Abstract
Amid the ongoing Global Plastics Treaty, high-quality circulation of halogen-containing plastics in an environmentally sound manner is a globally pressing issue. Current chemical dechlorination methods are limited by their inability to recycle PVC at the long-chain carbon level and the persistence of eco-toxic organochlorine byproducts. Herein, we propose a click dechlorination strategy for transforming waste PVC into valuable vitrimers via a one-step cascade thiol-ene click reaction and dynamic polymerization. Thermal activation of C-Cl bonds initiates β-elimination dechlorination, while disulfide bonds synchronously undergo homolytic cleavage, generating sulfur-centered radicals that drive precise sulfur-chlorine substitution and the formation of disulfide dynamic networks. This strategy achieves nearly complete chlorine extraction (93.88%) and produces vitrimers with tailorable mechanical and reprocessing properties, spanning from soft elastomers with 784% elongation to rigid plastics with a yield strength of 34 MPa. The significant advantage of this strategy is backbone protective precise dechlorination, enabling ecosystem toxicity reduced by 99.51% compared with widely adopted pyrolysis methods. This work introduces a sustainable pathway for upcycling PVC into valuable materials, marking significant progress in chlorinated plastic recycling.