Polyimine-Based Self-Healing Composites: A Review on Dynamic Covalent Thermosets for Sustainable and High-Performance Applications

Polyimine-based composites have emerged as a promising class of dynamic covalent thermosets, combining high mechanical strength, thermal stability, self-healing, recyclability, and reprocessability. This review systematically summarizes recent advances in polyimine synthesis, highlighting dynamic covalent chemistry (DCC) strategies such as imine exchange and reversible Schiff base reactions. Structural customization can be achieved by incorporating reinforcing phases such as carbon nanotubes, graphene, and bio-based fibers. Advanced fabrication methods—including solution casting, hot pressing, and interfacial polymerization—enable precise integration of these components while preserving structural integrity and adaptability. Mechanical performance analysis emphasizes the interplay between dynamic bonds, interfacial engineering, and multiscale design strategies. Polyimine composites exhibit outstanding performance characteristics, including a self-healing efficiency exceeding 90%, a tensile strength reaching 96.2 MPa, and remarkable chemical recyclability. Emerging engineering applications encompass sustainable green materials, flexible electronics, energy storage devices, and flame-retardant systems. Key challenges include balancing multifunctionality, enhancing large-scale processability, and developing low-energy recycling strategies. Future efforts should focus on interfacial optimization and network adaptivity to accelerate the industrial translation of polyimine composites, advancing next-generation sustainable materials.