高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

动态二硫键/氢键双交联的高韧性自愈合聚氨酯水凝胶

杨兵1,丁霞1,徐钧2,李烨3,谷瑞2,张会1,侯昭升2   

  1. 1. 山东管理学院智能工程学院
    2. 山东师范大学化学化工与材料科学学院
    3. 济南康桥医药科技有限公司
  • 收稿日期:2025-04-03 修回日期:2025-06-20 网络首发:2025-07-07 发布日期:2025-07-07
  • 通讯作者: 侯昭升 E-mail:houzs@sdnu.edu.cn
  • 基金资助:
    山东省自然科学基金（批准号: ZR2022MB099）资助

Robust, Self-healing Polyurethane Hydrogel Enabled by Dual Crosslinking of Dynamic Disulfide and Hydrogen Bonds

YANG Bing1, DING Xia1, XU Jun2, LI Ye3, GU Rui2, ZHANG Hui1, HOU Zhaosheng2   

  1. 1. School of Intelligence Engineering, Shandong Management University 2. College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University 3. Jinan Kangqiao Pharmaceutical Co., Ltd.
  • Received:2025-04-03 Revised:2025-06-20 Online First:2025-07-07 Published:2025-07-07
  • Contact: HOU Zhaosheng E-mail:houzs@sdnu.edu.cn
  • Supported by:
    Supported by the Natural Science Foundation of Shandong Province, China(No.ZR2022MB099)

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摘要： 本研究通过动态共价二硫键/非共价氢键协同交联策略构建了自愈合聚氨酯水凝胶。主要以合成的四官能度3,3'-二硫基双丙烷-1,2-二醇为交联剂对聚乙二醇基聚氨酯预聚物进行扩链固化，经溶剂置换法获得聚氨酯水凝胶（SPUG），并通过冷冻干燥得到相应的干胶（DSPUG）。对凝胶（或干胶）的理化性能进行详细的研究，结果表明DSPUG具有优异的热稳定(T5% > 250 ℃)和远低于室温的玻璃化转变温度(< 0 ℃)；随着二硫键含量的增加，水凝胶的表面亲水性和平衡溶胀率逐渐降低，保水性能力增强。力学测试表明SPUG 呈现弹性形变，具有优异的拉伸、压缩韧性和压缩抗疲劳性能，交联度适中的SPUG-II的最大拉伸强度、断裂伸长率、断裂韧性和90%形变压缩强度分别达112.2 kPa，459.4%，267.6 kJ/m3和302.8 kPa。动态键赋予SPUG多重响应性：在50 ℃下自愈合2 h的自愈合效率高于90%；氧化还原刺激可实现凝胶-溶胶可逆转变。MTT法实验证实72 h后的细胞增殖率大于80%，展现出良好的细胞相容性。该水凝胶具有优异的力学性能、凝胶-溶胶可逆转变、高效的自愈合性能、良好的细胞相容性，在医用材料领域展现出较高的应用前景。

关键词: 聚氨酯水凝胶, 自愈合, 韧性, 二硫键, 氢键

Abstract: This study developed a new kind of self-healing polyurethane hydrogels (SPUGs) through a synergistic crosslinking strategy combining dynamic covalent disulfide bonds and non-covalent hydrogen bonds. A specifically synthesized quadrifunctional crosslinker, 3,3'-disulfanediylbis(propane-1,2-diol), was employed to react with poly(ethylene glycol)-based polyurethane prepolymers, followed by solvent-exchange method to produce SPUGs. The physicochemical properties of SPUGs and lyophilized gels (DSPUGs) were characterized comprehensively, and the results revealed that the dual-crosslinked systems exhibited enhanced thermal stability (T5% >250 ℃) and low glass transition temperature (<0 ℃). With the increase of disulfide bond content, the surface hydrophilicity and equilibrium swelling ratio of SPUGs reduced, while water-retaining capacity increased. Mechanical tests demonstrated that SPUGs were elastic deformation and exhibited outstanding tensile properties, compressive toughness and fatigue-resistant capacities. SPUG-II with a moderate crosslinking density achieved a maximum tensile strength of 112.2 kPa, elongation at break of 459.4%, fracture toughness of 267.6 kJ/m3, and compressive strength of 302.8 kPa at 90% strain. The double dynamic bonds endowed SPUGs with high self-healing efficiency (≥90% at 50 ℃ for 2 h) and redox-triggered reversible gel-sol transitions. Methyl thiazolyl tetrazolium (MTT) assays confirmed favorable cytocompatibility with cell survival rate exceeding 80% after 72h incubations. The SPUG hydrogels with superior mechanical properties, reversible gel-sol transitions, high self-healing capability, and good biocompatibility indicated promising candidates in biomedical applications.

Key words: Polyurethane hydrogel, Self-healing, Toughness, Disulfide bond, Hydrogen bond

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