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5-硝基-3-(三硝基甲基)-1H-1,2,4-三唑富氮含能离子盐的合成与性能
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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(22475102)


Synthesis and Performance of 5-Nitro-3-(trinitromethyl)-1H-1,2,4- triazole Nitrogen-Rich Energetic Ionic Salts
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School of Chemistry and Chemical Engineering,Nanjing University of Science and Technology

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    摘要:

    为了进一步平衡5-硝基-3-(三硝基甲基)-1H-1,2,4-三唑的能量和安全性,以2-(5-氨基-1H-1,2,4-三唑-3-基)乙酸为原料,采用银盐置换的方式合成了4种富氮含能离子盐。通过核磁共振、傅里叶红外光谱、差示扫描量热仪、热失重分析仪和单晶衍射仪对所有新化合物的结构进行了表征。结果表明5-硝基-3-(三硝基甲基)-1H-1,2,4-三唑铵盐、肼盐和胍盐有着比前体更高的起始分解温度;且肼盐与胍盐和三氨基胍盐属于不同的晶系,三者有着不同的晶体堆积方式和密度,但在分子间弱相互作用力方面三者具有一致性,即分子间H…O相互作用的贡献最大,且随着N…O和O…O作用的比例减小,富氮含能离子盐对机械刺激的敏感度降低;最后,通过对分子静电势的分布情况的分析,补充说明了5-硝基-3-(三硝基甲基)-1H-1,2,4-三唑成盐之后撞击感度的变化。在四种离子化合物中,肼盐爆轰性能突出(D=8634 m·s-1p=30.2 GPa,Isp=263.5 s),但感度较高。而三氨基胍盐有优异的综合性能,不仅在爆速方面与肼盐相当(D=8627 m·s-1),生成焓较前体提升近1.4倍(ΔHf =0.644 kJ·g-1),且机械感度良好(IS=10.3 J,FS=150 N)。

    Abstract:

    To further balance the energy and safety of 5-nitro-3-(trinitromethyl)-1H-1,2,4-triazole, four nitrogen-rich energetic ionic salts were synthesized using 2-(5-amino-1H-1,2,4-triazole-3-yl) acetic acid as a starting material through a silver salt substitution reaction. The structures of all new compounds were characterized using nuclear magnetic resonance, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and single crystal X-ray diffraction. The results indicate that the ammonium salt, hydrazine salt, and guanidine salt of 5-nitro-3-(trinitromethyl)-1H-1,2,4-triazole exhibit higher initial decomposition temperature than that of the precursor. Moreover, the hydrazine salt and guanidine salt belong to the different crystal systems with distinct crystal packing arrangements and densities. However, they share consistent characteristics in terms of intermolecular weak interactions, with the H…O interaction being the predominant contributor. With the decreasing of the ratios of N…O and O…O interactions, the sensitivity of the nitrogen-rich energetic ionic salts to mechanical stimuli decreases. Finally, the analysis of the distribution of molecular electrostatic potential supplements the explanation for the change in impact sensitivity of 5-nitro-3-(trinitromethyl)-1H-1,2,4-triazole after salt formation. Among the four ionic compounds, the hydrazine salt exhibits outstanding detonation performance (D=8634 m·s-1p=30.2 GPa, Isp=263.5 s) with relative high sensitivity. In contrast, the triaminoguanidine salt demonstrates excellent overall performance. It has a detonation velocity comparable to that of the hydrazine salt (D=8627 m·s-1), a heat of formation nearly 1.4 times greater than that of the precursor (ΔHf=0.644 kJ·g-1), and a low mechanical sensitivity (IS=10.3 J, FS=150 N).

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王显锋,杨峰,许元刚,等. 5-硝基-3-(三硝基甲基)-1H-1,2,4-三唑富氮含能离子盐的合成与性能[J]. 含能材料,DOI:10.11943/CJEM2024224.

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  • 收稿日期: 2024-08-23
  • 最后修改日期: 2024-09-22
  • 录用日期: 2024-09-18
  • 在线发布日期: 2024-09-18
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