High-density zero-oxygen-equilibrium hydrogen-free high-energy propellant component and preparation method thereof
By preparing 1,2-bis(5-azido-1-(trinitromethyl)-1H-1,2,4-triazole-3-yl)diazane compounds, the problem of synthesis of high-density zero-oxygen balanced hydrogen-free high-energy propellant components in the prior art was solved, and the propellant components with high energy performance and environmentally friendly characteristic signals were achieved, which was suitable for the field of high-energy propellant.
Patent Information
- Application Number
- CN202510590577.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-08
- Publication Date
- 2025-07-18
AI Technical Summary
The prior art is difficult to synthesize high-density, zero-oxygen balanced hydrogen-free high-energy propellant components. The synthesis route is complex and the yield is low, so it cannot meet the needs of high-energy propellants.
Using 1,2-bis(5-azido-1-(trinitromethyl)-1H-1,2,4-triazole-3-yl)diazane compound, the high-density zero-oxygen equilibrium hydrogen-free high-energy propellant component is prepared by reacting potassium hydroxide solution with chloroacetone and nitrate in nitrosulfur mixed acid.
The hydrogen-free high-energy propellant component with high density and zero oxygen balance has high specific impulse, excellent detonation performance and environmentally friendly signal, and is simple to synthesis and easy to engineer and amplify.
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Figure CN120329147A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a high - density zero - oxygen - balance hydrogen - free high - energy propellant component and its preparation method, belonging to the technical field of energetic materials. Background Art
[0002] Oxygen balance is a thermochemical parameter that measures whether the oxygen elements contained in energetic materials are in excess or deficiency after completely oxidizing the combustible elements. In energetic materials with zero - oxygen balance, the oxygen contained is just enough to completely oxidize the combustible elements, that is, all hydrogen is converted into water and all carbon is converted into carbon dioxide.
[0003] Countries around the world have made great efforts in developing energetic materials with zero - oxygen balance, and only a few compounds have been synthesized. For example, hexanitrobenzene with zero - oxygen balance exhibits a high detonation velocity, but its chemical stability is poor and it decomposes rapidly in humid air; octanitrocubane with zero - oxygen balance has an extremely high crystal density and excellent detonation performance. However, its complex synthesis route results in its small - scale synthesis only in the laboratory.
[0004] In 2024, the research group of Si - Ping Pang (J. Mater. Chem. A, 2024, 12, 32230 - 32238) synthesized 2,9 - bis(trinitromethyl)bis([1,2,4]triazolo[1,5 - d:5’,1’ - f][1,2,3,4]tetrazine) with zero - oxygen balance, and its specific impulse is as high as 269 s, but the synthesis route is long and the yield of the final product is low. Therefore, synthesizing high - density, zero - oxygen - balance hydrogen - free energetic compounds that can be used as high - energy propellant components remains a huge challenge. Summary of the Invention
[0005] The purpose of the present invention is to provide a high - density zero - oxygen - balance hydrogen - free high - energy propellant component and its preparation method.
[0006] Technical solutions for achieving the purpose of the present invention:
[0007] First, the present invention provides an organic energetic compound named 1,2 - bis(5 - azido - 1 - (trinitromethyl)-1H - 1,2,4 - triazol - 3 - yl)diazene, with the chemical formula C6N 20 O 12 , and its carbon dioxide oxygen balance is zero. The structural formula is:
[0008]
[0009] Second, the present invention provides a preparation method for the organic energetic compound described in the first aspect, including:
[0010] (1) Step of adding 1,2-bis(5-azido-1H-1,2,4-triazol-3-yl)diazene into potassium hydroxide solution, then dropwise adding chloroacetone and stirring for reaction to prepare 1,1'-(diazene-1,2-diylbis(5-azido-1H-1,2,4-triazole-3,1-diyl))bis(propan-2-one);
[0011]
[0012] (2) Step of dissolving 1,1'-(diazene-1,2-diylbis(5-azido-1H-1,2,4-triazole-3,1-diyl))bis(propan-2-one) in a mixed acid of nitric acid and sulfuric acid at -5 °C and carrying out a nitration reaction to prepare 1,2-bis(5-azido-1-(trinitromethyl)-1H-1,2,4-triazol-3-yl)diazene;
[0013]
[0014] Preferably, in step (1), the molar ratio of 1,2-bis(5-azido-1H-1,2,4-triazol-3-yl)diazene, potassium hydroxide, and chloroacetone is 1:2 - 2.5:2.1 - 2.5.
[0015] Preferably, in step (1), the reaction temperature is 20 - 90 °C, preferably 50 - 90 °C, and the reaction time is 10 - 24 h.
[0016] Preferably, in step (1), the potassium hydroxide solution is 2 mol·L -1 .
[0017] Preferably, in step (1), the solvent of the reaction system is acetonitrile.
[0018] Preferably, in step (2), in the mixed acid of nitric acid and sulfuric acid, the volume ratio of 95 wt% fuming nitric acid to 98 wt% concentrated sulfuric acid is 1:1 - 2.
[0019] Preferably, in step (2), the dosage ratio of 1,1'-(diazene-1,2-diylbis(5-azido-1H-1,2,4-triazole-3,1-diyl))bis(propan-2-one) to the mixed acid of nitric acid and sulfuric acid is 1 mmol:2 - 3 mL.
[0020] Preferably, in step (2), the nitration reaction temperature is -5 - 30 °C, preferably 10 - 20 °C, and the reaction time is 8 - 15 h.
[0021] In the third aspect, the present invention provides the application of the organic energetic compound described in the first aspect as a solid propellant component.
[0022] Preferably, the application of the organic energetic compound as a component of a high-density zero-oxygen-balance hydrogen-free high-energy propellant.
[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0024] (1) For the organic energetic compound of the present invention, as a component of a zero-oxygen-balance hydrogen-free high-energy propellant, the oxygen balance of carbon dioxide is zero, indicating that it can be completely decomposed into gas products by itself without the need for an oxidizer, and the specific impulse of a single component is as high as 272 s. Different from the commonly used energetic components of propellants such as RDX and HMX, whose oxygen balance of carbon dioxide is negative and an additional oxidizer AP needs to be added to form a near-zero-oxygen-balance propellant formulation (generally with a specific impulse < 260 s).
[0025] (2) The decomposition temperature of the organic energetic compound of the present invention is 162 °C (peak temperature, heating rate 5 °C·min -1 ), there is no endothermic melting process before thermal decomposition, and the heat release of the decomposition peak is as high as 3518 J·g -1 , showing significant exothermic characteristics of high-energy substances.
[0026] (3) The density of the organic energetic compound of the present invention is 1.913 g·cm -3 , with excellent detonation performance, the calculated detonation pressure by EXPLO5 is 39.2 GPa, and the detonation velocity is 9495 m·s -1 ; the energy performance is higher than that of the commonly used energetic component HMX of propellants (density 1.905 g·cm -3 ; detonation velocity 9144 m·s -1 ; detonation pressure 39.2 GPa).
[0027] (4) The organic energetic compound of the present invention is simple to synthesize, has a high yield, and is easy to scale up for engineering.
[0028] (5) The organic energetic compound of the present invention consists of only three elements: carbon, nitrogen, and oxygen, and the decomposition products are only nitrogen and carbon dioxide, without generating products such as water and carbon monoxide, having the advantages of environmental friendliness and low signature. BRIEF DESCRIPTION OF THE DRAWINGS
[0029] The specification drawings forming a part of this application are used to provide a further understanding of this application. The schematic embodiments of this application and their descriptions are used to explain this application and do not constitute an improper limitation of this application.
[0030] Figure 1 It is the molecular structure diagram of the high-density zero-oxygen-balance hydrogen-free high-energy propellant component of the present invention.
[0031] Figure 2 It is the differential scanning calorimetry chart (heating rate 5 °C·min) of the high-density zero-oxygen-balance hydrogen-free high-energy propellant component of the present invention.-1 )。
[0032] Figure 3 This is the carbon-13 NMR spectrum of the components of the high-density zero-oxygen-balance hydrogen-free high-energy propellant of the present invention (the solvent is deuterated dimethyl sulfoxide).
[0033] Figure 4 This is the infrared spectrum of the components of the high-density zero-oxygen-balance hydrogen-free high-energy propellant of the present invention. Detailed implementation manners
[0034] It should be noted that the terms such as "upper", "lower", "left", "right", "middle", etc. cited in this specification are only for the sake of clarity in narration and are not used to limit the scope of implementation. The change or adjustment of their relative relationship, without substantial change in the technical content, should also be regarded as the scope of implementation of this application.
[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which this application belongs; the term "and / or" used herein includes any and all combinations of one or more of the related listed items.
[0036] For those conditions not specified in the examples, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. Among them, the raw material 1,2-bis(5-azido-1H-1,2,4-triazol-3-yl)diazene is prepared according to the method described in the literature Chem. Eur. J. 2012, 18(52), 16742-16753. The reagents or instruments used without indicating the manufacturer are all conventional products that can be obtained through commercial purchase.
[0037] As used herein, the term "about" is used to provide flexibility and imprecision associated with a given term, measurement, or value. Those skilled in the art can easily determine the degree of flexibility of a specific variable.
[0038] As used herein, the term "at least one of..." is intended to be synonymous with "one or more of...". For example, "at least one of A, B, and C" clearly includes only A, only B, only C, and their respective combinations.
[0039] Concentrations, amounts, and other numerical data may be presented herein in a range format. It should be understood that such range formats are used merely for convenience and brevity and should be interpreted flexibly as including not only the values explicitly recited as the limits of the range but also all individual values or sub-ranges subsumed within the stated range as if each value and sub-range were explicitly recited. For example, a numerical range of from about 1 to about 4.5 should be interpreted as including not only the explicitly recited limits of 1 to about 4.5 but also the individual numbers (such as 2, 3, 4) and sub-ranges (such as 1 to 3, 2 to 4, etc.). The same principle applies to ranges that recite only one numerical value, such as "less than about 4.5", which should be interpreted as including all of the above values and ranges. In addition, this interpretation should apply regardless of the breadth of the range or feature described.
[0040] The high-density zero-oxygen-balance hydrogen-free high-energy propellant component provided by the present invention is a pale yellow powdery solid. The crystal density is 1.913 g cm -3 (296K). It is insensitive to water, light, and steam, does not deteriorate after being stored in air for three months, has a thermal decomposition temperature higher than 160 °C, does not react with plastics and glass, and the surface color and shape do not change after being exposed to direct sunlight for a long time.
[0041] The preparation method of a high-density zero-oxygen-balance hydrogen-free high-energy propellant component according to the present invention has the following reaction equation:
[0042] The specific steps are as follows:
[0043] Step 1: Dissolve 1,2-bis(5-azido-1H-1,2,4-triazol-3-yl)diazene in acetonitrile, add a 2 mol·L -1 potassium hydroxide solution, and then dropwise add chloroacetone, and stir and react at 20-90 °C for 10-24 h. After the reaction is completed, spin-dry the solvent, add deionized water, ultrasonicate, filter, and wash the filter cake with water to obtain 1,1'-(diazene-1,2-diylbis(5-azido-1H-1,2,4-triazole-3,1-diyl))bis(propan-2-one);
[0044] Step 2: Dissolve 1,1'-(diazene-1,2-diylbis(5-azido-1H-1,2,4-triazole-3,1-diyl))bis(propan-2-one) in a mixed acid of nitric acid and sulfuric acid at -5 °C, react at -5-30 °C for 8-15 h, pour it into ice water for quenching, filter, and wash with ice water to obtain 1,2-bis(5-azido-1-(trinitromethyl)-1H-1,2,4-triazol-3-yl)diazene.
[0045] Example 1:
[0046] Dissolve 1,2-bis(5-azido-1H-1,2,4-triazol-3-yl)diazene (2.46 g, 10 mmol) in acetonitrile (20 mL), then add an aqueous solution of potassium hydroxide (1.12 g, 20 mmol) in water (10 mL). Dropwise add 2.2 equivalents of chloroacetone (2.04 g, 22 mmol) to the reaction mixture, and stir the reaction at 80 °C for 12 h. After the reaction is completed, rotary evaporate the solvent, add deionized water, sonicate, filter, and wash the filter cake with water to obtain 1,1’-(diazene-1,2-diylbis(5-azido-1H-1,2,4-triazole-3,1-diyl))bis(propan-2-one) with a yield of 61.5%;
[0047] Dissolve 1,1’-(diazene-1,2-diylbis(5-azido-1H-1,2,4-triazole-3,1-diyl))bis(propan-2-one) (1.43 g, 4 mmol) in a nitrosulfuric acid mixture of 95% fuming nitric acid (4 mL) and 98% concentrated sulfuric acid (4.8 mL) at -5 °C, stir the reaction at 25 °C for 12 h, pour it into ice water to quench, filter, and wash with ice water to obtain a high-density zero-oxygen balance hydrogen-free high-energy propellant component, namely 1,2-bis(5-azido-1-(trinitromethyl)-1H-1,2,4-triazol-3-yl)diazene, 1.8 g, with a yield of 82.6%.
[0048] Dissolve the high-density zero-oxygen balance hydrogen-free high-energy propellant component obtained in Example 1 in acetonitrile, and slowly volatilize it at room temperature to obtain light yellow needle-like single crystals, and perform single crystal X-ray diffraction testing. After analysis, the structure of 1,2-bis(5-azido-1-(trinitromethyl)-1H-1,2,4-triazol-3-yl)diazene is as Figure 1 shown.
[0049] Characterize the high-density zero-oxygen balance hydrogen-free high-energy propellant component obtained in Example 1, and the analysis results are as follows:
[0050] As Figure 2 shown in the differential scanning calorimetry chart, DSC: 162 °C (decomposition peak temperature, nitrogen, heating rate 5 °C·min -1 ), there is no endothermic melting process before thermal decomposition, and the heat release is as high as 3518 J·g -1 , showing significant exothermic characteristics of energetic compounds.
[0051] As Figure 3 shown in the nuclear magnetic carbon spectrum chart, 13 C NMR (DMSO-d6): δ 200.33, 166.43, 151.82 ppm.
[0052] As Figure 4 shown in the infrared spectrum chart, IR (ATR): 2173.01, 1633.69, 1598.92, 1549.19, 1495.59, 1352.70, 1274.03, 1205.79, 1036.91, 988.58, 860.23, 823.06, 791.96, 760.96, 675.80 cm -1 。
[0053] Elemental analysis C6N 20 O 12 (544.194): Measured value (calculated value) C 13.28 (13.24)%, N 51.39 (51.48)%.
[0054] For the high-density zero-oxygen-balance hydrogen-free high-energy propellant component obtained in Example 1, after testing, the impact sensitivity is 5 J and the friction sensitivity is 100 N. The sensitivity is close to that of the existing commonly used high-energy propellant components RDX and HMX.
[0055] For the high-density zero-oxygen-balance hydrogen-free high-energy propellant component obtained in Example 1, after calculation, the carbon dioxide oxygen balance is 0, the oxygen content is 35.28%, and the nitrogen-oxygen content is 86.76%. The decomposition product of 1 mol of this component is 10 mol of nitrogen gas and 6 mol of carbon dioxide gas, and it will not cause environmental pollution after use; and there is no water in the product, making it easier for the propellant to meet the requirements of low signature.
[0056] For the high-density zero-oxygen-balance hydrogen-free high-energy propellant component obtained in Example 1, its density was measured by a gas densitometer to be 1.913 g·cm -3 , and the calculated enthalpy of formation is 1365.8 kJ·mol -1 , the calculated detonation pressure by EXPLO5 is 39.2 GPa, and the detonation velocity is 9495 m·s -1 , having excellent energy performance higher than HMX. The heat of detonation is 6645 J·g -1 , higher than CL-20 (6530 J·g -1 ).
[0057] For the high-density zero-oxygen-balance hydrogen-free high-energy propellant component obtained in Example 1, the specific impulse calculated by EXPLO5 for the single component is as high as 272 s. Different from the commonly used propellant energy components such as RDX and HMX, their carbon dioxide oxygen balance is negative, and an additional oxidizer AP needs to be added to form a near-zero-oxygen-balance propellant formulation (the specific impulse is generally <260 s).
[0058] Example 2:
[0059] Dissolve 1,2-bis(5-azido-1H-1,2,4-triazol-3-yl)diazene (2.46 g, 10 mmol) in acetonitrile (20 mL), and then add an aqueous solution of potassium hydroxide (1.12 g, 20 mmol) in water (10 mL). Dropwise add 2.2 equivalents of chloroacetone (2.04 g, 22 mmol) to the reaction mixture, and stir the reaction at 25 °C for 12 h. After the reaction is completed, rotary evaporate the solvent, add deionized water, sonicate, filter, and wash the filter cake with water to obtain 1,1'-(diazene-1,2-diylbis(5-azido-1H-1,2,4-triazole-3,1-diyl))bis(propan-2-one) with a yield of 50.9%;
[0060] Dissolve 1,1'-(diazene-1,2-diylbis(5-azido-1H-1,2,4-triazole-3,1-diyl))bis(propan-2-one) (1.43 g, 4 mmol) in a nitrosulfuric acid mixture of 95% fuming nitric acid (4 mL) and 98% sulfuric acid (4.8 mL) at -5 °C, stir the reaction at -5 °C for 12 h, pour it into ice water for quenching, filter, and wash with ice water to obtain 1.2 g of 1,2-bis(5-azido-1-(trinitromethyl)-1H-1,2,4-triazol-3-yl)diazene with a yield of 55.0%.
[0061] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.
Claims
1. An organic energetic compound, characterized in that, Named 1,2-bis(5-azido-1-(trinitromethyl)-1H-1,2,4-triazol-3-yl)diazene, and its chemical formula is C6N 20 O 12 , and its structural formula is:
2. The preparation method of the organic energetic compound according to claim 1, characterized in that, Comprising: (1) A step of adding 1,2-bis(5-azido-1H-1,2,4-triazol-3-yl)diazene into a potassium hydroxide solution, and then dropwise adding chloroacetone and stirring for reaction to prepare 1,1'-(diazene-1,2-diylbis(5-azido-1H-1,2,4-triazole-3,1-diyl))bis(propan-2-one); (2) A step of dissolving 1,1'-(diazene-1,2-diylbis(5-azido-1H-1,2,4-triazole-3,1-diyl))bis(propan-2-one) in a mixed acid of nitric acid and sulfuric acid at -5°C and carrying out a nitration reaction to prepare 1,2-bis(5-azido-1-(trinitromethyl)-1H-1,2,4-triazol-3-yl)diazene; 3. The method according to claim 2, wherein In step (1), the molar ratio of 1,2-bis(5-azido-1H-1,2,4-triazol-3-yl)diazene, potassium hydroxide, and chloroacetone is 1:2 to 2.5:2.1 to 2.
5.
4. The method according to claim 2, characterized in that, In step (1), the reaction temperature is 20 to 90°C, preferably 50 to 90°C, and the reaction time is 10 to 24 h.
5. The method according to claim 2, characterized in that In step (1), the reaction system solvent is acetonitrile.
6. The method according to claim 2, wherein In step (2), in the mixed acid of nitric acid and sulfuric acid, the volume ratio of 95 wt% fuming nitric acid to 98 wt% concentrated sulfuric acid is 1:1 to 2.
7. The method according to claim 2, wherein In step (2), the dosage ratio of 1,1'-(diazene-1,2-diylbis(5-azido-1H-1,2,4-triazole-3,1-diyl))bis(propan-2-one) to the mixed acid of nitric acid and sulfuric acid is 1 mmol:2 to 3 mL.
8. The method according to claim 2, wherein In step (2), the nitration reaction temperature is -5 to 30°C, preferably 10 to 20°C, and the reaction time is 8 to 15 h.
9. Use of the organic energetic compound according to claim 1 as a solid propellant component.