A high-energy, low-sensitivity energetic material based on quaternary organic components and its synthesis method

Abstract

This invention discloses a high-energy, low-sensitivity energetic material based on a quaternary organic component and its synthesis method. The method uses 3-aminomethyl-4,5-diamino-1,2,4-triazole, dimethylamine, ammonium perchlorate, and perchloric acid as raw materials, and water as a solvent to prepare the target product [TATT][CH3NH2CH3][NH4](ClO4)7. The synthesis method of this invention is simple, uses readily available raw materials, is highly safe, has a mild reaction, and achieves a yield of up to 92%, enabling large-scale production of the product. This invention provides research ideas and experimental references for ensuring the supply of high explosives, explosive formulations, and pyrotechnics in wartime emergency situations.

Description

Technical Field

[0001] This invention belongs to the field of energetic materials, and relates to an energetic material based on quaternary organic components and its synthesis method. Background Technology

[0002] Explosives, as the energy source for the destructive effects of weapon systems, are chemical substances that, under certain external energy conditions, undergo rapid chemical reactions to generate large amounts of heat and gaseous products, performing work on the surrounding medium. In the new era, the development of high-tech weapons has placed higher demands on energetic materials; high energy, good safety, low cost, and environmental friendliness are particularly important. Therefore, obtaining novel high-energy, low-sensitivity compounds with high energy and good safety performance has become an important research direction in the field of energetic materials. Compared with neutral compounds, energetic ionic compounds have lower vapor pressures and higher enthalpies of formation, resulting in significant improvements in safety and energy density. Currently, the synthesis of energetic ionic compounds mainly focuses on binary and ternary components, while energetic ionic compounds based on quaternary organic components have never been reported. Summary of the Invention

[0003] The purpose of this invention is to provide an energetic material based on quaternary organic components and its synthesis method.

[0004] In a first aspect, the present invention provides an energetic material based on a quaternary organic component, named [TATT][CH3NH2CH3][NH4](ClO4)7, the structure of which is shown below:

[0005]

[0006] In a second aspect, the present invention provides a method for synthesizing energetic materials based on quaternary organic components as described in the first aspect, comprising:

[0007] The steps for preparing the target product using 3-aminomethyl-4,5-diamino-1,2,4-triazole, dimethylamine, ammonium perchlorate, and perchloric acid as raw materials, and water as a solvent.

[0008]

[0009] Preferably, the method includes the following steps: 3-aminomethyl-4,5-diamino-1,2,4-triazole, dimethylamine, ammonium perchlorate and perchloric acid are slowly added to water under stirring at room temperature, the temperature is raised, and after the reaction is complete, the mixture is cooled and filtered, washed with ethanol, and dried under vacuum to obtain the target product.

[0010] Preferably, the molar ratio of 3-aminomethyl-4,5-diamino-1,2,4-triazole, dimethylamine, ammonium perchlorate, and perchloric acid is 2:2:1:2 to 9.

[0011] Preferably, the reaction temperature is 25–100℃.

[0012] Ideally, the reaction time is 0.5 to 4 hours.

[0013] Thirdly, the present invention provides a crystal prepared from an energetic material based on a quaternary organic component as described in the first aspect, wherein the solid powder of the energetic material based on the quaternary organic component is slowly volatilized in an aqueous solution to precipitate crystals.

[0014] Preferably, the crystal is orthorhombic with space group Pnma and cell coefficients [missing information]. α=90°, β=93.529(2)°, γ=90°, Bond angle C(3)-N(2)-N(3)=112.2(8)°.

[0015] Fourthly, the present invention provides the use of the energetic material based on the quaternary organic components described in the first aspect as a high explosive.

[0016] Compared with the prior art, the present invention has the following advantages:

[0017] This invention uses a high-nitrogen-content triazole ring as the basic framework, and further reacts it with dimethylamine, ammonium perchlorate, and perchloric acid to obtain an organic four-component energetic ionic salt. Compared with commonly used single-element explosives, it has higher density and energy and better safety. Its single-crystal density is 1.831 g / cm³. 3 Its thermal decomposition temperature is 309℃, its detonation velocity reaches 8857m / s, and its detonation pressure reaches 35.1GPa, which is comparable to that of the traditional high-energy explosive RDX. Its impact sensitivity is 18J and its friction sensitivity is 252N, which are far lower than those of RDX. Attached Figure Description

[0018] Figure 1 The proton NMR spectrum of [TATT][CH3NH2CH3][NH4](ClO4)7;

[0019] Figure 2 The carbon NMR spectrum of [TATT][CH3NH2CH3][NH4](ClO4)7;

[0020] Figure 3 The diagram shows the single crystal structure of [TATT][CH3NH2CH3][NH4](ClO4)7. Detailed Implementation

[0021] The present invention will be further described below with reference to the embodiments.

[0022] Example 1:

[0023] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 65 °C and stirred for 2 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 92%.

[0024] Its proton and carbon spectra are as follows: Figure 1 and Figure 2 As shown, the data is as follows:

[0025] 1 H NMR (300MHz, DMSO-d6): δ = 8.43, 8.21, 8.09, 6.17, 4.11, 2.52. 13 C NMR (75MHz, DMSO-d6): δ = 151.8, 146.9, 34.7, 32.8ppm.

[0026] Example 2:

[0027] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 2.86 g (20 mmol) of 70% perchloric acid solution were added. The mixture was heated to 65 °C and stirred for 2 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 9%.

[0028] Example 3:

[0029] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 5.72 g (40 mmol) of 70% perchloric acid solution were added. The mixture was heated to 65 °C and stirred for 2 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 20%.

[0030] Example 4:

[0031] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 7.15 g (50 mmol) of 70% perchloric acid solution were added. The mixture was heated to 65 °C and stirred for 2 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 58%.

[0032] Example 5:

[0033] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 8.58 g (60 mmol) of 70% perchloric acid solution were added. The mixture was heated to 65 °C and stirred for 2 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 85%.

[0034] Example 6:

[0035] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 11.44 g (80 mmol) of 70% perchloric acid solution were added. The mixture was heated to 65 °C and stirred for 2 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 78%.

[0036] Example 7:

[0037] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 12.87 g (90 mmol) of 70% perchloric acid solution were added. The mixture was heated to 65 °C and stirred for 2 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 51%.

[0038] Example 8:

[0039] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 25 °C and stirred for 2 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 10%.

[0040] Example 9:

[0041] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 35 °C and stirred for 2 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 21%.

[0042] Example 10:

[0043] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 45 °C and stirred for 2 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 59%.

[0044] Example 11:

[0045] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 55 °C and stirred for 2 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 81%.

[0046] Example 12:

[0047] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 75 °C and stirred for 2 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 71%.

[0048] Example 13:

[0049] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 85 °C and stirred for 2 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 44%.

[0050] Example 14:

[0051] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 90 °C and stirred for 2 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 11%.

[0052] Example 15:

[0053] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 100 °C and stirred for 2 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 2%.

[0054] Example 16:

[0055] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 65 °C and stirred for 0.5 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 12%.

[0056] Example 17:

[0057] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 65 °C and stirred for 1 hour. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 49%.

[0058] Example 18:

[0059] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 65 °C and stirred for 1.5 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 83%.

[0060] Example 19:

[0061] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 65 °C and stirred for 2.5 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 79%.

[0062] Example 20:

[0063] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 65 °C and stirred for 3 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 60%.

[0064] Example 21:

[0065] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 65 °C and stirred for 3.5 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol. The residue was then dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 32%.

[0066] Example 22:

[0067] 2.56 g (20 mmol) of 3-aminomethyl-4,5-diamino-1,2,4-triazole and 1.18 g (10 mmol) of ammonium perchlorate were added to 50 mL of water. Then, 1.11 g (20 mmol) of 40% dimethylamine aqueous solution and 10.78 g (70 mmol) of 70% perchloric acid solution were added. The mixture was heated to 65 °C and stirred for 4 hours. After cooling, the mixture was filtered, and the residue was washed three times with ethanol and dried under vacuum to obtain a white powdery solid [TATT][CH3NH2CH3][NH4](ClO4)7, with a yield of approximately 11%.

[0068] The obtained white powder solid [TATT][CH3NH2CH3][NH4](ClO4)7 was dissolved in water and volatilized to obtain single crystals, the structure of which is as follows: Figure 3 As shown.

[0069] The density of this single crystal is 1.831 g / cm³. 3 The thermal decomposition temperature is 309℃, the detonation velocity is 8857m / s, the detonation pressure is 35.1GPa, the impact sensitivity is 18J, and the friction sensitivity is 252N.

Claims

1. An energetic material based on a quaternary organic component, characterized in that, Its structure is as follows:

2. A method for synthesizing energetic materials based on quaternary organic components, characterized in that, include: The steps for preparing the target product using 3-aminomethyl-4,5-diamino-1,2,4-triazole, dimethylamine, ammonium perchlorate, and perchloric acid as raw materials, and water as a solvent.

3. The method as described in claim 2, characterized in that, Specifically, the following steps are included: 3-Aminomethyl-4,5-diamino-1,2,4-triazole, dimethylamine, ammonium perchlorate, and perchloric acid were slowly added to water under stirring at room temperature. The mixture was heated, and after the reaction was complete, it was cooled, filtered, washed with ethanol, and dried under vacuum to obtain the target product.

4. The method as described in claim 2, characterized in that, The molar ratio of 3-aminomethyl-4,5-diamino-1,2,4-triazole, dimethylamine, ammonium perchlorate, and perchloric acid is 2:2:1:2 to 9.

5. The method as described in claim 2, characterized in that, The reaction temperature is 25–100℃.

6. The method as described in claim 2, characterized in that, The reaction time is 0.5 to 4 hours.

7. An energetic material crystal based on a quaternary organic component, characterized in that, The solid powder of the energetic material based on quaternary organic components as described in claim 1 is slowly volatilized in an aqueous solution to precipitate crystals.

8. The crystal as described in claim 7, characterized in that, The crystal is orthorhombic, with space group Pnma and a unit cell coefficient of [missing information]. α=90°, β=93.529(2)°, γ=90°, Bond angle C(3)-N(2)-N(3)=112.2(8)°.

9. Use of an energetic material based on a quaternary organic component as described in claim 1, or an energetic material crystal based on a quaternary organic component as described in claim 7 or 8, as a high explosive.

Images