Synthesis,Characterization And Properties Of Derivatives Of Aminonitroguanidine(ANQ)

Four new energetic compounds based on aminonitroguanidines(ANQ)were synthesized:N1,N2-di(2-nitroguanidino)propane-1,2-diimine(DNPD),N-nitro-2-(propan-2-ylidene)hydrazine-1-carboxmidamide(NPYHC),1-(1-amino-2,2-dinitrovinyl)amino-3-nitroguanidine(ADANG)and 3-nitroamino-5-amino-2,4-2H-1,2,4-triazole(NATZ).These compounds were characterized by infrared spectrum(IR),nuclear magnetic resonance(NMR)and elemental analysis(EA).Single crystals of DNPD and NPYHC were obtained by solvent evaporation method and the structures were determined:DNPD DMSO:C7H16N10O5S,monoclinic,P21/n and NPYHC·3H20:C4H15N5O5,triclinic,P-1.The structures of the four compounds were optimized using the Guassian program at the DFT/B3LYP 6-31G(d)level.The bond lengths,bond angles and torsion angles were obtained.The frontier orbit,mulliken charges and molecular surface electrostatic potential were analyzed through quantum chemical calculation.The thermal behavior of these four compounds were analyzed by differential scanning calorimetry(DSC)and thermogravimetric(TG)methods.At a heating rate of 10 0C min-1,both NPYHC and ADANG present only one intense exothermic decomposition process and the peak temperatures were 164.79? and 201.36?,respectively.Whereas,DNPD and NATZ contain two consecutive exothermic decomposition processes.The thermal decomposition kinetic parameters were calculated by Ozawa and Kissinger methods at various heating rates,and then the optimal mechanism equations during the decomposition were obtained:DNPD:d?/dT=1018.32/?(1-?)2/3 exp(-2.1×105/RT)NPYHC:d?/dT=4×1020.06/??3/4 exp(-1.87×105/RT)ADANG:d?/dT=2×1025.98/?(1-?)[-ln(1-?)]1/2 exp(-2.54×105/RT)NATZ:d?/dT=3×1019.97/2×?(1-?)[-ln(1-?)]1/3 exp(-1.87×105/RT)The specific heat capacity equations of DNPD,NPYHC,ADANG and NATZ were determined on Micro-DSCIII,and their standard molar heat capacities were 396.34,203.24,332.09 and 154.32 J·mol-1·K-1,respectively.After that,the values of HT-H298.15,ST-S298.15 and GT-G298.15 from 283 to 333 K were calculated.To evaluate the thermal safety of the four compounds,the self-accelerating decomposition temperatures of them were calculated as:226.27,161.55,177.42 and 151.93? and the thermal explosion critical temperatures were 236.87,171.02,184.24 and 160.55?,respectively.The detonation velocity and detonation pressure of four compounds were calculated by the Kamlet-Jacobs equation.Of the compounds studied,ADANG exhibits the best detonation performance,which detonation velocity was 9.11 km s-1 and detonation pressure was 37.42 GPa.The impact sensitivity of DNPD,NPYHC,ADANG and NATZ were>21.56,19.6,21.56 and>23.52J,the results suggest that they are all insensitive Finally,the copper salt of NATZ was synthesized and its catalytic effect on the thermal decomposition of AP,RDX and HMX were studied.The results show that it has a better catalytic effect on AP.