基于环状二硫单体的光响应聚合与动态重构高分子材料研究进展

路欣雅; 张维; 王艳玲; 潘庆燕

doi:10.14028/j.cnki.1003-3726.2026.26.123

您当前的位置：

首页 >

文章列表页 >

基于环状二硫单体的光响应聚合与动态重构高分子材料研究进展

综述 | 更新时间：2026-07-16

- 基于环状二硫单体的光响应聚合与动态重构高分子材料研究进展
- Research Progress on Photoresponsive Polymerization and Dynamic Reconstruction of Polymer Materials Based on Cyclic Disulfide Monomers
- 高分子通报 2026年
- 作者机构：
  
  青岛科技大学高分子科学与工程学院　青岛 266042
  山东省产品质量检验研究院　济南 250102
  国家市场监督管理总局技术创新中心(绿色包装评价)　济南 250102
- 作者简介：
  
  qingyanpan@qust.edu.cn
- 基金信息：
  
  国家自然科学基金(22475116)
- DOI：10.14028/j.cnki.1003-3726.2026.26.123
  中图分类号：
- 收稿：2026-03-03，
  
  录用：2026-05-07，
  
  网络首发：2026-07-09，
- 稿件说明：
移动端阅览
路欣雅, 张维, 王艳玲, 潘庆燕. 基于环状二硫单体的光响应聚合与动态重构高分子材料研究进展. 高分子通报, 2026, 39(8), 1345–1360.

Lu, X. Y.; Zhang, W.; Wang, Y. L.; Pan, Q. Y. Research progress on photoresponsive polymerization and dynamic reconstruction of polymer materials based on cyclic disulfide monomers. Polym. Bull. (in Chinese), 2026, 39(8), 1345–1360.
路欣雅, 张维, 王艳玲, 潘庆燕. 基于环状二硫单体的光响应聚合与动态重构高分子材料研究进展. 高分子通报, 2026, 39(8), 1345–1360. DOI： 10.14028/j.cnki.1003-3726.2026.26.123.

Lu, X. Y.; Zhang, W.; Wang, Y. L.; Pan, Q. Y. Research progress on photoresponsive polymerization and dynamic reconstruction of polymer materials based on cyclic disulfide monomers. Polym. Bull. (in Chinese), 2026, 39(8), 1345–1360. DOI： 10.14028/j.cnki.1003-3726.2026.26.123.

摘要

光聚合技术因其高效、环保和空间可控性广泛应用于高分子材料领域，但传统光聚合材料因永久交联结构而难以修复和回收，限制了其可持续应用。二硫键作为一种具有光响应性的动态共价键，可在紫外光照射下发生可逆断裂与重组，赋予材料自修复、重塑形、可降解回收等动态功能，成为构建共价自适应网络(CANs)的理想单元。本文系统总结了基于二硫键的光聚合高分子材料的研究进展。首先阐述了二硫键的光化学反应机理，二硫单体的设计策略与合成方法。其次，概述了二硫键化合物的光聚合机制，并重点介绍了单晶态二硫键聚合物的独特光聚合特性。还总结了二硫键光聚合高分子材料在自修复、可回收、智能响应和生物医学等方面的典型应用。最后，分析了当前研究面临的挑战，并对未来发展前景进行了展望。

Abstract

Photopolymerization is widely adopted in polymer science because of its high efficiency

environmental benefits

and spatial controllability. However

conventional photopolymerized materials

which feature permanently crosslinked networks

are inherently difficult to repair or recycle

thereby limiting their sustainable application. Disulfide bonds

as photoresponsive dynamic covalent linkages

can undergo reversible cleavage and recombination under ultraviolet irradiation

imparting functionalities such as self-healing

reshaping

and degradable recycling of materials. These attributes make them ideal building blocks for constructing covalent adaptable networks (CANs). This review systematically summarizes the recent progress in disulfide-based photopolymerized materials. The review begins with an overview of the photochemical mechanism of disulfide bonds and design strategies and synthetic methods for disulfide-containing monomers. Subsequently

the photopolymerization behavior of disulfide compounds is discussed

emphasizing the unique characteristics observed in single-crystal systems. Furthermore

the typical applications of disulfide-based photopolymerized materials are summarized

particularly in the fields of self-healing

recyclability

stimuli-responsive behavior

and biomedicine. Finally

the current challenges and future perspectives in this field are presented.

关键词

Keywords

references

Andrzejewska, E . Photopolymerization kinetics of multifunctional monomers . Prog. Polym. Sci. , 2001 , 26 ( 4 ), 605 – 665 .

Lai, H. ; Peng, X. ; Li, L. ; Zhu, D. ; Xiao, P . Novel monomers for photopolymer networks . Prog. Polym. Sci. , 2022 , 128 , 101529 .

Decker, C . Photoinitiated crosslinking polymerisation . Prog. Polym. Sci. , 1996 , 21 ( 4 ), 593 – 650 .

Ligon, S. C. ; Husár, B. ; Wutzel, H. ; Holman, R. ; Liska, R . Strategies to reduce oxygen inhibition in photoinduced polymerization . Chem. Rev. , 2014 , 114 ( 1 ), 557 – 589 .

Bagheri, A. ; Jin, J. Y . Photopolymerization in 3D printing . ACS Appl. Polym. Mater. , 2019 , 1 ( 4 ), 593 – 611 .

Casado, U. M. ; Altuna, F. I. ; Miccio, L. A . A review on the role of crosslinked polymers in renewable energy: complex network analysis of innovations in sustainability . Sustainability , 2025 , 17 ( 10 ), 4736 .

Hammer, L. ; van Zee, N. J. ; Nicolaÿ, R . Dually crosslinked polymer networks incorporating dynamic covalent bonds . Polymers , 2021 , 13 ( 3 ), 396 .

Chakma, P. ; Konkolewicz, D . Dynamic covalent bonds in polymeric materials . Angew. Chem. Int. Ed. , 2019 , 58 ( 29 ), 9682 – 9695 .

Black, S. P. ; Sanders, J. K. M. ; Stefankiewicz, A. R . Disulfide exchange: exposing supramolecular reactivity through dynamic covalent chemistry . Chem. Soc. Rev. , 2014 , 43 ( 6 ), 1861 – 1872 .

Yan, T. W. ; Balzer, A. H. ; Herbert, K. M. ; Epps, T. H. ; Korley, L. T. J . Circularity in polymers: addressing performance and sustainability challenges using dynamic covalent chemistries . Chem. Sci. , 2023 , 14 ( 20 ), 5243 – 5265 .

陈兴幸 , 钟倩云 , 王淑娟 , 吴宥伸 , 谭继东 , 雷恒鑫 , 黄绍永 , 张彦峰 . 动态共价键高分子材料的研究进展 . 高分子学报 , 2019 , 50 ( 5 ), 469 – 484 .

Zhang, Q. ; Qu, D. H. ; Feringa, B. L. ; Tian, H . Disulfide-mediated reversible polymerization toward intrinsically dynamic smart materials . J. Am. Chem. Soc. , 2022 , 144 ( 5 ), 2022 – 2033 .

Ochmann, M. ; Hussain, A. ; von Ahnen, I. ; Cordones, A. A. ; Hong, K. ; Lee, J. H. ; Ma, R. ; Adamczyk, K. ; Kim, T. K. ; Schoenlein, R. W. ; Vendrell, O. ; Huse, N . UV-photochemistry of the disulfide bond: evolution of early photoproducts from picosecond X-ray absorption spectroscopy at the sulfur K-edge . J. Am. Chem. Soc. , 2018 , 140 ( 21 ), 6554 – 6561 .

Klepel, F. ; Ravoo, B. J . Dynamic covalent chemistry in aqueous solution by photoinduced radical disulfide metathesis . Org. Biomol. Chem. , 2017 , 15 ( 18 ), 3840 – 3842 .

Jin, S. B. ; Oh, D. X. ; Park, J . Dynamic disulfide chemistry for functional polymers: self-healing, vitrimer behavior, and biochemical/electronic applications . ChemSusChem , 2026 , 19 ( 1 ), e202501023 .

Sousa, S. F. ; Neves, R. P. P. ; Waheed, S. O. ; Fernandes, P. A. ; Ramos, M. J . Structural and mechanistic aspects of S―S bonds in the thioredoxin-like family of proteins . Biol. Chem. , 2019 , 400 ( 5 ), 575 – 587 .

Zhao, X. L. ; Tian, P. X. ; Li, Y. D. ; Zeng, J. B . Biobased covalent adaptable networks: towards better sustainability of thermosets . Green Chem. , 2022 , 24 ( 11 ), 4363 – 4387 .

Beaupre, D. M. ; Weiss, R. G . Thiol- and disulfide-based stimulus-responsive soft materials and self-assembling systems . Molecules , 2021 , 26 ( 11 ), 3332 .

Bongiardina, N. J. ; Soars, S. M. ; Podgorski, M. ; Bowman, C. N . Radical-disulfide exchange in thiol-ene-disulfidation polymerizations . Polym. Chem. , 2022 , 13 ( 27 ), 3991 – 4003 .

Zhang, R. H. ; Nie, T. Q. ; Fang, Y. F. ; Huang, H. ; Wu, J . Poly(disulfide)s: from synthesis to drug delivery . Biomacromolecules , 2022 , 23 ( 1 ), 1 – 19 .

鞠小兵 , 张玉含 , 孙芳 . 芳香族二硫化物光吸收及光引发性能研究 . 北京化工大学学报(自然科学版) , 2022 , 49 ( 6 ), 14 – 22 .

Pięta, M. ; Purohit, V. B. ; Pietrasik, J. ; Plummer, C. M . Disulfide-containing monomers in chain-growth polymerization . Polym. Chem. , 2023 , 14 ( 1 ), 7 – 31 .

Zhang, M. L. ; Jiang, S. L. ; Gao, Y. J. ; Nie, J. ; Sun, F . Design of a disulfide bond-containing photoresist with extremely low volume shrinkage and excellent degradation ability for UV-nanoimprinting lithography . Chem. Eng. J. , 2020 , 390 , 124625 .

Zhang, M. L. ; Jiang, S. L. ; Gao, Y. J. ; Nie, J. ; Sun, F . UV-nanoimprinting lithography photoresists with no photoinitiator and low polymerization shrinkage . Ind. Eng. Chem. Res. , 2020 , 59 ( 16 ), 7564 – 7574 .

Kazancioglu, E. O. ; Koyuncu, U. ; Arsu, N . Synthesis and characterization of a thioxanthone derivative photoinitiator with a dynamic disulfide bond and in situ synthesis of AuNps within a polymer matrix . Prog. Org. Coat. , 2025 , 204 , 109268 .

Nelson, B. R. ; Cione, J. T. ; Kirkpatrick, B. E. ; Kreienbrink, K. M. ; Dhand, A. P. ; Burdick, J. A. ; Shields IV, C. W. ; Anseth, K. S. ; Bowman, C. N . Multifunctional dithiolane monomers for multi-scale, recyclable light-driven additive manufacturing . Polym. Chem. , 2025 , 16 ( 18 ), 2108 – 2116 .

Zhu, Z. B. ; Li, X. M. ; Liu, L. ; Xu, Y. K. ; Qu, D. H. ; Tian, H. ; Zhang, Q . Single-crystalline poly(disulfide)s enabled by photoTriggered topochemical ring-opening polymerization of 1, 2-dithiolane . J. Am. Chem. Soc. , 2025 .

Trujillo-Lemon, M. ; Fairbanks, B. D. ; Sias, A. N. ; McLeod, R. R. ; Bowman, C. N . 1, 2-Dithiolane/yne photopolymerizations to generate high refractive index polymers . Polym. Chem. , 2025 , 16 ( 10 ), 1176 – 1187 .

Alraddadi, M. A. ; Chiaradia, V. ; Stubbs, C. J. ; Worch, J. C. ; Dove, A. P . Renewable and recyclable covalent adaptable networks based on bio-derived lipoic acid . Polym. Chem. , 2021 , 12 ( 40 ), 5796 – 5802 .

Wang, B. S. ; Qu, D. H . The many ways for reversible polymerization of 1, 2-dithiolanes . Chem. Lett. , 2023 , 52 ( 6 ), 496 – 502 .

Pal, S. ; Shin, J. ; DeFrates, K. ; Arslan, M. ; Dale, K. ; Chen, H. ; Ramirez, D. ; Messersmith, P. B . Recyclable surgical, consumer, and industrial adhesives of poly(α-lipoic acid) . Science , 2024 , 385 ( 6711 ), 877 – 883 .

Barcan, G. A. ; Zhang, X. Y. ; Waymouth, R. M . Structurally dynamic hydrogels derived from 1,2-dithiolanes . J. Am. Chem. Soc. , 2015 , 137 ( 17 ), 5650 – 5653 .

Zhu, T. Y. ; Lei, R. S. ; Wang, B. W. ; Du, T. Y. ; Xia, W. ; Liu, Y . Bio-sourced 4-aryl-1, 2-dithiolanes for recyclable poly(disulfide)s with high performance . Angew. Chem. Int. Ed. , 2025 , 64 ( 26 ), e202503677 .

Scheutz, G. M. ; Rowell, J. L. ; Wang, F. S. ; Abboud, K. A. ; Peng, C. H. ; Sumerlin, B. S . Synthesis of functional 1, 2-dithiolanes from 1, 3-bis-tert-butyl thioethers . Org. Biomol. Chem. , 2020 , 18 ( 33 ), 6509 – 6513 .

Spessa, A. ; Bongiovanni, R. ; Vitale, A . A novel disulfide-containing monomer for photoinitiator-free self-healable photocured coatings . Prog. Org. Coat. , 2024 , 187 , 108098 .

Wang, K. ; Wang, Z. Z . Shrinkage stress evolution during photopolymerization: theory and experiments . J. Mech. Phys. Solids , 2023 , 178 , 105350 .

Chen, J. T. ; Jiang, S. L. ; Gao, Y. J. ; Sun, F . Reducing volumetric shrinkage of photopolymerizable materials using reversible disulfide-bond reactions . J. Mater. Sci. , 2018 , 53 ( 23 ), 16169 – 16181 .

Liu, H. C. ; Liu, C. ; Liu, Y. P. ; Jiang, Y. Z. ; Li, X. Y. ; Bai, Y. N . Rapid repair and degradation: a study of high-performance recyclable vitrimer epoxy resin based on disulfide bonds . Polym. Test. , 2024 , 137 , 108528 .

You, G. D. ; Li, X. ; Ren, K. W. ; Ai, T. ; Niu, Y. H . Effect of disulfide bond density on the properties of polyurethane/epoxy interpenetrating networks . Materials , 2025 , 18 ( 7 ), 1636 .

Sun, M. ; Felsenthal, L. M. ; Kim, S. ; Choi, E. Y. ; Reed, L. J. ; Elling, B. R. ; Dichtel, W. R . Covalent adaptable networks: reprocessable cross-linked polymers . Chem. Rev. , 2026 , 126 ( 3 ), 1829 – 1948 .

Cook, W. D. ; Chausson, S. ; Chen, F. ; Le Pluart, L. ; Bowman, C. N. ; Scott, T. F . Photopolymerization kinetics, photorheology and photoplasticity of thiol–ene–allylic sulfide networks . Polym. Int. , 2008 , 57 ( 3 ), 469 – 478 .

Kloxin, C. J. ; Bowman, C. N . Covalent adaptable networks: smart, reconfigurable and responsive network systems . Chem. Soc. Rev. , 2013 , 42 ( 17 ), 7161 – 7173 .

Jadoun, S . Synthesis, mechanism, and applications of self-healing materials . Biomed. Mater. Devices , 2024 , 2 ( 1 ), 225 – 240 .

Caglayan, C. ; Kim, G. ; Yun, G. J . CNT-reinforced self-healable epoxy dynamic networks based on disulfide bond exchange . ACS Omega , 2022 , 7 ( 48 ), 43480 – 43491 .

Xue, X. ; Li, C. ; Yu, X. B. ; Chenchai, K. ; Zhang, X. Y. ; Zhang, X. S. ; Zhang, G. X. ; Zhang, D. Q . Photo-patternable and healable polymer semiconductor enabled by dynamic covalent disulfide bonding . Angew. Chem. Int. Ed. , 2025 , 64 ( 16 ), e202425172 .

Machado, T. O. ; Stubbs, C. J. ; Chiaradia, V. ; Alraddadi, M. A. ; Brandolese, A. ; Worch, J. C. ; Dove, A. P . A renewably sourced, circular photopolymer resin for additive manufacturing . Nature , 2024 , 629 ( 8014 ), 1069 – 1074 .

Lendlein, A. ; Langer, R . Biodegradable, elastic shape-memory polymers for potential biomedical applications . Science , 2002 , 296 ( 5573 ), 1673 – 1676 .

Yang, C. ; Wu, B. Y. ; Wang, H. J. ; Zhao, Q. ; Chen, D . Orthogonal light triggering of dynamic polymer networks toward on-demand shape evolution control . Matter , 2025 , 8 ( 11 ), 102292 .

Wu, S. Y. ; Wang, H. X. ; Li, B. ; Wu, L. X . Near-infrared photothermal polymerization of thioctic acid triggered by polyoxometalate crosslinker . Angew. Chem. Int. Ed. , 2026 , 65 ( 12 ), e23605 .

温惠云 , 彭佳佳 , 薛伟明 , 邹玥 , 范代娣 . 二硫键连接的纳米粒子用于细胞内药物递释的研究进展 . 中国医药工业杂志 , 2018 , 49 ( 4 ), 397 – 408 .

Meng, F. H. ; Hennink, W. E. ; Zhong, Z. Y . Reduction-sensitive polymers and bioconjugates for biomedical applications . Biomaterials , 2009 , 30 ( 12 ), 2180 – 2198 .

Oishi, M. ; Hayama, T. ; Akiyama, Y. ; Takae, S. ; Harada, A. ; Yamasaki, Y. ; Nagatsugi, F. ; Sasaki, S. ; Nagasaki, Y. ; Kataoka, K . Supramolecular assemblies for the cytoplasmic delivery of antisense oligodeoxynucleotide: polyion complex (PIC) micelles based on poly(ethylene glycol)-SS-oligodeoxynucleotide conjugate . Biomacromolecules , 2005 , 6 ( 5 ), 2449 – 2454 .

Lu, J. H. ; Dai, Y. H. ; He, Y. H. ; Zhang, T. ; Zhang, J. ; Chen, X. M. ; Jiang, C. T. ; Lu, H . Organ/cell-selective intracellular delivery of biologics via N -acetylated galactosamine-functionalized polydisulfide conjugates . J. Am. Chem. Soc. , 2024 , 146 ( 6 ), 3974 – 3983 .

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

面向可持续发展的高分子科学教学实验设计: 含席夫碱型动态共价键的可修复热固性材料的制备与表征

前线聚合研究及应用进展（下）

含荧光生色基团烯类单体及其聚合物的光化学行为

吸光度与光聚合动力学

聚合物量子点的制备及其对Zn-MnO2正极性能的改性——一个大学化学综合实验设计