Polymer and composite materials are increasingly used in technology as an alternative to metals. One of the key components of the composites is a polymeric binder, usually not having fire-resistant properties, there is a need to use the fire-protective coatings (FPC). However, the temperature of the coke formation known FPC quite high and does not provide reliable fire protection of polymers. The aim of this work is to study the possible implementation of the response of the ammonium polyphosphate (APF) with pentaerythrytol (PEr) at lower temperatures and to study process flow. It is established that the decrease in the temperature of the coke formation intumescent systems is possible by increasing the ratio APF:PEr = 4,2:1. Thus, volatile products form in the fields of foaming. The excess of the APF promotes thermal decomposition of carbon sources at a lower temperature (25-30 °C lower) and as a consequence the formation of foam coke observed at 60-65 °C lower than when the ratio APF:PEr = 3:1. Methods of XPS and IR spectroscopy characterized products of thermal decomposition of the samples when heated to 350 °C. It is shown that the main components of the products of thermal decomposition are P2O5, amorphous carbon, the products of incomplete degradation of phospho-organic polymer and presumably phosphorus oxinitride.