Dynamic covalent chemistry opens up great opportunities for a sustainable society by producing reprocessable networks of polymers and even thermosets. However, achieving the closed-loop recycling of polymers with high performance remains a grand challenge. The introduction of aromatic monomers and fluorine into covalent adaptable networks is an attractive method to tackle this challenge. Therefore, we present a facile and universal strategy to focus on the design and applications of polyimine vitrimers containing trifluoromethyl diphenoxybenzene backbones in applications of dynamic covalent polymers. In this study, fluorine-containing polyimine vitrimer networks (FPIVs) were fabricated, and the results revealed that the FPIVs not only exhibited good self-healability, malleability and processability without the aid of any catalyst, but also possessed decent mechanical strength, superior toughness and thermal stability. We hope that this work could provide a novel pathway for the design of high-performance polyimine vitrimers by recycling of plastic wastes.

To achieve energy saving and emission reduction goals, recyclable and healable thermoset materials are highly attractive. Polymer copolymerization has been proven to be a critical strategy for preparing high‐performance polymeric materials. However, it remains a huge challenge to develop high‐performance recyclable and healable thermoset materials. Here, polyimine dynamic networks based on two monomers with bulky pendant groups, which not only displayed mechanical properties higher than the strong and tough polymers, e.g., polycarbonate, but also excellent self‐repairing capability and recyclability as thermosets are developed. Owing to the stability of conjugation effect by aromatic benzene rings, the final polyimine networks are far more stable than the reported counterparts, exhibiting excellent hydrolysis resistance under both alkaline condition and most organic solvents. These polyimine materials with conjugation structure can be completely depolymerized into monomers recovery in an acidic aqueous solution at ambient temperature. Resulting from the bulky pendant units, this method allows the exchange reactions of conjugation polyimine vitrimer easily within minutes for self‐healing function. Moreover, the introduction of trifluoromethyl diphenoxybenzene backbones significantly increases tensile properties of polyimine materials. This work provides an effective strategy for fabricating high‐performance polymer materials with multiple functions.