Polyimine covalent adaptable networks (CANs) exhibit several dynamic characteristics (such as recyclability and reprocessability) that are beneficial for compensating for the disadvantages of traditional petroleum-based synthetic thermosetting resins, and are therefore suggested as potential substitutes for environmentally unfriendly resins. However, owing to the lack of sufficient stability of imine bonds and their linked molecular chains, most polyimine CANs do not exhibit superior properties in applications with high stability requirements, such as strong water resistance, high heat resistance, and excellent mechanical strength. In this study, we designed and synthesized a new class of aromatic petroleum-based polyimine CANs to improve the stability of imine bonds and molecular chains employing the conjugation effect of the two benzene rings to C=N and aromatic structures. In contrast, these CANs simultaneously demonstrate superior water resistance (water absorption: 0.14–0.15%) and heat resistance (5% weight loss (T_d5%): 434–441 °C; glass transition temperature (T_g): 217–239 °C) than that of previously reported polyimine CANs (water absorption: 0.90–90%; T_d5%: 200–348 °C; T_g: 47–215 °C). They have outstanding mechanical properties that are almost unaffected by adsorbed water. Meanwhile, the resins exhibited remarkable resistance to ordinary acids, bases, oxidants, salts, solvents, and oils, except for several special solvents. In addition, like other polyimine CANs, they maintain their dynamic behavior characteristics, including degradability, recyclability, malleability, reprocessability, and rehealability. This study provides a new method to improve the comprehensive performance of polyimine CANs through reasonable molecular structure design.

聚亚胺共价适应性网络 (CAN) 具有多种动态特性（例如可回收性和可再加工性），有利于弥补传统石油基合成热固性树脂的缺点，因此被建议作为环境不友好树脂的潜在替代品。然而，由于亚胺键及其连接的分子链缺乏足够的稳定性，大多数聚亚胺CAN在高稳定性要求的应用中没有表现出优异的性能，例如强耐水性、高耐热性和优异的机械强度。在这项研究中，我们设计并合成了一类新型芳香族石油基聚亚胺 CAN，利用两个苯环与 C=N 和芳香族结构的共轭作用，提高亚胺键和分子链的稳定性。相比之下，这些 CAN 同时表现出优异的耐水性（吸水率：0.14–0.15%）和耐热性（5% 的重量损失（T _d5% ): 434–441 °C; 玻璃化转变温度 ( T _g )：217–239 °C) 高于之前报道的聚亚胺 CAN（吸水率：0.90–90%；T _d5%：200–348 °C；T _g: 47–215 °C)。它们具有出色的机械性能，几乎不受吸附水的影响。同时，该树脂对除几种特殊溶剂外的普通酸、碱、氧化剂、盐、溶剂和油类表现出显着的耐受性。此外，与其他聚亚胺 CAN 一样，它们保持其动态行为特征，包括可降解性、可回收性、延展性、可再加工性和再修复性。本研究为通过合理的分子结构设计来提高聚亚胺CANs的综合性能提供了一种新方法。