大连理工大学任伟民 团队通过单质硫的控制分解开发了一种精确合成聚二硫化物的方法。相关研究成果发表在2022年2月7日出版的国际知名学术期刊《德国应用化学》。

利用单质硫（S8）构建含硫聚合物对硫资源利用或制备高性能聚合物具有重要意义。目前，S8的随机分解阻碍了其直接用于含硫聚合物的精确合成。

该文中，研究人员提供了一种有效的策略来控制S8的分解，从而合成聚二硫化物，这是一种很有前途的含动态键聚合物。在该策略中，以MTBD（7-甲基-1,5,7-三氮杂双环[4.4.0]dec-5-烯）为催化剂，以[PPN]SbF 6（[PPN]+为双（三苯基膦）亚胺）为助催化剂，实现了一个硫原子（有序地从S8衍生）与环硫醚的完全交替共聚。令人高兴的是，活性聚合特性和良好的单体相容性能够使用多种聚二硫化物。此外，利用密度泛函理论（DFT）对共聚过程进行了阐述。

附：英文原文

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

Author: Wei-Min Ren, Ji-Yan Chao, Tian-Jun Yue, Bai-Hao Ren, Ge-Ge Gu, Xiao-Bing Lu

Issue&Volume: 2022-02-07

Abstract: The usage of elemental sulfur (S  8  ) for constructing sulfur-containing polymers is of great significance in terms of sulfur resource utilization or fabricating high-performance polymers. Currently, the random disassembly of S  8  hinders its direct use in the precise synthesis of sulfur-containing polymers. Herein, we provide an effective strategy for controlling the dismantlement of S  8  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 S  8  , with episulfides is achieved with MTBD (7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene) as catalyst and [PPN]SbF  6  ([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.

DOI: 10.1002/anie.202115950

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202115950