Nitrogen-rich oxygen tri-component high-energy density material and synthesis method thereof
By preparing nitrogen- and oxygen-rich three-component high-energy-density materials, the problem of component adjustment in energetic materials was solved by utilizing ionization reactions and intermolecular forces, achieving a balance between high energy density and low sensitivity, with performance superior to traditional materials.
Patent Information
- Application Number
- CN202411881785.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-19
- Publication Date
- 2026-06-23
AI Technical Summary
In the existing technology, there is a lack of effective adjustment methods to achieve a balance between high energy density and low sensitivity when preparing energetic materials, especially when introducing different component ionic salts, which leads to poor material performance.
Using 4,5-diamino-3-aminomethyl-1,2,4-triazole, perchloric acid, and hydroxylamine as raw materials, nitrogen- and oxygen-rich three-component high-energy-density materials are prepared through ionization reactions and intermolecular forces. The specific steps include controlling the proportion of raw materials and the reaction temperature and time.
A nitrogen-oxygen-rich three-component material with high density, high detonation velocity, and high thermal stability was obtained, with a density of 1.95 g/cm3, a detonation velocity of 9512 m/s, a thermal decomposition temperature of 250℃, low sensitivity, and overall performance superior to traditional HMX.
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Figure CN122255074A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of energetic materials and relates to a nitrogen- and oxygen-rich three-component high-energy-density material and its synthesis method. Background Technology
[0002] The pursuit of a balance between high energy and low sensitivity is a perennial theme in energetic materials research. Nitrogen-rich heterocyclic frameworks have attracted significant attention from researchers due to their advantages, including high energy density, high heat of formation, high nitrogen content, clean detonation products, and low sensitivity. Among all five-membered nitrogen-rich heterocycles, 1,2,4-triazole possesses high nitrogen content and strong modifiability, allowing for energetic modification to enhance compound performance. Constructing energetic ionic salts is an effective method for preparing energetic materials. The properties of ionic salts can be adjusted by changing the component ions with different properties, resulting in a richer variety of higher-energy and safer energetic materials. However, research on simultaneously introducing two different component ionic salts to modulate the performance of 1,2,4-triazole has not yet been reported. Summary of the Invention
[0003] The purpose of this invention is to provide a nitrogen- and oxygen-rich three-component high-energy-density material and its preparation method, which uses inexpensive and readily available raw materials, is simple to operate, and has high reaction yield and high product purity.
[0004] In a first aspect, the present invention provides a nitrogen- and oxygen-rich three-component high-energy-density material, the structure of which is shown below:
[0005]
[0006] Secondly, the present invention provides a method for preparing a nitrogen- and oxygen-rich three-component high-energy-density material, comprising the following steps: using nitrogen-rich compound 4,5-diamino-3-aminomethyl-1,2,4-triazole 1, perchloric acid, and hydroxylamine as raw materials, and simultaneously introducing hydroxylamine cations and perchlorate anions through ionization reactions and intermolecular forces to prepare target compound 2.
[0007]
[0008] Furthermore, the amount of perchloric acid used is 1.5-3 times the equivalent of 4,5-diamino-3-aminomethyl-1,2,4-triazole 1, preferably 2.5 times the equivalent.
[0009] Furthermore, the amount of hydroxylamine used is 1-1.5 equivalents of 4,5-diamino-3-aminomethyl-1,2,4-triazole 1, preferably 1.5 equivalents.
[0010] Furthermore, the reaction temperature is 25-100℃, preferably 60-80℃, and more preferably 80℃.
[0011] Furthermore, the reaction time is 1-3 hours, preferably 2 hours.
[0012] Thirdly, the present invention provides a crystal prepared from the nitrogen- and oxygen-rich three-component high-energy-density material described in the first aspect.
[0013] Furthermore, the density of this crystal is 1.95 g / cm³ at a testing temperature of 285 K. 3 The unit cell parameters are a = 10.3871(3), b = 10.3180(2), c = 15.0483(4), α = 90°, β = 102.35°, γ = 90°, the unit cell volume is 1575.4(3), and the space group is -P2ybc.
[0014] Fourthly, the present invention provides the use of the nitrogen- and oxygen-rich three-component high-energy-density material described in the first aspect or the crystal described in the third aspect as an explosive.
[0015] Compared with the prior art, the present invention has the following advantages:
[0016] (1) This invention simultaneously introduces the nitrogen-rich heterocyclic skeleton 4,5-diamino-3-aminomethyl-1,2,4-triazole and the nitrogen-rich cationic hydroxylamine ion and the oxygen-rich anionic perchlorate ion into a single molecule through ionization reaction and intermolecular forces, obtaining a nitrogen-rich oxygen-high energy density material with a three-component structure. This synthesis method has been rarely reported. The reaction process is simple, and the overall yield is as high as 96%.
[0017] (2) The nitrogen- and oxygen-rich three-component high-energy-density material 2 of this invention has a room-temperature crystal density as high as 1.95 g / cm³. 3 It has a detonation velocity of 9512 m / s and a thermal decomposition temperature of 250℃. Its impact sensitivity is 2J and its friction sensitivity is 128N. Its overall performance is comparable to that of traditional high-energy explosives (HMX), and it has great application potential. Attached Figure Description
[0018] Figure 1 The hydrogen NMR spectrum of target product 2;
[0019] Figure 2 The carbon NMR spectrum of the target product 2;
[0020] Figure 3 The image shows the single crystal of the target product 2. Detailed Implementation
[0021] The present invention will be further described below with reference to the embodiments.
[0022] Example 1:
[0023] 1.28 g (10 mmol) of 4,5-diamino-3-aminomethyl-1,2,4-triazole was added to 20 mL of water, and 4.31 g (30 mmol) of 70% perchloric acid solution was slowly added dropwise, followed by 0.51 g (10 mmol) of hydroxylamine aqueous solution. The mixture was heated to 60 °C and stirred for 1 hour. After cooling, the mixture was filtered, washed with water, and dried under vacuum to obtain 4.26 g of white powdery solid 2, with a yield of 92%.
[0024] The proton and carbon spectra of target product 2 are as follows: Figure 1 and Figure 2 As shown, the data is as follows:
[0025] 1 H NMR (300MHz, DMSO-d6): δ = 3.85 (br), 4.18 (s), 5.90 (s), 6.90 (s), 7.07 (s), 7.24 (s), 8.42 (s) ppm; 13 C NMR (125MHz, DMSO-d6): δ = 32.9, 146.8, 151.9ppm; Elemental analysis for C3H14N7O 12 Cl3 (462.53): C 7.79, H 3.05, N 21.20%; found: C 7.69, H 3.10, N21.03%.
[0026] Example 2
[0027] The rest is the same as in Example 1, except that the molar ratio of 4,5-diamino-3-aminomethyl-1,2,4-triazole to perchloric acid is changed from 1:3 to 1:2.5, yielding 4.31 g of white powdery solid 2, with a yield of 93%.
[0028] Example 3
[0029] The rest is the same as in Example 1, except that the molar ratio of 4,5-diamino-3-aminomethyl-1,2,4-triazole to hydroxylamine is changed from 1:1 to 1:1.5, yielding 4.36 g of white powdery solid 2, with a yield of 94%.
[0030] Example 4
[0031] The rest is the same as in Example 1, except that the reaction temperature was increased from 60℃ to 100℃, yielding 4.31g of white powdery solid 2, with a yield of 93%.
[0032] Example 5
[0033] The rest is the same as in Example 1, except that the reaction temperature was changed from 60℃ to 25℃, yielding 4.08g of white powdery solid 2, with a yield of 88%.
[0034] Example 6
[0035] The rest is the same as in Example 1, except that the reaction temperature was increased from 60℃ to 80℃, yielding 4.40g of white powdery solid 2, with a yield of 95%.
[0036] Example 7
[0037] The rest is the same as in Example 6, except that the reaction time was increased from 1 hour to 2 hours, yielding 4.45 g of white powdery solid 2, with a yield of 96%.
[0038] Example 8
[0039] The process was the same as in Example 6, except that the reaction time was increased from 1 hour to 3 hours, yielding 4.45 g of white powdery solid 2, with a yield of 96%.
[0040] The compound has a detonation velocity of 9512 m / s, a detonation pressure of 38.6 GPa, a thermal decomposition temperature of 250℃, an impact sensitivity of 2 J, and a friction sensitivity of 128 N.
[0041] After being allowed to stand in an aqueous solution, the crystal precipitates out, and its crystal structure is as follows: Figure 3 As shown.
[0042] The resulting crystals had a density as high as 1.95 g / cm³ at a testing temperature of 285 K. 3 The unit cell parameters are a = 10.3871(3), b = 10.3180(2), c = 15.0483(4), α = 90°, β = 102.35°, γ = 90°, the unit cell volume is 1575.4(3), and the space group is -P2ybc.
Claims
1. A nitrogen- and oxygen-rich three-component high-energy-density material, characterized in that, Its structure is as follows:
2. A method for preparing a nitrogen- and oxygen-rich three-component high-energy-density material, characterized in that, include: The steps for preparing target compound 2 are as follows: using nitrogen-rich compound 4,5-diamino-3-aminomethyl-1,2,4-triazole 1, perchloric acid, and hydroxylamine as raw materials, hydroxylamine cations and perchlorate anions are simultaneously introduced through ionization reactions and intermolecular forces.
3. The method as described in claim 2, characterized in that, The amount of perchloric acid used is 1.5-3 times the equivalent of 4,5-diamino-3-aminomethyl-1,2,4-triazole 1, preferably 2.5 times the equivalent.
4. The method as described in claim 2, characterized in that, The amount of hydroxylamine used is 1 to 1.5 equivalents of 4,5-diamino-3-aminomethyl-1,2,4-triazole 1, preferably 1.5 equivalents.
5. The method as described in claim 2, characterized in that, The reaction temperature is 25-100℃, preferably 60-80℃, and more preferably 80℃.
6. The method as described in claim 2, characterized in that, The reaction time is 1-3 hours, preferably 2 hours.
7. A crystal prepared from the nitrogen-oxygen-rich three-component high-energy-density material as described in claim 1.
8. The crystal as described in claim 7, characterized in that, The density of this crystal is 1.95 g / cm³ at a testing temperature of 285 K. 3 The unit cell parameters are a = 10.3871(3), b = 10.3180(2), c = 15.0483(4), α = 90°, β = 102.35°, γ = 90°, the unit cell volume is 1575.4(3), and the space group is -P2ybc.
9. Use of a nitrogen-oxygen-rich three-component high-energy-density material as described in claim 1 or a crystal as described in claim 7 or 8 as an explosive.