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Anionic ring-opening polymerization of ε-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 M n . 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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Sanda et al. (1999) studied this question.
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