Radical Copolymerization Behavior of 2,2-Dimethyl-5-methylene-1,3-dioxolan-4-one with Common Monomers

Radical copolymerization of 2,2-dimethyl-1,3-dioxolan-4-one (DMDO) consisting of a hybrid structure of acrylate and vinyl ether moieties with styrene, methyl methacrylate, and vinyl acetate was examined. The radical copolymerization was carried out without a solvent or in chlorobenzene in the presence of 3 mol-% of 2,2′-azoisobutyronitrile at 60°C for 20 h to obtain the copolymers with number-average molecular weights of 1 400-700 000 in 27–86% yields. No ring-opening occurred but vinyl polymerization of DMDO selectively proceeded in the copolymerization. The monomer reactivity ratios were evaluated as r1 = 6.42, r2 = 0.08 (M1, DMDO; M2, styrene) by the Fineman-Ross method. The Alfrey-Price Q- and e-values of DMDO were calculated as 5.97 and –0.13, respectively. Ab initio molecular orbital calculations were carried out to compare the reactivity of DMDO with methyl α-methoxyacrylate and vinyl ether.