Controlled/Living Free-Radical Copolymerization Of Allyl Glycidyl Ether

Benzyl ¹H-imidazole-l-carbodithioate (BICDT) and 4,4'-bis(imidazole -l-carbodithioatemethyl)biphenyl (ICTMP ) were successfully synthesized and characterized. An investigation of the copolymerization behavior of allyl glycidyl ether (AGE), an epoxy-functional monomer with methyl acrylate (MA) was performed using BICDT and ICTMP as RAFT agents under ⁶⁰Co γ-ray irradiation and thermal initiation condition.The polymerizations of AGE and MA revealed good characteristics of free radical living polymerization under ⁶⁰Co γ-ray irradiation and thermal initiation condition. The molecular weight of the obtained polymer increases linearly with monomer conversion, molecular weight distribution is very narrow, and a linear relationship between In([M]₀/[M]) and polymerization time exists. The polymer structures were characterized by ¹H NMR spectra. No evidence was found for the reaction of epoxy groups.Monofunctional and bifunctinal MacroRAFT agents of polystyrene were obtained respectively by polymerizations of styrene in the presence of BICDT and ICTMP via the thermal initiation. Then eopolymerizations of AGE with MA were performed to prepare the functional block copolymers in the presence of PSt macroRAFT agents, diblock copolymers and triblock copolymers, polystyrene-b- poly(methyl acrylate/allyl glycidyl ether) and poly(methyl acrylate/allyl glycidyl ether)-b-polstyrene- poly(methyl acrylate/allyl glycidyl ether), were obtained with controlled molecular weight and a narrow distributuion of molecular weight and the structures of these copolymers were confirmed by ¹H NMR spectra. This work developed a promising strategy for the preparation of novel epoxy resins by controlled/living free radical copolymerizations of AGE with vinyl monomers.