Theoretical study on stabilization mechanisms of nitrate esters using aromatic amines as stabilizers

The propellants of nitrate esters can be stabilized by some aromatic amines practically. To probe the mechanism of this phenomenon, we performed DFT calculations on: (1) The decompositions of nitrate esters (with and without the catalysis of NO2) and (2) the reaction between the stabilizers and the nitro dioxide (NO2 is released during the storage of nitrate esters). The structures on the reaction paths (reactants, intermediates and products) were optimized at the (U)B3LY13/6-31G** level. It was shown that NO2 lowers the activation energy barrier in the decomposition of nitrate ester by 11.82-17.86 kJ/mol and efficiently catalyzes the rupture of 0 NO2 bond. However, the aromatic amines, typical stabilizers for nitrate esters, can easily eliminate NO2 with activation barriers as low as 27-113 kJ/mol (with one exception of 128 kJ/mol). These values are, for most cases, lower or much lower than the activation energy barriers for reactions between nitrate esters and NO2 (127-137 kJ/mop. Consequently, the stabilizers can block the NO2 catalysis for the decompositions of nitrate esters. (C) 2017 Elsevier B.V. All rights reserved.