An efficient ring-opening copolymerization of thiiranes with elemental sulfur in the presence of the fluoride anion.

Sulfurization of selected thiiranes such as 2-phenylthiirane (styrene sulfide), 2,3-tetramethylenethiirane (cyclohexene sulfide) and 2-(α-thienyl)thiirane was carried out, leading to sulfur-rich polymers. The activation of the S 8 molecule was initiated by the fluoride anion (F−) delivered by tetrabutylammonium fluoride (TBAF) dissolved in tetrahydrofuran (THF). The opening of the thiirane ring, followed by the copolymerization process, was initiated by the fluoropolysulfide anions (FS x −) generated in situ. The anionic copolymerizations were carried out under mild conditions, below the floor temperature of S 8 (159 °C), and a variable ratio of monomers (thiirane/sulfur) was applied to obtain polysulfides with a diversified sulfur content. Polysulfides were characterized using analytical (elemental analysis, gel permeation chromatography), spectroscopic (Raman spectroscopy, FTIR), and thermal (thermogravimetry (TGA), differential scanning calorimetry (DSC)) methods. Mechanistic interpretation of sulfur transfer in the anionic copolymerization of thiiranes with S 8 , in the presence of the fluoride anion, has been discussed. [Display omitted] • A series of polysulfides derived from thiiranes and elemental sulfur were synthesized. • Polymers with sulfur rank controlled by thiirane/sulfur ratio were obtained. • Structure of obtained copolymers was confirmed by vibrational spectroscopy. • Influence of sulfur rank on thermal stability and phase structure was shown. • Protocol for efficient sulfur waste management was elaborated. [ABSTRACT FROM AUTHOR]