Ring-Opening Terpolymerisation of Elemental Sulfur Waste with Propylene Oxide and Carbon Disulfide via Lithium...

Elemental sulfur, a waste product of the oil refinement process, represents a promising raw material for the synthesis of degradable polymers. We show that simple lithium alkoxides facilitate the polymerisation of elemental sulfur S₈ with industrially relevant propylene oxide (PO) and CS₂ (a base chemical sourced from waste S₈ itself) to give poly(monothiocarbonate-alt-S_x) in which x can be controlled by the amount of supplied sulfur. The in situ generation of thiolate intermediates obtained by a rearrangement, which follows CS₂ and PO incorporation, allows to combine S₈ and epoxides into one polymer sequence that would otherwise not be possible. Mechanistic investigations reveal that alkyl oligosulfide intermediates from S₈ ring opening and sulfur chain length equilibration represent the better nucleophiles for inserting the next PO if compared to the trithiocarbonates obtained from the competing CS₂ addition, which causes the sequence selectivity. The polymers can be crosslinked in situ with multifunctional thiols to yield reprocessable and degradable networks. Our report demonstrates how mechanistic understanding allows to combine intrinsically incompatible building blocks for sulfur waste utilisation.