Polymerization of allene by organometallic initiation
作者:
William P. Baker,
期刊:
Journal of Polymer Science Part A: General Papers
(WILEY Available online 1963)
卷期:
Volume 1,
issue 2
页码: 655-670
ISSN:0449-2951
年代: 1963
DOI:10.1002/pol.1963.100010207
出版商: John Wiley&Sons, Inc.
数据来源: WILEY
摘要:
AbstractAllene has been polymerized to a high molecular weight by several transition metal salts reduced by aluminum triisobutyl. The polymer contained three types of unsaturation: vinylidene, vinyl, andcis;notransunsaturation was found. A hypothesized mechanism accounted for these facts by two competitive rates: reaction of a linear intermediate with monomer to form again the linear intermediate plus one vinylidene unit, and isomerization of the linear intermediate to a cyclic intermediate which ultimately yielded one vinylidene and one vinyl orcisunit after reaction with monomer. Thus, the ratio of the two rates was controlled by the concentration of allene. The suggested mechanism proved to predict accurately the effect of the conditions of polymerization upon the structures of the resulting polymers. The nature of the transition metal also proved of importance in determining the path of polymerization as did temperature, solvent, degree of agitation, and copolymerization. Polyallene was found to exist in three crystalline forms as well as an amorphous form.
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