CHINESE JOURNAL OF ENERGETIC MATERIALS
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4-羟基-3,5-二硝基吡唑含能离子化合物的合成、晶体结构及性能
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1.西南科技大学环境友好能源材料国家重点实验室, 四川 绵阳 621010;2.西南科技大学材料科学与工程学院, 四川 绵阳 621010

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国家自然科学基金资助(21905236)


Synthesis, Crystal Structure and Properties of Ionic Energetic Compounds Based on 4-Hydroxyl-3,5- dinitropyrazolate Anion
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1.State Key Laboratory of Environment-friendly Energy Materials, Southwest University of Science and Technology, Mianyang 621010, China;2.School of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621010, China

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    摘要:

    以3,5-二硝基-4-溴吡唑(1)为底物,经水解与中和反应合成了4-羟基-3,5-二硝基吡唑(H-DNOP,2),并利用其酸性,设计、合成了DNOP的三种离子型含能化合物(3~5)。采用核磁、红外、X 射线单晶衍射等手段对化合物3~5的结构进行表征;利用差示扫描量热仪-热重联用研究了化合物3-5的三种离子盐的热性能,其中肼盐(3)的热分解温度最高为210.3 ℃。采用BAM测试方法测试了撞击感度和摩擦感度,并基于等键方程和Kamlet-Jacobs方程预测了其能量参数。结果表明,三种含能化合物的实测感度较低,撞击感度均为36 J,摩擦感度均为360 N,比三硝基甲苯(TNT)(撞击感度为15 J,摩擦感度为353 N)和黑索今(RDX)(撞击感度为7.4 J,摩擦感度为120 N)钝感;三种化合物理论爆速为7758~8288 m·s-1,爆压为26.06~29.96 GPa。

    Abstract:

    4-hydroxy-3,5-dinitropyrazole(H-DNOP, 2) was synthesized from 3,5-dinitro4-bromopyrazole(1) by hydrolysis and neutralization reaction. Three kinds of ionic energetic compounds (3-5) of DNOP were designed and synthesized by using its acidity. The structures of compounds 3-5 were characterized by FT-IR, NMR spectrum, elemental analysis as well as single-crystal X-ray diffraction, and their thermal stabilities were investigated by differential scanning calorimetry and thermogravimetry (DSC-TG). The maximum decomposition temperature of hydrazine salt (3) was Td=210.3 ℃. The impact sensitivity and friction sensitivity were measured by BAM method, while the detonation parameters were predicted based on the isodesmic reactions and the Kamlet-Jacobs equation. The results show that the measured impact sensitivity and friction sensitivity of the threecompounds 3-5 are all 36 J and 360 N, which are less sensitive than those of TNT(IS=15 J,FS=353 N) and RDX(IS=7.4 J,FS=120 N). The theoretical detonation velocities of the three compounds are 7758-8288 m·s-1, and the detonation pressures are 26.06-29.96 GPa, respectively.

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伍波,蒋绣俄,胡平,等.4-羟基-3,5-二硝基吡唑含能离子化合物的合成、晶体结构及性能[J].含能材料, 2021, 29(8):713-720. DOI:10.11943/CJEM2021113.
WU Bo, JIANG Xiu-e, HU Ping, et al. Synthesis, Crystal Structure and Properties of Ionic Energetic Compounds Based on 4-Hydroxyl-3,5- dinitropyrazolate Anion[J]. Chinese Journal of Energetic Materials, 2021, 29(8):713-720. DOI:10.11943/CJEM2021113.

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历史
  • 收稿日期: 2021-04-24
  • 最后修改日期: 2021-06-24
  • 录用日期: 2021-06-04
  • 在线发布日期: 2021-06-10
  • 出版日期: 2021-08-25