Synthesis of ortho-methyltetrahydrophthalimide functional benzoxazine containing phthalonitrile group: Thermally activated polymerization behaviors and properties of its polymer

Abstract

Two novel benzoxazine monomers, oHMTI-a and oHMTI-pn, have been obtained via the modified Mannich condensation from ortho-4-methyltetrahydrophalimide functional phenol, paraformaldehyde, and aniline/4-aminophthalonitrile, respectively. The chemical structures of both benzoxazine monomers have been studied by Fourier transform infrared (FT-IR) and 1H and 13C nuclear magnetic resonance (NMR) spectra. Their polymerization processes are investigated using in-situ FT-IR and different scanning calorimetry (DSC). Specifically, the phthalonitrile group in oHMTI-pn can react at a relatively lower temperature without adding any catalysts, which suggests the presence of the thermal synergistic polymerization effect in this benzoxazine monomer. In addition, the thermal and fire related properties of the resulting polybenzoxazines are evaluated by thermogravimetric analysis (TGA) and micro-scale combustion calorimetry (MCC). The polybenzoxazine derived from oHMTI-pn shows both high thermal stability and outstanding flame retardancy, with a T g of 350°C, a T d10 value of 417°C, a high char yield value of 65%, and a very low heat release capacity value of 35.2 J/(g·K).