Melamine as cross‐linking agent for mono‐cyclic benzoxazine with aldehyde groups: higher crosslinking density and thermal properties

Abstract

Benzoxazine resin shows great potential as matrix for high performance composites, possessing good processabilty, dielectric property, mechanical property, and thermal properties, but its further application is limited by low crosslinking density and poor curing activity, especially for mono‐cyclic benzoxazines. In this work, melamine, a tertiary amine with a stable triazine structure, was introduced into the aldehyde‐containing mono‐cyclic benzoxazine, in order to achieve higher crosslinking density, higher curing activity, and better thermal properties. The chemical structure of prepolymers was verified by Fourier transform infrared spectroscopy (FTIR), 1H nuclear magnetic resonance (1H NMR) spectra, the curing behavior was investigated by differential scanning calorimetry, the thermal properties of polymers were studied by thermogravimetric analysis (TGA) and thermal mechanical analysis (TMA). It was found that the introduction of trifunctional melamine (MA) could lower curing temperature and promote the curing degree. Additionally, a proper amount of MA could increase the crosslinking density and thermal properties of the resultant polybenzoxazine. For example, poly(BZ‐3MA) showed the highest thermal stability with the temperature at 5% weight loss (Td5) of 415°C, carbon residue (Yc) of 67.7%, 23°C, and 2.9% higher than those of poly(BZ). Moreover, the glass transition temperature of poly(BZ‐5MA) reached 204.06°C, 36.51°C higher than that of poly(BZ).