Carbocationic Polymerization in the Presence of Sterically Hindered Bases. IV. The Polymerization of Isobutylene by the “H2O”/AICI3Initiating System
作者:
J.P. Kennedy,
R.T. Chou,
V.S. C. Chang,
期刊:
Journal of Macromolecular Science: Part A - Chemistry
(Taylor Available online 1982)
卷期:
Volume 18,
issue 1
页码: 39-46
ISSN:0022-233X
年代: 1982
DOI:10.1080/00222338208056657
出版商: Taylor & Francis Group
数据来源: Taylor
摘要:
The effect of 2,6-di-tert-butyl-pyridine (DtBP) on isobutylene polymerization induced by AlCl3in n-hexane, CH2Cl2, and n-hexane/CH2Cl2mixtures has been investigated. Polymerization carried out in the presence of DtBP invariably yielded much reduced yields, much elevated molecular weights, and noticeably narrower molecular weight dispersities than those carried out under identical conditions except in the absence of this hindered pyridine. As expected, conversions increase while [Mbar]n's decrease and [Mbar]w/[Mbar]n's broaden with increasing [AlCl3] in the absence of DtBP; however, in the presence of DtBP, increasing [AlCl3]'s lead to increased conversions, increasing [Mbar]n's, and narrowing [Mbar]w/[Mbar]n's. At constant [AlCl3], increasing [DtBP] tends to decrease yields but at the same time increases [Mbar]nand narrow [Mbar]w/[Mbar]n. Directionally these effects remain similar by changing the polarity of the medium. The proposition of proton scavenging during chain transfer to monomer by the hindered pyridine helps to explain these observations.
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