NMR spectroscopic characterization of polyhalodisulfides via sulfenyl chloride inverse vulcanization with sulfur monochloride

摘要: The preparation of sulfur containing polymers from inexpensive, commodity sulfur base chemicals is an emerging field of polymer chemistry as a route to consume elemental sulfur generated from fossil fuel refining. Recently a new process, termed, sulfenyl chloride inverse vulcanization has been developed that exploits the high reactivity and miscibility of sulfur monochloride, (S2Cl2) with a broad range of allylic monomers to prepare soluble, high molar mass linear polymers, segmented block copolymers and crosslinked thermosets with greater synthetic precision than achieved using classical inverse vulcanization with elemental sulfur. However, the ring-opening of episulfonium intermediates from this polymerization can proceed via Markovnikov, anti-Markovnikov, or alternative pathways resulting in complex regioisomeric microstructures, particularly when used with allylic ester monomers. Hence, to accelerate …