Ring‐Opening Terpolymerisation of Elemental Sulfur Waste with Propylene Oxide and Carbon Disulfide via Lithium Catalysis

Abstract 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 S 8 with industrially relevant propylene oxide (PO) and CS 2 (a base chemical sourced from waste S 8 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 CS 2 and PO incorporation, allows to combine S 8 and epoxides into one polymer sequence that would otherwise not be possible. Mechanistic investigations reveal that alkyl oligosulfide intermediates from S 8 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 CS 2 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.