A Duo and a Trio of Triazoles as Very Thermostable and Insensitive Energetic Materials

Abstract

The triazole moiety with a high heat of formation and a high nitrogen content has been investigated for decades in combination with other nitrogen-rich heterocyclic rings in the field of energetic materials. A novel strategy for the construction of both thermally stable and mechanically insensitive energetic materials using a multi-aminotriazole system is now described. Using this methodology, two series of energetic materials were created on the basis of a duo of triazoles, 5-amino-3-(3,4-diamino-1,2,4-triazol-5-yl)-1H-1,2,4-triazole (TT), and a trio of triazoles, 4,5-di­(3,4-diamino-1,2,4-triazol-5-yl)-2H-1,2,3-triazole (TTT). Their nitrogen-rich salts were also synthesized. Compound TT exhibits an excellent onset decomposition temperature (T d = 341 °C), which is superior to that of the conventional heat-resistant explosive hexanitrostilbene (HNS) (T d = 318 °C). The nitrogen-rich salt 4,5-di­(3,4-diamino-1,2,4-triazol-5-yl)-2H-1,2,3-triazolium 3,4,5-trinitropyrazol-1-ide (TTT-1) exhibits both remarkable detonation properties and low sensitivities (D v = 8715 m s–1; P = 32.6 GPa; IS > 40 J; FS > 360 N), which are superior to those of the traditional explosive LLM-105 (D v = 8639 m s–1; P = 31.7 GPa; IS = 20 J; FS = 360 N). Therefore, this methodology of building a multi-aminotriazole system could effectively assist in the design of thermally stable and mechanically insensitive energetic materials in future exploration.

Design of functionalized bridged 1,2,4-triazole N-oxides as high energy density materials and their comprehensive correlations

“…E ES ¼ 4.60 À 0.733a + 0.724d + 9.16r b/d À 5.14C R,OR (14) where E ES is the electric spark sensitivity in J, r b/d is the ratio of the number of H to O atoms, C R,OR is the existence of alkyl (-R) or alkoxy groups (-OR), while in this study the values of C R,OR were zero. The equations of predicting shock sensitivities are given as eqn ( 15)-( 19 View Article Online…”

“…[8][9][10][11] Prominent families are triazole and tetrazole compounds that have been studied over the last couple of years with growing interest. [12][13][14][15][16] Compared to the single heterocycle ring, bis-azoles with C-C connection show that promising properties arose from the higher heat of formation, which can be proved in good examples 5,5 0 -bistetrazoles 17 and 5,5 0 -bistriazoles. 18 A further way of developing energetic azoles is introducing Noxides onto the ring to improve the oxygen balance without losing energy or stability.…”

High-Energy-Density Materials: An Amphoteric N-Rich Bis(triazole) and Salts of Its Cationic and Anionic Species

“…Indeed, those salts have been prepared and will be described in the present paper, with full characterization of their properties in the solution and solid state, including measurements of the sensitivities in the solid state for the energetic compounds. Some energetic salts of the 1 dication (nitrate and perchlorate) have recently been studied, independently from us, by the groups of Shreeve and Cheng/Yang, with possible application as gas-generating agents, propellants, or explosives. We note that a compound similar to 1 but containing one fewer NH 2 group (% N 67.4) was used by Shreeve in 2010, while another one containing one more NH 2 group (% N 71.4) was described by us. ,, …”

Synthesis and Physicochemical Properties of Energetic 1,2,4,5‐Tetrazinyl Derivatives of 5‐Nitro‐2,4‐dihydro‐1,2,4‐triazol‐3‐one

“…Thus, heat-resistant, low-sensitivity and fast-burning compounds have been obtained. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] Despite the fact that many energetic materials have been synthesized in the series of 1,2,4-triazole, [15][16][17][18][19][20][21][22][23][24][25][26] currently only a few examples of their use in reactions with tetrazine derivatives are known. [27][28][29][30][31][32] These include both symmetrically and unsymmetrically substituted s-tetrazines, linked to the triazole ring (Figure 1).…”