New Polymerization Reactions

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This project is concerned with the development of new chemical reactions for the repetitive formation of sp3-sp3 carbon-carbon bonds. The products of these reactions, carbon backbone polymers, comprise some of the most important synthetic materials known. Traditional methods for polymer synthesis involve polymerization of alkenes. The project will study new reactions involving the polymerization of ylides and diazoalkane monomers with Lewis acidic catalyst/initiators. These reactions build the carbon backbone one carbon at a time and provide exceptional control over molecular weight and polydispersity. Novel polymer topologies, not readily available by conventional olefin polymerization, will also be studied using these new reactions. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Kenneth J. Shea of the Department of Chemistry at the University of California, Irvine. Professor Shea's research efforts revolve around synthetic and mechanistic organic chemistry and span polymers, functional materials and catalysis. His research is of broad interest to polymer scientists for establishing structure/property relationships, for synthesizing polymer compatibilizing and blending agents, as standards for molecular weight calibration, and as surface modifiers for commodity plastics. His method can also be used to synthesize polymers for testing fundamental concepts of polymer physics such as the influence of topology on polymer diffusion, melt behavior, crystallization and solution viscosity. In addition, since many olefins do not readily polymerize, these alternative synthetic methods can serve as an entry to completely new substances and properties. Collaborations with the major producers of polyethylene have been established which will lead to extensive characterization of the properties of these materials.