The Steric Course of the Cationic Polymerization of Vinyl and Related Monomers. The Counterion Effect

Toyoki Kunitake

研究成果: Contribution to journalArticle査読

11 被引用数 (Scopus)

抄録

Polymerization with many triphenylmethyl salts was conducted for a-methylstyrene, isobutyl vinyl ether, t-butyl vinyl ether, and spiro[2,4]hepta-4,6-diene (SHD). The variation of polymer structure (the isotactic unit content for the first three monomer systems and the amount of the 1,4-addition structure for SHD) showed fairly simple correlations with the counteranion size. The results can be interpreted in terms of the tightness of the propagating ion pair within the framework of a theory of the cationic propagation which had been proposed. When the counteranion radius was greater than 3.5 Å, the counteranion exerts a parallel influence on the tightness of the growing ion pair without regard to the monomer structure. However, in the case of smaller counterions, the tightness appears to be determined by the relative sizes of counteranion and monomer. The penta-coordinated counteranions gave rise to the polymer structure which would arise from tighter ion pairs than expected from their sizes alone. The polymer structure was also affected by the initiator concentration in these cases. These results are attributed to peculiar characteristics of penta-coordinated anions.

本文言語英語
ページ(範囲)797-816
ページ数20
ジャーナルJournal of Macromolecular Science: Part A - Chemistry
9
5
DOI
出版ステータス出版済み - 8 1975

All Science Journal Classification (ASJC) codes

  • 工学(全般)

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