Synthesis of Umbelliferone-Based, Thermally Stable, and Intrinsically Flame-Retardant Mono-Oxazine Benzoxazines: Understanding the Aminic Moiety’s Influence on Thermal Properties

A naturally sourced phenolic compound, umbelliferone, has been used to synthesize four monofunctional benzoxazines, two of which have been previously synthesized from aniline and furfurylamine. This study contributes two more-using benzylamine and phenethylamine-to provide insight into how the amine's aromatic group and aliphatic chain length influence resulting properties. The proposed chemical structures of the novel monomers are confirmed by ¹H nuclear magnetic resonance (¹H-NMR) and ¹H-¹H nuclear Overhauser effect spectroscopy (NOESY). The polymerization behavior of each resin is determined by differential scanning calorimetry (DSC). The thermal degradation pattern and the flammability of each polymer are assessed by thermogravimetric analysis (TGA) and microscale combustion calorimetry (MCC), respectively. Char yields between 49% and 63% suggest the thermoset materials to be thermally stable and competitive for thermally demanding applications. All four polybenzoxazines demonstrate non-ignitable behavior, with heat release capacities below 100 J/g·K. Structure-property analyses on the two newly synthesized compounds have been provided to deepen our existing understanding of umbelliferone-benzoxazine systems, particularly regarding the effect of the aminic moiety on thermal properties.