Effect of cationic monomer structure on the aggregation behavior of amphoteric acrylic polymer around isoelectric point

Amphoteric polymer can be used as retanning agent in leather manufacture.It is particularly useful in chrome-free tanning systems since it can regulate the charge properties of chrome-free leather and enhance the fixation of anionic post-tanning chemicals in leather.However,the aggregation and precipitation of amphoteric polymer retanning agents around the isoelectric point(pl)hinder their wide application.Herein,we synthesized five amphoteric acrylic polymers(AAPs)by free radical copolymerization with acrylic acid and five different cationic acrylic monomers.The effect of cationic monomer structure on the aggregation behavior of AAPs was investigated.The aggregation of AAPs in aqueous solution showed pH and concentration dependence.Light scattering analysis showed that Poly(AAA-co-MAPTAC)and Poly(AA-co-DMAPMA)were in the shape of coiled linear flexible chains with small particle size(R_(g)7.6 nm and 14.8 nm,respectively)near the pl.However,Poly(AA-co-DAC),Poly(AA-co-DMC)and Poly(AA-co-DMAEMA)were in the shape of hollow spheres and exhibited serious aggregation.Quantum chemical calculations suggested that the amide groups in the cationic monomers MAPTAC and DMAPMA enhanced the nucleophilicity of AAPs.Thus the corresponding AAPs could carry a large number of cationic charges to slow their aggregation when the pH just climbed over the pl.The results are expected to provide theoretical reference for the synthesis and wide-spread application of AAPs.

Effect of cationic monomer structure on the aggregation behavior of amphoteric acrylic polymer around isoelectric point

Amphoteric polymer can be used as retanning agent in leather manufacture. It is particularly useful in chrome-free tanning systems since it can regulate the charge properties of chrome-free leather and enhance the fixation of anionic post-tanning chemicals in leather. However, the aggregation and precipitation of amphoteric polymer retanning agents around the isoelectric point (pI) hinder their wide application. Herein, we synthesized five amphoteric acrylic polymers (AAPs) by free radical copolymerization with acrylic acid and five different cationic acrylic monomers. The effect of cationic monomer structure on the aggregation behavior of AAPs was investigated. The aggregation of AAPs in aqueous solution showed pH and concentration dependence. Light scattering analysis showed that Poly (AA-co-MAPTAC) and Poly (AA-co-DMAPMA) were in the shape of coiled linear flexible chains with small particle size (Rg 7.6 nm and 14.8 nm, respectively) near the pI. However, Poly (AA-co-DAC), Poly (AA-co-DMC) and Poly (AA-co- DMAEMA) were in the shape of hollow spheres and exhibited serious aggregation. Quantum chemical calculations suggested that the amide groups in the cationic monomers MAPTAC and DMAPMA enhanced the nucleophilicity of AAPs. Thus the corresponding AAPs could carry a large number of cationic charges to slow their aggregation when the pH just climbed over the pI. The results are expected to provide theoretical reference for the synthesis and widespread application of AAPs.

Graft Polymerization of Acrylic Acid and Acrylamide onto BOPET Corona Films

The graft polymerization of acrylic acid(A) and acrylamide(B) was carried out onto bi-oriented polyester BOPET corona film.The influence of monomer concentration,reducer concentration and reaction time on the graft polymerization was investigated.The surface tension of the films increased with an increase of monomer concentration,till the concentration of monomer A reached 1.5×10^(-2)g/mL and the concentration of monomer B reached 4.0×10^(-2)g/mL.The surface tension of the films reached a maximum value at 7×10^(-4)M of reducer concentration and subsequently decreased with further increase in reducer concentration.The surface tension of the films increased with the increase of the reaction time apparently within 50min.The grafted corona BOPET films were characterized with IR and XPS.The presence of graft on the film surface was confirmed.The attenuation experiments on grafted corona BOPET films in air at 50℃ and in water were carried out to investigate the persistence of graft polymerization of acrylic acid and arylamide onto BOPET corona films.

Influence of Reactive Diluent on UV-curing of AcrylateTerminated Hyperbranched Polymers

A Aeries of hydroxylic hyperbranched polymers were derived from 2,2-bis(methylol) propionic acid and tris(methylol) propane reacted with acrylic acid to various extents. The obtained acrylated hyperbranched polymers alone or with a monofunctional diluent, isobornylene acrylate(IBOA) were further cured by UV radiation. The cured films based on the modified polymers alone all demonstrated poor mechanical properties due to their high network densities and low moving ability of polymer chains. For the composite systems, the cured films demonstrated improved mechanical properties due to the low network densities and high chain moving ability. With more IBOA included in the systems, acrylate groups can react to a higher extent during the curing process.

Nonionic Polymerizable Emulsifier in High-Solids-Content Acrylate Emulsion Polymerization

Stable high-solids-content acrylate emulsion were obtained with a nonionic polymerizable emulsifier allyloxy nonylphenoxy poly （ethyleneoxy） （10） ether （ANPEO10）, and a conventional emulsifier OP-10 as a reference sample. 1H NMR proves that the polymerizable emulsifier ANPEO10 has been incorporated into the resulted acrylate polymers. TEM demonstrates that there are some differences in the particle morphologies. AFM proves that the polymerizable emulsifier ANPEO10 migrating to the surface of the emulsion film was much less than the conventional emulsifier OP-10. The polymerizable emulsifier ANPEO10 can enhance the adhesion with glass plate compared to the conventional emulsifier. Furthermore, with increasing amount of emulsifier, the surface free energy of the films first decreased and then increased, and the adhesion with glass plate is initially enhanced and then attenuated. The water-resistance and solvent-resistance of the films prepared by the polymerizable emulsifier ANPEO10 are superior to those prepared by the conventional emulsifier OP-10.

Acrylate Copolymers as Impact Modifi er for Epoxy Resin

P（BA-GMA）（PBG）, having various molecular weights, was synthesized by in situ polymerization of butyl acrylate（BA） and glycidyl methacrylate（GMA）, and further used as a modifier to improve the comprehensive properties of the epoxy curing system. The copolymers were characterized by gel permeation chromatography（GPC）. The effects of various molecular weights of copolymers on the mechanical properties, thermal performance, and phase behavior of the curing system were carefully evaluated. The experimental results of differential scanning calorimetry（DSC） and dynamic mechanical analysis（DMA） showed that glass transition temperature decreased and the tan δ peak shifted to a lower temperature with decreasing molecular weight of copolymer. Mechanical properties analysis of curing films showed that the impact strength and fracture toughness increased significantly upon the addition of PBG, indicating good toughness of the modified epoxy resins. From scanning electron microscopy（SEM） studies of the fracture surfaces of ER/PBG systems, the fracture behavior of epoxy matrix was changed from brittleness to toughness.

PHOTOSENSITIVITY OF CERIC ION INITIATED METHYL ACRYLATE POLYMERIZATION

The polymerization of methyl acrylate was sensitive to UV light. Under UV light,the rate of polymerization is 8 times as high as the rate in dark.The overall activation energy was decreased by the UV light (313nm).A tentative explanation is given and the mechanism is discussed.

Structural Design and Property Characterization of Bi-functional Photorefractive Polymer

A novel bi-functional photorefractive acrylate polymer with pendant carbazolyl groups and azo derivatives as side chains was synthesized. Photorefractive experiments showed a high two-beam coupling gain coefficient of 93 cm(-1), diffraction efficiency of 12% and electro-optic coefficient of 26 pm/V were obtained.

PHOTOSENSITIVITY OF Ce (Ⅳ) INITIATED METHYL ACRYLATE POLYMERIZATION

The influences of UV light irradiation (313 nm) and diffused daylight on the polymerization of methyl acrylate initiated by the ceric ammonium nitrate without any reducing agent have been studied both in aqueous nitric acid and in pure water. The rate of polymerization was found to be accelerated and the overall activation energy and the induction time were found to be decreased sharply by the UV light irradiation. Under UV light, the rate of polymerization is 8 times as high as the rate in dark. The rate of polymerization was found to attain a maximum with the increase of nitric acid concentration and the rate of polymerization became less sensitive to UV light in the presence of nitric acid whereas the induction period reduced outstandingly. Based on the experimental results, the mechanism is proposed.

STRUCTURE OF 1-BROMOMETHYL-7, 7-DIMETHYLBICYCLO[2.2.1]HEPT-2-YL ACRYLATE AND THE PROPERTIES OF ITS POLYMER

In this paper, the structure of 1-bromomethyl-7,7-dimethyl btcyclo[2.2.1]hept-2-yl acrylate has been studied by X-ray diffraction, and the relation between the molecular structure and the properties of polymerization and its polymer have been discussed.

有机硅氧烷改性丙烯酸乳液的研究

用含不饱和双键有机硅单体与丙烯酸酯单体共聚,使乳液的性能得到改观.着重研究了乳化剂的用量及其配比,丙烯酸单体的用量,有机硅功能单体种类、用量及聚合工艺对乳液及涂膜性能的影响.

Optimizing Heavy-duty Anticorrosive Performances of Coating Films Formed by Acrylate-vinylidene Chloride Copolymer Latexes through Twice-painting Technique

Twice-painting technique was adopted to prepare heavy-duty anticorrosive coating films formed by aqueous latexes of copolymers of vinylidene chloride（VDC） with an acrylate, namely methyl acrylate（MA）, ethyl acrylate（EA）, butyl acrylate（BA） or 2-ethylhexyl acrylate（EHA）. Harsh salt-spray corrosion tests demonstrated that the optimized twicepainting technique was that the acidic latex solution was adjusted to p H 5-6 for the first painting, while it was utilized directly for the second painting. The test of 600 h of harsh salt-spray corrosion showed that MA-VDC85 coating could protect the steel excellently, whereas the other acrylate-VDC coatings with 75%-90% VDC content could not protect the steel so effectively. Further corrosion test showed that（1） MA-VDC85 coating protected steel from loss of metallic luster for at least 1000 h of salt-spray corrosion;（2） adhesion of MA-VDC85 coating to steel was excellent for at least 800 h of saltspray corrosion, but became very poor after 1000 h. Differential scanning calorimetry, thermogravimetric analysis, X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy were used to evaluate the corroded MA-VDC85 film.

SYNTHESIS AND CHARACTERIZATION OF AN ACRYLATE POLYMER CONTAINING CHLORINE-1,3-DIOXALANE GROUPS IN SIDE CHAINS

Poly[2-（4-chlorophenyl）-l,3-dioxolan-4-yl]methyl acrylate, poly（CPhDMA）, was synthesized with radical polymerization process using 2,2＇-azobisisobutyronitrile as radical initiator in 1,4-dioxane at 60℃. The structure of poly（CPhDMA） was confirmed by means of UV-Vis, FT-IR, 1H-NMR, and 13C-NMR spectral techniques. The molecular weight distribution values of the polymer were determined with gel permeation chromatography （GPC）. The number-average molecular weight （Mn）, weight-average molecular weight （Mw） and polydispersity index （PDI） values of poly（CPhDMA） were determined to be 10300, 21600 and 2.097, respectively. The thermal degradation kinetics of the polymer was investigated by using TG/DTG-DTA and DSC analyses at different heating rates in dynamic nitrogen atmosphere. The apparent activation energy values obtained by Flynn-Wall-Ozawa and Friedman methods were found to be 91.68 and 85.23 kJ mo1-1, respectively, for thermal decomposition of poly（CPhDMA）. Also, the thermal degradation activation energy value of poly（CPhDMA） was calculated by using the Kissinger method based on the DTG, DTA and DSC data. Then the mechanism function of it was determined by master plots method. Finally, electrical and optical properties of poly（CPhDMA） were determined by four-point probe and UV-Vis techniques, respectively.