Adjacent N→O and C–NH₂ groups — a highly efficient amphoteric structure for energetic materials resulting from tautomerization proved by crystal engineering

Abstract

Existing amphoteric energetic materials (EMs) are very scarce, and their amphoteric structures are difficult to reproduce and protonate. Herein, adjacent N→O and C-NH2 groups (O←N=C-NH2) were found to be a...

Amphoteric Ionization and Cocrystallization Synergistically Applied to Two Melamine-Based N-Oxides: Achieving Regulation for the Comprehensive Performance of Energetic Materials

“… a Decomposition temperature (onset) from DSC at 10.0 °C min –1 . b Measured density (gas pycnometer). c Experimental molar enthalpy of combustion determined by oxygen bomb calorimetry. d Heat of formation calculated from enthalpy of combustion. e Oxygen balance based on CO for C a H b N c M d Cl e O f (M represents Cd or Zn) calculated by OB = 1600­[ f – a – ( b – e )/2 – d ]/ M w , where M w is the molecular weight. f Detonation pressure and detonation velocity calculated by the developed Kamlet-Jacobs equations. − g Impact sensitivity. h Value taken from ref . i Value taken from ref . j Values taken from ref . k Values taken from ref . …”

“…2,4,6-Triamino-1,3,5-triazine 1,3-dioxide (TTDO), 4,6-diamino-3-hydroxy-2-oxo-2,3-dihydro-1,3,5-triazine 1oxide (DDTO, and their potassium salts were synthesized according to our previous report. 17 2.4. Guanidinium 4,6-Diamino-2-imino-3-oxido-2,3-dihydro-1,3,5-triazine 1-Oxide (GUA + TTDO − ).…”

“…All reagents purchased commercially were used as received. 2,4,6-Triamino-1,3,5-triazine 1,3-dioxide (TTDO), 4,6-diamino-3-hydroxy-2-oxo-2,3-dihydro-1,3,5-triazine 1-oxide (DDTO, and their potassium salts were synthesized according to our previous report …”

“…2,4,6-Triamino-1,3,5-triazine 1,3-dioxide (TTDO) and 4,6diamino-3-hydroxy-2-oxo-2,3-dihydro-1,3,5-triazine 1-oxide (DDTO), which are two insensitive N-oxides synthesized from low-cost melamine, were proved to be efficiently amphoteric energetic materials as a result of tautomerization in our recent study. 17 Their amphoteric properties were preliminarily disclosed by the synthesis of their potassium and nitrate salts. In addition, perchlorate salts of TTDO were reported.…”

“…For instance, combining the ionized energetic compounds with nitrogen-rich counterions (such as guanidinium-based cations and azole-based anions) , and high-energetic counterions (such as hydroxylammonium cations and dinitramide anions) , can increase the nitrogen content and the detonation performance of energetic materials, respectively. However, amphoteric energetic compounds, which can significantly increase the efficiency of ionizing energetic compounds, remain scarce. − …”