由甲基铝氧烷活化的角型茂金属催化剂引发的烯烃聚合过程中形成的反应中间体：通过 NMR 方法鉴定的链载中间体。

Reactive intermediates formed during olefin polymerization by methylalumoxane-activated ansa-zirconocene catalysts: identification of a chain-carrying intermediate by NMR methods.

机构信息

Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Science, Pr. Lavrentieva 5, Novosibirsk, RU-630090, Russia.

出版信息

J Am Chem Soc. 2010 Jan 20;132(2):452-3. doi: 10.1021/ja909157r.

DOI:10.1021/ja909157r

PMID:20020742

Abstract

Addition of 1-hexene to methylalumoxane-activated catalyst systems based on rac-Me(2)Si(ind)(2)ZrMe(2) causes, concurrent with polyhexene formation and diminution of the otherwise prevalent cation rac-Me(2)Si(ind)(2)Zr(mu-Me)(2)AlMe(2), formation of a hitherto unobserved species rac-Me(2)Si(ind)(2)Zr(mu-R)(mu-Me)AlMe(2), where R is a Zr-bound polyhexyl chain. As hexene is increasingly consumed, this cation decays, mainly back to rac-Me(2)Si(ind)(2)Zr(mu-Me)(2)AlMe(2) and, in part, to some species containing a Zr-bound allylic chain end.

摘要

1-己烯的添加到基于 rac-Me(2)Si(ind)(2)ZrMe(2)的甲基铝氧烷活化催化剂体系中，与聚己烯的形成和通常存在的阳离子rac-Me(2)Si(ind)(2)Zr(mu-Me)(2)AlMe(2)的减少同时发生，形成了一种迄今未观察到的物种rac-Me(2)Si(ind)(2)Zr(mu-R)(mu-Me)AlMe(2)，其中 R 是 Zr 结合的聚己基链。随着己烯的不断消耗，这种阳离子会分解，主要回到rac-Me(2)Si(ind)(2)Zr(mu-Me)(2)AlMe(2)，部分则回到一些含有 Zr 结合的烯丙基链末端的物种。