An energetic complex k-bte and a continuous preparation method and application thereof

Abstract

The application provides a kind of energetic complex K-BTE and its continuous preparation method and application, by taking 1,2-di (tetrazole-5-yl) ethane as starting material, ligand solution and metal ion salt solution are continuously injected into continuous flow reaction unit by injection pump respectively, by filtering, washing, drying, obtain energetic complex crystal, develop a kind of simple continuous process, mild reaction conditions new energetic complex preparation method, and first of all, a kind of novel structure, excellent comprehensive performance energetic complex K-BTE is prepared, in addition to the characteristics of high thermal stability, energetic complex K-BTE also has the advantages of simple and efficient process method, process safety controllable, the thermal decomposition temperature of K-BTE is as high as 366.5 DEG C, the actual measured impact sensitivity is greater than 40J, the friction sensitivity is between 240N-360N, while having catalytic effect on thermal decomposition of ammonium perchlorate.The excellent performance of K-BTE makes it have great application potential as an energetic complex in the field of catalytic solid propellant combustion efficiency.

Description

Technical Field

[0001] This invention relates to the field of energetic materials technology, specifically to an energetic complex K-BTE and its continuous preparation method and application. Background Technology

[0002] Energetic coordination compounds have significant scientific value in various fields such as materials science, chemical engineering, and military applications. Especially in the field of energetic materials, the development of high-energy-density, high-performance energetic coordination compounds is a key research focus. In recent decades, the development of energetic materials has focused on achieving a balance between higher performance, superior thermal stability, and lower sensitivity. Tetraazole compounds, due to the large number of N-N, N=N, and CN bonds in their molecular structure, can release a large amount of energy during decomposition or explosion, and also exhibit relatively good thermal stability, thus showing promising application prospects.

[0003] 1,2-Di(tetrazol-5-yl)ethane, a type of tetrazolium compound, possesses flexible and torsion-like C-C bonds in its structure, enabling it to form more coordination modes when used as a ligand in complexes. Furthermore, the presence of numerous hydrogen bonds in its complex molecules enhances intermolecular interactions, thereby improving thermal stability. Compared to traditional CHON-based energetic materials, tetrazolium energetic complexes exhibit milder sensitivity and superior heat resistance. Compared to traditional batch synthesis methods, continuous flow synthesis effectively reduces the risk of explosion during the synthesis of tetrazolium complexes, allows for precise control of reaction conditions, improves synthesis efficiency and product quality, and provides a more efficient and safer route for the synthesis and crystal form control of energetic complexes. Summary of the Invention

[0004] To address the problem of complex preparation processes in existing technologies, this invention provides an energetic complex K-BTE, its continuous preparation method, and its applications, in order to resolve the contradiction between high energy density and thermal stability in existing energetic materials.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0006] This application discloses an energetic complex K-BTE, with the following structural formula:

[0007] .

[0008] Preferably, the energetic complex K-BTE has the following preparation route:

[0009] .

[0010] This application also discloses a continuous preparation method for the energetic complex K-BTE, comprising the following steps:

[0011] S1. Select a solvent to prepare a 1,2-bis(tetrazol-5-yl)ethane solution, control the dissolution temperature at 25-50℃, stir and dissolve for 20 minutes, filter to remove impurities, and transfer the filtered 1,2-bis(tetrazol-5-yl)ethane solution to container A for heat preservation.

[0012] S2. Select a solvent to prepare a potassium salt solution, control the temperature at 25℃~50℃, and transfer the prepared solution to container B for heat preservation.

[0013] S3. The continuous flow reactor is vented using a solvent. The 1,2-bis(tetrazol-5-yl)ethane solution in container A and the potassium salt solution in container B are introduced into the continuous flow reactor in a certain proportion using a transfer pump. The temperature inside the reactor is adjusted, and the reaction solution is collected. A large amount of pale yellow crystals precipitate in the reaction solution. After filtration, washing, and drying, the target product K-BTE is obtained.

[0014] Preferably, in steps S1 and S2, the solvent is one or more of deionized water and N,N-dimethylformamide.

[0015] Preferably, in step S2, the potassium salt used to prepare the potassium salt solution is one or more of potassium hydroxide, potassium carbonate, and potassium bicarbonate.

[0016] Preferably, in step S3, the molar ratio of the 1,2-bis(tetrazol-5-yl)ethane solution to the potassium salt solution is 1:1~3.

[0017] Preferably, the concentration of the 1,2-bis(tetrazol-5-yl)ethane solution is 0.1~1 mol / L, the concentration of the potassium salt solution is 0.1~3 mol / L, and the introduction flow rate of both the 1,2-bis(tetrazol-5-yl)ethane solution and the potassium salt solution is 0.1~20 mL / min.

[0018] Preferably, in step S3, the reaction temperature is 25–50°C and the reaction residence time is 1–10 min.

[0019] This application also discloses the application of an energetic complex K-BTE as an energetic material.

[0020] This invention presents a novel energetic complex, K-BTE, prepared for the first time using a simple, continuous, and mild reaction method. K-BTE exhibits high thermal stability, along with a simple, efficient, safe, and controllable process. Its thermal decomposition temperature reaches 366.5℃, with a measured impact sensitivity greater than 40 J and a friction sensitivity between 240 N and 360 N. Furthermore, it catalyzes the thermal decomposition of ammonium perchlorate. These superior properties make K-BTE a promising candidate for improving the combustion efficiency of solid propellants, providing a new, efficient, and safe approach for the synthesis and crystal form control of energetic complexes. Attached Figure Description

[0021] Figure 1 This is a packing diagram of the K-BTE molecular structure prepared in Example 1 of the present invention;

[0022] Figure 2 The molecular structure diagram of K-BTE prepared in Example 1 of this invention;

[0023] Figure 3 The image shows the DSC pattern of K-BTE prepared in Example 1 of this invention;

[0024] Figure 4 This is a process flow diagram of the K-BTE preparation in Example 1 of the present invention. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0026] Example 1:

[0027] This embodiment discloses an energetic complex K-BTE and its application as an energetic material, with the following structural formula:

[0028] .

[0029] The preparation route of the energetic complex K-BTE is as follows:

[0030] .

[0031] Combination Figure 4 As shown in the figure, this embodiment also discloses a continuous preparation method for the energetic complex K-BTE, which includes the following steps:

[0032] S1. Add 16.62g of 1,2-bis(tetrazol-5-yl)ethane to 100mL of deionized water, stir and dissolve at 45℃ for 20min, filter to remove impurities, and transfer the aqueous solution of 1,2-bis(tetrazol-5-yl)ethane to container A for incubation.

[0033] S2. Add 5.61g of KOH to 100mL of deionized water, dissolve it completely, and then transfer the solution to container B.

[0034] S3. Set the temperature inside the continuous flow reactor to 45℃. Use solvent to exhaust the continuous flow reactor. Use a metering pump to pump 1,2-bis(tetrazol-5-yl)ethane solution and potassium salt solution into the exhaust continuous flow reactor at a flow rate of 1 mL / min. The reaction residence time is 10 min. Collect the reaction solution in container C. A large amount of pale yellow crystals precipitate in the reaction solution. After filtration, washing and drying, K-BTE product is obtained with a yield of 68.2%. Sampling was performed and characterized by infrared spectroscopy and elemental analysis: Infrared spectroscopy: IR (KBr)ν: 3400.23, 2973.32, 2869.57, 2698.97, 2257.20, 2065.05, 1884.44, 1653.86, 1577.27, 1479.95, 1411.50, 1201.74, 1147.14, 1057.42, 1022.63, 988.18, 773.95, 701.27; Elemental analysis: The molecular formula of potassium 1,2-bis(tetraazol-5-yl)ethane is C4H 12 N8O4K2, theoretical values: C 15.27, H 3.82, N 35.64; measured values: C 15.31, H 3.85, N 35.66.

[0035] Select crystals of appropriate size, using Rigaku Saturn 724. + Diffraction analysis was performed using a CCD-type X-ray single-crystal diffractometer at a test temperature of 163.15 K, employing monochromatic Mo Kα rays with a wavelength of λ = 0.71073 Å. The crystal structure was determined using SHELXS-97 software, combined with F... 2 The molecular structure of K-BTE was accurately analyzed and optimized using direct methods and full-matrix least squares method, and the results are as follows: Figure 1 and Figure 2 As shown in the figure. The thermal stability of K-BTE was analyzed using differential scanning calorimetry. K-BTE was heated in an argon atmosphere at a heating rate of 10 °C / min. The first obvious exothermic peak appeared when the temperature reached 366.5 °C. The test results are shown in the figure. Figure 3As shown. Further testing revealed that the actual impact sensitivity was greater than 40J, and the friction sensitivity was between 240N and 360N.

[0036] Example 2:

[0037] This embodiment discloses an energetic complex K-BTE and its application as an energetic material. The difference between this embodiment and Example 1 lies in the different conditions and parameters of the preparation process of the energetic complex. The specific preparation method is as follows:

[0038] S1. Add 16.62g of 1,2-bis(tetrazol-5-yl)ethane to 100mL of DMF, stir and dissolve at 35℃ for 20min, filter to remove impurities, and transfer the 1,2-bis(tetrazol-5-yl)ethane solution to container A for incubation.

[0039] S2. Add 5.61g of KOH to 100mL of deionized water, dissolve it completely, and then transfer the solution to container B.

[0040] S3. Set the temperature inside the continuous flow reactor to 35℃. Use a metering pump to pump the 1,2-bis(tetrazol-5-yl)ethane solution and potassium salt solution into the vented continuous flow reactor at a flow rate of 2 mL / min. The reaction residence time is 8 min. The reaction solution is collected in container C. A large amount of pale yellow crystals precipitate in the reaction solution. After filtration, washing and drying, K-BTE product is obtained with a yield of 61.6%.

[0041] Example 3:

[0042] This embodiment discloses an energetic complex K-BTE and its application as an energetic material. The difference between this embodiment and Example 1 lies in the different conditions and parameters of the preparation process of the energetic complex. The specific preparation method is as follows:

[0043] S1. Add 16.62g of 1,2-bis(tetrazol-5-yl)ethane to 100mL of deionized water, stir and dissolve at 25℃ for 30min, filter to remove impurities, and transfer the aqueous solution of 1,2-bis(tetrazol-5-yl)ethane to container A for incubation.

[0044] S2. Add 13.81g of K2CO3 to 100mL of deionized water, and after it is fully dissolved, transfer the solution to container B.

[0045] S3. Set the temperature inside the continuous flow reactor to 30℃. Use solvent to exhaust the continuous flow reactor. Use a metering pump to pump 1,2-bis(tetrazol-5-yl)ethane solution and potassium salt solution into the exhaust continuous flow reactor at a flow rate of 1 mL / min. The reaction residence time is 10 min. Collect the reaction solution in container C. A large amount of pale yellow crystals precipitate in the reaction solution. After filtration, washing and drying, K-BTE product is obtained with a yield of 60.5%.

[0046] In summary, this invention presents a novel energetic complex, K-BTE, with a simple, continuous process and mild reaction conditions. For the first time, K-BTE has been successfully prepared, yielding a novel energetic complex with excellent overall performance. Besides its high thermal stability, K-BTE also boasts a simple, efficient, safe, and controllable process. Its thermal decomposition temperature reaches 366.5℃, its measured impact sensitivity is greater than 40 J, and its friction sensitivity is between 240 N and 360 N. Furthermore, it exhibits catalytic activity in the thermal decomposition of ammonium perchlorate. The superior properties of K-BTE make it a promising energetic complex for improving the combustion efficiency of solid propellants, providing a new, efficient, and safe approach for the synthesis and crystal form control of energetic complexes.

[0047] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An energetic complex K-BTE, characterized in that, The structural formula is as follows: ； The preparation route of the energetic complex K-BTE is as follows: ； A continuous preparation method for the energetic complex K-BTE includes the following steps: S1. Select a solvent to prepare a 1,2-bis(tetrazol-5-yl)ethane solution, control the dissolution temperature at 25-50℃, stir and dissolve for 20 minutes, filter to remove impurities, and transfer the filtered 1,2-bis(tetrazol-5-yl)ethane solution to container A for heat preservation. S2. Select a solvent to prepare a potassium salt solution, control the temperature at 25℃~50℃, and transfer the prepared solution to container B for heat preservation. The potassium salt used to prepare the potassium salt solution is one or more of potassium hydroxide, potassium carbonate, and potassium bicarbonate. S3. The continuous flow reactor is vented using a solvent. The 1,2-bis(tetrazol-5-yl)ethane solution in container A and the potassium salt solution in container B are introduced into the continuous flow reactor in a certain proportion through a transfer pump. The temperature inside the reactor is adjusted, and the reaction liquid after the reaction is collected. A large amount of pale yellow crystals precipitate in the reaction liquid. After filtration, washing and drying, the target product K-BTE is obtained. The molar ratio of 1,2-bis(tetrazol-5-yl)ethane solution to potassium salt solution is 1:1~3; In steps S1 and S2, the solvent is one or more of deionized water and N,N-dimethylformamide.

2. The energetic complex K-BTE according to claim 1, characterized in that, The concentration of the 1,2-bis(tetrazol-5-yl)ethane solution was 0.1~1 mol / L, the concentration of the potassium salt solution was 0.1~3 mol / L, and the introduction flow rate of both the 1,2-bis(tetrazol-5-yl)ethane solution and the potassium salt solution was 0.1~20 mL / min.

3. The energetic complex K-BTE according to claim 1, characterized in that, In step S3, the reaction temperature is 25–50°C and the reaction residence time is 1–10 min.

4. An application of the energetic complex K-BTE as described in claim 1 as an energetic material.

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