RAFT copolymerization of methyl methacrylate and di(ethylene glycol) methyl ether methacrylate in a hexylpyridinium ionic liquid

Smart polymers undergo significant physical or chemical changes in response to stimuli like temperature and pH. Achieving a narrow molecular weight distribution is crucial for their sensitivity. Reversible addition–fragmentation chain transfer (RAFT) in ionic liquids is an effective method for synthesizing such polymers due to its favorable kinetics and environmental benefits. Most studies use imidazolium ionic liquids, while pyridinium ionic liquids are less common despite their easy synthesis. This study reports the first successful RAFT copolymerization of di(ethylene glycol) methyl ether methacrylate (DEGMEMA) and methyl methacrylate in N-hexylpyridinium hexafluorophosphate ([HPY][PF₆]). Both linear and hyperbranched copolymers (M_n > 25,000) with narrow molecular weight distribution were synthesized, showing observable temperature responses and biocompatibility. The linear copolymers had a desirable dispersity (Ð) of less than 1.10, while the hyperbranched copolymer had a Ð of 2.034. The lower critical solution temperatures (LCSTs) of the copolymers were close to or below the LCST of PDEGMEMA (26°C). This study indicates that pyridinium ionic liquids can be explored as a suitable solvent for synthesizing methacrylate-based smart polymers.