Methyl Acrylate Copolymers Research Articles

PH-responsive dual pulse multiparticulate dosage form for treatment of rheumatoid arthritis

Background: Dual pulse multiparticulate systems may provide relief from circadian disorder rheumatoid arthritis. Aim: The aim of this study was to develop a pH-responsive dual pulse multiparticulate dosage form containing a model drug ketoprofen, a nonsteroidal anti-inflammatory drug used for rheumatoid arthritis. Method: The pellets were prepared by using extrusion–spheronization method and the core pellets were coated with a pH-sensitive poly(methyl) acrylate copolymer (Eudragit® L100-55, Eudragit® S100) to achieve site-specific drug release with a lag time. The formulated pellets were characterized for shape and size uniformity, friability, surface morphology studies, coating uniformity, and drug–excipient compatibility studies. In vitro dissolution test was used for comparison of drug release profiles of various coated pellets. Results: The particle size of core and polymer-coated pellets was found to be in the range of 0.95–1.3 and 1.42–1.61 mm, respectively. The pellets were spherical in shape with smooth texture and uniformity in size. The dual pulse was aimed at release after a lag time of 2 and 5 hours. In vitro dissolution tests were carried out for the first and second dose pellets in a USP type II dissolution apparatus in media-simulating pH conditions of the gastrointestinal tract. The first dose release of the ketoprofen from the formulated pellets was established in pH 1.2 for a period of 2 hours, followed by pH 6.8. The second dose pellets were passed through pH 1.2, pH 6.8 followed by pH 7.5 for the rest of the study. Conclusion: The study concluded that the formulated multiparticulate dosage form of ketoprofen was able to relieve circadian symptoms of rheumatoid arthritis during midnight and early morning.

The influence of solution‐state conditions and stirring rate on the assembly of poly(acrylic acid)‐containing amphiphilic triblock copolymers with multi‐amines

AbstractIn the effort towards making nanoscale objects and assemblies feasible for use as functional materials, it is imperative to obtain control over the fundamental architectures and essential to understand what experimental conditions cause the manifestation of specific morphologies. A number of factors are known to influence the shape during the self‐assembly of amphiphilic block copolymers in solution, including solvent composition, polymer length, hydrophobicity versus hydrophilicity, as well as the addition of additives that can interact with segments of the block copolymers. This research, focused on developing an understanding of the micellar architectures accessed by the amphiphilic triblock copolymer of acrylic acid, methyl acrylate, and styrene, PAA85‐b‐PMA40‐b‐PS35, as a function of the stirring rate, together with other factors, when undergoing coassembly with ethylenediamine or diethylenetriamine in water/tetrahydrofuran solutions. The work demonstrates that the rate at which the polymer solution was stirred impacts the shape of the solution‐state assemblies formed by the triblock copolymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

In-Situ Direct Mechanistic Transformation from RAFT to Living Cationic Polymerization for (Meth)acrylate−Vinyl Ether Block Copolymers

In-situ direct mechanistic transformation from living radical to cationic polymerization was investigated using a trithiocarbonate-type reversible addition−fragmentation chain-transfer (RAFT) agent and an azo-initiator for RAFT polymerization of (meth)acrylates followed by the addition of a Lewis acid catalyst for the sequential living cationic block polymerization of vinyl ethers. Prior to the mechanistic transformation reaction, the possibility of living cationic polymerization was examined via activation of the thioester bond by Lewis acids, such as SnCl4, EtAlCl2, and ZnCl2. The CH3CH(OiBu)SC(S)SEt/SnCl4-initiating system induced living cationic polymerization of isobutyl vinyl ether (IBVE) in the presence of ethyl acetate (EtOAc) as an additive in toluene at 20 °C to give polymers with controlled molecular weights and narrow molecular weight distributions (MWDs) (Mw/Mn = 1.18). The RAFT copolymerization of methyl acrylate (MA) or methacrylate (MMA) and IBVE was then first carried out using (CH3)2C(CN...

Poly(acrylonitrile-co-methyl acrylate) copolymers: Correlation between copolymer composition, morphology and positron annihilation lifetime parameters

A series of poly(acrylonitrile-co-methyl acrylate) copolymers of differing copolymer compositions are synthesized through free radical emulsion copolymerisation of methyl acrylate (MA) and acrylonitrile (AN) and by variation of the monomer feed ratios. The copolymers are characterized by NMR, SEC, WAXD, DMA, and positron annihilation lifetime spectroscopy. Results show that, there is a linear decrease in the glass transition temperature (Tg) of the copolymers and the MA content. There is also a progressive decrease in the crystallinity of the copolymers with increasing MA content. Positron results show a sigmoidal variation in the ortho positronium lifetime with an increasing MA content. The low MA content, semi-crystalline copolymers show a positive deviation from the linear additive relationship between the o-Ps lifetime and MA content, whereas the higher MA content amorphous copolymers show a negative deviation from the linear additive behavior. The o-PS intensity shows a linear behavior with MA content with a slight deviation from the additive linear behavior for the very high-content MA copolymer. These variations in the measured positron lifetime parameters are interpreted in terms of the copolymer morphology. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Characterization of Electron Beam Irradiated Ethylene Methyl Acrylate Copolymer

The effect of electron beam dose on the mechanical, thermal, and electrical properties over ethylene methylacrylate (EMA) copolymer was investigated. The copolymer (Elvaloy 1224) was subjected to electron beam radiation at different doses for cross-linking, with the incorporation of the sensitizer trimethylolpropane trimethacrylate (TMPTMA) at various levels. It was observed that the mechanical properties reached an optimum level around 60 kGy radiation dose and 1 phr sensitizer. Beyond that, an increase in irradiation dose or sensitizer level contributed little to modify the properties further. These observations were supported from spectral studies. Improved thermal behavior was observed from the thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) thermograms. The electrical properties were affected very little by irradiation.

Metal-Catalyzed Simultaneous Chain- and Step-Growth Radical Polymerization: Marriage of Vinyl Polymers and Polyesters

All polymerization reactions are categorized into two large different families, chain- and step-growth polymerizations, which are typically incompatible. Here, we report the simultaneous chain- and step-growth polymerization via the metal-catalyzed radical copolymerization of conjugated vinyl monomers and designed monomers possessing unconjugated C horizontal lineC and active C-Cl bonds. Especially, almost ideal linear random copolymers containing both vinyl polymer and polyester units in a single polymer chain were formed by the CuCl/1,1,4,7,10,10-hexamethyltriethylenetetramine- or RuCp*Cl(PPh(3))(2)-catalyzed copolymerization of methyl acrylate (MA) for the chain-growth polymerization and 3-butenyl 2-chloropropionate (1) for the step-growth polymerization. In contrast, other transition metal catalysts, such as CuCl with tris[2-(dimethylamino)ethyl]amine or N,N,N',N'',N''-pentamethyldiethylenetriamine and FeCl(2)/PnBu(3), resulted in branched structures via the concomitant chain-growth copolymerization of 1 with MA. The polymerization mechanism was studied in detail by NMR and MALDI-TOF-MS analyses of the polymerizations as well as the model reactions. Furthermore, a series of copolymers changing from random to multiblock polymer structures were obtained by varying the feed ratios of the two monomers. These copolymers can be easily degraded into lower molecular weight oligomers or polymers via methanolysis of the ester-linkages in the main chain using sodium carbonate.

Synthesis of graft copolymers from a linear polyolefin through a combination of coordination polymerization and atom transfer radical polymerization

AbstractThis article reports on a facile route for the preparation of methyl acrylate and methyl methacrylate graft copolymers via a combination of catalytic olefin copolymerization and atom transfer radical polymerization (ATRP). The chemistry first involved a transforming process from ethylene/allylbenzene copolymers to a polyolefin multifunctional macroinitiator with pendant sulfonyl chloride groups. The key to the success of the graft copolymerization was ascribed to a fast exchange rate between the dormant species and active radical species by optimization of the various experimental parameters. Polyolefin‐g‐poly(methyl methacrylate) and polyolefin‐g‐poly(methyl acrylate) graft copolymers with controlled architecture and various graft lengths were, thus, successfully prepared under dilute ATRP conditions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Engineering properties of electron beam‐crosslinked ethylene methyl acrylate copolymer

AbstractEffect of electron beam on mechanical, thermal, and morphological properties of ethylene methyl acrylate copolymer, grade Elvaloy 1335 has been investigated. The copolymer was subjected to varying doses of electron beam radiation with different proportion of the sensitizer trimethylolpropane trimethacrylate (TMPTMA). It was observed that with increase in electron beam dose, the physicomechanical properties of the crosslinked copolymer improve, reaches an optimum level and subsequently deteriorates. The thermal properties as envisaged from thermogravimetric analysis and differential scanning calorimetric studies revealed stability of the crosslinked irradiated samples over that of the unirradiated ones. The thermal stability was also found to attain the maximum at the same level of radiation and sensitizer. The morphological studies showed consistency with the mechanical properties. Based on the overall study, it may be concluded that ethylene methyl acrylate copolymer with 1 phr TMPTMA at 60 kGy radiation dose is the optimum condition within the range studied in this investigation. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

The effect of surface roughness on adhesive properties of acrylate copolymers

The effect of surface roughness on the adhesive properties of statistical, uncrosslinked butyl acrylate–methyl acrylate copolymers with different molecular weights ( M w=54 000, 192 000, and 600 000 g/mol) has been investigated using a combination of probe tack test and simultaneous video-optical imaging. Steel probes with different average surface roughnesses ( R a=2.9, 41.2, and 291.7 nm) have been used. The debonding process in a tack experiment is mainly controlled by the viscoelastic properties of the polymer, which control deformation and break of fibrils. However, increasing the probe surface roughness leads to a decrease of the maximum force during debonding and, correspondingly, the work of adhesion in a tack experiment decreases. Surface roughness has a strong effect on the initial cavitation process. The total number of cavities increases with increase in roughness, while their size decreases. The number of cavities increases slowly at the beginning of debonding, then rapidly increases as the force increases, and finally levels off, when the maximum force is reached. Two types of cavities are observed during debonding. Cavities of the first type appear at the beginning of debonding and their size increases slowly, while cavities of the second type appear at a higher stress level, when peak in force is approached, and their growth rate is about five times higher than that of cavities of the first type. Cavities even grow when the force has passed its maximum and eventually stop growing when the characteristic stress plateau is reached. Nevertheless, the growth rate for both cavity types is found to be independent of the surface roughness, but it is controlled by the viscoelastic properties of the polymers used and, accordingly, it decreases significantly with increase in molecular weight.

High‐Strain Shape‐Memory Polymers

AbstractShape‐memory polymers (SMPs) are self‐adjusting, smart materials in which shape changes can be accurately controlled at specific, tailored temperatures. In this study, the glass transition temperature (Tg) is adjusted between 28 and 55 °C through synthesis of copolymers of methyl acrylate (MA), methyl methacrylate (MMA), and isobornyl acrylate (IBoA). Acrylate compositions with both crosslinker densities and photoinitiator concentrations optimized at fractions of a mole percent demonstrate fully recoverable strains at 807% for a Tg of 28 °C, at 663% for a Tg of 37 °C, and at 553% for a Tg of 55 °C. A new compound, 4,4′‐di(acryloyloxy)benzil (referred to hereafter as Xini) in which both polymerizable and initiating functionalities are incorporated in the same molecule, was synthesized and polymerized into acrylate shape‐memory polymers, which were thermomechanically characterized yielding fully recoverable strains above 500%. The materials synthesized in this work were compared to an industry standard thermoplastic SMP, Mitsubishi's MM5510, which showed failure strains of similar magnitude, but without full shape recovery: residual strain after a single shape‐memory cycle caused large‐scale disfiguration. The materials in this study are intended to enable future applications where both recoverable high‐strain capacity and the ability to accurately and independently position Tg are required.

Effect of boric acid on thermal stability of poly (acrylonitrile-methyl acrylate)

AbstractA series of acrylonitrile(AN)-methyl acrylate (MA) copolymers (AN/MA) with molar ratios of 100/0-70/30 were synthesized by water depositing polymerization. One to three percent of boric acid (BA) was adopted as a stabilizer to enhance the thermal stability of AN/MA. The copolymers and the mixtures of copolymers treated with BA were characterized by using Fourier Transform Infrared Spectroscopy (FTIR), Nuclear Magnetic Resonance (1H NMR), Gel Permeation Chromatography (GPC), Differential Scanning Calorimetry (DSC), Thermogravimetry (TG), X-ray diffraction (XRD) and Optic Microscope. The results show that melting point (Tm), glass transition temperature (Tg) and crystallinity of the copolymer decreased while decomposition temperature (Td) increased with the increase of MA content. Tm of AN/MA dropped to 174 °C and Td rose up to 321 °C when 15 mol% MA was incorporated. It was worthy to note that Tm of the copolymers increased conspicuously after being treated with BA. Stability of AN/MA with a molar ratio of 85/15 containing 1 wt% BA improved remarkably. The mixture can be kept stable up to 30 min at 220 °C.

Interface localization of carbon nanotubes in blends of two copolymers

The localization of unpurified and unfunctionalized multiwall carbon nanotubes (MWNTs) in an immiscible polymer blend has been studied. The sea-island morphology of ternary blends of a copolyamide 6/12 (PA6/12), a copolymer of ethylene and methyl acrylate (EMA) and MWNTs was studied by SEM and TEM. Depending on the mixing sequence, the MWNTs are localized either in the PA phase or at the interface. The localization of the MWNTs is determined both by the thermodynamics of the minimization of the interfacial energies and by a partial (irreversible) adsorption of the macromolecules of the first copolymer in contact with the MWNTs during the mixing step. The adsorption phenomenon is proved by TGA, EELS, modification of the MWNTs and decantation tests. It is attributed to non-covalent and non-specific interactions occurring between the CH groups of the polymers and the MWNTs.

Synthesis of porous acrylonitrile/methyl acrylate copolymer beads by suspended emulsion polymerization and their adsorption properties after amidoximation

Porous acrylonitrile (AN)/methyl acrylate (MA) copolymer beads were prepared by suspended emulsion polymerization. The cyano groups in AN/MA copolymer beads were converted to amidoxime (AO) groups by reaction with hydroxylamine hydrochloride (NH(2)OH.HCl) to remove metal ions in aqueous solution. The untreated AN/MA and amidoximated AN/MA (AO AN/MA) copolymer beads were characterized by FTIR spectroscopy, SEM, and porous structural analysis. Both mesopores and macropores were presented in AN/MA and AO AN/MA copolymer beads. Qualitative experiments of adsorption were conducted to evaluate modified and unmodified resins on fixing Hg(2+), Ag(+), Cu(2+), Fe(3+) and Pb(2+) from aqueous solution using batch extractions. It was found that AO AN/MA copolymer beads have excellent adsorption capacities for Hg(2+), Ag(+) and Cu(2+), especially for Hg(2+), and it have good selectivity for Hg(2+). The equilibrium was established in 10h through adsorption kinetics study. The Langmuir model was much better than the Freundlich model to describe the isothermal process.

Thermal and mechanical properties of polymer‐nanocomposites based on ethylene methyl acrylate and multiwalled carbon nanotube

AbstractThe ethylene methyl acrylate copolymer (EMA) and multiwalled carbon nanotube (MWNT) based composites were prepared by solution mixing as well as by melt processing of the films obtained after solution mixing. Field emission scanning electron microscopy, transmission electron microscopy, and XRD were used to characterize morphologies of various composites. MWNTs were found to be more dispersed in the composites prepared by melt process after solution process. There was no obvious agglomeration of MWNTs at lower % loading (up to 2.5%) in the polymer matrices especially the composites are prepared solution plus melt mixing and consequently better interaction between MWNTs and EMA matrix was anticipated. XRD and differential scanning calorimetry studied showed that the nanotubes affect the crystallization process and subsequently their role as a nucleating agent was established. These are reflected in the mechanical properties of the composites. Dynamic mechanical analysis showed that the storage modulus of the composites drop very sharply beyond 2.5 wt% of MWNT content with increasing % strain and it reflects the Payne effect (a substantial decrease in the storage modulus of a particle‐reinforced polymer with an increase in the amplitude of dynamic oscillations). The influence of concentration of filler was also realized by frequency sweep experiment. The incorporation of MWNTs in EMA offered a stabilizing effect since onset of degradation occurs at higher temperatures for composites. POLYM. COMPOS., 31:1168–1178, 2010. © 2009 Society of Plastics Engineers

High selective purification of flavonoids from natural plants based on polymeric adsorbent with hydrogen-bonding interaction

The efficient purification method of high purity flavonoids from natural plants was reported. A series of polymeric adsorbents with novel structure were synthesized based on the copolymerization of methyl acrylate (MA) and ethylene glycol dimethacrylate (EDGMA). Functional groups, such as ester, amino or amide group, were introduced into the adsorbent matrix, respectively, to produce the hydrogen-bonding interaction and enhance the adsorption selectivity towards flavone compounds. The influences of matrix structure and functional groups of synthesized adsorbents on the adsorption selectivity were investigated. The resins were applied to purify flavonoids in natural plants. It was illuminated that the adsorbent No. 3B with 15% EGDMA content and amide groups performed optimal selectivity to flavone compounds in Scutellaria barbata D.Don, from which the purity of flavonoids in extracts was obtained more than 50%, obviously higher than that from commercial adsorbents. The result of adsorption thermodynamics experiment showed that the isosteric adsorption enthalpy of No. 3B was in the range of 25–30 kJ/mol, which testified that the adsorption mechanism was related to hydrogen-bonding interaction. The method showed its universality via good effects on the purification of total flavonoids from Ginkgo biloba L., Radix puerariae and Hypericum perforatum L.

Melt-processable acrylonitrile–methyl acrylate copolymers and melt-spun fibers containing MicroPCMs

Acrylonitrile–methyl acrylate (AN–MA molar ratio 85/15) copolymer and copolymers containing 5–25 wt% of microencapsulated phase change materials (MicroPCMs) were synthesized by aqueous redox initiated polymerization. MicroPCMs were incorporated into the copolymer at the step of polymerization. The copolymers were processed by environment friendly, solvent-free melt-spinning. The structures and properties of the copolymers and as-spun fibers containing MicroPCMs were characterized by Nuclear Magnetic Resonance (1H NMR), Gel Permeation Chromatography (GPC), Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TG), Scanning Electronic Microscope (SEM), X-ray Diffraction (XRD), and Melting Index (MI). The results show that the composition of AN–MA copolymer agrees well with the feeding ratio of AN and MA. The copolymers containing MicroPCMs can be processed at 200 °C. The crystalline enthalpies of the fibers containing 20 and 25 wt% of MicroPCMs are 21 and 25 J/g, respectively; and they increase steadily as the contents of MicroPCMs increase. Tensile strengths of the as-spun fibers are in the range of 1.0–3.2 cN/dtex. The fibers are potentially used as raw materials to fabricate thermo-regulated fabric for comfort clothing.

Characterization of Ethylene Copolymers with Liquid Chromatography and Melt Rheology Methods

AbstractSummary: Melt rheology and polymer chromatography methods were applied to characterize molecular heterogeneities in products of free radical copolymerization of ethylene with methyl acrylate and vinyl acetate comonomers performed in continuously stirred tank and tubular reactors. We found that the ethylene–vinyl acetate copolymers made in both reactors had similar linear viscoelastic properties typical to branched products of the high pressure process. But the ethylene–methyl acrylate copolymers obtained in the tubular reactor had unusually high melt viscosity at low shear rate and much lower onset of shear thinning despite the narrower molecular weight distribution and the lower overall amount of long‐chain branches compare to their autoclave counterparts with similar average molecular weight and chemical composition. Using interaction polymer chromatography method called gradient elution at critical point of adsorption we found that ethylene‐acrylate copolymers from the tubular reactor had very broad chemical composition distribution, which was consistent with a significant difference in reactivity ratios between ethylene and acrylate comonomers. Such chemical composition heterogeneity can be a reason for the observed unusual rheological properties of these copolymers.

Removal of copper and lead from aqueous solution by carboxylic acid functionalized deacetylated konjac glucomannan

Carboxylic acid functionalized deacetylated konjac glucomannan was synthesized by free radical graft copolymerization of methyl acrylate (MA) and methyl methacrylate (MMA) onto the backbone of deacetylated konjac glucomannan with subsequent chemical activation of the ester groups in the side chains of the resulting graft copolymer by sodium hydroxide. Effects of sodium hydroxide concentration and hydrolyzed time on the conversion of ester groups into carboxylic acid groups were studied. A comprehensive adsorption study of Cu 2+ and Pb 2+ ions from aqueous solution was also conducted regarding the effects of initial pH, adsorbent dosage, time, and initial concentration. The new konjac glucomannan adsorbent offered high removal efficiency, fast adsorption rate and high uptake capacity for Cu 2+ and Pb 2+ ions. The maximum removal efficiency at pH 5.0 was found to 98% for Cu 2+ and 99% for Pb 2+ ions. The kinetic data were fitted well to pseudo-second-order model. The maximum uptake capacity of Cu 2+ and Pb 2+ ions onto carboxylic acid functionalized deacetylated konjac glucomannan was found to 64.5 mg g −1 and 191.3 mg g −1, respectively. The isotherm adsorption data was well described by the Langmuir isotherm model.

Polymer electrolyte membranes having sulfoalkyl grafts into ETFE film prepared by radiation‐induced copolymerization of methyl acrylate and methyl methacrylate

AbstractPolymer electrolyte membranes (PEMs) containing alkylsulfonic acid grafts can be prepared by radiation‐induced graft copolymerization of methyl acrylate (MA) and methyl methacrylate (MMA) into a poly(ethylene‐co‐tetrafluoroethylene) film followed by sulfonation of the MA units in the copolymer grafts using an equimolar complex of chlorosulfonic acid and 1,4‐dioxane (ClSO3H‐Complex). PEMs with MA/MMA copolymer grafts that are 33%–79% MA units were prepared by preirradiation with a dose of 20 kGy and grafting in bulk comonomers at 60°C. The grafted films are treated with ClSO3H‐Complex to obtain PEMs with ion exchange capacity of 0.36‐0.81 mmol/g (sulfonation degrees of 20%–40%) and proton conductivity of 0.04‐0.065 S/cm. These values can be controlled by changing the MA content the sulfonation occurring at an α‐carbonyl carbon. The PEMs with higher MMA content showed higher durability in water (80°C) and under oxidative conditions (3% H2O2) at 60°C. This is because the PMMA grafts in the PEMs have no proton at an α‐carbonyl carbon, which is considered to be a trigger of the degradation of grafting polymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Micro- and Nanoscale Hydrogel Systems for Drug Delivery and Tissue Engineering

The pursuit for targeted drug delivery systems has led to the development of highly improved biomaterials with enhanced biocompatibility and biodegradability properties. Micro- and nanoscale components of hydrogels prepared from both natural and artificial components have been gaining significant importance due to their potential uses in cell based therapies, tissue engineering, liquid micro-lenses, cancer therapy, and drug delivery. In this review some of the recent methodologies used in the preparation of a number of synthetic hydrogels such as poly(N-isopropylacrylamide) (pNIPAm), poly(ethylene glycol) (PEG), poly(ethylene oxide) (PEO), polyvinyl alcohol methylacrylate co-polymers (PVA-MA) and polylactic acid (PLA), as well as some of the natural hydrogels and their applications have been discussed in detail.