A nitrogen-rich condensed ring energetic compound and a preparation method thereof
By preparing a nitrogen-rich fused-ring energetic compound of 6-azidotetrazole[1,5-b][1,2,4]triazine-7-amine, the environmental pollution and stability problems of initiating explosives were solved, and the application of green initiating explosives with high energy density and low sensitivity was realized.
Patent Information
- Application Number
- CN202411683515.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-22
- Publication Date
- 2025-11-07
- Estimated Expiration
- 2044-11-22
Smart Images
Figure CN119504763B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of energetic materials, and particularly relates to a nitrogen-rich condensed ring energetic compound and a preparation method thereof. BACKGROUND
[0002] Primary explosive is a sensitive explosive which can heat and burn under the action of weak external excitation energy such as heat, electricity, light, machinery, impact and friction, and can rapidly initiate and detonate. Primary explosive has high sensitivity, short growth period of detonation, and detonation wave generated by detonation is used to initiate explosive, so it is also called primary explosive. As the initial charge of the explosive device, primary explosive is filled in various initiating devices and is widely used in explosive devices. Primary explosive is usually used to initiate explosive. According to the composition, primary explosive can be divided into single-element primary explosive, mixed primary explosive and complex salt primary explosive; according to the excitation mode, primary explosive can be divided into needle-sticking explosive, percussion explosive, friction explosive and conductive explosive.
[0003] A kind of primary explosive should have certain temperature and humidity resistance, sufficient initiation ability, appropriate sensitivity, qualified stability, good charging process performance and other basic requirements; in addition, it is required that the preparation raw material is cheap and easy to obtain, the production process is simple, the operation is safe, the environmental pollution is avoided, and it is green and environmentally friendly. At present, the most commonly used primary explosive includes lead azide, lead styphnate and 2,4-dinitro-diazophenol (DDNP), etc. However, the industrial application of the above-mentioned primary explosive can easily lead to environmental pollution and health hazards, and is listed as a "highly concerned substance". Therefore, a new type of environmentally friendly primary explosive has become a research trend of energetic compounds.
[0004] Multi-nitro nitrogen-rich energetic derivatives have high energy, high density and high enthalpy of formation due to the presence of a large number of C-N bonds and N-N bonds in their molecular structure, and their decomposition products are non-polluting nitrogen, which is considered to be a substitute for high-energy materials. Although multi-nitro nitrogen-rich compounds have good density and detonation performance, they usually have low stability. For example, 1,1'-dinitroamino-5,5'-tetrazolium di-potassium salt (K2DNABT) has extremely short deflagration-to-detonation (DDT) behavior, and has high sensitivity to friction, impact and electrostatic discharge. However, the synthesis steps are complex (6-step reaction), the total yield is low (<14.7%), and the mechanical sensitivity is extremely high (IS=1J, FS≤1N), which limits its further application. Therefore, while increasing the nitrogen content of energetic materials, it is important to further improve the stability of energetic materials.
[0005] In summary, it is of great significance to develop a new type of nitrogen-rich energetic material with simple synthesis steps, good stability and green and non-polluting. SUMMARY
[0006] In a first aspect, the present application provides a 6-azidotetrazol[1,5-b][1,2,4]triazin-7-amine nitrogen-rich fused ring energetic compound; the fused ring molecular structure contains N5 chain, azido group and amino structure, and its chemical structural formula is shown as Formula I:
[0007]
[0008] In a second aspect, the present application provides a preparation method of a 6-azidotetrazol[1,5-b][1,2,4]triazin-7-amine nitrogen-rich fused ring energetic compound, comprising the following steps:
[0009] In step 1, 3,5,6-trichloro-1,2,4-triazine and an aminating reagent are used as raw materials, 3,5,6-trichloro-1,2,4-triazine is dissolved in a polar solvent, then the aminating reagent is added for reaction, solid phase is separated and washed and dried to obtain compound A; the structural formula of the compound A is shown as Formula II:
[0010]
[0011] In step 2, compound A is dissolved in a mixed solvent, and a nucleophilic substitution reaction is carried out with an azidation reagent, solid phase is separated and washed and dried to obtain a 6-azidotetrazol[1,5-b][1,2,4]triazin-7-amine nitrogen-rich fused ring energetic compound; the fused ring molecular structure contains N5 chain, azido group and amino structure, and its chemical structural formula is shown as Formula I:
[0012]
[0013] As a preferred solution, the polar solvent in step 1 is one or more of acetonitrile and ethanol.
[0014] As a preferred solution, the aminating reagent in step 1 is ammonia water.
[0015] As a preferred solution, the molar ratio of 3,5,6-trichloro-1,2,4-triazine to the aminating reagent in step 1 is 1:1.2-1:1.5, the reaction time is 12-24 hours, the temperature when the aminating reagent is added is 0-2℃, and the reaction temperature is 18-20℃.
[0016] As a preferred solution, the solid phase washing solvent in step 1 is deionized water.
[0017] As a preferred solution, the azidation reagent in step 2 is one or more of sodium azide, azidotrimethylsilane and azidophosphoric acid diphenyl ester.
[0018] As a preferred solution, the mixed solvent in step 2 is one or more of a mixture of acetone and water and a mixture of acetonitrile and water.
[0019] As a preferred solution, the molar ratio of compound A to the azide reagent in step 2 is 1:2.4-1:3.0, the reaction time is 18-36 hours, and the reaction temperature is 75-85°C.
[0020] As a preferred solution, the solid phase washing solvent in step 2 is deionized water.
[0021] In a third aspect, the application provides the use of the 6-azidotetrazol[1,5-b][1,2,4]triazin-7-amine in energetic materials. The energetic material is used in the field of green primary explosive as a novel nitrogen-rich energetic material.
[0022] The above technical solution has the following beneficial effects:
[0023] (1) The 6-azidotetrazol[1,5-b][1,2,4]triazin-7-amine provided by the application has high nitrogen content and high energy density. Its impact sensitivity is 12 J, friction sensitivity is 48 N, detonation velocity reaches 8761 m / s -1 , and detonation pressure reaches 29.3 GPa. The above performance indicators are superior to lead styphnate and DDNP.
[0024] (2) The energetic compound is obtained by ammoniation and azidation using 3,5,6-trichloro-1,2,4-triazine as a raw material. The method is simple and reliable, has high yield, good stability, is suitable for large-scale production, and has low production cost. BRIEF DESCRIPTION OF DRAWINGS
[0025] Figure 1 NMR carbon spectrum of compound A obtained in Example 1;
[0026] Figure 2 NMR hydrogen spectrum of compound A obtained in Example 1;
[0027] Figure 3 NMR carbon spectrum of compound I obtained in Example 1;
[0028] Figure 4 NMR hydrogen spectrum of compound I obtained in Example 1;
[0029] Figure 5 Single crystal molecular structure diagram of compound I obtained in Example 1;
[0030] NMR spectrum Figures 1-4 The abscissa represents the chemical shift, and the ordinate represents the intensity of the peak. DETAILED DESCRIPTION
[0031] In order to make the technical scheme of the present application clearer, the present application will be further described in detail below in combination with specific examples. The examples are only used to further illustrate the present application and cannot be understood as limiting the protection scope of the present application. Some non-essential improvements and adjustments made by the ordinary skilled in the art according to the above description of the present application still belong to the protection scope of the present application.
[0032] Example 1
[0033] Step 1: 15.0 g (0.081 mol) of 3,5,6-trichloro-1,2,4-triazine was added into 80 mL of acetonitrile; 13.6 ml of 28% mass concentration of ammonia water was added thereto at 0°C, and the temperature was raised to 20°C, and the reaction was carried out for 12 hours; after the reaction was completed, filtration was carried out under reduced pressure, water washing and drying were carried out, and 12.2 g of white solid was obtained, which was solid product A.
[0034] Elemental analysis was carried out on the obtained solid product A, and the mass percentage of each element was obtained as follows: C was 21.78%, H was 1.20%, Cl was 42.95%, and N was 34.07%.
[0035] NMR analysis was carried out on the obtained solid product A, and in addition to water peak and solvent peak, only one group of amino peaks was obtained, which was consistent with the structural characteristics, and the NMR analysis results were as follows: Figure 1 Figure 2
[0036] Step 2: 1.65 g (0.01 mol) of solid product A was weighed, and at room temperature, the solid product A was added into 30 mL of a mixed solution of acetone and water (the volume ratio of acetone to water was 5:1), and then 2.76 g of azido trimethylsilane reagent (0.024 mol) was added into the reaction system in batches, and after the dropwise addition was completed, the temperature was gradually raised to reflux state, and the reaction was carried out for 24 hours; after the reaction was completed, filtration was carried out under reduced pressure, deionized water washing and drying were carried out, and 1.57 g of white solid product I was obtained, which was 6-azidotetrazol[1,5-b][1,2,4]triazin-7-amine.
[0037] Elemental analysis was carried out on the obtained solid product I, and the mass percentage of each element was obtained as follows: C was 20.31%, H was 1.17%, and N was 78.52%, which was consistent with the element mass percentage in the compound 6-azidotetrazol[1,5-b][1,2,4]triazin-7-amine (C: 20.23%, H: 1.13%, N: 78.64%).
[0038] NMR analysis was carried out on the obtained solid product I, and the NMR chemical shift was assigned, and in addition to water peak and solvent peak, only one group of amino peaks was obtained, which was consistent with the structural characteristics, and the NMR analysis results were as follows: Figure 3 Figure 4
[0039] The crystal structure analysis of the obtained solid product I, combined with the crystal structure diagram, proves that the solid product I prepared is a 6-azidotetrazol[1, 5-b][1, 2, 4]triazin-7-amine rich nitrogen-containing ring energetic compound. The crystal structure diagram is shown in Figure 5 .
[0040] The above structural identification data proves that the obtained solid product I is 6-azidotetrazol[1, 5-b][1, 2, 4]triazin-7-amine.
[0041] Example 2
[0042] Step 1: 10.0 g (0.081 mol) of 3, 5, 6-trichloro-1, 2, 4-triazine was added into 80 mL of ethanol, and 9.1 ml of 28% mass concentration of ammonia water was added at 0℃, and then the temperature was increased to 20℃, and reacted for 12 hours; after the reaction was completed, the product was filtered under reduced pressure, washed with water and dried to obtain 7.6 g of white solid, which was solid product A.
[0043] Elemental analysis was performed on the obtained solid product A, and the mass percentage of each element was obtained as follows: C was 21.75%, H was 1.24%, Cl was 42.91%, and N was 34.10%.
[0044] NMR analysis was performed on the obtained solid product A, and there was only one group of amino peaks in addition to the water peak and the solvent peak, which was consistent with the structural characteristics. The NMR analysis results were consistent with those of Example 1, and were shown in Figure 1 、 Figure 2 .
[0045] Step 2: 3.30 g (0.02 mol) of solid product A was weighed and added into 60 mL of a mixed solution of acetonitrile and water (volume ratio of acetone to water was 5:1) at room temperature, and then 13.76 g of diphenyl phosphorazide (0.050 mol) was added into the reaction system in batches, and after the dropwise addition was completed, the temperature was gradually increased to reflux state, and reacted for 24 h. After the reaction was completed, the product was filtered under reduced pressure, washed with deionized water and dried to obtain 3.20 g of white solid product I, which was 6-azidotetrazol[1, 5-b][1, 2, 4]triazin-7-amine.
[0046] Elemental analysis was performed on the obtained solid product I, and the mass percentage of each element was obtained as follows: C was 20.33%, H was 1.19%, and N was 75.48%.
[0047] NMR analysis was performed on the obtained solid product I, and there was only one group of amino peaks in addition to the water peak and the solvent peak, which was consistent with the structural characteristics. The NMR analysis results were consistent with those of Example 1, and were shown in Figure 3 、 Figure 4 .
[0048] The crystal structure analysis of the obtained solid product I, combined with the crystal structure diagram, proves that the obtained is 6-azidotetrazol[1,5-b][1,2,4]triazin-7-amine rich nitrogen-containing energetic compound. The crystal structure is consistent with that of Example 1, see Figure 5 .
[0049] The above structure identification data proves that the obtained solid product I is 6-azidotetrazol[1,5-b][1,2,4]triazin-7-amine.
[0050] Example 3
[0051] The EXPL05 software (version 6.05) is used to calculate and test the detonation velocity and detonation pressure and other indexes of the 6-azidotetrazol[1,5-b][1,2,4]triazin-7-amine rich nitrogen-containing energetic compound prepared in Example 1, to predict the detonation performance; the differential scanning calorimeter is used to determine the decomposition temperature of the 6-azidotetrazol[1,5-b][1,2,4]triazin-7-amine rich nitrogen-containing energetic compound prepared in Example 1, and the specific results are shown in Table 1.
[0052] Table 1: Performance data of the 6-azidotetrazol[1,5-b][1,2,4]triazin-7-amine rich nitrogen-containing energetic compound prepared in Example 1
[0053]
[0054] Wherein, [a] represents the thermal decomposition temperature, the unit is [℃]; [b] represents the density, the unit is [g·cm 3 ]; [c] represents the oxygen balance (C0), the unit is [%]; [d] represents the molar enthalpy of formation, the unit is [kJ·mol 1 ]; [e] represents the detonation velocity, the unit is [m·s 1 ]; [f] represents the detonation pressure, the unit is [GPa]; [g] represents the impact sensitivity, the unit is [J]; [h] represents the friction sensitivity, the unit is [N].
[0055] The EXPL05 software (version 6.05) is used to calculate and test the detonation velocity and detonation pressure and other indexes of the 6-azidotetrazol[1,5-b][1,2,4]triazin-7-amine rich nitrogen-containing energetic compound prepared in Example 2, to predict the detonation performance; the differential scanning calorimeter is used to determine the decomposition temperature of the 6-azidotetrazol[1,5-b][1,2,4]triazin-7-amine rich nitrogen-containing energetic compound prepared in Example 2, and the specific results are basically consistent with those of Example 1.
[0056] The above test results show that the 6-azidotetrazol[1,5-b][1,2,4]triazin-7-amine nitrogen-rich energetic compound can be prepared according to the preparation method shown in Examples 1-2, and the compound has excellent performance, high nitrogen content and high energy density, and the impact sensitivity, friction sensitivity, detonation velocity and detonation pressure performance indexes are all better than those of lead styphnate and DDNP.
[0057] The above examples only express several embodiments of the present application, and the description is more specific and detailed, but it cannot be understood as limiting the scope of the patent of the present application. It should be pointed out that for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the present application, which all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.
Claims
1. A nitrogen-rich condensed energetic compound, characterized in that, The nitrogen-rich condensed energetic compound is 6-azidotetrazolo[1,5-b][1,2,4]triazin-7-amine, and its chemical structural formula is shown as Formula I:
2. A process for the preparation of the nitrogen-rich condensed energetic compound of claim 1, characterized in that, The method comprises the following steps: In step 1, 3, 5, 6-trichloro-1, 2, 4-triazine and an aminating agent are used as raw materials, 3, 5, 6-trichloro-1, 2, 4-triazine is dissolved in a polar solvent, then the aminating agent is added for reaction, solid phase is separated and washed and dried to obtain compound A; the structural formula of the compound A is shown as Formula II: In step 2, compound A is dissolved in a mixed solvent, nucleophilic substitution reaction is carried out with an azidation agent, solid phase is separated and washed and dried to obtain 6-azidotetrazolo[1, 5-b][1, 2, 4]triazin-7-amine; the mixed solvent is a mixture of acetone and water, the volume ratio of the acetone to water is 5:1; the azidation agent is diphenyl phosphorazidate.
3. The process for preparing the nitrogen-rich condensed energetic compound according to claim 2, characterized in that, In step 1, the polar solvent is one or more of acetonitrile and ethanol.
4. The process for preparing the nitrogen-rich condensed energetic compound according to claim 3, characterized in that, In step 1, the aminating agent is ammonia water.
5. The process for preparing the nitrogen-rich condensed energetic compound according to claim 4, characterized in that, In step 1, the molar ratio of 3, 5, 6-trichloro-1, 2, 4-triazine to the aminating agent is 1:1.2-1:1.5, the reaction time is 12-24 hours, the temperature for adding the aminating agent is 0-2 ℃, and the reaction temperature is 18-20 ℃.
6. The process for preparing the nitrogen-rich condensed energetic compound according to claim 2, wherein In step 2, the molar ratio of compound A to the azidation agent is 1:2.4-1:3.0, the reaction time is 18-36 hours, and the reaction temperature is 75-85 ℃.
7. Application of the nitrogen-rich condensed energetic compound in claim 1 in an energetic material.
8. Application of the nitrogen-rich condensed energetic compound in claim 1 in a primary explosive.