Chemically Recyclable CO 2 ‐Based Solid Polyesters with Facile Property Tunability

Synthesizing chemically recyclable solid polymeric materials is a significant strategy to potentially achieve carbon neutral production of new polymers and alleviate plastic pollution, especially when the synthesis is based on CO 2 and inexpensive co‐feedstocks available in large scales. Additionally, polymeric materials should have high enough molecular weight to exhibit distinguished properties from low molar mass polymers to serve for a broader range of application scenarios. However, up to now, strategies for developing solid‐state CO 2 ‐based chemically recyclable polyesters with both high molecular weight and facile property tunability are still unprecedented. Herein, a brand‐new synthetic route is developed to synthesize chemically recyclable CO 2 ‐based solid polyesters with high molecular weight ( M n up to 587.7 kg mol −1 ) and narrow dispersity ( Đ < 1.2), which should further broaden the potential application scenarios of new CO 2 ‐based polyesters. Additionally, complete monomer recovery from poly( δLH 2 ) material is also achieved. The preserved terminal alkene groups allow facile property tuning of the polyesters via photo‐initiated thiol‐ene click reactions, enabling more potential utilities and further functionalizations.