Conversion of diverse post-consumer PVC waste materials to PE via dual catalytic tandem dehydrochlorination–hydrogenation†

Chemical recycling of polyvinyl chloride (PVC) waste poses challenges due to its high chloride content and varied additive formulations. We present a dual catalytic system enabling full conversion of post-consumer PVC waste via tandem dehydrochlorination–hydrogenation. Using a ZnCl₂ catalyst (0.1–0.2 eq.) for dehydrochlorination and a Ru catalyst (1.0 mol%) for hydrogenation, it directly converts PVC into a lower molecular weight polyethylene (PE)-like polymer. It prevents the problematic formation of polyenes and aromatic char during thermal processing. The system tolerates common additives (e.g. plasticisers and Pb-, Zn- and Ca/Zn-based stabilisers) and effectively dechlorinates materials with high inorganic filler content. The method can process PVC materials with a wide range of M_n values (29 000–120 000 g mol⁻¹). Methyl cyclohexanecarboxylate emerges as a suitable solvent for the tandem reaction, thereby producing 100% dechlorinated products with low molar mass averages (M_n ∼ 2400 g mol⁻¹ and M_w ∼ 5000 g mol⁻¹) and allows additive removal. X-ray absorption spectroscopy (XAS) and a study of the reactivity of a model compound elucidate the Ru-catalyst structure and the chain splitting mechanism. This tandem process yields soluble short-chained polymer fragments, facilitating industrial processing and additive removal from chlorinated plastic waste.