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

孟逸豪; 吴江; 陈素怡; 田立勇; 张扬帆; 吴彦城; 甘锋

doi:10.11777/j.issn1000-3304.2026.26233

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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

研究论文 | 更新时间：2026-11-04

- 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
- Synthesis of Polythioimides via Esterification and Sulfur-Oxygen Exchange Reaction of Hydroxyl-containing Polyimides
- 高分子学报 2026年页码：1-12
- 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
  中图分类号：
- 收稿：2026-07-02，
  
  录用：2026-07-30，
  
  网络首发：2026-11-03，
- 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.

关键词

Keywords

references

Kausar A. ; Zulfiqar S. ; Sarwar M. I. Recent developments in sulfur-containing polymers . Polym. Rev. , 2014 , 54 ( 2 ), 185 - 267 . doi: 10.1080/15583724.2013.863209 http://dx.doi.org/10.1080/15583724.2013.863209

Kumagai S. ; Sato M. ; Ma C. ; Nakai Y. M. ; Kameda T. ; Saito Y. ; Watanabe A. ; Watanabe C. ; Teramae N. ; Yoshioka T. A comprehensive study into the thermo-oxidative degradation of sulfur-based engineering plastics . J. Anal. Appl. Pyrolysis , 2022 , 168 , 105754 . doi: 10.1016/j.jaap.2022.105754 http://dx.doi.org/10.1016/j.jaap.2022.105754

Song H. Y. ; Meng J. L. ; Jiang X. F. Sulfur-containing sustainable polymers: synthetic pathways, degradation mechanisms, and multifunctional applications . Natl. Sci. Rev. , 2025 , 12 ( 12 ), nwaf 475 . doi: 10.1093/nsr/nwaf475 http://dx.doi.org/10.1093/nsr/nwaf475

Mazumder K. ; Voit B. ; Banerjee S. Recent progress in sulfur-containing high refractive index polymers for optical applications . ACS Omega , 2024 , 9 ( 6 ), 6253 - 6279 . doi: 10.1021/acsomega.3c08571 http://dx.doi.org/10.1021/acsomega.3c08571

Hyder M. K. M. Z. ; Ochiai B. Synthesis of a selective scavenger for Ag(I), Pd(II), and Au(III) based on cellulose filter paper grafted with polymer chains bearing thiocarbamate moieties . Chem. Lett. , 2017 , 46 ( 4 ), 492 - 494 . doi: 10.1246/cl.160983 http://dx.doi.org/10.1246/cl.160983

Yue T. J. ; Ren W. M. ; Lu X. B. Copolymerization involving sulfur-containing monomers . Chem. Rev. , 2023 , 123 ( 24 ), 14038 - 14083 . doi: 10.1021/acs.chemrev.3c00437 http://dx.doi.org/10.1021/acs.chemrev.3c00437

Deng Y. X. ; Huang Z. T. ; Feringa B. L. ; Tian H. ; Zhang Q. ; Qu D. H. Converting inorganic sulfur into degradable thermoplastics and adhesives by copolymerization with cyclic disulfides . Nat. Commun. , 2024 , 15 , 3855 . doi: 10.1038/s41467-024-48097-4 http://dx.doi.org/10.1038/s41467-024-48097-4

Yue T. J. ; Wang L. Y. ; Ren W. M. The synthesis of degradable sulfur-containing polymers: precise control of structure and stereochemistry . Polym. Chem. , 2021 , 12 ( 46 ), 6650 - 6666 . doi: 10.1039/d1py01065d http://dx.doi.org/10.1039/d1py01065d

Wang Y. F. ; Hay A. S. A facile synthesis and the polymerization of macrocyclic 1,4-phenylene sulfide (PPS) oligomers . Macromolecules , 1996 , 29 ( 14 ), 5050 - 5053 . doi: 10.1021/ma9602740 http://dx.doi.org/10.1021/ma9602740

Purohit V. B. ; Pięta M. ; Pietrasik J. ; Plummer C. M. Recent advances in the ring-opening polymerization of sulfur-containing monomers . Polym. Chem. , 2022 , 13 ( 34 ), 4858 - 4878 . doi: 10.1039/d2py00831a http://dx.doi.org/10.1039/d2py00831a

Chen X. ; Qin A. J. ; Tang B. Z. Green synthesis of sulfur-containing polymers by carbon disulfide-based spontaneous multicomponent polymerization . Green Chem. , 2024 , 26 ( 2 ), 857 - 865 . doi: 10.1039/d3gc02415f http://dx.doi.org/10.1039/d3gc02415f

Tonkin S. J. ; Gibson C. T. ; Campbell J. A. ; Lewis D. A. ; Karton A. ; Hasell T. ; Chalker J. M. Chemically induced repair, adhesion, and recycling of polymers made by inverse vulcanization . Chem. Sci. , 2020 , 11 ( 21 ), 5537 - 5546 . doi: 10.1039/d0sc00855a http://dx.doi.org/10.1039/d0sc00855a

Zhu X. F. ; Lu X. Y. ; Qi H. ; Wang Y. H. ; Wu G. P. Sulfur-containing polymers derived from SO 2 : synthesis, properties, and applications. Polym. Chem. , 2022 , 13 ( 37 ), 5282 - 5299 . doi: 10.1039/d2py00685e http://dx.doi.org/10.1039/d2py00685e

Welterlich I. ; Tieke B. Dithioketopyrrolopyrrole (DTPP)-based conjugated polymers prepared upon thionation with Lawesson's reagent . Polym. Chem. , 2013 , 4 ( 13 ), 3755 . doi: 10.1039/c3py00396e http://dx.doi.org/10.1039/c3py00396e

Hacioglu A. ; Baddam V. ; Kerr A. ; Kehrein J. ; Bunker A. ; Luxenhofer R. Thionation of poly(2-ethyl-2-oxazoline) and its effect on solubility and cloud point . Macromolecules , 2024 , 57 ( 21 ), 10368 - 10378 . doi: 10.1021/acs.macromol.4c01341 http://dx.doi.org/10.1021/acs.macromol.4c01341

Pahlavanlu P. ; Tilley A. J. ; McAllister B. T. ; Seferos D. S. Microwave synthesis of thionated naphthalene diimide-based small molecules and polymers . J. Org. Chem. , 2017 , 82 ( 23 ), 12337 - 12345 . doi: 10.1021/acs.joc.7b02162 http://dx.doi.org/10.1021/acs.joc.7b02162

Kharchenko O. ; Hryniuk A. ; Krupka O. ; Hudhomme P. Synthesis of thionated perylenediimides: state of the art and first investigations of an alternative to lawesson's reagent . Molecules , 2024 , 29 ( 11 ), 2538 . doi: 10.3390/molecules29112538 http://dx.doi.org/10.3390/molecules29112538

Wu J. ; Zhang J. L. ; Su S. Z. ; Meng Y. H. ; Liu M. Q. ; Li B. Y. ; Fan L. F. ; Wu Y. C. ; Gan F. From polyimide to polythioimide: a silicon etherification-mediated sulfur-oxygen exchange pathway . Macromolecules , 2026 , 59 ( 2 ), 1055 - 1067 . doi: 10.1021/acs.macromol.5c02937 http://dx.doi.org/10.1021/acs.macromol.5c02937

Tanks J. ; Tamura K. Room-temperature material recycling/upcycling of polyamide waste enabled by cosolvent-tunable dissolution kinetics . Angew. Chem. Int. Ed. , 2025 , 64 ( 31 ), e 202502474 . doi: 10.1002/anie.202502474 http://dx.doi.org/10.1002/anie.202502474

Ozturk T. ; Ertas E. ; Mert O. Use of Lawesson's reagent in organic syntheses . Chem. Rev. , 2007 , 107 ( 11 ), 5210 - 5278 . doi: 10.1021/cr040650b http://dx.doi.org/10.1021/cr040650b

Ma H. ; Kang Y. S. ; Xu W. Q. ; Shen Y. C. ; Yu H. C. ; Hu H. ; Tang X. C. ; Xu J. F. ; Zhang X. An immediate bacterial-responsive supramolecular thio-naphthalene diimide: a real-time NIR-II photothermal anti-bacterial . Angew. Chem. Int. Ed. , 2025 , 64 ( 24 ), e 202505069 . doi: 10.1002/anie.202505069 http://dx.doi.org/10.1002/anie.202505069

Huang Y. Z. ; Yu Y. J. ; Hu R. R. ; Tang B. Z. Multicomponent polymerizations of elemental sulfur, CH 2 Cl 2 , and aromatic amines toward chemically recyclable functional aromatic polythioureas . J. Am. Chem. Soc. , 2024, 146 ( 21 ), 14685 - 14696 . doi: 10.1021/jacs.4c02155 http://dx.doi.org/10.1021/jacs.4c02155

Wu Y. C. ; Chen Z. G. ; Ji J. Q. ; Zhou Y. B. ; Huang H. H. ; Liu S. M. ; Zhao J. Q. Multifunctional polyimides by direct silyl ether reaction of pendant hydroxy groups: toward low dielectric constant, high optical transparency and fluorescence . Eur. Polym. J. , 2020 , 132 , 109742 . doi: 10.1016/j.eurpolymj.2020.109742 http://dx.doi.org/10.1016/j.eurpolymj.2020.109742

Nguyen V. N. ; Qi S. J. ; Kim S. ; Kwon N. ; Kim G. ; Yim Y. ; Park S. ; Yoon J. An emerging molecular design approach to heavy-atom-free photosensitizers for enhanced photodynamic therapy under hypoxia . J. Am. Chem. Soc. , 2019 , 141 ( 41 ), 16243 - 16248 . doi: 10.1021/jacs.9b09220 http://dx.doi.org/10.1021/jacs.9b09220

Jena S. ; Routray C. ; Dutta J. ; Biswal H. S. Hydrogen bonding directed reversal of 13 C NMR chemical shielding . Angew. Chem. , 2022 , 134 ( 41 ), e 202207521 . doi: 10.1002/ange.202207521 http://dx.doi.org/10.1002/ange.202207521

Xiang H. N. ; Wang J. P. ; Guo Z. H. ; Chen Y. C. ; Jiang B. H. ; Ye S. T. ; Yi W. B. Functional polythioamides derived from thiocarbonyl fluoride . Angew. Chem. Int. Ed. , 2023 , 62 ( 45 ), e 202313779 . doi: 10.1002/anie.202313779 http://dx.doi.org/10.1002/anie.202313779

Li M. ; Wang L. ; Zhang L. ; Li C. B. ; Xing B. ; Fan Y. Z. ; Wang H. C. Selective trapping of In(III) ions under σ - π * bond synergistic effects by modulating lewis basicity of capture sites on nanofibers . Langmuir , 2025 , 41 ( 13 ), 8582 - 8591 . doi: 10.1021/acs.langmuir.4c05032.s001 http://dx.doi.org/10.1021/acs.langmuir.4c05032.s001

Zheng X. L. ; Li Y. ; Li W. D. ; Pei X. L. ; Ye D. D. Chitosan derived efficient and stable Pd nano-catalyst for high efficiency hydrogenation . Int. J. Biol. Macromol. , 2023 , 241 , 124615 . doi: 10.1016/j.ijbiomac.2023.124615 http://dx.doi.org/10.1016/j.ijbiomac.2023.124615

Smirnov M. Y. ; Kalinkin A. V. ; Pashis A. V. ; Sorokin A. M. ; Noskov A. S. ; Kharas K. C. ; Bukhtiyarov V. I. Interaction of Al 2O3 and CeO2 surfaces with SO2 and SO2 + O2 studied by X-ray photoelectron spectroscopy. J. Phys. Chem. B , 2005 , 109 ( 23 ), 11712 - 11719 . doi: 10.1021/jp0508249 http://dx.doi.org/10.1021/jp0508249

Kumar S. ; Bashri M. ; Gaber S. ; Martínez J. I. ; O'Connor M. J. ; Varghese S. ; Belec B. ; Luckachan G. E. ; Shetty D. Enhanced selective gold recovery from e-waste via synergistic hetero-atom controlled quasi-planar benzoxazine-based covalent organic frameworks . Mater. Horiz. , 2025 , 12 ( 20 ), 8472 - 8480 . doi: 10.1039/d5mh00698h http://dx.doi.org/10.1039/d5mh00698h

Hu T. T. ; Ren B. Z. ; Zhao L. Ligand-mediated tuning of Pd-Au nanoalloys for selective H 2 O 2 production in direct synthesis from H 2 and O 2 . Catalysts , 2025 , 15 ( 6 ), 544 . doi: 10.3390/catal15060544 http://dx.doi.org/10.3390/catal15060544

Liang J. ; Rosa L. G. ; Scoles G. Nanostructuring, imaging and molecular manipulation of dithiol monolayers on Au(111) surfaces by atomic force microscopy . J. Phys. Chem. C , 2007 , 111 ( 46 ), 17275 - 17284 . doi: 10.1021/jp076470y http://dx.doi.org/10.1021/jp076470y

Mondal S. ; Ray J. ; Sarma D. Metallogels as functional catalysts: Bridging soft materials with sustainable transformations . ChemCatChem , 2025 , 17 ( 17 ), e 00640 . doi: 10.1002/cctc.202500640 http://dx.doi.org/10.1002/cctc.202500640

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