“Living” free radical ring-opening polymerization of 2-methylene-4-phenyl-1,3-dioxolane by atom transfer radical polymerization

The “living” free radical ring-opening polymerization of 2-methylene-4-phenyl-1,3-dioxolane (MPDO) in the presence of ethyl α-bromobutyrate/CuBr/2,2′-bipyridine at various temperatures has been investigated. In comparison with the conventional ring-opening polymerization of MPDO, a lower content of ring-opened unit in the polymer was found. The results of ln[M]0/[M]) against polymerization time, (Mn)th and (Mn)NMR vs conversion, and GPC of the polymers are strongly indicative of the “living” polymerization process. Initiator efficiency was measured. The mechanism of polymerization, and the effect of pyridine on the polymerization mechanism were discussed.