CHINESE JOURNAL OF ENERGETIC MATERIALS
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不对称1,2,4,5-四嗪类化合物DPHX和DMHT的结构、热行为和热安全性
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西北大学化工学院

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国家自然科学基金(21673179,21504067),大学生创新创业训练计划国创项目(201710697038)。


Structure, Thermal Behavior and Thermal Safety of Asymmetric 1,2,4,5-Tetrazine Compounds DPHX and DMHT
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School of Chemical Engineering,Northwest University, Xi'an 710069, China

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    摘要:

    为寻求性能良好的不对称1, 2, 4, 5-四嗪类含能化合物,合成了3-[(对硝基苯基)亚甲基腙]-6-(3, 5-二甲基吡唑)-S-四嗪(DPHX)和3-[(2, 4-二硝基苯基)亚甲基腙]-6-(3, 5-二甲基吡唑)-S-四嗪(DMHT)并培养出单晶,通过元素分析、红外以及X-射线单晶衍射对其结构进行表征。运用差示扫描量热仪(DSC)研究了DPHX和DMHT的热分解行为和热分解动力学,并由Kissinger法计算得到其表观活化能。利用热分解动力学的研究结果对DPHX和DMHT的热安全性进行了研究。结果表明, 二者均为单斜晶系,空间群为P21/c,两种化合物表观活化能分别为176.20 kJ·mol-1和229.29 kJ-mol-1。DPHX的自加速分解温度(TSADT)为191.83 ℃,热点火温度(Tbe)为206.20 ℃,热爆炸临界温度(Tbp)为213.78 ℃,DMHT的TSADT为203.91 ℃,Tbe为212.24 ℃,Tbp为218.34 ℃。因此,DMHT较DPHX热稳定好,热安全性高。

    Abstract:

    To seek forasymmetric 1, 2, 4, 5-tetrazine energetic compounds with good properties, 3-(p-nitrobenzyl methylene)-6-(3, 5-dimethylpyrazol-1-yl)hydrazone-s-tetrazine(DPHX) and 3-(m-dintrobenzyl methylene)-6-(3, 5-dimethylpyrazol-1-yl) hydrazone-s-tetrazine (DMHT) were synthesized, and their single crystals were cultrivate and their structures were characterized by EA, IR and X-ray single crystal diffraction. The thermal decomposition behaviorand thermal decomposition kinetics of DPHX and DMHT were studied by differential scanning calorimeter(DSC). Their apparent activation energies were calculated by Kissinger's method. The thermal safety of DPHX and DMHT was studied by the results of thermal decomposition kinetics. Results show that both of them are monoclinic with space group P21/c. The apparent activation energies of the two compounds are 176.20 and 229.29 kJ·mol-1, respectively. The self-accelerating decomposition temperature (TSADT), thermal ignition temperature (Tbe) and critical temperature of thermal explosion(Tbp) are 191.83, 206.20℃ and 213.78 ℃ for DPHX, respectively, and TSADT=203.91 ℃, Tbe=212.24 ℃, Tbp=218.34 ℃ for DMHT, respectively. Therefore, DMHT is more stable than DPHX and has higher thermal safety.

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引用本文

曾天,韩雪,陈湘,等.不对称1,2,4,5-四嗪类化合物DPHX和DMHT的结构、热行为和热安全性[J].含能材料, 2018, 26(10):856-863. DOI:10.11943/CJEM2018128.
ZENG Tian, HAN Xue, CHEN Xiang, et al. Structure, Thermal Behavior and Thermal Safety of Asymmetric 1,2,4,5-Tetrazine Compounds DPHX and DMHT[J]. Chinese Journal of Energetic Materials, 2018, 26(10):856-863. DOI:10.11943/CJEM2018128.

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历史
  • 收稿日期: 2018-05-10
  • 最后修改日期: 2018-09-19
  • 录用日期: 2018-08-17
  • 在线发布日期: 2018-09-06
  • 出版日期: 2018-10-25