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

本研究的重点是开发新的α -氢氮氧化物，用于介导活性自由基聚合的功能化乙烯基单体。利用氟相化学的平行合成将被用于文库的制备。反过来，这些文库将被筛选为聚合引发剂的功效。聚合性能的实验反馈加上旨在降低n -烷氧胺的C-O键的键解离能的空间变化将用于制备更好的引发剂。将制备水溶性氮氧化物，将这种受控聚合方法扩展到水介质。该方法将提供非常低的多分散性和控制分子量的聚合物，生成定义良好的随机共聚物和嵌段共聚物，并为开发具有复杂分子结构的先进材料提供途径。有了这个奖项，有机和大分子化学项目支持加州大学圣克鲁斯分校化学系Rebecca Braslau博士的研究。Braslau教授将专注于开发新的氮氧化物，用于“活的”自由基聚合。这项研究，包括与IBM的Craig Hawker博士正在进行的合作，将导致对生物技术，微电子制造和催化剂设计具有重要意义的材料的生产。该研究对研究生和本科生的教育也有更广泛的影响。

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.