Citation: LI Jing, CHEN Li-Zhen, WANG Jian-Long, LAN Guan-Chao, HOU Huan, LI Man. Crystal Structure and Thermal Decomposition Kinetics of Byproduct of Synthesis of RDX: 3,5-Dinitro-1-oxygen-3,5-diazacyclohexane[J]. Acta Physico-Chimica Sinica, ;2015, 31(11): 2049-2056. doi: 10.3866/PKU.WHXB201510092 shu

Crystal Structure and Thermal Decomposition Kinetics of Byproduct of Synthesis of RDX: 3,5-Dinitro-1-oxygen-3,5-diazacyclohexane

1.
School of Chemical Engineering and Environment, North University of China, Taiyuan 030051, P. R. China

Corresponding author: WANG Jian-Long,
Received Date: 16 July 2015
Available Online: 8 October 2015
Fund Project: 国家自然科学基金(11447219) (11447219)

A new cyclic byproduct was formed during hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) preparation by direct nitration. Silicone column chromatography with acetone and dichloromethane in various ratios as the eluent was used to separate 3,5-dinitro-1-oxygen-3,5-diazacyclohexane from the product mixture. A single crystal of 3,5-dinitro-1-oxygen-3,5-diazacyclohexane was grown from acetone, and characterized using elemental analysis, Fourier-transform infrared (FTIR) spectroscopy, ¹H nuclear magnetic resonance (NMR) spectroscopy, and mass spectrometry (MS). Its structure was determined using an X-ray single-crystal diffractometer. The results indicate that the crystal molecular weight is 178.12. It belongs to the monoclinic system with the space group P121/n1, a = 0.58128(13) nm, b = 1.72389(14) nm, c = 0.71072(6) nm, β = 112.056°, V = 0.66006(16) nm³, Z = 4, D_C= 1.792 g·cm^-3, μ = 0.17 mm^-1, and F(000) = 368.0; the final deviation factor R is 0.0397. Differential scanning calorimetrythermogravimetry (DSC-TG) was used to investigate the thermal behavior of the title compound. Sharp peaks were observed at 383.15 K (melting) and 519.05 K (decomposition). The kinetic parameters were obtained using the Kissinger and Flynn-Wall-Ozawa methods and the TG data at different heating rates. The Coats-Redfern method was used to study the thermal decomposition mechanism of 3,5-dinitro-1-oxygen-3,5-diazacyclohexane. The results show that the title compound is a low-melting-point compound with good stability; its apparent activation energy and pre-exponential factor, calculated using the Kissinger equation, are 212.32 kJ·mol^-1 and 6.20×10²⁰ s^-1, respectively. The apparent activation energy, calculated using the Flynn-Wall-Ozawa equation, is 210.39 kJ·mol^-1. G(α) = (1-α)^-1-1 (n = 2) obtained using Coats-Redfern method is regarded as the most appropriate thermal decomposition kinetic equation.
- RDX,
- 3,5-Dinitro-1-oxygen-3,5-diazacyclohexane,
- Crystal structure,
- Thermal decomposition kinetics,
- Apparent activation energy,
- Mechanism
1. [1]
  (1) Ren, T. S. Chemistry and Technology of Nitramine and Nitrate Explosives; Ordnance Industry Press: Beijing, 1994; pp 27-41. [任特生. 硝胺及硝酸酯炸药化学与工艺学. 北京: 兵器工业出版社, 1994: 27-41.]
2. [2]
  (2) Bachmann, W. E. J. Am. Chem. Soc. 1949, 71 (5), 1842. doi: 10.1021/ja01173a092
3. [3]
  (3) Duiming, W. J.; Millard, B.; Nutt, C. W. J. Chem. Soc. 1952, 1264.
4. [4]
  (4) Willson, F. G.; Forster, A.; Rorberts, E. Cyclo-Trimethyle-netrinitramine. US, 2525252, 1950-10-10.
5. [5]
  (5) Agrawal, J. P.; Hodgson, R. D. J. Hazard. Mater. 2007, 1-2 (146), 431.
6. [6]
  (6) Wang, Q. L. Ammonium Nitrate Explosive; National Defense Industry Press: Beijing, 1984; p 150. [王起来. 硝铵炸药. 北京: 国防工业出版社, 1984: 150.]
7. [7]
  (7) Yu, X. H. Discussion about Nitrolysis Method of RDX. In Conference Proceedings on China Material Seminar, China Material Seminar, Beijing, 2002. [余咸旱. 关于黑索今硝解方法的探讨. 2002年中国材料研讨会论文集. 北京: 中国材料研究会, 2002.]
8. [8]
  (8) Gilpin, V.; Winkler, C. A. Can. J. Chem. 1952, 10 (30), 743.
9. [9]
  (9) Bell, J. A.; Dunstan, I. J. Chem. Soc. 1969, 11 (5), 1559.
10. [10]
  (10) Fang, Z. J.; Wang, S. F.; Chen, J.; Li, F. P. Chin. J. Explos. Propell. 1992, No. 1, 45. [方志杰, 王绍芳, 陈驹, 李福平. 火炸药学报, 1992, No. 1, 45.]
11. [11]
  (11) He, Z. Y.; Luo, J.; Lü , C. X.; Wang, P.; Xu, R.; Li, J. S. J. Energ. Mater. 2012, 20 (1), 5. [何志勇, 罗军, 吕春绪, 汪平, 徐蓉, 李金山. 含能材料, 2012, 20 (1), 5.]
12. [12]
  (12) Song, H. Y.; Wang, P.; Qin, G. M.; Ge, Z. X.; Wang, B. Z.; Meng, Z. H.; Li, Q. X. Chin. J. Org. Chem. 2010, 30 (3), 414. [宋红燕, 王鹏, 覃光明, 葛忠学, 王伯周, 孟子晖, 李清霞. 有机化学, 2010, 30 (3), 414.]
13. [13]
  (13) Yu, B. Study of Nitrolysis Mechanism during RDX Synthesis by Direct Nitration in Acid Ionic Liquid. M. S. Dissertation, Nanjing University of Science & Technology, Nanjing, 2009. [郁波. 酸性离子液体催化下直接法合成黑索金及硝解机理研究[D]. 南京: 南京理工大学, 2009.]
14. [14]
  (14) Shen, Y.; Li, Y. X.; Gao, Z. Q.; Tan, Q. Q.; Wang, J. L.; Cao, D. L. Chem. Ind. Eng. Prog. 2014, 33 (4), 1041. [沈勇, 李永祥, 高志强, 谭情请, 王建龙, 曹端林. 化工进展, 2014, 33 (4), 1041.]
15. [15]
  (15) Fang, Z. J.; Wang, S. F.; Chen, J.; Chen, L.; Li, F. P. Chin. J. Explos. Propell. 1992, No. 3, 1. [方志杰, 王绍芳, 陈驹, 陈里, 李福平. 火炸药学报, 1992, No. 3, 1.]
16. [16]
  (16) Zuo, J. Q. Solving and Analysis of Activation Energy in Thermal Analysis. M. S. Dissertation, Nanjing University of Science & Technology, Nanjing, 2006. [左金琼. 热分析中活化能的求解与分析[D]. 南京: 南京理工大学, 2006.]
17. [17]
  (17) Liu, Z. H. Introduction to Thermal Analysis, 1st ed.; Chemical Industry Press: Beijing, 1991. [刘振海. 热分析导论[M]. 第一版. 北京: 化学工业出版社, 1991.]
18. [18]
  (18) Sheldrick, G. M. SHELXS-97, Program for X-ray Crystal Structure Refinement; Gö ttingen University: Germany, 1997.
19. [19]
  (19) Sheldrick, G. M. SHELXS-97, Program for X-ray Crystal Structure Solution; Gö ttingen University: Germany, 1997.
20. [20]
  (20) Gotor, F. J.; Criado, J. M. Thermochim. Acta 2002, 383 (1-2), 53. doi: 10.1016/S0040-6031(01)00658-X
21. [21]
  (21) Choi, C. S.; Prince, E. Acta Crystallogr. B 1972, No. 28, 2857.
22. [22]
  (22) Kissinger, H. E. Anal. Chem. 1957, 29 (11), 1702. doi: 10.1021/ac60131a045
23. [23]
  (23) Ozawa, T. Bull. Chem. Soc. Jpn. 1965, 38 (11), 1881. doi: 10.1246/bcsj.38.1881
24. [24]
  (24) Schawe, J. E. K. Thermochim. Acta 2002, 388 (1-2), 299. doi: 10.1016/S0040-6031(02)00041-2
25. [25]
  (25) Coats, A. W.; Redfern, J. P. Nature 1964, 201 (4914), 68. doi: 10.1038/201068a0
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