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 Tg values and predominantly amorphous character, whereas succinic-acid-based analogs show higher Tonset 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.