Energetic materials, their preparation and use as explosives and self-igniting propellants

Abstract

The application discloses an energetic material, a preparation method thereof and application of the energetic material as explosives and self-ignition propellants. I C 12 H 12 N 10 or M Ⅱ C8H6N8; wherein, M I is selected from Co, Ni and Cu; M Ⅱ is selected from Zn. The energetic material is convenient to synthesize, has good thermal stability, excellent mechanical sensitivity, excellent propelling performance and specific impulse, has a significant energy density advantage, can effectively solve the problem of continuous evaporation of hydrazine propellants during storage, avoid the risk of internal pressure increase of a fuel tank, and overcome the problems of liquid fuel in the storage and transportation process. Therefore, the innovative high-performance energetic material has excellent performance and wide application potential, and has great commercial value in the fields of aviation, aerospace and military.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of energetic materials, and particularly relates to a new type of energetic material and a preparation method thereof, and application thereof in the fields of explosives and self-combustion propellants. BACKGROUND

[0002] Energetic materials play a crucial role in key fields such as explosives, propellants, and pyrotechnics. Current market self-combustion propellants, such as hydrazine and its derivatives, dinitrogen tetroxide, and liquid oxygen kerosene, have advantages in synthesis process and cost, but have obvious shortcomings in energy density and storage and transportation. With the continuous progress of aerospace technology, there is an increasing demand for self-combustion propellants with superior performance. At the same time, solid fuel engines, as a new technology, are gradually attracting widespread attention in the industry. Although research on solid fuels is still in its early stages, the potential for improving energy density and simplifying storage and transportation processes has already been realized. Therefore, developing commercialized solid self-combustion propellants with high performance has become an important and urgent research direction in the field of energetic materials. SUMMARY

[0003] The present application aims to provide a type of energetic material and a preparation method thereof and application as explosives and self-combustion propellants. The energy density of the energetic material is much higher than that of the current commercial hydrazine self-combustion propellant, and it is simple to synthesize and easy to store and transport, making it a high-performance energetic material.

[0004] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0005] One of the purposes of the present application is to protect a type of energetic material, whose chemical formula is M I C 12 H 12 N 10 or M Ⅱ C8H6N8, wherein M I is selected from one of Co, Ni, and Cu; M Ⅱ is selected from Zn.

[0006] For the energetic material with the chemical formula M 1 C 12 H 12 N 10 , as an embodiment, when M I is selected from Co, its crystal structure is monoclinic, the space group is I2 / a , the unit cell parameters are a =15.1244~15.1258 Å, b =7.3091~7.3096 Å, c =14.9704~14.9718 Å,α = 90.00°, β = 110.393~110.404°, γ = 90.00°, Z = 4.

[0007] For the energetic material of the chemical formula M 1 C 12 H 12 N 10 , as an implementation form, when M I is selected from Ni, the crystal structure is monoclinic, the space group is C2 / c , the unit cell parameters are a = 17.0631~17.0642 Å, b = 7.2272~7.2274 Å, c = 14.9584~14.9594 Å, α = 90.00°, β = 125.523~125.532°, γ = 90.00°, Z = 4.

[0008] For the energetic material of the chemical formula M 1 C 12 H 12 N 10 , as an implementation form, when M I is selected from Cu, the crystal structure is triclinic, the space group is P-1 , the unit cell parameters are a = 7.6794~7.6796 Å, b = 8.9293~8.9295 Å, c = 11.8172~11.8173 Å, α = 93.5190~93.5200°, β = 95.7540~95.7550°, γ = 106.672~106.674°, Z = 2.

[0009] For the energetic material of the chemical formula M Ⅱ C8H6N8, as an implementation form, when M Ⅱ is selected from Zn, the crystal structure is monoclinic, the space group is P2 1 / c , the unit cell parameters are a = 13.2102~13.2115 Å, b = 11.8863~11.8873 Å,c = 7.5328-7.5334 Å, α = 90.00°, β = 94.534-94.543°, γ = 90.00°, Z = 4.

[0010] Further, the energetic material has a thermal stability ≥ 130 °C.

[0011] Further, the energetic material has an impact sensitivity ≥ 40 J.

[0012] Further, the energetic material has a friction sensitivity ≥ 360 N.

[0013] Further, the energetic material has a volume energy density ≥ 30 kJ·cm −3 .

[0014] Further, the energetic material has a specific impulse ≥ 210 s.

[0015] The second object of the present application is to protect the preparation method of the energetic material, and the reaction formula is as follows:

[0016] .

[0017] Specifically, the preparation of the energetic material is to dissolve sodium dicyanamide (NaDCA) and imidazole ligand in water, and slowly drop into the aqueous solution of metal salt containing M I or M Ⅱ element, react, filter, and stand in air for several days to obtain the product. This method has simple steps, high purity and high yield of the product, and is suitable for large-scale industrial production.

[0018] Further, the molar ratio of sodium dicyanamide, imidazole ligand and metal salt containing M I or M Ⅱ element is 2:2:1.

[0019] Further, the imidazole ligand is 2-methylimidazole (2-Mim).

[0020] Further, the metal salt is nitrate, chloride, sulfate or bromide of the corresponding metal element.

[0021] Further, the reaction temperature is room temperature, and the reaction time is 0.5-1 hour. In operation, the skilled person in the art can select appropriate reaction time and reaction temperature according to actual needs, and the reaction is sufficient.

[0022] Further, the obtained energetic material can be a blocky large single crystal or a crystal powder.

[0023] The third object of the present application is to protect the use of the energetic material.

[0024] One aspect of the use is to provide an explosive containing at least one of any of the above-mentioned energetic materials, the energetic material prepared by any of the above-mentioned methods.

[0025] Another aspect of the use is to provide a self-ignition propellant containing at least one of any of the above-mentioned energetic materials, the energetic material prepared by any of the above-mentioned methods.

[0026] The beneficial effects that can be produced by the present application include but are not limited to:

[0027] (1) The present application provides a new type of energetic material. The energetic material has excellent stability and safety. The experimentally determined thermal stability is ≥ 130 ℃, the impact sensitivity is ≥ 40 J, the friction sensitivity is ≥ 360 N, the volume energy density is ≥ 30 kJ·cm −3 , and the specific impulse is ≥ 210 s. The energy density of the energetic material provided by the present application significantly surpasses the current market commercial hydrazine-dinitrogen tetraoxide propellant. It not only achieves a major breakthrough in energy release efficiency, but also overcomes the problem of increased internal pressure of the fuel tank during storage due to continuous evaporation of hydrazine self-ignition propellant, as well as the inconvenience of liquid fuel in storage and transportation. These innovative features make the present application have significant commercial application value in the field of high-performance energetic materials, indicating great potential in space propulsion technology and related industrial applications.

[0028] (2) The present application provides a preparation method of the energetic material. The method has simple steps, and the obtained energetic material has high purity, good crystallinity and high yield, and is suitable for large-scale industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 Sample P1 prepared for the examples # -P4 # The XRD diffraction theoretical spectrum obtained by single crystal data fitting and the experimentally measured XRD diffraction spectrum of P1

[0030] Figure 2 Sample P1 prepared for the examples # -P4 # The crystal structure schematic diagram (without hydrogen atoms) of P1 # , P2 # , P3 # , and P4 # .

[0031] Figure 3 Sample P1 prepared for the examples #P4 # Ignition delay time test diagram of P4. DETAILED DESCRIPTION

[0032] In order to make the content of the present application more convenient to understand, the technical solutions of the present application are further described below in combination with specific embodiments, but the present application is not limited thereto.

[0033] Example 1 Preparation of CoC8H6N8 12 H 12 N 10 Example 1 Preparation of CoC8H6N8

[0034] 178 mg of sodium dicyanamide and 164 mg of 2-methylimidazole were dissolved in water, and then a solution containing 155 mg of CoSO4was slowly added dropwise into the mixed system. After reaction at room temperature for 30 minutes, filtration was performed, and after volatilization in air for several days, red crystals of CoC8H6N8were obtained, which were marked as P1. 12 H 12 N 10 Example 1 Preparation of CoC8H6N8 # .

[0035] Example 2 Preparation of NiC8H6N8 12 H 12 N 10 Example 2 Preparation of NiC8H6N8

[0036] 178 mg of sodium dicyanamide and 164 mg of 2-methylimidazole were dissolved in water, and then a solution containing 238 mg of NiCl2·6H2O was slowly added dropwise into the mixed system. After reaction at room temperature for 30 minutes, filtration was performed, and after volatilization in air for several days, green crystals of NiC8H6N8were obtained, which were marked as P2. 12 H 12 N 10 Example 2 Preparation of NiC8H6N8 # .

[0037] Example 3 Preparation of CuC8H6N8 12 H 12 N 10 Example 3 Preparation of CuC8H6N8

[0038] 178 mg of sodium dicyanamide and 164 mg of 2-methylimidazole were dissolved in water, and then a solution containing 170 mg of CuCl2·2H2O was slowly added dropwise into the mixed system. After reaction at room temperature for 30 minutes, filtration was performed, and after volatilization in air for several days, blue crystals of CuC8H6N8were obtained, which were marked as P3. 12 H 12 N 10 Example 3 Preparation of CuC8H6N8 # .

[0039] Example 4 Preparation of ZnC8H6N8

[0040] ​​​Dissolve 178 mg of sodium dicyanamide and 164 mg of 2-methylimidazole in water, then slowly dropwise add an aqueous solution containing 225 mg of ZnBr2 into the mixture. After reacting at room temperature for 30 minutes, filter and evaporate in the air for several days to obtain white crystals of ZnC8H6N8, which are marked as P4. # .

[0041] Structural characterization of samples

[0042] Sample P1 # ~P4 # The X-ray powder diffraction phase analysis (XRD) of the ground samples was carried out on a Rigaku MiniFlex600 X-ray diffractometer with a Cu target, a Kα radiation source (λ = 0.1540598 nm), a voltage of 40 kV, a current of 20 mA, and a test angle of 2. θ Range 5~50°, test speed 5° per minute. At the same time, sample P1 # ~P4 # X-ray single crystal diffraction was performed on a Mercury CCD single crystal diffractometer with a Mo target and a Kα radiation source (λ = 0.07107 nm) at a test temperature of 100~298 K, and the structure was roughly solved by SHELXTL.

[0043] The XRD diffraction pattern obtained by fitting the single crystal data is compared with the experimental XRD diffraction pattern. Figure 1 As shown. Figure 1 It can be seen that the XRD diffraction pattern obtained by fitting the single crystal data is highly consistent with the experimentally measured XRD diffraction pattern, proving that the obtained sample is a sample of high purity and high crystallinity.

[0044] P1 # ~P4 # The unit cell parameters are shown in Table 1, and the crystal structure diagram is shown in Figure 2 As shown. Figure 2 It can be seen that among the four compounds, the imidazole ligand adopts a monodentate coordination mode, while the dicyandiamide ion chooses a bidentate coordination mode between the nitrogen atoms at both ends and the metal center and a monodentate coordination mode. # 、P2 # Showing a six-coordinate structure, P3 # It is a five-coordinate structure, P4 # It is a four-coordinate structure. All structures are one-dimensional chain structures.

[0045] Specifically, with P1 # The structural analysis of P1 # In the monoclinic space group I2 / acrystallizes and exhibits one-dimensional chain structure. The crystallographic asymmetric unit contains half of the M I center, one 2-Mim ligand and one DCA - anion. The M I center is six-coordinated by two 2-Mim ligands and four DCA − anions, providing a distorted octahedron. The neutral ligand 2-Mim is distributed on both sides of the main chain by terminal coordination. Due to the stretching of the DCA - anions in the horizontal plane, a one-dimensional long chain polymer structure is formed by the bridging coordination mode of μ2-κΝ21:κΝ23and μ2-κΝ21#2:κΝ23#2. The distance between adjacent M I atoms along the c-axis is 7.31 Å. These one-dimensional chains are stacked by van der Waals forces, generating a three-dimensional supramolecular network. b

[0046] Similarly, P2 # exhibits similar coordination environment and packing mode as P1 # , crystallizes in monoclinic space group P2 C2 / c / c with one-dimensional chain characteristics.

[0047] P3 # crystallizes in triclinic space group P1 P-1 , which is aperiodic structure according to single-crystal X-ray diffraction analysis data. It consists of a M I center, two DCA anions and two 2-Mim ligands as the basic asymmetric unit. The coordination environment of the M I center is a five-coordination mode, forming a distorted triangle by 2-Mim ligands and two nitrogen atoms. In addition, one DCA anion with μ2-κΝ31:κΝ33coordination mode is bidentate coordination to connect adjacent M I atoms, while the other is as terminal coordination mode. These one-dimensional chains are staggered along the c-axis by van der Waals forces. bc

[0048] P4 # crystallizes in monoclinic space group P2 P2 1 / c / c with good structural characteristics. Each asymmetric unit includes a M Ⅱ center, one 2-Mim ligand and two DCA anions. The M Ⅱ center is four-coordinated by one 2-Mim ligand and three DCA anions. Some DCA anions exhibit terminal coordination, while other anions exhibit bridging coordination by two terminal nitrogen atoms, similar to compound P3 # ​​The coordination observed in the meso is similar. These one-dimensional structures are stacked along bc the van der Waals forces, forming a regularly alternating network structure.

[0049] Table 1 M I C 12 H 12 N 10 (M I = Co, Ni, Cu) and M Ⅱ C8H6N8(M Ⅱ = Zn) related crystallographic parameters

[0050]

[0051] 2. Sensitivity experiment and drop experiment

[0052] The friction sensitivity experiment was carried out on samples P1 # ~P4 # , and the specific steps were as follows: according to the national military standard test standard of energetic materials, BAM sensitivity tester FSKM-10 produced by Czech OZM company was used, and the value corresponding to the 50% ignition rate of the compound was determined through dozens of tests.

[0053] The oxidizing agent used in the drop test was fuming nitric acid with a concentration of 98%, the sample mass was about 10 mg, the drop height was about 25 cm, and the value of the ignition delay time of the compound was determined through more than five tests. The delay ignition time was 39 ms, 70 ms, 65 ms and 100 ms, respectively.

[0054] The energetic property experimental data of samples P1 # ~P4 # are shown in Table 2.

[0055] Table 2 M I C 12 H 12 N 10 (M I = Co, Ni, Cu) and M Ⅱ C8H6N8(M Ⅱ = Zn) related performance parameters

[0056]

[0057] From the above experimental results, it can be seen that the thermal stability of the energetic material provided by the present application is not less than 130 ℃, the impact sensitivity is ≥40 J, the friction sensitivity is ≥360 N, and the volume energy density is not less than 30 kJ·cm −3The specific impulse is not less than 210 s, the ignition delay time is up to 39 ms at the shortest, and the energy density is much higher than that of the currently commercial hydrazine-based self-ignition propellant, so it is a new type of energetic material with excellent performance and has important commercial application value.

[0058] The above merely describes preferred embodiments of the present application, and any equivalent changes and modifications made within the scope of the present application should be included in the scope of the present application.

Claims

1. A class of energetic materials characterized by: The chemical formula of the energetic material is M I C 12 H 12 N 10 or M Ⅱ C8H6N8, among which M I One selected from Ni and Cu; M Ⅱ selected from Zn; Dissolve sodium dicyanamide and imidazole ligands in water and slowly drop the mixture containing M I or M Ⅱ The aqueous solution of metal salt of the element is reacted, filtered, and evaporated in the air to obtain the obtained product; the imidazole ligand is 2-methylimidazole.

2. The energetic material according to claim 1, wherein For the chemical formula M 1 C 12 H 12 N 10 energetic materials, when M I When selected from Ni, its crystal structure is monoclinic and the space group is C2 / c , the unit cell parameters are a =17.0631~17.0642 Å, b =7.2272~7.2274 Å, c =14.9584~14.9594 Å, α =90.00°, β =125.523~125.532°, γ =90.00°, Z =4; When M I When selected from Cu, its crystal structure is triclinic and the space group is P-1 , the unit cell parameters are a =7.6794~7.6796 Å, b =8.9293~8.9295 Å, c =11.8172~11.8173 Å, α =93.5190~93.5200°, β =95.7540~95.7550°, γ =106.672~106.674°, Z =2.

3. The energetic material according to claim 1, wherein For the chemical formula M Ⅱ Energetic materials of C8H6N8, when M Ⅱ When selected from Zn, its crystal structure is monoclinic and the space group is P2 1 / c , the unit cell parameters are a =13.2102~13.2115Å, b =11.8863~11.8873 Å, c =7.5328~7.5334 Å, α =90.00°, β =94.534~94.543°, γ =90.00°, Z =4.

4. The energetic material according to claim 1, wherein The energetic material has a thermal stability of ≥130°C, an impact sensitivity of ≥40 J, a friction sensitivity of ≥360 N, and a volume energy density of ≥30 kJ·cm −3 ;Specific impulse ≥210 s.

5. A method for preparing an energetic material according to claim 1, characterized in that: Dissolve sodium dicyanamide and imidazole ligands in water and slowly drop the mixture containing M I or M Ⅱ The aqueous solution of metal salt of the element is reacted, filtered, and evaporated in the air to obtain the obtained product; the imidazole ligand is 2-methylimidazole.

6. The method for preparing an energetic material according to claim 5, wherein: The molar ratio of the used sodium dicyandiamide, imidazole ligand and metal salt is 2:2:

1.

7. The method for preparing an energetic material according to claim 5, wherein: The reaction temperature is room temperature and the reaction time is 0.5-1 hour.

8. An explosive characterized by: Contains at least one of the energetic materials according to any one of claims 1 to 4 and the energetic materials prepared by the method according to any one of claims 5 to 7.

9. A hypergolic propellant, characterized in that: Contains at least one of the energetic materials according to any one of claims 1 to 4 and the energetic materials prepared by the method according to any one of claims 5 to 7.

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