丙烯腈-丁二烯-异戊二烯三元共聚物的合成

采用乳液聚合法于5℃合成了丙烯腈-丁二烯-异戊二烯三元共聚物(NBIR)。考察了单体配比、引发剂、乳化剂及相对分子质量调节剂用量对乳液聚合反应速率的影响,并通过傅里叶变换红外光谱、核磁共振氢谱与核磁共振碳谱对NBIR的组成及微观结构进行了表征。结果表明,随着乳化剂、引发剂用量的增加,聚合反应速率均增大;单体配比、相对分子质量调节剂对聚合反应速率无明显影响。固定总单体用量为100份、丙烯腈用量为33份,当丁二烯/异戊二烯(质量比)为50.0/17.0、33.5/33.5、17.0/50.0时,所得NBIR的结合丙烯腈质量分数均为33.3%左右,结合异戊二烯质量分数从19.7%增加到51.6%,其结合量均大于单体投料量;而结合丁二烯质量分数从47.2%下降到15.1%,其结合量均小于单体投料量。改变单体配比对NBIR聚丁二烯链段的1,2-结构含量和聚异戊二烯链段的3,4-结构含量均无明显影响。     

丙烯腈-丁二烯-苯乙烯三元共聚物／碳纳米管复合材料电磁性能的初步研究

通过紫外光辐照制备了丙烯腈-丁二烯-苯乙烯三元共聚物脓纳米管（ABS／CNTs）复合材料。在CNTs的质量分数为5％时，复合材料体积电阻率（ρv）比基体树脂下降了10^7Ω·cm。在20～100℃温度范围内，复合材料的ρv受温度影响不大。扫描电镜观察表明：紫外光辐照下的CNTs在ABS基体中均匀分布，容易形成导电网络。复合材料在2～10GHz的微波频段内，具有较宽的介电损耗（约为21-50）。     

丁二烯-丙烯腈-异戊二烯三元共聚物的耐低温性能及分子模拟

通过核磁共振波谱和傅里叶变换红外光谱分析了丁二烯-丙烯腈-异戊二烯三元无规共聚物(NBIR)及其加氢产物(HNBIR)的结构特征,并以凝胶渗透色谱法和差示扫描量热法测定了其相对分子质量、玻璃化转变温度等结构参数。分析了核磁共振波谱特征峰的峰位并按峰面积定量计算了NBIR的结构组成及基团含量,以此为基础采用分子模拟法构建了NBIR的分子模型,并通过分子动力学方法模拟计算了HNBIR的内聚能密度、玻璃化转变温度、半分解温度等参数。结果表明,HNBIR中的结合丙烯腈含量是影响其耐低温及耐油性能的关键因素,而氢化度的增大使得共聚物的热稳定性得以提高,耐低温性能减弱。分子模拟计算结果与实验测试数据吻合得较好。     

苯乙烯-丙烯腈-顺丁烯二酸酐三元共聚物的应用

介绍了苯乙烯-丙烯腈-顺丁烯二酸酐三元共聚物(SAM)在工程塑料高性能化方面的用途,以及其本身作为基体材料使用时的性能;阐述了经SAM增容后,聚酰胺6/丙烯腈-丁二烯-苯乙烯三元共聚物(ABS)合金所展示的优异低温抗冲击性能。从应用和生产角度,表明了SAM按其组成不同分别可用作基体树脂、增容剂、耐热ABS的基础原料等。国内已有批量的SAM产品推向市场。     

丙烯腈-丁二烯-异戊二烯三元无规共聚物的催化加氢及表征

以三(三苯基膦)氯化铑[RhCl(PPh3)3]为催化剂,甲苯为溶剂,对自制的丙烯腈-丁二烯-异戊二烯三元无规共聚物(NBIR)进行催化加氢,考察了反应温度、催化剂用量对加氢反应的影响,采用核磁共振氢谱、傅里叶变换红外光谱、差示扫描量热分析和热重分析等方法对氢化物进行了分析表征。结果表明,在反应温度为145℃、反应压力为3 MPa、催化剂质量分数占原胶的0.46%、反应时间为3 h的条件下,该催化剂对NBIR有最高加氢反应活性,氢化度可达到76.1%,氢化物只有1个玻璃化转变温度(-15.9℃),耐热分解性明显改善。     

丙烯腈-N-苯基马来酰胺-苯乙烯三元共聚物改性ABS

采用丙烯腈-N-苯基马来酰胺-苯乙烯三元共聚物对ABS 757树脂进行改性,从而提高ABS树脂的热性能,同时ABS树脂的拉伸强度增大,硬度增大,而且ABS树脂向高刚性、高模量的方向发展.丙烯腈-N-苯基马来酰胺-苯乙烯三元共聚物中N-苯基马来酰胺的含最对共混物的熔体质量流动速率有很大的影响,通过改变三元共聚物中N-苯基马来酰胺的含量,可使共混树脂的加工性能得到提高.     

丙烯腈-丁二烯-苯乙烯三元共聚物/丁腈橡胶热塑性硫化胶的相容及Mullins效应研究

采用动态硫化方法制备丙烯腈 丁二烯 苯乙烯三元共聚物（ABS）/丁腈橡胶（NBR）热塑性硫化胶（TPV）,以氯化聚乙烯（CPE）为相容剂改善其界面相容性,研究CPE用量对TPV物理性能、Mullins效应和微观结构的影响。结果表明：CPE可显著改善ABS/NBR TPV的界面相容性,当CPE用量为6份时,TPV的综合性能较好;TPV在单轴循环拉伸过程中存在明显的Mullins效应,在相同的拉伸比下,TPV的最大应力、内耗能和损耗因子在第1次加载 卸载循环中最大,在第2次循环拉伸时显著下降,但随后下降幅度减小;与未相容TPV相比,相容TPV具有较高的瞬时残余形变、应力软化因子和损耗因子。扫描电子显微镜分析结果表明,相容TPV的断面较为平整,NBR硫化胶粒子均匀分散在TPV的表面。     

嵌段型丙烯腈-丁二烯-苯乙烯树脂的制备与性能

针对丙烯腈-丁二烯-苯乙烯(ABS)树脂中的橡胶粒子相形态难以精确调控的问题,提出采用可逆加成断裂链转移(RAFT)乳液聚合合成苯乙烯-丙烯腈无规共聚物和苯乙烯-丙烯腈/丁二烯嵌段共聚物,并通过共混制备嵌段型ABS树脂,研究嵌段共聚物分子结构对材料相形态和机械性能的影响。结果表明,通过乳液共混可制得橡胶粒子均匀分散的ABS树脂,与市售产品相比,采用两嵌段共聚物为增韧剂的嵌段型ABS树脂具有优异的综合性能,将增韧剂改为三嵌段共聚物,材料的拉伸断裂韧性能进一步提升,但缺口冲击性能下降明显。     

丙烯酸丁酯-苯乙烯-丙烯腈共聚物/二氧化钛复合薄膜的制备、表征及性能

先以丙烯酸丁酯、苯乙烯和丙烯腈为原料,通过种子乳液聚合制得了以聚丙烯酸丁酯为核、苯乙烯-丙烯腈共聚物为壳的核壳接枝共聚物ASA;再以钛酸正四丁酯和偶联剂γ-(甲基丙烯酰氧基)丙基三甲氧基硅(KH-570)为原料,经水解缩合生成KH-570-g-TiO<,2>粒子.将ASA与KH-570-g-TiO<,2>粒子按照一定比...     

苯乙烯-马来酸酐-丙烯酸丁酯三元共聚物的合成及性能

以苯乙烯(St)、马来酸酐(MAh)及丙烯酸丁酯(BA)为原料合成了苯乙烯-马来酸酐-丙烯酸丁酯三元共聚物(SMB)并作为环氧树脂(E-51)韧性固化剂。测定了SMB的酸酐值;采用红外光谱对SMB及SMB/E-51固化物进行表征;通过热重分析考察了该SMB/E-51固化体系的热性能;比较了不同配比的SMB/E-51固化产物在150℃经过不同时间后的剪切强度;通过扫描电子显微镜对比了SMB与马来酸酐/苯乙烯共聚物(SMA)分别作为环氧树脂固化剂时所得的固化产物的冲击断面形貌。结果表明,该固化剂的酸酐值为0.356 mol/100 g。E-51/SMB固化产物具有良好的耐热性能,最大失重速率温度(Tmax)达430℃;当E-51/SMB的质量比为1/1.2时,固化产物表现出较佳的力学性能和热稳定性,在150℃下保温36 h后,对不锈钢的搭接剪切强度达到15.40 MPa,高于在相同条件和最佳配比下的E-51/SMA固化产物;且E-51/SMB固化体系的韧性也优于E-51/SMA固化体系。     

Preparation of poly(vinyl acetate) latex with ultrasonic and redox initiation

The high water solubility of vinyl acetate (VAc) monomer increases the need for a good initiator system to speed up the polymerization and remove unreacted monomers. Ultrasonic energy can be used to initiate VAc redox emulsion polymerization in the absence of an inert gas and with sodium dodecyl sulfate as a surfactant. Combining ultrasonic energy and a redox initiator at the ambient temperature leads to a higher conversion and higher rate of polymer production in comparison with just using a redox initiator. Ultrasonic energy plays an important role in synthesizing and controlling the polymer structure. The particle size distribution is an important variable in the formulation of latex paint. Ultrasonic energy has an effect on the particle size distribution and average molecular weight of VAc polymer. The particle size increases with an increase in the monomer conversion for ultrasonic polymerization, whereas the particle size stays constant with the monomer conversion for redox polymerization. An ultrasonic polymer has a broader particle size distribution than a redox polymer. The average molecular weight of poly(vinyl acetate) falls with an increase in the sonication time, whereas it increases with time for a redox polymer. Ultrasonic energy also produces a stable, milky white, opaque latex. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 812–817, 2005     

Preparation and characterization of monodisperse magnetic poly(styrene butyl acrylate methacrylic acid) microspheres in the presence of a polar solvent

Magnetic poly(styrene butyl acrylate methacrylic acid) [P(St–BA–MAA)] microspheres were prepared by emulsifier‐free emulsion polymerization in the presence of a polar solvent and a ferrofluid prepared by a coprecipitation method. The effects of some polymerization parameters, such as the medium polarity, reaction temperature, initiator content, and surfactant content in the ferrofluid, on the particle diameter and particle size distribution of magnetic P(St–BA–MAA) microspheres were examined in detail. The results showed that the electrostatic repulsion in the polymerization system significantly affected the monodispersity of the resulting magnetic polymer microspheres. The proper electrostatic repulsion, achieved through changes in the medium polarity and amount of surfactant in the polymerization system, improved the monodispersity, but a higher or lower repulsion led to a decrease in the monodispersity. Although the existence of surfactant and magnetite particles reduced the monodispersity more or less, the polymerization behavior of an emulsifier‐free emulsion polymerization in the presence of the ferrofluid was analogous to that of a conventional emulsifier‐free emulsion polymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1733–1738, 2003     

液体聚异戊二烯/天然橡胶复合材料的制备与性能

制备了4种3,4-结构摩尔分数不同的液体聚异戊二烯(LIR),考察了芳烃油及不同3,4-结构摩尔分数的LIR作为增塑剂对于天然橡胶(NR)的交联密度、物理机械性能、动态力学性能及微观结构的影响.结果表明,随着LIR中3,4-结构摩尔分数的增加,NR的交联密度增加.LIR不仅起到增塑的作用,还可与NR形成共交联网络.与芳...     

种子法制备聚合物乳液技术的进展

从建筑乳液的生产现状、自生种子法与外加种子法的区别、种子乳液的特点及外加种子法生产的乳液特性等方面介绍了种子法制备乳液技术的进展。     

Kinetics of atom transfer radical polymerization of crosslinkable terpolymer P(MMA‐BA‐HEMA)

A crosslinkable terpolymer P(MMA‐BA‐HEMA) was prepared by atom transfer radical copolymerization of 2‐hydroxyethyl methacrylate, methyl methacrylate and butyl acrylate. The structure of the terpolymer was characterized by ¹H NMR and gel permeation chromatography. The effects on the polymerization of ligand, initiator, solvent, CuCl₂ added in the initial stage and reaction temperature were investigated. The optimal reaction conditions were ethyl 2‐bromopropionate as initiator, CuCl/PMDETA as catalyst, cyclohexanone as solvent, catalyst/ligand = 1:1.5, [M]₀:[I]₀ = 200:1 and temperature 70 °C. The reaction followed first‐order kinetics with respect to monomer concentration, indicating the best control over the polymerization process, a constant concentration of the propagating radical during the polymerization, efficient control over M_n of the polymer and low polydispersity (M_w/M_n < 1.3). © 2013 Society of Chemical Industry     

Preparation of polystyrene/poly(methyl methacrylate) core‐shell composite particles by suspension‐emulsion combined polymerization

Suspension‐emulsion combined polymerization process, in which methyl methacrylate (MMA) emulsion polymerization constituents (EPC) were drop wise added to styrene (St) suspension polymerization system, was applied to prepare polystyrene/poly(methyl methacrylate) (PS/PMMA) composite particles. The influences of the feeding condition and the composition of EPC on the particle feature of the resulting composite polymer particles were investigated. It was found that PS/PMMA core‐shell composite particles with a narrow particle size distribution and a great size would be formed when the EPC was added at the viscous energy dominated particle formation stage of St suspension polymerization with a suitable feeding rate, whereas St‐MMA copolymer particles or PS/PMMA composite particles with imperfect core‐shell structure would be formed when the EPC was added at the earlier or later stage of St suspension polymerization, respectively. It was also showed that the EPC composition affected the composite particles formation process. The individual latex particles would exist in the final product when the concentrations of MMA monomer, sodium dodecyl sulfate emulsifier, and potassium persulfate initiator were great in the EPC. Considering the feature of St suspension polymerization and the morphology of PS/PMMA composite particles, the formation mechanism of PS/PMMA particles with core‐shell structure was proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

含氟单体改性丁腈橡胶的制备与性能

采用含氟单体甲基丙烯酸六氟丁酯、丁二烯、丙烯腈与反应型偶联剂直接进行乳液共聚制备含氟单体改性丁腈橡胶,考察了反应型偶联剂的种类及用量对聚合产物结构及性能的影响。结果表明,反应型偶联剂Q 2可与丁二烯、丙烯腈、含氟单体进行四元共聚,当含氟单体甲基丙烯酸六氟丁酯与偶联剂Q 2的质量比为1.50/1.50时,含氟单体改性丁腈橡胶的综合性能较佳,拉伸强度达到25.5 MPa,扯断伸长率为377%,耐热空气老化性能较好。     

Swelling properties of copolymers of styrene and divinylbenzene containing sulfonic and carboxylic acid groups

Copolymers of styrene, divinylbenzene, and acrylic acid that have undergone sulfonation exhibited good water absorbency properties. Removal of the lower molecular weight fraction in the surface region of the copolymer particles by toluene extraction before sulfonation has further increased the water swelling capacity of the sulfonated copolymers. The extent of swelling of the UV‐irradiated copolymer could be related to the ratio of divinylbenzene to styrene. The less crosslinked copolymers were shown to absorb more water. The incorporation of more carboxylate groups in the copolymer could further increase its swelling capacity. Without UV irradiation, the carboxylate containing copolymer was found to absorb more water than the sulfonated copolymer. UV irradiation has induced more effective crosslinking in the carboxylate containing copolymer, hence impairing its water absorbency. By replacing styrene and divinylbenzene partially with butyl acrylate, whereby the amount of crosslinking was reduced, the copolymer was able to absorb water 110 times of its dry weight. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Recalculation of the monomer reactivity and experimental differences in emulsion and microemulsion copolymerizations of partially water‐soluble monomers

On the basis of the copolymerization data for the emulsion and microemulsion polymerizations of ethyl acrylate and methyl methacrylate, the monomer concentrations at the copolymerization loci were calculated, with the assumption that the sum of their concentrations at the polymerization loci was equal to unity. The equivalency of the locus and feed concentrations, as for styrene, was invalid because of the partial water solubility of both the monomers. Consequently, the locus concentration rather than the initial feed concentration was used to recalculate the monomer reactivity at the actual site of polymerization, and this was called the true reactivity ratio. The apparent reactivity ratios for emulsion and bulk polymerizations were different, whereas those for microemulsion and bulk polymerizations were similar. This difference was attributed to the mode of polymerization in the emulsions and microemulsions, leading to different copolymer compositions for similar initial feed concentrations. This was verified experimentally from the thermal properties and particle size distribution measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2802–2810, 2002