CHINESE JOURNAL OF ENERGETIC MATERIALS
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吸电子基取代五唑化合物的热稳定性理论研究
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1.南京理工大学化学与化工学院, 江苏 南京 210094;2.国家民用爆破器材质量监督检验中心, 江苏 南京 210094

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国家自然科学基金(21771108、22135003)


A Theoretical Study on the Stability of Electron Withdrawing Group Substituted Pentazoles
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Affiliation:

1.School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China;2.National Quality Supervision and Inspection Center for Industrial Explosive Materials, Nanjing 210094, China

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    摘要:

    五唑化合物是当前含能材料领域的一个研究热点,但现有五唑化合物的稳定性普遍偏低。为研发性能更优的新型五唑化合物,基于对已有结构的分析,设计了五唑的系列非芳环吸电子基取代衍生物(N5(CH2x-1R,R=—NO2,—CF3,—CN,—CHO,—COOH,x=1,2,3,4),采用密度泛函理论方法,计算了与N5环直接相连的侧链化学键的解离能EBD和N5环的分解能垒Ea,并与部分供电子基取代物的结果进行比较,分析讨论了取代基与相关的键长、键级、键临界点电子密度、N5环的电荷和氧平衡对EBDEa的影响规律。结果表明,所有分子的Ea均远小于EBD,表明N5环的稳定性是决定五唑分子稳定性的关键因素。对于R与N5直接相连的分子(x=1,即N5R),R为吸电子基时的Ea小于R为供电子基或H时的Ea随N5环破裂键键长减小、键级增大及临界点电子密度的增大,Ea总体呈增大趋势。N5环是强吸电子基,直接连接强吸电子或强供电子基会使N5环上的负电荷过少或过多,因而都不利于N5环稳定。

    Abstract:

    Pentazoles are currently a research hotspot in the field of energetic materials, however, the stability of existing pentazoles is generally not high. In order to develop new pentazoles with better properties, based on the analyses of the available structures, 20 substituted derivatives of HN5 with the electron-withdrawing groups, i.e.,N5(CH2x-1R(R=—NO2,—CF3,—CN, —CHO, —COOH; x=1, 2, 3, 4), were designed and studied by using the density functional theory method. The bond dissociation energy (EBD) of the bonds linked with the N5 ring and the activation energy (Ea) of the cracking of the N5 ring were calculated and compared with that of some pentazoles substituted by the electron-donating groups, and the effects of substituents on EBD and Ea were discussed. Results show that the Ea of all molecules is much smaller than EBD, indicating that the stability of the N5 ring is the key factor to determine the stability of the pentazoles. When R is directly connected to the N5 ring (N5R), the Ea of N5R with R being an electron-withdrawing group is smaller than that of N5R with R being an H or an electron-donating group. The N5 ring is a strong electron-withdrawing group, and bearing too much or too little negative charges is not conducive to the stability of the N5 ring.

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引用本文

王靖,高贫,王桂香,等.吸电子基取代五唑化合物的热稳定性理论研究[J].含能材料, 2022, 30(1):12-19. DOI:10.11943/CJEM2021192.
WANG Jing, GAO Pin, WANG Gui-xiang, et al. A Theoretical Study on the Stability of Electron Withdrawing Group Substituted Pentazoles[J]. Chinese Journal of Energetic Materials, 2022, 30(1):12-19. DOI:10.11943/CJEM2021192.

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历史
  • 收稿日期: 2021-07-21
  • 最后修改日期: 2021-11-18
  • 录用日期: 2021-11-15
  • 在线发布日期: 2021-11-17
  • 出版日期: 2022-01-25