Poly(thiocarbonate) Synthesis from Carbonyl Sulfide (or Carbon Disulfide), Diol, and Dichlorides: A Step Growth Route to PE-like Sulfur-containing Polymers

Yue Sun; Yu-Xiang Cao; Hao-Xuan Huang; Shu-Zhe Shen; Yan-Ni Xia; Tong Shao; Cheng-Jian Zhang; Xing-Hong Zhang

doi:10.1007/s10118-025-3392-9

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Poly(thiocarbonate) Synthesis from Carbonyl Sulfide (or Carbon Disulfide), Diol, and Dichlorides: A Step Growth Route to PE-like Sulfur-containing Polymers

RESEARCH ARTICLE | Updated：2025-09-26

- Poly(thiocarbonate) Synthesis from Carbonyl Sulfide (or Carbon Disulfide), Diol, and Dichlorides: A Step Growth Route to PE-like Sulfur-containing Polymers
- Poly(thiocarbonate) Synthesis from Carbonyl Sulfide (or Carbon Disulfide), Diol, and Dichlorides: A Step Growth Route to PE-like Sulfur-containing Polymers
- 高分子科学（英文） 2025年43卷第10期页码：1774-1784
- Affiliations：
  
  State Key Laboratory of Biobased Transportation Fuel Technology, International Research Center for X Polymers, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
- Author bio：
  
  chengjian.zhang@zju.edu.cn (C.J.Z.)
  xhzhang@zju.edu.cn (X.H.Z.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 223B2119, U23A2083, 52373014 and 52203129).;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-025-3392-9.
- DOI：10.1007/s10118-025-3392-9
  中图分类号：
- 收稿：2025-04-28，
  
  修回：2025-05-26，
  
  录用：2025-06-05，
  
  网络首发：2025-09-10，
  
  纸质出版：2025-10-05
- Accepted：
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Sun, Y.; Cao, Y. X.; Huang, H. X.; Shen, S. Z.; Xia, Y. N.; Shao, T.; Zhang, C. J.; Zhang, X. H. Poly(thiocarbonate) synthesis from carbonyl sulfide (or carbon disulfide), diol, and dichlorides: a step growth route to pe-like sulfur-containing polymers. Chinese J. Polym. Sci. 2025, 43, 1774–1784

Yue Sun, Yu-Xiang Cao, Hao-Xuan Huang, et al. Poly(thiocarbonate) Synthesis from Carbonyl Sulfide (or Carbon Disulfide), Diol, and Dichlorides: A Step Growth Route to PE-like Sulfur-containing Polymers[J]. Chinese Journal of Polymer Science, 2025, 43(10): 1774-1784.
Sun, Y.; Cao, Y. X.; Huang, H. X.; Shen, S. Z.; Xia, Y. N.; Shao, T.; Zhang, C. J.; Zhang, X. H. Poly(thiocarbonate) synthesis from carbonyl sulfide (or carbon disulfide), diol, and dichlorides: a step growth route to pe-like sulfur-containing polymers. Chinese J. Polym. Sci. 2025, 43, 1774–1784 DOI： 10.1007/s10118-025-3392-9.

Yue Sun, Yu-Xiang Cao, Hao-Xuan Huang, et al. Poly(thiocarbonate) Synthesis from Carbonyl Sulfide (or Carbon Disulfide), Diol, and Dichlorides: A Step Growth Route to PE-like Sulfur-containing Polymers[J]. Chinese Journal of Polymer Science, 2025, 43(10): 1774-1784. DOI： 10.1007/s10118-025-3392-9.

摘要

We developed a step growth polymerization of diol/COS(CS

)/dichloride yielding poly(thiocarbonate)s. By suppressing oxygen-sulfur exchange reactions

structurally controlled poly(monothiocarbonate)s were obtained by polymerization of diol/COS/dichloride

exhibiting mechanical properties comparable to high-density polyethylene

while alcoholysis granted recyclability. CS

-based polymerizations allowed tunable structures and properties

via

oxygen-sulfur exchange reaction regulation.v

Abstract

The facile synthesis of high-valued polymers from waste molecules or low-cost common chemicals presents a significant challenge. Here

we develop a series of degradable poly(thiocarbonate)s from the new step-growth polymerization of diols

carbonyl sulfide (COS

or carbon disulfide

)

and dichlorides. Diols and dichlorides are common chemicals

and COS (CS

) is released as industrial waste. In addition to abundant feedstocks

the method is efficient and performed under mild conditions

using common organic bases as catalysts

and affording unprecedented polymers. When COS

diols

and dihalides were used as monomers

optimized conditions could completely suppress the oxygen-sulfur exchange reaction

enabling the efficient synthesis of well-defined poly(monothiocarbonate)s with melting points ranging from 48 °C to 101 °C. These polymers

which have a structure similar to polyethylene with low-density in-chain polar groups

exhibit remarkable toughness and ductility that rival those of high-density polyethylene (melting point: 90 °C

tensile strength: 21.6±0.7 MPa

and elongation at break: 576%). Moreover

the obtained poly(monothiocarbonate)s can be chemically degraded by alcoholysis to yield small-molecule diols and dithiols. When CS

was used in place of COS

a pronounced oxygen-sulfur exchange reaction occurred. By optimizing reaction condition

it was found that polymers with ―S(C＝O)S― and ―S(C＝S)S― as the main repeating units exhibited high thermal stability and crystallinity. Thus

a new approach for regulating the structure of polythiocarbonates

via

the oxygen-sulfur exchange reaction is developed. Overall

the polymers hold great potential f

or green materials due to their facile synthesis

readily available feedstocks

excellent performance

and chemical degradability.

关键词

Keywords

references

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