5种4,6-二硝基苯并连三唑-1-氧化物含能离子盐的合成、表征与性能研究

Synthesis,Characterization and Performances of Five Energetic Ionic Salts Based 4,6-Dinitro-benzotriazol-3-ium-1-oxide

以1,3,5-三硝基-2-氯苯和水合肼为起始原料,经过取代、环化反应得到4,6-二硝基苯并连三唑-1-氧化物(DNBTO),收率55.3%,并采用酸碱中和、离子交换等反应设计并合成了DNBTO的羟胺盐(HA-DNBTO)、三氨基胍盐(TAG-DNBTO)、脒基脲盐(M-DNBTO)、3,6-二肼基-1,2,4,5-四嗪盐(DHT-DNBTO)以及乙二酰肼盐(OH-DNBTO)5种含能离子盐。用红外光谱、1 H NMR、13 C NMR及元素分析等进行了结构表征;采用DSC和TG-DTG法研究了DNBTO及其5种含能离子盐的热行为。用Gaussian 09程序和VLW爆轰方程,计算了DNBTO及5种含能离子盐的物化及爆轰性能。结果表明,升温速率10℃/min时,DNBTO、HA-DNBTO、TAG-DNBTO、M-DNBTO、DHT-DNBTO和OH-DNBTO的放热分解峰温度分别为201.3、213.0、209.9、240.5、133.7、197.7℃,M-DNBTO表现出更好的热稳定性;DNBTO及其5种含能离子盐的密度在1.59~1.69g/cm3之间,爆速在6 783.6~7 681.3m/s之间;DHT-DNBTO的生成焓最高,为1 081.4kJ/mol;HA-DNBTO的爆轰性能最佳,爆速为7 681.3m/s,爆压为25.5GPa。

Using1,3,5trinitro2chloro benzene and hydrazine hydrate as primary material,4,6dinitrobenzo triazol3ium1oxide(DNBTO)was synthesized via one step reaction of substitution and cyclization with a yield of55.3%.Five energetic ionic salts,4,6dinitrobenzo triazol3ium1oxide hydroxylammonium salt(HA DNBTO),4,6dinitrobenzo triazol3ium1oxide triaminoguanidinium salt(TAG DNBTO),4,6dinitrobenzo triazol3ium1oxide guanylureaium salt(M DNBTO),bis(4,6dinitrobenzo triazol3ium1oxide)3,6dihydrazino1,2,4,5tetrazine salt(DHT DNBTO)and bis(4,6dinitrobenzo triazol3ium1oxide)oxalylhydrazinium salt(OH DNBTO),were designed and synthesized by acid base neutralization and ion exchange etc.reactions and their structures were characterized by FT IR,1H NMR,13C NMR and elemental analysis.The thermal behaviors for DNBTO and its five energetic ionic salts were studied by DSC and TG DTG.The physicochemical and detonation properties of DNBTO and five energetic ionic salts were calculated by Gaussian09program and VLW equation.The results show that the peak temperatures of exothermic decomposition reaction at10℃/min for DNBTO、HA DNBTO、TAG DNBTO、M DNBTO、DHT DNBTO and OH DNBTO were201.3,213.0,209.9,240.5,133.7,197.7℃,respectively,revealing that M DNBTO has a better thermal stability.The densities of DNBTO and five energetic ionic salts are between1.59-1.69g/cm3,the detonation velocities are between6783.6-7681.3m/s,and DHT DNBTO has the highest enthalpy of formation,which is1081.4kJ/mol.HA DNBTO has better detonation property than other DNBTO base energetic ionic salts.The detonation velocity and pressure of HA DNBTO are7681.3m/s and25.5GPa,respectively.