Metal-Catalyzed Olefin Polymerizations: Mechanistic Studies and Catalyst Design

莫里斯·布鲁克哈特，北卡罗来纳大学教堂山分校化学系，因其对烯烃聚合和共聚催化剂的持续研究而得到无机化学、生物无机化学和金属有机化学计划的支持。这些新型金属催化剂具有官能团耐受性和新颖的聚合物微结构。对这些聚合和共聚的详细机理研究将为设计新的催化剂提供见解。特别关注的焦点包括：(A)中性Ni(II)催化剂与功能化烯烃(如甲基丙烯酸酯和乙酸乙烯酯)的反应性；(B)各种Ni(II)催化剂用于一氧化碳与烯烃共聚的详细机理；以及(C)Ni(II)和Pd(II)双亚胺催化剂及其类似物和超活性铁和钴乙烯聚合催化剂的机理特征。为了了解金属催化的烯烃聚合的基本方面，人们进行了大量的研究，这些研究的结果已经被用于开发新的催化剂。这些都是非常重要的贡献，因为美国每年生产的聚烯烃超过300亿磅。大多数商用的烯烃聚合催化剂都是基于早期过渡金属或稀土金属。在本项目中，将研究一系列用途广泛的后过渡金属催化剂。这些研究将为催化剂在聚合过程中如何相互连接烯烃提供基本的机理信息，并指导具有潜在工业应用的新催化剂体系的开发。

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.