A novel alicyclic polythiocarbonate with a complex structure sequence has been synthesized by a convenient one-pot polymerization of carbon disulfide (CS2) and cyclohexene oxide (CHO) with Zn-CoⅢ double-metal cyanide complex (DMCC) as the catalyst.The catalytic activity of the Zn-CoⅢ DMCC could reach to 445 g polymer/g catalyst when the reaction temperature was 100℃ and molar ratio of CHO/CS2 was 2Further increasing or decreasing the temperature resulted in a decrease in the catalytic activity.The weight-average molecular weight (Mw) of the obtained copolymer was in the range of 1.1×103～1.3×103 with a molecular weight distribution (MWD) of 1.57～1.71The copolymer has terminated —OH and —SH groups from the results of FTIR spectrum and Raman spectrum.Furthermore

one carbonate unit —O(O)CO—

and four thiocarbonate units —S(O)-CO—

—S(O)CS—

—S(S)CO—

and —S(S)CS— in the copolymer were found from 1H and 13C-NMR spectra

and the monothiocarbonate unit (—S(O)CO—) was the main unit in the copolymer

which was consistent with the results from FTIR spectrum.Cyclohexene sulfide

which was a direct evidence for O—S atom-exchange reaction

was detected by GC-MS technique from the products.Only hexahydro-benzo［1

3］oxathiol-2-one

hexahydro-benzo ［1

3］ dithiol-2-one

and hexahydro-benzo ［1

3］ dithiole-2-thione(theoretically six five-membered cyclic products) were detected due to the monomer structural factors and thermodynamical factors.The copolymer chain structure and variety of cyclic products indicates that an O—S atom-exchange reaction existed in the copolymerization.Further efforts and experiments are on going in order to further explore the mechanism of the atom-exchange copolymerization and with a view to synthesizing a sulfur-containing polymer with high molecular weights

controllable stereochemical structures

as well as high catalytic activity.