Abstract
AbstractAlthough the solventless method for synthesizing benzoxazine resins has the advantage of low cost, the impurities involved in the products such as oligomers and original phenols significantly weaken the properties of polybenzoxazines. Herein, the commercialized BA‐a (benzoxazine derived from bisphenol‐A, aniline, and formaldehyde) resin obtained from a solventless method is modified by phthalonitrile through the reaction between phenol groups and 4‐nitrophtahlonitrile. The structures of obtained resins have been confirmed by 1H and 13C nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR). In addition, the ring‐opening polymerization behavior of each resin has been studied by differential scanning calorimetry and in situ FTIR. Furthermore, the thermal properties of the cross‐linked thermosets were measured by thermomechanical analysis and thermogravimetric analysis. The phthalonitrile‐functionalized benzoxazine resin shows a low polymerization temperature with the maximum of exothermic peak centered at 218.7 °C, and its corresponding polybenzoxazine exhibits excellent thermal stability, with a high Td5 value (346 °C) and high char yield (42.78%).
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