Introduction:
Covalent adaptable networks (CANs) have recently emerged as a transformative class of polymeric materials that combine structural robustness with dynamic functionality. Unlike conventional thermosets, CANs incorporate reversible covalent linkages that enable reprocessability, repairability, and recyclability. In particular, the development of bio-based CANs is of significant interest, as they align with global sustainability goals while simultaneously delivering advanced performance in shape-memory and shape-shifting applications.

Methods:
In this work, we designed and synthesized bio-derived polyester-based CANs incorporating dynamic β-keto carboxylate linkages under catalyst-free conditions. The polymers were fabricated from carbohydrate- and renewable-based precursors, and their structural characteristics were confirmed using FTIR and NMR spectroscopy. Thermal and mechanical properties were evaluated through DSC, DMA, and UTM testing, while stress relaxation experiments were performed to probe the adaptability of the network under thermal stimuli.

Results:
The synthesized CANs exhibited excellent tensile strength and notable dynamic malleability, with efficient stress relaxation observed at elevated temperatures. The materials demonstrated rapid self-healing at 150 °C and could be fully reprocessed multiple times without significant loss of performance or deterioration in structural integrity.

Conclusions:
This study highlights the potential of fully bio-based CANs as multifunctional, recyclable, and programmable materials. Their combination of mechanical resilience, environmental sustainability, and advanced responsive behaviors provides a highly promising platform for next-generation polymer systems, including applications in self-healing coatings, recyclable plastics, smart functional devices, and sustainable material technologies.