Sustainable upcycling of polyethylene waste to compatibilizers and valuable chemicals

Controllable functionalization of polyethylene (PE) waste could generate new polymeric materials that are generally difficult to manufacture sustainably while also addressing the growing plastics waste problem. However, these modifications remain challenging due to the inherent stability of the PE backbone. Non-thermal atmospheric plasma enables molecular activation under mild conditions while utilizing renewable energy but is primarily employed for surface modification, as plasmas do not penetrate the bulk of materials. Herein, controllable bulk oxidative functionalization of PE wax (PEW) and low-density PE (LDPE) of varying molecular weights was achieved, with up to 6 mol% oxygen incorporation, by manipulating melt viscosity. This functionalization was accomplished either through temperature adjustment or by introducing a melt viscosity modifier, removable <i>via</i> simple extraction methods, to reduce LDPE viscosity, enhance diffusion and chain mobility, and enable bulk oxidation. The oxidized LDPE induces compatibilization in blends of poly(lactic acid) (PLA) and LDPE with improved interfacial adhesion and mechanical properties, such as a 70% increase in elongation-at-break values <i>vs.</i> the control. These findings pave the way for catalyst-free upcycling of direct plastics waste and plastics waste-derived products, enabling the creation of high-value products across various markets.