Self-healable polymer networks from bio-based platform chemicals through Passerini and Diels–Alder reactions: a preliminary study

• Published in: Iranian polymer journal Vol. 32; no. 10; pp. 1307 - 1319
• Main Authors: Li, Qinsheng, Li, Yupeng, Li, Yaru, Huang, Qinghua, Hu, Zhongyu, Yang, Yuping, Xiong, Zhenhua, Cheng, Chuanjie
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01.10.2023; Springer Nature B.V
• Subjects: Acid resistance; Adipic acid; Biomass; Bismaleimides; Ceramics; Chemistry; Chemistry and Materials Science; Composites; Crosslinking; Cycloaddition; Diels-Alder reactions; Ethyl acetate; Furfural; Glass; Natural Materials; Networks; Original Research; Polymer Sciences; Polymers; Thermodynamic properties; Platform chemicals; Furfural; Self-healable polymers; Passerini reaction; Diels–Alder reaction
• ISSN: 1026-1265; 1735-5265
• DOI: 10.1007/s13726-023-01206-4

It is urgent and important to design and prepare functional polymers utilizing biomass or bio-based platform chemicals due to fossil resource/energy crisis. We designed and synthesized two linear polymers LP 1 and LP 2 from bio-based platform chemical furfural as well as other biomass-derived feedstock adipic acid and 1,6-hexadiamine using efficient and 100% atom-economy Passerini three-component reaction. The number-average molecular weights of LP 1 and LP 2 are 2189 da and 5464 da, respectively. The products LP 1 and LP 2 were crosslinked with N,N ´-4,4´-diphenylmethyene bismaleimide (BMI) through Diels–Alder cycloaddition reactions to form the corresponding polymer networks CP 1 and CP 2 , respectively. Both CP 1 and CP 2 showed good chemical resistance to acid and ethyl acetate, but relatively poor resistance toward base and THF. Gel fraction values of CP 1 and CP 2 were 82% and 74%, respectively, indicating that most of the linear segments of LP 1 and/or LP 2 were crosslinked after Diels–Alder reactions. Thermal property analysis indicated that the two polymer networks were at rubbery state as their T g values were 14.78 and 7.00 °C, respectively. Td 10 values of CP 1 and CP 2 were 151 °C and 131 °C, respectively. The presence of dynamic D–A bonds caused both CP 1 and CP 2 to exhibit intrinsic self-healable performance at 60 °C or higher. Furthermore, CP 2 also showed rapid self-healing behavior (within 3 min) under UV (360 nm) irradiation due to the existence of dynamic disulfide bonds in the main chain. Graphical abstract