Thermally Reversible and Recyclable Polyethylene Networks via Furan-Maleimide Diels-Alder Dynamic Covalent Chemistry

The formation of recyclable polyethylene materials is significantly limited by traditional crosslinking methods, which involve solvent-heavy processes and permanent chemical bonds that cannot be undone. Herein, we report an environmentally friendly and scalable approach to construct a thermo-reversible polyethylene network (PE-g-DA) via solvent-free, one-step melt processing based on furan-maleimide Diels-Alder (D-A) dynamic covalent chemistry. Furan-functionalized polyethylene was dynamically crosslinked with bismaleimide during melt mixing, fully compatible with conventional polyolefin processing techniques. FTIR spectroscopy, temperature-dependent solubility, and differential scanning calorimetry collectively confirm the reversible formation and dissociation of D-A adducts, enabling thermal switching of the network structure. Equilibrium swelling experiments based on the Flory-Rehner model indicate that the crosslink density can be precisely controlled by varying the bismaleimide content. As a result, PE-g-DA exhibits significantly enhanced tensile strength while maintaining high ductility at moderate crosslink densities. Notably, the dynamic network allows efficient thermal reprocessing, with recycled samples retaining approximately 93% and 80% of their original tensile strength after the first and second reprocessing cycles, respectively. Moreover, intrinsic thermal self-healing behavior is directly visualized by scanning electron microscopy at 120 °C. This work demonstrates that combining dynamic Diels-Alder chemistry with solvent-free melt processing offers a practical and sustainable route to recyclable, reprocessable, and self-healable polyethylene materials with clear potential for large-scale industrial production.