用二[二(2-乙基己基)磷酸]异辛酸钕盐/氢化二异丁基铝/一氯二乙基铝催化体系制备高顺式丁二烯-异戊二烯共聚物  

Synthesis of high cis-1,4-unit butadiene-isoprene copolymers with Nd(P_(204))_2EHA/Al(i-Bu)_2H/Al Et_2Cl catalyst

作　　者：郑文洁[1] 惠林海 张璐 高可可 胡雁鸣[1] 张学全[1] ZHENG Wen-jie;HUI Lin-hai;ZHANG Lu;GAO Ke-ke;HU Yan-ming;ZHANG Xue-quan(Key Laboratory of Synthetic Rubber, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China;Shandong Non-Metallic Materials Institute, Jinan 250031, China)

机构地区：[1]中国科学院长春应用化学研究所合成橡胶重点实验室,长春130022 [2]山东非金属材料研究所,济南250031

出　　处：《合成橡胶工业》2018年第4期245-249,共5页China Synthetic Rubber Industry

基　　金：国家重点研发计划资助项目[2017 YFB 0307100(2017 YFB 0307103)]

摘　　要：以二[二(2-乙基己基)磷酸]异辛酸钕盐[Nd(P_(204))_2EHA,简称Nd]/氢化二异丁基铝(简称Al)/一氯二乙基铝催化体系催化丁二烯-异戊二烯共聚合,考察了催化剂用量、n(Al)/n(Nd)和共聚单体比对聚合的影响。结果表明,该催化体系在n(Al)/n(Nd)为10时即具有高活性,且所得共聚物具有高的分子量(数均分子量大于10×10~4)和窄分子量分布(分布指数小于2.0),特别是其中的丁二烯和异戊二烯链节的顺式-1,4-结构摩尔分数均超过了97%。随n(Al)/n(Nd)增大,聚合物的收率增加,同时由于链转移反应增强导致聚合物的分子量降低、分子量分布变宽。随着共聚单体中丁二烯用量的增加,共聚物中异戊二烯链节的顺式-1,4-结构含量增加,而丁二烯链节基本不变,顺式-1,4-结构摩尔分数保持在约99.4%。Copolymerization of butadiene and isoprene was conducted with neodymium di [bis （2-ethylhexyl） phosphate ] 2-ethylhexanoate （ Nd （ P204） 2 EHA, simplified as Nd ）/diisobutylaluminum hydride （ Al （i-Bu） 2 H, simplified as Al ）/diethylaluminum chloride （AIEt2Cl, simplified as Cl） catalyst, and the effects of catalyst loading level, n （Al）/n （ Nd）, and monomer feed ratio on the polymerization were studied. The results showed that catalyst was highly effective in the copolymerization even at low n （Al）/ n（Nd） of 10. The yielding copolymers had high molecular weight （M^-n more than 10 × 10^4） , quite narrow molecular weight distribution （M^-w/M^-n less than 2.0）, and most importantly, high c/s-1,4-unit contents of butadiene and isoprene segments （ mole fraction more than 97%）. The increase of n （Al）/ n（Nd） led to an increase of the polymer yield, while the molecular weight of the resulted polymer decreased and the molecular weight distribution became broad due to the enhanced chain transfer reaction. With increasing the butadiene content in the monomer feed, the c/s-1,4-unit content of isoprene segment in the copolymer increased, meanwhile the cis-1,4-unit content of butadiene segment was almost unchanged and stayed around 99.4% （mole fraction）.

关 键 词：钕系催化剂 丁二烯-异戊二烯共聚物 顺式-1 4-结构 立构规整性 共聚合 

分 类 号：TQ333.2[化学工程—橡胶工业]