Controlled “living” anionic polymerization of glycidyl methacrylate

The living anionic polymerization of glycidyl methacrylate (GMA) in THF at low temperature initiated with diphenyl hexyl lithium, 9‐anthracenyl methyl lithium, and α‐methylstyryl lithium leads to well characterized homo‐ and block copolymers, with predictable {article}{empty}{document}Mₙ ̄{document} and narrow molecular weight distributions and with all the oxirane groups intact. Broadening of the molecular weight distributions above a certain and very critical {article}{empty}{document}Mₙ ̄{document} supported the idea that the living polymerization at low temperature might proceed in micelle‐like structures. Diffusional restriction of the monomer access towards the living centers, due to lesser solvation and increasing compactness of the polymer coils is thought to give rise to broadening of the molecular weight distribution of PGMA homo‐and block copolymers.