An energetic complex Cs-BTE and its continuous preparation method and application

Abstract

This invention provides an energetic complex Cs-BTE, its continuous preparation method, and its applications. Starting with 1,2-bis(tetraazol-5-yl)ethane, a ligand solution and a metal ion salt solution are continuously injected into a continuous flow reaction unit via a syringe pump. After filtration, washing, and drying, energetic complex crystals are obtained. This invention develops a novel, simple, continuous, and mild method for preparing energetic complexes. For the first time, an energetic complex Cs-BTE with a novel structure and excellent overall performance was prepared. In addition to high thermal stability, Cs-BTE also possesses the advantages of a simple, efficient, safe, and controllable process. The thermal decomposition temperature of Cs-BTE reaches 375.5℃, with a measured impact sensitivity greater than 40 J and a friction sensitivity greater than 360 N. It also exhibits a catalytic effect on the thermal decomposition of ammonium perchlorate. The superior performance of Cs-BTE makes it a promising energetic complex for catalyzing the combustion efficiency of solid propellants.

Description

Technical Field

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

[0002] Energetic complexes, as functional materials that combine energy properties with stable structures, demonstrate irreplaceable scientific value and application potential in materials science, chemical production, and national defense. One of the core research directions in the field of energetic materials is how to overcome the performance contradiction between high energy density and high thermal stability, while simultaneously ensuring the safety and controllability of the materials during preparation and use.

[0003] 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 possess relatively excellent thermal stability, making them a key research focus in energetic coordination compounds in recent years. 1,2-Di(tetraazol-5-yl)ethane, as an important derivative of tetraazole compounds, exhibits unique flexible and torsionible C-C bonds in its molecular structure, allowing for more diverse coordination modes when forming complexes with metal ions. Simultaneously, the numerous hydrogen bonds within its complex molecules significantly enhance intermolecular interactions, further improving the thermal stability of the material. Compared to traditional CHON-based energetic materials, it is easier to achieve a balance between low sensitivity and high heat resistance.

[0004] However, existing technologies for preparing energetic complexes still have significant limitations: on the one hand, traditional batch synthesis methods are difficult to precisely control reaction conditions, which not only leads to poor product quality stability, but also increases the risk of explosion during the synthesis of tetrazolium compounds due to problems such as excessively high local concentrations and uneven heat transfer in the reaction system; on the other hand, the reported tetrazolium complexes still have room for improvement in terms of energy density, thermal stability and catalytic performance, especially lacking materials that can simultaneously meet the requirements of high thermal decomposition temperature, low mechanical sensitivity and efficient catalytic activity on key components of solid propellants.

[0005] To address the aforementioned issues, developing a technology that allows for continuous and controllable processes, mild reaction conditions, and the preparation of tetrazolium-based energetic complexes with excellent overall performance has become a key requirement for promoting the development of the energetic materials field. Summary of the Invention

[0006] To address the problem of complex preparation processes in existing technologies, this invention provides an energetic complex Cs-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.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] This application discloses an energetic complex Cs-BTE, with the following structural formula:

[0009] .

[0010] Preferably, the energetic complex Cs-BTE has the following preparation route:

[0011] .

[0012] This application also discloses a continuous preparation method for the energetic complex Cs-BTE, comprising the following steps:

[0013] S1. Select a solvent to prepare a 1,2-bis(tetrazol-5-yl)ethane solution, control the dissolution temperature at 25-60℃, stir and dissolve for 20 min, filter to remove impurities, transfer the filtered 1,2-bis(tetrazol-5-yl)ethane solution to container A and keep it warm;

[0014] S2. Select a solvent to prepare a cesium salt solution, control the temperature at 25℃~50℃, and transfer the prepared solution to container B for heat preservation.

[0015] S3. The continuous flow reactor is vented using a solvent. The 1,2-bis(tetrazol-5-yl)ethane solution in container A and the cesium 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 light yellow crystals precipitate in the reaction solution. After filtration, washing, and drying, the target product Cs-BTE is obtained.

[0016] Preferably, in steps S1 and S2, the solvent is one or more of deionized water and N,N-dimethylformamide.

[0017] Preferably, in step S2, the cesium salt used to prepare the cesium salt solution is one or more of cesium hydroxide, cesium carbonate, and cesium bicarbonate.

[0018] Preferably, in step S3, the molar ratio of the 1,2-bis(tetrazol-5-yl)ethane solution to the cesium salt solution is 1:1~3.

[0019] Preferably, the concentration of the 1,2-bis(tetrazol-5-yl)ethane solution is 0.1~1 mol / L, the concentration of the cesium salt solution is 0.1~3 mol / L, and the introduction flow rates of both the 1,2-bis(tetrazol-5-yl)ethane solution and the cesium salt solution are 0.1~20 mL / min.

[0020] Preferably, in step S3, the reaction temperature is 25–70°C and the reaction residence time is 1–10 min.

[0021] This application also discloses the application of an energetic complex Cs-BTE as an energetic material.

[0022] The beneficial effects of this invention are as follows:

[0023] This invention presents a novel energetic complex, Cs-BTE, prepared for the first time using a simple, continuous, and mild reaction method. Cs-BTE exhibits high thermal stability, along with a simple, efficient, safe, and controllable process. Its thermal decomposition temperature reaches 375.5℃, with a measured impact sensitivity greater than 40 J and a friction sensitivity greater than 360 N. Furthermore, it catalyzes the thermal decomposition of ammonium perchlorate. The superior properties of Cs-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. Attached Figure Description

[0024] Figure 1 This is a packing diagram of the Cs-BTE molecular structure prepared in Example 1 of the present invention;

[0025] Figure 2 The molecular structure diagram of Cs-BTE prepared in Example 1 of this invention is shown.

[0026] Figure 3 The image shows the DSC pattern of Cs-BTE prepared in Example 1 of this invention;

[0027] Figure 4 This is a process flow diagram of Cs-BTE prepared in Example 1 of the present invention. Detailed Implementation

[0028] 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.

[0029] Example 1:

[0030] This embodiment discloses an energetic complex Cs-BTE and its application as an energetic material, the structural formula of which is as follows:

[0031] .

[0032] The preparation route of the energetic complex Cs-BTE is as follows:

[0033] .

[0034] Combination Figure 4 As shown, this embodiment also discloses a continuous preparation method for the energetic complex Cs-BTE, including the following steps:

[0035] S1. Add 16.62g of 1,2-bis(tetrazol-5-yl)ethane to 100mL of deionized water, stir and dissolve for 20min at 45℃, filter to remove impurities, and transfer the aqueous solution of 1,2-bis(tetrazol-5-yl)ethane to container A for incubation.

[0036] S2. Add 16.79g of CsOH·H2O to 100mL of deionized water, and after it is fully dissolved, transfer the solution to container B.

[0037] S3. Set the temperature inside the continuous flow reactor to 50℃. Use solvent to vent the continuous flow reactor. Pump the 1,2-bis(tetrazol-5-yl)ethane solution in container A and the cesium salt solution in container B into the vented continuous flow reactor at a flow rate of 1 mL / min using a metering pump. The reaction residence time is 10 min. Collect the reaction solution in container C. A large amount of light yellow crystals precipitate in the reaction solution. After filtration, washing and drying, Cs-BTE product is obtained with a yield of 72.6%. Sampling was performed and characterized by infrared spectroscopy and elemental analysis: Infrared spectroscopy: IR (KBr)ν: 3395.75, 2197.98, 1662.74, 1566.05, 1477.24, 1402.84, 1315.00, 1197.72, 1121.96, 1064.33, 1022.11, 951.87, 767.93, 701.85, 645.14; Elemental analysis: The molecular formula of 1,2-bis(tetraazol-5-yl)ethane cesium salt is C4H8N8O2Cs2, theoretical value: C 10.32, H 1.72, N 24.04; measured value: C 10.41, H 1.74, N 24.14.

[0038] 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 153.15 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 Cs-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 2As shown in the figure. The thermal stability of Cs-BTE was analyzed by differential scanning calorimetry. Cs-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 375.5 °C. The test results are shown in the figure. Figure 3 As shown. Further testing revealed that the measured impact sensitivity was greater than 40J and the friction sensitivity was greater than 360N.

[0039] Example 2:

[0040] This embodiment discloses an energetic complex Cs-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:

[0041] S1. Add 16.62g of 1,2-bis(tetrazol-5-yl)ethane to 100mL of DMF, stir and dissolve at 30℃ for 20min, filter to remove impurities, and transfer the 1,2-bis(tetrazol-5-yl)ethane solution to container A for incubation.

[0042] S2. Add 16.79g of CsOH·H2O to 100mL of deionized water, and after it is fully dissolved, transfer the solution to container B.

[0043] 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 cesium salt solution into the exhaust continuous flow reactor at a flow rate of 5 mL / min. The reaction residence time is 5 min. Collect the reaction solution in container C. A large amount of light yellow crystals precipitate in the reaction solution. After filtration, washing and drying, Cs-BTE product is obtained with a yield of 66.8%.

[0044] Example 3:

[0045] This embodiment discloses an energetic complex Cs-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:

[0046] S1. Add 16.62g of 1,2-bis(tetrazol-5-yl)ethane to 100mL of deionized water, stir and dissolve at 30℃ for 30min, filter to remove impurities, and transfer the aqueous solution of 1,2-bis(tetrazol-5-yl)ethane to container A for incubation.

[0047] S2. Add 32.58g of Cs2CO3 to 100mL of deionized water, and after it is fully dissolved, transfer the solution to container B.

[0048] S3. Set the temperature inside the continuous flow reactor to 30℃. Use solvent to exhaust the continuous flow reactor. Pump 1,2-bis(tetrazol-5-yl)ethane solution and cesium salt solution into the exhaust continuous flow reactor at a flow rate of 2 mL / min using a metering pump. The reaction residence time is 10 min. Collect the reaction solution in container C. A large amount of light yellow crystals precipitate in the reaction solution. After filtration, washing and drying, Cs-BTE product is obtained with a yield of 71.1%.

[0049] In summary, this invention presents a novel energetic complex, Cs-BTE, with a simple, continuous process and mild reaction conditions. For the first time, a novel energetic complex with excellent overall performance has been prepared. Besides its high thermal stability, Cs-BTE also boasts the advantages of a simple, efficient, safe, and controllable process. Cs-BTE exhibits a high thermal decomposition temperature of 375.5℃, a measured impact sensitivity greater than 40J, and a friction sensitivity greater than 360N. Furthermore, it catalyzes the thermal decomposition of ammonium perchlorate. The superior performance of Cs-BTE makes it a promising energetic complex for catalyzing the combustion efficiency of solid propellants.

[0050] 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 Cs-BTE, characterized in that, The structural formula is as follows:

2. A continuous process for the preparation of the energetic complex Cs-BTE according to claim 1, characterized in that, Comprising the following steps: S1, selecting a solvent to prepare a 1,2-bis(tetrazol-5-yl)ethane solution, controlling the dissolution temperature to be 25-60℃, stirring for 20min, filtering out impurities, transferring the filtered 1,2-bis(tetrazol-5-yl)ethane solution to container A and keeping warm; S2, selecting a solvent to prepare a cesium salt solution, controlling the temperature to be 25℃-50℃, transferring the prepared solution to container B for keeping warm; S3, using a solvent to exhaust the continuous flow reactor, introducing the 1,2-bis(tetrazol-5-yl)ethane solution in container A and the cesium salt solution in container B into the continuous flow reactor in a certain proportion through a delivery pump, adjusting the temperature in the reactor, collecting the reaction liquid, and a large amount of light yellow crystals precipitated in the reaction liquid, which are filtered, washed, and dried to obtain the target product Cs-BTE.

3. The continuous process for the preparation of the energetic complex Cs-BTE according to claim 2, characterized in that, In steps S1 and S2, the solvent is one or more of deionized water and N,N-dimethylformamide.

4. The continuous process for the preparation of the energetic complex Cs-BTE according to claim 2, characterized in that, In step S2, the cesium salt used to prepare the cesium salt solution is one or more of cesium hydroxide monohydrate, cesium carbonate, and cesium bicarbonate.

5. The continuous process for the preparation of the energetic complex Cs-BTE according to claim 2, characterized in that, In step S3, the molar ratio of the 1,2-bis(tetrazol-5-yl)ethane solution to the cesium salt solution is 1:1-3.

6. The continuous process for the preparation of the energetic complex Cs-BTE according to claim 2, characterized in that, The concentration of the 1,2-bis(tetrazol-5-yl)ethane solution is 0.1-1mol / L, the concentration of the cesium salt solution is 0.1-3mol / L, and the introduction flow rate of the 1,2-bis(tetrazol-5-yl)ethane solution and the cesium salt solution is 0.1-20mL / min.

7. The continuous process for the preparation of the energetic complex Cs-BTE according to claim 3, characterized in that, In step S3, the reaction temperature is 25-70℃, and the reaction residence time is 1min-10min.

8. Use of the energetic complex Cs-BTE based on claim 1 as an energetic material.

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