Polyvinyl chloride (PVC) is the world’s third-most widely manufactured thermoplastic, but has the lowest recycling rate. The development of PVC-like plastics that can be depolymerized back to monomer contributes to a circular plastic economy, but has not been accessed. Here, we develop a series of chemically recyclable plastics from the reversible copolymerization of cyclic anhydride with chloral. The copolymerization is highly efficient through the anionic or cationic mechanism under mild conditions, yielding polyesters with tunable structure and properties from multiple commercial monomers. Notably, these polyesters manifest mechanical properties comparable to PVC and polystyrene. Meanwhile, such polyesters are flame-retardant like PVC due to high chloride content. Of significance, these polyesters can be depolymerized back to starting monomers at high temperatures owing to the reversibility of the copolymerization, leading to a circular economy. Overall, the readily available monomers, simple synthesis, advantageous performance, and practical recyclability make the polymers promising for applications.
Our society is pursuing chemically recyclable polymers to accelerate the green revolution in plastics. Here, we develop a recyclable polyester library from the alternating copolymerization of aldehyde and cyclic anhydride. Although these two monomer sets have little or no thermodynamic driving force for homopolymerization, their copolymerization demonstrates the unexpected alternating characteristics. In addition to readily available monomers, the method is performed under mild conditions, uses common Lewis/Brønsted acids as catalysts, achieves the facile tuning of polyester structure using two distinct monomer sets, and yields 60 polyesters. Interestingly, the copolymerization exhibits the chemical reversibility attributed to its relatively low enthalpy, which makes the resulting polyesters perform closed-loop recycling to monomers at high temperatures. This study provides a modular, efficient, and facile synthesis of recyclable polyesters using sustainable monomers.