Polymerization of 4-methylene-1,3-dioxolane derivatives

Abstract

4-Methylene-1,3-dioxolane derivatives such as 2-thienyl-4-methylene-1,3-dioxolane(TMD), 2-thienyl-2-methyl-4-methylene-1,3-dioxolane(TMMD), and 2-furyl-4-methylene-1,3-dioxolane(FMD) were synthesized, and their polymerization behaviors under various conditions were investigated. It was observed that no polymerization took place in the presence of various radical initiators. While, these monomers exhibited quite different behaviors in cationic polymerization. The reactivity of TMMD was lower than that of TMD. And some crosslinked polymers were obtained from FMD in the presence of boron trifluoride. Infrared spectra of those polymers from TMMD, TMD, and FMD showed characteristic carbonyl stretching bands. This indicates that the polymerization takes place in such a manner that the carbon-carbon double bond opening is coupled with a concurrent ring opening in the propagation step to give ketoether sequences. Copolymerization studies of these monomers with comonomers such as AN and MMA were conducted. With MMA, copolymers were obtained in low conversions. On the other hand, the alternating copolymers were obtained with AN. The copolymerization of these monomers with MA gave rise spontaneously to the alternating copolymers by the participation of charge-transfer complexes. However, it could not determined due to the overlapping peaks of UV spectra and the equilibrium constant(K) is seems to be small.