Dynamic Covalent Adaptable Polyimide Hybrid Dielectric Films with Superior Recyclability

Polyimides (PIs) used in advanced electrical and electronic devices can be electrically/mechanically damaged, resulting in a significant waste of resources. Closed‐loop chemical recycling may prolong the service life of synthetic polymers. However, the design of dynamic covalent bonds for preparing chemically recyclable crosslinked PIs remains a challenging task. Herein, new crosslinked PI films containing a PI oligomer, chain extender, and crosslinker are reported. They exhibit superior recyclability and excellent self‐healable ability owing to the synergistic effect of the chain extender and crosslinker. The produced films can be completely depolymerized in an acidic solution at ambient temperature, leading to efficient monomer recovery. The recovered monomers may be used to remanufacture crosslinked PIs without deteriorating their original performance. In particular, the designed films can serve as corona‐resistant films with a recovery rate of approximately 100%. Furthermore, carbon fiber reinforced composites (CFRCs) with PI matrices are suitable for harsh environments and can be recycled multiple times at a non‐destructive recycling rate up to 100%. The preparation of high‐strength dynamic covalent adaptable PI hybrid films from simple PI oligomers, chain extenders, and crosslinkers may provide a solid basis for sustainable development in the electrical and electronic fields. A dynamic crosslinked polyimide film (DCPI) is designed by introducing a chain extender. This DCPI film has excellent superior recyclability at the monomer level and self‐healable ability. Moreover, the DCPI is a good corona‐resistant film and a matrix of sustainable carbon fiber‐reinforced composites.