High-energy super-heat-resistant explosive and synthesis method thereof
Patent Information
- Application Number
- CN202411057600.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-02
- Publication Date
- 2026-02-03
AI Technical Summary
大多数耐热含能化合物的制备相当复杂，热分解温度高于350℃的耐热含能材料(Td>350℃，与TATB相当)仍然很少
[0018] (1) The synthesis method of the present application is simple, one-step synthesis, the experimental process is safe and efficient, and meets the conditions for scale-up production.
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Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the field of energetic materials, and relates to a high-energy super-heat-resistant explosive and a synthesis method thereof, in particular to a high-energy super-heat-resistant explosive N2-(5-amino-4-nitro-1H-pyrazol-3-yl)-N6-(3-amino-4-nitro-1H-pyrazol-5-yl)-3,5-dinitropyridine-2,4,6-triamine and a synthesis method thereof. BACKGROUND
[0002] High-energy materials (EM) are a specific class of metastable compounds that can release a large amount of energy very rapidly upon initiation. Generally, EMs with high thermal decomposition temperatures (T d > 250℃) are usually classified as heat-resistant explosives. In recent years, due to the wide application of high-heat-resistant explosives in military, civil and aerospace fields, great attention has been paid to the development of high-heat-resistant explosives.
[0003] The existing conventional energetic materials are not stable enough under high-temperature and high-pressure environment for a long time and are easy to decompose. Therefore, the development of heat-resistant explosives is of great significance to the progress of national defense equipment, aerospace technology and modern industrial development. The preparation of most heat-resistant energetic compounds is quite complex, and heat-resistant energetic materials (T d > 350℃, comparable to TATB) with a thermal decomposition temperature higher than 350℃ are still rare. At the same time, the low detonation performance of super-heat-resistant explosives still needs to be solved. So far, there are very few super-heat-resistant explosives with detonation performance comparable to that of commonly used secondary explosive RDX (detonation velocity: 8795m / s -1 ). SUMMARY
[0004] The application provides a high-energy super-heat-resistant explosive and a synthesis method thereof.
[0005] The high-energy super-heat-resistant explosive provided by the application is N2-(5-amino-4-nitro-1H-pyrazol-3-yl)-N6-(3-amino-4-nitro-1H-pyrazol-5-yl)-3,5-dinitropyridine-2,4,6-triamine (UH-1), and its structural formula is as follows:
[0006]
[0007] The synthesis method of the high-energy super-heat-resistant explosive provided by the application comprises the following steps:
[0008] 2,6-dichloro-3,5-dinitropyridin-4-amine (I) and 4-nitro-1H-pyrazole-3,5-diamine (II) are reacted in an organic solvent to produce N2-(5-amino-4-nitro-1H-pyrazol-3-yl)-N6-(3-amino-4-nitro-1H-pyrazol-5-yl)-3,5-dinitropyridine-2,4,6-triamine (UH-1), and the reaction formula is as follows:
[0009]
[0010] Preferably, the molar ratio of 2,6-dichloro-3,5-dinitropyridin-4-amine and 4-nitro-1H-pyrazole-3,5-diamine is 1:2.0-3.0.
[0011] Preferably, the organic solvent is acetone, acetonitrile, methanol, ethanol, N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO). In the specific mode of the present application, DMF and DMSO are taken as examples.
[0012] Preferably, the reaction temperature is 25-120℃, more preferably 80-120℃, and the reaction time is 1-24h, more preferably 3-12h.
[0013] Preferably, after the reaction is completed, the reaction solution is subjected to the following post-treatment: the reaction solution is cooled to room temperature, water is added and stirred, a precipitate is separated out, the precipitate is collected by filtration, washed with ice water, and dried to obtain N2-(5-amino-4-nitro-1H-pyrazol-3-yl)-N6-(3-amino-4-nitro-1H-pyrazol-5-yl)-3,5-dinitropyridine-2,4,6-triamine.
[0014] Preferably, the volume ratio of the organic solvent and water is 1:2-100, and the stirring time is 2-48h.
[0015] Preferably, the volume ratio of the organic solvent and ice water is 1:2-10.
[0016] Preferably, the drying temperature is 30-50℃, and the drying time is 2-48h.
[0017] Compared with the prior art, the present application has the following advantages:
[0018] (1) The synthesis method of the present application is simple, one-step synthesis, the experimental process is safe and efficient, and meets the conditions for scale-up production.
[0019] (2) The UH-1 of the present application exhibits the highest detonation velocity among the super heat-resistant explosives (thermal decomposition temperature > 350℃) so far, and the detonation velocity can reach 8889m / s -1This solves the problem of low detonation performance of ultra-heat resistant explosives. Meanwhile, UH-1's overall performance (thermal decomposition temperature: 365℃, detonation velocity: 8889 m / s) is also improved. -1 (Sensitivity: 360N, 35J) is superior to the currently classic superheat-resistant explosive triaminotrinitrobenzene (TATB, thermal decomposition temperature: 350℃, detonation velocity: 8179m / s, sensitivity: 360N, 50J), and has the potential to replace the heat-resistant explosives TATB and hexanitrozimine (HNS). Attached Figure Description
[0020] Figure 1 The crystal structure diagram of N2-(5-amino-4-nitro-1H-pyrazol-3-yl)-N6-(3-amino-4-nitro-1H-pyrazol-5-yl)-3,5-dinitropyridine-2,4,6-triamine;
[0021] Figure 2 The 1H NMR spectrum of (N2-(5-amino-4-nitro-1H-pyrazol-3-yl)-N6-(3-amino-4-nitro-1H-pyrazol-5-yl)-3,5-dinitropyridine-2,4,6-triamine;
[0022] Figure 3 The carbon spectrum of N2-(5-amino-4-nitro-1H-pyrazole-3-yl)-N6-(3-amino-4-nitro-1H-pyrazole-5-yl)-3,5-dinitropyridine-2,4,6-triamine. Detailed Implementation
[0023] The present invention will be further described below with reference to specific embodiments and accompanying drawings.
[0024] In the examples below, 2,6-dichloro-3,5-dinitropyridine-4-amine was prepared according to reference [New J. Chem. 2018, 42, 11259-11263], and 4-nitro-1H-pyrazole-3,5-diamine was prepared according to reference [Tetrahedron Lett. 2003, 44, 5943-5945].
[0025] Example 1
[0026] (1) 4-Nitro-1H-pyrazole-3,5-diamine (0.42 g, 2.0 mmol) was dissolved in 10 mL of DMF, and 2,6-dichloro-3,5-dinitropyridine-4-amine (0.25 g, 1.0 mmol) was added. The reaction was carried out at 80 °C for 3 hours. After cooling to 25 °C, 100 mL of water was added to the DMF solution, resulting in a large amount of precipitate. The precipitate was collected by filtration, washed with 50 mL of ice water, and dried for 10 hours to obtain 0.41 g of compound UH-1 as a brown solid, with a yield of 88.9%.
[0027] 1 H NMR (500 MHz, DMSO d6): δ = 7.32 (s, 2H), 8.39 (s, 6H) ppm. 13 C NMR (126 MHz, DMSO d6): δ = 114.04, 139.91, 141.65, 147.15, 147.95, 151.32 ppm. IR (KBr): 3351.5, 3325.6, 3255.4, 3061.7, 3058.1, 1645.3, 1593.4, 1571.7, 1514.8, 1509.3, 1473.0, 1441.0, 1393.8, 1358.7, 1340.7, 1315.7, 1248.3, 1235.3, 1192.0, 1184.3, 1050.7, 798.9, 747.8, 738.6, 650.3, 328.0, 379.7, 277.4, 273.0, 237.5, 185.0 cm -1 Elemental analysis for C 11 H 10 N 14 O8(466.29): calcd C, 28.33; H, 2.16; N, 42.05 %. Found: C 28.31, H 2.20, N 42.03 %.
[0028] Example 2
[0029] 4-nitro-lH-pyrazole-3,5-diamine (0.63 g, 3.0 mmol) was dissolved in 20 mL DMF and 2,6-dichloro-3,5-dinitropyridin-4-amine (0.25 g, 1.0 mmol) was added. The reaction was carried out at 100 °C for 12 hours. After cooling to 25 °C, 500 mL water was added to the DMF solution, resulting in a large amount of precipitate. The precipitate was collected by filtration, washed with 50 mL ice water, and oven dried for 5 hours to obtain compound UH-l as a brown solid, 0.33 g in 60.9% yield.
[0030] Example 3
[0031] Compound UH-1 was obtained as a brown solid, 0.37 g in total, in a yield of 80.0% after 4-nitro-lH-pyrazole-3,5-diamine (0.42 g, 2.0 mmol) was dissolved in 10 mL of DMSO and 2,6-dichloro-3,5-dinitropyridin-4-amine (0.25 g, 1.0 mmol) was added. The reaction was carried out at 120 °C for 5 hours. After cooling to 25 °C 1000 mL of water was added to the DMF solution, resulting in a large amount of precipitate. The precipitate was collected by filtration, washed with 50 mL of ice water, and dried in an oven for 10 hours.
[0032] Example 4
[0033] Compound UH-1 was obtained as a brown solid, 0.37 g in total, in a yield of 80.0% after 4-nitro-lH-pyrazole-3,5-diamine (0.42 g, 2.0 mmol) was dissolved in 10 mL of DMSO and 2,6-dichloro-3,5-dinitropyridin-4-amine (0.25 g, 1.0 mmol) was added. The reaction was carried out at 120 °C for 5 hours. After cooling to 25 °C 1000 mL of water was added to the DMF solution, resulting in a large amount of precipitate. The precipitate was collected by filtration, washed with 50 mL of ice water, and dried in an oven for 10 hours.
Claims
1. A high-energy, ultra-heat-resistant explosive, characterized in that, N2-(5-amino-4-nitro-1) H -pyrazole-3-yl)-N6-(3-amino-4-nitro-1 H -pyrazol-5-yl)-3,5-dinitropyridine-2,4,6-triamine, its structural formula is: 。 2. The method for synthesizing high-energy, ultra-heat-resistant explosives according to claim 1, characterized in that, Includes the following steps: 2,6-Dichloro-3,5-dinitropyridine-4-amine and 4-nitro-1 H -Pyrazole-3,5-diamine reacts in an organic solvent to prepare N2-(5-amino-4-nitro-1-diamine). H -pyrazole-3-yl)-N6-(3-amino-4-nitro-1 H -pyrazol-5-yl)-3,5-dinitropyridine-2,4,6-triamine, the reaction formula is as follows: 。 3. The synthesis method according to claim 2, characterized in that, 2,6-Dichloro-3,5-dinitropyridine-4-amine and 4-nitro-1 H The molar ratio of pyrazole-3,5-diamine is 1:2.0~3.
0.
4. The synthesis method according to claim 2, characterized in that, The organic solvent is acetone, acetonitrile, methanol, ethanol, DMF, or DMSO.
5. The synthesis method according to claim 2, characterized in that, The reaction temperature is 25~120℃, and the reaction time is 1~24h.
6. The synthesis method according to claim 2, characterized in that, The reaction temperature is 80~120℃, and the reaction time is 3~12h.
7. The synthesis method according to claim 2, characterized in that, After the reaction was completed, the reaction solution was post-treated as follows: the reaction solution was cooled to room temperature, water was added and stirred, a precipitate was formed, the precipitate was collected by filtration, washed with ice water and dried to obtain N2-(5-amino-4-nitro-1-yl) H -pyrazole-3-yl)-N6-(3-amino-4-nitro-1 H (-pyrazol-5-yl)-3,5-dinitropyridine-2,4,6-triamine.
8. The synthesis method according to claim 7, characterized in that, The volume ratio of organic solvent to water is 1:2~100, and the stirring time is 2~48h.
9. The synthesis method according to claim 7, characterized in that, The volume ratio of organic solvent to ice water is 1:2~10.
10. The synthesis method according to claim 7, characterized in that... The drying temperature is 30~50℃, and the drying time is 2~48h.