A Bio‐Based Polybenzoxazine Derived from Diphenolic Acid with Intrinsic Flame Retardancy, High Glass Transition Temperature and Dielectric Properties

A bio-based benzoxazine monomer, diphenolic methyl ester hexafluoro diamino benzoxazine (DPME-HFBz), was successfully synthesized from diphenolic acid (DPA), and the chemical structure was successfully verified. The curing kinetics were studied via non-isothermal differential scanning calorimetry (DSC). The activation energies of DPME-HFBz were calculated by Kissinger and Ozawa methods to be 136.15 and 139.92 kJ/mol, respectively, and the reaction order was calculated to be first order. Owing to the large number of hydrogen bonds after polymerization, poly(DPME-HFBz) presented an ultra-high glass transition temperature of 312 °C and a high initial decomposition temperature (350 °C under air and 345 °C under nitrogen). Because of the excellent charring ability (50.2% residue under nitrogen), the LOI value of poly(DPME-HFBz) was as high as 38%. Poly(DPME-HFBz) also exhibited a very low heat release capacity (HRC) of 90 J/(g·K). In addition, poly(DPME-HFBz) had a dielectric constant (Dk) of 1.88 at 1.5 MHz, which was much lower than the Dk of the reported low-dielectric polymers. This work provides an efficient and sustainable strategy for the synthesis of benzoxazine thermosetting materials with excellent comprehensive properties.