Metal-Catalyzed Olefin Polymerizations: Mechanistic Studies and Catalyst Design

金属催化烯烃聚合：机理研究和催化剂设计

• 批准号: 0107810
• 负责人: Maurice Brookhart
• 金额: $ 47.5万
• 依托单位: University of North Carolina at Chapel Hill
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-08-01 至 2007-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0107810&HistoricalAwards=false
• 关键词: Metal; Catalyzed; Olefin; Polymerizations; Mechanistic

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.

位于查佩尔山的北卡罗来纳州大学化学系的Maurice Brookhart因其对烯烃聚合和共聚催化剂的持续研究而得到无机、生物无机和有机化学计划的支持。这些后金属催化剂提供官能团耐受性和新颖的聚合物微结构。这些聚合和共聚反应的详细机理研究应产生设计新的催化剂的见解。具体重点包括：（a）中性Ni（II）催化剂与官能化烯烃如丙烯酸甲酯和乙酸乙烯酯的反应性;（B）使用各种Ni（II）催化剂的一氧化碳与烯烃共聚的详细机理;和（c）Ni（II）和Pd（II）二亚胺催化剂、它们的类似物和超活性铁和钴乙烯聚合催化剂的机理特征。 金属催化烯烃聚合的基础研究已被广泛用于开发新的催化剂。这些都是非常重要的贡献，因为美国每年生产超过300亿磅的聚烯烃。大多数商业烯烃聚合催化剂基于前过渡金属或镧系金属。在这个项目中，一系列高度通用的后过渡金属催化剂将被研究。这些研究将提供有关催化剂在聚合过程中如何将烯烃彼此连接的基本机理信息，并指导具有潜在工业应用的新催化剂体系的开发。