NSF Award
2404236
With the support of the Macromolecular, Supramolecular and Nanochemistry program in the Division of Chemistry, Alexandru D. Asandei of the University of Connecticut is developing new methods for the precise synthesis of novel fluorinated polymeric materials with complex architectures, as well as exploring the re/upcycling of commercial fluoropolymers. Fluoropolymers are contrasted to conventional polymers with even simple homo/random fluoropolymers exhibiting outstanding chemical, thermal and flame resistance, biocompatibility, and unique electronic properties which render them important in high-end applications such as battery, aerospace, sensing, medical device, building, construction, and automotive industries. However, the chemical tools for the precise synthesis of analogous complex fluoropolymer materials (blocks, grafts etc.) are lacking. Thus, the project goals include the development of the required novel chemistry, to explore hitherto unknown and unavailable materials with potentially superior properties and applications leading to the associated societal benefits. This project provides training and education to undergraduate and graduate students, including minority and female students, in synthetic organic, organometallic, and polymer chemistry. The project also has strong industrial impact, important outreach activities, and the results will be broadly disseminated in the scientific literature and national and international meetings. <br/><br/>While technologically important, fluoropolymers suffer from a number of factors that have hampered new developments. These factors include a combination of very low monomer reactivity, very high propagating polymer chain end reactivity, complex and often hazardous laboratory setups, and the general lack of appropriate polymer chemistry tools (initiators, catalysts, coupling agents etc.). Accordingly, fluoroalkenes remain some of the most challenging monomers for both controlled radical and coordination polymerizations, where manipulation of molecular weight, polydispersity and architecture/sequence are of paramount importance for the emerging properties. In addition, current re/upcycling of industrial fluoropolymers remain minimal. The proposed research aims at developing innovative and environmentally conscious chemistry (e.g. water, visible light catalysis etc.), to overcome the above deficiencies, and significantly enlarges the fluoro, organic and polymer synthesis toolbox, while providing access to novel fluoropolymer materials. This includes the elaboration of novel, functional, universal radical initiating systems that enable both controlled radical fluoro/regular alkene polymerizations and chain end derivatizations/couplings towards the synthesis of multiblock copolymers, in-depth mechanistic investigations on optimizing polymerization parameters and understanding the structure/property/function in the resulting fluoropolymers, as well as exploration of the coordination polymerization of fluoroalkenes, and the up/recycling of industrial fluoropolymers.<br/><br/>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.
