Homolytic fracture of inorganic crystalline materials enhances the mechano-chemical degradation of polypropylene.

Mechano-chemistry can depolymerize plastics to their monomers. The conversion of polyolefins, however, suffers from low chain cleavage rates and the low stability of radical intermediates. Therefore, insights into the degradation mechanism are crucial to obtain higher yields. Herein, we promote the mechano-chemical degradation of polypropylene by milling with sand as an additive, which increases depolymerization yields by a factor of 25. Fracture of sand crystals causes homolytic cleavage of Si-O bonds resulting in unpaired surface electrons, which possess radical reactivity and can initiate degradation reactions of polypropylene, ultimately resulting in smaller hydrocarbons. We show that this mechanism based on surface radicals dominates over alternative pathways based on locally increased temperature or surface roughening of grinding spheres. While inorganic materials, such as glass fiber in composites, are typically unwanted in (chemical) recycling scenarios, we show that they can be exploited to drive mechano-chemical depolymerization. Our study illustrates that control over the radical-based degradation mechanism during the mechano-chemical conversion of polyolefins is key to increase yields and technological viability.