基于稀土催化在苯乙烯中合成苯乙烯/异戊二烯/丁二烯三元共聚物  

Synthesis of Styrene/Isoprene/Butadiene Terpolymer in Styrene Based on Rare Earth Catalyst

作　　者：李立[1,2] 许蔷[1,2] 庄彬彬[1,2] 张长浩[1,2] 王玉荣[1,2] 李杨[1,2] 

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116024 [2]辽宁省高分子科学与工程重点实验室,辽宁大连116024

出　　处：《高分子材料科学与工程》2015年第9期1-6,共6页Polymer Materials Science & Engineering

基　　金：国家自然科学基金重点资助项目(21034001);国家科技支撑计划(2013BAH03B01)

摘　　要：采用钕系稀土催化剂Nd(P204)3/Al(i-Bu)2H/CHCl3,以苯乙烯为溶剂兼做单体,进行苯乙烯(St)/异戊二烯(Ip)/丁二烯(Bd)三元共聚合反应,制备St/Ip/Bd三元集成橡胶(SIBR)。研究了经Ip、Bd陈化的催化剂对聚合活性的影响,重点考察了催化剂各组成用量对共聚合的影响。结果表明,催化剂中只有加入Ip或Bd陈化后才具有聚合活性;随着[Al]、[Cl]、[Nd]用量的增加,SIBR中St组分含量逐渐升高并在一定范围内可实现调控;[Cl]用量变化对SIBR高立体选择性和相对分子质量控制稳定性最好,其Ip、Bd组分1,4-结构含量均在98%以上,重均相对分子质量均控制在2×105左右;[Al]、[Nd]用量增加,SIBR相对分子质量下降、相对分子质量分布变窄;SIBR只有1个Tg,且随着St和Ip组分含量增加而升高;合成了Ip、Bd组分1,4-结构高立体选择性(>95%)的无规SIBR。By using Nd（P204）3/Al（ i-Bu）2H/CHCl3 as catalyst, while styrene （St） as solvent and monomer, the copolymerization of styrene（St） / isoprene（Ip） /butadiene（Bd） could be carried out, and the St/Ip/Bd integrated rubber（SIBR） could be prepared. The effect of catalyst aged by Ip or Bd on the SIBR terpolmerization reactivity was discussed and the influence of component content of catalyst was investigated on the copolymerization. The results show that the polymerization could be catalyzed activity only after the ternary catalytic systems aged with Ip or Bd; as the increase of ratio of [-Al], [ Cl], and [Nd], St component content in SIBR increases and in a certain range could be controlled; the ratio of [Cl] affects minimally on the stereoselectivity and molecular weight of SIBR, the content of Ip-1,4 and Bd-1,4 structure is above 98% and the Mw of SIBR is all controlled at about 2 × 10^5 ; with the increase of ratio of [Al] and [Nd], the molecular weight Mw and molecular weight distribution index Mw/Mn of SIBR drop; the SIBR has only one Tg, which increases with the increase of St and Ip content; the random SIBR containing Ip, Bd component 1,4-structure with high stereoselectivity（ 〉95 % ）is synthesized.

关 键 词：钕系稀土催化剂 苯乙烯/异戊二烯/丁二烯 共聚合反应 组分含量调控 

分 类 号：TQ316.61[化学工程—高聚物工业]