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1,4-二氨基-3,6-二硝基吡唑[4,3-c]并吡唑的制备及热分解机理
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西安近代化学研究所

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国家自然科学基金资助 21805222和21875185国家自然科学基金资助(21805222和21875185)


Preparation and Thermal Decomposition Mechanism of 1,4-Diamino-3,6-dinitropyrazolo[4,3-c]pyrazole
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1.Xi’an Modern Chemistry Research Institute,Xi’an Shaan’xi 710065;2.China

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    摘要:

    以3,6-二硝基吡唑[4,3-c]并吡唑(DNPP)为原料,经N-胺化反应合成了1,4-二氨基-3,6-二硝基吡唑[4,3-c]并吡唑(DADNP),采用红外光谱、核磁共振(1H NMR、13C NMR)、质谱及元素分析等手段表征了化合物结构;利用差示扫描量热仪(DSC)、热重仪(TG)、固相原位热红外检测仪(RSFTIR)、热重-质谱联用技术(TG-MS)等热分析方法研究了DADNP的热分解过程和机理,结果表明,DADNP热分解反应的活化能和指前因子分别为166.45 kJ·mol-1和1016.53 s-1。DADNP的热分解过程主要包含两个阶段,第一阶段分别在电离源或加热条件下,DADNP分子中C─NO2首先发生断裂,生成NO2小分子;第二阶段是吡唑并吡唑环的进一步破裂及二次氧化反应,生成HCN、N2H2等小分子。

    Abstract:

    1,4-Diamino-3,6-dinitropyrazolo[4,3-c]pyrazole(DADNP) was synthesized by N-amination reaction, and its structure was characterized by NMR, IR, MS and element analysis. The thermal decomposition kinetics and mechanism were studied by means of different heating rate differential scanning calorimetry(DSC), rapid-scan fourier transform infrared spectroscopy(RSFTIR) and thermogravimetry-mass spectrometer(TG-MS) coupling technique. The results show that the apparent activation energy and pre-exponential constant of the exothermic decomposition reaction of DADNP obtained by Kissinger method are 166.45 kJ·mol-1, 1016.53 s-1. The decomposition of DADNP includes two stages, which begins with the rupture of C─NO2 with subsequent loss of NO2 under electron impact and heating condition, respectively. In the first stage of decomposition, the rupture of one C─NO2 and one pyrazole ring in DADNP molecule with the release of NO2 and N2H2 occur under electron impact condition, whereas the homolysis of two C─NO2 bonds occur with the loss of two molecular NO2 under heating condition.

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李亚南,胡建建,陈涛,等.1,4-二氨基-3,6-二硝基吡唑[4,3-c]并吡唑的制备及热分解机理[J].含能材料, 2019, 27(12):1025-1030. DOI:10.11943/CJEM2018344.
LI Ya-nan, HU Jian-jian, CHEN Tao, et al. Preparation and Thermal Decomposition Mechanism of 1,4-Diamino-3,6-dinitropyrazolo[4,3-c]pyrazole[J]. Chinese Journal of Energetic Materials, 2019, 27(12):1025-1030. DOI:10.11943/CJEM2018344.

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历史
  • 收稿日期: 2018-12-11
  • 最后修改日期: 2019-06-05
  • 录用日期: 2019-03-19
  • 在线发布日期: 2019-05-28
  • 出版日期: 2019-12-25