Cationic ring-opening polymerization of ϵ-thionocaprolactone was examined. The corresponding polythioester with the number-average molecular weight (Mn ) of 57,000 was obtained in the polymerization with 1 mol % of BF3 · OEt2 as an initiator in CH2Cl2 at 28 °C for 5 h with quantitative monomer conversion. The Mn of the polymer increased with the solvent polarity and monomer-to-initiator ratio. No polymerization took place below −30 °C, and the monomer conversion and Mn of the polymer increased with the temperature in the range of −15 to 28 °C. The increase of initial monomer concentration was effective to improve the monomer conversion and the Mn of the obtained polymer.
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Sanda et al. (2000) studied this question.
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