To ensure ammunition safety, a protective structure and pressure detection system are essential
however, there is a lack of an accurate constitutive model to describe the mechanical response characteristics of protective structures composed of various polymer materials. In this work, a constitutive model for the composite structure based on the superposition principle is successfully constructed derived from the quasi-static compression behavior of rigid polyurethane foam (RPUF), silicone rubber foam (SRF), and flexible pressure sensors (FPSs) through experimental investigations. The constitutive model accurately reflects the influence of each type of polymer foam on the mechanical performance of composite structures, underscoring the significance of thickness ratios. Test results within the temperature range of 25 °C to 55 °C validate the model's accuracy, with an average fitting error of 8.6%. Furthermore, a multi-channel pressure detection system has been integrated into the composite structure. Under conditions of out-of-plane loads ranging from 0 to 10 kilonewtons, the accuracy of the pressure monitoring system, adjusted using the constructed model, has improved by 16%. The constitutive model and the pressure sensing system effectively predict the mechanical properties of the protective structure and enable real-time force state monitoring, which is crucial for ammunition safety and has broader applications for safeguarding other objects.