Journal of South China University of Technology(Natural Science) >

2025 , Vol. 53 >Issue 11: 141 - 149

DOI: https://doi.org/10.12141/j.issn.1000-565X.250115

Chemistry & Chemical Engineering

Controlled Anionic Polymerization of Propylene Sulfide and Strategy for Synthesis of Sulfur-Rich Copolymers

  • ZHANG Hongxin ,
  • ZHU Hongxuan ,
  • SUN Duzheng ,
  • WANG Guohu ,
  • LIU Fengzhuang
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  • School of Chemical Engineering，Qinghai University，Xining 810016，Qinghai，China
张鸿鑫（1991—），男，博士生，副教授，主要从事高分子合成化学、功能高分子材料合成研究。E-mail： mszh.xin@qhu.edu.cn

Received date: 2025-04-21

  Online published: 2025-05-07

Supported by

the National Natural Science Foundation of China(52263001);the Natural Science Foundation of Qinghai Province(2022-ZJ-944Q)

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Abstract

Ring-opening polymerization of cyclic sulfur compounds is one of the important methods to synthesize sulfur-containing polymers. However, in traditional anionic polymerization techniques, the high reactivity of sulfur-centered anions tends to induce chain transfer side reactions, leading to products with broad molecular mass distributions and structural variations. These issues severely restrict the precise control over polymer chain structure and compromise the controllability and reproducibility of material properties. To solve this problem, this study presents a synergistic catalytic system that combines triethylborane (Et3B), phosphazene base t BuP1 and a thiol initiator to facilitate efficient and controlled anionic ring-opening polymerization of propylene sulfide. Experimental results show that adding Et3B at 0 ℃ effectively blocks the chain transfer reaction of sulfur anions to monomers and prevents the formation of disulfide bonds. Density functional theory calculations confirm that Et3B stabilizes the active sulfur-centered anion intermediates through strong B-S coordination, significantly reducing their nucleophilic reactivity and enabling precise control over the polymerization process. Based on these findings, a “one-pot, two-step” strategy for efficient synthesis of sulfur-rich polymers is developed. By using the dual-component catalytic system, an alternating copolymer of carbon disulfide and propylene sulfide can be synthesized as a macro-chain transfer agent, followed by the direct addition of styrene monomer to successfully create a well-defined polystyrene-co-poly(carbon disulfide-alt-propylene sulfide) terpolymer without isolating the intermediate. This work presents a novel pathway for the precise synthesis of sulfur-rich polymers.

Key words： propylene sulfide; triethylborane; anionic ring-opening polymerization; copolymerization

Cite this article

ZHANG Hongxin , ZHU Hongxuan , SUN Duzheng , WANG Guohu , LIU Fengzhuang . Controlled Anionic Polymerization of Propylene Sulfide and Strategy for Synthesis of Sulfur-Rich Copolymers[J]. Journal of South China University of Technology(Natural Science), 2025 , 53(11) : 141 -149 . DOI: 10.12141/j.issn.1000-565X.250115

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