A biobased benzoxazine resin (Dz-f) demonstrating excellent thermal properties was synthesized from daidzein and furfurylamine by using a microwave heating method. The chemical structure of synthesized benzoxazine monomer was identified by FTIR and NMR ( H and C NMR) before it was cured and its thermal properties evaluated by differential scanning calorimetry (DSC), TGA, and dynamic mechanical analysis (DMA). The cured resin p(Dz-f) exhibited a glass transition temperature (T ) of 391 °C, a very high char yield of 68.7 %, and outstanding thermal stability; the T value obtained was the highest thermal stability value ever reported for polybenzoxazine with a high biobased content. Moreover, Dz-f demonstrated a satisfying processability, which was rare for the high-performance thermosetting resins. This work provided us with a new strategy for the preparation of high biocontent resins with excellent thermal properties. In addition, the combination of biobased feedstocks with a microwave-assisted heating method as well as the potential application of this approach in high-end fields might perpetuate remarkable progress towards the sustainable development of the polymeric industry.

Epoxy resins with high thermal and mechanical performance as well as good resistance to fire are difficult to synthesize. In this work, a high-performance intrinsically flame-retardant epoxy resin (diglycidyl ether of daidzein (DGED)) was synthesized from renewable daidzein using an efficient one-step process, without the addition of additional flame retardants. The structure of DGED was confirmed by Fourier transform infrared (FTIR), 1 H NMR, and 13 C NMR before it was cured with 4,4′diaminodiphenylmethane (DDM). A commercial diglycidyl ether of bisphenol A (DGEBA) was cured with the same curing agent. Results indicated that the cured DGED/DDM system possessed glass transition temperature (T g ) of up to 205 °C (172 °C for DGEBA/DDM), and tensile strength, tensile modulus, flexural strength, and flexural modulus of 83, 2972, 131, and 2980 MPa, respectively, all much higher than those of cured DGEBA/DDM. The cured DGED/DDM system demonstrated excellent flame-retardant properties, showing a residual char of 42.9% at 800 °C, limiting oxygen index (LOI) of 31.6%, and flammability rating of V-0 in UL94 test. This work provides us an efficient method to prepare high-performance epoxy resin from renewable resource.