2,6-二氨基-3,7-二硝亚胺基-2,4,6,8-四氮杂双环[3.3.0]辛烷的合成及爆轰性能

Synthesis and Detonation Property of 2,6-Diamino-3,7-dis(nitroinino)-2,4,6,8-tetrazabicyclo [3.3.0] octane

以二硝基甘胍为原料,二苯基次膦酰羟胺(Dpp ONH2)为胺化试剂,经脱氢、胺化两步反应得到一种新型高能量密度化合物2,6-二氨基-3,7-二硝亚胺基-2,4,6,8-四氮杂双环[3.3.0]辛烷(二氨基二硝基甘胍)。采用红外光谱(FTIR)、核磁(NMR)、质谱(MS)对目标结构进行了表征。研究了影响二氨基二硝基甘胍产率的因素,并通过正交试验确定了各个因素对目标产物影响的大小,确定了在Dpp ONH_2/MeCN胺化体系下,反应时间为48 h、温度为40℃、Dpp ONH2与二硝基甘胍钠盐的摩尔比为3∶1时二氨基二硝基甘胍的产率最高,为35.07%。运用Gaussian 03程序包,采用密度泛函理论(DFT)的B3LYP/6-31++G(d,p)方法,对其结构优化,并基于其优化结构,对该化合物的爆轰性能进行预测。用Monte-Carlo方法求得该化合物的理论密度为1.73 g·cm^(-3);设计等键等电子反应得到其标准摩尔生成热为416.09 k J·mol^(-1);Kamlet-Jacobs公式计算得到该化合物爆速为8.90 km·s^(-1),爆压为34.27GPa。理论计算结果说明该化合物密度、爆压、爆速均与RDX接近。

2,6-Diamino-3,7-dis(nitroimino)-2,4,6,8-tetrazabicyclo[3.3.0]octane,a new energetic compound,was synthesized from 3,7-bis(nitroimino)-2,4,6,8-tetraazabicyclo[3.3.0]octane and DppONH 2 via neutralization reaction and amination reaction.The structure of 2,6-diamino-3,7-dis(nitroimino)-2,4,6,8-tetrazabicyclo[3.3.0]octane was characterized by infrared(IR)spectroscopy,nuclear magnetic resonance(NMR)and mass spectrometer(MS).The factors effecting the yield of target compound was investigated by orthogonal experiment.Results indicates that the yield of 2,6-diamino-3,7-dis(nitroimino)-2,4,6,8-tetrazabicyclo[3.3.0]octane is the highest(35.07%)under the conditions of reaction time 48 h,reaction temperature 40℃and 3∶1 as mole ratio.The stable geometry of the compound was completely optimized at the B3LYP/6-31G++(d,p)theoretical level of density functional theory(DFT).The theoretical density of the target compound is 1.73 g·cm-3 by Monte-Carlo method.The heat of formation is 416.09 kJ·mol-1 via isodesmic reaction.The detonation velocity and detonation pressure are 8.90 km·s-1 and 34.27 GPa predicted by Kamlet-Jacobs formula.All the results show that the theoretical density,detonation velocity and detonation pressure are closed to that of RDX.