Anion-containing energetic complex based on pttz and its preparation method and application
By preparing PTTz-based anionic energetic complexes, the energy density and stability issues caused by solvent molecule coordination were resolved, resulting in high-energy-density and stable laser-initiated explosives suitable for use in explosives, propellants, and the catalytic decomposition of ammonium perchlorate.
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 energetic complexes are prone to solvent molecules coordinating with metal ions during preparation, resulting in reduced energy density and unstable crystal structure. Furthermore, traditional detonators are easily sensitive to external stimuli and are difficult to integrate with laser detonation technology.
An anionic energetic complex based on PTTz was prepared by a solvothermal method. The complex was formed by 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine with metal ions. A stable crystal structure was obtained by combining acid solution and a specific molar ratio.
The prepared complex exhibits good detonation response under laser irradiation, high energy density, and stability, making it suitable for laser-initiated explosives. It can also catalyze the decomposition of ammonium perchlorate, reducing its high-temperature decomposition peak temperature.
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Figure CN122127339A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of energetic material preparation technology in organic synthesis. More specifically, this invention relates to an anionic energetic complex based on PTTz, its preparation method and application. Background Technology
[0002] Energetic complexes are a novel branch of energetic materials, formed by the coordination bonds between energetic ligands and metal ions. They possess advantages such as tunable structure and high energy density, showing great promise in defense, aerospace, and other fields. They can be used as initiators in various weapons and ammunition, or as energetic catalysts in propellants. However, during the preparation of energetic complexes, solvent molecules readily coordinate with metal ions. When these coordinated solvent molecules desorb, they not only reduce the energy density of the complex but also cause pressure changes in the low-temperature region, damaging the crystal structure and leading to a decline in its stability and key properties such as thermal detonation, thus limiting its large-scale application.
[0003] Laser-initiated detonation technology, as a novel and safe detonation method, avoids risks such as electromagnetic interference and electrostatic discharge, and is suitable for complex environments. Energetic complexes possess excellent optical absorption properties, and the combination of the two can construct an efficient and safe detonation system. Currently, my country's detonating explosives are still mainly traditional products such as lead azide, picric acid, and DDNP. These detonators are sensitive to external stimuli, easily causing explosions, and some are toxic, highly hygroscopic, or lack sufficient power. Furthermore, they have poor compatibility with laser-initiated detonation technology, requiring the addition of sensitizers, increasing costs and affecting reliability.
[0004] In summary, energetic complexes hold promise as a replacement for traditional initiators, but existing initiation systems still suffer from numerous drawbacks due to defects in the coordination solvent molecules. Therefore, developing energetic complexes that can overcome solvent molecule defects, possess high energy and stability, and are compatible with laser-initiated detonation technology, and constructing novel initiation systems, has become a pressing problem in the field of energetic materials and has significant practical implications. 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, a PTTz-based anionic energetic complex is provided, the general structural formula of which is [X m (PTTz) p Y t (H2O) k ] n·zH2O; where X is a metal ion, Y is an acid radical anion; PTTz is 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetrazine; m ranges from 1 to 5, p ranges from 1 to 5, t ranges from 1 to 5, k ranges from 0 to 2, z ranges from 0 to 2, and n ranges from ≥1.
[0007] Preferably, X is specifically Ag. + Cu 2+ Co 2+ Ni 2+ One of them, Y specifically is NO3. - ClO4 - One of them.
[0008] Preferably, the PTTz-based anionic energetic complex specifically includes [Ag2(PTTz)2(NO3)2]. n ·2H2O, [Ag2(PTTz)2(ClO4)2(H2O)] n ·H2O, [Cu(PTTz)2(NO3)2(H2O)2] n ·H2O, [Cu(PTTz)2(ClO4)2(H2O)2] n , [Co(PTTz)2(NO3)2(H2O)2] n ·2H2O, [Co(PTTz)2(ClO4)2(H2O)2] n ·H2O, [Ni(PTTz)2(NO3)2(H2O)2] n ·H2O, [Ni(PTTz)2(ClO4)2(H2O)2] n One of the components of ·2H2O.
[0009] A method for preparing anionic energetic complexes based on PTTz as described above includes: preparing the complexes by a solvothermal method using 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine and metal nitrate as raw materials.
[0010] Preferably, the method for preparing the PTTz-based anionic energetic complex specifically includes: dissolving a metal nitrate in an acid solution, then adding PTTz, and allowing it to evaporate naturally at room temperature to obtain the PTTz-based anionic energetic complex.
[0011] Preferably, the metal nitrate is one of silver nitrate and copper nitrate; the molar volume ratio of the metal nitrate to PTTz is 0.01~1.0 : 0.01~1.0.
[0012] Preferably, the acid solution is one of nitric acid solution and perchloric acid solution; the volume ratio of water to nitric acid in the nitric acid solution is 2~6:1, and the volume ratio of water to perchloric acid in the perchloric acid solution is 2~6:1; the molar volume ratio of the metal nitrate to the acid solution is 0.01~1.0 mol:5~20 mL.
[0013] Application of a PTTz-based anionic energetic complex as described above, or a PTTz-based anionic energetic complex prepared by the preparation method described above, in laser-initiated explosives.
[0014] Application of a PTTz-based anionic energetic complex as described above, or a PTTz-based anionic energetic complex prepared by the preparation method described above, in explosives.
[0015] Application of a PTTz-based anionic energetic complex as described above, or a PTTz-based anionic energetic complex prepared by the preparation method described above, in propellants.
[0016] Application of a PTTz-based anionic energetic complex as described above, or a PTTz-based anionic energetic complex prepared by the method described above, in the catalysis of ammonium perchlorate.
[0017] The present invention provides at least the following beneficial effects: The PTTz-based anionic energetic complex prepared by the present invention 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. Simultaneously, the PTTz-based anionic energetic complex of the present invention exhibits excellent catalytic activity, capable of catalyzing the decomposition of ammonium perchlorate and reducing the peak temperature of ammonium perchlorate decomposition at high temperatures.
[0018] 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
[0019] Figure 1 This is a diagram of the minimum asymmetric unit structure of ECP-1, the product of Embodiment 1 of the present invention; Figure 2 This is a diagram of the minimum asymmetric unit structure of ECP-2, the product of Embodiment 2 of the present invention; Figure 3 This is a diagram of the laser-initiated detonation process of the ECP-2 prepared in Example 2 of the present invention. Detailed Implementation
[0020] 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.
[0021] 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.
[0022] In this invention, PTTz refers to 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine, with the structural formula: .
[0023] The preparation method of PTTz is as follows: 3-hydrazino-6-(1H-pyrazol-1-yl)-1,2,4-tetraazine (1.50 g, 10.0 mmol), hydrochloric acid (0.6 ml), and triethyl orthoformate (5 ml) are dispersed in 50 ml of 1,4-dioxane and stirred at 100 °C for 24 h. After the reaction is complete, the mixture is filtered and washed with ice water to obtain a yellow powder, yielding 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine (1.63 g, 87%), i.e., the yellow powder PTTz.
[0024] The structural analysis results of PTTz are as follows: 1 H NMR (400 MHz, d6-DMSO) δ / ppm: 6.84 (s, 1H), 8.13 (s, 1H), 9.03 (s, 1H), 10.06 (s, 1H) δ; 13 C NMR (400 MHz, d6-DMSO) δ / ppm: 110.57, 131.81, 137.84, 145.76), 149.22, 150.81.
[0025] Example 1 A method for preparing anionic energetic complexes based on PTTz, specifically: 1.69 mg of AgNO3 was dissolved in 5 mL of nitric acid solution (H2O to HNO3 volume ratio 4:1), followed by the addition of 1.88 mg of PTTz. The solution was allowed to evaporate naturally at room temperature, yielding red needle-like crystals, which are the PTTz-based anionic energetic complex [Ag2(PTTz)2(NO3)2]. n ·2H2O, denoted as ECP-1.
[0026] Example 2 A method for preparing anionic energetic complexes based on PTTz, specifically: 1.87 mg of Cu(NO3)2 was dissolved in 5 mL of perchloric acid solution (H2O to HClO4 volume ratio 4:1), followed by the addition of 1.88 mg of PTTz. The solution was allowed to evaporate naturally at room temperature, yielding purple needle-like crystals, which are the PTTz-based anionic energetic complex [Cu(PTTz)2(ClO4)2(H2O)2]. n This is designated as ECP-2.
[0027] Example 3 A method for preparing anionic energetic complexes based on PTTz, specifically: 1.69 mg of AgNO3 was dissolved in 5 mL of perchloric acid solution (H2O to HClO4 volume ratio 4:1), followed by the addition of 1.88 mg of PTTz. The solution was allowed to evaporate naturally at room temperature, yielding red needle-like crystals, which are the PTTz-based anionic energetic complex [Ag2(PTTz)2(ClO4)2(H2O)]. n H2O, denoted as ECP-3.
[0028] Example 4 A method for preparing anionic energetic complexes based on PTTz, specifically: 1.87 mg of Cu(NO3)2 was dissolved in 5 mL of nitric acid solution (H2O to HNO3 volume ratio 4:1), followed by the addition of 1.88 mg of PTTz. The solution was allowed to evaporate naturally at room temperature, yielding purple needle-like crystals, which are the PTTz-based anionic energetic complex [Cu(PTTz)2(NO3)2(H2O)2]. n H2O, denoted as ECP-4.
[0029] Example 5 A method for preparing anionic energetic complexes based on PTTz, specifically: 291 mg of Co(NO3)2·6H2O was dissolved in 5 mL of nitric acid solution (H2O to HNO3 volume ratio 4:1), followed by the addition of 1.88 mg of PTTz. The solution was allowed to evaporate naturally at room temperature, yielding purple needle-like crystals, which are the PTTz-based anionic energetic complex [Co(PTTz)2(NO3)2(H2O)2]. n H2O, denoted as ECP-5.
[0030] Example 6 A method for preparing anionic energetic complexes based on PTTz, specifically: 291 mg of Co(NO3)2·6H2O was dissolved in 5 mL of perchloric acid solution (H2O to HClO4 volume ratio 4:1), followed by the addition of 1.88 mg of PTTz. The solution was allowed to evaporate naturally at room temperature, yielding purple needle-like crystals, which are the PTTz-based anionic energetic complex [Co(PTTz)2(ClO4)2(H2O)2]. n H2O, denoted as ECP-6.
[0031] Example 7 A method for preparing anionic energetic complexes based on PTTz, specifically: 291 mg of Ni(NO3)2·6H2O was dissolved in 5 mL of nitric acid solution (H2O to HNO3 volume ratio 4:1), followed by the addition of 1.88 mg of PTTz. The solution was allowed to evaporate naturally at room temperature, yielding purple needle-like crystals, which are the PTTz-based anionic energetic complex [Ni(PTTz)2(NO3)2(H2O)2]. n H2O, denoted as ECP-7.
[0032] Example 8 A method for preparing anionic energetic complexes based on PTTz, specifically: 291 mg of Ni(NO3)2·6H2O was dissolved in 5 mL of perchloric acid solution (H2O to HClO4 volume ratio 4:1), followed by the addition of 1.88 mg of PTTz. The solution was allowed to evaporate naturally at room temperature, yielding purple needle-like crystals, which are the PTTz-based anionic energetic complex [Ni(PTTz)2(ClO4)2(H2O)2]. n ·2H2O, denoted as ECP-8.
[0033] Comparative Example 1 The copper complex Cu(HPDCA)₂(NO₃)₂(ClO₄)₂, which also contains anion, is used. The ligand [HPDCA] in the copper complex... + The preparation method is based on protonated pyridine-4-carbonylhydrazine, and is described in the references of Chao Zhang; Shaoqun Li; Anion-Engineered Energetic Cu(II)-Based Complexes to Balance High Energy and LowSensitivity[J]. Inorganic Chemistry, 2025, 64: 21694-21703.
[0034] Comparative Example 2 1.87 mg of Cu(NO3)2 was dissolved in 5 mL of H2O, followed by the addition of 1.88 mg of PTTz. The mixture was allowed to evaporate naturally at room temperature, but no complex was obtained.
[0035] Comparative Example 3 Dissolving 1.87 mg of Cu(NO3)2 in 5 mL of H2O water, followed by adding 1.88 mg of PTTz, and then hydrothermally volatilizing at 60 °C, resulted in no complex being obtained.
[0036] Figures 1-2 This is a diagram of the minimum asymmetric unit structure of ECP-1, the product of Example 1, and ECP-2, the product of Example 2, of the present invention.
[0037] To determine the structure of the complexes, the crystal structures of ECP-1 and ECP-2 prepared in Examples 1 and 2 were tested, and the test results are shown in Table 1.
[0038] Table 1 Figure 3 This diagram illustrates the laser-initiated detonation process of ECP-2 prepared in Example 2 of the present invention. Laser-initiated detonation test: The complexes [Cu(PTTz)2(ClO4)2(H2O)2] prepared in Example 2 and Comparative Example 1 were tested. n Laser-initiated detonation experiments were conducted on Cu(HPDCA)₂(NO₃)₂(ClO₄)₂. 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 laser optical path system primarily provides the laser beam and measures the energy of a single laser beam (6 mJ). The initiation system is the main site where the sample responds to the laser. The data acquisition system, consisting of a high-speed camera and a computer, records the combustion or detonation process of the sample. The illumination optical path prevents the high-speed camera from being overexposed during recording. The experimental results are as follows: Figure 3 As shown, [Cu(PTTz)2(ClO4)2(H2O)2] prepared in Example 2 n Detonation occurred after 6.05 ms, capturing the instant of deflagration-to-detonation (DDT), with an initiation threshold of 36.3 mJ. In contrast, the copper complex Cu(HPDCA)2(NO3)2(ClO4)2 of Comparative Example 1, which also contains anions, detonated after 8.3 ms, capturing the instant of deflagration-to-detonation (DDT), with an initiation threshold of 78 mJ. [Cu(PTTz)2(ClO4)2(H2O)2] prepared in Example 2... n The detonation performance of the compound is superior to that of the copper complex Cu(HPDCA)2(NO3)2(ClO4)2, which also contains anions in Comparative Example 1, demonstrating the unique advantages of the fused ring ligand prepared in this invention in the field of laser detonation.
[0039] [Cu(PTTz)2(ClO4)2(H2O)2] prepared in Example 2 n An experiment was conducted to catalyze the decomposition of ammonium perchlorate (AP). When 5% of [Cu(PTTz)2(ClO4)2(H2O)2] was added... n When tested at a heating rate of 10℃ / min, the peak temperature of AP high-temperature decomposition decreased by 81℃, demonstrating a good catalytic effect.
[0040] Comparative Examples 2 and 3 show that without external acid adjustment, simply mixing metal nitrates with PTTz fails to yield crystalline products of the corresponding complexes, regardless of whether room-temperature or hydrothermal volatilization is used. The selected PTTz ligand possesses abundant coordination sites, and its typical chelation coordination mode significantly enhances its coordination ability with the metal center. By controlling pH to suppress ligand ionization and maintain its electroneutrality, the system must introduce oxygen-rich anions to achieve charge balance after the ligand coordinates with the metal center. This is crucial for the stable formation and crystallization of such complexes.
[0041] 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. A PTTz-based anionic energetic complex, characterized in that, The general structural formula of the PTTz-based anionic energetic complex is [X m (PTTz) p Y t (H2O) k ] n ·zH2O; where X is a metal ion, Y is an acid radical anion; PTTz is 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetrazine; m ranges from 1 to 5, p ranges from 1 to 5, t ranges from 1 to 5, k ranges from 0 to 2, z ranges from 0 to 2, and n ranges from ≥1.
2. The PTTz-based anionic energetic complex as described in claim 1, characterized in that, The X specifically refers to Ag. + Cu 2+ Co 2+ Ni 2+ One of them, Y specifically is NO3. - ClO4 - One of them.
3. The PTTz-based anionic energetic complex as described in claim 1, characterized in that, The PTTz-based anionic energetic complexes specifically include [Ag2(PTTz)2(NO3)2]. n ·2H2O, [Ag2(PTTz)2(ClO4)2(H2O)] n ·H2O, [Cu(PTTz)2(NO3)2(H2O)2] n ·H2O, [Cu(PTTz)2(ClO4)2(H2O)2] n , [Co(PTTz)2(NO3)2(H2O)2] n ·2H2O, [Co(PTTz)2(ClO4)2(H2O)2] n ·H2O, [Ni(PTTz)2(NO3)2(H2O)2] n ·H2O, [Ni(PTTz)2(ClO4)2(H2O)2] n One of the components of ·2H2O.
4. A method for preparing anionic energetic complexes based on PTTz as described in any one of claims 1-3, characterized in that, include: It was prepared by a solvothermal method using 6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine and metal nitrate as raw materials.
5. A method for preparing anionic energetic complexes based on PTTz as described in claim 4, characterized in that, Specifically, it includes: Metal nitrates were dissolved in an acid solution, and then PTTz was added. The mixture was allowed to evaporate naturally at room temperature to obtain an anionic energetic complex based on PTTz.
6. The method for preparing anionic energetic complexes based on PTTz as described in claim 5, characterized in that, The metal nitrate is one of silver nitrate and copper nitrate; the molar volume ratio of the metal nitrate to PTTz is 0.01~1.0 : 0.01~1.
0.
7. The method for preparing anionic energetic complexes based on PTTz as described in claim 5, characterized in that, The acid solution is either a nitric acid solution or a perchloric acid solution; the volume ratio of water to nitric acid in the nitric acid solution is 2~6:1, and the volume ratio of water to perchloric acid in the perchloric acid solution is 2~6:1; the molar volume ratio of the metal nitrate to the acid solution is 0.01~1.0 mol: 5~20 mL.
8. The application of a PTTz-based anionic energetic complex as described in any one of claims 1-3, or a PTTz-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 a PTTz-based anionic energetic complex as described in any one of claims 1-3, or a PTTz-based anionic energetic complex prepared by the preparation method as described in any one of claims 4-7, in a propellant.
10. The application of a PTTz-based anionic energetic complex as described in any one of claims 1-3, or a PTTz-based anionic energetic complex prepared by the preparation method as described in any one of claims 4-7, in the catalysis of ammonium perchlorate.