Electron-microscopic procedure for acrylic rubber

The electron-microscopic visualization of acrylic rubber dispersed in a heterogeneous structural resin composition consisting of a rubber-modified two-phase plastic comprising essentially a butyl acrylate rubber phase and an acrylonitrile–styrene copolymer phase, respectively, has been accomplished. This procedure consists of the following: The molded resin specimen is treated with hydrazine hydrate solution to produce the acrylic acid hydrazides. Allow the treated specimen to soak in osmium tetroxide solution. The acrylic rubber may be indirectly fixed and stained. Some micrographs of ultrathin sections of two or three resin compositions, cut by an ultramicrotome, are presented.     

高导热苯乙烯丙烯酸树脂复合材料制备及导热性能

苯乙烯丙烯酸树脂为墨粉主要组分,其导热性能提升可显著提高墨粉导热性能,进而延长打印、复印机使用寿命。通过在苯乙烯丙烯酸树脂中添加碳纳米管、石墨烯高导热单一或复合填料,在苯乙烯丙烯酸树脂构建连通导热网络以提高其导热性能。当苯乙烯丙烯酸树脂中添加0.75wt%多壁碳纳米管时,其导热系数可提高至0.1644 W/(m?K),增幅为31.31%;添加1.0wt%羧基改性多壁碳纳米管时,苯乙烯丙烯酸树脂导热系数可提高至0.1751 W/(m?K),增幅为39.86%;在苯乙烯丙烯酸树脂添加多壁羧基改性碳纳米管和石墨烯混合填料时,苯乙烯丙烯酸树脂导热系数可提升至0.2093 W/(m?K),增幅达到67.17%。表明碳纳米管和石墨烯混合填料可在苯乙烯丙烯酸树脂中形成有效的导热网络,从而显著提高苯乙烯丙烯酸树脂导热性能。     

Toughening of nylon 6 with grafted rubber impact modifiers

Recent work has shown that nylon 6/acrylonitrile–butadiene–styrene (ABS) blends can be made tough by the addition of some polymer additives that are chemically reactive with nylon 6 and physically compatible with the styrene-acrylonitrile copolymer (SAN) phase of ABS. Imidized acrylic polymers (IA) represent a successful example of such additives that improve the dispersion of ABS in the nylon 6 matrix and render the blends tough. This article examines the possibility of toughening nylon 6 with ethylene/propylene/diene elastomer grafted with SAN copolymer (EPDM-g-SAN). This EPDM-g-SAN consists of 50% rubber and 50% SAN by weight. However, it was found that the same IA that works well to disperse ABS materials of similar rubber content is not as effective for EPDM-g-SAN, primarily because the EPDM forms the continuous phase, not SAN, and, thus, interfaces with nylon 6 during melt blending. Maleated elastomers like maleic anhydride grafted ethylene–propylene copolymer (EPR-g-MA) and styrene–(ethylene-co-butylene)–styrene triblock copolymer (SEBS-g-MA) were more effective for dispersing EPDM-g-SAN in the nylon 6 matrix than IA. Various mechanisms that improve the dispersion are discussed. © 1995 John Wiley & Sons, Inc.     

印刷用苯丙乳液研究进展

就印刷用苯丙乳液的研究现状及其性能要求做了详细论述,重点介绍了对印刷用苯丙乳液光泽、黏度等性能的影响因素。简要地对印刷用苯丙乳液的未来方向做了展望。     

水性纳米改性苯丙防锈底漆的研制

本试验选用无皂聚合工艺制备的水性苯丙防锈乳液为基料,氧化铁红与三聚磷酸铝组成防锈体系,添加纳米SiO_2浆料,制备的水性纳米改性苯丙防锈底漆性能达到溶剂型醇酸防锈涂料的水平,并分析了乳液、防锈颜料、纳米SiO_2对水性苯丙防锈底漆性能的影响。     

Application of photosensitive surfactant based on natural rubber in emulsion polymerizations

Summary Photosensitive surfactant was prepared by incorporation of maleic anhydride to natural rubber, followed by introduction of cinnamate groups and neutralization of the remaining carboxylic groups. The surfactant was used in emulsion polymerization of styrene and acrylic monomers, giving rise to stable reactive emulsion. Coated onto HDPE, this emulsion lead to solid films which were submitted to UV irradiation.     

Preparation and reticulation of styrene acrylic/epoxy complex latex

The styrene acrylic/epoxy (SA/EP) complex latex with high content of epoxy resin was successfully prepared through emulsion polymerization initiated by both water-soluble and oil-soluble initiators. The resulting complex latex demonstrated regular spherical morphology with a diameter ranging 150–300 nm and with a narrow size distribution. The compatibility between epoxy and styrene acrylic improved due to the styrene acrylic grafting epoxy formation during grafting copolymerization. The factors influencing the structure and storage time of the complex latex were investigated and the corresponding mechanism was revealed. The SA/EP complex latex can form crosslinking structure with epoxy curing agent at room temperature. The crosslinked complex latex film shows good mechanical properties and excellent chemical resistance. These SA/EP complex latexes show great potential in developing high-performance aqueous paints and adhesive.     

H2O2-induced graft polymerization of acrylic acid/styrene mixtures on poly(ethylene terephthalate) fibers

Graft polymerization of acrylic acid/styrene mixtures on poly(ethylene terephthalate) fibers using H₂O₂ as initiator was investigated under different conditions including acrylic acid/styrene ratio, monomer mixtures concentration, initiator concentration, polymerization temperature, pH of polymerization medium, addition of metallic salts, and use of solvent/water mixture instead of aqueous medium. It was found that the rate and extent of grafting for acrylic acid/styrene mixtures were much higher than those of single monomers, indicating a synergestic effect. Maximum percent grafting occurred when acrylic acid/styrene mixture at a ratio of 30:70 was used. Increasing the monomer mixture concentration from 2% to 40% was accompanied by a significant enhancement in percent grafting. The latter increased also significantly as the H₂O₂ concentration increased from 10 to 150 meq/L; a further increase in H₂O₂ concentration decreased grafting. No grafting took place at 65°C even after 4 h. Raising the polymerization temperature to 75°C expedited grafting; the magnitude of the latter increased by increasing the temperature up to 95°C. Addition of copper sulphate and ferrous ammonium sulphate to the polymerization system offset grafting, the opposite holds true for lithium chloride provided that its concentration does not exceed 15 mmole/L. Methyl alchol/water mixture (20:80) constituted the optimal medium for polymerization. Grafting of acrylic acid/styrene mixtures to poly(ethylene terephtalate) fibers resulted in considerable improvement in moisture regain of the latter.     

环氧改性丙烯酸乳液涂料的研制

采用三元复合乳化剂体系和核壳乳液聚合工艺,制得环氧树脂改性的苯丙乳液。研究了乳化剂、反应温度、环氧树脂的用量、三乙烯四胺固化剂对环氧改性苯丙乳液综合性能的影响,确定了适宜的反应条件和配方。     

Graft polymerization of some vinyl monomers onto acrylic rubber. I. Chain transfer and grafting reaction

The grafting reactions of styrene (St), methyl methacrylate (MMA), and vinyl acetate (VAc) were investigated in the presence of n-butyl acrylate–acrylonitrile copolymer. Results showed that the nature of monomer and initiator were the major factors influencing the grafting activity. The grafting efficiency was 0.87 for St, 0.26 for MMA, and 0.18 for VAc under the most favorable conditions. Acrylic rubber reduced the rate of polymerization, and the retarding effect increased in the order St, MMA, VAc. The chain transfer constants for acrylic rubber were evaluated to be 4.8 × 10^?4 for St, 1.27 × 10^?3 for MMA, and 1.45 × 10^?3 for VAc. The rate of polymerization and the grafting efficiency decreased with increasing acrylonitrile content in acrylic rubber, while the chain transfer constant of St for acrylic rubber remained practically unchanged.     

Herstellung von Copolymeren mit definierter Zusammensetzungsverteilung im Zulaufverfahren

The possibility of the computation of binary and ternary copolymerization for semi-batch reactions is demonstrated. For that purpose the conversion must be known as a function of time and length of the monomer feed program. The computer simulations are successfully applied to the binary system methacrylic acid (N-dimethylaminoethyl)ester/styrene and to the ternary systems methacrylic acid (N-dimethylaminoethyl)ester/styrene/acrylonitrile as well as to methacrylic acid (2-hydroxyethyl)ester/styrene/acrylic acid n-butylester. The computation of the chemical conversion heterogeneity is possible with these simulations. Furthermore by these computations it is possible to find monomer feed programs by which copolymers with defined distribution of the chemical composition are generated. This procedure allows to generate a more homogeneous terpolymer methacrylic acid (2-hydroxylethyl)ester/styrene/acrylic acid butylester by computed monomer feed programs instead of the normally very heterogeneous terpolymer system. It is shown for the ternary system methacrylic acid (N-dimethylaminoethyl)ester/styrene/acrylonitrile which initial monomer compositions must be chosen in order to generate chemically homogenous terpolymers. In the latter system an internal ternary azeotropic region supposedly exists.     

硅溶胶偶联改性苯丙乳液机理研究

选用适当添加量(0.25%)的KH-560为偶联剂,实现了硅溶胶与苯丙偶联连接,采用透射电镜(TEM)和红外光谱(IR)对复合乳液微观结构及键合机理进行探讨,并提出了硅溶胶偶联苯丙的结构模型。     

Thermal and physicomechanical properties of gamma‐irradiated EPDM/waste newsprint microfibers composites treated using acrylic styrene emulsion as a coupling agent

This investigation deals mainly with thermal stability and crosslinking density of EPDM/newsprint microfibers composites. The recycled newsprint microfibers were treated using a different ratio of acrylic styrene emulsion (5, 10, and 15 wt% fiber) as a bonding agent to reinforce EPDM rubber matrix. The effect of microfibers content, namely, 5 up to 50 phr (part per hundred part of rubber) and the effect of ionizing radiation on EPDM/newsprint microfibers composites properties were investigated. The microfibers structure and EPDM/microfibers composite were investigated using X‐ray diffraction and FTIR analysis; the results indicate that bonding has occurred between the treated newsprint microfibers and EPDM polymer matrix. EPDM/untreated newsprint microfibers composites have achieved higher crosslinking density than EPDM matrix up to 50 phr microfibers content and up to 100 kGy then decreased with increasing gamma irradiation dose. Meanwhile treatment of the microfibers using 10 wt% acrylic styrene leads to improve crosslinking density at any microfibers content. Thermogravimetric analysis (TGA) was carried out for the microfibers and their composites. TGA indicated that the thermal stability of microfiber was enhanced using acrylic styrene. Whereas there is a slight improvement in thermal stability and activation energy of the composites due to adding treated microfibers using 10 phr microfiber content treated using10 wt% acrylic styrene emulsion and irradiated with 60 kGy gamma radiation dose. J. VINYL ADDIT. TECHNOL., 25:E91–E106, 2019. © 2018 Society of Plastics Engineers     

Improving water solubility of poly(acrylic acid‐co‐styrene) copolymers by adding styrene sulfonic acid as a termonomer

Acrylic acid is often used to make water‐soluble polymers while styrene is often modified to add special functions to polymers. However, when styrene and acrylic acid are copolymerized, the resulting polymer is much less water soluble. To regain water solubility, the effect of styrene sulfonic acid on solubility of poly(acrylic acid‐co‐styrene) copolymers was investigated. Even though acrylic acid polymers are known for their water solubility, the presence of styrene units within acrylic acid copolymers reduces the solubility of the copolymer substantially at the natural pH of the solutions. By adding styrene sulfonic acid as a termonomer, polymers that are water soluble at the natural pH of the polymerization could be obtained. The solubility of the polymer after removal of the solvent and by redissolving at different concentrations and pH levels is also reported. Solubility increases at higher pH especially with low styrene concentration in the copolymer. It was found that incorporation of as little as 5 mol % of styrene into poly(acrylic acid) reduced the aqueous solubility to less than 0.5 g dL^?1 at pH 7. Upon adding 7 mol % styrene sulfonic acid as a termonomer, the water solubility increased to 5 g dL^?1 at pH 7. At higher levels of styrene, more styrene sulfonic acid was needed, especially at low pH. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

引发剂,乳化剂对苯丙核／壳乳液合成的影响

采用预乳化工艺和半连续种子乳液聚合技术合成了具有核／壳结构的苯丙乳液,研究了引发剂种类、乳化剂用量及两阶段乳化剂用量比等对苯丙核／壳乳液合成的影响。     

Effect of acrylic acid neutralization on ‘livingness’ of poly[styrene‐ran‐(acrylic acid)] macro‐initiators for nitroxide‐mediated polymerization of styrene

BACKGROUND: The effect of acrylic acid neutralization on the degradation of alkoxyamine initiators for nitroxide‐mediated polymerization (NMP) was studied using styrene/acrylic acid and styrene/sodium acrylate random copolymers (20 mol% initial acrylate feed concentration) as macro‐initiators. The random copolymers were re‐initiated with fresh styrene in 1,4‐dioxane at 110 °C at SG1 mediator/BlocBuilder^® unimolecular initiator ratios of 5 and 10 mol%. RESULTS: The value of k_pK (k_p = propagation rate constant, K = equilibrium constant) was not significantly different for styrene/acrylic acid and styrene/sodium acrylate compositions at 110 °C (k_pK = 2.4 × 10^?6–4.6 × 10^?6 s^?1) and agreed closely with that for styrene homopolymerization at the same conditions (k_pK = 2.7 × 10^?6–3.0 × 10^?6 s^?1). All random copolymers had monomodal, narrow molecular weight distributions (polydispersity index M?_w/M?_n = 1.10–1.22) with similar number‐average molecular weights M?_n = 19.3–22.1 kg mol^?1. Re‐initiation of styrene/acrylic acid random copolymers with styrene resulted in block copolymers with broader molecular weight distributions (M?_w/M?_n = 1.37–2.04) compared to chains re‐initiated by styrene/sodium acrylate random copolymers (M?_w/M?_n = 1.33). CONCLUSIONS: Acrylic acid degradation of the alkoxyamines was prevented by neutralization of acrylic acid and allowed more SG1‐terminated chains to re‐initiate the polymerization of a second styrenic block by NMP. Copyright © 2008 Society of Chemical Industry     

负离子溶液聚合法高苯乙烯橡胶的合成及其性能

以环己烷为溶剂、苯乙烯和丁二烯为单体、n-BuLi为引发剂、二乙二醇二甲醚(2 G)为结构调节剂,通过活性负离子溶液聚合合成了高苯乙烯橡胶,研究了引发剂种类、聚合温度、2 G/n-BuLi(摩尔比)、苯乙烯/丁二烯(质量比)、相对分子质量及其分布对共聚橡胶力学性能的影响。结果表明,当苯乙烯/丁二烯为60/40、2 G/n-BuLi为1.0时,在(65±2)℃下可聚合得到力学性能较好的高苯乙烯橡胶,其数均分子量为15×104~20×104、分子量分布为1.40左右。     

Acrylic acid containing copolymers as reactive compatibilitzers for toughening nylon 6

Nylon 6 has been toughened by rubber particles that were dispersed within the matrix via additives that physically interact with the elastomer phase but chemically react with the polyamide phase. To disperse a core-shell impact modifier having a poly(methyl methacrylate) or PMMA shell, most of the work presented is based on the use of a styrene/acrylic acid copolymer containing 8 wt% acrylic acid, SAA8. SAA8 is miscible with PMMA and should located in the PMMA grafted chains of the impact modifier while chemically reacting with the nylon 6 matrix; hence, it should aid in both the dispersal and strenghtening the modifier-matrix interface. Microscopy and mechnical properties confirm that SAA8 does function in this way but less effectively than styrene/maleic anhydride copolymers, which are also miscible with PMMA but evidently react more effectively with the polyamides. The use of ethylene/acrylic acid copolymer for dispersal of the coreshell impact modifier and a styrene/ethylene-butene/styrene block copolymer in nylon 6 was also briefly considered. Low-temperature toughness of the blends proved to be a much more critical test of the effectiveness of such additives than room temperature impact strenght.     

Enhancing water swelling ability and mechanical properties of water‐swellable rubber by PAA/SBS nanofiber mats

Investigation of the potential use of nanofibers to reinforce composites has gained significance in many applications. In this article, the nanofiber mats of poly(acrylic acid) (PAA) and styrene–butadiene–styrene (SBS) triblock copolymer with composites structure were interweaved by double needle electrospinning process. The multiple nanofiber mats were added to conventional water‐swellable rubber (WSR). Improved mechanical and physical properties of WSR were obtained. Enhancement of the swellability of WSR + PAA/SBS nanofiber mats was derived from the PAA constituent absorbing water from the surface into the bulk and introducing random internal water channels between discontinuous superabsorbent polymers. The role of SBS nanofibers in the composite of WSR + PAA/SBS nanofiber mats was more related to the mechanical properties, where the breaking force of the composite increased to twice that of the conventional WSR. Interestingly, after immersion of the WSR + PAA/SBS nanofiber mats in water for 1 week, there was only a slight decrease in their mechanical properties of less than 5% compared to the dry state. The mechanisms and effects of the nanofiber mats in enhancing the mechanical and water swelling properties of WSR are also discussed. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44213.     

Modification of partially carboxymethylated cotton via crafting with acrylic acid and styrene using gamma radiation

Partially carboxymethylated cottons (PCMC) having 15.549, 27.409, and 46.834 meq ? COOH/100 g cellulose as well as untreated cotton and alkali-treated cotton, which was prepared in an analogous manner to PCMC but, in the absence of monochloroacetic acid, were graft-copolymerized with either acrylic acid or styrene using gamma radiation under different conditions. Moisture regain and dyeing properties of the copolymers so obtained were investigated. It was found that the graft yeld increases by increasing monomer concentration and radiation dose irrespective of the monomer or substrate used. Using water/methanol mixtures as polymerization media are advantageous for grafting of styrene onto the substrates in question. The graft yields of PCMCs are much lower than those of unmodified and alkali-treated cottons when they were grafted with acrylic acid. In case of styrene on the other hand, the graft yields for PCMCs are higher than the corresponding yields obtained with the unmodified and alkali-treated cottons. Poly(acrylic acid)–PCMC graft copolymers show much higher moisture regain than PCMCs particulary when the carboxylic groups of the graft were in the sodium form. The opposite holds true for polystyrene–PCMC graft copolymers which exhibit much lower moisture regain as compared with PCMCs. The color strength of PCMC dyed with direct or reactive dyes decreases significantly after being copolymerized with poly(acrylic acid) prior to dyeing. On the other hand, this copolymerization improves the affinity of PCMCs for the basic dye and brings about perceptible shade. Polystyrene–PCMC graft copolymers acquire higher color strength than the PCMC when dyed with direct, disperse, and basic dyes but lower color strength upon dyeing with the reactive dye. Also reported were the moisture regain and dyeability of unmodified and alkali-treated cotton before and after copolymerization with acrylic acid or styrene for comparison.