Enhancing Efficiency of Atom Transfer Radical Polymerization

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Polymers are used in a wide range of products including household appliances, furniture, automotive components, electronics, medical devices, and pharmaceuticals. Atom transfer radical polymerization (ATRP) is an important method for synthesis of well-defined polymers. ATRP is already commercially used by several companies world-wide and therefore, it is critically important to enhance efficiency of the polymerization process and minimize its environmental impact. The Macromolecular, Supramolecular and Nanochemistry Program of the Chemistry Division supports research of Prof. Matyjaszewski of Carnegie-Mellon University (CMU) to increase our fundamental understanding of the correlation between structure and activities of ATRP catalysts. The results of this research could lead to more efficient catalysts and new catalysts in benign media, such as water, and affect commercial production of well-defined polymers made by ATRP. The generated information is disseminated via timely publications, at (inter)national meetings, and at CMU web-site. The knowledge gained is also shared with industry through the Controlled Radical Polymerization (CRP) Consortium. In addition, this project provides education and research training opportunities to undergraduate and graduate students, preparing them for careers in academia or polymer industry. The proposed research activities include design, synthesis and evaluation of new highly active, selective and stable copper(Cu)- and iron(Fe)-based ATRP catalysts. The project encompasses computational modeling, kinetic and mechanistic studies, and polymer synthesis and characterization. The mechanism of reduction (comproportionation/disproportionation) and activation processes by Cu(0) and Cu(I)in aqueous media are investigated. Improved livingness and efficiency of new catalyst in benign media can impact various areas of polymer science by giving access to complex (co)polymers with better controlled architecture. New active iron-based catalysts should be less expensive and less toxic than copper-based systems, and potentially can also expand range of polymerizable monomers and open new avenues for synthesis of well-defined polymers for advanced applications.