Tough Epoxy Vitrimer with Hybrid Networks and Its Applications in Reprocessable Composites

Progress in the ever‐growing vitrimer chemistry opens up great opportunities for a sustainable society by producing reprocessable thermosets. However, most vitrimers suffer from the conflict between mechanical performance and dynamic reactivity, hindering the development of industrial applications. Herein, a facile but universal material design strategy is proposed to yield tough epoxy vitrimers while preserving excellent reprocessability. Copolymerization and bond exchange reactions can build covalent bridges between heterogeneous polymer networks, thus leading to a hybrid dynamic covalent polymer network containing hard and soft segments. Tailorable mechanical and thermal properties are obtained by controlling the ratio of hard‐to‐soft components. The resulting epoxy vitrimer can balance strength and stretchability while exhibiting brittle‐to‐ductile transformation in tensile tests. Enhanced fracture toughness is achieved compared to both pristine hard and soft vitrimers. The resulting vitrimers exhibit excellent processability and potential applications in composite fabrication, welding and reshaping, and multiple shape memory functions. This work presents a feasible approach to satisfying the demands of mechanical performance and dynamic reactivity in the design of epoxy vitrimers. The material design principle will be applicable to a wide range of vitrimer systems to pursue desirable properties.