Unraveling the Mechanism of Polymerization with the Phillips Catalyst

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 copol...

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Published in:Organometallics 2010-11, Vol.29 (22), p.6111-6116
Main Authors: McGuinness, David S, Davies, Noel W, Horne, James, Ivanov, Ivan
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Language:English
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description 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.
doi_str_mv 10.1021/om100883n
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