Specific features of thermal decomposition of organic azides

摘要

The kinetics, mechanism, and products of thermal decomposition of nitrogen bearing heterocyclic azides in a melt and in a solution have been studied. The results obtained, together with literature data, indicate that the mechanism of decomposition of a heterocyclic azide depends significantly on its structure. If the azide molecule does not contain hydrogen, then the intermediate nitrene cannot enter into its characteristic hydrogen abstraction reaction. As a result, the decomposition mechanism and kinetic parameters of the reaction change: in particular, the values of the pre-exponential factor increase. Intermediate nitrenes can be relatively long-lived. The change in the reaction mechanism results in a change in the composition of the condensed products: during the decomposition, both linear oligomers and flat polyconjugate carbon-nitride networks can be formed. The results obtained were used to explain the cause of a high impact sensitivity of cyanuric triazide. It turned out that the high sensitivity is kinetic but not thermodynamic in its nature.