Methyl Acrylate Copolymers Research Articles

Elastic interface in few‐layer graphene/poly(vinylidenefluoride‐trifluoroethylene‐chlorofluoroethylene) nanocomposite with improved polarization

AbstractPolymer film capacitor exhibits extensive applications in advanced electronics because of its flexibility and huge power density. The current research interests of polymer capacitor are addressed on large energy density and high charge–discharge efficiency of composite film. Here we developed the compatible elastic interface composed of hyperbranched poly(methyl acrylate) copolymer in graphene/poly(vinylidenefluoride‐trifluoroethylene‐chlorofluoroethylene) (P(VDF‐TrFE‐CFE)) nanocomposite with high energy capability. This hyperbranched copolymer comprising polyethylene core that was grafted with poly(methyl acrylate) (PMA) segments and pyrene units was synthesized by atom transfer radical polymerization. The few‐layer graphene was exfoliated with assistance of hyperbranched copolymer that was attached on surface of flakes via π‐π non‐covalent interactions between pyrene groups and delocalized π electrons of nanosheets. Graphene/P(VDF‐TrFE‐CFE) nanocomposite film was prepared by solution casting method. The compatibility between graphene and fluoropolymer is greatly improved due to the elastic interphase of PMA segments in hyperbranched copolymer, which enhances the interfacial polarization and decreases the accumulation of charge carriers under high electric field. The energy density of 7.0 J/cm3 with charge–discharge efficiency of 60% at 300 MV/m is achieved for 0.1 wt% nanocomposite. This work reveals an effective architecture of polymer composite with elastic interface to increase the energy capability of polymer dielectric film.

Rigidifying Cation-Tunable Nickel Catalysts Increases Activity and Polar Monomer Incorporation in Ethylene and Methyl Acrylate Copolymerization.

In this study, we synthesized and characterized two nickel complexes featuring conformationally rigid bisphosphine mono-oxide ligands, where one has an o-methoxyphenyl (Ni2) and the other has an o-(2-methoxyethoxy)phenyl (Ni3) substituent on the P═O moiety. We performed metal binding studies using Ni3 and found that its reaction with Li+ and Na+ most likely produced 1:1 and 1:1/2:1 nickel:alkali species in solution, respectively. The nickel complexes were competent catalysts for ethylene homopolymerization and copolymerization, with activities up to 3.8 × 103 and 8.1 × 10 kg mol-1 h-1, respectively. In reactions of ethylene with methyl acrylate (1.0 M), the addition of Li+ to Ni3 led to a 5.4-fold enhancement in catalyst activity and a 1.9-fold increase in polar monomer incorporation in comparison to those by Ni3 alone under optimized conditions. A comparison with other nickel catalysts reported for ethylene and methyl acrylate copolymerization revealed that our nickel-alkali catalysts are competitive with some of the most efficient Ni-based systems developed thus far.

Amylopectin graft copolymers for oil sands tailings treatment

AbstractThe oil sands industry has contributed to the Canadian economy for over 50 years. Challenges have arisen, however, due to worldwide concerns regarding the long‐term environmental impact of waste by‐products generated in the bitumen extraction process from oil sands. Reclaiming legacy tailings and reducing the number of ponds are two of these challenges. This article describes the synthesis and characterization of amylopectin‐graft‐hydrolyzed‐poly(methyl acrylate) copolymers with different graft lengths and densities, and how they can be used to treat oil sands tailings. Flocculation and dewatering results depend strongly on how the hydrophobic amylopectin backbones are combined with the hydrophilic hydrolyzed poly(methyl acrylate) grafts. These hybrid polymers, combining a natural backbone with synthetic grafts, seem to be an attractive alternative to treat oil sands and probably other mineral ore tailings.

Selective distribution of conductive carbonaceous inclusion in thermoplastic elastomer: A wet chemical approach of promoting dual percolation and inhibiting radiation pollution in X-band

Reinforced polymer blend is a well-practiced area of interest adopted by materials scientist throughout the world due to its tunable end properties. The present study has been fueled by developing an immiscible thermoplastic elastomeric blend (polystyrene/ethylene-co- methyl acrylate copolymer) with loading of conducting carbon black (Vulcan XC 72); an overworked conductive clustered carbon filler. The work emphasized selective dispersion of carbon particulates in one phase (ethylene-co-methyl acrylate copolymer) resulting lowering of electrical percolation and excellent EMI shielding effectiveness in low loading. The conductive blend was also cross-checked to establish their superiority in physico-mechanical, rheological behaviors and thermal stability. The microscopic analysis has implied dispersed islands of clustered carbon particles inside blend ensuing path for electronic hopping. The segregated microstructure also has been correlated to their frequency dependent conductivity, skin depth analysis and EMI shielding measurement.

Functional copolymer binder for nickel-rich cathode with exceptional cycling stability at high temperature through coordination interaction

The P(AN-MA) binder can alleviate electrolyte decomposition and inhibit NCA cathode structure degradation at high temperature through the coordination interaction between electron-rich C N groups and active Ni 3+ on the surface of NCA. • The NCA cathode exhibits improved cycling performances at 55 °C with P(AN-MA). Nickel-rich layered oxide LiNi 1 − x − y Co x Al y O 2 (NCA) with high theoretical capacity is a promising cathode material for the next-generation high-energy batteries. However, it undergoes a rapid capacity fading when operating at high temperature due to the accelerated cathode/electrolyte interfacial reactions and adhesive efficacy loss of conventional polyvinylidenefluoride (PVdF) binder. Herein, poly(acrylonitrile- co -methyl acrylate) copolymer is designed with electron-rich C N groups as a novel binder for LiNi 0.8 Co 0.1 Al 0.1 O 2 cathode at high temperature. The electron-rich C N groups are able to coordinate with the active Ni 3+ on the surface of NCA, alleviating electrolyte decomposition and cathode structure degradation. Moreover, the strong adhesive ability is conducive to maintain integrity of electrodes upon cycling at 55 °C. In consequence, the NCA electrodes with this functional binder display improved cycling stability (81.5% capacity retention after 100 cycles) and rate performance at 55 °C.

Copolymers of Methyl Acrylate and Vinylazoles: Synthesis, Thermolabile Properties, and Grafting of Polyamine Chains

New copolymers of methyl acrylate with 1-vinylimidazole, 1-vinyl-1,2,4-triazole, and 4-vinyl-1,2,3-triazole are synthesized by radical copolymerization. It is shown that the reactivity ratios for methyl acrylate and 1-vinylimidazole are 0.83 ± 0.09 and 0.25 ± 0.02, for methyl acrylate and 1-vinyl-1,2,4-triazole are 1.0 ± 0.04 and 0.27 ± 0.01, and for methyl acrylate and (4-vinyl-1Н-1,2,3-triazolyl)-methyl pivalate are 0.56 ± 0.03 and 2.90 ± 0.20, respectively. The behavior of the copolymers in aqueous media and their thermoresponsive properties are studied by potentiometric titration and dynamic light scattering. Copolymer macromolecules occur in aqueous solutions in the form of large associates the fraction of which increases upon heating; in some cases, an insoluble phase is formed. It is found that the copolymers with the grafted oligopropylamine moieties containing N-vinylazole units can interact with the DNA oligonucleotide, stimulating their research as agents for the delivery of nucleic acids to living cells.

Quantification and Effect of Residual Water in Solid Polymer Electrolytes

In the context of the urgent modern energy challenges, lithium-metal (LMB) and lithium-ion batteries (LIB) are conceivable candidates for long term electrochemical storage of renewable energies. As such, while many possible electrolytes are being investigated, solid polymer electrolytes (SPE) are potential replacements for the classic liquid electrolytes that are used in today’s commercial LIB developed and patented by Sony Energitech in 1991. Despite offering non-flammable properties, eliminating the need for heavy casings and allowing the use of higher-energy density lithium at the anode, these electrolytes still suffer from low ionic conductivities. Therefore, plenty of novel SPE systems are being developed and proposed for their captivating properties.Oftentimes, these systems seem appealing but are hardly reproducible in laboratory settings, basing oneself solely upon the published experimental conditions. An interesting inter-laboratory study was published, in which the same thiophosphate ceramic-based solid electrolyte samples were distributed across 11 different research groups. The relative standard deviation calculated from reported conductivities reached a value of 50%. (1) Recently, it has been shown that different post-drying procedures influenced the water content of electrodes which in turn affected the electrochemical properties of LIBs. (2) In SPEs, amongst different factors that could affect ionic conductivities, we believe that water plays a non-neglectable role. Knowing that relative humidity is strongly affected by the local climate, conditions can vary from laboratory to laboratory from a day to another. Being a factor that isn’t controlled effortlessly, samples’ water content can easily be overlooked. However, only a few recent papers mention that matter.(3) The issue is that on one hand, even though some authors reported enhanced ionic conductivities with an increased water content of SPEs, others claim the opposite to be true, which makes the subject ambiguous.(4) On the other hand, very few SPE systems have been studied, which makes the effect of water unclear.In this study, three different types of polymers, poly(ethylene oxide) (PEO), poly(acrylonitrile) (PAN), and acrylonitrile methyl acrylate copolymer latex (AMAC), two different lithium salts (LiTFSI and LiClO4), and two different processing methods (Wet solution casting and solvent-free dry mixing) have been used to prepare different SPE samples. Samples of PEO-LiTFSI, PAN-LiClO4, and AMAC-LiTFSI with different water contents have been prepared and analysed following a strict reproducible drying/doping protocol. Different electrochemical parameters such as the ionic conductivity, the activation barrier and the electrochemical stability window have been assessed in different samples and correlated to their respective water contents. It has been shown that water does indeed influence SPEs and that it’s a factor that needs to be taken into consideration for reproducibility purposes. 1: S.Ohno, T. Bernges, J. Buchheim, M. Duchardt, A. K. Hatz, M. A. Kraft, H. Kwak, A. L. Santhosha, Z. Liu, N. Minafra, F. Tsuji, A. Sakuda, R. Schlem, S. Xiong, Z. Zhang, P. Adelhelm, H. Chen, A. Hayashi, Y. S. Jung, B. V. Lotsch, B. Roling, N. M. Vargas-Barbosa, W. G. Zeier, ACS Energy Lett., 5, 910-915 (2020).2: F. Huttner, W. Haselrieder, A. Kwade, Energy Technol., 8, 1900245 (2020).3: B. Commarieu, A. Paolella, S. Collin-Martin, C. Gagnon, A. Vijh, A. Guerfi, K. Zaghib, J. Power Sources, 436, 226852 (2019).4: M. Z. Munshi, B. B. Owens, Appl. Phys. Commun., 8 (1987). TOTAL Classification: Restricted Distribution TOTAL - All rights reserved

Ethylene methyl acrylate copolymer (EMA) assisted dispersion of few-layer graphene nanoplatelets (GNP) in poly(ethylene terephthalate) (PET)

The inclusion of ethylene methyl acrylate copolymer (EMA) during the melt mixing of composites of poly(ethylene terephthalate) (PET) and graphene nanoplatelets (GNP) results in increased melt viscosity and shear stresses acting on the molten composite. This is due to ester groups of the acrylates in the co-monomer unit of EMA reacting via transesterification with PET creating cross-linked structures, as confirmed by solid state 13C magic-angle-spinning, nuclear magnetic resonance spectroscopy (13C MAS NMR), Fourier transform infrared (FTIR) spectroscopy and, isothermal time sweep oscillatory rheology measurements. The increase in shear stresses assists the exfoliation of the GNP in the PET matrix, resulting in lower electrical and percolation threshold values. The electrical percolation decreased from a volume fraction of 0.017 to 0.005 GNP and an AC conductivity of the PET-GNP composite on inclusion of EMA as high as 10 S/m attained. The rheological percolation threshold value halved from a volume fraction of ~0.0237 to ~0.0117. Both EMA and GNP had a nucleating effect on the PET, as the crystallization temperature (Tc) of PET increased by > 20 °C and the crystalline content (Xc) by >25%.

Strategy for Scalable Comb Block Polyolefin Synthesis. Efficient Graft of Isotactic Polypropylene to a Commercial Broad Molecular Weight Distribution, Hyperbranched, Ethylene Methylacrylate Copolymer

Judicious selection and use of a readily available, reactive polyolefin backbone can facilitate scalable comb block construction. This can be further assisted by appropriate grafting chemistry. In ...

Anionic Copolymerization of Acrylonitrile with Methyl Acrylate under the Action of a Novel Initiating System Based on a Bicyclic Tertiary Amine and Ethylene Oxide

Anionic copolymerization of acrylonitrile with methyl acrylate under the action of the 1,4-diazabicyclo[2.2.2]octane–ethylene oxide initiating system was studied. Similarly to the anionic homopolymerization of acrylonitrile, the copolymerization is accompanied by the intra- and intermolecular chain transfer to the polymer. The influence of the copolymerization conditions on the intensity of the chain transfer leading to the formation of highly branched and hyperbranched copolymers was examined. The acrylonitrile–methyl acrylate copolymerization constants were determined: r1 = 1.25 ± 0.06 and r2 = 0.18 ± 0.07. Quantum-chemical calculations of the thermodynamic parameters of the copolymerization were made.

UV-Curable Biobased Polyacrylates Based on a Multifunctional Monomer Derived from Furfural.

The controlled polymerization of a new biobased monomer, 4-oxocyclopent-2-en-1-yl acrylate (4CPA), was established via reversible addition–fragmentation chain transfer (RAFT) (co)polymerization to yield polymers bearing pendent cyclopentenone units. 4CPA contains two reactive functionalities, namely, a vinyl group and an internal double bond, and is an unsymmetrical monomer. Therefore, competition between the internal double bond and the vinyl group eventually leads to gel formation. With RAFT polymerization, when aiming for a degree of polymerization (DP) of 100, maximum 4CPA conversions of the vinyl group between 19.0 and 45.2% were obtained without gel formation or extensive broadening of the dispersity. When the same conditions were applied in the copolymerization of 4CPA with lauryl acrylate (LA), methyl acrylate (MA), and isobornyl acrylate, 4CPA conversions of the vinyl group between 63 and 95% were reached. The additional functionality of 4CPA in copolymers was demonstrated by model studies with 4-oxocyclopent-2-en-1-yl acetate (1), which readily dimerized under UV light via [2 + 2] photocyclodimerization. First-principles quantum mechanical simulations supported the experimental observations made in NMR. Based on the calculated energetics and chemical shifts, a mixture of head-to-head and head-to-tail dimers of (1) were identified. Using the dimerization mechanism, solvent-cast LA and MA copolymers containing 30 mol % 4CPA were cross-linked under UV light to obtain thin films. The cross-linked films were characterized by dynamic scanning calorimetry, dynamic mechanical analysis, IR, and swelling experiments. This is the first case where 4CPA is described as a monomer for functional biobased polymers that can undergo additional UV curing via photodimerization.

Controllable synthesis of silica nanoparticle size and packing efficiency onto PVP‐functionalized PMMA via a sol–gel method

ABSTRACTThis study aimed to investigate synthesis and adsorption behavior of silica nanoparticles onto polyvinylpyrrolidone (PVP)‐functionalized poly(methyl methacrylate) under various conditions such as methanol/water ratio, ammonium hydroxide concentration, polymer contents, tetraethylorthosilicate contents, and total volume of solvent via sol–gel method. First, the copolymerization of methyl acrylate as a comonomer and 1‐dodecanethiol as a chain transfer agent increased the thermal stability of the product; however, the uniformity of the PMMA particles decreased because of the chain transfer reaction. Second, the adsorption behavior and size of silica nanoparticles could be controlled by adjusting the silica synthesis conditions. The adsorbed silica particle size was greatly influenced by the ammonium hydroxide concentration and the addition of water further enhanced the size increase. However, increasing the water content reduced the packing efficiency of the adsorbed silica particles. Increasing the PVP‐functionalized PMMA content at a fixed TEOS content linearly decreased the silica particle size. But TEOS concentration did not significantly affect the silica particle size. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 662–672

Emulsion copolymers of methyl acrylate and decyl (meth)acrylate: synthesis and properties

Emulsion copolymers of methyl acrylate and decyl (meth)acrylate: synthesis and properties

Biocompatibility and adhesive strength properties of poly(methyl acrylate-co-acrylic acid) as a function of acrylic acid content

Metals and metal alloys are widely used in medical devices that contact blood and/or tissue, and various coating materials for the metal parts have been proposed to improve surface properties such as biocompatibility. This study aims to understand the performance of new coating materials, copolymers of methyl acrylate and acrylic acid, in terms of their biocompatibility and adhesive strength to a metal surface. Blood compatibility was investigated through platelet and coagulation system responses. Cytocompatibility was studied in three cell-line types (endothelium, smooth muscle, and fibroblasts) in terms of cell viability and morphology; these tests showed that compatibility depended on the cell types and acrylic acid content of the copolymers. Because of their blood compatibility and adhesion strength, the methyl acrylate and acrylic acid copolymers containing 10–24 mol% acrylic acid were found to be excellent candidates as potential coating materials for devices contacting blood.

Superhydrophobic Paraloid B72

Paraloid B72 is a very important product in the conservation and restoration science and practice, particularly for cultural heritage and artistic objects. It is an inherent hydrophilic copolymer of methyl acrylate and ethyl methacrylate. In this study, superhydrophobicity is induced in Paraloid coatings by embedding silica (SiO2) nanoparticles into the polymer matrix, at appropriate concentration. Coatings are deposited on glass, marble, brass and wood. Nanoparticles form microscale clusters which enhance the roughness of the polymer surface. Nanoparticles have negligible, moderate and enormous effects on the colour of treated marble, wood and brass, respectively. The Paraloid + SiO2 composite coatings show good chemical stability.

Effect of Long-Chain Branch of Poly(methyl acrylate-co-1-octene) on the Vulcanization and Mechanical Properties

The unsaturated linear (UL) copolymer of methyl acrylate (MA), 1-octene, and allyl glycidyl ether (AGE) and the long-chain branch (LCB) copolymer of MA, 1-octene, and 1,7-octadiene were synthesized, respectively, via AlCl3-catalyzed radical copolymerization, and then both UL and LCB copolymers were vulcanized using dicumyl peroxide (DCP) curing system. For UL copolymer, cross-linking heat first increases with DCP dosages and then decreases when DCP dosages increases further to 2.5, that is quite reasonable to relate with cross-link and degradation reactions during vulcanization. However, the reaction heat flow curves of DCP-LCB curing system with DCP dosages ranging from 1.5 phr to 3.5 phr exhibit a bimodal-like “crosslinking” endotherm, suggesting a two-stage reaction of intramolecular cross-linking and intermolecular cross-linking. Results from dynamic mechanical analysis and tensile tests confirm that LCB copolymers are propitious to form effective networks at low DCP dosages and to keep the vulcanized...

Insight into Copolymerization of Methyl (Meth)Acrylate and 1-Octene with Aluminum Trichloride

Aluminum trichloride (AlCl3) catalyzed copolymerization of polar monomers, including both methyl methacrylate (MMA) and methyl acrylate (MA), with nonpolar 1-octene is investigated. The copolymerization of MMA and 1-octene produces copolymers with acceptable productivity in the present of AlCl3, but no alternating copolymer can be obtained even in a 1-octene rich condition (n(1-octene)/n(MMA) = 6.14/1). However, AlCl3-catalyzed copolymerization of MA and 1-octene unveils that MA is more feasible than MMA to copolymerize with 1-octene for the formation of alternating copolymer. An alternating copolymer of MA and 1-octene can be obtained even at MA-rich conditions (n(1-octene)/n(MA) = 0.58/1). Meanwhile, temperature shows a significant impact on the copolymerization behaviors. Performing AlCl3-catalyzed copolymerization of MA and 1-octene at lower temperature leads to an increase in the molecular weight and the incorporation of MA into the backbone of the copolymer, probably due to low temperature-enhanced complexation between AlCl3 and the ester functionality.

Elastoviscous Systems Based on Solutions of Chitosan–Methyl Acrylate and Chitosan Succinamide–Methyl Acrylate Copolymers

Rheological studies of solutions of amphiphilic copolymers based on hydrophilic polysaccharides chitosan (CT) and chitosan succinamide (CTS) sodium salt with methyl acrylate (MA) synthesized by radical copolymerization have been conducted. It has been found that the hydrophobic interaction of poly(methyl acrylate) blocks in solutions of CT–MA and CTS–MA copolymers leads to an increase in the degree of structuring of macromolecules; this feature leads to the formation of an elastoviscous system without introducing of an additional crosslinking agent.

Properties of Methacrylic Acid–Methyl Acrylate Copolymers of Varied Structure

Physicomechanical and surface properties of films of copolymers of methacrylic acid with methyl acrylate, which have close compositions and molecular masses (Mn ≈ 5.7 × 104) and various chain structures (gradient copolymer and statistical copolymer), were studied. The thermodynamic characteristics of the copolymers were determined; two glass-transition points (29.6 and 141.0°C) were found for the gradient copolymer, and one glass-transition point of 40.1°C, for the copolymer with a statistical distribution of units along the chain. It was found that more mechanically strong films with tensile stress of 2.8 MPa are characteristic of the gradient copolymer. The wetting method was used to determine by using the Hood–Kaelble–Dann–Fowkes approach the surface Gibbs energies of the films and their polar and dispersion components. Atomic-force microscopy was used to find heterogeneities (0.1–0.3 μm) on the surface of a film of a statistical copolymer, whereas the film of a gradient polymer has a homogeneous structure.

Chlorambucil loaded in mesoporous polymeric microspheres as oral sustained release formulations with enhanced hydrolytic stability

Chlorambucil, a chemotherapeutic agent, is usually administered orally to treat chronic lymphocytic leukemia and some other types of cancers in regimens of conventional and metronomic chemotherapies. However, the hydrolytic instability of chlorambucil is a major limitation in achieving the optimum therapeutic performance. In this work, mesoporous polymeric microspheres were prepared by free radical suspension copolymerization of methyl acrylate and divinylbenzene in the presence of porogen. Chlorambucil was loaded into the mesoporous polymeric microspheres through adsorption of the drug in aqueous media with high loading capacity up to more than 350 mg/g. Chlorambucil-loaded mesoporous polymeric microspheres showed sustained release property in media simulating gastrointestinal fluids, with nearly zero order release kinetics. Furthermore, the mesoporous polymeric microspheres as carriers greatly stabilized chlorambucil against its hydrolysis. The hydrolyzation percentage of chlorambucil that was adsorbed on the microspheres after incubation for 36 h in media simulating gastrointestinal fluids was less than 10%, while more than 90% of free chlorambucil hydrolyzed after incubation in the same media for 4 h. The chlorambucil-loaded mesoporous polymeric microspheres may be used as oral sustained release formulations, especially as oral formulations for the application in metronomic chemotherapy.