Aerobic oxidation of alkylarenes and polystyrene waste to benzoic acids via a copper-based catalyst

The chemical recycling of polystyrene (PS) waste to value-added aromatic compounds is an attractive but formidable challenge due to the inertness of the C-C bonds in the polymer backbone. Here we develop a light-driven, copper-catalyzed protocol to achieve aerobic oxidation of various alkylarenes or real-life PS waste to benzoic acid and oxidized styrene oligomers. The resulting oligomers can be further transformed under heating conditions, thus achieving benzoic acid in up to 65% total yield through an integrated one-pot two-step procedure. Mechanistic studies show that the CuCl₂ catalyst undergoes Ligand-to-Metal Charge Transfer (LMCT) to generate a chlorine radical, which triggers activation of the C-H bond and subsequent oxidative cleavage of C-C bonds. The practicality and scalability of this strategy are demonstrated by depolymerization of real-life PS foam on a gram scale, thus showing promising application potential in chemical recycling of PS waste.