Abstract
The cationic polymerization of 1,3-dioxolane (DOL) initiated with methyl fluorosulfonate was investigated in deuteriochloroform (CDCl3) or nitromethane-d3 (CD3NO2) at five different temperatures ranging from −20 to 5°C by means of 1H- and 13C-NMR spectroscopy. Only an ester growing species was observed in CDCl3 solution throughout the polymerization, while the simultaneous presence of ester and ionic species was confirmed in CD3NO2 solution, except in the final stage of the polymerization where the ionic species was barely detectable. Kinetic analysis of the polymerization in CDCl3 gave the rate constant of propagation, which varied from 0.7×10−2 (−20°C) to 2.3×102 l/mol· s (5°C). The activation enthalpy ΔHp‡ and the activation entropy ΔSp‡ for the polymerization in CDCl3 were evaluated from the temperature dependence of the kp values: ΔHp‡=6.1±0.4 kcl/mol and ΔSp‡=−42±1 al/mol· deg. On the basis of these results, the mechanism of the polymerization of DOL by superacid derivatives is discussed in comparison with that for tetrahydrofuran.
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Yokoyama, Y., Okada, M. & Sumitomo, H. Kinetic Studies on the Cationic Polymerization of 1,3-Dioxolane Initiated with Methyl Fluorosulfonate. Polym J 11, 365–370 (1979). https://doi.org/10.1295/polymj.11.365
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DOI: https://doi.org/10.1295/polymj.11.365