CHINESE JOURNAL OF ENERGETIC MATERIALS
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3,3′-双(2-硝胺基-1,3,4-噁二唑-4-基)-5,5′-联-1,2,4-噁二唑及其含能离子盐的合成及性能
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中国工程物理研究院化工材料研究所, 四川 绵阳 621999

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国家自然科学基金面上基金(21875228);国家自然科学基金青年基金(21702196)


Synthesis and Properties of 3,3′-Bis(2-nitroamino-1,3,4-oxadiazol-4-yl)-5,5′-linked-1,2,4-oxadiazole and Its Energetic Salts
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Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621999, China

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    摘要:

    以乙二肟为原料,经取代、环化、硝化等五步反应合成了四联环含能化合物3,3"-双(2-硝胺基-1,3,4-噁二唑-4-基)-5,5"-联-1,2,4-噁二唑(BNOBO)。利用BNOBO的酸性,设计、合成了BNOBO的铵盐、肼盐和羟胺盐等三种含能离子盐(5-7)。并采用红外光谱、核磁等进行了结构表征。采用溶剂挥发法培养了BNOBO铵盐的晶体,该晶体属于单斜晶系,C2/c空间群,晶胞参数为a=12.7490(8) nm,b=9.5957(7) nm,c=18.5965(12) nm,V=2272.1(3) nm3Z=4。利用差示扫描量热(DSC)和热重(TG)等热分析方法研究了BNOBO及其三种离子盐的热性能,基于密度仪获得的实测密度,运用EXPLO5 v6.02软件计算了目标化合物的爆轰性能,并利用BAM感度仪测试了撞击和摩擦感度。研究结果表明,所得化合物中BNOBO的热分解温度最高为215 ℃,其密度最高为1.90 g·cm-3、BNOBO的计算爆速和爆压分别达到8789 m·s-1和32.7 GPa,离子盐5的撞击感度大于20 J,摩擦感度为220 N。

    Abstract:

    A new energetic compound 3,3"-bis(2-nitroamino-1,3,4-oxadiazol-4-yl)-5,5"-linked-1,2,4-oxadiazole (BNOBO) was synthesized starting from glyoxime through a five-step reaction. Based on the acidity of BNOBO, three energetic salts (5-7) were obtained through the reactions between BNOBO and aqueous ammonia, hydrazine and hydroxylamine, respectively. The structures of as-synthesized compounds were characterized by single-crystal X-ray diffraction, IR, NMR and element analysis. The crystal of BNOBO ammonium salt was obtained through solvent evaporation method ,the obtained results show that it belongs to a monoclinic system and C2/c space group with a=12.7490(8) nm, b=9.5957(7) nm, c=18.5965(12) nm, V=2272.1(3) nm3 and Z=4. Their thermal stability, density, detonation properties and sensitivity were evaluated by TG/DSC analysis, densitometer, EXPLO5 v6.02 software and BAM sensitivity tester, respectively. Among these new energetic compounds, BNOBO possesses the highest measured density of 1.90 g·cm-3 and the highest onset decomposition temperature of 215 ℃. The calculated detonation velocity and pressure of BNOBO are as high as 8789 m·s-1 and 32.7 GPa, respectively. These new energetic compounds also exhibit relatively low mechanical sensitivities, in which energetic salt 5 display the low impact sensitivity of more than 20 J and friction sensitivity of 220 N.

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廖思丞,邓沐聪,宋思维,等.3,3′-双(2-硝胺基-1,3,4-噁二唑-4-基)-5,5′-联-1,2,4-噁二唑及其含能离子盐的合成及性能[J].含能材料, 2020, 28(7):632-637. DOI:10.11943/CJEM2019278.
LIAO Si-cheng, DENG Mu-cong, SONG Si-wei, et al. Synthesis and Properties of 3,3′-Bis(2-nitroamino-1,3,4-oxadiazol-4-yl)-5,5′-linked-1,2,4-oxadiazole and Its Energetic Salts[J]. Chinese Journal of Energetic Materials, 2020, 28(7):632-637. DOI:10.11943/CJEM2019278.

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  • 收稿日期: 2019-11-01
  • 最后修改日期: 2020-03-13
  • 录用日期: 2019-12-02
  • 在线发布日期: 2019-12-16
  • 出版日期: 2020-07-25