1,3,5-三(甲硝胺基)-2,4,6-三硝基苯的合成、单晶结构与性能

Synthesis,Crystal Structure and Properties of 1,3,5-Tris(methylnitroamino)-2,4,6-trinitrobenzene

以1,3,5-三氯-2,4,6-三硝基苯(化合物1,TCTNB)为原料,经甲胺化、硝化反应得到1,3,5-三(甲硝胺基)-2,4,6-三硝基苯(化合物3)。优化合成工艺获得了制备的最佳工艺条件,总产率达74.7%。采用傅里叶红外光谱仪、核磁共振仪、差示扫描量热仪、热重分析仪和X射线单晶衍射仪等对化合物3及其中间产物进行了表征。单晶数据显示,化合物3晶体属于三斜晶系,P1空间群。采用Kissinger法、Rogers法和Arrhenius法计算化合物3的表观活化能Ea为157.81 kJ·mol^(-1),指前因子A为12.79×10^(16) min^(-1),分解速率常数k为2.91×10^(-11),热爆炸临界温度Tb为206.52℃。采用Kamlet-Jacobs半经验方程预测化合物3的爆速为7990 m·s^(-1),爆压为26.6 GPa。

1,3,5-Tris(methylnitroamino)-2,4,6-trinitrobenzene(3)was synthesized through methylamination and nitration starting from 1,3,5-trichloro-2,4,6-trinitrobenzene(1,TCTNB),of which the optimal process was obtained with a total yield up to 74.7%.Compound 3 and its intermediate were characterized by FT-IR,NMR,DSC-TG,X-ray single-crystal diffraction,etc.Crystal data show compound 3 crystal belongs to a triclinic system with space group P1.The thermal decomposition kinetic parameters of compound 3 were calculated by Kissinger,Rogers and Arrhenius methods,showing that the apparent activation energy,Ea,is 157.81 kJ·mol^(-1),the pre-exponential factor,A,is 12.79×10^(16) min^(-1),the decomposition rate constant,k,is 2.91×10^(11),and the thermal explosion critical point,Tb,is 206.52℃.The detonation velocity and detonation pressure of compound 3 were 7990 m·s^(-1) and 26.6 GPa through Kamlet-Jacobs equation calculation.