Potassium‐, Ammonium‐, Hydrazinium‐, Guanidinium‐, Aminoguanidinium‐, Diaminoguanidinium‐, Triaminoguanidinium‐ and Melaminiumnitroformate – Synthesis, Characterization and Energetic Properties

Abstract

Energetic salts containing the nitroformate (trinitromethanide) anion with several nitrogen‐rich cations were investigated, including ammonium nitroformate (ANF), melaminium nitroformate (MNF), guanidinium nitroformate monohydrate (GNFH), aminoguanidinium nitroformate (AGNF), diaminoguanidinium nitroformate (DAGNF) as well as triaminoguanidinium nitroformate (TAGNF). All salts were characterized using vibrational spectroscopy (IR, Raman), mass spectrometry, multinuclear NMR spectroscopy and elemental analysis. The thermal decomposition of the salts was monitored using differential scanning calorimetry. In addition, the impact, friction and electrostatic sensitivity data were determined. Theoretical calculations were carried out in order to predict performance data such as detonation velocities and detonation pressures. The crystal structures of ANF, MNF, GNFH, AGNF, DAGNF and TAGNF were determined using single crystal X‐ray diffraction. In addition, a second polymorph of MNF was determined crystallographically as well as the crystal structures of MNF with methanol and MNF with dimethylsulfoxide. Finally, new polymorphs of potassium nitroformate (KNF) and hydrazinium nitroformate (HNF) were characterized using single crystal X‐ray diffraction.

Crystal structures, thermal decompositions and sensitivity properties of [Cu(ethylenediamine)2(nitroformate)2] and [Cd(ethylenediamine)3](nitroformate)2

“…In the Cd(II) center, the dihedral angles between the rings are almost 90 • , leading to the least steric hindrance and the stable space structure. Nitroformate anions in the two title complexes have both the characteristic C-N 3 plane and the typical conformation of the nitro groups, which have been previously described in the literatures [5,[7][8][9][10][11][12]. There exist two conformations of nitroformate anions in the Cu(II) center and the Cd(II) center, respectively.…”

“…However, the application of nitroform is severely constrained for its strong acidity and low decomposition temperature which is 298 K. Therefore, nitroform needs to cooperate with other compounds to form novel stable substances. Nitroformate salts have been widely studied [2][3][4][5][6][7][8][9][10][11][12]. For instance, hydrazinium nitroformate is a promising energetic oxidizer used to replace ammonium perchlorate in rocket propellant [13][14][15][16].…”

Enthalpy of formation of guanidine and its amino and nitro derivatives

“…NQ2Tz is of interest as promising high-performance propellant additive [5,6]. In the last years, much attention was focused on the guanidinium-based energetic salts involving various cations (guanidinium, aminoguanidinium, diaminoguanidinium, triaminoguanidinium, nitroguanidinium) [7][8][9][10][11]. Ionic energetic materials based on guanidines form strong hydrogen bonding networks and can show remarkable stability and considerable insensitivity to physical stimuli, as well as good explosive performance [9].…”

1,2,4‐Triazolium‐Cation‐Based Energetic Salts

“…[14][15][16] Tetrazole-based energetic materials seem to show the best compromise between high heats of formation and good thermal stabilities. On the other hand, the presence of one carbon atom in the ring limits the introduction of functionality, whereas triazole-based energetic materials can be much more readily derivatised, for example, to the dinitro [17] diamino [18] or diazido [19] compounds; the presence of two carbon atoms allows the easy introduction and/or combination of two of the aforementioned highly endothermic functional groups, allowing the formation of compounds with high positive heats of formation (i.e., high performances).…”