Dramatic decrease of the cis content and molecular weight of cis-transoidal polyphenylacetylene at 23°C in solutions prepared in air

被引：68

作者：

Percec, V ^{[1
]}

Rudick, JG ^{[1
]}

Nombel, P ^{[1
]}

Buchowicz, W ^{[1
]}

机构：

[1] Univ Penn, Dept Chem, Roy & Diana Vagelos Labs, Philadelphia, PA 19104 USA

来源：

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY | 2002年 / 40卷 / 19期

关键词：

cis-transoidal polyphenylacetylene; intramolecular cyclization; cis-trans isomerization; chain cleavage; living polymerization; isomerization;

D O I：

10.1002/pola.10421

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

The thermal cis-trans isomerization of cis-transoidal polyphenylacetylene (PPA) synthesized with Noyori's catalyst [Rh(CdropCPh)(norbornadiene)(PPh3)(2)] has been investigated under both ambient and inert atmospheres in solution and in bulk. In all cases, an intramolecular cyclization results in cis-trans isomerization, and subsequent chain cleavage produces 1,3,5-triphenylbenzene. This reaction is accelerated by the presence of air, particularly when the reaction takes place in solution. Decreases in the cis content and molecular weight show that the intramolecular cyclization process takes place at 23 degreesC in solution. The mechanism of this reaction is identical to that reported previously for cis-cisoidal and cis-transoidal PPA synthesized with Ziegler-Natta catalysts. (C) 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3212-3220, 2002.

引用

页码：3212 / 3220

页数：9

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