Unraveling the Mechanism of Polymerization with the Phillips Catalyst

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• 作者：David S. McGuinness ; Noel W. Davies ; James Horne ; Ivan Ivanov
• 刊名：Organometallics
• 出版年：2010
• 出版时间：November 22, 2010
• 年：2010
• 卷：29
• 期：22
• 页码：6111-6116
• 全文大小：785K
• 年卷期：v.29,no.22(November 22, 2010)
• ISSN：1520-6041

文摘

The mechanism of polymer chain growth at the Phillips catalyst has been studied, with the three prevailing mechanistic proposals, the Cosee−Arlman, Green−Rooney, and metallacycle mechanisms, considered. Through analysis of low molecular weight oligomers/polymers formed during ethylene/α-olefin copolymerization with labeled monomers, it is shown that the isotopomer distribution is inconsistent with a metallacycle mechanism. Further analysis of polymer formed by copolymerization of labeled ethylene was used to rule out a Green−Rooney mechanism. The results support the notion of chain growth via a Cossee−Arlman process.