Synthesis of Self-Healing Bio-Based Tannic Acid-Based Methacrylates By Thermoreversible Diels–Alder Reaction

This investigation reports the effective use of the Diels–Alder (DA) click reaction in the preparation of self-healing bio-based dendritic methacrylates having reactive furfuryl functionality. Bio-based methacrylates were synthesized by modifying tannic acid with glycidyl methacrylate and furfuryl functionality was introduced by atom transfer radical polymerization with varied amount of furfuryl methacrylate monomer. The thermoreversible network was successfully achieved by DA and retro-DA reaction between the furfuryl groups and a bifunctional maleimide crosslinker, bismaleimide. This process was studied by nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and solvent exposure tests. Differential scanning calorimetry analysis was used to determine the endothermic retro-DA reaction in the DA adduct. The self-healing property of the above crosslinked material was demonstrated by monitoring the repair of a scratch in the polymer film upon heating and cooling. This was analyzed by scanning electron microscopy. POLYM. ENG. SCI., 60:140–150, 2020. © 2019 Society of Plastics Engineers