Design and Preparation of Alpha-Hydrogen Nitroxides for 'Living' Free Radical Polymerization

用于“活性”自由基聚合的α-氮氧化合物的设计和制备

• 批准号: 0078852
• 负责人: Rebecca Braslau
• 金额: $ 37.26万
• 依托单位: University of California-Santa Cruz
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2000
• 资助国家: 美国
• 起止时间: 2000-08-01 至 2004-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0078852&HistoricalAwards=false
• 关键词: Design; Preparation; Alpha; Hydrogen; Nitroxides

The focus of this research is the development of new alpha-hydrogen nitroxides for the mediation of "living" free radical polymerization of functionalized vinyl monomers. Parallel synthesis utilizing fluorous phase chemistry will be employed for the preparation of libraries. The libraries, in turn, will be screened for efficacy as polymerization initiators. Experimental feedback from polymerization performance coupled with steric variations aimed at lowering the bond dissociation energy of the C-O bond of the N-alkoxyamines will be used to prepare even better initiators. Water soluble nitroxides will be prepared to extend this controlled polymerization method to aqueous media. The methodology will afford polymers of very low polydispersities and controlled molecular weights, generating well defined random and block copolymers, and provide access to the development of advanced materials with complex molecular architectures.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Rebecca Braslau of the Department of Chemistry at the University of California -Santa Cruz. Professor Braslau will focus her work on developing new nitroxides for application in "living" free radical polymerization. The research, that includes an on-going collaboration with Dr. Craig Hawker at IBM, will lead to the production of materials having importance to biotechnology, microelectronic fabrication and catalyst design. The research also has broader impact in the education of graduate and undergraduate students.

本研究的重点是开发新的α-氢氮氧化物，用于介导官能化乙烯基单体的“活性”自由基聚合。将采用利用氟相化学的平行合成来制备文库。 反过来，将筛选文库作为聚合引发剂的功效。 来自聚合性能的实验反馈加上旨在降低N-烷氧基胺的C-O键的键离解能的空间变化将用于制备甚至更好的引发剂。 将制备水溶性氮氧自由基以将这种受控聚合方法扩展到水性介质。 该方法将提供非常低的多分散性和可控的分子量的聚合物，生成定义明确的无规和嵌段共聚物，并提供访问的复杂分子结构的先进材料的开发。有了这个奖项，有机和大分子化学计划是支持博士的研究丽贝卡Braslau的化学系在加州-圣克鲁斯大学。 Braslau教授将专注于开发新的氮氧化物，用于“活性”自由基聚合。 这项研究包括与IBM的克雷格霍克博士正在进行的合作，将导致生产对生物技术、微电子制造和催化剂设计具有重要意义的材料。 该研究还对研究生和本科生的教育产生了更广泛的影响。