Method for high and low temperature gradient dissolution of hydrogen-bond-rich explosive and application of method in weapon system

Abstract

The invention discloses a method for high and low temperature gradient dissolution of hydrogen-bond-rich explosives, and belongs to the field of TATB application. The method sequentially comprises the following steps: preparing a tetrabutylammonium fluoride / aqueous solution, namely a deep eutectic solvent A, with the molar ratio of 10: 0.5-10: 1.5; the method comprises the following steps: adding excessive TATB powder into a deep-eutectic solvent A, stirring at room temperature, and heating to the boiling point of water in stages; and measuring the TATB content at each section of temperature, and converting the TATB content into the solubility of the TATB at different temperatures. According to the method provided by the invention, gradient dissolution of the TATB at high and low temperatures can be realized, the solubility of the TATB at the high temperature is more than two times that of the TATB at the low temperature, the high and low temperature solubility difference (delta S) reaches 70mg / mL, a solvent solution can be provided for cooling recrystallization of the TATB, and the method has important application value in weapon systems. In addition, the invention further discloses application of the method for high and low temperature gradient dissolution of the hydrogen-bond-rich explosive in a weapon system.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen-rich explosives, and specifically relates to a method for high-low temperature gradient dissolution of hydrogen-rich explosives and its application in weapon systems. Background Technology

[0002] Hydrogen-rich explosives, such as 1,3,5-triamino-2,4,6-trinitrobenzene (1,3,5-triamino-2,4,6- trinitrobenzene (TATB), structural formula as follows Figure 1 As shown, TATB not only possesses high energy but also excellent safety performance, making it crucial for applications in weapon systems. High-temperature dissolution-cooling recrystallization is an important method for controlling the crystal morphology of materials; however, TATB's poor solubility and lack of suitable solvents make it difficult to control its morphology through high-temperature dissolution-cooling recrystallization, thus limiting its development and application to some extent. Although tetrabutylammonium fluoride, a eutectic solvent, can dissolve TATB at room temperature, increasing the temperature does not effectively improve its solubility, making it difficult to form a gradient dissolution characteristic at high and low temperatures. Furthermore, TATB is extremely hydrophobic; adding water to the solvent greatly weakens its solubility. Therefore, under normal circumstances, water is not actively introduced as a solvent component in TATB-related solvents. Summary of the Invention

[0003] In view of this, the present invention addresses the need for high and low temperature gradient dissolution during TATB recrystallization by innovatively introducing water molecules as hydrogen bond donors for the eutectic solvent. Through the hydrogen bonding between water molecules and tetrabutylammonium fluoride in the solvent, the dissolution of TATB by tetrabutylammonium fluoride is inhibited at room temperature and promoted at high temperature.

[0004] In this invention, unless otherwise specified, low temperature refers to room temperature, i.e., 25°C, and high temperature refers to 90°C.

[0005] The specific solution of the present invention is as follows: A method for high-low temperature gradient dissolution of hydrogen-bonded explosives, characterized by comprising the following steps in sequence: Prepare tetrabutylammonium fluoride / water solution with a molar ratio of 10:0.5 to 10:1.5, i.e. eutectic solvent A; Add excess TATB powder to eutectic solvent A, stir at room temperature, and then gradually heat to the boiling point of water. The TATB content at each temperature was measured, and the solubility of TATB at different temperatures was calculated.

[0006] In the present application, water molecules are introduced into tetrabutylammonium fluoride solvent as hydrogen bond donors to form a new type of eutectic solvent. By adjusting the molar ratio of tetrabutylammonium fluoride to water molecules, the high and low temperature solubility characteristics of TATB are realized, that is, the solubility of TATB increases with increasing temperature. Among them, water molecules in tetrabutylammonium fluoride solvent can play the role of temperature-sensitive dissolution switch. That is, at low temperature, water molecules form strong hydrogen bond interaction with fluoride ions to inhibit the dissolution of TATB in tetrabutylammonium fluoride; at high temperature, the hydrogen bond interaction is weakened, resulting in the release of free fluoride ions, thereby promoting the dissolution of TATB.

[0007] Preferably, the eutectic solvent A is a tetrabutylammonium fluoride / water solution with a molar ratio of 10:0.75-10:1.25; more preferably, the eutectic solvent A is a tetrabutylammonium fluoride / water solution with a molar ratio of 10:1.

[0008] Preferably, the specific preparation steps of the eutectic solvent A are as follows: add water to tetrabutylammonium fluoride until the molar ratio of tetrabutylammonium fluoride to water is 10:0.5-10:1.5, stir at room temperature until there is no solid residue in the water, and obtain the eutectic solvent A after standing.

[0009] Preferably, the specific steps of the step of gradually increasing the temperature to the boiling point of water after stirring at room temperature are as follows: stir at room temperature for 30 min; increase the temperature to 50°C and keep it at this temperature for 30 min; continue to increase the temperature to 70°C and keep it at this temperature for 30 min; continue to increase the temperature to 90°C and keep it at this temperature for 30 min.

[0010] Preferably, the TATB content at each temperature is measured by liquid chromatography external standard method; more preferably, the specific steps of the liquid chromatography external standard method are as follows: take samples of the sample to be measured at different temperatures, filter through a 0.45µm filter membrane; dilute with dimethyl sulfoxide (DMSO) and shake well; take an appropriate amount of the diluted sample solution and inject it into a liquid chromatograph to determine the TATB content; more preferably, in the step of diluting with DMSO, the dilution concentration is 0.04mg / mL.

[0011] Preferably, in the step of converting the solubility of TATB at different temperatures, a TATB standard substance is used as a reference.

[0012] Particularly preferably, a method for high and low temperature gradient dissolution of hydrogen bond-rich explosives comprises the following steps in sequence: Add water to tetrabutylammonium fluoride until the molar ratio of tetrabutylammonium fluoride to water is 10:0.5-10:1.5, stir at room temperature until there is no solid residue in the water, and obtain the eutectic solvent A after standing; An excess of TATB powder was added to the eutectic solvent A, and after stirring at room temperature for 30 min, a sample was taken for solubility analysis; the temperature was raised to 50℃, and maintained at this temperature for 30 min, a sample was taken for solubility analysis; the temperature was continuously raised to 70℃, and maintained at this temperature for 30 min, a sample was taken for solubility analysis; the temperature was continuously raised to 90℃, and maintained at this temperature for 30 min, at this time, there was still a small amount of residual TATB solid in the eutectic solvent A, a sample was taken for solubility analysis; The solubility analysis was performed by liquid chromatography external standard method.

[0013] Meanwhile, the application also provides a method for high-low temperature gradient dissolution of hydrogen bond-rich explosives and application of the method in weapon systems.

[0014] The application has the following beneficial effects: (1) The application innovatively introduces water molecules as hydrogen bond donors of the eutectic solvent, and by regulating the molar ratio of the water molecules and the hydrogen bond acceptor tetrabutylammonium fluoride, the dissolution of the tetrabutylammonium fluoride to TATB is inhibited at low temperature, and the dissolution of the tetrabutylammonium fluoride to TATB is promoted at high temperature, so as to realize the high-low temperature gradient dissolution characteristics of the TATB solubility increasing with the increase of temperature.

[0015] (2) Based on the method of the application, the solubility of TATB at high temperature is more than twice that at low temperature, and the high-low temperature solubility difference (ΔS) reaches 70 mg / mL, which provides a solvent solution for the TATB recrystallization by the cooling method, and has important application value in weapon systems, wherein the high-low temperature solubility difference (ΔS) = solubility at high temperature - solubility at low temperature.

[0016] (3) The method for high-low temperature gradient dissolution of hydrogen bond-rich explosives provided by the application can support the basic research and engineering application of TATB refining and purification, morphology control, etc. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 is a structural formula of TATB; Figure 2 is the solubility of TATB at different temperatures under the condition of Example 2; Figure 3 is the solubility of TATB at different temperatures under the condition of Comparative Example 1; Figure 4 is the solubility of TATB at different temperatures under the condition of Comparative Example 3; Figure 5 is the solubility of TATB at different temperatures under the condition of Comparative Example 4. DETAILED DESCRIPTION

[0018] The specific examples listed in the present application are only as examples of the present application, and the present application is not limited to the specific examples described below. Any equivalent modifications and substitutions of the examples described below are also within the scope of the present application for those skilled in the art. Therefore, equivalent transformations and modifications made without departing from the spirit and scope of the present application should be encompassed within the scope of the present application. The specific conditions not mentioned in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer. All reagents or instruments not mentioned by the manufacturer are conventional products available on the market. In order to better illustrate the present application, numerous specific details are given in the following specific embodiments. Those skilled in the art should understand that the present application can also be implemented without certain specific details. In some embodiments, methods, means, apparatus and steps well known to those skilled in the art are not described in detail in order to highlight the main idea of the present application.

[0019] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Units used in the specification are international standard units, and the numerical values and numerical ranges appearing in the present application should be understood to include systematic errors inevitable in industrial production, unless otherwise specified.

[0020] The features and properties of the present application are further described in detail below in conjunction with the examples.

[0021] I. Experimental design 1. Example 1 Preparation of solvent: 20 g of tetrabutylammonium fluoride was weighed into a glass beaker, and water was added until the molar ratio of tetrabutylammonium fluoride to water was 10:0.5. The mixture was stirred at room temperature until no solid residue was left in the solution, and the solution was a transparent colorless liquid. After standing for a period of time, eutectic solvent A was obtained.

[0022] TATB dissolution: 1 g of excess TATB powder was added to 10 mL of eutectic solvent A, and the mixture was stirred at room temperature for 30 min. The sample was taken for solubility analysis. The temperature was increased to 50°C, and the sample was taken for solubility analysis after keeping at this temperature for 30 min. The temperature was further increased to 70°C, and the sample was taken for solubility analysis after keeping at this temperature for 30 min. The temperature was further increased to 90°C, and the sample was taken for solubility analysis after keeping at this temperature for 30 min. At this time, there was still a small amount of residual TATB solid in the eutectic solvent A, and the sample was taken for solubility analysis.

[0023] Solubility analysis: The solubility of TATB at different temperatures was determined by liquid chromatography external standard method, namely solubility analysis. The specific steps were as follows: 1 mL of the sample solution to be tested was accurately taken and filtered through a 0.45 μm filter membrane; diluted with DMSO to 0.04 mg / mL and shaken uniformly; 5.0 μL of the diluted sample solution was injected into the liquid chromatograph to determine the content of TATB, and the solubility of TATB at different temperatures was converted based on the TATB standard substance.

[0024] 2. Example 2 Preparation of solvent: Except that the molar ratio of tetrabutylammonium fluoride to water was adjusted to 10:1, the rest was the same as in Example 1.

[0025] TATB dissolution: The same as in Example 1.

[0026] Solubility analysis: The same as in Example 1.

[0027] 3. Example 3 Preparation of solvent: Except that the molar ratio of tetrabutylammonium fluoride to water was adjusted to 10:1.5, the rest was the same as in Example 1.

[0028] TATB dissolution: The same as in Example 1.

[0029] Solubility analysis: The same as in Example 1.

[0030] 4. Comparative Example 1 Preparation of solvent: Except that the molar ratio of tetrabutylammonium fluoride to water was adjusted to 10:0.3 to obtain the eutectic solvent B, the rest was the same as in Example 1.

[0031] TATB dissolution: Except that the eutectic solvent A was adjusted to the eutectic solvent B, the rest was the same as in Example 1.

[0032] Solubility analysis: The same as in Example 1.

[0033] 5. Comparative Example 2 Preparation of solvent: Except that the molar ratio of tetrabutylammonium fluoride to water was adjusted to 10:2, the rest was the same as in Example 2.

[0034] TATB dissolution: The same as in Comparative Example 2.

[0035] Solubility analysis: The same as in Example 1.

[0036] 6. Comparative Example 3 Preparation of solvent: Except that the molar ratio of tetrabutylammonium fluoride to water was adjusted to 10:10, the rest was the same as in Example 2.

[0037] TATB dissolution: The same as in Comparative Example 2.

[0038] Solubility analysis: The same as in Example 1.

[0039] 7. Comparative Example 4 Preparation of the solvent: Except that the water was replaced by DMSO, the rest was the same as Example 1, i.e. 20 g of tetrabutylammonium fluoride was weighed into a glass beaker, and DMSO was added until the molar ratio of tetrabutylammonium fluoride to DMSO was 10:0.5, and stirred at room temperature until there were no solid residues in the mixed solution, and the solution was a transparent colorless liquid. After standing for a period of time, eutectic solvent C was obtained.

[0040] TATB dissolution: Except that the eutectic solvent A was replaced by eutectic solvent C, the rest was the same as Example 1.

[0041] Solubility analysis: The same as Example 1.

[0042] 8. Comparative Example 5 Preparation of the solvent: Except that the molar ratio of tetrabutylammonium fluoride to DMSO was adjusted to 10:1.5, the rest was the same as Comparative Example 4.

[0043] TATB dissolution: The same as Comparative Example 4.

[0044] Solubility analysis: The same as Example 1.

[0045] 9. Comparative Example 6 Preparation of the solvent: Except that the water was replaced by N,N-dimethylformamide (DMF), the rest was the same as Example 1, i.e. 20 g of tetrabutylammonium fluoride was weighed into a glass beaker, and DMF was added until the molar ratio of tetrabutylammonium fluoride to DMF was 10:0.5, and stirred at room temperature until there were no solid residues in the mixed solution, and the solution was a transparent colorless liquid. After standing for a period of time, eutectic solvent D was obtained.

[0046] TATB dissolution: Except that the eutectic solvent A was replaced by eutectic solvent D, the rest was the same as Example 1.

[0047] Solubility analysis: The same as Example 1.

[0048] 10. Comparative Example 7 Preparation of the solvent: Except that the molar ratio of tetrabutylammonium fluoride to DMF was adjusted to 10:1.5, the rest was the same as Comparative Example 6.

[0049] TATB dissolution: The same as Example 6.

[0050] Solubility analysis: The same as Example 1.

[0051] 11. Comparative Example 8 Preparation of the solvent: except that the water was adjusted to acetonitrile, the rest was the same as Example 1, i.e. 20 g of tetrabutylammonium fluoride was weighed into a glass beaker, acetonitrile was added until the molar ratio of tetrabutylammonium fluoride to acetonitrile was 10:0.5, stirring at room temperature until there were no solid residues in the mixed solution, the solution was a transparent colorless liquid, after standing for a period of time, the eutectic solvent E was obtained.

[0052] TATB dissolution: except that the eutectic solvent A was adjusted to the eutectic solvent E, the rest was the same as Example 1.

[0053] Dissolution analysis: the same as Example 1.

[0054] 12. Comparative Example 9 Preparation of the solvent: except that the molar ratio of tetrabutylammonium fluoride to acetonitrile was adjusted to 10:1.5, the rest was the same as Comparative Example 8.

[0055] TATB dissolution: the same as Example 8.

[0056] Dissolution analysis: the same as Example 1.

[0057] II. Analysis of results Figure 2 For the solubility of TATB at different temperatures under the conditions of Example 2, it can be seen that the solubility of TATB at low temperature, i.e. 25°C, is 55 mg / mL, and the solubility of TATB at high temperature, i.e. 90°C, is 125 mg / mL, the solubility of TATB at high temperature is more than twice that at low temperature, and the difference in solubility between high and low temperatures (AS) reaches 70 mg / mL, which indicates that the solvent has a significant high-low temperature gradient dissolution effect on the dissolution of TATB.

[0058] Figure 3 For the solubility of TATB at different temperatures under the conditions of Comparative Example 1, it can be seen that the solubility of TATB at low temperature, i.e. room temperature, i.e. 25°C, is 75 mg / mL, and the solubility of TATB at high temperature, i.e. 90°C, is 85 mg / mL, the difference in solubility between high and low temperatures (AS) is only 10 mg / mL, which is 14.3% of AS in Example 2, which indicates that the solvent B has no significant high-low temperature gradient dissolution effect on the dissolution of TATB.

[0059] Figure 4 For the solubility of TATB at different temperatures under the conditions of Comparative Example 3, it can be seen that the solubility of TATB at low temperature, i.e. 25°C, is 10 mg / mL, and the solubility of TATB at high temperature, i.e. 90°C, is 12 mg / mL, the difference in solubility between high and low temperatures (AS) is only 2 mg / mL, which is 2.9% of AS in Example 2, which indicates that the solvent has no high-low temperature gradient dissolution effect on the dissolution of TATB.

[0060] Figure 5For the solubility of TATB at different temperatures under the condition of Comparative Example 4, it can be seen that the solubility of TATB at low temperature of 25℃ is 120 mg / mL, and the solubility of TATB at high temperature of 90℃ is 125 mg / mL, and the difference (ΔS) of solubility between high and low temperature is only 5 mg / mL, which is 7.1% of ΔS in Example 2, which indicates that the solvent C has no obvious high and low temperature gradient dissolution effect on the dissolution of TATB.

[0061] The high and low temperature solubility performance analysis of Examples 1-3 and Comparative Examples 1-9 is shown in Table 1.

[0062] Table 1 High and low temperature solubility performance analysis of Examples 1-3 and Comparative Examples 1-9

[0063] From Table 1, the following conclusions can be drawn: (1) From Examples 1-3, when the hydrogen bond donor is water, and the molar ratio of the hydrogen bond acceptor tetrabutylammonium fluoride to the hydrogen bond donor water is 10:0.5-10:1.5, the difference of high and low temperature solubility can reach 70 mg / mL (Example 2). This indicates that the eutectic solvent A of tetrabutylammonium fluoride / water solution with a molar ratio of 10:0.5-10:1.5 has obvious high and low temperature gradient dissolution effect on the dissolution of TATB.

[0064] (2) Compared with Examples 1-3, only adjusting the molar ratio of tetrabutylammonium fluoride to water to 10:0.3 (Comparative Example 1), 10:2 (Comparative Example 2) and 10:10 (Comparative Example 3), the difference of high and low temperature solubility ΔS is low, which is 10 mg / mL, 2 mg / mL and 2 mg / mL respectively, and there is no obvious high and low temperature gradient dissolution effect. This further indicates that adjusting the molar ratio of tetrabutylammonium fluoride to water in the eutectic solvent is a key condition for TATB to have obvious high and low temperature gradient dissolution effect.

[0065] (3) Compared with Example 1, only adjusting the hydrogen bond donor from water to DMSO (Comparative Example 4), DMF (Comparative Example 6) and acetonitrile (Comparative Example 8), the difference of high and low temperature solubility ΔS is low, which is 5 mg / mL, 6 mg / mL and 7 mg / mL respectively, and there is no obvious high and low temperature gradient dissolution effect. This indicates that only when the eutectic solvent is tetrabutylammonium fluoride / water solution with a specific molar ratio, can TATB have obvious high and low temperature gradient dissolution effect.

[0066] (4) Compared with Example 3, only the hydrogen bond donor is changed from water to DMSO (Comparative Example 5), DMF (Comparative Example 7) and acetonitrile (Comparative Example 9), and the high-low temperature solubility difference ΔS is low, which is 5 mg / mL, 8 mg / mL and 8 mg / mL respectively, and there is no obvious high-low temperature gradient dissolution effect. This further indicates that only when the eutectic solvent is a specific molar ratio of tetrabutylammonium fluoride / water solution, can the dissolution of TATB have an obvious high-low temperature gradient dissolution effect.

[0067] In summary, only by using tetrabutylammonium fluoride as the hydrogen bond acceptor and water as the hydrogen bond donor, and keeping the molar ratio of tetrabutylammonium fluoride to water at 10:0.5 to 10:1.5, can TATB have a significant high-low temperature gradient dissolution effect.

[0068] The above examples only express the specific embodiments of the present application, which are described in detail and specifically, but cannot be understood as a limitation on the protection scope of the present application. It should be noted that for those skilled in the art, without departing from the technical concept of the present application, a number of modifications and improvements can be made, which are all within the protection scope of the present application.

Claims

1. A method for high-low temperature gradient dissolution of hydrogen-bonded rich explosives, characterized by, Comprise the following steps in sequence: Preparation of a tetrabutylammonium fluoride / water solution with a molar ratio of 10:0.5~10:1.5, i.e. a low eutectic solvent A; Add an excess of TATB powder to the low eutectic solvent A, and after stirring at room temperature, gradually increase the temperature to the boiling point of water; Measure the TATB content at each temperature, and convert to obtain the solubility of TATB at different temperatures.

2. The method for high and low temperature gradient dissolution of hydrogen bond rich explosives of claim 1, wherein, The low eutectic solvent A is a tetrabutylammonium fluoride / water solution with a molar ratio of 10:0.75~10:1.

25.

3. The method for high and low temperature gradient dissolution of hydrogen bond rich explosives of claim 2, wherein, The low eutectic solvent A is a tetrabutylammonium fluoride / water solution with a molar ratio of 10:

1.

4. The method for high and low temperature gradient dissolution of hydrogen bond rich explosives of claim 1, wherein, The specific preparation steps of the low eutectic solvent A are as follows: add water to tetrabutylammonium fluoride until the molar ratio of tetrabutylammonium fluoride to water is 10:0.5~10:1.5, stir at room temperature until there is no solid residue in the water, and after standing, obtain the low eutectic solvent A.

5. The method for high and low temperature gradient dissolution of hydrogen bond rich explosives of claim 1, wherein, The specific steps of stirring at room temperature and then gradually increasing the temperature to the boiling point of water are as follows: stir at room temperature for 30 min, increase the temperature to 50℃, and keep at this temperature for 30 min; continue to increase the temperature to 70℃, and keep at this temperature for 30 min; continue to increase the temperature to 90℃, and keep at this temperature for 30 min.

6. The method for high and low temperature gradient dissolution of hydrogen bond rich explosives of claim 1, wherein, The TATB content at each temperature is measured by liquid chromatography external standard method.

7. The method for high and low temperature gradient dissolution of hydrogen bond rich explosives of claim 6, wherein, The specific steps of the liquid chromatography external standard method are as follows: take the sample to be measured at different temperatures, filter through a 0.45µm filter membrane; dilute with DMSO, shake well; take an appropriate amount of diluted sample solution and inject it into the liquid chromatograph to determine the TATB content.

8. The method for high and low temperature gradient dissolution of hydrogen bond rich explosives of claim 7, wherein, In the step of diluting with DMSO, the dilution concentration is 0.04mg / mL.

9. The method for high and low temperature gradient dissolution of hydrogen bond rich explosives of claim 1, wherein, In the step of converting to obtain the solubility of TATB at different temperatures, a TATB standard substance is used as a reference.

10. Use of the method for high and low temperature gradient dissolution of hydrogen bond-rich explosives according to any one of claims 1-9 in a weapon system.

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