New Strategies for Accessible Anionic Polymerizations

Anionic polymerization is a powerful approach for making advanced polymer materials with precise structures and properties. These materials are important in many technologies, including tires, adhesives, electronics, and packaging. However, current methods for performing these reactions often require specialized equipment, extremely cold temperatures, and highly reactive chemicals, making them difficult, expensive, and potentially unsafe to use. This project will develop safer, simpler, and more energy-efficient approaches for producing high-performance polymers by enabling anionic polymerizations to operate at room temperature or higher temperatures using inexpensive and less hazardous starting materials. These advances will make the preparation of advanced materials more accessible to researchers and industry while reducing energy use, waste generation, and manufacturing complexity. The project will directly support Advanced Manufacturing by creating more efficient and practical chemical processes for producing next-generation polymeric materials. In addition, the project will provide educational outreach activities that introduce local students and the broader public to the importance of polymers in everyday life, promote interest in science and engineering, and enhance public understanding of the role of scientific research in addressing societal challenges. This project will develop new strategies for controlled anionic polymerization of vinyl monomers through the use of reversible chemical reactions that regulate polymer chain growth. The research will establish polymerization methods that operate at elevated temperatures while reducing or eliminating the need for highly reactive alkyl lithium initiators, which are commonly required in traditional anionic polymerizations. Specifically, the project will investigate one-pot polymerization approaches using thermally latent initiators and carbon dioxide-mediated control of polymerization through reversible decarboxylation reactions. Carbon dioxide provides an attractive mediator because it is inexpensive, abundant, and nontoxic. In parallel, the project will develop an anionic reversible addition-fragmentation chain-transfer (RAFT) polymerization strategy that uses aldehydes as chain-transfer agents capable of undergoing reversible aldol reactions. Together, these approaches will expand the accessibility of anionic polymerization by providing safer, more energy-efficient, and operationally simpler methods for synthesizing well-defined polymer materials with advanced functional properties. 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.