A tetrazine energetic material and its preparation method and application

Abstract

This application discloses a tetrazine energetic material and its preparation method and application, which belongs to the field of laser detonation and ignition technology. The energetic material includes MC2H x N 10 O y crystal; M is selected from any one of Mn, Fe, Co, Cu, Zn, Cd, and Ni; when M is selected from any one of Mn, Fe, Co, Cu, Zn, and Cd, x=8, y=7; when M is Ni, x=10, y=8. The tetrazine energetic material, as a laser detonation ignition material, generally requires lower laser detonation ignition energy than previously reported compounds and overcomes the serious ClO4 ‑ Despite the shortcomings of ion contamination and high laser ignition threshold, it has important commercial application value in the field of laser initiation and ignition.

Description

Technical Field

[0001] The present application relates to a tetrazine energetic material and a preparation method and application thereof, belonging to the field of laser initiation and ignition technology. Background Art

[0002] Laser ignition technology has become a new type of ignition technology developed in recent years and has received more and more attention. As a new type of ignition technology, laser ignition technology has the advantages of high output energy, high ignition efficiency, high controllability, and high safety. By combining laser ignition technology with energetic materials, the safety and reliability of the use of ignition technology in the current complex external environment can be greatly improved. Therefore, it is very important to study the application of laser ignition technology in the field of energetic materials. Energetic coordination compounds (ECCs) have rich assembly modes and more flexible design, so they have become a research hotspot for scientific researchers in the field of laser ignition. A large number of ECCs that can be used for laser ignition have been reported. However, these ECCs usually contain ClO4 - Ions, such as [(TriTzPyr)3Fe][ClO4]2, [Fe(MTZ)6](ClO4)2, Cu(H2DAPZCA)2(ClO4)4·2H2O, Cu(HAPZCA)2(ClO4)4, etc. ClO4 - Ion pollution of water environment has become one of the most serious environmental problems. - Ions are also harmful to human health, especially thyroid function, which in turn affects human metabolism. Based on the above reasons, the goal of this application is to design and synthesize a class of laser-responsive and ClO4-free - ionic, environmentally friendly new ECCs. Summary of the Invention

[0003] According to one aspect of the present application, a tetrazine energetic material is provided as a laser initiation ignition charge, which requires a lower laser initiation ignition energy than the reported compounds and overcomes the serious ClO4 - Despite the shortcomings of ion contamination and high laser ignition threshold, it has important commercial application value in the field of laser initiation and ignition.

[0004] The tetrazine energetic materials described in this application include MC2H x N 10 O y crystals;

[0005] M is selected from any one of Mn, Fe, Co, Cu, Zn, Cd, and Ni;

[0006] When M is selected from any one of Mn, Fe, Co, Cu, Zn, and Cd, x=8, y=7;

[0007] When M is Ni, x=10, y=8.

[0008] Optionally, the MC2H x N 10 O y The crystal structure is a 0D fullerene-like planar structure.

[0009] Optionally, when M is selected from any one of Mn, Fe, Co, Cu, Zn, and Cd, the MC2H x N 10 O y The crystals belong to the P1 space group;

[0010] When M is Ni, the MC2H x N 10 O y The crystals belong to the P21 / c space group.

[0011] Optionally, when M is selected from any one of Mn, Fe, Co, Cu, Zn, and Cd, the MC2H x N 10 O y The unit cell parameters of the crystal are: α=74~78°; β=81~85°; γ=80~84°; Z=0.4~0.6.

[0012] Preferably, when M is selected from any one of Mn, Fe, Co, Cu, Zn, and Cd, the MC2H x N 10 O y The unit cell parameters of the crystal are: α=74.5~77.0°; β=81.5~84.9°; γ=80.5~83.5°; Z=0.5.

[0013] Preferably, when M is selected from any one of Mn, Fe, Co, Cu, Zn, and Cd, the MC2H x N 10 O y The unit cell parameters of the crystal are: α=74.80~77.25°; β=81.8~84.90°; γ=80.70~83.50°;

[0014]

[0015] Optionally, when M is Ni, the MC2H x N 10 O y The unit cell parameters of the crystal are:

[0016] α=85~93°; β=90~93°; γ=87~93°;

[0017] Z=0.4~0.6.

[0018] Preferably, when M is Ni, the MC2H x N 10 O y The unit cell parameters of the crystal are:

[0019] α=87.5~92.5°; β=90.5~93.0°;

[0020] γ=88.5~92.50°; Z=0.5.

[0021] Preferably, when M is Ni, the MC2H x N 10 O y The unit cell parameters of the crystal are:

[0022] α=88.20~91.50°;

[0023] β=91.50~93.0°; γ=89.00~91.50°;

[0024] Optionally, the MC2H x N 10 O y The nitrogen content of the crystal is 33-43%; the decomposition temperature is 100-105° C.; the impact sensitivity is 3-5 J; the friction sensitivity is 60-175 N; and the electrostatic spark sensitivity is 40-45 mJ.

[0025] In another aspect, the present application provides a method for preparing the energetic material, comprising: reacting a mixture comprising a metal salt containing M, a ligand, and a solvent to obtain the energetic material;

[0026] The M is selected from any one of Mn, Fe, Co, Cu, Zn, Cd, and Ni;

[0027] The ligand is 3,6-dihydrazino-1,2,4,5-tetrazine.

[0028] Optionally, the M-containing metal salt is selected from any one or more of M-containing perchlorates, nitrates, and halogen-containing metal salts.

[0029] Optionally, the solvent is nitric acid.

[0030] Optionally, the molar ratio of the metal salt containing M to the ligand is (1-3): (1-4);

[0031] The molar number of the metal salt containing M is calculated based on the molar number of M.

[0032] Optionally, the concentration of the nitric acid is 10-35 wt %; preferably, the concentration of the nitric acid is 15-30 wt %.

[0033] Optionally, the added amount of the M-containing metal salt and the solvent is (20-120) mg: (5-20) mL.

[0034] Optionally, the added amounts of the M-containing metal salt and solvent are independently selected from any value among 75 mg:8 mL, 80 mg:15 mL, 30 mg:10 mL, 60 mg:10 mL, 25 mg:5 mL, 120 mg:8 mL, 60 mg:20 mL, 20 mg:5 mL, 20 mg:20 mL, 120 mg:5 mL, 120 mg:20 mL, or a range value between any two of the above.

[0035] Optionally, the reaction temperature is 25-60°C.

[0036] Optionally, the reaction temperature is independently selected from any one of 25°C, 35°C, 45°C, 50°C, 60°C, or a range between any two of the above values.

[0037] In another aspect, the present application provides a use of the energetic material as a laser detonation ignition charge.

[0038] The beneficial effects of this application include:

[0039] 1) The energetic material provided in this application has a simple synthesis method, a very low laser initiation threshold, and is environmentally friendly. Experimental measurements show that the compound has an impact sensitivity of no more than 5J, a friction sensitivity of no more than 175N, and an electrostatic spark sensitivity within the range of 40-45mJ.

[0040] 2) The energetic material described in this application is lower than most of the currently reported laser detonation ignition materials and does not contain ClO4 – Ions have important commercial application value in the field of green high-performance energetic materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 For this application CuC2H8N10 Powder diffraction pattern of O7;

[0042] Figure 2 For this application CuC2H8N 10 Crystal structure diagram of O7;

[0043] Figure 3 For this application NiC2H 10 N 10 Crystal structure diagram of O8;

[0044] Figure 4 CuC2H8N 10 O7 hot needle test diagram;

[0045] Figure 5 This is a schematic diagram of the laser detonation ignition test device;

[0046] Figure 6 CuC2H8N 10 Schematic diagram of O7 as laser detonation ignition charge at a laser energy of 4.2mJ. DETAILED DESCRIPTION

[0047] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0048] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0049] N a The calculation method of % is:

[0050] T dec b 、IS c , FS d 、ESD e The testing instruments are TGA / DSC 1 / 1100 thermogravimetric analyzer, BFH-12 impact sensitivity meter, FSKM-10 friction sensitivity meter and Xspark 8 electrostatic spark sensitivity tester.

[0051] The powder diffraction instrument was a Rigaku Miniflex 600 powder X-ray diffractometer.

[0052] The hot needle test method is to place a 20 mg sample in a loose state on a copper plate and trigger it with a high-temperature iron needle heated under a Bunsen burner for 3 minutes.

[0053] Example 1

[0054] Compound MnC2H8N 10The synthesis method of O7 is as follows: Mn(NO3)2·4H2O (75.30 mg) and ligand DHT (14.21 mg) were added to 8 mL of 30% mass fraction nitric acid solvent, and the mixture was placed at a reaction temperature of 45°C for 72 hours, and then cooled to room temperature and filtered to obtain a large amount of MnC2H8N 10 O7 dark brown crystals.

[0055] The MnC2H8N 10 The structure of O7 black-brown crystal is a 0D fullerene-like planar structure.

[0056] Example 2

[0057] Compound FeC2H8N 10 The synthesis method of O7 is as follows: Fe(NO3)3·9H2O (80.80 mg) and ligand DHT (42.63 mg) were added to 16 mL of 20% mass fraction nitric acid solvent, and the mixture was reacted at 35°C for 96 hours, then cooled to room temperature and filtered to obtain a large amount of FeC2H8N 10 O7 black crystal.

[0058] The FeC2H8N 10 The structure of O7 black crystal is a 0D fullerene-like planar structure.

[0059] Example 3

[0060] Compound CoC2H8N 10 Synthesis method of O7: Co(NO3)2·6H2O (29.10 mg) and ligand DHT (28.42 mg) were added to 10 mL of 15% mass fraction nitric acid solvent, and the mixture was reacted at 45°C for 96 hours, then cooled to room temperature and filtered to obtain a large amount of chemical formula CoC2H8N 10 O7 deep red crystals.

[0061] The CoC2H8N 10 The structure of the O7 deep red crystal is a 0D fullerene-like planar structure.

[0062] Example 4

[0063] Compound NiC2H 10 N 10 Synthesis method of O8: Ni(NO3)2·6H2O (58.16 mg) and ligand DHT (14.21 mg) were added to 10 mL of 15% mass fraction nitric acid solvent, and the mixture was reacted at 25°C for 24 hours, then cooled to room temperature and filtered to obtain a large amount of NiC2H 10 N 10O8 reddish-brown crystals.

[0064] Figure 3 NiC2H 10 N 10 The crystal structure diagram of O8, which has a 0D fullerene-like planar structure.

[0065] Example 5

[0066] Compound CuC2H8N 10 The synthesis method of O7 is as follows: Cu(NO3)2·3H2O (24.16 mg) and ligand DHT (14.21 mg) were added to 5 mL of 15% mass fraction nitric acid solvent, and the mixture was placed at a reaction temperature of 25°C for 24 hours, and then cooled to room temperature and filtered to obtain a large amount of CuC2H8N 10 O7 black crystal.

[0067] Figure 1 CuC2H8N 10 The powder diffraction pattern of O7 shows that the spectrum measured by the experimental instrument is highly consistent with the spectrum obtained by crystal data simulation, indicating that the compound samples used in the experiment are all pure samples, ensuring the reliability of the samples used in subsequent tests.

[0068] Figure 2 CuC2H8N 10 The crystal structure of O7 is a 0D fullerene-like planar structure.

[0069] Figure 4 20mgCuC2H8N 10 O7 hot needle test diagram, from the figure we can see that the high temperature hot needle heated by the Bunsen burner is 10 Upon O7 contact, smoke began to form immediately, followed by a large, bright flame.

[0070] Figure 5 Figure 1 is a schematic diagram of the laser initiation ignition test device. To determine the minimum laser initiation threshold E (E = P × T) of the sample, the sample (about 20 mg) was placed in an Al2O3 crucible and the pulse power (P = 3 W) and pulse intensity (I = 15.3 W·cm) were determined within a certain T (pulse duration) range. -2 ) irradiates it. As T decreases, the output laser energy (E) also decreases accordingly. After multiple experiments, the critical energy at which the sample can be accurately triggered, namely the minimum laser triggering threshold, is finally determined.

[0071] Figure 6 20mg CuC2H8N was recorded 10The experimental phenomenon of O7 as laser ignition ignition charge at laser energy of 4.2mJ is shown in the figure. 10 O7 was successfully ignited and detonated, with a large, bright flame clearly observed.

[0072] Example 6

[0073] Compound ZnC2H8N 10 Synthesis method of O7: Add the mixture of Zn(NO3)2·6H2O (119.00 mg) and ligand DHT (14.21 mg) into 8 mL of 25% mass fraction nitric acid solvent, place it at a reaction temperature of 50°C for 120 hours, then cool it to room temperature and filter it to obtain a large amount of chemical formula ZnC2H8N 10 O7 deep red crystal.

[0074] The ZnC2H8N 10 The structure of O7 deep red crystal is a 0D fullerene-like planar structure.

[0075] Example 7

[0076] Compound CdC2H8N 10 Synthesis method of O7: Cd(NO3)2·4H2O (61.70 mg) and ligand DHT (14.21 mg) were added to 20 mL of 25% mass fraction nitric acid solvent, placed in a reaction temperature of 60°C for 36 hours, then cooled to room temperature and filtered to obtain a large amount of chemical formula CdC2H8N 10 O7 black crystal.

[0077] The CdC2H8N 10 The structure of O7 black crystal is a 0D fullerene-like planar structure.

[0078] The relevant crystallographic parameters of the above crystals are shown in Table 1.

[0079] Table 1

[0080]

[0081] Table 1

[0082]

[0083] The performance parameters of the above crystals are shown in Table 2.

[0084] Table 2

[0085]

[0086] Among them, N a = nitrogen content; T decb = decomposition temperature; IS c = Impact sensitivity; FS d = Friction sensitivity; ESD e = Static spark sensitivity.

[0087] The above descriptions are merely a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application discloses the preferred embodiments as above, they are not intended to limit the present application. Any technical personnel familiar with the present profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A tetrazine energetic material, characterized in that: Including MC2H x N 10 O y crystals; M is selected from any one of Mn, Fe, Co, Cu, Zn, Cd, and Ni; When M is selected from any one of Mn, Fe, Co, Cu, Zn, and Cd, x=8, y=7, and its chemical formula is [M(DHT)(NO3)(H2O)](NO3); When M is Ni, x=10, y=8, and its chemical formula is [Ni(DHT)(H2O)2](NO3)2; Among them, DHT is the ligand 3,6-dihydrazino-1,2,4,5-tetrazine.

2. The tetrazine energetic material according to claim 1, characterized in that The MC2H x N 10 O y The crystal structure is a 0D fullerene-like planar structure.

3. The tetrazine energetic material according to claim 1, characterized in that When M is selected from any one of Mn, Fe, Co, Cu, Zn, and Cd, the MC2H x N 10 O y The crystals belong to the P1 space group; When M is Ni, the MC2H x N 10 O y The crystals belong to the P21 / c space group.

4. The tetrazine energetic material according to claim 1, characterized in that When M is selected from any one of Mn, Fe, Co, Cu, Zn, and Cd, the MC2H x N 10 O y The unit cell parameters of the crystal are: α=74~78°;β=81~85°;γ=80~84°; Z＝0.4～0.6。 5. The tetrazine energetic material according to claim 4, characterized in that: When M is selected from any one of Mn, Fe, Co, Cu, Zn, and Cd, the MC2H x N 10 O y The unit cell parameters of the crystal are: α＝74.5～77.0°；β＝81.5～84.9°； γ=80.5~83.5°; Z=0.5。 6. The tetrazine energetic material according to claim 5, characterized in that: When M is selected from any one of Mn, Fe, Co, Cu, Zn, and Cd, the MC2H x N 10 O y The unit cell parameters of the crystal are: α＝74.80～77.25°； β=81.8~84.90°;γ=80.70~83.50°; 7. The tetrazine energetic material according to claim 1, characterized in that: When M is Ni, the MC2H x N 10 O y The unit cell parameters of the crystal are: α=85~93°; β=90~93°; γ=87~93°; Z=0.4~0.

6.

8. The tetrazine energetic material according to claim 7, characterized in that: When M is Ni, the MC2H x N 10 O y The unit cell parameters of the crystal are: α=87.5~92.5°; β=90.5~93.0°; γ=88.5~92.50°; Z=0.

5.

9. The tetrazine energetic material according to claim 8, characterized in that: When M is Ni, the MC2H x N 10 O y The unit cell parameters of the crystal are: α=88.20~91.50°; β=91.50~93.0°; γ=89.00~91.50°; 10. The tetrazine energetic material according to claim 1, characterized in that: The MC2H x N 10 O y The nitrogen content of the crystal is 33-43%; the decomposition temperature is 100-105° C.; the impact sensitivity is 3-5 J; the friction sensitivity is 60-175 N; and the electrostatic spark sensitivity is 40-45 mJ.

11. A method for preparing the tetrazine energetic material according to any one of claims 1 to 10, characterized in that: include: reacting a mixture comprising a metal salt containing M, a ligand, and a solvent to obtain the energetic material; The M is selected from any one of Mn, Fe, Co, Cu, Zn, Cd, and Ni; The ligand is 3,6-dihydrazino-1,2,4,5-tetrazine; The metal salt containing M is selected from nitrates containing M; The solvent is nitric acid.

12. The method for preparing the tetrazine energetic material according to claim 11, characterized in that: The molar ratio of the metal salt containing M to the ligand is (1-3): (1-4); The molar number of the metal salt containing M is calculated based on the molar number of M.

13. The method for preparing the tetrazine energetic material according to claim 11, characterized in that: The concentration of the nitric acid is 10-35 wt%.

14. The method for preparing the tetrazine energetic material according to claim 11, characterized in that: The added amounts of the metal salt containing M and the solvent are (20-120) mg: (5-20) mL.

15. The method for preparing the tetrazine energetic material according to claim 11, characterized in that: The reaction temperature is 25-60°C.

16. Use of the tetrazine energetic material according to any one of claims 1 to 10 as a laser detonation ignition powder, propellant or additive.

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