Triazole energetic compound is a kind of interesting nitrogen-rich energetic materials owing to their unique characteristics, such as high nitrogen content, high positive enthalpy and strong power, and are extensively applied to the field of energetic materials, such as insensitive high explosives, propellants and pyrotechnics[1-2].Recently, there are many information about triazole energetic compounds in the available literature, for example, 1, 2, 4-triazole[3-11], 1, 2, 3-triazole[12-16] and their derivatives.However, triazole ionic salts have been paid much more attention owing to higher density and energy, better thermal stability than those of non-ionic salts.
Hydrazinium 3, 5-dinitroamino-1, 2, 4-triazole(HDNAT) is a new and unexplored triazole ionic salt compound(scheme 1) and exhibits excellent thermal stability(194-196 ℃), high nitrogen content(57.01%), high density(1.89 g·cm-3) and detonation velocity(9000 m·s-1 by 1.80 g·cm-3).HDNAT can be applied to the field of propellants and gas-forming agents, especially propellants in order to increase burning rate.
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Scheme1 The synthetic route of HDNAT |
Using nitroguanidine and formaldehyde as starting materials, HDNAT was firstly designed and synthesized by condensation, nitrification and hydrazinolysis reaction(Scheme 1), HDNAT and its intermediates were characterized by the means of NMR, IR and elemental analysis.The properties of physico-chemistry and detonation for HDNAT were obtained by tests and calculation.
2 Experimental 2.1 Synthesis of bis(nitroguanidine) methane(1)Nitroguanidine(10.4 g, 0.10mol), formaldehyde(4.0 mL, 0.05 mol) was added into 60.0 mL of 10% hydrochloric acid at room temperature and the mixture was heated for 1h at 70 ℃.The solution was cooled to 20 ℃, and the white precipitate was filtered to obtain 10.6 g solid with a yield of 96.4%.1H NMR(DMSO-d6, 500 MHz), δ:8.1487(s, 4H, 2NH2), 4.5965(s, 2H, 2NH), 3.3488(s, 2H, CH2); 13C NMR(DMSO-d6, 125 MHz), δ:159.081, 72.858;IR(KBr, ν/cm-1):3420, 3330, 3253, 3118, 2988, 1661, 1596, 1520, 1295, 896;Anal.calcd for C3H8N8O4:C 16.36, H 3.64, N 50.91;found C 16.46, H 3.75, N 51.10.
2.2 Synthesis of 2, 4-dinitroimino-1, 5-dinitro-1, 3, 5-triazine(2)Bis(nitroguanidine) methane(1)(5.0 g, 0.023 mol) was added in batches in nitric acid(24 mL, 100%) and Ac2O(24 mL, 100%) at 0-5 ℃, then the mixture was heated for 3 h at 20 ℃.After 30 min the white precipitate was formed, which was removed by filtration, washed by dichloromethane to obtain 4.8 g solid with a yield of 71.2%, m.p.:100-104 ℃(dec.).1H NMR(DMSO-d6, 500 MHz), δ:12.7553(s, H, NH), 6.2888(s, 2H, CH2); 13C NMR(DMSO-d6, 125 MHz), δ:148.557, 58.998;IR(KBr, ν/cm-1):3169, 3061, 2974, 1654, 1557, 1396, 1296, 899;Anal.calcd for C3H3N9O8:C 12.29, H 1.02, N 43.00;found C 12.52, H 1.32, N 43.21.
2.3 Synthesis of HDNAT2, 4-Dinitroimino-1, 5-dinitro-1, 3, 5-triazine(2)(4.0 g, 13.6 mmol) was dissolved in 40 mL water and hydrazine hydrate(1.8 mL, 27.2 mmol) was added dropwise.The mixture was heated for 30 min at 30 ℃ and the solution was cooled to 10 ℃, and the white precipitate was filtered to obtain 2.8 g solid with a yield of 92.8%, m.p.:194-196 ℃(dec.).1H NMR(DMSO-d6, 500 MHz), δ:7.9228, 13.4263;13C NMR(DMSO-d6, 125 MHz), δ:150.937;IR(KBr, ν/cm-1):3319, 3180, 1586, 1542, 1367, 1253, 983, 719;Anal.calcd for C2H7N9O4:C 10.86, H 3.17, N 57.01;found C 11.09, H 3.26, N 57.37.
2.4 Properties of HDNATTable 1 is some properties of HDNAT.The properties of physico-chemistry and detonation for HDNAT, including the appearance, density, dissolubility and melting point were obtained by the tests.Its detonation properties, such as friction sensitivity, impact sensitivity, H50 and detonation velocity were obtained by national standard method, and detonation pressure was calculated by VLW method[17].
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Tab.1 Properties of HDNAT |
Hydrazinium 3, 5-dinitroamino-1, 2, 4-triazole(HDNAT), a novel triazole ionic salt compound, was synthesized for the first time with a total yield of 63.69% and high nitrogen content of 57.01%, a high density 1.89 g·cm-3 and a high detonation velocity 9000 m·s-1 and a excellent thermal stability.However, HDNAT shows high sensitivity(friction sensitivity of 92%, impact sensitivity of 100% and H50 of 26.8 cm), and might be potentially useful as propellants.
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A novel energetic material,hydrazinium 3,5-dinitroamino-1,2,4-triazole(HDNAT) was designed and synthesized for the first time via condensation,nitrification and hydrazinolysis reaction.In addition,some main properties of physico-chemistry and detonation for HDNAT were obtained by test or calculation.