Piperazine cyanurate (PCA) is designed and synthesized via hydrogen-bonding selfassembly reactions between piperazine and cyanuric acid. Chemical structure and morphology of PCA are investigated by Fourier transform infrared spectroscopy and scanning electron microscopy, respectively. The prepared PCA is combined with ammonium polyphosphate (APP) to prepare flame-retardant polypropylene (PP) composites. Thermostability, flammability, and combustion characteristics of PP composites are analyzed. The maximum thermal decomposition rate of flameretarded PP composites has an apparent reduction compared with that of pure PP, and obvious char is left for this intumescent flame retardant (IFR) system of APP and PCA. A high limiting oxygen index value and UL-94 V-0 rating are achieved with addition of APP and PCA. In cone calorimetry test, heat and smoke releases of PP are significantly decreased by this IFR system. Gaseous decomposition products during the thermal decomposition of flame-retardant composites are studied. Chemical structure and morphology of char residues are analyzed. The results illustrate that APP and PCA have a superb synergistic action in the aspect of improvement in fire safety of PP. A possible flame-retardant mechanism is concluded to reveal the synergism between APP and PCA. K E Y W O R D S intumescent flame retardant, mechanism, polypropylene, synergism 1 | INTRODUCTION Polymeric materials, which are now universally used in many areas, have been important to modern life for many years. Polypropylene (PP) is one of the universal polymers and has many advantages, such as easy processability, corrosion resistance, and low cost. However, it is a kind of easily combustible material, which seriously restricts its applications. Because of its emission of poisonous gases while burning, PP has high fire hazard potential for human life. 1,2 Therefore, PP materials must be modified with flame-retardant additives in order to achieve desired flame-retardant performance and meet the requirements in some application fields. Currently, considerable effort has been devoted to explore methods of reducing the inflammability of PP. Various flame retardants, such as metallic hydroxide, expandable graphite, halogencontaining flame retardants, and phosphorous-containing compounds, have been successfully developed to endow PP with flame retardancy. 3 For instance, metal hydroxides, including aluminum hydroxide and magnesium hydroxide, are used in PP, but mechanical properties of PP materials are easily destroyed by high loading of fillers. 4 As a kind of halogen flame retardants, bromine-containing compound has been regarded as the most effective flame retardant for PP. 5 However, some halogen-containing flame retardants are being phased out because of their health and environmental hazards,