CHINESE JOURNAL OF ENERGETIC MATERIALS
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1,2-双(5,5′-二硝胺基-1,3,4-噁二唑-2-)乙烷的合成与性能
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航天化学动力技术重点实验室,湖北航天化学技术研究所, 湖北 襄阳 441003

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国家自然科学基金项目(21875061)


Synthesis and Properties of 1,2-Bis(5,5′-dinitramino-1,3,4-oxadiazol-2-)ethane
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Science and Technology on Aerospace Chemical Power Laboratory, Hubei Institute of Aerospace Chemotechnology, Xiangyang 441003, China

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    摘要:

    为了得到钝感的1,3,4-噁二唑类含能化合物,以丁二酸二甲酯和溴化氰为起始原料,通过肼解、环化、硝化反应合成了1,2-双(5,5′-二硝胺基-1,3,4-噁二唑-2-)乙烷(BNOE),总收率为49.93%。采用元素分析、傅里叶变化红外光谱和核磁对其结构进行了表征。用热重-差示扫量热仪研究了其热稳定性,依据GJB5891-2006方法测试了感度,采用密度瓶法测试了密度,用量子化学软件Gaussian 09计算了固相生成焓,采用EXPLO 5 V6.02程序预估了其爆轰性能。结果表明,BNOE 的起始分解温度为202.2 ℃,热分解峰温为208.6 ℃,撞击感度为8.6 J,摩擦感度为88%,静电感度为108.1 mJ,实测密度为1.714 g·cm-3,固相生成焓为48.25 kJ·mol-1,计算爆压为22.6 GPa,计算爆速为7663 m·s-1。采用Gaussian 09分析了5-甲基-2-氨基-1,3,4-噁二唑(NAOz)的环化反应机理,认为其反应分为肼解反应和成环反应两个阶段。

    Abstract:

    In order to obtain insensitive 1,3,4-oxadiazole energetic compounds, 1,2-bis(5,5′-dinitramino-1,3,4-oxadiazol-2-)ethane(BNOE) was synthesized via hydrazinolysis, cyclization and nitration using dimethyl succinate and cyanogen bromide as raw materials with a total yield of 49.93%. Its structure was characterized by elemental analysis, FT-IR and NMR. The thermal decomposition process was studied by TG-DSC, and the mechanical sensitivities were tested according to the GJB5891-2006 method. The density was measured using the density bottle method. The solid-state heat of formation (HOF) was calculated with Gaussian 09 software. The detonation parameters were calculated with EXPLO 5 v6.02 software. Results show that the onset decomposition temperature of BNOE is 202.2 ℃ and thermal decomposition peak temperature is 208.6 ℃. The sensitivity towards impact, friction, and electrostatic of BNOE is 8.6 J, 88%, and 108.1 mJ, respectively. The measured density is 1.714 g·cm-3, the solid heat of formation is 48.25 kJ·mol-1. The calculated detonation velocity and pressure is 7663 m·s-1 and 22.6 GPa, respectively. The study on cyclization mechanism of 5-methyl-2-amino-1,3,4-oxadiazole (NAOz) by Gaussian 09 show that the reaction proceeds in two stages: hydrazinolysis and ring formation.

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马英杰,卢艳华,曹一林,等.1,2-双(5,5′-二硝胺基-1,3,4-噁二唑-2-)乙烷的合成与性能[J].含能材料, 2020, 28(7):678-684. DOI:10.11943/CJEM2019320.
MA Ying-jie, LU Yan-hua, CAO Yi-lin, et al. Synthesis and Properties of 1,2-Bis(5,5′-dinitramino-1,3,4-oxadiazol-2-)ethane[J]. Chinese Journal of Energetic Materials, 2020, 28(7):678-684. DOI:10.11943/CJEM2019320.

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历史
  • 收稿日期: 2019-12-22
  • 最后修改日期: 2020-05-07
  • 录用日期: 2020-04-13
  • 在线发布日期: 2020-04-27
  • 出版日期: 2020-07-25