Citation: YANG Jin, LIU Qing, REN Yinghui, ZHANG Xianbo, MA Haixia, XU Kangzhen, ZHAO Fengqi, HU Rongzu. A New Energetic Material-Tetrazine Cobalt Salt:Synthesis, Thermal Decomposition Kinetics and Thermal Safety[J]. Chinese Journal of Applied Chemistry, ;2017, 34(8): 928-935. doi: 10.11944/j.issn.1000-0518.2017.08.160466 shu

A New Energetic Material-Tetrazine Cobalt Salt:Synthesis, Thermal Decomposition Kinetics and Thermal Safety

YANG Jin ^a ,
LIU Qing ^a ,
REN Yinghui ^a,, ,
ZHANG Xianbo ^a ,
MA Haixia ^a ,
XU Kangzhen ^a ,
ZHAO Fengqi ^b ,
HU Rongzu ^b

a.
School of Chemical Engineering Northwest University, Xi'an 710069, China
b.
Science and Technology on Combustion and Explosion Laboratory, Xi'an Modern Chemistry Research Institute, Xi'an 710065, China

Corresponding author: REN Yinghui, nwuryh@163.com
Received Date: 17 November 2016
Revised Date: 31 January 2017
Accepted Date: 11 April 2017

Fund Project: the National Defense Pre-Research Foundation of China No.***3401Supported by the National Defense Pre-Research Foundation of China(No.***3401)

Figures(4)

Tetrazine compounds have great applications in energetic materials field, which is attributed to its high energy, insensitivity, high burning rate, low pressure and good thermal stability properties. However, they have disadvantages of low density and thermal stability. To enhance the low properties of tetrazine compounds, a series of the tetrazine derivatives have attracted considerable attention. 3, 6-Bis(1-H-1, 2, 3, 4-tetrazole-5-amino)-1, 2, 4, 5-tetrazine(BTATz), as a high-nitrogen energetic material, has good catalytic performance and application prospect. Therefore, we synthesized 1, 2, 4, 5-tetrazine (s-tetrazine) cobalt salt with potassium salt of BTATz and cobalt nitrate in an aqueous solution. Its structure was characterized with elemental analysis, Fourier transform infrared spectrometer(FTIR) and inductively coupled plasma mass spectrometry(ICP-MS). Its chemical formula is Co(C₄H₂N₁₄)·4H₂O. The thermal behavior and thermal decomposition reaction kinetics were also investigated with differential scanning calorimetric(DSC) and thermal gravimetric-differential thermal gravimetric(TG-DTG) methods. The self-accelerating decomposition temperature(T_SADT), thermal ignition temperature(T_TIT), critical temperature of thermal explosion(T_b) and the adiabatic time-to-explosion(t_TIAD) were calculated as the important parameters to estimate the thermal safety, and the value were 509.69 K, 556.31 K, 524.93 K and 88.40 s, respectively. The adiabatic time-to-explosion is longer than those of Ca salt, Mg salt and Sr salt and the exothermic capacity is higher than that of its ligand BTATz. Therefore, it is expected to be a good combustion catalyst.
- s-tetrazine,
- cobalt salt,
- thermal decomposition mechanism,
- thermal safety
1. [1]
  XUE Jinqiang, SHANG Bingkun, WANG Wei. Research Advances in Tetrazine-based High-nitrogen Molecular and Ionic Energetic Compounds[J]. Chem Propellants Polym Mater, 2011,9(4):91-99.
2. [2]
  Hickey M A, Chavez D E, Naud D. Preparation of 3, 3'-Azobis(6-amino-1, 2, 4, 5-tetrazine):US Patent, 6342589[P], 2002.
3. [3]
  Hickey M A, Chavez D E, Naud D. 3, 6-Bis(1H-1, 2, 3, 4-Tetrazol-5-ylamino)-1, 2, 4, 5-Tetrazine or Salt Thereof:US Patent, 6657059[P], 2003.
4. [4]
  YUE Shouti, YANG Shiqing. Synthesis and Properties of 3, 6-Bis(1H-1, 2, 3, 4-tetrazol-5-yl amino)-1, 2, 4, 5-tetrazine[J]. Chinese J Energ Mater, 2004,12(3):155-157.
5. [5]
  WANG Bozhou, LAI Weipeng, LIU Qian. Synthesis, Characterization and Quantum Chemistry Study on 3, 6-Bis(1H-1, 2, 3, 4-tetrazol-5-yl-amino)-1, 2, 4, 5-tetrazine[J]. Chinese J Org Chem, 2008,28(3):422-428.
6. [6]
  Saikia A, Sivabalan R, Polke B G. Burn Rate Measurements of HMX, TATB, DHT, DAAF, and BTATz[J]. J Hazard Mater, 2009,170(1):306-311. doi: 10.1016/j.jhazmat.2009.04.095
7. [7]
  ZHANG Xinggao, ZHU Hui, YANG Shiqing. Study on Thermal Decomposition Kinetics and Mechanism of Nitrogen-rich Compound BTATz[J]. J Propul Technol, 2007,8(3):322-326.
8. [8]
  Chavez D E, Hiskey M A, Naud D L. Tetrazine Exposives[J]. Propellants Explos Pyrotech, 2004,29(4):209-215. doi: 10.1002/(ISSN)1521-4087
9. [9]
  Son S F, Berghout H L, Bolme C A. Burn Rate Measurements of HMX, TATB, DHT, DAAF, and BTATz[J]. Ptoc Combust Inst, 2000,28(1):919-924. doi: 10.1016/S0082-0784(00)80298-2
10. [10]
  Li N, Zhao F Q, Luo Y. Dissolution Properties of 3, 6-Bis(1H-1, 2, 3, 4-tetrazol-5-ylamino)-1, 2, 4, 5-tetrazine in N-Methyl Pyrrolidone and Dimethyl Sulfoxide[J]. J Solution Chem, 2014,43(7):1250-1258. doi: 10.1007/s10953-014-0198-8
11. [11]
  Zhang X B, Ren Y H, Li W. A Novel Magnesium Salt Based on BTATz:Crystal Structure, Thermal Behavior and Thermal Safety[J]. Chem Res Chinese Univ, 2013,29(4):627-631. doi: 10.1007/s40242-013-2350-1
12. [12]
  Zhang X B, Ren Y H, Li W. 3, 6-Bis(1H-1, 2, 3, 4-tetrazol-5-yl-amino)-1, 2, 4, 5-Tetrazine-Based Energetic Strontium(Ⅱ) Complexes:Synthesis, Crystal Structure and Thermal Properties[J]. J Coord Chem, 2013,66(12):2051-2064. doi: 10.1080/00958972.2013.796040
13. [13]
  REN Yinghui, ZHAO Fengqi, YI Jianhua, et al. Energetic Metal Complexes of BTATz and Its Method of Preparation:CN, 201110149420.2[P], 2011(in Chinese).
14. [14]
  LI Wen, REN Yinghui, ZHAO Fengqi. Nitrogen-rich Energetic Zinc Salt on BTATz:Syntheses and Thermodynamic[J]. J Funct Mater, 2013,44(22):3326-3329. doi: 10.3969/j.issn.1001-9731.2013.22.026
15. [15]
  LI Wen, REN Yinghui, ZHAO Fengqi. Effects of Lead Complex-Based BTATz on Thermal Behaviors, Non-Isothermal Reaction Kinetics and Combustion Properties of DB/RDX-CMDB Propellants[J]. Acta Phys Chim Sin, 2013,29(10):2087-2094. doi: 10.3866/PKU.WHXB201308301
16. [16]
  REN Yinghui, LI Wen, ZHANG Xianbo. Nonisothermal Decomposition Kinetics and Thermal Safety of Ag₂(BTATz)·2H₂O(BTATz=3, 6-Bis(1-H-1, 2, 3, 4-Tetrazole-5-Amino)-1, 2, 4, 5-Tetrazine)[J]. Chinese J Appl Chem, 2013,30(9):1036-1041.
17. [17]
  Yi J H, Zhang F Q, Wang B Z. Thermal Behaviors, Non-isothermal Decomposition Reaction Kinetics, Thermal Safety and Burning Rates of BTATz-CMDB Propellant[J]. J Hazard Mater, 2010,181(3):432-439.
18. [18]
  Yi J H, Zhao F Q, Wang B Z. BTATz-HNIW-CMDB Propellants Decomposition Reaction Kinetics and Thermal Safety[J]. J Therm Anal Calorim, 2014,115(2):1227-1234. doi: 10.1007/s10973-013-3400-0
19. [19]
  ZHANG Chao. Study on New High Burning Rate Component-Derivatives of BTATz:Synthesis, Characterization and Properties[D]. Xi'an:School of Chemical Engineering, Northwest University 2012(in Chinese).
20. [20]
  XU Kangzhen, SONG Jirong, ZHAO Fengqi. Special Heat Capacity, Thermodynamic Properties and Adiabatic Time-to-Explosion of 1, 1-Diamino-2, 2-dinitroethylene[J]. Acta Chim Sin, 2007,65(25):2827-2831.
21. [21]
  Kissinger H E. Reaction Kinetics in Differential Thermal Analysis[J]. Anal Chem, 1957,29(11):1702-1706. doi: 10.1021/ac60131a045
22. [22]
  Ozawa T B. A New Method of Analyzing Thermogravimatric Data[J]. Bull Chem Soc Jpn, 1965,38(11):1881-1886. doi: 10.1246/bcsj.38.1881
23. [23]
  HU Rongzu, SHI Qizhen. Thermal Analysis Kinetics[M]. Beijing:SciencePress, 2001(in Chinese).
24. [24]
  LI Dan. High Nitrogen Organic Metal Complexes and Energetic Ionic Compounds:Synthesis, Structure, Thermodynamic Properties and Theoretical Calculation[D]. Xi'an:School of Chemical Engineering, Northwest University, 2010(in Chinese).
25. [25]
  Ren Y H, Yi J H, Zhao F Q. Synthesis, Decomposition Reaction Kinetics and Thermal Safety of Bismuth Complex of Picric Acid[J]. Chinese J Explos Propellants, 2011,33(5):19-24.
26. [26]
  HUANG Huajiang. Practical Computer Simulation of Chemical Processes-MATLAB's Application in Chemical Engineering[M]. Beijing:Chemical Industry Press, 2004(in Chinese).
27. [27]
  Hu R Z, Gao H X, Zhao F Q. Estimation of Critical Temperature of Thermal Explosion for Some Furazano-fused Cyclic Compouds Using Non-isothermal DSC[J]. Chinese J Energ Mater, 2009,17(6):635-642.
28. [28]
  WANG Yun, FENG Changgen, ZHENG Rao. Prediction of Thermal Safety of Energetic Materials[J]. Chinese J Energy Mater, 2000,8(3):119-121.
29. [29]
  HU Rongzu, GAO Hongxu, ZHAO Fengqi. Thermal Safety of 1, 1'-Dimethyl -5, 5'-azotetrazole and 2, 2'-Dimethyl-5, 5'-azotetrazole[J]. Chinese J Energy Mater, 2011,19(2):126-131.
30. [30]
  ZHANG Xianbo. Synthesis, Crystal Structure, Thermal Properties and Performance of High Nitrogen Tetrazine BTATz Metal Salts/Complexes[D]. Xi'an:School of Chemical Engineering, Northwest University, 2013(in Chinese).
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