Energetic complex K-BTE as well as continuous preparation method and application thereof

Abstract

The invention provides an energetic complex K-BTE and a continuous preparation method and application thereof.The continuous preparation method comprises the steps that 1, 2-bis (tetrazole-5-yl) ethane serves as an initial raw material, a ligand solution and a metal ion salt solution are continuously injected into a continuous flow reaction unit through an injection pump, and energetic complex crystals are obtained through filtering, washing and drying; a novel energetic complex preparation method which is simple and continuous in process and mild in reaction condition is developed, the energetic complex K-BTE which is novel in structure and excellent in comprehensive performance is prepared for the first time, and the energetic complex K-BTE has the characteristic of high thermal stability and also has the advantages of being simple and efficient in process method and safe and controllable in process; the thermal decomposition temperature of K-BTE reaches up to 366.5 DEG C, the actually measured impact sensitivity is greater than 40J, the friction sensitivity is between 240N and 360N, and meanwhile, the thermal decomposition of ammonium perchlorate is catalyzed. Due to the excellent performance of the K-BTE, the K-BTE has huge application potential in the field of catalyzing the combustion efficiency of solid propellants as an energetic complex.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of energetic materials, in particular to an energetic complex K-BTE and a continuous preparation method and application thereof. BACKGROUND

[0002] Energetic complexes have important scientific value in many fields such as materials, chemical industry, military industry, etc. In particular, in the field of energetic materials, it is the research focus of researchers to develop energetic complexes with high energy density and excellent performance. In recent decades, the development of energetic materials has focused on balancing higher performance, more excellent thermal stability and lower sensitivity. Tetrazole compounds have a good application prospect because they can release a large amount of energy in the process of decomposition or explosion due to the presence of a large number of N-N bonds, N=N bonds and C-N bonds in the molecular structure, and have relatively good thermal stability.

[0003] As a kind of tetrazole compound, 1,2-bis(tetrazol-5-yl)ethane has more coordination modes when it forms a complex as a ligand due to the flexibility and twistability of the C-C bond in its structure. In addition, there are more hydrogen bonds in the complex molecules, which can enhance the intermolecular interaction force and thus improve the thermal stability. Compared with traditional C-H-O-N energetic materials, tetrazole energetic complexes have more moderate sensitivity and more excellent heat resistance. Compared with traditional pot synthesis methods, the continuous flow synthesis method can effectively reduce the explosion risk of tetrazole complexes during synthesis, and can accurately control the reaction conditions, improve the synthesis efficiency and product quality, and provide a more efficient and safer way for the synthesis and crystal form control of energetic complexes. SUMMARY

[0004] In view of the problem of complex preparation process in the prior art, the present application provides an energetic complex K-BTE and a continuous preparation method and application thereof, so as to solve the contradiction between high energy density and thermal stability of existing energetic materials.

[0005] To achieve the above object, the present application realizes the following technical solutions:

[0006] The present application discloses an energetic complex K-BTE, the structural formula of which is as follows:

[0007] .

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

[0009] .

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

[0011] S1, a 1,2-bis(tetrazol-5-yl)ethane solution is prepared by selecting a solvent, the dissolution temperature is controlled to be 25-50℃, stirring and dissolving for 20 min, filtering out impurities, and transferring the filtered 1,2-bis(tetrazol-5-yl)ethane solution to a container A for incubation;

[0012] S2, a potassium salt solution is prepared by selecting a solvent, the temperature is controlled to be 25-50℃, and the prepared solution is transferred to a container B for incubation;

[0013] S3, the continuous flow reactor is exhausted by using a solvent, the 1,2-bis(tetrazol-5-yl)ethane solution in the container A and the potassium salt solution in the container B are introduced into the continuous flow reactor in a certain proportion by a delivery pump, the temperature in the reactor is adjusted, a large amount of light yellow crystals are precipitated in the reaction liquid, and the target product K-BTE is obtained after filtration, washing and drying treatment.

[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 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℃, and the reaction residence time is 1-10 min.

[0019] The application also discloses an application of the 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, 16.62 g of 1,2-bis(tetrazol-5-yl)ethane was added to 100 mL of deionized water, stirred and dissolved at 45°C for 20 min, and the impurities were removed by filtration. The aqueous solution of 1,2-bis(tetrazol-5-yl)ethane was transferred to container A for incubation;

[0033] S2, 5.61 g of KOH was added to 100 mL of deionized water, and after being dissolved, the solution was transferred to container B;

[0034] S3, the temperature in the continuous flow reactor was set to 45°C, the solvent was used to exhaust the continuous flow reactor, and the 1,2-bis(tetrazol-5-yl)ethane solution and potassium salt solution were pumped into the exhausted continuous flow reactor at a flow rate of 1 mL / min by using a metering pump, the reaction residence time was 10 min, and the reaction liquid was collected in container C. A large amount of light yellow crystals was precipitated in the reaction liquid, which was filtered, washed, and dried to obtain K-BTE finished product with a yield of 68.2%. The sample was characterized by infrared spectroscopy and elemental analysis: infrared spectrum: IR (KBr) v: 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 1,2-bis(tetrazol-5-yl)ethane potassium salt is C4H 12 N8O4K2, the theoretical value: C 15.27, H 3.82, N 35.64; the measured value: C 15.31, H 3.85, N 35.66.

[0035] The selected crystal of appropriate size was subjected to diffraction analysis using a Rigaku Saturn 724 + CCD type X-ray single crystal diffractometer, the test temperature was 163.15 K, and the graphite monochromatic Mo Kα ray with a wavelength λ = 0.71073 Å was selected. The crystal structure was analyzed and optimized using the software SHELXS-97, combined with the direct method and full matrix least squares method, and the results are shown in 2 and Figure 1 and Figure 2 The thermal stability of K-BTE was analyzed by differential scanning calorimetry. K-BTE was heated at a heating rate of 10°C / min in an argon atmosphere, and the first obvious exothermic peak appeared at a temperature of 366.5°C. The test results are shown in Figure 3The impact sensitivity is greater than 40 J and the friction sensitivity is between 240 N and 360 N.

[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 is that the conditions and parameters of the preparation process of the energetic complex are different. The specific preparation method is as follows:

[0038] S1, 16.62 g of 1,2-bis(tetrazole-5-yl)ethane was added to 100 mL of DMF, stirred and dissolved at 35 DEG C for 20 min, filtered and impurities, and the 1,2-bis(tetrazole-5-yl)ethane solution was transferred to container A for incubation;

[0039] S2, 5.61 g of KOH was added to 100 mL of deionized water, and the solution was transferred to container B after being dissolved;

[0040] S3, the temperature in the continuous flow reactor was set to 35 DEG C, and the 1,2-bis(tetrazole-5-yl)ethane solution and potassium salt solution were pumped into the exhaust continuous flow reactor at a flow rate of 2 mL / min by a metering pump, the reaction residence time was 8 min, and the reaction liquid was collected in container C. A large amount of light yellow crystals was precipitated in the reaction liquid, which was filtered, washed and dried to obtain K-BTE finished product 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 is that the conditions and parameters of the preparation process of the energetic complex are different. The specific preparation method is as follows:

[0043] S1, 16.62 g of 1,2-bis(tetrazole-5-yl)ethane was added to 100 mL of deionized water, stirred and dissolved at 25 DEG C for 30 min, filtered and impurities, and the 1,2-bis(tetrazole-5-yl)ethane solution was transferred to container A for incubation;

[0044] S2, 13.81 g of K2CO3 was added to 100 mL of deionized water, and the solution was transferred to container B after being dissolved;

[0045] S3, set the temperature in the continuous flow reactor to 30 DEG C, exhaust the continuous flow reactor by using solvent, pump 1,2-bis(tetrazol-5-yl)ethane solution and potassium salt solution into the exhausted continuous flow reactor by using a metering pump at a flow rate of 1 mL / min, the reaction residence time is 10 min, collect the reaction liquid in container C, a large amount of light yellow crystals is precipitated in the reaction liquid, after filtration, washing and drying, K-BTE product is obtained, the yield is 60.5%.

[0046] In summary, the present application is a new energetic complex preparation method with simple continuous process and mild reaction conditions, and an energetic complex K-BTE with novel structure and excellent comprehensive performance is prepared for the first time. The energetic complex K-BTE has the characteristics of high thermal stability, simple and efficient process method, and safe and controllable process. The thermal decomposition temperature of K-BTE is as high as 366.5 DEG C, the actual measured impact sensitivity is greater than 40 J, the friction sensitivity is between 240 N and 360 N, and K-BTE has catalytic effect on the thermal decomposition of ammonium perchlorate. The excellent performance of K-BTE makes it have great application potential in the field of catalytic solid propellant combustion efficiency as an energetic complex, and provides a new efficient and safe way for the synthesis and crystal form control of energetic complex.

[0047] The above examples are only used to illustrate the technical solutions of the present application, but not limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can be modified, or some technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. An energetic complex K-BTE, characterized in that, The structural formula is as follows: 。 2. The energetic complex K-BTE according to claim 1, characterized in that The preparation route is as follows: 。 3. A continuous process for the preparation of the energetic complex K-BTE according to claim 2, characterized in that, The method comprises the following steps: S1, 1,2-bis(tetrazol-5-yl)ethane solution is prepared by selecting a solvent, the dissolution temperature is controlled to be 25-50 DEG C, stirring dissolution is performed for 20 min, impurities are removed by filtration, and the filtered 1,2-bis(tetrazol-5-yl)ethane solution is transferred to container A for heat preservation; S2, a potassium salt solution is prepared by selecting a solvent, the temperature is controlled to be 25 DEG C-50 DEG C, and the prepared solution is transferred to container B for heat preservation; S3, the continuous flow reactor is exhausted by 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 by a delivery pump, the temperature in the reactor is adjusted, a large amount of light yellow crystals are precipitated in the reaction liquid, and the target product K-BTE is obtained through filtration, washing and drying treatment.

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

5. The continuous process for the preparation of energetic complex K-BTE according to claim 3, characterized in that, In step S2, the potassium salt used for preparing the potassium salt solution is one or more of potassium hydroxide, potassium carbonate and potassium bicarbonate.

6. The continuous process for the preparation of energetic complex K-BTE according to claim 3, characterized in that, 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.

7. The continuous process for the preparation of energetic complex K-BTE according to claim 3, characterized in that, 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 rates of the 1,2-bis(tetrazol-5-yl)ethane solution and the potassium salt solution are both 0.1-20 mL / min.

8. The continuous process for the preparation of energetic complex K-BTE according to claim 3, characterized in that, In step S3, the reaction temperature is 25-50 DEG C, and the reaction residence time is 1 min-10 min.

9. Application of the energetic complex K-BTE based on the energetic complex of claim 1 as an energetic material.

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