Pentahexacyclic heat-resistant energetic compound as well as preparation method and application thereof
The construction of a five-link hexacyclic heat-resistant compound through bridge reactions has solved the problems of the thermal decomposition temperature and preparation process of the existing heat-resistant energy-resistant compound, and achieved the effects of high thermal decomposition temperature, excellent energy and simple synthesis.
Patent Information
- Application Number
- CN202510046609.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-13
- Publication Date
- 2025-06-13
AI Technical Summary
There are not many substances with thermal decomposition temperatures higher than 330°C in existing heat-resistant compounds, and most of them have complex preparation processes, low yields, and insufficient energy and safety.
By bridging the N-H active site with the nucleochlorohexacyclic heat-resistant energy-containing compound, a penta-hexacyclic-based five-membered ring compound is constructed. This process uses alkali as catalyst, the reaction temperature and time are adjustable, and the synthesis is relatively simple.
The prepared quincate hexacyclic heat-resistant energy-containing compound has a thermal decomposition temperature of 330-395℃, excellent energy, low sensitivity, simple synthesis technology, and suitable for industrial applications.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of energetic materials, and particularly relates to a class of pentacyclohexyl-based heat-resistant energetic compounds, their preparation methods and applications. Background Art
[0002] Heat-resistant energetic compounds are an important branch in the field of energetic materials. They usually have a relatively high thermal decomposition temperature (the decomposition temperature generally exceeds 300 °C) and are widely used in special high-temperature military and civilian fields such as hypersonic weapons, aerospace vehicles, and oil / gas extraction. Therefore, the design and development of new high-performance heat-resistant energetic materials are of extremely important significance for national defense construction, aerospace scientific and technological progress, and modern industrial development. In the past few decades, some typical heat-resistant energetic compounds have been synthesized, including monocyclic 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) (T d = 350 °C) and 2,6-diamino-3,5-dinitro-1-oxypyrazine (LLM-105) (T d = 342 °C), polycyclic tetranitrodibenzodiazapentalene (TACOT) (Td = 395 °C), and bicyclic 2,2',4,4',6,6'-hexanitrodiphenylethylene (HNS, hexanitrostilbene, T d = 316 °C) and 2,6-bis(picrylamino)-3,5-dinitropyridine (PYX) (T d = 350 °C), etc. Although these classical heat-resistant energetic compounds meet the requirements of thermal stability, they also have certain limitations, such as limited modifiable sites, long reaction steps, low yields, low energy, poor safety, etc. Therefore, it is still an urgent and continuous goal to effectively design and develop new single-component heat-resistant energetic compounds with high thermal stability, good safety, and high energy through a simple synthesis process.
[0003] The pentacyclohexyl skeleton has multiple active sites, and multiple functional groups can be introduced to improve the comprehensive performance of energetic compounds. In addition, the synthesis of pentacyclohexyl compounds is relatively simple. Usually, two aromatic rings can be combined to obtain the pentacyclohexyl skeleton through -C-C-, -NH-NH-, and -NH- bridging units, and excellent heat-resistant energetic compounds can be obtained by functional modification with heat-resistant groups such as -CH 3 , -NH 2 , etc.
[0004] In summary, there is an urgent need in this field to develop pentacyclohexyl-based heat-resistant energetic compounds with excellent performance, good thermal stability, and simple synthesis processes. Summary of the Invention
[0005] Aiming at the above deficiencies in the prior art, the main technical problem to be solved by the present invention is as follows: In the prior art, an important parameter of heat-resistant energetic compounds is the thermal decomposition temperature. There are still not many heat-resistant energetic compounds with a thermal decomposition temperature higher than 330 °C, and the preparation of most heat-resistant energetic compounds is relatively complex. The purpose of the present invention is to provide a class of penta-linked hexacyclic heat-resistant energetic compounds, their preparation methods and applications. A penta-linked hexacyclic heat-resistant energetic compound is constructed by using a nitrogen-rich azole five-membered ring compound containing an N-H active site to bridge a nitrogen-rich chlorinated six-membered ring compound. The thermal decomposition temperature of this class of compounds is 330-395 °C, and they have the characteristics of excellent energy, low sensitivity, and simple synthesis.
[0006] In order to achieve the above object, the present invention provides the following technical solutions.
[0007] The first aspect of the present invention provides a class of penta-linked hexacyclic heat-resistant energetic compounds, which include the following compounds:
[0008]
[0009] Furthermore, the thermal decomposition temperature of the penta-linked hexacyclic heat-resistant energetic compound is 330-395 °C.
[0010] The second aspect of the present invention provides a preparation method of the class of penta-linked hexacyclic heat-resistant energetic compounds, which includes the following steps:
[0011] Dissolve the nitrogen-rich azole five-membered ring compound containing an N-H active site in a certain amount of solvent, add an alkali as a catalyst, and then add the nitrogen-rich chlorinated six-membered ring compound for reaction. After the reaction is completed, filter, and wash and dry the solid-phase product to obtain the penta-linked hexacyclic heat-resistant energetic compound respectively.
[0012] Furthermore, the nitrogen-rich azole five-membered ring compounds containing an N-H active site are 3,5-diamino-4-nitropyrazole and 3,5-diamino-1,2,4-triazole respectively.
[0013] Furthermore, the catalyst is one of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, pyridine, 2,4,6-trimethylpyridine.
[0014] Furthermore, the nitrogen-rich chlorinated six-membered ring compounds are 2-chloro-5-nitropyrimidine-4,6-diamine, 6-trichloro-1,3,5-triazine-2,4-diamine, and 6-chloro-3,5-dinitropyridine-2,4-diamine respectively.
[0015] Furthermore, the molar ratio of the nitrogen-rich azole five-membered ring compound containing an N-H active site to the nitrogen-rich chlorinated six-membered ring compound is 1-1.5:1.
[0016] Further, the molar ratio of the catalyst to the nitrogen-rich five-membered azole compound containing N-H active sites is 1 to 1.5:1.
[0017] Further, the temperature during the reaction is 50 to 120 °C, and the reaction time is 0.5 to 24 hours.
[0018] Further, the solvent is one of water, methanol, ethanol, acetonitrile, 1,4-dioxane, isopropanol, and N,N-dimethylformamide.
[0019] The third aspect of the present invention provides the application of the described class of pentacyclohexyl heat-resistant energetic compounds in energetic materials.
[0020] Compared with the prior art, the present invention has the following beneficial effects:
[0021] The present invention provides a class of pentacyclohexyl heat-resistant energetic compounds, their preparation methods and applications. The present invention constructs pentacyclohexyl heat-resistant energetic compounds by bridging nitrogen-rich chlorinated six-membered ring compounds with nitrogen-rich five-membered azole compounds containing N-H active sites; the thermal decomposition temperature of this class of compounds is 330 - 395 °C. The heat-resistant energetic compounds prepared by the present invention also have excellent energy and low sensitivity, etc., and have application potential in the field of heat-resistant energetic compounds. The preparation method of the compounds provided by the present invention is simple in synthesis and easy to industrialize, and has application potential in the preparation of heat-resistant explosives. Description of the Drawings
[0022] Figure 1 are the single crystal structure diagrams of Compounds I, III - VI;
[0023] Figure 2 are the DSC diagrams of Compounds I - VI. Detailed Embodiments
[0024] In order to enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below in conjunction with specific embodiments and drawings, but the specific embodiments cited are not intended to limit the present invention.
[0025] The first aspect of the present invention provides a class of pentacyclohexyl heat-resistant energetic compounds, including the following compounds:
[0026]
[0027] Among them, the thermal decomposition temperature of the compound is 330 - 395 °C.
[0028] The second aspect of the present invention provides a preparation method of a class of pentacyclohexyl heat-resistant energetic compounds, including the following steps:
[0029] Dissolve the nitrogen-rich five-membered azole ring compound containing N-H active sites in a certain amount of solvent, add a base as a catalyst, and then add the nitrogen-rich six-membered chlorinated ring compound for reaction. After the reaction is completed, filter, and wash and dry the solid-phase product to obtain a penta-linked six-ring-based heat-resistant energetic compound respectively; use distilled water and ethanol for washing.
[0030] Among them, the nitrogen-rich five-membered azole ring compounds containing N-H active sites are 3,5-diamino-4-nitropyrazole and 3,5-diamino-1,2,4-triazole respectively.
[0031] The catalyst is one of inorganic sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and organic triethylamine, pyridine, 2,4,6-trimethylpyridine.
[0032] The nitrogen-rich six-membered chlorinated ring compounds are 2-chloro-5-nitropyrimidine-4,6-diamine, 6-trichloro-1,3,5-triazine-2,4-diamine and 6-chloro-3,5-dinitropyridine-2,4-diamine respectively.
[0033] The molar ratio of the nitrogen-rich five-membered azole ring compound containing N-H active sites to the nitrogen-rich six-membered chlorinated ring compound is 1-1.5:1.
[0034] The molar ratio of the catalyst to the nitrogen-rich five-membered azole ring compound containing N-H active sites is 1-1.5:1.
[0035] According to the present invention, the reaction temperature is 50-120 °C and the reaction time is 0.5-24 hours.
[0036] The solvent is one or more of water, methanol, ethanol, acetonitrile, 1,4-dioxane, isopropanol, N,N-dimethylformamide.
[0037] The third aspect of the present invention provides the application of a class of penta-linked six-ring-based heat-resistant energetic compounds in energetic materials.
[0038] It should be noted that the experimental methods used in the present invention are all conventional methods without special instructions; the reagents and materials used can be purchased on the market without special instructions.
[0039] Example 1
[0040] Synthesis of Compound I
[0041] The nitrogen-rich five-membered azole compound 3,5-diamino-4-nitropyrazole (1.00 g, 6.99 mmol) containing N-H active sites was dissolved in ethanol (25 mL), and sodium bicarbonate (0.88 g, 10.48 mmol) was added. The mixture was stirred for 30 min. 2-Chloro-5-nitropyrimidine-4,6-diamine (1.32 g, 6.99 mmol), a nitrogen-rich six-membered ring chloro compound, was weighed and added to this solution. The reaction mixture was stirred at 70 °C for 6 h. After the reaction was completed, the solid product was filtered out, washed with 5 mL of distilled water, and dried to obtain the yellow solid product I. Yield: 1.92 g, 92.8%.
[0042] Properties of Product I:
[0043] Appearance: Yellow powdery solid;
[0044] Peak decomposition temperature: 390.3 °C.
[0045] The properties of Compound I prepared in this example are shown in Table 1.
[0046] Table 1 Properties of Compound I
[0047]
[0048] Figure 2 a is the DSC diagram of Compound I.
[0049] From Figure 2 the DSC curve of a, it can be seen that Compound I has high thermal stability, and the exothermic peak is located at 390.3 °C.
[0050] Example 2
[0051] Synthesis of Compound II
[0052] The nitrogen-rich five-membered azole compound 3,5-diamino-1,2,4-triazole (1.00 g, 10.10 mmol) containing N-H active sites was dissolved in acetonitrile (25 mL), and sodium carbonate (1.27 g, 15.15 mmol) was added. The mixture was stirred for 30 min. 2-Chloro-5-nitropyrimidine-4,6-diamine (1.91 g, 10.10 mmol) was weighed and added to this solution. The reaction mixture was stirred at 80 °C for 6 h. After the reaction was completed, the solid product was filtered under reduced pressure, washed with 5 mL of distilled water, and dried to obtain the yellow solid product II. Yield: 2.23 g, 87.5%.
[0053] Properties of Product II:
[0054] Appearance: Yellow powdery solid;
[0055] Peak decomposition temperature: 375.8 °C.
[0056] The properties of Compound II prepared in this example are shown in Table 2.
[0057] Table 2 Properties of Compound II
[0058]
[0059] Figure 2 b is the DSC diagram of Compound II.
[0060] From Figure 2 the DSC curve of b, it can be seen that Compound II has high thermal stability and the exothermic peak is located at 375.8 °C.
[0061] Example 3
[0062] Synthesis of Compound III
[0063] Dissolve the nitrogen-rich five-membered ring compound 3,5-diamino-4-nitropyrazole (1.00 g, 6.99 mmol) containing N-H active sites in isopropanol (25 mL), add potassium hydroxide (0.59 g, 10.48 mmol), and stir the reaction for 30 min. Weigh the nitrogen-rich six-membered ring compound 6-trichloro-1,3,5-triazine-2,4-diamine (1.01 g, 6.99 mmol) and add it to this solution. Stir the reaction mixture at 80 °C for 8 hours. After the reaction is completed, filter out the solid product under reduced pressure, wash it with 5 mL of distilled water, and dry it to obtain a yellowish-brown solid product III. Yield: 1.58 g, 89.6%.
[0064] Properties of Product III:
[0065] Appearance: Yellowish-brown powdery solid;
[0066] Decomposition temperature peak: 387.2 °C.
[0067] The properties of Compound III prepared in this example are shown in Table 3.
[0068] Table 3 Properties of Compound III
[0069]
[0070] Figure 2 c is the DSC diagram of Compound III.
[0071] From Figure 2 the DSC curve of c, it can be seen that Compound III has high thermal stability and the exothermic peak is located at 387.2 °C.
[0072] Example 4
[0073] Synthesis of Compound IV
[0074] Dissolve the nitrogen-rich five-membered azole compound 3,5-diamino-1,2,4-triazole (1.00 g, 10.10 mmol) containing N-H active sites in acetonitrile (25 mL), add sodium hydrogencarbonate (1.27 g, 15.15 mmol), and stir the reaction for 30 min. Weigh the nitrogen-rich six-membered chloro ring compound 6-trichloro-1,3,5-triazine-2,4-diamine (1.46 g, 10.10 mmol) and add it to this solution. Stir the reaction mixture at 80 °C for 10 hours. After the reaction is completed, filter out the solid product under reduced pressure, wash it with 5 mL of distilled water and ethanol, and dry it to obtain the white solid product Ⅳ. Yield: 1.89 g, 90.0%.
[0075] Properties of product Ⅳ:
[0076] Appearance: White powdery solid;
[0077] Peak decomposition temperature: 380.4 °C.
[0078] The properties of the compound Ⅳ prepared in this example are shown in Table 4.
[0079] Table 4 Properties of compound Ⅳ
[0080]
[0081] Figure 2 d is the DSC diagram of compound Ⅳ.
[0082] From Figure 2 It can be seen from the DSC curve of d that the thermal stability of compound Ⅳ is relatively high, and the exothermic peak is located at 380.4 °C.
[0083] Example 5
[0084] Synthesis of compound Ⅴ
[0085] Dissolve the nitrogen-rich five-membered azole compound 3,5-diamino-4-nitropyrazole (1.00 g, 6.99 mmol) containing N-H active sites in water (25 mL), add sodium hydrogencarbonate (0.88 g, 10.48 mmol), weigh the nitrogen-rich six-membered chloro ring compound 6-chloro-3,5-dinitropyridine-2,4-diamine (1.63 g, 6.99 mmol) and add it to this solution. Heat the reaction mixture to 100 °C and stir the reaction for 6 hours. After the reaction is completed, filter, wash, and dry to obtain the yellow solid product Ⅴ. Yield: 2.12 g, 89.2%.
[0086] Properties of product Ⅴ:
[0087] Appearance: Yellow powdery solid;
[0088] Peak decomposition temperature: 342.7 °C.
[0089] The properties of compound V prepared in this example are shown in Table 5.
[0090] Table 5 Properties of Compound V
[0091]
[0092] Figure 2 e is the DSC diagram of compound V.
[0093] From Figure 2 the DSC curve of e, it can be seen that compound V has good thermal stability, and the exothermic peak is located at 342.7 °C.
[0094] Example 6
[0095] Synthesis of Compound VI
[0096] Dissolve the nitrogen-rich azole five-membered ring compound 3,5-diamino-1,2,4-triazole (1.00 g, 10.10 mmol) containing N-H active sites in ethanol (25 mL), add sodium hydrogencarbonate (1.27 g, 15.15 mmol), and weigh the nitrogen-rich chloro six-membered ring compound 6-chloro-3,5-dinitropyridine-2,4-diamine (2.35 g, 10.10 mmol) and add it to this solution. Heat the reaction mixture to 80 °C and stir for 6 hours. After the reaction is completed, filter, wash, and dry to obtain the yellow solid product VI. Yield: 2.68 g, 89.6%.
[0097] Properties of product VI:
[0098] Appearance: Yellow powdery solid;
[0099] Decomposition temperature peak: 337.6 °C.
[0100] The properties of compound VI prepared in this example are shown in Table 6.
[0101] Table 6 Properties of Compound VI
[0102]
[0103] Figure 2 f is the DSC diagram of compound VI.
[0104] From Figure 2 the DSC curve of f, it can be seen that compound VI has good thermal stability, and the exothermic peak is located at 337.6 °C.
[0105] According to the above results, it can be known that the thermal decomposition temperature of compounds I-VI is 337.6 - 390.3 °C, and the detonation velocity is 8163 - 8337 m s -1, the impact sensitivities are all > 50 J, and they are potential candidate materials for heat-resistant energetic compounds.
[0106] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art should understand that several modifications, improvements, and equivalent replacements can be made to these embodiments without departing from the principles and spirit of the present invention. These modifications, improvements, and equivalent replacements are also considered to fall within the protection scope of the claims of the present invention. The scope of the present invention is defined by the appended claims.
Claims
1. A type of five-linked six-ring heat-resistant energetic compound, characterized in that: Includes the following compounds:
2. The five-linked six-ring heat-resistant energetic compound according to claim 1, characterized in that: The thermal decomposition temperature of the five-linked six-ring heat-resistant energetic compound is 330-395°C.
3. A method for preparing a type of five-linked six-ring based heat-resistant energetic compound according to claim 1, characterized in that: The following steps are involved: A nitrogen-rich azole five-membered ring compound containing an NH active site is dissolved in a certain amount of solvent, a base is added as a catalyst, and then a nitrogen-rich chlorinated six-membered ring compound is added to react. After the reaction is completed, the reaction is filtered, and the solid phase product is washed and dried to obtain a five-linked six-ring based heat-resistant energetic compound.
4. The method for preparing a type of five-linked six-ring-based heat-resistant energetic compound according to claim 3, characterized in that: The nitrogen-rich azole five-membered ring compounds containing NH active sites are 3,5-diamino-4-nitropyrazole and 3,5-diamino-1,2,4-triazole.
5. The method for preparing a type of five-linked six-ring-based heat-resistant energetic compound according to claim 3, characterized in that: The catalyst is one of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, pyridine and 2,4,6-trimethylpyridine.
6. The method for preparing a type of five-linked six-ring-based heat-resistant energetic compound according to claim 3, characterized in that: The nitrogen-rich chlorinated six-membered ring compounds are 2-chloro-5-nitropyrimidine-4,6-diamine, 6-trichloro-1,3,5-triazine-2,4-diamine and 6-chloro-3,5-dinitropyridine-2,4-diamine.
7. The method for preparing a type of five-linked six-ring-based heat-resistant energetic compound according to claim 3, characterized in that: The molar ratio of the nitrogen-rich azole five-membered ring compound containing NH active sites to the nitrogen-rich chlorinated six-membered ring compound is 1 to 1.5:
1.
8. The method for preparing a type of five-linked six-ring-based heat-resistant energetic compound according to claim 3, characterized in that: The molar ratio of the catalyst to the nitrogen-rich azole five-membered ring compound containing NH active sites is 1 to 1.5:
1.
9. The method for preparing a type of five-linked six-ring-based heat-resistant energetic compound according to claim 3, characterized in that: The reaction temperature is 50 to 120° C., and the reaction time is 0.5 to 24 hours.
10. The method for preparing a type of five-linked six-ring-based heat-resistant energetic compound according to claim 3, characterized in that: The solvent is one of water, methanol, ethanol, acetonitrile, 1,4-dioxane, isopropanol and N,N-dimethylformamide.
11. Use of the five-linked six-ring based heat-resistant energetic compound according to claim 1 in energetic materials.