Biobased high-performance tri-furan functional bis-benzoxazine resin derived from renewable guaiacol, furfural and furfurylamine

[Display omitted] •A novel bio-based tri-furan functional bis-benzoxazine resin has been successfully synthesized.•This tri-furan functional benzoxazine shows much higher thermal stability compared with guaiacol-based mono-benzoxazine.•The polybenzoxazine derived from tri-furan functional bis-benzoxazine exhibits low coefficient of thermal expansion.•The newly obtained polybenzoxazine also possesses the advantage of low flammability. A novel fully biobased tri-furan functional bis-benzoxazine resin has been synthesized using guaiacol, furfural, furfurylamine and paraformaldehyde as raw materials via a two-step reaction approach. The detailed chemical structure of this newly obtained bis-benzoxazine monomer has been identified by NMR and FT-IR spectroscopies and elemental analysis. In addition, another bio-based benzoxazine monomer has also been synthesized based on the Mannich condensation of guaiacol, furfurylamine and paraformaldehyde for comparison. The polymerization behaviors of benzoxazines are investigated by DSC and in situ FT-IR, and the thermal and fire-related performances of resulting thermosets are investigated by TGA and micro-scale combustion calorimetry (MCC), respectively. Notably, the corresponding polybenzoxazine derived from the newly developed tri-furan functional bis-benzoxazine shows very excellent thermal stability with a Tg of 290 °C and a Td10 (the temperature at a weight loss of 10%) of 375 °C in nitrogen atmosphere. Moreover, a non-ignitable polybenzoxazine has also been achieved as shown by the very low heat release capacity (30.4 J g−1 K−1) and total heat release value (5.8 kJ/g), making this bio-based thermosetting resin a promising material for high-performance applications.