Reversible Vitrimisation of Single‐Use Plastics and their Mixtures

Abstract Vitrimers are promising next‐generation materials, often exhibiting superior properties such as mechanical strength and solvent resistance compared to their thermoplastic counterparts, while still featuring recyclability due to their dynamic covalent crosslinks. The most common strategy to recycle vitrimers is via mechanical reprocessing at high temperatures, while others utilize chemical degradation to reobtain the constituent monomers. This work presents a new approach toward reprocessing by selectively breaking of the vitrimer's crosslinks, turning it back into a thermoplastic. This allows for reprocessing to be achieved in a more sustainable manner such as at lower temperatures and shorter times. After the desired shape has been obtained, facile re‐crosslinking turns the material into a vitrimer, with full restoration of thermal stability, mechanical properties, and gel fraction. To achieve this, a carbene C─H insertion strategy is utilized to introduce an imine‐based crosslinker into various thermoplastics and plastic mixtures to convert them into vitrimers. Properties typical of vitrimers such as a retained polymer network at high temperatures, and an Arrhenius‐type relationship between stress relaxation rate and temperature are observed, while its mechanical properties such as elongation at break and tensile toughness, particularly for plastic mixtures are significantly enhanced, first by crosslinking, then further enhanced up to 8 folds by the reversible crosslinking process.