硫黄
化学
环氧丙烷
聚合物
二硫化碳
聚合
锂(药物)
亲核细胞
催化作用
有机化学
烷基
高分子化学
环氧乙烷
医学
共聚物
内分泌学
作者
Cesare Gallizioli,David Battke,Helmut Schlaad,Peter Deglmann,Alex J. Plajer
标识
DOI:10.1002/anie.202319810
摘要
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‐Sx) 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.
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