{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,13]],"date-time":"2026-10-13T20:47:02Z","timestamp":1791924422613,"version":"4.3.4"},"reference-count":29,"publisher":"American Chemical Society (ACS)","issue":"40","license":[{"start":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T00:00:00Z","timestamp":1790640000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006407","name":"Natural Science Foundation of Henan Province","doi-asserted-by":"publisher","award":["262300421327"],"award-info":[{"award-number":["262300421327"]}],"id":[{"id":"10.13039\/501100006407","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100011447","name":"Science and Technology Department of Henan Province","doi-asserted-by":"publisher","award":["HNGD2025024"],"award-info":[{"award-number":["HNGD2025024"]}],"id":[{"id":"10.13039\/501100011447","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100003489","name":"Henan University of Technology","doi-asserted-by":"publisher","award":["21421358"],"award-info":[{"award-number":["21421358"]}],"id":[{"id":"10.13039\/501100003489","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,13]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Developing vanillin-derived thermosets that combine mechanical robustness with repairability and chemical recyclability remains a central challenge in replacing petroleum-derived cross-linked polymers. Vanillin offers a renewable aromatic platform for this purpose because it can introduce rigidity while providing functional groups for dynamic network construction. Here, we report a series of vanillin-derived imine-cross-linked polymer networks (VD-TAM) prepared from a benzoxazine-containing dialdehyde monomer (VD), decanediamine (DM), and tris(2-aminoethyl)amine (TAM). By fixing the aldehyde\/amine functional-group ratio at 1:1 and the VD content while varying the relative contributions of flexible DM segments and trifunctional TAM junctions, the network structure was systematically regulated. This design allowed the amine structure-dependent balance between network rigidity and imine-exchange dynamics to be evaluated. Increasing the TAM content raised the glass-transition temperature from 49.3 to 72.2 \u00b0C, the DMA-derived effective cross-link density from 5.31 \u00d7 10\u20134 to 16.43 \u00d7 10\u20134 mol cm\u20133, and the tensile strength from 40.37 to 56.33 MPa, while decreasing the elongation at break from 124.47 to 7.29%. Stress-relaxation analysis confirmed thermally activated network relaxation associated with imine exchange, with apparent activation energies for macroscopic network relaxation increasing from 35.83 to 49.22 kJ mol\u20131 as the network became more constrained. The dynamic imine network further enabled thermal reprocessing, shape-memory behavior, and efficient self-healing, with VD-TAM-50 showing a representative tensile-strength recovery of 93.5% after healing at 90 \u00b0C for 20 min and retaining 90.9% of its tensile strength after two reprocessing cycles. In addition, acid-triggered imine hydrolysis allowed recovery of the VD monomer, indicating a potential route toward monomer recovery and future closed-loop material design. These results demonstrate that amine-structure regulation provides an effective strategy for designing vanillin-derived imine networks with balanced mechanical performance, dynamic adaptability, and chemical recyclability.<\/jats:p>","DOI":"10.1021\/acsomega.6c07945","type":"journal-article","created":{"date-parts":[[2026,9,30]],"date-time":"2026-09-30T04:02:25Z","timestamp":1790740945000},"page":"61937-61945","source":"Crossref","is-referenced-by-count":0,"title":["Amine-Structure-Regulated\nVanillin-Derived Imine-Cross-Linked\nNetworks for Reprocessable, Self-Healing, and Chemically Recyclable\nThermosets"],"prefix":"10.1021","volume":"11","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1538-4417","authenticated-orcid":true,"given":"Jinling","family":"Li","sequence":"first","affiliation":[{"name":"Henan University of Technology , , ,","place":["Zhengzhou, China, 450001"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yaoyao","family":"Zhang","sequence":"additional","affiliation":[{"name":"Henan University of Technology , , ,","place":["Zhengzhou, China, 450001"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yangguang","family":"Xiang","sequence":"additional","affiliation":[{"name":"Henan University of Technology , , ,","place":["Zhengzhou, China, 450001"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yanyan","family":"He","sequence":"additional","affiliation":[{"name":"Henan University of Technology , , ,","place":["Zhengzhou, China, 450001"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lixiang","family":"Zhu","sequence":"additional","affiliation":[{"name":"Henan University of Technology , , ,","place":["Zhengzhou, China, 450001"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9690-3746","authenticated-orcid":true,"given":"Yunchao","family":"Jia","sequence":"additional","affiliation":[{"name":"Henan University of Technology , , ,","place":["Zhengzhou, China, 450001"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,29]]},"reference":[{"key":"2026101315070607500_cit1","doi-asserted-by":"publisher","first-page":"1437","DOI":"10.1038\/s41563-026-02646-y","article-title":"Chain Entanglements\nEnable Regeneration of High-Performance Thermosets","volume":"25","author":"Xu","year":"2026","journal-title":"Nat. Mater."},{"key":"2026101315070607500_cit2","doi-asserted-by":"publisher","first-page":"101935","DOI":"10.1016\/j.progpolymsci.2025.101935","article-title":"Recyclable\nFire-Retardant\nBio-Based Thermosets: From Molecular Engineering to Performances and\nApplications","volume":"162","author":"Guo","year":"2025","journal-title":"Prog. Polym. Sci."},{"key":"2026101315070607500_cit3","doi-asserted-by":"publisher","first-page":"354","DOI":"10.1038\/nature21001","article-title":"Sustainable\nPolymers from Renewable\nResources","volume":"540","author":"Zhu","year":"2016","journal-title":"Nature"},{"key":"2026101315070607500_cit4","doi-asserted-by":"publisher","first-page":"2311242","DOI":"10.1002\/adma.202311242","article-title":"Bio-Based Thermosetting\nResins: From Molecular Engineering to Intrinsically Multifunctional\nCustomization","volume":"36","author":"Zhao","year":"2024","journal-title":"Adv. Mater."},{"key":"2026101315070607500_cit5","doi-asserted-by":"publisher","first-page":"1036","DOI":"10.1021\/acssuschemeng.1c07523","article-title":"Fully Bio-Based High-Performance Thermosets with Closed-Loop Recyclability","volume":"10","author":"Hong","year":"2022","journal-title":"ACS Sustainable Chem. Eng."},{"key":"2026101315070607500_cit6","doi-asserted-by":"publisher","first-page":"9805","DOI":"10.1021\/acssuschemeng.4c02186","article-title":"New Generation of Recyclable\nHigh-Performance Biobased Epoxy Thermosets and Composites","volume":"12","author":"Dinu","year":"2024","journal-title":"ACS Sustainable Chem. Eng."},{"key":"2026101315070607500_cit7","doi-asserted-by":"publisher","first-page":"201","DOI":"10.1007\/s10118-020-2479-6","article-title":"An Interfacial Dynamic\nCrosslinking Approach toward Catalyst-Free and Mechanically Robust\nElastomeric Vitrimer with a Segregated Structure","volume":"39","author":"Zhu","year":"2021","journal-title":"Chin. J. Polym. Sci."},{"key":"2026101315070607500_cit8","doi-asserted-by":"publisher","first-page":"898","DOI":"10.1002\/1521-3773(20020315)41:6&lt;898::AID-ANIE898&gt;3.0.CO;2-E","article-title":"Dynamic\nCovalent Chemistry","volume":"41","author":"Rowan","year":"2002","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026101315070607500_cit9","doi-asserted-by":"publisher","first-page":"9682","DOI":"10.1002\/anie.201813525","article-title":"Dynamic Covalent\nBonds in Polymeric Materials","volume":"58","author":"Chakma","year":"2019","journal-title":"Angew. Chem.,\nInt. Ed."},{"key":"2026101315070607500_cit10","doi-asserted-by":"publisher","first-page":"541","DOI":"10.1038\/s41578-021-00412-x","article-title":"Dynamic and Reconfigurable Materials from Reversible\nNetwork Interactions","volume":"7","author":"Webber","year":"2022","journal-title":"Nat. Rev. Mater."},{"issue":"12","key":"2026101315070607500_cit11","doi-asserted-by":"publisher","first-page":"7829","DOI":"10.1021\/acs.chemrev.3c00926","article-title":"New Advances in Covalent\nNetwork Polymers via Dynamic Covalent Chemistry","volume":"124","author":"Lei","year":"2024","journal-title":"Chem. Rev."},{"key":"2026101315070607500_cit12","doi-asserted-by":"publisher","first-page":"1543","DOI":"10.1038\/s41467-025-68263-6","article-title":"Dynamic Decrosslinking\nEnables Self-Healing, Reprocessability, and Upcycling in Polyurethane\nNetworks","volume":"17","author":"Kong","year":"2026","journal-title":"Nat. Commun."},{"issue":"6","key":"2026101315070607500_cit13","doi-asserted-by":"publisher","first-page":"1456","DOI":"10.1016\/j.matt.2019.09.004","article-title":"Malleable and Recyclable\nThermosets: The Next Generation of Plastics","volume":"1","author":"Jin","year":"2019","journal-title":"Matter"},{"key":"2026101315070607500_cit14","doi-asserted-by":"publisher","first-page":"126487","DOI":"10.1016\/j.polymer.2023.126487","article-title":"Extrudable Robust and\nRecyclable Bio-Based Epoxy Vitrimer via Tailoring the Topology of\na Dual Dynamic-Covalent-Bond Network","volume":"289","author":"Wang","year":"2023","journal-title":"Polymer"},{"key":"2026101315070607500_cit15","doi-asserted-by":"publisher","first-page":"555","DOI":"10.13550\/j.jxhg.20250054","article-title":"Preparation\nand Properties of Vanillin-Based Polymers Incorporating Dynamic Disulfide\nBonds","volume":"43","author":"Zhao","year":"2026","journal-title":"Fine Chem."},{"key":"2026101315070607500_cit16","doi-asserted-by":"publisher","DOI":"10.1002\/smm2.1309","article-title":"Imine-Linked\nCovalent Organic Frameworks: Recent Advances in Design, Synthesis,\nand Application","volume":"5","author":"Huang","year":"2024","journal-title":"SmartMater"},{"key":"2026101315070607500_cit17","doi-asserted-by":"publisher","first-page":"130","DOI":"10.1007\/s10965-026-04826-5","article-title":"Recent Advances\nin Schiff Base Driven Self-Healing Vitrimers with Dynamic Covalent\nNetworks for Sustainable Applications","volume":"33","author":"Parihar","year":"2026","journal-title":"J. Polym.\nRes."},{"key":"2026101315070607500_cit18","doi-asserted-by":"publisher","first-page":"24070017","DOI":"10.11896\/cldb.24070017","article-title":"All-Biomass\nBased Schiff Base Vitrimer: Combining Excellent Mechanical Properties\nwith Recyclability and Stimulus Responsiveness","volume":"39","author":"Xiang","year":"2025","journal-title":"Mater. Rep."},{"key":"2026101315070607500_cit19","doi-asserted-by":"publisher","first-page":"2904","DOI":"10.1002\/adma.201505245","article-title":"Repairable\nWoven Carbon Fiber Composites\nwith Full Recyclability Enabled by Malleable Polyimine Networks","volume":"28","author":"Taynton","year":"2016","journal-title":"Adv. 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Mater."},{"key":"2026101315070607500_cit22","doi-asserted-by":"publisher","DOI":"10.1126\/science.adj9989","article-title":"Closed-Loop\nRecyclability of a Biomass-Derived Epoxy-Amine\nThermoset by Methanolysis","volume":"384","author":"Wu","year":"2024","journal-title":"Science"},{"key":"2026101315070607500_cit23","doi-asserted-by":"publisher","first-page":"4363","DOI":"10.1039\/D2GC01325H","article-title":"Biobased\nCovalent\nAdaptable Networks: Towards Better Sustainability of Thermosets","volume":"24","author":"Zhao","year":"2022","journal-title":"Green Chem."},{"key":"2026101315070607500_cit24","doi-asserted-by":"publisher","first-page":"1816","DOI":"10.1002\/macp.201500194","article-title":"Renewable Polymers Prepared from\nVanillin and Its Derivatives. Macromol","volume":"216","author":"Zhang","year":"2015","journal-title":"Chem.\nPhys."},{"key":"2026101315070607500_cit25","doi-asserted-by":"publisher","first-page":"35","DOI":"10.1021\/acssuschemeng.5b01344","article-title":"Vanillin Production from Lignin and\nIts Use as a Renewable Chemical","volume":"4","author":"Fache","year":"2016","journal-title":"ACS Sustainable\nChem. Eng."},{"key":"2026101315070607500_cit26","doi-asserted-by":"publisher","first-page":"1892","DOI":"10.1021\/acs.macromol.7b00097","article-title":"Vanillin-Derived\nHigh-Performance Flame Retardant Epoxy Resins: Facile Synthesis and\nProperties","volume":"50","author":"Wang","year":"2017","journal-title":"Macromolecules"},{"key":"2026101315070607500_cit27","doi-asserted-by":"publisher","first-page":"15463","DOI":"10.1021\/acssuschemeng.8b03925","article-title":"Vanillin-Based\nPolyschiff Vitrimers:\nReprocessability and Chemical Recyclability","volume":"6","author":"Geng","year":"2018","journal-title":"ACS Sustainable Chem. Eng."},{"key":"2026101315070607500_cit28","doi-asserted-by":"publisher","first-page":"7739","DOI":"10.1021\/acssuschemeng.4c00052","article-title":"Biobased Polybenzoxazine Vitrimer\nwith Imine Bonds:\nShape Memory, Reprocessing, and Degradation","volume":"12","author":"Qu","year":"2024","journal-title":"ACS Sustainable Chem. Eng."},{"key":"2026101315070607500_cit29","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.202301708","article-title":"Weldable,\nReprocessable, and Water-resistant Polybenzoxazine Vitrimer Crosslinked\nby Dynamic Imine Bonds","volume":"17","author":"Zhang","year":"2024","journal-title":"ChemSusChem"}],"container-title":["ACS Omega"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acsomega.6c07945","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/acsodf\/article-pdf\/11\/40\/61937\/68706257\/acsomega.6c07945.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/acsodf\/article-pdf\/11\/40\/61937\/68706257\/acsomega.6c07945.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,13]],"date-time":"2026-10-13T20:05:47Z","timestamp":1791921947000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/acsodf\/article\/11\/40\/61937\/5442057\/Amine-Structure-Regulated-Vanillin-Derived-Imine"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,29]]},"references-count":29,"journal-issue":{"issue":"40","published-online":{"date-parts":[[2026,9,29]]},"published-print":{"date-parts":[[2026,10,13]]}},"URL":"https:\/\/doi.org\/10.1021\/acsomega.6c07945","relation":{},"ISSN":["2470-1343"],"issn-type":[{"value":"2470-1343","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,29]]}}}