Anionic ring-opening polymerization of -thionocaprolactone was examined. When organolithiums, Grignard reagents, and lithium tert-butoxide were used as the initiators, the corresponding polythiocarboxylic-O-ester was selectively formed. When potassium tert-butoxide and 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU) were used, the corresponding polythiocarboxylic-S-ester was predominantly formed. The monomer conversion and M n of the obtained polymer increased with the polymerization temperature. Elongation of polymerization time resulted in decrease of the polymer yield and Mn. The polymerization in tetrahydrofuran (THF) proceeded faster compared with the polymerization in toluene. Formation of a cyclic dimer was observed in the polymerization in THF.
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