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Updated: Jan 7, 2026

Scale-up Chemical Synthesis of Thermally-activated Delayed Fluorescence Emitters Based on the Dibenzothiophene-S,S-Dioxide Core
Published on: October 24, 2017
Synthesis of Umbelliferone-Based, Thermally Stable, and Intrinsically Flame-Retardant Mono-Oxazine Benzoxazines:
Trey Coughlin1, Koki Weng1, Maria Laura Salum1
1Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, OH 44106, USA.
Abstract:
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.
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