Synthesis and Thermodynamic Properties of M2L[M=Li, Na; L=3,6-Bis（1H-1,2,3,4-tetrazol-5-yl-amino）-1,2,4,5-tetrazine]

Two novel energetic alkalic metal salts of 3,6-bis（1H-1,2,3,4-tetrazol-5-yl-amino）-l,2,4,5-tetrazine （BTATz）, Li2（BTATz）. 6H20（compound 1） and Na2（BTATz）. 2H20（compound 2）, have been synthesized by the reac- tion of BTATz with lithinnl hydroxide or sodium hydroxide in dimethylsulfoxide（DMSO） solution, respectively, and their structures were characterized by means of elemental analysis and Fourier transform infrared spectrometry（FTIR） Moreover, the single-crystal structure of compound 1 was determined by single crystal X-ray diffraction. It crystal- lizes in the monoclinic space group P1/c. Furthermore, their thermal decomposition behaviors were investigated by means of differential scanning calorimetry（DSC） and thermogravimetry-differential thermal gravimetry（TG-DTG）. The results show that the exothermic decomposition peak temperatures for compounds 1 and 2 were 642.65 and 644.46 K, respectively, and the kinetic equations of the main exothermic decomposition were also derived from non-isothermal method. Additionally, the thermal safety of the two compounds was evaluated by calculating self-accelerating decomposition temperature（TSADT） and critical temperature of thermal explosion（Tb）. The results（the TSADT and Tb values are 605.43 and 635.69 K for compound 1; 607.38 and 638.96 K for compound 2） reveal that the two compounds exhibit better thermal safety than BTATz.

Synthesis and Thermal Properties of Three Energetic Ion Salts of 3,6-Bis[(1H-1,2,3,4-tetrazol-5-yl)-amino]- 1,2,4,5-tetr azine

Three energetic ion salts of 3,6-bis[(1H-1,2,3,4-tetrazol-5-yl)-amino]-1,2,4,5-tetrazine(BTATz), namely, methylamine salt(compound 1), ethylenediamine salt(compound 2), and diethylamine salt(compound 3), were synthesized and characterized by elemental analysis, Fourier transform infrared spectrometry, NMR spectroscopy, and ^13C NMR spectroscopy. The crystal structure of compound 1 was determined by single-crystal X-ray crystallography, and structural analysis revealed that it belonged to the monoclinic system with P21/c space group. In addition, the thermal behavior of the three compounds was studied by differential scanning calorimetry and thermogravimetry techniques. The thermal decomposition peak temperatures of the compounds were 574.89, 545.60, and 606.72 K, indicating that the three ion salts exhibited good thermal stability. Tlie kinetic mechanism equations of the main decomposition process and the entropy of activation(△S^≠), enthalpy of activation(△H^≠), and Gibbs free energy of activation(△G^≠) of the three compounds were also obtained. Moreover, the thermal safety of the compounds was evaluated by the values of the self^accelerated decomposition temperature(Tsadt)5 thermal ignition temperature(TTIT), and critical temperature of thermal explosion(7b). The results showed that all the compounds demonstrated good thermal safety, and the thermal safety of compound 3 was better than that of the others.

Novel Magnesium Salt Based on BTATz： Crystal Structure, Thermal Behavior and Thermal Safety

A new high-energy organic magnesium salt [Mg（H2O）6]（BTATz）·2H2O[BTATz=3,6-bis（1H-1,2,3,4-tetrazol-5-yl-amino）-1,2,4,5-tetrazine] was synthesized and characterized by elemental analysis and Fourier transform infrared（FTIR） spectrometry.Its crystal structure was determined by X-ray single crystal diffraction.The crystal belongs to monoclinic system with space group C2/c and a=2.1329（7） nm,b=0.52275（16） nm,c=1.5909（5） nm,β=100.471（6）°,V=1.7443（9） nm3,Z=4,μ=0.361 mm-1,F（000）=900 and Dc=1.644 g/cm3.Meanwhile,the thermal behavior of [Mg（H2O）6]（BTATz）·2H2O was studied under the non-isothermal conditions by differential scanning calorimetry（DSC） and thermalgravity-differential thermalgravity（TG-DTG） methods.The enthalpy,apparent activation energy and per-exponential factor of the main exothermic decomposition reaction are 898.88 J/g,139.2 kJ/mol and 1010.48 S-1,respectively.The values of the self-accelerating decomposition temperature（TsADT）,the thermal ignition temperature（TTIT） and the critical temperature of thermal explosion（Tb） for [Mg（H2O）6]（BTATz）.2H2O are 515.13,532.08 and 565.99 K,respectively.