Structure-Reactivity Correlation in Atom Transfer Radical Polymerization and Addition Processes

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The Organic and Macromolecular Chemistry Program support Professor Krzysztof Matyjaszewski of the Department of Chemistry at Carnegie Mellon University for research on atom transfer radical polymerization, which is based on the use of radical polymerization to convert monomer to polymer. The purpose of the proposed research is to perform a systematic mechanistic investigation into the transition metal catalyzed atom transfer radical polymerization (ATRP) and addition (ATRA).The main goal is to determine the structure of the catalytic and intermediate species in both ATRP and ATRA, and to build a comprehensive structure-reactivity relationship for alkyl, (pseudo)halogen, transition metal, and ligand components of these reactions under different conditions. The ability of ATRP and ATRA to produce well-controlled products depends heavily on these kinetic parameters, and therefore their determination is of vital importance in the development of new and more efficient catalysts. The systematic investigation of the structures and reactivities of the species involved in ATRA and ATRP will lead to a greater depth of understanding of these reactions. This will advance and optimize both synthetic methods, such as the development of more effective catalysts, and expansion of the range of polymerizable monomers to alpha-olefins, vinyl acetate and acrylic acid, which will allow new materials to be produced more efficiently and with greater yields and selectivity.The Organic and Macromolecular Program supports Professor Krzysztof Matyjaszewski of the Department of Chemistry at Carnegie Mellon University whose research program has substantial technological and economic significance. Living radical polymerization can be used to produce new classes of advanced materials for applications in electronics, fabrication, and environmental uses. Results from the fundamental studies emerging from this research will impact advances in many technologies including sensors, which are important to security issues. This project will also continue to educate and train students in several technologically significant areas of polymer chemistry and material science.