A case study on the thermal degradation of an acrylate-type polyurethane wood coating using thermogravimetry coupled with evolved gas analysis

•Thermal degradation of an acrylate-type PU wood coating (PUA) and a flame-retardant variant (PUA-FR).•Determination of multistage thermal degradation processes of PUA and PUA-FR by TGA and DTG.•Identification of main volatile decomposition products by gas phase FTIR.•Conclusions on decomposition mechanisms of PUA and the mode of action of TCPP. The thermochemical properties of a solvent-borne two-component polyurethane acrylate based wood coating (PUA) and of a flame-retardant counterpart (PUA-FR) treated with tris(1-chloro-2-propyl)phosphate (TCPP) were studied using thermogravimetry coupled with Fourier-transformed infrared spectroscopy (FTIR) within a temperature range between 50 and 600 °C. Data were analyzed regarding structural features of the cured coating material, particularly with respect to its thermal decomposition behavior. It became obvious that the thermal degradation of PUA occurred in a four-step process in the following order: I) Initial degradation of polyacrylate segments connected with the evaporation of the residual solvent. II) The cleavage of the polymer backbone of polyacrylate segments leading to the formation of the corresponding acrylate monomers. III) The degradation of alkyl methacrylate monomers associated with the elimination of carbon dioxide and the respective alkyl side chains. IVa) The dissociation of urethane bonds indicated by a rapid release of isocyanates, cyanuric acid, isocyanic acid and small proportions of hydroxyl-containing moieties; IVb) The decarboxylation of urethane-isocyanurate segments under the formation of primary/secondary amines and olefins. In the case of PUA-FR, steps II) and III) were found to be mainly suppressed by TCPP at the expense of the decarboxylation of the ester side chains while degradation step IVa) was also retarded significantly.