N-1,4,6-三硝基六氢咪唑[4,5-d]咪唑-2(1H)-亚硝胺的合成与性能

Synthesis and Property Prediction of N-(1,4,6-trinitrohexahydroimid-azo[4,5-d]imidazole-2(1H)-ylidene) nitramide

以六氢咪唑[4,5-d]咪唑-2(1H)-亚胺为原料,通过三个阶段硝化反应合成了一种新型多环氮杂环含能化合物:N^(-1),4,6-三硝基六氢咪唑[4,5-d]咪唑-2(1H)-亚硝胺(TNINA),总收率55%。采用红外光谱(IR)、核磁共振(NMR)、质谱(MS)对目标产物以及中间体进行了表征,同时研究了时间、温度、乙酸酐与硝酸体积比等因素对第三阶段硝化反应的影响。利用热重分析(TG)和差示扫描量热仪(DSC)研究了TNINA的热性能,DSC结果显示其热分解温度为214.4℃,且放热过程瞬间完成。用Monte-Carlo方法估算TNINA的理论密度为1.91 g·cm^(-3),真密度仪测得其密度为1.89 g·cm^(-3)。用Kamlet-Jacobs方程估算出其爆热为5513.26 kJ·kg^(-1),爆速为8.836 km·s^(-1),爆压为35.80 GPa,撞击感度H50的计算值为41 cm,测试值为53 cm。理论计算结果与实验数据说明TNINA与RDX相比拥有更优异的爆轰性能与更低的感度。

N-（1,4,6-trinitrohexahydroimidazo[4,5-d]imidazol-2（1H）-ylidene）nitramide（TNINA）, a energetic nitrogenous poly-heterocyclic compound, was synthesized with a total yield of 47% by three stages of nitration reaction using hexahydroimidazo[4,5-d]imidazol-2（1H）-imine as raw material. The factors affecting the third nitration reactions such as reaction time, reaction tempterature and volume ratio of acetic anhydride to nitric acid were investigated as well. The title compound and its intermediates were characterized by IR, NMR and MS. Its thermal stability was analyzed by DSC and TG and the temperature of decomposition was 214.4 ℃, and exothermic process was finished instantly. The theoretical density of TNINA after optimizing predicted by Monte-Carlo method is 1.91 g·cm^-3 ,and experimental value is 1.89 g·cm^-3. The heat of detonation, detonation velocity and detonation pressure predicted by Kamlet-Jacobs formula are 5513.26 kJ·kg^-1, 8.836 km·s^-1, 35.80 GPa, and the theoretical and experimental impact sensitivity（H50） is 41 cm and 53 cm. All the results show that TNINA have better detonation performance and more insensitive than RDX.