A flame retardant rigid polyurethane foam (RPUF) system containing functionalized graphene oxide (fGO), expandable graphite (EG), and dimethyl methyl phosphonate (DMMP) was prepared and investigated. The results show that the limiting oxygen index (LOI) of the flame-retardant-polyurethane-fGO (FRPU/fGO) composites reached 28.1% and UL-94 V-0 rating by adding only 0.25 g fGO. The thermal degradation of FRPU samples was studied using thermogravimetric analysis (TG) and the Fourier transform infrared (FT-IR) analysis. The activation energies (E_a) for the main stage of thermal degradation were obtained using the Kissinger equation. It was found that the fGO can considerably increase the thermal stability and decrease the flammability of RPUF. Additionally, the E_a of FRPU/fGO reached 191 kJ·mol⁻¹, which was 61 kJ·mol⁻¹ higher than that of the pure RPUF (130 kJ·mol⁻¹). Moreover, scanning electron microscopy (SEM) results showed that fGO strengthened the compactness and the strength of the “vermicular” intumescent char layer improved the insulation capability of the char layer to gas and heat.

Organic modified kaolinite-urea intercalation complex (KUIC) was prepared using dimethyl sulfoxide (DMSO) as the precursor of kaolinite intercalation. Its structure was characterized by Fourier transform infrared (FTIR) and X-ray diffraction (XRD). Subsequently, as a synergistic agent, KUIC was combined with flame retardant ammonium polyphosphate (APP) to improve the flame retardant and smoke suppression performance of unsaturated polyester (UP) resin. A cone calorimeter (CONE) was used to study its flame retardancy and smoke suppression, and a scanning electron microscope (SEM) and thermogravimetry (TG) were used to study the micro morphology of the char and flame retardant mechanism. The results show that 12 phr of APP and 3 phr of KUIC were doped into UP to obtain a 28.0% limiting oxygen index (LOI) value. Compared with UP, the heat release rate and smoke production of UP/APP/KUIC composites were greatly decreased. Meanwhile, KUIC indeed enhanced the mechanical properties of UP.