CHINESE JOURNAL OF ENERGETIC MATERIALS
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NTO·(3,5-DATr)含能离子盐和NTO/IMZ含能共晶的制备、晶体结构及性能
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作者单位:

北京理工大学爆炸科学与技术国家重点实验室, 北京 100081

作者简介:

毕玉帆(1996-),男,硕士研究生,主要从事含能材料的合成研究。e-mail:bitbyf_0182@163.com

通讯作者:

张建国(1974-),男,教授,主要从事含能材料研究。e-mail:zjgbit@bit.edu.cn

基金项目:

国家自然科学基金资助(U1830134)


Preparation, Crystal Structure and Performance Characterization of NTO·(3,5-DATr) Energetic Ionic Salt and NTO/IMZ Energetic Co-crystal
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Affiliation:

State Key Laboratory of Explosion Science and Technology,Beijing Institute of Technology, Beijing 100081, China

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    摘要:

    为改善钝感炸药3-硝基-1,2,4-三唑-5-酮(NTO)的酸性,将NTO分别与3,5-二氨基-1,2,4-三唑(3,5-DATr)、咪唑(IMZ)反应,制备得到了NTO·(3,5-DATr)含能离子盐()和NTO/IMZ含能共晶()。通过溶剂挥发法培养得到了单晶,利用X-射线单晶衍射仪确定了其晶体结构。晶体属于单斜晶系,空间群为P21/cMr=229.19,晶胞参数a=3.5687(7) Å,b=17.245(3) Å,c=14.655(3) Å,β=93.79(3),V=899.9(3) Å3Z=4,Dc=1.692 g·cm-3;晶体属于正交晶系,空间群为PbcnMr=207.17,晶胞参数a=16.9398(16) Å,b=5.6802(5) Å,c=17.9111(19) Å,V=1723.4(3)Å3Z=4,Dc=1.597 g·cm-3。采用差示扫描量热法(DSC)和热失重法(TG)研究了其热分解行为,结果表明二者均具有良好的热稳定性。运用Gaussian 09程序对化合物结构进行优化并计算其生成焓,用EXPLO 5软件对二者的爆速和爆压进行了评估(D=7662.3 m·s-1p=21.0 GPa;D=6490.2 m·s-1p=14.6 GPa)。采用BAM方法测试了其机械感度,结果表明,二者均对撞击和摩擦钝感(IS>40 J,FS>360 N)。利用pH计测试了化合物标样的pH值,在0.01 mol·L-1的标准溶液中NTO,的pH值分别为2.92(22.8 ℃), 4.10(22.7 ℃),4.98(22.8 ℃),表明盐和共晶的形成在一定程度上改善了NTO的酸性。

    Abstract:

    In order to decrease the acidity of insensitive explosive 3-nitro-1,2,4-triazol-5-one (NTO), NTO·(3,5-DATr) energetic ionic salt () and NTO/IMZ energetic co-crystal () were prepared by the reactions of NTO with 3,5-diamino-1,2,4-triazole (3,5-DATr) and imidazole(IMZ). The single crystals were obtained by solvent volatilization, and the crystal structures were measured by single crystal X-ray diffraction. Crystal belongs to monoclinic crystal system, space group P21/c, with Mr=229.19,a=3.5687(7) Å,b=17.245(3) Å,c=14.655(3) Å,β=93.79(3)°,V=899.9(3) Å3Z=4,Dc=1.692 g·cm-3;Crystal belongs to orthorhombic crystal system,space group Pbcn,with Mr=207.17,a=16.9398(16) Å,b=5.6802(5) Å,c=17.9111(19) Å, V=1723.4(3) Å3Z=8, Dc=1.597 g·cm-3. Differential scanning calorimetry (DSC) and thermal weight loss method (TG) were used to test their thermal decomposition properties, and the results show that both and have good thermal stability. The Gaussian 09 program was used to optimize the molecular structures and calculate their enthalpy of formation. Software EXPLO 5 was used to calculate the detonation velocity and pressure ofD=7662.3 m·s-1p=21.0 GPa) and D=6490.2 m·s-1p=14.6 GPa). The mechanical sensitivity was tested by the BAM method. Results show that both of them are insensitive towards impact and friction (IS > 40 J, FS > 360 N). The pH value of standard samples were measured by pH meter. The pH values of NTO, Ⅰ, and in 0.01 mol·L-1 standard solution are 2.92 (22.8 ℃), 4.10 (22.7 ℃), and 4.98 (22.8 ℃), respectively, indicating that the formation of salt and co-crystal significantly decrease the acidity of NTO.

    表 4 Ⅰ和Ⅱ的氢键数据Table 4 Hydrogen bonds present in Ⅰ and Ⅱ
    表 2 Ⅰ和Ⅱ的键长数据Table 2 Bond lengths for Ⅰ and Ⅱ
    表 7 Table 7 Comparison of performances of Ⅰ and Ⅱ with conventional iexplosives TNT and RDX
    表 1 Ⅰ和Ⅱ的晶体结构数据及精修参数Table 1 Crystal data and structure refinement parameters for Ⅰ and Ⅱ
    表 3 Ⅰ和Ⅱ的键角数据Table 3 Bond angles for Ⅰ and Ⅱ
    表 5 Ⅰ和Ⅱ在不同升温速率的第一放热分解峰Table 5 First exothermic decomposition peaks of Ⅰ and Ⅱ at different heating rates
    图1 (a) Ⅰ的晶体结构图 (b) Ⅰ的平面结构 (c) Ⅰ的分子间氢键作用 (d) Ⅰ的晶胞堆积图Fig.1 (a) Crystal structure of Ⅰ(b) Plane structure of Ⅰ (c) Intermolecular hydrogen bonding of Ⅰ (d) Molecular packing diagram of Ⅰ
    图2 (a)Ⅱ的晶体结构图 (b) Ⅱ中H2O分子占比 (c) Ⅱ的分子间氢键作用 (d) Ⅱ的晶胞堆积图Fig.2 (a) Crystal structure of Ⅱ (b) Percentage of H2O molecules in Ⅱ (c) Intermolecular hydrogen bonding of Ⅱ (d) Molecular packing diagram of Ⅱ
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引用本文

毕玉帆,陆祖嘉,董文帅,等. NTO·(3,5-DATr)含能离子盐和NTO/IMZ含能共晶的制备、晶体结构及性能[J].含能材料, 2022, 30(2):111-120. DOI:10.11943/CJEM2021094.
BI Yu-fan, LU Zu-jia, DONG Wen-shuai, et al. Preparation, Crystal Structure and Performance Characterization of NTO·(3,5-DATr) Energetic Ionic Salt and NTO/IMZ Energetic Co-crystal[J]. Chinese Journal of Energetic Materials, 2022, 30(2):111-120. DOI:10.11943/CJEM2021094.

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  • 收稿日期: 2021-04-16
  • 最后修改日期: 2021-05-19
  • 录用日期: 2021-07-20
  • 在线发布日期: 2022-03-17
  • 出版日期: 2022-02-25