The structure of hexagonal boron nitride (h-BN) is similar to that of graphite before functionalization and exfoliation. For applications in polymer nanocomposites, chemical exfoliation is a more economically attractive route to few-layer h-BN nanosheets. A thermal oxidation process of h-BN powder could achieve large scale exfoliation and hydroxylated functionalization, as described in prior literature. In this report, hydroxylated h-BN (BNO) was prepared by heating h-BN under air, and then covalently incorporated into epoxy resin modified with (3-isocyanatopropyl)triethoxysilane to prepare epoxy resin (EP) nanocomposites by sol–gel process. The structure and morphology of BNO were well characterized. BNO was dispersed in the EP matrix with the form of mainly exfoliated and intercalated structures, and formed strong interfacial interaction with the matrix. Thermogravimetric analysis results revealed that BNO significantly improved thermal stability and thermal oxidative resistance of EP nanocomposites at high temperature. The char yield and the temperature at 50 wt% mass loss were increased and the maximum mass loss rate was remarkably reduced. Moreover, the addition of 3 wt% BNO led to extremely high T_g of EP nanocomposite, 42.7 °C higher than that of pure EP, due to improved crosslinking density and confinement effect of BNO sheets on the mobility of polymer networks. Cone calorimeter test results indicated that fire safety properties of EP nanocomposites were also enhanced by the addition of BNO, such as 53.1% reduction in peak heat release rate and 32.6% decrease in total heat release, and decreased release of smoke and toxic gases. The mechanism for enhanced fire retardancy is that thermally stable condensed barrier consisting of h-BN sheets and silicon dioxide for heat and mass transfer protects the matrix from further combustion.

Owing to the outstanding mechanical strength and modulus, high T _g , anti-flammability and anti-bacterial property, this fully bio-based epoxy thermoset is a promising substitute for DGEBA-based thermoset in high performance fire safe applications.