Abstract
The cationic polymerization mechanism of β,β-dimethyl-β-propiolactone (DMPL) was studied by examining the microstructure of copolymers with 1,3-dioxolane (DOL), 3,3-bis(chloromethyl)oxacyclobutane (BCMO) and styrene (St), using high-resolution NMR. DMPL copolymerizes almost randomly with DOL and BCMO, but hardly copolymerizes with St at all. The relative reactivities of the cyclic monomers are BCMO>DOL>DMPL in accord with the order of monomer basicity. Ring opening polymerization of DMPL occurs through alkyl–oxygen fission, with the oxonium ion more likely to be the propagating species than the carbonium ion.
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Yamashita, Y., Kondo, S. & Ito, K. Cationic Copolymerization of β, β-Dimethyl-β-propiolactone with 1,3-Dioxolane, 3,3-Bis(chloromethyl)oxacyclobutane and Styrene. High-Resolution NMR Studies on Sequence Distribution of Copolymers. Polym J 1, 327–333 (1970). https://doi.org/10.1295/polymj.1.327
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DOI: https://doi.org/10.1295/polymj.1.327