5-甲基-4-硝基-1H-吡唑-3-(2H)-酮及其含能离子化合物的合成与性能

摘要

A new energetic compound 5-methyl-4-nitro-1H-pyrazol-3-(2H)-one (MNPO) was synthesized with total yield of 68％,using ethyl 3-oxobutanoate as raw material.Corresponding ion salts were prepared via.metathesis reaction and neutraliza-tion reaction by the reactions of MNPO with a series of high nitrogen cation.Their structures were characterized by single-crystal X-ray diffraction,Fourier transform infrared(FT-IR) spectroscopy,nuclear magnetic resonance(1H NMR、13C NMR)spectrometry,elemental analyses and other means.Their thermal decomposition temperatures were measured by thermogravimetry(TG) and differential scanning calorimetry(DSC).Their detonation performances were calculated with Explo5 v6.02 software.Results show that the crystal of MNPO belongs to orthorhombic system,and its space group is Pbca with crstal parameters of a=71495 (18) nm,b=1.1639(3) nm,c=1.3834(3) nm,V=1.1512(5) nm3 and Z=8.For energetic ion salts of MNPO with densities of 1.62-1.74 g · cm-3,their decomposition temperatures are in the range of 181-272 ℃,theoretical detonation velocities are greater than 7000 m · s-1 and detonation pressures are greater than 15 GPa.The measured impact and friction sensitivities are low,in which,the impact sensitivity of ammonium salt of MNPO is 28 J and the friction sensitivity 240 N.%以乙酰乙酸乙酯为原料合成了一种新型含能化合物——5-甲基-4-硝基-1 H-吡唑-3-(2H)-酮(MNPO),总收率68％,通过复分解反应和中和反应,由MNPO与一系列高氮阳离子反应,制备出了相应的含能离子化合物.采用X-射线单晶衍射(XRD)、傅里叶变换红外光谱(FT-IR)、核磁共振(1H NMR、13C NMR)谱、元素分析等手段对其结构进行了表征.利用热重法(TG)-差示扫描量热法(DSC)测定了其热分解温度;运用Explo5 v6.02软件对其爆轰性能进行计算.结果表明,MNPO晶体属于正交晶系,Pbca空间群,晶胞参数为a=0.71495 (18) nm,b=1.1639(3) nm,c=1.3834(3) nm,V=1.1512(5) nm3,Z=8.对密度范围为1.62 ～1.74 g· cm-3的MNPO的含能离子化合物,它们的热分解onset温度范围为181 ～272℃,理论爆速大于7000 m·s-1,爆压大于15 GPa;实测撞击及摩擦感度低,其中MNPO的铵盐的撞击感度为28 J,摩擦感度为240 N.