Alternating Terpolymers through Cyclopolymerization and Subsequent Orthogonal Functionalization

A method for the synthesis of functionalized alternating copolymers by reversible deactivation radical polymerization was developed. Copolymerization by reversible addition-fragmentation chain transfer of hexenyl vinyl ether with a novel fluorinated divinyl monomer yields alternating cyclopolymers that can be chemoselectively modified by three distinct orthogonal functionalization reactions. Along the thiol-ene click reaction and amidation, a third functionalization was achieved via NHC-catalyzed transesterification or acylation resulting in a small library of ABC-type alternating terpolymers.