3-amino-5-hydrazino-1, 2, 4-triazole energetic complex and preparation method thereof

Abstract

The invention discloses a 3-amino-5-hydrazino-1, 2, 4-triazole energetic complex and a preparation method thereof, belongs to the technical field of energetic materials, and particularly relates to the 3-amino-5-hydrazino-1, 2, 4-triazole energetic complex and the preparation method thereof.The preparation method includes the steps that 3-amino-5-hydrazino-1, 2, 4-triazole hydrochloride and metal salt are stirred to react in a solvent, and after the reaction is completed, the metal salt is added into the solvent to react, so that the 3-amino-5-hydrazino-1, 2, 4-triazole is obtained; and cooling, carrying out suction filtration, washing and drying to obtain the 3-amino-5-hydrazino-1, 2, 4-triazole energetic complex. The 3-amino-5-hydrazino-1, 2, 4-triazole energetic complex prepared by the preparation method disclosed by the invention has excellent thermal stability, relatively high mechanical sensitivity and good detonation performance, and has the potential of being applied to propellants as a novel energetic material. The preparation method is simple in process, environment-friendly and pollution-free.

Description

Technical Field

[0001] The invention belongs to the technical field of energetic materials, and in particular relates to a 3-amino-5-hydrazino-1,2,4-triazole energetic complex and a preparation method thereof. Background Art

[0002] Energetic materials are compounds or mixtures that contain explosive groups or oxidants and combustibles. Under certain external energy stimulation, they can undergo redox reactions on their own and release a large amount of energy (usually accompanied by a large amount of gas and heat). Traditional energetic materials include compounds composed of carbon, hydrogen, oxygen, and nitrogen, such as TNT, RDX, HMX, and CL-20. There is an inevitable inherent contradiction between its energy characteristics and safety performance, that is, the higher the energy, the worse the safety. Energetic complexes are a branch of energetic materials. Compared with traditional CHON-based energetic materials, due to the presence of metal elements, they have the advantages of stable structure, good stability, and high energy insensitivity. They have become a new type of energetic material with good application prospects developed in recent years.

[0003] Triazole compounds have a high nitrogen content and are typical representatives of nitrogen-rich compounds. They can be widely used in military and civilian applications such as high-energy insensitive explosives and environmentally friendly fireworks, and are one of the hot topics in the field of energetic materials research at home and abroad. Among them, 3-amino-5-hydrazine-1,2,4-triazole is a typical high-energy insensitive triazole energetic ligand, which is the energy source for constructing high-energy density materials containing energetic complexes, giving them good safety performance and detonation performance. Summary of the invention

[0004] In view of the above research status, the purpose of the present invention is to propose a 3-amino-5-hydrazino-1,2,4-triazole energetic complex and a preparation method thereof.

[0005] The technical scheme of the present invention is: 3-amino-5-hydrazine-1,2,4-triazole energetic complex, which includes the chemical represented by the following chemical structural formula: {[M(AHTr)2](Cl2)·2H2O} n . Where M is the metal ion Mn 2+ 、Ni 2+ 、Zn 2+ 、Cd 2+ and Cu 2+ AHTr is a 3-amino-5-hydrazino-1,2,4-triazole ligand.

[0006] The energetic complex of the present invention is divided into cations, anions and ligands according to the composition. The cation is Mn 2 + 、Ni 2+ 、Zn 2+ 、Cd2+ and Cu 2+ etc.; anion is Cl - ; The ligand is 3-amino-5-hydrazino-1,2,4-triazole, and different energetic complexes can be obtained by adjusting the cation.

[0007] The preparation method of 3-amino-5-hydrazino-1,2,4-triazole energetic complex comprises the following steps:

[0008] Step 1: Weigh 3-amino-5-hydrazino-1,2,4-triazole hydrochloride, dissolve it in water, add LiOH·H2O to adjust the pH of the solution, and heat the solution.

[0009] Step 2: Weigh a metal salt and dissolve it in methanol. Add it dropwise into an aqueous solution of 3-amino-5-hydrazino-1,2,4-triazole under vigorous stirring. Continue stirring the reaction for 2 hours. When a precipitate is precipitated, cool, filter, wash and dry to obtain the corresponding energetic complex.

[0010] Furthermore, the pH of the solution in the above step 1 is 4 to 9, and the solution temperature is -20 to 100°C.

[0011] Furthermore, the molar ratio of 3-amino-5-hydrazino-1,2,4-triazole to the metal salt in the above step 2 is 1:0.5-2.0.

[0012] Furthermore, the solvent in the above step 2 is one or a mixture of water, methanol, ethanol, methyl acetate, ethyl acetate, ethyl ether, propyl ether, benzene and toluene.

[0013] In the present invention, the 3-amino-5-hydrazino-1,2,4-triazole hydrochloride is homemade in the laboratory. The specific preparation method can be found in Yang Zhenli, Liu Feng, He Zhiwei, etc. A 3-hydrazino-5-amino-1H-1,2,4-triazole energetic ion salt and its preparation method: CN114105878A[P].2023-05-26.

[0014] The structure of 3-amino-5-hydrazine-1,2,4-triazole energetic complex was characterized by EA, FT-IR and X-ray single crystal diffraction analysis. The thermal decomposition characteristics of the new complex were analyzed by DSC, and its friction sensitivity and impact sensitivity were tested, and its detonation parameters were calculated to study its potential application as a new energetic material.

[0015] Beneficial results of the present invention:

[0016] (1) The preparation process of the 3-amino-5-hydrazino-1,2,4-triazole energetic complex of the present invention is simple, requires few instruments and equipment, has low production cost, and is environmentally friendly and pollution-free during the production process.

[0017] (2) Compared with traditional energetic materials, the 3-amino-5-hydrazino-1,2,4-triazole energetic complex of the present invention has good safety performance and detonation performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The present invention will be further described below in conjunction with the accompanying drawings.

[0019] Figure 1 It is a schematic diagram of the synthesis method of the present invention;

[0020] Figure 2 {[Mn(AHTr)2](Cl2)·2H2O} prepared in Example 1 of the present invention n DSC curve of

[0021] Figure 3 {[Mn(AHTr)2](Cl2)·2H2O} prepared in Example 1 of the present invention n Infrared spectrum of

[0022] Figure 4 {[Ni(AHTr)2](Cl2)·2H2O} prepared in Example 2 of the present invention n DSC curve of

[0023] Figure 5 {[Ni(AHTr)2](Cl2)·2H2O} prepared in Example 2 of the present invention n Infrared spectrum of

[0024] Figure 6 {[Zn(AHTr)2](Cl2)·2H2O} prepared in Example 3 of the present invention n DSC curve of

[0025] Figure 7 {[Zn(AHTr)2](Cl2)·2H2O} prepared in Example 3 of the present invention n Infrared spectrum of

[0026] Figure 8 {[Cd(AHTr)2](Cl2)·2H2O} prepared in Example 4 of the present invention n Molecular structure diagram and unit cell stacking diagram;

[0027] Fig. 9 {[Cd(AHTr)2](Cl2)·2H2O} prepared in Example 4 of the present invention n Coordination environment diagram and 1D chain structure diagram;

[0028] Fig.10{[Cd(AHTr)2](Cl2)·2H2O} prepared in Example 4 of the present invention n DSC curve of

[0029] Fig.11 {[Cd(AHTr)2](Cl2)·2H2O} prepared in Example 4 of the present invention n Infrared spectrum of

[0030] Fig.12 {[Cd(AHTr)2](Cl2)·2H2O} prepared in Example 4 of the present invention n The unit cell packing diagram of

[0031] Fig.13 {[Cd(AHTr)2](Cl2)·2H2O} prepared in Example 4 of the present invention n 1D chain structure diagram;

[0032] Fig.14 {[Cu(AHTr)2](Cl2)·2H2O} prepared in Example 5 of the present invention n DSC curve of

[0033] Fig.15 {[Cu(AHTr)2](Cl2)·2H2O} prepared in Example 5 of the present invention n Infrared spectrum of . DETAILED DESCRIPTION

[0034] The present invention is further described below in conjunction with specific embodiments to make the purpose, technical methods and advantages of the present invention clearer. It should be noted that the present invention is not limited to the following specific embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0035] Example 1

[0036] {[Mn(AHTr)2](Cl2)·2H2O} n The synthetic method comprises the following specific steps:

[0037] Step 1: Weigh 3-amino-5-hydrazino-1,2,4-triazole hydrochloride (1.87 g, 10 mmol), dissolve it in 20 mL of water, then add LiOH·H2O to adjust the pH value of the solution to 6-7, and heat the solution to 80°C.

[0038] Step 2: Weigh MnCl2 (0.63 g, 5 mmol), dissolve it in 5 mL of methanol, and add it dropwise to the aqueous solution of 3-amino-5-hydrazino-1,2,4-triazole under vigorous stirring. Continue to stir the reaction at 80°C for 2 h. A white precipitate is precipitated. Cool it to room temperature, then filter it with suction, wash it with water, and dry the filter cake to obtain a white powder solid with a yield of 25%.

[0039] The {[Mn(AHTr)2](Cl2)·2H2O} prepared by the above method n Elemental analysis was performed, and the results were: theoretical values: C 12.32%, H 4.13%, N 43.09%; experimental values: C 12.21%, H 4.06%, N 43.15%.

[0040] The sample was taken in an airtight aluminum crucible with a volume of about 0.3 mg and then stirred under nitrogen atmosphere (nitrogen flow rate was 80 ml min -1 ), with a heating rate of 10℃·min -1 The DSC curve is as follows: Figure 2 As shown in Figure 1, the first exothermic decomposition peak temperature is 202.8°C, and the second exothermic decomposition peak temperature is 286.4°C. Its infrared spectrum is as follows Figure 3 As shown, the main peaks are: v = 3324, 3240, 3152, 1790, 1680, 1658, 1576, 1386, 1313, 1249, 1218, 1175, 1072, 849 cm -1 After further testing, the theoretical detonation velocity is 6682.3 m·s -1 The measured impact sensitivity is greater than 40J and the friction sensitivity is greater than 360N.

[0041] Example 2

[0042] {[Ni(AHTr)2](Cl2)·2H2O} n The synthetic method comprises the following specific steps:

[0043] Step 1: Same as Example 1;

[0044] Step 2: Weigh NiCl2 (0.65 g, 5 mmol), dissolve it in 5 mL of methanol, add it dropwise to the aqueous solution of 3-amino-5-hydrazino-1,2,4-triazole under vigorous stirring, continue to stir the reaction at 80 ° C for 2 h, a light purple precipitate is precipitated, cool to room temperature, then filter, wash with water, dry the filter cake to obtain a light purple powder solid, the yield is 21%.

[0045] {[Ni(AHTr)2](Cl2)·2H2O} prepared by the above method nElemental analysis was performed, and the results were: theoretical values: C 12.20%, H 4.09%, N 42.68%; experimental values: C 12.27%, H 4.01%, N 42.72%.

[0046] The sample was taken in an airtight aluminum crucible with a volume of about 0.3 mg and then stirred under nitrogen atmosphere (nitrogen flow rate was 80 ml min -1 ), with a heating rate of 10℃·min -1 The DSC curve is as follows: Figure 4 As shown in Figure 1, the first exothermic decomposition peak temperature is 295.3°C, and the second exothermic decomposition peak temperature is 455.7°C. Its infrared spectrum is as follows Figure 5 As shown, the main peaks are: υ = 3310, 3242, 1659, 1588, 1355, 1242, 1213, 1088, 1046, 826 cm -1 After further testing, the theoretical detonation velocity is 6824.4 m·s -1 The measured impact sensitivity is greater than 40J and the friction sensitivity is greater than 360N.

[0047] Example 3

[0048] {[Zn(AHTr)2](Cl2)·2H2O} n The synthetic method comprises the following specific steps:

[0049] Step 1: Same as Example 1;

[0050] Step 2: Weigh ZnCl2 (0.68 g, 5 mmol), dissolve it in 5 mL of methanol, and add it dropwise to the aqueous solution of 3-amino-5-hydrazino-1,2,4-triazole under vigorous stirring. Continue to stir the reaction at 80°C for 2 h. A white precipitate will precipitate. Cool it to room temperature, then filter it, wash it with water, and dry the filter cake to obtain a white powder solid with a yield of 32%.

[0051] {[Zn(AHTr)2](Cl2)·2H2O} prepared by the above method n Elemental analysis was performed, and the results were: theoretical value C 13.18%, H 3.32%, N 46.11%; experimental value C 13.11%, H 3.38%, N 46.17%.

[0052] The sample was taken in an airtight aluminum crucible with a volume of about 0.3 mg and then stirred under nitrogen atmosphere (nitrogen flow rate was 80 ml min -1 ), with a heating rate of 10℃·min -1 The DSC curve is as follows: Figure 6 As shown in Figure 1, the first exothermic decomposition peak temperature is 319.5°C, and the second exothermic decomposition peak temperature is 354.3°C. Its infrared spectrum is shown in Figure 1. Figure 7 As shown, the main peaks are: υ = 3357, 3292, 1663, 1588, 1576, 1318, 1311, 1249, 1218, 1172, 1080, 1040, 825 cm -1 After further testing, the theoretical detonation velocity is 720.4 m·s -1 The measured impact sensitivity is greater than 40J and the friction sensitivity is greater than 360N.

[0053] Example 4

[0054] {[Cd(AHTr)2](Cl2)·2H2O} n The synthetic method comprises the following specific steps:

[0055] Step 1: Same as Example 1;

[0056] Step 2: Weigh CdCl2 (0.92 g, 5 mmol), dissolve it in 5 mL of methanol, add it dropwise to the aqueous solution of 3-amino-5-hydrazino-1,2,4-triazole under vigorous stirring, continue to stir the reaction at 80°C for 2 h, a white precipitate is precipitated, cool to room temperature, then filter, wash with water, and dry the filter cake to obtain a white powder solid with a yield of 37%.

[0057] {[Cd(AHTr)2](Cl2)·2H2O} prepared by the above method n Elemental analysis was performed, and the results were: theoretical value C 10.73%, H 3.60%, N 37.55%; experimental value C 10.67%, H 3.66%, N 37.63%.

[0058] The sample was taken in an airtight aluminum crucible with a volume of about 0.3 mg and then stirred under nitrogen atmosphere (nitrogen flow rate was 80 ml min -1 ), with a heating rate of 10℃·min -1 The DSC curve is as follows: Fig.10 As shown in Figure 1, the first exothermic decomposition peak temperature is 298.4°C, and the second exothermic decomposition peak temperature is 363.7°C. Its infrared spectrum is as follows Fig.11 As shown, the main peaks are: υ = 3359, 3279, 3154, 1674, 1586, 1385, 1310, 1249, 1214, 1165, 1073, 1036, 848 cm -1 After further testing, the theoretical detonation velocity is 7525.3 m·s -1 The measured impact sensitivity is greater than 40J and the friction sensitivity is greater than 360N.

[0059] Crystals of suitable size were selected and scanned in an ω-θ mode on an X-ray single crystal diffractometer at 298(2)K using MoK monochromatized by a graphite monochromator. α ray Diffraction data were collected, and all the collected diffraction points were corrected using Lp (polarization factor and Lorentz factor correction) and semi-empirical absorption methods. The crystal structure was analyzed and the data were refined using the SHELXS-97 program and the SHELXL-97 program. The complex {[Cd(AHTr)2](Cl2)·2H2O} n The crystallographic data are listed in Table 1.

[0060] Table 1

[0061]

[0062]

[0063] Complex {[Cd(AHTr)2](Cl2)·2H2O} n Molecular structure Figure 8 As shown, it belongs to the triclinic system, P-1 space group, and the unit cell parameters are α=101.51°,β=94.439(2)°,γ=93.9820°Each unit cell contains 2 molecules, and the unit cell volume is The crystal density is 1.976 g cm -3 The asymmetric unit contains two AHTr molecular ligands, a central Cd(II) ion and two Cl - Anion. Its coordination diagram is as follows Fig. 9 As shown, the Cd(II) ion presents a slightly distorted octahedral coordination configuration, the two Cl- anions and the two N5 and N11 from the ligand AHTr hydrazine group form its equatorial plane, and the N3 and N9 on the two AHTr triazole rings occupy the axis points respectively. The dihedral angles ∠N5-N4-C1-N2 in the two AHTrs are 169.4°, and the dihedral angles ∠N11-N10-C3-N8 are -156.0°, indicating that the N5 and N11 in their hydrazine groups are slightly bent out of the plane where the triazole ring is located, the dihedral angles ∠N2-N1-C2-N6 are 178.6°, and the dihedral angles ∠N8-N7-C4-N12 are -178.7°. The amino groups in the ligand AHTr structure are all coplanar with the triazole ring. The bond lengths of Cd-Cl are and The Cd-N bond length is between 2.272(4) and The bond angle ranges from 71.15 (16)° to 166.67 (12)°. There are hydrogen bonds of the types NH…N, NH…Cl, NH…O and OH…Cl in its molecular structure. The bond lengths of these hydrogen bonds are between A large number of hydrogen bonds connect the 1D chains to form a stable 3D network structure ( Fig. 9 ).

[0064] Example 5

[0065] {[Cu(AHTr)2](Cl2)·2H2O} n The synthetic method comprises the following specific steps:

[0066] Step 1: Same as Example 1;

[0067] Step 2: Weigh CuCl2 (0.67 g, 5 mmol), dissolve it in 5 mL of methanol, and add it dropwise to the aqueous solution of 3-amino-5-hydrazino-1,2,4-triazole under vigorous stirring. Continue to stir the reaction at 80°C for 2 h. A light green precipitate is precipitated. Cool it to room temperature, then filter it, wash it with water, and dry the filter cake to obtain a powder solid with a yield of 28%.

[0068] {[Cu(AHTr)2](Cl2)·2H2O} prepared by the above method n Elemental analysis was performed, and the results were: theoretical value C13.25%, H 3.34%, N 46.35%; experimental value C13.28%, H 3.40%, N 46.42%.

[0069] The sample was taken in an airtight aluminum crucible with a volume of about 0.3 mg and then stirred under nitrogen atmosphere (nitrogen flow rate was 80 ml min -1 ), with a heating rate of 10℃·min -1 The DSC curve is as follows: Fig.12 As shown in Figure 1, the first exothermic decomposition peak temperature is 147.4°C, and the second exothermic decomposition peak temperature is 423.8°C. Its infrared spectrum is shown in Figure 1. Fig.13 As shown, the main peaks are: υ = 3378, 3292, 3116, 2905, 1655, 1578, 1325, 1296, 1219, 1100, 1055, 1010, 864cm -1 After further testing, the theoretical detonation velocity is 7065.8 m·s -1 The measured impact sensitivity is greater than 40J and the friction sensitivity is greater than 360N.

[0070] The above are only several preferred embodiments of the present invention, and there is no limitation on the present application in any form. It should be understood that any technician familiar with the technical field can design many other modifications and implementations within the technical scope disclosed by the present invention, and these modifications and implementations should be included in the protection scope of the present invention.

Claims

1. A 3-amino-5-hydrazino-1,2,4-triazole energetic complex, characterized in that: It includes chemicals shown in the following chemical structure formula: {[M(AHTr)2](Cl2)·2H2O}. Where M is the metal ion Mn 2+ 、Ni 2+ 、Zn 2+ 、Cd 2+ and Cu 2+ AHTr is a 3-amino-5-hydrazino-1,2,4-triazole ligand.

2. A method for preparing the 3-amino-5-hydrazino-1,2,4-triazole energetic complex as claimed in claim 1, characterized in that: The following steps are involved: Step 1: Weigh 3-amino-5-hydrazino-1,2,4-triazole hydrochloride, dissolve it in water, add LiOH·H2O to adjust the pH of the solution, and heat the solution. Step 2: Weigh a metal salt and dissolve it in methanol. Add it dropwise into an aqueous solution of 3-amino-5-hydrazino-1,2,4-triazole under vigorous stirring. Continue stirring the reaction for 2 hours. When a precipitate is precipitated, cool, filter, wash and dry to obtain the corresponding energetic complex.

3. The method for preparing the 3-amino-5-hydrazino-1,2,4-triazole energetic complex according to claim 2, characterized in that: The pH value of the solution in step 1 is 4 to 9, and the temperature of the solution is -20 to 100°C.

4. The method for preparing the 3-amino-5-hydrazino-1,2,4-triazole energetic complex according to claim 2, characterized in that: The molar ratio of 3-amino-5-hydrazino-1,2,4-triazole to the metal salt in step 2 is 1:0.5-2.

0.

5. The method for preparing the 3-amino-5-hydrazino-1,2,4-triazole energetic complex according to claim 2, characterized in that: The solvent in step 2 is one of water, methanol, ethanol, methyl acetate, ethyl acetate, ethyl ether, propyl ether, benzene and toluene or a mixture thereof.

6. The method for preparing the 3-amino-5-hydrazino-1,2,4-triazole energetic complex according to claim 2, characterized in that: The metal salt in step 2 is one of chloride metal salts, perchlorate metal salts and nitrate metal salts.

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