Controlled Disassembly of Elemental Sulfur: An Approach to the Precise Synthesis of Polydisulfides

The usage of elemental sulfur (S₈) for constructing sulfur-containing polymers is of great significance in terms of sulfur resource utilization or fabrication of high-performance polymers. Currently, the random disassembly of S₈ hinders its direct use in the precise synthesis of sulfur-containing polymers. Herein, we provide an effective strategy for controlling the dismantlement of S₈ to synthesize polydisulfides, a promising category of dynamic bonds containing polymers. In this strategy, the completely alternating copolymerization of one sulfur atom, which is orderly derived from S₈, with episulfides is achieved with MTBD (7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene) as catalyst and [PPN]SbF₆ ([PPN]⁺ is bis(triphenylphosphine)iminium) as cocatalyst. Delightedly, the living- polymerization feature, and the good monomer compatibility allows for the access to diverse polydisulfides. Furthermore, the density functional theory (DFT) was employed to elaborate the copolymerization process.