High‐Performance Biodegradable Polyesters via Polyanhydride‐Mediated Polyesterification

Synthesizing biodegradable plastics which match the properties and performance of commercially available polymers is a timely challenge. In this study, we show how polyanhydrides are privileged reactive partners in polyesterification reactions with polyols, affording biodegradable polyesters with mechanical properties comparable to those of commercially available polymers, such as PVC, PS, and PE. The approach involves two steps: (i) converting (activating) dicarboxylic acids into polyanhydrides using non-toxic isopropenyl acetate (iPAc) as the mediator under homo-/hetero-geneous catalysis and (ii) reacting polyanhydrides with polyols to yield thermoplastic and thermoset polyesters with tunable mechanical properties (9 examples; glass transition temperatures of 7°C-49°C, ultimate tensile strengths of 0.4-38 MPa, tensile moduli of 3-1300 MPa and elongations at break of 1%-178%). Our approach not only is carried out under milder conditions compared to conventional polycondensation methods but also is versatile and simple. The synthesized polymers may find applications as biodegradable packaging materials.