Publications Details

Post-polymerization modification of polymethacrylates enabled by keto-enol tautomerization

Easterling, Charles P.; Coste, Guilhem; Sanchez, Jose E.; Fanucci, Gail E.; Sumerlin, Brent S.

We report a post-polymerization modification strategy to functionalize methacrylic copolymers through enol-ester transesterification. A new monomer, vinyl methacryloxy acetate (VMAc), containing both enol-ester and methacryloyl functionality, was successfully copolymerized with methyl methacrylate (MMA) by selective reversible addition-fragmentation chain transfer (RAFT) polymerization. Post-polymerization modification of pendent enol esters proceeded through an "irreversible"transesterification process, driven by the low nucleophilicity of the tautomerization product, to result in high conversion under mild conditions.