Chalcogenide hybrid inorganic/organic polymers (CHIPs) via inverse vulcanization and dynamic covalent polymerizations

We report on the preparation and modification of chalcogenide hybrid inorganic/organic polymer (CHIPs) via the inverse vulcanization of elemental sulfur with styrenics to afford low glass transition (Tg) copolymers. Furthermore, poly(sulfur-random-styrene) (poly(S-r-Sty)) can be further utilized as reactive liquid resins that are miscible with a wider range of styrenic, acrylate and allylic comonomers. We describe a new process termed, dynamic covalent polymerization (DCP), where the dynamic S–S bonds in poly(S-r-Sty) liquid polysulfides were thermally activated to generate sulfur radicals that added to vinylic comonomers to prepare novel terpolymer CHIPs. Using this sequential process we demonstrate the ability to incorporate functional comonomers that were otherwise immiscible with liquid sulfur.