两种富氮稠环型1,2,5-噁二唑类含能盐的合成及性能

Synthesis and Properties of Two 1,2,5-Oxadiazole based Energetic Salts with Nitrogen-Rich Fused Ring Skeleton

以5,6-二肼基-[1,2,5]噁二唑并[3,4-b]吡嗪(1)为原料合成了5,5′-(肼-1,2-二亚基亚胺)双(5,7-2H‑[1,2,5]噁二唑并[3,4-e][1,2,4]三唑并[4,3-a]吡嗪-8(4H)-亚胺)高氯酸盐(2)和5,5′-(二氮烯-1,2-二亚基)双([1,2,5]噁二唑并[3,4-e][1,2,4]三唑并[4,3-a]吡嗪-8(7H)-亚胺)硝酸盐(3)两种富氮含能盐。采用核磁共振(NMR)、傅里叶红外光谱(FT-IR)、元素分析(EA)、X-射线单晶衍射(XRD)等多种手段对含能离子盐2和3的结构进行了表征,利用差示扫描量热法(DSC)研究其热分解行为,运用BAM标准测试方法获得摩擦感度和撞击感度,同时基于等键反应方程与EXPLO5软件预测其爆轰性能。结果表明,化合物2和3的晶体均属于单斜晶系,分别属于Pn和P21/n空间群,二者的晶体结构中阳离子部分具有良好的平面性,晶体堆积图中观察到了大量氢键。化合物2和3的热分解温度分别为154℃和130℃,理论爆速分别为7722 m·s^(-1)和8008 m·s^(-1),理论爆压分别为26.3 GPa和28.4 GPa,摩擦感度均为360 N,撞击感度均大于40 J。化合物2和3在爆轰性能、摩擦感度、撞击感度性能上均优于传统炸药TNT。

Two nitrogen-rich energetic salts,5,5′-(hydrazine-1,2-diyl)bis(5,7-dihydro-[1,2,5]oxadiazolo[3,4-e][1,2,4]triazolo[4,3-a]pyrimidine-8(4H)-one)perchlorate(2)and 5,5′-(diazene-1,2-diyl)bis([1,2,5]oxadiazolo[3,4-e][1,2,4]triazolo[4,3-a]pyrimidine-8(7H)-one)nitrate(3)were accomplished from the raw material of 5,6-diamino-[1,2,5]oxadiazolo[3,4-b]pyrazine(1).Structure characterization of energetic ionic salts 2 and 3 were achieved through various techniques,including Nuclear Magnetic Resonance Spectroscopy(NMR),Fourier Transform infrared spectroscopy(FTIR),elemental analysis(EA)and X-ray single crystal diffraction(XRD).Their thermal decomposition behaviors were investigated using differential scanning calorimetry(DSC)method,while their friction and impact sensitivities were identified according to BAM standard test meth-ods.Moreover,their detonation performances were predicted based on the combination of Isodesmic Reactions and EXPLO5 software.The results prove that compounds 2 and 3 crystallize in the monoclinic system,belonging to space groups Pn and P21/n,respectively.The cationic parts of their crystal structures show good planarity and intensive hydrogen bonds in the crystal packing are observed.The thermal decomposition temperatures of compounds 2 and 3 are 154℃and 130℃,respectively.Their theoretical detonation velocities are 7722 m·s^(-1) and 8008 m·s^(-1),while their theoretical detonation pressures are 26.3 GPa and 28.4 GPa,respectively.Their friction sensitivities are both 360 N,and impact sensitivities are greater than 40 J.Compounds 2 and 3 outperform traditional explosives TNT in terms of detonation performance,friction sensitivity,and impact sensitivity.