CN113443948B - Porous aromatic skeleton EPAF-6 material, NTO composite salt energetic material and preparation method thereof - Google Patents
Porous aromatic skeleton EPAF-6 material, NTO composite salt energetic material and preparation method thereof Download PDFInfo
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- CN113443948B CN113443948B CN202110770974.8A CN202110770974A CN113443948B CN 113443948 B CN113443948 B CN 113443948B CN 202110770974 A CN202110770974 A CN 202110770974A CN 113443948 B CN113443948 B CN 113443948B
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0008—Compounding the ingredient
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Abstract
The invention relates to a porous aromatic skeletonAn EPAF-6 material and NTO composite salt energetic material and a preparation method thereof, which take energetic monomers of cyantraniliprole acyl chloride and 4- (4H-1,2, 4-triazole-4-yl) -4H-1,2, 4-triazole as raw materials to design and synthesize a high-stability g-C 3 N 4 The novel high-energy low-sensitivity NTO @ EPAF-6 composite salt energetic material is successfully prepared by combining a nitrogen-rich cation porous aromatic skeleton EPAF-6 material with high-energy strong-acid elementary explosive NTO through charge interaction. The invention enriches the variety of novel high-energy low-sensitivity energetic materials and also provides a new research strategy for inhibiting the problem of acidic corrosion of NTO energetic single-substance explosives.
Description
Technical Field
The invention belongs to the field of energetic materials, and relates to a porous aromatic skeleton EPAF-6 material, an NTO composite salt energetic material and a preparation method thereof.
Background
The high-energy single-substance explosive is widely applied to military and civil fields such as weapons and ammunitions, space propellant, mining engineering, pyrotechnic technology and the like. NTO (3-nitro-1, 2, 4-triazole-5-ketone) is a white crystal, is a high-energy low-sensitivity single-substance explosive which is widely concerned in recent years, and has great development prospect. However, the acidity of NTO causes severe corrosion of metals causing a series of compatibility problems, which greatly limits the practical application of NTO. The strong acidity of NTO is manifested in two aspects: (1) residual nitric acid in the synthesis preparation process; (2) the active hydrogen at the N4 position in the molecular structure is more easily dissociated in a solvent, thereby exhibiting strong acidity. Therefore, the development of research on inhibition and protection of NTO single-substance explosive acid corrosion is of great significance.
Disclosure of Invention
The invention provides a porous aromatic skeleton EPAF-6 material and an NTO composite salt energetic material and a preparation method thereof, wherein energy-containing monomers of cyanuric chloride and 4- (4H-1,2, 4-triazole-4-yl) -4H-1,2, 4-triazole are used as raw materials to synthesize a novel g-C 3 N 4 The nitrogen-rich energetic cation porous aromatic skeleton EPAF-6 material is combined with high-energy single-substance explosive NTO to successfully obtain a novel composite salt energetic material NTO @ EPAF-6 with both high energy and low sensitivity. The high energy of the material is ensured, and simultaneously, the problems of acidic corrosion of NTO to metal and the like are greatly inhibited through charge interaction, and the research and development of a novel energetic material with high performance and high stability are realized.
Porous Aromatic Frameworks (PAFs), a class of novel Porous materials composed of aromatic building blocks connected by carbon-carbon bonds, have experienced rapid development over the past decade. PAFs materials have various high-porosity structures and ultrahigh chemical stability, and can resist various severe conditions such as strong acid, strong alkali, solvents, heat, humidity and the like. In addition, the aromatic group building units have rich structural types and good chemical reaction activity, and the PAFs structure and pore canal properties can be regulated and controlled by designing the structural units and modifying the PAFs framework, so that different performances are shown to be applied to various fields. Compared with a neutral polymer skeleton, the ionic polymer material has greater advantages in designing and adjusting the porous material with advanced functions. In addition to dynamic blocking or control, and adjustment of the pore size of the material framework by balancing ion exchange and mixing, the presence of charge can also impart selective interaction capability of the pore framework with guest molecules. Therefore, the porous aromatic skeleton PAFs material with the cationic skeleton is combined with NTO to prepare salt, so that the problem of acidic corrosion of the NTO can be effectively solved.
The invention is realized by the following technical scheme:
the porous aromatic skeleton EPAF-6 material has the following structure:
the g-C 3 N 4 The preparation method of the EPAF-6 material with the basic nitrogen-rich cation porous aromatic framework comprises the following two steps:
production method (1): weighing a certain amount of cyanuric chloride and 4- (4H-1,2, 4-triazole-4-yl) -4H-1,2, 4-triazole in a pyrex glass tube, adding a proper amount of solvent, and carrying out ultrasonic treatment on the mixed solution for a period of time. The freezing and vacuumizing operation is carried out under the protection of nitrogen and liquid nitrogen, and the tube is sealed under the vacuum condition by using butane/oxygen flame after three cycles of freezing, vacuumizing and unfreezing. After the glass tube containing the mixed solution was warmed to room temperature, it was placed in an oven at 80-120 ℃ for reaction for 2-4 days. The glass tube was removed from the oven and cooled to room temperature and the product was filtered. Then washed with anhydrous methanol and dried overnight under vacuum at 80 ℃ to give g-C 3 N 4 The base contains an energy-carrying cation porous aromatic framework EPAF-6 material.
Production method (2): weighing a certain amount of cyanuric chloride and 4- (4H-1,2, 4-triazole-4-yl) -4H-1,2, 4-triazole in a double-mouth bottle, adding a proper amount of solvent, and carrying out ultrasonic treatment on the mixed solution for a period of time. The reaction was stirred in an oil bath at 80-120 ℃ for 1-3 days under nitrogen protection and the product was filtered. Washing with anhydrous methanol, and vacuum drying at 80 deg.C overnight to obtain g-C 3 N 4 The base contains an energy-carrying cation porous aromatic framework EPAF-6 material.
The reaction solvent is dioxane, mesitylene, anhydrous acetonitrile and toluene.
The invention also provides an NTO composite salt energetic material which is an NTO and EPAF-6 composite salt energetic material, and the preparation of the composite material is realized by adopting an ion exchange method. Weighing a certain mass of NTO in a glass bottle, adding a proper amount of solvent to fully dissolve the NTO, and then adding the EPAF-6 material. The glass bottle is placed in an oil bath at the temperature of 25-50 ℃ and continuously stirred (the stirring speed is 200-400r/min) for 24 hours to obtain the NTO @ EPAF-6 composite salt energetic material.
The solvent is any one of water, water and ethanol, water and methanol, water and N, N-dimethylformamide; the volume ratio of the mixed solvent is 3: 1,2: 1,1:1.
Compared with the prior art, the invention has the beneficial effects that:
1. g-C prepared by the invention 3 N 4 The EPAF-6 material with the basic nitrogen-rich cation porous aromatic skeleton has a cation charge characteristic skeleton, high energy density, high thermal stability and stability, and is a novel energetic material with great application potential.
2. The successful preparation of the NTO @ EPAF-6 composite salt energetic material enables the acidic corrosion of NTO to be effectively inhibited, the safety performance of the NTO @ EPAF-6 composite salt energetic material to be remarkably improved, meanwhile, the good detonation performance is still kept, and a new research idea of the high-energy high-stability energetic material is provided.
3. The preparation method has the advantages of mild preparation conditions, simple process, convenient operation and high yield, and can meet the actual industrial production requirements.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The following is a detailed description of specific examples of the preparation of the NTO @ EPAF-6 composite salt energetic material of the present invention.
Example 1
The invention uses monomers of energy-containing cyanuric chloride and 4- (4H-1,2, 4-triazole-4-yl) -4H-1,2, 4-triazole as raw materials to polymerize into g-C 3 N 4 The synthesis route and the structure of the energy-containing cation porous aromatic skeleton EPAF-6 material and the NTO composite salt energy-containing material are as follows:
138.5mg of cyantranylchloride (0.5mmol) and 102mg of 4- (4H-1,2, 4-triazol-4-yl) -4H-1,2, 4-triazol (0.75mmol) are weighed into a 10mL pyrex glass tube, 3mL of mesitylene is added, and the mixed solution is subjected to ultrasound for 5 min. The freezing and vacuumizing operation is carried out under the protection of nitrogen and liquid nitrogen, and the tube is sealed under the vacuum condition by using butane/oxygen flame after three cycles of freezing, vacuumizing and unfreezing. After the glass tube containing the mixed solution was warmed to room temperature, it was placed in an oven at 120 ℃ for reaction for 3 days. The glass tube was removed from the oven and cooled to room temperature and the product was filtered. Then washing with absolute methanol, and drying overnight in vacuum at 80 ℃ to obtain the cationic porous aromatic skeleton EPAF-6 material. 800mg NTO was weighed into a glass vial, 40mL deionized water was added to dissolve it thoroughly, and 400mg EPAF-6 material was added. The glass bottle is placed in an oil bath at 50 ℃ and continuously stirred (the stirring speed is 200-.
Table 1 shows the impact sensitivity and detonation properties of EPAF-6 and NTO @ EPAF-6 composite salt energetic materials prepared according to the invention based on example 1. It can be seen from the table that EPAF-6 and NTO @ EPAF-6 composite salt energetic materials both show low sensitivity and good detonation performance.
TABLE 1 impact sensitivity and detonation behavior of EPAF-6 and NTO @ EPAF-6 composite energetic materials
Example 2
138.5mg of cyanuric chloride (0.5mmol) and 102mg of 4- (4H-1,2, 4-triazol-4-yl) -4H-1,2, 4-triazol (0.75mmol) are weighed into a 10mL pyrex glass tube, 3mL of anhydrous acetonitrile is added, and the mixed solution is subjected to ultrasound for 5 min. The freezing and vacuumizing operation is carried out under the protection of nitrogen and liquid nitrogen, and the tube is sealed under the vacuum condition by using butane/oxygen flame after three cycles of freezing, vacuumizing and unfreezing. After the glass tube containing the mixed solution was warmed to room temperature, it was placed in an oven at 120 ℃ for reaction for 3 days. The glass tube was removed from the oven and cooled to room temperature and the product was filtered. Then washing with absolute methanol, and drying overnight in vacuum at 80 ℃ to obtain the cationic porous aromatic skeleton EPAF-6 material. 800mg NTO was weighed into a glass vial, 40mL deionized water was added to dissolve it thoroughly, and 400mg EPAF-6 material was added. The glass bottle is placed in an oil bath at 50 ℃ and continuously stirred (the stirring speed is 200-.
Example 3
1.39g of cyanuric chloride (5mmol) and 1.02g of 4- (4H-1,2, 4-triazol-4-yl) -4H-1,2, 4-triazol (7.5mmol) are weighed into a 100mL double-neck bottle, 30mL of anhydrous acetonitrile is added, and the mixed solution is subjected to ultrasound for a period of time. The reaction was stirred in a 120 ℃ oil bath for 2 days under nitrogen protection and the product was filtered. Then washing with absolute methanol, and drying overnight in vacuum at 80 ℃ to obtain the cationic porous aromatic skeleton EPAF-6 material. 800mg NTO was weighed into a glass vial, 40mL deionized water was added to dissolve it thoroughly, and 400mg EPAF-6 material was added. The glass bottle is placed in an oil bath at 40 ℃ and continuously stirred (the stirring speed is 200-.
Example 4
Weighing 1.39g of cyanuric chloride (5mmol) and 1.02g of 4- (4H-1,2, 4-triazol-4-yl) -4H-1,2, 4-triazol (7.5mmol) in a 100mL double-neck bottle, adding 30mL of mesitylene, and carrying out ultrasound treatment on the mixed solution for a period of time. The reaction was stirred in a 100 ℃ oil bath for 2 days under nitrogen and the product was filtered. Then washing with absolute methanol, and drying overnight in vacuum at 80 ℃ to obtain the cationic porous aromatic skeleton EPAF-6 material. 800mg NTO was weighed into a glass vial, 40mL deionized water was added to dissolve it thoroughly, and 400mg EPAF-6 material was added. The glass bottle is placed in an oil bath at 30 ℃ and continuously stirred (the stirring speed is 200-.
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. The porous aromatic skeleton EPAF-6 material is characterized by having the following structure:
2. the preparation method of the porous aromatic skeleton EPAF-6 material as claimed in claim 1, characterized in that the material is prepared from energy-containing monomers of cyanuric chloride and 4- (4H-1,2, 4-triazole-4-yl) -4H-1,2, 4-triazole as raw materials.
3. The method for preparing a porous aromatic skeleton EPAF-6 material according to claim 2, characterized in that it comprises the following steps:
weighing a certain amount of cyanuric chloride and 4- (4H-1,2, 4-triazole-4-yl) -4H-1,2, 4-triazole in a pyrex glass tube, adding a proper amount of solvent, and carrying out ultrasonic treatment on the mixed solution for a period of time;
performing freeze-pumping operation under the protection of nitrogen and liquid nitrogen, performing three cycles of freezing, vacuumizing and unfreezing, and then sealing the tube under the vacuum condition by using butane and oxygen flame;
when the glass tube filled with the mixed solution is heated to room temperature, placing the glass tube in an oven at 80-120 ℃ for reaction for 2-4 days;
taking out the glass tube from the oven, cooling to room temperature, and filtering the product; then washed with anhydrous methanol and dried overnight under vacuum at 80 ℃ to give g-C 3 N 4 Radical energetic cation porous aromatic framework EPAF-6A material.
4. The method for preparing a porous aromatic skeleton EPAF-6 material according to claim 2, characterized in that it comprises the following steps:
weighing a certain amount of cyanuric chloride and 4- (4H-1,2, 4-triazole-4-yl) -4H-1,2, 4-triazole in a double-mouth bottle, adding a proper amount of solvent, and carrying out ultrasonic treatment on the mixed solution for a period of time;
stirring and reacting in an oil bath at the temperature of 80-120 ℃ for 1-3 days under the protection of nitrogen, and filtering a product;
washing with anhydrous methanol, and vacuum drying at 80 deg.C overnight to obtain g-C 3 N 4 The base contains an energy-carrying cation porous aromatic framework EPAF-6 material.
5. The method for preparing the porous aromatic skeleton EPAF-6 material according to claim 3 or 4, wherein the solvent is dioxane, mesitylene, anhydrous acetonitrile or toluene.
6. A preparation method of an NTO composite salt energetic material is characterized by comprising the following steps:
weighing a certain mass of NTO in a glass bottle, adding a proper amount of solvent to fully dissolve the NTO, and then adding the porous aromatic skeleton EPAF-6 material of claim 1;
and placing the glass bottle in an oil bath at the temperature of 25-50 ℃ for continuously stirring for 24 hours at the stirring speed of 200-400r/min to obtain the NTO @ EPAF-6 composite salt energetic material.
7. The preparation method of the NTO composite salt energetic material according to claim 6, wherein the solvent is any one of the following: water, water and ethanol, water and methanol, water and N, N-dimethylformamide; the volume ratio of the mixed solvent is 3: 1,2: 1 or 1: 1.
8. An NTO composite salt energetic material, which is prepared by the preparation method of claim 6 or 7.
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| CN112358370A (en) * | 2020-09-20 | 2021-02-12 | 北京理工大学 | CL-20 and NTO eutectic explosive and preparation method thereof |
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