Nitro-Tetrazole and Its High Nitrogen-Contented Compounds

22 4 2010 4 PROGRESS IN CHEMISTRY Vol. 22 No. 4 Apr. 2010 * 1 1 1 2 1. 100081 2. 621900 5- O626. 28 TQ56 A 1005-281X 2010 04-069-09 Nitro-Tetrazole and Its High Nitrogen-Contented Compounds Li Zhimin 1 Zhang Jianguo 1 Zhang Tonglai 1 Shu Yuanjie 2 1. State Key Laboratory of Explosion Science and Technology Beijing Institute of Technology Beijing 100081 China 2. Institute of Chemical Materials China Academy of Engineering Physics Mianyang 621900 China Abstract Nitro-tetrazole and its high nitrogen-contented compounds are a family of important energetic materials which exhibit the excellent performance and distinctive structure character. Recently they have attracted more and more attention in the field of energetic materials due to their widely potential applications in the areas of primary explosives propellant burning catalyst high energy explosives gas-generating agents and so on. The structure of nitro-tetrazole and its thermal decomposition mechanism are discussed. The process in nitro-tetrazole and its salts as well as coordination complexes are reviewed in this paper in which the synthesis characterization and application about them are mainly summarized. Salts of nitro-tetrazole comprise of alkali metal salts alkaline earth metal salts transition metal salts amine salts and high nitrogen-contented azoles salts according to the difference of the cations. In addition the coordination compounds can be classified to coordination complex cations and coordination complex anions considering the coordinated mode. On this basis the development trends of the nitrotetrazole and its high nitrogen-contented compounds are prospected. Key words high nitrogen compounds green primary explosives nitro-tetrazole Contents 1 Introduction 2 Nitro-tetrazole Salts of nitro-tetrazole. 1 Alkali metal salts 2009 5 2009 8 * No. 10776002 209111200 Corresponding author e-mail zhangjianguobit@ yahoo. com. cn

640 22. 2 Alkaline earth metal salts. Transition metal salts. 4 Amine salts. 5 High nitrogen-contented azoles salts 4 Coordination complexes of nitro-tetrazole 4. 1 Coordination complex cations 4. 2 Coordination complex anions 5 Conclusion and prospects 1 1-2- 5-5 a e 1-2- 5- -1H- 5- -2H- 5- -5H- 5-14 BLYP 6-1G * C- N- 1H- 2H- 1 10 5-5-nitro-tetrazole 5-NT 5-1H- 5 2H- N- 11 5- N N C N N- RDX 6 HMX 4 CL-20 6 N- 12 1 H 1997 2 CH 2 N 4 80. 0% 6 1H- 5C H 1N H 2H- 5H- 5H- H K a = 1. 2 10-5 11 H N- Koldobskii 15 5-20% 4 1 2009 Klap tke 16 5

4 641 5-25% 17 18 X 5- -2H 1 98 10 RDX HMX CL-20 16 16 1 Table 1 Selected crystallographic data of nitro-tetrazole 16 formula CHN 5 O 2 crystal system monoclinic space group P2 1 a / 5. 58 4 b / 9. 4799 7 c / 8. 190 8 β / 106. 99 9 V / 402. 44 6 Z 4 ρ / g cm - 1. 899 5-5-. 1 19 200 17 18 1 1N 2N 2 2 4N 5C 197 Herz 19 5-5- 5-1N 2N Scheme 1 5-1N 2N 4N 5C 5- CuH 5-NT 5-1N 2N CuH 5-NT

642 22 2 Table 2 Physical chemical and energetic properties of salts of nitro-tetrazole 20 formula Li 5-NT H 2 O Na 5-NT 2H 2 O K 5-NT Rb 5-NT Cs 5-NT impact / J 25 > 0 10 5 10 friction / N 24 ~ 60 < 5 < 5 < 5 flame explodes explodes explodes explodes explodes Dec. / 270 200 195 192 194 ρ / g cm - 1. 609 1. 71 2. 027 2. 489 2. 986 - Δ c U / cal g - 1 1 40 15 1 200 20 - Δ c H / kj mol - 1 940 15 850 20 - Δ f H / kj mol - 1 610 55 60 65 Klap tke 20 Scheme 2 5-5- Table 5-19 Selected crystallographic data of alkali metal salts of 5-nitro-tetrazole 19 P1 4 P2 1 / c Cc C2 / c 4 2 8 formula Li 5-NT H 2 O Na 5-NT 2H 2 O K 5-NT Rb 5-NT Cs 5-NT crystal system # mono. triclinic mono. mono. mono. space group P2 1 / c P 1 P2 1 / c Cc C2 / c a / 7. 6556 1 6. 4266 9 4. 8268 11. 915 5 15. 9926 5 b / 1. 0629 2 7. 875 2 1. 1717 8 5. 1626 2 4. 8284 1 c / 7. 54 1 8. 180 7. 942 6 8. 6760 14. 709 4 α / 90 104. 66 2 90 90 90 β / 100. 66 2 109. 78 2 96. 6 7 9. 824 4 104. 607 γ / 90 110. 28 2 90 90 90 V / 722. 8 2 1. 7 2 501. 84 6 52. 4 4 1098. 72 5 Z 4 2 4 4 8 ρ / g cm - 1. 609 1. 71 2. 027 2. 489 2. 986 #mono means crystal system of monoclinic.. 2 TNT TNT RDX 5 Klap tke 21 5-5- 5-180 5- Scheme

4 64 5- Scheme. 22 5-190 5-22 25 29. 5 259. 5 5-0. 04ml g - 1 100 48h 5-5- RDX HMX PETN 5-5- 5-248 5s 070. 2J g - 1 6 0m s - 1 2. 96g cm - 192. 4 5-1976 1981 5-5- HMX CL-20 5- CuHNT NT 2 4H 2 O 5- Ⅱ 5-20 80 Spear 5- Scheme 4 2 Scheme 4 5-1. 8 2. 0g cm - 1. 6 1. 8g cm - 1. 0 1. 4g cm -. 2g cm - 5- RDX HMX C N Scheme 5 5- RDX HMX C N N N 5- Hg N 0. 214 0. 297 10-10 m Hg O TNT RDX 26 28 TNT 29 0 1 2 180 5-1

644 22 Scheme 5 1 Fig. 1 1 Synthesis of amine salts of 5-nitro-tetrazole 1 1 4- -5-1 - -5-1 -4-1 2 4-4 5- -1 2 4-2 7 Klap tke 2 1 5- -4- -5-1 5- -4-5- 1 5- -4- KI 1 5- -4-1 5- -4-5- 5- X 1 5- -4- -5- P2 1 2 1 2 1 4 1. 629g cm - a = 5. 214 1 b = 12. 798 c = 14. 002 2 4 P2 1 / c P2 1 / c C2 / c P2 1 / n P2 1 P2 1 2 1 2 1 6 4 1 7 9 N O S 8. 5 4. 1 5-1 5-

4 645 9 40 Cat x M NT y L 6-y Cat M NT 5- L H 2 O Huynh 41 Hiskey 4 Co Cu Fe Mg Ni Zn Cr 5- H 5-5- 40 2 NH Fig. 2 5-Nitro-tetrazolato-N2-ferrate coordination complex anions and representative cations 40 5-5- 5-5- 4. 2 Huynh 40 20 Co Cu Ni Zn Co ClO - 4 NO - BrO - MnO - 4 N - 2 C NO 2 - N NO 2-2h 40 7

646 22 5- Ⅲ BNCP BNCP 1994 Sandia 5 DDT 5- Ⅲ CP CP Pb N 2 DDT 44 5 BNCP Co NH 4 CO NO CTCN 2. 5h Na N 4 CNO 2 NaNT 5- NaOH BNCP 44 BNCP P2 1 / n 45 a = 10. 0149 11 b = 10. 587 11 β = 109. 0140 10 c = 14. 8241 16 V = 1479. 2 Z = 4 Kissinger BNCP 178. kj mol - 1 Ozawa BNCP 260 278 54 4 4 2 Talawar M B Sivabalan R Mukundan T et al. J. Hazard. 54 4 Mater. 2009 161 589 607 Table 4 Sensitivity of nitro-tetrazole complexes 54 Dickson P M Field J E. Proc. R. Soc. Lond. A. 199 411 item BNCP BNNP MNCuP MNZnP impact h 50% / cm 2 0 0 6 friction / N 0 0 4. 8 140 BNCP 187. 5kJ mol - 1 10 min - 1 BNCP 289. 6 10% BNCP 46 1628 BNCP Talawar 54 400 5- BNNP 5- MNZnP 20 5- MNCuP 4 BNCPMNZnP 160 1 Badgujar D M Talawar M B Asthana S N et al. J. Hazard. Mater. 2008 151 289 05 59 75 4 Yang S Q Xu S L Lei Y P. Chinese Journal of Energetic Materials 2006 14 6

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