Fully Bio‐Based Dynamic Polyester Networks With Intrinsic Reprocessability, Self‐Healing, and Mechanical Durability

ABSTRACT Fully bio‐based dynamic polyester covalent adaptable networks were synthesized through catalyst‐free transesterification of carbohydrate‐derived monomers, enabling a sustainable and repairable polymer platform. FTIR and swelling analyses confirm clean network formation and solvent‐resistant cross‐linking, while DMTA and DSC establish that the materials are amorphous with well‐defined thermal transitions and composition‐dependent cross‐link densities. The materials retain adequate ≥ 93% elongation and ≥ 97% tensile strength after reprocessing. The networks exhibit characteristic viscoelasticity, temperature‐responsive stress relaxation, and moderate activation energies associated with β‐hydroxy ester exchange. Mechanical testing demonstrates excellent resilience, with reprocessed and healed samples retaining nearly all their original tensile and thermomechanical properties. Thermogravimetric analysis confirms that the networks remain thermally stable well above the service temperature. The materials can be repeatedly reshaped, welded into seamless interfaces, autonomously healed after damage, and consistently support significant mechanical loads, underscoring their structural integrity. Collectively, these results highlight the potential of DPC‐n polyesters as recyclable, reprocessable, and self‐healing materials designed to meet the demands of durable and sustainable polymer applications.