An anion-containing energetic complex based on anpttz and preparation method and application thereof

Abstract

This invention discloses an anionic energetic complex based on ANPTTz, its preparation method, and its applications. The method includes preparing the complex via a volatilization method using 6-(4-nitro-1H-pyrazole-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine and a metal nitrate as raw materials. The anionic energetic complex based on ANPTTz exhibits a detonation response upon laser irradiation, demonstrating good safety and detonation performance. It can be used as a laser-initiated explosive or as a component of explosives and propellants, showing promising application prospects in the field of high-energy insensitive energetic materials.

Description

Technical Field

[0001] This invention belongs to the field of energetic materials technology. More specifically, this invention relates to an anionic energetic complex based on ANPTTz, its preparation method, and its application. Background Technology

[0002] Energetic complexes, as organometallic compounds with high explosive properties, have shown significant application potential in the field of energetic materials. These materials are not only suitable for initiating charges in weapon munitions but can also serve as high-energy catalysts in solid propellant systems, thereby enhancing energy output and combustion performance. However, during their synthesis, solvent molecules readily enter the complex lattice and participate in coordination, forming solvated complexes. These retained solvent molecules desorb when the material is heated or excited, not only reducing the overall energy density of the system but also potentially generating internal pressure due to rapid release at low temperatures. This, in turn, affects the material's chemical stability and explosive heat effect, limiting its practical application effectiveness.

[0003] With the development of detonation technology, laser detonation, as a new and reliable initiation method, has attracted increasing attention due to its excellent resistance to electromagnetic interference, static electricity, and stray currents. This technology often relies on light-sensitive coordination compounds as initiating agents. Currently, the initiating agents commonly used in China are still mainly traditional varieties such as lead azide, lead picrate, and DDNP (dinitrodiazophenol). These agents are generally sensitive to external mechanical impact, friction, and thermal stimulation, and are prone to accidental explosions during production, storage, and use, causing safety accidents and personal injury.

[0004] Therefore, developing novel energetic complexes that combine high safety, good detonation performance, and adaptability to laser-initiated detonation requirements has become an important and urgent research topic in the field of energetic materials. Summary of the Invention

[0005] One object of the present invention is to solve at least the above-mentioned problems and / or defects, and to provide at least the advantages described below.

[0006] To achieve these objectives and other advantages of the present invention, an anionic energetic complex based on ANPTTz is provided, the general chemical formula of which is [M x (ANPTTz) y B z ] n·qH2O, where n≥1, x ranges from 1 to 5, y ranges from 1 to 5, z ranges from 1 to 5, q ranges from 0 to 5, M is a metal cation, B is an acid radical anion, and ANPTTz is 6-(4-nitro-1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine.

[0007] Preferably, M is specifically Ag. + Co 2+ Cu 2+ Ni 2+ One of them, B specifically is NO3. - ClO4 - One of them.

[0008] Preferably, the anionic energetic complex based on ANPTTz specifically includes: [Ag2(ANPTTz)2(ClO4)2] n [Ag2(ANPTTz)4(NO3)2(H2O)] n ·2H2O, [Co(ANPTTz)2(ClO4)2(H2O)2] n [Co(ANPTTz)3(NO3)3] n ·H2O, [Cu(ANPTTz)2(ClO4)2(H2O)2] n [Cu(ANPTTz)2(NO3)2(H2O)2] n [Ni(ANPTTz)3(ClO4)2] n H2O, [Ni(ANPTTz)3(NO3)2] n One of the components of H2O.

[0009] A method for preparing anionic energetic complexes based on ANPTTz as described above includes: using 6-(4-nitro-1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine and metal nitrate as raw materials, and preparing anionic energetic complexes based on ANPTTz by a volatilization method.

[0010] Preferably, the preparation method of the anionic energetic complex based on ANPTTz specifically includes: first preparing ANPTTz for later use, dissolving a metal nitrate in a mixed solution, then adding ANPTTz, allowing it to evaporate naturally at room temperature to obtain crystals, i.e., the anionic energetic complex based on ANPTTz.

[0011] Preferably, the metal nitrate is one of AgNO3, Co(NO3)2·6H2O, Cu(NO3)2, and Ni(NO3)2·6H2O, and the molar ratio of ANPTTz to the metal nitrate is 0.01~3.0:0.01~1.0.

[0012] Preferably, the mixed solution is prepared by mixing H2O with HClO4 or HNO3 in a volume ratio of 4 to 6:1.

[0013] Preferably, the ratio of the metal nitrate to the mixed solution is 0.01~0.03 mmol: 1~20 mL.

[0014] An application of the ANPTTz-based anionic energetic complex as described above, wherein the ANPTTz-based anionic energetic complex is used as a laser-initiated explosive.

[0015] An application of the ANPTTz-based anionic energetic complex as described above, wherein the ANPTTz-based anionic energetic complex is used as a combustion catalyst for composite propellants or modified dual-base propellants.

[0016] An application of the ANPTTz-based anionic energetic complex as described above, wherein the ANPTTz-based anionic energetic complex is used as a catalyst for the decomposition of ammonium perchlorate.

[0017] The present invention provides at least the following beneficial effects: The anionic energetic complex based on ANPTTz exhibits a detonation response upon laser irradiation, demonstrating excellent safety and detonation performance. It can be used as a laser-initiated explosive or as a component of explosives and propellants, showing promising application prospects in the field of high-energy insensitive energetic materials. Furthermore, the anionic energetic complex based on ANPTTz exhibits excellent catalytic activity, reducing the peak temperature of AP high-temperature decomposition by 76°C.

[0018] This invention employs the neutral fused-ring ligand 6-(4-nitro-1H-pyrazole-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine, which has a rich and varied coordination mode, numerous theoretical coordination sites, and chelate coordination, thereby reducing solvent molecule coordination. Furthermore, the anion can fill the channels of the metal-organic framework, effectively increasing the density. The ligand 6-(4-nitro-1H-pyrazole-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine exhibits good thermal stability, with a thermal decomposition temperature >300℃, while the nitro group improves the oxygen balance of the ligand. The oxygen-rich anionic energetic complexes constructed by coordinating with a metal center possess both high energy and low sensitivity. Therefore, the anionic energetic complexes based on ANPTTz of this invention generally exhibit excellent thermal stability. This invention utilizes neutral ligands to obtain oxygen-rich anion-energetic complexes in situ, which provides greater safety and is more suitable for large-scale industrial production.

[0019] Other advantages, objectives and features of the present invention will become apparent in part from the following description, and in part from those skilled in the art through study and practice of the invention. Attached Figure Description

[0020] Figure 1 This is a diagram of the minimum asymmetric unit structure of ECP-1 prepared in Example 1 of the present invention; Figure 2 This is a diagram of the minimum asymmetric unit structure of ECP-2 prepared in Example 2 of the present invention; Figure 3 This is a diagram of the laser-initiated detonation process of ECP-1 prepared in Example 1 of the present invention. Detailed Implementation

[0021] The present invention will now be described in further detail with reference to the accompanying drawings, so that those skilled in the art can implement it based on the description.

[0022] It should be understood that terms such as “having,” “comprising,” and “including” as used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0023] Example 1 A method for preparing anionic energetic complexes based on ANPTTz, comprising: Step 1: Cyanogen bromide (2.12 g, 20.0 mmol) was added to a stirred solution of 3-hydrazino-6-(4-nitro-1H-pyrazol-1-yl)-1,2,4-tetraazine (2.23 g, 10.0 mmol) in 3M HCl (15 mL). The solution was stirred at room temperature for 24 h. The dark purple precipitate was collected by filtration and washed with water (50 mL) and MeCN (10 mL) to obtain 6-(4-nitro-1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine (1.66 g, 67%), a dark purple powder ANPTTz, with the following structural formula: ; Step 2: Weigh AgNO3 (169 mg, 1.0 mmol) and dissolve it in 5 mL of a mixed solution of H2O and HClO4 (volume ratio 4:1). Then add ANPTTz (248 mg, 1.0 mmol) and allow it to evaporate naturally at room temperature to obtain purple needle-like crystals, which are the anionic energetic complex based on ANPTTz [Ag2(ANPTTz)2(ClO4)2]. n This is designated as ECP-1. Figure 1 This is the minimum asymmetric unit structure diagram of ECP-1.

[0024] Example 2 A method for preparing anionic energetic complexes based on ANPTTz, comprising: Step 1: Add cyanogen bromide (2.12 g, 20.0 mmol) to a stirred solution of 3-hydrazino-6-(4-nitro-1H-pyrazol-1-yl)-1,2,4-tetraazine (2.23 g, 10.0 mmol) in 3M HCl (15 mL). Stir the solution at room temperature for 24 h. Collect the dark purple precipitate by filtration and wash with water (50 mL) and MeCN (10 mL) to obtain 6-(4-nitro-1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine (1.66 g, 67%) as a dark purple powder ANPTTz. Step 2: Weigh AgNO3 (169 mg, 1.0 mmol) and dissolve it in 5 mL of a mixed solution of H2O and HNO3 (volume ratio 4:1). Then add ANPTTz (248 mg, 1.0 mmol) and allow it to evaporate naturally at room temperature to obtain purple needle-like crystals, which are the anionic energetic complex based on ANPTTz [Ag2(ANPTTz)4(NO3)2(H2O)]. n ·2H2O, denoted as ECP-2. Figure 2 This is the minimum asymmetric unit structure diagram of ECP-2.

[0025] To determine the structure of the complex, the crystal structure of the products obtained in Examples 1 and 2 was tested. The test results are shown in Table 1. Through data such as atomic coordinates, coordination bond relationships, and space groups, it was proved that the prepared complex is a novel structure, such as ligand coordination mode, metal-ligand bond length, and anion interaction mode.

[0026] Table 1 Laser-induced detonation test: The complex [Ag2(ANPTTz)(ClO4)2] prepared in Example 1 n A laser-initiated detonation test was conducted. The laser-initiated detonation device consists of a laser optical path system, an initiation system, a data acquisition system, and an illumination optical path. The laser optical path system's main functions include providing laser light and measuring the energy of a single laser beam (6 mJ). The initiation system is the primary site where the sample responds to the laser. The data acquisition system, consisting of a high-speed camera and a computer, primarily records the deflagration or detonation process of the sample. The illumination optical path is designed to prevent the high-speed camera from being overexposed during recording. The test results are as follows: Figure 3 As shown, [Ag2(ANPTTz)(ClO4)2] n Detonation occurred after 93.35 ms, capturing the moment of deflagration-to-detonation (DDT), with an initiation threshold of 560.1 mJ.

[0027] The complex [Ag2(ANPTTz)2(ClO4)2] prepared in Example 1 n Data on the catalytic decomposition of ammonium perchlorate (AP) were obtained. Adding 5% energetic metal coordination polymer and 10℃ / min can reduce the peak temperature of AP high-temperature decomposition by 76℃, which shows good catalytic effect.

[0028] Example 3 A method for preparing anionic energetic complexes based on ANPTTz, specifically: Step 1: Same as in Example 1; Step 2: Weigh out Co(NO3)2·6H2O (291 mg, 1.0 mmol) and dissolve it in 5 mL of a mixed solution of H2O and HClO4 (volume ratio 4:1). Then add ANPTTz (466 mg, 2.0 mmol) and allow it to evaporate naturally at room temperature to obtain needle-like crystals, which are the anionic energetic complex based on ANPTTz [Co(ANPTTz)2(ClO4)2(H2O)2]. n This is designated as ECP-3.

[0029] Example 4 A method for preparing anionic energetic complexes based on ANPTTz, specifically: Step 1: Same as in Example 1; Step 2: Weigh out Co(NO3)2·6H2O (291 mg, 1.0 mmol) and dissolve it in 5 mL of a mixed solution of H2O and HNO3 (volume ratio 4:1). Then add ANPTTz (699 mg, 3.0 mmol) and allow it to evaporate naturally at room temperature to obtain needle-like crystals, which are the anionic energetic complex [Co(ANPTTz)3(NO3)3] based on ANPTTz. n H2O, denoted as ECP-4.

[0030] Example 5 A method for preparing anionic energetic complexes based on ANPTTz, specifically: Step 1: Same as in Example 1; Step 2: Weigh out Cu(NO3)2 (187 mg, 1.0 mmol) and dissolve it in 5 mL of a mixed solution of H2O and HClO4 (volume ratio 4:1). Then add ANPTTz (466 mg, 2.0 mmol) and allow it to evaporate naturally at room temperature to obtain needle-like crystals, which are the anionic energetic complex based on ANPTTz [Cu(ANPTTz)2(ClO4)2(H2O)2]. n This is designated as ECP-5.

[0031] Example 6 A method for preparing anionic energetic complexes based on ANPTTz, specifically: Step 1: Same as in Example 1; Step 2: Weigh Cu(NO3)2 (187 mg, 1.0 mmol) and dissolve it in 5 mL of a mixed solution of H2O and HNO3 (volume ratio 4:1). Then add ANPTTz (466 mg, 2.0 mmol) and allow it to evaporate naturally at room temperature to obtain needle-like crystals, which are the anionic energetic complex [Cu(ANPTTz)2(NO3)2(H2O)2] based on ANPTTz. n This is designated as ECP-6.

[0032] Example 7 A method for preparing anionic energetic complexes based on ANPTTz, specifically: Step 1: Same as in Example 1; Step 2: Weigh 290 mg (1.0 mmol) of Ni(NO3)2·6H2O and dissolve it in 5 mL of a mixed solution of H2O and HClO4 (volume ratio 4:1). Then add ANPTTz (699 mg, 3.0 mmol) and allow it to evaporate naturally at room temperature to obtain needle-like crystals, which are the anionic energetic complex [Ni(ANPTTz)3(ClO4)2] based on ANPTTz. n H2O, denoted as ECP-7.

[0033] Example 8 A method for preparing anionic energetic complexes based on ANPTTz, specifically: Step 1: Same as in Example 1; Step 2: Weigh 290 mg (1.0 mmol) of Ni(NO3)2·6H2O and dissolve it in 5 mL of a mixed solution of H2O and HNO3 (volume ratio 4:1). Then add ANPTTz (699 mg, 3.0 mmol) and allow it to evaporate naturally at room temperature to obtain needle-like crystals, which are the anionic energetic complex [Ni(ANPTTz)3(NO3)2] based on ANPTTz. n H2O, denoted as ECP-8.

[0034] Comparative Example 1 ANPTTz was prepared first according to the method in Example 1. AgNO3 (169 mg, 1.0 mmol) was weighed and dissolved in 5 mL of H2O, and then ANPTTz (216 mg, 1.0 mmol) was added. It was allowed to evaporate naturally at room temperature, and no complex was obtained. In this comparative example, HClO4 was not added, and the remaining steps were the same as in Example 1.

[0035] Comparative Example 2 ANPTTz was prepared first according to the method in Example 1. AgNO3 (169 mg, 1.0 mmol) was weighed and dissolved in 5 mL of H2O, and then ANPTTz (233 mg, 1.0 mmol) was added. The mixture was then hydrothermally volatilized at 60 °C, but no complex was obtained.

[0036] This invention uses ANPTTz and silver nitrate as raw materials. By adding perchloric acid or nitric acid to adjust the pH of the system, ligand ionization is inhibited and it is kept electroneutrally, thereby achieving oxygen-rich anions (ClO4). - NO3 -By directionally introducing ANPTTz and then allowing it to evaporate naturally at room temperature, the single-crystal structure of the target complex was successfully prepared. Comparative Examples 1 and 2 show that without external acid adjustment, simply mixing the metal nitrate with ANPTTz cannot yield a crystalline product of the complex, regardless of whether room temperature or hydrothermal evaporation methods are used. The selected ANPTTz ligand has abundant coordination sites, and its typical chelation coordination mode can significantly enhance its coordination ability with the metal center. By controlling the pH, ligand ionization is suppressed and its electroneutrality is maintained. After the ligand coordinates with the metal center, the system must introduce oxygen-rich anions to achieve charge balance, which is also the key to the stable formation and crystallization of this type of complex.

[0037] Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and illustrations shown and described herein.

Claims

1. An anionic energetic complex based on ANPTTz, characterized in that, The general chemical formula of the anionic energetic complex based on ANPTTz is [M x (ANPTTz) y B z ] n ·qH2O, where n≥1, x ranges from 1 to 5, y ranges from 1 to 5, z ranges from 1 to 5, q ranges from 0 to 5, M is a metal cation, B is an acid radical anion, and ANPTTz is 6-(4-nitro-1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine.

2. The anionic energetic complex based on ANPTTz as described in claim 1, characterized in that, The M specifically refers to Ag. + Co 2+ Cu 2+ Ni 2+ One of them, B specifically refers to NO3. - ClO4 - One of them.

3. The anionic energetic complex based on ANPTTz as described in claim 1, characterized in that, The specific anionic energetic complexes based on ANPTTz include: [Ag2(ANPTTz)2(ClO4)2] n [Ag2(ANPTTz)4(NO3)2(H2O)] n ·2H2O, [Co(ANPTTz)2(ClO4)2(H2O)2] n [Co(ANPTTz)3(NO3)3] n ·H2O, [Cu(ANPTTz)2(ClO4)2(H2O)2] n [Cu(ANPTTz)2(NO3)2(H2O)2] n [Ni(ANPTTz)3(ClO4)2] n H2O, [Ni(ANPTTz)3(NO3)2] n One of the components of H2O.

4. A method for preparing anionic energetic complexes based on ANPTTz as described in any one of claims 1-3, characterized in that, include: Anionic energetic complexes based on ANPTTz were prepared by volatilization using 6-(4-nitro-1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine and metal nitrates as raw materials.

5. The method for preparing anionic energetic complexes based on ANPTTz as described in claim 4, characterized in that, Specifically, it includes: First, ANPTTz is prepared for later use. The metal nitrate is dissolved in the mixed solution, and then ANPTTz is added. It is allowed to evaporate naturally at room temperature to obtain crystals, which are the anionic energetic complexes based on ANPTTz.

6. The method for preparing anionic energetic complexes based on ANPTTz as described in claim 5, characterized in that, The metal nitrate is one of AgNO3, Co(NO3)2·6H2O, Cu(NO3)2, and Ni(NO3)2·6H2O. The molar ratio of ANPTTz to the metal nitrate is 0.01~3.0:0.01~1.

0. The mixed solution is prepared by mixing H2O with HClO4 or HNO3 in a volume ratio of 4~6:

1.

7. The method for preparing anionic energetic complexes based on ANPTTz as described in claim 5, characterized in that, The ratio of the metal nitrate to the mixed solution is 0.01~0.03 mmol: 1~20 mL.

8. An application of the anionic energetic complex based on ANPTTz as described in any one of claims 1-3, characterized in that, The anionic energetic complex based on ANPTTz is used as a laser-initiated explosive.

9. An application of the anionic energetic complex based on ANPTTz as described in any one of claims 1-3, characterized in that, The aforementioned anionic energetic complex based on ANPTTz is used as a combustion catalyst for composite propellants or modified dual-base propellants.

10. An application of the anionic energetic complex based on ANPTTz as described in any one of claims 1-3, characterized in that, The anionic energetic complex based on ANPTTz was used as a catalyst for the decomposition of ammonium perchlorate.

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