Journal of the Korean Society of Propulsion Engineers (한국추진공학회지)

The Korean Society of Propulsion Engineers (한국추진공학회)
권호 표지
DOI QR코드

DOI QR Code

Synthesis and Characterization of Tetrazine Derivatives as High Energy Propellants

테트라진 계열의 추진 물질 합성 연구

  • Lee, Woonghee (Energetic Materials & Pyrotechnics Department, Hanwha Corporation Defence R&D Center) ;
  • Park, Youngchul (Advanced Propulsion Technology Center, Agency for Defense Development) ;
  • Joo, Young-Hyuk (Energetic Materials & Pyrotechnics Department, Hanwha Corporation Defence R&D Center)
  • Received : 2013.06.01
  • Accepted : 2013.10.25
  • Published : 2013.12.01
Download PDF
⟨ Previous Next ⟩

Abstract

Traditional propellants release toxic gases during combustion that are harmful to the environment. This study describes a novel synthetic process of two high nitrogen containing tetrazines, TATTz and BTATz, which can be adapted as solid fuels for a solution to environmental concerns. The compounds were characterized by NMR, IR spectroscopy, and differential scanning calorimetry(DSC). Detonation properties were calculated with the EXPLO5 program based on calculated heats of formation and measured densities.

기존에 사용되어 온 추진제들은 연소 시 많은 양의 유해가스 발생으로 환경적인 문제점이 있다. 본 논문에서는 이러한 문제점을 개선하기 위하여 고체 연료로 적용 가능한 tetrazine 계열의 저탄소 고질소 화합물인 TATTz와 BTATz에 대한 합성공정을 확립하였다. 또한, 문헌에 빠져있는 구체적인 공정법 및 특성 분석 결과를 서술하였다. 합성된 모든 물질들은 분광분석 (NMR, IR)을 이용한 구조분석, DSC를 이용한 열분석, 측정된 밀도와 계산된 생성열을 근거로 폭발속도, 폭발압력 등을 계산하였다(EXPLO5).

Keywords

References

  1. Chavez, D.E., Gilardi, R.D. and Hiskey, M.A. "3,3-Azobis(6-amino-1,2,4,5- tetrazine): a novel high-nitrogen energetic material," Angewante Chemie International Edition, Vol. 39, No. 10, May, pp. 1791-1793, 2000. https://doi.org/10.1002/(SICI)1521-3773(20000515)39:10<1791::AID-ANIE1791>3.0.CO;2-9
  2. Chavez, D.E. and Hiskey, M.A., "1,2,4,5-Tetrazine based energetic materials," Journal of Energetic Materials, Vol. 17, pp. 357-377, 1999. https://doi.org/10.1080/07370659908201796
  3. Boger, D.L. and Weinreb, S.M., Hetero Diels-Alder Methodology in Organic Synthesis, Academic Press, New York, pp. 239-299, 1987.
  4. Panek, J.S. and Zhu, B., "Synthesis of aromatic 1,2-diazines by inverse electron demand Diels-lder reaction of polymer-supported 1,2,4,5-tetrazines," Tetrahedron Letters, Vol. 37, pp. 8151-8154, 1996. https://doi.org/10.1016/0040-4039(96)01866-7
  5. Boger, D.L., Coleman, R.S., Panek, J.S. and Yohannes, D.J., "Thermal cyclo addition of dimethyl 1,2,4,5-tetrazine-3, 6-dicarboxylate with electron-rich olefins: 1,2-diazine and pyrrole introduction. Preparation of octamethylporphin (OMP)," Journal of Organic Chemistry, Vol. 49, pp. 4405-4409, 1984. https://doi.org/10.1021/jo00197a015
  6. Boger, D.L. and Zhang, M.J., "Total synthesis of (${\pm}$)-cis and (${\pm}$)-trans-Trikentrin A: Diels-Alder reactions of heteroaromatic azadienes," Journal of the American Chemical Society, Vol. 113, pp. 4230-4234, 1991. https://doi.org/10.1021/ja00011a026
  7. Audebert, P., Sadki, S., Miomandre, F., Clavier, G., Vernieres, M.C., Saoud, M. and Hapiot, P., "New functionalized tetrazines: synthesis, electrochemical and spectroscopic properties," New Journal of Chemistry, Vol. 28, pp. 387-392, 2004. https://doi.org/10.1039/b310737j
  8. Novak, Z., Bostai, B., Csekei, M., Lorincz, K. and Kotschy, A., "Selective nucleofilic substitution on tetrazines," Heterocycles, Vol. 60, pp. 2653-2668, 2003. https://doi.org/10.3987/COM-03-9875
  9. Farago, J., Novak, Z., Schlosser, G., Csampai, A. and Kotschy, A., "The azaphilic addition of organometallic reagents on tetrazines: scope and limitations," Tetrahedron, Vol. 60, pp. 1991-1996, 2004. https://doi.org/10.1016/j.tet.2004.01.013
  10. Wilkes, M.C., "Azaphilic addition of methyl lithium to 3,6-bisalkylthio-1,2,4,5- tetrazines: a remarkable dochotomy," Journal of Heterocyclic Chemistry, Vol. 28, pp. 1163-1164, 1991. https://doi.org/10.1002/jhet.5570280457
  11. Novak, Z. and Kotschy, A., "The first cross-coupling reactions on tetrazines," Organic Letters, Vol. 5, pp. 3495-3497, 2003. https://doi.org/10.1021/ol035312w
  12. Glidewell, C., Lightfoot, P., Royles, B.J.L. and Smith, D.M.J., "The inverse electrondemand Diels-Alder reaction in polymer synthesis. Part 4. The preparation and crystal structures of some bis(1,2,4,5-tetrazines)," Journal of Chemical Society Perkin Trans. 2, pp. 1167-1174, 1997.
  13. Sakya, S.M., Groskopf, K.K. and Boger, D.L., "3-Methoxy-6-methylthio-1,2,4,5-tetra zine," Tetrahedron Letters, Vol. 38, pp. 3805-3808, 1997. https://doi.org/10.1016/S0040-4039(97)00751-X
  14. Boger, D.L., Schaum, R.P. and Garbaccio, R.M., "Regioselective inverse electron demand Diels-Alder reactions of N-acyl 6-amino-3-methylthio-1,2,4,5-tetrazines," Journal of Organic Chemistry, Vol. 63, pp. 6329-6337, 1998. https://doi.org/10.1021/jo980795g
  15. Chavez, D.E., Hiskey, M.A. and Naud, D.L., "Tetrazine explosives," Propellants, Explosives, Pyrotechnics, Vol. 29, pp. 209-215, 2004. https://doi.org/10.1002/prep.200400050
  16. Kerth, J., and Lobbecke, S., "Synthesis and Characterization of 3,3'-Azobis(6-Amino-1,2,4,5-Tetrazine) DAAT - A New Promising Nitrogen-Rich Compound," Propellants, Explosives, Pyrotechnics, Vol. 27, pp. 111-118, 2004.
  17. Chavez, D.E. Hiskey, M.A. and Gilardi, R. D., "Novel high-nitrogen materials based on nitroguanyl substituted tetrazines," Organic Letters, Vol. 6, pp. 2889-2891, 2004. https://doi.org/10.1021/ol049076g
  18. Koppes, W.M. and Sitzmann, M.E., "Low-Smoke Gas Generating Low Order Pressure Pulse Compositions," US 7,220,328, 2007.
  19. Koppes, W., Insensitive Munition & Energetic Materials Technology Symposium, Bristol, UK, 2006.
  20. Koppes, W. and Sitzmann, M., "Triazolyl-Aminotriazine Compositions, Including Salts," US 6,846,926, 2005.
  21. Koppes, W.M., Sitzmann, M.E. and Gilardi, R.D., Proceedings International Pyrotechnics Seminars, Vol. 29, pp. 711-714, 2002.
  22. Joo, Y.H., Twamley, B., Garg, S. and Shreeve, J.M., "Energetic Nitrogen-Rich Derivatives of 1,5-Diaminotetrazole," Angewante Chemie International Edition, Vol. 47, pp. 6236-6239, 2008. https://doi.org/10.1002/anie.200801886
  23. Parr, R.G. and Yang, W., Density Functioal Theory of Atoms and Molecules, Oxford University Press, New York, 1989.
  24. Ye, C., Shreeve, J.M., "Rapid and Accurate Estimation of Densities of Room-Temperature Ionic Liquids and Salts," Journal of Physical Chemistry A, Vol. 111, pp. 1456-1461, 2007. https://doi.org/10.1021/jp066202k
  25. Ye, C., Shreeve, J.M., "New Atom/Group Volume Additivity Method to Compensate for the Impact of Strong Hydrogen Bonding on Densities of Energetic Materials," Journal of Chemical Engineering Data, Vol. 53, pp. 520-524, 2008. https://doi.org/10.1021/je700617n
  26. Teipel, U., Energetic Materials, VCH, Weinheim, 2005.