CHINESE JOURNAL OF ENERGETIC MATERIALS
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5-氨基-2H-吡唑-3,4-双酮-3-肟-4-腙及其含能离子盐的合成与性能调控
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南京理工大学化学与化工学院, 江苏 南京 210094

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基金项目:

国家自然科学基金(22305121)


Synthesis and Performance Adjustments of 5-amino-2H-pyrazol-3,4-dione-3-oxime-4-hydrazone and Its Energetic Salts
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Affiliation:

School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

Fund Project:

Grant support: National Natural Science Foundation of China (No. 22305121)

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    摘要:

    以4-氯-3,5-二硝基-1H-吡唑为原料,经胺化及取代/还原反应得到5-氨基-2H-吡唑-3,4-双酮-3-肟-4-腙(3),并制备了3种含能离子盐——高氯酸盐(4)、硝酸盐(5)和5,5΄-二硝氨基-3,3΄-偶氮-1,2,4-噁二唑盐(6)。通过溶剂挥发法得到了化合物34的单晶,并通过X-射线单晶衍射法对其进行表征。通过核磁共振波谱、红外光谱等方法对含能化合物3~6的结构进行表征;通过真密度仪、差示扫描量热仪、撞击感度仪、摩擦感度仪等对其性能进行测试;同时理论计算了其生成焓和爆轰性能。结果表明,化合物3为平面构型,酮肟和酮腙具有显著的双键特征,降低了吡唑环的共轭性,使其易于成盐。成盐后不同阴离子对中性化合物的性能有着多方面的影响。其中高氯酸根阴离子不但改善了化合物的氧平衡,还提高了化合物的密度,使得高氯酸盐4的爆速和爆压(8499 m·s-1,30.2 GPa)相比中性化合物3(8072 m·s-1,22.5 GPa)有一定程度提升;另外5,5΄-二硝氨基-3,3΄-偶氮-1,2,4-噁二唑显著提高了中性化合物3的分解温度,由135 ℃上升至285 ℃。结果表明通过阴阳离子的合理搭配,可以有效调控目标含能化合物的性能。

    Abstract:

    5-amino-2H-pyrazol-3,4-dione-3-oxime-4-hydrazone (3) and its perchlorate (4), nitrate (5) and 5,5′-dinitramino-3,3′-azo-1,2,4-oxadiazolate salts (6) were prepared from 4-chloro-3,5-dinitro-1H-pyrazole via amination and substitution/reduction reactions. The single crystals of 3 and 4 were obtained by solvent evaporation method and the crystals were characterized by single crystal X-ray diffraction. The structures of energetic compounds 3-6 were characterized by nuclear magnetic resonance spectroscopy and infrared spectroscopy. Moreover, the capacities of those compounds were confirmed by gas pycnometer, differential scanning calorimetry, impact and friction sensitivity testers. Their enthalpies of formation and detonation parameters were estimated using theoretical calculation methods. The results show that 3 has a planar molecular configuration. The ketone oxime and ketone hydrazone have unique double bond characteristics, reducing the conjugation of the pyrazole ring and making it easier to form salts. After salt formation, different anions have various effects on the performance of the neutral compound. Among those examined anions, the perchlorate anion not only improves the oxygen balance, but also increases the density, resulting in the detonation velocity and pressure of 4 (8499 m·s-1 and 30.2 GPa) higher than 3 (8072 m·s-1 and 22.5 GPa). In addition, 5,5′-dinitramino-3,3′-azo-1,2,4-oxadiazole significantly increases the decomposition temperature of 3, rising from 135 ℃ to 285 ℃. These results indicate that a rational combination of anions and cations can effectively regulate the performances of target energetic compound.

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引用本文

胡李劲草,孙环宇,安子伟,等.5-氨基-2H-吡唑-3,4-双酮-3-肟-4-腙及其含能离子盐的合成与性能调控[J].含能材料, 2024, 32(6):608-614. DOI:10.11943/CJEM2023270.
HU Li-jing-cao, SUN Huan-yu, AN Zi-wei, et al. Synthesis and Performance Adjustments of 5-amino-2H-pyrazol-3,4-dione-3-oxime-4-hydrazone and Its Energetic Salts[J]. Chinese Journal of Energetic Materials, 2024, 32(6):608-614. DOI:10.11943/CJEM2023270.

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  • 收稿日期: 2023-12-25
  • 最后修改日期: 2024-03-18
  • 录用日期: 2024-02-29
  • 在线发布日期: 2024-02-29
  • 出版日期: 2024-06-25