用稀土催化剂制备高顺式丁二烯-异戊二烯共聚物  

Synthesis of butadiene-isoprene copolymer having high cis-1,4-unit contents with rare earth catalyst

作　　者：徐端端[1] 胡雁鸣[1] 李杨[1] 张学全[2] 王玉荣[1] 张春庆[1] 

机构地区：[1]大连理工大学化工学院高分子材料系精细化工国家重点实验室,辽宁大连116012 [2]中国科学院长春应用化学研究所,吉林长春130022

出　　处：《合成橡胶工业》2011年第4期272-276,共5页China Synthetic Rubber Industry

基　　金：国家自然科学基金资助项目(20974016)

摘　　要：以酸性膦酸酯钕Nd(P507)3(简称Nd)、氢化二异丁基铝(简称Al)、三氯甲烷(简称Cl)和三氯乙酸乙酯(简称ETCA)为催化体系,在环己烷溶剂中进行丁二烯/异戊二烯共聚合。考察了催化剂组成、陈化温度和时间及聚合温度等对聚合过程的影响。结果表明,在[Al]/[Nd]为20、[Cl]/[Nd]为10、[ETCA]/[Nd]为1.0及聚合温度为50℃的条件下,聚合物收率可达80%以上;所得共聚物具有相对分子质量较高(数均分子量为8.9×104)和分子量分布窄(多分散指数为2.06)的特点;产物为高顺式丁二烯-异戊二烯共聚物,其中丁二烯和异戊二烯链节的顺式-1,4-结构摩尔分数均在95%以上,且其微观结构不受反应条件的影响。The copolymerization of butadiene（Bd） and isoprene（Ip） were carried out in cyclohexane with the rare earth catalyst comprised of Nd（P507）3（Nd）,Al（i-Bu）2H（Al）,CHCl3（Cl） and CH3CH2OOCCCl3（ETCA）.The effects of catalyst components,mole ratios of Al/Nd and Cl/Nd,catalyst aging temperature and time,and polymerization temperature on the copolymerization of Bd and Ip were investigated.The results showed that copolymer yield was up to 81% at polymerization temperature of 50 ℃,mole ratio of Al/Nd 20,mole ratio of Cl/Nd 10,and mole ratio of ETCA/Nd 1.0.The produced copolymer had higher relative molecular mass（number average molecular weight 8.9×104） and narrow molecular weight distribution（polydispersion index 2.06）.Both the cis-1,4-unit mole fraction of Bd and Ip of the copolymer were over 95%,regardless of the polymerization conditions.

关 键 词：丁二烯 异戊二烯 共聚物 稀土催化剂 配位聚合 

分 类 号：TQ330.6[化学工程—橡胶工业]