Dynamics-Driven Controlled Polymerization to Synthesize Fully Renewable Poly(ester-ether)s

Producing aromatic poly(ester-ether)s from completely renewable feedstocks is almost inaccessible via existing ring-opening polymerization or melt polycondensation methods. Herein, we report a practical strategy to synthesize fully biobased poly(ester-ether)s in a one-pot/two-component manner via industrial melt polycondensation. The polymerization process was controlled by applying Sc(OTf)(3) as a catalyst and bio-based 2,5-furandicarboxylic acid and ethylene glycol as the substrate template to afford poly(ester-ether)s with a controlled oligoethylene glycol segment in the range from 10 to 92%. Studying the mechanism and model kinetics of Sc(OTf)(3)-catalyzed etherification reactions provided complete insights into the formation process and impetus of poly(ester-ether)s, validating that a butterfly effect occurred in the reaction process. In contrast to flexible conventional polyethers, computational studies revealed that the unique rigidity of the etherification moiety leads to superior thermal and mechanical properties of poly(ester-ether)s. This synthetic protocol demonstrates applicability and versatility, exemplified by using various bio-based diacids/diesters to synthesize a series of poly(ester-ether)s. We envisage that this work will improve the privileged position that renewable poly(ester-ether)s hold as functional materials and broaden their applicability in diverse fields.

Automated summary

A practical strategy was reported to synthesize fully biobased poly(ester-ether)s via industrial melt polycondensation, using Sc(OTf)(3) as a catalyst and bio-based 2,5-furandicarboxylic acid and ethylene glycol as substrates. The resulting poly(ester-ether)s had controlled oligoethylene glycol segments, with computational studies showing superior thermal and mechanical properties compared to conventional polyethers. This synthetic protocol demonstrates applicability and versatility in synthesizing functional materials from renewable sources.