional thermally induced free radical miniemulsion copolymerization. The kinetics of the polymerization process in the absence and in the presence of the oxocluster is also investigated.

Structural coloration of chitosan coated cellulose fabrics by electrostatic self-assembled poly (styrene-methyl methacrylate-acrylic acid) photonic crystals.

PubMed

Yavuz, Gönül; Zille, Andrea; Seventekin, Necdet; Souto, Antonio P

2018-08-01

The structural coloration of a chitosan-coated woven cotton fabric obtained by glutaraldehyde-stabilized deposition of electrostatic self-assembled monodisperse and spherically uniform (250 nm) poly (styrene-methyl methacrylate-acrylic acid) photonic crystal nanospheres (P(St-MMA-AA)) was investigated. Bright iridescent coatings displaying different colors in function of the viewing angle were obtained. The SEM, diffuse reflectance spectroscopy, TGA, DSC and FTIR analyses confirm the presence of structural color and the glutaraldehyde and chitosan ability to provide durable chemical bonding between cotton fabric and photonic crystal (PCs) coating with the highest degradation temperature and the lowest enthalpy. The coatings are characterized by a mixture of face-centered cubic and hexagonal close-packed arrays alternating random packing regions. For the first time a cost-efficient structural coloration with high washing and light fastness using self-assembled P(St-MMA-AA) photonic crystals was successfully developed onto woven cotton fabric using chitosan and/or glutaraldehyde as stabilizing agent opening new strategies for the development of dye-free coloration of textiles. Copyright © 2018 Elsevier Ltd. All rights reserved.

Palladium/IzQO-Catalyzed Coordination-Insertion Copolymerization of Ethylene and 1,1-Disubstituted Ethylenes Bearing a Polar Functional Group.

PubMed

Yasuda, Hina; Nakano, Ryo; Ito, Shingo; Nozaki, Kyoko

2018-02-07

Coordination-insertion copolymerization of ethylene with 1,1-disubstituted ethylenes bearing a polar functional group, such as methyl methacrylate (MMA), is a long-standing challenge in catalytic polymerization. The major obstacle for this process is the huge difference in reactivity of ethylene versus 1,1-disubstituted ethylenes toward both coordination and insertion. Herein we report the copolymerization of ethylene and 1,1-disubstituted ethylenes by using an imidazo[1,5-a]quinolin-9-olate-1-ylidene-supported palladium catalyst. Various types of 1,1-disubstituted ethylenes were successfully incorporated into the polyethylene chain. In-depth characterization of the obtained copolymers and mechanistic inferences drawn from stoichiometric reactions of alkylpalladium complexes with methyl methacrylate and ethylene indicate that the copolymerization proceeds by the same coordination-insertion mechanism that has been postulated for ethylene.

Methyl methacrylate

Integrated Risk Information System (IRIS)

Methyl methacrylate ; CASRN 80 - 62 - 6 ( 03 / 02 / 98 ) Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments f

21 CFR 177.2000 - Vinylidene chloride/methyl acrylate/methyl methacrylate polymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... methacrylate polymers. 177.2000 Section 177.2000 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF...: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.2000 Vinylidene chloride/methyl acrylate/methyl methacrylate polymers. The vinylidene chloride/methyl acrylate...

21 CFR 177.2000 - Vinylidene chloride/methyl acrylate/methyl methacrylate polymers.

Code of Federal Regulations, 2011 CFR

2011-04-01

... methacrylate polymers. 177.2000 Section 177.2000 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF...: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.2000 Vinylidene chloride/methyl acrylate/methyl methacrylate polymers. The vinylidene chloride/methyl acrylate...

21 CFR 177.2000 - Vinylidene chloride/methyl acrylate/methyl methacrylate polymers.

Code of Federal Regulations, 2012 CFR

2012-04-01

... methacrylate polymers. 177.2000 Section 177.2000 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF...: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.2000 Vinylidene chloride/methyl acrylate/methyl methacrylate polymers. The vinylidene chloride/methyl acrylate...

21 CFR 177.2000 - Vinylidene chloride/methyl acrylate/methyl methacrylate polymers.

Code of Federal Regulations, 2013 CFR

2013-04-01

... methacrylate polymers. 177.2000 Section 177.2000 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF...: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.2000 Vinylidene chloride/methyl acrylate/methyl methacrylate polymers. The vinylidene chloride/methyl acrylate...

DEGRADATION OF POLY(METHYL METHACRYLATE) IN SOLUTION

EPA Science Inventory

The rate of degradation of poly(methyl methacrylate) (PMMA) to methyl methacrylate (MMA) was investigated in the liquid phase with toluene as the solvent. The degradation experiments were carried out in a tubular flow reactor at 1000 psig (6.8 MPa) and at four different temperat...

RAFT Dispersion Alternating Copolymerization of Styrene with N-Phenylmaleimide: Morphology Control and Application as an Aqueous Foam Stabilizer

PubMed Central

2016-01-01

We report a new nonaqueous polymerization-induced self-assembly (PISA) formulation based on the reversible addition–fragmentation chain transfer (RAFT) dispersion alternating copolymerization of styrene with N-phenylmaleimide using a nonionic poly(N,N-dimethylacrylamide) stabilizer in a 50/50 w/w ethanol/methyl ethyl ketone (MEK) mixture. The MEK cosolvent is significantly less toxic than the 1,4-dioxane cosolvent reported previously [YangP.; Macromolecules2013, 46, 8545−8556]. The core-forming alternating copolymer block has a relatively high glass transition temperature (Tg), which leads to vesicular morphologies being observed during PISA, as well as the more typical sphere and worm phases. Each of these copolymer morphologies has been characterized by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies. TEM studies reveal micrometer-sized elliptical particles with internal structure, with SAXS analysis suggesting an oligolamellar vesicle morphology. This structure differs from that previously reported for a closely related PISA formulation utilizing a poly(methacrylic acid) stabilizer block for which unilamellar platelet-like particles are observed by TEM and SAXS. This suggests that interlamellar interactions are governed by the nature of the steric stabilizer layer. Moreover, using the MEK cosolvent also enables access to a unilamellar vesicular morphology, despite the high Tg of the alternating copolymer core-forming block. This was achieved by simply conducting the PISA synthesis at a higher temperature for a longer reaction time (80 °C for 24 h). Presumably, MEK solvates the core-forming block more than the previously utilized 1,4-dioxane cosolvent, which leads to greater chain mobility. Finally, preliminary experiments indicate that the worms are much more efficient stabilizers for aqueous foams than either the spheres or the oligolamellar elliptical vesicles. PMID:27708458

Analysis of residual monomers in dendritic methacrylate copolymers and composites by HPLC and headspace-GC/MS.

PubMed

Viljanen, Eeva K; Langer, Sarka; Skrifvars, Mikael; Vallittu, Pekka K

2006-09-01

The aim of this study was to analyze the residual monomer content of photopolymerized dendritic methacrylate copolymers and particulate filler composites. Headspace-gas chromatography/mass spectrometry (HS-GC/MS) was compared with high performance liquid chromatography (HPLC). The resin mixtures consisted of a dendritic methacrylate monomer, methyl methacrylate and acetoacetoxyethyl methacrylate in varied proportions. In addition, one of the composites contained 1,4-butanediol dimethacrylate. Camphorquinone and 2-(N,N-dimethylamino)ethyl methacrylate were used as the light-activated initiator system. The content of residual methyl methacrylate and acetoacetoxyethyl methacrylate after 40 s photopolymerization were analyzed with HPLC and HS-GC/MS. The content of residual methyl methacrylate decreased and residual acetoacetoxyethyl methacrylate increased with increasing concentration of acetoacetoxyethyl methacrylate in the resin mixture. The results with both methods had the same trend. The addition of acetoacetoxyethyl methacrylate enhanced the copolymerization of methyl methacrylate, but did not decrease the total residual monomer content. The HS-GC/MS method was found to be a feasible method in the analysis of low-boiling residuals in dental polymers.

The chemistry of dimethacrylate-styrene networks, and, Development of flame retardant, halogen-free fiber reinforced vinyl ester composites

NASA Astrophysics Data System (ADS)

Rosario, Astrid Christa

One of the major classes of polymer matrix resins under consideration for structural composite applications in the infrastructure and construction industries is vinyl ester resin. Vinyl ester resin is comprised of low molecular weight poly(hydroxyether) oligomers with methacrylate endgroups diluted with styrene monomer. The methacrylate endgroups cure with styrene via free radical copolymerization to yield thermoset networks. The copolymerization behavior of these networks was monitored by Fourier Transform Infrared Spectroscopy (FTIR) at various cure conditions. Reactions of the carbon-carbon double bonds of the methacrylate (943 cm-1) and styrene (910 cm-1 ) were followed independently. Oligomers possessing number average molecular weights of 700 g/mole were studied with systematically increasing levels of styrene. The Mortimer-Tidwell reactivity ratios indicated that at low conversion more styrene was incorporated into the network at lower cure temperatures. The experimental vinyl ester-styrene network compositions deviated significantly from those predicted by the Meyer-Lowry integrated copolymer equation at higher conversion, implying that the reactivity ratios for these networks may change with conversion. The kinetic data were used to provide additional insight into the physical and mechanical properties of these materials. In addition to establishing the copolymerization kinetics of these materials, the development of halogen free fiber reinforced vinyl ester composites exhibiting good flame properties was of interest. Flame retardant vinyl ester resins are used by many industries for applications requiring good thermal resistance. The current flame-retardant technology is dependent on brominated vinyl esters, which generate high levels of smoke and carbon monoxide. A series of halogen free binder systems has been developed and dispersed in the vinyl ester to improve flame retardance. The binder approach enables the vinyl ester resin to maintain its low

Synthesis and properties study of the uniform nonspherical styrene/methacrylic acid copolymer latex particles.

PubMed

Wang, Wenqin; Ren, Guohong; Yang, Yanqiong; Cai, Wujin; Chen, Tao

2015-01-13

A facile method to prepare the nonspherical amphiphilic random copolymer of poly(styrene-co-methacrylic acid) (poly(St-co-PMAA)) latex particles with well-defined shapes and high yields by one-step batch emulsifier-free polymerization was demonstrated. In our strategy, only varying the molar ratio of styrene (St) to methacrylic acid (MAA), no seed-particles, no cross-linker, and no multistep control procedures were needed. Due to the presence of carboxyl groups on the surface of (poly(St-co-PMAA) latex particles, these latex particles can be used as templates for fabricating core-shell nonspherical functional materials, such as poly(St-co-PMAA)@SiO2 and poly(St-co-PMAA)@polypyrrole). The corresponding nonspherical hollow structures (SiO2 and polypyrrole) could be obtained after removal of the templates. In addition, poly(St-co-PMAA) latex particles exhibit interesting morphologies in ethanol.

Second-order nonlinear optical properties of composite material of an azo-chromophore with a tricyanodiphenyl acceptor in a poly(styrene-co-methyl methacrylate) matrix

NASA Astrophysics Data System (ADS)

Shelkovnikov, Vladimir; Selivanova, Galina; Lyubas, Gleb; Korotaev, Sergey; Shundrina, Inna; Tretyakov, Evgeny; Zueva, Ekaterina; Plekhanov, Alexander; Mikerin, Sergey; Simanchuk, Andrey

2017-07-01

The composite material of new synthesized 4-((4-(N,N-n-dibutylamino) phenyl)diazenyl)-biphenyl-2,3,4-tricarbonitrile (GAS dye) in commercial poly(styrene-co-methyl methacrylate) (PSMMA) was prepared, poled and its nonlinear optical properties compared with DR1 dye were studied. High thermal stability of the composite material was revealed, and the maximal concentration of the chromophore was found to reach ∼20 wt%. The dipole moment, polarizability tensor, and first hyperpolarizability tensor of the investigated dyes were calculated by within the framework of the coupled perturbed density functional theory. A nanosecond second-harmonic generation Maker fringes technique was used which is capable of providing the magnitude of the second-order nonlinearity of optical materials at a wavelength of 1064 nm. For the tested GAS-PSMMA composite material, maximal coefficient d33 was found to be 50 pm/V. The nonlinear optical response, which was achieved here, shows possible usefulness of the GAS dye as a component for molecular design of nonlinear-optical materials with advanced characteristics.

21 CFR 882.5300 - Methyl methacrylate for cranioplasty.

Code of Federal Regulations, 2010 CFR

2010-04-01

... methacrylate for cranioplasty. (a) Identification. Methyl methacrylate for cranioplasty (skull repair) is a self-curing acrylic that a surgeon uses to repair a skull defect in a patient. At the time of surgery...

21 CFR 73.3127 - Vinyl alcohol/methyl methacrylate-dye reaction products.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Vinyl alcohol/methyl methacrylate-dye reaction... Vinyl alcohol/methyl methacrylate-dye reaction products. (a) Identity. The color additives are formed by... methacrylate-dye reaction product listed under this section into commerce shall submit to the Food and Drug...

21 CFR 73.3127 - Vinyl alcohol/methyl methacrylate-dye reaction products.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Vinyl alcohol/methyl methacrylate-dye reaction... Vinyl alcohol/methyl methacrylate-dye reaction products. (a) Identity. The color additives are formed by... methacrylate-dye reaction product listed under this section into commerce shall submit to the Food and Drug...

Preparation and characterization of pH-sensitive methyl methacrylate-g-starch/hydroxypropylated starch hydrogels: in vitro and in vivo study on release of esomeprazole magnesium.

PubMed

Kumar, Pankaj; Ganure, Ashok Laxmanrao; Subudhi, Bharat Bhushan; Shukla, Shubhanjali

2015-06-01

In the present study, novel hydrogels were prepared through graft copolymerization of methyl methacrylate onto starch and hydroxypropylated starch for intestinal drug delivery. The successful grafting has been confirmed by FTIR, NMR spectroscopy, and elemental analysis. Morphological examination of copolymeric hydrogels by scanning electron microscopy (SEM) confirms the macroporous nature of the copolymers. The high decomposition temperature was observed in thermograms indicating the thermal stability of the hydrogels. To attain a hydrogel with maximum percent graft yield, the impact of reaction variables like concentration of ceric ammonium nitrate as initiator and methyl methacrylate as monomer were consistently optimized. X-ray powder diffraction and differential scanning calorimetric analysis supported the successful entrapment of the drug moiety (esomeprazole magnesium; proton pump inhibitor) within the hydrogel network. Drug encapsulation efficiency of optimized hydrogels was found to be >78%. Furthermore, swelling capacity of copolymeric hydrogels exhibited a pH-responsive behavior which makes the synthesized hydrogels potential candidates for controlled delivery of medicinal agents. In vitro drug release was found to be sustained up to 14 h with 80-90% drug release in pH 6.8 solution; however, the cumulative release was 40-45% in pH 1.2. The gastrointestinal transit behavior of optimized hydrogel was determined by gamma scintigraphy, using (99m)Tc as marker. The amount of radioactive tracer released from the labeled hydrogel was minimal when the hydrogel was in the stomach, whereas it increased as hydrogel reached in intestine. Well-correlated results of in vitro and in vivo analysis proved their controlled release behavior with preferential delivery into alkaline pH environment.

Isoprene-styrene copolymer elastomer and tetrahydrofurfuryl methacrylate mixtures for soft prosthetic applications.

PubMed

Nazhat, S N; Parker, S; Patel, M P; Braden, M

2001-09-01

Novel elastomer/methacrylate systems have been developed for potential soft prosthetic applications. Mixtures of varying compositions of an isoprene-styrene copolymer elastomer and tetrahydrofurfuryl methacrylate (SIS/THFMA) formed one-gel systems and were heat cured with a peroxide initiator. The blends were characterised in terms of sorption in deionised water and simulated body fluids (SBF), tensile properties and viscoelastic parameters of storage modulus and tan delta, as well as glass transition temperatures using dynamic mechanical analysis (DMA). DMA data gave two distinct peaks in tan delta, a lower temperature transition due to the isoprene phase in SIS and one at high temperature thought to be a combination of THFMA and the styrene phase in SIS. The tensile data showed a clear phase inversion within the mid range compositions changing from plastic to elastomeric behaviour. The sorption studies in deionised water showed a two stage uptake with an initial Fickian region that was linear to t 1/2 followed by a droplet growth/clustering system. The slope of the linear region was dependent on the composition ratio. The extent of overall uptake was osmotically dependent as all materials equilibrated at a much lower uptake in SBF. The diffusion coefficients were found to be concentration dependent.

Homogeneous graft copolymerization of styrene onto cellulose in a sulfur dioxide-diethylamine-dimethyl sulfoxide cellulose solvent

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

Tsuzuki, M.; Hagiwara, I.; Shiraishi, N.

1980-12-01

Graft copolymerization of styrene onto cellulose was studied in a homogeneous system (SO/sub 2/(liquid)- diethylamine (DEA)-dimethyl sulfoxide (DMSO) medium)) by ..gamma..-ray mutual irradiation technique. At the same time, homopolymerization of styrene was also examined separately in DMSO, SO/sub 2/-DMSO, DEA-DMSO, and SO/sub 2/-DEA-DMSO media by the same technique. Polymerization of styrene hardly occurs on concentrations above 10 mole SO/sub 2/-DEA complex per mole glucose unit. Maximum percent grafting was obtained in concentrations of 4 mole, after which it decreased rapidly. Total conversion and percent grafting increased with the irradiation time. The value (=0.55) of the slope of the total conversionmore » rate plotted against the dose was only a little higher than the 1/2 which was expected from normal kinetics. No retardation in homopolymerization of styrene in DMSO, SO/sub 2/-DMSO, and DEA-DMSO was evident, while the retardation of homopolymerization in the SO/sub 2/-DEA-DMSO medium was measurable. Sulfur atoms were detected in the polymers obtained in both of SO/sub 2/-DMSO and SO/sub 2/-DEA-DMSO solutions. All of the molecular weights of polymers obtained in the present experiment were very low (3.9 x 10/sup 3/-1.75 x 10/sup 4/).« less

21 CFR 177.1030 - Acrylonitrile/butadiene/styrene/methyl methacrylate copolymer.

Code of Federal Regulations, 2011 CFR

2011-04-01

... monomer content of the finished copolymer articles is not more than 11 parts per million as determined by a gas chromatographic method titled “Determination of Residual Acrylonitrile and Styrene Monomers... article shall yield not more than 0.0025 milligram per square inch of acrylonitrile monomer when exposed...

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.

21 CFR 882.5030 - Methyl methacrylate for aneurysmorrhaphy.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Methyl methacrylate for aneurysmorrhaphy. 882.5030 Section 882.5030 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES NEUROLOGICAL DEVICES Neurological Therapeutic Devices § 882.5030 Methyl...

21 CFR 882.5300 - Methyl methacrylate for cranioplasty.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Methyl methacrylate for cranioplasty. 882.5300 Section 882.5300 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES NEUROLOGICAL DEVICES Neurological Therapeutic Devices § 882.5300 Methyl...

A study of the gamma radiation induced molecular weight changes in poly (phenyl methacrylate), poly (methyl methacrylate) and their copolymers

NASA Astrophysics Data System (ADS)

Hussain, R.; Mohammad, D.

The homopolymers and copolymers of phenyl methacrylate and methyl methacrylate synthesized by free radical polymerization were characterized by infra red and nuclear magnetic resonance spectroscopy. The molecular weight changes produced as a result of gamma irradiation in an argon atmosphere were monitored as a function of dose absorbed by the sample. The radiation induced effects have been discussed in terms of G(Scission), energy absorbed per break and number of bonds broken per gram in a polymer sample. The results reveal that poly (phenyl methacrylate) is more stable than poly (methyl methacrylate) while, the radiation stability of the copolymers depends upon the concentrations of the respective monomers.

Flexural properties of ethyl or methyl methacrylate-UDMA blend polymers.

PubMed

Kanie, Takahito; Kadokawa, Akihiko; Arikawa, Hiroyuki; Fujii, Koichi; Ban, Seiji

2010-10-01

Light-curing polyethyl methacrylate (PEMA)-urethane dimethacrylate (UDMA) resins and polymethyl methacrylate (PMMA)-UDMA resins were prepared by two processes. For first step, PEMA or PMMA powders were fully dissolved in ethyl methacrylate (EMA) or methyl methacrylate (MMA) and then the PEMA-EMA/PMMA-MMA mixtures were mixed with UDMA. The flexural properties of cured PEMA-UDMA and PMMA-UDMA polymers were measured using two PEMA (Mw: 300,000-400,000 and 650,000-1,000,000) and three PMMA (Mw: 30,000-60,000, 350,000 and 650,000-1,000,000) powders with different molecular weight, four mixing ratios of PMMA-MMA, and three mixing ratios of PMMA-MMA mixture and UDMA oligomer. Polymers with PMMA(Mw: 350,000) MMA=25/50, and with PMMA(Mw: 350,000)-MMA/UDMA=1/2 and =1/1, showed no-fracture in a flexural test at 1 mm/min and flexural strength and flexural modulus showed no significant difference compared with those of commercially available heat- and self-curing acrylic resins (p>0.01). Within limitation of this investigation, methyl methacrylate-UDMA blend polymer of this composition is available for denture base resin.

[Chest granuloma secondary to methyl methacrylate. Case report].

PubMed

Martínez-Bistrain, Ricardo; Robles García, Verónica; Cornejo-Morales, Ivonne

2010-01-01

We present the case of a patient with a history of a massive left hemithorax crushing injury in 1985; the exact management of the lesion is unknown. Twenty years later he had a thoracic fistula with a culture that was reported as positive for Enteroccocus faecalis and Staphyloccocus epidermidis. The patient was referred by the chest surgery service with the diagnosis of rib osteomyelitis once complementary imaging tests were performed (plain X-rays, CAT scan and MRI). The patient underwent surgery at our service; a granulomatous reaction secondary to a foreign body (methyl methacrylate and Ethibon) was reported. Chest reconstruction for massive lesions is possible with methyl methacrylate. Imaging studies involve the well-known difficulty to identify this material, given that it may produce signals and densities that are difficult to interpret by specialized physicians.

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.

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...

Organic inorganic hybrid coating (poly(methyl methacrylate)/monodisperse silica)

NASA Astrophysics Data System (ADS)

Rubio, E.; Almaral, J.; Ramírez-Bon, R.; Castaño, V.; Rodríguez, V.

2005-04-01

Polymethylmethacrylate-silica hybrid coatings were prepared from methyl methacrylate and monodisperse colloidal silica prepared by the Stöber method. The surfaces of the spheres were successfully modified by chemical reaction with 3-(trimethoxysilyl) propyl methacrylate (TMSPM) to compatibilise the organic and inorganic components of the precursor solution mixture. The coatings were deposited by dip-coating on glass substrates. They result with good properties of homogeneity, optical transparence, hardness and adhesion.

Preparation of a bio-composite of sericin-g-PMMA via HRP-mediated graft copolymerization.

PubMed

He, Min; Hu, Haoran; Wang, Ping; Fu, Haitian; Yuan, Jiugang; Wang, Qiang; Fan, Xuerong

2018-05-26

Silk sericin (SS) derived from silkworms has the characteristics of anti-oxidation, antibacterial, and biocompatibility, however, high solubility in water restricted its applications in biomedical fields. In the present work, SS was enzymatically graft-copolymerized with a hydrophobic vinyl monomer of methyl methacrylate (MMA), through a free radical reaction, through the combination use of hydrogen peroxide and horseradish peroxidase (HRP). Efficacy of the HRP-mediated reaction was examined by means of FTIR, SDS-PAGE, and SEC chromatogram. A bio-composite of SS-graft-polymethyl methacrylate (SS-g-PMMA) was constructed subsequently, the corresponding wettability, thermal behavior, and biocompatibility of the obtained composite were examined, respectively. The data reveal that MMA was successfully copolymerized with the reactive sites in sericin chains, resulting in a noticeable increase in the molecular weight. For the membrane of SS-g-PMMA, the surface hydrophobicity was evidently improved compared to that of the untreated, according to the determined data of water contact angle and dissolution ratio. The current work develops an eco-friendly technique for reuse of the industrial waste like sericin, and provides a novel method for preparation of the sericin-based biomaterials as well. Copyright © 2018 Elsevier B.V. All rights reserved.

Chemically induced graft copolymerization of 2-hydroxyethyl methacrylate onto polyurethane surface for improving blood compatibility

NASA Astrophysics Data System (ADS)

He, Chunli; Wang, Miao; Cai, Xianmei; Huang, Xiaobo; Li, Li; Zhu, Haomiao; Shen, Jian; Yuan, Jiang

2011-11-01

To improve hydrophilicity and blood compatibility properties of polyurethane (PU) film, we chemically induced graft copolymerization of 2-hydroxyethyl methacrylate (HEMA) onto the surface of polyurethane film using benzoyl peroxide as an initiator. The effects of grafting temperature, grafting time, monomer and initiator concentrations on the grafting yields were studied. The maximum grafting yield value was obtained 0.0275 g/cm2 for HEMA. Characterization of the films was carried out by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), water contact angle measurements. ATR-FTIR data showed that HEMA was successfully grafted onto the PU films surface. Water contact angle measurement demonstrated the grafted films possessed a relatively hydrophilic surface. The blood compatibility of the grafted films was preliminarily evaluated by a platelet-rich plasma adhesion test and hemolysis test. The results of platelet adhesion experiment showed that polyurethane grafted polymerization with monomer of 2-hydroxyethyl methacrylate had good blood compatibility featured by the low platelet adhesion. Hemolysis rate of the PU-g-PHEMA films was dramatically decreased than the ungrafted PU films. This kind of new biomaterials grafted with HEMA monomers might have a potential usage for biomedical applications.

Proton-transfer lasers based on solid copolymers of modified 2-(2'-hydroxyphenyl)benzimidazoles with methacrylate monomers

NASA Astrophysics Data System (ADS)

Costela, A.; García-Moreno, I.; Mallavia, Ricardo; Amat-Guerri, F.; Barroso, J.; Sastre, R.

1998-06-01

We report on the lasing action of two newly synthesized 2-(2'-hydroxyphenyl) benzimidazole derivatives copolymerized with methyl methacrylate. The laser samples were transversely pumped with a N 2 laser at 337 nm. The influence on the proton-transfer laser performance of the distance between the chromophore group and the polymeric main chain and of the rigidity of the polymeric host matrix, were studied. Significant increases in lasing efficiency and photostability are demonstrated for some of the new materials, as compared to those previously obtained with related proton-transfer dyes also covalently bound to methacrylic monomers.

A nonaqueous potentiometric titration study of the dissociation of t-butyl methacrylate-methacrylic acid copolymers.

PubMed

Nakatani, Kiyoharu; Yamashita, Jun; Sekine, Tomomi; Toriumi, Minoru; Itani, Toshiro

2003-05-01

The dissociation of t-butyl methacrylate-methacrylic acid copolymers in dimethyl sulfoxide was analyzed by a nonaqueous potentiometric titration technique. The negative logarithm of the dissociation constant of the monomer unit of a methacrylic acid (MAA) monotonously increased with the increasing degree of dissociation corresponding to the titrant/MAA amount ratio, and was highly influenced by the copolymerization ratio. The results are discussed in terms of the suppression of the dissociation of MAA by a neighboring charged methacrylate anion unit.

Occupational asthma due to methyl methacrylate and cyanoacrylates.

PubMed Central

Lozewicz, S; Davison, A G; Hopkirk, A; Burge, P S; Boldy, D A; Riordan, J F; McGivern, D V; Platts, B W; Davies, D; Newman Taylor, A J

1985-01-01

Five patients had asthma provoked by cyanoacrylates and one by methyl methacrylate, possibly because of the development of a specific hypersensitivity response. Acrylates have wide domestic as well as industrial uses, and inhalation of vapour emitted during their use can cause asthma. PMID:4071461

Acrylates and Methacrylates,

DTIC Science & Technology

1987-09-15

and methacrylic acids and especially their esters. Acrylic and methacrylic monomers can be polymerized and copolymerized with other vinyl monomers by...contributed to reduction in the cost/value of these monomers and to expansion of the market for sale. For the first time acrylic acid was obtained in...a-dibromopropionic acid . In the Soviet Union for the development of the method of * production of acrylates the synthesis of methylacrylate began in

Modification of flax fibres by radiation induced emulsion graft copolymerization of glycidyl methacrylate

NASA Astrophysics Data System (ADS)

Moawia, Rihab Musaad; Nasef, Mohamed Mahmoud; Mohamed, Nor Hasimah; Ripin, Adnan

2016-05-01

Flax fibres were modified by radiation induced graft copolymerization of glycidyl methacrylate (GMA) by pre-irradiation method in an emulsion medium. The effect of reaction parameters on the degree of grafting (DOG) such as concentration of bleaching agent, absorbed dose, monomer concentration, temperature and reaction time were investigated. The DOG was found to be dependent on the investigated parameters. The incorporation of poly(GMA) grafts in the bleached flax fibres was confirmed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The structural and mechanical changes were evaluated by X-ray diffraction (XRD) and mechanical tester, respectively. The results revealed that reacting bleached flax fibres irradiated with 20 kGy with 5% GMA emulsion containing 0.5% polyoxyethylene-sorbitan monolaurate (Tween 20) surfactant at 40 °C for 1 h led to a maximum DOG of 148%. The grafted fibres showed sufficient mechanical strength and hydrophobicity which make them promising precursors for development of adsorbents after appropriate chemical treatments.

Solid coatings deposited from liquid methyl methacrylate via Plasma Polymerization

NASA Astrophysics Data System (ADS)

Wurlitzer, Lisa; Maus-Friedrichs, Wolfgang; Dahle, Sebastian

2016-09-01

The polymerization of methyl methacrylate via plasma discharges is well known today. Usually, plasma-enhanced chemical vapor deposition (PECVD) is used to deposit polymer coatings. Solid coatings are formed out of the liquid phase from methyl methacrylate via dielectric barrier discharge. The formation of the coating proceeds in the gas and the liquid phase. To learn more about the reactions in the two phases, the coatings from MMA monomer will be compared to those from MMA resin. Finally, attenuated total reflection infrared spectroscopy, confocal laser scanning microscopy and X-ray photoelectron spectroscopy are employed to characterize the solid coatings. In conclusion, the plasma enhanced chemical solution deposition is compared to the classical thermal polymerization of MMA.

21 CFR 882.5030 - Methyl methacrylate for aneurysmorrhaphy.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Methyl methacrylate for aneurysmorrhaphy. 882.5030 Section 882.5030 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES... reinforce intracranial aneurysms that are not amenable to conservative management, removal, or obliteration...

Thermally Switchable Thin Films of an ABC Triblock Copolymer of Poly(n-butyl methacrylate)-poly(methyl methacrylate)-poly(2-fluoroethyl methacrylate)

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

Zhang, Shanju; Liu, Zhan; Bucknall, David G.

2011-01-01

The thermo-responsive behavior of polymer films consisting of novel linear triblock copolymers of poly(n-butyl methacrylate)-poly(methyl methacrylate)-poly(2-fluoroethyl methacrylate) (PnBuMA-PMMA-P2FEMA) are reported using differential scanning calorimetry (DSC), atomic forcing microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and contacting angle (CA) measurements. The surface morphology, wettability and chemical structure of thin films of these triblock copolymers on silicon wafers as a function of temperature have been investigated. It has been shown that the wettability of the films is thermally switchable. Detailed structural analysis shows that thermo-responsive surface composition changes are produced. The underlying mechanism of the thermoresponsive behavior is discussed.

Predicting the chromatographic retention of polymers: poly(methyl methacrylate)s and polyacryate blends.

PubMed

Bashir, Mubasher A; Radke, Wolfgang

2007-09-07

The suitability of a retention model especially designed for polymers is investigated to describe and predict the chromatographic retention behavior of poly(methyl methacrylate)s as a function of mobile phase composition and gradient steepness. It is found that three simple yet rationally chosen chromatographic experiments suffice to extract the analyte specific model parameters necessary to calculate the retention volumes. This allows predicting accurate retention volumes based on a minimum number of initial experiments. Therefore, methods for polymer separations can be developed in relatively short time. The suitability of the virtual chromatography approach to predict the separation of polymer blend is demonstrated for the first time using a blend of different polyacrylates.

Tuning Surface Properties of Poly(methyl methacrylate) Film Using Poly(perfluoromethyl methacrylate)s with Short Perfluorinated Side Chains.

PubMed

Sohn, Eun-Ho; Ha, Jong-Wook; Lee, Soo-Bok; Park, In Jun

2016-09-27

To control the surface properties of a commonly used polymer, poly(methyl methacrylate) (PMMA), poly(perfluoromethyl methacrylate)s (PFMMAs) with short perfluorinated side groups (i.e., -CF3, -CF2CF3, -(CF3)2, -CF2CF2CF3) were used as blend components because of their good solubility in organic solvents, low surface energies, and high optical transmittance. The surface energies of the blend films of PFMMA with the -CF3 group and PMMA increased continuously with increasing PMMA contents from 17.6 to 26.0 mN/m, whereas those of the other polymer blend films remained at very low levels (10.2-12.6 mN/m), similar to those of pure PFMMAs, even when the blends contained 90 wt %PMMA. Surface morphology and composition measurements revealed that this result originated from the different blend structures, such as lateral and vertical phase separations. We expect that these PFMMAs will be useful in widening the applicable window of PMMA.

Concentrations and stability of methyl methacrylate, glutaraldehyde, formaldehyde and nickel sulfate in commercial patch test allergen preparations.

PubMed

Siegel, Paul D; Fowler, Joseph F; Law, Brandon F; Warshaw, Erin M; Taylor, James S

2014-05-01

Epicutaneous patch tests are used to reproduce allergy and diagnose allergic contact dermatitis. Reliable allergen test preparations are required. The purpose of the present study was to measure the actual concentrations of nickel(II) sulfate hexahydrate (NiSO4 ), methyl methacrylate, formaldehyde, and glutaraldehyde, and to compare them with the labelled concentrations, in commercial patch test allergen preparations found in dermatology clinics where patch testing is routinely performed. The commercial in-date and out-of-date patch test allergen preparations concentrations of NiSO4 , methyl methacrylate, formaldehyde and glutaraldehyde from one to three participating clinics were analysed with chromatographic or wet chemical techniques. NiSO4 and formaldehyde concentrations were at or above the labelled concentrations; however, formaldehyde loss occurred with storage. NiSO4 particulate was uniformly distributed throughout the petrolatum. 'In-use' methyl methacrylate reagent syringes all contained ≤ 56% of the 2% label concentration, with no observable relationship with expiration date. Lower methyl methacrylate cocentrations were consistently measured at the syringe tip end, suggesting loss resulting from methyl methacrylate's volatility. The concentrations of glutaraldehyde patch test allergen preparations ranged from 27% to 45% of the labelled (1% in pet.) concentration, independently of expiration date. Some false-negative methyl methacrylate, formaldehyde or glutaraldehyde patch test results may be attributable to instability of the test preparations. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Hot embossing and thermal bonding of poly(methyl methacrylate) microfluidic chips using positive temperature coefficient ceramic heater.

PubMed

Wang, Xia; Zhang, Luyan; Chen, Gang

2011-11-01

As a self-regulating heating device, positive temperature coefficient ceramic heater was employed for hot embossing and thermal bonding of poly(methyl methacrylate) microfluidic chip because it supplied constant-temperature heating without electrical control circuits. To emboss a channel plate, a piece of poly(methyl methacrylate) plate was sandwiched between a template and a microscopic glass slide on a positive temperature coefficient ceramic heater. All the assembled components were pressed between two elastic press heads of a spring-driven press while a voltage was applied to the heater for 10 min. Subsequently, the embossed poly(methyl methacrylate) plate bearing negative relief of channel networks was bonded with a piece of poly(methyl methacrylate) cover sheet to obtain a complete microchip using a positive temperature coefficient ceramic heater and a spring-driven press. High quality microfluidic chips fabricated by using the novel embossing/bonding device were successfully applied in the electrophoretic separation of three cations. Positive temperature coefficient ceramic heater indicates great promise for the low-cost production of poly(methyl methacrylate) microchips and should find wide applications in the fabrication of other thermoplastic polymer microfluidic devices.

Restoration of frontal contour with methyl methacrylate.

PubMed

Schultz, R C

1979-10-01

Of the various materials currently available for reconstruction of bony frontal deformities, bone cement (methyl methacrylate) has been judged to be superior in its simplicity, reliability, and aesthetic potential. It is uniquely suited to reconstruction of irregular defects of the forehead. Its biological characteristics, advantages, and hazards are presented along with the techniques of its use. Clinical examples illustrate the results obtained with minimal preparation, surgical time, and morbidity.

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

Preparation and Characterization of InP/Poly(methyl methacrylate) Nanocomposite Films.

PubMed

Kwon, Younghoon; Kim, Jongsung

2017-04-01

Quantum dots (QDs) are nanocrystalline semiconductors with many unusual optical properties. They exhibit very high fluorescence intensities and possess exceptional stability against photo-bleaching. In this study, we report the preparation of InP QDs-poly(methyl methacrylate) (PMMA) hybrids by fabricating QDs via a thermal decomposition reaction, followed by radical polymerization. The InP QDs were synthesized using indium(III) chloride and tris(dimethylamino)phosphine. Flexible composite films were obtained by radical polymerization using methyl methacrylate (MMA) as the monomer and 2,2′-azobis(2-methylpropionitrile) (AIBN) as a radical initiator. The PL intensity of the QDs was lowered upon composite formation with PMMA. However, the composites exhibited higher thermal stability than pure PMMA.

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.

Grafting of poly[(methyl methacrylate)-block-styrene] onto cellulose via nitroxide-mediated polymerization, and its polymer/clay nanocomposite.

PubMed

Karaj-Abad, Saber Ghasemi; Abbasian, Mojtaba; Jaymand, Mehdi

2016-11-05

For the first time, nitroxide-mediated polymerization (NMP) was used for synthesis of graft and block copolymers using cellulose (Cell) as a backbone, and polystyrene (PSt) and poly(methyl metacrylate) (PMMA) as the branches. For this purpose, Cell was acetylated by 2-bromoisobutyryl bromide (BrBiB), and then the bromine group was converted to 4-oxy-2,2,6,6-tetramethylpiperidin-1-oxyl group by a substitution nucleophilic reaction to afford a macroinitiator (Cell-TEMPOL). The macroinitiator obtained was subsequently used in controlled graft and block copolymerizations of St and MMA monomers to yield Cell-g-PSt and Cell-g-(PMMA-b-PSt). The chemical structures of all samples as representatives were characterized by FTIR and (1)H NMR spectroscopies. In addition, Cell-g-(PMMA-b-PSt)/organophilic montmorillonite nanocomposite was prepared through a solution intercalation method. TEM was used to evaluate the morphological behavior of the polymer-clay system. It was demonstrated that the addition of small percent of organophilic montmorillonite (O-MMT; 3wt.%) was enough to improve the thermal stability of the nanocomposite. Copyright © 2016 Elsevier Ltd. All rights reserved.

Preparation of Optically Transparent Films of Poly(methyl methacrylate) (PMMA) and Montmorillonite

DTIC Science & Technology

2001-11-01

methacrylate] [PMMA] and Montmorillonite DISTRIBUTION: Approved for public release, distribution unlimited This paper is part of the following report...Society V6.4 Preparation of Optically Transparent Films of Poly(methyl methacrylate) (PMMA) and Montmorillonite Elena Vasiliul, Chyi-Shan Wang"’ 2...exchanged with 1.40 meq/g of dimethyl dehydrogenated tallow ammonium from a sodium montmorillonite , Cloisite Na+ (CNa). Since the cation-exchange

Iodinated glycidyl methacrylate copolymer as a radiopaque material for biomedical applications.

PubMed

Dawlee, S; Jayabalan, M

2013-07-01

Polymeric biomaterial was synthesized by copolymerizing 50:50 mol% of monomers, glycidyl methacrylate and methyl methacrylate. Iodine atoms were then grafted to the epoxide groups of glycidyl methacrylate units, rendering the copolymer radiopaque. The percentage weight of iodine in the present copolymer was found to be as high as 23%. The iodinated copolymer showed higher glass transition temperature and thermal stability in comparison with unmodified polymer. Radiographic analysis showed that the copolymer possessed excellent radiopacity. The iodinated copolymer was cytocompatible to L929 mouse fibroblast cells. The in vivo toxicological evaluation by intracutaneous reactivity test of the copolymer extracts has revealed that the material was nontoxic. Subcutaneous implantation of iodinated copolymer in rats has shown that the material was well tolerated. Upon explantation and histological examination, no hemorrhage, infection or necrosis was observed. The samples were found to be surrounded by a vascularized capsule consisting of connective tissue cells. The results indicate that the iodinated copolymer is biocompatible and may have suitable applications as implantable materials.

Composite poly(methyl methacrylate-methacrylic acid-2-hydroxyethyl methacrylate) latex for immunoassay. The case of plasminogen.

PubMed

Miksa, B; Wilczynska, M; Cierniewski, C; Basinska, T; Slomkowski, S

1995-01-01

Poly(methyl methacrylate-methacrylic acid-2-hydroxyethyl methacrylate) latex (ACRYLAT) was synthesized by radical precipitation polymerization. The mass median diameter (MMD) and the geometrical standard deviation (GSD) of the ACRYLAT particles were 138 nm and 1.2, respectively. The concentration of the titrable carboxylic groups in the surface layer of latex particles was equal to 8.41 x 10(-6) mol m-2. Latex was able to bind up to 2.82 x 10(-7) mol of 1-aminopyrene per 1 m2 of the surface of the latex particles due to the ionic interactions between carboxylate anions and ammonium cations of protonated 1-aminopyrene. ACRYLAT was able to immobilize covalently human serum albumin in amounts up to 0.23 mg m-2. Aggregation of ACRYLAT with immobilized HSA, induced with specific antibodies (anti-HSA), was investigated turbidimetrically. The results indicated that in the model turbidimetric immunoassay, ACRYLAT coated with HSA can be used for the detection of anti-HSA in the goat anti-HSA serum diluted from 50 to 7000-fold. Immobilization of rabbit antibodies to plasminogen (anti-Plg) to ACRYLAT via the epsilon-aminocaproic acid linkers provided particles which were used for the development of the turbidimetric immunoassay for plasminogen. In this assay plasminogen could be detected in concentration ranging from 0.75 to 75 micrograms ml-1 in the blood plasma.

Rotational characterization of methyl methacrylate: Internal dynamics and structure determination

NASA Astrophysics Data System (ADS)

Herbers, Sven; Wachsmuth, Dennis; Obenchain, Daniel A.; Grabow, Jens-Uwe

2018-01-01

Rotational constants, Watson's S centrifugal distortion coefficients, and internal rotation parameters of the two most stable conformers of methyl methacrylate were retrieved from the microwave spectrum. Splittings of rotational energy levels were caused by two non equivalent methyl tops. Constraining the centrifugal distortion coefficients and internal rotation parameters to the values of the main isotopologues, the rotational constants of all single substituted 13C and 18O isotopologues were determined. From these rotational constants the substitution structures and semi-empirical zero point structures of both conformers were precisely determined.

Surface Molecularly Imprinted Polymer of Chitosan Grafted Poly(methyl methacrylate) for 5-Fluorouracil and Controlled Release

PubMed Central

Zheng, Xue-Fang; Lian, Qi; Yang, Hua; Wang, Xiuping

2016-01-01

The molecular surface imprinted graft copolymer of chitosan with methyl methacrylate (MIP-CS-g-PMMA) were prepared by free radical polymerization with 5-fluorouracil (5-FU) as the template molecule using initiator of ammonium persulfate as adsorption system. MIPs were characterized by FTIR, X-ray diffraction, thermo-gravimetric analysis, 1H NMR and SEM. The mechanism of graft copolymerization and factors affected graft reaction were studied in details, and the optimum reaction conditions (to the highest %G and %E as the standard) were obtained at [MMA] 1.2 mol/L, [Chitosan] 16.67 mol/L, [initiator] 0.0062 mol/L, temperature 60 °C and reaction time 7 h. MIPs exhibited high recognition selectivity and excellent combining affinity to template molecular. The in vitro release of the 5-FU was highly pH-dependent and time delayed. The release behavior showed that the drugs did not release in simulated gastric fluid (pH = 1.0), and the drug release was small in the simulated small intestinal fluid (pH = 6.8), and drug abrupt release will be produced in the simulated colon fluid (pH = 7.4), indicating excellent colon-specific drug delivery behavior. PMID:26892676

21 CFR 73.3127 - Vinyl alcohol/methyl methacrylate-dye reaction products.

Code of Federal Regulations, 2014 CFR

2014-04-01

... coloring effect. (2) As part of the manufacturing process, the lenses containing the color additives are... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Vinyl alcohol/methyl methacrylate-dye reaction products. 73.3127 Section 73.3127 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND...

21 CFR 73.3127 - Vinyl alcohol/methyl methacrylate-dye reaction products.

Code of Federal Regulations, 2012 CFR

2012-04-01

... coloring effect. (2) As part of the manufacturing process, the lenses containing the color additives are... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Vinyl alcohol/methyl methacrylate-dye reaction products. 73.3127 Section 73.3127 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND...

21 CFR 73.3127 - Vinyl alcohol/methyl methacrylate-dye reaction products.

Code of Federal Regulations, 2013 CFR

2013-04-01

... coloring effect. (2) As part of the manufacturing process, the lenses containing the color additives are... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Vinyl alcohol/methyl methacrylate-dye reaction products. 73.3127 Section 73.3127 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND...

Effect of epoxidation on 30% poly(methyl methacrylate)-grafted natural rubber polymer electrolytes

NASA Astrophysics Data System (ADS)

Nazir, Khuzaimah; Aziz, Ahmad Fairoz; Adam, Nurul Ilham; Yahya, Muhd Zu Azhan; Ali, Ab Malik Marwan

2015-08-01

Epoxidized 30% poly(methyl methacrylate)-grafted natural rubber (EMG 30) as a polymer host in solid polymer electrolytes (SPEs) has been investigated. EMG30 was synthesized via performicepoxidation method onto 30% poly(methyl methacrylate)-grafted natural rubber (MG30) and the formations of epoxy group were discussed. The EMG30 were characterized by proton nuclear magnetic resonance (1HNMR) to investigate their chemical structure and differential scanning calorimeter to determine their crystallinity. A new peak in 1HNMR spectra (2.71 ppm) confirmed the appearance of epoxy group. SPE based on EMG30 doped with 40 wt% LiCF3SO3 show the highest conductivity. The complexation between EMG30 and LiCF3SO3 were confirmed by attenuated total reflection Fourier transform infrared (ATR-FTIR).

Effect of epoxidation on 30% poly(methyl methacrylate)-grafted natural rubber polymer electrolytes

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

Nazir, Khuzaimah; Aziz, Ahmad Fairoz; Adam, Nurul Ilham

Epoxidized 30% poly(methyl methacrylate)-grafted natural rubber (EMG 30) as a polymer host in solid polymer electrolytes (SPEs) has been investigated. EMG30 was synthesized via performicepoxidation method onto 30% poly(methyl methacrylate)-grafted natural rubber (MG30) and the formations of epoxy group were discussed. The EMG30 were characterized by proton nuclear magnetic resonance ({sup 1}HNMR) to investigate their chemical structure and differential scanning calorimeter to determine their crystallinity. A new peak in {sup 1}HNMR spectra (2.71 ppm) confirmed the appearance of epoxy group. SPE based on EMG30 doped with 40 wt% LiCF{sub 3}SO{sub 3} show the highest conductivity. The complexation between EMG30 and LiCF{submore » 3}SO{sub 3} were confirmed by attenuated total reflection Fourier transform infrared (ATR-FTIR)« less

Dual-Responsive pH and Temperature Sensitive Nanoparticles Based on Methacrylic Acid and Di(ethylene glycol) Methyl Ether Methacrylate for the Triggered Release of Drugs.

PubMed

Khine, Yee Yee; Jiang, Yanyan; Dag, Aydan; Lu, Hongxu; Stenzel, Martina H

2015-08-01

A series of thermo-and pH-responsive poly(methyl methacrylate)-block-poly[methacrylic acid-co-di(ethylene glycol) methyl ether methacrylate] PMMA-b-P[MAA-co-DEGMA] block copolymers were synthesized by RAFT polymerization and self-assembled into micelles. The molar ratio of MAA was altered from 0-12% in order to modulate the lower critical solution temperature (LCST) of PDEGMA. The release of the drug albendazole from the micelle was strongly dependent on the temperature and the LCST value of the polymer. Systems below the LCST released the drug slowly while increasing the temperature above the LCST or decreasing the pH value to 5 resulted in the burst-like release of the drug. ABZ delivered in this pH-responsive drug carrier had a higher toxicity than the free drug or the drug delivered in a non-responsive drug carrier. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

21 CFR 177.1635 - Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene).

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Poly(p-methylstyrene) and rubber-modified poly(p... Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene). Poly(p-methylstyrene) and rubber-modified poly(p-methylstyrene) identified in this section may be safely used as components of articles...

21 CFR 177.1635 - Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene).

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Poly(p-methylstyrene) and rubber-modified poly(p... Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene). Poly(p-methylstyrene) and rubber-modified poly(p-methylstyrene) identified in this section may be safely used as components of articles...

Methacrylic Zwitterionic, Thermoresponsive, and Hydrophilic (Co)Polymers via Cu(0)-Polymerization: The Importance of Halide Salt Additives.

PubMed

Simula, Alexandre; Anastasaki, Athina; Haddleton, David M

2016-02-01

The synthesis of hydrophilic, thermoresponsive, and zwitterionic polymethacrylates is reported by Cu(0)-mediated reversible deactivation radical polymerization in water and/or water/alcohol mixtures. The predisproportionation of [Cu(I) (PMDETA)Cl] in water prior to initiator and monomer addition is exploited to yield well-defined polymethacrylates with full monomer conversions in 30 min. The addition of supplementary halide salts (NaCl) enables the synthesis of various molecular weight poly[poly(ethylene glycol) methyl ether methacrylate] (PEGMA475) (DPn = 10-80, Mn ≈ 10,000-40 000 g mol(-1)) with full monomer conversion and narrow molecular weight distributions attained in all cases (Đ ≈ 1.20-1.30). A bifunctional PEG initiator (average Mn ≈ 1000 g mol(-1)) is utilized for the polymerization of a wide range of methacrylates including 2-dimethylaminoethyl methacrylate, 2-morpholinoethyl methacrylate, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, and 2-methacryloyloxyethyl phosphorylcholine. Despite the high water content, high end group fidelity is demonstrated by in situ chain extensions and block copolymerizations with PEGMA475 yielding well-defined functional telechelic pentablock copolymers within 2.5 h. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

21 CFR 177.1635 - Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene).

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Poly(p-methylstyrene) and rubber-modified poly(p... Components of Single and Repeated Use Food Contact Surfaces § 177.1635 Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene). Poly(p-methylstyrene) and rubber-modified poly(p-methylstyrene) identified...

Controlled Degradation of Poly(Ethyl Cyanoacrylate-Co-Methyl Methacrylate)(PECA-Co-PMMA) Copolymers

USDA-ARS?s Scientific Manuscript database

This paper describes a method for modifying poly(ethyl cyanoacrylate) in order to control the degradation and the stability as well as the glass transition temperatures. Copolymers of poly(ethyl cyanoacrylate-co-methyl methacrylate) (PECA-co-PMMA) with various compositions were synthesized by free ...

21 CFR 175.360 - Vinylidene chloride copolymer coatings for nylon film.

Code of Federal Regulations, 2014 CFR

2014-04-01

... is applied as a continuous film over one or both sides of a base film produced from nylon resins... produced by copolymerizing vinylidene chloride with one or more of the monomers acrylic acid, acrylonitrile, ethyl acrylate, methacrylic acid, methyl acrylate, methyl methacrylate (CAS Reg. No. 80-62-6; maximum...

Facile Synthesis of Thick Films of Poly(methyl methacrylate), Poly(styrene), and Poly(vinyl pyridine) from Au Surfaces

PubMed Central

Saha, Sampa

2011-01-01

Atom transfer radical polymerization (ATRP) is commonly used to grow polymer brushes from Au surfaces, but the resulting film thicknesses are usually significantly less than with ATRP from SiO2 substrates. On Au, growth of poly(methyl methacrylate) (PMMA) blocks from poly(tert-butyl acrylate) brushes occurs more rapidly than growth of PMMA from initiator monolayers, suggesting that the disparity between growth rates from Au and SiO2 stems from the Au surface. Radical quenching by electron transfer from Au is probably not the termination mechanism because polymerization from thin, cross-linked initiators gives film thicknesses that are essentially the same as the thicknesses of films grown from SiO2 under the same polymerization conditions. However, this result is consistent with termination through desorption of thiols from non-cross-linked films, and reaction of these thiols with growing polymer chains. The enhanced stability of cross-linked initiators allows ATRP at temperatures up to ~100 °C and enables the growth of thick films of PMMA (350 nm), polystyrene (120 nm) and poly(vinyl pyridine) (200 nm) from Au surfaces in 1 hour. At temperatures >100 °C, the polymer brush layers delaminate as large area films. PMID:21728374

Optical Properties of Nanocellulose Dispersions in Water, Dimethylformamide and Poly(Methyl Methacrylate)

DTIC Science & Technology

2013-10-01

measurements for cellulose and PMMA thin- films . ..13  v List of Tables Table 1. Recorded optical data for nanocellulose in water...applications beyond thin films . In particular, the effects of nanocellulose fibers in higher concentrations, processed in different solvents, and...Optical Properties of Nanocellulose Dispersions in Water, Dimethylformamide and Poly(Methyl Methacrylate) by James F. Snyder, Joshua Steele

Plasma-Enhanced Copolymerization of Amino Acid and Synthetic Monomers

DTIC Science & Technology

2011-12-16

Langmuir 2012, 28, 1833−18451839 The final copolymerization study utilizing a liquid inorganic component, titanium isopropoxide , and solid L-tyrosine was...conducted with the two monomers being vaporized and exposed to the plasma simultaneously. Titanium isopropoxide was heated in a liquid state to...hydroxyethyl methacrylate (HEMA), and titanium tetraiso- propoxide (TTIP). The organic and inorganic functional monomers used were chosen to demonstrate the

Characterization of γ-radiation induced polymerization in ethyl methacrylate and methyl acrylate monomers solutions

NASA Astrophysics Data System (ADS)

Baccaro, Stefania; Casieri, Cinzia; Cemmi, Alessia; Chiarini, Marco; D'Aiuto, Virginia; Tortora, Mariagrazia

2017-12-01

The present work is focused on the γ-radiation induced polymerization of ethyl methacrylate (EMA) and methyl acrylate (MA) monomers mixture to obtain a co-polymer with specific features. The effect of the irradiation parameters (radiation absorbed dose, dose rate) and of the environmental atmosphere on the features of the final products was investigated. Attenuated Total Reflectance - Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Nuclear Magnetic Resonance high-resolution analyses of hydrogen and carbon nuclei (1H and 13C NMR) were applied to follow the γ-induced modifications by monitoring the co-polymerization process and allowed the irradiation parameters optimization. Diffusion-Ordered NMR (DOSY-NMR) data were used to evaluate the co-polymers polydispersity and polymerization degree. Since the last parameter is strongly influenced by the γ radiation and environmental conditions, a comparison among samples prepared and irradiated in air and under nitrogen atmosphere was carried out. In presence of oxygen, higher radiation was required to obtain a full solid co-polymer since a partial amount of energy released to the samples was involved in competitive processes, i.e. oxygen-containing free radicals formation and primary radicals recombination. Irrespectively to the environmental atmosphere, more homogeneous samples in term of polymerization degree dispersion was achieved at lower dose rates. At radiation absorbed doses higher than those needed for the formation of the co-polymer, while in case of samples irradiated in air heavy depolymerization was verified, a sensible increase of the samples stability was attained if the irradiation was performed under nitrogen atmosphere.

The Tensile and Shear Bond Strengths of Poly (Methyl Methacrylate) Processed on Electrolytically Etched Ticonium.

DTIC Science & Technology

1986-05-01

METHYL NETHACRYLATE) PROCESSED ON ELECTROLYTICALLY ETCHED TICONIUM A THESIS Presented to the Faculty of The University of Texas Graduate School of...were cast utilizing the manufacturer’s directions for investment, burnout , and casting. Two groups of metal specimens were prepared: 20 for...STRENGTHS OF POLY (METHYL METHACRYLATE) PROCESSED ON ELECTROLYTICALLY ETCHED TICONIUM JOHN EDWARD ZURASKY, M.S. The University of Texas Graduate School

Synthesis and characterization of functionalized methacrylates for coatings and biomedical applications

NASA Astrophysics Data System (ADS)

Shemper, Bianca Sadicoff

The research presented in this dissertation involves the design of polymers for biomaterials and for coatings applications. The development of non-wettable, hard UV-curing, or reactive coatings is discussed. The biomaterials section involves the syntheses of linear and star-like polymers of the functionalized monomer poly(propylene glycol) monomethacrylate (PPGM) via atom transfer radical polymerization (ATRP) (Chapter II). Its copolymerization with a perfluoroalkyl ethyl methacrylate monomer (1H,1H,2H,2H-heptadecafluorodecyl methacrylate) and the syntheses of linear and star-like amphiphilic copolymers containing the fluorinated monomer and poly(ethyleneglycol) methyl ether methacrylate (MPEGMA) are discussed in Chapter III. The four-arm amphiphilic block copolymer obtained showed unique associative properties leading to micellization in selective solvents. Chapter IV includes research involving the design of films with low surface energy by incorporating fluorine into the polymer. The synthesis, characterization and polymerization of a perfluoroalkylether-substituted methacrylic acid (C8F7) are discussed, and the properties of coatings obtained after its photopolymerization on different substrates are evaluated to confirm formation of low-surface energy polymeric coatings. Subsequently, hard coatings based on methyl (alpha-hydroxymethyl)acrylate (MHMA) were prepared via photopolymerization using UV-light. Firstly, mechanistic investigations into the photopolymerization behavior of (alpha-hydroxymethyl)acrylates (RHMA's) are reported (Chapter V). RHMA derivatives were photopolymerized with various multifunctional acrylates and methacrylates and the effect of crosslinker type and degree of functionality on photopolymerization rates and conversions was investigated. Then, in Chapter VI the synthesis of a series of new crosslinkers is described and their photopolymerization kinetics was investigated in bulk. The effect of these novel crosslinkers on the

40 CFR 721.10153 - Modified methyl methacrylate, 2-hydroxyethyl methacrylate polymer (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

...-hydroxyethyl methacrylate polymer (generic). 721.10153 Section 721.10153 Protection of Environment...-hydroxyethyl methacrylate polymer (generic). (a) Chemical substance and significant new uses subject to... methacrylate polymer (PMN P-08-6) is subject to reporting under this section for the significant new uses...

40 CFR 721.10153 - Modified methyl methacrylate, 2-hydroxyethyl methacrylate polymer (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

...-hydroxyethyl methacrylate polymer (generic). 721.10153 Section 721.10153 Protection of Environment...-hydroxyethyl methacrylate polymer (generic). (a) Chemical substance and significant new uses subject to... methacrylate polymer (PMN P-08-6) is subject to reporting under this section for the significant new uses...

40 CFR 721.10153 - Modified methyl methacrylate, 2-hydroxyethyl methacrylate polymer (generic).

Code of Federal Regulations, 2012 CFR

2012-07-01

...-hydroxyethyl methacrylate polymer (generic). 721.10153 Section 721.10153 Protection of Environment...-hydroxyethyl methacrylate polymer (generic). (a) Chemical substance and significant new uses subject to... methacrylate polymer (PMN P-08-6) is subject to reporting under this section for the significant new uses...

40 CFR 721.10153 - Modified methyl methacrylate, 2-hydroxyethyl methacrylate polymer (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

...-hydroxyethyl methacrylate polymer (generic). 721.10153 Section 721.10153 Protection of Environment...-hydroxyethyl methacrylate polymer (generic). (a) Chemical substance and significant new uses subject to... methacrylate polymer (PMN P-08-6) is subject to reporting under this section for the significant new uses...

40 CFR 721.10153 - Modified methyl methacrylate, 2-hydroxyethyl methacrylate polymer (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

...-hydroxyethyl methacrylate polymer (generic). 721.10153 Section 721.10153 Protection of Environment...-hydroxyethyl methacrylate polymer (generic). (a) Chemical substance and significant new uses subject to... methacrylate polymer (PMN P-08-6) is subject to reporting under this section for the significant new uses...

Poly(methyl methacrylate) coating of soft magnetic amorphous and crystalline Fe,Co-B nanoparticles by chemical reduction.

PubMed

Fernández Barquín, L; Yedra Martínez, A; Rodríguez Fernández, L; Rojas, D P; Murphy, F J; Alba Venero, D; Ruiz González, L; González-Calbet, J; Fdez-Gubieda, M L; Pankhurst, Q A

2012-03-01

The structural and magnetic properties of a collection of nanoparticles coated by Poly(methyl methacrylate) through a wet chemical synthesis have been investigated. The particles display either an amorphous (M = Fe, Co) M-B arrangement or a mixed structure bcc-Fe and fcc-Co + amorphous M-B. Both show the presence of a metal oxi-hydroxide formed in aqueous reduction. The organic coating facilitates technological handling. The cost-effective synthesis involves a reduction in a Poly(methyl methacrylate) aqueous solution of iron(II) or cobalt(II) sulphates (< 0.5 M) by sodium borohydride (< 0.5 M). The particles present an oxidized component, as deduced from X-ray diffraction, Mössbauer and Fe- and Co K-edge X-ray absorption spectroscopy and electron microscopy. For the ferrous alloys, this Fe-oxide is alpha-goethite, favoured by the aqueous solution. The Poly(methyl methacrylate) coating is confirmed by Fourier transform infrared spectroscopy. In pure amorphous core alloys there is a drastic change of the coercivity from bulk to around 30 Oe in the nanoparticles. The mixed structured alloys also lie in the soft magnetic regime. Magnetisation values at room temperature range around 100 emu/g. The coercivity stems from multidomain particles and their agglomeration, triggering the dipolar interactions.

Fabrication, modification, and application of poly(methyl methacrylate) microfluidic chips.

PubMed

Chen, Yun; Zhang, Luyan; Chen, Gang

2008-05-01

Poly(methyl methacrylate) (PMMA) is particularly useful for microfluidic chips with the features of low price, excellent optic transparency, attractive mechanical and chemical properties, ease of fabrication and modification, biocompatibility, etc. During the past decade, significant progress in the PMMA microfluidic chips has occurred. This review, which contains 120 references, summarizes the recent advances and the key strategies in the fabrication, modification, and application of PMMA microfluidic chips. It is expected that PMMA microchips should find a wide range of applications and will lead to the creation of truly disposable microfluidic devices.

Methacrylate derivatives incorporating pyroglutamic acid.

PubMed

Smith, Tara J; Mathias, Lon J

2002-01-01

Methacrylates containing pyroglutamic acid were synthesized in good yields. Methyl alpha-pyroglutamyl methylacrylate (PyMM) and methyl alpha-pyroglutamidoundecanoyl methylacrylate (PyUM) give very fast photopolymerization rates both in homopolymerizations and with widely used commercial monomers N-vinyl pyrrolidinone (NVP) and hydroxyethyl methacrylate (HEMA). Soluble or cross-linked homopolymers can be obtained depending upon polymerization temperature. Pyroglutamic methacrylates polymerize without added initiator in the melt. Solution cast, photocured, and thermally cured coatings gave good to excellent adhesion to poly(ethylene terephthalate) and glass surfaces.

Novel functionalized fluorescent polymeric nanoparticles for immobilization of biomolecules

NASA Astrophysics Data System (ADS)

Jain, Swati; Chattopadhyay, Sruti; Jackeray, Richa; Abid, C. K. V. Zainul; Singh, Harpal

2013-07-01

Novel, size controlled fluorescent polymeric nanoparticles (FPNP) were synthesized having acetoacetoxy functionality on the surface for immobilization of biomolecules which can be utilized as biomarkers and labels in fluoroimmunoassays. Core-shell nanoparticles of poly(styrene, St-methyl methacrylate, MMA-acetoacetoxy ethyl methacrylate, AAEM), stabilized by various concentrations of surfactant, sodium lauryl sulphate (SLS), were obtained by facile miniemulsion co-polymerization encapsulated with pyrene molecules in their hydrophobic core. Analytical, spectroscopic and imaging characterization techniques revealed the formation of stable, monodisperse, spherical nano sized particles exhibiting high luminescence properties. Particles with 1% SLS (S1) showed good dispersion stability and fluorescence intensity and were chosen as ideal candidates for further immobilization studies. Steady state fluorescence studies showed 10 times higher fluorescence intensity of S1 nanoparticles than that of pyrene solution in solvent-toluene at the same concentration. Environmental factors such as pH, ionic strength and time were found to have no effect on fluorescence intensity of FPNPs. Surface β-di-ketone groups were utilized for the covalent immobilization of enzyme conjugated antibodies without any activation or pre-treatment of nanoparticles.Novel, size controlled fluorescent polymeric nanoparticles (FPNP) were synthesized having acetoacetoxy functionality on the surface for immobilization of biomolecules which can be utilized as biomarkers and labels in fluoroimmunoassays. Core-shell nanoparticles of poly(styrene, St-methyl methacrylate, MMA-acetoacetoxy ethyl methacrylate, AAEM), stabilized by various concentrations of surfactant, sodium lauryl sulphate (SLS), were obtained by facile miniemulsion co-polymerization encapsulated with pyrene molecules in their hydrophobic core. Analytical, spectroscopic and imaging characterization techniques revealed the formation of stable

Exposure to volatile methacrylates in dental personnel.

PubMed

Hagberg, Stig; Ljungkvist, Göran; Andreasson, Harriet; Karlsson, Stig; Barregård, Lars

2005-06-01

Dental personnel are exposed to acrylates due to the acrylic resin-based composites and bonding agents used in fillings. It is well known that these compounds can cause contact allergy in dental personnel. However, in the 1990s, reports emerged on asthma also caused by methacrylates. The main volatile acrylates in dentistry are 2-hydroxyethyl methacrylate and methyl methacrylate. The aim of this study was to quantify the exposure to these acrylates in Swedish dental personnel. We studied the exposure to 2-hydroxyethyl methacrylate and methyl methacrylate in five randomly selected public dental clinics and at the Faculty of Odontology at Göteborg University. In total, 21 whole-day and 46 task-specific short-term (1-18 min) measurements were performed. The median 8-hour time-weighted averages were 2.5 microg/m3 (dentists) and 2.9 microg/m3 (dental nurses) for 2-hydroxyethyl methacrylate, and 0.8 microg/m3 (dentists) and 0.3 microg/m3 (dental nurses) for methyl methacrylate. The maximum short-term exposure levels were 79 microg/m3 for 2-hydroxyethyl methacrylate and 15 microg/m3 for methyl methacrylate, similar in dentists and dental nurses. The observed levels are much lower than in complete denture fabrication. We found only one previous study in dentistry and it showed similar results (though it reported short-term measurements only). Irritant effects would not be expected in healthy people at these levels. Nevertheless, occupational respiratory diseases due to methacrylates may occur in dental personnel, and improvements in the handling of these chemicals in dentistry are warranted. This includes better vials for the bonding agents and avoiding evaporation from discarded materials.

Preparation of poly(methyl methacrylate) microcapsules by in situ polymerization on the surface of calcium carbonate particles.

PubMed

Sato, Katsuhiko; Nakajima, Tatsuya; Anzai, Jun-ichi

2012-12-01

Poly(methyl methacrylate) (PMMA) microcapsules were prepared by the in situ polymerization of methyl methacrylate (MMA) and N,N'-methylenebisacrylamide on the surface of calcium carbonate (CaCO(3)) particles, followed by the dissolution of the CaCO(3) core in ethylenediaminetetraacetic acid solution. The microcapsules were characterized using fluorescence microscopy, atomic force microscopy, scanning electron microscopy, and Fourier transform infrared spectroscopy. The average sizes of the CaCO(3) particles and PMMA capsules were 3.8±0.6 and 4.0±0.6 μm, respectively. A copolymer consisting of MMA and rhodamine B-bearing MMA was also used to prepare microcapsules for fluorescent microscopy observations. Fluorescein isothiocyanate-labeled bovine serum albumin was enclosed in the PMMA microcapsules and its release properties were studied. Copyright © 2012 Elsevier Inc. All rights reserved.

Reactivity ratios and sequence structures of the copolymers prepared using photo-induced copolymerization of MMA with MTMP.

PubMed

Liu, Xiaoxuan; Zhang, Yongtao; Cui, Yanyan; Dong, Zhixian

2012-05-01

4-Methacryloyl-2,2,6,6-tetramethyl-piperidine (MTMP) was applied as reactive hindered amine piperidine. Photo-induced copolymerization of methyl methacrylate (MMA, M(1)) with MTMP (M(2)) was carried out in benzene solution at ambient temperature. The reactivity ratios for these monomers were measured by running a series of reactions at various feed ratios of initial monomers, and the monomer incorporation into copolymer was determined using (1)H NMR. Reactivity ratios of the MMA/MTMP system were measured to be r(1)= 0.37 and r(2)= 1.14 from extended Kelen-Tüdos method. The results show that monomer MTMP prefers homopolymerization to copolymerization in the system, whereas monomer MMA prefers copolymerization to homopolymerization. Sequence structures of the MMA/MTMP copolymers were characterized using (1)H NMR. The results show that the sequence structure for the main chain of the MMA/MTMP copolymers is mainly composed of a syndiotactic configuration, only with a little heterotactic configuration. Three kinds of the sequences of rr, rr', and lr' in the syndiotactic configuration are found. The sequence-length distribution in the MMA/MTMP copolymers is also obtained. For f(1)= 0.2, the monomer unit of MMA is mostly separated by MTMP units, and for f(1)= 0.6, the alternating tendency prevails and a large number of mono-sequences are formed; further up to f(1)= 0.8, the monomer unit of MTMP with the sequence of one unit is interspersed among the chain of MMA. Copyright © 2012 John Wiley & Sons, Ltd.

Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(III) amine-bis(phenolate) complex.

PubMed

Dean, Rebecca K; Devaine-Pressing, Katalin; Dawe, Louise N; Kozak, Christopher M

2013-07-07

A diamine-bis(phenolate) chromium(III) complex, {CrCl[O2NN'](BuBu)}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.

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

Synthesis and characterization of organic-inorganic polymers from new methacrylate monomers and silane derivatives

NASA Astrophysics Data System (ADS)

Nicolescu, F. Adriana; Jerca, Victor V.; Albu, Ana M.; Vasilescu, D. Sorin; Vuluga, D. Mircea

2009-09-01

We report the synthesis of five new hybrid polymeric structures obtained by free radical copolymerization of some organic azo-based methacrylate monomers and 3-methacryloxypropyl trimethoxysilane (MEMO). The copolymers are soluble in common solvents like methylene chloride, chloroform, dichlorbenzene, dimethylsulfoxide, dimethylformamide. The copolymeric structures might be interesting from the point of view of nonlinear optical response due to a rich content in chromophoric units determined by H-NMR spectroscopy. The structures were also characterized by FT-IR spectroscopy, TGA and SEC analysis.

A comparative study of the decomposition of pig carcasses in a methyl methacrylate box and open air conditions.

PubMed

Li, Liangliang; Wang, Jiangfeng; Wang, Yu

2016-08-01

Analysis of the process of decomposition is essential in establishing the postmortem interval. However, despite the fact that insects are important players in body decomposition, their exact function within the decay process is still unclear. There is also limited knowledge as to how the decomposition process occurs in the absence of insects. In the present study, we compared the decomposition of a pig carcass in open air with that of one placed in a methyl methacrylate box to prevent insect contact. The pig carcass in the methyl methacrylate box was in the fresh stage for 1 day, the bloated stage from 2 d to 11 d, and underwent deflated decay from 12 d. In contrast, the pig carcass in open air went through the fresh, bloated, active decay and post-decay stages; and 22.3 h (0.93 d), 62.47 h (2.60 d), 123.63 h (5.15 d) and 246.5 h (10.27 d) following the start of the experiment respectively, prior to entering the skeletonization stage. A large amount of soft tissue were remained on the pig carcass in the methyl methacrylate box on 26 d, while only scattered bones remained on the pig carcass in open air. The results indicate that insects greatly accelerate the decomposition process. Copyright © 2016 Elsevier Ltd and Faculty of Forensic and Legal Medicine. All rights reserved.

Structural modification of poly(methyl methacrylate) by proton irradiation

NASA Astrophysics Data System (ADS)

Choi, H. W.; Woo, H. J.; Hong, W.; Kim, J. K.; Lee, S. K.; Eum, C. H.

2001-01-01

A general survey is presented on the structural modification of poly(methyl methacrylate) (PMMA) by proton implantation. The implanted PMMA films were characterized by FT-IR attenuated total reflection (FT-IR ATR), Raman, Rutherford backscattering spectroscopy (RBS), gel permeation chromatography (GPC) and surface profiling. The ion fluence of 350 keV protons ranged from 2×10 14 to 1×10 15 ions/cm 2. The IR and Raman spectra showed the reduction of peaks from the pendant group of PMMA. The change of absorption and composition was observed by UV-VIS and RBS, respectively. These results showed that the pendant group is readily decomposed and eliminated by proton irradiation. The change of molecular weight distribution was also measured by GPC and G-value of scission was estimated to be 0.67.

Electrospun poly(methyl methacrylate) fibrous mat showing piezoelectric properties

NASA Astrophysics Data System (ADS)

Nobeshima, Taiki; Ishii, Yuya; Sakai, Heisuke; Uemura, Sei; Yoshida, Manabu

2018-05-01

A piezoelectric effect, such as actuation behavior with voltage application, could be observed from a poly(methyl methacrylate) (PMMA) fibrous mat fabricated by electrospinning. This fibrous mat increased or decreased its thickness in accordance with the polarity of the applied voltage, which appears to be an inverse piezoelectric effect. The appearance d T constant was as large as 8.5 nm/V owing to the softness of the fibrous structure, and the coupling constant K T = 0.31 indicated its efficient piezoelectric property. This piezoelectric behavior was repeatedly observed to be stable at room temperature. In addition, the polarization components of the fibrous mat, which are considered to be the origin of its piezoelectric effect, and its relaxation behavior were confirmed from the results of thermally stimulated current measurements.

Fracture resistance of Kevlar-reinforced poly(methyl methacrylate) resin: a preliminary study.

PubMed

Berrong, J M; Weed, R M; Young, J M

1990-01-01

The reinforcing effect of Kevlar fibers incorporated in processed poly(methyl methacrylate) resin samples was studied using 0% (controls), 0.5%, 1%, and 2% by weight of the added fibers. The samples were subjected to impact testing to determine fracture resistance, and sample groups were statistically compared using an ANOVA. Each reinforced sample had significantly greater fracture resistance (P less than 0.05) than the control, and no difference was found either within or between control groups. The use of reinforcing Kevlar fibers appears to enhance the fracture resistance of acrylic resin denture base materials.

Initiation precursors and initiators in laser-induced copolymerization of styrene and maleic anhydride in acetone

NASA Technical Reports Server (NTRS)

Miner, Gilda A.; Meador, Willard E.; Chang, C. Ken

1990-01-01

The initiation step of photopolymerized styrene/maleic anhydride copolymer was investigated at 365 nm. UV absorption measurements provide decisive evidence that the styrene/maleic anhydride charge transfer complex is the sole absorbing species; however, key laser experiments suggest intermediate reactions lead to a monoradical initiating species. A mechanism for the photoinitiation step of the copolymer is proposed.

Durability of Poly(Methyl Methacrylate) Lenses Used in Concentrating Photovoltaic Technology (Revised) (Presentation)

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

Miller, D. C.; Carloni, J. D.; Pankow, J. W.

2012-01-01

Concentrating photovoltaic (CPV) technology recently gained interest based on its expected low levelized cost of electricity, high efficiency, and scalability. Many CPV systems employ Fresnel lenses composed of poly(methyl methacrylate) (PMMA) to obtain a high optical flux density on the cell. The optical and mechanical durability of these lenses, however, is not well established relative to the desired surface life of 30 years. Our research aims to quantify the expected lifetime of PMMA in key market locations (FL, AZ, and CO).

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

Properties of cellulase as template molecule on chitosan—methyl methacrylate membrane

NASA Astrophysics Data System (ADS)

Lian, Qi; Zheng, Xuefang; Wu, Haixia; Song, Shitao; Wang, Dongjun

2015-12-01

In this study, a novel molecular imprinting membrane made of chitosan and methyl methacrylate (MMA) was fabricated with cellulase as template molecule and the thermal response to cellulase was characterized. The film was characterized by infrared spectroscopy (IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and the permeation experiment. The results showed that the space structure of the film was as similar as the cellulase. Moreover, the membrane had advanced molecular imprinting capability to cellulase comparing to pepsin and pectinase at any temperature and the film had excellent ability to identify specific template molecule (cellulase) at the synthesis temperature compared to other temperatures.

Cellulose nanocrystals as a reinforcing material for electrospun poly(methyl methacrylate) fibers: formation, properties and nanomechanical characterization

Treesearch

Hong Dong; Kenneth E. Strawhecker; James A. Snyder; Joshua A. Orlicki; Richard S. Reiner; Alan W. Rudie

2012-01-01

Uniform fibers composed of poly(methyl methacrylate) (PMMA) reinforced with progressively increasing contents of cellulose nanocrystals (CNCs), up to 41 wt% CNCs, have been successfully produced by electrospinning. The morphological, thermal and nanomechanical properties of the composite sub-micron fibers were investigated. The CNCs derived from wood pulp by sulfuric...

Optical reflectivity study of silicon ion implanted poly(methyl methacrylate)

NASA Astrophysics Data System (ADS)

Hadjichristov, Georgi B.; Stefanov, Ivan L.; Florian, Bojana I.; Blaskova, Gergana D.; Ivanov, Victor G.; Faulques, Eric

2009-11-01

The optical reflectivity (both specular and off-specular) of poly(methyl methacrylate) (PMMA) implanted with silicon ions (Si +) at energy of 50 keV, is studied in the spectral range 0.25-25 μm. The effect from the Si + implantation on the reflectivity of two PMMA materials is examined in the dose range from 10 14 to 10 17 ions/cm 2 and is linked to the structure formed in this ion implanted plastic. As compared to the pristine PMMA, an enhancement of the reflectivity of Si + implanted PMMA is observed, that is attributed to the modification of the subsurface region of PMMA upon the ion implantation. The ion-produced subsurface organic interface is also probed by laser-induced thermo-lens.

Radiation grafting of methyl methacrylate onto polyethylene separators for lithium secondary batteries

NASA Astrophysics Data System (ADS)

Gwon, Sung-Jin; Choi, Jae-Hak; Sohn, Joon-Yong; An, Sung-Jun; Ihm, Young-Eon; Nho, Young-Chang

2008-08-01

Micro-porous polyethylene separator was modified by radiation grafting of methyl methacrylate in order to improve its affinity with a liquid electrolyte. The degree of grafting (DOG) increased with the monomer concentration and grafting time. The morphological change of the modified separator was investigated by scanning electron microscopy. The degree of crystallinity upon grafting was reduced due to the formation of an amorphous PMMA layer. The electrolyte uptake and the ionic conductivity of the separator increased with an increase in the DOG. The ionic conductivity reached 2.0 mS/cm for the grafted polyethylene separator with 127 wt% DOG.

Stable-isotope-based labeling of styrene-degrading microorganisms in biofilters.

PubMed

Alexandrino, M; Knief, C; Lipski, A

2001-10-01

Deuterated styrene ([(2)H(8)]styrene) was used as a tracer in combination with phospholipid fatty acid (PLFA) analysis for characterization of styrene-degrading microbial populations of biofilters used for treatment of waste gases. Deuterated fatty acids were detected and quantified by gas chromatography-mass spectrometry. The method was evaluated with pure cultures of styrene-degrading bacteria and defined mixed cultures of styrene degraders and non-styrene-degrading organisms. Incubation of styrene degraders for 3 days with [(2)H(8)]styrene led to fatty acids consisting of up to 90% deuterated molecules. Mixed-culture experiments showed that specific labeling of styrene-degrading strains and only weak labeling of fatty acids of non-styrene-degrading organisms occurred after incubation with [(2)H(8)]styrene for up to 7 days. Analysis of actively degrading filter material from an experimental biofilter and a full-scale biofilter by this method showed that there were differences in the patterns of labeled fatty acids. For the experimental biofilter the fatty acids with largest amounts of labeled molecules were palmitic acid (16:0), 9,10-methylenehexadecanoic acid (17:0 cyclo9-10), and vaccenic acid (18:1 cis11). These lipid markers indicated that styrene was degraded by organisms with a Pseudomonas-like fatty acid profile. In contrast, the most intensively labeled fatty acids of the full-scale biofilter sample were palmitic acid and cis-11-hexadecenoic acid (16:1 cis11), indicating that an unknown styrene-degrading taxon was present. Iso-, anteiso-, and 10-methyl-branched fatty acids showed no or weak labeling. Therefore, we found no indication that styrene was degraded by organisms with methyl-branched fatty fatty acids, such as Xanthomonas, Bacillus, Streptomyces, or Gordonia spp.

Method of uranium reclamation from aqueous systems by reactive ion exchange. [US DOE patent application; anion exchange resin of copolymerized divinyl-benzene and styrene having quarternary ammonium groups and bicarbonate ligands

DOEpatents

Maya, L.

1981-11-05

A reactive ion exchange method for separation and recovery of values of uranium, neptunium, plutonium, or americium from substantially neutral aqueous systems of said metals comprises contacting said system with an effective amount of a basic anion exchange resin of copolymerized divinyl-benzene and styrene having quarternary ammonium groups and bicarbonate ligands to achieve nearly 100% sorption of said actinyl ion onto said resin and an aqueous system practically free of said actinyl ions. The method is operational over an extensive range of concentrations from about 10/sup -6/ M to 1.0 M actinyl ion and a pH range of about 4 to 7. The method has particulr application to treatment of waste streams from Purex-type nuclear fuel reprocessing facilities and hydrometallurgical processes involving U, Np, P, or Am.

Fluorescence-based Sensing of 2,4,6-Trinitrotoluene (TNT) Using a Multi-channeled Poly(methyl methacrylate) (PMMA) Microimmunosensor

DTIC Science & Technology

2010-01-22

Davidson, Y.Y.; McWhorter, C.S.; Soper , S.A.; McCarley, R.L. Surface modification of poly(methyl methacrylate) used in the fabrication of microanalytical...J.; Hupert, M.L.; Patterson, D.; Gottert, J.; McCarley, R.L.; Nikitopoulos, D.; Murphy, M.C.; Soper , S.A. Highly efficient circulating tumor cell

Nonchemically amplified resists for deep-UV lithography

NASA Astrophysics Data System (ADS)

Ganesan, Ramakrishnan; Kim, Sumin; Youn, Seul Ki; Cho, Youngook; Yun, Jei-Moon; Kim, Jin-Baek

2007-03-01

A novel monomer containing a diazoketo functional group was designed and synthesized. Polymers were synthesized using the diazoketo-functionalized monomer and their physical properties were evaluated. The polymers were synthesized by radical copolymerization of cholic acid 3-diazo-3-ethoxycarbonyl-2-oxo-propyl ester methacrylate, methyl methacrylate, and γ-butyrolacton-2-yl methacrylate. These polymers showed 0.7 μm line and space patterns using a mercury-xenon lamp in a contact printing mode.

Preparation and Characterization of Mesoporous Zirconia Made by Using a Poly (methyl methacrylate) Template

NASA Astrophysics Data System (ADS)

Duan, Guorong; Zhang, Chunxiang; Li, Aimei; Yang, Xujie; Lu, Lude; Wang, Xin

2008-03-01

Superfine powders of poly (methyl methacrylate) (PMMA) have been prepared by means of an emulsion polymerization method. These have been used as templates in the synthesis of tetragonal phase mesoporous zirconia by the sol gel method, using zirconium oxychloride and oxalic acid as raw materials. The products have been characterized by infrared spectroscopy, X-ray diffraction analysis, transmission electron microscopy, N2 adsorption-desorption isotherms, and pore size distribution. The results indicate that the average pore size was found to be 3.7 nm.

Poly(styrene-co-N-methacryloyl-l-phenylalanine methyl ester)-functionalized magnetic nanoparticles as sorbents for the analysis of sodium benzoate in beverages.

PubMed

Ji, Shilei; Li, Nan; Qi, Li; Wang, Minglin

2017-01-01

In this study, poly(styrene-co-N-methacryloyl-l-phenylalanine methyl ester)-functionalized magnetic nanoparticles were constructed and used as magnetic solid-phase extraction sorbents for analysis of food preservatives in beverages. To prepare the poly(amino acid)-based sorbents, N-methacryloyl-l-phenylalanine methyl ester, and styrene served as the functional monomers and modified onto the magnetic nanoparticles via free radical polymerization. Interestingly, compared with propylparaben and potassium sorbate, the proposed poly(amino acid)-based sorbents showed a good selectivity to sodium benzoate. The adsorption capacity of the sorbents to sodium benzoate was 6.08 ± 0.31 mg/g. Moreover, the fast adsorption equilibrium could be reached within 5 min. Further, the resultant poly(amino acid)-based sorbents were applied in the analysis of sodium benzoate in real beverage samples. The results proved that the proposed magnetic solid-phase extraction sorbents have a great potential for the analysis of preservatives in food samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pyrogallol-imprinted polymers with methyl methacrylate via precipitation polymerization

NASA Astrophysics Data System (ADS)

Mehamod, Faizatul Shimal; Othman, Nor Amira; Bulat, Ku Halim Ku; Suah, Faiz Bukhari Mohd

2018-06-01

Molecular simulation techniques are important to study the understanding of chemical and physical properties of any material. Computational modeling is considered as time reducer in finding the best recipes for Molecularly-Imprinted Polymers (MIPs). In this study, Pyrogallol-imprinted polymers (PIP) and non-imprinted polymers (NIPs) were synthesized via precipitation polymerization using Pyrogallol (Py), methyl methacrylate (MMA), divinylbenzene (DVB) as template, functional monomer and cross-linker, respectively. The recipe was according to the results from computational techniques. The synthesized PIP and NIPs were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) and UV-visible spectroscopy (UV-vis). Studies on adsorption isotherm showed that PIP and NIPs follow Scatchard isotherm models. Sorption kinetic study found that PIP and NIPs follow pseudo-second order which indicates the rate-limiting step is the surface adsorption. The imprinting factor of PIP was determined by selectivity study and showed the value of k >1, which proved that PIP was selective toward Pyrogallol compared to NIP.

Tensile strength and water absorption of alumina filled poly (methyl methacrylate) denture base material.

PubMed

Nizam, A; Mohamed, S H; Arifin, A; Mohd Ishak, Z A; Samsudin, A R

2004-05-01

The aim of this study was to evaluate the tensile properties and water absorption of denture base material prepared from high molecular weight poly methyl methacrylate (PMMA) and alumina (Al2O3) as particulate filler. Specimens for mechanical testing were prepared by adding composite powder to the monomer followed by hand mixing as in dental laboratory procedure. The tensile strength of the prepared denture base material was slightly higher than commercial denture base material, while the water absorption was almost the same for all formulation of denture base materials.

Temperature-responsive copolymeric hydrogel systems synthetized by ionizing radiation

NASA Astrophysics Data System (ADS)

López-Barriguete, Jesús Eduardo; Bucio, Emilio

2017-06-01

Eight different systems of hydrogel copolymers with diverse temperature responsiveness were prepared to elaborate membranes for their biomedical application. The hydrogels were synthesized using poly(N-isopropylacrylamide) (PNIPAAm) and poly(N-vinylcaprolactam) (PNVCL), which have a low critical solution temperature (LCST) close to that of the human body temperature. The networks were synthesized using gamma radiation at a dose rate of 11.2 kGy h-1, and dose of 50 kGy. The LCST of each system was measured by differential scanning calorimetry (DSC). The effect of using hydrophilic monomers of acrylic acid (AAc), methacrylic acid (MAAc), dimethyl acrylamide (DMAAm), and hydroxyethyl methacrylate (HEMA) for the copolymerization on the critical point was evaluated. Five viable systems were obtained, with the best hydrogel being that of poly(NIPAAm-co-DMAAm), which an LCST at 39.8 °C. All the samples were characterized by FTIR-ATR, DSC, TGA, X-Ray Diffraction, and SEM. The proportion of monomers during the formation of the copolymers was decisive in the displacement of the LCST.

Generalized peripheral neuropathy in a dental technician exposed to methyl methacrylate monomer

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

Donaghy, M.; Rushworth, G.; Jacobs, J.M.

1991-07-01

A 58-year-old dental prosthetic technician developed generalized sensorimotor peripheral neuropathy. Neurophysiologic studies showed a generalized sensorimotor neuropathy of axonal degeneration type. Examination of a sural nerve biopsy showed a moderately severe axonal neuropathy with loss of large myelinated fibers and unmyelinated axons. There was evidence of slow ongoing degeneration and considerable fiber regeneration. Electron microscopy showed increased numbers of filaments in a few fibers. These findings show resemblances to the nerve changes caused by another acrylic resin, acrylamide. They suggest that the neuropathy may have been caused by 30 years of occupational cutaneous and inhalational exposure to methyl methacrylate monomermore » since they excluded other recognized causes of neuropathy.« less

Raman spectra of bilayer graphene covered with Poly(methyl methacrylate) thin film

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

Xia Minggang; Center on Experimental Physics, School of Science, Xi'an Jiaotong University, 710049; Su Zhidan

The Raman spectra of bilayer graphene covered with poly(methyl methacrylate) (PMMA) were investigated. Both the G and 2D peaks of PMMA-coated graphene were stiff and broad compared with those of uncovered graphene. This could be attributed to the residual strain induced by high-temperature baking during fabrication of the nanodevice. Furthermore, the two 2D peaks stiffened and broadened with increasing laser power, which is just the reverse to uncovered graphene. The stiffness is likely caused by graphene compression induced by the circular bubble of the thin PMMA film generated by laser irradiation. Our findings may contribute to the application of PMMAmore » in the strain engineering of graphene nanodevices.« less

Early stages of styrene-isoprene copolymerization in gas phase clusters probed by resonance enhanced multiphoton ionization.

PubMed

Mahmoud, Hatem; Germanenko, Igor N; El-Shall, M Samy

2006-04-06

We present direct evidence for the formation of the covalent bonded styrene (isoprene)(2) oligomer and the isoprene dimer ions following resonance ionization of the gas phase styrene-isoprene binary clusters. The application of resonance ionization to study polymerization reactions in clusters provides new information on the structure and mechanism of formation of the early stages of polymerization and holds considerable promise for the discovery of new initiation mechanisms and for the development of novel materials with unique properties.

Bioinspired Hydroxyapatite/Poly(methyl methacrylate) Composite with a Nacre-Mimetic Architecture by a Bidirectional Freezing Method.

PubMed

Bai, Hao; Walsh, Flynn; Gludovatz, Bernd; Delattre, Benjamin; Huang, Caili; Chen, Yuan; Tomsia, Antoni P; Ritchie, Robert O

2016-01-06

Using a bidirectional freezing technique, combined with uniaxial pressing and in situ polymerization, "nacre-mimetic" hydroxyapatite/poly(methyl methacrylate) (PMMA) composites are developed by processing large-scale aligned lamellar ceramic scaffolds. Structural and mechanical characterization shows "brick-and-mortar" structures, akin to nacre, with interesting combinations of strength, stiffness, and work of fracture, which provide a pathway to making strong and tough lightweight materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radiation-grafted proton exchange membranes based on co-grafting from binary monomer mixtures into poly(ethylene-co-tetrafluoroethylene) (ETFE) film

NASA Astrophysics Data System (ADS)

Sohn, Joon-Yong; Sung, Hae-Jun; Song, Joo-Myung; Shin, Junhwa; Nho, Young-Chang

2012-08-01

In this study, proton exchange membranes (PEMs) based on a poly(ethylene-co-tetrafluoroethylene) (ETFE) film were synthesized through the graft copolymerization of styrene and VTMS (vinyltrimethoxysilane), or styrene and TMSPM (3-(trimethoxysilyl) propyl methacrylate) binary monomer systems using a simultaneous irradiation method. The prepared membranes with the similar degrees of grafting were investigated by measuring ion exchange capacity, proton conductivity, water uptake, chemical stability, and dimensional stability. The results indicate that the silane-crosslinked proton exchange membrane (PEM) has not only lower water uptake and dimensional change but also high proton conductivity at low humidity condition compared to non-crosslinked poly(ethylene-co-tetrafluoroethylene)-g-poly(styrene sulfonic acid) (ETFE-g-PSSA). Also, the chemical stability of silane-crosslinked fuel cell membranes was more improved than that of non-crosslinked fuel cell membrane.

Flexible poly(methyl methacrylate)-based neural probe: An affordable implementation

NASA Astrophysics Data System (ADS)

Gasemi, Pejman; Veladi, Hadi; Shahabi, Parviz; Khalilzadeh, Emad

2018-03-01

This research presents a novel technique used to fabricate a deep brain stimulation probe based on a commercial poly(methyl methacrylate) (PMMA) polymer. This technique is developed to overcome the high cost of available probes crucial for chronic stimulation and recording in neural disorders such as Parkinson’s disease and epilepsy. The probe is made of PMMA and its mechanical properties have been customized by controlling the reaction conditions. The polymer is adjusted to be stiff enough to be easily inserted and, on the other hand, soft enough to perform required movements. As cost is one of the issues in the use of neural probes, a simple process is proposed for the production of PMMA neural probes without using expensive equipment and operations, and without compromising performance and quality. An in vivo animal test was conducted to observe the recording capability of a PMMA probe.

Affinity monolith-integrated poly(methyl methacrylate) microchips for on-line protein extraction and capillary electrophoresis.

PubMed

Sun, Xiuhua; Yang, Weichun; Pan, Tao; Woolley, Adam T

2008-07-01

Immunoaffinity monolith pretreatment columns have been coupled with capillary electrophoresis separation in poly(methyl methacrylate) (PMMA) microchips. Microdevices were designed with eight reservoirs to enable the electrically controlled transport of selected analytes and solutions to carry out integrated immunoaffinity extraction and electrophoretic separation. The PMMA microdevices were fabricated reproducibly and with high fidelity by solvent imprinting and thermal bonding methods. Monoliths with epoxy groups for antibody immobilization were prepared by direct in situ photopolymerization of glycidyl methacrylate and ethylene glycol dimethacrylate in a porogenic solvent consisting of 70% 1-dodecanol and 30% cyclohexanol. Antifluorescein isothiocyanate was utilized as a model affinity group in the monoliths, and the immobilization process was optimized. A mean elution efficiency of 92% was achieved for the monolith-based extraction of fluorescein isothiocyanate (FITC)-tagged human serum albumin. FITC-tagged proteins were purified from a contaminant protein and then separated electrophoretically using these devices. The developed immunoaffinity column/capillary electrophoresis microdevices show great promise for combining sample pretreatment and separation in biomolecular analysis.

Affinity Monolith-Integrated Poly(methyl Methacrylate) Microchips for On-Line Protein Extraction and Capillary Electrophoresis

PubMed Central

Sun, Xiuhua; Yang, Weichun; Pan, Tao; Woolley, Adam T.

2008-01-01

Immunoaffinity monolith pretreatment columns have been coupled with capillary electrophoresis separation in poly(methyl methacrylate) (PMMA) microchips. Microdevices were designed with 8 reservoirs to enable the electrically controlled transport of selected analytes and solutions to carry out integrated immunoaffinity extraction and electrophoretic separation. The PMMA microdevices were fabricated reproducibly and with high fidelity by solvent imprinting and thermal bonding methods. Monoliths with epoxy groups for antibody immobilization were prepared by direct in-situ photopolymerization of glycidyl methacrylate and ethylene dimethacrylate in a porogenic solvent consisting of 70% dodecanol and 30% hexanol. Anti-fluorescein isothiocyanate (FITC) was utilized as a model affinity group in the monoliths, and the immobilization process was optimized. A mean elution efficiency of 92% was achieved for the monolith-based extraction of FITC-tagged human serum albumin. FITC-tagged proteins were purified from a contaminant protein and then separated electrophoretically using these devices. The developed immunoaffinity column/capillary electrophoresis microdevices show great promise for combining sample pretreatment and separation in biomolecular analysis. PMID:18479142

Analysis of the Hazardous Material Reutilization Facilities at SUBASE Bangor and NS San Diego

DTIC Science & Technology

1990-12-01

soprene * styrene methyl acrylate methyl methacrylate *turpentine? varnish 9 GROUP IV: OXIDES AND PEROXIDE -rORKING COMPOUNDS a) Gases b) Liquids...lead fluorine GROUP XV: POISON a GROUP XVI: OXIDIZERS .a) Solid a) Solid phosphorus red ammonium nitrate phosphorus white/, ammonium perchlorate yellow

TiO2 Nanowires/Poly(Methyl Methacrylate) Based Hybrid Photodetector: Improved Light Detection.

PubMed

Saha, S; Mondal, A; Choudhur, B; Goswami, T; Sarkar, M B; Chattopadhyay, K K

2016-03-01

Hybrid photodetector with a maximum external quantum efficiency of ~3.08% in the UV region at 370 nm, was fabricated by spin-coated poly(methyl methacrylate) (PMMA) polymer onto glancing angle deposited (GLAD) vertically aligned TiO2 nanowire (NW) arrays. The TiO2 NWs/PMMA detector shows excellent rectification and constant 1.3 times photo-responsivity in the reverse bias condition from -1 V to -10 V. The photodiode possesses a low ideality factor of 5.1 as compared to bared TiO2 NWs device of 7.1. The hybrid device produces sharp turn-on of -0.8 s and turn-off transient of -0.9 s respectively.

Manufacture of poly(methyl methacrylate) microspheres using membrane emulsification

PubMed Central

Bux, Jaiyana; Manga, Mohamed S.; Hunter, Timothy N.

2016-01-01

Accurate control of particle size at relatively narrow polydispersity remains a key challenge in the production of synthetic polymer particles at scale. A cross-flow membrane emulsification (XME) technique was used here in the preparation of poly(methyl methacrylate) microspheres at a 1–10 l h−1 scale, to demonstrate its application for such a manufacturing challenge. XME technology has previously been shown to provide good control over emulsion droplet sizes with careful choice of the operating conditions. We demonstrate here that, for an appropriate formulation, equivalent control can be gained for a precursor emulsion in a batch suspension polymerization process. We report here the influence of key parameters on the emulsification process; we also demonstrate the close correlation in size between the precursor emulsion and the final polymer particles. Two types of polymer particle were produced in this work: a solid microsphere and an oil-filled matrix microcapsule. This article is part of the themed issue ‘Soft interfacial materials: from fundamentals to formulation’. PMID:27298430

Preparation of Tea Tree Oil/Poly(styrene-butyl methacrylate) Microspheres with Sustained Release and Anti-Bacterial Properties

PubMed Central

Lin, Guanquan; Chen, Huayao; Zhou, Hongjun; Zhou, Xinhua; Xu, Hua

2018-01-01

Using butyl methacrylate (BMA) and styrene (St) as monomers and divinylbenzene (DVB) as a crosslinking agent, P(St-BMA) microspheres were prepared by suspension polymerization. Tea tree oil (TTO) microspheres were prepared by adsorbing TTO on P(St-BMA) microspheres. The structure and surface morphology of P(St-BMA) microspheres and TTO microspheres were characterized by Fourier transformed infrared spectroscopy (FTIR), optical microscopy, and Thermogravimetric analysis (TGA). In doing so, the structural effect of P(St-BMA) microspheres on oil absorption and sustained release properties could be investigated. The results show that the surface of the P(St-BMA) microspheres in the process of TTO microsphere formation changed from initially concave to convex. The TTO microspheres significantly improved the stability of TTO, which was found to completely decompose as the temperature of the TTO increased from about 110 °C to 150 °C. The oil absorption behavior, which was up to 3.85 g/g, could be controlled by adjusting the monomer ratio and the amount of crosslinking agent. Based on Fickian diffusion, the sustained release behavior of TTO microspheres was consistent with the Korsmeyer-Pappas kinetic model. After 13 h of natural release, the anti-bacterial effect of the TTO microspheres was found to be significantly improved compared to TTO. PMID:29723967

On the degelation of networks – Case of the radiochemical degradation of methyl methacrylate – ethylene glycol dimethacrylate copolymers

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

Richaud, Emmanuel; Gilormini, Pierre; Verdu, Jacques

2016-05-18

Methyl methacrylate networks were synthetized and submitted to radiochemical degradation. Ageing was monitored by means of sol-gel analysis and glass transition temperature measurements. Networks were shown to undergo exclusively chain scission process leading to the degelation of network. The critical conversion degree corresponding to degelation (loss of all elastically active chains) is discussed regarding a statistical theory.

Review of methyl methacrylate (MMA)/tributylborane (TBB)-initiated resin adhesive to dentin.

PubMed

Taira, Yohsuke; Imai, Yohji

2014-01-01

This review, focusing mainly on research related to methyl methacrylate/tributylborane (MMA/TBB) resin, presents the early history of dentin bonding and MMA/TBB adhesive resin, followed by characteristics of resin bonding to dentin. Bond strengths of MMA/TBB adhesive resin to different adherends were discussed and compared with other bonding systems. Factors affecting bond strength (such as conditioners, primers, and medicaments used for dental treatment), bonding mechanism, and polymerization characteristics of MMA/TBB resin were also discussed. This review further reveals the unique adhesion features between MMA/TBB resin and dentin: in addition to monomer diffusion into the demineralized dentin surface, graft polymerization of MMA onto dentin collagen and interfacial initiation of polymerization at the resin-dentin interface provide the key bonding mechanisms.

Study of two cohorts of workers exposed to methyl methacrylate in acrylic sheet production

PubMed Central

Tomenson, J; Bonner, S; Edwards, J; Pemberton, M; Cummings, T; Paddle, G

2000-01-01

OBJECTIVES—To study mortality among 4324 workers at two United Kingdom factories, Darwen, Lancashire and Wilton, Cleveland, producing polymethyl methacrylate (PMMA) sheet. The Darwen factory is still active, but the Wilton one was closed in 1970. Also, to investigate patterns of mortality after exposure to methyl methacrylate; in particular, mortality from colon and rectal cancer.
METHODS—All male employees at the Darwen factory with a record of employment in 1949-88 and all men ever employed at the Wilton factory (1949-70) were investigated. The vital status of both cohorts was ascertained on 31 December 1995. The exposure of 1526 subjects at the Darwen plant who were engaged from 1949 onwards could be characterised. The mean duration of exposure was 7.6 years at 13.2 ppm (8 hour time weighted average), although exposures in some work groups were as high as 100 ppm. It was not possible to calculate the cumulative exposure of workers first employed at the Darwen plant before 1949 or workers at the Wilton factory.
RESULTS—In the Darwen cohort, 622 deaths were identified and a further 700 deaths in the Wilton cohort. Mortalities for the cohort were compared with national and local rates and expressed as standardised mortality ratios (SMRs). In the subcohort of Darwen workers with more than minimal exposure to MMA, reduced mortalities compared with national and local rates, were found for all causes (SMR 94), and colorectal cancer (SMR 92), but mortality from all cancers was slightly increased (SMR 104). No relations were found with cumulative exposure to MMA. In the subcohort of Wilton workers, mortality from all causes of death was significantly reduced (SMR 89), but mortality from all cancers (SMR 103) and colorectal cancer (SMR 124) were increased. The excess of colorectal cancer was confined to employees with less than 1 year of employment.
CONCLUSION—The study provided no clear evidence that employment at the factories or exposure to

Increased cellular uptake of lauryl gallate loaded in superparamagnetic poly(methyl methacrylate) nanoparticles due to surface modification with folic acid.

PubMed

Feuser, Paulo Emilio; Arévalo, Juan Marcelo Carpio; Junior, Enio Lima; Rossi, Gustavo Rodrigues; da Silva Trindade, Edvaldo; Rocha, Maria Eliane Merlin; Jacques, Amanda Virtuoso; Ricci-Júnior, Eduardo; Santos-Silva, Maria Claudia; Sayer, Claudia; de Araújo, Pedro H Hermes

2016-12-01

Lauryl gallate loaded in superparamagnetic poly(methyl methacrylate) nanoparticles surface modified with folic acid were synthesized by miniemulsion polymerization in just one step. In vitro biocompatibility and cytotoxicity assays on L929 (murine fibroblast), human red blood, and HeLa (uterine colon cancer) cells were performed. The effect of folic acid at the nanoparticles surface was evaluated through cellular uptake assays in HeLa cells. Results showed that the presence of folic acid did not affect substantially the polymer particle size (~120 nm), the superparamagnetic behavior, the encapsulation efficiency of lauryl gallate (~87 %), the Zeta potential (~38 mV) of the polymeric nanoparticles or the release profile of lauryl gallate. The release profile of lauryl gallate from superparamagnetic poly(methyl methacrylate) nanoparticles presented an initial burst effect (0-1 h) followed by a slow and sustained release, indicating a biphasic release system. Lauryl gallate loaded in superparamagnetic poly(methyl methacrylate) nanoparticles with folic acid did not present cytotoxicity effects on L929 and human red blood cells. However, free lauryl gallate presented significant cytotoxic effects on L929 and human red blood cells at all tested concentrations. The presence of folic acid increased the cytotoxicity of lauryl gallate loaded in nanoparticles on HeLa cells due to a higher cellular uptake when HeLa cells were incubated at 37 °C. On the other hand, when the nanoparticles were incubated at low temperature (4 °C) cellular uptake was not observed, suggesting that the uptake occurred by folate receptor mediated energy-dependent endocytosis. Based on presented results our work suggests that this carrier system can be an excellent alternative in targeted drug delivery by folate receptor.

Atomic Level Cleaning of Poly Methyl Methacrylate Residues from the Graphene Surface Using Radiolized Water at High Temperatures (Postprint)

DTIC Science & Technology

2017-09-05

AFRL-RX-WP-JA-2017-0321 ATOMIC LEVEL CLEANING OF POLY-METHYL- METHACRYLATE RESIDUES FROM THE GRAPHENE SURFACE USING RADIOLIZED WATER AT...N. Zakharov and Eric A. Stach Brookhaven National Laboratory Jennifer Carpena-Nunez National Research Council 9 March 2017 Interim Report...Distribution Statement A. Approved for public release: distribution unlimited. © 2017 AIP PUBLISHING (STINFO COPY) AIR FORCE RESEARCH

Methyl methacrylate and respiratory sensitization: A Critical review

PubMed Central

Borak, Jonathan; Fields, Cheryl; Andrews, Larry S; Pemberton, Mark A

2011-01-01

Methyl methacrylate (MMA) is a respiratory irritant and dermal sensitizer that has been associated with occupational asthma in a small number of case reports. Those reports have raised concern that it might be a respiratory sensitizer. To better understand that possibility, we reviewed the in silico, in chemico, in vitro, and in vivo toxicology literature, and also epidemiologic and occupational medicine reports related to the respiratory effects of MMA. Numerous in silico and in chemico studies indicate that MMA is unlikely to be a respiratory sensitizer. The few in vitro studies suggest that MMA has generally weak effects. In vivo studies have documented contact skin sensitization, nonspecific cytotoxicity, and weakly positive responses on local lymph node assay; guinea pig and mouse inhalation sensitization tests have not been performed. Cohort and cross-sectional worker studies reported irritation of eyes, nose, and upper respiratory tract associated with short-term peaks exposures, but little evidence for respiratory sensitization or asthma. Nineteen case reports described asthma, laryngitis, or hypersensitivity pneumonitis in MMA-exposed workers; however, exposures were either not well described or involved mixtures containing more reactive respiratory sensitizers and irritants.The weight of evidence, both experimental and observational, argues that MMA is not a respiratory sensitizer. PMID:21401327

Effect of Mesoporous Diatomite Particles on the Kinetics of SR&NI ATRP of Styrene and Butyl Acrylate

NASA Astrophysics Data System (ADS)

Khezri, Khezrollah; Ghasemi, Moosa; Fazli, Yousef

2018-05-01

Mesoporous diatomite particles were employed to prepare different poly(styrene-co-butyl acrylate)/diatomite nanocomposites. Diatomite nanoplatelets were used for in situ copolymerization of styrene and butyl acrylate by SR&NI ATRP to synthesize well-defined poly(styrene-co-butyl acrylate) nanocomposites. Nitrogen adsorption/desorption isotherm is applied to examine surface area and structural characteristics of the diatomite nanoplatelets. Evaluation of pore size distribution and morphological studies were also performed by SEM and TEM. Conversion and molecular weight determinations were carried out using gas and size exclusion chromatography respectively. Addition of 3 wt% pristine mesoporous diatomite nanoplatelets leads to increase of conversion from 73 to 89%. Molecular weight of poly(styrene-co-butyl acrylate) chains increases from 17,115 to 20,343 g·mol-1 by addition of 3 wt% pristine mesoporous diatomite; however, polydispersity index values increases from 1.14 to 1.37. Increasing thermal stability of the nanocomposites is demonstrated by TGA. Differential scanning calorimetry shows an increase in glass transition temperature from 35.26 to 39.61°C by adding 3 wt% of mesoporous diatomite nanoplatelets.

Bacillus sp. PS35 Lipase-Immobilization on Styrene-Divinyl Benzene Resin and Application in Fatty Acid Methyl Ester Synthesis.

PubMed

Palanisamy, Kanmani; Kuppamuthu, Kumaresan; Jeyaseelan, Aravind

2015-09-01

Lipase is an enzyme with immense application potential. Ester synthesis by lipase catalysis in organic media is an area of key industrial relevance. Enzymatic preparations with traits that cater to the needs of this function are hence being intensely researched. The objectives of the study were to immobilize the lipase from Bacillus sp. PS35 by cross-linking and adsorption onto styrene-divinyl benzene (Sty-Dvb) hydrophobic resin and to comparatively characterize the free and immobilized lipase preparations. The work also aimed to apply the immobilized lipase for catalysing the fatty acid methyl ester (FAME) synthesis from palm oil and optimize the process parameters for maximizing the yield. In this study, the purified lipase from Bacillus sp. PS35 was immobilized by adsorption onto styrene-divinyl benzene hydrophobic resin with gluteraldehyde cross-linking. The immobilized enzyme showed better pH and temperature stabilities than the free lipase. Organic solvent stability was also enhanced, with the relative activity in the presence of methanol being shifted from 53% to 81%, thereby facilitating the enzyme's application in fatty acid methyl ester synthesis. It exhibited remarkable storage stability over a 30-day period and after 20 repetitive uses. Cross-linking also reduced enzyme leakage by 49%. The immobilized lipase was then applied for biodiesel production from palm oil. Methanol and oil molar ratio of 5:1, three step methanol additions, and an incubation temperature of 50°C were established to be the ideal conditions favoring the transesterification reaction, resulting in 97% methyl ester yield. These promising results offer scope for further investigation and process scale up, permitting the enzyme's commercial application in a practically feasible and economically agreeable manner.

Carbon nanotube-poly(methyl methacrylate) hybrid films: preparation using diazonium salt chemistry and mechanical properties.

PubMed

Mammeri, Fayna; Teyssandier, Joan; Darche-Dugaret, Clément; Debacker, Sabine; Le Bourhis, Eric; Chehimi, Mohamed Mehdi

2014-11-01

The poor miscibility of carbon nanotubes (CNTs) in common organic solvents and organic monomers requires their modification by suitable functional (reactive or not) groups prior to their incorporation in thermoplastic polymers. Dispersion behavior of carbon nanotubes and mechanical properties of various CNT-poly(methylmethacrylate) (PMMA) nanocomposites were investigated. We studied the influence of the surface chemistry through the use of diazonium salts as an elegant and environmentally friendly platform to provide a suitable sidewall functionalization by methyl methacrylate functions. We used either a molecular size functional group through the grafting of methacryloxypropyltrimethoxysilane or a macromolecular size one, consisting in PMMA brushes grown by SI-ATRP in order to study the influence of the length of methacrylate function on the dispersion of CNT in PMMA. The hardness and the elastic indentation modulus of all hybrid films were obtained through nanoindentation measurements and found to increase, using ATRP-modified CNTs, suggesting a better dispersion of CNTs in PMMA due to optimal inorganic-organic interactions promoted by the short chains of PMMA. Copyright © 2014 Elsevier Inc. All rights reserved.

Dielectric and optical study of poly (methyl methacrylate) (PMMA) / Fe2O3 films

NASA Astrophysics Data System (ADS)

Anita, Chimankar, O. P.; Bansod, A. R.; Sannakki, Basavaraja

2013-06-01

Organic/inorganic polymer composite films containing poly (methyl-methacrylate) (PMMA)/ ferric oxide Fe2O3 were prepared following solution casting technique. Dielectric Properties of films has been studied using LCR meter at room temperature 26°C. Also optical properties have been studied using digital abbey refractometer. The dielectric behavior of films have been studied as a function of concentration, and at lower frequencies over the range 100 Hz-25 KHz, The results elucidate that 70:30 and 50:50 wt% of PMMA/Fe2O3 composite films posses optimal conducting properties due to observed electronic polarisability dip at 40Wt% of Fe2O3.

Synthesis of [.sup.13C] and [.sup.2H] substituted methacrylic acid, [.sup.13C] and [.sup.2H] substituted methyl methacrylate and/or related compounds

DOEpatents

Alvarez, Marc A [Santa Fe, NM; Martinez, Rodolfo A [Santa Fe, NM; Unkefer, Clifford J [Los Alamos, NM

2008-01-22

The present invention is directed to labeled compounds of the formulae ##STR00001## wherein Q is selected from the group consisting of --S--, --S(.dbd.O)--, and --S(.dbd.O).sub.2--, Z is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group selected from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each independently selected from the group consisting of a C.sub.1-C.sub.4 lower alkyl, an aryl, and an alkoxy group, and X is selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl group, and a fully-deuterated C.sub.1-C.sub.4 lower alkyl group. The present invention is also directed to a process of preparing labeled compounds, e.g., process of preparing [.sup.13C]methacrylic acid by reacting a (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13CH.sub.2)-- aryl sulfone precursor with .sup.13CHI to form a (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13C(.sup.13CH.sub.3).sub.2)-- aryl sulfone intermediate, and, reacting the (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13C(.sup.13CH.sub.3).sub.2)-- aryl sulfone intermediate with sodium hydroxide, followed by acid to form [.sup.13C]methacrylic acid. The present invention is further directed to a process of preparing [.sup.2H.sub.8]methyl methacrylate by reacting a (HOOC--C(C.sup.2H.sub.3).sub.2-- aryl sulfinyl intermediate with CD.sub.3I to form a (.sup.2H.sub.3COOC--C(C.sup.2H.sub.3).sub.2)-- aryl sulfinyl intermediate, and heating the(.sup.2H.sub.3COOC--C(C.sup.2H.sub.3).sub.2)-- aryl sulfinyl intermediate at temperatures and for time sufficient to form [.sup.2H.sub.8]methyl methacrylate.

Sub-5 nm Domains in Ordered Poly(cyclohexylethylene)-block-poly(methyl methacrylate) Block Polymers for Lithography.

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

Kennemur, Justin; Yao, Li; Bates, Frank Stephen

2014-01-01

A series of poly(cyclohexylethylene)-block-poly- (methyl methacrylate) (PCHE PMMA) diblock copolymers with varying molar mass (4.9 kg/mol Mn 30.6 kg/mol) and narrow molar mass distribution were synthesized through a combination of anionic and atom transfer radical polymerization (ATRP) techniques. Heterogeneous catalytic hydrogenation of -(hydroxy)polystyrene (PS-OH) yielded -(hydroxy)poly(cyclohexylethylene) (PCHEOH) with little loss of hydroxyl functionality. PCHE-OH was reacted with -bromoisobutyryl bromide (BiBB) to produce an ATRP macroinitiator used for the polymerization of methyl methacrylate. PCHE PMMA is a glassy, thermally stable material with a large effective segment segment interaction parameter, eff = (144.4 6.2)/T (0.162 0.013), determined by meanfield analysis of order-to-disordermore » transition temperatures (TODT) measured by dynamic mechanical analysis and differential scanning calorimetry. Ordered lamellar domain pitches (9 D 33 nm) were identified by small-angle X-ray scattering from neat BCPs containing 43 52 vol % PCHE ( f PCHE). Atomic force microscopy was used to show 7.5 nm lamellar features (D = 14.8 nm) which are some of the smallest observed to date. The lowest molar mass sample (Mn = 4.9 kg/mol, f PCHE = 0.46) is characterized by TODT = 173 3 C and sub-5 nm nanodomains, which together with the sacrificial properties of PMMA and the high overall thermal stability place this material at the forefront of high- systems for advanced nanopatterning applications.« less

Simple, green, and clean removal of a poly(methyl methacrylate) film on chemical vapor deposited graphene

NASA Astrophysics Data System (ADS)

Park, J.-H.; Jung, W.; Cho, D.; Seo, J.-T.; Moon, Y.; Woo, S. H.; Lee, C.; Park, C.-Y.; Ahn, J. R.

2013-10-01

The clean removal of a poly(methyl methacrylate) (PMMA) film on graphene has been an essential part of the process of transferring chemical vapor deposited graphene to a specific substrate, influencing the quality of the transferred graphene. Here we demonstrate that the clean removal of PMMA can be achieved by a single heat-treatment process without the chemical treatment that was adopted in other methods of PMMA removal. The cleanness of the transferred graphene was confirmed by four-point probe measurements, synchrotron radiation x-ray photoemission spectroscopy, optical images, and Raman spectroscopy.

Preparation and characterization of poly(methyl methacrylate) and poly(maleic anhydride-co-diallyl phthalate) grafted carbon black through γ-ray irradiation

NASA Astrophysics Data System (ADS)

Bo, Yang; Cui, Jiayang; Cai, Yangben; Xu, Shiai

2016-02-01

In this study, the grafting polymerization of methyl methacrylate (MMA) monomer and maleic anhydride/diallyl phthalate (MAH/DAP) co-monomer onto the surface of carbon black (CB) were carried out at room temperature and normal pressure by γ-ray irradiation. The surface chemistry of grafted CBs were characterized by infrared spectroscopy (IR), thermo-gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The results show that there are some remanent polymers on the surface of modified CBs after extract for 48 h, indicating that poly(methyl methacrylate) (PMMA) and poly(MAH-co-DAP) have been successfully grafted onto the surface of CB without using initiator due to the high energy of γ-ray irradiation. Dynamic light scattering (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) reveal that the grafted CBs have smaller average aggregate size and better dispersibility than that of CB in absolute ethanol. In addition, it was found that the amount of oxygen groups and the irradiation doses/dose rates have little effect on the grafting degree of CB.

Volatile methacrylates in dental practices.

PubMed

Marquardt, Wolfgang; Seiss, Mario; Hickel, Reinhard; Reichl, Franz X

2009-04-01

In recent years, an increase of occupational respiratory diseases, such as asthma caused by methacrylates, has been observed in dental personnel. In this study, the exposure of dental personnel to various volatile methacrylates was investigated. The air levels of methacrylates were measured during filling treatment while bonding agents were used in 4 dental practices in Munich, Germany. Short-term air sampling (15 min) was performed using solid phase microextraction (SPME). The SPME fibers were coated with carbowax/divinyl benzene to enrich the analytes. For analysis, the analytes were thermically desorbed from the fiber and subsequently analyzed directly by gas chromatography/mass spectrometry. The methacrylates methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (HEMA), ethylene glycol dimethacrylate (EGDMA), and triethylene glycol dimethacrylate (TEG-DMA) were identified in the air of dental practices. The exposure levels of the four methacrylates varied during the filling treatments. The maximum concentrations found were 0.4 mg/m3 for MMA, 45 microg/m3 for HEMA, 13 microg/m3 for EGDMA, and 45 microg/m3 for TEG-DMA. The detection of TEG-DMA correlated with the application of bonding agents during performance of dental fillings. Exposure levels of different methacrylates were observed at all investigated dental practices. The maximum levels of MMA measured in this study were at least 200 times lower than the toxicologically relevant maximum allowable concentrations defined in various countries. Nevertheless, the exposure levels of methacrylates should be kept as low as possible due to the allergenic potential of some methacrylates.

A mechanistic investigation on copolymerization of ethylene with polar monomers using a cyclophane-based Pd(II) alpha-diimine catalyst.

PubMed

Popeney, Chris S; Guan, Zhibin

2009-09-02

A detailed mechanistic investigation of the copolymerization of ethylene and methyl acrylate (MA) by a Pd(II) cyclophane-based alpha-diimine catalyst is reported. Our previous observations of unusually high incorporations of acrylates in copolymerization using this catalyst (J. Am. Chem. Soc. 2007, 129, 10062) prompted us to conduct a full mechanistic study on ethylene/MA copolymerization, which indicates a dramatic departure from normal Curtin-Hammett kinetic behavior as observed in copolymerization using the normal Brookhart type of Pd(II) alpha-diimine catalysts. Further investigation reveals that this contrasting behavior originates from the axial blocking effect of the cyclophane ligand hindering olefin substitution and equilibration. In equilibrium studies of ethylene with nitriles, the cyclophane catalyst was found to more strongly favor the linearly binding nitrile ligands as compared to the standard acyclic Pd(II) alpha-diimine catalysts. Ethylene exchange rates in the complexes [(N--N)PdMe(C(2)H(4))](+) (N--N = diimine) were measured by 2D EXSY NMR spectroscopy and found to be over 100 times slower in the cyclophane case. Measurement of the slow equilibration of ethylene, methyl acrylate, and 4-methoxystyrene in cyclophane-based Pd(II) olefin complexes by (1)H NMR and fitting of the obtained kinetic plots allowed for the estimation of exchange rates and equilibrium constants of the olefins. After extrapolation to typical polymerization temperature, DeltaG(double dagger) = 20.6 and 16.4 kcal/mol for ethylene-methyl acrylate exchange in the forward (ethylene displacement by methyl acrylate) and reverse directions, respectively. These values are of similar magnitude to the previously determined migratory insertion barriers of ethylene (DeltaG(double dagger) = 18.9 kcal/mol) and methyl acrylate (DeltaG(double dagger) = 16.3 kcal/mol) under equivalent conditions, but contrast strongly to the rapid olefin exchange seen in the Brookhart acyclic catalyst. The

Methyl methacrylate as a healing agent for self-healing cementitious materials

NASA Astrophysics Data System (ADS)

Van Tittelboom, K.; Adesanya, K.; Dubruel, P.; Van Puyvelde, P.; De Belie, N.

2011-12-01

Different types of healing agents have already been tested on their efficiency for use in self-healing cementitious materials. Generally, commercial healing agents are used while their properties are adjusted for manual crack repair and not for autonomous crack healing. Consequently, the amount of regain in properties due to self-healing of cracks is limited. In this research, a methyl methacrylate (MMA)-based healing agent was developed specifically for use in self-healing cementitious materials. Various parameters were optimized including the viscosity, curing time, strength, etc. After the desired properties were obtained, the healing agent was encapsulated and screened for its self-healing efficiency. The decrease in water permeability due to autonomous crack healing using MMA as a healing agent was similar to the results obtained for manually healed cracks. First results seem promising: however, further research needs to be undertaken in order to obtain an optimal healing agent ready for use in practice.

Optical characterization of poly(methyl methacrylate) implanted with low energy ions

NASA Astrophysics Data System (ADS)

Gupta, Renu; Kumar, Vijay; Goyal, Parveen Kumar; Kumar, Shyam

2012-12-01

The samples of poly(methyl methacrylate) (PMMA) were subjected to 100 keV N+ and Ar+ ion implantation up to a maximum fluence of 2 × 1016 ions/cm2. The effect of ion implantation on the optical energy gap and the refractive index has been studied through UV-visible spectroscopy. The results clearly indicate a decrease in the values of optical energy gap and an increase in the values of refractive index as an effect of ion implantation corresponding to both of the ions. It has also been observed that the changes induced by the implanted ions are more pronounced for N+ ions in comparison to Ar+ ions. This variation has been correlated with the calculated ranges of these ions in PMMA polymer using Stopping and Range of Ions in Matter (SRIM) code. Finally, an attempt has been made to correlate all the observed changes with the induced structural changes as revealed through Raman spectroscopy.

Superparamagnetic poly(methyl methacrylate) beads for nattokinase purification from fermentation broth.

PubMed

Yang, Chengli; Xing, Jianmin; Guan, Yueping; Liu, Huizhou

2006-09-01

An effective method for purification of nattokinase from fermentation broth using magnetic poly(methyl methacrylate) (PMMA) beads immobilized with p-aminobenzamidine was proposed in this study. Firstly, magnetic PMMA beads with a narrow size distribution were prepared by spraying suspension polymerization. Then, they were highly functionalized via transesterification reaction with polyethylene glycol. The surface hydroxyl-modified magnetic beads obtained were further modified with chloroethylamine to transfer the surface amino-modified magnetic functional beads. The morphology and surface functionality of the magnetic beads were examined by scanning electron microscopy and Fourier transform infrared. An affinity ligand, p-aminobenzamidine was covalently immobilized to the amino-modified magnetic beads by the glutaraldehyde method for nattokinase purification directly from the fermentation broth. The purification factor and the recovery of the enzyme activity were found to be 8.7 and 85%, respectively. The purification of nattokinase from fermentation broth by magnetic beads only took 40 min, which shows a very fast purification of nattokinase compared to traditional purification methods.

Dynamic fracture behavior of single and contacting Poly(methyl methacrylate) particles

DOE PAGES

Parab, Niranjan D.; Guo, Zherui; Hudspeth, Matthew C.; ...

2017-09-19

Fracture behaviors of single, two, and multiple contacting spherical Poly (methyl methacrylate) (PMMA) particles were recorded using high speed synchrotron X-ray phase contrast imaging. A miniaturized Kolsky bar setup was used to apply dynamic compressive loading on the PMMA particles. In both single and two particle experiments, cracking initiated near the center of the particles and propagated towards the contacts. The crack bifurcated near the contact points for single particle experiments, thus forming conical fragments. The crack bifurcation and subsequent conical fragment formation was observed only at the particle-particle contact for two particle experiments. The particles were observed to fracturemore » in hemispherical fragments normal to the contact plane in the multiparticle experiments. The observed failure mechanisms strongly suggest that the maximum tensile stress near the center of the particle is the critical parameter governing fracture of the particles. Moreover, the compressive stress under the contact areas led to the bifurcation and subsequent conical fragment formation.« less

Dynamic fracture behavior of single and contacting Poly(methyl methacrylate) particles

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

Parab, Niranjan D.; Guo, Zherui; Hudspeth, Matthew C.

Fracture behaviors of single, two, and multiple contacting spherical Poly (methyl methacrylate) (PMMA) particles were recorded using high speed synchrotron X-ray phase contrast imaging. A miniaturized Kolsky bar setup was used to apply dynamic compressive loading on the PMMA particles. In both single and two particle experiments, cracking initiated near the center of the particles and propagated towards the contacts. The crack bifurcated near the contact points for single particle experiments, thus forming conical fragments. The crack bifurcation and subsequent conical fragment formation was observed only at the particle-particle contact for two particle experiments. The particles were observed to fracturemore » in hemispherical fragments normal to the contact plane in the multiparticle experiments. The observed failure mechanisms strongly suggest that the maximum tensile stress near the center of the particle is the critical parameter governing fracture of the particles. Moreover, the compressive stress under the contact areas led to the bifurcation and subsequent conical fragment formation.« less

Bacillus sp. PS35 Lipase-Immobilization on Styrene-Divinyl Benzene Resin and Application in Fatty Acid Methyl Ester Synthesis

PubMed Central

Palanisamy, Kanmani; Kuppamuthu, Kumaresan; Jeyaseelan, Aravind

2015-01-01

Background Lipase is an enzyme with immense application potential. Ester synthesis by lipase catalysis in organic media is an area of key industrial relevance. Enzymatic preparations with traits that cater to the needs of this function are hence being intensely researched. Objective The objectives of the study were to immobilize the lipase from Bacillus sp. PS35 by cross-linking and adsorption onto styrene-divinyl benzene (Sty-Dvb) hydrophobic resin and to comparatively characterize the free and immobilized lipase preparations. The work also aimed to apply the immobilized lipase for catalysing the fatty acid methyl ester (FAME) synthesis from palm oil and optimize the process parameters for maximizing the yield. Materials and Methods In this study, the purified lipase from Bacillus sp. PS35 was immobilized by adsorption onto styrene-divinyl benzene hydrophobic resin with gluteraldehyde cross-linking. Results The immobilized enzyme showed better pH and temperature stabilities than the free lipase. Organic solvent stability was also enhanced, with the relative activity in the presence of methanol being shifted from 53% to 81%, thereby facilitating the enzyme’s application in fatty acid methyl ester synthesis. It exhibited remarkable storage stability over a 30-day period and after 20 repetitive uses. Cross-linking also reduced enzyme leakage by 49%. The immobilized lipase was then applied for biodiesel production from palm oil. Methanol and oil molar ratio of 5:1, three step methanol additions, and an incubation temperature of 50°C were established to be the ideal conditions favoring the transesterification reaction, resulting in 97% methyl ester yield. Conclusions These promising results offer scope for further investigation and process scale up, permitting the enzyme’s commercial application in a practically feasible and economically agreeable manner. PMID:28959298

Residual methyl methacrylate monomer, water sorption, and water solubility of hypoallergenic denture base materials.

PubMed

Pfeiffer, Peter; Rosenbauer, Ernst-Ulrich

2004-07-01

Denture base materials have the potential to cause irritation and allergic reaction to the oral mucosa. Water sorption and water solubility of denture base resins affect dimensional behavior and denture stability. A correlation between residual monomer and water sorption exists. This in vitro study compared the amount of residual monomer, quantity of water sorption, and solubility of 4 denture base materials purported to be hypoallergenic with those of a polymethyl methacrylate-based (PMMA) heat-polymerizing acrylic resin. The denture base resins Sinomer (heat-polymerized, modified methacrylate), Polyan (thermoplastic, modified methacrylate), Promysan (thermoplastic, enterephthalate-based), and Microbase (microwave polymerized, polyurethane-based), which are purported to be hypoallergenic, and Paladon 65 (heat-polymerized, methacrylate, control group) were examined. Specimens of each material were tested for residual methyl methacrylate (MMA) monomer (% wt, n=3), amount of water sorption (microg/mm3, n=5) and water solubility (microg/mm3, n=5), according to ISO 1567:2000. The residual MMA monomer concentrations were determined by gas chromatography (GC). The data were analyzed with 1-way ANOVA and the Bonferroni-Dunn multiple comparisons post hoc analysis for each test variable (alpha=.05). Significantly lower residual MMA monomer was shown for Sinomer and Polyan compared to the PMMA control group (0.90 +/- 0.20% wt, P<.05). Sinomer contained 0.31% +/- 0.00% wt MMA monomer, and Polyan exhibited residual MMA monomer content of 0.44% +/- 0.01% wt. Promysan and Microbase did not contain detectable residual MMA. Water sorption of Promysan (16.21 +/- 0.96 microg/mm3) was significantly lower than Paladon 65 (23.04 +/- 3.13 microg/mm3, P<.0001), whereas water solubility of the hypoallergenic denture base materials (0.34-0.84 +/- 0.05-0.09 microg/mm3) was not significantly lower than the PMMA material (0.40 +/- 0.06 microg/mm3, P>.05). Except for Sinomer, the tested

Improved biocompatibility of poly (styrene-b-(ethylene-co-butylene)-b-styrene) elastomer by a surface graft polymerization of hyaluronic acid.

PubMed

Li, Xiaomeng; Luan, Shifang; Shi, Hengchong; Yang, Huawei; Song, Lingjie; Jin, Jing; Yin, Jinghua; Stagnaro, Paola

2013-02-01

Hyaluronic acid (HA) is an important component of extracellular matrix (ECM) in many tissues, providing a hemocompatible and supportive environment for cell growth. In this study, glycidyl methacrylate-hyaluronic acid (GMHA) was first synthesized and verified by proton nuclear magnetic resonance ((1)H NMR) spectroscopy. GMHA was then grafted to the surface of biomedical elastomer poly (styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) via an UV-initiated polymerization, monitored by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). The further improvement of biocompatibility of the GMHA-modified SEBS films was assessed by platelet adhesion experiments and in vitro response of murine osteoblastic cell line MC-3T3-E1 with the virgin SEBS surface as the reference. It showed that the surface modification with HA strongly resisted platelet adhesion whereas improved cell-substrate interactions. Copyright © 2012 Elsevier B.V. All rights reserved.

Influence of acrylonitrile butadiene rubber on recyclability of blends prepared from poly(vinyl chloride) and poly(methyl methacrylate).

PubMed

Suresh, Sunil S; Mohanty, Smita; Nayak, Sanjay K

2018-06-01

The current investigation deals with the recycling possibilities of poly(vinyl chloride) and poly(methyl methacrylate) in the presence of acrylonitrile butadiene rubber. Recycled blends of poly(vinyl chloride)/poly(methyl methacrylate) are successfully formed from the plastic constituents, those are recovered from waste computer products. However, lower impact performance of the blend and lower stability of the poly(vinyl chloride) phase in the recycled blend restricts its further usage in industrial purposes. Therefore, effective utilisation acrylonitrile butadiene rubber in a recycled blend was considered for improving mechanical and thermal performance. Incorporation of acrylonitrile butadiene rubber resulted in the improvement in impact performance as well as elongation-at-break of the recycled blend. The optimum impact performance was found in the blend with 9 wt% acrylonitrile butadiene rubber, which shows 363% of enhancement as compared with its parent blend. Moreover, incorporated acrylonitrile butadiene rubber also stabilises the poly(vinyl chloride) phase present in the recycled blend, similarly Fourier transform infrared spectroscopy studies indicate the interactions of various functionalities present in the recycled blend and acrylonitrile butadiene rubber. In addition to this, thermogravimetric analysis indicates the improvement in the thermal stability of the recycled blend after the addition of acrylonitrile butadiene rubber into it. The existence of partial miscibility in the recycled blend was identified using differential scanning calorimetry and scanning electron microscopy.

Zinc oxide nanowire-poly(methyl methacrylate) dielectric layers for polymer capacitive pressure sensors.

PubMed

Chen, Yan-Sheng; Hsieh, Gen-Wen; Chen, Shih-Ping; Tseng, Pin-Yen; Wang, Cheng-Wei

2015-01-14

Polymer capacitive pressure sensors based on a dielectric composite layer of zinc oxide nanowire and poly(methyl methacrylate) show pressure sensitivity in the range of 2.63 × 10(-3) to 9.95 × 10(-3) cm(2) gf(-1). This represents an increase of capacitance change by as much as a factor of 23 over pristine polymer devices. An ultralight load of only 10 mg (corresponding to an applied pressure of ∼0.01 gf cm(-2)) can be clearly recognized, demonstrating remarkable characteristics of these nanowire-polymer capacitive pressure sensors. In addition, optical transmittance of the dielectric composite layer is approximately 90% in the visible wavelength region. Their low processing temperature, transparency, and flexible dielectric film makes them a highly promising means for flexible touching and pressure-sensing applications.

Synthesis of acrylates and methacrylates from coal-derived syngas

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

Spivey, J.J.; Gogate, M.R.; Jang, B.W.L.

1995-12-31

Acrylates and methacrylates are among the most widely used chemical intermediates in the world. One of the key chemicals of this type is methyl methacrylate. Of the 4 billion pounds produced each year, roughly 85% is made using the acetone-cyanohydrin process, which requires handling of large quantities of hydrogen cyanide and produces ammonium sulfate wastes that pose an environmental disposal challenge. The U.S. Department of Energy and Eastman Chemical Company are sharing the cost of research to develop an alternative process for the synthesis of methyl methacrylate from syngas. Research Triangle Institute is focusing on the synthesis and testing ofmore » active catalysts for the condensation reactions, and Bechtel is analyzing the costs to determine the competitiveness of several process alternatives. Results thus far show that the catalysts for the condensation of formaldehyde and the propionate are key to selectively producing the desired product, methacrylic acid, with a high yield. These condensation catalysts have both acid and base functions and the strength and distribution of these acid-base sites controls the product selectivity and yield.« less

Viscosity of nonelectrolyte liquid mixtures. III Binary mixtures of methyl methacrylate with hydrocarbons, haloalkanes, and alkylamines

NASA Astrophysics Data System (ADS)

Oswal, S. L.; Patel, B. M.; Shah, H. R.; Oswal, P.

1994-07-01

Measurements of the viscosity η and the density ϱ are reported for 14 binary mixtures of methyl methacrylate (MMA) with hydrocarbons, haloalkanes, and alkylamines at 303.15 K. The viscosity data have been correlated with equations of Grunberg and Nissan, of McAllister, and of Auslaender. Furthermore, excess viscosity Δ In η and excess Gibbs energy of activation ΔG* E of viscous flow have been calculated and have been used to predict molecular interactions occurring in present binary mixtures. The results show the existence of specific interactions in MMA + aromatic hydrocarbons, MMA + haloalkanes, and MMA + primary amines.

Nano-imprint lithography using poly (methyl methacrylate) (PMMA) and polystyrene (PS) polymers

NASA Astrophysics Data System (ADS)

Ting, Yung-Chiang; Shy, Shyi-Long

2016-04-01

Nano-imprinting lithography (NIL) technology, as one of the most promising fabrication technologies, has been demonstrated to be a powerful tool for large-area replication up to wafer-level, with features down to nanometer scale. The cost of resists used for NIL is important for wafer-level large-area replication. This study aims to develop capabilities in patterning larger area structure using thermal NIL. The commercial available Poly (Methyl Methacrylate) (PMMA) and Polystyrene (PS) polymers possess a variety of characteristics desirable for NIL, such as low material cost, low bulkvolumetric shrinkage, high spin coating thickness uniformity, high process stability, and acceptable dry-etch resistance. PMMA materials have been utilized for positive electron beam lithography for many years, offering high resolution capability and wide process latitude. In addition, it is preferable to have a negative resist like PMMA, which is a simple polymer with low cost and practically unlimited shelf life, and can be dissolved easily using commercial available Propylene glycol methyl ether acetate (PGMEA) safer solvent to give the preferred film thickness. PS is such a resist, as it undergoes crosslinking when exposed to deep UV light or an electron beam and can be used for NIL. The result is a cost effective patterning larger area structure using thermal nano-imprint lithography (NIL) by using commercial available PMMA and PS ploymers as NIL resists.

Influence of the volumes of bis-acryl and poly(methyl methacrylate) resins on their exothermic behavior during polymerization.

PubMed

Ha, Jung-Yun; Kim, Sung-Hun; Kim, Kyo-Han; Kwon, Tae-Yub

2011-01-01

This study aimed to evaluate the influence of the volumes of a bis-acryl resin (Luxatemp) and a poly(methyl methacrylate) resin (Jet) on their exothermic behaviors during polymerization based on vinyl group conversion. The number of vinyl groups reacted and exotherm were determined based on weight percent of methacrylate groups using FTIR spectroscopy. Temperature changes during polymerization at 23°C were recorded for 20 minutes using a multiple cavity mold overlying a thermocouple. The number of vinyl groups reacted and exotherm of Luxatemp were consistently lower than those of Jet at each resin volume. Mean peak temperature rises of Luxatemp and Jet were in the range of 2.0-6.6°C and 4.2-11.6°C respectively, with Luxatemp and Jet taking 2 and 10 minutes respectively to reach their peak temperatures. As their resin volumes increased, their peak temperatures and total peak areas were also observed to increase significantly (p<0.01).

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

Using aligned poly(3-hexylthiophene)/poly(methyl methacrylate) blend fibers to detect volatile organic compounds

NASA Astrophysics Data System (ADS)

Chan, Shun-Hsiang; Lin, Tz-Feng; Wu, Ming-Chung; Chen, Shih-Hsuan; Su, Wei-Fang; Lai, Chao-Sung

2018-04-01

In this study, we developed a novel sensing material fabricated using a poly(3-hexylthiophene) (P3HT)/poly(methyl methacrylate) (PMMA) blend fiber on a glass substrate. The sensing materials can easily be used for sensing toluene vapor detected from extinction spectral changes. The extinction spectra variation is noted from the absorption of volatile organic compounds in a highly specific surface area of fibrous coating. An electrospinning technique is applied to generate a nonwoven structure and uniaxial orientation by fibrous coating. The response of the uniaxially orientated fibrous film is even improved at several toluene vapor concentrations. The best detection limit of this well-aligned fibrous film is up to 200 ppm for toluene vapor.

[Analysis of the character of film decomposition of methyl methacrylate (MMA) coated urea by infrared spectrum].

PubMed

Li, Dong-po; Wu, Zhi-jie; Liang, Cheng-hua; Chen, Li-jun; Zhang, Yu-lan; Nie, Yan-xi

2012-03-01

The degradability characteristics of film with 4 kinds of methyl methacrylate coated urea amended with inhibitors were analyzed by FITR, which was purposed to supply theoretical basis for applying the FITR analysis method to film decomposition and methyl methacrylate coated urea fertilizers on farming. The result showed that the chemical component, molecule structure and material form of the membrane were not changed because of adding different inhibitors to urea. the main peaks of expressing film degradation process were brought by the -C-H of CH3 & CH2, -OH, C-O, C-C, C-O-C, C=O, C=C flexing vibrancy in asymmetry and symmetry in 3 479-3 195, 2 993--2 873, 1 741-1 564, 1 461-925 and 850-650 cm(-1). The peak value changed from smooth to tip, and from width to narrow caused by chemical structural transform of film The infrared spectrum of 4 kinds of fertilizers was not different remarkably before 60 days, and the film was slowly degraded. But degradation of the film was expedited after 60 days, it was most quickened at 120 day, and the decomposition rate of film was decreased at 310 day. The substantiality change of film in main molecule structure of 4 kinds of fertilizers didn't happen in 310 days. The main component of film materials was degraded most slowly in brown soil. The speed of film degradation wasn't heavily impacted by different inhibitors. The characteristic of film degradation may be monitored entirely by infrared spectrum. The degradation dynamic, chemical structure change, degradation speed difference of the film could be represented through infrared spectrum.

Network formation of nanofibrillated cellulose in solution blended poly(methyl methacrylate) composites.

PubMed

Littunen, Kuisma; Hippi, Ulla; Saarinen, Tapio; Seppälä, Jukka

2013-01-02

Composites of poly(methyl methacrylate) (PMMA) and nanofibrillated cellulose (NFC) were prepared by solution blending and further processed by injection and compression molding. To improve adhesion at the PMMA/NFC interface, the nanofibrils were covalently grafted with PMMA. Formation of a percolating nanofibril network was observed between 1 and 5 wt.% of NFC by dynamic rotational rheometry in molten state. This observation was further supported by the behavior of glass transition temperature which decreased at low NFC concentrations but recovered above the percolation threshold, indicating a decreased mobility of the matrix polymer. This effect was more pronounced with ungrafted NFC, possibly due to a stronger network. The unmodified NFC induced a minor degradation of the molar mass of PMMA. As thin plates, the composites were transparent at low NFC concentrations but became partially aggregated at the highest NFC concentrations. Despite the continuous NFC network, tensile testing showed no improvement of the mechanical properties. Copyright © 2012 Elsevier Ltd. All rights reserved.

Formation of a periodic diffractive structure based on poly(methyl methacrylate) with ion-implanted silver nanoparticles

NASA Astrophysics Data System (ADS)

Galyautdinov, M. F.; Nuzhdin, V. I.; Fattakhov, Ya. V.; Farrakhov, B. F.; Valeev, V. F.; Osin, Yu. N.; Stepanov, A. L.

2016-02-01

We propose to form optical diffractive elements on the surface of poly(methyl methacrylate) (PMMA) by implanting the polymer with silver ions ( E = 30 keV; D = 5.0 × 1014 to 1.5 × 1017 ion/cm2; I = 2 μA/cm2) through a nickel grid (mask). Ion implantation leads to the nucleation and growth of silver nanoparticles in unmasked regions of the polymer. The formation of periodic surface microstructures during local sputtering of the polymer by incident ions was monitored using an optical microscope. The diffraction efficiency of obtained gratings is demonstrated under conditions of their probing with semiconductor laser radiation in the visible spectral range.

The formation of hollow poly(methyl methacrylate)/multiwalled carbon nanotube nanocomposite cylinders by microwave irradiation.

PubMed

Wang, Huan; Feng, Jiyun; Hu, Xijun; Ming Ng, Ka

2009-03-04

Poly(methyl methacrylate) (PMMA)/multiwalled carbon nanotube (MWCNT) nanocomposite particles with 1, 2 and 4 wt% of MWCNTs were prepared by mechanical grinding of PMMA and MWCNT powders in a mortar at room temperature. Both scanning electron microscopy and Raman scattering characterizations revealed that these nanocomposite particles consist of a PMMA core and a MWCNT shell. The PMMA/MWCNT nanocomposite particles were used to fabricate the corresponding nanocomposites in the form of a hollow cylinder with various diameters and heights under 700 W microwave irradiation within 1 min. A mechanism for the fast microwave assisted forming process is proposed. These experimental results may lead to a new technology for forming hollow polymeric articles that is different from the conventional injection and blowing process.

Photoimaging of the multiple filamentation of femtosecond laser pulses in poly(methyl methacrylate) doped with 2,2-difluoro-4-(9-anthracyl)-6-methyl-1,3,2-dioxaborine

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

Kulchin, Yu N; Vitrik, O B; Chekhlenok, A A

2013-12-31

We have studied the filamentation of femtosecond laser pulses (λ = 800 nm, ∼42 fs pulse duration) in poly(methyl methacrylate) doped with 2,2-difluoro-4-(9-anthracyl)-6-methyl-1,3,2- dioxaborine and the associated photomodification of the material. The results demonstrate that multiple filamentation occurs at pulse energies above 5 μJ. At a pulse energy of 1.5 mJ, it is accompanied by supercontinuum generation. The average filament length in PMMA is 9 mm and the filament diameter is ∼10 μm. An incident power density of ∼10{sup 12} W cm{sup -2} ensures inscription of the filament pattern owing to two-photon photochemical processes. Preliminary exposure to continuous light atmore » λ = 400 nm enables an ordered filament pattern to be written. (interaction of laser radiation with matter)« less

Is chlorhexidine-methacrylate as effective as chlorhexidine digluconate in preserving resin dentin interfaces?

PubMed

Abu Nawareg, Manar; Elkassas, Dina; Zidan, Ahmed; Abuelenain, Dalia; Abu Haimed, Tariq; Hassan, Ali H; Chiba, Ayaka; Bock, Thorsten; Agee, Kelli; Pashley, David H

2016-02-01

The aim of the current study was to evaluate the effect of 2% CHX and 2% CHX-methacrylate compared to the resin-dentin bonds created by a two-step etch-and-rinse adhesive system after 24h, 6min and 12min. Microtensile bond strengths and interfacial nanoleakage within resin-dentin interfaces created by Adper Single Bond 2, with or without CHX or CHX-methacrylate pre-treatment for 30s on acid-etched dentin surfaces, were evaluated after 24h, 6min and 12min of storage in distilled water at 37°C. Twelve months of storage resulted in a significant decrease in microtensile bond strength in the control group, and significant increases in silver nanoleakage. In contrast, Single Bond 2+CHX, and to a greater extent CHX-methacrylate, significantly reduced the rate of deterioration of resin-dentin interfaces over the 12min water storage period, in terms of bond strength. Similar to Single Bond 2+CHX, Single Bond+CHX-methacrylates reduced the degradation of resin-bonded interfaces over a 12 month storage period. Thus it can be concluded that Single Bond 2+CHX-methacrylate may be important to improve durability of bonded interfaces and therefore, prolong the life span of adhesive restorations. Although CHX primers have been shown to enhance the durability of etch-and-rinse adhesives, that protection is lost after 2h. The use of CHX-methacrylate should last much longer since it may copolymerize with adhesive monomers, unlike CHX. Copyright © 2015 Elsevier Ltd. All rights reserved.

Preparation and properties of optically transparent, pressure-cured poly(methyl methacrylate) composites

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

Weaver, K.D.

The objective of this work was to develop optically transparent glass fiber reinforced poly(methyl methacrylate) composites by matching the refractive index of the glass fiber to that of the PMMA matrix. A pressure curing process [65[degrees]C under 6.9 MPa N[sub 2] for 18 hrs] is described for preparing composites 10 [times] 15 [times] 0.6 cm which typically contain [approximately]10 vol% of 13[mu]m diameter fiber and have 84% optical transmission (92% maximum for PMMA) at 600 nm and 25[degrees]C. Evidence is presented relating the interfacial bonding strength and the optical transmission of transparent, glass fiber (13 [mu]m) reinforced PMMA composites. Themore » temperature dependent (20-50[degrees]C) transmission of composites containing uncoated fiber and fiber coated with divinyltetramethyl disilazane or 3-(trimethoxysilyl)propyl methacrylate was found to decrease in the same order as the bond strength of the PMMA/fiber interface, namely, silane coated, disilazane coated, and uncoated fiber. By using annealed (1 1/3 hours/400[degrees]C) 13 [mu]m BK10 fiber, these pressure-cured composites function optically as ultra-violet Solid Matrix Christiansen Filters. The composite filters have an optical transmission of 51% at 51[degrees]C and 305 nm with a half-height bandwidth of only 28 nm, which is more wavelength selective than reported solid matrix Christiansen filters and typical band pass filters. While the density (1.18-1.19 g/ml at 23[degrees]C) and coefficient of thermal expansion (9.9[times]10[sup [minus]5] K[sup [minus]1]) show no change at these curing conditions, the minimum stress to craze (33 wt% toluene in isobutyl acetate) for pressure-cured [65[degrees]C/6.9 MPa N[sub 2]/18 hrs] PMMA was found to be improved.« less

Hydrogen peroxide filled poly(methyl methacrylate) microcapsules: potential oxygen delivery materials.

PubMed

Mallepally, Rajendar R; Parrish, Chance C; Mc Hugh, Mark A M; Ward, Kevin R

2014-11-20

This paper describes the synthesis of H₂O₂-H₂O filled poly(methyl methacrylate) (PMMA) microcapsules as potential candidates for controlled O₂ delivery. The microcapsules are prepared by a water-in-oil solvent emulsion and evaporation method. The results of this study describe the effect of process parameters on the characteristics of the microcapsules and on their in vitro performance. The size of the microcapsules, as determined from scanning electron microscopy, ranges from ∼5 to 30 μm and the size distribution is narrow. The microcapsules exhibit an internal morphology with entrapped H₂O₂-H₂O droplets randomly distributed in the PMMA continuous phase. In vitro release studies of 4.5 wt% H₂O₂-loaded microcapsules show that ∼70% of the H₂O₂ releases in 24h. This corresponds to a total O₂ production of ∼12 cc/gram of dry microcapsules. Shelf-life studies show that the microcapsules retain ∼84 wt% of the initially loaded H₂O₂ after nine months storage at 2-8 °C, which is an attractive feature for clinical applications. Copyright © 2014 Elsevier B.V. All rights reserved.

CEC with new monolithic stationary phase based on a fluorinated monomer, trifluoroethyl methacrylate.

PubMed

Yurtsever, Arda; Saraçoğlu, Berna; Tuncel, Ali

2009-02-01

A new, fluorinated monolithic stationary phase for CEC was first synthesized by a single-stage, thermally initiated copolymerization of a fluorinated monomer, 2,2,2-trifluoroethyl methacrylate (TFEM) and ethylene dimethacrylate (EDMA) in the presence of a porogen mixture. In this preparation, 2-acrylamido-2-methyl-1-propanesulfonic acid was used as the charge-bearing monomer. The porogen mixture was prepared by mixing isoamylalcohol and 1,4-butanediol. A clear increase in the electroosmotic mobility was observed with increasing pH. The electroosmotic mobility decreased with increasing ACN concentration. Poly(TFEM-co-EDMA) monolith prepared under optimized polymerization conditions was successfully used in the separation of alkylbenzenes and phenols by CEC. The best chromatographic separation for alkylbenzenes was performed with lower ACN concentrations (i.e. 60% v/v) with respect to the common acrylic-based CEC monoliths. The theoretical plate numbers up to 220 000 plates/m were achieved in the reversed phase separation of phenols. Poly(TFEM-co-EDMA) monolith also allowed the simultaneous separation of aniline and benzoic acid derivatives by a single run and by using a lower ACN concentration in the mobile phase with respect to the similar electrochromatographic separations. A stable retention behaviour in reversed phase separation of alkylbenzenes was obtained with the poly(TFEM-co-EDMA) monolith.

A New Poly(Methyl Methacrylate) Membrane Dialyzer, NF, with Adsorptive and Antithrombotic Properties.

PubMed

Oshihara, Wataru; Fujieda, Hiroaki; Ueno, Yoshiyuki

2017-01-01

Poly(methyl methacrylate) (PMMA) membranes adsorb several kinds of proteins and can remove high-molecular-weight proteins, including uremic toxins, which are not removed efficiently by hemodialysis or hemodiafiltration. However, the antithrombogenicity of PMMA membranes is insufficient due to their adsorptive properties. Coagulation during hemodialysis occurs because proteins that are adsorbed to the PMMA membrane undergo structural changes and are recognized by platelets, which are then activated by adhesion to the membrane surface. In developing a new PMMA membrane dialyzer, NF, we intended to inhibit platelet adhesion to the membrane surface by suppressing the structural change in the proteins adsorbed on the membrane. In addition, we give examples of clinical trials of the NF in Japan and describe its advantages. Key Message: PMMA membrane dialyzers have been used for 40 years. The PMMA dialyzer NF can suppress the adhesion of platelets to the membrane while maintaining protein adsorption. © 2017 S. Karger AG, Basel.

Reconstruction of large cranial defects with poly-methyl-methacrylate (PMMA) using a rapid prototyping model and a new technique for intraoperative implant modeling.

PubMed

Unterhofer, Claudia; Wipplinger, Christoph; Verius, Michael; Recheis, Wolfgang; Thomé, Claudius; Ortler, Martin

Reconstruction of large cranial defects after craniectomy can be accomplished by free-hand poly-methyl-methacrylate (PMMA) or industrially manufactured implants. The free-hand technique often does not achieve satisfactory cosmetic results but is inexpensive. In an attempt to combine the accuracy of specifically manufactured implants with low cost of PMMA. Forty-six consecutive patients with large skull defects after trauma or infection were retrospectively analyzed. The defects were reconstructed using computer-aided design/computer-aided manufacturing (CAD/CAM) techniques. The computer file was imported into a rapid prototyping (RP) machine to produce an acrylonitrile-butadiene-styrene model (ABS) of the patient's bony head. The gas-sterilized model was used as a template for the intraoperative modeling of the PMMA cranioplasty. Thus, not the PMMA implant was generated by CAD/CAM technique but the model of the patients head to easily form a well-fitting implant. Cosmetic outcome was rated on a six-tiered scale by the patients after a minimum follow-up of three months. The mean size of the defect was 74.36cm 2 . The implants fitted well in all patients. Seven patients had a postoperative complication and underwent reoperation. Mean follow-up period was 41 months (range 2-91 months). Results were excellent in 42, good in three and not satisfactory in one patient. Costs per implant were approximately 550 Euros. PMMA implants fabricated in-house by direct molding using a bio-model of the patients bony head are easily produced, fit properly and are inexpensive compared to cranial implants fabricated with other RP or milling techniques. Copyright © 2017 Polish Neurological Society. Published by Elsevier Urban & Partner Sp. z o.o. All rights reserved.

Dynamics of Surface Reorganization of Poly(methyl methacrylate) in Contact with Water

NASA Astrophysics Data System (ADS)

Horinouchi, Ayanobu; Atarashi, Hironori; Fujii, Yoshihisa; Tanaka, Keiji

2013-03-01

New tools for tailor-made diagnostics, such as DNA arrays and tips for micro-total-analysis systems, are generally made from polymers. In these applications, the polymer surface is in contact with a water phase. However, despite the importance of detailed knowledge of the fundamental interactions of polymer interfaces with liquids, such studies are very limited. As an initial benchmark for designing and constructing specialized biomedical surfaces containing polymer, aggregation states and dynamics of chains at the water interface should be systematically examined. We here apply time-resolved contact angle measurement to study the dynamics of the surface reorganization of poly(methyl methacrylate) (PMMA) in contact with water. By doing the measurements at various temperatures, it is possible to discuss the surface dynamics of PMMA based on the apparent activation energy. Also, sum-frequency generation spectroscopy revealed that the surface reorganization involves the conformational changes in the main chain part as well as the side chains. Hence, the dynamics observed here may reflect the segmental motion at the outermost region of the PMMA film, in which water plays as a plasticizer.

Temperature dependent impedance spectroscopy and Thermally Stimulated Depolarization Current (TSDC) analysis of disperse red 1-co-poly(methyl methacrylate) copolymers

NASA Astrophysics Data System (ADS)

Ko, Yee Song; Cuervo-Reyes, Eduardo; Nüesch, Frank A.; Opris, Dorina M.

2016-04-01

The dielectric relaxation processes of polymethyl methacrylates that have been functionalized with Disperse Red 1 (DR1) in the side chain (DR1-co-MMA) were studied with temperature dependent impedance spectroscopy and thermally stimulated depolarization current (TSDC) techniques. Copolymers with dipole contents which varied between 10 mol% and 70 mol% were prepared. All samples showed dipole relaxations above the structural-glass transition temperature (Tg). The β-relaxation of the methyl methacrylate (MMA) repeating unit was most visible in DR1(10%)-co-MMA and rapidly vanishes with higher dipole contents. DSC data reveal an increase of the Tg by 20 °C to 125°C with the inclusion of the dipole into the polymethyl methacrylate (PMMA) as side chain. The impedance data of samples with several DR1 concentrations, taken at several temperatures above Tg, have been fitted with the Havriliak-Negami (HN) function. In all cases, the fits reveal a dielectric response that corresponds to power-law dipolar relaxations. TSDC measurements show that the copolymer can be poled, and that the induced polarization can be frozen by lowering the temperature well below the glass transition. Relaxation strengths ΔƐ estimated by integrating the depolarization current are similar to those obtained from the impedance data, confirming the efficient freezing of the dipoles in the structural glass state.

Monolithic column modified with bifunctional ionic liquid and styrene stationary phases for capillary electrochromatography.

PubMed

Mao, Zhenkun; Chen, Zilin

2017-01-13

A novel monolithic column with ionic liquid and styrene-modified bifunctional group was prepared for capillary electrochromatography (CEC) by in situ copolymerization in a ternary porogenic solvent. Ionic liquid (1-allyl-methylimidazolium chloride, AlMeIm + Cl - ) and styrene served as the bifunctional monomer, while ethylene dimethacrylate (EDMA) was used as the cross-linker. The monomer of AlMeIm + Cl - was introduced as anion-exchange group, while styrene as hydrophobic and aromatic group; the similar conjugated structure in AlMeIm + Cl - and styrene was beneficial for offeing obvious synergistic effect. The bifunctional stationary phase possessed powerful selectivity for the separation of neutral compounds, acidic analytes and phenols. The highest column efficiency was 2.70×10 5 platesm -1 (theoretical plates, N) for toluene. A relatively strong electroosmotic flow (EOF) was obtained in a wide range of pH values from 2.0 to 12.0, which could successfully achieve the rapid separation of the analytes within 10min. The proposed monolithic column was characterized by scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR). The results indicated that the resultant monolithic column had good permeability and excellent mechanical stability. Good reproducibility was obtained with relative standard deviations (RSDs) of the retention time in the range of 0.24-0.47% and 0.81-2.17% for run-to-run (n=5) and day-to-day (n=5), while 1.09-2.70% and 0.98-1.70% for column-to-column (n=3) and batch-to-batch (n=3), respectively. The combination of AlMeIm + Cl - and styrene was a promising option in the fabrication of the organic polymer monolithic column. Copyright © 2016 Elsevier B.V. All rights reserved.

Quaternary ammonium silane-functionalized, methacrylate resin composition with antimicrobial activities and self-repair potential

PubMed Central

Gong, Shi-qiang; Niu, Li-na; Kemp, Lisa K.; Yiu, Cynthia K.Y.; Ryou, Heonjune; Qi, Yi-pin; Blizzard, John D.; Nikonov, Sergey; Brackett, Martha G.; Messer, Regina L.W.; Wu, Christine D.; Mao, Jing; Brister, L. Bryan; Rueggeberg, Frederick A.; Arola, Dwayne D.; Pashley, David H.; Tay, Franklin R.

2012-01-01

Design of antimicrobial polymers for enhancing healthcare issues and minimizing environmental problems is an important endeavor with both fundamental and practical implications. Quaternary ammonium silane-functionalized methacrylate (QAMS) represents an example of antimicrobial macromonomers synthesized by a sol-gel chemical route; these compounds possess flexible Si-O-Si bonds. In present work, a partially-hydrolyzed QAMS copolymerized with bis-GMA is introduced. This methacrylate resin was shown to possess desirable mechanical properties with both a high degree of conversion and minimal polymerization shrinkage. Kill-on-contact microbiocidal activities of this resin were demonstrated using single-species biofilms of Streptococcus mutans (ATCC 36558), Actinomyces naeslundii (ATCC 12104) and Candida albicans (ATCC 90028). Improved mechanical properties after hydration provided the proof-of-concept that QAMS-incorporated resin exhibits self-repair potential via water-induced condensation of organic modified silicate (ormosil) phases within the polymerized resin matrix. PMID:22659173

From the N-Heterocyclic Carbene-Catalyzed Conjugate Addition of Alcohols to the Controlled Polymerization of (Meth)acrylates.

PubMed

Ottou, Winnie Nzahou; Bourichon, Damien; Vignolle, Joan; Wirotius, Anne-Laure; Robert, Fredéric; Landais, Yannick; Sotiropoulos, Jean-Marc; Miqueu, Karinne; Taton, Daniel

2015-06-22

Among various N-heterocyclic carbenes (NHCs) tested, only 1,3-bis(tert-butyl)imidazol-2-ylidene (NHC(tBu) ) proved to selectively promote the catalytic conjugate addition of alcohols onto (meth)acrylate substrates. This rather rare example of NHC-catalyzed 1,4-addition of alcohols was investigated as a simple means to trigger the polymerization of both methyl methacrylate and methyl acrylate (MMA and MA, respectively). Well-defined α-alkoxy poly(methyl (meth)acrylate) (PM(M)A) chains, the molar masses of which could be controlled by the initial [(meth)acrylate]0/[ROH]0 molar ratio, were ultimately obtained in N,N-dimethylformamide at 25 °C. A hydroxyl-terminated poly(ethylene oxide) (PEO-OH) macro-initiator was also employed to directly access PEO-b-PMMA amphiphilic block copolymers. Investigations into the reaction mechanism by DFT calculations revealed the occurrence of two competitive concerted pathways, involving either the activation of the alcohol or that of the monomer by NHC(tBu) . © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shock response of poly[methyl methacrylate] (PMMA) measured with embedded electromagnetic gauges

NASA Astrophysics Data System (ADS)

Lacina, David; Neel, Christopher; Dattelbaum, Dana

2018-05-01

The shock response of poly[methyl methacrylate] (PMMA) acquired from two providers, Spartech and Rohm & Haas, has been measured to investigate the shock response variations related to material pedigree. These measurements have also been used to examine the effects of viscoelasticity on Spartech PMMA. Measurements of the Hugoniot curves, release wave speeds, and index of refraction have been acquired up to previously unexplored stresses, ˜10.7 GPa, for Spartech PMMA. In-situ, time-resolved particle velocity wave profiles, as a function of time and depth, were obtained using twelve separate electromagnetic gauge elements embedded at different depths in the PMMA. A comparison of the new data to the shock response data for Rohm and Haas PMMA, used as a "standard" material in shock compression studies, shows that there are no significant differences in shock response for the two materials. From the index of refraction measurements, the apparent particle velocity correction for a PMMA window exhibits an interesting oscillation, increasing at up = 0.3 km/s after decreasing up to that point. The results are generalized into guidelines for sourcing PMMA for use in shock studies.

Functionalization of poly(methyl methacrylate) (PMMA) as a substrate for DNA microarrays

PubMed Central

Fixe, F.; Dufva, M.; Telleman, P.; Christensen, C. B. V.

2004-01-01

A chemical procedure was developed to functionalize poly(methyl methacrylate) (PMMA) substrates. PMMA is reacted with hexamethylene diamine to yield an aminated surface for immobilizing DNA in microarrays. The density of primary NH2 groups was 0.29 nmol/cm2. The availability of these primary amines was confirmed by the immobilization of DNA probes and hybridization with a complementary DNA strand. The hybridization signal and the hybridization efficiency of the chemically aminated PMMA slides were comparable to the hybridization signal and the hybridization efficiency obtained from differently chemically modified PMMA slides, silanized glass, commercial silylated glass and commercial plastic Euray™ slides. Immobilized and hybridized densities of 10 and 0.75 pmol/cm2, respectively, were observed for microarrays on chemically aminated PMMA. The immobilized probes were heat stable since the hybridization performance of microarrays subjected to 20 PCR heat cycles was only reduced by 4%. In conclusion, this new strategy to modify PMMA provides a robust procedure to immobilize DNA, which is a very useful substrate for fabricating single use diagnostics devices with integrated functions, like sample preparation, treatment and detection using microfabrication and microelectronic techniques. PMID:14718554

Controlling of free radical copolymerization of styrene and maleic anhydride via RAFT process for the preparation of acetaminophen drug conjugates

NASA Astrophysics Data System (ADS)

Sütekin, S. Duygu; Atıcı, Ayşe Bakar; Güven, Olgun; Hoffman, Allan S.

2018-07-01

The presence of maleic anhydride moiety in styrene-maleic anhydride (SMA) copolymer makes it a versatile substrate for conjugation of drugs. In this study biocompatible styrene-maleic anhydride (SMA) copolymer with alternating structure was synthesized by gamma irradiation at room temperature in the presence of 2-phenyl-2-propyl benzodithioate (PPB). The poly(styrene-alt-maleic anhydride) (poly(St-alt-MA)) with narrow molecular weight distribution (Đ: 1.1-1.3) was prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization. The synthesized poly(St-alt-MA) structure was characterized by ATR-FTIR spectroscopy, elemental analysis and 1H NMR spectroscopy and molecular weight and dispersity were determined by size exclusion chromatography (SEC). SMA copolymers were further conjugated with acetaminophen via ester linkage and FT-IR, 1H NMR investigation indicated that the acetaminophen was attached to poly(St-alt-MA). Drug release profile of the polymer-drug conjugate was followed by high performance liquid chromatography (HPLC). The drug-conjugate system was found to follow first order release kinetics with Hixson-Crowell model while drug release mechanism was found as non-Fickian diffusion after testing various kinetic models.

Installation Restoration Program. Stage 3. McClellan Air Force Base. Quality Assurance Project Plan

DTIC Science & Technology

1990-03-01

Dibromomethane 5.0 trans- 1,2-Dichloropropene 5.0 1,2-Dibromoethane 4.8 total- 1,4-Dichlorobutene 2.6 Methyl methacrylate 28 1,1, 1,2-Trichloropropane 3.9...trans- 1,2-DCE); • Methyl ethyl ketone (MEK); • Carbon disulfide; • Dichlorobenzene; * Chloroform; and * Methylene chloride. Contaminants reported in soil...2-Hexanone 10 4- Methyl -2-pentanone 10 Tetrachloroethene 4.1 1, 1,2,2-Tetrachloroethane 5.0 Toluene 5.0 Chlorobenzene 5.0 Ethylbenzene 5.0 Styrene 3.0

Facile Fabrication of Gradient Surface Based on (meth)acrylate Copolymer Films

NASA Astrophysics Data System (ADS)

Zhang, Y.; Yang, H.; Wen, X.-F.; Cheng, J.; Xiong, J.

2016-08-01

This paper describes a simple and economic approach for fabrication of surface wettability gradient on poly(butyl acrylate - methyl methacrylate) [P (BA-MMA)] and poly(butyl acrylate - methyl methacrylate - 2-hydroxyethyl methacrylate) [P (BA-MMA-HEMA)] films. The (meth)acrylate copolymer [including P (BA-MMA) and P (BA-MMA-HEMA)] films are hydrolyzed in an aqueous solution of NaOH and the transformation of surface chemical composition is achieved by hydrolysis in NaOH solution. The gradient wetting properties are generated based on different functional groups on the P (BA-MMA) and P (BA-MMA-HEMA) films. The effects of both the surface chemical and surface topography on wetting of the (meth)acrylate copolymer film are discussed. Surface chemical composition along the materials length is determined by XPS, and surface topography properties of the obtained gradient surfaces are analyzed by FESEM and AFM. Water contact angle system (WCAs) results show that the P (BA-MMA-HEMA) films provide a larger slope of the gradient wetting than P (BA-MMA). Moreover, this work demonstrates that the gradient concentration of chemical composition on the poly(meth) acrylate films is owing to the hydrolysis processes of ester group, and the hydrolysis reactions that have negligible influence on the surface morphology of the poly(meth) acrylate films coated on the glass slide. The gradient wettability surfaces may find broad applications in the field of polymer coating due to the compatibility of (meth) acrylate polymer.

Physical properties of agave cellulose graft polymethyl methacrylate

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

Rosli, Noor Afizah; Ahmad, Ishak; Abdullah, Ibrahim

2013-11-27

The grafting polymerization of methyl methacrylate and Agave cellulose was prepared and their structural analysis and morphology were investigated. The grafting reaction was carried out in an aqueous medium using ceric ammonium nitrate as an initiator. The structural analysis of the graft copolymers was carried out by Fourier transform infrared and X-ray diffraction. The graft copolymers were also characterized by field emission scanning electron microscopy (FESEM). An additional peak at 1732 cm{sup −1} which was attributed to the C=O of ester stretching vibration of poly(methyl methacrylate), appeared in the spectrum of grafted Agave cellulose. A slight decrease of crystallinity indexmore » upon grafting was found from 0.74 to 0.68 for cellulose and grafted Agave cellulose, respectively. Another evidence of grafting showed in the FESEM observation, where the surface of the grafted cellulose was found to be roughed than the raw one.« less

High optical and switching performance electrochromic devices based on a zinc oxide nanowire with poly(methyl methacrylate) gel electrolytes

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

Chun, Young Tea; Chu, Daping, E-mail: dpc31@cam.ac.uk; Neeves, Matthew

2014-11-10

High performance electrochromic devices have been fabricated and demonstrated utilizing a solid polymer electrolyte and zinc oxide (ZnO) nanowire (NW) array counter electrode. The poly(methyl methacrylate) based polymer electrolyte was spin coated upon hydrothermally grown ZnO NW array counter electrodes, while electron beam evaporated NiO{sub x} thin films formed the working electrodes. Excellent optical contrast and switching speeds were observed in the fabricated devices with active areas of 2 cm{sup 2}, exhibiting an optical contrast of 73.11% at the wavelength of 470 nm, combined with a fast switching time of 0.2 s and 0.4 s for bleaching and coloration, respectively.

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.

Wood-Polymer composites obtained by gamma irradiation

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

Gago, J.; Lopez, A.; Rodriguez, J.

2007-10-26

In this work we impregnate three Peruvian woods (Calycophy spruceanum Be, Aniba amazonica Meiz and Hura crepitans L) with styrene-polyester resin and methyl methacrylate. The polymerization of the system was promoted by gamma radiation and the experimental optimal condition was obtained with styrene-polyester 1:1 and 15 kGy. The obtained composites show reduced water absorption and better mechanical properties compared to the original wood. The structure of the wood-polymer composites was studied by light microscopy. Water absorption and hardness were also obtained.

Poly(meth)acrylates obtained by cascade reaction.

PubMed

Popescu, Dragos; Keul, Helmut; Moeller, Martin

2011-04-04

Preparation, purification, and stabilization of functional (meth)acrylates with a high dipole moment are complex, laborious, and expensive processes. In order to avoid purification and stabilization of the highly reactive functional monomers, a concept of cascade reactions was developed comprising enzymatic monomer synthesis and radical polymerization. Transacylation of methyl acrylate (MA) and methyl methacrylate (MMA) with different functional alcohols, diols, and triols (1,2,6-hexanetriol and glycerol) in the presence of Novozyme 435 led to functional (meth)acrylates. After the removal of the enzyme by means of filtration, removal of excess (meth)acrylate and/or addition of a new monomer, e.g., 2-hydroxyethyl (meth)acrylate the (co)polymerization via free radical (FRP) or nitroxide mediated radical polymerization (NMP) resulted in poly[(meth)acrylate]s with predefined functionalities. Hydrophilic, hydrophobic as well as ionic repeating units were assembled within the copolymer. The transacylation of MA and MMA with diols and triols carried out under mild conditions is an easy and rapid process and is suitable for the preparation of sensitive monomers. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Detonation Characteristics of Plastic Explosives Based on Attractive Nitramines with Polyisobutylene and Poly(methyl methacrylate) Binders

NASA Astrophysics Data System (ADS)

Elbeih, Ahmed; Pachman, Jiri; Zeman, Svatopluk; Vávra, Pavel; Trzciński, Waldemar A.; Akštein, zbyněk

2012-10-01

Four highly brisant nitramines, RDX (1,3,5-trinitro-1,3,5-triazinane), HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane), BCHMX (cis-1,3,4,6-tetranitro-octahydroimidazo-[4,5-d]imidazole), and ɛ-HNIW (ɛ-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane), were studied as extruded plastic explosives bonded by two plastic matrices based on polyisobutylene (C4 matrix) and poly-methylmethacrylate (plasticized by dioctyl-adipate) binders. The detonation velocities, D, were measured experimentally. Detonation parameters were also calculated by means of the Kamlet and Jacobs method and CHEETAH and EXPLO5 codes. These detonation parameters showed that plastic-bonded explosives (PBXs) based on BCHMX are more powerful explosives than those based on RDX. The Urizar coefficient for poly(methyl methacrylate) binder was also calculated.

Increased functionality of methyl oleate using alkene metathesis

USDA-ARS?s Scientific Manuscript database

A series of alkene cross metathesis reactions were performed using a homogeneous ruthenium based catalyst. Using this technology, a variety of functional groups can be incorporated into the biobased starting material, methyl oleate. Trans-stilbene, styrene, methyl cinnamate and hexen-3-ol were all s...

Hydrophobic modification of cellulose isolated from Agave angustifolia fibre by graft copolymerisation using methyl methacrylate.

PubMed

Rosli, Noor Afizah; Ahmad, Ishak; Abdullah, Ibrahim; Anuar, Farah Hannan; Mohamed, Faizal

2015-07-10

Graft copolymerisation of methyl methacrylate (MMA) onto Agave angustifolia was conducted with ceric ammonium nitrate (CAN) as the redox initiator. The maximum grafting efficiency was observed at CAN and MMA concentrations of 0.91 × 10(-3) and 5.63 × 10(-2)M, respectively, at 45°C for 3h reaction time. Four characteristic peaks at 2995, 1738, 1440, and 845 cm(-1), attributed to PMMA, were found in the IR spectrum of grafted cellulose. The crystallinity index dropped from 0.74 to 0.46, while the thermal stability improved upon grafting. The water contact angle increased with grafting yield, indicating increased hydrophobicity of cellulose. SEM images showed the grafted cellulose to be enlarged and rougher. The changes in the physical nature of PMMA-grafted cellulose can be attributed to the PMMA grafting in the amorphous regions of cellulose, causing it to expand at the expense of the crystalline component. Copyright © 2015 Elsevier Ltd. All rights reserved.

The chemical modification and characterization of polypropylene membrane with environment response by in-situ chlorinating graft copolymerization

NASA Astrophysics Data System (ADS)

Zhang, Yue; Liu, Jiankai; Hu, Wenjie; Feng, Ying; Zhao, Jiruo

2017-08-01

In this study, a novel chemical surface modification method of polyolefin membranes is applied following the in-situ chlorinating graft copolymerization (ISCGC). Polypropylene (PP)/methyl methacrylate (MMA) system was used as an example. A unique structure was formed by the modification process on the original membrane surface and the product exhibited an environmental response. Chlorine free radicals were generated using ultraviolet and heat and were used to capture the hydrogen in the polymer chains on the substrate surface. The formed macromolecular radicals could react with MMA over 2 h to achieve a high coverage ratio polymer on the PP membrane surface. The graft copolymers were characterized using FTIR, 1H-NMR, DSC, and XPS, which all proved the feasibility of chemically modifying the PP membrane surface by ISCGC. The surface morphology of the grafted PP membrane was characterized using SEM and AFM. The results showed that the grafted product presents a uniform, neat, and dense mastoid structure with an average thickness of 4.44 μm, which was expected to be similar to the brush-like surface structure. The contact angle and AFM tests indicated that the product surface is responsive to solvent and pH. The experimental results showed that the PP membrane surface structure can be reconstructed using ISCGC, a method that can be used for environment-responsive polymer materials. Moreover, the product has the characteristics of polymer interfacial brush.

Experimental Study and Modelling of Poly (Methyl Methacrylate) and Polycarbonate Compressive Behavior from Low to High Strain Rates

NASA Astrophysics Data System (ADS)

El-Qoubaa, Z.; Colard, L.; Matadi Boumbimba, R.; Rusinek, A.

2018-06-01

This paper concerns an experimental investigation of Polycarbonate and Poly (methyl methacrylate) compressive behavior from low to high strain rates. Experiments were conducted from 0.001/s to ≈ 5000/s for PC and from 0.001/s to ≈ 2000/s for PMMA. The true strain-stress behavior is established and analyzed at various stain rates. Both PC and PMMA mechanical behavior appears as known, to be strain rate and temperature dependent. The DSGZ model is selected for modelling the strain-stress curves while the yield stress is reproduced using the cooperative model and a modified Eyring equation based on Eyring first process theory. All the three models predictions are in agreement with experiments performed on PC and PMMA.

Experimental Study and Modelling of Poly (Methyl Methacrylate) and Polycarbonate Compressive Behavior from Low to High Strain Rates

NASA Astrophysics Data System (ADS)

El-Qoubaa, Z.; Colard, L.; Matadi Boumbimba, R.; Rusinek, A.

2018-03-01

This paper concerns an experimental investigation of Polycarbonate and Poly (methyl methacrylate) compressive behavior from low to high strain rates. Experiments were conducted from 0.001/s to ≈ 5000/s for PC and from 0.001/s to ≈ 2000/s for PMMA. The true strain-stress behavior is established and analyzed at various stain rates. Both PC and PMMA mechanical behavior appears as known, to be strain rate and temperature dependent. The DSGZ model is selected for modelling the strain-stress curves while the yield stress is reproduced using the cooperative model and a modified Eyring equation based on Eyring first process theory. All the three models predictions are in agreement with experiments performed on PC and PMMA.

Poly(methyl methacrylate) as a self-assembled gate dielectric for graphene field-effect transistors

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

Sanne, A.; Movva, H. C. P.; Kang, S.

We investigate poly(methyl methacrylate) (PMMA) as a low thermal budget organic gate dielectric for graphene field effect-transistors (GFETs) based on a simple process flow. We show that high temperature baking steps above the glass transition temperature (∼130 °C) can leave a self-assembled, thin PMMA film on graphene, where we get a gate dielectric almost for “free” without additional atomic layer deposition type steps. Electrical characterization of GFETs with PMMA as a gate dielectric yields a dielectric constant of k = 3.0. GFETs with thinner PMMA dielectrics have a lower dielectric constant due to decreased polarization arising from neutralization of dipoles and charged carriersmore » as baking temperatures increase. The leakage through PMMA gate dielectric increases with decreasing dielectric thickness and increasing electric field. Unlike conventional high-k gate dielectrics, such low-k organic gate dielectrics are potentially attractive for devices such as the proposed Bilayer pseudoSpin Field-Effect Transistor or flexible high speed graphene electronics.« less

Adsorption and electron-induced polymerization of methyl methacrylate on Ru(101xAF0)

NASA Astrophysics Data System (ADS)

Hedhili, M. N.; Yakshinskiy, B. V.; Wasielewski, R.; Ciszewski, A.; Madey, T. E.

2008-05-01

The adsorption and electron irradiation of methyl methacrylate (MMA) on a Ru(101¯0) surface have been studied using x-ray photoelectron spectroscopy (XPS), temperature programmed desorption (TPD), and low energy ion scattering. TPD analysis indicates that a monolayer of MMA chemisorbs and dissociates on the Ru(101¯0) surface. The reaction products observed upon heating include H2, CO, CO2, and a small amount of MMA. Physisorbed multilayers of MMA desorb at temperatures around 170K. Electron irradiation of physisorbed MMA at 140K leads to a modification of the MMA film: The XPS spectra show an increase in thermal stability of the film with retention of the MMA structure, and indicate that electron irradiation induces polymerization. An increase in the electron bombardment fluence induces a degradation of the formed polymerized species and leads to the accumulation of carbon on the Ru surface. These results are relevant to the accumulation of carbon on surfaces of Ru films that serve as capping layers on Mo /Si multilayer mirrors used in extreme ultraviolet lithography.

Syntheses and Post-Polymerization Modifications of Well-Defined Styrenic Polymers Containing Three-Membered Heterocyclic Functionalities

NASA Astrophysics Data System (ADS)

McLeod, David Charles

Macromolecules that contain electrophilic moieties, such as benzyl halides, activated esters, and epoxides, will readily undergo efficient nucleophilic substitution reactions with a wide variety of compounds under mild conditions, and are therefore ideally suited to act as "universal" precursors to functional materials. Epoxide-containing polymers derived from the radical polymerization of commercially-available glycidyl methacrylate are often employed in this role; however, methacrylic polymers suffer from certain limitations as a result of the incorporated ester groups, which are not stabile in the presence of strong nucleophiles, acids, bases, or esterase enzymes. Styrenic polymers that do not contain labile carbonyl moieties are usually the precursors of choice when high chemical stability is desired in the end product, but the production of functional materials from epoxide-containing styrenic polymers is relatively unexplored. In this dissertation, improved methods were developed for synthesizing 4-vinylphenyloxirane (4VPO) and 4-vinylphenyl glycidyl ether (4VPGE), two of the better-known epoxide-containing styrenic monomers, in high-yield and purity. Well-defined, epoxide-containing styrenic polymers with targeted molecular weights, narrow molecular weight distributions, and controlled architectures (specifically, linear and star-shaped homopolymers, as well as linear block copolymers with styrene) were produced from 4VPO and 4VPGE for the first time using reversible-deactivation radical polymerization techniques, such as low-catalyst-concentration atom transfer radical polymerization (LCC ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. The robust nature and utility of poly4VPO and poly4VPGE were then demonstrated by the efficient, ring-opening modification of the pendant epoxide groups with a structurally- and functionally-diverse array of alcohols under acidic conditions at ambient temperature. The macromolecular

Two Players Make a Formidable Combination: In Situ Generated Poly(acrylic anhydride-2-methyl-acrylic acid-2-oxirane-ethyl ester-methyl methacrylate) Cross-Linking Gel Polymer Electrolyte toward 5 V High-Voltage Batteries.

PubMed

Ma, Yue; Ma, Jun; Chai, Jingchao; Liu, Zhihong; Ding, Guoliang; Xu, Gaojie; Liu, Haisheng; Chen, Bingbing; Zhou, Xinhong; Cui, Guanglei; Chen, Liquan

2017-11-29

Electrochemical performance of high-voltage lithium batteries with high energy density is limited because of the electrolyte instability and the electrode/electrolyte interfacial reactivity. Hence, a cross-linking polymer network of poly(acrylic anhydride-2-methyl-acrylic acid-2-oxirane-ethyl ester-methyl methacrylate) (PAMM)-based electrolyte was introduced via in situ polymerization inspired by "shuangjian hebi", which is a statement in a traditional Chinese Kungfu story similar to the synergetic effect of 1 + 1 > 2. A poly(acrylic anhydride) and poly(methyl methacrylate)-based system is very promising as electrolyte materials for lithium-ion batteries, in which the anhydride and acrylate groups can provide high voltage resistance and fast ionic conductivity, respectively. As a result, the cross-linking PAMM-based electrolyte possesses a significant comprehensive enhancement, including electrochemical stability window exceeding 5 V vs Li + /Li, an ionic conductivity of 6.79 × 10 -4 S cm -1 at room temperature, high mechanical strength (27.5 MPa), good flame resistance, and excellent interface compatibility with Li metal. It is also demonstrated that this gel polymer electrolyte suppresses the negative effect resulting from dissolution of Mn 2+ ions at 25 and 55 °C. Thus, the LiNi 0.5 Mn 1.5 O 4 /Li and LiNi 0.5 Mn 1.5 O 4 /Li 4 Ti 5 O 12 cells using the optimized in situ polymerized cross-linking PAMM-based gel polymer electrolyte deliver stable charging/discharging profiles and excellent rate performance at room temperature and even at 55 °C. These findings suggest that the cross-linking PAMM is an intriguing candidate for 5 V class high-voltage gel polymer electrolyte toward high-energy lithium-on batteries.

40 CFR 721.10526 - 2-Propenoic acid, 2-methyl-, 2-hydroxyethyl ester, telomers with C18-26-alkyl acrylate, 1...

Code of Federal Regulations, 2013 CFR

2013-07-01

...-dodecanethiol, N-(hydroxymethyl)-2-methyl-2-propenamide, polyfluorooctyl methacrylate and vinylidene chloride, 2...-alkyl acrylate, 1-dodecanethiol, N-(hydroxymethyl)-2-methyl-2-propenamide, polyfluorooctyl methacrylate... 40 Protection of Environment 32 2013-07-01 2013-07-01 false 2-Propenoic acid, 2-methyl-, 2...

40 CFR 721.10526 - 2-Propenoic acid, 2-methyl-, 2-hydroxyethyl ester, telomers with C18-26-alkyl acrylate, 1...

Code of Federal Regulations, 2014 CFR

2014-07-01

...-dodecanethiol, N-(hydroxymethyl)-2-methyl-2-propenamide, polyfluorooctyl methacrylate and vinylidene chloride, 2...-alkyl acrylate, 1-dodecanethiol, N-(hydroxymethyl)-2-methyl-2-propenamide, polyfluorooctyl methacrylate... 40 Protection of Environment 31 2014-07-01 2014-07-01 false 2-Propenoic acid, 2-methyl-, 2...

Periodic nanostructures formed on a poly-methyl methacrylate surface with a femtosecond laser for biocompatibility improvement

NASA Astrophysics Data System (ADS)

Takenaka, Keisuke; Tsukamoto, Masahiro; Sato, Yuji; Ooga, Takahiro; Asai, Satoru; Murai, Kensuke

2018-06-01

Poly(methyl methacrylate) (PMMA) is widely used as a biomaterial. The formation of periodic nanostructures on the surface is necessary to improve the biocompatibility. A method was proposed and developed to form periodic nanostructures on a PMMA surface. A PMMA plate was placed on titanium (Ti) plate, and then the Ti plate was irradiated with a laser through the PMMA plate. We try to effectively produce periodic nanostructures on PMMA with a femtosecond laser at a fundamental wavelength by increasing the contact pressure and using titanium (Ti) plate. The contact pressure between PMMA and Ti required to form a periodic nanostructure is 300 kPa, and for a contact pressure of 2400 kPa, periodic nanostructures are formed in 62% of the laser-irradiated area on the PMMA surface. These results suggest that the formation efficiency of the periodic nanostructure depends on the laser conditions and the contact pressure.

Flexible fiber-reinforced composites with improved interfacial adhesion by mussel-inspired polydopamine and poly(methyl methacrylate) coating.

PubMed

Yi, Mi; Sun, Hongyang; Zhang, Hongcheng; Deng, Xuliang; Cai, Qing; Yang, Xiaoping

2016-01-01

To obtain a kind of light-curable fiber-reinforced composite for dental restoration, an excellent interfacial adhesion between the fiber and the acrylate resin matrix is quite essential. Herein, surface modification on glass fibers were carried out by coating them with poly(methyl methacrylate) (PMMA), polydopamine (PDA), or both. The PMMA or PDA coating was performed by soaking fibers in PMMA/acetone solution or dopamine aqueous solution. PDA/PMMA co-coated glass fibers were obtained by further soaking PDA-coated fibers in PMMA/acetone solution. These modified fibers were impregnated with bisphenol A glycidyl methacrylate (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA) (5:5, w/w) dental resin at a volume fraction of 75%, using unmodified fibers as reference. Light-cured specimens were submitted to evaluations including flexural properties, morphological observation, dynamic mechanical thermal analysis (DMTA) and pull-out test. In comparison with unmodified glass fibers, all the modified glass fibers showed enhancements in flexural strength and modulus of Bis-GMA/TEGDMA resin composites. Results of DMTA and pull-out tests confirmed that surface modification had significantly improved the interfacial adhesion between the glass fiber and the resin matrix. Particularly, the PDA/PMMA co-coated glass fibers displayed the most efficient reinforcement and the strongest interfacial adhesion due to the synergetic effects of PDA and PMMA. It indicated that co-coating method was a promising approach in modifying the interfacial compatibility between inorganic glass fiber and organic resin matrix. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Fluorescence-based sensing of 2,4,6-trinitrotoluene (TNT) using a multi-channeled poly(methyl methacrylate) (PMMA) microimmunosensor.

PubMed

Charles, Paul T; Adams, Andre A; Howell, Peter B; Trammell, Scott A; Deschamps, Jeffrey R; Kusterbeck, Anne W

2010-01-01

Fluorescence immunoassays employing monoclonal antibodies directed against the explosive 2,4,6-trinitrotoluene (TNT) were conducted in a multi-channel microimmunosensor. The multi-channel microimmunosensor was prepared in poly (methyl methacrylate) (PMMA) via hot embossing from a brass molding tool. The multi-channeled microfluidic device was sol-gel coated to generate a siloxane surface that provided a scaffold for antibody immobilization. AlexaFluor-cadaverine-trinitrobenzene (AlexaFluor-Cad-TNB) was used as the reporter molecule in a displacement immunoassay. The limit of detection was 1-10 ng/mL (ppb) with a linear dynamic range that covered three orders of magnitude. In addition, antibody crossreactivity was investigated using hexahydro-1,3,5-triazine (RDX), HMX, 2,4-dinitrotoluene (DNT), 4-nitrotoluene (4-NT) and 2-amino-4,6-DNT.

Fluorescence-based Sensing of 2,4,6-Trinitrotoluene (TNT) Using a Multi-channeled Poly(methyl methacrylate) (PMMA) Microimmunosensor

PubMed Central

Charles, Paul T.; Adams, Andre A.; Howell, Peter B.; Trammell, Scott A.; Deschamps, Jeffrey R.; Kusterbeck, Anne W.

2010-01-01

Fluorescence immunoassays employing monoclonal antibodies directed against the explosive 2,4,6-trinitrotoluene (TNT) were conducted in a multi-channel microimmunosensor. The multi-channel microimmunosensor was prepared in poly (methyl methacrylate) (PMMA) via hot embossing from a brass molding tool. The multi-channeled microfluidic device was sol-gel coated to generate a siloxane surface that provided a scaffold for antibody immobilization. AlexaFluor-cadaverine-trinitrobenzene (AlexaFluor-Cad-TNB) was used as the reporter molecule in a displacement immunoassay. The limit of detection was 1–10 ng/mL (ppb) with a linear dynamic range that covered three orders of magnitude. In addition, antibody crossreactivity was investigated using hexahydro-1,3,5-triazine (RDX), HMX, 2,4-dinitrotoluene (DNT), 4-nitrotoluene (4-NT) and 2-amino-4,6-DNT. PMID:22315573

Ionogels Based on Poly(methyl methacrylate) and Metal-Containing Ionic Liquids: Correlation between Structure and Mechanical and Electrical Properties.

PubMed

Zehbe, Kerstin; Kollosche, Matthias; Lardong, Sebastian; Kelling, Alexandra; Schilde, Uwe; Taubert, Andreas

2016-03-16

Ionogels (IGs) based on poly(methyl methacrylate) (PMMA) and the metal-containing ionic liquids (ILs) bis-1-butyl-3-methlimidazolium tetrachloridocuprate(II), tetrachloride cobaltate(II), and tetrachlorido manganate(II) have been synthesized and their mechanical and electrical properties have been correlated with their microstructure. Unlike many previous examples, the current IGs show a decreasing stability in stress-strain experiments on increasing IL fractions. The conductivities of the current IGs are lower than those observed in similar examples in the literature. Both effects are caused by a two-phase structure with micrometer-sized IL-rich domains homogeneously dispersed an IL-deficient continuous PMMA phase. This study demonstrates that the IL-polymer miscibility and the morphology of the IGs are key parameters to control the (macroscopic) properties of IGs.

Cranioplasty using polymethyl methacrylate implant constructed from an alginate impression and wax elimination technique.

PubMed

Abdulai, Ae; Iddrissu, Mi; Dakurah, Tk

2006-03-01

Summary This is a retrospective review of the record charts. A joint study by maxillofacial and neurosurgical units, department of surgery, Korle Bu Teaching Hospital, Accra, Ghana, a tertiary and premier health care centre. Seventeen consecutive patients with various cranial defects treated using prefabricated acrylic methyl methacrylate implants. The cranioplasty on all the patients took place at an average of about 12 months after the initial surgery. These included complications during and after surgery. X-ray views of the skull, ranging from true lateral to anterior-posterior, were taken at follow-up and examined to ascertain the stability of the graft by looking out for any adverse bony changes around it or loosening of any of the steel sutures securing it to the skull. A total of 17 patients (5 males and 12 females) with a mean age of 30.4 years were treated. Follow-up period ranged from 9 months to two years. In all cases the surgical procedure was uneventful and the cosmetic results were good. There was no significant change in the size and shape of the preformed methyl methacrylate implant after autoclaving. Cranioplasty using prefabricated acrylic methyl methacrylate implants apart from being affordable also ensure shorter operative time and good aesthetic result.

Fabrication of superhydrophilic and antireflective silica coatings on poly(methyl methacrylate) substrates

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

Geng, Zhi; Graduate University of Chinese Academy of Sciences; He, Junhui, E-mail: jhhe@mail.ipc.ac.cn

2012-06-15

Graphical abstract: Self-cleaning and antireflection properties were successfully achieved by assembling (PDDA/S-20){sub n} coatings on PMMA substrates followed by oxygen plasma treatment. Highlights: ► Porous silica coatings were created by layer-by-layer assembly on PMMA substrates. ► Silica coatings were treated by oxygen plasma. ► Porous silica coatings were highly antireflective and superhydrophilic on PMMA substrates. -- Abstract: Silica nanoparticles of ca. 20 nm in size were synthesized, from which hierarchically porous silica coatings were fabricated on poly(methyl methacrylate) (PMMA) substrates via layer-by-layer (LbL) assembly followed by oxygen plasma treatment. These porous silica coatings were highly transparent and superhydrophilic. The maximummore » transmittance reached as high as 99%, whereas that of the PMMA substrate is only 92%. After oxygen plasma treatment, the time for a water droplet to spread to a contact angle of lower than 5° decreased to as short as 0.5 s. Scanning and transmission electron microscopy were used to observe the morphology and structure of nanoparticles and coating surfaces. Transmission and reflection spectra were recorded on UV–vis spectrophotometer. Surface wettability was studied by a contact angle/interface system. The influence of mesopores on the transmittance and wetting properties of coatings was discussed on the basis of experimental observations.« less

Nanoindentation and surface roughness profilometry of poly methyl methacrylate denture base materials.

PubMed

Zafar, Muhammad Sohail; Ahmed, Naseer

2014-01-01

Polymers have a wide range of applications in dentistry. Poly methyl methacrylate (PMMA) is the most popular for making orthodontic retainers, dentures as well as synthetic teeth. Prior to clinical applications, the appliances are polished in the dental laboratory to achieve smooth, polished and comfortable surfaces. The objective of this study was to analyze the surface roughness profiles of PMMA dentures polished using two different approaches. In addition, the effects of ultrasonication and sandblasting were also evaluated on the fitting surface of PMMA dentures. This was an in vitro study using non-contact mode surface roughness profilometer and nano-indenter. Samples were polished using two different techniques (Standard and modified). Both cold cure and heat cure PMMA denture surfaces were evaluated for roughness, nanohardness and elastic modulus. The absolute hardness was recorded 297.72±19.04 MPa and 229.93±18.53 MPa for heat cured PMMA and cold cured PMMA. Manufactured acrylic teeth were harder (319.20±12.58 MPa) with an elastic modulus of (4.34±1.86 GPa). Modified polishing techniques (group 3) produced smoother surface. It was concluded that elastic moduli of acrylic tooth and heat cure PMMA is not very different. Surface treatments such as ultrasonication or sandblasting do not affect the roughness profiles of denture fitting surfaces.

Segmental and local dynamics of stacked thin films of poly(methyl methacrylate)

NASA Astrophysics Data System (ADS)

Hayashi, Tatsuhiko; Fukao, Koji

2014-02-01

The glass transition temperature and the dynamics of the α and β processes have been investigated using differential scanning calorimetry and dielectric relaxation spectroscopy during successive annealing processes above the glass transition temperature for stacked thin films of poly(methyl methacrylate) (PMMA) of various thicknesses. The glass transition temperature and the dynamics of the α process (segmental motion) of as-stacked PMMA thin films exhibit thin-film-like behavior, insofar as the glass transition temperature is depressed and the dynamics of the α process are faster than those of the bulk system. Annealing at high temperature causes the glass transition temperature to increase from the reduced value and causes the dynamics of the α process to become slower approaching those of the bulk. Contrary to the segmental motion, the relaxation time of the β process (local motion) of the stacked PMMA thin films is almost equal to that of the bulk PMMA and is unaffected by the annealing process. However, the relaxation strengths of both the α process and β process show a strong correlation between each other. The sum of the relaxation strengths remains almost unchanged, while the individual relaxation strengths change during the annealing process. The fragility index of the stacked PMMA thin films increases with annealing, which suggests that the glassy state of the stacked thin films changes from strong to fragile.

Energetic Polyoxetane Thermoplastic Elastomers: Synthesis and Characterization

DTIC Science & Technology

1988-12-01

Stockmayer, L. D. Moore, M. Fixman, and B. N. Epstein, Copolymers in Dilute Solution. I. Preliminary Results for Styrene- Methyl Methacrylate , J. Polym. Sci... methyl groups of p-dicumyl chloride showed a singlet peak at about 2.0 ppm. The integration ratio of the peak at 2.0 ppm and 7.6 ppm is about 3 within...were prepared by Aerojet. 1H and 13C NMR spectra of polymer solutions in deuteriochloro- form (CDCl3), MSD Isotopes, Montreal, Quebec, Canada, were

Poly(methyl methacrylate)-graft-oligoamines as low cytotoxic and efficient nonviral gene vectors.

PubMed

Wang, Yong-Qiang; Sun, Yun-Xia; Hong, Xin-Lin; Zhang, Xian-Zheng; Zhang, Gao-Yong

2010-01-01

A series of poly(methyl methacrylate)-graft-oligoamines (PMMA-g-oligoamines), including PMMA-g-DETA, PMMA-g-TETA and PMMA-g-TEPA, were synthesized through aminolysis of the PMMA with diethylenetriamine, triethylenetetramine and tetraethylenepentamine. Agarose gel retardation assay indicated that PMMA-g-oligoamines had good binding capability with plasmid DNA, and the binding capability increased with increasing length of oligoamines and content of nitrogen (N%). The results of particle size, zeta potential and morphology observation further showed that the PMMA-g-oligoamines could condense DNA efficiently and the PMMA-g-oligoamine/DNA complexes were uniform nanospheres. The in vitro cell viability indicated that PMMA-g-oligoamines were less toxic than 25 kDa PEI, though the cytotoxicity of PMMA-g-oligoamines increased slightly with increasing length of oligoamines as well as the N% of PMMA-g-oligoamines. The transfection efficiency of PMMA-g-oligoamines/DNA complexes in 293 T and HeLa cells demonstrated that PMMA-g-oligoamines could transfect cells efficiently with increasing the length of oligoamines, especially PMMA-g-TEPA with highest N%, and showed similar transfection capability as 25 kDa PEI. The cellular uptake study showed that the distribution of YOYO-1 labeled DNA in the cytoplasm and nuclei increased gradually with increasing length of oligoamines.

[Fabrications of a poly (methyl methacrylate) (PMMA) microfluidic chip-based DNA analysis device].

PubMed

Du, Xiao-Guang

2009-12-01

A DNA analysis device based on poly(methyl methacrylate) (PMMA) microfluidic chips was developed. A PMMA chip with cross microchannels was fabricated by a simple hot embossing. Microchannels were modified with a static adsorptive coating method using 2% hydroxyethyl cellulose. A high-voltage power unit, variable in the range 0-1 800 V, was used for on-chip DNA sample injection and gel electrophoretic separation. High speed, high resolution DNA analysis was obtained with the home-built PMMA chip in a sieving matrix containing 2% hydroxyethyl cellulose with a blue intercalating dye, TO-PRO-3 (TP3), by using diode laser induced fluorescence detection based on optical fibers with a 670 nm long-pass filter. The DNA analysis device was applied for the separation of phiX-174/HaeIII DNA digest sample with 11 fragments ranging from 72 to 1 353 bp. A separation efficiency of 1.14 x 10(6) plates/m was obtained for the 603 bp fragments, while the R of 271/281 bp fragments was 1.2. The device was characterized by simple design, low cost for fabrication and operation, reusable PMMA chips, and good reproducibility. A portable microfluidic device for DNA analysis can be developed for clinical diagnosis and disease screening.

A novel bonding method for large scale poly(methyl methacrylate) micro- and nanofluidic chip fabrication

NASA Astrophysics Data System (ADS)

Qu, Xingtian; Li, Jinlai; Yin, Zhifu

2018-04-01

Micro- and nanofluidic chips are becoming increasing significance for biological and medical applications. Future advances in micro- and nanofluidics and its utilization in commercial applications depend on the development and fabrication of low cost and high fidelity large scale plastic micro- and nanofluidic chips. However, the majority of the present fabrication methods suffer from a low bonding rate of the chip during thermal bonding process due to air trapping between the substrate and the cover plate. In the present work, a novel bonding technique based on Ar plasma and water treatment was proposed to fully bond the large scale micro- and nanofluidic chips. The influence of Ar plasma parameters on the water contact angle and the effect of bonding conditions on the bonding rate and the bonding strength of the chip were studied. The fluorescence tests demonstrate that the 5 × 5 cm2 poly(methyl methacrylate) chip with 180 nm wide and 180 nm deep nanochannels can be fabricated without any block and leakage by our newly developed method.

Metal-Free Atom Transfer Radical Polymerization of Methyl Methacrylate with ppm Level of Organic Photocatalyst.

PubMed

Huang, Zhicheng; Gu, Yu; Liu, Xiaodong; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2017-05-01

It is well known that the recently developed photoinduced metal-free atom transfer radical polymerization (ATRP) has been considered as a promising methodology to completely eliminate transition metal residue in polymers. However, a serious problem needs to be improved, namely, large amount of organic photocatalysts should be used to keep the controllability over molecular weights and molecular weight distributions. In this work, a novel photocatalyst 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) with strong excited state reduction potential is successfully used to mediate a metal-free ATRP of methyl methacrylate just with parts per million (ppm) level usage under irradiation of blue light emitting diode at room temperature, using ethyl α-bromophenyl-acetate as a typical initiator with high initiator efficiency. The polymerization kinetic study, multiple controlled "on-off" light switching cycle regulation, and chain extension experiment confirm the "living"/controlled features of this promising photoinduced metal-free ATRP system with good molecular weight control in the presence of ppm level photocatalyst 4CzIPN. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene and poly(methyl methacrylate) composite laminates on flexible substrates for volatile organic compound detection

NASA Astrophysics Data System (ADS)

Rattanabut, Chanoknan; Wongwiriyapan, Winadda; Muangrat, Worawut; Bunjongpru, Win; Phonyiem, Mayuree; Song, Young Jae

2018-04-01

In this paper, we present a gas sensor for volatile organic compound (VOC) detection based on graphene and poly(methyl methacrylate) (GR/PMMA) composite laminates fabricated using CVD-grown graphene. Graphene was transferred to a poly(ethylene terephthalate) (PET) substrate by PMMA-supported wet transfer process without PMMA removal in order to achieve the deposition of GR/PMMA composite laminates on PET. The GR/PMMA and graphene sensors show completely different sensitivities to VOC vapors. The GR/PMMA and graphene sensors showed the highest sensitivities to dichloromethane (DCM). The response of the GR/PMMA sensor to DCM was 3 times higher than that of the graphene sensor but the GR/PMMA sensor hardly responded to acetone, chloroform, or benzene. The sensing mechanism of the graphene sensor can be based on the dielectric constant of VOCs, the size of VOC molecule, and electron hopping effects on defect graphene, while that of the GR/PMMA sensor can be explained in terms of the polymer swelling owing to the Hansen solubility parameter.

Microfluidic-Assisted Production of Size-Controlled Superparamagnetic Iron Oxide Nanoparticles-Loaded Poly(methyl methacrylate) Nanohybrids.

PubMed

Ding, Shukai; Attia, Mohamed F; Wallyn, Justine; Taddei, Chiara; Serra, Christophe A; Anton, Nicolas; Kassem, Mohamad; Schmutz, Marc; Er-Rafik, Meriem; Messaddeq, Nadia; Collard, Alexandre; Yu, Wei; Giordano, Michele; Vandamme, Thierry F

2018-02-06

In this paper, superparamagnetic iron oxide nanoparticles (SPIONs, around 6 nm) encapsulated in poly(methyl methacrylate) nanoparticles (PMMA NPs) with controlled sizes ranging from 100 to 200 nm have been successfully produced. The hybrid polymeric NPs were prepared following two different methods: (1) nanoprecipitation and (2) nanoemulsification-evaporation. These two methods were implemented in two different microprocesses based on the use of an impact jet micromixer and an elongational-flow microemulsifier. SPIONs-loaded PMMA NPs synthesized by the two methods presented completely different physicochemical properties. The polymeric NPs prepared with the micromixer-assisted nanoprecipitation method showed a heterogeneous dispersion of SPIONs inside the polymer matrix, an encapsulation efficiency close to 100 wt %, and an irregular shape. In contrast, the polymeric NPs prepared with the microfluidic-assisted nanoemulsification-evaporation method showed a homogeneous dispersion, an almost complete encapsulation, and a spherical shape. The properties of the polymeric NPs have been characterized by dynamic light scattering, thermogravimetric analysis, and transmission electron microscope. In vitro cytotoxicity assays were also performed on the nanohybrids and pure PMMA NPs.

21 CFR 177.1030 - Acrylonitrile/butadiene/styrene/methyl methacrylate copolymer.

Code of Federal Regulations, 2010 CFR

2010-04-01

... conditions of use C, D, E, F, and G described in table 2 of § 176.170(c) of this chapter with a high... inspection at the National Archives and Records Administration (NARA). For information on the availability of... and Records Administration (NARA). For information on the availability of this material at NARA, call...

Ionic Liquids as a Medium for Ionic Chain Polymerizations: An Environmentally Responsible Approach to Macromolecular Synthesis with Controlled Architecture

DTIC Science & Technology

2004-09-16

published in non peer-reviewed journals: 1. Gross, SM, Hamilton JL. "Polymer Gels for Use in Lithium Polymer Batteries", Nebraska Academy of Science...a process for the anionic polymerization of styrene and methyl methacrylate in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ...Current polymer electrolyte composites used for these applications typically comprise polyethers with ethylene carbonate solvents containing lithium

Effect of moisture on the physical and durability properties of methyl methacrylate polymer concrete

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

Fontana, J.J.; Reams, W.

1983-01-01

The compressive strength of methyl methacrylate PC composites decays very rapidly as the moisture content of the coarse aggregate is increased from 0 to 1 wt %. The durability of the PC also shows evidence of decay. Addition of silane coupling agent, such as A-1120, to the monomer component of a PC composite increases the compressive strength of such composites made with moist coarse aggregates. The compressive strengths of such PC composites are as high as a normal PCC used in highway applications. The durability of PC composites made with a silane additive seems to increase as the composite undergoesmore » freeze-thaw cycling which reinforces the justification that such materials can be used for PCC repairs without a sacrifice in use lifespans. However, for the convenience of using moist aggregates, one must endure the additional cost of the silane coupling agent. If it costs more than $0.02/lb to dry the aggregate, and one is willing to accept the reduced strengths associated with moist aggregates, then the use of a silane coupling agent can be cost effective. 3 figures, 4 tables.« less

Lithography exposure characteristics of poly(methyl methacrylate) (PMMA) for carbon, helium and hydrogen ions

NASA Astrophysics Data System (ADS)

Puttaraksa, Nitipon; Norarat, Rattanaporn; Laitinen, Mikko; Sajavaara, Timo; Singkarat, Somsorn; Whitlow, Harry J.

2012-02-01

Poly(methyl methacrylate) is a common polymer used as a lithographic resist for all forms of particle (photon, ion and electron) beam writing. Faithful lithographic reproduction requires that the exposure dose, Θ, lies in the window Θ0⩽Θ<Θ, where Θ0 and Θ represent the clearing and cross-linking onset doses, respectively. In this work we have used the programmable proximity aperture ion beam lithography systems in Chiang Mai and Jyväskylä to determine the exposure characteristics in terms of fluence for 2 MeV protons, 3 MeV 4He and 6 MeV 12C ions, respectively. After exposure the samples were developed in 7:3 by volume propan-2-ol:de-ionised water mixture. At low fluences, where the fluence is below the clearing fluence, the exposed regions were characterised by rough regions, particularly for He with holes around the ion tracks. As the fluence (dose) increases so that the dose exceeds the clearing dose, the PMMA is uniformly removed with sharp vertical walls. When Θ exceeds the cross-linking onset fluence, the bottom of the exposed regions show undissolved PMMA.

The Morphology of Emulsion Polymerized Latex Particles

DOE R&D Accomplishments Database

Wignall, G. D.; Ramakrishnan, V. R.; Linne, M. A.; Klein, A.; Sperling, L. H.; Wai, M. P.; Gelman, R. A.; Fatica, M. G.; Hoerl, R. H.; Fisher, L. W.

1987-11-01

Under monomer starved feed conditions, emulsion polymerization of perdeuterated methyl methacrylate and styrene in the presence of preformed polymethylmethacrylate latexes resulted in particles with a core-shell morphology, as determined by small-angle neutron scattering (SANS) analysis for a hollow sphere. The locus of polymerization of the added deuterated monomer is therefore at the particle surface. In similar measurements a statistical copolymer of styrene and methyl methacrylate was used as seed particles for further polymerization of trideuteromethyl methacrylate. The resulting polymer latex was again shown to have a core-shell morphological structure as determined by SANS. SANS experiments were also undertaken on polystyrene latexes polymerized by equilibrium swelling methods, with deuterated polymer forming the first or second step. The experiments covered a molecular weight range of 6 x 10{sup 4} 10{sup 6} the molecular weights are consistent with the experimental errors, indicating that the deuterium labeled molecules are randomly distributed in the latex. These results led to the finding that the polymer chains were constrained in the latex particles by factors of 2 to 4 from the relaxed coil dimensions. For M < 10{sup 6} g/mol SANS gave zero angle scattering intensities much higher than expected on the basis of a random distribution of labeled molecules. Several models were examined, including the possible development of core-shell structures at lower molecular weights.

Synthesis, characterization, and corrosion protection properties of poly( N-(methacryloyloxymethyl) benzotriazole- co-methyl methacrylate) on mild steel

NASA Astrophysics Data System (ADS)

Srikanth, A. P.; Lavanya, A.; Nanjundan, S.; Rajendran, N.

2006-12-01

The copolymers from different feed ratios of N-(methacryloyloxymethyl) benzotriazole (MMBT) and methyl methacrylate (MMA) has been synthesised using free radical solution polymerization technique and characterized using FT-IR and 13C NMR spectroscopy. The thermal stability of the polymers was studied using theremogravimetrtic analysis (TGA). The corrosion behaviors of mild steel specimens dip coated with different composition of copolymers have been evaluated by potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) method. These electrochemical properties were observed in 0.1 M HCl medium. The polarization and impedance measurements showed different corrosion protection efficiency with change in composition of the copolymers. It was found that the corrosion protection properties are owing to the barrier effect of the polymer layer covered on the mild steel surfaces. However, it was observed that the copolymer obtained from 1:1 mole ratio of MMBT and MMA exhibited better protection efficiency than other combinations.

Development of flow systems by direct-milling on poly(methyl methacrylate) substrates using UV-photopolymerization as sealing process.

PubMed

Rodrigues, Eunice R G O; Lapa, Rui A S

2009-03-01

An alternative process for the design and construction of fluidic devices is presented. Several sealing processes were studied, as well as the hydrodynamic characteristics of the proposed fluidic devices. Manifolds were imprinted on polymeric substrates by direct-write milling, according to Computer Assisted Design (CAD) data. Poly(methyl methacrylate) (PMMA) was used as substrate due to its physical and chemical properties. Different bonding approaches for the imprinted channels were evaluated and UV-photopolymerization of acrylic acid (AA) was selected. The hydrodynamic characteristics of the proposed flow devices were assessed and compared to those obtained in similar flow systems using PTFE reactors and micro-pumps as propulsion units (multi-pumping approach). The applicability of the imprinted reactors was evaluated in the sequential determination of calcium and magnesium in water samples. Results obtained were in good agreement with those obtained by the reference procedure.

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.

Superparamagnetic polymer emulsion particles from a soap-free seeded emulsion polymerization and their application for lipase immobilization.

PubMed

Cui, Yanjun; Chen, Xia; Li, Yanfeng; Liu, Xiao; Lei, Lin; Zhang, Yakui; Qian, Jiayu

2014-01-01

Using emulsion copolymer of styrene (St), glycidyl methacrylate (GMA) and 2-hydroxyethyl methacrylate (HEMA) as seed latexes, the superparamagnetic polymer emulsion particles were prepared by seeded emulsion copolymerization of butyl methacrylate (BMA), vinyl acetate (VAc) and ethylene glycol dimethacrylate in the presence of the seed latexes and superparamagnetic Fe3O4/SiOx nanoparticles (or Fe3O4-APTS nanoparticles) through a two-step process, without addition of any emulsifier. The magnetic emulsion particles named P(St-GMA-HEMA)/P(BMA-VAc) were characterized by transmission electron microscope and vibrating sample magnetometry. The results showed that the magnetic emulsion particles held a structure with a thinner shell (around 100 nm) and a bigger cavity (around 200 nm), and possessed a certain level of magnetic response. The resulting magnetic emulsion particles were employed in the immobilization of lipase by two strategies to immobilized lipase onto the resulting magnetic composites directly (S-1) or using glutaraldehyde as a coupling agent (S-2), thus, experimental data showed that the thermal stability and reusability of immobilized lipase based on S-2 were higher than that of S-1.

Photovoltaic and thermal properties of electrolytes based on electrospun poly(vinylidene fluoride-hexafluoro propylene)/poly(methyl methacrylate) nanofibers for dye-sensitized solar cells.

PubMed

Jang, Young-Wook; Won, Du-Hyun; Kim, Young-Keun; Hwang, Won-Pill; Jang, Sung-Il; Jeong, Sung-Hoon; Kim, Mi-Ra; Lee, Jin-Kook

2014-08-01

We prepared electrospun polymer nanofibers by electrospnning method and investigated about their applications to dye-sensitized solar cells (DSSCs). Electrospun polymer nanofibers applied to the polymer matrix in electrolyte for DSSCs. To improve the stiffness of polymer nanofiber, poly(vinylidene fluoride-hexafluoro propylene)/Poly(methyl methacrylate) (PVDF-HFP/PMMA) blend nanofibers were prepared and examined. In the electrospun PVDF-HFP/PMMA (1:1) blend nanofibers, the best results of VOC, JSC, FF, and efficiency of the DSSC devices showed 0.71 V, 12.8 mA/cm2, 0.61, and 5.56% under AM 1.5 illumination.

FAST TRACK COMMUNICATION: Poly(methyl methacrylate)-palladium clusters nanocomposite formation by supersonic cluster beam deposition: a method for microstructured metallization of polymer surfaces

NASA Astrophysics Data System (ADS)

Ravagnan, Luca; Divitini, Giorgio; Rebasti, Sara; Marelli, Mattia; Piseri, Paolo; Milani, Paolo

2009-04-01

Nanocomposite films were fabricated by supersonic cluster beam deposition (SCBD) of palladium clusters on poly(methyl methacrylate) (PMMA) surfaces. The evolution of the electrical conductance with cluster coverage and microscopy analysis show that Pd clusters are implanted in the polymer and form a continuous layer extending for several tens of nanometres beneath the polymer surface. This allows the deposition, using stencil masks, of cluster-assembled Pd microstructures on PMMA showing a remarkably high adhesion compared with metallic films obtained by thermal evaporation. These results suggest that SCBD is a promising tool for the fabrication of metallic microstructures on flexible polymeric substrates.

Ionogels Based on Poly(methyl methacrylate) and Metal-Containing Ionic Liquids: Correlation between Structure and Mechanical and Electrical Properties

PubMed Central

Zehbe, Kerstin; Kollosche, Matthias; Lardong, Sebastian; Kelling, Alexandra; Schilde, Uwe; Taubert, Andreas

2016-01-01

Ionogels (IGs) based on poly(methyl methacrylate) (PMMA) and the metal-containing ionic liquids (ILs) bis-1-butyl-3-methlimidazolium tetrachloridocuprate(II), tetrachloride cobaltate(II), and tetrachlorido manganate(II) have been synthesized and their mechanical and electrical properties have been correlated with their microstructure. Unlike many previous examples, the current IGs show a decreasing stability in stress-strain experiments on increasing IL fractions. The conductivities of the current IGs are lower than those observed in similar examples in the literature. Both effects are caused by a two-phase structure with micrometer-sized IL-rich domains homogeneously dispersed an IL-deficient continuous PMMA phase. This study demonstrates that the IL-polymer miscibility and the morphology of the IGs are key parameters to control the (macroscopic) properties of IGs. PMID:26999112

A ring to rule them all: a cyclic ketene acetal comonomer controls the nitroxide-mediated polymerization of methacrylates and confers tunable degradability.

PubMed

Delplace, Vianney; Guégain, Elise; Harrisson, Simon; Gigmes, Didier; Guillaneuf, Yohann; Nicolas, Julien

2015-08-18

2-Methylene-4-phenyl-1,3-dioxolane (MPDL) was successfully used as a controlling comonomer in NMP with oligo(ethylene glycol) methyl ether methacrylate (MeOEGMA) to prepare well-defined and degradable PEG-based P(MeOEGMA-co-MPDL) copolymers. The level of ester group incorporation is controlled, leading to reductions in molecular weight of up to 95% on hydrolysis. Neither the polymer nor its degradation products displayed cytoxicity. The method was also successfully applied to methyl methacrylate.

Use of hydrophobically modified inulin for the preparation of polymethyl methacrylate/polybutyl acrylate latex particles using a semicontinuous reactor.

PubMed

Obiols-Rabasa, M; Ramos, J; Forcada, J; Esquena, J; Solans, C; Levecke, B; Booten, K; Tadros, Tharwat F

2010-06-01

The seeded semicontinuous emulsion copolymerization of methyl methacrylate (MMA) and butyl acrylate (BuA) stabilized with a graft polymeric surfactant based on inulin, INUTEC SP1, as well as its mixture with sodium lauryl sulfate (SLS) is described. The mixture of SLS and Brij58 (alcohol ethoxylated) and the mixture of SLS and Pluronic P85 (block copolymer PEO-PPO-PEO) are also used as surfactant systems. The addition of methacrylic acid (MAA) or acrylic acid (AA) as comonomers is also studied. Previous results proved this inulin-derivative surfactant, INUTEC SP1, to be very effective on synthesizing latexes using a very low surfactant concentration. The kinetic features of the emulsion polymerization (instantaneous conversion and total conversion) were gravimetrically determined along the reactions. Latex dispersions were characterized by photon correlation spectroscopy (PCS) and transmission electron microscopy (TEM) to obtain the average particle size, the particle size distributions (PSDs) as well as the polydispersity index (PdI). The stability was determined by turbidimetry measurements and expressed in terms of critical coagulation concentration. The results showed that the use of the graft polymeric surfactant allowed obtaining highly stable nanoparticles, at low surfactant concentrations and high solid contents (up to 37 wt %). This is an improvement with respect to previous works, in which a mixture of the graft polymeric surfactant with another surfactant was required to obtain stable nanoparticles with low polydispersity, at high solid content. In the present work, low polydispersity was achieved using INUTEC as the only emulsifier, which was related to the absence of secondary nucleations. When a mixture of INUTEC SP1 and SLS is used, a wider PSD is obtained due to secondary nucleations. Replacing INUTEC SP1 by other nonionic surfactants such as Brij58 or Pluronic P85 leads to an increase of average particle size and wider PSD.

Thermo-sensitive polymer nanospheres as a smart plugging agent for shale gas drilling operations.

PubMed

Wang, Wei-Ji; Qiu, Zheng-Song; Zhong, Han-Yi; Huang, Wei-An; Dai, Wen-Hao

2017-01-01

Emulsifier-free poly(methyl methacrylate-styrene) [P(MMA-St)] nanospheres with an average particle size of 100 nm were synthesized in an isopropyl alcohol-water medium by a solvothermal method. Then, through radical graft copolymerization of thermo-sensitive monomer N -isopropylacrylamide (NIPAm) and hydrophilic monomer acrylic acid (AA) onto the surface of P(MMA-St) nanospheres at 80 °C, a series of thermo-sensitive polymer nanospheres, named SD-SEAL with different lower critical solution temperatures (LCST), were prepared by adjusting the mole ratio of NIPAm to AA. The products were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, thermogravimetric analysis, particle size distribution, and specific surface area analysis. The temperature-sensitive behavior was studied by light transmittance tests, while the sealing performance was investigated by pressure transmission tests with Lungmachi Formation shales. The experimental results showed that the synthesized nanoparticles are sensitive to temperature and had apparent LCST values which increased with an increase in hydrophilic monomer AA. When the temperature was higher than its LCST value, SD-SEAL played a dual role of physical plugging and chemical inhibition, slowed down pressure transmission, and reduced shale permeability remarkably. The plugged layer of shale was changed to being hydrophobic, which greatly improved the shale stability.

Triblock copolyampholytes from 5-(N,N-dimethyl amino)isoprene styrene, and methacrylic acid: Synthesis and solution properties

NASA Astrophysics Data System (ADS)

Bieringer, R.; Abetz, V.; Müller, A. H. E.

ABC triblock copolymers of the type poly[5-(N,N-dimethyl amino)isoprene]-block-polystyrene-block-poly(tert-butyl methacrylate) (AiST) were synthesized and hydrolyzed to yield poly[5-(N,N-dimethyl amino)isoprene]-block-polystyrene-block-poly(methacrylic acid) (AiSA) triblock copolyampholytes. Due to a complex solubility behavior the solution properties of these materials had to be investigated in THF/water solvent mixtures. Potentiometric titrations of AiSA triblock copolyampholytes showed two inflection points with the A block being deprotonated prior to the Ai hydrochloride block thus forming a polyzwitterion at the isoelectric point (iep). The aggregation behavior was studied by dynamic light scattering (DLS) and freeze-fracture/transmission electron microscopy (TEM). Large vesicular structures with almost pH-independent radii were observed.

Supercritical CO2 drying of poly(methyl methacrylate) photoresist for deep x-ray lithography: a brief note

NASA Astrophysics Data System (ADS)

Shukla, Rahul; Abhinandan, Lala; Sharma, Shivdutt

2017-07-01

Poly(methyl methacrylate) (PMMA) is an extensively used positive photoresist for deep x-ray lithography. The post-development release of the microstructures of PMMA becomes very critical for high aspect ratio fragile and freestanding microstructures. Release of high aspect ratio comb-drive microstructure of PMMA made by one-step x-ray lithography (OXL) is studied. The effect of low-surface tension Isopropyl alcohol (IPA) over water is investigated for release of the high aspect ratio microstructures using conventional and supercritical (SC) CO2 drying. The results of conventional drying are also compared for the samples released or dried in both in-house developed and commercial SC CO2 dryer. It is found that in all cases the microstructures of PMMA are permanently deformed and damaged while using SC CO2 for drying. For free-standing high aspect ratio microstructures of PMMA made by OXL, it is advised to use low-surface tension IPA over DI water. However, this brings a limitation on the design of the microstructure.

Synthesis and Characterization of Novel Fluorine-Containing Water-Based Antirust Coating

NASA Astrophysics Data System (ADS)

Wang, Huiru; Wang, Xin; Zhao, Xiongyan

2018-01-01

A fluorine-containing polyacrylate copolymer emulsion was synthesized by a seed emulsion polymerization method, in which styrene(St) and butyl acrylate (BA) were used as main monomers and dodecafluoroheptyl methacrylate(DFMA) as fluorine-containing monomer. The structure and properties were characterized by Fourier transform infrared spectrum (FT-IR), scanning electron microscopy (SEM), particle size analysis, differential scanning calorimetry (DSC). The FTIR results showed that DFMA was effectively involved in the emulsion copolymerization, and the formed emulsion particles had a narrow particle size distribution. From the results salt spray test presented, it seems when the content of DFMA was 5wt% anti-rust performance of emulsion is relatively better. DSC and TGA also showed that their film exhibited higher thermal stability than that of fluorine-free emulsion.

Synthesis of Fe3O4 poly(styrene-glycidyl methacrylate) magnetic porous microspheres and application in the immobilization of Klebsiella sp. FD-3 to reduce Fe(III)EDTA in a NO(x) scrubbing solution.

PubMed

Wang, Xiaoyan; Zhou, Zuoming; Jing, Guohua

2013-02-01

Magnetic poly(styrene-glycidyl methacrylate) porous microspheres (MPPM) with high magnetic contents were prepared by surfactant reverse micelles and emulsion polymerization of monomers, in which the well-dispersed Fe(3)O(4) nanoparticles were modified by polyethylene glycol (PEG) and oleic acid (OA) respectively. The characterizations showed that both of the OA-MPPM and the PEG-MPPM were ferromagnetic, however, the OA-MPPM was used to immobilize the bacteria for more advantages. Therefore, the effects of monomer ratio, surfactant, crosslinker and amount of Fe(3)O(4) on the structure, morphology and magnetic contents of the OA-MPPM were investigated. Then, the OA-MPPM was utilized to immobilize Klebsiella sp. FD-3, an iron-reducing bacterium for Fe(III)EDTA reduction applied in NO(x) removal. Compared with free bacteria, the immobilized FD-3 showed a better tolerance to the unbeneficial pH and temperature conditions. Copyright © 2012 Elsevier Ltd. All rights reserved.

Wax inhibitor based on ethylene vinyl acetate with methyl methacrylate and diethanolamine for crude oil pipeline

NASA Astrophysics Data System (ADS)

Anisuzzaman, S. M.; Abang, S.; Bono, A.; Krishnaiah, D.; Karali, R.; Safuan, M. K.

2017-06-01

Wax precipitation and deposition is one of the most significant flow assurance challenges in the production system of the crude oil. Wax inhibitors are developed as a preventive strategy to avoid an absolute wax deposition. Wax inhibitors are polymers which can be known as pour point depressants as they impede the wax crystals formation, growth, and deposition. In this study three formulations of wax inhibitors were prepared, ethylene vinyl acetate, ethylene vinyl acetate co-methyl methacrylate (EVA co-MMA) and ethylene vinyl acetate co-diethanolamine (EVA co-DEA) and the comparison of their efficiencies in terms of cloud point¸ pour point, performance inhibition efficiency (%PIE) and viscosity were evaluated. The cloud point and pour point for both EVA and EVA co-MMA were similar, 15°C and 10-5°C, respectively. Whereas, the cloud point and pour point for EVA co-DEA were better, 10°C and 10-5°C respectively. In conclusion, EVA co-DEA had shown the best % PIE (28.42%) which indicates highest percentage reduction of wax deposit as compared to the other two inhibitors.

Synthesis of tetraaza bromide macrocyclic and studies of its effect on poly(methyl methacrylate) grafted natural rubber (MG49) - lithium tertrafluoroborate (LiBF{sub 4}) films

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

Mariam, Siti Nor; Yamin, Bohari M.; Ahmad, Azizan

2013-11-27

Good Poly(Methyl Methacrylate) Grafted natural Rubber (MG49) films with homogeneous and smooth surface were obtained in the presence of Lithium Tertrafluoroborate (LiBF{sub 4}) and 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7,14-dienium bromide, (Me{sub 6}N{sub 4}H{sub 4})Br{sub 2} as dopants. The conductivity was found to be 3.63×10{sup −6} S/cm an increase by seven fold compare to the undoped MG49.

Fabrication of poly(methyl methacrylate)-MoS{sub 2}/graphene heterostructure for memory device application

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

Shinde, Sachin M.; Tanemura, Masaki; Kalita, Golap, E-mail: kalita.golap@nitech.ac.jp

2014-12-07

Combination of two dimensional graphene and semi-conducting molybdenum disulfide (MoS{sub 2}) is of great interest for various electronic device applications. Here, we demonstrate fabrication of a hybridized structure with the chemical vapor deposited graphene and MoS{sub 2} crystals to configure a memory device. Elongated hexagonal and rhombus shaped MoS{sub 2} crystals are synthesized by sulfurization of thermally evaporated molybdenum oxide (MoO{sub 3}) thin film. Scanning transmission electron microscope studies reveal atomic level structure of the synthesized high quality MoS{sub 2} crystals. In the prospect of a memory device fabrication, poly(methyl methacrylate) (PMMA) is used as an insulating dielectric material asmore » well as a supporting layer to transfer the MoS{sub 2} crystals. In the fabricated device, PMMA-MoS{sub 2} and graphene layers act as the functional and electrode materials, respectively. Distinctive bistable electrical switching and nonvolatile rewritable memory effect is observed in the fabricated PMMA-MoS{sub 2}/graphene heterostructure. The developed material system and demonstrated memory device fabrication can be significant for next generation data storage applications.« less

Evaluate styrene production

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

Hagopian, C.R.; Lewis, P.J.; McDonald, J.J.

1983-02-01

Improvements and innovations in styrene production since 1966 are outlined. Rigorous process models are attributed to the changes. Such models are used to evaluate the effects of changing raw material costs, utility costs, and available catalyst choices. The process model can also evaluate the best operating configuration and catalyst choice for a plant. All specified innovations are incorporated in the Mobil/Badger ethylbenzene and the Cosden/Badger styrene processes (both of which are schematicized). Badger's training programs are reviewed. Badger's Styrenics Business Team converts information into plant design basis. A reaction model with input derived from isothermal and adiabatic pilot plant unitsmore » is at the heart of complete computer simulation of ethylbenzene and styrene processes.« less

Ototoxic effects of occupational exposure to styrene and co-exposure to styrene and noise.

PubMed

Sliwińska-Kowalska, Mariola; Zamyslowska-Szmytke, Ewa; Szymczak, Wieslaw; Kotylo, Piotr; Fiszer, Marta; Wesolowski, Wiktor; Pawlaczyk-Luszczynska, Malgorzata

2003-01-01

Ototoxicity of styrene and the synergistic action of styrene and noise have been shown in rats. The respective data in humans are scarce and equivocal. This study evaluated the effects of occupational exposure to styrene and combined exposures to styrene and noise on hearing. The study group, comprised of 290-yacht yard and plastic factory workers, was exposed to a mixture of organic solvents, having styrene as its main compound. The reference group, totaling 223 subjects, included (1) white-collar workers, exposed neither to solvents nor noise and (2) metal factory workers, exposed exclusively to noise. All subjects were assessed by means of a detailed questionnaire and underwent otorhinolaryngological and audiometric examinations. Multiple logistic regression analysis revealed almost a 4-fold (or 3.9; 95% CI = 2.4-6.2) increase in the odds of developing hearing loss related to styrene exposure. The factors adjusted for were: age, gender, current occupational exposure to noise, and exposure to noise in the past. In cases of the combined exposures to styrene and noise, the odds ratios were two to three times higher than the respective values for styrene-only and noise-only exposed subjects. The mean hearing thresholds--adjusted for age, gender, and exposure to noise--were significantly higher in the solvent-exposed group than in the unexposed reference group at all frequencies tested. A positive linear relationship existed between an averaged working life exposure to styrene concentration and a hearing threshold at the frequencies of 6 and 8 kHz. This study provides the epidemiological evidence that occupational exposure to styrene is related to an increased risk of hearing loss. Combined exposures to noise and styrene seem to be more ototoxic than exposure to noise alone.

Effect of powder to liquid ratio on tensile strength and glass transition temperature of alumina filled poly methyl methacrylate (PMMA) denture base material.

PubMed

Mohamed, S H; Arifin, A; Mohd Ishak, Z A; Nizam, A; Samsudin, A R

2004-05-01

The aim of this study was to evaluate the mechanical properties and glass transition temperature (Tg) of a denture base material prepared from high molecular weight poly methyl methacrylate (PMMA) and alumina (Al2O3). The glass transition temperature was studied by using differential scanning calorimetry (DSC). The effect of powder-to-liquid ratio was investigated. The result showed that the tensile properties and the Tg were slightly effected by the powder-to-liquid ratio. The ratio of 2.2:1 by weight of powder to liquid was found to be the best ratio for mixing the material to give the best result in this formulation.

Redox-Controlled Olefin (Co)Polymerization Catalyzed by Ferrocene-Bridged Phosphine-Sulfonate Palladium Complexes.

PubMed

Chen, Min; Yang, Bangpei; Chen, Changle

2015-12-14

The facile and reversible interconversion between neutral and oxidized forms of palladium complexes containing ferrocene-bridged phosphine sulfonate ligands was demonstrated. The activity of these palladium complexes could be controlled using redox reagents during ethylene homopolymerization, ethylene/methyl acrylate copolymerization, and norbornene oligomerization. Specifically in norbornene oligomerization, the neutral complexes were not active at all whereas the oxidized counterparts showed appreciable activity. In situ switching between the neutral and oxidized forms resulted in an interesting "off" and "on" behavior in norbornene oligomerization. This work provides a new strategy to control the olefin polymerization process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation, thermal property and morphology analysis of waterborne polyurethane-acrylate

NASA Astrophysics Data System (ADS)

Zhao, Zhenyu; Jing, Zefeng; Qiu, Fengxian; Dai, Yuting; Xu, Jicheng; Yu, Zongping; Yang, Pengfei

2017-01-01

A series of waterborne polyurethane-acrylate (WPUA) dispersions were prepared with isophorone diisocyanate (IPDI), polyether polyol (NJ-210), dimethylol propionic acid (DMPA), hydroxyethyl methyl acrylate (HEMA), different proportions of methyl methacrylate (MMA) and ethyl acrylate (MMA and EA) and initiating agent by the emulsion co-polymerization. The structures, thermal properties and morphology of WPUA films were characterized with FT-IR, DSC, SEM and AFM. Performances of the dispersions and films were studied by means of apparent viscidity, particle size and polydispersity, surface tension and mechanical properties. The obtained WPUA have great potential application such as coatings, leather finishing, adhesives, sealants, plastic coatings and wood finishes.

Supramolecular Cross-Links in Poly(alkyl methacrylate) Copolymers and Their Impact on the Mechanical and Reversible Adhesive Properties.

PubMed

Heinzmann, Christian; Salz, Ulrich; Moszner, Norbert; Fiore, Gina L; Weder, Christoph

2015-06-24

Hydrogen-bonded, side-chain-functionalized supramolecular poly(alkyl methacrylate)s were investigated as light- and temperature-responsive reversible adhesives that are useful for bonding and debonding on demand applications. Here, 2-hydroxyethyl methacrylate (HEMA) was functionalized with 2-ureido-4[1H]pyrimidinone (UPy) via a hexamethylenediisocyanate (HMDI) linker, to create a monomer (UPy-HMDI-HEMA) that serves to form supramolecular cross-links by way of forming quadruple hydrogen bonded dimers. UPy-HMDI-HEMA was copolymerized with either hexyl methacrylate or butyl methacrylate to create copolymers comprising 2.5, 5, or 10 mol % of the cross-linker. The mechanical properties of all (co)polymers were investigated with stress-strain experiments and dynamic mechanical analysis. Furthermore, the adhesive properties were studied at temperatures between 20 and 60 °C by testing single lap joints formed with stainless steel substrates. It was found that increasing the concentration of the UPy-HMDI-HEMA cross-linker leads to improved mechanical and adhesive properties at elevated temperatures. Concurrently, the reversibility of the bond formation remained unaffected, where rebonded samples displayed the same adhesive strength as regularly bonded samples. Debonding on demand abilities were also tested exemplarily for one copolymer, which for light-induced debonding experiments was blended with a UV-absorber that served as light-heat converter. Single lap joints were subjected to a constant force and heated or irradiated with UV light until debonding occurred. The necessary debonding temperature was comparable for direct heating and UV irradiation and varied between 28 and 82 °C, depending on the applied force. The latter also influenced the debonding time, which under the chosen conditions ranged from 30 s to 12 min.

High-pressure copolymerization of C 2H 4 and CO

NASA Astrophysics Data System (ADS)

Buback, M.; Tups, H.

1986-05-01

Kinetics of the free radical high-pressure copolymerization of ethylene and carbon monoxide using thermal, chemical, and laser-photochemical initiation have been investigated via quantitative infrared and near infrared spectroscopy up to 2300 bar and 513 K. The slow thermal copolymerization is influenced by the formation of metal carbonyls inside the stainless steel cell. With chemical initiation, using 120 ppm oxygen, ethylene and CO polymerize to polyketone without any indication of additional products. The photo-copolymerization induced by an exciplex laser working on the KrF line at 248 nm, has been studied between 486 K and 513 K up to 2300 bar and for CO mole fractions up to 3 percent. Overall quantum yields of about 2000 copolymerizing molecules per one absorbed laser photon are observed.

Zwitterionic sulfobetaine-grafted poly(vinylidene fluoride) membrane with highly effective blood compatibility via atmospheric plasma-induced surface copolymerization.

PubMed

Chang, Yung; Chang, Wan-Ju; Shih, Yu-Ju; Wei, Ta-Chin; Hsiue, Ging-Ho

2011-04-01

Development of nonfouling membranes to prevent nonspecific protein adsorption and platelet adhesion is critical for many biomedical applications. It is always a challenge to control the surface graft copolymerization of a highly polar monomer from the highly hydrophobic surface of a fluoropolymer membrane. In this work, the blood compatibility of poly(vinylidene fluoride) (PVDF) membranes with surface-grafted electrically neutral zwitterionic poly(sulfobetaine methacrylate) (PSBMA), from atmospheric plasma-induced surface copolymerization, was studied. The effect of surface composition and graft morphology, electrical neutrality, hydrophilicity and hydration capability on blood compatibility of the membranes were determined. Blood compatibility of the zwitterionic PVDF membranes was systematically evaluated by plasma protein adsorption, platelet adhesion, plasma-clotting time, and blood cell hemolysis. It was found that the nonfouling nature and hydration capability of grafted PSBMA polymers can be effectively controlled by regulating the grafting coverage and charge balance of the PSBMA layer on the PVDF membrane surface. Even a slight charge bias in the grafted zwitterionic PSBMA layer can induce electrostatic interactions between proteins and the membrane surfaces, leading to surface protein adsorption, platelet activation, plasma clotting and blood cell hemolysis. Thus, the optimized PSBMA surface graft layer in overall charge neutrality has a high hydration capability and the best antifouling, anticoagulant, and antihemolytic activities when comes into contact with human blood. © 2011 American Chemical Society

Styrene exposure and risk of cancer

PubMed Central

Huff, James; Infante, Peter F.

2011-01-01

Styrene is widely used in the manufacture of synthetic rubber, resins, polyesters and plastics. Styrene and the primary metabolite styrene-7,8-oxide are genotoxic and carcinogenic. Long-term chemical carcinogenesis bioassays showed that styrene caused lung cancers in several strains of mice and mammary cancers in rats and styrene-7,8-oxide caused tumours of the forestomach in rats and mice and of the liver in mice. Subsequent epidemiologic studies found styrene workers had increased mortality or incidences of lymphohematopoietic cancers (leukaemia or lymphoma or all), with suggestive evidence for pancreatic and esophageal tumours. No adequate human studies are available for styrene-7,8-oxide although this is the primary and active epoxide metabolite of styrene. Both are genotoxic and form DNA adducts in humans. PMID:21724974

Predictors of occupational exposure to styrene and styrene-7,8-oxide in the reinforced plastics industry.

PubMed

Serdar, B; Tornero-Velez, R; Echeverria, D; Nylander-French, L A; Kupper, L L; Rappaport, S M

2006-10-01

To identify demographic and work related factors that predict blood levels of styrene and styrene-7,8-oxide (SO) in the fibreglass reinforced plastics (FRP) industry. Personal breathing-zone air samples and whole blood samples were collected repeatedly from 328 reinforced plastics workers in the Unuted States between 1996 and 1999. Styrene and its major metabolite SO were measured in these samples. Multivariable linear regression analyses were applied to the subject-specific levels to explain the variation in exposure and biomarker levels. Exposure levels of styrene were approximately 500-fold higher than those of SO. Exposure levels of styrene and SO varied greatly among the types of products manufactured, with an 11-fold range of median air levels among categories for styrene and a 23-fold range for SO. Even after stratification by job title, median exposures of styrene and SO among laminators varied 14- and 31-fold across product categories. Furthermore, the relative proportions of exposures to styrene and SO varied among product categories. Multivariable regression analyses explained 70% and 63% of the variation in air levels of styrene and SO, respectively, and 72% and 34% of the variation in blood levels of styrene and SO, respectively. Overall, air levels of styrene and SO appear to have decreased substantially in this industry over the last 10-20 years in the US and were greatest among workers with the least seniority. As levels of styrene and SO in air and blood varied among product categories in the FRP industry, use of job title as a surrogate for exposure can introduce unpredictable measurement errors and can confound the relation between exposure and health outcomes in epidemiology studies. Also, inverse relations between the intensity of exposure to styrene and SO and years on the job suggest that younger workers with little seniority are typically exposed to higher levels of styrene and SO than their coworkers.

Self-assembly and omniphobic property of fluorinated unit end-functionalized poly(methyl methacrylate)

NASA Astrophysics Data System (ADS)

Junyan, Liang; Pingdi, Xu; Jingxian, Bao; Ling, He; Nan, Zhu

2018-03-01

The self-assembly behavior of fluorinated unit end-functionalized poly(methyl methacrylate) (PDFHM-ef-PMMA) in solution and its influence on the surface microstructure, elemental composition and omniphobic property of cast film was investigated in this work. Specifically, three mixed solutions of tetrahydrofuran (THF)/methanol (MeOH), THF/H2O and THF/H2O/MeOH in various compositions were employed separately as the selective solvents. In THF/MeOH solution, the aggregate morphologies of PDFHM-ef-PMMA changed gradually from core-shell spheres to worm, and then to elliptical vesicles as MeOH content increased. In THF/H2O solution, spherical and bowl-shaped aggregates with significantly larger sizes than those in THF/MeOH solution were favored despite lower H2O content. The further addition of MeOH to THF/H2O mixture could reduce the size of aggregate but hardly change original aggregate morphology. During the film formation process, those self-assembled aggregates in THF/MeOH solution fused with one another to form a smooth surface. When such surface was fully covered by fluorinated segments, the outstanding hexadecane and water slide-off properties and ink-resistant property required for antifouling application were demonstrated. Instead, the aggregates formed in THF/H2O/MeOH mixture were subjected to secondary aggregation of PDFHM-ef-PMMA chains during solvent evaporation, leading to the formation of a particulate film with poor adhesion towards glass plate and hexadecane-repellent property.

Responses of Vascular Endothelial Cells to Photoembossed Topographies on Poly(Methyl Methacrylate) Films

PubMed Central

Qiu, Lin; Hughes-Brittain, Nanayaa F.; Bastiaansen, Cees W. M.; Peijs, Ton; Wang, Wen

2016-01-01

Failures of vascular grafts are normally caused by the lack of a durable and adherent endothelium covering the graft which leads to thrombus and neointima formation. A promising approach to overcome these issues is to create a functional, quiescent monolayer of endothelial cells on the surface of implants. The present study reports for the first time on the use of photoembossing as a technique to create polymer films with different topographical features for improved cell interaction in biomedical applications. For this, a photopolymer is created by mixing poly(methyl methacrylate) (PMMA) and trimethylolpropane ethoxylate triacrylate (TPETA) at a 1:1 ratio. This photopolymer demonstrated an improvement in biocompatibility over PMMA which is already known to be biocompatible and has been extensively used in the biomedical field. Additionally, photoembossed films showed significantly improved cell attachment and proliferation compared to their non-embossed counterparts. Surface texturing consisted of grooves of different pitches (6, 10, and 20 µm) and heights (1 µm and 2.5 µm). The 20 µm pitch photoembossed films significantly accelerated cell migration in a wound-healing assay, while films with a 6 µm pitch inhibited cells from detaching. Additionally, the relief structure obtained by photoembossing also changed the surface wettability of the substrates. Photoembossed PMMA-TPETA systems benefited from this change as it improved their water contact angle to around 70°, making it well suited for cell adhesion. PMID:27941669

Carrier transport in flexible organic bistable devices of ZnO nanoparticles embedded in an insulating poly(methyl methacrylate) polymer layer.

PubMed

Son, Dong-Ick; Park, Dong-Hee; Choi, Won Kook; Cho, Sung-Hwan; Kim, Won-Tae; Kim, Tae Whan

2009-05-13

The bistable effects of ZnO nanoparticles embedded in an insulating poly(methyl methacrylate) (PMMA) polymer single layer by using flexible polyethylene terephthalate (PET) substrates were investigated. Transmission electron microscopy (TEM) images revealed that ZnO nanoparticles were formed inside the PMMA polymer layer. Current-voltage (I-V) measurement on the Al/ZnO nanoparticles embedded in an insulating PMMA polymer layer/ITO/PET structures at 300 K showed a nonvolatile electrical bistability behavior with a flat-band voltage shift due to the existence of the ZnO nanoparticles, indicative of trapping, storing, and emission of charges in the electronic states of the ZnO nanoparticles. The carrier transport mechanism of the bistable behavior for the fabricated organic bistable device (OBD) structures is described on the basis of the I-V results by analyzing the effect of space charge.

Mono- and dinuclear bioxazoline-palladium complexes for the stereocontrolled synthesis of CO/styrene polyketones.

PubMed

Scarel, Alessandro; Durand, Jérôme; Franchi, Davide; Zangrando, Ennio; Mestroni, Giovanni; Carfagna, Carla; Mosca, Luca; Seraglia, Roberta; Consiglio, Giambattista; Milani, Barbara

2005-10-07

The coordination chemistry of the chiral bioxazoline ligand (4S,4'S)-2,2'-bis(4-isopropyl-4,5-dihydrooxazole) to Pd(II) provides evidence that the ligand bonding can occur either through chelation of one Pd(II) ion leading to a mononuclear species with the expected cis geometry, or by double bridging of two Pd(II) ions giving a dinuclear complex with trans geometry. The species in solution are identified by 1H NMR spectroscopy. Both the mononuclear and the dinuclear complexes promote the CO/styrene copolymerization, yielding the corresponding polyketone with a fully or a predominantly isotactic microstructure, depending on the reaction medium. The nature of the anion present in the palladium precatalysts affects the polyketone stereochemistry. MALDI-TOF analysis of the copolymers synthesized reveals the presence of p-hydroxyphenolic end-groups, thus confirming and explaining the role of 1,4-hydroquinone as a molecular weight regulator.

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 Sol-Gel-Modified Poly(methyl methacrylate) Electrophoresis Microchip with a Hydrophilic Channel Wall

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

Chen, Gang; Xu, Xuejiao; Lin, Yuehe

2007-07-27

A sol-gel method was employed to fabricate a poly(methyl methacrylate) (PMMA) electrophoresis microchip that contains a hydrophilic channel wall. To fabricate such a device, tetraethoxysilane (TEOS) was injected into the PMMA channel and was allowed to diffuse into the surface layer for 24 h. After removing the excess TEOS, the channel was filled with an acidic solution for 3 h. Subsequently, the channel was flushed with water and was pretreated in an oven to obtain a sol-gel-modified PMMA microchip. The water contact angle for the sol-gel-modified PMMA was 27.4° compared with 66.3° for the pure PMMA. In addition, the electro-osmoticmore » flow increased from 2.13×10-4 cm2 V-1 s-1 for the native-PMMA channel to 4.86×10-4 cm2 V-1 s-1 for the modified one. The analytical performance of the sol-gel-modified PMMA microchip was demonstrated for the electrophoretic separation of several purines, coupled with amperometric detection. The separation efficiency of uric acid increased to 74 882.3 m-1 compared with 14 730.5 m-1 for native-PMMA microchips. The result of this simple modification is a significant improvement in the performance of PMMA for microchip electrophoresis and microfluidic applications.« less

Miscible blends of biobased poly(lactide) with poly(methyl methacrylate): Effects of chopped glass fiber incorporation

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

Cousins, Dylan S.; Lowe, Corinne; Swan, Dana

Poly(lactide) (PLA) and poly(methyl methacrylate) (PMMA) are melt compounded with chopped glass fiber using laboratory scale twin-screw extrusion. Physical properties are examined using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), thermogravimetric analysis (TGA), tensile testing, impact testing, X-ray computed tomography (CT) scanning, and field emission scanning electron microscopy (FE-SEM). Molecular weight is determined using gel permeation chromatography (GPC). Miscibility of the blends is implied by the presence of a single glass transition temperature and homogeneous morphology. PLA/PMMA blends tend to show positive deviations from a simple linear mixing rule in their mechanical properties (e.g., tensile toughness, modulus, andmore » stress at break). The addition of 40 wt % glass fiber to the system dramatically increases physical properties. Across all blend compositions, the tensile modulus increases from roughly 3 GPa to roughly 10 GPa. Estimated heat distortion temperatures (HDTs) are also greatly enhanced; the pure PLA sample HDT increases from 75 degrees C to 135 degrees C. Fiber filled polymer blends represent a sustainable class of earth abundant materials which should prove useful across a range of applications.« less

Static adsorptive coating of poly(methyl methacrylate) microfluidic chips for extended usage in DNA separations.

PubMed

Du, Xiao-Guang; Fang, Zhao-Lun

2005-12-01

A simple and robust static adsorptive (dynamic) coating process using 2% hydroxyethylcellulose was developed for surface modification of poly(methyl methacrylate) (PMMA) microfluidic chips for DNA separations, suitable for usage over extended periods, involving hundreds of runs. The coating medium was also used as a sieving matrix for the DNA separations following the coating process. Four consecutive static treatments, by simply filling the PMMA chip channels with sieving matrix once every day, were required for obtaining a stable coating and optimum performance. The performance of the coated chips at different phases of the coating process was studied by consecutive gel electrophoretic separations with LIF detection using a PhiX-174/HaeIII DNA digest sample. The coated chip, with daily renewal of the sieving matrix, showed high stability in performance during a 25-day period of systematic study, involving more than 100 individual runs. The performance of the coated chip also remained almost the same after 3 months of continuous usage, during which over 200 separations were performed. The average precision of migration time for the 603-bp fragment was 1.31% RSD (n = 6) during the 25-day study, with a separation efficiency of 6.5 x 10(4) plates (effective separation length 5.4 cm).

Tuning the critical solution temperature of polymers by copolymerization

NASA Astrophysics Data System (ADS)

Schulz, Bernhard; Chudoba, Richard; Heyda, Jan; Dzubiella, Joachim

2015-12-01

We study statistical copolymerization effects on the upper critical solution temperature (CST) of generic homopolymers by means of coarse-grained Langevin dynamics computer simulations and mean-field theory. Our systematic investigation reveals that the CST can change monotonically or non-monotonically with copolymerization, as observed in experimental studies, depending on the degree of non-additivity of the monomer (A-B) cross-interactions. The simulation findings are confirmed and qualitatively explained by a combination of a two-component Flory-de Gennes model for polymer collapse and a simple thermodynamic expansion approach. Our findings provide some rationale behind the effects of copolymerization and may be helpful for tuning CST behavior of polymers in soft material design.

Experimental and Numerical Study on Effect of Sample Orientation on Auto-Ignition and Piloted Ignition of Poly(methyl methacrylate)

PubMed Central

Peng, Fei; Zhou, Xiao-Dong; Zhao, Kun; Wu, Zhi-Bo; Yang, Li-Zhong

2015-01-01

In this work, the effect of seven different sample orientations from 0° to 90° on pilot and non-pilot ignition of PMMA (poly(methyl methacrylate)) exposed to radiation has been studied with experimental and numerical methods. Some new and significant conclusions are drawn from the study, including a U-shape curve of ignition time and critical mass flux as sample angle increases for pilot ignition conditions. However, in auto-ignition, the ignition time and critical mass flux increases with sample angle α. Furthermore, a computational fluid dynamic model have been built based on the Fire Dynamics Simulator (FDS6) code to investigate the mechanisms controlling the dependence on sample orientation of the ignition of PMMA under external radiant heating. The results of theoretical analysis and modeling results indicate the decrease of total incident heat flux at sample surface plays the dominant role during the ignition processes of auto-ignition, but the volatiles gas flow has greater influence for piloted ignition conditions. PMID:28793421

Kinetic study of Candida antarctica lipase B immobilization using poly(methyl methacrylate) nanoparticles obtained by miniemulsion polymerization as support.

PubMed

Valério, Alexsandra; Nicoletti, Gabrieli; Cipolatti, Eliane P; Ninow, Jorge L; Araújo, Pedro H H; Sayer, Cláudia; de Oliveira, Débora

2015-03-01

With the objective to obtain immobilized Candida antarctica lipase B (CalB) with good activity and improved utilization rate, this study evaluated the influence of enzyme and crodamol concentrations and initiator type on the CalB enzyme immobilization in nanoparticles consisting of poly(methyl methacrylate) (PMMA) obtained by miniemulsion polymerization. The kinetic study of immobilized CalB enzyme in PMMA nanoparticles was evaluated in terms of monomer conversion, particle size, zeta potential, and relative activity. The optimum immobilization condition for CalB was compared with free enzyme in the p-NPL hydrolysis activity measurement. Results showed a higher CalB enzyme stability after 20 hydrolysis cycles compared with free CalB enzyme; in particular, the relative immobilized enzyme activity was maintained up to 40%. In conclusion, PMMA nanoparticles proved to be a good support for the CalB enzyme immobilization and may be used as a feasible alternative catalyst in industrial processes.

Isolation and characterization of styrene metabolism genes from styrene-assimilating soil bacteria Rhodococcus sp. ST-5 and ST-10.

PubMed

Toda, Hiroshi; Itoh, Nobuya

2012-01-01

Styrene metabolism genes were isolated from styrene-assimilating bacteria Rhodococcus sp. ST-5 and ST-10. Strain ST-5 had a gene cluster containing four open reading frames which encoded styrene degradation enzymes. The genes showed high similarity to styABCD of Pseudomonas sp. Y2. On the other hand, strain ST-10 had only two genes which encoded styrene monooxygenase and flavin oxidoreductase (styAB). Escherichia coli transformants possessing the sty genes of strains ST-5 and ST-10 produced (S)-styrene oxide from styrene, indicating that these genes function as styrene degradation enzymes. Metabolite analysis by resting-cell reaction with gas chromatography-mass spectrometry revealed that strain ST-5 converts styrene to phenylacetaldehyde via styrene oxide by styrene oxide isomerase (styC) reaction. On the other hand, strain ST-10 lacked this enzyme, and thus accumulated styrene oxide as an intermediate. HPLC analysis showed that styrene oxide was spontaneously isomerized to phenylacetaldehyde by chemical reaction. The produced phenylacetaldehyde was converted to phenylacetic acid (PAA) in strain ST-10 as well as in strain ST-5. Furthermore, phenylacetic acid was converted to phenylacetyl-CoA by the catalysis of phenylacetate-CoA ligase in strains ST-5 and ST-10. This study proposes possible styrene metabolism pathways in Rhodococcus sp. strains ST-5 and ST-10. Copyright © 2011 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Effect of Al2O3 in poly(methyl methacrylate) composite polymer electrolytes

NASA Astrophysics Data System (ADS)

Sun, C. C.; You, A. H.; Teo, L. L.; Thong, L. W.

2018-05-01

In this work, the effect of inert fillers on poly(methyl methacrylate) (PMMA) composite polymer electrolytes (CPEs) are investigated. The PMMA-LiCF3SO3-EC-Al2O3 composite polymer electrolytes were prepared using solution casting method at room temperature. Lithium trifluoromethanesulfonate (LiCF3SO3) is used as the electrolyte salt which plays an important role in Li ion transfer. In order to soften the polymer matrix, ethylene carbonate (EC) is introduced into the CPEs to help in the disassociation of lithium salt ion pairs. Nano sized aluminium oxide (Al2O3) is then incorporated to enhance mechanical strength and ionic conductivity of the polymer electrolyte. The optimum of 2 wt.% 50 nm Al2O3 was added into the PMMA polymer electrolyte sample. Through Electrochemical Impedance Spectroscopy (EIS) measurements, the highest ionic conductivity at room temperature is determined as 1.52×10-4 S/cm. FTIR spectra analysis showed CH2 twisting mode at 1383.43 cm-1, C=O stretching mode at 1721.56 cm-1 which proven the interaction between host polymer and lithium salt and CH3 stretching mode at 2981.34 cm-1. XRD analysis had also been performed to study the structural behaviour of the PMMA polymer electrolyte. The intense peak at position 2θ angle of 15.04°, 30.92° and 45.58° occur upon interaction with Al2O3. Lastly, the surface morphology is studied through SEM+EDX analysis.

Addition of zinc methacrylate in dental polymers: MMP-2 inhibition and ultimate tensile strength evaluation.

PubMed

Henn, Sandrina; de Carvalho, Rodrigo Varella; Ogliari, Fabrício Aulo; de Souza, Ana Paula; Line, Sergio Roberto Peres; da Silva, Adriana Fernandes; Demarco, Flávio Fernando; Etges, Adriana; Piva, Evandro

2012-04-01

This study evaluated the effect of zinc methacrylate (ZM) on the inhibition of matrix metalloproteinase 2 (MMP-2) and the ultimate tensile strength (UTS) of an experimental polymer. Enzymes secreted from mouse gingival tissues were analyzed by gelatin zymography in buffers containing 5 mM CaCl(2) (Tris-CaCl(2)) in 50 mM Tris-HCl buffer with various concentrations of ZM (0.5, 1, 2, 4, 8, and 16 mM). The matrix metalloproteinases present in the conditioned media were characterized by immunoprecipitation. The polymer UTS evaluation was performed in eight groups with various concentrations of ZM (0, 0.5, 1, 2.5, 5, 10, 20, and 30 wt.%), in a mechanical testing machine. MMP-2 (62 kDa) was detected in the zymographic assays and inhibited by ZM in all tested concentrations. UTS data were submitted to one-way ANOVA and Tukey's test (α = 0.05), and no significant differences were observed among groups, except in the polymer containing 30% ZM, presenting a significantly lower value when compared with the control group (p < 0.05). The results suggest that ZM inhibits MMP-2 expression in all concentrations tested, while small concentrations did not affect the ultimate tensile strength of the polymer. Zinc methacrylate is a metalloproteinase inhibitor that can be copolymerized with other methacrylate monomers. Yet, the addition of ZM did not affect the resin bond strength. Thus, in vivo tests should be performed to evaluate the performance of this material.

2-Isopropenyl-2-oxazoline: Well-Defined Homopolymers and Block Copolymers via Living Anionic Polymerization

DOE PAGES

Feng, Hongbo; Changez, Mohammad; Hong, Kunlun; ...

2016-12-23

Poly(2-isopropenyl-2-oxazoline) (PIPOx) has drawn significant attention for numerous applications. However, the successful living anionic polymerization of 2-isopropenyl-2-oxazoline has not been reported previously. In this paper, we describe how well-defined PIPOx with quantitative yields, controlled molecular weights from 6800 to over 100 000 g/mol and low polydispersity indices (PDI ≤ 1.17) were synthesized successfully via living anionic polymerization using diphenylmethylpotassium/diethylzinc (DPM-K/Et 2Zn) in tetrahydrofuran (THF) at 0 °C. In particular, we report the precise synthesis of well-defined PIPOx with the highest molecular weight ever reported (over 100 000 g/mol) and low PDI of 1.17. The resulting polymers were characterized by 1Hmore » and 13C nuclear magnetic resonance spectroscopy (NMR) along with size exclusion chromatography (SEC). Additionally, the reactivity of living PIPOx was investigated by crossover block copolymerization with styrene (St), 2-vinylpyridine (2VP), and methyl methacrylate (MMA). It was found that the nucleophilicity of living PIPOx is of this order: living PS > living P2VP > living PMMA > living PIPOx. The self-assembly behavior in bulk of PIPOx-b-PS-b-PIPOx triblock copolymers having different block ratios of 10:80:10 and 25:50:25 was studied using transmission electron microscopy (TEM). Finally, the formation of spherical and lamellar nanostructures, respectively, was observed.« less

2-Isopropenyl-2-oxazoline: Well-Defined Homopolymers and Block Copolymers via Living Anionic Polymerization

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

Feng, Hongbo; Changez, Mohammad; Hong, Kunlun

Poly(2-isopropenyl-2-oxazoline) (PIPOx) has drawn significant attention for numerous applications. However, the successful living anionic polymerization of 2-isopropenyl-2-oxazoline has not been reported previously. In this paper, we describe how well-defined PIPOx with quantitative yields, controlled molecular weights from 6800 to over 100 000 g/mol and low polydispersity indices (PDI ≤ 1.17) were synthesized successfully via living anionic polymerization using diphenylmethylpotassium/diethylzinc (DPM-K/Et 2Zn) in tetrahydrofuran (THF) at 0 °C. In particular, we report the precise synthesis of well-defined PIPOx with the highest molecular weight ever reported (over 100 000 g/mol) and low PDI of 1.17. The resulting polymers were characterized by 1Hmore » and 13C nuclear magnetic resonance spectroscopy (NMR) along with size exclusion chromatography (SEC). Additionally, the reactivity of living PIPOx was investigated by crossover block copolymerization with styrene (St), 2-vinylpyridine (2VP), and methyl methacrylate (MMA). It was found that the nucleophilicity of living PIPOx is of this order: living PS > living P2VP > living PMMA > living PIPOx. The self-assembly behavior in bulk of PIPOx-b-PS-b-PIPOx triblock copolymers having different block ratios of 10:80:10 and 25:50:25 was studied using transmission electron microscopy (TEM). Finally, the formation of spherical and lamellar nanostructures, respectively, was observed.« less

Surface modification of copolymerized films from three-armed biodegradable macromers - An analytical platform for modified tissue engineering scaffolds.

PubMed

Müller, Benno M; Loth, Rudi; Hoffmeister, Peter-Georg; Zühl, Friederike; Kalbitzer, Liv; Hacker, Michael C; Schulz-Siegmund, Michaela

2017-03-15

The concept of macromers allows for a broad adjustment of biomaterial properties by macromer chemistry or copolymerization. Copolymerization strategies can also be used to introduce reactive sites for subsequent surface modification. Control over surface features enables adjustment of cellular reactions with regard to site and object of implantation. We designed macromer-derived polymer films which function as non-implantable analytical substrates for the investigation of surface properties of equally composed scaffolds for bone tissue engineering. To this end, a toolbox of nine different biodegradable, three-armed macromers was thermally cross-copolymerized with poly(ethylene glycol)-methacrylate (PEG-MA) to films. Subsequent activation of PEG-hydroxyl groups with succinic anhydride and N-hydroxysuccinimid allowed for covalent surface modification. We quantified the capacity to immobilize analytes of low (amino-functionalized fluorescent dye, Fcad, and RGD-peptides) and high (alkaline phosphatase, ALP) molecular weight. Fcad grafting level was controlled by macromer chemistry, content and molecular weight of PEG-MA, but also the solvent used for film synthesis. Fcad molar amount per surface area was twentyfive times higher on high-swelling compared to low-swelling films, but differences became smaller when large ALP (appr. 2:1) were employed. Similarly, small differences were observed on RGD peptide functionalized films that were investigated by cell adhesion studies. Presentation of PEG-derivatives on surfaces was visualized by atomic force microscopy (AFM) which unraveled composition-dependent domain formation influencing fluorescent dye immobilization. Surface wetting characteristics were investigated via static water contact angle. We conclude that macromer ethoxylation and lactic acid content determined film swelling, PEG domain formation and eventually efficiency of surface decoration. Surfaces of implantable biomaterials are the site of interaction with a

Sequential interpenetrating polymer networks produced from vegetable oil based polyurethane and poly(methyl methacrylate).

PubMed

Kong, Xiaohua; Narine, Suresh S

2008-08-01

Sequential interpenetrating polymer networks (IPNs) were prepared using polyurethane produced from a canola oil based polyol with primary terminal functional groups and poly(methyl methacrylate) (PMMA). The properties of the material were studied and compared to the IPNs made from commercial castor oil using dynamic mechanical analysis, differential scanning calorimetry, as well as tensile measurements. The morphology of the IPNs was investigated using scanning electron microscopy and transmission electron microscopy. The chemical diversity of the starting materials allowed the evaluation of the effects of dangling chains and graftings on the properties of the IPNs. The polymerization process of canola oil based IPNs was accelerated because of the utilization of polyol with primary functional groups, which efficiently lessened the effect of dangling chains and yielded a higher degree of phase mixing. The mechanical properties of canola oil based IPNs containing more than 75 wt % PMMA were comparable to the corresponding castor oil based IPNs; both were superior to those of the constituent polymers due to the finely divided rubber and plastic combination structures in these IPNs. However, when PMMA content was less than 65 wt %, canola oil based IPNs exhibited a typical mechanical behavior of rigid plastics, whereas castor oil based IPNs showed a typical mechanical behavior of soft rubber. It is proposed that these new IPN materials with high performance prepared from alternative renewable resources can prove to be valuable substitutes for existing materials in various applications.

Facile synthesis of graphene by pyrolysis of poly(methyl methacrylate) on nickel particles in the confined microzones

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

Hong, Ningning; Yang, Wei; Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute of University of Science and Technology of China, Suzhou, Jiangsu, 215123

2012-12-15

Graphical abstract: Display Omitted Highlights: ► The GNWs with few defects were synthesized by pyrolyzing PMMA on nickel particles. ► PMMA as carbon source was easily prepared and safe to handle. ► Nickel microparticles were directly used as catalysts without any pre-treatment. ► The method can be used for the low cost and bulk production of graphene. -- Abstract: In this work, multi-layer graphene has been prepared by pyrolyzing poly(methyl methacrylate) (PMMA) on nickel microparticles in the confined microzones formed by organophilic montmorillonite (OMT). Gram-scale of product can be obtained per day by using this method. The obtained graphene wasmore » evaluated by scanning and transmission electron microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermogravimetric analysis. Pyrolytic conditions such as the system composition of the composites, reaction temperature and the size of catalyst are important parameters affecting the morphology and yield of the final product. Based on the experimental observations and reported literatures, a possible formation process is discussed. The synthesis method of graphene is simple, low-cost, and scalable, which is promising for the application in many fields.« less

Aging phenomena in poly(methyl methacrylate) thin films: Memory and rejuvenation effects

NASA Astrophysics Data System (ADS)

Fukao, K.; Sakamoto, A.

2005-04-01

The aging dynamics in thin films of poly(methyl methacrylate) (PMMA) have been investigated through dielectric measurements for different types of aging processes. The dielectric constant was found to decrease with increasing aging time at an aging temperature in many cases. An increase in the dielectric constant was also observed in the long-time region (⩾11h) near the glass transition temperature for thin films with thickness less than 26nm . In the constant-rate mode including a temporary stop at a temperature Ta , the memory of the aging at Ta was found to be kept and then to be recalled during the subsequent heating process. In the negative-temperature cycling process, a strong rejuvenation effect has been observed after a temperature shift from the initial temperature T1 to the second temperature T2 (=T1+ΔT) when ΔT≈-20K . Furthermore, a full memory effect has also been observed for the temperature shift from T2 to T1 . This suggests that the aging at T1 is totally independent of that at T2 for ΔT≈-20K . As ∣ΔT∣ decreases, the independence of the aging between the two temperatures was found to be weakened—i.e., the effective time, which is a measure of the contribution of the aging at T1 to that at T2 , is a decreasing function of ∣ΔT∣ in the negative region of ΔT . As the film thickness decreases from 514nmto26nm , the ∣ΔT∣ dependence of the effective time was found to become much stronger. The contribution of the aging at T2 to that at T1 disappears more rapidly with increasing ∣ΔT∣ in thin-film geometry than in the bulk state.

Preparation and Characterization of Injectable Brushite Filled-Poly (Methyl Methacrylate) Bone Cement

PubMed Central

Rodriguez, Lucas C.; Chari, Jonathan; Aghyarian, Shant; Gindri, Izabelle M.; Kosmopoulos, Victor; Rodrigues, Danieli C.

2014-01-01

Powder-liquid poly (methyl methacrylate) (PMMA) bone cements are widely utilized for augmentation of bone fractures and fixation of orthopedic implants. These cements typically have an abundance of beneficial qualities, however their lack of bioactivity allows for continued development. To enhance osseointegration and bioactivity, calcium phosphate cements prepared with hydroxyapatite, brushite or tricalcium phosphates have been introduced with rather unsuccessful results due to increased cement viscosity, poor handling and reduced mechanical performance. This has limited the use of such cements in applications requiring delivery through small cannulas and in load bearing. The goal of this study is to design an alternative cement system that can better accommodate calcium-phosphate additives while preserving cement rheological properties and performance. In the present work, a number of brushite-filled two-solution bone cements were prepared and characterized by studying their complex viscosity-versus-test frequency, extrusion stress, clumping tendency during injection through a syringe, extent of fill of a machined void in cortical bone analog specimens, and compressive strength. The addition of brushite into the two-solution cement formulations investigated did not affect the pseudoplastic behavior and handling properties of the materials as demonstrated by rheological experiments. Extrusion stress was observed to vary with brushite concentration with values lower or in the range of control PMMA-based cements. The materials were observed to completely fill pre-formed voids in bone analog specimens. Cement compressive strength was observed to decrease with increasing concentration of fillers; however, the materials exhibited high enough strength for consideration in load bearing applications. The results indicated that partially substituting the PMMA phase of the two-solution cement with brushite at a 40% by mass concentration provided the best combination of the

Enhanced electrical conductivity of poly(methyl methacrylate) filled with graphene and in situ synthesized gold nanoparticles

NASA Astrophysics Data System (ADS)

Feng, Jie; Athanassiou, Athanassia; Bonaccorso, Francesco; Fragouli, Despina

2018-06-01

The improvement of the electrical conductivity of polymers by incorporating graphene has been intensively studied in recent years. To further boost the electrical conductivity, blending third-party additives into the polymer/graphene systems has been demonstrated as a viable strategy. Herein, we propose a simple route to increase the electrical conductivity of poly(methyl methacrylate) (PMMA)/graphene nanoplatelet (GnP) composites, by the in situ synthesis of gold nanoparticles directly into the solid film. In particular, PMMA, GnPs and a gold precursor are solution blended to form the composite films. The subsequent heat-induced formation of gold nanoparticles directly in the solid state film, cause the significant decrease of the percolation threshold of GnPs loading, from 3% to 1% by weight in the composite. This is attributed to the preferential formation of the gold nanoparticles onto the GnPs, with synergistic effects beneficial for the improvement of the electrical conductivity. The formation procedure of the gold nanoparticles, and their arrangement into the composite matrix are studied. We demonstrate that following this straightforward process it is possible to form nanocomposites able to conduct efficiently electric current even at low graphene loadings preserving at the same time the mechanical properties of the polymer matrix.

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.

Three Dimensional Assembly in Directed Self-assembly of Block Copolymers

DOE PAGES

Segal-Peretz, Tamar; Zhou, Chun; Ren, Jiaxing; ...

2016-09-02

The three-dimensional assembly of poly (styrene-b-methyl methacrylate) (PS-b-PMMA) in chemoepitaxy and graphoepitaxy directed self-assembly (DSA) was investigated using scanning transmission electron microscopy (STEM) tomography. The tomographic characterization revealed hidden morphologies and defects at the BCP- chemical pattern interface in lamellar DSA, and probed the formation of cylinders at the bottom of cylindrical DSA for contact hole shrink. Lastly, future work will include control over 3D assembly in sub-10 nm processes.

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

Segal-Peretz, Tamar; Zhou, Chun; Ren, Jiaxing

The three-dimensional assembly of poly (styrene-b-methyl methacrylate) (PS-b-PMMA) in chemoepitaxy and graphoepitaxy directed self-assembly (DSA) was investigated using scanning transmission electron microscopy (STEM) tomography. The tomographic characterization revealed hidden morphologies and defects at the BCP- chemical pattern interface in lamellar DSA, and probed the formation of cylinders at the bottom of cylindrical DSA for contact hole shrink. Lastly, future work will include control over 3D assembly in sub-10 nm processes.

Catalysts for CO2/epoxide ring-opening copolymerization

PubMed Central

Trott, G.; Saini, P. K.; Williams, C. K.

2016-01-01

This article summarizes and reviews recent progress in the development of catalysts for the ring-opening copolymerization of carbon dioxide and epoxides. The copolymerization is an interesting method to add value to carbon dioxide, including from waste sources, and to reduce pollution associated with commodity polymer manufacture. The selection of the catalyst is of critical importance to control the composition, properties and applications of the resultant polymers. This review highlights and exemplifies some key recent findings and hypotheses, in particular using examples drawn from our own research. PMID:26755758

Composite plasma polymerized sulfonated polystyrene membrane for PEMFC

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

Nath, Bhabesh Kumar; Khan, Aziz; Chutia, Joyanti, E-mail: jchutiaiasst@gmail.com

2015-10-15

Highlights: • Methyl methane sulfonate (MMS) is used as the sulfonating agent. • The proton conductivity of the membrane is found to be 0.141 S cm{sup −1}. • Power density of fuel cell with styrene/MMS membrane is 0.5 W cm{sup −2}. • The membrane exhibits thermal stability up to 140 °C. - Abstract: This work presents the introduction of an organic compound methyl methane sulfonate (MMS) for the first time in fabrication of polystyrene based proton exchange membrane (PEM) by plasma polymerization process. The membrane is fabricated by co-polymerizing styrene and MMS in capacitively coupled continuous RF plasma. The chemicalmore » composition of the plasma polymerized polymer membrane is investigated using Fourier Transform Infrared Spectroscopy which reveals the formation of composite structure of styrene and MMS. The surface morphology studied using AFM and SEM depicts the effect of higher partial pressure of MMS on surface topography of the membrane. The proton transport property of the membrane studied using electrochemical impedance spectroscopy shows the achievement of maximum proton conductivity of 0.141 S cm{sup −1} which is comparable to Nafion 117 membrane. Fuel cell performance test of the synthesized membrane shows a maximum power density of 500 mW cm{sup −2} and current density of 0.62 A cm{sup −2} at 0.6 V.« less

Mesoscale simulation of the formation and dynamics of lipid-structured poly(ethylene oxide)-block-poly(methyl methacrylate) diblock copolymers.

PubMed

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

2015-05-21

Twelve poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) copolymers with lipid-like structures were designed and investigated by MesoDyn simulation. Spherical and worm-like micelles as well as bicontinuous, lamellar and defected lamellar phases were obtained. A special structure, designated B2412, with two lipid structures connected by their heads, was found to undergo four stages prior to forming a spherical micelle phase. Two possible assembly mechanisms were found via thermodynamic and dynamic process analyses; namely, the fusion and fission of micelles in dynamic equilibrium during the adjustment stage. Water can be encapsulated into these micelles, which can affect their size, particularly in low concentration aqueous solutions. The assignment of weak negative charges to the hydrophilic EO blocks resulted in a clear effect on micelle size. Surprisingly, the largest effect was observed with EO blocks with -0.5 e, wherein an ordered perfect hexagonal phase was formed. The obtained results can be applied in numerous fields of study, including adsorption, catalysis, controlled release and drug delivery.

[Monitoring of methyl methacrylate monomer released from autopolymerized denture base polymers during processing using time-of-flight mass spectrometer].

PubMed

Ma, Yu-juan; Cui, Hua-peng; Li, Hai-yang

2011-04-01

To analyze the amount and tendency of methyl methacrylate (MMA) released from autopolymerized denture base polymer (self-curing resin) during processing using time-of-flight mass spectrometer (TOF-MS). Self-curing resin was mixed in the container using a ratio of 2 g of powder to 1 g of liquid in accordance with the manufacturer's instructions for 40 s as a specimen. The amount of MMA released from the specimen was continuously monitored and simultaneously recorded every minute by TOF-MS since immediately after mixing. A total of five specimens were monitored. The amount of MMA increased dramatically at 11 min [(45.2 ± 3.5) mg/L] after mixing, and reached the highest level at 13 min [(228.9 ± 22.6) mg/L], then become stable at 23 min [(8.8 ± 2.3) mg/L] after mixing. The releasing tendency of MMA could be analyzed accurately with continuously monitoring during processing. The amount of MMA released from self-curing resin changed rapidly and the processing was complicated and changeful.

UV-initiated template copolymerization of AM and MAPTAC: Microblock structure, copolymerization mechanism, and flocculation performance.

PubMed

Li, Xiang; Zheng, Huaili; Gao, Baoyu; Sun, Yongjun; Liu, Bingzhi; Zhao, Chuanliang

2017-01-01

Flocculation as the core technology of sludge pretreatment can improve the dewatering performance of sludge that enables to reduce the cost of sludge transportation and the subsequent disposal costs. Therefore, synthesis of high-efficiency and economic flocculant is remarkably desired in this field. This study presents a cationic polyacrylamide (CPAM) flocculant with microblock structure synthesized through ultraviolet (UV)-initiated template copolymerization by using acrylamide (AM) and methacrylamido propyl trimethyl ammonium chloride (MAPTAC) as monomers, sodium polyacrylate (PAAS) as template, and 2,2'-azobis [2-(2-imidazolin-2-yl) propane] dihydrochloride (VA-044) as photoinitiator. The microblock structure of the CPAM was observed through nuclear magnetic resonance ( 1 H NMR and 13 C NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM) analyses. Furthermore, thermogravimetric/differential scanning calorimetry (TG/DSC) analysis was used to evaluate its thermal decomposition property. The copolymerization mechanism was investigated through the determination of the binding constant M K and study on polymerization kinetics. Results showed that the copolymerization was conducted in accordance with the I (ZIP) template polymerization mechanism, and revealed the coexistence of bimolecular termination free-radical reaction and mono-radical termination in the polymerization process. Results of sludge dewatering tests indicated the superior flocculation performance of microblock flocculant than random distributed CPAM. The residual turbidity, filter cake moisture content, and specific resistance to filtration reached 9.37 NTU, 68.01%, and 6.24 (10 12  m kg -1 ), respectively, at 40 mg L -1 of template poly(AM-MAPTAC) and pH 6.0. Furthermore, all flocculant except commercial CPAM showed a wide scope of pH application. Copyright © 2016 Elsevier Ltd. All rights reserved.

Radiation synthesis of poly[(dimethylaminoethyl methacrylate)-co-(ethyleneglycol dimethacrylate)] hydrogels and its application as a carrier for anticancer delivery

NASA Astrophysics Data System (ADS)

Mazied, Nabila A.; Ismail, Sahar A.; Abou Taleb, Manal F.

2009-11-01

The use of hydrogels as carriers for anticancer delivery has been a subject of significant recent research. In our recent work, we have shown that diffusion-controlled delivery of flutamide from hydrogels containing poly (dimethylaminoethyl methacrylate (DMAEMA)/ethyleneglycol dimethacrylate (EGDMA)) can be possible and controlled by the three-dimensional structure. Hydrogels based essentially on dimethylaminoethyl methacrylate and different ratios of ethyleneglycol dimethacrylate monomers were synthesized using gamma radiation copolymerization. The influence of copolymer composition and pH value of the surrounding medium on swelling behavior into the glassy polymer were discussed. The results showed that the ratio of EGDMA in the comonomer feeding solution has a great effect on the gel fraction and water content in the final hydrogel. In this regard, it was observed that the increase of EGDMA ratio decreased these properties. The ability of the prepared copolymer to be used as drug carrier for anticancer drug-delivery system was estimated using flutamide as a model drug. In vitro drug-release studies in different buffer solutions show that the basic parameters affecting the drug release behavior of hydrogel are the pH of the solution and DMAEMA content of hydrogel.

Long-term clinical outcome analysis of poly-methyl-methacrylate cranioplasty for large skull defects.

PubMed

Jaberi, Joby; Gambrell, Kenneth; Tiwana, Paul; Madden, Chris; Finn, Rick

2013-02-01

The goal of secondary cranioplasty is permanent cerebral protection in an esthetically acceptable fashion. Reconstruction of cranial defects can be performed with several different materials. Alloplastic materials, such as preformed methyl-methacrylate (PMMA) cranioplasties, are an alternative frequently used at our institution. This retrospective analysis was designed to review the outcomes of PMMA cranioplasty for skull defect reconstruction. Seventy consecutive patients who had 78 PMMA cranioplasties placed from 2003 through 2010 were identified. Mechanism of injury, location of cranioplasty, type of original repair, postoperative complications, and follow-up time were reviewed. Of the 70 patients, 6 patients had failure and removal of their original PMMA cranioplasty and reinsertion of another, and 2 patients had failure and removal of 2 cranioplasties with replacement of a third, creating a total of 78 PMMA cranioplasties placed. The predominant mechanism of injury was trauma (64%). The most frequent postoperative complication was infection (13%). With the exception of the 2 patients with implant exposure, no patients reported an unacceptable cosmetic result. An overall complication rate of 24% was seen. The results of previous studies have shown that infection and complication rates of cranioplasties accomplished with bone cement are substantially higher, that titanium-based implants may obscure follow-up imaging for tumor patients, and that the outcomes regarding hydroxyapatite-based ceramics, although similar to PMMA, are associated with a much higher cost. PMMA remains a cost-effective and proven method to repair cranial defects that fulfills the goals of cranial reconstruction for skull defects. Copyright © 2013 American Association of Oral and Maxillofacial Surgeons. All rights reserved.

Methyl 3-[3',4'-(methylenedioxy)phenyl]-2-methyl glycidate: an ecstasy precursor seized in Sydney, Australia.

PubMed

Collins, Michael; Heagney, Aaron; Cordaro, Frank; Odgers, David; Tarrant, Gregory; Stewart, Samantha

2007-07-01

Five 44 gallon drums labeled as glycidyl methacrylate were seized by the Australian Customs Service and the Australian Federal Police at Port Botany, Sydney, Australia, in December 2004. Each drum contained a white, semisolid substance that was initially suspected to be 3,4-methylenedioxymethylamphetamine (MDMA). Gas chromatography-mass spectroscopy (GC/MS) analysis demonstrated that the material was neither glycidyl methacrylate nor MDMA. Because intelligence sources employed by federal agents indicated that this material was in some way connected to MDMA production, suspicion fell on the various MDMA precursor chemicals. Using a number of techniques including proton nuclear magnetic resonance spectroscopy ((1)H NMR), carbon nuclear magnetic resonance spectroscopy ((13)C NMR), GC/MS, infrared spectroscopy, and total synthesis, the unknown substance was eventually identified as methyl 3-[3',4'(methylenedioxy)phenyl]-2-methyl glycidate. The substance was also subjected to a published hydrolysis and decarboxylation procedure and gave a high yield of the MDMA precursor chemical, 3,4-methylenedioxyphenyl-2-propanone, thereby establishing this material as a "precursor to a precursor."

Synthesis and Characterization of Graft Copolymers Poly(isoprene-g-styrene) of High Molecular Weight by a Combination of Anionic Polymerization and Emulsion Polymerization

DOE PAGES

Wang, Wenwen; Wang, Weiyu; Li, Hui; ...

2015-01-14

In this study, high molecular weight “comb-shaped” graft copolymers, poly(isoprene-g-styrene), with polyisoprene as the backbone and polystyrene as side chains, were synthesized via free radical emulsion polymerization by copolymerization of isoprene with a polystyrene macromonomer synthesized using anionic polymerization. A small amount of toluene was used in order to successfully disperse the macromonomer. Both a redox and thermal initiation system were used in the emulsion polymerization, and the latex particle size and distribution were investigated by dynamic light scattering. The structural characteristics of the macromonomer and comb graft copolymers were investigated through use of size exclusion chromatography, spectroscopy, microscopy, thermalmore » analysis, and rheology. While the macromonomer was successfully copolymerized to obtain the desired multigraft copolymers, small amounts of unreacted macromonomer remained in the products, reflecting its reduced reactivity due to steric effects. Nevertheless, the multigraft copolymers obtained were very high in molecular weight (5–12 × 10 5 g/mol) and up to 10 branches per chain, on average, could be incorporated. A material incorporating 29 wt% polystyrene exhibits a disordered microphase separated morphology and elastomeric properties. As a result, these materials show promise as new, highly tunable, and potentially low cost thermoplastic elastomers.« less

Synthesis and characterization of polymeric materials derived from 2,5-diketopiperazines and pyroglutamic acid

NASA Astrophysics Data System (ADS)

Parrish, Dennis Arch

The research presented in this dissertation describes the investigation of 2,5-diketopiperazines (DKPs) as property modifiers for addition polymers and the self association behavior of pyroglutamic acid derivatives. The first project involved the copolymerization of methyl methacrylate and styrene with DKP-based methacrylate monomers. Low incorporations of serine- and aspartame-based DKPs in the copolymer resulted in dramatic increases in the glass transition temperature (Ts). The research presented in Chapter II focuses on the ring-opening reactions of pyroglutamic diketopiperazine (pyDKP). The original intent was to synthesize polymers containing backbone DKPs through ring-opening polymerization of the five-membered rings. However, it was discovered that regioselective ring-opening occurs at the six-membered ring to give pyroglutamic acid derivatives. Since this reaction had not been reported previously, the focus of research was altered to investigate the scope and limitations of the new reaction. The ring-opening reactions of pyDKP with diamines to give bispyroglutamides is described in Chapter IV. While these materials are not polymeric, they display polymeric behavior. It was found that multi-functional pyroglutamides display Tgs during thermal analysis, exhibit high thermal stability, and form melt-drawn fibers. In contrast, the materials have low solution viscosities and are freely soluble in water, ethanol, and chloroform. This behavior is attributed to non-covalent supramolecular associations. The final part of this dissertation involved the investigation of thermoreversible organic solvent gelators. The ring-opening reaction of pyDKP with long alkyl amines unexpectedly gelled the reaction solvent. A series of analogous gelators were synthesized, and the minimum concentration required for gelation in various solvents was determined. It was found that the nature of the solvent, alkyl chain length, and optical activity of the gelator determined gelator

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.

Nano-engineered Drug Combinations for Breast Cancer Treatment

DTIC Science & Technology

2013-08-01

dextran),41 or poly(acrylamide-co-acrylic acid ),42 poly(methyl methacrylate),40 poly(styrene),40 and poly(vinyl cinnamate )40, 43, 44 in separate...pH, this polymer is stable and water insoluble, but at acidic pH the polymer becomes de-protected and water-soluble (Figure 6.A). Thus, particles...made of such a polymer will stay intact in the blood stream and will only start to dissolve away and release their cargo in environments with an acidic

PEG-PLA-PEG block copolymeric nanoparticles for oral immunization against hepatitis B.

PubMed

Jain, Arvind K; Goyal, Amit K; Mishra, Neeraj; Vaidya, Bhuvaneshwar; Mangal, Sharad; Vyas, Suresh P

2010-03-15

PLA/PLGA nanoparticles are well known as efficient vaccine delivery systems, but they have got limitation in oral vaccine delivery because of their sensitivity to harsh gastric environment. The aim of present study was to improve the stability of PLA nanoparticles in such environment by copolymerizing PLA with PEG. Nanoparticles were formulated using different block copolymers AB, ABA and BAB (where 'A' is PLA and 'B' is PEG) encapsulating hepatitis B surface antigen (HBsAg) to evaluate their efficacy as oral vaccine delivery system. The results of in vitro studies engrave the efficiency of copolymeric nanoparticles to retain encapsulated antigen and average particle size even after 2 h incubation in simulated gastric fluid and simulated intestinal fluid. Fluorescence microscopic studies indicated efficient uptake of copolymeric nanoparticles by gut mucosa of immunized mice model as compared to control. Finally copolymeric and PLA nanoparticles, encapsulating HBsAg, were evaluated for their adjuvancity in generating immune response after oral administration. PLA nanoparticles could not generate an effective immune response due to stability issues. On the other hand, oral administration of copolymeric nanoparticles exhibited effective levels of humoral immunity along with the mucosal (sIgA) and cellular immune response (T(H)1). The results of in vitro and in vivo studies demonstrate that BAB nanoparticles depict enhanced mucosal uptake leading to effective immune response as compared to other copolymeric nanoparticles. Present study indicates the efficacy of BAB nanoparticles as a promising carrier for oral immunization. 2009 Elsevier B.V. All rights reserved.

Prediction of Three-Dimensional Downward Flame Spread Characteristics over Poly(methyl methacrylate) Slabs in Different Pressure Environments.

PubMed

Zhao, Kun; Zhou, Xiao-Dong; Liu, Xue-Qiang; Lu, Lei; Wu, Zhi-Bo; Peng, Fei; Ju, Xiao-Yu; Yang, Li-Zhong

2016-11-22

The present study is aimed at predicting downward flame spread characteristics over poly(methyl methacrylate) (PMMA) with different sample dimensions in different pressure environments. Three-dimensional (3-D) downward flame spread experiments on free PMMA slabs were conducted at five locations with different altitudes, which provide different pressures. Pressure effects on the flame spread rate, profile of pyrolysis front and flame height were analyzed at all altitudes. The flame spread rate in the steady-state stage was calculated based on the balance on the fuel surface and fuel properties. Results show that flame spread rate increases exponentially with pressure, and the exponent of pressure further shows an increasing trend with the thickness of the sample. The angle of the pyrolysis front emerged on sample residue in the width direction, which indicates a steady-burning stage, varies clearly with sample thicknesses and ambient pressures. A global non-dimensional equation was proposed to predict the variation tendency of the angle of the pyrolysis front with pressure and was found to fit well with the measured results. In addition, the dependence of average flame height on mass burning rate, sample dimension and pressure was proposed based on laminar diffusion flame theory. The fitted exponent of experimental data is 1.11, which is close to the theoretical value.

Effect of silver ion-induced disorder on morphological, chemical and optical properties of poly (methyl methacrylate)

NASA Astrophysics Data System (ADS)

Arif, Shafaq; Saleemi, Farhat; Rafique, M. Shahid; Naab, Fabian; Toader, Ovidiu; Mahmood, Arshad; Aziz, Uzma

2016-11-01

Ion implantation is a versatile technique to tailor the surface properties of polymers in a controlled manner. In the present study, samples of poly (methyl methacrylate) (PMMA) have been implanted with 400 keV silver (Ag+) ion beam to various ion fluences ranging from 5 × 1013 to 5 × 1015 ions/cm2. The effect of Ag+ ion-induced disorder on morphological, chemical and optical properties of PMMA is analyzed using Atomic Force Microscope (AFM), Fourier transform infrared spectroscopy (FTIR) and ultraviolet-visible (UV-Vis) spectroscopy. Furthermore, the electrical conductivity of pristine and implanted PMMA is measured using four probe apparatus. The AFM images revealed the growth of nano-sized grainy structures and hillocks above the surface of implanted PMMA. The FTIR spectra confirmed the modifications in chemical structure of PMMA along with the formation of sbnd Cdbnd Csbnd carbon contents. The refractive index, extinction coefficient and photoconductivity of implanted PMMA have been found to increase as a function of ion fluence. Simultaneously, indirect optical band gap is reduced from 3.13 to 0.81 eV at a relatively high fluence (5 × 1015 ions/cm2). A linear correlation has been established between the band gap and Urbach energies. Moreover, the electrical conductivity of Ag+ implanted PMMA has increased from 2.14 × 10-10 (pristine) to 9.6 × 10-6 S/cm.

Ecotoxicity hazard assessment of styrene.

PubMed

Cushman, J R; Rausina, G A; Cruzan, G; Gilbert, J; Williams, E; Harrass, M C; Sousa, J V; Putt, A E; Garvey, N A; St Laurent, J P; Hoberg, J R; Machado, M W

1997-07-01

The ecotoxicity of styrene was evaluated in acute toxicity studies of fathead minnows (Pimephales promelas), daphnids (Daphnia magna), amphipods (Hyalella azteca), and freshwater green algae (Selenastrum capricornutum), and a subacute toxicity study of earthworms (Eisenia fostida). Stable exposure levels were maintained in the studies with fathead minnows, daphnids, and amphipods using sealed, flowthrough, serial dilution systems and test vessels. The algae were evaluated in a sealed, static system. The earthworms were exposed in artificial soil which was renewed after 7 days. Styrene concentrations in water and soil were analyzed by gas chromatography with flame ionization detection following extraction into hexane. Test results are based on measured concentrations. Styrene was moderately toxic to fathead minnows, daphnids, and amphipods: fathead minnow: LC50 (96 hr), 10 mg/liter, and NOEC, 4.0 mg/liter; daphnids: EC50 (48 hr), 4.7 mg/liter, and NOEC, 1.9 mg/liter; amphipods: LC50 (96 hr), 9.5 mg/liter, and NOEC, 4.1 mg/liter. Styrene was highly toxic to green algae: EC50 (96 hr), 0.72 mg/liter, and NOEC, 0.063 mg/liter; these effects were found to be algistatic rather than algicidal. Styrene was slightly toxic to earthworms: LC50 (14 days), 120 mg/kg, and NOEC, 44 mg/kg. There was no indication of a concern for chronic toxicity based on these studies. Styrene's potential impact on aquatic and soil environments is significantly mitigated by its volatility and biodegradability.

Microwave absorption properties of reduced graphene oxide strontium hexaferrite/poly(methyl methacrylate) composites

NASA Astrophysics Data System (ADS)

Acharya, Sanghamitra; Ray, J.; Patro, T. U.; Alegaonkar, Prashant; Datar, Suwarna

2018-03-01

The key factors to consider when designing microwave absorber materials for eradication of electromagnetic (EM) pollution are absorption of incident EM waves and good impedance matching. By keeping these things in mind, flexible microwave absorber composite films can be fabricated by simple gel casting techniques using reduced graphene oxide (RGO) and strontium ferrite (SF) in a poly(methyl methacrylate) (PMMA) matrix. SF nanoparticles are synthesized by the well known sol-gel method. Subsequently, reduced graphene oxide (RGO) and SF nanocomposite (RGOSF) are prepared through a chemical reduction method using hydrazine. The structure, morphology, chemical composition, thermal stability and magnetic properties of the nanocomposite are characterized in detail by various techniques. The SF particles are found to be nearly 500 nm and decorated on RGO sheets as revealed by field emission scanning electron microscopy and transmission electron microscopy analysis. Fourier transform infrared and and Raman spectroscopy clearly show the presence of SF in the graphene sheet by the lower peak positions. Finally, ternary polymer composites of RGO/SF/PMMA are prepared by an in situ polymerization method. Magnetic and dielectric studies of the composite reveal that the presence of RGO/SF/PMMA lead to polarization effects contributing to dielectric loss. Also, RGO surrounding SF provides a conductive network in the polymer matrix which is in turn responsible for the magnetic loss in the composite. Thus, the permittivity as well as the permeability of the composite can be controlled by an appropriate combination of RGO and SF in PMMA. More than 99% absorption efficiency is achieved by a suitable combination of magneto-dielectric coupling in the X-band frequency range by incorporating 9 wt% of RGO and 1 wt% of SF in the polymer matrix.

Assessment of the skin sensitising potency of the lower alkyl methacrylate esters.

PubMed

Kimber, Ian; Pemberton, Mark A

2014-10-01

There is continued interest in, and imperatives for, the classification of contact allergens according to their relative skin sensitising potency. However, achieving that end can prove problematic, not least when there is an apparent lack of concordance between experimental assessments of potency and the prevalence allergic contact dermatitis as judged by clinical experience. For the purpose of exploring this issue, and illustrating the important considerations that are required to reach sound judgements about potency categorisation, the lower alkyl methacrylate esters (LAM) have been employed here as a case study. Although the sensitising potential of methyl methacrylate (MMA) has been reviewed previously, there is available new information that is relevant for assessment of skin sensitising potency. Moreover, for the purposes of this article, analyses have been extended to include also other LAM for which relevant data are available: ethyl methacrylate (EMA), n-butyl methacrylate (nBMA), isobutyl methacrylate (iBMA), and 2-ethylhexyl methacrylate (EHMA). In addressing the skin sensitising activity of these chemicals and in drawing conclusions regarding relative potency, a number of sources of information has been considered, including estimates of potency derived from local lymph node assay (LLNA) data, the results of guinea pig assays, and data derived from in silico methods and from recently developed in vitro approaches. Moreover, clinical experience of skin sensitisation of humans by LAM has also been evaluated. The conclusion drawn is that MMA and other LAM are contact allergens, but that none of these chemicals has any more than weak skin sensitising potency. We have also explored here the possible bases for this modest sensitising activity. Finally, the nature of exposure to LAM has been reviewed briefly and on the basis of that information, together with an understanding of skin sensitising potency, a risk assessment has been prepared. Copyright © 2014

Effect of glycidyl methacrylate (GMA) incorporation on water uptake and conductivity of proton exchange membranes

NASA Astrophysics Data System (ADS)

Sproll, Véronique; Schmidt, Thomas J.; Gubler, Lorenz

2018-03-01

The aim of this work was to investigate how hygroscopic moieties like hydrolyzed glycidyl methacrylate (GMA) influence the properties of sulfonated polysytrene based proton exchange membranes (PEM). Therefore, several membranes were synthesized by electron beam treatment of the ETFE (ethylene-alt-tetrafluoroethylene) base film with a subsequent co-grafting of styrene and GMA at different ratios. The obtained membranes were sulfonated to introduce proton conducting groups and the epoxide moiety of the GMA unit was hydrolyzed for a better water absorption. The PEM was investigated regarding its structural composition, water uptake and through-plane conductivity. It could be shown that the density of sulfonic acid groups has a higher influence on the proton conductivity of the PEM than an increased water uptake.

[Studies on the industrial styrene poisoning (Part X). Determination of styrene in biological materials by gas chromatography (author's transl)].

PubMed

Teramoto, K; Horiguchi, S

1980-09-01

For monitoring solvents exposure, it is useful to determine not only metabolites of the solvents in urine but also the solvents themselves in blood and tissues. In a series of studies on the industrial styrene poisoning, we have been determining styrene in blood and other tissues as occasion calls. Our examination of the method is presented in this report. The outline on the method is as follows: Aliquots of 0.5g of tissues being added 5 ml of n-hexane are homogenized by a high-speed homogenizer (Polytoron) for 10 to 30 seconds and the filtrates containing extracts are analyzed for styrene by gas chromatography. The linearity was ascertained from the calibration curve obtained by adding the known quantities of styrene (4, 10, 20, 40, 100 ppm) to the blood, liver and adipose tissues of rats. Rates of recoveries of styrene from the above tissues were 92 to 101 per cent. Reproducibility of this method was examined by repeating determinations of styrene in the blood, liver and adipose tissues of rats exposed to 500 ppm styrene for 4 hours, the coefficients of variation being 2.8 to 14.0 per cent. There was an approximately linear relationship between the styrene concentration (0 to 1,000 ppm) of the exposed air and those in the blood of exposed rats. We conclude that our simple and rapid method is applicable to determination of solvents other than styrene in organs and tissues by combining suitable solvents for extraction and packings of gas chromatography.

Plasma copolymerization of ethylene and tetrafluoroethylene

NASA Technical Reports Server (NTRS)

Golub, Morton A.; Wydeven, Theodore; Cormia, Robert D.

1992-01-01

An IR and XPS study of the low-pressure, radiofrequency, glow-discharge plasma copolymerization of ethylene (ET) and tetrafluoroethylene (TFE) is presented. The potential for creating Tefzel- or Teflon-like coatings on various polymeric substrates for use in advanced life support systems is examined.

40 CFR 721.6620 - Alkanaminium, polyalkyl-[(2-methyl-1-oxo-2-propenyl)oxy] salt, polymer with acrylamide and...

Code of Federal Regulations, 2010 CFR

2010-07-01

...-oxo-2-propenyl)oxy] salt, polymer with acrylamide and substituted alkyl methacrylate. 721.6620 Section... Substances § 721.6620 Alkanaminium, polyalkyl-[(2-methyl-1-oxo-2-propenyl)oxy] salt, polymer with acrylamide...-propenyl)oxy] salt, polymer with acrylamide and substituted alkyl methacrylate (PMN P-87-252) is subject to...

40 CFR 721.6620 - Alkanaminium, polyalkyl-[(2-methyl-1-oxo-2-propenyl)oxy] salt, polymer with acrylamide and...

Code of Federal Regulations, 2011 CFR

2011-07-01

...-oxo-2-propenyl)oxy] salt, polymer with acrylamide and substituted alkyl methacrylate. 721.6620 Section... Substances § 721.6620 Alkanaminium, polyalkyl-[(2-methyl-1-oxo-2-propenyl)oxy] salt, polymer with acrylamide...-propenyl)oxy] salt, polymer with acrylamide and substituted alkyl methacrylate (PMN P-87-252) is subject to...

Skin sensitization potency of methyl methacrylate in the local lymph node assay: comparisons with guinea-pig data and human experience.

PubMed

Betts, Catherine J; Dearman, Rebecca J; Heylings, Jon R; Kimber, Ian; Basketter, David A

2006-09-01

There is compelling evidence that contact allergens differ substantially (by 4 or 5 orders of magnitude) with respect to their inherent skin-sensitizing potency. Relative potency can now be measured effectively using the mouse local lymph node assay (LLNA) and such data form the basis of risk assessment and risk management strategies. Such determinations also facilitate distinctions being drawn between the prevalence of skin sensitization to a particular contact allergen and inherent potency. The distinction is important because chemicals that are implicated as common causes of contact allergy are not necessarily potent sensitizers. One example is provided by nickel that is undoubtedly a common cause of allergic contact dermatitis, but is a comparatively weak sensitizer in predictive tests. In an attempt to explore other examples of contact allergens where there may exist a discrepancy between prevalence and potency, we describe here analyses conducted with methyl methacrylate (MMA). Results of LLNA studies have been interpreted in the context of historical clinical data on occupational allergic contact dermatitis associated with exposure to MMA.

Toward the design of alkynylimidazole fluorophores: computational and experimental characterization of spectroscopic features in solution and in poly(methyl methacrylate).

PubMed

Barone, Vincenzo; Bellina, Fabio; Biczysko, Malgorzata; Bloino, Julien; Fornaro, Teresa; Latouche, Camille; Lessi, Marco; Marianetti, Giulia; Minei, Pierpaolo; Panattoni, Alessandro; Pucci, Andrea

2015-10-28

The possibilities offered by organic fluorophores in the preparation of advanced plastic materials have been increased by designing novel alkynylimidazole dyes, featuring different push and pull groups. This new family of fluorescent dyes was synthesized by means of a one-pot sequential bromination-alkynylation of the heteroaromatic core, and their optical properties were investigated in tetrahydrofuran and in poly(methyl methacrylate). An efficient in silico pre-screening scheme was devised as consisting of a step-by-step procedure employing computational methodologies by simulation of electronic spectra within simple vertical energy and more sophisticated vibronic approaches. Such an approach was also extended to efficiently simulate one-photon absorption and emission spectra of the dyes in the polymer environment for their potential application in luminescent solar concentrators. Besides the specific applications of this novel material, the integration of computational and experimental techniques reported here provides an efficient protocol that can be applied to make a selection among similar dye candidates, which constitute the essential responsive part of those fluorescent plastic materials.

Styrene

Integrated Risk Information System (IRIS)

Styrene ; CASRN 100 - 42 - 5 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effects )

N-acetyl cysteine (NAC)-mediated detoxification and functionalization of poly(methyl methacrylate) bone cement.

PubMed

Tsukimura, Naoki; Yamada, Masahiro; Aita, Hideki; Hori, Norio; Yoshino, Fumihiko; Chang-Il Lee, Masaichi; Kimoto, Katsuhiko; Jewett, Anahid; Ogawa, Takahiro

2009-07-01

Currently used poly(methyl methacrylate) (PMMA)-based bone cement lacks osteoconductivity and induces osteolysis and implant loosening due to its cellular and tissue-toxicity. A high percentage of revision surgery following the use of bone cement has become a significant universal problem. This study determined whether incorporation of the amino acid derivative N-acetyl cysteine (NAC) in bone cement reduces its cytotoxicity and adds osteoconductivity to the material. Biocompatibility and bioactivity of PMMA-based bone cement with or without 25mm NAC incorporation was examined using rat bone marrow-derived osteoblastic cells. Osteoconductive potential of NAC-incorporated bone cement was determined by microCT bone morphometry and implant biomechanical test in the rat model. Generation of free radicals within the polymerizing bone cement was examined using electron spin resonance spectroscopy. Severely compromised viability and completely suppressed phenotypes of osteoblasts on untreated bone cement were restored to the normal level by NAC incorporation. Bone volume formed around 25mm NAC-incorporated bone cement was threefold greater than that around control bone cement. The strength of bone-bone cement integration was 2.2 times greater for NAC-incorporated bone cement. For NAC-incorporated bone cement, the spike of free radical generation ended within 12h, whereas for control bone cement, a peak level lasted for 6 days and a level greater than half the level of the peak was sustained for 20 days. NAC also increased the level of antioxidant glutathione in osteoblasts. These results suggest that incorporation of NAC in PMMA bone cement detoxifies the material by immediate and effective in situ scavenging of free radicals and increasing intracellular antioxidant reserves, and consequently adds osteoconductivity to the material.

21 CFR 177.1810 - Styrene block polymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Styrene block polymers. 177.1810 Section 177.1810... FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1810 Styrene block polymers. The styrene...

21 CFR 177.1810 - Styrene block polymers.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Styrene block polymers. 177.1810 Section 177.1810... FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1810 Styrene block polymers. The styrene...

21 CFR 177.1810 - Styrene block polymers.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Styrene block polymers. 177.1810 Section 177.1810... FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1810 Styrene block polymers. The styrene...

21 CFR 177.1810 - Styrene block polymers.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Styrene block polymers. 177.1810 Section 177.1810... FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1810 Styrene block polymers. The styrene...

Directed self-assembly of poly(styrene)-block-poly(acrylic acid) copolymers for sub-20nm pitch patterning

NASA Astrophysics Data System (ADS)

Cheng, Jing; Lawson, Richard A.; Yeh, Wei-Ming; Jarnagin, Nathan D.; Peters, Andrew; Tolbert, Laren M.; Henderson, Clifford L.

2012-03-01

Directed self-assembly (DSA) of block copolymers is a promising technology for extending the patterning capability of current lithographic exposure tools. For example, production of sub-40 nm pitch features using 193nm exposure technologies is conceivably possible using DSA methods without relying on time consuming, challenging, and expensive multiple patterning schemes. Significant recent work has focused on demonstration of the ability to produce large areas of regular grating structures with low numbers of defects using self-assembly of poly(styrene)-b-poly(methyl methacrylate) copolymers (PS-b-PMMA). While these recent results are promising and have shown the ability to print pitches approaching 20 nm using DSA, the ability to advance to even smaller pitches will be dependent upon the ability to develop new block copolymers with higher χ values and the associated alignment and block removal processes required to achieve successful DSA with these new materials. This paper reports on work focused on identifying higher χ block copolymers and their associated DSA processes for sub-20 nm pitch patterning. In this work, DSA using polystyrene-b-polyacid materials has been explored. Specifically, it is shown that poly(styrene)-b-poly(acrylic acid) copolymers (PS-b-PAA) is one promising material for achieving substantially smaller pitch patterns than those possible with PS-b-PMMA while still utilizing simple hydrocarbon polymers. In fact, it is anticipated that much of the learning that has been done with the PS-b-PMMA system, such as development of highly selective plasma etch block removal procedures, can be directly leveraged or transferred to the PS-b-PAA system. Acetone vapor annealing of PS-b-PAA (Mw=16,000 g/mol with 50:50 mole ratio of PS:PAA) and its self-assembly into a lamellar morphology is demonstrated to generate a pattern pitch size (L0) of 21 nm. The χ value for PS-b-PAA was estimated from fingerprint pattern pitch data to be approximately 0.18 which

21 CFR 177.1810 - Styrene block polymers.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Styrene block polymers. 177.1810 Section 177.1810...) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1810 Styrene block polymers. The styrene block polymers identified in paragraph (a...

“Uncontrolled” Preparation of Disperse Poly(lactide)- block -poly(styrene)- block -poly(lactide) for Nanopatterning Applications

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

Vanderlaan, Marie E.; Hillmyer, Marc A.

We report the facile synthesis of well-defined ABA poly(lactide)-block-poly(styrene)-block-poly(lactide) (LSL) triblock copolymers having a disperse poly(styrene) midblock (Ð = 1.27–2.24). The direct synthesis of telechelic α,ω-hydroxypoly(styrene) (HO-PS-OH) midblocks was achieved using a commercially available difunctional free radical diazo initiator 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide]. Poly(lactide) (PLA) end blocks were subsequently grown from HO-PS-OH macroinitiators via ring-opening transesterification polymerization of (±)-lactide using the most common and prevalent catalyst system available, tin(II) 2-ethylhexanoate. Fourteen LSL triblock copolymers with total molar masses Mn,total = 24–181 kg/mol and PLA volume fractions fPLA = 0.15–0.68 were synthesized and thoroughly characterized. The self-assembly of symmetric triblocks was analyzed in themore » bulk using small-angle X-ray scattering and in thin films using grazing incidence small-angle X-ray scattering and atomic force microscopy. We demonstrate both the bulk and thin film self-assembly of LSL disperse triblocks gave well-organized nanostructures with uniform domain sizes suitable for nanopatterning applications.« less

Unbiased phosphoproteomic method identifies the initial effects of a methacrylic acid copolymer on macrophages

PubMed Central

Chamberlain, Michael Dean; Wells, Laura A.; Lisovsky, Alexandra; Guo, Hongbo; Isserlin, Ruth; Talior-Volodarsky, Ilana; Mahou, Redouan; Emili, Andrew; Sefton, Michael V.

2015-01-01

An unbiased phosphoproteomic method was used to identify biomaterial-associated changes in the phosphorylation patterns of macrophage-like cells. The phosphorylation differences between differentiated THP1 (dTHP1) cells treated for 10, 20, or 30 min with a vascular regenerative methacrylic acid (MAA) copolymer or a control methyl methacrylate (MM) copolymer were determined by MS. There were 1,470 peptides (corresponding to 729 proteins) that were differentially phosphorylated in dTHP1 cells treated with the two materials with a greater cellular response to MAA treatment. In addition to identifying pathways (such as integrin signaling and cytoskeletal arrangement) that are well known to change with cell–material interaction, previously unidentified pathways, such as apoptosis and mRNA splicing, were also discovered. PMID:26261332

ROMP- and RAFT-Based Guanidinium-Containing Polymers as Scaffolds for Protein Mimic Synthesis.

PubMed

Sarapas, Joel M; Backlund, Coralie M; deRonde, Brittany M; Minter, Lisa M; Tew, Gregory N

2017-05-17

Cell-penetrating peptides are an important class of molecules with promising applications in bioactive cargo delivery. A diverse series of guanidinium-containing polymeric cell-penetrating peptide mimics (CPPMs) with varying backbone chemistries was synthesized and assessed for delivery of both GFP and fluorescently tagged siRNA. Specifically, we examined CPPMs based on norbornene, methacrylate, and styrene backbones to determine how backbone structure impacted internalization of these two cargoes. Either charge content or degree of polymerization was held constant at 20, with diguanidinium norbornene molecules being polymerized to both 10 and 20 repeat units. Generally, homopolymer CPPMs delivered low amounts of siRNA into Jurkat T cells, with no apparent backbone dependence; however, by adding a short hydrophobic methyl methacrylate block to the guanidinium-rich methacrylate polymer, siRNA delivery to nearly the entire cell population was achieved. Protein internalization yielded similar results for most of the CPPMs, though the block polymer was unable to deliver proteins. In contrast, the styrene-based CPPM yielded the highest internalization for GFP (≈40 % of cells affected), showing that indeed backbone chemistry impacts protein delivery, specifically through the incorporation of an aromatic group. These results demonstrate that an understanding of how polymer structure affects cargo-dependent internalization is critical to designing new, more effective CPPMs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

2-diethylaminoethyl-dextran methyl methacrylate copolymer nonviral vector: still a long way toward the safety of aerosol gene therapy.

PubMed

Zarogoulidis, P; Hohenforst-Schmidt, W; Darwiche, K; Krauss, L; Sparopoulou, D; Sakkas, L; Gschwendtner, A; Huang, H; Turner, F J; Freitag, L; Zarogoulidis, K

2013-10-01

Revealing the lung tumor genome has directed the current treatment strategies toward targeted therapy. First line treatments targeting the genome of lung tumor cells have been approved and are on the market. However, they are limited by the small number of patients with the current investigated genetic mutations. Novel treatment administration modalities have been also investigated in an effort to increase the local drug deposition and disease control. In the current study, we investigated the safety of the new nonviral vector 2-diethylaminoethyl-dextran methyl methacrylate copolymer (DDMC; Ryujyu Science), which belongs to the 2-diethylaminoethyl-dextran family by aerosol administration. Thirty male BALBC mice, 2 month old, were included and divided into three groups. However, pathological findings indicated severe emphysema within three aerosol sessions. In addition, the CytoViva technique was applied for the first time to display the nonviral particles within the pulmonary tissue and emphysema lesions, and a spectral library of the nonviral vector was also established. Although our results in BALBC mice prevented us from further investigation of the DDMC nonviral vector as a vehicle for gene therapy, further investigation in animals with larger airways is warranted to properly evaluate the safety of the vector.

Design and characterization of an adhesive matrix based on a poly(ethyl acrylate, methyl methacrylate).

PubMed

Cilurzo, Francesco; Minghetti, Paola; Pagani, Stefania; Casiraghi, Antonella; Montanari, Luisa

2008-01-01

The main issue in the development of transdermal patches made of poly(ethyl acrylate, methyl methacrylate) (Eudragit NE 40D, PMM) is the shrinkage phenomenon during the spreading of the latex onto the release liner. To solve this problem, the latex is usually freeze-dried and then re-dissolved in an organic solvent (method 1). To simplify the production process, we prepared an adhesive matrix by adding to the commercial PMM latex a plasticizer and an additive (anti-shrinkage agent) that avoids the shrinkage of the water dispersion spread onto the release liner (method 2). In some cases the active ingredient itself, such as potassium diclofenac (DK) and nicotine (NT), works as anti-shrinkage agent. In this work, the effects of the preparation method, types and concentrations of the plasticizer (triacetin and tributyl citrate) on the adhesive properties of the transdermal patches were investigated. The adhesive properties of the prepared patch were determined by texture analysis, peel adhesion test and shear adhesion. The PMM/plasticizer interactions were evaluated by ATR-FTIR spectroscopy. Furthermore, the in vitro skin permeation profiles of DK and NT released from the patch were determined by Franz cell method. Generally speaking, the variables that mainly modify the adhesive properties are the concentration and type of the plasticizer. The skin permeation profiles of DK and NT from the patch prepared by method 2 overlapped with those obtained with the commercial products. The results underline that the PMM latex can be used conveniently in the development of transdermal patches.

Synthesis of poly(methyl methacrylate) core/chitosan-mixed-polyethyleneimine shell nanoparticles and their antibacterial property.

PubMed

Inphonlek, Supharat; Pimpha, Nuttaporn; Sunintaboon, Panya

2010-06-01

The core-shell nanoparticles possessing poly(methyl methacrylate) (PMMA) core coated with chitosan (CS), polyethyleneimine (PEI), and chitosan-mixed-polyethyleneimine (CS/PEI) shells were synthesized in this work. The emulsifier-free emulsion polymerization triggered by a redox initiating system from t-butylhydroperoxide (TBHP) and amine groups on CS and/or PEI was used as a synthetic method. In the CS/PEI systems, the amount of CS was kept constant (0.5g), while the amount of PEI was varied from 0.1 to 0.5g. The surface and physico-chemical properties of prepared nanoparticles were then examined. FTIR spectra indicated the presence of grafted PMMA on CS and/or PEI, and the weight fraction of incorporated PEI in the CS/PEI nanoparticles. All nanoparticles were spherical in shape with uniform size distribution illustrated by scanning electron microscopy (SEM). The introduction of PEI to CS nanoparticles yielded the higher monomer conversion, grafting efficiency, and grafting percentage compared with the CS nanoparticles. The size of CS/PEI nanoparticles was smaller than the original CS and PEI nanoparticles, and tended to decrease with increasing amount of PEI introduced. The introduction of PEI also brought the higher colloidal stability to the nanoparticles as indicated by zeta-potential measurement and isoelectric point analysis. The nanoparticles exhibited a promising antibacterial activity against Staphylococcus aureus and Escherichia coli. The nanoparticle-bacteria interaction was studied via SEM. The results suggested that they would be useful as effective antibacterial agents. Copyright 2010 Elsevier B.V. All rights reserved.

Adsorption of Poly(methyl methacrylate) on Concave Al2O3 Surfaces in Nanoporous Membranes

PubMed Central

Nunnery, Grady; Hershkovits, Eli; Tannenbaum, Allen; Tannenbaum, Rina

2009-01-01

The objective of this study was to determine the influence of polymer molecular weight and surface curvature on the adsorption of polymers onto concave surfaces. Poly(methyl methacrylate) (PMMA) of various molecular weights was adsorbed onto porous aluminum oxide membranes having various pore sizes, ranging from 32 to 220 nm. The surface coverage, expressed as repeat units per unit surface area, was observed to vary linearly with molecular weight for molecular weights below ~120 000 g/mol. The coverage was independent of molecular weight above this critical molar mass, as was previously reported for the adsorption of PMMA on convex surfaces. Furthermore, the coverage varied linearly with pore size. A theoretical model was developed to describe curvature-dependent adsorption by considering the density gradient that exists between the surface and the edge of the adsorption layer. According to this model, the density gradient of the adsorbed polymer segments scales inversely with particle size, while the total coverage scales linearly with particle size, in good agreement with experiment. These results show that the details of the adsorption of polymers onto concave surfaces with cylindrical geometries can be used to calculate molecular weight (below a critical molecular weight) if pore size is known. Conversely, pore size can also be determined with similar adsorption experiments. Most significantly, for polymers above a critical molecular weight, the precise molecular weight need not be known in order to determine pore size. Moreover, the adsorption developed and validated in this work can be used to predict coverage also onto surfaces with different geometries. PMID:19415910

Effect of end segment on physicochemical properties and platelet compatibility of poly(propylene glycol)-initiated poly(methyl methacrylate).

PubMed

Fukuda, Chihiro; Yahata, Chie; Kinoshita, Takuya; Watanabe, Takafumi; Tsukamoto, Hideo; Mochizuki, Akira

2017-10-01

It is well known that polyether-based copolymers have good blood compatibility, although many mechanisms have been proposed to explain their favorable performance. Our objective in carrying out the present study was to obtain a better understanding of the effect of the (poly)ether segment on blood compatibility. Therefore, we synthesized poly(propylene glycol) (PPG)-based initiators for atom transfer polymerization, where the number of propylene glycol (PG) units in the PPG (Pn(PG) was varied from 1 to 94. Methyl methacrylate (MMA) was polymerized using the initiators, resulting in the formation of polyMMAs with a PG-based ether part at the polymer terminal. We mainly investigated the effects of Pn(PG) on the surface properties and platelet compatibility of the PPG-polyMMA. X-ray photoelectron spectroscopy and surface contact angle (CA) analysis revealed the exposure of the PG units at the surface of the polymer. The platelet compatibility of the polymers was improved compared with a commercial polyMMA, even when Pn(PG) = 1. These results suggest that PG units have an important influence on favorable blood compatibility, regardless of the Pn(PG) value. We also investigated protein adsorption behavior in terms of the amount and deformation of fibrinogen adsorbed on the polymer surface.

Human Fetal Osteoblast Response on Poly(Methyl Methacrylate)/Polystyrene Demixed Thin Film Blends: Surface Chemistry Vs Topography Effects.

PubMed

D'Sa, Raechelle A; Raj, Jog; Dickinson, Peter J; McCabe, Fiona; Meenan, Brian J

2016-06-22

Recent advances in materials sciences have allowed for the development and fabrication of biomaterials that are capable of providing requisite cues to instigate cells to respond in a predictable fashion. We have developed a series of poly(methyl methacrylate)/polystyrene (PMMA/PS) polymer demixed thin films with nanotopographies ranging from nanoislands to nanopits to study the response of human fetal osteoblast cells (hFOBs). When PMMA was in excess in the blend composition, a nanoisland topography dominated, whereas a nanopit topography dominated when PS was in excess. PMMA was found to segregate to the top of the nanoisland morphology with PS preferring the substrate interface. To further ascertain the effects of surface chemistry vs topography, we plasma treated the polymer demixed films using an atmospheric pressure dielectric barrier discharge reactor to alter the surface chemistry. Our results have shown that hFOBs did not have an increased short-term cellular response on pristine polymer demixed surfaces. However, increasing the hydrophilicty/wettability of the surfaces by oxygen functionalization causes an increase in the cellular response. These results indicate that topography alone is not sufficient to induce a positive cellular response, but the underlying surface chemistry is also important in regulating cell function.

Superparamagnetic poly(methyl methacrylate) nanoparticles surface modified with folic acid presenting cell uptake mediated by endocytosis

NASA Astrophysics Data System (ADS)

Feuser, Paulo Emilio; Jacques, Amanda Virtuoso; Arévalo, Juan Marcelo Carpio; Rocha, Maria Eliane Merlin; dos Santos-Silva, Maria Claudia; Sayer, Claudia; de Araújo, Pedro H. Hermes

2016-04-01

The encapsulation of superparamagnetic nanoparticles (MNPs) in polymeric nanoparticles (NPs) with modified surfaces can improve targeted delivery and induce cell death by hyperthermia. The goals of this study were to synthesize and characterize surface modified superparamagnetic poly(methyl methacrylate) with folic acid (FA) prepared by miniemulsion polymerization (MNPsPMMA-FA) and to evaluate their in vitro cytotoxicity and cellular uptake in non-tumor cells, murine fibroblast (L929) cells and tumor cells that overexpressed folate receptor (FR) β, and chronic myeloid leukemia cells in blast crisis (K562). Lastly, hemolysis assays were performed on human red blood cells. MNPsPMMA-FA presented an average mean diameter of 135 nm and a saturation magnetization (Ms) value of 37 emu/g of iron oxide, as well as superparamagnetic behavior. The MNPsPMMA-FA did not present cytotoxicity in L929 and K562 cells. Cellular uptake assays showed a higher uptake of MNPsPMMA-FA than MNPsPMMA in K562 cells when incubated at 37 °C. On the other hand, MNPsPMMA-FA showed a low uptake when endocytosis mechanisms were blocked at low temperature (4 °C), suggesting that the MNPsPMMA-FA uptake was mediated by endocytosis. High concentrations of MNPsPMMA-FA showed hemocompatibility when incubated for 24 h in human red blood cells. Therefore, our results suggest that these carrier systems can be an excellent alternative in targeted drug delivery via FR.

Application of methyl methacrylate copolymers to the development of transdermal or loco-regional drug delivery systems.

PubMed

Cilurzo, Francesco; Selmin, Francesca; Gennari, Chiara G M; Montanari, Luisa; Minghetti, Paola

2014-07-01

Methyl methacrylate copolymers (Eudragit®) have been exploited to develop transdermal patches, medicated plasters (hereinafter patches) and, more recently, film-forming sprays, microsponges and nanoparticles intended to be applied on the skin. The article reviews the information regarding the application of Eudragits in the design and development of these dosage forms focusing on the impact of formulative variables on the skin drug penetration and the patch adhesive properties. Eudragits combined with a large amount of plasticizers are used to design the pressure-sensitive adhesives, specialized materials used in the patch development. They have to assure the drug skin penetration and the contact with the skin. Most of the studies mainly deal with the former aspect. The authors used a Eudragit type opportunely plasticized to merely investigate the in vitro or in vivo skin permeability of a loaded drug. However, the summa of these data evidenced that a strict connection between the matrix hydrophilicity and drug penetration probably exists. The criticisms of adhesion are addressed in a limited number of papers reporting data on technological properties, namely tack, shear adhesion and peel adhesion, while the structural data of the Eudragit adhesives, rheology and surface free energy are not described, excepting the case of Eudragit E. Among other applications, micro- and nanosystems exploiting the ionizable nature of some Eudragits can offer novel opportunities to develop pH-sensitive drug delivery systems suitable for triggering its release onto the skin.

Carbon Nanotube Composites from Modified Plant Oils

NASA Astrophysics Data System (ADS)

McAninch, Ian; Wool, Richard

2006-03-01

Carbon nanotubes (CNTs) with their impressive mechanical properties are ideal reinforcement material. Acrylated epoxidized soy oil (AESO) has been previously shown to have favorable interactions with carbon nanotubes. CNTs mixed into AESO, both with and without styrene as a co-monomer, using mechanical shear mixing showed dispersion only on the micron level, resulting in modest mechanical property improvements. Greater improvements were seen, especially in the rubbery modulus, when the resin's viscosity was kept high, either through a reduction of the styrene content, or by curing at a lower temperature. CNTs were also dispersed via sonication in methyl methacrylate. The resulting dispersion was then mixed with AESO. The resulting composites showed better CNT dispersion, with no micron-sized aggregates, as verified using SEM and optical microscopy. The mechanical properties also showed greater improvement.

Physical properties of sequential interpenetrating polymer networks produced from canola oil-based polyurethane and poly(methyl methacrylate).

PubMed

Kong, Xiaohua; Narine, Suresh S

2008-05-01

Sequential interpenetrating polymer networks (IPNs) were prepared using polyurethane (PUR) synthesized from canola oil-based polyol with terminal primary functional groups and poly(methyl methacrylate) (PMMA). The properties of the material were evaluated by dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and modulated differential scanning calorimetry (MDSC), as well as tensile properties measurements. The morphology of the IPNs was investigated using scanning electron microscopy (SEM) and MDSC. A five-phase morphology, that is, sol phase, PUR-rich phase, PUR-rich interphase, PMMA-rich interphase, and PMMA-rich phase, was observed for all the IPNs by applying a new quantitative method based on the measurement of the differential of reversing heat capacity versus temperature from MDSC, although not confirmed by SEM, most likely due to resolution restrictions. NCO/OH molar ratios (cross-linking density) and compositional variations of PUR/PMMA both affected the thermal properties and phase behaviors of the IPNs. Higher degrees of mixing occurred for the IPN with higher NCO/OH molar ratio (2.0/1.0) at PUR concentration of 25 wt %, whereas for the IPN with lower NCO/OH molar ratio (1.6/1.0), higher degrees of mixing occurred at PUR concentration of 35 wt %. The mechanical properties of the IPNs were superior to those of the constituent polymers due to the finely divided rubber and plastic combination structures in these IPNs.

75 FR 9438 - Americas Styrenics, LLC-Marietta Plant a Subsidiary of Americas Styrenics, LLLC Formerly Known as...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-03-02

... workers of the subject firm. The workers are engaged in the production of styrene monomer and polystyrene... increased customer imports of styrene monomer and polystyrene pellets. The amended notice applicable to TA-W...

Methacrylated monosaccharides as the modifiers for carbochain polymers: Synthesis, mechanical/thermal properties and biodegradability of hybrids

NASA Astrophysics Data System (ADS)

Yakushev, P.; Bershtein, V.; Bukowska-Śluz, I.; Sobiesiak, M.; Gawdzik, B.

2016-05-01

Methacrylated derivatives of glucose (MGLU) and galactose (MGAL) were synthesized by the procedure described by Vogel, and their copolymers with methyl methacrylate (MMA) and MMA/N-vinyl pyrrolidone (MMA/NVP) (1:1) mixture were obtained with the aim to modify some properties of carbochain polymers, in particular to generate their biodegradability. These hybrids of synthetic and natural products, with 10, 20 or 30 wt. % modifiers, were characterized by DMA and TGA methods and in the biodegradation tests. Increasing Tg values by 20-30°C was registered in all cases whereas thermal stability was improved only for PMMA due to modification. On the contrary, only for hybrids based on hygroscopic MMA/NVP copolymer the essential biodegradability could be generated.

Synthesis of polymer hybrid latex poly(methyl methacrylate-co-butyl acrylate) with organo montmorillonite via miniemulsion polymerization method for barrier paper

NASA Astrophysics Data System (ADS)

Chanra, J.; Budianto, E.; Soegijono, B.

2018-03-01

Hybrid polymer latex based on combination of organic-inorganic materials, poly(methyl methacrylate-co-butyl acrylate) (PMMBA) and organo-montmorillonite (OMMT) were synthesized via miniemulsion polymerization technique. Modification of montmorillonite (MMT) through the incorporation of myristyltrimethylammonium bromide (MTAB) into the clay’s interlayer spaces were investigated by Small-Angle X-ray Scattering (SAXS), Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA) and Transmission Electron Microscopy (TEM). Barrier property and thermal stability of polymer latex film sample were investigated through its Water Vapor Transmission Rate (WVTR) and Thermogravimetric Analysis (TGA). The results indicated that addition of OMMT as filler in PMMBA increased the barrier property and thermal stability of the latex film. Addition of 8.0% (wt) OMMT increased the barrier property and thermal stability. Miniemusion polymerization process with higher addition (>8.0 wt%) of OMMT resulting in high latex viscosity, particle size, and high amount of coagulum. The utilization of this hybrid polymer could benefits paper and board industries to produce high quality barrier paper for food packaging.

Using mid-Infrared External Reflectance Spectroscopy to Distinguish Between Different Commercially Produced Poly[Methyl MethAcrylate] (PMMA) Samples - A Null Result

NASA Astrophysics Data System (ADS)

Fajardo, Mario; Neel, Christopher; Lacina, David

2017-06-01

We report (null) results of experiments testing the hypothesis that mid-infrared (mid-IR) spectroscopy can be used to distinguish samples of poly[methyl methacrylate] (PMMA) obtained from different commercial suppliers. This work was motivated by the desire for a simple non-destructive and non-invasive test for pre-sorting PMMA samples prior to use in shock and high-strain-rate experiments, where PMMA is commonly used as a standard material. We discuss: our choice of mid-IR external reflectance spectroscopy, our approach to recording reflectance spectra at near-normal (θ = 0 + / - 5 degree) incidence and for extracting the wavelength-weighted absorption spectrum from the raw reflectance data via a Kramers-Krönig analysis. We employ extensive signal, which necessitates adopting a special experimental protocol to mitigate the effects of instrumental drift. Finally, we report spectra of three PMMA samples with different commercial pedigrees, and show that they are virtually identical (+ / - 1 % error, 95% confidence); obviating the use of mid-IR reflectance spectroscopy to tell the samples apart.

Photophysical and lasing properties of new analogs of the boron-dipyrromethene laser dye pyrromethene 567 incorporated into or covalently bounded to solid matrices of poly(methyl methacrylate).

PubMed

López Arbeloa, F; Bañuelos Prieto, J; López Arbeloa, I; Costela, A; García-Moreno, I; Gómez, C; Amat-Guerri, F; Liras, M; Sastre, R

2003-07-01

The photophysical, lasing and thermostability properties of newly synthesized analogs of the commercial dye pyrromethene 567 (PM567) have been measured in polymeric matrices of poly(methyl methacrylate) both when used as a dopant and when covalently bounded to the polymeric chain. These analogs have an acetoxy or a polymerizable methacryloyloxy group at the end of a polymethylene chain at Position 8 of the PM567 chromophore core. Clear correlations between photophysical and lasing characteristics are observed. Linking chain lengths with three or more methylene units give the highest fluorescence quantum yields (as high as 0.89) and lasing efficiencies (as high as 41%). The covalent linkage of the chromophore to the polymeric chain via the methacryloyloxy group improves the photostability of the PM567 chromophore.

Rehabilitation of orbital cavity after orbital exenteration using polymethyl methacrylate orbital prosthesis.

PubMed

Jain, Sumeet; Jain, Parul

2016-01-01

Squamous cell carcinoma of the eyelid is the second most common malignant neoplasm of the eye with the incidence of 0.09 and 2.42 cases/100 000 people. Orbital invasion is a rare complication but, if recognized early, can be treated effectively with exenteration. Although with advancements in technology such as computer-aided design and computer-aided manufacturing, material science, and retentive methods like implants, orbital prosthesis with stock ocular prosthesis made of methyl methacrylate retained by anatomic undercuts is quiet effective and should not be overlooked and forgotten. This clinical report describes prosthetic rehabilitation of two male patients with polymethyl methacrylate resin orbital prosthesis after orbital exenteration, for squamous cell carcinoma of the upper eyelid. The orbital prosthesis was sufficiently retained by hard and soft tissue undercuts without any complications. The patients using the prosthesis are quite satisfied with the cosmetic results and felt comfortable attending the social events.

Synthesis of 3'-, or 5'-, or internal methacrylamido-modified oligonucleotides

DOEpatents

Golova, Julia B.; Chernov, Boris K.

2010-04-27

New modifiers were synthesized for incorporation of a methacrylic function in 3'-, 5'- and internal positions of oligonucleotides during solid phase synthesis. A modifier was used for synthesis of 5'-methacrylated oligonucleotides for preparation of microarrays by a co-polymerization method.

CYP2F2-generated metabolites, not styrene oxide, are a key event mediating the mode of action of styrene-induced mouse lung tumors.

PubMed

Cruzan, G; Bus, J; Hotchkiss, J; Harkema, J; Banton, M; Sarang, S

2012-02-01

Styrene induces lung tumors in mice but not in rats. Although metabolism of styrene to 7,8-styrene oxide (SO) by CYP2E1 has been suggested as a mediator of styrene toxicity, lung toxicity is not attenuated in CYP2E1 knockout mice. However, styrene and/or SO metabolism by mouse lung Clara cell-localized CYP2F2 to ring-oxidized cytotoxic metabolite(s) has been postulated as a key metabolic gateway responsible for both lung toxicity and possible tumorigenicity. To test this hypothesis, the lung toxicity of styrene and SO was evaluated in C57BL/6 (WT) and CYP2F2⁻/⁻ knockout mice treated with styrene (400 mg/kg/day, gavage, or 200 or 400 mg/kg/day, ip) or S- or R-SO (200 mg/kg/day, ip) for 5 days. Styrene treated WT mice displayed significant necrosis and exfoliation of Clara cells, and cumulative BrdU-labeling index of S-phase cells was markedly increased in terminal bronchioles of WT mice exposed to styrene or S- or RSO. In contrast, Clara and terminal bronchiole cell toxicity was not observed in CYP2F2⁻/⁻ mice exposed to either styrene or SO. This study clearly demonstrates that the mouse lung toxicity of both styrene and SO is critically dependent on metabolism by CYP2F2. Importantly, the human isoform of CYP2F, CYP2F1, is expressed at much lower levels and likely does not catalyze significant styrene metabolism, supporting the hypothesis that styrene-induced mouse lung tumors may not quantitatively, or possibly qualitatively, predict lung tumor potential in humans. Copyright © 2011 Elsevier Inc. All rights reserved.

Vertical phase separation of 6,13-bis(triisopropylsilylethynyl) pentacene/poly(methyl methacrylate) blends prepared by electrostatic spray deposition for organic field-effect transistors

NASA Astrophysics Data System (ADS)

Onojima, Norio; Hara, Kazuhiro; Nakamura, Ayato

2017-05-01

Blend films composed of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) and poly(methyl methacrylate) (PMMA) were prepared by electrostatic spray deposition (ESD). ESD is considered as an intermediate process between dry and wet processes since the solvent present in small droplets can almost be evaporated before arriving at the substrate. Post-drying treatments with the time-consuming evaporation of residual solvents can be omitted. However, it is still not clear that a vertically phase-separated structure can be formed in the ESD process since the vertical phase separation of the blend films is associated with the solvent evaporation. In this study, we fabricated bottom-gate, top-contact organic field-effect transistors based on the blend films prepared by ESD and the devices exhibited transistor behavior with small hysteresis. This result demonstrates that the vertical phase separation of a blend film (upper TIPS pentacene active layer/bottom PMMA gate insulator) can occur in the facile one-step ESD process.

Fabrication of metallized nanoporous films from the self-assembly of a block copolymer and homopolymer mixture.

PubMed

Li, Xue; Zhao, Shuying; Zhang, Shuxiang; Kim, Dong Ha; Knoll, Wolfgang

2007-06-19

Inorganic compound HAuCl4, which can form a complex with pyridine, is introduced into a poly(styrene-block-2-vinylpyridine) (PS-b-P2VP) block copolymer/poly(methyl methacrylate) (PMMA) homopolymer mixture. The orientation of the cylindrical microdomains formed by the P2VP block, PMMA, and HAuCl4 normal to the substrate surface can be generated via cooperative self-assembly of the mixture. Selective removal of the homopolymer can lead to porous nanostructures containing metal components in P2VP domains, which have a novel photoluminescence property.

Activity, conformation and dynamics of cutinase adsorbed on poly(methyl methacrylate) latex particles.

PubMed

Baptista, R P; Santos, A M; Fedorov, A; Martinho, J M G; Pichot, C; Elaïssari, A; Cabral, J M S; Taipa, M A

2003-05-08

The adsorption of a recombinant cutinase from Fusarium solani pisi onto the surface of 100 nm diameter poly(methyl methacrylate) (PMMA) latex particles was evaluated. Adsorption of cutinase is a fast process since more than 70% of protein molecules are adsorbed onto PMMA at time zero of experiment, irrespective of the tested conditions. A Langmuir-type model fitted both protein and enzyme activity isotherms at 25 degrees C. Gamma(max) increased from 1.1 to 1.7 mg m(-2) and U(max) increased from 365 to 982 U m(-2) as the pH was raised from 4.5 to 9.2, respectively. A decrease (up to 50%) in specific activity retention was observed at acidic pH values (pH 4.5 and 5.2) while almost no inactivation (eta(act) congruent with 87-94%) was detected upon adsorption at pH 7.0 and 9.2. Concomitantly, far-UV circular dichroism (CD) spectra evidenced a reduction in the alpha-helical content of adsorbed protein at acidic pH values while at neutral and alkaline pH the secondary structure of adsorbed cutinase was similar to that of native protein. Fluorescence anisotropy decays showed the release of some constraints to the local motion of the Trp69 upon protein adsorption at pH 8.0, probably due to the disruption of the tryptophan-alanine hydrogen bond when the tryptophan interacts with the PMMA surface. Structural data associated with activity measurements at pH 7.0 and 9.2 showed that cutinase adsorbs onto PMMA particles in an end-on orientation with active site exposed to solvent and full integrity of cutinase secondary structure. Hydrophobic interactions are likely the major contribution to the adsorption mechanism at neutral and alkaline pH values, and a higher amount of protein is adsorbed to PMMA particles with increasing temperature at pH 9.2. The maximum adsorption increased from 88 to 140 mg cutinase per g PMMA with temperature raising from 25 to 50 degrees C, at pH 9.2.

Pulmonary function and oxidative stress in workers exposed to styrene in plastic factory: occupational hazards in styrene-exposed plastic factory workers.

PubMed

Sati, Prakash Chandra; Khaliq, Farah; Vaney, Neelam; Ahmed, Tanzeel; Tripathi, Ashok K; Banerjee, Basu Dev

2011-11-01

Styrene is a volatile organic compound used in factories for synthesis of plastic products. The pneumotoxicity of styrene in experimental animals is known. The aim of the present study was to study the effect of styrene on lung function and oxidative stress in occupationally exposed workers in plastic factory. Thirty-four male workers, between 18 and 40 years of age, exposed to styrene for atleast 8 hours a day for more than a year were studied, while 30 age- and sex-matched healthy subjects not exposed to styrene served as controls. Assessment of lung functions showed a statistically significant reduction (p < 0.05) in most of the lung volumes, capacities (FVC, FEV(1), VC, ERV, IRV, and IC) and flow rates (PEFR, MEF(75%), and MVV) in the study group (workers) as compared to controls. Malondialdehyde (MDA) was observed to be significantly high (p < 0.05) while ferric-reducing ability of plasma (FRAP) was significantly low (p < 0.05) in styrene-exposed subjects. Reduced glutathione (GSH) level was significantly depleted in exposed subjects as compared to control group. The mean value of serum cytochrome c in styrene-exposed subjects was found to be 1.1 ng/ml (0.89-1.89) while in control its levels were under detection limit (0.05 ng/ml). It shows that styrene inhalation by workers leads to increased level of oxidative stress, which is supposed to be the cause of lung damage.

Investigation of styrene in the liver perfusion/cell culture system. No indication of styrene-7,8-oxide as the principal mutagenic metabolite produced by the intact rat liver.

PubMed

Beije, B; Jenssen, D

1982-03-01

Mutagenic effect of styrene and styrene-7,8-oxide was studied with the isolated perfused rat liver as metabolizing system and Chinese hamster V79 cells as genetic target cells. Styrene-7,8-oxide which is mutagenic per se was rapidly metabolized by the perfused rat liver. Thus no mutagenic effect was detected neither in the perfusion medium nor in the bile. However when styrene was added to the perfusion system, an increase in V79 mutants was observed regardless of where in the circulating perfusion medium the V79 cells were placed: the same effect was obtained with V79 cells close to the liver as well as at a distance from the liver. No mutagenic effect was observed in the bile. Simultaneous analysis of the styrene-7,8-oxide concentration in the perfusion medium, suggest that this metabolite is not the cause of the mutagenic effect observed during perfusion with styrene. The effect of the two test compounds on some liver functions was also studied. Both styrene and styrene-7,8-oxide changed the bile flow without affecting bile acid secretion: styrene caused a reduction in bile flow as compared to control perfusions and styrene-7,8-oxide increased the bile flow. Styrene, but not styrene-7,8-oxide, reduced gluconeogenesis from lactate. Styrene had no effect on the liver's capacity to incorporate amino acids into plasma proteins, whereas styrene-7,8-oxide reduced the amino acid incorporation. The microsomal cytochrome P-450 content was not affected by the two test compounds. No alteration in microsomal N- and C-oxygenation of N,N-dimethylaniline (DMA) was observed with styrene-7,8-oxide or the lower styrene dose used (240 mumol), whereas the higher styrene concentration (480 mumol) reduced N-oxygenation and thus also the total DNA metabolism. It is suggested that the results on styrene and styrene-7,8-oxide found here using the liver perfusion/cell culture system mimic the metabolism expected to be found in the intact animal, thus indicating that styrene-7,8-oxide is

Curcumin delivery from poly(acrylic acid-co-methyl methacrylate) hollow microparticles prevents dopamine-induced toxicity in rat brain synaptosomes.

PubMed

Yoncheva, Krassimira; Kondeva-Burdina, Magdalena; Tzankova, Virginia; Petrov, Petar; Laouani, Mohamed; Halacheva, Silvia S

2015-01-01

The potential of poly(methyl methacrylate-co-acrylic acid) (PMMA-AA) copolymers to form hollow particles and their further formulation as curcumin delivery system have been explored. The particles were functionalized by crosslinking the acrylic acid groups via bis-amide formation with either cystamine (CYS) or 3,3'-dithiodipropionic acid dihydrazide (DTP) which simultaneously incorporated reversibility due to the presence of disulfide bonds within the crosslinker. Optical micrographs showed the formation of spherical hollow microparticles with a size ranging from 1 to 7 μm. Curcumin was loaded by incubation of its ethanol solution with aqueous dispersions of the cross-linked particles and subsequent evaporation of the ethanol. Higher loading was observed in the microparticles with higher content of hydrophobic PMMA units indicating its influence upon the loading of hydrophobic molecules such as curcumin. The in vitro release studies in a phosphate buffer showed no initial burst effect and sustained release of curcumin that correlated with the swelling of the particles under these conditions. The capacity of encapsulated and free curcumin to protect rat brain synaptosomes against dopamine-induced neurotoxicity was examined. The encapsulated curcumin showed greater protective effects in rat brain synaptosomes as measured by synaptosomal viability and increased intracellular levels of glutathione. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of barium-coated halloysite nanotube addition on the cytocompatibility, mechanical and contrast properties of poly(methyl methacrylate) cement.

PubMed

Jammalamadaka, Uday; Tappa, Karthik; Weisman, Jeffery A; Nicholson, James Connor; Mills, David K

2017-01-01

Halloysite nanotubes (HNTs) were investigated as a platform for tunable nanoparticle composition and enhanced opacity in poly(methyl methacrylate) (PMMA) bone cement. Halloysite has been widely used to increase the mechanical properties of various polymer matrices, in stark contrast to other fillers such as barium sulfate that provide opacity but also decrease mechanical strength. The present work describes a dry deposition method for successively fabricating barium sulfate nanoparticles onto the exterior surface of HNTs. A sintering process was used to coat the HNTs in barium sulfate. Barium sulfate-coated HNTs were then added to PMMA bone cement and the samples were tested for mechanical strength and tailored opacity correlated with the fabrication ratio and the amount of barium sulfate-coated HNTs added. The potential cytotoxic effect of barium-coated HNTs in PMMA cement was also tested on osteosarcoma cells. Barium-coated HNTs were found to be completely cytocompatible, and cell proliferation was not inhibited after exposure to the barium-coated HNTs embedded in PMMA cement. We demonstrate a simple method for the creation of barium-coated nanoparticles that imparted improved contrast and material properties to native PMMA. An easy and efficient method for coating clay nanotubes offers the potential for enhanced imaging by radiologists or orthopedic surgeons.

Metabolism of styrene to styrene oxide and vinylphenols in cytochrome P450 2F2- and P450 2E1-knockout mouse liver and lung microsomes

PubMed Central

Shen, Shuijie; Li, Lei; Ding, Xinxin; Zheng, Jiang

2014-01-01

Pulmonary toxicity of styrene is initiated by cytochromes P450-dependent metabolic activation. P450 2E1 and P450 2F2 are considered to be two main cytochrome P450 (CYP) enzymes responsible for styrene metabolism in mice. The objective of the current study was to determine the correlation between the formation of styrene metabolites (i.e. styrene oxide and 4-vinylphenol) and pulmonary toxicity of styrene, using Cyp2e1- and Cyp2f2-null mouse models. Dramatic decrease in the formation of styrene glycol and 4-vinylphenol was found in Cyp2f2-null mouse lung microsomes, relative to that in the wild-type mouse lung microsomes. However, no significant difference in the production of the styrene metabolites was observed between lung microsomes obtained from Cyp2e1-null and the wild-type mice. The knock–out and wild-type mice were treated with styrene (6.0 mmol/kg, ip), and cell counts and LDH activity in bronchoalveolar lavage fluids were monitored to evaluate the pulmonary toxicity induced by styrene. Cyp2e1-null mice displayed similar susceptibility to lung toxicity of styrene as the wild-type animals. However, Cyp2f2-null mice were resistant to styrene-induced pulmonary toxicity. In conclusion, both P450 2E1 and P450 2F2 are responsible for the metabolic activation of styrene. The latter enzyme plays an important role in styrene-induced pulmonary toxicity. Both styrene oxide and 4-vinylphenol are suggested to participate in the development of lung injury induced by styrene. PMID:24320693

Metabolism of styrene to styrene oxide and vinylphenols in cytochrome P450 2F2- and P450 2E1-knockout mouse liver and lung microsomes.

PubMed

Shen, Shuijie; Li, Lei; Ding, Xinxin; Zheng, Jiang

2014-01-21

Pulmonary toxicity of styrene is initiated by cytochromes P450-dependent metabolic activation. P450 2E1 and P450 2F2 are considered to be two main cytochrome P450 enzymes responsible for styrene metabolism in mice. The objective of the current study was to determine the correlation between the formation of styrene metabolites (i.e., styrene oxide and 4-vinylphenol) and pulmonary toxicity of styrene, using Cyp2e1- and Cyp2f2-null mouse models. A dramatic decrease in the formation of styrene glycol and 4-vinylphenol was found in Cyp2f2-null mouse lung microsomes relative to that in the wild-type mouse lung microsomes; however, no significant difference in the production of the styrene metabolites was observed between lung microsomes obtained from Cyp2e1-null and the wild-type mice. The knockout and wild-type mice were treated with styrene (6.0 mmol/kg, ip), and cell counts and LDH activity in bronchoalveolar lavage fluids were monitored to evaluate the pulmonary toxicity induced by styrene. Cyp2e1-null mice displayed a susceptibility to lung toxicity of styrene similar to that of the wild-type animals; however, Cyp2f2-null mice were resistant to styrene-induced pulmonary toxicity. In conclusion, both P450 2E1 and P450 2F2 are responsible for the metabolic activation of styrene. The latter enzyme plays an important role in styrene-induced pulmonary toxicity. Both styrene oxide and 4-vinylphenol are suggested to participate in the development of lung injury induced by styrene.

Supercritical fluid processing: a new dry technique for photoresist developing

NASA Astrophysics Data System (ADS)

Gallagher-Wetmore, Paula M.; Wallraff, Gregory M.; Allen, Robert D.

1995-06-01

Supercritical fluid (SCF) technology is investigated as a dry technique for photoresist developing. Because of their unique combination of gaseous and liquid-like properties, these fluids offer comparative or improved efficiencies over liquid developers and, particularly carbon dioxide, would have tremendous beneficial impact on the environment and on worker safety. Additionally, SCF technology offers the potential for processing advanced resist systems which are currently under investigation as well as those that may have been abandoned due to problems associated with conventional developers. An investigation of various negative and positive photoresist systems is ongoing. Initially, supercritical carbon dioxide (SC CO2) as a developer for polysilane resists was explored because the exposure products, polysiloxanes, are generally soluble in this fluid. These initial studies demonstrated the viability of the SCF technique with both single layer and bilayer systems. Subsequently, the investigation focused on using SC CO2 to produce negative images with polymers that would typically be considered positive resists. Polymers such as styrenes and methacrylates were chemically modified by fluorination and/or copolymerization to render them soluble in SC CO2. Siloxane copolymers and siloxane-modified methacrylates were examined as well. The preliminary findings reported here indicate the feasibility of using SC CO2 for photoresist developing.

Effects of propylene, methyl methacrylate and isopropanol poisoning on spatial performance of a proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Reshetenko, Tatyana V.; St-Pierre, Jean

2018-02-01

This paper studies the effects of propylene, methyl methacrylate (MMA) and isopropanol (IPA) in air on the spatial performance of proton exchange membrane fuel cells (PEMFCs). The introduction of 100 ppm C3H6 into the oxidant stream resulted in a performance decrease of 130 mV at 1.0 A cm-2, whereas 20 ppm MMA caused a voltage loss of 80 mV. A moderate performance decline of 60 mV was detected in the presence of 5.3ṡ103 ppm IPA in air. Spatial electrochemical impedance spectroscopy (EIS) data showed an increase in charge and mass transfer resistances under exposure to C3H6 and MMA, although IPA did not affect the impedance. The observed PEMFC performances, local current redistributions and EIS data can be explained by the adsorption of contaminants on the Pt surface, their subsequent transformations, and their impacts on the electrochemical surface area and oxygen reduction mechanism. It was assumed that the studied contaminants were oxidized mainly to CO2 via electrochemical and chemical pathways under the operating conditions and at the cathode potential. Self-recovery of PEMFC performance was observed for each contaminant after halting its introduction into the air. Possible contaminant oxidation/reduction mechanisms and their correlations with spatial performance and EIS are presented and discussed.

Synthesis and Characterization of Poly (styrene-co-butyl acrylate)/Silica Aerogel Nanocomposites by in situ AGET ATRP: Investigating Thermal Properties

NASA Astrophysics Data System (ADS)

Khezri, Khezrollah; Fazli, Yousef

2017-10-01

Hydrophilic silica aerogel nanoparticles surface was modified with hexamethyldisilazane. Then, the resultant modified nanoparticles were used in random copolymerization of styrene and butyl acrylate via activators generated by electron transfer for atom transfer radical polymerization. Conversion and molecular weight determinations were performed using gas and size exclusion chromatography respectively. Addition of modified nanoparticles by 3 wt% results in a decrease of conversion from 68 to 46 %. Molecular weight of copolymer chains decreases from 12,500 to 7,500 g.mol-1 by addition of 3 wt% modified nanoparticles; however, PDI values increase from 1.1 to 1.4. Proton nuclear magnetic resonance spectroscopy results indicate that the molar ratio of each monomer in the copolymer chains is approximately similar to the initial selected mole ratio of them. Increasing thermal stability of the nanocomposites is demonstrated by thermal gravimetric analysis. Differential scanning calorimetry also shows a decrease in glass transition temperature by increasing modified silica aerogel nanoparticles.

Temperature-independent zero-birefringence polymer for liquid crystal displays

NASA Astrophysics Data System (ADS)

Shikanai, M. D.; Tagaya, A.; Koike, Y.

2016-03-01

A polymer film that shows almost no orientational birefringence even when the polymer main chain is in an oriented state and almost no temperature dependence of orientational birefringence in the temperature range from around -40 to 85 °C was prepared. This temperature range is important because it is where in-car liquid crystal displays (LCDs) are generally used; therefore, it is desirable to have constant orientational birefringence over this range. We suggest a method to compensate for the intrinsic birefringence and temperature coefficient of intrinsic birefringence of individual polymers by copolymerizing monomers of homopolymers that display opposite signs of the two parameters described above. Analysis of four types of polymers, methyl methacrylate (MMA), 2,2,2-trifluoroethyl methacrylate, benzyl methacrylate (BzMA), and phenyl methacrylate (PhMA), reveal that they possess both positive and negative signs of their temperature coefficient of intrinsic birefringence. Using this approach, we prepare P(MMA/PhMA/BzMA) (39:23:38 wt. %), which exhibits almost no intrinsic birefringence and almost no temperature dependence of intrinsic birefringence. The retardation of this polymer film when drawn uniaxially scarcely changed (between 0.3 and 0.8 nm) between 12 and 70 °C, which is small enough not to cause image degradation in LCDs.

Adsorption and covalent binding of fibrinogen as a method for probing the chemical composition of poly(styrene/α-tert-butoxy-ω-vinylbenzyl-polyglycidol) microsphere surfaces.

PubMed

Gosecka, Monika; Chehimi, Mohamed M; Basinska, Teresa; Slomkowski, Stanislaw; Makowski, Tomasz

2017-12-01

We investigated the distribution of polyglycidol and polystyrene on the surface of poly(styrene/α-tert-butoxy-ω-vinylbenzyl-polyglycidol) microspheres (random distribution or segregated into hydrophilic and hydrophobic patches), using fibrinogen (Fb) as a macromolecular probe. The fibrinogen was adsorbed or covalently attached to the surface of the poly(styrene-co-α-tert-butoxy-ω-vinylbenzyl-polyglycidol) (P(S/PGLy)) microspheres. The P(S/PGLy) particles were prepared by emulsion copolymerization of styrene and α-tert-butoxy-ω-vinylbenzyl-polyglycidol (PGLy) macromonomer initiated with potassium persulfate. The polymerizations yielded P(S/PGLy) particles with various surface fractions of polyglycidol, depending on the amount of added macromonomer and the addition process. In some syntheses, the entire macromonomer amount was added once at the beginning of the polymerization, while in others, the macromonomer was added gradually after the formation of particle seeds from pure polystyrene. XPS studies revealed that the fraction of polyglycidol in the interfacial layer of the microspheres was larger when the entire amount of macromonomer was added at the beginning of the polymerization than when it was added after formation of the polystyrene seeds. Studies of fibrinogen adsorption provided the first evidence of segregation of the hydrophobic (polystyrene) and hydrophilic (polyglycidol) components at the surface of the composite P(S/PGLy) microspheres into patches. The hydrophobic patches are composed mainly of polystyrene. However, they also contain a small amount of polyglycidol chains, making the adsorption of fibrinogen weaker than the adsorption onto the pure polystyrene. Studies of covalent immobilization of fibrinogen on the microspheres via 1,3,5-trichlorotriazine confirmed these findings. Copyright © 2017 Elsevier B.V. All rights reserved.

Stable and pH-responsive core-shell nanoparticles based on HEC and PMAA networks via template copolymerization

NASA Astrophysics Data System (ADS)

Zhang, Y.; Jin, Q.; Chen, Y.; Zhao, J.

2011-10-01

Taking advantage of the specific hydrogen bonding interactions, stable and pH-responsive core-shell nanoparticles based on hydroxyethyl cellulose (HEC) and polymethacrylic acid (PMAA) networks, with a < D h > size ranging from 190 to 250 nm, can be efficiently prepared via facile one-step co-polymerization of methacrylic acid (MAA) and N, N'-methylenebisacrylamide (MBA) on HEC template in water. Using dynamic light scattering, electrophoretic light scattering, fluorescence spectrometry, thermo-gravimetric analysis, TEM, and AFM observations, the influence of crosslinker MBA as well as the reaction parameters were studied. The results show that after the introduction of crosslinker MBA, the nanoparticles became less compact; their size exhibited a smaller pH sensitivity, and their stability against pH value was improved greatly. Furthermore, the size, structure, and pH response of the nanoparticles can be adjusted via varying the reaction parameters: nanoparticles of smaller size, more compact structure, and higher swelling capacity were produced as pH value of the reaction medium increased or the HEC/MAA ratio decreased; while nanoparticles of smaller size, less compact structure and smaller swelling capacity were produced as the total feeding concentration increased.

Dynamics of poly(ethylene oxide) in a blend with poly(methyl methacrylate): a quasielastic neutron scattering and molecular dynamics simulations study.

PubMed

Genix, A-C; Arbe, A; Alvarez, F; Colmenero, J; Willner, L; Richter, D

2005-09-01

In this paper, we have addressed the question of the dynamic miscibility in a blend characterized by very different glass-transition temperatures, Tg, for the components: poly(ethylene oxide) and poly(methyl methacrylate) (PEO/PMMA). The combination of quasielastic neutron scattering with isotopic labeling and fully atomistic molecular dynamics simulations has allowed us to selectively investigate the dynamics of the two components in the picosecond-10 nanoseconds scale at temperatures close and above the Tg of the blend. The main focus was on the PEO component, i.e., that of the lowest Tg, but first we have characterized the dynamics of the other component in the blend and of the pure PEO homopolymer as reference. In the region investigated, the dynamics of PMMA in the blend is strongly affected by the alpha-methyl rotation; an additional process detected in the experimental window 65 K above the blend-Tg can be identified as the merged alphabeta process of this component that shows strong deviations from Gaussian behavior. On the other hand, pure PEO displays entropy driven dynamics up to very large momentum transfers. Such kind of motion seems to freeze when the PEO chains are in the blend. There, we have directly observed a very heterogeneous and moreover confined dynamics for the PEO component. The presence of the hardly moving PMMA matrix leads to the creation of little pockets of mobility where PEO can move. The characteristic size of such confined islands of mobility might be estimated to be of approximately 1 nm. These findings are corroborated by the simulation study, which has been an essential support and guide in our data analysis procedure.

Low-temperature radiation copolymerization of tetrafluoroethylene with perfluorovinyl ethers

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

Kim, I.P.; Pirozhnaya, L.N.; Loginova, N.N.

1986-12-01

The copolymerization of perfluorovinyl ethers with tetrafluoroethylene at low temperature was studied and compared with the process conducted with chemical initiation in bulk or aqueous medium. A calorimetric method was used for studying the kinetics of copolymerization, the phase state of the system, and the phase transition dynamics. Ampules containing the samples of monomers and mixtures were irradiated at 77/sup 0/K with /sup 60/Co ..gamma.. rays with a dose rate of 25 kGy/h. Radiolysis in the solid phase at 77/sup 0/K with a 130 kGy dose resulted in the formation of 0.5-1.0 wt.% of a polymer, and this polymer wasmore » soluble in the monomer.« less

Styrene-Associated Health Outcomes at a Windblade Manufacturing Plant

PubMed Central

McCague, Anna-Binney; Cox-Ganser, Jean M.; Harney, Joshua M.; Alwis, K. Udeni; Blount, Benjamin C.; Cummings, Kristin J.; Edwards, Nicole; Kreiss, Kathleen

2015-01-01

Background Health risks of using styrene to manufacture windblades for the green energy sector are unknown. Methods Using data collected from 355 (73%) current windblade workers and regression analysis, we investigated associations between health outcomes and styrene exposure estimates derived from urinary styrene metabolites. Results The median current styrene exposure was 53.6 mg/g creatinine (interquartile range: 19.5–94.4). Color blindness in men and women (standardized morbidity ratios 2.3 and 16.6, respectively) was not associated with exposure estimates, but was the type previously reported with styrene. Visual contrast sensitivity decreased and chest tightness increased (odds ratio 2.9) with increasing current exposure. Decreases in spirometric parameters and FeNO, and increases in the odds of wheeze and asthma-like symptoms (odds ratios 1.3 and 1.2, respectively) occurred with increasing cumulative exposure. Conclusions Despite styrene exposures below the recommended 400 mg/g creatinine, visual and respiratory effects indicate the need for additional preventative measures in this industry. PMID:26305283

REDUCING STYRENE EMISSIONS FROM SPRAYED FILLED RESINS

EPA Science Inventory

Styrene emissions are coming under increasing study as the U.S. Environmental Protection Agency (EPA) develops maximum achievable control technology standards. During the manufacture of fiber-reinforced plastics/composites products, styrene, a volatile organic compound and a haz...

Preparation of methacrylic acid-modified rice husk improved by an experimental design and application for paraquat adsorption.

PubMed

Hsu, Shih-Tong; Chen, Lung-Chuan; Lee, Cheng-Chieh; Pan, Ting-Chung; You, Bing-Xuan; Yan, Qi-Feng

2009-11-15

Methacrylic acid (MAA) grafted rice husk was synthesized using graft copolymerization with Fenton's reagent as the redox initiator and applied to the adsorption of paraquat. The highest grafting percentage of 44.3% was obtained using the traditional kinetic method. However, a maximum grafting percentage of 65.3% was calculated using the central composite design. Experimental results based on the recipes predicted from the statistical analysis are consistent with theoretical calculations. A representative polymethacrylic acid-g-rice husk (PMAA-g-rice husk) copolymer was hydrolyzed to a salt type and applied to the adsorption of paraquat. The adsorption equilibrium data correlate more closely with the Langmuir isotherm than with the Freundlich equation. The maximum adsorption capacity of modified rice husk is 292.5mg/g-adsorbent. This value exceeds those for Fuller's earth and activated carbon, which are the most common binding agents used for paraquat. The samples at various stages were characterized by solid-state (13)C NMR spectroscopy.

Photophysical properties and photoisomerization processes of Methyl Red embedded in rigid polymer

NASA Astrophysics Data System (ADS)

Lee, Geon Joon; Kim, Dongho; Lee, Minyung

1995-01-01

The photophysical properties of Methyl Red molecules embedded in a poly(methyl methacrylate) (PMMA) matrix were investigated with photoinduced absorption, absorption kinetics, steady-state, and time-resolved luminescence spectroscopy. The excited singlet (S1) state lifetimes for trans and cis isomers of Methyl Red in PMMA at room temperature have been measured as 35 and 420 ps, respectively. The excited triplet (T1) state energy level and its lifetime at 77 K were also obtained. A slow trans-cis isomerization process having a time constant of a few hundred seconds was observed for the illuminated Methyl Red in rigid polymer. Based on measured photophysical properties and dynamic processes, an energy-level diagram for Methyl Red molecules in rigid polymer is introduced to explain these observations.

Synthesis of amphipathic block copolymers based on polyisobutylene and polyoxyethylene and their application in emulsion polymerization

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

Sar, B.

1992-12-31

Polymer colloids stabilized by polymeric surfactants are of great interest both commercially and academically. It has been found that these materials enhance latex stabilization in a number of applications. The polymeric surfactants are amphipathic block and graft copolymers containing both hydrophilic and hydrophobic moieties. The current study involved the synthesis of a series of amphipathic triblock copolymers, polyisobutylene-block-polyoxyethylene-block-polyisobutylene (PIB-b-POE-b-PIB), for use in the emulsion polymerization of styrene (STY), methyl methacrylate (MMA), and vinyl acetate (VAc). The stabilizing effectiveness of these triblock copolymers was studied as a function of their blocklength. When the molecular weight of the POE center block wasmore » changed from M{sub n} = 2,000 to 20,000 g/mole, stable lattices were obtained in emulsion polymerization with MMA, STY, and VAc as the monomers. In all cases, the polymerization rates remained constant, while the number of particles/volume decreased with increasing POE chain length. When the molecular weight of the PIB end blocks was changed from M{sub n} = 400 to 2,600 g/mole keeping the molecular weight of the POE center block constant at M{sub n} = 20,000 g/mole, the poly(methyl methacrylate) and poly(vinyl acetate) lattices exhibited similar behavior, i.e., the number of particles and particle sizes remained the same, but the rate of polymerization reached a maximum at 87 wt% POE content. In the case of poly(styrene) both the rate of polymerization and the number of particles remained constant. The emulsion polymerization of other monomers such as butadiene, acrylonitrile, methyl acrylate, ethyl acrylate, and butyl acrylate was carried out by using one triblock copolymer, i.e., PIB(400)-b-POE (8,000)-b-PIB-(400). Stable lattices were also formed in all cases.« less

In-plane and out-of-plane defectivity in thin films of lamellar block copolymers

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

Mahadevapuram, Nikhila; Mitra, Indranil; Bozhchenko, Alona

2015-10-29

We investigate the ordering of poly(styrene-b-methyl methacrylate) (PS-PMMA) lamellar copolymers (periodicity L 0 = 46 nm) confined between a free surface and brushed poly(styrene-r-methyl methacrylate) silicon substrate. The processing temperature was selected to eliminate wetting layers at the top and bottom interfaces, producing approximately neutral boundaries that stabilize perpendicular domain orientations. The PS-PMMA film thickness (t = 0.5L 0–2.5L 0) and brush grafting density (Σ = 0.2–0.6 nm –2) were systematically varied to examine their impacts on in-plane and out-of-plane ordering. Samples were characterized with a combination of high-resolution microscopy, X-ray reflectivity, and grazing-incidence small-angle X-ray scattering. In-plane order atmore » the top of the film (quantified through calculation of orientational correlation lengths) improved with t n, where the exponent n increased from 0.75 to 1 as Σ decreased from 0.6 to 0.2 nm –2. Out-of-plane defects such as tilted domains were detected in all films, and the distribution of domain tilt angles was nearly independent of t and Σ. These studies demonstrate that defectivity in perpendicular lamellar phases is three-dimensional, comprised of in-plane topological defects and out-of-plane domain tilt, with little or no correlation between these two types of disorder. As a result, strong interactions between the block copolymer and underlying substrate may trap both kinds of thermally generated defects.« less

Carbon black reinforced polymethyl methacrylate (PMMA)-based composite particles: preparation, characterization, and application

NASA Astrophysics Data System (ADS)

Liang, Tian; Yan, Chunjie; Zhou, Sen; Zhang, Yonghan; Yang, Bipeng

2017-10-01

Carbon black (CB) is an excellent filler to reinforce polymers because of its unique thermal and mechanical properties. Thus, a type of modified carbon black (MCB) was developed, which led to reduced filler aggregation in methyl methacrylate (MMA) monomers and resulted in homogeneous dispersion in the polymethyl methacrylate (PMMA) substrate. The PMMA-MCB composite particles that were prepared in this work possessed remarkable and stable properties. Therefore, they can be used as an ultra-lightweight proppant (ULWP). Fourier transform infrared spectroscopy showed that CB was successfully modified and the MCB was well dispersed in the PMMA matrix. Results of crushing rate and differential scanning calorimetry demonstrated that MCB could significantly enhance the thermal and mechanical performance of the ULWP. Heat treatment of the ULWP under a nitrogen atmosphere could also clearly enhance its performance in various aspects. The process of modifying CB, the approach of synthesizing PMMA-MCB composite particles, and their mechanism were systematically investigated in this work.

Bond strength of poly(methyl methacrylate) denture base material to cast titanium and cobalt-chromium alloy.

PubMed

Matsuda, Yasuhiro; Yanagida, Hiroaki; Ide, Takako; Matsumura, Hideo; Tanoue, Naomi

2010-06-01

The shear bond strength of an auto-polymerizing poly(methyl methacrylate) denture base resin material to cast titanium and cobalt-chromium alloy treated with six conditioning methods was investigated. Disk specimens (10 mm in diameter and 2.5 mm in thickness) were cast from pure titanium and cobalt-chromium alloy. The specimens were wet ground to a final surface finish of 600 grit, air dried, and treated with the following bonding systems: 1) air abraded with 50-70-microm-grain alumina (SAN); 2) air abraded with 50-70-microm-grain alumina + conditioned with Alloy Primer (ALP); 3) air abraded with 50-70-microm-grain alumina + conditioned with AZ Primer (AZP); 4) air abraded with 50-70-microm-grain alumina + conditioned with Estenia Opaque Primer (EOP); 5) air abraded with 50-70-microm-grain alumina + conditioned with Metal Link Primer (MLP), and 6) treated with ROCATEC system (ROC). A denture base material (Palapress Vario) was then applied to each metal specimen. Shear bond strengths were determined before and after 10,000 thermocycles. The strengths decreased after thermocycling in all combinations. Among the treatment methods assessed, groups 2 and 4 showed significantly (p < 0.05) enhanced shear bond strengths for both metals. In group 4, the strength in MPa (n = 7) after thermocycling for cobalt-chromium alloy was 38.3, which was statistically (p < 0.05) higher than that for cast titanium (34.7). Air abrasion followed by the application of two primers containing a hydrophobic phosphate monomer (MDP) effectively improved the strength of the bond of denture base material to cast titanium and cobalt-chromium alloy.

Kinetics for the Sequential Infiltration Synthesis of Alumina in Poly(methyl methacrylate): An Infrared Spectroscopic Study

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

Biswas, Mahua; Libera, Joseph A.; Darling, Seth B.

Sequential infiltration synthesis (SIS) is a method for growing inorganic materials within polymers in an atomically controlled fashion. This technique can increase the etch resistance of optical, electron-beam, and block copolymer (BCP) lithography resists and is also a flexible strategy for nanomaterials synthesis. Despite this broad utility, the kinetics of SIS remain poorly understood, and this knowledge gap must be bridged in order to gain firm control over the growth of inorganic materials inside polymer films at a large scale. In this paper, we explore the reaction kinetics for Al 2O 3 SIS in PMMA using in situ Fourier transformmore » infrared spectroscopy. First, we establish the kinetics for saturation adsorption and desorption of trimethyl aluminum (TMA) in PMMA over a range of PMMA film thicknesses deposited on silicon substrates. These observations guide the selection of TMA dose and purge times during SIS lithography to achieve robust organic/inorganic structures. Next, we examine the effects of TMA desorption on BCP lithography by performing SIS on silicon surfaces coated with polystyrene-block-poly(methyl methacrylate) films. After etching the organic components, the substrates are examined using scanning electron microcopy to evaluate the resulting Al 2O 3 patterns. Finally, we examine the effects of temperature on Al 2O 3 SIS in PMMA to elucidate the infiltration kinetics. The insights provided by these measurements will help extend SIS lithography to larger substrate sizes for eventual commercialization and expand our knowledge of precursor-polymer interactions that will benefit the SIS of a wide range of inorganic materials in the future.« less

Effect of additive particles on mechanical, thermal, and cell functioning properties of poly(methyl methacrylate) cement

PubMed Central

Khandaker, Morshed; Vaughan, Melville B; Morris, Tracy L; White, Jeremiah J; Meng, Zhaotong

2014-01-01

The most common bone cement material used clinically today for orthopedic surgery is poly(methyl methacrylate) (PMMA). Conventional PMMA bone cement has several mechanical, thermal, and biological disadvantages. To overcome these problems, researchers have investigated combinations of PMMA bone cement and several bioactive particles (micrometers to nanometers in size), such as magnesium oxide, hydroxyapatite, chitosan, barium sulfate, and silica. A study comparing the effect of these individual additives on the mechanical, thermal, and cell functional properties of PMMA would be important to enable selection of suitable additives and design improved PMMA cement for orthopedic applications. Therefore, the goal of this study was to determine the effect of inclusion of magnesium oxide, hydroxyapatite, chitosan, barium sulfate, and silica additives in PMMA on the mechanical, thermal, and cell functional performance of PMMA. American Society for Testing and Materials standard three-point bend flexural and fracture tests were conducted to determine the flexural strength, flexural modulus, and fracture toughness of the different PMMA samples. A custom-made temperature measurement system was used to determine maximum curing temperature and the time needed for each PMMA sample to reach its maximum curing temperature. Osteoblast adhesion and proliferation experiments were performed to determine cell viability using the different PMMA cements. We found that flexural strength and fracture toughness were significantly greater for PMMA specimens that incorporated silica than for the other specimens. All additives prolonged the time taken to reach maximum curing temperature and significantly improved cell adhesion of the PMMA samples. The results of this study could be useful for improving the union of implant-PMMA or bone-PMMA interfaces by incorporating nanoparticles into PMMA cement for orthopedic and orthodontic applications. PMID:24920906

Effect of additive particles on mechanical, thermal, and cell functioning properties of poly(methyl methacrylate) cement.

PubMed

Khandaker, Morshed; Vaughan, Melville B; Morris, Tracy L; White, Jeremiah J; Meng, Zhaotong

2014-01-01

The most common bone cement material used clinically today for orthopedic surgery is poly(methyl methacrylate) (PMMA). Conventional PMMA bone cement has several mechanical, thermal, and biological disadvantages. To overcome these problems, researchers have investigated combinations of PMMA bone cement and several bioactive particles (micrometers to nanometers in size), such as magnesium oxide, hydroxyapatite, chitosan, barium sulfate, and silica. A study comparing the effect of these individual additives on the mechanical, thermal, and cell functional properties of PMMA would be important to enable selection of suitable additives and design improved PMMA cement for orthopedic applications. Therefore, the goal of this study was to determine the effect of inclusion of magnesium oxide, hydroxyapatite, chitosan, barium sulfate, and silica additives in PMMA on the mechanical, thermal, and cell functional performance of PMMA. American Society for Testing and Materials standard three-point bend flexural and fracture tests were conducted to determine the flexural strength, flexural modulus, and fracture toughness of the different PMMA samples. A custom-made temperature measurement system was used to determine maximum curing temperature and the time needed for each PMMA sample to reach its maximum curing temperature. Osteoblast adhesion and proliferation experiments were performed to determine cell viability using the different PMMA cements. We found that flexural strength and fracture toughness were significantly greater for PMMA specimens that incorporated silica than for the other specimens. All additives prolonged the time taken to reach maximum curing temperature and significantly improved cell adhesion of the PMMA samples. The results of this study could be useful for improving the union of implant-PMMA or bone-PMMA interfaces by incorporating nanoparticles into PMMA cement for orthopedic and orthodontic applications.

The imaging study of a novel photopolymer used in I-line negative-tone resist

NASA Astrophysics Data System (ADS)

Liu, Lu; Zou, Yingquan

2010-04-01

By copolymerization of 2-(2-diazo-3-oxo-3-(4-dimethylaminophenyl)propionyloxy)ethyl methacrylate (DODMAPPEA), methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA), a photoactive polymer for negative-tone resist is synthesized and its photolithographic properties are investigated. Since the maximum-absorption wavelength of the photoactive monomer DODMAPPEA is 356nm and it still has a comparatively large absorption at 365nm (I-line), the copolymer poly(DODMAPPEA -co-MMA-co-HEMA) is anticipated to be used in I-line single component negative-tone resist. Upon irradiaton, the diazoketo groups which are in the side chains of the copolymers undergo the wolff rearrangement, affording ketenes that react with hydroxyl to provide cross-linking photoproducts and a negative image is obtained. Besides that, cross-linking agent hexamethoxymethylmelamine (HMMM) is added to the resist system and high sensitivity is expected. This kind of copolymer has great value in I-line non-CARs, TFT-LCD and IC discrete devices processing and the anti-dry etching ability is enhanced by the introduction of the benzene ring. In addition, this copolymer still has potential value in Ultra-violate lithographic plate.

CYP2E1 Metabolism of Styrene Involves Allostery

PubMed Central

Hartman, Jessica H.; Boysen, Gunnar

2012-01-01

We are the first to report allosterism during styrene oxidation by recombinant CYP2E1 and human liver microsomes. At low styrene concentrations, oxidation is inefficient because of weak binding to CYP2E1 (Ks = 830 μM). A second styrene molecule then binds CYP2E1 with higher affinity (Kss = 110 μM) and significantly improves oxidation to achieve a kcat of 6.3 nmol · min−1 · nmol CYP2E1−1. The transition between these metabolic cycles coincides with reported styrene concentrations in blood from exposed workers; thus, this CYP2E1 mechanism may be relevant in vivo. Scaled modeling of the in vitro-positive allosteric mechanism for styrene metabolism to its in vivo clearance led to significant deviations from the traditional model based on Michaelis-Menten kinetics. Low styrene levels were notably much less toxic than generally assumed. We interrogated the allosteric mechanism using the CYP2E1-specific inhibitor and drug 4-methylpyrazole, which we have shown binds two CYP2E1 sites. From the current studies, styrene was a positive allosteric effector on 4-methylpyrazole binding, based on a 10-fold increase in 4-methylpyrazole binding affinity from Ki 0.51 to Ksi 0.043 μM. The inhibitor was a negative allosteric effector on styrene oxidation, because kcat decreased 6-fold to 0.98 nmol · min−1 · nmol CYP2E1−1. Consequently, mixtures of styrene and other molecules can induce allosteric effects on binding and metabolism by CYP2E1 and thus mitigate the efficiency of their metabolism and corresponding effects on human health. Taken together, our elucidation of mechanisms for these allosteric reactions provides a powerful tool for further investigating the complexities of CYP2E1 metabolism of drugs and pollutants. PMID:22807108

Enantiomeric fraction of styrene glycol as a biomarker of occupational risk exposure to styrene.

PubMed

Lima, J J; Aguilar, A; Sánchez, F G; Díaz, A N

2017-02-01

This work reports a new analytical approach for monitoring the enantiomeric ratios of styrene glycol (SG), encountered during the manufacture of plastics, by chiral liquid chromatography and the application as a biomarker for exposure to styrene. The isomers were separated using an AGP column running in the reverse phase and isocratic mode with a mobile phase consisting of 20 mM phosphate buffer saline (pH 4.15) and methanol at a flow rate of 0.8 mL/min. Photometric, polarimetric, and circular dichroism detectors were employed. The chromatographic enantioselective resolution (Rs) and selectivity index (α) values were determined to be 1.60 and 1.48 (by photometric detection), respectively. Calibration curves used for the quantification of the SG enantiomers were linear with a correlation coefficient >0.99; the detection limits were in the range of 0.03-0.16 μg, depending on the detector used. Recovery assays on synthetic samples (in triplicate) covering the full range of enantiomeric fractions (0.0-1.0) show accuracy values below 5% for the enantiomeric fraction (EF) in every case. An alternative method based on the measurement of anisotropy factors for the determination of EF, which is faster and does not require the separation of enantiomers, has also been developed. The enantiomeric excess of the toxicant biomarker styrene glycol has been determined. No previous direct enantioselective determination of styrene glycol was published. Copyright © 2016 Elsevier Ltd. All rights reserved.

POLYMERIZATION AND COPOLYMERIZATION OF TETRACYANOETHYLENE UNDER THE EFFECT OF POLYMERS WITH A CONJUGATED SYSTEM,

DTIC Science & Technology

reactivity monomers such as tetracyanoethylene (I), anthracene, naphthacene and pentacene . I was polymerized alone or copolymerized with anthracene...naphthacene, or pentacene . Soluble fractions of polyphenylene or polyanthryl were used as the catalyst in various concentrations so as to vary the...magnitude as high as that of anthracene, and had an activation energy of 8-11 kcal/mol. Naphthacene, pentacene , and polyphenylene also copolymerized

Phosphonic acid based exchange resins

DOEpatents

Horwitz, E. Philip; Alexandratos, Spiro D.; Gatrone, Ralph C.; Chiarizia, Ronato

1995-01-01

An ion exchange resin for extracting metal ions from a liquid waste stream. An ion exchange resin is prepared by copolymerizing a vinylidene diphosphonic acid with styrene, acrylonitrile and divinylbenzene.

Phosphonic acid based ion exchange resins

DOEpatents

Horwitz, E. Philip; Alexandratos, Spiro D.; Gatrone, Ralph C.; Chiarizia, Ronato

1994-01-01

An ion exchange resin for extracting metal ions from a liquid waste stream. An ion exchange resin is prepared by copolymerizing a vinylidene disphosphonic acid with styrene, acrylonitrile and divinylbenzene.

Phosphonic acid based ion exchange resins

DOEpatents

Horwitz, E. Philip; Alexandratos, Spiro D.; Gatrone, Ralph C.; Chiarizia, Ronato

1996-01-01

An ion exchange resin for extracting metal ions from a liquid waste stream. An ion exchange resin is prepared by copolymerizing a vinylidene diphosphonic acid with styrene, acrylonitrile and divinylbenzene.

Occupational asthma in the furniture industry: is it due to styrene?

PubMed

Oner, Ferda; Mungan, Dilşad; Numanoglu, Numan; Demirel, Yavuz

2004-01-01

Styrene, a volatile monomer, has been reported as a cause of occupational asthma in a few case reports. The aim of this study was to investigate the risk for asthma in relation to exposure to styrene in a large number of workers. A total of 47 workers with a history of exposure to styrene were included in the study. To establish whether asthma was present, each patient underwent a clinical interview, pulmonary function testing and bronchial challenge with methacholine. Specific bronchial challenges with styrene and serial peak expiratory flow (PEF) measurement at home and at work were carried out in subjects with a diagnosis of asthma to evaluate the relationship between their asthma and exposure to styrene in the workplace. Among the 47 subjects, 5 workers had given a history of work-related symptoms, and 3 of them had a positive methacholine challenge test. Specific bronchial challenges with styrene and serial PEF measurement were subsequently carried out in these 3 subjects. Although provocation tests with styrene were negative in the 3 workers, 1 worker had PEF rate records compatible with occupational asthma. We established one patient with occupational asthma from a group of people who have excessive styrene exposure. This finding may be suggestive but is not conclusive about the causative role of styrene in occupational asthma. Since styrene is a frequently used substance in the furniture industry, it is worth performing further studies to investigate the relationship between styrene and occupational asthma. Copyright 2004 S. Karger AG, Basel

Interchain coupled chain dynamics of poly(ethylene oxide) in blends with poly(methyl methacrylate): coupling model analysis.

PubMed

Ngai, K L; Wang, Li-Min

2011-11-21

Quasielastic neutron scattering and molecular dynamics simulation data from poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends found that for short times the self-dynamics of PEO chain follows the Rouse model, but at longer times past t(c) = 1-2 ns it becomes slower and departs from the Rouse model in dependences on time, momentum transfer, and temperature. To explain the anomalies, others had proposed the random Rouse model (RRM) in which each monomer has different mobility taken from a broad log-normal distribution. Despite the success of the RRM, Diddens et al. [Eur. Phys. Lett. 95, 56003 (2011)] extracted the distribution of friction coefficients from the MD simulations of a PEO/PMMA blend and found that the distribution is much narrower than expected from the RRM. We propose a simpler alternative explanation of the data by utilizing alone the observed crossover of PEO chain dynamics at t(c). The present problem is just a special case of a general property of relaxation in interacting systems, which is the crossover from independent relaxation to coupled many-body relaxation at some t(c) determined by the interaction potential and intermolecular coupling/constraints. The generality is brought out vividly by pointing out that the crossover also had been observed by neutron scattering from entangled chains relaxation in monodisperse homopolymers, and from the segmental α-relaxation of PEO in blends with PMMA. The properties of all the relaxation processes in connection with the crossover are similar, despite the length scales of the relaxation in these systems are widely different.

Interchain coupled chain dynamics of poly(ethylene oxide) in blends with poly(methyl methacrylate): Coupling model analysis

NASA Astrophysics Data System (ADS)

Ngai, K. L.; Wang, Li-Min

2011-11-01

Quasielastic neutron scattering and molecular dynamics simulation data from poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends found that for short times the self-dynamics of PEO chain follows the Rouse model, but at longer times past tc = 1-2 ns it becomes slower and departs from the Rouse model in dependences on time, momentum transfer, and temperature. To explain the anomalies, others had proposed the random Rouse model (RRM) in which each monomer has different mobility taken from a broad log-normal distribution. Despite the success of the RRM, Diddens et al. [Eur. Phys. Lett. 95, 56003 (2011)] extracted the distribution of friction coefficients from the MD simulations of a PEO/PMMA blend and found that the distribution is much narrower than expected from the RRM. We propose a simpler alternative explanation of the data by utilizing alone the observed crossover of PEO chain dynamics at tc. The present problem is just a special case of a general property of relaxation in interacting systems, which is the crossover from independent relaxation to coupled many-body relaxation at some tc determined by the interaction potential and intermolecular coupling/constraints. The generality is brought out vividly by pointing out that the crossover also had been observed by neutron scattering from entangled chains relaxation in monodisperse homopolymers, and from the segmental α-relaxation of PEO in blends with PMMA. The properties of all the relaxation processes in connection with the crossover are similar, despite the length scales of the relaxation in these systems are widely different.

Photoactuation behavior of styrene-b-isoprene-b-styrene filled with covalently modified carbon nanotubes

NASA Astrophysics Data System (ADS)

Mosnáček, Jaroslav; Ilčíková, Markéta; Chorvát, Dušan; Czaniková, Klaudia; Krupa, Igor

2012-07-01

Styrene-b-isoprene-b-styrene (Kraton) was used as polymer matrix for preparation of multiwall carbon nanotubes (MWCNT) based nanocomposites. In order to suppress aggregation of the he carbon nanotubes and to improve the interations with the Kraton matrix, the MWCNT were modified with cholesteryl molecules and/or polystyrene chains. The effect of the modification on the composite materials was evaluated by using DMTA. The nanocomposite materials were thermoformed to achieve Braille text elements and their elastic response to light (photoactuation) was tested by atomic force microscopy in a contact mode.

Production of super-smooth articles

DOEpatents

Duchane, David V.

1983-01-01

Super-smooth rounded or formed articles made of thermoplastic materials including various poly(methyl methacrylate) or acrylonitrile-butadiene-styrene copolymers are produced by immersing the articles into a bath, the composition of which is slowly changed with time. The starting composition of the bath is made up of at least one solvent for the polymer and a diluent made up of at least one nonsolvent for the polymer and optional materials which are soluble in the bath. The resulting extremely smooth articles are useful as mandrels for laser fusion and should be useful for a wide variety of other purposes, for example lenses.

A multicenter study on the audiometric findings of styrene-exposed workers.

PubMed

Morata, Thais C; Sliwinska-Kowalska, Mariola; Johnson, Ann-Christin; Starck, Jukka; Pawlas, Krystyna; Zamyslowska-Szmytke, Ewa; Nylen, Per; Toppila, Esko; Krieg, Edward; Pawlas, Natalia; Prasher, Deepak

2011-10-01

The objective of this study was to evaluate hearing loss among workers exposed to styrene, alone or with noise. This cross-sectional study was conducted as part of NoiseChem, a European Commission 5th Framework Programme research project, by occupational health institutes in Finland, Sweden, and Poland. Participants' ages ranged from 18-72 years (n = 1620 workers). Participants exposed to styrene, alone or with noise, were from reinforced fiberglass products manufacturing plants (n = 862). Comparison groups were comprised of workers noise-exposed (n = 400) or controls (n = 358). Current styrene exposures ranged from 0 to 309 mg/m(3), while mean current noise levels ranged from 70-84 dB(A). Hearing thresholds of styrene-exposed participants were compared with Annexes A and B from ANSI S3.44, 1996. The audiometric thresholds of styrene exposed workers were significantly poorer than those in published standards. Age, gender, and styrene exposure met the significance level criterion in the multiple logistic regression for the binary outcome 'hearing loss' (P = 0.0000). Exposure to noise (<85 dBA p = 0.0001; ≥85 dB(A) p = 0.0192) interacted significantly with styrene exposure. Occupational exposure to styrene is a risk factor for hearing loss, and styrene-exposed workers should be included in hearing loss prevention programs.

Composite Polylactic-Methacrylic Acid Copolymer Nanoparticles for the Delivery of Methotrexate

PubMed Central

Sibeko, Bongani; Choonara, Yahya E.; du Toit, Lisa C.; Modi, Girish; Naidoo, Dinesh; Khan, Riaz A.; Kumar, Pradeep; Ndesendo, Valence M. K.; Iyuke, Sunny E.; Pillay, Viness

2012-01-01

The purpose of this study was to develop poly(lactic acid)-methacrylic acid copolymeric nanoparticles with the potential to serve as nanocarrier systems for methotrexate (MTX) used in the chemotherapy of primary central nervous system lymphoma (PCNSL). Nanoparticles were prepared by a double emulsion solvent evaporation technique employing a 3-Factor Box-Behnken experimental design strategy. Analysis of particle size, absolute zeta potential, polydispersity (Pdl), morphology, drug-loading capacity (DLC), structural transitions through FTIR spectroscopy, and drug release kinetics was undertaken. Molecular modelling elucidated the mechanisms of the experimental findings. Nanoparticles with particle sizes ranging from 211.0 to 378.3 nm and a recovery range of 36.8–86.2 mg (Pdl ≤ 0.5) were synthesized. DLC values were initially low (12 ± 0.5%) but were finally optimized to 98 ± 0.3%. FTIR studies elucidated the comixing of MTX within the nanoparticles. An initial burst release (50% of MTX released in 24 hours) was obtained which was followed by a prolonged release phase of MTX over 84 hours. SEM images revealed near-spherical nanoparticles, while TEM micrographs revealed the presence of MTX within the nanoparticles. Stable nanoparticles were formed as corroborated by the chemometric modelling studies undertaken. PMID:22919501

Multidetector thermal field-flow fractionation as a unique tool for the tacticity-based separation of poly(methyl methacrylate)-polystyrene block copolymer micelles.

PubMed

Greyling, Guilaume; Pasch, Harald

2015-10-02

Poly(methyl methacrylate)-polystyrene (PMMA-PS) micelles with isotactic and syndiotactic coronas are prepared in acetonitrile and subjected to thermal field-flow fractionation (ThFFF) analysis at various conditions of increasing temperature gradients. It is shown for the first time that multidetector ThFFF provides comprehensive information on important micelle characteristics such as size (Dh), shape (Rg/Rh), aggregation number (Z), thermal diffusion (DT) and Soret coefficients (ST) as a function of temperature from a single injection. Moreover, it is found that micelles exhibit a unique decreasing trend in DT as a function of temperature which is independent of the tacticity of the corona and the micelle preparation method used. It is also demonstrated that ThFFF can monitor micelle to vesicle transitions as a function of temperature. In addition to ThFFF, it is found from DLS analysis that the tacticity of the corona influences the critical micelle concentration and the magnitude to which micelles expand/contract with temperature. The tacticity does not, however, influence the critical micelle temperature. Furthermore, the separation of micelles based on the tacticity of the corona highlight the unique capabilities of ThFFF. Copyright © 2015 Elsevier B.V. All rights reserved.

Heat resistant polymers of oxidized styrylphosphine

NASA Technical Reports Server (NTRS)

Paciorek, K. J. L. (Inventor)

1978-01-01

Homopolymers, copolymers and terpolymers of a styrene based monomer are prepared by polymerizing at least one oxidized styrylphosphine monomer or by polymerizing p-diphenylphosphinestyrene and then oxidizing the polymerized monomer with an organoazide. Copolymers can also be prepared by copolymerizing styrene with at least one oxidized styrylphosphine monomer. Flame resistant vinyl based polymers whose degradation products are non toxic and non corrosive are obtained.

Bacterial degradation of styrene in waste gases using a peat filter.

PubMed

Arnold, M; Reittu, A; von Wright, A; Martikainen, P J; Suihko, M L

1997-12-01

A biofiltration process was developed for styrene-containing off-gases using peat as filter material. The average styrene reduction ratio after 190 days of operation was 70% (max. 98%) and the mean styrene elimination capacity was 12 g m-3 h-1 (max. 30 g m-3 h-1). Efficient styrene degradation required addition of nutrients to the peat, adjustment of the pH to a neutral level and efficient control of the humidity. Maintenance of the water balance was easier in a down-flow than in an up-flow process, the former consequently resulting in much better filtration efficiency. The optimum operation temperature was around 23 degrees C, but the styrene removal was still satisfactory at 12 degrees C. Seven different bacterial isolates belonging to the genera Tsukamurella, Pseudomonas, Sphingomonas, Xanthomonas and an unidentified genus in the gamma group of the Proteobacteria isolated from the microflora of active peat filter material were capable of styrene degradation. The isolates differed in their capacity to decompose styrene to carbon dioxide and assimilate it to biomass. No toxic intermediate degradation products of styrene were detected in the filter outlet gas or in growing cultures of isolated bacteria. The use of these isolates in industrial biofilters is beneficial at low styrene concentrations and is safe from both the environmental and public health points of view.

The Iodochlorination of Styrene: An Experiment that Makes a Difference

ERIC Educational Resources Information Center

Amiet, R. Gary; Urban, Sylvia

2008-01-01

The iodochlorination of styrene, involving the addition of iodine monochloride to styrene, followed by the sodium methoxide-initiated dehydrohalogenation of the product results in a variable mixture of substituted styrenes by way of various substitution and elimination reaction mechanisms. As a result individual results are obtained for each…

Using graphene/styrene-isoprene-styrene copolymer composite thin film as a flexible microstrip antenna for the detection of heptane vapors

NASA Astrophysics Data System (ADS)

Olejnik, Robert; Matyas, Jiri; Slobodian, Petr; Riha, Pavel

2018-03-01

Most portable devices, such as mobile phones or tablets, use antennas made of copper. This paper demonstrates the possible use of antenna constructed from electrically conductive polymer composite materials for use in those applications. The method of preparation and the properties of the graphene/styrene-isoprene-styrene copolymer as flexible microstrip antenna are described in this contribution. Graphene/styrene-isoprene-styrene copolymer toluene solution was prepared by means of ultrasound and the PET substrate was dip coated to reach a fine thin film. The main advantages of using PET as a substrate are low weight and flexibility. The final size of the flexible microstrip antenna was 10 × 25 mm with thickness of 0.48 mm (PET substrate 0.25 mm) with a weight of 0.110 g. The resulting antenna operates at a frequency of 1.8 GHz and gain ‑40.02 dB.

The profile of adsorbed plasma and serum proteins on methacrylic acid copolymer beads: Effect on complement activation.

PubMed

Wells, Laura A; Guo, Hongbo; Emili, Andrew; Sefton, Michael V

2017-02-01

Polymer beads made of 45% methacrylic acid co methyl methacrylate (MAA beads) promote vascular regenerative responses in contrast to control materials without methacrylic acid (here polymethyl methacrylate beads, PMMA). In vitro and in vivo studies suggest that MAA copolymers induce differences in macrophage phenotype and polarization and inflammatory responses, presumably due to protein adsorption differences between the beads. To explore differences in protein adsorption in an unbiased manner, we used high resolution shotgun mass spectrometry to identify and compare proteins that adsorb from human plasma or serum onto MAA and PMMA beads. From plasma, MAA beads adsorbed many complement proteins, such as C1q, C4-related proteins and the complement inhibitor factor H, while PMMA adsorbed proteins, such as albumin, C3 and apolipoproteins. Because of the differences in complement protein adsorption, follow-up studies focused on using ELISA to assess complement activation. When incubated in serum, MAA beads generated significantly lower levels of soluble C5b9 and C3a/C3a desarg in comparison to PMMA beads, indicating a decrease in complement activation with MAA beads. The differences in adsorbed protein on the two materials likely alter subsequent cell-material interactions that ultimately result in different host responses and local vascularization. Copyright © 2016 Elsevier Ltd. All rights reserved.

Production of biorenewable styrene: utilization of biomass-derived sugars and insights into toxicity.

PubMed

Lian, Jieni; McKenna, Rebekah; Rover, Marjorie R; Nielsen, David R; Wen, Zhiyou; Jarboe, Laura R

2016-05-01

Fermentative production of styrene from glucose has been previously demonstrated in Escherichia coli. Here, we demonstrate the production of styrene from the sugars derived from lignocellulosic biomass depolymerized by fast pyrolysis. A previously engineered styrene-producing strain was further engineered for utilization of the anhydrosugar levoglucosan via expression of levoglucosan kinase. The resulting strain produced 240 ± 3 mg L(-1) styrene from pure levoglucosan, similar to the 251 ± 3 mg L(-1) produced from glucose. When provided at a concentration of 5 g L(-1), pyrolytic sugars supported styrene production at titers similar to those from pure sugars, demonstrating the feasibility of producing this important industrial chemical from biomass-derived sugars. However, the toxicity of contaminant compounds in the biomass-derived sugars and styrene itself limit further gains in production. Styrene toxicity is generally believed to be due to membrane damage. Contrary to this prevailing wisdom, our quantitative assessment during challenge with up to 200 mg L(-1) of exogenously provided styrene showed little change in membrane integrity; membrane disruption was observed only during styrene production. Membrane fluidity was also quantified during styrene production, but no changes were observed relative to the non-producing control strain. This observation that styrene production is much more damaging to the membrane integrity than challenge with exogenously supplied styrene provides insight into the mechanism of styrene toxicity and emphasizes the importance of verifying proposed toxicity mechanisms during production instead of relying upon results obtained during exogenous challenge.

Contact allergy to epoxy (meth)acrylates.

PubMed

Aalto-Korte, Kristiina; Jungewelter, Soile; Henriks-Eckerman, Maj-Len; Kuuliala, Outi; Jolanki, Riitta

2009-07-01

Contact allergy to epoxy (meth)acrylates, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy) phenyl]propane (bis-GMA), 2,2-bis[4-(2-hydroxy-3-acryloxypropoxy)phenyl]-propane (bis-GA), 2,2-bis[4-(methacryl-oxyethoxy)phenyl] propane (bis-EMA), 2,2-bis[4-(methacryloxy)phenyl]-propane (bis-MA), and glycidyl methacrylate (GMA) is often manifested together with contact allergy to diglycidyl ether of bisphenol A (DGEBA) epoxy resin. To analyse patterns of concomitant allergic reactions to the five epoxy (meth)acrylates in relation to exposure. We reviewed the 1994-2008 patch test files at the Finnish Institute of Occupational Health (FIOH) for reactions to the five epoxy (meth)acrylates, and examined the patients' medical records for exposure. Twenty-four patients had an allergic reaction to at least one of the studied epoxy (meth)acrylates, but specific exposure was found only in five patients: two bis-GMA allergies from dental products, two bis-GA allergies from UV-curable printing inks, and one bis-GA allergy from an anaerobic glue. Only 25% of the patients were negative to DGEBA epoxy resin. The great majority of allergic patch test reactions to bis-GMA, bis-GA, GMA and bis-EMA were not associated with specific exposure, and cross-allergy to DGEBA epoxy resin remained a probable explanation. However, independent reactions to bis-GA indicated specific exposure. Anaerobic sealants may induce sensitization not only to aliphatic (meth)acrylates but also to aromatic bis-GA.

Alternating copolymerization of fluoroalkenes with carbon monoxide.

PubMed

Fujita, Tomoyuki; Nakano, Koji; Yamashita, Makoto; Nozaki, Kyoko

2006-02-15

The palladium-catalyzed alternating copolymerization of fluoroalkenes, represented as CH(2)=CH-CH(2)-C(n)F(2n+1), with CO was performed using (R,S)-BINAPHOS (2e) as a ligand. The CH(2)-C(n)F(2n+1) group is the most electronegative substituent ever reported for the copolymerization (Taft's sigma value of 0.90 for CH(2)CF(3)). The copolymer obtained from CH(2)=CH-CH(2)-C(8)F(17) (1a) existed as a mixture of polyspiroketal and polyketone, while that from CH(2)=CH-CH(2)-C(4)F(9) (1b) was a pure polyspiroketal, as was revealed by infrared and (13)C-CP/MAS NMR spectroscopies. The terminal structure of the polymer from 1b was confirmed by MALDI-TOF MS spectrometry. Detailed NMR studies suggested that the much higher reactivity with (R,S)-BINAPHOS (2e) than that with the conventional ligand DPPP (2a) can be attributed to the unique 1,2-insertion of the fluoroalkene into acylpalladium species. The existence of an electronegative substituent on the alpha-carbon of the palladium center is successfully avoided in the 1,2-insertion mechanism.

Insertion of a pentacene layer into the gold/poly(methyl methacrylate)/heavily doped p-type Si/indium device leading to the modulation of resistive switching characteristics

NASA Astrophysics Data System (ADS)

Hung, Cheng-Chun; Lin, Yow-Jon

2018-01-01

In order to get a physical insight into the pentacene interlayer-modulated resistive switching (RS) characteristics, the Au/pentacene/poly(methyl methacrylate) (PMMA)/heavily doped p-type Si (p+-Si)/In and Au/PMMA/p+-Si/In devices are fabricated and the device performance is provided. The Au/pentacene/PMMA/p+-Si/In device shows RS behavior, whereas the Au/PMMA/p+-Si/In device exhibits the set/reset-free hysteresis current-voltage characteristics. The insertion of a pentacene layer is a noticeable contribution to the RS characteristic. This is because of the occurrence of carrier accumulation/depletion in the pentacene interlayer. The transition from carrier depletion to carrier accumulation (carrier accumulation to carrier depletion) in pentacene occurring under negative (positive) voltage induces the process of set (reset). The switching conduction mechanism is primarily described as space charge limited conduction according to the electrical transport properties measurement. The concept of a pentacene/PMMA heterostructure opens a promising direction for organic memory devices.

Improved surface hydrophilicity and antifouling property of polysulfone ultrafiltration membrane with poly(ethylene glycol) methyl ether methacrylate grafted graphene oxide nanofillers

NASA Astrophysics Data System (ADS)

Wang, Haidong; Lu, Xiaofei; Lu, Xinglin; Wang, Zhenghui; Ma, Jun; Wang, Panpan

2017-12-01

In this study, the GO-g-P(PEGMA) nanoplates were first synthesized by grafting hydrophilic poly (poly (ethylene glycol) methyl ether methacrylate) via surface-initiated atom transfer radical polymerization (SI-ATRP) method. A novel polysulfone (PSF) nanocomposite membrane using GO-g-P(PEGMA) nanoplates as nanofillers was fabricated. FTIR, TGA, 1H NMR, GPC and TEM were applied to verify the successful synthesis of the prepared nanoplates, while SEM, AFM, XPS, contact angle goniometry and filtration experiments were used to characterize the fabricated nanocomposite membranes. It was found that the new prepared nanofillers were well dispersed in organic PSF matrix, and the PSF/GO-g-P(PEGMA) nanocomposite membrane showed significant improvements in water flux and flux recovery rate. Based on the results of resistance-in-series model, the nanocomposite membrane exhibited superior resistance to the irreversible fouling. The excellent filtration and antifouling performance are attributed to the segregation of GO-g-P(PEMGA) nanofillers toward the membrane surface and the pore walls. Notably, the blended nanofillers appeared a stable retention in/on nanocomposite membrane after 30 days of washing time. The demonstrated method of synthesis GO-g-P(PEGMA) in this study can also be extended to preparation of other nanocomposite membrane in future.

Investigation of triacetin effect on indomethacin release from poly(methyl methacrylate) microspheres: evaluation of interactions using FT-IR and NMR spectroscopies.

PubMed

Yuksel, Nilufer; Baykara, Meltem; Shirinzade, Hanif; Suzen, Sibel

2011-02-14

The purpose of this study was to form indomethacin (IND)-loaded poly(methyl methacrylate) (PMMA) microspheres having an extended drug release profile over a period of 24h. Microspheres were prepared by solvent evaporation method using sucrose stearate as a droplet stabilizer. When PMMA was used alone for the preparation of microspheres, only 44% of IND could be released at the end of 8h. Triacetin was added to PMMA, as a minor phase, and the obtained microspheres showed a high yield process with recovery of 89.82% and incorporation efficiency of 102.3%. A desired release profile lasting 24h was achieved. Differential scanning calorimetry (DSC) analysis showed that IND was found to be in an amorphous state in the microspheres. Fourier transform infrared (FT-IR) and nuclear magnetic resonance ((1)H NMR) spectra suggested that there might be a hydrogen bond present between the IND hydroxyl group and PMMA. No interaction between triacetin and IND or PMMA as the formation of secondary bonds was observed. The release enhancement of IND from microspheres was attributed to the physical plasticization effect of triacetin on PMMA and, to some extent, the amorphous state of the drug. Copyright © 2010 Elsevier B.V. All rights reserved.

Custom CAD-CAM healing abutment and impression coping milled from a poly(methyl methacrylate) block and bonded to a titanium insert.

PubMed

Proussaefs, Periklis

2016-11-01

This article describes a technique in which a custom-made computer-aided design and computer-aided manufacturing (CAD-CAM) healing abutment milled from a poly(methyl methacrylate) (PMMA) block is fabricated and bonded to a titanium metal insert. An impression is made during dental implant surgery, and the CAD-CAM custom-made healing abutment is fabricated before second-stage surgery while appropriate healing time is allowed for the dental implant to osseointegrate. The contours of the healing abutment are based on the contours of a tentatively designed definitive prosthesis. The healing tissue obtains contours that will be compatible with the contours of the definitive prosthesis. After the milling process is complete, a titanium metal insert is bonded to the healing abutment. Placement of the custom-made CAD-CAM healing abutment at second-stage surgery allows the tissue to obtain contours similar to those of the definitive prosthesis. A custom-made CAD-CAM impression coping milled from a PMMA block and with a titanium insert is used for the definitive impression after the soft tissue has healed. This technique allows guided soft tissue healing by using a custom-made CAD-CAM healing abutment and impression coping. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Determination of thermodynamic properties of poly (cyclohexyl methacrylate) by inverse gas chromatography.

PubMed

Kaya, Ismet; Pala, Cigdem Yigit

2014-07-01

In this work, some thermodynamic properties of poly (cyclohexyl methacrylate) were studied by inverse gas chromatography (IGC). For this purpose, the polymeric substance was coated on Chromosorb W and which was filled into a glass column. The retention times (t(r)) of the probes were determined from the interactions of poly (cyclohexyl methacrylate) with n-pentane, n-hexane, n-heptane, n-octane, n-decane, methanol, ethanol, 2-propanol, butanol, acetone, ethyl methyl ketone, benzene, toluene and o-xylene by IGC technique. Then, the specific volume (Vg(0)) was determined for each probe molecule. By using (1/T; lnVg(0)) graphics, the glass transition temperature of poly (cyclohexyl methacrylate) was found to be 373 K. The adsorption heat under the glass transition temperature (deltaH(a)), and partial molar heat of sorption above the glass transition (deltaH1(S)), partial molar free energy of sorption (deltaG1(S)) and partial molar entropy of sorption (deltaS1(S)) belonging to sorption for every probe were calculated. The partial molar heat of mixing at infinite dilution (deltaH1(infinity)), partial molar free energy of mixing at infinite dilution (deltaG1(infinity)), Flory-Huggins interaction parameter (chi12(infinity)) and weight fraction activity coefficient (a1/w1)(infinity) values of polymer-solute systems were calculated at different column temperatures. The solubility parameters (delta2) of the polymer were obtained by IGC technique.

Accelerated cell sheet detachment by copolymerizing hydrophilic PEG side chains into PNIPAm nanocomposite hydrogels.

PubMed

Liu, Dan; Wang, Tao; Liu, Xinxing; Tong, Zhen

2012-10-01

One-end-connected short poly(ethylene glycol) (PEG) side chains were facilely introduced into the poly(N-isopropylacrylamide) (PNIPAm) nanocomposite hydrogel (NC gel) via in situ copolymerization of NIPAm monomer and PEG macromonomer in the aqueous suspension of hectorite clay Laponite XLS. The NC gels were characterized with Fourier transform infrared and x-ray photoelectron spectroscopy for the composition, DSC and transmittance for the phase separation temperature, dynamic mechanical spectra and swelling ratio for the interaction. Increasing the PEG content led to a small increase in the storage modulus and the lower critical solution temperature (LCST) of the copolymerized NC gels, and the LCST of the copolymerized NC gels was still below 37 °C. The L929 cell adhesion and proliferation on the surface of these NC gels were not suppressed by the incorporation of hydrophilic PEG side chains. By lowering temperature below the LCST, the cell sheet spontaneously detached from the copolymerized NC gels. The surface morphology and surface wettability of the NC gels were detected by atom force microscope and contact angle measurement. A rough and hydrophilic surface induced by a small amount of PEG side chains was found to be favorable to accelerate the cell sheet detachment, probably due to the enhanced water permeation into the gel-cell sheet interface.

Copper-catalyzed radical carbooxygenation: alkylation and alkoxylation of styrenes.

PubMed

Liao, Zhixiong; Yi, Hong; Li, Zheng; Fan, Chao; Zhang, Xu; Liu, Jie; Deng, Zixin; Lei, Aiwen

2015-01-01

A simple copper-catalyzed direct radical carbooxygenation of styrenes is developed utilizing alkyl bromides as radical resources. This catalytic radical difunctionalization accomplishes both alkylation and alkoxylation of styrenes in one pot. A broad range of styrenes and alcohols are well tolerated in this transformation. The EPR experiment shows that alkyl halides could oxidize Cu(I) to Cu(II) in this transformation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Original research paper. Characterization and taste masking evaluation of microparticles with cetirizine dihydrochloride and methacrylate-based copolymer obtained by spray drying.

PubMed

Amelian, Aleksandra; Szekalska, Marta; Ciosek, Patrycja; Basa, Anna; Winnicka, Katarzyna

2017-03-01

Taste of a pharmaceutical formulation is an important parameter for the effectiveness of pharmacotherapy. Cetirizine dihydrochloride (CET) is a second-generation antihistamine that is commonly administered in allergy treatment. CET is characterized by extremely bitter taste and it is a great challenge to successfully mask its taste; therefore the goal of this work was to formulate and characterize the microparticles obtained by the spray drying method with CET and poly(butyl methacrylate-co-(2-dimethylaminoethyl) methacrylate-co-methyl methacrylate 1:2:1 copolymer (Eudragit E PO) as a barrier coating. Assessment of taste masking by the electronic tongue has revealed that designed formulations created an effective taste masking barrier. Taste masking effect was also confirmed by the in vivo model and the in vitro release profile of CET. Obtained data have shown that microparticles with a drug/polymer ratio (0.5:1) are promising CET carriers with efficient taste masking potential and might be further used in designing orodispersible dosage forms with CET.

Phosphonic acid based ion exchange resins

DOEpatents

Horwitz, E.P.; Alexandratos, S.D.; Gatrone, R.C.; Chiarizia, R.

1996-07-23

An ion exchange resin is described for extracting metal ions from a liquid waste stream. An ion exchange resin is prepared by copolymerizing a vinylidene diphosphonic acid with styrene, acrylonitrile and divinylbenzene. 10 figs.

Phosphonic acid based ion exchange resins

DOEpatents

Horwitz, E.P.; Alexandratos, S.D.; Gatrone, R.C.; Chiarizia, R.

1994-01-25

An ion exchange resin is described for extracting metal ions from a liquid waste stream. An ion exchange resin is prepared by copolymerizing a vinylidene diphosphonic acid with styrene, acrylonitrile and divinylbenzene. 9 figures.

Phosphonic acid based exchange resins

DOEpatents

Horwitz, E.P.; Alexandratos, S.D.; Gatrone, R.C.; Chiarizia, R.

1995-09-12

An ion exchange resin is described for extracting metal ions from a liquid waste stream. An ion exchange resin is prepared by copolymerizing a vinylidene diphosphonic acid with styrene, acrylonitrile and divinylbenzene. 10 figs.

Self-Assembly of Magnetic Nanoparticles at the Surface and Within Block Copolymer Films

NASA Astrophysics Data System (ADS)

Xu, Chen; Ohno, Kohji; Composto, Russell

2007-03-01

We investigate the self-assembly of magnetic Fe3O4 nanoparticles in thin films of a symmetric block copolymer of poly(styrene-b-methyl methacrylate), PS-b-PMMA (75 kg/mol). The Fe3O4 nanoparticles (4nm) are grafted by poly(methyl methacrylate) (PMMA) (2.7 kg/mol) brushes to improve their compatibility. The weight percent of Fe3O4 in PS-b-PMMA is 1, 4 and 10. The Fe3O4 reside at the intermaterial dividing surface and also form small disk-like aggregates within the PMMA phase. The addition of Fe3O4 slows down the transition from perpendicular to parallel lamellae morphology at the surface and slowing down increases as weight percent Fe3O4 increases. Using cross-sectional TEM, nanoparticles are found to be rejected from the parallel lamellae and gather preferentially within the perpendicular lamellae. These studies demonstrate that the Fe3O4 particles influence thin film morphology and visa versa. Because of widespread interest in nanodevices, this study shows that arrays of functional nanoparticles can be formed using block copolymer templates.

Poly(2-(diethylamino)ethyl methacrylate)-based, pH-responsive, copolymeric mixed micelles for targeting anticancer drug control release.

PubMed

Chen, Quan; Li, Siheng; Feng, Zixiong; Wang, Meng; Cai, Chengzhi; Wang, Jufang; Zhang, Lijuan

2017-01-01

We have demonstrated a novel drug delivery system to improve the selectivity of the current chemotherapy by pH-responsive, polymeric micelle carriers. The micelle carriers were prepared by the self-assembly of copolymers containing the polybasic poly(2-(diethylamino) ethyl methacrylate) (PDEAEMA) block. The mixed copolymers exhibited a comparatively low critical micelle concentration (CMC; 1.95-5.25 mg/L). The resultant mixed micelles were found to be <100 nm and were used to encapsulate the anticancer drug doxorubicin (DOX) with pretty good drug-loading content (24%) and entrapment efficiency (55%). Most importantly, the micelle carrier exhibited a pH-dependent conformational conversion and promoted the DOX release at the tumorous pH. Our in vitro studies demonstrated the comparable level of DOX-loaded mixed micelle delivery into tumor cells with the free DOX (80% of the tumor cells were killed after 48 h incubation). The DOX-loaded mixed micelles were effective to inhibit the proliferation of tumor cells after prolonged incubation. Overall, the pH-responsive mixed micelle system provided desirable potential in the controlled release of anticancer therapeutics.

CASE-COHORT STUDY OF STYRENE EXPOSURE AND ISCHEMIC HEART DISEASE INVESTIGATORS

EPA Science Inventory

Investigators examined workers exposed to styrene while working in styrene-butadiene polymer manufacturing plants between 1943 and 1982. Workers who had died from ischemic heart disease were compared to a subgroup of all men employed in two styrene-butadiene polymer manufac...

Development of form stable Poly(methyl methacrylate) (PMMA) coated thermal phase change material for solar water heater applications

NASA Astrophysics Data System (ADS)

Munusamy, Y.; Shanmugam, S.; Shi-Ying, Kee

2018-04-01

Phase change material (PCM) is one of the most popular and widely used thermal energy storage material in solar water heater because it able to absorb and release a large amount of latent heat during a phase change process over a narrow temperature range. However the practical application of PCM is limited by two major issues; 1) leakage which leads to material loss and corrosion of tank and 2) large volume change during phase change process which cause pressure build up in the tank. In this work, form-stable PCM was prepared by coating myristic acid with Poly(methyl methacrylate) (PMMA) to prevent leakage of PCM. PMMA was mixed with different weight percentage (0.1, 0.2, 0.3, 0.4 and 0.5 wt%) of dicumyl peroxide (DCP). The purpose of adding DCP to PMMA is to crosslink the polymer and to increase the mechanical strength of PMMA to hold the myristic acid content inside the coating during the phase change process. Leakage test results showed that PMMA mixed with 0.1% DCP exhibit 0% leakage. This result is further supported by Field Emission Scanning Electron Microscopy (FESEM) images and Fourier transform infrared spectroscopy (FTIR) analysis results, where a compact and uniform coating without cracks were formed for PCM coated with PMMA with 0.1% DCP. Differential scanning calorimetry (DSC) results shows that the melting point of form-stable PCM is 55°C, freezing point is 50°C, the latent heat of melting and freezing is 67.59 J/g.

Nanotopographic Substrates of Poly (Methyl Methacrylate) Do Not Strongly Influence the Osteogenic Phenotype of Mesenchymal Stem Cells In Vitro

PubMed Central

Janson, Isaac A.; Kong, Yen P.; Putnam, Andrew J.

2014-01-01

The chemical, mechanical, and topographical features of the extracellular matrix (ECM) have all been documented to influence cell adhesion, gene expression, migration, proliferation, and differentiation. Topography plays a key role in the architecture and functionality of various tissues in vivo, thus raising the possibility that topographic cues can be instructive when incorporated into biomaterials for regenerative applications. In the literature, there are discrepancies regarding the potential roles of nanotopography to enhance the osteogenic phenotype of mesenchymal stem cells (MSC). In this study, we used thin film substrates of poly(methyl methacrylate) (PMMA) with nanoscale gratings to investigate the influence of nanotopography on the osteogenic phenotype of MSCs, focusing in particular on their ability to produce mineral similar to native bone. Topography influenced focal adhesion size and MSC alignment, and enhanced MSC proliferation after 14 days of culture. However, the osteogenic phenotype was minimally influenced by surface topography. Specifically, alkaline phosphatase (ALP) expression was not increased on nanotopographic films, nor was calcium deposition improved after 21 days in culture. Ca: P ratios were similar to native mouse bone on films with gratings of 415 nm width and 200 nm depth (G415) and 303 nm width and 190 nm depth (G303). Notably, all surfaces had Ca∶P ratios significantly lower than G415 films. Collectively, these data suggest that, PMMA films with nanogratings are poor drivers of an osteogenic phenotype. PMID:24594848

Diffusion-regulated phase-transfer catalysis for atom transfer radical polymerization of methyl methacrylate in an aqueous/organic biphasic system.

PubMed

Ding, Mingqiang; Jiang, Xiaowu; Peng, Jinying; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2015-03-01

A concept based on diffusion-regulated phase-transfer catalysis (DRPTC) in an aqueous-organic biphasic system with copper-mediated initiators for continuous activator regeneration is successfully developed for atom transfer radical polymerization (ICAR ATRP) (termed DRPTC-based ICAR ATRP here), using methyl methacrylate (MMA) as a model monomer, ethyl α-bromophenylacetate (EBrPA) as an initiator, and tris(2-pyridylmethyl)amine (TPMA) as a ligand. In this system, the monomer and initiating species in toluene (organic phase) and the catalyst complexes in water (aqueous phase) are simply mixed under stirring at room temperature. The trace catalyst complexes transfer into the organic phase via diffusion to trigger ICAR ATRP of MMA with ppm level catalyst content once the system is heated to the polymerization temperature (75 °C). It is found that well-defined PMMA with controlled molecular weights and narrow molecular weight distributions can be obtained easily. Furthermore, the polymerization can be conducted in the presence of limited amounts of air without using tedious degassed procedures. After cooling to room temperature, the upper organic phase is decanted and the lower aqueous phase is reused for another 10 recycling turnovers with ultra low loss of catalyst and ligand loading. At the same time, all the recycled catalyst complexes retain nearly perfect catalytic activity and controllability, indicating a facile and economical strategy for catalyst removal and recycling. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intratumoral gene therapy versus intravenous gene therapy for distant metastasis control with 2-diethylaminoethyl-dextran methyl methacrylate copolymer non-viral vector-p53.

PubMed

Baliaka, A; Zarogoulidis, P; Domvri, K; Hohenforst-Schmidt, W; Sakkas, A; Huang, H; Le Pivert, P; Koliakos, G; Koliakou, E; Kouzi-Koliakos, K; Tsakiridis, K; Chioti, A; Siotou, E; Cheva, A; Zarogoulidis, K; Sakkas, L

2014-02-01

Lung cancer still remains to be challenged by novel treatment modalities. Novel locally targeted routes of administration are a methodology to enhance treatment and reduce side effects. Intratumoral gene therapy is a method for local treatment and could be used either in early-stage lung cancer before surgery or at advanced stages as palliative care. Novel non-viral vectors are also in demand for efficient gene transfection to target local cancer tissue and at the same time protect the normal tissue. In the current study, C57BL/6 mice were divided into three groups: (a) control, (b) intravenous and (c) intatumoral gene therapy. The novel 2-Diethylaminoethyl-Dextran Methyl Methacrylate Copolymer Non-Viral Vector (Ryujyu Science Corporation) was conjugated with plasmid pSicop53 from the company Addgene for the first time. The aim of the study was to evaluate the safety and efficacy of targeted gene therapy in a Lewis lung cancer model. Indeed, although the pharmacokinetics of the different administration modalities differs, the intratumoral administration presented increased survival and decreased distant metastasis. Intratumoral gene therapy could be considered as an efficient local therapy for lung cancer.

Engineering Styrene Monooxygenase for Biocatalysis: Reductase-Epoxidase Fusion Proteins.

PubMed

Heine, Thomas; Tucker, Kathryn; Okonkwo, Nonye; Assefa, Berhanegebriel; Conrad, Catleen; Scholtissek, Anika; Schlömann, Michael; Gassner, George; Tischler, Dirk

2017-04-01

The enantioselective epoxidation of styrene and related compounds by two-component styrene monooxygenases (SMOs) has targeted these enzymes for development as biocatalysts. In the present work, we prepare genetically engineered fusion proteins that join the C-terminus of the epoxidase (StyA) to the N-terminus of the reductase (StyB) through a linker peptide and demonstrate their utility as biocatalysts in the synthesis of Tyrain purple and other indigoid dyes. A single-vector expression system offers a simplified platform for transformation and expansion of the catalytic function of styrene monooxygenases, and the resulting fusion proteins are self-regulated and couple efficiently NADH oxidation to styrene epoxidation. We find that the reductase domain proceeds through a sequential ternary-complex mechanism at low FAD concentration and a double-displacement mechanism at higher concentrations of FAD. Single-turnover studies indicate an observed rate constant for FAD-to-FAD hydride transfer of ~8 s -1 . This step is rate limiting in the styrene epoxidation reaction and helps to ensure that flavin reduction and styrene epoxidation reactions proceed without wasteful side reactions. Comparison of the reductase activity of the fusion proteins with the naturally occurring reductase, SMOB, and N-terminally histidine-tagged reductase, NSMOB, suggests that the observed changes in catalytic mechanism are due in part to an increase in flavin-binding affinity associated with the N-terminal extension of the reductase.

Sustainable Triblock Copolymers for Application as Thermoplastic Elastomers

NASA Astrophysics Data System (ADS)

Ding, Wenyue; Wang, Shu; Ganewatta, Mitra; Tang, Chuanbing; Robertson, Megan

Thermoplastic elastomers (TPEs), combining the processing advantages of thermoplastics with the flexibility and extensibility of elastomeric materials, have found versatile applications in industry, including electronics, clothing, adhesives, and automotive components. ABA triblock copolymers, in which A represents glassy endblocks and B the rubbery midblock, are commercially available as TPEs, such as poly(styrene-b-butadiene-b-styrene) (SBS) or poly(styrene-b-isoprene-b-styrene) (SIS). However, the commercial TPEs are derived from fossil fuels. The finite availability of fossil fuels and the environmental impact of the petroleum manufacturing have led to the increased interest in the development of alternative polymeric materials from sustainable sources. Rosin acids are promising replacement for the petroleum source due to their abundance in conifers, rigid molecular structures, and ease of functionalization. In this study, we explored the utilization of a rosin acid derivative, poly(dehydroabietic ethyl methacrylate) (PDAEMA), as a sustainable alternative for the glassy domain. The triblock copolymer poly(dehydroabietic ethyl methacrylate-b-n-butyl acylate-b-dehydroabietic ethyl methacrylate) (DnBD) was synthesized and characterized. DnBD exhibited tunable morphological and thermal properties. Tensile testing revealed elastomeric behavior.

One-pot preparation of a sulfamethoxazole functionalized affinity monolithic column for selective isolation and purification of trypsin.

PubMed

Xiao, Yuan; Guo, Jialiang; Ran, Danni; Duan, Qianqian; Crommen, Jacques; Jiang, Zhengjin

2015-06-26

A facile and efficient "one-pot" copolymerization strategy was used for the preparation of sulfonamide drug (SA) functionalized monolithic columns. Two novel SA-immobilized methacrylate monolithic columns, i.e. poly(GMA-SMX-co-EDMA) and poly(GMA-SAA-co-EDMA) were prepared by one-pot in situ copolymerization of the drug ligand (sulfamethoxazole (SMX) or sulfanilamide (SAA)), the monomer (glycidyl methacrylate, GMA) and the cross-linker (ethylene dimethacrylate, EDMA) within 100 μm i.d. capillaries under optimized polymerization conditions. The physicochemical properties and column performance of the fabricated monolithic columns were characterized by elemental analysis, scanning electron microscopy and micro-HPLC. Satisfactory column permeability, efficiency and separation performance were obtained on the optimized poly(GMA-SMX-co-EDMA) monolithic column for small molecules, such as a standard test mixture and eight aromatic ketones. Notably, it was found that the poly(GMA-SMX-co-EDMA) monolith showed a selective affinity to trypsin, while the poly(GMA-SAA-co-EDMA) monolith containing sulfanilamide did not exhibit such affinity at all. This research not only provides a novel monolith for the selective isolation and purification of trypsin, but it also offers the possibility to easily prepare novel drug functionalized methacrylate monoliths through a one-pot copolymerization strategy. Copyright © 2015 Elsevier B.V. All rights reserved.

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...

Controlled protein adsorption on PMOXA/PAA based coatings by thermally induced immobilization

NASA Astrophysics Data System (ADS)

Mumtaz, Fatima; Chen, Chaoshi; Zhu, Haikun; Pan, Chao; Wang, Yanmei

2018-05-01

In this work, poly(2-methyl-2-oxazoline-random-glycidyl methacrylate) (PMOXA-r-GMA) and poly(acrylic acid)-block-poly(glycidyl methacrylate) (PAA-b-PGMA) copolymers were synthesized via cationic ring-opening polymerization (CROP) of 2-methyl-2-oxazoline (MOXA) and reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylic acid (AA) followed by their random and block copolymerization with glycidyl methacrylate (GMA), respectively, and then characterized carefully. PMOXA/PAA based coatings were then prepared by simply spin coating the mixture of PMOXA-r-GMA and PAA-b-PGMA copolymer solutions onto silicon/glass substrates followed by annealing at 110 °C. The coatings were rigorously characterized by using X-ray photoelectron spectroscopy (XPS), the static water contact angle (WCA) test, ellipsometry and atomic force microscopy (AFM). The results demonstrated that the coating based mixed PMOXA/PAA brushes with desired surface composition could be attained by simply maintaining their percentage in the mixture of PMOXA-r-GMA and PAA-b-PGMA copolymer solutions. Finally, the switchable behavior of PMOXA/PAA based coatings toward bovine serum albumin (BSA) adsorption was investigated by fluorescein isothiocyanate-labelled BSA (FITC-BSA) assay and quartz crystal microbalance with dissipation monitoring (QCM-D), which indicated that the coating based mixed PMOXA/PAA brushes could control BSA adsorption/desorption from very low to high amount (>90% desorption) through adjusting the composition of PMOXA-r-GMA and PAA-b-PGMA solution used in preparing PMOXA/PAA based coatings upon pH and ionic strength change. Furthermore, PMOXA/PAA based coatings displayed efficient repeatability of reversible BSA adsorption/desorption cycles.

Organocatalytic atroposelective synthesis of axially chiral styrenes

NASA Astrophysics Data System (ADS)

Zheng, Sheng-Cai; Wu, San; Zhou, Qinghai; Chung, Lung Wa; Ye, Liu; Tan, Bin

2017-05-01

Axially chiral compounds are widespread in biologically active compounds and are useful chiral ligands or organocatalysts in asymmetric catalysis. It is well-known that styrenes are one of the most abundant and principal feedstocks and thus represent excellent prospective building blocks for chemical synthesis. Driven by the development of atroposelective synthesis of axially chiral styrene derivatives, we discovered herein the asymmetric organocatalytic approach via direct Michael addition reaction of substituted diones/ketone esters/malononitrile to alkynals. The axially chiral styrene compounds were produced with good chemical yields, enantioselectivities and almost complete E/Z-selectivities through a secondary amine-catalysed iminium activation strategy under mild conditions. Such structural motifs are important precursors for further transformations into biologically active compounds and synthetic useful intermediates and may have potential applications in asymmetric synthesis as olefin ligands or organocatalysts.

Osteo-odonto-keratoprosthesis (OOKP) and the testing of three different adhesives for bonding bovine teeth with optical poly-(methyl methacrylate) (PMMA) cylinder.

PubMed

Weisshuhn, K; Berg, I; Tinner, D; Kunz, C; Bornstein, M M; Steineck, M; Hille, K; Goldblum, D

2014-07-01

Preparation of the lamina during osteo-odonto-keratoprosthesis (OOKP) design is complex, and its longevity and watertightness important. To date, only acrylic bone cements have been used for bonding the optical cylinder to the tooth dentine. Our aim was to evaluate different dental adhesives for OOKP preparation. Specimens of bovine teeth were produced by preparing 1.5-mm thick dentine slices with holes having a diameter of 3.5 mm. Each group (n=10 per group) was luted with either classic poly-(methyl methacrylate) (PMMA) bone cement, universal resin cement or glass ionomer cement. All specimens underwent force measurement using a uniaxial traction machine. The highest mean force required to break the bond was measured for PMMA bone cement (128.2 N) followed by universal resin cement (127.9 N), with no statistically significant difference. Glass ionomer cement showed significantly lower force resistance (78.1 N). Excellent bonding strength combined with easy application was found for universal resin cement, and thus, it is a potential alternative to acrylic bone cement in OOKP preparation. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

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.

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

Code of Federal Regulations, 2010 CFR

2010-04-01

... parts by weight of a grafted rubber consisting of (i) 8-12 parts of butadiene/styrene elastomer... limitations are determined by an infrared spectro-photo-metric method titled “Infrared Spectro-photo-metric...

Biomonitoring of styrene occupational exposures: Biomarkers and determinants.

PubMed

Persoons, Renaud; Richard, Justine; Herve, Claire; Montlevier, Sarah; Marques, Marie; Maitre, Anne

2018-06-22

High styrene exposures are still experienced in various occupational settings, requesting regular exposure assessments. The aims of this study were to study occupational exposures in various industrial sectors and to determine factors influencing styrene urinary metabolites levels. Biomonitoring was conducted in 141 workers from fiberglass-reinforced plastic (FRP) manufacture, thermoplastic polymers production, vehicle repair shops and cured-in-place pipe lining (CIPP). Urinary styrene (StyU) as well as Mandelic (MA) / Phenyglyoxylic Acids (PGA) were quantified at the beginning and at the end of week, and multivariate linear regression models were used. StyU levels revealed very low, rarely exceeding 3 µg.L -1 . Highest concentrations of MA + PGA were observed in FRP sector, with levels reaching up to 1100 mg.g -1 of creatinine. Factors influencing end-of-week MA + PGA concentrations were levels at the beginning of week, open molding processes, proximity to the emission source, respiratory protection, styrene content in raw materials. Elevated levels were also observed during CIPP process, whereas thermoplastic injection and vehicle repair shop workers exhibited much lower exposures. Intervention on process (decreasing styrene proportion, using closed molding), protective equipment (local exhaust ventilation, respiratory protection) and individual practices (stringent safety rules) are expected to decrease occupational exposures. Urinary MA + PGA remain the most appropriate biomarkers for occupational biomonitoring. Copyright © 2018. Published by Elsevier B.V.

A Review on the Modification of Polysaccharide Through Graft Copolymerization for Various Potential Applications

PubMed Central

Kumar, Deepak; Pandey, Jyoti; Raj, Vinit; Kumar, Pramendra

2017-01-01

Introduction: Graft copolymerization is one of the most promising technique uses to modify the properties of naturally available polymers with a minimum loss in their native characteristics. Methods and Materials: Graft copolymerization is a very significant technique to add hybrid properties in backbone of polymers. The grafting generally initiated through the formation of free radical centers on the polymer backbone as well as monomer. Results: Grafted polysaccharides have various applications in different important scientific areas such as drug delivery, pharmaceutical field, plastic industry, waste water treatment, tannery effluent treatment, textile industry, agriculture area, etc. all of this fascinated us to summarize the major research articles over the last two decades outlining different methods of grafting, surface modification, graft copolymerization of synthetic and natural polymers. Conclusion: Various redox initiator systems viz. Ceric ammonium nitrate, per sulfate, Irradiation, FAS-H2O2 etc. is also explored for grafting of vinyl through conventional and non-conventional techniques. PMID:29151987

Chest wall reconstruction with methacrylate prosthesis in Poland syndrome.

PubMed

Arango Tomás, Elisabet; Baamonde Laborda, Carlos; Algar Algar, Javier; Salvatierra Velázquez, Angel

2013-10-01

Poland syndrome is a rare congenital malformation. This syndrome was described in 1841 by Alfred Poland at Guy's Hospital in London. It is characterized by hypoplasia of the breast and nipple, subcutaneous tissue shortages, lack of the costosternal portion of the pectoralis major muscle and associated alterations of the fingers on the same side. Corrective treatment of the chest and soft tissue abnormalities in Poland syndrome varies according to different authors. We report the case of a 17-year-old adolescent who underwent chest wall reconstruction with a methyl methacrylate prosthesis. This surgical procedure is recommended for large anterior chest wall defects, and it prevents paradoxical movement. Moreover it provides for individual remodeling of the defect depending on the shape of the patient's chest. Copyright © 2012 SEPAR. Published by Elsevier Espana. All rights reserved.

Comparison of mouse strains for susceptibility to styrene-induced hepatotoxicity and pneumotoxicity

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

Carlson, G.P.

1997-10-01

Styrene is known to cause both hepatotoxicity and pneumotoxicity in mice. Strain differences have been reported by other investigators suggesting that Swiss mice are less susceptible than non-Swiss mice to styrene-induced liver damage. In this study, All and C57BL16 mice were found to be similar to non-Swiss albino (NSA) mice in susceptibility whereas CD-1 (Swiss) mice were more resistant to hepatotoxicity as assessed by serum sorbitol dehydrogenase levels and pneumotoxicity as determined by gamma-glutamyltranspeptidase and lactate dehydrogenase measurements in bronchoalveolar ravage fluid. Styrene was hepatotoxic in CD-1 mice treated with pyridine to induce CYP2E1. CYP2E1 apoprotein levels and p-nitrophenol hydroxylasemore » activities in control and pyridine-induced mice were similar in the two strains. Hepatic and pulmonary microsomal preparations from both strains metabolized styrene to styrene oxide at similar rates. CD-1 mice were as susceptible as the NSA mice to the effects of styrene oxide. The data suggest that there are no differences in the bioactivation of styrene to styrene oxide or innate susceptibility to the active metabolite that would account for the differences between the CD-1 and NSA mice. 26 refs., 6 tabs.« less

Sulfonated Styrene-(ethylene-co-butylene)-styrene/Montmorillonite Clay Nanocomposites: Synthesis, Morphology, and Properties

PubMed Central

2008-01-01

Sulfonated styrene-(ethylene-butylene)-styrene triblock copolymer (SSEBS) was synthesized by reaction of acetyl sulfate with SEBS. SSESB-clay nanocomposites were then prepared from hydrophilic Na-montmorillonite (MT) and organically (quaternary amine) modified hydrophobic nanoclay (OMT) at very low loading. SEBS did not show improvement in properties with MT-based nanocomposites. On sulfonation (3 and 6 weight%) of SEBS, hydrophilic MT clay-based nanocomposites exhibited better mechanical, dynamic mechanical, and thermal properties, and also controlled water–methanol mixture uptake and permeation and AC resistance. Microstructure determined by X-ray diffraction, atomic force microscopy, and transmission electron microscopy due to better dispersion of MT nanoclay particles and interaction of MT with SSEBS matrix was responsible for this effect. The resulting nanocomposites have potential as proton transfer membranes for Fuel Cell applications.

Structure/property relationships in methacrylate/dimethacrylate polymers for dental applications

NASA Astrophysics Data System (ADS)

Mehlem, Jeremy John

as in their final state. Using these methods the size of the high and low cross-link density phase was examined and determined to be on the order of 50--150 nanometers. Model compounds based on phenylethyl methacrylate were formulated to determine how of nadic methyl anhydride and maleic anhydride incorporate into dimethacrylate resin systems.

Influences of MAA on the porous morphology of P(St-MAA) latex particles produced by batch soap-free emulsion polymerization followed by stepwise alkali/acid post-treatment.

PubMed

Deng, Wei; Li, Ronglong; Zhang, Mengjun; Gong, Lixiang; Kan, Chengyou

2010-09-01

Soap-free P(St-MAA) latex particles with variable styrene (St)/methacrylic acid (MAA) ratio were synthesized by batch emulsion copolymerization at 70 degrees C for 7h, and the particles with porous structure were obtained after stepwise alkali/acid post-treatment. The effects of MAA amount on the particle morphologies after the alkali and the stepwise alkali/acid post-treatments were investigated by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Results indicated that the alkali-treated latex particles showed anomalous structure with rough surface, and no hollow was clearly identified inside them. When these alkali-treated particles were further treated with acid solution, the particle surface became much smoother, and porous morphology appeared. It was found that when the MAA amount was less than or equal to 4mol%, no obvious morphological variation was observed; while the latex particles showed clearly porous structure as the MAA amount increased to 6mol%; with the further increase of MAA amount to 8mol%, the pore size decreased distinctly. Copyright 2010 Elsevier Inc. All rights reserved.

Novel Cobalt(II) complexes containing N,N-di(2-picolyl)amine based ligands; Synthesis, characterization and application towards methyl methacrylate polymerisation

NASA Astrophysics Data System (ADS)

Ahn, Seoung Hyun; Choi, Sang-Il; Jung, Maeng Joon; Nayab, Saira; Lee, Hyosun

2016-06-01

The reaction of [CoCl2·6H2O] with N‧-substituted N,N-di(2-picolyl)amine ligands such as 1-cyclohexyl-N,N-bis(pyridin-2-ylmethyl)methanamine (LA), 2-methoxy-N,N-bis(pyridin-2-ylmethyl)ethan-1-amine (LB), and 3-methoxy-N,N-bis(pyridin-2-ylmethyl)propan-1-amine (LC), yielded [LnCoCl2] (Ln = LA, LB and LC), respectively. The Co(II) centre in [LnCoCl2] (Ln = LA, and LC) adopted distorted bipyramidal geometries through coordination of nitrogen atoms of di(2-picolyl)amine moiety to the Co(II) centre along with two chloro ligands. The 6-coordinated [LBCoCl2] showed a distorted octahedral geometry, achieved through coordination of the two pyridyl units, two chloro units, and bidentate coordination of nitrogen and oxygen in the N‧-methoxyethylamine to the Co(II) centre. [LCCoCl2] (6.70 × 104 gPMMA/molCo h) exhibited higher catalytic activity for the polymerisation of methyl methacrylate (MMA) in the presence of modified methylaluminoxane (MMAO) compared to rest of Co(II) complexes. The catalytic activity was considered as a function of steric properties of ligand architecture and increased steric bulk around the metal centre resulted in the decrease catalytic activity. All Co(II) initiators yielded syndiotactic poly(methylmethacrylate) (PMMA).

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...

Styrene vapor control systems in FRP yacht plants.

PubMed

Todd, W F

1985-01-01

The production of large (greater than 25-ft) fiber-reinforced plastic (FRP) yachts has presented problems of styrene exposure in excess of the Occupational Safety and Health Administration permissible exposure level (OSHA PEL) of 100 ppm. Also, the National Institute for Occupational Safety and Health (NIOSH) is currently recommending a 10-hour workshift, 40-hour workweek time weighted average (TWA) of 50 ppm for styrene. Meeting this challenge will require a system of engineering, work practice, personal protective equipment, and monitoring control measures. NIOSH has performed a study of the engineering controls in three FRP yacht plants. Work practices and the use of personal protective equipment (PPE) were also considered in the evaluation. The three systems evaluated included a dilution system, a local ventilation system, and a push-pull ventilation system. The cost of constructing and operating these systems was not evaluated in this study. Study results indicated that each type of ventilation system can meet the present PEL of 100 ppm styrene; however, it is not certain that these systems can meet a lower PEL of 50 ppm styrene.

40 CFR 721.10151 - Modified styrene, divinylbenzene polymer (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... polymer (generic). 721.10151 Section 721.10151 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10151 Modified styrene, divinylbenzene polymer (generic). (a) Chemical... as modified styrene, divinylbenzene polymer (PMN P-07-642) is subject to reporting under this section...

40 CFR 721.10151 - Modified styrene, divinylbenzene polymer (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... polymer (generic). 721.10151 Section 721.10151 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10151 Modified styrene, divinylbenzene polymer (generic). (a) Chemical... as modified styrene, divinylbenzene polymer (PMN P-07-642) is subject to reporting under this section...

40 CFR 721.10151 - Modified styrene, divinylbenzene polymer (generic).

Code of Federal Regulations, 2012 CFR

2012-07-01

... polymer (generic). 721.10151 Section 721.10151 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10151 Modified styrene, divinylbenzene polymer (generic). (a) Chemical... as modified styrene, divinylbenzene polymer (PMN P-07-642) is subject to reporting under this section...

40 CFR 721.10151 - Modified styrene, divinylbenzene polymer (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... polymer (generic). 721.10151 Section 721.10151 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10151 Modified styrene, divinylbenzene polymer (generic). (a) Chemical... as modified styrene, divinylbenzene polymer (PMN P-07-642) is subject to reporting under this section...

40 CFR 721.10151 - Modified styrene, divinylbenzene polymer (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... polymer (generic). 721.10151 Section 721.10151 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10151 Modified styrene, divinylbenzene polymer (generic). (a) Chemical... as modified styrene, divinylbenzene polymer (PMN P-07-642) is subject to reporting under this section...

Mechanical characterization and validation of poly (methyl methacrylate)/multi walled carbon nanotube composite for the polycentric knee joint.

PubMed

Arun, S; Kanagaraj, S

2015-10-01

Trans femoral amputation is one of the most uncomfortable surgeries in patient׳s life, where the prosthesis consisting of a socket, knee joint, pylon and foot is used to do the walking activities. The artificial prosthetic knee joint imitates the functions of human knee to achieve the flexion-extension for the above knee amputee. The objective of present work is to develop a light weight composite material for the knee joint to reduce the metabolic cost of an amputee. Hence, an attempt was made to study the mechanical properties of multi walled carbon nanotubes (MWCNT) reinforced Poly (methyl methacrylate) (PMMA) prepared through melt mixing technique and optimize the concentration of reinforcement. The PMMA nanocomposites were prepared by reinforcing 0, 0.1, 0.2, 0.25, 0.3 and 0.4 wt% of MWCNT using injection moulding machine via twin screw extruder. It is observed that the tensile and flexural strength of PMMA, which were studied as per ASTM D638 and D790, respectively, were increased by 32.9% and 26.3% till 0.25 wt% reinforcement of MWCNT. The experimental results of strength and modulus were compared with theoretical prediction, where a good correlation was noted. It is concluded that the mechanical properties of PMMA were found to be increased to maximum at 0.25 wt% reinforcement of MWCNT, where the Pukanszky model and modified Halpin-Tsai model are suggested to predict the strength and modulus, respectively, of the PMMA/MWCNT composite, which can be opted as a suitable materiel for the development of polycentric knee joint. Copyright © 2015 Elsevier Ltd. All rights reserved.

Lignin model compounds as bio-based reactive diluents for liquid molding resins.

PubMed

Stanzione, Joseph F; Sadler, Joshua M; La Scala, John J; Wool, Richard P

2012-07-01

Lignin is a copious paper and pulping waste product that has the potential to yield valuable, low molecular weight, single aromatic chemicals when strategically depolymerized. The single aromatic lignin model compounds, vanillin, guaiacol, and eugenol, were methacrylated by esterification with methacrylic anhydride and a catalytic amount of 4-dimethylaminopyridine. Methacrylated guaiacol (MG) and methacrylated eugenol (ME) exhibited low viscosities at room temperature (MG: 17 cP and ME: 28 cP). When used as reactive diluents in vinyl ester resins, they produced resin viscosities higher than that of vinyl ester-styrene blends. The relative volatilities of MG (1.05 wt% loss in 18 h) and ME (0.96 wt% loss in 18 h) measured by means of thermogravimetric analysis (TGA) were considerably lower than that of styrene (93.7 wt% loss in 3 h) indicating the potential of these chemicals to be environmentally friendly reactive diluents. Bulk polymerization of MG and ME generated homopolymers with glass transition temperatures (T(g)s) of 92 and 103 °C, respectively. Blends of a standard vinyl ester resin with MG and ME (50 wt % reactive diluent) produced thermosets with T(g)s of 127 and 153 °C, respectively, which are comparable to vinyl ester-styrene resins, thus demonstrating the ability of MG and ME to completely replace styrene as reactive diluents in liquid molding resins without sacrificing cured-resin thermal performance. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Equilibrium Polymerization of Butyl Methacrylate in Bulk and in Nanopore Confinement

NASA Astrophysics Data System (ADS)

Tian, Qian; Simon, Sindee

The equilibrium between monomer and polymer in free radical polymerization can be shifted towards monomer under nanoconfinement. This decrease in ceiling temperature is due to a decrease in the entropy associated with the constrained polymer chains, resulting in a larger negative change in entropy of reaction. Here, we investigate the equilibrium polymerization of butyl methacrylate (BMA) in bulk and in nanopore confinement with differential scanning calorimetry (DSC) using di-tert-butyl peroxide (DTBP) as initiator. This system has several advantages compare to the previously studied system of methyl methacrylate (MMA) initiated with 2,2'-azo-bis-isobutyronitrile (AIBN), namely, a reduced rate of reaction, higher boiling point of monomer, and higher initiator utilization temperature range, all of which facilitate the study of the reaction at high temperatures near the ceiling temperature. Interestingly, for BMA, there is no change in limiting conversion between material reacted in bulk and that in controlled pore glass having pore diameters of 7.5 and 50 nm. This unexpected result may be due to the greater flexibility of the PBMA chains compared to PMMA, suggesting that in the BMA/PBMA system, the degree of confinement is relatively low. Future studies will continue to investigate how the entropy change on reaction is affected by confinement.

Water-stable diblock polystyrene-block-poly(2-vinyl pyridine) and diblock polystyrene-block-poly(methyl methacrylate) cylindrical patterned surfaces inhibit settlement of zoospores of the green alga Ulva.

PubMed

Grozea, Claudia M; Gunari, Nikhil; Finlay, John A; Grozea, Daniel; Callow, Maureen E; Callow, James A; Lu, Zheng-Hong; Walker, Gilbert C

2009-04-13

Nanopatterned surfaces with hydrophobic and hydrophilic domains were produced using the diblock copolymer polystyrene-block-poly(2-vinyl pyridine) (PS-b-P2VP) and polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA). The PS-b-P2VP diblock copolymer, mixed with the cross-linker benzophenone and spin-coated onto silicon wafers, showed self-assembled cylindrical structures, which were retained after UV treatment for cross-linking. The thin films displayed cylindrical domains after immersion in water. This study shows that pattern retention in water is possible for a long period of time, at least for two weeks in pure water and three weeks in artificial seawater. The PS-b-PMMA diblock showed self-assembled cylindrical structures. PS-b-P2VP and PS-b-PMMA cylindrical patterned surfaces showed reduced settlement of zoospores of the green alga Ulva compared to unpatterned surfaces. The copolymers were investigated using atomic force microscopy and X-ray photoelectron spectroscopy.

Occupational Styrene Exposure on Auditory Function Among Adults: A Systematic Review of Selected Workers.

PubMed

Pleban, Francis T; Oketope, Olutosin; Shrestha, Laxmi

2017-12-01

A review study was conducted to examine the adverse effects of styrene, styrene mixtures, or styrene and/or styrene mixtures and noise on the auditory system in humans employed in occupational settings. The search included peer-reviewed articles published in English language involving human volunteers spanning a 25-year period (1990-2015). Studies included peer review journals, case-control studies, and case reports. Animal studies were excluded. An initial search identified 40 studies. After screening for inclusion, 13 studies were retrieved for full journal detail examination and review. As a whole, the results range from no to mild associations between styrene exposure and auditory dysfunction, noting relatively small sample sizes. However, four studies investigating styrene with other organic solvent mixtures and noise suggested combined exposures to both styrene organic solvent mixtures may be more ototoxic than exposure to noise alone. There is little literature examining the effect of styrene on auditory functioning in humans. Nonetheless, findings suggest public health professionals and policy makers should be made aware of the future research needs pertaining to hearing impairment and ototoxicity from styrene. It is recommended that chronic styrene-exposed individuals be routinely evaluated with a comprehensive audiological test battery to detect early signs of auditory dysfunction.

[Degradation of styrene by coupling ultraviolet and biofiltration].

PubMed

Sha, Hao-Lei; Yang, Guo-Jing; Xia, Jing-Fen

2013-12-01

Purification of styrene by ultraviolet (UV)-biofiltration was studied in this paper. The light source and the biofilm carrier were ozone producing lamp at 185 nm and the peat, palm fiber, porous acticarbon, respectively. Styrene inlet concentration was controlled between 320-583 mg x m(-3), and the removal efficiency remained above 95% after stabilization. The UV converted styrene into more soluble and biodegradable intermediates, such as alcohol, aldehyde and acid, thus the performance of biofilter can be improved. In the stable operation stage, the variation of inlet concentration did not affect the removal efficiency when the total residence time (TRT) was long, however, the inlet concentration obviously affected the removal efficiency when the TRT decreased. The removal load of coupling system increased linearly with increasing inlet load, and the removal efficiency was higher than 95% under a TRT of 102 s. When TRT was 68 s and the inlet load was low, the variation of removal load complied with the law described above, but it gradually deviated from the straight line and tended to stabilized at a certain value when the inlet load became higher than 30 g x (m3 x h)(-). If considering the fluctuation of styrene concentration only, the contribution rate of ultraviolet photolysis to styrene removal was greater than that of the biofilter, and the removal effect could be restored on the fourth day, after closing the system for ten days and restarting.

A poly(alkyl methacrylate-divinylbenzene-vinylbenzyl trimethylammonium chloride) monolithic column for solid-phase microextraction.

PubMed

Liu, Wan-Ling; Lirio, Stephen; Yang, Yicong; Wu, Lin-Tai; Hsiao, Shu-Ying; Huang, Hsi-Ya

2015-05-22

In this study, an organic polymer monolithic columns, which were prepared via in situ polymerization of alkyl methacrylate-ester (AMA), divinylbenzene (DVB) and vinylbenzyl trimethylammonium chloride (VBTA, charged monomer), were developed as adsorbent for solid-phase microextraction (SPME). Different parameters affecting the extraction efficiency for nine (9) non-steroidal anti-inflammatory drugs (NSAIDs) such as the ratio of the stearyl methacrylate (SMA) to DVB monomer, column length, sample pH, extraction flow rate and desorption solvent were investigated to obtain the optimal SPME condition. Also, the permeability for each poly(AMA-DVB-VBTA) monolithic column was investigated by adding porogenic solvent (poly(ethylene glycol), PEG). Using the optimized condition, a series of AMA-based poly(AMA-DVB-VBTA) monolith columns were developed to determine the effect the extraction efficiency of NSAIDs by varying the alkyl chain length of the methacrylate ester (methyl-, butyl-, octyl-, or lauryl-methacrylate; (MMA, BMA, OMA, LMA)). Results showed that decreasing the AMA chain length increases the extraction efficiency of some NSAIDs (i.e. sulindac (sul), naproxen (nap), ketoprofen (ket) and indomethacin (idm)). Among the poly(AMA-DVB-VBTA) monolithic columns, poly(BMA-DVB-VBTA) showed a highly repeatable extraction efficiency for NSAIDs with recoveries ranging from 85.0 to 100.2% with relative standard deviation (RSD) less than 6.8% (n=3). The poly(BMA-DVB-VBTA) can also be reused for at least 50 times without any significant effect in extraction efficiency for NSAIDs. Finally, using the established conditions, the poly(BMA-DVB-VBTA) was used to extract trace-level NSAIDs (100μgL(-1)) in river water with good recoveries ranging from 75.8 to 90.8% (RSD<14.9%). Copyright © 2015 Elsevier B.V. All rights reserved.

Polyethylenimine-immobilized core-shell nanoparticles: synthesis, characterization, and biocompatibility test.

PubMed

Ratanajanchai, Montri; Soodvilai, Sunhapas; Pimpha, Nuttaporn; Sunintaboon, Panya

2014-01-01

Herein, we prepared PEI-immobilized core-shell particles possessing various types of polymer cores via a visible light-induced surfactant-free emulsion polymerization (SFEP) of three vinyl monomers: styrene (St), methyl methacrylate (MMA), and 2-hydroxyethyl methacrylate (HEMA). An effect of monomers on the polymerization and characteristics of resulting products was investigated. Monomers with high polarity can provide high monomer conversion, high percentage of grafted PEI, stable particles with uniform size distribution but less amino groups per particles. All prepared nanoparticles exhibited a core-shell nanostructure, containing PEI on the shell with hydrodynamic size around 140-230nm. For in-vitro study in Caco-2 cells, we found that the incorporation of PEI into these core-shell nanoparticles can significantly reduce its cytotoxic effect and also be able to internalized within the cells. Accordingly, these biocompatible particles would be useful for various biomedical applications, including gene transfection and intracellular drug delivery. © 2013.

PROPERTY ANALYSIS OF TRIGLYCERIDE-BASED THERMOSETS. (R829576)

EPA Science Inventory

Triglycerides with acrylate functionality were prepared from various oils and
model triglycerides. The triglyceride-acrylates were homopolymerized and copolymerized
with styrene. The cross-link densities of the resulting polymer networks were
predicted utilizing the F...

Cooperative effects for CYP2E1 differ between styrene and its metabolites

PubMed Central

Hartman, Jessica H.; Boysen, Gunnar; Miller, Grover P.

2014-01-01

Cooperative interactions are frequently observed in the metabolism of drugs and pollutants by cytochrome P450s; nevertheless, the molecular determinants for cooperativity remain elusive. Previously, we demonstrated that steady-state styrene metabolism by CYP2E1 exhibits positive cooperativity.We hypothesized that styrene metabolites have lower affinity than styrene toward CYP2E1 and limited ability to induce cooperative effects during metabolism. To test the hypothesis, we determined the potency and mechanism of inhibition for styrene and its metabolites toward oxidation of 4-nitrophenol using CYP2E1 Supersomes® and human liver microsomes.Styrene inhibited the reaction through a mixed cooperative mechanism with high affinity for the catalytic site (67 μM) and lower affinity for the cooperative site (1100 μM), while increasing substrate turnover at high concentrations. Styrene oxide and 4-vinylphenol possessed similar affinity for CYP2E1. Styrene oxide behaved cooperatively like styrene, but 4-vinylphenol decreased turnover at high concentrations. Styrene glycol was a very poor competitive inhibitor. Among all compounds, there was a positive correlation with binding and hydrophobicity.Taken together, these findings for CYP2E1 further validate contributions of cooperative mechanisms to metabolic processes, demonstrate the role of molecular structure on those mechanisms and underscore the potential for heterotropic cooperative effects between different compounds. PMID:23327532

Structure-toxicity relationship study of para-halogenated styrene analogues in CYP2E1 transgenic cells

PubMed Central

Chung, Jou-Ku; Shen, Shuijie; Jiang, Zhiteng; Yuan, Wei; Zheng, Jiang

2012-01-01

Styrene is one of the most important industrial intermediates consumed in the world and is mainly used as a monomer for reinforced plastics and rubber. Styrene has been found to be hepatotoxic and pneumotoxic in humans and experimental animals. The toxicity of styrene is suggested to be metabolism-dependent. Styrene-7,8-oxide has been considered as the major metabolite responsible for styrene-induced cytotoxicity. The objective of the study was to investigate the correlation between cytotoxicity of styrene and chemical and biochemical properties of the vinyl group of styrene by development of structure activity relationships (SAR). 4-Fluorostyrene, 4-chlorostyrene and 4-bromostyrene were selected for the SAR study. Cytotoxicity of styrene and the halogenated styrene derivatives with an order of 4-bromostyrene > 4-chlorostyrene > 4-fluorostyrene ≈ styrene was observed in CYP2E1 transgenic cells. Similar orders in the efficiency of the metabolism of styrene and the halogenated styrene analogues to their oxides and in the electrophilicity of the corresponding oxides were observed. Additionally, the order of the potency of cellular glutathione depletion and the degree of protein adduction induced by styrene and the halogenated styrenes were consistent with that of their cytotoxicities. The wild-type cells were less susceptible to the toxicity of the corresponding model compounds than CYP2E1 cells. The present study provided insight into the roles of the biochemical and chemical properties of styrene in its cytotoxicity. PMID:22366341

Comparing in situ removal strategies for improving styrene bioproduction.

PubMed

McKenna, Rebekah; Moya, Luis; McDaniel, Matthew; Nielsen, David R

2015-01-01

As an important conventional monomer compound, the biological production of styrene carries significant promise with respect to creating novel sustainable materials. Since end-product toxicity presently limits styrene production by previously engineered Escherichia coli, in situ product removal by both solvent extraction and gas stripping were explored as process-based strategies for circumventing its inhibitory effects. In solvent extraction, the addition of bis(2-ethylhexyl)phthalate offered the greatest productivity enhancement, allowing net volumetric production of 836 ± 64 mg/L to be reached, representing a 320 % improvement over single-phase cultures. Gas stripping rates, meanwhile, were controlled by rates of bioreactor agitation and, to a greater extent, aeration. A periodic gas stripping protocol ultimately enabled up to 561 ± 15 mg/L styrene to be attained. Lastly, by relieving the effects of styrene toxicity, new insight was gained regarding subsequent factors limiting its biosynthesis in E. coli and strategies for future strain improvement are discussed.

Ammonium methacrylate

Integrated Risk Information System (IRIS)

Ammonium methacrylate ; CASRN 16325 - 47 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcin

Statistical Ring Opening Metathesis Copolymerization of Norbornene and Cyclopentene by Grubbs' 1st-Generation Catalyst.

PubMed

Nikovia, Christiana; Maroudas, Andreas-Philippos; Goulis, Panagiotis; Tzimis, Dionysios; Paraskevopoulou, Patrina; Pitsikalis, Marinos

2015-08-27

Statistical copolymers of norbornene (NBE) with cyclopentene (CP) were prepared by ring-opening metathesis polymerization, employing the 1st-generation Grubbs' catalyst, in the presence or absence of triphenylphosphine, PPh₃. The reactivity ratios were estimated using the Finemann-Ross, inverted Finemann-Ross, and Kelen-Tüdos graphical methods, along with the computer program COPOINT, which evaluates the parameters of binary copolymerizations from comonomer/copolymer composition data by integrating a given copolymerization equation in its differential form. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the mean sequence length, which were derived using the monomer reactivity ratios. The kinetics of thermal decomposition of the copolymers along with the respective homopolymers was studied by thermogravimetric analysis within the framework of the Ozawa-Flynn-Wall and Kissinger methodologies. Finally, the effect of triphenylphosphine on the kinetics of copolymerization, the reactivity ratios, and the kinetics of thermal decomposition were examined.

Occupational styrene exposure induces stress-responsive genes involved in cytoprotective and cytotoxic activities.

PubMed

Strafella, Elisabetta; Bracci, Massimo; Staffolani, Sara; Manzella, Nicola; Giantomasi, Daniele; Valentino, Matteo; Amati, Monica; Tomasetti, Marco; Santarelli, Lory

2013-01-01

The aim of this study was to evaluate the expression of a panel of genes involved in toxicology in response to styrene exposure at levels below the occupational standard setting. Workers in a fiber glass boat industry were evaluated for a panel of stress- and toxicity-related genes and associated with biochemical parameters related to hepatic injury. Urinary styrene metabolites (MA+PGA) of subjects and environmental sampling data collected for air at workplace were used to estimate styrene exposure. Expression array analysis revealed massive upregulation of genes encoding stress-responsive proteins (HSPA1L, EGR1, IL-6, IL-1β, TNSF10 and TNFα) in the styrene-exposed group; the levels of cytokines released were further confirmed in serum. The exposed workers were then stratified by styrene exposure levels. EGR1 gene upregulation paralleled the expression and transcriptional protein levels of IL-6, TNSF10 and TNFα in styrene exposed workers, even at low level. The activation of the EGR1 pathway observed at low-styrene exposure was associated with a slight increase of hepatic markers found in highly exposed subjects, even though they were within normal range. The ALT and AST levels were not affected by alcohol consumption, and positively correlated with urinary styrene metabolites as evaluated by multiple regression analysis. The pro-inflammatory cytokines IL-6 and TNFα are the primary mediators of processes involved in the hepatic injury response and regeneration. Here, we show that styrene induced stress responsive genes involved in cytoprotection and cytotoxicity at low-exposure, that proceed to a mild subclinical hepatic toxicity at high-styrene exposure.

Occupational Styrene Exposure Induces Stress-Responsive Genes Involved in Cytoprotective and Cytotoxic Activities

PubMed Central

Strafella, Elisabetta; Bracci, Massimo; Staffolani, Sara; Manzella, Nicola; Giantomasi, Daniele; Valentino, Matteo; Amati, Monica; Tomasetti, Marco; Santarelli, Lory

2013-01-01

Objective The aim of this study was to evaluate the expression of a panel of genes involved in toxicology in response to styrene exposure at levels below the occupational standard setting. Methods Workers in a fiber glass boat industry were evaluated for a panel of stress- and toxicity-related genes and associated with biochemical parameters related to hepatic injury. Urinary styrene metabolites (MA+PGA) of subjects and environmental sampling data collected for air at workplace were used to estimate styrene exposure. Results Expression array analysis revealed massive upregulation of genes encoding stress-responsive proteins (HSPA1L, EGR1, IL-6, IL-1β, TNSF10 and TNFα) in the styrene-exposed group; the levels of cytokines released were further confirmed in serum. The exposed workers were then stratified by styrene exposure levels. EGR1 gene upregulation paralleled the expression and transcriptional protein levels of IL-6, TNSF10 and TNFα in styrene exposed workers, even at low level. The activation of the EGR1 pathway observed at low-styrene exposure was associated with a slight increase of hepatic markers found in highly exposed subjects, even though they were within normal range. The ALT and AST levels were not affected by alcohol consumption, and positively correlated with urinary styrene metabolites as evaluated by multiple regression analysis. Conclusion The pro-inflammatory cytokines IL-6 and TNFα are the primary mediators of processes involved in the hepatic injury response and regeneration. Here, we show that styrene induced stress responsive genes involved in cytoprotection and cytotoxicity at low-exposure, that proceed to a mild subclinical hepatic toxicity at high-styrene exposure. PMID:24086524

Leaching of styrene and other aromatic compounds in drinking water from PS bottles.

PubMed

Ahmad, Maqbool; Bajahlan, Ahmad S

2007-01-01

Bottled water may not be safer, or healthier, than tap water. The present studies have proved that styrene and some other aromatic compounds leach continuously from polystyrene (PS) bottles used locally for packaging. Water sapmles in contact with PS were extracted by a preconcentration technique called as "purge and trap" and analysed by gas chromatograph-mass spectrometer (GC/MS). Eleven aromatic compounds were identified in these studies. Maximum concentration of styrene in PS bottles was 29.5 microg/L. Apart from styrene, ethyl benzene, toluene and benzene were also quantified but their concentrations were much less than WHO guide line values. All other compounds were in traces. Quality of plastic and storage time were the major factor in leaching of styrene. Concentration of styrene was increased to 69.53 microg/L after one-year storage. In Styrofoam and PS cups studies, hot water was found to be contaminated with styrene and other aromatic compounds. It was observed that temperature played a major role in the leaching of styrene monomer from Styrofoam cups. Paper cups were found to be safe for hot drinks.

Nonvolatile memory characteristics of organic thin film transistors using poly(2-hydroxyethyl methacrylate)-based polymer multilayer dielectric

NASA Astrophysics Data System (ADS)

Chen, Ying-Chih; Su, Yan-Kuin; Yu, Hsin-Chieh; Huang, Chun-Yuan; Huang, Tsung-Syun

2011-10-01

A wide hysteresis width characteristic (memory window) was observed in the organic thin film transistors (OTFTs) using poly(2-hydroxyethyl methacrylate) (PHEMA)-based polymer multilayers. In this study, a strong memory effect was also found in the pentacene-based OTFTs and the electric characteristics were improved by introducing PHEMA/poly(methyl methacrylate) (PMMA)/PHEMA trilayer to replace the conventional PHEMA monolayer or PMMA/PHEMA and PHEMA/PMMA bilayer as the dielectric layers of OTFTs. The memory effect was originated from the electron trapping and slow polarization of the dielectrics. The hydroxyl (-OH) groups inside the polymer dielectric were the main charge storage sites of the electrons. This charge-storage phenomenon could lead to a wide flat-band voltage shift (memory window, △VFB = 22 V) which is essential for the OTFTs' memory-related applications. Moreover, the fabricated transistors also exhibited significant switchable channel current due to the charge-storage and slow charge relaxation.

Continuous-flow Heck synthesis of 4-methoxybiphenyl and methyl 4-methoxycinnamate in supercritical carbon dioxide expanded solvent solutions

PubMed Central

Lau, Phei Li; Allen, Ray W K

2013-01-01

Summary The palladium metal catalysed Heck reaction of 4-iodoanisole with styrene or methyl acrylate has been studied in a continuous plug flow reactor (PFR) using supercritical carbon dioxide (scCO2) as the solvent, with THF and methanol as modifiers. The catalyst was 2% palladium on silica and the base was diisopropylethylamine due to its solubility in the reaction solvent. No phosphine co-catalysts were used so the work-up procedure was simplified and the green credentials of the reaction were enhanced. The reactions were studied as a function of temperature, pressure and flow rate and in the case of the reaction with styrene compared against a standard, stirred autoclave reaction. Conversion was determined and, in the case of the reaction with styrene, the isomeric product distribution was monitored by GC. In the case of the reaction with methyl acrylate the reactor was scaled from a 1.0 mm to 3.9 mm internal diameter and the conversion and turnover frequency determined. The results show that the Heck reaction can be effectively performed in scCO2 under continuous flow conditions with a palladium metal, phosphine-free catalyst, but care must be taken when selecting the reaction temperature in order to ensure the appropriate isomer distribution is achieved. Higher reaction temperatures were found to enhance formation of the branched terminal alkene isomer as opposed to the linear trans-isomer. PMID:24367454

Biomimetic Hydrogel Materials

DOEpatents

Bertozzi, Carolyn , Mukkamala, Ravindranath , Chen, Oing , Hu, Hopin , Baude, Dominique

2003-04-22

Novel biomimetic hydrogel materials and methods for their preparation. Hydrogels containing acrylamide-functionalized carbohydrate, sulfoxide, sulfide or sulfone copolymerized with a hydrophilic or hydrophobic copolymerizing material selected from the group consisting of an acrylamide, methacrylamide, acrylate, methacrylate, vinyl and a derivative thereof present in concentration from about 1 to about 99 wt %. and methods for their preparation. The method of use of the new hydrogels for fabrication of soft contact lenses and biomedical implants.

Biomimetic hydrogel materials

DOEpatents

Bertozzi, Carolyn; Mukkamala, Ravindranath; Chen, Qing; Hu, Hopin; Baude, Dominique

2000-01-01

Novel biomimetic hydrogel materials and methods for their preparation. Hydrogels containing acrylamide-functionalized carbohydrate, sulfoxide, sulfide or sulfone copolymerized with a hydrophilic or hydrophobic copolymerizing material selected from the group consisting of an acrylamide, methacrylamide, acrylate, methacrylate, vinyl and a derivative thereof present in concentration from about 1 to about 99 wt %. and methods for their preparation. The method of use of the new hydrogels for fabrication of soft contact lenses and biomedical implants.

Encapsulation of Piper cabralanum (Piperaceae) nonpolar extract in poly(methyl methacrylate) by miniemulsion and evaluation of increase in the effectiveness of antileukemic activity in K562 cells.

PubMed

Mendes, Anderson Nogueira; Filgueiras, Lívia Alves; Siqueira, Monica Regina Pimentel; Barbosa, Gleyce Moreno; Holandino, Carla; de Lima Moreira, Davyson; Pinto, José Carlos; Nele, Marcio

2017-01-01

This study aimed to synthesize and characterize nanoparticles (NPs) of poly(methyl methacrylate) (PMMA) and evaluate their ability to incorporate plant extracts with antitumor activity and low dissolution in aqueous media. The extract used was n -hexane partition of the methanol extract of Piper cabralanum (PCA-HEX). PMMA NPs were obtained using the mini-emulsion method, which was able to encapsulate almost 100% of PCA-HEX. The synthesized polymeric particles presented with a size of 200 nm and a negative charge. Cytotoxicity tests by MTT and trypan blue assays showed that NPs without PCA-HEX did not kill leukemic cells (K562 cells). NPs containing PCA-HEX were able to enhance cell death when compared to pure extract. The results showed that PMMA NPs could be useful as a drug delivery system as they can enhance the antitumor activity of the PCA-HEX extract by more than 20-fold. PMMA NPs containing plant extracts with antitumor activities may be an alternative to control the evolution of diseases such as leukemia.

Encapsulation of Piper cabralanum (Piperaceae) nonpolar extract in poly(methyl methacrylate) by miniemulsion and evaluation of increase in the effectiveness of antileukemic activity in K562 cells

PubMed Central

Mendes, Anderson Nogueira; Filgueiras, Lívia Alves; Siqueira, Monica Regina Pimentel; Barbosa, Gleyce Moreno; Holandino, Carla; de Lima Moreira, Davyson; Pinto, José Carlos; Nele, Marcio

2017-01-01

This study aimed to synthesize and characterize nanoparticles (NPs) of poly(methyl methacrylate) (PMMA) and evaluate their ability to incorporate plant extracts with antitumor activity and low dissolution in aqueous media. The extract used was n-hexane partition of the methanol extract of Piper cabralanum (PCA-HEX). PMMA NPs were obtained using the mini-emulsion method, which was able to encapsulate almost 100% of PCA-HEX. The synthesized polymeric particles presented with a size of 200 nm and a negative charge. Cytotoxicity tests by MTT and trypan blue assays showed that NPs without PCA-HEX did not kill leukemic cells (K562 cells). NPs containing PCA-HEX were able to enhance cell death when compared to pure extract. The results showed that PMMA NPs could be useful as a drug delivery system as they can enhance the antitumor activity of the PCA-HEX extract by more than 20-fold. PMMA NPs containing plant extracts with antitumor activities may be an alternative to control the evolution of diseases such as leukemia. PMID:29200848

Catalytic copolymerization of CO and ethylene with a charge neutral palladium(II) zwitterion.

PubMed

Lu, Connie C; Peters, Jonas C

2002-05-15

The synthesis of a zwitterionic Pd(II) complex supported by an anionic bis(phosphino)borate ligand, Ph(2)B(CH(2)PPh(2))(2) (abbreviated as [Ph(2)BP(2)]), is reported. The new complex, [Ph(2)BP(2)]PdMe(THF), is active for CO and ethylene copolymerization. The copolymerization activity and polyketone molecular weight for the neutral, zwitterionic system are compared with those for the cationic systems [R(2)E(CH(2)PPh(2))(2)PdMe(THF)][B(C(6)F(5))(4)] where ER(2) = SiPh(2) and CH(2). Surprisingly, the more electron rich zwitterionic system is a catalyst of activity comparable to that of the more conventional cationic systems.

Ring-Opening Copolymerization of Epoxides and Cyclic Anhydrides with Discrete Metal Complexes: Structure-Property Relationships.

PubMed

Longo, Julie M; Sanford, Maria J; Coates, Geoffrey W

2016-12-28

Polyesters synthesized through the alternating copolymerization of epoxides and cyclic anhydrides compose a growing class of polymers that exhibit an impressive array of chemical and physical properties. Because they are synthesized through the chain-growth polymerization of two variable monomers, their syntheses can be controlled by discrete metal complexes, and the resulting materials vary widely in their functionality and physical properties. This polymer-focused review gives a perspective on the current state of the field of epoxide/anhydride copolymerization mediated by discrete catalysts and the relationships between the structures and properties of these polyesters.

Formation of styrene dependent on fermentation management during wheat beer production.

PubMed

Schwarz, Katrin J; Stübner, René; Methner, Frank-Jürgen

2012-10-15

Styrene is formed by the thermal decarboxylation of cinnamic acid during wort boiling or by enzymatic decarboxylation during fermentation. The enzymatic reactions proceed in parallel to the decarboxylation of ferulic- and p-cumaric acid to 4-vinylguaiacol and 4-vinylphenol by the same decarboxylase enzyme. However, the formation of styrene occurs much faster and all available cinnamic acid in wort was converted completely within a few hours. Moreover, the comparison of various manufacturing parameters shows that a higher fermentation temperature of 25 °C compared to 16 °C and an open fermentation management lead to a rapid decrease of styrene. This allows minimising the content of styrene in beer while maintaining the typical wheat beer flavours. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

Monodispersepoly[BMA-co-(COPS-I)] Particles by Soap-Free Emulsion Copolymerization and Its Optical Properties as Photonic Crystals.

PubMed

Lee, Ki Chang; Choo, Hun Seung

2015-10-01

In order to study the surfactant-free emulsion copolymerization of benzyl methacrylate (BMA) with sodium 1-allyloxy-2-hydroxypropane sulfonate (COPS-I) and the resulting optical properties, a series of experiments was carried out at various reaction conditions such as the changes of BMA concentration, COPS-I concentration, BMA concentration under a fixed COPS-I amount, initiator and divinyl benzene (DVB) concentration. All the latices showed highly monodispersed spherical particles in the size range of 144~435 nm and the respective shiny structural colors from their colloidal photonic crystals. It is found that the changes in such polymerization factors greatly affect the number of particles and particle diameter, polymerization rate, molecular weight, zeta-potential, and refractive indices. The increase of number of particles led to the increased rate of polymerization and zeta-potential of the latices, on the other hand, to the decreased molecular weight. Refractive indices and the reflectivity increased with COPS-I concentration, on the other hand, and decreased with DVB concentration. Especially, refractive indices of the resulting poly[BMA-co-(COPS-I)] colloidal photonic crystals showed much higher values of 1.65~2.21 than that of polystyrene, due to the formation of core-shell shaped morphology. Monodisperse and high refractive index of poly[BMA-co-(COPS-I)] particles prepared in this work could be used for the study in photonic crystals and electrophoretic display.

The effect of processing temperature and time on the structure and fracture characteristics of self-reinforced composite poly(methyl methacrylate).

PubMed

Wright, D D; Gilbert, J L; Lautenschlager, E P

1999-08-01

A novel material, self-reinforced composite poly(methyl methacrylate) (SRC-PMMA) has been previously developed in this laboratory. It consists of high-strength PMMA fibers embedded in a matrix of PMMA derived from the fibers. As a composite material, uniaxial SRC-PMMA has been shown to have greatly improved flexural, tensile, fracture toughness and fatigue properties when compared to unreinforced PMMA. Previous work examined one empirically defined processing condition. This work systematically examines the effect of processing time and temperature on the thermal properties, fracture toughness and fracture morphology of SRC-PMMA produced by a hot compaction method. Differential scanning calorimetry (DSC) shows that composites containing high amounts of retained molecular orientation exhibit both endothermic and exothermic peaks which depend on processing times and temperatures. An exothermic release of energy just above Tg is related to the release of retained molecular orientation in the composites. This release of energy decreases linearly with increasing processing temperature or time for the range investigated. Fracture toughness results show a maximum fracture toughness of 3.18 MPa m1/2 for samples processed for 65 min at 128 degrees C. Optimal structure and fracture toughness are obtained in composites which have maximum interfiber bonding and minimal loss of molecular orientation. Composite fracture mechanisms are highly dependent on processing. Low processing times and temperatures result in more interfiber/matrix fracture, while higher processing times and temperatures result in higher ductility and more transfiber fracture. Excessive processing times result in brittle failure. Copyright 1999 Kluwer Academic Publishers

Dynamics of a poly(ethylene oxide) tracer in a poly(methyl methacrylate) matrix: remarkable decoupling of local and global motions.

PubMed

Haley, Jeffrey C; Lodge, Timothy P

2005-06-15

The tracer diffusion coefficient of unentangled poly(ethylene oxide) (PEO, M=1000 gmol) in a matrix of poly(methyl methacrylate) (PMMA, M=10 000 gmol) has been measured over a temperature range from 125 to 220 degrees C with forced Rayleigh scattering. The dynamic viscosities of blends of two different high molecular weight PEO tracers (M=440 000 and 900 000 gmol) in the same PMMA matrix were also measured at temperatures ranging from 160 to 220 degrees C; failure of time-temperature superposition was observed for these systems. The monomeric friction factors for the PEO tracers were extracted from the diffusion coefficients and the rheological relaxation times using the Rouse model. The friction factors determined by diffusion and rheology were in good agreement, even though the molecular weights of the tracers differed by about three orders of magnitude. The PEO monomeric friction factors were compared with literature data for PEO segmental relaxation times measured directly with NMR. The monomeric friction factors of the PEO tracer in the PMMA matrix were found to be from two to six orders of magnitude greater than anticipated based on direct measurements of segmental dynamics. Additionally, the PEO tracer terminal dynamics are a much stronger function of temperature than the corresponding PEO segmental dynamics. These results indicate that the fastest PEO Rouse mode, inferred from diffusion and rheology, is completely separated from the bond reorientation of PEO detected by NMR. This result is unlike other blend systems in which global and local motions have been compared.

Synthesis and characterization of a thermo-sensitive poly( N-methyl acryloylglycine methyl ester) used as a drug release carrier

NASA Astrophysics Data System (ADS)

Deng, Kui-Lin; Zhong, Hai-Bin; Jiao, Yi-Suo; Fan, Ting; Qiao, Xiao; Zhang, Peng-Fei; Ren, Xiao-Bo

2010-06-01

In this article, poly( N-methyl acryloylglycine methyl ester) (PNMAME) was prepared as a novel thermosensitive material with a lower critical solution temperature (LCST) at around 49.5°C. The chemical structures of the monomer NMAME and PNMAME were characterized by 1H NMR and IR measurements. The LCST was investigated systematically as a function of PNMAME concentration, inorganic salt solution and pH value. The results indicated that LCST of PNMAME was obviously dependent on PNMAME concentration and pH. The LCST was increased with a decrease in pH value and PNMAME concentration. To obtain a thermo-sensitive hydrogel with the phase transition temperature close to human body temperature, the copolymerization was conducted between NMAME and N-acryloylglycine ethyl ester (NAGEE). The release behavior of caffeine was evaluated at different temperatures and contents of cross-linkers ( N, N-methylenebis(acrylamide) (NMBA)). The increase of cross-linker content led to a decrease in the release rate of caffeine due to higher crossing density in the hydrogel network. In addition, a faster release of caffeine from the hydrogel with 3% NMBA at 37°C was found in contrast to that at 18°C.

Estrogenic reduction of styrene monomer degraded by Phanerochaete chrysosporium KFRI 20742.

PubMed

Lee, Jae-Won; Lee, Soo-Min; Hong, Eui-Ju; Jeung, Eui-Bae; Kang, Ha-Young; Kim, Myung-Kil; Choi, In-Gyu

2006-04-01

The characteristic biodegradation of monomeric styrene by Phanerochaete chrysosporium KFRI 20742, Trametes versicolor KFRI 20251 and Daldinia concentrica KFRI 40-1 was carried out to examine the resistance, its degradation efficiency and metabolites analysis. The estrogenic reduction effect of styrene by the fungi was also evaluated. The mycelium growth of fungi differentiated depending on the concentration levels of styrene. Additionally P. chrysosporium KFRI 20742 showed superior mycelium growth at less than 200 mg/l, while D. concentrica KFRI 40-1 was more than 200 mg/l. The degradation efficiency reached 99% during one day of incubation for all the fungi. Both manganese-dependent peroxidase and laccase activities in liquid medium were the highest at the initial stage of incubation, whereas the lowest was after the addition of styrene. However, both activities were gradually recovered after. The major metabolites of styrene by P. chrysosporium KFRI 20742 were 2-phenyl ethanol, benzoic acid, cyclohexadiene-1,4-dione, butanol and succinic acid. From one to seven days of incubating the fungi, the expression of pS2 mRNA widely known as an estrogen response gene was decreased down to the level of baseline after one day. Also, the estrogenic effect of styrene completely disappeared after treatment with supernatant of P. chrysosporium KFRI 20742 from one week of culture down to the levels of vehicle.

Fabrication and physical properties of transparent poly (methyl-methacrylate)-layered silicate nanocomposites

NASA Astrophysics Data System (ADS)

Vasiliu, Elena

Transparent polymer nanocomposites have promising potential for protective coating applications with improved surface resistance, higher temperature performance and low gas permeability for containers and films. Extremely thin protective layers are required for improved performance of various electronic devices in aviation, aerospace and medical equipment as well as for lenses and fiber optics in optical communications. This research study developed a method for fabricating optically transparent nanocomposites of poly(methyl-methacrylate)(PMMA) and a commercial organically-modified layered silicate CloisiteRTM 6A (C6A). The nanocomposites were produced by dispersing C6A and PMMA separately in a common solvent xylene followed by mixing the two solutions by mechanical stirring and/or ultrasonic agitation and then removing the solvent by evaporation. Processing conditions such as the mixing methods and times and the rates of solvent removal were investigated in order to achieve a high degree of dispersion and exfoliation of C6A in the polymer matrix and produce a nanocomposite material with high optical transparency. Small-angle x-ray scattering (SAXS) was used to monitor the morphology of the C6A after each processing step. Thin films of PMMA/C6A nanocomposites were produced by casting and spraying. SAXS results suggest that C6A was partially exfoliated in the composite material with an average of 2 to 3 platelets per crystallite. Transmission electron microscopy (TEM) confirmed the existence of both exfoliated and intercalated C6A in PMMA. One mm thick discs were obtained by molding the sprayed films. The optical transmission of the nanocomposite films and discs was measured with an UV/VIS spectrometer. The spectroscopic results served to identify the best process for producing PMMA-C6A films of high optical transparency. Even the nanocomposite films containing up to 20 wt.% C6A prepared by this process exhibited optical transmittance in the range of 80 to 90

High temperature concrete composites containing organosiloxane crosslinked copolymers

DOEpatents

Zeldin, A.; Carciello, N.; Kukacka, L.; Fontana, J.

High temperature polymer concrete composites comprising about 10 to 30% by weight of a liquid monomer mixture is described. It consists essentially of an organosiloxane polymer crosslinked with an olefinically unsaturated monomer selected from the group consisting of styrene, methyl methacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate, n-phenylmalimide, divinyl benzene and mixtures thereof. About 70 to 90% by weight of an inert inorganic filler system containing silica sand and portland cement, Fe/sub 2/O/sub 3/, carbon black or mixtures thereof. Optionally a free radical initiator such as di-tert-butyl peroxide, azobisisobyutyronitrile, benzoyl peroxide, lauryl peroxide and other organic peroxides are used to initiate crosspolymerization of the monomer mixture in the presence of the inorganic filler.

Effect of Storage in Distilled Water for Three Months on the Antimicrobial Properties of Poly(methyl methacrylate) Denture Base Material Doped with Inorganic Filler

PubMed Central

Chladek, Grzegorz; Basa, Katarzyna; Mertas, Anna; Pakieła, Wojciech; Żmudzki, Jarosław; Bobela, Elżbieta; Król, Wojciech

2016-01-01

The colonization of poly(methyl methacrylate) (PMMA) denture base materials by pathogenic microorganisms is a major problem associated with the use of prostheses, and the incorporation of antimicrobial fillers is a method of improving the antimicrobial properties of these materials. Numerous studies have demonstrated the initial in vitro antimicrobial effectiveness of this type of material; however, reports demonstrating the stability of these fillers over longer periods are not available. In this study, silver sodium hydrogen zirconium phosphate was introduced into the powder component of a PMMA denture base material at concentrations of 0.25%, 0.5%, 1%, 2%, 4%, and 8% (w/w). The survival rates of the gram-positive bacterium Staphylococcus aureus, gram-negative bacterium Escherichia coli and yeast-type fungus Candida albicans were established after fungal or bacterial suspensions were incubated with samples that had been previously stored in distilled water. Storage over a three-month period led to the progressive reduction of the initial antimicrobial properties. The results of this study suggest that additional microbiological tests should be conducted for materials that are treated with antimicrobial fillers and intended for long-term use. Future long-term studies of the migration of silver ions from the polymer matrix and the influence of different media on this ion emission are required. PMID:28773451

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

Binding of leachable components of polymethyl methacrylate (PMMA) and peptide on modified SPR chip

NASA Astrophysics Data System (ADS)

Szaloki, M.; Vitalyos, G.; Harfalvi, J.; Hegedus, Cs

2013-12-01

Many types of polymers are often used in dentistry, which may cause allergic reaction, mainly methyl methacrylate allergy due to the leachable, degradable components of polymerized dental products. The aim of this study was to investigate the interaction between the leachable components of PMMA and peptides by Fourier-transform Surface Plasmon Resonance (FT SPR). In our previous work binding of oligopeptides (Ph.D.-7 and Ph.D.-12 Peptide Library Kit) was investigated to PMMA surface by phage display technique. It was found that oligopeptides bounded specifically to PMMA surface. The most common amino acids were leucine and proline inside the amino acids sequences of DNA of phages. The binding of haptens, as formaldehyde and methacrylic acid, to frequent amino acids was to investigate on the modified gold SPR chip. Self assembled monolayer (SAM) modified the surface of gold chip and ensured the specific binding between the haptens and amino acids. It was found that amino acids bounded to modified SPR gold and the haptens bounded to amino acids by creating multilayer on the chip surface. By the application of phage display and SPR modern bioanalytical methods the interaction between allergens and peptides can be investigated.

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.

Comparison of the uptake of methacrylate-based nanoparticles in static and dynamic in vitro systems as well as in vivo.

PubMed

Rinkenauer, Alexandra C; Press, Adrian T; Raasch, Martin; Pietsch, Christian; Schweizer, Simon; Schwörer, Simon; Rudolph, Karl L; Mosig, Alexander; Bauer, Michael; Traeger, Anja; Schubert, Ulrich S

2015-10-28

Polymer-based nanoparticles are promising drug delivery systems allowing the development of new drug and treatment strategies with reduced side effects. However, it remains a challenge to screen for new and effective nanoparticle-based systems in vitro. Important factors influencing the behavior of nanoparticles in vivo cannot be simulated in screening assays in vitro, which still represent the main tools in academic research and pharmaceutical industry. These systems have serious drawbacks in the development of nanoparticle-based drug delivery systems, since they do not consider the highly complex processes influencing nanoparticle clearance, distribution, and uptake in vivo. In particular, the transfer of in vitro nanoparticle performance to in vivo models often fails, demonstrating the urgent need for novel in vitro tools that can imitate aspects of the in vivo situation more accurate. Dynamic cell culture, where cells are cultured and incubated in the presence of shear stress has the potential to bridge this gap by mimicking key-features of organs and vessels. Our approach implements and compares a chip-based dynamic cell culture model to the common static cell culture and mouse model to assess its capability to predict the in vivo success more accurately, by using a well-defined poly((methyl methacrylate)-co-(methacrylic acid)) and poly((methyl methacrylate)-co-(2-dimethylamino ethylmethacrylate)) based nanoparticle library. After characterization in static and dynamic in vitro cell culture we were able to show that physiological conditions such as cell-cell communication of co-cultured endothelial cells and macrophages as well as mechanotransductive signaling through shear stress significantly alter cellular nanoparticle uptake. In addition, it could be demonstrated by using dynamic cell cultures that the in vivo situation is simulated more accurately and thereby can be applied as a novel system to investigate the performance of nanoparticle systems in vivo

Influence of temperature on styrene emission from a vinyl ester resin thermoset composite material.

PubMed

Crawford, Shaun; Lungu, Claudiu T

2011-08-15

Composite materials made with vinyl ester resins are lighter, stronger and corrosion resistant compared to most metals, and are increasingly being used as building materials and in public transportation. Styrene monomer is used as both a diluent and strengthener in the production of vinyl ester resin (VER) composites. Some researchers contend that free styrene in VER composites is available to diffuse out of the material into air, perhaps leading to adverse health effects via inhalation exposures in humans, yet there is no known data on styrene emissions from these materials in the literature. In this study, a typical VER composite made with resin containing 38% by weight styrene, reinforced with E-glass fiber and formed using a vacuum assisted resin transfer method was characterized for styrene emissions by environmental test chamber (ETC) methodology. Styrene concentrations in the ETC were measured over a temperature range of 10 to 50 °C. Initial evaporative styrene emissions increase with increasing temperature. There is a nearly linear relationship in the total mass of styrene emitted and emission factor as emissions increase with increasing temperature. Styrene emission factors appear to vary for different materials, which could indicate more complex processes or the influence of material physical properties on emission rates. These results can be used to validate and improve mass transfer emission models for the prediction of volatile organic compound concentrations in indoor environments. Published by Elsevier B.V.

EVALUATION OF TRICKLE-BED AIR BIOFILTER PERFORMANCE FOR STYRENE REMOVAL

EPA Science Inventory

A pilot-scale trickle-bed air biofilter (TBAB) was evaluated for the removal of styrene from a waste gas stream. Six-millimeter (6 mm) Celite pellets (R-635) were used as the biological attachment medium. The operating parameters considered in the study included the styrene vol...

Company-level, semi-quantitative assessment of occupational styrene exposure when individual data are not available.

PubMed

Kolstad, Henrik A; Sønderskov, Jette; Burstyn, Igor

2005-03-01

In epidemiological research, self-reported information about determinants and levels of occupational exposures is difficult to obtain, especially if the disease under study has a high mortality rate or follow-up has exceeded several years. In this paper, we present a semi-quantitative exposure assessment strategy for nested case-control studies of styrene exposure among workers of the Danish reinforced plastics industry when no information on job title, task or other indicators of individual exposure were readily available from cases and controls. The strategy takes advantage of the variability in styrene exposure level and styrene exposure probability across companies. The study comprised 1522 cases of selected malignancies and neurodegenerative diseases and controls employed in 230 reinforced plastics companies and other related industries. Between 1960 and 1996, 3057 measurements of styrene exposure level obtained from 191 companies, were identified. Mixed effects models were used to estimate expected styrene exposure levels by production characteristics for all companies. Styrene exposure probability within each company was estimated for all but three cases and controls from the fraction of laminators, which was reported by a sample of 945 living colleagues of the cases and controls and by employers and dealers of plastic raw materials. The estimates were validated from a subset of 427 living cases and controls that reported their own work as laminators in the industry. We computed styrene exposure scores that integrated estimated styrene exposure level and styrene exposure probability. Product (boats), process (hand and spray lamination) and calendar year period were the major determinants of styrene exposure level. Within-company styrene exposure variability increased by calendar year and was accounted for when computing the styrene exposure scores. Exposure probability estimates based on colleagues' reports showed the highest predictive values in the

Backfilling-Free Strategy for Biopatterning on Intrinsically Dual-Functionalized Poly[2-Aminoethyl Methacrylate-co-Oligo(Ethylene Glycol) Methacrylate] Films.

PubMed

Lee, Bong Soo; Lee, Juno; Han, Gyeongyeop; Ha, EunRae; Choi, Insung S; Lee, Jungkyu K

2016-07-20

We demonstrated protein and cellular patterning with a soft lithography technique using poly[2-aminoethyl methacrylate-co-oligo(ethylene glycol) methacrylate] films on gold surfaces without employing a backfilling process. The backfilling process plays an important role in successfully generating biopatterns; however, it has potential disadvantages in several interesting research and technical applications. To overcome the issue, a copolymer system having highly reactive functional groups and bioinert properties was introduced through a surface-initiated controlled radical polymerization with 2-aminoethyl methacrylate hydrochloride (AMA) and oligo(ethylene glycol) methacrylate (OEGMA). The prepared poly(AMA-co-OEGMA) film was fully characterized, and among the films having different thicknesses, the 35 nm-thick biotinylated, poly(AMA-co-OEGMA) film exhibited an optimum performance, such as the lowest nonspecific adsorption and the highest specific binding capability toward proteins. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

40 CFR 721.3800 - Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene...

Code of Federal Regulations, 2010 CFR

2010-07-01

... polyoxyethylene fatty acid, ester with styrenated phenol, ethylene oxide adduct. 721.3800 Section 721.3800... Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene oxide adduct. (a... generically as formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene...

Utilization of Methacrylates and Polymer Matrices for the Synthesis of Ion Specific Resins

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

Czerwinski, Kenneth

2013-10-29

Disposal, storage, and/or transmutation of actinides such as americium (Am) will require the development of specific separation schemes. Existing efforts focus on solvent extraction systems for achieving suitable separation of actinide from lanthanides. However, previous work has shown the feasibility of ion-imprinting polymer-based resins for use in ion-exchange-type separations with metal ion recognition. Phenolic-based resins have been shown to function well for Am-Eu separations, but these resins exhibited slow kinetics and difficulties in the imprinting process. This project addresses the need for new and innovative methods for the selective separation of actinides through novel ion-imprinted resins. The project team willmore » explore incorporation of metals into extended frameworks, including the possibility of 3D polymerized matrices that can serve as a solid-state template for specific resin preparation. For example, an anhydrous trivalent f-element chain can be formed directly from a metal carbonate, and methacrylic acid from water. From these simple coordination complexes, molecules of discrete size or shape can be formed via the utilization of coordinating ligands or by use of an anionic multi-ligand system incorporating methacrylate. Additionally, alkyl methyl methacrylates have been used successfully to create template nanospaces, which underscores their potential utility as 3D polymerized matrices. This evidence provides a unique route for the preparation of a specific metal ion template for the basis of ion-exchange separations. Such separations may prove to be excellent discriminators of metal ions, even between f-elements. Resins were prepared and evaluated for sorption behavior, column properties, and proton exchange capacity.« less

Polymerization of styrene with cyclopentadienyl nickel complex/methylaluminoxane

NASA Astrophysics Data System (ADS)

Yu, Dongping; Zhang, Danfeng

2017-09-01

Polystyrene was synthesized by Cp(CH2CH2OCH3)NiCl(PPh3) in the presence of methylaluminoxane (MAO). This complex displayed a very high activity for styrene polymerization up to 107 g.mol-1Nih-1. 76.6% styrene was converted to polystyrene (PS) with an average molecular (Mn) of 1.13×105 at 50 °C in 30 min. The structure of the obtained polymer was characterized by 1H NMR and FT-IR.

Occupational styrene exposure for twelve product categories in the reinforced-plastics industry.

PubMed

Lemasters, G K; Carson, A; Samuels, S J

1985-08-01

Approximately 1500 occupational styrene exposure values from 28 reinforced-plastic manufacturers were collected retrospectively from companies and state and federal agencies. This report describes the major types of manufacturing processes within the reinforced-plastics industry and reports on the availability, collection and analysis of historical exposure information. Average exposure to styrene in most open-mold companies (24-82 ppm) was generally 2-3 times the exposure in press-mold companies (11-26 ppm). Manufacturers of smaller boats had mean styrene exposures of 82 ppm as compared to 37 ppm for yacht companies. There was considerable overlap in styrene exposure among job titles classified as directly exposed within open- and press-mold processing.

POTENTIAL FOR REDUCING STYRENE EXPOSURES FROM COPIED PAPER THROUGH USE OF LOW-EMITTING TONERS

EPA Science Inventory

The paper reports results of tests, conducted using 53-L chambers to determine styrene emission rates from freshly copied paper produced on a single photocopier using two toners manufactured for the copier having different styrene contents. Copied-paper styrene emissions with bot...

A general theory of kinetics and thermodynamics of steady-state copolymerization.

PubMed

Shu, Yao-Gen; Song, Yong-Shun; Ou-Yang, Zhong-Can; Li, Ming

2015-06-17

Kinetics of steady-state copolymerization has been investigated since the 1940s. Irreversible terminal and penultimate models were successfully applied to a number of comonomer systems, but failed for systems where depropagation is significant. Although a general mathematical treatment of the terminal model with depropagation was established in the 1980s, a penultimate model and higher-order terminal models with depropagation have not been systematically studied, since depropagation leads to hierarchically-coupled and unclosed kinetic equations which are hard to solve analytically. In this work, we propose a truncation method to solve the steady-state kinetic equations of any-order terminal models with depropagation in a unified way, by reducing them into closed steady-state equations which give the exact solution of the original kinetic equations. Based on the steady-state equations, we also derive a general thermodynamic equality in which the Shannon entropy of the copolymer sequence is explicitly introduced as part of the free energy dissipation of the whole copolymerization system.

Flexible resistive switching device based on poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/poly(4-vinylphenol) (PVP) composite and methyl red heterojunction

NASA Astrophysics Data System (ADS)

Hassan, Gul; Ali, Shawkat; Bae, Jinho; Lee, Chong Hyun

2017-04-01

To obtain a desired performance of non-volatile memory applications, heterojunction-based resistive switching devices have tremendous attractions. In this paper, we demonstrate resistive switching characteristics for heterojunction of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/poly(4-vinylphenol) (PVP) composite and methyl red sandwiched in between bottom and top silver (Ag) electrodes. The proposed heterojunction layers are fabricated through spin coater at 3000 rpm for 60 s each, and the Ag electrodes are deposited through a commercialized inkjet printer DMP-3000 on polyethyleneterephthalate (PET) substrate. To verify the proposed device, the resistive switching on dual polarity voltage of ±10.2 V is measured over more than 500 endurance cycles. The paper also presents an R off/ R on ratio which can adjust through an active layer's area and a blending ratio of the PEDOT:PSS and PVP. By applying the area of 100 μm2 and the blending ratio of 3:1, we achieve the higher R off/ R on ratio of 121, and its high resistance state (HRS) and low resistance state (LRS) are observed as 3000 kΩ and 24.7 kΩ, respectively. To maintain a long retention time, the device is encapsulated with PDMS, which changes a little variations of 52 Ω for HRS 498 Ω for LRS over 60 days. For the flexible realization to be utilized in wearable applications, it can be easily applied on a plastic substrate using printed technologies.