CAREER: Exploiting the Brook Rearrangement for Anionic Migration Polymerization (AMP)

With the joint support of the Macromolecular, Supramolecular and Nanochemistry program in the Division of Chemistry and the Established Program to Stimulate Competitive Research (EPSCoR), Professor Aaron Teator of the University of Kansas will develop new polymerization methods with enhanced control over molecular structure. While current synthetic approaches have led to incredible high-performance materials, the available structure space is limited to monomers designed to undergo chain growth by shifting electrons through existing carbon-carbon double bonds. In this research, a through-space transfer of electrons facilitated by functional group migration will be used to control the growth of polymer chains. This will allow for precise control over the number of carbons in each repeat unit based on monomer design. Careful optimization of this approach, coupled with a thorough kinetic and mechanistic exploration will provide access to a new class of synthetic polymers. This proposal has the potential to deliver fundamental knowledge in multiple areas of chemistry, including small molecule reactivity, mechanistic analysis, and polymer methods development. The associated education plan complements and enhances the project by integrating chemical research with education and using societally relevant plastics to generate excitement about organic synthesis. This project will focus on the development of chain-growth polymerizations centered on anionic silyl migration as a key propagation step. In the first objective, careful optimization of reaction conditions will establish through-space active site transfer as a viable approach for chain-growth polymerization. This will provide important fundamental scientific discoveries related to reactivity, reaction design, and structure that will serve as the foundation to expand the approach to a platform methodology. In the second objective, a thorough analysis of reaction kinetics will further mechanistic understanding of the polymerization and aid in the development of design principles to both improve the current approach and enhance future iterations. In the last objective, systematic characterization of thermal, mechanical, and physical properties will reveal important structure-property relationships. This research has the potential to establish a new platform method for the preparation of functional polymers with broad appeal to the organic and polymer communities. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.