Captodative Initiators and Monomers: A New Synthetic Approach to High Polymers

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This research involves development of a new approach to radical initiated polymerization based on the concept of captodative stabilization, and the use of new initiating systems based on reversible dimerization of cyclic captodative radicals. New monomers will be synthesized that will allow evaluation of the balance between radical stabilization and reactivity. Dehydroalanine derivatives (which are known to be highly active radical monomers) will be examined first to evaluate tacticity, copolymerizability, and the use of reversible termination by coupling to generate radical block copolymers. Analogs of dehydroalanines will then be synthesized in which the captodative groups include combinations of nitrile, nitrate, sulfonate, or phosphonate derivatives with amine, hydroxyl, sulfhydryl, or silyl functionality. Bond strengths and charge distributions of monomers and intermediates will be calculated and correlated with empirical data.