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.