Circular Cross-Linked Polyethylene Enabled by In-Chain Ketones

Cross-linked polyethylenes (PEs) are widely employed, but the permanent links between the chains impede recycling. We show that via imine formation with diamines keto-functionalized polyethylenes from both free-radical (keto-low-density PE, keto-LDPE) and catalytic (keto-high-density PE, keto-HDPE) nonalternating ethylene-CO copolymerization can be cross-linked efficiently in the melt, resulting in gel fractions of the formed cross-linked PEs of up to 85% and improved tensile properties. The imine-based cross-links in the material can be hydrolyzed at 140 °C to recycle up to 97% of the initial thermoplastic keto-polyethylene. Low keto contents of ≤1.5 mol % are found ideal to retain PE-like thermal properties, achieve sufficient cross-link density, and maintain circular recyclability.