The Insertion Reactions of Olefins into Metal-Ethyl Bonds in the Vanadium Compounds-Ethyl Aluminum Ziegler Catalyst System. A Proposed Mechanism for the Syndiotactic Polymerization of α-Olefin

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概要

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• In order to clarify the mechanism of the syndiotactic polymerization of olefin, the insertion reaction of several olefins into metal-ethyl bonds in VCl<SUB>4</SUB>-AlEt<I><SUB>n</SUB></I>Cl<SUB>3−<I>n</I></SUB>, VOCl<SUB>3</SUB>-AlEt<I><SUB>n</SUB></I>Cl<SUB>3−<I>n</I></SUB>, and V(AA)<SUB>3</SUB>-AlEt<I><SUB>n</SUB></I>Cl<SUB>3−<I>n</I></SUB> systems were studied. Cyclohexene was easily inserted into metal-ethyl bonds in these catalysts to give a metal-ethylcyclohexyl bond at −70°C. Pentene-1 and 4-methylpentene-1 gave (<U>Remark: Graphics omitted.</U>) (I) and (<U>Remark: Graphics omitted.</U>) (II). At −70°C with VCl<SUB>4</SUB>-AlEt<SUB>2</SUB>Cl, where the syndiotactic polymerization of propylene proceeds, four times as much (II) as (I) was obtained. However, at 0°C or in the VCl<SUB>4</SUB>-AlEt<SUB>3</SUB> catalyst system, the amount of (I) exceeded the amount of (II). With the VOCl<SUB>3</SUB>-AlEt<I><SUB>n</SUB></I>Cl<SUB>3−<I>n</I></SUB> or the V(AA)<SUB>3</SUB>-AlEt<SUB>3</SUB>Cl<SUB>3−<I>n</I></SUB> system, the selectivity for the formation of metal-alkyl (II) was decreased. The above results lead to the conclusion that, in the course of syndiotactic polymerization, the secondary metal-alkyl bond (II) was an intermediate of the polymerization. By means of this mechanism every experimental result reported can be explained without difficulty.

• 公益社団法人 日本化学会の論文

著者

• SUZUKI Toshimitsu

  Department of Chemical Engineering

• Takegami Yoshinobu

  Department of Fuel Chemistry Faculty of Engineering Kyoto University

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