Bio-Based and Solvent-Free Epoxy Vitrimers Based on Dynamic Imine Bonds with High Mechanical Performance

Conventional epoxy thermosets, with irreversible crosslinking networks, cannot be reprocessed and recycled. Furthermore, the utilization of petroleum-based materials accelerates the depletion of non-renewable resources. The introduction of dynamic covalent bonds and the use of bio-based materials for thermosets can effectively address the above issues. Herein, a series of bio-based epoxy vitrimers with dynamic covalent imine bonds were synthesized via a simple solvent-free, one-pot method using vanillin-derived aldehyde monomers, 4,4-diaminodiphenylsulfone (DDS) and bisphenol F diglycidyl ether (BFDGE) as raw materials. The effect of crosslinking density, crosslinking structure and imine bond content on the resulting bio-based vitrimers was studied, demonstrating their excellent thermal properties, UV shielding and solvent resistance, as well as outstanding mechanical properties compared to those of the previously reported vitrimers. In particular, the cured neat resin of vitrimer had a maximum tensile strength of 109 MPa and Young's modulus of 6257 MPa, which are higher than those of previously reported imine-based vitrimers. The dynamic imine bonds endow these vitrimers with good reprocessability upon heating (over 70% recovery) and degradation under acidic conditions, enabling recycling by physical routes and gentle degradation by chemical routes. This study demonstrates a simple and effective process to prepare high-performance bio-based and recycled epoxy thermosets.