Esterification of hydroxylated polymers with 2-sulfobenzoic acid cyclic anhydride: A facile approach for the synthesis of near-monodisperse strong acid homopolymers and diblock copolymers

Abstract

A convenient two-step route was developed to prepare a range of low polydispersity strong acid homopolymers and several examples of well-defined diblock copolymers. Atom transfer radical polymerization (ATRP) of either 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate or glycerol monomethacrylate afforded the corresponding near-monodisperse hydroxylated homopolymers, while several diblock copolymer precursors were prepared by either (1) the one-pot ATRP of 2-hydroxypropyl methacrylate and 2-(diethylamino)ethyl methacrylate using sequential monomer addition or (2) the ATRP of either 2-hydroxypropyl methacrylate or glycerol monomethacrylate using a poly(ethylene oxide)-based macro-initiator. Excess 2-sulfobenzoic acid cyclic anhydride was used to fully esterify the hydroxy groups of these homopolymers and diblock copolymers under mild conditions. The resulting zwitterionic diblock copolymers undergo micellar self-assembly on adjusting the pH of the solution, while one of the anionic poly(ethylene oxide)-based diblock copolymers formed colloidal polyelectrolyte complexes in aqueous solution when mixed with a cationic poly(ethylene oxide)-based diblock copolymer.