One-Pot Preparation of Methacrylate/Styrene Alternating Copolymers via Radical Copolymerization and Alcoholysis Modification: Sequence Impacts on Glass Transition Temperature

A series of methacrylate/styrene alternating copolymers were efficiently and systematically synthesized via alternating copolymerization of saccharin methacrylamide (1) with styrene and subsequent one-pot alcoholysis transformation with alcohols. The saccharin amide bond in 1 was stable enough that 1 was used as a bench-stable monomer, but the bond became reactive toward alcohols after the copolymerization. Thanks to the specific feature, the postpolymerization modification could be performed under mild conditions despite easy handling of the monomer. The quantitative transformation as well as the alternating sequence were certainly supported by ¹H NMR and MALDI-TOF-MS analyses. The alternating copolymers carrying relatively short alkyl pendants expressed lower glass transition temperatures than those of the statistical counterparts. Moreover, the alternating copolymerization was controlled via a RAFT polymerization system, affording a unique block copolymer composed of alternating copolymer segments.