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 1 H− 1 H and 1 H− 13 C 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 M n between 16 and 103 kDa ( 1 H 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)].