化学学报 ›› 2012, Vol. 0 ›› Issue (04): 471-478.DOI: 10.6023/A1106081 上一篇    下一篇

研究论文

含能化合物(AIM)NO3 与(AIM)(HTNR)·H2O 的合成、晶体结构及性质研究

汤崭, 杨利, 乔小晶, 张同来, 张建国, 梁彦会   

  1. 爆炸科学与技术国家重点实验室 北京理工大学 北京 100081
  • 收稿日期:2011-06-08 修回日期:2011-09-08 出版日期:2012-02-28 发布日期:2011-11-01
  • 通讯作者: 杨利
  • 基金资助:

    爆炸科学与技术国家重点实验室(北京理工大学)重点基金(Nos. ZDKT10-01b, ZDKT08-01); 教育部新世纪优秀人才计划(No. NCET-09-0051)资助项目.

Synthesis, Crystal Structure and Thermal Analysis of Two New Energetic Compounds (AIM)NO3 and (AIM)(HTNR)稨2O

Tang Zhan, Yang Li, Qiao Xiaojing, Zhang Tonglai, Zhang Jianguo, Liang Yanhui   

  1. State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081
  • Received:2011-06-08 Revised:2011-09-08 Online:2012-02-28 Published:2011-11-01
  • Supported by:

    Project supported by the Foundation of State Key Laboratory of Explosion Science and Technology (Beijing Institute of Technology) of China (No. ZDKT10-01b, ZDKT08-01), Program for New Century Excellent Talents in University (No. NCET-10-0051).

利用2-叠氮咪唑(AIM)与硝酸(HNO3)和斯蒂芬酸(TNR), 采用直接法合成了新型含能化合物2-叠氮咪唑硝酸盐和2-叠氮咪唑斯蒂芬酸合水, 利用缓慢蒸发溶剂法培养出了可用于X 射线衍射的单晶. 利用X 射线单晶衍射测定了标题化合物的结构, 并利用元素分析和红外光谱的方法对其组成进行了表征. 实验研究表明2-叠氮咪唑硝酸盐晶体属于单斜晶系, 空间群为P21/c, 晶胞参数为a=17.034(3) Å, b=6.5214(13) Å, c=13.095(3) Å, β=111.78(3)°, V=1350.8(5) Å3; Dc=1.693 g/cm3; 分子式为C3N6O3H4, 是由AIM+和NO3- 结合成的离子化合物, 分子中含有大量的氢键, 结构较为稳定. 2-叠氮咪唑斯蒂芬酸合水晶体属于三斜晶系, 空间群为P1, 晶胞参数为a=6.4900(13) Å, b=7.4286(15) Å, c= 15.401(3) Å, α=101.57(3)°, β=98.56(3)°, γ=99.89(3)°, V=703.6(2) Å3; Dc=1.757 g/cm3; 分子式为C9H8N8O9, 是由 AIM+和HTNR-结合成的离子合水化合物. 利用差示扫描量热法(DSC)和热重-微分热重法(TG-DTG)对其热分解进行分析, 结果表明, 在10 ℃/min 的升温速率下, 两个化合物的热分解均出现1 个放热峰, 分解产物主要为气体物质. 最后对标题化合物进行感度性能测试, 结果表明(AIM)NO3 具有一定的火焰感度, 有望作为含能材料应用于相关领域.

关键词: 2-叠氮咪唑, 硝酸, 斯蒂芬酸, 晶体结构, 热分析, 感度

Two new energetic compounds (AIM)NO3 and (AIM)(HTNR)·H2O have been prepared directly by reacting 2-azidoimidazolium with HNO3 and 2,4,6-trinitroresorcinol (TNR). Single crystals suitable for X-ray measurement were obtained. The compounds were characterized by elemental analysis, fourier transform infrared (FTIR) spectra, single crystal X-ray diffraction, differential scanning calorimetry (DSC), and thermogravimetry-differential thermogravimetry (TG-DTG) analysis. (AIM)NO3 belongs to a monoclinic system with P21/c space group and cell parameters of a=17.034(3) Å, b=6.5214(13) Å, c=13.095(3) Å, β=111.78(3)°, V=1350.8(5) nm3; Dc=1.693 g/cm3. The compound is formed by AIM+ and NO3-, and belongs to an ionic compound. There are a lot of intramolecular and intermolecular hydrogen bonds existing in the compound, which makes the compound more stable. (AIM)(HTNR)·H2O belongs to a triclinic system with P1 space group and cell parameters of a=6.4900(13) Å, b=7.4286(15) Å, c=15.401(3) Å, α=101.57(3)°, β=98.56(3)°, γ=99.89(3)°, V=703.6(2) Å3; Dc=1.757 g/cm3. The compound is formed by AIM+ and HTNR-, and belongs to an ionic compound. Under nitrogen atmosphere with a heating rate of 10 ℃/min, the thermal decomposition of the title compounds show that there is only one exothermic process with released gas, respectively. Sensitivities of the title compounds have been studied and the result show that (AIM)NO3 has good flame sensitivity.

Key words: 2-azidoimidazolium, nitric acid, 2,4,6-trinitroresorcinol (TNR), crystal structure, thermal analysis, sensitivity