高温本体聚合合成ACS树脂的接枝率研究

研究了聚合条件、配方组成及氯化聚乙烯(CPE)的氯化度对高温本体聚合合成丙烯腈(AN) CPE苯乙烯(St)接枝共聚物（ACS）树脂接枝率的影响。结果表明,本体聚合合成ACS树脂过程中接枝反应主要发生在聚合转化率低于50 %的低转化率阶段;反应温度、引发剂及链转移剂用量是影响本体聚合合成ACS接枝率的主要因素;提高聚合反应温度、增加引发剂和链转移剂浓度均会导致接枝率显著下降;St/AN的质量比、CPE橡胶的含量及氯化度对接枝率的影响较小。     

MACS树脂的合成及性能研究

以氯化聚乙烯(CPE)、甲基丙烯酸甲酯(MMA)、丙烯腈(AN)和苯乙烯(St)为原料,以BPO为引发剂,通过溶胀悬浮聚合的方法合成了接技型MACS树脂,研究了各种因素对合成反应的影响以及产物的流变性和力学性能。     

活性自由基接枝聚合反应合成氯化聚乙烯接枝聚苯乙烯的研究

用氯化聚乙烯与铜试剂二乙基二硫代氨基甲酸钠反应合成了分子链上带有多个引发基团的大分子引发剂，用此引发剂引发苯乙烯聚合得到了氯化聚乙烯接枝聚苯乙烯（ＣＰＥ－ｇ－ＰＳ）接枝共聚物。采用紫外光谱、核磁共振氢谱对大分子引发剂和接枝共聚物进行了表征。结果表明：含有二乙基二硫代氨基甲酸酯的大分子引发剂可以在简单易行的聚合条件下合成可控结构接枝共聚物，并有很高的接枝率和接枝效率     

无卤阻燃ACS/PC合金的制备及性能

以聚碳酸酯(PC)为耐热树脂,磷酸酯为阻燃剂制备无卤阻燃丙烯腈-氯化聚乙烯-苯乙烯塑料(ACS)/PC合金,研究了ACS与PC的质量比、磷酸酯用量、增容剂用量等因素对阻燃ACS/PC合金综合性能的影响。结果表明,当ACS与PC的质量比为75∶25时综合性能最优;增容剂马来酸酐接枝(丙烯腈/苯乙烯)共聚物(AS-g-MAH)可以有效提高缺口冲击强度;磷酸酯与ACS存在协同增效作用,相对于阻燃丙烯腈-丁二烯-苯乙烯塑料/PC合金,阻燃ACS/PC合金的磷酸酯用量大幅下降。     

CPP—AN—ST—BA接枝共聚物的研究

采用加入ＭｇＣＯ３分散剂的悬浮聚合方法，对氯化聚丙烯－丙烯腈－苯乙烯－丙烯酸丁酯的接枝共聚进行了研究，进一步提高了共聚物的抗张强度和抗冲击强度。     

苯乙烯-丙烯腈-马来酸酐三元共聚物的合成及其在PC/ABS中的应用

采用本体聚合的方法,以苯乙烯、丙烯腈、马来酸酐为反应单体,加入引发剂、链转移剂合成了苯乙烯-丙烯腈-马来酸酐(SAM)三元共聚物.研究了引发剂种类、用量及链转移剂用量对三元共聚物摩尔质量的影响,寻求最优的合成条件;并以自制的SAM来增容聚碳酸酯(PC)/丙烯腈-丁二烯-苯乙烯(ABS)共混物,探讨了SAM对共混物性能的影响.通过红外(FTIR)、核磁(1H-NMR)、差示扫描量热仪(DSC)对三元聚合物结构进行了分析.研究表明:引发剂偶氮二异丁腈(AIBN)效果优于过氧化苯甲酰(BPO),苯乙烯、丙烯腈、马来酸酐物质的量之比为60:38:2,链转移剂十二硫醇(TDM)和引发剂偶氮二异丁腈(AIBN)的用量均为单体总质量的0.1%时,可获得摩尔质量为80 000g/mol左右的三元共聚物SAM;SAM对PC/ABS共混物起到了增容作用.     

α—SAN树脂的研制

α-SAN树脂是以α-甲基苯乙烯、苯乙烯和丙烯腈为原料,用悬浮共聚法制备的。本文从α-甲基苯乙烯的分子结构特点及其聚合机理考虑,选择丙烯腈和苯乙烯作为共聚单体,探讨了单体用量对共聚物性能的影响。研究了复合引发剂体系对聚合周期及共聚物单体残留量的影响。介绍了羟基磷酸钙-苯乙烯-顺丁烯二酸酐共聚物钠盐的制备方法,并以它作共聚反应的复合分散剂,减少了粘壁现象。对影响α-SAN树脂物理性能的诸因素进行了讨论。试验结果表明,α-甲基苯乙烯用量对聚合周期、产物分子量、熔体指数、玻璃化温度和冲击强度等均有显著的影响。     

增容剂对HDPE／AS合金流变和力学性能的影响

研究了增容剂氯化聚乙烯接枝（丙烯腈／苯乙烯）共聚物对ＨＤＰＥ／ＡＳ共混体系加工流变性能和力学性能的影响。增容剂使共混体系的塑化时间减少,且随着增容剂用量的增加,共混体系的平衡扭矩和拉伸强度增大,而断裂伸长率在ＨＤＰＥ／ＡＳ／ＰＥ－Ｃ－ｇ－ＡＳ＝８０／２０／４时出现极大值;螺杆转速的增加使共混体系的平衡扭矩增大。     

交联型聚丙烯酸丁酯胶乳的合成

以十二烷基硫酸钠为乳化剂，过硫酸铵为引发剂，丙烯酸丁酯经两步乳液聚合，合成了胶粒粒径大于２５０ｎｍ，凝胶含量大９０％，适用于合成丙烯酯酯－丙烯腈－苯乙烯共聚物的交联型聚丙烯酸丁酯胶乳。第一步乳液聚合配方及条件：乳化剂用量２％－４％，引发剂用量０．１％－０．４％，交联剂用量２．４％－２．８％；单体采用滴加乳液法或滴加单体法，聚合温度６０－７０℃，聚合时间３－４ｈ，第二步种子聚合条件：乳化剂用量／种子     

茚基钠/甲苯体系引发丙烯腈聚合的研究

本文采用茚基钠作为引发剂,对丙烯腈在甲苯中的聚合进行了研究,考察了引发剂用量、单体浓度、反应时间及反应温度对丙烯腈聚合的影响。发现茚基钠/甲苯体系对丙烯腈聚合反应具有一定的引发活性,且随着引发剂用量增加聚合反应转化率增大,聚合产物的分子量下降;延长聚合反应时间,转化率和分子量都增大;温度对聚合反应转化率影响不大,但对聚合产物分子量有明显影响。用粘度法对聚合产物的粘均分子量进行了表征。     

氯乙烯/N-苯基马来酰亚胺/丙烯腈三元悬浮共聚三元悬浮共聚

从氯乙烯/N-苯基马来酰亚胺/丙烯腈三元悬浮共聚的技术特点出发,研究了加料方式对聚合工艺及产物颗粒特性的影响,并在此基础上考察了引发剂体系的影响,确定了适宜的引发剂种类及用量。     

苯乙烯-异戊二烯-丁二烯三元乳液共聚合反应研究

以去离子水为分散介质、歧化松香酸钾和脂肪酸钠为乳化剂、十二硫醇为链转移剂、磷酸钠为电解质、过硫酸钾为引发剂,在50℃下,通过乳液聚合的方法合成了苯乙烯、异戊二烯、丁二烯三元共聚物(ESIBR)。考察了聚合温度、引发剂、链转移剂、电解质用量对三元乳液共聚合速率的影响,通过红外光谱仪(FTIR)与核磁共振(1H-NMR)对三元共聚物的组成及微观结构进行了分析表征。结果表明,随着聚合温度的升高,聚合速率显著加快,反应诱导期缩短;随着引发剂用量的增加,聚合反应速率增大;在实验范围内,链转移剂与电解质用量对共聚反应速率无明显影响。单体质量配比为S/I/B=28/36/36时,转化率在70%以内,共聚物中结合苯乙烯含量随着转化率的提高而增加,结合苯乙烯质量分数由20%增至26%;结合异戊二烯量随转化率的提高而降低,结合异戊二烯质量分数由47%降至41%;而结合丁二烯量却无明显变化,其质量分数基本都在33%左右。     

Polymerization kinetics of indene, methyl methacrylate and acrylonitrile and characterization of their terpolymer

The free radical terpolymerization of indene (In), methyl methacrylate (MMA) and acrylonitrile (AN) has been investigated. The rate of polymerization of all the binary systems involved has been measured dilatometrically for the homogeneous polymerization. The reactivity ratios of the three binary systems were calculated and were found to be equal to 0.031 and 0.397 for In/AN copolymers and 0.02 and 3.82 for In/MMA copolymers and finally 0.152 and 1.20 for AN/MMA copolymers. The rate of terpolymerization in bulk has been measured as well as the relationship between the monomer mixture composition and the obtained terpolymer in order to construct the compositional triangle. Also the effect of initiator concentration on the rate of terpolymerization was investigated. The activation energy of terpolymerization was determined. The terpolymers were characterized by spectral and thermo-gravimetric analyses. The data indicates that polyindene improves the thermal stability of the prepared terpolymers.     

钒化合物催化活化体系乙丙三元共聚合研究

采用自制的钒化合物为主催化剂,倍半烷基铝为助催化剂,三氯乙酸乙酯为活化剂,对乙烯、丙烯、乙叉降冰片烯三元共聚合进行了研究,结果表明,当活化剂采用三氯乙酸乙酯时乙丙三元共聚合活性要高于其它活化剂,在活化剂存在条件下,当活化剂与钒催化剂的物质的量比为12、催化剂用量为0.06mmol/(100 mL己烷)、铝比n(Al)/n(V)=40、聚合温度为常温时,乙丙三元聚合活性可提高3.1倍左右。     

Emulsion terpolymerization of dimethyl meta-isopropenyl benzyl isocyanate (TMI®) with acrylic monomers: Process development and kinetics

Dimethyl meta-isopropenyl benzyl isocyanate (TMI®) is a bifunctional monomer possessing a double bond and an isocyanate group. Emulsion terpolymerization of TMI with the acrylic monomers, methyl methacrylate and n-butyl acrylate, was studied. Polymerizations were carried out at 40°C using a redox initiator system in order to minimize the extent of hydrolysis of the isocyanate in the aqueous emulsion environment. The kinetics of the polymerization reaction were investigated. The polymerization rate was found to decrease with increasing TMI concentration. The effects of several preparative variables such as the monomer, surfactant, and initiator concentration on the polymerization kinetics was studied. Several semicontinuous polymerization processes were developed in order to enhance the incorporation of TMI at appreciable rates. These processes also allow us to control the polymer composition, latex particle size, and the locus of isocyanate groups in the latex particle. Process variables such as the mode of initiator addition (batch versus semicontinuous) were found to greatly influence the polymerization behavior. © 1996 John Wiley & Sons, Inc.     

Free‐radical terpolymerization of n‐butyl acrylate/butyl methacrylate/d‐limonene

d ‐Limonene (Lim) is a renewable monoterpene derived from citrus fruit peels. We investigated it for use as part of a more sustainable polymer formulation. The bulk free‐radical terpolymerization of n‐butyl acrylate (BA)/butyl methacrylate (BMA)/Lim was carried out at 80°C with benzoyl peroxide as the initiator. The terpolymerization was studied at various initial BA/BMA/Lim molar ratios, and the products were characterized for conversion, terpolymer composition, molecular weight, and glass‐transition temperature. Lim was observed to undergo a significant degradative chain‐transfer reaction, which greatly influenced the polymerization kinetics. The rate of polymerization, final conversion, and polymer molecular weight were all significantly reduced because of the presence of Lim. Nonetheless, polymers with relatively high weight‐average molecular weights (20,000–120,000 Da) were produced. The terpolymer composition was well predicted with the reactivity ratios estimated for each of the three copolymer subsystems. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42821.     

Simulation of kinetic analysis on terpolymerization of styrene/butyl methacrylate/methacrylic acid system

The simultaneous differential equations which connected the copolymerization kinetics of the component reaction in the multi-copolymerization system with the changing rate of the concentration of each monomer and radical, the concentration and the molecular weight of the polymer obtained are analysed in a number of ways. The distribution of the components and the degree of polymerization are also simulated. The styrene/butyl methacrylate/methacrylic acid terpolymerization system, using carbon tetrachloride as solvent and benzoyl peroxide as initiator, was chosen. The simulation model which satisfied the experimental values of the concentration of the multiple components in the system, the composition and molecular weight distribution and the number of chlorine atoms introduced into the copolymer ends is established. When the time interval changed, the effects on the distribution of the composition in copolymers and the distribution of the degree of polymerization were also calculated.     

Water‐soluble copolymers. II. Inverse emulsion terpolymerization of acrylamide,sodium acrylate,and acryloyloxyethyl trimethylammonium chloride

Inverse emulsion terpolymerization of acrylamide, sodium acrylate, and acryloyloxyethyl trimethylammonium chloride was investigated. Aqueous monomer solutions were emulsified in diesel oil with a blend of two surfactants (SPAN80 and TWEEN80) using 2,2′‐azobis(2‐amidinopropen)‐dihydrochloride as the initiator. The effects of temperature, initiator concentration, monomer concentration and composition, and emulsifier content on the polymerization conversion and the polymer intrinsic viscosity were examined. Polymer intrinsic viscosity increased with a decreasing concentration of initiator and an increasing concentration of monomer. The sizes of the latex particles of the terpolymer emulsions were observed with a scanning electron microscope, and the structure of the terpolymer was identified by FTIR spectroscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1381–1385, 2006     

环保型阻垢剂PESA的合成及阻硫酸盐垢性能研究

以马来酸酐为原料,钨酸钠为催化剂,双氧水为氧化剂,氢氧化钙为引发剂,采用溶液聚合法合成了聚环氧琥珀酸。研究了催化剂用量、环化pH、引发剂用量、聚合温度和聚合时间对PESA阻BaSO4垢性能的影响,并用原子吸收分光光度法对在最佳工艺条件下合成的产品进行了阻垢性能评价。结果表明,合成PESA的最佳工艺条件为马来酸酐9.8 g,催化剂用量0.33 g,环化pH为4,引发剂加量0.5 g,聚合温度82℃,聚合时间2 h。当PESA加量为8 mg/L时,对硫酸钡的阻垢率达98.0%;当PESA加量为40 mg/L时,对硫酸锶的阻垢率达90.4%。