1-三硝甲基-3-硝基-1,2,4-三唑的晶体结构及性能预估

为了获得1-三硝甲基-3-硝基-1,2,4-三唑(TNMNT)的晶体结构并对其性能进行预估,以3-硝基-1,2,4-三唑为原料,通过取代、硝化反应合成出了TNMNT,收率为62%,以无水乙醇为溶剂,用溶剂蒸发法培养得到纯的TNMNT单晶,并采用核磁共振谱、红外光谱与X-射线单晶衍射仪进行了结构表征。用DSC-TG法分析了热稳定性。用Gaussian 09 and EXPLO5(V6.02)程序分别计算了生成焓和爆轰参数。结果表明:TNMNT晶体属于单斜晶系,空间群P21/c,晶体参数为a=6.643(3),b=20.494(7),c=6.698(3),β=94.225(9)°,V=909.4(6)3,Z=4,Dc=1.922 g·cm~(-3),μ=0.190 mm~(-1),F(000)=528.0。5℃·min-1升温速率下,TNMNT的热分解峰温为158.3℃。它的标准生成焓为210.9 kJ·mol~(-1),爆速为9023 m·s~(-1),爆压为35.5 GPa。大量分子间和分子内氢键作用的存在使TNMNT分子稳定存在,硝仿基团的引入使TNMNT分子的能量提高。

Crystal Structure and Property Prediction of 1-Trinitromethyl-3-nitro-1,2,4-triazole

To get the crystal structure of 1-trinitromethyl-3-nitro-1,2,4-triazole(TNMNT) and estimate its properties, using 3-nitro-1,2,4-triazole as starting material, TNMNT was synthesized via substitution reaction and nitration reaction with total yield of 62%.The pure single crystal of TNMNT was cultured and obtained by solvent evaporation method using absolute ethyl alcohol as solvent.Its structure was characterized by NMR spectrometry, IR spectrometry, and single crystal X-ray diffractometer.The thermal stability was analyzed by the DSC-TG method.The enthalpy of formation and detonation parameters were calculated with Gaussian 09 and EXPLO5(V6.02) program, respectively.Results show that the crystal of TNMNT belongs to monoclinic system, space group is P21/c with crystal parameters of a=6.643(3), b=20.494(7), c=6.698(3), β=94.225(9)°, V=909.4(6), Z=4, Dc=1.922 g·cm-3, μ=0.190 mm-1, F(000)=528.0.The thermal decomposition peak temperature of TNMNT at a heating rate of 5 ℃·min-1 is 158.3 ℃.Its standard enthalpy of formation is 210.9 kJ·mol-1, detonation velocity 9023 m·s-1, and detonation pressure 35.5 GPa.The existence of numerous intermolecular and intramolecular hydrogen bonds makes the TNMNT molecule stably exist, and the introduction of the trinitromethyl moeity makes the energy of TNMNT molecule enhance.