河南大学纳米科学与材料工程学院特种功能材料教育部重点实验室 郑州 450046
zhanghuan@henu.edu.cn
yaoxi@henu.edu.cn
收稿:2026-02-10,
录用:2026-04-13,
移动端阅览
谢林婷, 李睿, 许晓苗, 张欢, 鞠婕, 姚晰. 芳香型席夫碱键的结构调控动态行为及其聚合物材料多功能应用. 高分子通报, doi: 10.14028/j.cnki.1003-3726.2026.26.066
Xie, L. T.; Li, R.; Xu X. M.; Zhang, H.; Ju, J.; Yao, X. Structure-regulated dynamic behavior of aromatic schiff base bonds and their polymer multifunctional applications. Polym. Bull. (in Chinese), doi: 10.14028/j.cnki.1003-3726.2026.26.066
谢林婷, 李睿, 许晓苗, 张欢, 鞠婕, 姚晰. 芳香型席夫碱键的结构调控动态行为及其聚合物材料多功能应用. 高分子通报, doi: 10.14028/j.cnki.1003-3726.2026.26.066 DOI:
Xie, L. T.; Li, R.; Xu X. M.; Zhang, H.; Ju, J.; Yao, X. Structure-regulated dynamic behavior of aromatic schiff base bonds and their polymer multifunctional applications. Polym. Bull. (in Chinese), doi: 10.14028/j.cnki.1003-3726.2026.26.066 DOI:
芳香型席夫碱键因其共轭结构和动态可逆性,在动态共价化学领域占据重要地位。与脂肪型席夫碱不同,芳香或杂芳香骨架的引入不仅使席夫碱键具有更优异的热/机械稳定性,也可以通过电子离域效应调节其动态交换能垒和刺激响应行为。本文总结了2种典型结构(芳基-烷基取代和全芳基取代)对芳香型席夫碱键稳定性及动态行为的影响规律;阐述了芳香型席夫碱键的水解/缩合平衡和交换反应机理,以及取代基电子效应和酸催化对动态交换路径的控制规律;梳理了基于芳香席夫碱键的聚合物材料在光/热诱导自修复、再加工与回收、阻燃性、抗菌和催化等领域的应用进展。通过总结芳香型席夫碱键的结构调控动态行为及其聚合物材料多功能应用,为进一步发展高稳定性和智能响应性的多功能芳香席夫碱聚合物提供参考。
Aromatic Schiff base bonds
due to conjugated structure and reversible dynamic characteristics
play an important role in dynamic covalent chemistry. Unlike aliphatic Schiff base bonds
the introduction of aromatic or heteroaromatic skeletons not only endows Schiff base bonds with improved thermal and mechanical stability
but also allows the dynamic exchange barrier and stimulus-responsive behaviors to be tuned by electronic delocalization. This paper summarizes the effects of two representative structural motifs (e.g.
aryl-alkyl and fully aryl substitution) on the stability and dynamic behavior of aromatic Schiff base bonds. Subsequently
it discusses the hydrolysis/condensation equilibrium and exchange mechanisms
and reveals the role of substituent electronic effects and acid catalysis in controlling dynamic exchange pathways. Recent progress in polymeric materials based on aromatic Schiff base are reviewed
focusing on applications in light-/heat-triggered self-healing
reprocessing and recycling
flame retardancy
antibacterial materials
and catalysis. This work provides a useful reference for the design and development of highly stable
smart
and multifunctional aromatic Schiff base polymers.
Chen, K. ; Zhu, H. X. ; Zhang, Z. Y. ; Shao, Y. Q. ; Yu, Q. H. ; Cao, X. L. ; Pan, S. Y. ; Mu, X. ; Gao, Z. H. ; Wang, D. ; Wei, S. Y. ; Han, S. Y . Self-healing polyurethane coatings based on dynamic chemical bond synergy under conditions of photothermal response . Chem. Eng. J. , 2023 , 474 , 145811 .
Liu, X. H. ; Zhang, E. D. ; Liu, J. M. ; Qin, J. J. ; Wu, M. Q. ; Yang, C. L. ; Liang, L. Y . Self-healing, reprocessable, degradable, thermadapt shape memory multifunctional polymers based on dynamic imine bonds and their application in nondestructively recyclable carbon fiber composites . Chem. Eng. J. , 2023 , 454 , 139992 .
Liu, Y. Y. ; Liu, G. L. ; Li, Y. D. ; Weng, Y. X. ; Zeng, J. B . Biobased high-performance epoxy vitrimer with UV shielding for recyclable carbon fiber reinforced composites . ACS Sustainable Chem. Eng. , 2021 , 9 ( 12 ), 4638 – 4647 .
Zhang, J. H. ; Jiang, C. ; Deng, G. Y. ; Luo, M. ; Ye, B. J. ; Zhang, H. J. ; Miao, M. H. ; Li, T. C. ; Zhang, D. H . Closed-loop recycling of tough epoxy supramolecular thermosets constructed with hyperbranched topological structure . Nat. Commun. , 2024 , 15 , 4869 .
Liu, Y. J. ; Tang, Z. H. ; Chen, Y. ; Wu, S. W. ; Guo, B. C . Programming dynamic imine bond into elastomer/graphene composite toward mechanically strong, malleable, and multi-stimuli responsive vitrimer . Compos. Sci. Technol. , 2018 , 168 , 214 – 223 .
Liang, F. Y. ; Liu, C. S. ; Geng, J. W. ; Chen, N. C. ; Lai, W. D. ; Mo, H. T. ; Liu, K. D . Chitosan-fucoidan encapsulating cinnamaldehyde composite coating films: preparation, pH-responsive release, antibacterial activity and preservation for litchi . Carbohydr. Polym. , 2024 , 333 , 121968 .
Tan, J. ; Namuangruk, S. ; Kong, W. F. ; Kungwan, N. ; Guo, J. ; Wang, C. C . Manipulation of amorphous-to-crystalline transformation: towards the construction of covalent organic framework hybrid microspheres with NIR photothermal conversion ability . Angew. Chem. Int. Ed. , 2016 , 55 ( 45 ), 13979 – 13984 .
Wei, Z. ; Yang, J. H. ; Liu, Z. Q. ; Xu, F. ; Zhou, J. X. ; Zrínyi, M. ; Osada, Y. ; Chen, Y. M . Novel biocompatible polysaccharide-based self-healing hydrogel . Adv. Funct. Mater. , 2015 , 25 ( 9 ), 1352 – 1359 .
Fan, Q. Y. ; Tang, Y. T. ; Sun, H. N. ; Guo, D. K. ; Ma, J. W. ; Guo, J. B . Cluster-triggered self-luminescence, rapid self-healing, and adaptive reprogramming liquid crystal elastomers enabled by dynamic imine bond . Adv. Mater. , 2024 , 36 ( 31 ), 2401315 .
He, C. L. ; Liang, F. C. ; Veeramuthu, L. ; Cho, C. J. ; Benas, J. S. ; Tzeng, Y. R. ; Tseng, Y. L. ; Chen, W. C. ; Rwei, A. ; Kuo, C. C . Super tough and spontaneous water-assisted autonomous self-healing elastomer for underwater wearable electronics . Adv. Sci. , 2021 , 8 ( 21 ), 2102275 .
Verdugo, P. ; Santiago, D. ; De la Flor, S. ; Serra, À . A biobased epoxy vitrimer with dual relaxation mechanism: a promising material for renewable, reusable, and recyclable adhesives and composites . ACS Sustainable Chem. Eng. , 2024 , 12 ( 15 ), 5965 – 5978 .
Subramaniyan, S. ; Najjarzadeh, N. ; Vanga, S. R. ; Liguori, A. ; Syrén, P. O. ; Hakkarainen, M . Designed for circularity: chemically recyclable and enzymatically degradable biorenewable Schiff base polyester-imines . ACS Sustainable Chem. Eng. , 2023 , 11 ( 8 ), 3451 – 3465 .
Zavalishin, M. N. ; Kiselev, A. N. ; Gamov, G. A . Schiff bases derived from pyridoxal 5′-phosphate and 2-X-phenylamine (X = H, OH, SH): substituent effects on UV-Vis spectra and hydrolysis kinetics . Molecules , 2024 , 29 ( 15 ), 3504 .
Ou, M. Y. ; Lian, R. C. ; Li, R. J. ; Cui, J. H. ; Guan, H. C. ; Zhu, J. H. ; Liu, L. ; Jiao, C. M. ; Chen, X. L . Facile strategy of preparing excellently thermal-insulating and fire-safe building materials based on an aromatic Schiff base dicarboxylic acid without additional flame retardants . J. Build. Eng. , 2023 , 78 , 107572 .
Cunha Almeida, T. ; Gonzaga Ribeiro, L. H. ; Ferreira dos Santos, L. B. ; da Silva, C. M. ; Tupinambá Branquinho, R. ; de Lana, M. ; Ramos Gadelha, F. ; de Fátima, Â . Synthesis, in vitro and in vivo anti-trypanosoma cruzi and toxicological activities of nitroaromatic Schiff bases . Biomed. Pharmacother. , 2018 , 108 , 1703 – 1711 .
Sęk, D. ; Siwy, M. ; Małecki, J. G. ; Kotowicz, S. ; Golba, S. ; Nowak, E. M. ; Sanetra, J. ; Schab-Balcerzak, E . Polycyclic aromatic hydrocarbons connected with Schiff base linkers: experimental and theoretical photophysical characterization and electrochemical properties . Spectrochim. Acta Part A Mol. Biomol. Spectrosc. , 2017 , 175 , 168 – 176 .
Li, L. ; Zhou, P. F. ; Wen, J. L. ; Sun, P. L. ; Guo, Z. X . Dispersion of single-walled carbon nanotubes by aromatic cyclic schiff bases via non-covalent interactions . Molecules , 2024 , 29 ( 13 ), 3179 .
Lei, Z. Q. ; Xie, P. ; Rong, M. Z. ; Zhang, M. Q . Catalyst-free dynamic exchange of aromatic Schiff base bonds and its application to self-healing and remolding of crosslinked polymers . J. Mater. Chem. A , 2015 , 3 ( 39 ), 19662 – 19668 .
Wei, Z. W. ; Lü, X. F. ; Wang, W. ; Mele, G. ; Jiang, Z. Y . Excellent removal performance of 4,4'-biphenyldicarboxaldehyde m-phenylenediamine Schiff base magnetic polymer towards phenanthrene and 9-phenanthrol: experimental, modeling and DFT calculations studies . J. Hazard. Mater. , 2023 , 441 , 129920 .
Ding, X. M. ; Chen, L. ; Xu, Y. J. ; Shi, X. H. ; Luo, X. ; Song, X. ; Wang, Y. Z . Robust epoxy vitrimer with simultaneous ultrahigh impact property, fire safety, and multipath recyclability via rigid-flexible imine networks . ACS Sustainable Chem. Eng. , 2023 , 11 ( 39 ), 14445 – 14456 .
Wu, J. N. ; Chen, L. ; Fu, T. ; Zhao, H. B. ; Guo, D. M. ; Wang, X. L. ; Wang, Y. Z . New application for aromatic Schiff base: high efficient flame-retardant and anti-dripping action for polyesters . Chem. Eng. J. , 2018 , 336 , 622 – 632 .
Zhao, P. P. ; Lu, P. ; Zhao, Z. Y. ; Chen, S. W. ; Li, X. Y. ; Deng, C. ; Wang, Y. Z . Aromatic Schiff base-based polymeric phase change materials for safe, leak-free, and efficient thermal energy management . Chem. Eng. J. , 2022 , 437 , 135461 .
Gan, J. Y. ; Zhou, J. ; Xu, Y. S. ; Zhang, T. ; Zhang, X. M . Flame-retardant and antibacterial waterborne polyurethane composites based on a Cu(Ⅱ)–phytate–aromatic schiff base complex . ACS Appl. Polym. Mater. , 2024 , 6 ( 16 ), 9974 – 9985 .
Zheng, G. Q. ; Wu, J. N. ; Zhang, L. ; Zhang, Q. ; Chen, L. ; Wang, X. L. ; Zhao, H. B. ; Liu, B. W. ; Wang, Y. Z . Tailoring cross-linking temperature via hydrogen bonding and steric hindrance towards high-performance fire-safe polymer . Polymer , 2024 , 298 , 126908 .
Ortiz-Sánchez, J. M. ; Gelabert, R. ; Moreno, M. ; Lluch, J. M . Theoretical study on the excited-state intramolecular proton transfer in the aromatic Schiff base salicylidene methylamine: an electronic structure and quantum dynamical approach . J. Phys. Chem. A , 2006 , 110 ( 14 ), 4649 – 4656 .
Balcar, H. ; Sedláček, J. ; Vohlídal, J. ; Zedník, J. ; Blechta, V . New polyacetylenes with aromatic Schiff's base pendant groups by polymerization of benzylidene-ring-substituted N -benzylidene-4-ethynylanilines with Rh-based catalysts . Macromol. Chem. Phys. , 1999 , 200 ( 12 ), 2591 – 2596 .
Khurshid, A. ; Saeed, A. ; Erben, M. F. ; Hökelek, T. ; Jabeen, E . DFT guided substitution effect on azomethine reactive center in newly synthesized Schiff base aromatic scaffolds; syntheses, characterization, single crystal XRD, Hirshfeld surface and crystal void analyses . J. Mol. Struct. , 2023 , 1273 , 134215 .
Ziółek, M. ; Sobczak, I . Photochromism and hydrolysis of aromatic Schiff base N, N′-bis(salicylidene)-p-phenylenediamine (BSP) studied in heterogeneous environments . J. Incl Phenom. Macrocycl. Chem. , 2009 , 63 ( 3 ), 211 – 218 .
Verma, C. ; Quraishi, M. A . Recent progresses in Schiff bases as aqueous phase corrosion inhibitors: design and applications . Coord. Chem. Rev. , 2021 , 446 , 214105 .
Vardhan, H. ; Mehta, A. ; Nath, I. ; Verpoort, F . Dynamic imine chemistry in metal–organic polyhedra . RSC Adv. , 2015 , 5 ( 82 ), 67011 – 67030 .
Burland, M. C. ; Meyer, T. Y. ; Baik, M. H . Proton as the simplest of all catalysts for 2 + 2 cycloadditions: DFT study of acid-catalyzed imine metathesis . J. Org. Chem. , 2004 , 69 ( 19 ), 6173 – 6184 .
Xu, X. W. ; Ma, S. Q. ; Wu, J. H. ; Yang, J. T. ; Wang, B. B. ; Wang, S. ; Li, Q. ; Feng, J. ; You, S. S. ; Zhu, J . High-performance, command-degradable, antibacterial Schiff base epoxy thermosets: synthesis and properties . J. Mater. Chem. A , 2019 , 7 ( 25 ), 15420 – 15431 .
Fan, W. H. ; Jin, Y. ; Shi, L. J. ; Zhou, R. ; Du, W. N . Developing visible-light-induced dynamic aromatic Schiff base bonds for room-temperature self-healable and reprocessable waterborne polyurethanes with high mechanical properties . J. Mater. Chem. A , 2020 , 8 ( 14 ), 6757 – 6767 .
Xin, X. ; Shi, W. ; Zhao, Y. ; Zhao, G. J. ; Li, Y. Q . Effectively regulation of the ESIPT pro cess via ring-annelation modification for Schiff base derivatives: a theoretical study . Dyes Pigm. , 2024 , 224 , 112020 .
Liu, X. Q. ; Zhou, J. H. ; Zheng, J . Visible light-induced self-healing fluorinated polyurethane-acrylate containing aromatic Schiff base . Colloids Surf. A Physicochem. Eng. Aspects , 2024 , 703 , 135352 .
Sasikala, H. ; Meganathan, M. K. ; Ramalingam, S . Self-healing aroma-Schiff base functionalized polyurethane for scratch resistant flexible fabrics . Prog. Org. Coat. , 2025 , 207 , 109431 .
Kianfar, M. ; Seyed Dorraji, M. S. ; Rasoulifard, M. H. ; Rahimi, A. ; Rahmani, S . Synthesis and application of aromatic Schiff base waterborne polyurethane as visible-light triggered self-healing polymer and anticorrosion coating using h-BN/GO/NiO nano-composite . Polym. Test. , 2024 , 141 , 108649 .
Tan, P. Y. ; Zhao, X. T. ; Zhang, Z. S. ; Wei, W. J. ; Zhou, J. H. ; Shao, Y. Q. ; Ma, X. J. ; Wei, S. Y. ; Gao, Z. H. ; Han, S. Y . A highly effective self-healing waterborne polyurethane vitrimer containing conjugated schiff base bonds driven by photothermal . ACS Appl. Polym. Mater. , 2024 , 6 ( 15 ), 8977 – 8988 .
Shao, Y. Q. ; Zhu, H. X. ; Chen, K. ; Jin, T. Y. ; Wang, Z. W. ; Luo, Z. X. ; Wang, J. H. ; Sun, H. Y. ; Wei, S. Y. ; Gao, Z. H . Castor oil-based epoxy vitrimer based on dual dynamic network with intrinsic photothermal self-healing capability . Polymers , 2025 , 17 ( 7 ), 897 .
Chen, P. C. ; Ding, Y. ; Wang, Y. Q. ; Zhao, H. Z. ; Li, P. C. ; Liu, Y. T. ; Gao, C. H . Functional bio-based vitrimer with excellent healing and recyclability based on conjugated deflection self-toughening . Chem. Eng. J. , 2023 , 474 , 145680 .
Wang, B. C. ; Dou, S. H. ; Wang, S. ; Wang, Y. ; Zhang, S. F. ; Lin, X. P. ; Ji, C. F. ; Dong, L . Molecular mechanism of saturated aldehyde oxidation: a DFT insight into volatiles forming from decanal thermal oxidation . Food Chem. , 2024 , 454 , 139751 .
Gao, P. ; Zheng, H. R. ; Guan, R. ; Lu, Y. ; Tao, L. X. ; Wang, X. F. ; Yin, J . Dynamic non-covalent interactions incorporated reprocessable waterborne polyurethane with visible light activated self-healing, antibacterial, anti-fouling, and strain sensor performances . Adv. Funct. Mater. , 2025 , 35 ( 43 ), 2507745 .
Yu, P. ; Wang, H. Y. ; You, C. Y. ; Jia, Z. C. ; Huang, Q. R. ; Wang, Y. ; Qu, Y. P. ; Dong, X. Y. ; Li, R. G. ; Xin, Y. M. ; He, H. F. ; Li, T. ; Yu, B . Reversible Schiff-base chemistry enables thermosetting smart composites with versatile properties . Compos. Commun. , 2024 , 52 , 102153 .
Liang, T. X. ; Cai, J. N. ; Liu, S. M. ; Lai, H. L. ; Zhao, J. Q . Chain extension and synergistic flame-retardant effect of aromatic Schiff base diepoxide on polyamide 6/aluminum diethylphosphinate composites . Materials , 2019 , 12 ( 14 ), 2217 .
Obradović, R. ; Joksimović, N. ; Janković, N. ; Kosanić, M. ; Matić, J. ; Milović, E. ; Bogdanović, G. A. ; Petronijević, J . Discovery of Schiff bases as potent antibacterial and antifungal agents . New J. Chem. , 2024 , 48 ( 40 ), 17492 – 17499 .
Alam, M. ; Alandis, N. M. ; Shaik, M. R. ; Khan, S. ; Alomar, S. Y . Synthesis, spectroscopic and biological activities of aromatic Schiff base . Asian J. Chem. , 2014 , 26 ( 21 ), 7377 – 7380 .
Kumar, D. ; Chadda, S. ; Sharma, J. ; Surain, P . Syntheses, spectral characterization, and antimicrobial studies on the coordination compounds of metal ions with Schiff base containing both aliphatic and aromatic hydrazide moieties . Bioinorg. Chem. Appl. , 2013 , 2013 , 981764 .
Palke, D. G. ; Narwade, S. C. ; Kathwate, S. H . Synthesis, characterization and biological studies of transition metal complexes of dehydroacetic acid Schiff bases derived from 3-aminomethyl pyridine . J. Mol. Struct. , 2025 , 1322 , 140335 .
Gul, R. ; Munir, W. ; Saleh, E. A. M. ; Shujah, S. ; Sirajuddin, M. ; Tabassum, S. ; Rehman, K. U. ; Khan, D. ; Al-Saeedi, S. I. ; Abdelrahman, E. A . Ferrocene based Schiff bases and their complexes: synthesis, characterization and biological evaluation . J. Organomet. Chem. , 2024 , 1003 , 122944 .
Rani, S. ; Lal, S. ; Arora, S. ; Jagdeva, G. ; Kumar, S . Schiff base of O-carboxymethyl chitosan and its complexes with transition metal ions: syntheses, structural, antimicrobial and thermal studies . Iran. Polym. J. , 2022 , 31 ( 9 ), 1093 – 1105 .
Yin, X. Q. ; Chen, J. H. ; Yuan, W. ; Lin, Q. ; Ji, L. ; Liu, F . Preparation and antibacterial activity of Schiff bases from O -carboxymethyl chitosan and para-substituted benzaldehydes . Polym. Bull. , 2012 , 68 ( 5 ), 1215 – 1226 .
Chen, L. ; Li, B. D. ; Liu, D. B . Schiff base complex coated Fe 3 O 4 nanoparticles: a highly recyclable nanocatalyst for selective oxidation of alkyl aromatics . Catal. Lett. , 2014 , 144 ( 6 ), 1053 – 1061 .
Taha, A. B. ; Hashmi, A. A . Synthesis, characterization, catalytic activity of Schiff base Cu-complex and Ni-complex for aromatic nitro compounds and methyl orange reduction . Next Mater. , 2025 , 8 , 100649 .
Boukachabia, M. ; Aribi-Zouioueche, L. ; Riant, O . Synthesis and evaluation of hemisalen type ligands based on chiral diamine and their use with ruthenium (Ⅱ) as water-soluble catalysts for the ATH of aromatic ketones . J. Organomet. Chem. , 2018 , 868 , 95 – 101 .
Islam, M. ; Mondal, P. ; Mukherjee, S. ; Mobarak, M. ; Roy, A. S. ; Mondal, S. ; Sarkar, S . Efficient liquid phase oxidation of olefins and aromatic alcohol catalyzed by reusable polymer anchored Schiff base complexes . J. Chem. Technol. Biotechnol. , 2010 , 85 ( 4 ), 460 – 470 .
Hasan, K. ; Joseph, R. G. ; Patole, S. P. ; Al-Qawasmeh, R. A . Development of magnetic Fe 3 O 4 -chitosan immobilized Cu(Ⅱ) Schiff base catalyst: an efficient and reusable catalyst for microwave assisted one-pot synthesis of propargylamines via A3 coupling . Catal. Commun. , 2023 , 174 , 106588 .
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