CHINESE JOURNAL OF ENERGETIC MATERIALS
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两种富氮稠环型1,2,5-噁二唑类含能盐的合成及性能
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南京理工大学化学与化工学院

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国家自然科学基金(22305124);江苏省自然科学基金(BK20220967)


Synthesis and Properties of Two 1,2,5-Oxadiazole based Energetic Salts with Nitrogen-Rich Fused Ring Skeleton
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School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology

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    摘要:

    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23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23的晶体均属于单斜晶系,分别属于PnP21/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23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23在爆轰性能、摩擦感度、撞击感度性能上均优于传统炸药TNT。

    Abstract:

    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 methods. 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 respectively 154 ℃ and 130 ℃. Their theoretical detonation velocities are respectively 7722 m·s-1 and 8008 m·s-1, while their theoretical detonation pressures are respectively 26.3 GPa and 28.4 GPa. 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.

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李涛,易文斌,于琼. 两种富氮稠环型1,2,5-噁二唑类含能盐的合成及性能[J]. 含能材料,DOI:10.11943/CJEM2024039.

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  • 收稿日期: 2024-01-25
  • 最后修改日期: 2024-04-23
  • 录用日期: 2024-04-14
  • 在线发布日期: 2024-04-17
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