An aprotic anion-containing energetic complex based on apttz and its preparation method and application

Abstract

This invention discloses an anionic energetic complex based on APTTz, its preparation method, and its applications. APTTz is 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine. The general structural formula of the anionic energetic complex based on APTTz is [X m (APTTz) p Y t ] n· In zH₂O, X is a metal cation, and Y is an acid radical anion; the values ​​of m range from 1 to 2, P range from 1 to 3, t range from 1 to 2, and z range from 0 to 2. The triazolotetraazine anionic energetic complex obtained in this invention 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. The APTTz-based anionic energetic complex prepared in this invention can be used as a combustion catalyst for composite propellants and modified double-base propellants, significantly improving the combustion rate of composite propellants and modified double-base propellants and reducing the platform pressure index.

Description

Technical Field

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

[0002] Energetic complexes are a class of special complexes formed by the coordination bonds between metal ions / atoms and energetic ligands. They possess both the structural characteristics of coordination compounds and the explosive properties of energetic materials. With their unique advantages such as high energy density, structural tunability, and controllable reaction, they have shown great potential in the field of energetic materials and have become one of the hot research directions in this field. In practical applications, energetic complexes have a dual core application scenario: on the one hand, their excellent initiation performance allows them to be widely used as initiators in the initiation systems of various weapons and ammunition, including conventional weapons such as shells, missiles, and torpedoes, as well as special munitions in the aerospace field, providing core support for the reliable initiation of weapon systems; on the other hand, as energetic catalysts, they can effectively regulate the combustion rate and combustion stability of propellants, making them widely applicable in rocket propellants, missile solid propellants, and other fields, significantly improving the dynamic performance and operational reliability of propulsion systems.

[0003] However, in the actual preparation of energetic complexes, the participation of solvent molecules in coordination is difficult to avoid due to limitations imposed by the preparation process and reaction system. The preparation of energetic complexes typically requires organic solvents (such as ethanol, acetonitrile, and dimethylformamide) or water as the reaction medium. These solvent molecules, possessing a certain coordination ability, easily compete with energetic ligands for coordination sites at the metal center, thus forming energetic complexes containing coordinating solvent molecules. These coordinating solvent molecules are gradually released during the storage, transportation, or practical application of energetic complexes. This process not only directly dilutes the density of the energetic groups, leading to a significant reduction in the energy level of the complex and failing to meet the expected initiation or propulsion performance requirements; more importantly, the release of solvent molecules at low temperatures generates local pressure accumulation, disrupting the crystal structure integrity of the energetic complex and causing a significant decrease in its thermodynamic and mechanical stability. This is accompanied by a reduction in key explosion performance parameters such as detonation heat and detonation velocity, severely restricting the practical application of energetic complexes in extreme environments (such as high-altitude low-temperature environments and deep-sea high-pressure environments).

[0004] Meanwhile, with the continuous iteration and upgrading of initiation technology, laser initiation technology, with its outstanding advantages of safety, reliability, precision, and controllability, has gradually replaced traditional initiation methods and become the mainstream development direction in the field of energetic material initiation. Laser initiation technology uses laser as the energy input source, achieving directional energy transfer through precise focusing of the laser beam. This effectively avoids safety hazards such as electromagnetic interference, electrostatic discharge, and stray currents present in traditional electric initiation methods, significantly improving the safety and controllability of the initiation process. It is particularly suitable for initiation operations in precision weapon systems and flammable and explosive environments. Compared to traditional initiation technologies, laser initiation not only enables precise control of the initiation timing but also reduces interference from the external environment, further lowering the risk of accidental initiation and providing technical assurance for the safe application of energetic materials.

[0005] Currently, my country's application of detonating explosives is still dominated by traditional varieties, mainly including lead azide (Pb(N3)2), picric acid (2,4,6-trinitrophenol), and dinitrodiazophenol (DDNP). Although these traditional detonating explosives possess certain detonation performance and have been used in various weapons and civilian blasting fields for many years, they have fatal safety shortcomings: most traditional detonating explosives are extremely sensitive to external stimuli (such as impact, friction, static electricity, temperature changes, etc.). During the entire process of production, storage, transportation, assembly, and use, they are highly susceptible to triggering explosive reactions due to accidental operation or environmental factors, leading to serious explosion accidents, causing huge property losses and casualties. In addition, some traditional detonating explosives also have problems such as serious environmental pollution, complex preparation processes, and limited room for performance improvement, making it difficult to meet the development requirements of modern weapons and equipment for high safety, high reliability, and high adaptability of detonation systems, and also unable to adapt to the application scenarios of new detonation technologies such as laser detonation.

[0006] In summary, while energetic complexes, as novel energetic materials, possess broad application prospects, the performance defects caused by coordination solvent molecules during their preparation process urgently need to be addressed. Laser-initiated detonation technology, as a safe and reliable new initiation method, provides a technological path for upgrading initiation systems, but existing traditional initiating explosives are no longer adequate for industry development needs. Therefore, developing novel energetic complexes with superior performance, high stability, and no significant solvent coordination defects, and combining them with laser-initiated detonation technology to construct a safer and more efficient initiation system to replace traditional sensitive initiating explosives, has become a key issue urgently needing breakthroughs in the field of energetic materials. This has significant practical and strategic value for improving the safety and advancement of my country's weaponry and ensuring the safe production of related industries. Summary of the Invention

[0007] 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.

[0008] To achieve these and other advantages according to the invention, the present invention provides an anionic energetic complex based on APTTz, wherein APTTz is 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine, and the general structural formula of the anionic energetic complex based on APTTz is [X m (APTTz) p Y t ] n· zH2O, where X is a metal cation and Y is an acid radical anion; m ranges from 1 to 2, P ranges from 1 to 3, t ranges from 1 to 2, z ranges from 0 to 2, and n ranges from 1 to 1.

[0009] Preferably, X specifically includes Ag. + Co 2+ Cu 2+ Ni 2+ One of them, Y specifically includes one of NO3⁻ and ClO4⁻; The APTTz-based anionic energetic complex specifically includes [Ag(APTTz)(ClO4)]. n [Ag2(APTTz)2(NO3)2] n [Co(APTTz)2(ClO4)2(H2O)2] n· H2O, [Co(APTTz)3(NO3)3] n· 2H2O, [Cu(APTTz)2(ClO4)2(H2O)2] n [Cu(APTTz)2(NO3)2(H2O)2] n [Ni(APTTz)2(NO3)2(H2O)2] n One of them.

[0010] Preferably, the structural formula of the 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine is as follows: .

[0011] A method for preparing an anionic energetic complex based on APTTz includes: dissolving a nitrate in an acid solution, then adding 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine, allowing it to volatilize naturally at room temperature or undergo a hydrothermal reaction at 40~100℃ to obtain the anionic energetic complex based on APTTz.

[0012] Preferably, the nitrate includes one of AgNO3, Co(NO3)2·6H2O, Cu(NO3)2, and Ni(NO3)2·6H2O.

[0013] Preferably, the acid solution includes HNO3 or HClO4 solution.

[0014] Preferably, the ratio of the amount of nitrate, acid solution, and 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine is 0.01~1.0 mmol: 1~5 mL: 0.01~3.0 mmol.

[0015] Preferably, the volume ratio of water to acid in the acid solution is 4:1 to 19:1.

[0016] An application of an APTTz-based anionic energetic complex, wherein the APTTz-based anionic energetic complex is used as a laser-initiated explosive.

[0017] An application of an APTTz-based anionic energetic complex, wherein the APTTz-based anionic energetic complex is used as a combustion catalyst for composite propellants and modified dual-base propellants.

[0018] The present invention has at least the following beneficial effects: the triazolotetraazine anionic energetic complex obtained by the present invention undergoes detonation response after being irradiated by laser, and has good safety performance and detonation performance. It can be used as a laser initiator or as a component of explosives and propellants, and has good application prospects in the field of high-energy insensitive energetic materials.

[0019] The APTTz-based anionic energetic complex prepared in this invention can be used as a combustion catalyst for composite propellants and modified double-base propellants, significantly improving the combustion rate of composite propellants and modified double-base propellants and reducing the plateau pressure index of composite propellants and modified double-base propellants.

[0020] 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

[0021] Figure 1 [Ag(APTTz)(ClO4)] prepared in Example 1 n The structural formula; Figure 2 [Ag2(APTTz)2(NO3)2] prepared in Example 2 n The structural formula; Figure 3 [Co(APTTz)2(ClO4)2(H2O)2] prepared in Example 3 n· The structural formula of H2O; Figure 4 [Co(APTTz)3(NO3)3] prepared in Example 4 n· The structural formula of 2H2O; Figure 5 [Cu(APTTz)2(ClO4)2(H2O)2] prepared in Example 5 n The structural formula; Figure 6 [Cu(APTTz)2(NO3)2(H2O)2] prepared in Example 6 n The structural formula; Figure 7 [Ni(APTTz)2(NO3)2(H2O)2] prepared in Example 7 n The structural formula; Figure 8 [Co(APTTz)2(ClO4)2(H2O)2] prepared in Example 3 n· Laser response test diagram of H2O; Figure 9 [Cu(APTTz)2(ClO4)2(H2O)2] prepared in Example 5 n Laser response test diagram; Figure 10 [Cu(APTTz)2(NO3)2(H2O)2] prepared in Example 6 n The laser response test diagram. Detailed Implementation

[0022] 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.

[0023] 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.

[0024] The preparation method of 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine (APTTz) used in each embodiment includes: 1.07 g of cyanogen bromide (10.0 mmol) was added to 1.78 g of 3-hydrazino-6-(1H-pyrazol-1-yl)-1,2,4,5-tetraazine (10.0 mmol) in 15 mL of 3 M HCl solution and stirred. The solution was stirred at room temperature for 24 hours. The dark purple precipitate was collected by filtration and washed with 50 mL of water and 10 mL of MeCN to give 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine (1.20 g, yield 59%) as a dark purple powder, APTTz. 1 H NMR (400 MHz, d 6 - DMSO)δ / ppm: 6.76 (s,1H,), 7.67 (s, 2H), 8.03 (s, 1H), 8.87 (s, 1H) δ; 13 C NMR (400MHz, d 6 -DMSO) δ / ppm: 109.70, 131.29, 144.66, 148.11, 149.46, 149.71.

[0025] The structural formula for APTTz is: .

[0026] Example 1 169 mg (1.0 mmol) of AgNO3 was dissolved in 5 mL of a mixed solution of H2O and HClO4 (volume ratio 4:1). Then, 216 mg (1.0 mmol) of APTTz was added, and the solution was allowed to evaporate naturally at room temperature to obtain purple needle-like crystals, namely [Ag(APTTz)(ClO4)]. n It is denoted as ECP-1, and its structural formula is as follows: Figure 1 As shown.

[0027] Example 2 169 mg (1.0 mmol) of AgNO3 was dissolved in 5 mL of a mixed solution of H2O and HNO3 (volume ratio 4:1). Then, 216 mg (1.0 mmol) of APTTz was added, and the solution was allowed to evaporate naturally at room temperature to obtain purple needle-like crystals, namely [Ag2(APTTz)2(NO3)2]. n It is denoted as ECP-2, and its structural formula is as follows: Figure 2 As shown.

[0028] Example 3 Weigh out 291 mg (1.0 mmol) of Co(NO3)2·6H2O and dissolve it in 5 mL of a mixed solution of H2O and HClO4 (volume ratio 4:1). Then add APTTz (432 mg, 2.0 mmol) and allow it to evaporate naturally at room temperature to obtain red needle-like crystals, namely [Co(APTTz)2(ClO4)2(H2O)2]. n· H2O, denoted as ECP-3, has the following structural formula: Figure 3 As shown.

[0029] Example 4 Weigh out 291 mg (1.0 mmol) of Co(NO3)2·6H2O and dissolve it in 5 mL of a mixed solution of H2O and HNO3 (volume ratio 4:1). Then add APTTz (648 mg, 3.0 mmol) and allow it to evaporate naturally at room temperature to obtain purple needle-like crystals, namely [Co(APTTz)3(NO3)3]. n· 2H₂O, denoted as ECP-4, has the following structural formula: Figure 4 As shown.

[0030] Example 5 Weigh out 187 mg (1.0 mmol) of Cu(NO3)2 and dissolve it in 5 mL of a mixed solution of H2O and HClO4 (volume ratio 4:1). Then add APTTz (432 mg, 2.0 mmol) and allow it to evaporate naturally at room temperature to obtain purple needle-like crystals, namely [Cu(APTTz)2(ClO4)2(H2O)2]. n It is designated as ECP-5, and its structural formula is as follows: Figure 5 As shown.

[0031] Example 6 Weigh out 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 APTTz (432 mg, 2.0 mmol) and allow it to evaporate naturally at room temperature to obtain purple needle-like crystals, namely [Cu(APTTz)2(NO3)2(H2O)2]. n It is designated as ECP-6, and its structural formula is as follows: Figure 6 As shown.

[0032] Example 7 Ni(NO3)2·6H2O (290 mg, 1.0 mmol) was weighed and dissolved in 5 mL of a mixed solution of H2O and HClO4 (volume ratio 4:1). Then, APTTz (432 mg, 2.0 mmol) was added, and the solution was allowed to evaporate naturally at room temperature to obtain purple needle-like crystals, namely [Ni(APTTz)2(NO3)2(H2O)2]. nIt is designated as ECP-7, and its structural formula is as follows: Figure 7 As shown.

[0033] Example 8 169 mg (1.0 mmol) of AgNO3 was dissolved in 5 mL of a mixed solution of H2O and HClO4 (volume ratio 4:1). Then, 108 mg (0.5 mmol) of APTTz was added, and the mixture was subjected to a hydrothermal reaction at 40 °C until purple needle-like crystals were obtained, namely [Ag(APTTz)(ClO4)]. n Its structural formula is the same as that of Example 1.

[0034] Example 9 Weigh out 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 APTTz (108 mg, 0.5 mmol) and perform a hydrothermal reaction at 100 °C until purple needle-like crystals are obtained, i.e., [Ag(APTTz)(ClO4)]. n Its structural formula is the same as that of Example 1.

[0035] To determine the structure of the complexes prepared in each embodiment, crystal structure testing was performed, and the results are as follows: Table 1. Crystal structure test results of samples from each embodiment. This invention uses 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine (APTTz) and corresponding metal nitrates as raw materials. By adding nitric acid (HNO3) or perchloric acid (HClO4) to adjust the pH of the system, the ligand ionization is suppressed and the system is kept electroneutrally, thereby achieving the directional introduction of oxygen-rich anions (NO3⁻, ClO4⁻). The single-crystal structure of the target complex was successfully prepared via a solvothermal reaction. Comparative experiments show that without external acid adjustment, simply mixing the metal nitrate with APTTz, regardless of whether room temperature volatilization or hydrothermal volatilization is used, cannot yield the crystalline product of the corresponding complex.

[0036] Existing literature (J. Am. Chem. Soc., 2016, 138, 4685–4692) used a solvent-antisolvent method to obtain APTTz-based Fe. 2⁺ Complexes were obtained, but this route has obvious limitations: on the one hand, the synthesis process is complicated and difficult to scale up, and the products are only partially crystalline, with the rest being amorphous powders; on the other hand, this work only achieved iron-based complexes containing ClO4⁻, and did not obtain complexes with other metal centers such as Co, Ni, and Cu, nor did it obtain related structures containing NO3⁻ anions.

[0037] The APTTz ligand selected in this invention has abundant coordination sites, and its typical chelation coordination mode can significantly enhance its coordination ability with the metal center. By inhibiting ligand ionization and maintaining its electroneutrality through pH regulation, the system must introduce oxygen-rich anions after the ligand coordinates with the metal center to achieve charge balance, which is also the key to the stable formation and crystallization of such complexes.

[0038] The complex [Co(APTTz)2(ClO4)2(H2O)2] prepared in Example 3 n· H2O was used for laser-initiated detonation experiments. The laser-initiated detonation device consisted of a laser optical path system, an initiation system, a data acquisition system, and an illumination optical path. The main functions of the laser optical path system included providing the laser beam and measuring the energy of a single laser beam (6 mJ). The initiation system was the primary site where the sample responded to the laser. The data acquisition system, consisting of a high-speed camera and a computer, recorded the deflagration or detonation process of the sample. The illumination optical path was designed to prevent the high-speed camera from being overexposed during recording. The test results are as follows: Figure 8 As shown, [Co(APTTz)2(ClO4)2(H2O)2] n· H2O detonated after 27.225 ms, capturing the moment of deflagration-to-detonation (DDT), with an initiation threshold of 163.35 mJ.

[0039] The complex [Cu(APTTz)2(ClO4)2(H2O)2] prepared in Example 5 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 main functions of the laser optical path system 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, records the deflagration or detonation process of the sample. The illumination optical path prevents the high-speed camera from being overexposed during recording. The test results are as follows: Figure 9 As shown, [Cu(APTTz)2(ClO4)2(H2O)2] n Detonation occurred after 16.025 ms, capturing the moment of deflagration-to-detonation (DDT), with an initiation threshold of 396.15 mJ.

[0040] The complex [Cu(APTTz)2(NO3)2(H2O)2] prepared in Example 6n 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 main functions of the laser optical path system 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, records the deflagration or detonation process of the sample. The illumination optical path prevents the high-speed camera from being overexposed during recording. The test results are as follows: Figure 10 As shown, [Cu(APTTz)2(NO3)2(H2O)2] n Detonation occurred after 120.15 ms, capturing the instant of deflagration-to-detonation (DDT). The initiation threshold was 720.9 mJ. The complex [Co(APTTz)3(NO3)3] prepared in Example 4 n· Combustion catalysis experiments were conducted using 2H₂O on composite propellants. [Cu(APTTz)₂(ClO₄)₂(H₂O)₂] n The mass percentage composition of the composite propellant formulation AC1 is: 12% hydroxyl-terminated polybutadiene, 15% aluminum powder, 65% ammonium perchlorate, and 2.5% [Co(APTTz)3(NO3)3]. n· The compound propellant formulations were: 2H₂O, 4% diisooctyl sebate, 1.3% toluene diisocyanate, and 0.2% tris(2-methyl-1-aziridine)phosphine oxide. The blank control group, compound propellant formulation AC0, was based on compound propellant formulation AC1 without the addition of the complex [Co(APTTz)₃(NO₃)₃]. n· 2H₂O. The combustion rates of composite propellants AC1 and ACO at pressures of 3 MPa, 5 MPa, 7 MPa, 9 MPa, 10 MPa, and 11 MPa were tested using GJB-770B method 706.1 (burning rate-target line method); the results showed that 2.5% [Co(APTTz)₃(NO₃)₃] n· The addition of 2H2O can increase the burning rate of the composite propellant at 10MPa by 63% and reduce the plateau pressure index from 0.6884 to 0.3893.

[0041] The complex [Cu(APTTz)2(ClO4)2(H2O)2] prepared in Example 5 n Combustion catalysis experiments were conducted on the modified double-base propellant. [Cu(APTTz)2(ClO4)2(H2O)2] n The modified double-base propellant formulation RC1 has the following mass percentage composition: 35% nitrocellulose, 25% nitroglycerin, 30% RDX, and 2.5% [Cu(APTTz)2(ClO4)2(H2O)2]. nThe propellant formulation RC0, a blank control group, was based on the modified double-base propellant formulation RC1 without the addition of the complex [Cu(APTTz)2(ClO4)2(H2O)2]. n The combustion rates of modified double-base propellants RC1 and RC0 were tested using GJB-770B method 706.1 (burning rate-target line method) at pressures of 2, 4, 6 MPa, 8 MPa, 10 MPa, 12 MPa, 14 MPa, 16 MPa, 18 MPa, 20 MPa, and 22 MPa. The results showed that 2.5% [Cu(APTTz)2(ClO4)2(H2O)2] n The addition of [a specific ingredient] can increase the burning rate of modified double-base propellant by 56% at 10 MPa and reduce the plateau pressure index at 6-12 MPa from 0.8933 to 0.2076.

[0042] The number of devices and processing scale described herein are for the purpose of simplifying the description of the invention. Applications, modifications, and variations of the invention will be readily apparent to those skilled in the art.

[0043] 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 APTTz, characterized in that, The APTTz is 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine, and the general structural formula of the APTTz-based anionic energetic complex is [X]. m (APTTz) p Y t ] n· zH2O, where X is a metal cation and Y is an acid radical anion; m ranges from 1 to 2, P ranges from 1 to 3, t ranges from 1 to 2, z ranges from 0 to 2, and n ranges from 1 to 1.

2. The APTTz-based anionic energetic complex as described in claim 1, characterized in that, The X specifically includes Ag + Co 2+ Cu 2+ Ni 2+ One of them, Y specifically includes one of NO3⁻ and ClO4⁻; The APTTz-based anionic energetic complex specifically includes [Ag(APTTz)(ClO4)]. n [Ag2(APTTz)2(NO3)2] n [Co(APTTz)2(ClO4)2(H2O)2] n· H2O, [Co(APTTz)3(NO3)3] n· 2H2O, [Cu(APTTz)2(ClO4)2(H2O)2] n [Cu(APTTz)2(NO3)2(H2O)2] n [Ni(APTTz)2(NO3)2(H2O)2] n One of them.

3. The APTTz-based anionic energetic complex as described in claim 1, characterized in that, The structural formula of the 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine is as follows: 。 4. A method for preparing an anionic energetic complex based on APTTz as described in any one of claims 1-3, characterized in that, Specifically, it includes: Nitrate was dissolved in an acid solution, followed by the addition of 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine. The mixture was allowed to volatilize naturally at room temperature or subjected to hydrothermal reaction at 40–100 °C to obtain an anionic energetic complex based on APTTz.

5. The method for preparing anionic energetic complexes based on APTTz as described in claim 4, characterized in that, The nitrate includes one of AgNO3, Co(NO3)2·6H2O, Cu(NO3)2, and Ni(NO3)2·6H2O.

6. The method for preparing anionic energetic complexes based on APTTz as described in claim 4, characterized in that, The acid solution includes HNO3 or HClO4 solution.

7. The method for preparing anionic energetic complexes based on APTTz as described in claim 4, characterized in that, The ratio of nitrate, acid solution, and 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine is 0.01~1.0 mmol: 1~5 mL: 0.01~3.0 mmol.

8. The method for preparing anionic energetic complexes based on APTTz as described in claim 4, characterized in that, In the acid solution, the volume ratio of water to acid is 4:1 to 19:

1.

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

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

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