The hydroxylammonium cation in tetrazole based energetic materials

摘要

Due to its basicity, hydroxylamine was used to deprotonate several tetrazole derivatives bearing an acidic proton. Namely, the monodeprotonated 5-nitriminotetrazolate (1), dideprotonated 5-nitriminotetrazolate (2), l-methyl-5-nitriminotetrazolate (3) and 2-methyl-5-nitraminotetrazolate salt (4) were synthesized. In the series of ethyl substituted 5-nitriminotetrazolates, the l-hydroxyethyl-5-nitriminotetrazolate (5) and the I -nitratoethyl-5-nitriminotetrazolate (6) could be isolated. Further, the monodeprotonated (7) and dideprotonated bistetrazolylamine salt (8), a cocrystallization product of (7) with one equivalent of bistetrazolylamine (9) as well as the 5H-tetrazolate (10) and the tetrazole-5-carboxamide salt (11) were synthesized. Additionally the azo-compounds dihydrox-ylammonium 5,5'- azotetrazolate (12) and the dihydroxylammonium salt of its oxide (13) besides a bistetrazole derivative, the bis-deprotonated 5,5-bistetrazolate (14) and a tetrazole amide oxime (15) were successfully synthesized. All compounds except from 4, 7 and 15 were fully characterized by single crystal X-ray diffraction. Additionally, 1 - 15 were characterized using vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, elemental analysis and DSC measurements. The heats of formation of 1 - 15 were calculated using the atomization method based on CBS-4M enthalpies. With these values and the experimental (X-ray) densities several detonation parameters such as the detonation pressure, velocity, energy and temperature were computed using the EXPLO5 code. In addition, the sensitivities towards impact, friction and electrical discharge were tested using the BAM drophammer, friction tester as well as a small scale electrical discharge device.