Metal‐Free, Mild, and Sustainable Synthesis of Bio‐Based Polyesters via EDC/DMAP‐Mediated Polycondensation: Structure–Property Relationships and Thermal Stability

In this work, we have developed a mild, metal‐free solution polycondensation protocol mediated by EDC and DMAP that enables the synthesis of bio‐based polyesters from thermally labile monomers while overcoming key limitations of high‐temperature melt polycondensation. We have prepared FDCA‐ and succinic acid‐based homopolyesters, revealing distinct structure–property relationships between rigid furanic and flexible aliphatic systems. In addition, this methodology was extended to heteropolyesters via one‐pot and sequential strategies, enabling compositional control. Structure–property relationships reveal that FDCA‐based furanic polyesters exhibit higher T g values and predominantly amorphous character, whereas succinic‐acid‐based analogs show higher T onset values and selective crystallinity. This library of polymers establishes EDC/DMAP‐mediated polycondensation as a versatile platform for sustainable materials design beyond the limits of conventional melt processing.