Well-Defined Glycopolymers from RAFT Polymerization: Poly(methyl 6-<i>O</i>-methacryloyl-α-<scp>d</scp>-glucoside) and Its Block Copolymer with 2-Hydroxyethyl Methacrylate

Abstract

The glycomonomer methyl 6-O-methacryloyl-α-d-glucoside was prepared by lipase-catalyzed transesterification of vinyl methacrylate with methyl α-d-glucoside in dry acetonitrile. The desired 6-O regioisomer was obtained in good yield and its structure confirmed by 1H−1H and 1H−13C correlation NMR spectroscopy. Reversible addition−fragmentation chain transfer (RAFT) polymerization of the unprotected monomer was performed directly in aqueous solution using (4-cyanopentanoic acid)-4-dithiobenzoate as the chain transfer agent to give poly(methyl 6-O-methacryloyl-α-d-glucoside) with Mn between 16 and 103 kDa (1H NMR) and polydispersities as low as 1.10. Chain extension of one of these polymers with 2-hydroxyethyl methacrylate afforded the novel hydrophilic−hydrophilic block copolymer poly[(methyl 6-O-methacryloyl-α-d-glucoside)-block-(2-hydroxyethyl methacrylate)].