Copolymerization Of Acrylic Monomers Research Articles

High‐Voltage Quasi‐Solid‐State Dye‐Sensitized Solar Cells Based on Copper Redox Shuttles

Electrolyte with copper redox shuttles has endowed dye‐sensitized solar cells (DSSCs) with a high open‐circuit voltage (V oc) over 1.0 V and promising efficiencies under the sun and indoor light, but further combining these copper redox shuttles with quasi‐solid‐state gel polymer electrolytes (GPEs) is still a great challenge. The crystallization of polymers inside GPEs is one of the important factors to limit the mass transport of large‐sized copper redox shuttles and dramatically reduce the efficiency of quasi‐solid‐state DSSCs. Herein, the copper‐based GPEs are fabricated via in situ UV‐induced copolymerization of acrylic monomers. This chemical cross‐linking strategy can significantly reduce the crystallinity of polymers inside the GPEs and thus improve the apparent diffusion coefficient two times compared with the generally used poly(ethylene oxide) GPEs. Finally, optimized GPEs, copolymerized by diacrylic and triacrylic monomers, successfully generate the quasi‐solid‐state DSSCs with an efficiency of 10.1% and a high V oc of 1.03 V. These photovoltaic parameters are comparable to those of DSSCs with liquid copper‐based electrolytes, demonstrating that the chemical cross‐linking is an effective strategy to fabricate high‐performance copper‐based GPEs. This strategy will facilitate the future efficiency and stability improvement of DSSCs for the commercial optoelectronic applications.

Preparation and properties of soap‐free emulsion of polyacrylate grafted by polyester with highHEMAcontent

AbstractA waterborne polyacrylate with high methacrylicacid‐β‐hydroxyethyl ester (HEMA) content is synthesized by copolymerization of acrylate monomers and unsaturated polyester in soap free seed semi‐continuous emulsion. The unsaturated polyester is prepared by transesterification between the polyester with high hydroxyl content and methyl methacrylate (MMA). The influences of the HEMA content, acrylic acid (AA)/ methacrylic acid (MAA), and butyl acrylate (BA)/ styrene (St) ratio on properties of the emulsion and crosslinked films are discussed. The emulsion modified by copolymerization yields a high hydroxyl value (167 mgKOH g−1) and a low acid value (30.5 mgKOH g−1). The high hydroxyl content not only provides crosslinked sites for improving properties but also facilitates further curing if it does not degrade the stability of the emulsion. The modification by compolymerization is superior to modification by blending. The emulsion is further cured with amino resin HMMM and the optimum curing ratio is 6:1 of emulsion: HMMM. The crosslinked films have a high hydrophobicity and the water absorption is only 2.46%. Meanwhile, the film has good mechanical properties with the tensile strength reaches 7.5 MPa and the Young's modulus is 97.64 MPa.

Molecularly imprinted nanoparticles with recognition properties towards diphtheria toxin for ELISA applications

Plastic antibodies can be used for in vitro neutralization of biomacromolecules with different fragments due to their potential in separation, purification, chemical sensor, catalysis and drug production studies. These polymer nanoparticles with binding affinity and selectivity comparable to natural antibodies were prepared using functional monomer synthesis and copolymerization of acrylic monomers via miniemulsion polymerization. As a result, the in vitro cytotoxic effect from diphtheria toxin was reduced by MIPs. In vitro imaging experiments of polymer nanoparticles (plastic antibodies) were performed to examine the interaction of diphtheria toxin with actin filaments, and MIPs inhibited diphtheria toxin damage on actin filaments. The enzyme-linked immunosorbent assay (ELISA) was performed with plastic antibodies labeled with biotin, and it was determined that plastic antibodies could also be used for diagnostic purposes. We report that molecularly imprinted polymers (MIPs), which are biocompatible polymer nanoparticles, can capture and reduce the effect of diphtheria toxic and its fragment A.

Copolymerization of Acrylic Monomers and Silane Group Containing Titanium Carbide Nanoparticles for Application to Ophthalmic Lens Materials.

This research was conducted to synthesis and application for high oxygen permeable ophthalmic lens materials. 2-(Trimethylsiloxy)ethyl methacrylate (2T), 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate (3T), [(1,1-Dimethyl-2-propynyl)oxy]trimethylsilane (TMS), Poly(ethylene glycol) methyl ether methacrylate (PEGMA), N-vinyl-2-pyrrolidone (NVP) and titanium carbide nanoparticles were used as additives for the basic combination of synthesized silicone monomer (SiD) and N,N-Dimethylacetamide (DMA). And also, the materials were copolymerized with ethylene glycol dimethacrylate (EGDMA) as the cross-linking agent, azobisisobutyronitrile (AIBN) as the initiator. The copolymerization with a small amount of silane of about 1% increased the oxygen permeability to 30.3˜33.52(cm²/sec)·(mlO₂/ml·mm Hg)·10-11, and in particular, the addition of titanium carbide nanoparticles was found to increase to 46.38 (cm²/sec)·(ml O₂/ml·mm Hg)·10-11. Surface modification was possible with various wetting agents. Especially, simultaneous use with titanium carbide nanoparticles increased the wettability while maintaining water content. These materials are considered to make synergy effect each other, so it can be used in functional hydrogel ophthalmic lenses.

Hybrid organic-inorganic materials on the basis of acrylic monomers and TEOS prepared by simultaneous UV-curing and sol-gel process

In this work cross-linked hybrid organic-inorganic membranes consisting of polymeric matrix functionalized with sulfonic groups and uniformly distributed silica domains have been successfully synthesized through in situ polymerization strategy via photo-initiated copolymerization of acrylic monomers (acrylonitrile AN, acrylamide AAm, 3-sulfopropyl acrylate potassium salt SPAK) and simultaneous formation of silica counterpart using TEOS-based sol-gel system. N,N′-methylenebis(acrylamide) (MBA) was used as a cross-linker. The ratio between monomers was maintained stable, whereas the amount of added sol-gel system was varied. The influence of inorganic component content on properties of hybrid polymer-inorganic membranes was investigated. Chemical composition, thermal properties, structure and morphology of the obtained hybrid membranes were investigated by ATR-FTIR, TGA, DSC, SEM and EFTEM. Proton conductivity of the synthesized membranes was high (7.6 to 13.5 mS/cm) and increases with an increase of silica content. The prepared membranes were thermally stable up to 90 °C, and exhibited proton conductivity and swelling coefficients sufficient for possible use as proton-conducting membranes.

Effect of Molecular Weight of WPU on the Heterogenic PUA Composite Latex Prepared by Soap-Free Emulsion Polymerization

Aqueous acrylic-polyurethane (PUA) composite emulsion was prepared by soap-free seeded emulsion copolymerization. Waterborne polyurethane (WPU) was used as the seeded emulsion and functioned as surfactant. The effect of molecular weight of WPU on the heterogenic was investigated. The molecular weight of WPU was controlled by varying the NCO/OH mole ratio. The GPC results confirmed that the molecular weight of WPU presented double distribution. And the molecular weight of WPU decreased with the increasing NCO/OH mole ratio. Surface tension test indicated that the molecular weight had little influence on the surface activity of WPU. However, after emulsion copolymerization of acrylic monomers, the morphology and properties of the PUA composite were impacted markedly by the molecular weight of WPU. With an increase in the NCO/OH mole ratio, the morphology of PUA composite latex changed from core-shell structures to fish bowl structure, and the mechanical properties of PUA films changed correspondingly.

Controlled Release of Vitamin B‐12 Using Hydrogels Synthesized by Free Radical and RAFT Copolymerization in scCO2

SummaryResearch in polymer network synthesis is mostly focused on materials with absorbent or controlled‐release properties. They are important in healthcare applications. Free radical copolymerization is the main route to obtain gels, using monomers and crosslinking agents, but the materials produced by this route are highly heterogeneous. These heterogeneities reduce the efficiency of chemical compounds used in controlled‐release applications. Our research is focused on creating new routes of polymer synthesis to reduce these heterogeneities. In this article, we compare gels synthesized by conventional free radical and by reversible addition‐fragmentation chain transfer (RAFT) copolymerization of acrylic monomers in supercritical carbon dioxide. These gels are evaluated for controlled drug delivery applications with vitamin B12. The materials were characterized by scanning electron microscopy (SEM), nitrogen adsorption (BET), differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). These characterization techniques allowed us to determine the morphology and texture of each hydrogel and to explain how vitamin release performance is affected by these characteristics of the hydrogel.

Synthesis of novel macrophotoinitiator for the photopolymerization of acrylate

ABSTRACTA new kind of macrophotoinitiator (MPI) was synthesized through the copolymerization of acrylic monomers and the polymerizable photoinitiator monomer 2959‐AA. Monomer 2959‐AA was obtained by an esterification reaction between acrylic acid (AA) and the water‐soluble photoinitiator Irgacure 2959 [2‐hydroxy‐4‐(2‐hydroxyethoxy)‐2‐methylpropiophenone]. By adjusting the monomer proportions in the MPIs, two series of MPIs with different 2959‐AA contents and different glass transition temperatures were obtained. The molecular structure of 2959‐AA was characterized by Fourier‐transform infrared spectroscopy, nuclear magnetic spectrometry, and mass spectrometry. Polymerization of 1, 6‐hexanediol diacrylate was initiated using Irgacure 2959 and 2959‐AA, and two series of MPIs to be polymerized were studied with a photo‐DSC test. Results showed that 2959‐AA had higher chemical reactivity than Irgacure 2959 because of the higher solubility of the former. It was evident from the experiments that 2959‐AA content in the MPI progressively increased the polymerization rate and monomer conversion when the glass transition temperatures of MPIs were similar. At the same 2959‐AA content, the polymerization rate slightly slowed down with increased glass transition temperature. However, the radical lifetime and polymerization time were prolonged. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40352.

Preparation of polymeric monoliths by copolymerization of acrylate monomers with amine functionalities for anion-exchange capillary liquid chromatography of proteins

Two novel polymeric monoliths for anion-exchange capillary liquid chromatography of proteins were prepared in a single step by a simple photoinitiated copolymerization of 2-(diethylamino)ethyl methacrylate and polyethylene glycol diacrylate (PEGDA), or copolymerization of 2-(acryloyloxy)ethyl trimethylammonium chloride and PEGDA, in the presence of selected porogens. The resulting monoliths contained functionalities of diethylaminoethyl (DEAE) as a weak anion-exchanger and quaternary amine as a strong anion-exchanger, respectively. An alternative weak anion-exchange monolith with DEAE functionalities was also synthesized by chemical modification after photoinitiated copolymerization of glycidyl methacrylate (GMA) and PEGDA. Important physical and chromatographic properties of the synthesized monoliths were characterized. The dynamic binding capacities of the three monoliths (24 mg/mL, 56 mg/mL and 32 mg/mL of column volume, respectively) were comparable or superior to values that have been reported for various other monoliths. Chromatographic performance was also similar to that provided by a modified poly(GMA-ethylene glycol dimethacrylate) monolith. Separation of standard proteins was achieved under gradient elution conditions using these monolithic columns. Peak capacities of 34, 58 and 36 proteins were obtained with analysis times of 20–30 min. This work represents a successful attempt to prepare functionalized monoliths via direct copolymerization of monomers with desired functionalities. Compared to earlier publications, additional surface modifications were avoided and the PEGDA crosslinker helped to improve the biocompatibility of the monolithic backbone.

New Developments in the Area of Solvent-Borne Acrylic Pressure-Sensitive Adhesives

Since their introduction half a century ago, acrylic pressure-sensitive adhesives have been successfully applied in many fields. In the last fifty years or so, acrylic pressure-sensitive adhesives (PSAs) have made tremendous strides from what was virtually a black art to what is now a sophisticated science. So much so that larger manufacturers of pressure-sensitive adhesives and even their polymer suppliers now use very expensive equipment to study pressure-sensitive adhesive behavior. The three properties which are useful in characterizing the nature of pressure-sensitive adhesives are tack, peel (adhesion) and shear (cohesion). The first measures the adhesive's ability to adhere quickly, the second its ability to resist removal by peeling, and the third its ability to hold in position when shear forces are exerted. The performances of pressure-sensitive adhesives, such as tack, peel and shear, based on polyacrylates synthesized through co-polymerization of acrylate monomers and formulated in organic solvents mixtures are, to a large degree, determined by the molecular weight of acrylic copolymer, polymerization method and especially by the type and quantity of the crosslinking agent added to the PSA. Newly developed solvent-borne PSAs are used in protective foils, removable and repositionable self-adhesive products, water-soluble PSAs and water-dispersible self-adhesive products, photoreactive UV-crosslinkable self-adhesive tapes, and dual-crosslinkable PSAs for self-adhesive tapes with post-crosslinking potential characterized by enhanced cohesion at higher temperatures. The mentioned water-soluble PSAs, water-dispersible self-adhesive products and photoreactive UV-crosslinkable self-adhesives are synthesized in organic solvents as solvent-borne acrylic PSAs.

Synthesis and copolymerization of pentachlorophenyl acrylate monomers

Pentachlorophenyl acrylate monomers were synthesized for the first time via the condensation reaction of acrylic acids with pentachlorophenol by using N,N’-dicyclohexylcarbodiimide as condensing agent. Copolymerization of the acrylate monomers with pentaerythritol tetraacrylate was studied. The preliminary results indicated that the acrylate foams can be produced on supercritical carbon dioxide drying.

Protein−Acrylamide Copolymer Hydrogels for Array-Based Detection of Tyrosine Kinase Activity from Cell Lysates

We describe the development of an array-based assay for the molecular level detection of tyrosine kinase activity directly from cellular extracts. Glutathione S-transferase-Crkl (GST-Crkl) fusion proteins are covalently immobilized into polyacrylamide gel pads via copolymerization of acrylic monomer and acrylic-functionalized GST-Crkl protein constructs on a polyacrylamide surface. The resulting hydrogels resist nonspecific protein adsorption, permitting quantitative and reproducible determination of Abl tyrosine kinase activity and inhibition, even in the presence of a complex cell lysate mixture. Half-maximal inhibition (IC50) values for imatinib mesylate inhibition of GST-Crkl (SH3) phosphorylation by v-Abl in a purified system and Bcr-Abl within a K562 cell lysate were determined to be 1.5 and 20 microM, respectively. Additionally, the protein-acrylamide copolymer arrays detected CML cell levels as low as 15% in a background of Bcr-Abl- leukemic cells and provided the framework for the parallel evaluation of six tyrosine kinase inhibitors. Such a system may have direct application to the detection and treatment of cancers resulting from upregulated tyrosine kinase activity, such as chronic myeloid leukemia (CML). These findings also establish a basis for screening tyrosine kinase inhibitors and provide a framework on which protein-protein interactions in other complex systems can be studied.

New Principle of Optical Data Recording Based on Reversible Transition “Selective Reflection—Absorbance” in Photochromic Cholesteric Copolymers

A new principle of information storage based on a realization of the reversible transition <<selective reflection-absorbance>> in photochromic liquid crystalline (LC) copolymers was suggested. For this purpose a new family of triple copolymers were synthesized by copolymerization of acrylic monomers, containing nematogenic (phenylbenzoate), chiral (cholesterol), and photochromic (spiropyran) fragments. Phase behaviour and optical properties of copolymers were studied. Isomerization of spiropyran groups and formation of merocyanine form under UV-irradiation (337 nm) of the polymer films was observed. It should be noted that the maximum of the absorbance of polymer films coincides with maximum of selective light reflection. As a result the disappearance of the selective light reflection in the irradiated regions of the films occurs. Scheme of the optical data recording and reading of information recorded on planarly oriented films of such copolymers was proposed.

A Comparative Study of the Graft Copolymerization of Acrylate Monomers on Starch and Dextrin.

A Comparative Study of the Graft Copolymerization of Acrylate Monomers on Starch and Dextrin.

A new type of multifunctional material based on dual photochromism of ternary chiral photochromic liquid crystalline copolymers for optical data recording and storage

An approach for the development of a new class of multifunctional photochromic liquid crystalline materials has been devised. Copolymerization of acrylic monomers allowed the preparation of ternary cholesteric copolymers containing nematogenic (phenyl benzoate), photochromic (azobenzene), and chiral photochromic side groups (benzylidene-p-menthanone). The phase behaviour and optical properties of such copolymers were studied. The synthesised copolymers are characterised by selective light reflection in the visible or IR spectral regions depending on the composition of the copolymers.

Detection of Antithyroglobulin Autoantibodies with Defined Epitopic Specificity by a Microparticle-Enhanced Nephelometric Immunoassay

To hydrophilic, polyfunctional spherical microparticles of predetermined diameter, produced by copolymerization of acrylic monomers, we covalently bound human thyroglobulin. The thyroglobulin-microsphere conjugate was agglutinated, in the presence of antimouse immunoglobulins antiserum, by four monoclonal antibodies, each recognizing a different antigenic domain on the thyroglobulin molecule. These agglutinations were quantified by measuring with a specially designed nephelometer the light scattered by clusters of the conjugates. Agglutination with the monoclonal antibody recognizing antigenic domain II of the thyroglobulin molecule was specifically inhibited by some human sera that contained antithyroglobulin autoantibodies. This allowed us to develop a microparticle-enhanced nephelometric immunoassay for these autoantibodies with defined epitopic specificity. Using this assay, we detected and quantified antithyroglobulin autoantibodies in serum samples from all eight patients examined with Hashimoto disease and from most (75%) patients with untreated Graves disease.

Synthesis and characterization of some acrylic monomer/sulfur dioxide copolymers

AbstractThe copolymerization of acrylic monomers (M) [acrolein (AL), methyl acrylate (MA), acrylamide (AM) and acrylonitrile (AN)] with liquid sulfur dioxide (S) at low temperature and high dilution in the presence of tert‐butyl hydroperoxide gives high SO2 incorporation into the resulting copolymers. Analysis of the composition of these polysulfones, by elemental analyses and 13C NMR, shows that they consist mostly of the MMM, SMM, MMS and MSM triad monomer sequences. Thermal (TG) analyses of selected samples demonstrate that their thermal stability, up to 30% weight loss, increases for different acrylic comonomers as follows: AL &lt; AM &lt; MA &lt; AN. Preliminary flammability tests revealed that flame retardancy increases with increasing SO2 content in the copolymer.

Some aspects of semi-continuous emulsion copolymerization

A semi-continuous emulsion copolymerization of acrylic monomers was investigated. Under the conditions used, the polymerization rate was equal to the rate of feeding of monomers and a steady state with a constant ratio of free monomers was reached. “Effective” reactivity ratios were calculated for several couples of monomers. Significant differences in the particle size distribution were found with monomers of different polarity. The extent of particle flocculation during the process was affected by the emulsifier distribution between the initial reactor charge and the monomer emulsion as well as by the electrolyte concentration. The tendency of particles to flocculate decreased with the increasing concentration of carboxylic groups on the particle surface. A different extent of acid hydrolysis of ester groups was observed by emulsion polymerization of various acrylic monomers.

Graft Copolymerization of Acrylic Monomers onto Biopolymers. Part I. Grafting of Poly(butyl Acrylate) onto Gelatin

Abstract Gelatin was graft copolymerized with poly(butyl acrylate) using potassium peroxy disulfate in aqueous medium. Effects of temperature, time, monomer concentration, and backbone concentration were studied. The percent grafting was found to increase initially and then decreased in all cases. Infrared, viscosity, and thermal analysis were carried out on the graft copolymers, and the mechanism of the graft copolymerization reaction was discussed.

Grafting of acrylate monomers in cotton fabrics

AbstractThe graft copolymerization of acrylate monomers, methyl, ethyl, n‐propyl, and n‐ or isobutyl, in cotton fabrics was carried out in the aqueous emulsion system by the ceric ion method. The rate of grafting decreases with increasing length of the ester group. The maximum improvement of dry crease recovery, thus raising its value, increases with increasing graft‐on shifts towards the higher extents of grafting, and with decreasing second‐order transition temperature of graft polymer. The improvement of wet crease recovery, equilibrated in the presence of a wetting agent, is always greater than that in the dry crease recovery even when the hydrophobic propyl or butyl acrylate‐grafted cotton levels off with increasing graft‐on. The improvement of crease recovery was explained by the stabilization of the opened fiber structures by grafting with acrylates, especially those having bulky ester groups, the entangled crosslinking between the graft polymers or the graft polymers and cellulose chains, and the consequently developed elastomeric or swelling, elastomeric behaviors due to the segmental movements in the amorphous regions of graft copolymer. Furthermore, from the measurements of water imbibition and repellency, moisture regains, tensile properties, stiffness, flex abrasion, and thermosetting properties, it has been concluded that the improvements of physical properties are remarkable in the propyl or butyl acrylate‐grafted cotton.