Methyl Acrylate Monomer Research Articles

Synthesis and viscoelastic properties of acrylated hyperbranched polyamidoamine UV-curable coatings with variable microstructures

Abstract Exact probe of microstructure of hyperbranched polymers is not either experimentally or theoretically a simple task. A simple yet useful approach was performed here to evaluate structure-performance relationships in hyperbranched polyamidoamine UV-curable (HPAMAMU) coatings. A series of homologous of HPAMAMU having hexamethylenediamine as core were synthesized via a two-step method, and then acrylated with glycidyl methacrylate. Formation of functional groups was confirmed by Fourier transform infrared and nuclear magnetic resonance spectroscopic analyses. To uncover structure-performance relationship, HPAMAMUs with different branching features were synthesized by reacting methyl acrylate and hexamethylenediamine monomers in the first step in 1:1, 1:2, 1:3 and 1:4 ratios. Rheological and calorimetric analyses simply provided with a deeper understanding of molecular-scale changes. Then, 7 wt.% of each hyperbranched polymer was added to a system of UV-curable epoxy methacrylate to probe the performance of the resulting coatings in terms of thermal, adhesion, physical and mechanical properties. The presence of such hyperbranched polymers decreased the glass transition temperature of HPAMAMUs, but improved adhesion and flexibility of hard and brittle epoxy acrylate coatings. Particular attention was paid to speculate change in properties in terms of structural evolutions.

Effects of monomer compatibility on sizing properties of feather keratin-g-P(AA-co-MA)

In order to endow feather keratin with good sizing properties for all-polyester or high-polyester yarns, methyl acrylate (MA) and acrylic acid (AA) monomers with a variation in feed molar ratio from 10/90 to 30/70 were grafted onto the molecular chains of native feather keratin under equal monomer concentration. Effects of monomer compatibility of MA/AA on sizing properties of the feather keratin-g-P(AA-co-MA) were studied in terms of apparent viscosity, contact angle of sizing paste on polyester fibers, mechanical properties of sizing film, and adhesion to polyester fibers. It was found that grafting MA & AA monomers with rational compatibility onto the molecular chains of feather keratin was an effective method to improve sizing properties of grafted feather keratin, such as adhesion to polyester fibers and toughness of sizing film. In view of overall performance of the grafted feather keratin sizes, the appropriate feed molar ratio of MA/AA should be 20/80.

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

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.

Dinuclear α‐Diimine NiII and PdII Complexes that Catalyze Ethylene Polymerization and Copolymerization

AbstractA series of dinucleating α‐diimine ligands and the corresponding nickel and palladium complexes were synthesized and characterized. The dinucleating α‐diimine ligands are designed to incorporate naphthalene‐, biphenylene‐, and xanthene‐bridged structures, which may lead to different metal–metal distances. The properties of these dinuclear complexes in ethylene polymerization and copolymerization with methyl acrylate are investigated. Higher catalytic activity, higher polyethylene molecular weight, and much lower polyethylene branching density were observed for the dinuclear Ni complexes compared with the mononuclear analogue in ethylene polymerization. For the dinuclear palladium complexes, much more dramatic differences in activity and polyethylene molecular weight were observed. Most interestingly, similar catalytic activities were observed for the dinuclear and mononuclear palladium complexes in ethylene–methyl acrylate copolymerization, whereas only the mononuclear complex was able to incorporate an appreciable amount of the methyl acrylate monomer.

Preparation and surface properties of poly(2,2,2-trifluoroethyl methacrylate) coatings modified with methyl acrylate

A series of copolymers of 2,2,2-trifluoroethyl methacrylate (FMA) and methyl acrylate (MA) with different copolymer compositions were synthesized by solution polymerization. The chemical structure of copolymers was characterized by fourier transform infrared spectroscopy (FTIR), 1H NMR, and 19F NMR. The reactivity ratios for FMA (r 1) and MA (r 2) were found to be 1.83 and 0.31 by the Fineman–Ross method and 1.91 and 0.34 by the Kelen–Tudos method, respectively. The glass transition temperature of the copolymers decreased with increasing MA content and ranged from 77.5 to 13.4°C for a feed composition of 90 mol% MA monomer, while, according to water contact angle data, the hydrophilic properties of the copolymer coatings increased with increasing MA feed composition. Remarkably, when the feed composition of MA was 60 mol%, the glass transition temperature was reduced to 29.2°C, while the obtained copolymer exhibited comparable hydrophobic property to the PFMA homopolymer.

Application of Starch in Modifying Acrylate Latex

The acrylate latex was a kind of production of emulsion polymerization of acrylate or methyl acrylate and other vinyl ester monomers. Starch was a biomaterial which found multiple applications in various branches. Novel approach to acrylate latex manufacture implied usage of composites e.g. the acrylate latex was being doped with starch to improve its properties and create biofriendly, naturally degrading material, and diminishing negative effect of polymeric waste production. In this paper, two methods that acrylate latex modified with starch are reviewed and summarized. The aim of the review is that provides the reference for use of the starch in modifying the acrylate latex.

Irradiated sodium–alginate/poly(ethylene oxide) blend films improved by methyl acrylate monomer

ABSTRACTSodium alginate (SA)‐based poly(ethylene oxide) (PEO) blend films were improved by methyl acrylate (MA) monomer and γ irradiation toward practical application. The films were prepared by a casting method and modified by glycerol (Gol) and mustard oil (MO). The SA‐based films were successfully produced with γ irradiation (12 kGy) with 10% PEO, 15% Gol, 20% MO, and 7% MA on a mass basis as optimized. The tensile strength (TS), tear strength (TT), elongation at break (EB), Young's modulus, moisture content, water vapor permeability (WVP), and structural properties of the blended films were determined. The thermal properties of the films were characterized by thermogravimetric analysis, dynamic mechanical analysis, and differential scanning calorimetry, and the structural features were examined with Fourier transform infrared spectroscopy. The ultimate results of this study show a rather remarkable enhancement in the tensile properties (30% TS and 67% TT) and reduction in EB (40%) of the SA‐based films with MA addition and γ irradiation. The as‐prepared SA‐based films demonstrated considerable reductions in the moisture content and WVP and also conferred a desired stability of the films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43562.

Effects of polycarboxylate superplasticizers with different molecular structure on the hydration behavior of cement paste

Effects of polycarboxylate (PCE) superplasticizers with different densities of carboxylate groups, functional group contents, molecular weight, and side chain polymerization degrees on the hydration behavior of Portland cement were investigated in this study. The experiments were conducted by using semi-adiabatic calorimeters equipped with a temperature measurement system. The water cement ratio (W/C) was 0.4, and the PCE dosage used was 0.3%. Besides, the Total Organic Carbon (TOC) experiments were taken to further study the delaying mechanism of different PCE on cement hydration. The ability to delay hydration increased in PCEs with high densities of carboxylate groups, short side chains, and high molecular weight and the copolymerization of methyl acrylate (MA) monomers decreased the heat flow peak. Nevertheless, the main hydration temperature peak and the maximum elevated temperature decreased when the density of the carboxylate groups increased. Moreover, PCEs with only a moderate molecular weight had the lowest hydration degree. The main hydration peak decreased but appeared in advance when the amount of MA monomers copolymerized with PCEs was increased; the hydration degree also decreased. PCEs only polymerized by methyl allyl polyethenoxy ether (TPEG400) macromonomer had a hydration degree of 69.46%. Absorption amount results indicate that PCEs affect the hydration of cement paste by absorbing PCEs on the surface of cement particles or encapsulating some cement particles to restrain cement hydration. PCEs grafted with MA hydrolyzed to carboxylic and hydroxyl groups, which can both restrain the hydration of cement paste.

Controlled release of multilaminated therapeutic lens containing drug

Event Abstract Back to Event Controlled release of multilaminated therapeutic lens containing drug Ji Yun Lee1, Dongjune Chung1 and Jong Hyun Ko1 1 Sungkyunkwan university, Department of interdisciplinary material science and engineering, Korea The ophthalmic diseases are occurred by increase of intraocular pressure. In other words, impediment of blood supply occurred from the ophthalmic nerves which were pressed by intraocular pressure on eye-ball. When the blood supply fails, the optic nerve is damaged and such damaged optic nerve causes eye disease. The success of the therapy of eye disease with ophthalmic drugs strongly depends on achieving sufficient drug concentration on the cornea for a sufficient period of time, but the typical delivery of drugs by eye drops which currently account for more than 90% of all ophthalmic formulations is very inefficient because drug is washed out mostly by tears and in some instances leads to serious side effects.[1] The bioavailability of ophthalmic drugs can be improved by a soft contact lens-based ophthalmic drug delivery system. It was reported that the drug is delivered to the cornea better when both hydrophilic groups and hydrophobic groups on the drug. Therefore, in this study, drug-soaking therapeutic contact lens was manufactured to increase treatment effect in extending duration of drug in eyeball. And further laminating acetazolamide to the lens, the lens was prepared in the multi-layer structure which can release the drug in stable pace. Radical solution polymerization of 2-hydroxyethyl methacrylate (HEMA), methylacrylate (MA) and ethylene glycol dimethacrylate (EGDMA) in the presence of a model compound, acetazolamide, were conducted using UV light and photo initiators. HEMA, MA monomer mixture and EGDMA were blended with the ratio of 17:1. And 1% Indomethacin (based on the monomer mixture weight) was inserted as releasing drug to manufacture drug-soaking therapeutic contact lens. To create a multilayer lens, after dissolving acetazolamide to monomer mixture to be used in outside layer, it was applied to the synthesis lens and photo-polymerization to obtain a multilayer lens. Specifically the hydrophobic concentration profiles were 0.125 wt%, 0.25 wt%, 0.5 wt% and 0.75 wt%, respectively. The mechanical properties and biological stability of therapeutic lens investigated. The manufactured lens was analyzed by FT-IR, visible light transmittance, contact angle, oxygen transmissibility (Dk) and swelling ratios. The biological stability was investigated through MTT assay. And release behavior of therapeutically relevant concentrations of drug was observed over 3 days. The synthesis of random copolymer was identified to FT-IR. Compared with common lens, it was confirmed that the lens was transparency exhibiting a transmittance more 90%. The swelling ratio was 35~40% and MTT assay indicated that all synthesized therapeutic lens was showed biocompatibility. Some noticeable differences in multi laminate among therapeutic lens having approximately the same drug content were revealed. The control group (not laminated), with a conventional drug release, shows a typical first-order release behavior: an initially high release rate followed by a rapidly declining drug release rate (drug burst effect). On the other hand, Multi laminated therapeutic lens with variation in the drug concentration group shows to control release pattern. Compared with the over 0.5wt% laminating concentration, 0.2wt% laminating concentration sample was shows high release rate initially. It was confirmed that 0.75wt% laminating concentration sample was release the drug on very steady pace more than 3days. The results indicated that photo laminating process provides a method to control initial drug burst.

Structure of Tough Multiple Network Elastomers by Small Angle Neutron Scattering

The chain conformation of model interpenetrated network elastomers was studied by small angle neutron scattering. Model double networks (DN) were made by first polymerizing and cross-linking partially deuterated ethyl acrylate in the presence of toluene, then by swelling these networks with either ethyl or methyl acrylate monomers subsequently polymerized. Model triple networks (TN) were made by repeating these swelling/polymerization steps one more time. The samples were then placed in the neutron beam at different stretching levels and the scattering patterns were acquired. We found that the swollen deuterated network only stretched affinely with the macroscopic strain above a critical length scale ξc For the DN, the critical length scale was of the order of the first network mesh size, while for the TN, the deuterated network polymerized first, stretched affinely down to a third of the mesh size clearly showing the high level of stretching of these chains inside the material.

Viscoelastic Behavior of Poly(Methyl Methacrylate-Co-Methyl Acrylate) Random Copolymer Studied by Dynamic Mechanical Analysis and Nanoindentation

The viscoelastic behavior of poly(methyl methacrylate) (PMMA) homopolymer and poly(methyl methacrylate-co-methyl acrylate) random copolymers was characterized by dynamic mechanical analysis and nanoindentation. Differential scanning calorimetric results showed only one glass transition, indicating the random distribution of comonomers in the copolymers. The α relaxation temperature (Tα) and activation energy (Hα) decreased with increasing content of methyl acrylate monomers (CMA%). The β relaxation temperature (Tβ) also decreased whereas the activation energy (Hβ) showed only small variations compared with Hα. Moreover, the indention displacement and creep compliance strongly depended on CMA%. Two creep stages were found in the creep compliance curves.

Methyl acrylate and methyl methacrylate oligomerization initiated by radicals generated via low-temperature treatment with molecular chlorine

By means of liquid chromatography, UV spectroscopy, calorimetry, and elemental analysis, it has been shown that the radicals generated spontaneously during low-temperature (77 K) mixing of the methyl acrylate (MA) and methyl methacrylate (MMA) monomers with molecular chlorine initiate the MA and/or MMA oligomerization reaction. The oligomerization and chlorination reactions occur as the mixtures prepared at 77 K are heated, having the reaction onset temperature below the chlorine melting point (170 K) and a maximal rate in the MA premelting region (180–190 K) for the MA-Cl2 mixture or the MMA melting range (220–230 K) for the MMA-Cl2 mixture.

Cobalt Bipyridine Bisphenolate Complex in Controlled/Living Radical Polymerization of Vinyl Monomers

Cobalt(II) bipyridine bisphenolate (CoII(BpyBph)) was applied to mediate the controlled/living radical polymerization of vinyl acetate (VAc), methyl acrylate (MA), and other vinyl monomers such as N-vinylpyrrolidone (NVP) and acrylonitrile (AN). The living characters of linear increased molecular weight with monomer conversion, relatively narrow molecular weight distribution, and the synthesis of block copolymer demonstrated by the formation of PVAc-b-PNVP were all observed. The polymerization of VAc was proposed to be mediated by the degenerative transfer (DT) process, but the polymerization of MA should be mainly controlled by the reversible termination (RT) process since the equilibrium constant (Keq = [CoIII–R]/[CoII][R•]) between cobalt(II) and organocobalt(III) was measured as 8.6 × 107 M–1. The correlation between Keq and the redox potential (E1/2) of cobalt complexes was preliminarily observed as a higher E1/2 leading to a larger Keq.

Potential neurotoxic effects of polymethylmethacrylate during cranioplasty

Cranioplasty for the surgical correction of cranial defects is often performed using polymethyl methacrylate (PMMA), or bone cement. Immediately prior to PMMA application, a liquid monomer form (methylacrylate) and a benzoyl peroxide accelerator are mixed resulting in polymerization, an exothermic reaction during which monomer linking and subsequent formation of solid polymer occur. The potential side effects of residual methylacrylate monomer toxicity and thermal damage of neural tissue during PMMA hardening have been described in various in vitro, animal, and cadaveric studies; however, clinically documented in vivo neurotoxicity in humans attributed to either of the above two mechanisms during PMMA cranioplasty is lacking. We present a series of four patients operated for removal of cerebellopontine angle lesions and two operated for the excision of parieto-occipital tumors who sustained cranial neuropathies and encephalopathies with transient or permanent neurological deficits that could not be attributed to surgical manipulation. We hypothesize that these complications most likely occurred due to thermal damage and/or chemical toxicity from exposure to PMMA during cranioplasty. Our case series indicates that even small volumes of PMMA used for cranioplasty may cause severe side effects related to thermal damage or to exposure of neural tissue to methylacrylate monomer.

Investigation of poly(methyl acrylate) grafted chitosan as a polymeric drug carrier

The graft copolymerization of methyl acrylate (MA) onto chitosan in aqueous medium was investigated using potassium persulfate (KPS) as initiator. The grafting conditions were optimized by studying the effects of the polymerization variables (the initiator concentration, the ratio of monomer to chitosan, and reaction temperature) on the percentage of grafting (PG). PG was found to depend on these variables, and the highest grafting percentage (256 %) could be obtained at chitosan = 1 g, KPS = 4.5 × 10−3 M, methyl acrylate monomer = 6 g, T = 60 °C and t = 180 min. The graft copolymer was characterized by Fourier transform infrared spectra analysis, thermogravimetry (differential thermogravimetry, differential scanning calorimetric), X-ray powder diffraction as well as CP-MAS 13C NMR spectroscopy. These analyses are highly confirmed the formation of poly(methyl acrylate) grafted chitosan (PMAGC). Furthermore, the gelation of the grafted polymers (PG 68, 122, 218 and 256 %) in distilled water has been studied, and the results revealed that the percentage of swelling number increase with increasing PG of the polymers. Controlled release of niacin (vitamin B3) from the hydrogel of the grafted polymers (PG 68, 122 and 256 %) in aqueous medium has been studied using ultraviolet absorption to follow quantities released at different times (for each experiment: PMAGC 100 mg, niacin 2.46 mg, distilled water 100 ml). The study was repeated again with same conditions except the using of 4.92 mg of niacin instead of 2.46 mg (PG of the grafted polymer is 256 %). The diffusion coefficient (D, cm2/h) of niacin from the hydrogel of the grafted polymer (PG 256 %) was calculated depending on Higuchi model (diffusion coefficient of the first load is 0.00194 cm2/h while 0.00255 cm2/h of the second load).

Grafting of Methyl Acrylate and Methyl Methacrylate onto Jute fiber: Physico-Chemical Characteristics of the Grafted Jute

The graft copolymerization of methyl acrylate and methyl methacrylate vinyl monomers onto jute fiber using potassium persulfate and ferrous sulfate redox system was investigated in an aqueous medium. Optimized reaction conditions for the graft copolymerization were established for parameter variables, of monomer concentration, initiator concentration, catalyst concentration, reaction time, and reaction temperature. The grafting degrees were found to depend on the above mentioned variables. A maximum graft yield of 17.3% for MA and 19.4% for MMA was obtained under effective optimized conditions for grafting. The attachment of the monomer on the grafted fiber was confirmed by FTIR studies. Dyeing was affected by monomer characteristics, and due to the development of hydrophobic nature on jute fiber by grafting, a lower amount of dye absorption occurred. Grafting has a favorable influence on tenacity, color fastness, and other properties of jute fiber.

Surface treatment of poly(ethylene terephthalate) by gamma-ray induced graft copolymerization of methyl acrylate and its toughening effect on poly(ethylene terephthalate)/elastomer blend

To improve the compatibility between ethylene-methyl acrylate-glycidyl methacrylate random terpolymer (E-MA-GMA) elastomer and poly(ethylene terephthalate) (PET), thereby enhance the toughening effect of E-MA-GMA on PET, γ-radiation-induced graft copolymerization technique was used to graft methyl acrylate (MA) monomer onto PET. The produced PET-g-PMA copolymer can be used as a self-compatibilizer in PET/E-MA-GMA blend since the copolymer contains the same segments, respectively, with PET and E-MA-GMA. The impact strength of PET/E-MA-GMA blend increased nearly by 30% in the presence of less than 0.1wt% PET-g-PMA compared with that of the neat PET/elastomer blend, without loss of the tensile strength of the blends. This work proposed a potential application of radiation-induced grafting copolymerization technique on the in-situ compatibilization of PET/elastomer blends so as to improve the integral mechanical properties of PET based engineering plastic.

Artificial molecular recognition material based biosensor for creatinine by electrochemical impedance analysis

An electrochemical impedimetric sensor based on molecular imprinted polymer (MIP) has been developed for the detection of creatinine. Creatinine MIP was prepared by using the functional monomer methylacrylate and cross-linker ethylene glycol dimethacrylate in presence of the template creatinine. The resultant polymer was washed with water, methanol and 1M HCl to extract the template from the polymer matrix. Formations of MIP, NIP (non-imprinted polymer) and template extraction were confirmed with vibrational Raman spectroscopic analysis. MIP incorporated carbon paste electrodes were used to develop a sensor for creatinine by applying electrochemical impedance spectroscopy (EIS) as transduction principle. Charge-transfer impedance (Rct) of the sensor system was determined in the absence and presence of creatinine. Interestingly, magnitude of Rct was found to increase with increasing concentrations of creatinine, which suggests the accumulation of creatinine into the polymer matrix. From the calibration plot, the low-detection-limit value was found to be ~20ngmL−1. The MIP electrode showed very good selectivity towards the specific recognition of creatinine in the presence of possible interferents like l-ascorbic acid and l-tryptophan. From the observations, we can conclude that the prepared imprinted polymer works successfully as an artificial biomolecular recognition element.

The characterization and photochromism of copolymer composite films containing phosphotungstic acid

The composite film (PWA/VPMA) was synthesized by introduced phosphotungstic acid (PWA) into the poly(vinylpyrrolidone and methyl acrylate) (VPMA), which was copolymerized with vinylpyrrolidone (VP) and methyl acrylate (MA) monomer. The microstructure, thermal stability, photochromic properties and mechanism were investigated via atomic force microscopy, Fourier transform infrared spectroscopy, differential thermal analysis, differential scanning calorimetry, ultraviolet–visible spectra and electron resonance spectra. The results indicated that the Keggin geometry of PWA and the basic structure of VPMA were not destroyed in the composite process. After PWA particles were introduced into the VPMA, the thermal stability of composite film was lowered due to the interaction between PWA and VPMA. Irradiated with UV light, PWA/VPMA composite film changed from colorless to blue and showed reversible photochromism. The appearance of W5+ in ESR spectra indicated that the photo-reduction process between PWA and copolymer matrix occurred according to the proton transfer mechanism.

Crystal structure and mechanical properties of UHMWPE-g-PMA fiber prepared by radiation grafting

Methyl acrylate (MA) monomer was grafted onto ultra-high molecular weight polyethylene (UHMWPE) fibers by γ-ray pre-irradiation induced graft polymerization. The grafting of MA on UHMWPE fiber was confirmed by thermogravimetric analysis and Fourier-transform infrared spectroscopy. The degree of grafting (DG) increased with an increase in absorbed dose and reached a significantly high value (approximately 200%) at 100kGy. Scanning electron microscopy analysis revealed that the surface of the UHMWPE-g-PMA fibers was covered by the MA grafting layer and became rough. The monoclinic crystalline and orientated intermediate phases were disordered by the grafting chains such that degree of orientation declined gradually with increasing DG. The tensile strength of UHMWPE-g-PMA fiber decreased with increasing dose but was independent of DG, whereas the fiber modulus declined with DG. UHMWPE-g-PMA fiber that possesses desirable mechanical properties could be obtained at a dose of less than 10kGy.