Energetic material, preparation thereof and application of energetic material as initiating explosive and pyrotechnic compound

Abstract

The invention discloses an energetic material, a preparation method thereof and application of the energetic material as an initiating explosive, an explosive and a pyrotechnic compound. The chemical formula of the energetic material is MC10H18B2N6; wherein M is selected from at least one of Mn, Fe, Co, Ni, Cu, Zn and Cd; the crystal structure of the energetic material belongs to a monoclinic system, and the space group is P21 / n. The obtained energetic material has excellent stability and safety, and is green and environment-friendly. Through experimental determination, the thermal stability is greater than or equal to 120 DEG C, the impact sensitivity is greater than or equal to 40J, and the friction sensitivity is greater than or equal to 240N. Compared with an existing commercial propellant (unsymmetrical dimethylhydrazine), the ignition delay time of the energetic material is equivalent, the defects that fuel and an oxidizing agent are seriously mixed and the combustion efficiency is low are overcome, and the energetic material has important commercial application value in the field of green high-performance energetic materials.

Description

Technical Field

[0001] This invention belongs to the field of energetic materials technology, specifically relating to an energetic material and its preparation method, as well as its application as an initiator, explosive and pyrotechnic agent. Background Technology

[0002] Energetic materials are mainly used in propellants, explosives, and pyrotechnics. Currently, commercially available rocket propellants are primarily divided into two systems: solid propellants and liquid propellants. Solid-liquid hybrid propellants attempt to combine the advantages of both, typically employing a combination of solid fuels (such as hydroxyl-terminated polybutadiene (HTPB)) and liquid oxidizers (such as liquid oxygen or nitrogen tetroxide). While theoretically offering advantages such as adjustable thrust, emergency shutdown capability, and high safety, these propellants suffer from the "mixing problem" of uneven fuel-oxidizer mixing and low combustion efficiency. This results in an average specific impulse lower than high-performance solid and liquid propellants, and the system complexity far exceeds that of solid rocket motors. Therefore, research on novel solid-liquid propellants focuses on developing high-energy, combustible, or self-igniting energetic fuels, such as gel fuels containing nano-metal particles (aluminum, boron) or energetic binders, aiming to improve combustion efficiency and energy levels. However, combustion stability and process reproducibility remain significant challenges, and the complex and costly integrated design of the entire propulsion system has prevented it from replacing the mainstream position of solid / liquid propellants for decades, limiting its commercial applications. At the same time, with the development of technology and the increasing requirements for environmental protection, there is a need for green propellants with better performance. Therefore, exploring green, high-performance, and commercially viable controllable propellants has become an important research direction for energetic materials. Summary of the Invention

[0003] The purpose of this invention is to provide an energetic material with an ignition delay time comparable to that of currently commercial propellants (unsymmetrical dimethylhydrazine), and with a thermal stability of not less than 120°C, an impact sensitivity of not less than 40J, and a friction sensitivity of not less than 240N; its combustion products have low environmental pollution, making it a green and high-performance energetic material.

[0004] To achieve the above objectives, the present invention adopts the following technical solution: One of the objectives of this invention is to protect an energetic material with the chemical formula MC. 10 H 18 B2N6, wherein M is selected from at least one metal element from Group IB, Group IIB, Group VIIB, and Group VIII.

[0005] The energetic material can be a bulk single crystal or a crystalline powder.

[0006] Preferably, M in the chemical formula is selected from at least one of Mn, Fe, Co, Ni, Cu, Zn, and Cd.

[0007] Furthermore, the crystal structure of the energetic material belongs to the monoclinic crystal system, with space group . P2 1 / n Its unit cell parameters a =4.60~5.50Å, b =15.00~19.60 Å, c =8.00~9.88 Å, α=90°, β=100°~105.00°, γ=90°, Z=1.

[0008] As one implementation method, when M is Mn, that is, the chemical formula of the energetic material is MnC 10 H 18 When B2N6 is used, its unit cell parameters are: a =4.31~4.41 Å, b =18.41~18.46 Å, c =8.70~8.71 Å, α=90°, β=103.00°, γ=90.00°, Z=1.

[0009] As one implementation method, when M is Fe, that is, the chemical formula of the energetic material is FeC 10 H 18 When B2N6 is used, its unit cell parameters are: a =4.91~4.95 Å, b =18.56~18.60 Å, c =8.30~8.31 Å, α=90°, β=104.00°, γ=90°, Z=1.

[0010] As one implementation, when M is Co, that is, the chemical formula of the energetic material is CoC. 10 H 18 When B2N6 is used, its unit cell parameters are: a =4.68~4.73 Å, b =17.40~17.49 Å, c =8.29~8.34 Å, α=90°, β=103.00°, γ=90°, Z=1.

[0011] As one implementation method, when M is Ni, that is, the chemical formula of the energetic material is NiC 10 H 18 When B2N6 is used, its unit cell parameters are: a =5.21~5.27 Å, b =18.30~18.35 Å, c =9.60~9.67 Å, ​​α=90°, β=104.00°, γ=90°, Z=1.

[0012] As one implementation method, when M is Cu, that is, the chemical formula of the energetic material is CuC 10 H 18 When B2N6 is used, its unit cell parameters are: a =4.63~4.66 Å, b =18.80~18.88 Å, c =8.79~8.80 Å, α=90°, β=104.00°, γ=90°, Z=1.

[0013] As one implementation method, when M is Zn, that is, the chemical formula of the energetic material is ZnC. 10 H 18 When B2N6 is used, its unit cell parameters are: a =5.08~5.24 Å, b =15.40~15.69Å, c =9.80~9.83 Å, α=90°, β=104.00°, γ=90°, Z=1.

[0014] As one implementation, when M is Cd, that is, the chemical formula of the energetic material is CdC 10 H 18 When B2N6 is used, its unit cell parameters are: a =4.99~5.01 Å, b =18.20~18.33Å, c =8.80~8.83 Å, α=90°, β=104°, γ=90°, Z=1.

[0015] Furthermore, the thermal stability of the energetic material is not lower than 120°C.

[0016] Furthermore, the impact sensitivity of the energetic material is not less than 40 J.

[0017] Furthermore, the friction sensitivity of the energetic material is not less than 240N.

[0018] A second objective of this invention is to protect the method for preparing the energetic material. This method is simple in its steps, yields a product with high purity and high yield, and is suitable for large-scale industrial production.

[0019] The reaction formula for preparing the energetic material is as follows: Its preparation method includes at least the following steps: An aqueous solution containing M metal salt, 4-methylimidazolium and sodium cyanoborogen is reacted at a reaction temperature of not less than 70°C for not less than 24 hours.

[0020] Further, the M metal salt is a hydrochloride, sulfate, permanganate, perchlorate and / or nitrate containing at least one of Mn, Fe, Co, Ni, Cu, Zn and Cd.

[0021] Furthermore, the molar ratio of the M metal salt, 4-methylimidazole, and sodium cyanoborogen in the aqueous solution is 1~4:1:1~4, preferably, the molar ratio of the three is 1.5:1:1~2.

[0022] Preferably, the reaction temperature is 70~90℃; optionally, the upper limit of the reaction temperature can be selected from 90℃ or 80℃, and the lower limit can be selected from 90℃, 80℃ or 70℃.

[0023] Those skilled in the art can select an appropriate reaction time according to actual needs, ensuring the reaction proceeds fully. Preferably, the reaction time is 24 to 96 hours. Optionally, the upper limit of the reaction time can be selected from 96 hours, 72 hours, or 48 hours, and the lower limit is 72 hours, 48 ​​hours, or 24 hours.

[0024] A third objective of this invention is to protect the application of the aforementioned energetic material. This energetic material has an ignition delay time comparable to currently commercially available propellants (unsymmetrical dimethylhydrazine), a thermal stability ≥120℃, an impact sensitivity ≥40J, a friction sensitivity ≥240N, and its explosion products cause minimal environmental pollution. It is a green, high-performance energetic material with significant commercial application value in the field of energetic materials.

[0025] One of the applications is as an initiator, which contains at least one of the above-mentioned energetic materials or energetic materials prepared by any of the above-mentioned methods.

[0026] The second application is as an explosive containing at least one of the above-mentioned energetic materials or energetic materials prepared by any of the above-mentioned methods.

[0027] The third application is as a pyrotechnic agent, which contains at least one of the above-mentioned energetic materials or energetic materials prepared by any of the above-mentioned methods.

[0028] The beneficial effects that this invention can produce include, but are not limited to: (1) This invention provides a novel energetic material with excellent stability and safety, and is environmentally friendly. Experimental measurements show that its thermal stability is ≥120℃, impact sensitivity is ≥40J, and friction sensitivity is ≥240N. The ignition delay time of this energetic material is comparable to that of currently commercial propellants (unsymmetrical dimethylhydrazine, UDMH), and it overcomes the serious drawbacks of fuel-oxidant mixing and low combustion efficiency, thus possessing significant commercial application value in the field of energetic materials.

[0029] (2) The present invention provides a method for preparing the above-mentioned energetic material. The method has simple steps and the resulting energetic material has high purity, good crystallinity and high yield, which is suitable for large-scale industrial production. Attached Figure Description

[0030] Figure 1 The theoretical XRD diffraction pattern obtained by fitting the single crystal data of sample P1# is compared with the experimentally measured XRD diffraction pattern.

[0031] Figure 2 The diagram shows the crystal structure of samples P1#-P7# (excluding hydrogen atoms), where (a) is the coordination environment diagram and (b) is the three-dimensional framework structure diagram of the crystal.

[0032] Figure 3 This is a diagram showing the droplet effect of fuming nitric acid on sample P5#. Detailed Implementation

[0033] To make the content of this invention easier to understand, the technical solution of this invention will be further described below with reference to specific embodiments, but this invention is not limited thereto.

[0034] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0035] Example 1 Sample Preparation According to Table 1, the raw materials of metal salt, 4-methylimidazole and cyanoboronium salt are prepared and mixed evenly, then loaded into a high-pressure reactor, a certain amount of water is added as a solvent, and the mixture is placed in an environment of 70~90℃ for 24~96 hours. After filtration, the corresponding energetic materials are obtained.

[0036] Table 1

[0037] Example 2: Structural Characterization of Samples Sample P1 prepared in Example 1 # ~P7 # After grinding, X-ray powder diffraction (XRD) phase analysis was performed on a Rigaku MiniFlex 600 X-ray diffractometer using a Cu target and a Kα radiation source (λ = 0.154184 nm). The results showed that the prepared samples were all of high purity and high crystallinity.

[0038] Sample P1 prepared in Example 1 # ~P7 #X-ray single-crystal diffraction was performed on a Mercury CCD single-crystal diffractometer using a Mo target, a Kα radiation source (λ = 0.07107 nm), and a test temperature of 293 K. The structure was analyzed using a SHELXTL-2014.

[0039] With P1 # As a typical example, a comparison is made between the theoretical XRD diffraction pattern obtained by fitting single-crystal data and the experimentally measured XRD diffraction pattern. Figure 1 As shown. By Figure 1 It can be seen that the XRD diffraction pattern obtained by fitting single-crystal data is highly consistent with the experimentally measured XRD diffraction pattern, proving that the obtained sample is a high-purity and highly crystalline sample. P2 # ~P7 # The results are the same as those of P1. # Similarly, the XRD diffraction pattern obtained by fitting single-crystal data is highly consistent with the experimentally measured XRD diffraction pattern, proving that the obtained sample is a high-purity and high-crystallinity sample.

[0040] X-ray powder diffraction and single-crystal diffraction results show that: Sample P1 # ~P7 # Both belong to the monoclinic crystal system. P2 1 / n Space group. Cell parameters are shown in Table 2, and a schematic diagram of the crystal structure is shown below. Figure 2 As shown.

[0041] Depend on Figure 2 It can be seen that sample P1 # ~P7 # They are isomorphic compounds, both passing through a 4-methylimidazole ligand ( A zero-dimensional structure composed of a metal center linked by cyanoboronhydride (N≡C-BH3). Specifically, in this zero-dimensional structure, each asymmetric unit consists of one M(II) atom and two CBH atoms. − It consists of an anion and two 4-methylimidazolium ligands, and its coordination mode is tetracoordinate (a).

[0042] Table 2 MC 10 H 18 Relevant crystallographic parameters of B2N6 (M = Mn, Fe, Co, Ni, Cu, Zn, Cd)

[0043] Example 3: Friction Sensitivity Experiment and Electrostatic Spark Sensitivity Experiment For sample P1 # ~P7 # The specific steps for conducting a friction sensitivity experiment are as follows: According to the national military standard testing standards for energetic materials, the FSKM-10 BAM friction sensitivity tester produced by OZM Company of the Czech Republic was used to determine the value corresponding to the 50% ignition rate of the compound through dozens of tests.

[0044] The ignition delay time of the compound was tested using a fuming nitric acid drop test.

[0045] Sample P1 # ~P7 # The experimental data on the energetic properties are shown in Table 3.

[0046] Table 3 MC 10 H 18 Relevant performance parameters of B2N6 (M = Mn, Fe, Co, Ni, Cu, Zn, Cd)

[0047] The experimental results above show that sample P1 # ~P7 # Its thermal stability is no less than 123℃, which is better than that of currently commercial propellants (unsymmetrical dimethylhydrazine, UDMH). Its impact sensitivity is no less than 40J, its friction sensitivity is no less than 240N, and its ignition delay time can be as short as 3~5 ms, which is comparable to that of commercial propellant UDMH. Moreover, its combustion products cause less environmental pollution. It is a high-performance energetic material with important commercial application value.

[0048] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.

Claims

1. An energetic material, characterized in that The chemical formula of the energetic material is MC 10 H 18 B2N6, wherein M is selected from at least one of Mn, Fe, Co, Ni, Cu, Zn, Cd.

2. The energetic material according to claim 1, characterized in that The crystal structure of the energetic material belongs to a monoclinic system, and a space group is P2 1 / n cell parameters thereof are a = 4.60~5.50 Å, b = 15.00~19.60 Å, c = 8.00~9.88 Å, α = 90°, β = 100°~105.00°, γ = 90°, Z = 1.

3. The energetic material according to claim 1, characterized in that when M is Mn, the crystal cell parameters of said energetic material are a = 4.31-4.41 A, b = 18.41-18.46 A, c = 8.70-8.71 A, a = 90°, β = 103.00°, γ = 90.00°, Z = 1 ; When M is Fe, the cell parameters of the energetic material are a = 4.91-4.95 A, b = 18.56-18.60 A, c = 8.30-8.31 A, a = 90°, β = 104.00°, γ = 90°, Z = 1; When M is Co, the crystal cell parameters of the energetic material are a = 4.68-4.73 A, b = 17.40-17.49 A, c = 8.29-8.34 A, a = 90°, β = 103.00°, γ = 90°, Z = 1; When M is Ni, the crystal cell parameters of the energetic material are a = 5.21-5.27 A, b = 18.30-18.35 A, c = 9.60-9.67 A, a = 90°, β = 104.00°, γ = 90°, Z = 1; When M is Cu, the cell parameters of the energetic material are a = 4.63-4.66 A, b = 18.80-18.88 A, c = 8.79-8.80 A, a = 90°, β = 104.00°, γ = 90°, Z = 1; When M is Zn, the cell parameters of the energetic material are a = 5.08-5.24 A, b = 15.40-15.69 A, c = 9.80-9.83 A, a = 90°, β = 104.00°, γ = 90°, Z = 1; When M is Cd, the cell parameters of the energetic material are a = 4.99-5.01 A, b = 18.20-18.33 A, c = 8.80-8.83 A, a = 90°, β = 104°, γ = 90°, Z = 1.

4. The energetic material of claim 1, wherein, The energetic material has a thermal stability of not less than 120 DEG C, an impact sensitivity of not less than 40 J, and a friction sensitivity of not less than 240 N.

5. A process for the production of an energetic material as claimed in any one of claims 1 to 4, characterized in that The aqueous solution containing the M metal salt, 4-methylimidazole and sodium cyanoborohydride is reacted at a reaction temperature of not less than 70 DEG C for not less than 24 hours.

6. The production method according to claim 5, characterized by, The molar ratio of the M metal salt, 4-methylimidazole and sodium cyanoborohydride in the aqueous solution is 1-4:1:1-4; wherein the M metal salt is at least one of hydrochloride, sulfate, permanganate, perchlorate and / or nitrate of Mn, Fe, Co, Ni, Cu, Zn, Cd.

7. The preparation method according to claim 5, characterized in that, The reaction temperature is 70-90 DEG C, and the reaction time is 24-96 hours.

8. A primary explosive characterised in that, The energetic material of any one of claims 1-4 or the energetic material prepared by the method of any one of claims 5-7.

9. An explosive characterized by, The energetic material of any one of claims 1-4 or the energetic material prepared by the method of any one of claims 5-7.

10. A pyrotechnic composition, characterized by The energetic material of any one of claims 1-4 or the energetic material prepared by the method of any one of claims 5-7.

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