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四氮杂大环含能化合物(TFFA)合成、表征与量子化学研究
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作者单位:

(西安近代化学研究所, 陕西 西安 710065)

作者简介:

王锡杰(1975-),女,副研,主要从事含能材料研究。e-mail: wxj599@126.com

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基金项目:

国防基础研究项目(B0920110051)


Synthesis, Characterization and Quantum Chemisitry Study of an Energetic Tetraaza Macrocyclic Compound(TFFA)
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(Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

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    摘要:

    以3, 4-双(3′-氨基呋咱-4′-基)呋咱氧化呋咱(DATF)和三氯异氰脲酸为原料, 通过氧化反应得到大环含能化合物四呋咱并[3, 4-c:3′′, 4′′-g:3′′′, 4′′′-k:3′′′′′, 4′′′′′-o]双氧化呋咱并[3′, 4′-c:3′′′′, 4′′′′-m] [1, 2, 9, 10]四氮杂环十六辛烯(TFFA), 产率为52.3%。采用核磁共振、红外光谱、质谱和元素分析等表征了结构, 并探讨了三氯异氰脲酸氧化DATF的反应机理。利用差示扫描量热法(DSC)、热重-微商热重法(TG-DTG)等研究了TFFA的热行为, 分解峰温为215.2 ℃, 表明其热稳定性较好。运用B3LYP方法, 在6-31G(d, p)基组水平上对TFFA的结构进行了优化, 在振动分析的基础上得到了温度对热力学性能影响的关系式; 通过Kamlet-Jacobs公式计算并预估了TFFA的物化与爆轰性能, 其密度1.86 g·cm-3、生成焓1905 kJ·mol-1、爆速8775 m·s-1、爆压38.92 GPa和爆热7015 kJ·kg-1

    Abstract:

    An energetic tetraaza macrocyclic compound, tetrafurazano[3, 4-c:3′′, 4′′-g: 3′′′, 4′′′-k:3′′′′′, 4′′′′′-o] furoxano[3′, 4′-c:3′′′′, 4′′′′-m][1, 2, 9, 10]tetraazacyclohexadeoctylene(TFFA)was synthesized by oxidation reaction from 3, 4-bis(4′-aminofurazano-3′-yl)furoxan(DATF) and trichloroisocyanuric acid as starting materials with a yield of 52.3%.Its structure was characterized by 1H NMR, 13C NMR, FT-IR, MS and elemental analysis. The reaction mechanism of DATF oxidation by trichloroisocyanuric acid was preliminarily discussed. The thermal behavior of TFFA was studied by DSC and TG-DTG. The structure of TFFA was optimized by B3LYP method with 6-31G** basis set. On the basis of vibrational analysis, the relationship between the thermodynamics properties and temperatures was obtained. The detonation properties of TFFA were predicted by Kamlet-Jacobs formula. Results show that thermal decomposition peak temperature of TFFA is at 215.2 ℃, which demonstrates that TFFA possesses good thermal stability and the density, detonation velocity, detonation pressure and explosion heat are 1.86 g·cm-3, 8775 m·s-1, 38.92 GPa and 7015 kJ·kg-1, respectively.

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王锡杰,廉鹏,王伯周,等.四氮杂大环含能化合物(TFFA)合成、表征与量子化学研究[J].含能材料, 2015, 23(2):106-112. DOI:10.11943/j. issn.1006-9941.2015.02.001.
WANG Xi-jie, LIAN Peng, WANG Bo-zhou, et al. Synthesis, Characterization and Quantum Chemisitry Study of an Energetic Tetraaza Macrocyclic Compound(TFFA)[J]. Chinese Journal of Energetic Materials, 2015, 23(2):106-112. DOI:10.11943/j. issn.1006-9941.2015.02.001.

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历史
  • 收稿日期: 2013-11-07
  • 最后修改日期: 2014-05-16
  • 录用日期: 2014-05-20
  • 在线发布日期: 2015-02-09
  • 出版日期: 2015-02-12