Elevated-Temperature Creep-Resistant Bio-based Aminal/Imine Hybrid Dynamic Covalent Cross-Linked Polymers

Hong-yun Hu; Zhen Yu; Jin-ping Ni; Zhao-bin Tang; Yan-lin Liu

doi:10.11777/j.issn1000-3304.2025.25168

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Elevated-Temperature Creep-Resistant Bio-based Aminal/Imine Hybrid Dynamic Covalent Cross-Linked Polymers

更新时间：2025-09-13

- Elevated-Temperature Creep-Resistant Bio-based Aminal/Imine Hybrid Dynamic Covalent Cross-Linked Polymers
- Acta Polymerica Sinica Pages: 1-11(2025)
- 作者机构：
  
  1.宁波大学材料科学与化学工程学院宁波 315211
  2.中国科学院宁波材料技术与工程研究所宁波 315201
- 作者简介：
  
  Zhen Yu, E-mail: yuzhen@nimte.ac.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25168
  CLC：
- CSTR：32057.14.GFZXB.2025.7459
- Received：11 July 2025，
  
  Accepted：22 August 2025，
  
  Published Online：13 September 2025，
- 稿件说明：
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胡宏运, 于震, 倪金平, 汤兆宾, 刘艳林. 高温抗蠕变生物基缩醛胺/亚胺杂化动态共价交联聚合物. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25168

Hu, H. Y.; Yu, Z.; Ni, J. P.; Tang, Z. B.; Liu, Y. L. Elevated-temperature creep-resistant bio-based aminal/imine hybrid dynamic covalent cross-linked polymers. Acta Polymerica Sinica, doi: 10.11777/j.‍issn1000-3304.2025.25168
胡宏运, 于震, 倪金平, 汤兆宾, 刘艳林. 高温抗蠕变生物基缩醛胺/亚胺杂化动态共价交联聚合物. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25168 DOI： CSTR： 32057.14.GFZXB.2025.7459.

Hu, H. Y.; Yu, Z.; Ni, J. P.; Tang, Z. B.; Liu, Y. L. Elevated-temperature creep-resistant bio-based aminal/imine hybrid dynamic covalent cross-linked polymers. Acta Polymerica Sinica, doi: 10.11777/j.‍issn1000-3304.2025.25168 DOI： 10.11777/j.issn1000-3304.2025.25168. CSTR： 32057.14.GFZXB.2025.7459.

摘要

动态共价聚合物网络(dynamic covalent polymer networks，DCPNs)为解决热固性树脂的回收难题开辟了有效途径，然而，由于动态键可逆反应，该类材料普遍高温抗蠕变性能较差，热学和力学性能、尺寸稳定性不足的缺陷将限制其实际应用. 因此，本工作以生物来源的香草醛和

-赖氨酸二异氰酸酯为原料、二乙烯三胺和4

4'-二氨基二苯胺为交联剂，制备了一类高性能生物基动态共价交联聚合物(PBVs). 结构分析结果表明，通过醛胺缩合反应成功构建了缩醛胺/亚胺杂化的DCPNs. 该材料展现出优异高温抗蠕变性，在拉伸强度约为70 MPa，

超过120 ℃的前提下，树脂的初始蠕变温度高达120 ℃. 同时，该材料在酸性条件下可以完全降解，并能通过热压工艺实现再加工. 本工作为发展兼具高温抗蠕变和可回收性的生物基热固性树脂提供了新思路，在可持续材料领域具有应用潜力.

Abstract

Dynamic covalent polymer networks (DCPNs) offer a promising solution to the recyclability challenges of thermosets. However

due to the reversible nature of the dynamic bonds

these materials typically exhibit poor elevated-temperature creep resistance. Deficiencies in thermal and mechanical properties

as well as dimensional stability

limit their practical applications. Herein

we report the synthesis of high-performance biobased dynamic covalent cross-linked polymers (PBVs) using vanillin and

-lysine diisocyanate as monomers

with diethylenetriamine and 4

‍4'-diaminodiphenylamine as crosslinkers. Structural analysis confirmed that the aldehyde-amine condensation reaction successfully formed a hybrid aminal/imine DCPN. The material demonstrated excellent elevated-temperature creep resistance

with a tensile strength of approximately 70 MPa and a

exceeding 120 ℃. Notably

the resin's initial creep temperature reached up to 120 ℃. Furthermore

the PBVs undergo complete degradation under acidic conditions and can be reprocessed

via

hot-pressing. This work presents a new strategy for developing biobased thermosets that simultaneously possess elevated-temperature creep resistance and recyclability

demonstrating significant potential for sustainable materials.

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Keywords

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