Thermal Decomposition of energetic materials. 39. Fast thermolysis patterns of poly(methyl), poly(ethyl), and primary alkylammonium mononitrate salts

Fast thermolysis (> 100°C/s)/FTIR spectroscopy of alkylammonium mononitrate salts is described in terms of the gas products and the temperature and time correlations of their evolution. The salts studied are [(CH3)nNH4‐n]NO3, n = 1–3; [(CH3CH2)nNH4‐n]NO3, n = 1–4; and [CH3(CH2)nNH3]NO3, n = 0–3. In addition to the patterns among the small molecule thermolysis products, the tendency to form nitrosamines, amides, and alkylnitrates is presented. The release of HNO3 qualitatively correlates with the basicity of the parent amine. The tertiary ammonium nitrate salts did not release HNO3(g). The release of NH3(g) appears only to occur when the residue can stabilize itself. Otherwise, the parent alkylamine is released. The formation of nitrosamines upon fast thermolysis of di‐ and trialkylammonium nitrate salts makes these materials a potential health risk in formulations. There is no evidence that the nitrate salts convert to nitrosamines through a nitramine intermediate.