Ring‐opening Polymerization of Enantiopure Bicyclic Ether‐ester Monomers toward Closed‐loop Recyclable and Crystalline Stereoregular Polyesters via Chemical Upcycling of Bioplastic

Abstract Although great successes have been achieved, the preparation of closed‐loop recyclable polyesters with high working temperatures still remains as a big challenge. Herein, we present the syntheses of a series of enantiopure bicyclic ether‐ester monomers by upcycling of poly(3‐hydroxybutyrate) bioplastic. The “living”/controlled ring‐opening polymerizations of these enantiopure monomers to produce stereoregular polyesters with controlled molecular weights and well‐defined chain ends were achieved. The effects of stereoconfiguration and substituent on polymerization kinetics and thermodynamics as well as the thermal properties of resultant polyesters were investigated. Of note, the stereoregular polyesters are semi‐crystalline materials with melting temperatures up to 176 °C, even higher than the commodity polyolefin plastics. These polyesters can be depolymerized back to recover pristine monomers, thus successfully establishing a closed‐loop life cycle.