Metal-Catalyzed Olefin Polymerizations: Mechanistic Studies and Catalyst Design

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Maurice Brookhart, Department of Chemistry, University of North Carolina at Chapel Hill, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program for his continued work investigating olefin polymerization and copolymerization catalysts. These late metal catalysts offer functional group tolerance and novel polymer microstructures. Detailed mechanistic studies of these polymerizations and copolymerizations should yield insights for designing new catalysts. Particular foci include: (a) the reactivity of neutral Ni(II) catalysts with functionalized olefins such as methylacrylate and vinyl acetate; (b) the detailed mechanism of copolymerization of carbon monoxide with olefins using various Ni(II) catalysts; and (c) the mechanistic features of Ni(II) and Pd(II) diimine catalysts, their analogs and super-active iron and cobalt ethylene polymerization catalysts. Intensive research has been directed toward understanding fundamental aspects of metal-catalyzed olefin polymerization and the results ofthese studies have been used to develop new catalysts. These have been enormously important contributions since over thirty billion pounds of polyolefin are produced in the United States each year. Most of the commercial olefin polymerization catalysts are based on early transition or lanthanide metals. In this project a series of highly versatile late transition metal catalysts will be investigated. These studies will provide fundamental mechanistic information on how catalysts join olefins to one another during the polymerization process as well as guide developments of new catalyst systems with potential industrial applications.