Preparation and Property Modulation of Vanillin‐Derived Epoxy Vitrimers

The utilization of biomass for the preparation of recyclable epoxy vitrimers is highly beneficial for material sustainability. Vanillin and maleic anhydride were utilized to synthesize a novel copolymer (VME) with epoxy groups. Subsequently, aliphatic epoxy resins with varying lengths of spacers were synthesized by using several carboxylic acids derived from biomass, and reacted with VME, respectively, to prepare recyclable epoxy vitrimers with high biomass contents. The optimized combination of the rigid aromatic structure of VME and the flexible structures of aliphatic epoxy endows the vitrimers with high mechanical properties and recycling efficiency. The research results show the length of the aliphatic spacer significantly influences the properties of vanillin‐derived vitrimers. The vitrimer introduced by the diglycidyl ester of sebacic acid exhibits high heat resistance ( T g = 155.2°C), tensile strength (72.9 MPa), and elongation at break (8.6%), as well as high recyclability (90.5% strength remaining at first recycle).