Rigid Biobased Vinylogous Urethane Vitrimers from d‑isosorbide/Furfural-Derived Monomers

Area of Science:

• Materials Science
• Polymer Chemistry
• Sustainable Chemistry

Background:

• Biobased covalent adaptable networks (CANs), or vitrimers, are sought after for their combination of high glass transition temperatures, mechanical robustness, and reprocessability.
• However, achieving these properties in vinylogous urethane vitrimer chemistry, especially with high renewable content, remains a challenge.

Purpose of the Study:

• To synthesize rigid, biobased vinylogous urethane CANs using d-isosorbide and a furfural-derived diamine.
• To investigate the thermomechanical properties, bond exchange dynamics, and reprocessability of these novel vitrimers.

Main Methods:

• Solvent-free bulk curing of d-isosorbide bis-acetoacetate with propane-2,2-di-(2-furylmethylamine) (PDFA) and other amines.
• Characterization of thermomechanical properties (glass transition temperature, thermal stability) and stress-relaxation behavior.
• Evaluation of reprocessability via compression molding and property retention after recycling.

Main Results:

• Successfully synthesized rigid vinylogous urethane CANs with up to 125 °C glass transition temperatures and 290 °C thermal stability.
• Demonstrated fast, catalyst-free bond exchange in the rubbery state, with tunable properties based on amine composition.
• Achieved efficient reprocessability and recyclability, largely preserving thermal and tensile properties.

Conclusions:

• Combining d-isosorbide with a rigid furfural-derived diamine is a viable strategy for creating high-performance, biobased vitrimers.
• These materials offer a promising route toward sustainable polymers with excellent mechanical properties, high service temperatures, and recyclability.