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

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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.