Synthesis of Polythioimides <italic style="font-style: italic">via </italic>Esterification and Sulfur-Oxygen Exchange Reaction of Hydroxyl-containing Polyimides

Yi-hao Meng; Jiang Wu; Su-yi Chen; Li-yong Tian; Yang-fan Zhang; Yan-cheng Wu; Feng Gan

doi:10.11777/j.issn1000-3304.2026.26233

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Synthesis of Polythioimides via Esterification and Sulfur-Oxygen Exchange Reaction of Hydroxyl-containing Polyimides

Research Article | 更新时间：2026-11-04

- Synthesis of Polythioimides via Esterification and Sulfur-Oxygen Exchange Reaction of Hydroxyl-containing Polyimides
- Acta Polymerica Sinica Pages: 1-12(2026)
- 作者机构：
  
  五邑大学纺织科学与工程学院江门 529020
- 作者简介：
  
  E-mail: gf@dhu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26233
  CLC：
- Received：02 July 2026，
  
  Accepted：30 July 2026，
  
  Online First：03 November 2026，
- 稿件说明：
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孟逸豪, 吴江, 陈素怡, 田立勇, 张扬帆, 吴彦城, 甘锋. 通过含羟基聚酰亚胺的酯化与硫氧交换反应合成聚硫代酰亚胺研究. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26233.

Meng, Y. H.; Wu, J.; Chen, S. Y.; Tian, L. Y.; Zhang, Y. F.; Wu, Y. C.; Gan, F. Synthesis of polythioimides via esterification and sulfur-oxygen exchange reaction of hydroxyl-containing polyimides. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26233.
孟逸豪, 吴江, 陈素怡, 田立勇, 张扬帆, 吴彦城, 甘锋. 通过含羟基聚酰亚胺的酯化与硫氧交换反应合成聚硫代酰亚胺研究. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26233. DOI： CSTR： 32057.14.GFZXB.2026.7711.

Meng, Y. H.; Wu, J.; Chen, S. Y.; Tian, L. Y.; Zhang, Y. F.; Wu, Y. C.; Gan, F. Synthesis of polythioimides via esterification and sulfur-oxygen exchange reaction of hydroxyl-containing polyimides. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26233. DOI： CSTR： 32057.14.GFZXB.2026.7711.

摘要

含硫聚合物具有独特的物理化学性质与丰富的功能，在热防护、膜分离、贵金属回收等领域具有广阔的应用前景. 聚硫代酰亚胺是一类新型含硫聚合物，兼具刚性分子骨架与硫代酰亚胺功能结构，理论上应呈现优异的性能与丰富的功能，但通过常规合成方法难以高效制备. 本研究提出一种结合侧链酯化改性与均相硫氧交换反应的合成策略：以含羟基可溶性聚酰亚胺为前驱体，通过酯化反应将低极性烷基链引入侧链，提高聚合物在二甲苯等弱极性溶剂中的溶解性，进而以劳森试剂为硫代化试剂，在均相体系中实现聚酰亚胺中C＝O向C＝S的定向转化，合成聚硫代酰亚胺. 傅里叶变换红外光谱、核磁共振波谱及X射线光电子能谱等表征结果表明，聚酰亚胺中可发生近定量的硫氧交换反应. 所得聚硫代酰亚胺具有良好的溶液加工性能，薄膜的玻璃化转变温度可达230.1 ℃. 由于硫代羰基的引入，聚硫代酰亚胺对Au

、Pd

和Pt

3种贵金属离子表现出优异的吸附选择性(去除率83.6%~99.7%)及原位还原能力，可将贵金属离子原位还原成小尺度(2~4 nm)金属纳米颗粒. 本研究拓展一类聚硫代酰亚胺合成新方法，并为此类高性能功能聚合物的合成及功能化应用提供新思路.

Abstract

Sulfur-containing polymers possess unique physicochemical properties and diverse functionalities

making them promising candidates for applications in thermal protection

membrane separation

and precious metal recovery. Polythioimides

as a new class of sulfur-containing polymers

feature rigid molecular backbones and distinctive thioimide repeating units

and are expected to exhibit both excellent performance and rich functionalities. However

conventional synthetic methods are inadequate for the efficient preparation of high-molecular-weight polythioimides. In this work

we proposed a combined strategy of side-chain esterification and homogeneous sulfur-oxygen exchange reaction. A hydroxyl-containing soluble polyimide was used as the precursor

and low-polarity alkyl chains were introduced onto the side chains through esterification to improve the polymer solubility in weakly polar solvents such as

-xylene. Subsequently

Lawesson's reagent was employed as the thionation agent to achieve the quantitative conversion of C＝O to C＝S within the imide rings under homogeneous conditions

affording polythioimides. Fourier transform infrared (FTIR) spectroscopy

nuclear magnetic resonance (NMR) spectroscopy

and X-ray photoelectron spectroscopy (XPS) characterizations confirmed the occurrence of near-quantitative sulfur-oxygen exchange. The resulting polythioimides exhibited good solution processability

and the glass transition temperature of the obtained films reached 230.1 ℃. Moreover

the polythioimides displayed excellent adsorption selectivity (removal efficiency: 83.6%-99.7%) toward Au

and Pt

as well as

in situ

reduction capability

enabling the formation of metal nanoparticles with small dimensions (2-4 nm). This work expands the synthetic methodology for polythioimides an

d offers new insights into the synthesis and functionalization of high-performance functional polymers.

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Synthesis of Polythioimides via Esterification and Sulfur-Oxygen Exchange Reaction of Hydroxyl-containing Polyimides

DOI：10.11777/j.issn1000-3304.2026.26233

摘要

Abstract

关键词

Keywords

references