Copolymerization of Propene and Nonconjugated Diene Involving Intramolecular Cyclization with Metallocene/Methylaluminoxane

Naofumi Naga, Takeshi Shiono, Tomiki Ikeda

研究成果: Article査読

88 被引用数 (Scopus)

抄録

Copolymerizations of propene with 1,5-hexadiene and 1,7-octadiene were carried out with isospecific rac-dimethylsilylenebis(indenyl)zirconium dichloride (1) and syndiospecific diphenylmethylene-(cyclopentadienyl)(9-fluorenyl)zirconium dichloride (2) combined with methylaluminoxane. Microstructures of the copolymers were determined by 1H NMR, 13C NMR, and DEPT (distortionless enhancement of polarization transfer) spectroscopies. Incorporation of nonconjugated dienes in the copolymer was higher with 2 than with 1. Intramolecular cycloaddition of the nonconjugated dienes proceeded regardless of the catalysts. Stereoselectivity in cycloaddition of 1,5-hexadiene was investigated based on the structures of isolated methylene-1,3-cyclopentane units. It was found that 1,5-hexadiene was inserted stereospecifically by enantiomorphic site control with both catalysts. The diastereoselectivity of the cyclization step of 1,2-inserted 1,5-hexadiene was, however, found to be independent of stereospecificity of the catalyst. The cyclization selectivity of 1,5-hexadiene copolymerization was higher than that of 1,7-octadiene copolymerization. I gave the copolymers with higher selective in cyclization than 2 in the propene/1,5-hexadiene copolymerization, while the opposite tendency was observed in the propene/1,7-octadiene copolymerization. Decrease of cyclization selectivity was observed with the increases of 1,5-hexadiene and 1,7-octadiene concentration in both copolymerizations. Propene insertion could disturb the cyclization of 1,2-inserted dienes, which declined the cyclization selectivity of the copolymers, except propene/1,5-hexadiene copolymerization with 2.

本文言語English
ページ(範囲)1348-1355
ページ数8
ジャーナルMacromolecules
32
5
DOI
出版ステータスPublished - 1999 3月 9
外部発表はい

ASJC Scopus subject areas

  • 有機化学
  • ポリマーおよびプラスチック
  • 無機化学
  • 材料化学

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