乙烯和降冰片烯加成共聚合催化体系  

Catalysts Used in Addition Copolymerization of Ethylene and Norbornene

作　　者：姚臻[1] 戴斌斌[1] 刘少杰[1] 曹堃[1] 傅建松[2] 谢家明[2] 

机构地区：[1]化学工程联合国家重点实验室浙江大学化工系聚合与聚合物工程研究所,杭州310027 [2]中国石油化工股份有限公司上海石化化工研究所,上海200540

出　　处：《化学进展》2010年第10期2024-2032,共9页Progress in Chemistry

基　　金：国家自然科学基金项目(No20576115);中国石化研发项目资助

摘　　要：在C5系列的综合利用中近年来备受关注的环烯烃共聚物是最具有发展潜力的高端产品之一。本文评述了用于乙烯和降冰片烯类共聚合体系新型加成催化剂的最新进展,包括茂金属催化剂、非茂金属催化剂和后过渡金属催化剂三大类。开发新型半夹心型催化剂是茂金属研究领域的热点,目前主要有两类:限定几何构型催化剂(CGC)以及Cp′MX3和Cp′M(R)X2(Cp′=茂基或取代茂基;M=Ti,Zr,Hf;X=卤素或烷基;R=OAr,NR2,NPR3)。非茂金属催化剂则具有亲电能力更强的活性中心及更开放的配位空间,通常具有更高的NB插入率,甚至在一定条件下具有类活性聚合的特征。后过渡金属催化剂由于对氧(或Lewis酸)更不敏感,导致对极性基团有更好的耐受性。此外,重点围绕配体结构对催化特性的影响,对如何提高分子量和环烯烃的有效插入率及其序列结构的调控等进行了对比和剖析,并展望其今后发展趋势。At present the cyclicolefin copolymer is one of the most promising alternative products with high level in the comprehensive utilization of C5 field,which has attracted more attention. The development of metallocene catalysts,non-metallocene catalysts and late transition metal catalysts used in ethylene-norbornene copolymerization are promptly reviewed. Developing new half-sandwich catalysts should be the hot spot in the field of metallocene catalysts. Half-sandwich catalysts can be further divided into two kinds,which are constrained geometry catalysts and Cp′ MX3 or Cp′ M （ R） X2 （ Cp′ = cyclopentadienyl group or substituted cyclopentadienyl group; M = Ti,Zr,Hf;X = halogen or alkyl; R = OAr,NR2,NPR3）. Non-metallocene catalysts have much more electrophilic metal center and more open active site,which lead to higher norbornene incorporation efficiency. In some certain conditions,it is even able to exhibit the characteristics of quasi-living polymerization. Compared to former transition metal catalysts,late transition metal catalysts should be less sensitive to oxygen and lewis acid, and owns better tolerance against the polar groups. Based on the characteristics of the copolymerization,the catalytic performance is analyzed firstly and then effect of ligand＇s structure on the catalytic property. Moreover, improving the incorporation efficiency of cyclic olefin and controlling the sequence and molecular weight should be the main focus on this paper. The future research in the area are also prospected.

关 键 词：加成共聚 降冰片烯 乙烯 茂金属催化剂 非茂金属催化剂 后过渡金属催化剂 

分 类 号：O632.1[理学—高分子化学] TQ325.1[理学—化学]