This work describes new fully bio-based vitrimers prepared from isosorbide, a renewable sugar-based chemical. Isosorbide was reacted with 4-hydroxypropionic acid, paraformaldehyde, mono-ethanolamine, and/or furfurylamine via consecutive solvent-free Fischer esterification and Mannich-like ring-closure reactions. The two-step synthesis led to the formation of a ditelechelic benzoxazine-terminated isosorbide monomer, containing ester bonds and aliphatic hydroxyl and/or furan groups. The atom economy factor yields 85%. The structural features of the resulting products were substantiated by spectroscopic techniques. The ringopening polymerization was monitored by rheological and differential scanning calorimetry (DSC) measurements. Very high T g values afforded by the isosorbide substructure were measured (from 143 to 193 °C), which increase with furan ring content. Internally catalyzed transesterification reactions conferred fast dynamic exchanges (τ* = 300 s at 180 °C). Self-healing and chemical and mechanical recycling were also demonstrated. Finally, the degradability of the sugar-based polybenzoxazine vitrimers was demonstrated as well. The materials were highly stable in pH-neutral water, even at 80 °C for 60 days, but owing to the isosorbide structure, pronounced degradation was observed under acidic or alkaline conditions. In summary, isosorbide is a suitable building block for the design of degradable and 100% recyclable high-T g polybenzoxazine vitrimers.

This work explores a new strategy, aiming for the synthesis of catalyst-free vitrimers by taking advantage of the abundant number of tertiary amines covalently bound into a polybenzoxazine network.

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