An anion-containing energetic complex based on npttz and a preparation method and application thereof
The preparation of anionic energetic complexes of NPTTz and metal nitrates in acidic solutions by volatilization method solves the problems of cumbersome preparation process and insufficient safety in the existing technology, and realizes efficient and stable preparation and application of energetic complexes, which are suitable for laser-initiated explosives and pyrotechnic explosives.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SOUTHWEAT UNIV OF SCI & TECH
- Filing Date
- 2026-02-13
- Publication Date
- 2026-06-02
AI Technical Summary
Existing preparation processes for energetic complexes are cumbersome and difficult to scale up. The products are mostly amorphous powders, and it is difficult to obtain complexes with multiple metal centers. Solvent molecules are prone to participating in coordination, affecting performance. Existing initiators are sensitive to external stimuli and are prone to accidents. Therefore, a safer laser initiator is sought.
Anionic energetic complexes were prepared by the natural volatilization of NPTTz and metal nitrates in acidic solution. The volatilization method introduces oxygen-rich anions to form a stable crystal structure, which is suitable for the preparation of complexes with various metal centers.
The prepared anionic energetic complexes have good thermal stability and safety performance, making them suitable for large-scale industrial production. As components of laser-initiated explosives and pyrotechnics, they exhibit excellent detonation performance and catalytic activity, reducing the decomposition temperature of catalysts.
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Abstract
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 NPTTz, its preparation method and application. Background Technology
[0002] Energetic complexes are compounds formed by coordinating metal ions with energetic ligands via coordinate bonds. They typically possess high energy density, good thermal stability, or specific sensitivity characteristics. Their coordination mechanisms are diverse, allowing for precise control of material properties such as energy, sensitivity, and thermal stability by adjusting the ligand type, metal ion species, and coordination ratio. Therefore, they have significant application potential in the field of energetic materials (such as propellants, initiators, and explosives). In the preparation of existing energetic complexes, solvent molecules readily participate in coordination, negatively impacting the complex's performance. Furthermore, laser-initiated detonation technology has become the mainstream initiation method for coordination compounds and other initiators because it avoids problems such as electromagnetic interference, electrostatic discharge, and stray currents. Currently, my country still primarily uses initiators such as trinitrophenol, lead azide, and dinitrodiazophenol (DDNP). These initiators are highly sensitive to external stimuli and prone to accidental explosions. Therefore, the search for safer laser-initiated detonators has significant application value.
[0003] The energy of energetic complexes originates from redox reactions, and the high oxygen content of oxygen-rich anions is key to achieving high-energy release. Therefore, researchers have dedicated themselves to obtaining energetic complexes containing oxygen-rich anions, achieving some success. Currently, the commonly used technique involves introducing anions using the charge difference between high-valence cations and low-valence anion ligands. However, during self-assembly, multiple ligands are often generated, resulting in charge equilibrium with the cation and preventing the introduction of anions, leading to significant uncertainty. Therefore, seeking safer, more effective, and suitable methods for large-scale industrial production to introduce oxygen-rich anions is of great importance.
[0004] Existing processes typically employ a solvent-antisolvent method to prepare complexes, but this route has significant limitations: firstly, the synthesis process is cumbersome, difficult to scale up, and the product is only partially crystalline, with the remainder being amorphous powder; secondly, while this process can produce iron-based complexes, it is difficult to obtain complexes with other metal centers such as Ag. Therefore, seeking a simple, high-yield, and versatile process for preparing complexes with multiple metals is of great importance. 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 NPTTz is provided, the general chemical formula of which is [M x (NPTTz) y A z (H2O) p ] n ·qH2O; where M is a metal ion, A is an acid radical anion; NPTTz is 6-(4-nitro-1H-pyrazole-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine; x ranges from 1 to 5, y ranges from 1 to 5, z ranges from 1 to 5, p ranges from 0 to 5, q ranges from 0 to 5, and n ranges from greater than or equal to 1.
[0007] Preferably, M is a metal ion Ag. + Co 2+ Cu 2+ Ni 2+ One of them; wherein A is an acid radical anion NO3. - ClO4 - One of them.
[0008] Preferably, the chemical formula of the NPTTz-based anionic energetic complex is [Ag3(NPTTz)3(ClO4)3]. n [Ag(NPTTz)(NO3)] n [Co(NPTTz)2(ClO4)2(H2O)2] n [Co(NPTTz)3(NO3)3] n ·H2O, [Cu(NPTTz)2(ClO4)2(H2O)2] n [Cu(NPTTz)2(NO3)2(H2O)2] n [Ni(NPTTz)3(ClO4)2] n H2O, [Ni(NPTTz)3(NO3)2] n One of the components of H2O.
[0009] A method for preparing an anionic energetic complex based on NPTTz as described above includes: preparing the complex by volatilization using 6-(4-nitro-1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine and the corresponding metal nitrate as raw materials.
[0010] Preferably, the method for preparing the NPTTz-based anionic energetic complex specifically includes: dissolving a metal nitrate in an acid solution, then adding NPTTz, allowing it to evaporate naturally at room temperature to obtain the NPTTz-based anionic energetic complex.
[0011] Preferably, the metal nitrate is one of AgNO3, Co(NO3)2·6H2O, Cu(NO3)2, and Ni(NO3)2·6H2O; the molar ratio of NPTTz to the metal nitrate is 0.01~3.0:0.01~1.0.
[0012] Preferably, the acid solution is an HClO4 solution or an HNO3 solution; in the HClO4 solution, the volume ratio of H2O to HClO4 is 1~10:1; in the HNO3 solution, the volume ratio of H2O to HNO3 is 1~10:1.
[0013] Preferably, the mass-to-volume ratio of the metal nitrate to the acid solution is 1~300 mg: 1~20 mL.
[0014] Preferably, the [Ag3(NPTTz)3(ClO4)3] is prepared... n The metal nitrate is AgNO3, and the acid solution is HClO4 solution.
[0015] Application of an NPTTz-based anionic energetic complex as described above, or an NPTTz-based anionic energetic complex prepared by the preparation method described above, in laser-initiated explosives.
[0016] Application of an NPTTz-based anionic energetic complex as described above, or an NPTTz-based anionic energetic complex prepared by the preparation method described above, in explosives.
[0017] Application of an NPTTz-based anionic energetic complex as described above, or an NPTTz-based anionic energetic complex prepared by the preparation method described above, in propellants.
[0018] Application of an NPTTz-based anionic energetic complex as described above, or an NPTTz-based anionic energetic complex prepared by the preparation method described above, in the catalysis of ammonium perchlorate.
[0019] The present invention provides at least the following beneficial effects: It offers a triazolotetraazine-based anionic energetic complex, synthesized via a volatilization method using 6-(4-nitro-1H-pyrazole-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine (NPTTz) and its corresponding nitrate as raw materials. This NPTTz-based anionic energetic complex 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, this NPTTz-based anionic energetic complex exhibits excellent catalytic activity, reducing the peak temperature of AP high-temperature decomposition by 77°C.
[0020] 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, 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 exhibits good thermal stability, with thermal decomposition stability >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 NPTTz-based anionic energetic complexes of this invention generally exhibit excellent thermal stability, all exceeding 200℃. 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.
[0021] Other advantages, objectives, and features of the present invention will be partly apparent from the following description. The details will also be understood by those skilled in the art through research and practice of the present invention. Attached Figure Description
[0022] 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 laser-initiated detonation process of ECP-1 prepared in Example 1 of the present invention. Detailed Implementation
[0023] 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.
[0024] 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.
[0025] In this invention, NPTTz refers to 6-(4-nitro-1H-pyrazole-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine; The structural formula of NPTTz is ; The preparation method of NPTTz includes: dispersing 3-hydrazino-6-(4-nitro-1H-pyrazol-1-yl)-1,2,4-tetraazine (1.79 g, 10.0 mmol), hydrochloric acid (0.6 mL), and triethyl orthoformate (5 mL) in 50 mL of 1,4-dioxane and stirring at 100 °C for 24 h; after the reaction is completed, the mixture is filtered and washed with ice water to obtain a yellow powder, which is 6-(4-nitro-1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine (1.26 g, 67%), which is the yellow powder NPTTz.
[0026] Example 1 A method for preparing anionic energetic complexes based on NPTTz, specifically: AgNO3 (169 mg, 1.0 mmol) was weighed and dissolved in 5 mL of a mixed solution of H2O and HClO4 (volume ratio 4:1). Then, NPTTz (233 mg, 1.0 mmol) was added, and the solution was allowed to evaporate naturally at room temperature to obtain red needle-like crystals, which are the NPTTz-based anionic energetic complex [Ag3(NPTTz)3(ClO4)3]. n This is designated as ECP-1.
[0027] Figure 1 The diagram shows the minimum asymmetric unit structure of ECP-1 prepared in Example 1.
[0028] To determine the structure of the complex, the ECP-1 prepared in Example 1 was subjected to crystal structure testing, and the test results are shown in Table 1: Table 1 Laser-initiated detonation test: The complex [Ag3(NPTTz)3(ClO4)3] prepared in Example 1 was tested. nA 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 2 As shown, [Ag3(NPTTz)3(ClO4)3] n Detonation occurred after 123.15 ms, capturing the moment of deflagration-to-detonation (DDT), with an initiation threshold of 738.9 mJ.
[0029] The energetic complex [Ag3(NPTTz)3(ClO4)3] prepared in Example 1 n Catalytic decomposition experiments of ammonium perchlorate (AP) were conducted by adding 5% of an energetic complex and adding [Ag3(NPTTz)3(ClO4)3] at a heating rate of 10 °C / min. n It can reduce the peak temperature of AP high-temperature decomposition by 77℃, demonstrating good catalytic effect.
[0030] Example 2 A method for preparing anionic energetic complexes based on NPTTz, specifically: 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, 233 mg (1.0 mmol) of NPTTz was added, and the solution was allowed to evaporate naturally at room temperature to obtain red needle-like crystals, which are the NPTTz-based anionic energetic complex [Ag(NPTTz)(NO3)]. n This is designated as ECP-2.
[0031] Example 3 A method for preparing anionic energetic complexes based on NPTTz, specifically: 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 NPTTz (466 mg, 2.0 mmol) and allow it to evaporate naturally at room temperature to obtain purple needle-like crystals, which are the NPTTz-based anionic energetic complex [Co(NPTTz)2(ClO4)2(H2O)2]. n This is designated as ECP-3.
[0032] Example 4 A method for preparing anionic energetic complexes based on NPTTz, specifically: 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 NPTTz (699 mg, 3.0 mmol) and allow it to evaporate naturally at room temperature to obtain purple needle-like crystals, which are the NPTTz-based anionic energetic complex [Co(NPTTz)3(NO3)3]. n H2O, denoted as ECP-4.
[0033] Example 5 A method for preparing anionic energetic complexes based on NPTTz, specifically: Cu(NO3)2 (187 mg, 1.0 mmol) was weighed and dissolved in 5 mL of a mixed solution of H2O and HClO4 (volume ratio 4:1). Then, NPTTz (466 mg, 2.0 mmol) was added, and the solution was allowed to evaporate naturally at room temperature to obtain purple needle-like crystals, which are the NPTTz-based anionic energetic complex [Cu(NPTTz)2(ClO4)2(H2O)2]. n This is designated as ECP-5.
[0034] Example 6 A method for preparing anionic energetic complexes based on NPTTz, specifically: Cu(NO3)2 (187 mg, 1.0 mmol) was dissolved in 5 mL of a mixed solution of H2O and HNO3 (volume ratio 4:1), followed by the addition of NPTTz (466 mg, 2.0 mmol). The solution was allowed to evaporate naturally at room temperature, yielding purple needle-like crystals, which are the NPTTz-based anionic energetic complex [Cu(NPTTz)2(NO3)2(H2O)2]. n This is designated as ECP-6.
[0035] Example 7 A method for preparing anionic energetic complexes based on NPTTz, specifically: 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, NPTTz (699 mg, 3.0 mmol) was added, and the solution was allowed to evaporate naturally at room temperature to obtain purple needle-like crystals, which are the NPTTz-based anionic energetic complex [Ni(NPTTz)3(ClO4)2]. n H2O, denoted as ECP-7.
[0036] Example 8 A method for preparing anionic energetic complexes based on NPTTz, specifically: Ni(NO3)2·6H2O (290 mg, 1.0 mmol) was weighed and dissolved in 5 mL of a mixed solution of H2O and HNO3 (volume ratio 4:1). Then, NPTTz (699 mg, 3.0 mmol) was added, and the solution was allowed to evaporate naturally at room temperature to obtain purple needle-like crystals, which are the NPTTz-based anionic energetic complex [Ni(NPTTz)3(NO3)2]. n H2O, denoted as ECP-8.
[0037] Comparative Example 1 AgNO3 (169 mg, 1.0 mmol) was weighed and dissolved in 5 mL of H2O, followed by the addition of NPTTz (233 mg, 1.0 mmol). The mixture was allowed to evaporate naturally at room temperature, but no complex was obtained. In this comparative example, HClO4 was not added, and the remaining steps were the same as in Example 1.
[0038] Comparative Example 2 AgNO3 (169 mg, 1.0 mmol) was weighed and dissolved in 5 mL of H2O, followed by the addition of NPTTz (233 mg, 1.0 mmol). The mixture was then hydrothermally volatilized at 60 °C, but no complex was obtained.
[0039] This invention uses NPTTz 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 neutral, thereby achieving oxygen-rich anions (ClO4). - NO3 - By directionally introducing NPTTz 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 NPTTz cannot yield a crystalline product of the complex, regardless of whether room temperature or hydrothermal evaporation methods are used. The selected NPTTz 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.
[0040] 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 NPTTz, characterized in that, The general chemical formula of the NPTTz-based anionic energetic complex is [M x (NPTTz) y A z (H2O) p ] n ·qH2O; where M is a metal ion, A is an acid radical anion; NPTTz is 6-(4-nitro-1H-pyrazole-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine; x ranges from 1 to 5, y ranges from 1 to 5, z ranges from 1 to 5, p ranges from 0 to 5, q ranges from 0 to 5, and n ranges from greater than or equal to 1.
2. The NPTTz-based anionic energetic complex as described in claim 1, characterized in that, M is a metal ion Ag. + Co 2+ Cu 2+ Ni 2+ One of them; wherein A is an acid radical anion NO3. - ClO4 - One of them.
3. The NPTTz-based anionic energetic complex as described in claim 1, characterized in that, The NPTTz-based anionic energetic complex specifically includes: [Ag3(NPTTz)3(ClO4)3] n [Ag(NPTTz)(NO3)] n [Co(NPTTz)2(ClO4)2(H2O)2] n [Co(NPTTz)3(NO3)3] n ·H2O, [Cu(NPTTz)2(ClO4)2(H2O)2] n [Cu(NPTTz)2(NO3)2(H2O)2] n [Ni(NPTTz)3(ClO4)2] n H2O, [Ni(NPTTz)3(NO3)2] n One of the components of H2O.
4. A method for preparing anionic energetic complexes based on NPTTz as described in any one of claims 1-3, characterized in that, include: It was prepared by volatilization using 6-(4-nitro-1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine and the corresponding metal nitrate as raw materials.
5. The method for preparing anionic energetic complexes based on NPTTz as described in claim 4, characterized in that, Specifically, it includes: Metal nitrates were dissolved in an acid solution, and then NPTTz was added. The mixture was allowed to evaporate naturally at room temperature to obtain an anionic energetic complex based on NPTTz.
6. The method for preparing anionic energetic complexes based on NPTTz 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 NPTTz to the metal nitrate is 0.01~3.0:0.01~1.0; The acid solution is an HClO4 solution or an HNO3 solution; in the HClO4 solution, the volume ratio of H2O to HClO4 is 1~10:1; in the HNO3 solution, the volume ratio of H2O to HNO3 is 1~10:
1.
7. The method for preparing anionic energetic complexes based on NPTTz as described in claim 5, characterized in that, The mass-to-volume ratio of the metal nitrate to the acid solution is 1~300mg:1~20mL.
8. The application of an NPTTz-based anionic energetic complex as described in any one of claims 1-3, or an NPTTz-based anionic energetic complex prepared by the preparation method as described in any one of claims 4-7, in laser-initiated explosives.
9. The use of an NPTTz-based anionic energetic complex as described in any one of claims 1-3, or an NPTTz-based anionic energetic complex prepared by the preparation method as described in any one of claims 4-7, in propellants.
10. The application of an NPTTz-based anionic energetic complex as described in any one of claims 1-3, or an NPTTz-based anionic energetic complex prepared by the preparation method as described in any one of claims 4-7, in the catalysis of ammonium perchlorate.