High-temperature-resistant energetic complex Li-ZDPT and preparation method thereof

Abstract

The application discloses a high-energy heat-resistant energetic complex Li-ZDPT and a preparation method thereof. A novel high-energy heat-resistant explosive preparation method with simple preparation process, mild reaction condition and high yield is developed by taking 3,5-diamino-4-nitro pyrazole as a starting material, and a high-energy heat-resistant explosive Li-ZDPT with novel structure and excellent comprehensive performance is prepared. In addition to the characteristics of high energy and high heat stability, the Li-ZDPT also has the advantages of simple preparation method and high yield. The thermal decomposition temperature of the Li-ZDPT is as high as 436 DEG C, the theoretical detonation velocity is 8096 m / s ‑1 , the actual measured impact sensitivity is greater than 40 J, and the friction sensitivity is greater than 360 N. The excellent comprehensive performance of the Li-ZDPT makes it have great application potential in the field of high-energy heat-resistant explosives.

Description

Technical Field

[0001] This invention relates to the field of energetic materials technology, and in particular to a high-energy heat-resistant energetic complex Li-ZDPT and its preparation method. Background Technology

[0002] As an important research branch in the field of energetic materials, heat-resistant explosives have wide applications in advanced weaponry and oil exploration. Existing heat-resistant explosives generally suffer from low energy levels, which has severely constrained the development of weaponry. Therefore, the development of high-energy heat-resistant explosives is an urgent practical need. Based on this, major military industrial units and research institutes both domestically and internationally have conducted extensive research on the design and preparation of novel high-energy heat-resistant explosives, achieving some preliminary progress. Current research results indicate that the essence of developing novel high-energy heat-resistant explosives lies in reconciling the contradiction between energy and thermal stability. However, energy and thermal stability, as an inherent contradiction in explosives, are difficult to integrate into traditional CHNO-type elemental explosives. Summary of the Invention

[0003] The purpose of this invention is to address the problems of low energy and complex preparation processes in existing heat-resistant explosives by providing a high-energy heat-resistant energetic complex, Li-ZDPT, and its preparation method. Using 3,5-diamino-4-nitropyrazole as the starting material, this invention develops a novel high-energy heat-resistant explosive preparation method with simple processing, mild reaction conditions, and high yield. A novel high-energy heat-resistant explosive, Li-ZDPT, with excellent comprehensive performance, has been prepared, demonstrating significant application potential in the field of high-energy heat-resistant explosives.

[0004] Compared with traditional heat-resistant explosives, Li-ZDPT has higher energy and safety, and is characterized by simple preparation process and high yield.

[0005] The present invention achieves the above objectives through the following technical solutions:

[0006] A high-energy, heat-resistant, energetic complex, Li-ZDPT, has the following structural formula:

[0007]

[0008] In another aspect, this invention provides a method for preparing the high-energy, heat-resistant, energetic complex Li-ZDPT, which has the following preparation route:

[0009]

[0010] The further proposed solution includes the following steps:

[0011] 3,5-Diamino-4-nitropyrazole was added to an organic solvent and stirred until completely dissolved. Then, an aqueous solution of LiOH was added, and the mixture was stirred for 2-8 minutes. Next, an acetonitrile solution of cyanogen bromide was added, and the reaction was allowed to proceed at room temperature for 40-60 minutes. After the reaction was complete, stirring was stopped. During the reaction, a large amount of orange powder precipitated. This precipitate was filtered and dried to obtain the target product, Li-ZDPT. Its chemical name is 2,6-diamino-9-amino-3,5-dinitropyrazoletriazine lithium salt.

[0012] A further embodiment is that the organic solvent is one or more of N,N'-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).

[0013] A further embodiment is that the molar ratio of 3,5-diamino-4-nitropyrazole, LiOH, and cyanogen bromide is 2:1.80-2.10:0.9-1.1.

[0014] In another aspect, the present invention also provides the use of the above-described complex or the complex obtained by the above-described preparation method in the field of energetic materials.

[0015] The beneficial effects of this invention are as follows:

[0016] This invention discloses a high-energy, heat-resistant, energetic complex Li-ZDPT (2,6-diamino-9-amino-3,5-dinitropyrazolotriazine lithium salt) and its preparation method. Besides possessing high energy and high thermal stability, Li-ZDPT also features a simple preparation method and high yield. The thermal decomposition temperature of Li-ZDPT reaches as high as 436℃, and the theoretical detonation velocity is 8096 m·s⁻¹. -1 The measured impact sensitivity is greater than 40J, and the friction sensitivity is greater than 360N. The excellent overall performance of Li-ZDPT gives it enormous application potential in the field of high-energy heat-resistant explosives. Attached Figure Description

[0017] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 The molecular structure diagram of Li-ZDPT, a high heat-resistant explosive prepared in Example 1 of this invention.

[0019] Figure 2 The image shows the TG-DSC diagram of Li-ZDPT, a high heat-resistant explosive prepared in Example 1 of this invention. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other implementation methods obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0021] Example 1. Preparation of high heat-resistant explosive Li-ZDPT

[0022] Add 1.44 g (10 mmol) of 3,5-diamino-4-nitropyrazole to 15 mL of DMF and stir continuously until completely dissolved. Then add 20 mL of 0.5 mol·L⁻¹ LiOH aqueous solution. 1 The mixture was stirred for 2 minutes, and then 20 mL of acetonitrile solution containing 0.53 g (5 mmol) of cyanogen bromide was added. The mixture was then reacted at room temperature for 40 minutes. After the reaction was complete, stirring was stopped, and a large amount of orange powder precipitated during the reaction. After filtration and drying, 1.13 g of the target product Li-ZDPT was obtained, with a yield of 63.8%.

[0023] Example 2. Preparation of the high heat-resistant explosive Li-ZDPT

[0024] Add 1.44 g (10 mmol) of 3,5-diamino-4-nitropyrazole to 15 mL of DMSO and stir continuously until completely dissolved. Then add 20 mL of 0.5 mol·L⁻¹ LiOH aqueous solution. 1 The mixture was stirred for 2 minutes, and then 20 mL of acetonitrile solution containing 0.53 g (5 mmol) of cyanogen bromide was added. The reaction was allowed to proceed at room temperature for 40 minutes. After the reaction was complete, stirring was stopped, and a large amount of orange powder precipitated during the reaction. After filtration and drying, 1.1 g of the target product Li-ZDPT was obtained, with a yield of 62%.

[0025] Example 3. Preparation of the high heat-resistant explosive Li-ZDPT

[0026] Add 1.44 g (10 mmol) of 3,5-diamino-4-nitropyrazole to 15 mL of DMF and stir continuously until completely dissolved. Then add 20 mL of 0.5 mol·L⁻¹ LiOH aqueous solution. -1 The mixture was stirred for 2 minutes, and then 20 mL of acetonitrile solution containing 0.58 g (5.5 mmol) of cyanogen bromide was added. The mixture was then reacted at room temperature for 40 minutes. After the reaction was complete, stirring was stopped, and a large amount of orange powder precipitated during the reaction. After filtration and drying, 1.15 g of the target product Li-ZDPT was obtained, with a yield of 65%.

[0027] Application Example 1. Molecular structure diagram of the high heat-resistant explosive Li-ZDPT

[0028] The crystal structure of the prepared Li-ZDPT sample was characterized using single-crystal X-ray diffraction. The specific experimental procedure was as follows: An Oxford Xcalibur diffractometer equipped with a CCD detector was used at room temperature, and data was acquired using Cu-Ka rays in an ω-scan mode. For the acquired single-crystal data, the crystal structure analysis methods in the SHELXTL software package, combined with the direct method of F2 and the full-matrix least squares method, were used to accurately analyze and optimize the molecular structure of Li-ZDPT. The results are shown below. Figure 1 As shown.

[0029] Application Example 2. TG-DSC diagram of the high heat-resistant explosive Li-ZDPT

[0030] The thermal stability of Li-ZDPT was analyzed by thermogravimetric-differential scanning calorimetry (TG-DSC) at 10 °C / min in an argon atmosphere. -1 The heating rate was adjusted to 418 °C for Li-ZDPT. TG and DSC analysis showed no significant changes in Li-ZDPT before 418 °C; the slight weight loss could be attributed to the slow escape of water molecules from the crystal. The first significant exothermic peak appeared in the DSC curve at 436 °C, indicating that the excellent thermal stability of Li-ZDPT makes it suitable for further application development. The results are as follows... Figure 2 As shown. Further testing revealed a theoretical detonation velocity of 8096 m / s. -1 The measured impact sensitivity is greater than 40J, and the friction sensitivity is greater than 360N.

[0031] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims. It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately. Furthermore, various different embodiments of the present invention can also be arbitrarily combined, as long as they do not violate the spirit of the present invention, they should also be considered as the content disclosed in the present invention.

Claims

1. A high-energy, heat-resistant, energetic complex Li-ZDPT, characterized in that, The structural formula is as follows: 。 2. The preparation method of the high-energy heat-resistant energetic complex Li-ZDPT as described in claim 1, characterized in that, Includes the following steps: 3,5-Diamino-4-nitropyrazole was added to an organic solvent and stirred until completely dissolved. Then, an aqueous solution of LiOH was added and the mixture was stirred for 2-8 minutes. Next, an acetonitrile solution of cyanogen bromide was added and the mixture was stirred at room temperature for 40-60 minutes. After the reaction was completed, stirring was stopped. During the reaction, a large amount of orange powder precipitated out. The precipitate was filtered and dried to obtain the target product Li-ZDPT.

3. The preparation method of the high-energy heat-resistant energetic complex Li-ZDPT as described in claim 2, characterized in that, The organic solvent is one or more of N,N'-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).

4. The preparation method of the high-energy heat-resistant energetic complex Li-ZDPT as described in claim 2, characterized in that, The molar ratio of 3,5-diamino-4-nitropyrazole, LiOH, and cyanogen bromide is 2:1.80~2.10:0.9~1.

1.

5. Use of the complex as described in claim 1 or the complex obtained by the preparation method described in claims 2-4 in the field of energetic materials.

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