Simultaneous FT-NIR and ESR analyses to yield propagation rate coefficients for polymerization of methyl methacrylate based monomers

A hyphenated instrumental approach has been used to obtain reliable values for the propagation rate coefficients as a function of conversion for polymerizations of methyl methacrylate (MMA) and a mixture of MMA and ethyleneglycol dimethacrylate (EGDMA) with a 1:1 concentration of double bonds, from near the onset of the Trommsdorf region into the glass region. ESR spectroscopy was used to measure the radical concentration while FT-NIR fibre-optic spectroscopy was employed to measure instantaneously the double-bond concentration within the temperature-controlled cavity of the ESR instrument during polymerization. The advantage of this approach to the measurement of the rate coefficient is that it is equally applicable to branching and linear polymerizations. For the polymerization of methyl methacrylate, the values of the rate coefficient at the lowest conversions at which reliable values could be obtained were in agreement with recently reported values obtained by the PLP-SEC method. For the lowest conversions, the values obtained were 403 1 mol(-1) s(-1) at 306 K for MMA and 5201 mol(-1) s(-1) at 310 K for a 1:1 mixture of MMA and EGDMA. (C) 2003 Society of Chemical Industry.

Biological effects of acrylic engineered particulate-systems

Polymeric particulate-systems are of great relevance due to their possible biomedical applications, among them as carriers for the nano- or microencapsulation of drugs. However, due to their unique specific properties, namely small size range, toxicity issues must be discarded before allowing its use on health-related applications. Several polymers, as poly(methyl methacrylate) (PMMA), have proved to be suitable for the preparation of particulate-systems. However, a major drawback of its use refers to incomplete drug release from particles matrix. Recent strategies to improve PMMA release properties mention the inclusion of other acrylic polymers as Eudragit (EUD) on particles formulation. Though PMMA and EUD are accepted by the FDA as biocompatible, their safety on particle composition lacks sufficient toxicological data. The main objective of this thesis was to evaluate the biological effects of engineered acrylic particulate-systems. Preparation, physicochemical characterization and in vitro toxicity evaluation were assessed on PMMA and PMMA-EUD (50:50) particles. The emulsification-solvent evaporation methodology allowed the preparation of particles with spherical and smooth surfaces within the micrometer range (±500 nm), opposing surface charges and different levels of hydrophobicity. It was observed that particles physicochemical properties (size and charge) were influenced by biological media composition, such as serum concentration, ionic strength or pH. In what concerns to the in vitro toxicological studies, particle cellular uptake was observed on different cell lines (macrophages, osteoblasts and fibroblasts). Cytotoxicity effects were only found after 72 h of cells exposure to the particles, while no oxidative damage was observed neither on osteoblasts nor fibroblasts. Also, no genotoxicity was found in fibroblast using the comet assay to assess DNA damage. This observation should be further confirmed with other validated genotoxicity assays (e.g. Micronucleus Assay). The present study suggests that the evaluated acrylic particles are biocompatible, showing promising biological properties for potential use as carriers in drug-delivery systems.

Micro- and nanostructuring of poly(ethylene-2,6-naphthalate) surfaces, for biomedical applications, using polymer replication techniques

Here we investigate the formation of superficial micro- and nanostructures in poly(ethylene-2,6-naphthalate) (PEN), with a view to their use in biomedical device applications, and compare its performance with a polymer commonly used for the fabrication of these devices, poly(methyl methacrylate) (PMMA). The PEN is found to replicate both micro- and nanostructures in its surface, albeit requiring more forceful replication conditions than PMMA, producing a slight increase in surface hydrophilicity. This ability to form micro/nanostructures, allied to biocompatibility and good optical transparency, suggests that PEN could be a useful material for production of, or for incorporation into, transparent devices for biomedical applications. Such devices will be able to be autoclaved, due to the polymer's high temperature stability, and will be useful for applications where forceful experimental conditions are required, due to a superior chemical resistance over PMMA.

Photoconductivity in molecularly doped poly (methylmethacrylate) sandwich cells

Poly(methyl)methacrylate was made photoconducting by molecular doping and the photoconductivity was investigated using modulated photocurrent technique . Low-temperature current-voltage measurements showed that the transport mechanism was thermally activated hopping. An experimental investigation of the photoconductivity action spectrum along with theoretical calculation enabled an estimation of the diffusion coefficient of the material. The presence of states with a distribution of lifetimes could be understood from the frequency response of the photocurrent . The photocurrent was due to the field-assisted dissociation of these states

Photoconductivity in Molecularly Doped Poly (methylmethacrylate)Sandwich Cells

Poly(methyl)methacrylate was made photoconducting by molecular doping and the photoconductivity was investigated using modulated photocurrent technique . Low-temperature current-voltage measurements showed that the transport mechanism was thermally activated hopping. An experimental investigation of the photoconductivity action spectrum along with theoretical calculation enabled an estimation of the diffusion coefficient of the material. The presence of states with a distribution of lifetimes could be understood from the frequency response of the photocurrent . The photocurrent was due to the field-assisted dissociation of these states.

Excitation wavelength dependence of energy transfer in dye mixture doped polymer optical fibre preforms

Dependence of energy transfer parameters on excitation wavelength has been investigated in poly (methyl methacrylate) (PMMA) optical fibre preforms doped with C 540:Rh B dye mixture by studying the fluorescence intensity and the lifetime variations. A fluorescence spectrophotometer was used to record the excitation spectra of the samples for the emission wavelengths 495 and 580 nm. The fluorescence emission from the polymer rods was studied at four specific excitation wavelengths viz; 445, 465, 488 and 532 nm. The fluorescence lifetime of the donor molecule was experimentally measured in polymer matrix by time correlated single photon counting technique. The energy transfer rate constants and transfer efficiencies were calculated and their dependence on the acceptor concentration was analysed for three excitation wavelengths. It was found that any change in the excitation wavelength leads to significant variations in the quenching characteristics, which in turn affect the calculated energy transfer parameters.

Ordering on multiple lengthscales in a series of side group liquid crystal block copolymers containing a cholesteryl-based mesogen

Hierarchical ordering in a side group liquid crystal block copolymer is investigated by differential scanning calorimetry, polarized optical microscopy, small-angle X-ray and neutron scattering (SAXS and SANS) and transmission electron microscopy (TEM). A series of block copolymers with a range of compositions was prepared by atom transfer radical polymerization, comprising a polystyrene block and a poly(methyl methacrylate) block bearing chiral cholesteryl mesogens. Smectic ordering is observed as well as microphase separation of the block copolymer. Lamellar structures were observed for far larger volume fractions than for coil-coil copolymers (up to a volume fraction of liquid crystal block, f(LC) = 0.8). A sample with f(LC) = 0.86 exhibited a hexagonal-packed cylinder morphology, as confirmed by SAXS and TEM. The matrix comprised the liquid crystal block, with the mesogens forming smectic layers. For the liquid crystal homopolymer and samples with high f(LC), a smectic-smectic phase transition was observed below the clearing point. At low temperature, the smectic phase comprises coexisting domains with monolayer S-A,S-1 coexisting with interdigitated S-A,S-d domains. At high temperature a SA,1 phase is observed. This is the only structure observed for samples with lower f(LC). These unprecedented results point to the influence of block copolymer microphase separation on the smectic ordering.

Miscibility studies in poly(methyl vinyl ether)/hydroxypropylcellulose binary system in aqueous solutions and solid state

The phase separation behaviour in aqueous mixtures of poly(methyl vinyl ether) and hydroxypropylcellulose has been studied by cloud points method and viscometric measurements. The miscibility of these blends in solid state has been assessed by infrared spectroscopy; methanol vapours sorption experiments and scanning electron microscopy. The values of Gibbs energy of mixing of the polymers and their blends with methanol as well as between each other were calculated. It was found that in solid state the polymers can interact with methanol very well but the polymer-polymer interactions are unfavourable. Although in aqueous solutions the polymers exhibit some intermolecular interactions their solid blends are not completely miscible. (C) 2005 Elsevier Ltd. All rights reserved.

Desevolvimento de nanocompósitos de poli(metacrilato de metila)/argila processados por mistura no estado fundido

Poly(methyl methacrylate)/clay nanocomposites were prepared by melt mixing using a montmorillonite-rich clay (MMT). The clay in natura was treated with acrylic acid to facilitate the dispersion in the polymer matrix. A masterbatch of PMMA/clay was prepared and combined with the pure PMMA and then subjected to extrusion process using singlescrew and twin-screw extruders followed by injection. Nanocomposites were processed with clay contents of 1, 3, 5 and 8 wt.%. The effect of shear processing on the morphology of the nanocomposites was evaluated by XRD, SEM and TEM. Thermal and mechanical properties of the nanocomposites were investigated through TGA, DSC, HDT, VICAT, tensile and impact tests, to evaluate the effect of the addition of clay to the PMMA matrix. Flammability tests were also conducted to investigate the effect of the addition of clay on the flame retardation properties. SEM images of the nanocomposites indicated the presence of clay agglomerates, which resulted in the reduction of properties such as thermal stability, mechanical strength and impact resistance, and increased the rate of burning for materials processed by both extrusion routes

Processamento e caracterização de compósitos Poli(METACRILATO DE METILA)/Sílica (PMMA/SiO2)

Currently the search for new materials with properties suitable for specific applications has increased the number of researches that aim to address market needs. The poly (methyl methacrylate) (PMMA) is one of the most important polymers of the family of polyacrylates and polymethacrylates, especially for its unique optical properties and weathering resistance, and exceptional hardness and gloss. The development of polymer composites by the addition of inorganic fillers to the PMMA matrix increases the potential use of this polymer in various fields of application. The most commonly used inorganic fillers are particles of silica (SiO2), modified clays, graphite and carbon nanotubes. The main objective of this work is the development of PMMA/SiO2 composites at different concentrations of SiO2, for new applications as engineering plastics. The composites were produced by extrusion of tubular film, and obtained via solution for application to commercial PMMA plates, and also by injection molding, for improved the abrasion and scratch resistance of PMMA without compromising transparency. The effects of the addition of silica particles in the polymer matrix properties were evaluated by the maximum tensile strength, hardness, abrasion and scratch resistance, in addition to preliminary characterization by torque rheometry and melt flow rate. The results indicated that it is possible to use silica particles in a PMMA matrix, and a higher silica concentration produced an increase of the abrasion and scratch resistance, hardness, and reduced tensile strength

Matrizes poliméricas puras e modificadas para adsorção do gás sulfeto de hidrogênio

The underground natural gas found associated or not with oil is characterized by a mixture of hydrocarbons and residual components such as carbon dioxide (CO2), nitrogen gas (N2) and hydrogen sulfide (H2S), called contaminants. The H2S especially promotes itself as a contaminant of natural gas to be associated with corrosion of pipelines, to human toxicity and final applications of Natural Gas (NG). The sulfur present in the GN must be fully or partially removed in order to meet the market specifications, security, transport or further processing. There are distinct and varied methods of desulfurization of natural gas processing units used in Natural Gas (UPGN). In order to solve these problems have for example the caustic washing, absorption, the use of membranes and adsorption processes is costly and great expenditure of energy. Arises on such findings, the need for research to active processes of economic feasibility and efficiency. This work promoted the study of the adsorption of sulfide gas in polymer matrices hydrogen pure and modified. The substrates of Poly(vinyl chloride) (PVC), poly(methyl methacrylate) (PMMA) and sodium alginate (NaALG) were coated with vanadyl phosphate compounds (VOPO4.2H2O), vanadium pentoxide (V2O5), rhodamine B (C28H31N2O3Cl) and ions Co2+ and Cu2+, aiming to the adsorption of hydrogen sulfide gas (H2S). The adsorption tests were through a continuous flow of H2S in a column system (fixed bed reactor) adsorption on a laboratory scale. The techniques used to characterize the adsorbents were Infrared spectroscopy (FTIR), thermogravimetry analysis (TGA), X-ray fluorescence (XRF), the X-ray diffraction (XRD) electron microscopy (SEM). Such work indicates, the results obtained, the adsorbents modified PMMA, PVC and NaALG have a significant adsorptive capacity. The matrix that stood out and had the best adsorption capacity, was to ALG modified Co2+ with a score of 12.79 mg H2S / g matrix

Effect of methyl methacrylate monomer on bond strength of denture base resin to acrylic teeth

Bond failures at the acrylic teeth and denture base resin interface are still a common clinical problem in prosthodontics. The effect of methyl methacrylate (MMA) monomer on the bond strength of three types of denture base resins (Acron MC, Lucitone 550 and QC-20) to two types of acrylic teeth (Biotone and Trilux) was evaluated. Twenty specimens were produced for each denture base resin/acrylic tooth combination and were randomly divided into control (acrylic teeth received no surface treatment) and experimental groups (MMA was applied to the surface of the acrylic teeth for 180 s) and were submitted to shear tests (1 mm/mm). Data (MPa) were analyzed using three-way ANOVA/Student's test (alpha = 0.05). MMA increased the bond strength of Lucitone denture base resins and decreased the bond strength of QC-20. No difference was detected for the bond strength of Acron MC base resin after treatment with MMA. (C) 2008 Elsevier Ltd. All rights reserved.

Fluorescence study of the interaction between metal ions and methyl methacrylate methacrylic acid copolymers in aqueous solutions: thallium(I), calcium(II), and terbium(III)

The binding of the cations thallium(I), calcium(II) and terbium(III) to methyl methacrylate-methacrylic acid copolymers with different fractions of acid groups (x) has been studied in aqueous solution at, various pH values using the fluorescence of covalently bonded 9-vinyl anthracene as a probe. In all cases, the extent of binding increases as a function of the charge of the polymer with either increasing fraction of carboxylic acids or of pH. However, differences are observed in the behavior of the three cations, With Tl(I), quenching of the anthracene group fluorescence is observed. indicating that the thallium(I) approaches the probe and suggesting that the alkylanthracene is probably in a relatively polar region. Binding constants have been determined from anthracene quenching data and from studies with the fluorescent-probe sodium pyrenetetrasulfonate, Good agreement is obtained between the two methods, and values for the binding constants increase from 250 to 950 M-1 as x increases from 0.39 to 1. It is suggested that the cation is held in the polyelectrolyte domain, partly by Debye-Huckel effects and partly by more specific interactions. Stronger binding is found with calcium(II) and terbium(III), and in this case increases in fluorescence intensity are observed on complexation due to the anthracene group being in a more hydrophobic region, probably as a result of conformational changes in the polymer chain. In the former case the stoichiometry of the interaction was determined from the fluorescence data to involve two carboxylate groups bound per calcium. Association constants were found using murexide as an indicator of free calcium to vary from 8400 to 37 000 M-1 as x increases from 0.39 to 1. It is suggested that in this case specific calcium(II)-carboxylate interactions contribute to the binding. With terbium(III), a greater increase in the probe fluorescence intensity was observed than with calcium, and it is suggested that the interaction with the polymer is even stronger, leading to a more pronounced conformational change in the polymer. It is proposed that the terbium(III) interacts with sis carboxylic groups on the polymer chain, with three being coordinated and three attracted by electrostatic interactions.

Morphological, mechanical and rheological properties of nylon 6/acrylonitrile-butadiene-styrene blends compatibilized with MMA/MA copolymers

The morphological, mechanical and rheological properties of nylon 6/acrylonitrile-butadiene-styrene blends compatibilized with MMA-MA [poly(methyl methacrylate-comaleic anhydride)] copolymers were studied. A twin screw extruder was used for melt-blended the polymers and the injection moulding process was used to mold the samples. The main focus was on nylon 6/ ABS blends compatibilized with one MMA-MA copolymer. This copolymer has PMMA segments that appear to be miscible with the styrene-acrylonitrile (SAN) phase of ABS and the anhydride groups can react with amine end groups of the nylon 6 (Ny6) to form graft copolymers at the interface between Ny6 and ABS rich phases. Tensile and impact and morphological properties were enhanced by the incorporation of this copolymer. Transmission electron microscopy (TEM) observations revealed that the ABS domains are finely dispersed in nylon 6 matrix and led to the lowest ductile-brittle transition temperatures and highest impact properties. It can be concluded that the MMA-MA copolymer is an efficient alternative for the reactive compatibilization and can be used as a compatibilizer for nylon 6/ABS blends.© 2003 Kluwer Academic Publishers.

Morphology of Nylon 6/Acrylonitrile-Butadiene-Styrene Blends Compatibilized by a Methyl Methacrylate/Maleic Anhydride Copolymer

The morphologies of nylon 6/acrylonitrile-butadiene-styrene blends compatibilized with a methyl methacrylate/maleic anhydride copolymer, with 3-20 wt % maleic anhydride, were examined by transmission electron microscopy. Some staining techniques were employed for identifying the various phases. The binary blends were immiscible and exhibited poor mechanical properties that stemmed from the unfavorable interactions among their molecular segments. This produced an unstable and coarse phase morphology and weak interfaces among the phases in the solid state. The presence of the copolymer in the blends clearly led to a more efficient dispersion of the acrylonitrile-butadiene-styrene phase and consequently optimized Izod impact properties. © 2003 Wiley Periodicals, Inc.