钪半茂金属催化间同立构苯乙烯聚合及苯乙烯-乙烯共聚：苯乙烯-乙烯共聚物中前所未有的间同立构苯乙烯-苯乙烯序列的引入。

Scandium half-metallocene-catalyzed syndiospecific styrene polymerization and styrene-ethylene copolymerization: unprecedented incorporation of syndiotactic styrene-styrene sequences in styrene-ethylene copolymers.

作者信息

Luo Yunjie, Baldamus Jens, Hou Zhaomin

机构信息

Organometallic Chemistry Laboratory, RIKEN (The Institute of Physical and Chemical Research), Hirosawa 2-1, Wako, Saitama 351-0198, Japan.

出版信息

J Am Chem Soc. 2004 Nov 3;126(43):13910-1. doi: 10.1021/ja046063p.

DOI:10.1021/ja046063p

PMID:15506737

Abstract

On treatment with 1 equiv of [Ph3C][B(C6F5)4], the scandium half-sandwich bis(alkyl) complex (C5Me4SiMe3)Sc(CH2SiMe3)2(THF) showed extremely high activity (up to 1.36 x 104 kg of sPS/(mol Sc.h)) and syndiospecificity (rrrr > 99%) for the polymerization of styrene at room temperature in toluene. More remarkably, this catalyst system could also effect the syndiospecific copolymerization of styrene with ethylene to yield styrene-ethylene copolymers having syndiotactic styrene-styrene sequences. The styrene content in the copolymers could be easily controlled by changing the styrene feed and could reach higher than 80 mol %. This is the first example of formation of such types of styrene-ethylene copolymers, which are expected to show novel properties.

摘要

在用1当量的[Ph3C][B(C6F5)4]处理时，钪半夹心双（烷基）配合物(C5Me4SiMe3)Sc(CH2SiMe3)2(THF)在室温下于甲苯中对苯乙烯聚合表现出极高的活性（高达1.36×104千克间规聚苯乙烯/（摩尔钪·小时））和间同立构规整性（rrrr＞99%）。更值得注意的是，该催化剂体系还能实现苯乙烯与乙烯的间同立构共聚，生成具有间同立构苯乙烯 - 苯乙烯序列的苯乙烯 - 乙烯共聚物。通过改变苯乙烯进料，共聚物中的苯乙烯含量可轻松控制，且能达到高于80摩尔%。这是形成此类苯乙烯 - 乙烯共聚物的首个例子，预计其将展现出新颖的性能。