Block Poly(carbonate‐ester) Ionomers as High‐Performance and Recyclable Thermoplastic Elastomers

Thermoplastic elastomers based on polyesters/carbonates have the potential to maximize recyclability, degradability and renewable resource use. However, they often underperform and suffer from the familiar trade‐off between strength and extensibility. Herein, we report well‐defined reprocessable poly(ester‐b‐carbonate‐b‐ester) elastomers with impressive tensile strengths (60 MPa), elasticity (>800 %) and recovery (95 %). Plus, the ester/carbonate linkages are fully degradable and enable chemical recycling. The superior performances are attributed to three features: (1) Highly entangled soft segments; (2) Fully reversible strain‐induced crystallization and (3) Precisely placed Zn(II)‐carboxylates dynamically crosslinking the hard domains. The one‐pot synthesis couples controlled cyclic monomer ring‐opening polymerization and alternating epoxide/anhydride ring‐opening copolymerization. Efficient convresion to ionomers is achieved by reacting vinyl‐epoxides to install Zn(II)‐carboxylates.