Polymers from sugars and CS₂: synthesis and ring-opening polymerisation of sulfur-containing monomers derived from 2-deoxy-d-ribose and d-xylose

Abstract

Cyclic thionocarbonate and xanthate monomers were synthesised directly from ribose- and xylose-derived diols and CS2, and yielded novel sugar-based polymers with regioregular sulfur-containing linkages.

Polymers from sugars and CS2: ring opening copolymerisation of a d-xylose anhydrosugar oxetane

“…under UV radiation). 19,21 The synthesis of polythiocarbonates is possible through polycondensation, [22][23][24][25] the ring-opening polymerisation (ROP) of cyclic thiocarbonates, 26,27 polyalkylation of trithiocarbonates 28,29 or the ring-opening copolymerisation (ROCOP) of CS 2 15, 30-33 and COS 11,[34][35][36][37][38] with cyclic ethers (epoxides and oxetane). ROCOP methods are particularly interesting given the array of synthetic possibilities provided by the pool of cyclic ethers usable, coupled with the polymerisation control brought by existing ROCOP catalysts.…”

“…[43][44][45] Our group has previously used CS 2 to synthesise a series of cyclic thiocarbonates for ROP towards sugar-derived polythiocarbonates. 27 However, the synthesis of these monomers was challenging, necessitating extensive purification (e.g. successive column chromatography) to be suitable for ROP techniques.…”

Enabling Oxygen–Sulfur Exchange Reaction to Produce Semicrystalline Copolymers from Carbon Disulfide and Ethylene Oxide

“…However, this route has rarely been investigated. [ 10,12 ] Early explorations led to the polymers with very complicated structures. [ 13,14 ] Obstacle of this process lies in the side reaction named as oxygen–sulfur exchange reaction (O–S ER), which was successively disclosed by our group using zinc–cobalt double metal cyanide complex [ 15 ] and by the Darensbourg group using (salen)Cr complex accompanied with organic salts.…”

Control of Crystallinity and Stereocomplexation of Synthetic Carbohydrate Polymers from d‐ and l‐Xylose

“…Polymers formed this way often feature carbonate [2a–f] or related (e.g. thiocarbonate [5] or phosphoester [6] ) linkages, which can have limited thermal stability and be susceptible to chemical (e.g. hydrolytic) degradation, [2b] and may not be suited to some applications.…”