We report in this work the preparation and in-depth characterization of thermo-reversible healable materials based on lignin, a major naturally occurring aromatic biopolymer. Following an environmentally friendly chemical pathway, a derivative of soda lignin (SL) bearing maleimide groups and poly-functional furan linkers were clicked through the furan – maleimide Diels – Alder (D-A) polymerization in a solvent free media and without the use of catalyst. The furan linkers were obtained by the thiol – epoxy reaction between furfuryl glycidyl ether and thiols of functionalities from 2 to 4. The different degree of substitution of maleimide lignin derivatives and linker functionalities allowed the tuning of the thermo-mechanical properties of the resultant materials. The latter exhibit on demand thermally induced disassembly and reassembly of the polymeric networks when heated at 110–130 °C and then cured at 60 °C, providing controlled self-healing properties and an efficient reprocessing with a limited impact on the thermo-mechanical properties and the thermal stability of the final materials. This study provides interesting perspectives for the production of renewable lignin-based aromatic polymers, demonstrating that an effective chemical modification together with tailored molecular architectures could pave the way for the development of high value-added materials from this underused aromatic feedstock.

我们在这项工作中报告了基于木质素（一种主要的天然存在的芳香生物聚合物）的热可逆可愈合材料的制备和深入表征。遵循环境友好的化学途径，在无溶剂介质中，无需使用催化剂，即可通过带有呋喃-马来酰亚胺狄尔斯-阿尔德（DA）的聚合反应，点击带有马来酰亚胺基团的苏打木质素（SL）和多官能呋喃连接基的衍生物。呋喃连接基是通过糠基缩水甘油醚和官能度为2至4的硫醇之间的硫醇-环氧反应获得的。马来酰亚胺木质素衍生物的取代度和连接基的官能度不同，可以调节所得材料的热机械性能。后者在110-130°C加热，然后在60°C固化时，可以按需表现出对聚合物网络的热诱导分解和重新组装，从而提供可控的自愈性能和有效的再加工工艺，对热机械性能的影响有限以及最终材料的热稳定性。这项研究为可再生的木质素基芳族聚合物的生产提供了有趣的观点，证明了有效的化学修饰以及量身定制的分子结构可以为利用这种未被充分利用的芳族原料开发高附加值的材料铺平道路。提供受控的自我修复性能和有效的再加工工艺，对最终材料的热机械性能和热稳定性影响有限。这项研究为可再生的木质素基芳族聚合物的生产提供了有趣的观点，证明了有效的化学修饰以及量身定制的分子结构可以为利用这种未被充分利用的芳族原料开发高附加值的材料铺平道路。提供受控的自我修复性能和有效的再加工工艺，对最终材料的热机械性能和热稳定性影响有限。这项研究为可再生的木质素基芳族聚合物的生产提供了有趣的观点，证明了有效的化学修饰以及量身定制的分子结构可以为利用这种未被充分利用的芳族原料开发高附加值的材料铺平道路。