Organoborane Strategy for Polymers Bearing Lactone, Ester, and Alcohol Functionality

Vinyl alcohol–methacrylatecopolymers have intriguing functionally rich structures but are synthetically inaccessible from vinyl acetate, the traditional precursor to polyvinyl alcohol. We report a solution via BN 2-vinylnaphthalene (BN2VN), an aromatic vinyl borane monomer. Conventional free radical copolymerization of BN2VN and methyl methacrylate (MMA) is facile. Conversion of BN2VN side chains to VA side chains is accomplished in organic solvents with Me3NO·2H2O and avoids MMA hydrolysis. The VA–MMA copolymer rapidly lactonizes to give an unprecedented macromolecule bearing both acyclic and cyclic ester residues. Methanolysis furnishes the statistical copolymer bearing vinyl alcohol, methyl methacrylate, and lactone residues. tert-Butyl methacrylate-BN2VN copolymers were shown to not lactonize.