EAGER: CAS: Metal Mediated Perfluoroalkyl Halide Activation towards Functional Group Interconversion and Coordination Polymerization of Fluoroalkenes

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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 approaches to the synthesis of fluorinated polymers. Unlike conventional plastics, the typically nonflammable fluorinated polymers display not only high chemical and thermal resistance, but also very important electronic properties which render them indispensable in building and construction, automotive, aeronautics and aerospace industrial applications. This research will focus on developing efficient synthetic methodology to prepare fluorinated polymers with different architectures and functionalities. This project will provide training and education to undergraduate and graduate students in synthetic polymer chemistry, and development of educational material for distance-learning programs offered by the University of Connecticut to industry professionals. Outreach activities will focus on involvement of minority and female high school students in research and will be accomplished via collaborations with high school teachers. Fluorinated alkenes are among the most challenging monomers for controlled radical or coordination polymerizations. This is due to their low inherent reactivity, the low activity of their polymeric chain ends and especially to the lack of appropriate chemistry for such reactions, including initiators and catalysts. Thus, the synthesis, characterization and applications of complex fluorinated architectures lag far behind those derived from nonfluorinated monomers. This research will focus on the development of novel fluorine chemistry to overcome these deficiencies. Transition metal catalysts will be developed and utilized to interconvert inert perfluorinated alkyl halides to ones more susceptible to homolytic or heterolytic cleavage in the initiation as well as in the control of radical or ionic polymerizations of fluoromonomers. The studies will include detailed mechanistic investigations of the catalytic cycle aiming at correlating reaction parameters (strength of fluorinated alkyl-pseudohalogen bond, monomer, metal, ligand, solvent and temperature) with polymerization kinetics. This research aims to provide novel polymers with unique properties as well as potential applications in the re/upcycling of polluting perfluoroalkyl substances.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.