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新型低感含能材料N-(氟偕二硝基乙基)-1,5-二氨基四唑-1H的晶体结构及其热稳定性
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作者单位:

1.中国工程物理研究院化工材料研究所, 四川 绵阳 621999;2.西南石油大学材料科学与工程学院, 四川 成都 610500

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国家自然科学青年基金项目(11402237)和国家自然科学基金-中国工程物理研究院联合基金重点项目(U1530262)中国工程物理研究院科学技术发展基金项目(2015B0302055)


Crystal Structure and Thermal Stability of the Novel Low-Sensitive Energetic Material N-(2-fluoro-2,2-dinitroethyl)-1,5-diaminotetrazole-1H
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Affiliation:

1.Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621999, China;2.School of Materials Science and Engineering, Southwest Petroleum University, Chengdu 610500, China

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    摘要:

    以1,5-二氨基四唑-1H、氟偕二硝基乙醇为原料,在常温下通过曼尼希反应一步合成了N-(氟偕二硝基乙基)-1,5-二氨基四唑-1H。采用X-射线单晶衍射分析表征了其单晶结构,表明其属于斜方晶系,空间群Pca21,173 K下的晶体密度为1.77 g·cm-3;采用Hirshfeld表面对晶体中各种作用进行了分析,晶体内占主导地位的分子间相互作用及其分布为(R为比例缩写):RO…H / H…O=27.0%,RN…H/H…N=21.5%,RF…O/O…F/F…H/H…F/N…F/F…N=15.9%,主要为氢键及卤键作用;采用热重及差示扫描量热分析(TG-DSC)研究了其热稳定性,5 ℃·min-1升温速率下,只有一个尖锐的分解峰温177.32 ℃,质量损失为92.53%,化合物分解较完全;用Kissinger法与Ozawa法分别计算了其活化能EK=213.228 kJ·mol-1EO=209.984 kJ·mol-1。采用场发射-扫描电镜(FE-SEM)观察了产物的微观形貌,其具有类似空间网状的多孔结构。

    Abstract:

    N-(2-fluoro-2, 2-dinitroethyl) -1, 5-diaminotetrazole-1H was synthesized by a one-step Mannich reaction under mild conditions using 1, 5-diaminotetrazole-1H and 2, 2-fluorodinitroethanol as starting materials. Its molecular structure was deter- mined by X-ray single crystal diffraction analysis. It crystallizes in orthorhombic system, space group Pca21, with a crystal densi- ty of 1.77 g·cm-3 at 173 K. The different interactions in crystal were analyzed by Hirshfeld surface. In the analysis, the dominant intermolecular interactions in the crystal and their distributions were (R is a proportional abbreviation):RO…H/H…O=27.0%, RN…H/H…N=21.5%, RF…O/O…F/F…H/H…F/N…F/F…N=15.9%, mainly hydrogen bonding and halogen bonding interactions. The thermal stability was studied by thermogravimetry and differential scanning calorimetry(TG-DSC). At a heating rate of 5 ℃·min-1, there was only one sharp decomposition peak with the temperature at 177.32 ℃, and the mass loss was 92.53% demonstrating a nearly complete decomposition at such temperature. Its activation energy were calculated by using Kissinger method and Ozawa method as 213.228 kJ·mol-1, 209.984 kJ·mol-1 respectively, which were shown. A spatial reticulated porous structure were observed according to the field emission-scanning electron microscopy(FE-SEM)analyses.

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李杰,张国杰,马卿,等.新型低感含能材料N-(氟偕二硝基乙基)-1,5-二氨基四唑-1H的晶体结构及其热稳定性[J].含能材料, 2018, 26(11):945-950. DOI:10.11943/CJEM2018189.
LI Jie, ZHANG Guo-jie, MA Qing, et al. Crystal Structure and Thermal Stability of the Novel Low-Sensitive Energetic Material N-(2-fluoro-2,2-dinitroethyl)-1,5-diaminotetrazole-1H[J]. Chinese Journal of Energetic Materials, 2018, 26(11):945-950. DOI:10.11943/CJEM2018189.

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  • 收稿日期: 2018-07-10
  • 最后修改日期: 2018-10-07
  • 录用日期: 2018-09-04
  • 在线发布日期: 2018-09-18
  • 出版日期: 2018-11-25