Thermoreversible Diels–Alder Crosslinked Networks in Recycled Poly(ethylene terephthalate) for Reprocessability and Self-Healing

A thermoreversible dynamic covalent network was constructed in recycled polyethylene terephthalate (RPET) via Diels–Alder (DA) chemistry to enhance mechanical performance, reprocessability, and self-healing. Furan-functionalized RPET (RPET-3F) was first prepared from maleated RPET (RPET-MA), followed by crosslinking with bismaleimide (BMI) at different feed ratios. FTIR spectra confirmed the successful grafting of furan groups and the formation of DA adducts. With increasing BMI content, the gel fraction and crosslink density increased substantially, whereas the swelling ratio decreased, indicating the progressive development of a three-dimensional network. RPET-3F-2B showed the highest network integrity among all samples. DSC analysis revealed a distinct retro-DA dissociation peak at 143 °C and a recrosslinking peak near 124 °C, confirming the thermal reversibility of the DA network. Owing to the optimized network structure, RPET-3F-2B exhibited the best mechanical properties and excellent reprocessability, retaining stable performance after three hot-pressing cycles. After repeated reprocessing, its tensile strength remained 74% higher than that of RPET-MA, while the elongation at break was still improved by about 10%. Moreover, the sample showed efficient thermally induced self-healing at 150 °C, with surface cracks nearly disappearing after 4 h. These results demonstrate that DA chemistry offers a promising route to the high-value reutilization of RPET into recyclable, multifunctional polymer materials.