Energetic compound with polyamino triazole as skeleton, energetic ionic salt of energetic compound and preparation method of energetic ionic salt

Abstract

The invention discloses an energetic compound with polyamino triazole as a skeleton, energetic ionic salt of the energetic compound and a preparation method of the energetic ionic salt. The preparation method of the energetic compound comprises the following steps: carrying out a reaction on 5-nitro-1H-pyrazole-3-carboxylic acid and triaminoguanidine monohydrochloride to obtain 3-hydrazino-5-(5-nitro-1H-pyrazole-3-yl)-4H-1, 2, 4-triazole-4-amine, and carrying out a reaction on the 3-hydrazino-5-(5-nitro-1H-pyrazole-3-yl)-4H-1, 2, 4-triazole-4-amine to obtain the The preparation method comprises the following steps: reacting 3-hydrazino-5-(5-nitro-1H-pyrazol-3-yl)-4H-1, 2, 4-triazole-4-amine with nitrile bromide under the condition of hydrochloric acid to generate 6-(5-nitro-1H-pyrazol-3-yl)-7H-[1, 2, 4] triazolo [4, 3-b] [1, 2, 4] triazole-3, 7-diamine. The energetic compound and the energetic ionic salt prepared by the invention have high nitrogen content, positive enthalpy of formation and good detonation performance, and the preparation process disclosed by the invention is safe and reasonable, short in reaction time and high in yield.

Description

Technical Field

[0001] The invention belongs to the technical field of energetic materials, and in particular relates to an energetic compound with polyaminotriazole as a skeleton, an energetic ion salt thereof and a preparation method thereof. Background Art

[0002] Energetic materials are an important part of explosives technology. In recent years, nitrogen-rich energetic materials have attracted extensive attention from the material science, physics, organic and theoretical chemistry communities due to their high density, good thermal stability, green decomposition products and important applications in propellants, explosives and pyrotechnics. In addition, the high nitrogen content of the target N-heterocyclic skeleton ensures a large number of C=N and N=N bonds in the molecular structure, which leads to high positive heat of formation in the compound. It has become one of the important research directions of new energetic materials.

[0003] Nitrogen-rich five-membered heterocycles such as pyrazole, triazole, tetrazole, and pentazole are the most promising frameworks in the field of energetic materials. Among these five-membered heterocycles, triazole, which has high density, high heat of formation, and relatively low sensitivity, is widely used to prepare nitrogen-rich energetic materials with higher density, stability, and heat of formation.

[0004] Amino groups play an important role in reducing sensitivity, increasing nitrogen content and improving thermal stability by forming intermolecular / intramolecular hydrogen bonds. Therefore, the development of nitrogen-rich energetic materials based on polyaminotriazoles is considered to be a promising approach to achieve a good balance between high energy, good thermal stability and low sensitivity in the next generation of energetic materials. It is particularly important to develop an energetic compound with polyaminotriazole as the skeleton. Summary of the invention

[0005] The purpose of the present invention is to overcome the shortcomings of the prior art and to provide an energetic compound 6-(5-nitro-1H-pyrazol-3-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diamine with a polyaminotriazole skeleton, an energetic ion salt thereof and a preparation method thereof. The energetic material of the present invention has a polyaminotriazole skeleton, has a high formation enthalpy, a high detonation velocity and good thermal stability, and can be used in the field of energetic materials.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows: The present invention provides an energetic compound with a polyaminotriazole as a skeleton, and its structural formula is as follows: .

[0007] The present invention also provides an energetic ion salt with a polyaminotriazole as a skeleton, and its general structural formula is as follows: .

[0008] The present invention also provides a method for preparing the energetic compound with polyaminotriazole as the skeleton, comprising the following steps: Step 1: Mix 5-nitro-1H-pyrazole-3-carboxylic acid and triaminoguanidine monohydrochloride, add them into a system of orthophosphoric acid and phosphorus pentoxide to react, and prepare 3-hydrazino-5-(5-nitro-1H-pyrazol-3-yl)-4H-1,2,4-triazole-4-amine; Step 2, dissolving the 3-hydrazino-5-(5-nitro-1H-pyrazol-3-yl)-4H-1,2,4-triazole-4-amine obtained in step 1 in dilute hydrochloric acid, adding cyanogen bromide, and reacting at a certain temperature to obtain 6-(5-nitro-1H-pyrazol-3-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diamine.

[0009] Furthermore, in the above-mentioned method for preparing an energetic compound with a polyaminotriazole skeleton, the molar ratio of 5-nitro-1H-pyrazole-3-carboxylic acid to triaminoguanidine monohydrochloride in step 1 is 1:0.8~2, the reaction temperature is 120°C~130°C, and the reaction time is 8~16h.

[0010] Furthermore, in the above-mentioned method for preparing an energetic compound with a polyaminotriazole skeleton, after the reaction in step 1 is completed, the pH of the reaction mixture is adjusted to neutral.

[0011] Furthermore, in the above-mentioned method for preparing an energetic compound with a polyaminotriazole skeleton, the molar ratio of 3-hydrazino-5-(5-nitro-1H-pyrazol-3-yl)-4H-1,2,4-triazole-4-amine to cyanogen bromide in step 2 is 1:1-1:2, the reaction temperature is 55-65°C, and the reaction time is 2-6h; Furthermore, in the above-mentioned method for preparing an energetic compound with a polyaminotriazole as a skeleton, after the reaction in step 2 is completed, the precipitate is collected by filtration, the precipitate is dissolved in water, the pH is adjusted to neutral, the precipitate is filtered, washed, and dried to obtain the 6-(5-nitro-1H-pyrazol-3-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diamine.

[0012] The present invention also provides a method for preparing the energetic ion salt with polyaminotriazole as the skeleton, comprising the following steps: Step 1: Mix 5-nitro-1H-pyrazole-3-carboxylic acid and triaminoguanidine monohydrochloride, add them into a system of orthophosphoric acid and phosphorus pentoxide to react, and prepare 3-hydrazino-5-(5-nitro-1H-pyrazol-3-yl)-4H-1,2,4-triazole-4-amine; Step 2, dissolving the 3-hydrazino-5-(5-nitro-1H-pyrazol-3-yl)-4H-1,2,4-triazole-4-amine obtained in step 1 in dilute hydrochloric acid, adding cyanogen bromide, and reacting at a certain temperature to obtain 6-(5-nitro-1H-pyrazol-3-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diamine; Step 3: The 6-(5-nitro-1H-pyrazol-3-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diamine obtained in step 2 is reacted with an acid to form a salt, thereby obtaining the energetic ion salt with a polyaminotriazole skeleton.

[0013] Furthermore, in the above-mentioned method for preparing the energetic ion salt with polyaminotriazole as the skeleton, the acid is at least one of a hydrochloric acid aqueous solution, a nitric acid aqueous solution and a perchloric acid aqueous solution.

[0014] Furthermore, in the above-mentioned method for preparing the energetic ion salt with polyaminotriazole as the skeleton, the concentration of the hydrochloric acid aqueous solution is 1 mol / L, the concentration of the nitric acid aqueous solution is 1 mol / L, and the concentration of the perchloric acid aqueous solution is 1 mol / L.

[0015] Compared with the prior art, the present invention has the following beneficial effects: First, the present invention forms intermolecular / intramolecular hydrogen bonds by constructing amino groups, thereby reducing sensitivity, increasing nitrogen content and improving thermal stability. After measurement and calculation, the density of the neutral compound 6-(5-nitro-1H-pyrazol-3-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diamine is 1.798 g·cm -1 , the decomposition temperature is 302℃, and the formation enthalpy is 663.89 kJ·mol -1 , the explosion speed is 8091m·s -1 , with an explosion pressure of 24.06 GPa, it is a high-energy density explosive with extremely high potential.

[0016] Second, the present invention prepares a series of energetic ion salts, which have a high density of 1.65-1.84 g·cm -1 The formation enthalpy is between 515.11-828.49 kJ·mol -1 , is a good high energy density explosive.

[0017] Third, the preparation method provided by the present invention is safe and reasonable, has mild reaction conditions, high yield, low production cost, basically no three wastes, and is environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1is the crystal structure diagram of compound 4 of the present invention; Figure 2 is the crystal structure diagram of compound 5 of the present invention; Figure 3 is the crystal structure diagram of compound 6 of the present invention; Figure 4 is the infrared image of compound 2 of the present invention; As shown in the figure, 3335.11 cm -1 , 3283.76 cm -1 , 3187.68 cm -1 It is the NH stretching vibration of the amino and hydrazine groups in compound 2 and the unsaturated CH stretching vibration of the pyrazole; 1563.58 cm -1 , 1357.77 cm -1 It is the stretching vibration of the nitro group on pyrazole.

[0019] Figure 5 is the infrared image of compound 3 of the present invention; As shown in the figure, 3336.29 cm -1 , 3286.43 cm -1 , 3188.71 cm -1 It is the NH stretching vibration of the amino group in 3 and the unsaturated CH stretching vibration of the pyrazole; 1503.33 cm -1 , 1357.22 cm -1 It is the stretching vibration of the nitro group on pyrazole.

[0020] Figure 6 is the infrared image of compound 4 of the present invention; As shown in the figure, 3322.33 cm -1 , 3244.93 cm -1 , 3159.92 cm -1 It is the NH stretching vibration of the amino group in compound 4 and the unsaturated CH stretching vibration of the pyrazole; 1530.71 cm -1 , 1375.42 cm -1 , 1329.72 cm -1 It is the stretching vibration of the nitro group on pyrazole.

[0021] Figure 7 is the infrared image of compound 5 of the present invention; As shown in the figure, 3260.04 cm -1 , 3215.01 cm -1 , 3177.43 cm -1 is the NH stretching vibration of the amino group in compound 5; 1532.56 cm-1 , 1359.28 cm -1 , is the stretching vibration of pyrazole and the nitro group on the nitrate group.

[0022] Figure 8 is the infrared image of compound 6 of the present invention; As shown in the figure, 3635.64 cm -1 , 1638.27 cm -1 is the OH stretching and bending vibration of the residual solvent water in compound 6; 3337.33 cm -1 , 3245.90 cm -1 , 3131.89 cm -1 It is the NH stretching vibration of the amino group in 2; 1555.16 cm -1 , 1367.80 cm -1 , is the stretching vibration of the nitro group on pyrazole.

[0023] Fig. 9 It is the DSC chart of compound 3 of the present invention; As shown in the figure, the initial decomposition temperature of compound 3 is 302.8℃ Fig.10 is the DSC diagram of compound 4 of the present invention; As shown in the figure, the initial decomposition temperature of compound 4 is 260.6℃ Fig.11 is the DSC diagram of compound 5 of the present invention; As shown in the figure, the initial decomposition temperature of compound 5 is 220.0℃ Fig.12 It is the DSC chart of compound 6 of the present invention.

[0024] As shown in the figure, the initial decomposition temperature of compound 6 is 231.6℃ DETAILED DESCRIPTION

[0025] The present invention is further described in detail below in conjunction with embodiments.

[0026] Those skilled in the art will appreciate that the following examples are only used to illustrate the present invention and should not be considered to limit the scope of the present invention. If no specific techniques or conditions are specified in the examples, they are carried out according to the techniques or conditions described in the literature in this area or according to the product instructions. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased.

[0027] The general synthesis route of the energetic compound and energetic ion salt of the present invention is as follows:

[0028] .

[0029] Example 1

[0030] Preparation of compound 2: Phosphorus pentoxide (20.0 g, 0.15 mol) was added to an aqueous solution of orthophosphoric acid (85 wt%, 70.0 g, 0.60 mol), and then heated to 50 °C with stirring. A well-stirred mixture of 5-nitro-1H-pyrazole-3-carboxylic acid (compound 1) (7.85 g, 50.0 mmol) and triaminoguanidine monohydrochloride TAG (9.17 g, 65 mmol) was added to the above solution. The mixture was heated to 120 °C and continued to be heated at this temperature for 8-16 h. The mixture was then cooled to room temperature and poured into ice water (200 mL). The pH of the mixture was adjusted to neutral using sodium hydroxide solution. During the reaction, a large amount of precipitate was precipitated. The precipitate was filtered and dried to obtain 3-hydrazino-5-(5-nitro-1H-pyrazol-3-yl)-4H-1,2,4-triazole-4-amine (Compound 2) with a yield of 6.1660 g and a yield rate of 54.8%.

[0031] .

[0032] Example 2

[0033] Preparation of compound 3: Compound 2 (2.25 g, 10.0 mmol) was dissolved in dilute hydrochloric acid (25 mL, 2 M), and then cyanogen bromide (2.12 g, 20.0 mmol) was added. The solution was heated at 60 °C with stirring for 2 h, refluxed for 3 h, and then cooled in a refrigerator for 3 h to form a light yellow precipitate, which was collected by filtration. The light yellow solid was dissolved in distilled water (15 mL), and sodium bicarbonate was added to adjust the pH to neutral. The precipitate was filtered, washed, and air-dried to obtain 6-(5-nitro-1H-pyrazol-3-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diamine (compound 3), with a yield of 1.7125 g and a yield of 68.5%. Its density was measured by Ultrapyc 5000 Micro true density meter (manufacturer: Anton Paar Technology Co., Ltd.) and was 1.798 g cm -1 The decomposition temperature of the compound is 302°C as measured by DSC, and the formation enthalpy is 663.89 kJ·mol -1 , the explosion speed is 8091m·s -1 , the explosion pressure is 24.06GPa.

[0034] .

[0035] Example 3 ;

[0036] Preparation of compound 4: In 10 ml of deionized water, compound 3 and 1 equivalent of 1 mol / L hydrochloric acid solution were added to deionized water in sequence, heated to 70°C, and reacted for 30 minutes. After the reaction, the solution was dried by spin drying to obtain compound 4. Its structure is shown in Figure 1 The density of the sample was measured by Ultrapyc 5000 Micro true density meter (manufacturer: Anton Paar Technology Co., Ltd.) and was found to be 1.655 g·cm -1 The decomposition temperature of the compound is 260°C as measured by DSC, and the formation enthalpy is 515.11 kJ·mol -1 , the explosion speed is 6831m·s -1 , the explosion pressure is 16.79GPa.

[0037] Preparation of compound 5: In 10 ml of deionized water, compound 3 and 1 equivalent of 1 mol / L nitric acid solution were added to deionized water in sequence, heated to 70°C, reacted for 30 minutes, and after the reaction was completed, the solution was spin-dried to obtain compound 5. Its structure is shown in Figure 2 The density of the sample was measured by Ultrapyc 5000 Micro true density meter (manufacturer: Anton Paar Technology Co., Ltd.) and was 1.739 g·cm -1 The decomposition temperature of the compound is 220°C as measured by DSC, and the formation enthalpy is 511.65 kJ·mol -1 , the explosion speed is 8051m·s -1 , the explosion pressure is 25.33GPa.

[0038] Preparation of compound 6: In 10 ml of deionized water, compound 3 and 1 equivalent of 1 mol / L perchloric acid solution were added to deionized water in sequence, heated to 70°C, and reacted for 30 minutes. After the reaction, the solution was dried by spin drying to obtain compound 6. Its structure is shown in Figure 3 The density of the sample was measured by Ultrapyc 5000 Micro true density meter (manufacturer: Anton Paar Technology Co., Ltd.) and was found to be 1.842 g·cm -1 The decomposition temperature of the compound is 231°C as measured by DSC, and the formation enthalpy is 828.49 kJ·mol -1 , the explosion speed is 8522m·s -1 , the explosion pressure is 31.54GPa.

[0039] The above embodiments describe the implementation methods of the present invention in detail, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in the field without departing from the purpose of the present invention. The above description is only a preferred feasible embodiment of the present invention, and does not limit the scope of rights of the present invention. All equivalent structural changes made by using the contents of the present invention specification are included in the scope of rights of the present invention.

Claims

1. An energetic compound with a polyaminotriazole skeleton, characterized in that: Its structural formula is as follows: 。 2. An energetic ion salt with a polyaminotriazole skeleton, characterized in that: Its general structure is as follows: 。 3. The method for preparing an energetic compound with a polyaminotriazole skeleton as claimed in claim 1, characterized in that: The steps include: Step 1: Mix 5-nitro-1H-pyrazole-3-carboxylic acid and triaminoguanidine monohydrochloride, add them into a system of orthophosphoric acid and phosphorus pentoxide to react, and prepare 3-hydrazino-5-(5-nitro-1H-pyrazol-3-yl)-4H-1,2,4-triazole-4-amine; Step 2, dissolving the 3-hydrazino-5-(5-nitro-1H-pyrazol-3-yl)-4H-1,2,4-triazole-4-amine obtained in step 1 in dilute hydrochloric acid, adding cyanogen bromide, and reacting at a certain temperature to obtain 6-(5-nitro-1H-pyrazol-3-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diamine.

4. The method for preparing an energetic compound with a polyaminotriazole skeleton according to claim 3, characterized in that: In step 1, the molar ratio of 5-nitro-1H-pyrazole-3-carboxylic acid to triaminoguanidine monohydrochloride is 1:0.8-2, the reaction temperature is 120° C.-130° C., and the reaction time is 8-16 h.

5. The method for preparing an energetic compound with a polyaminotriazole skeleton according to claim 4, characterized in that: After the reaction in step 1 is completed, the pH of the reaction mixture is adjusted to neutral.

6. The method for preparing an energetic compound with a polyaminotriazole skeleton according to claim 3, characterized in that: In step 2, the molar ratio of 3-hydrazino-5-(5-nitro-1H-pyrazol-3-yl)-4H-1,2,4-triazole-4-amine to cyanogen bromide is 1:1-1:2, the reaction temperature is 55-65° C., and the reaction time is 2-6 hours.

7. The method for preparing an energetic compound with a polyaminotriazole skeleton according to claim 3, characterized in that: After the reaction in step 2 is completed, the precipitate is collected by filtration, dissolved in water, the pH is adjusted to neutral, the precipitate is filtered, washed and dried to obtain the 6-(5-nitro-1H-pyrazol-3-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diamine.

8. The method for preparing the energetic ion salt with polyaminotriazole as the skeleton as claimed in claim 2, characterized in that: The steps include: Step 1: Mix 5-nitro-1H-pyrazole-3-carboxylic acid and triaminoguanidine monohydrochloride, add them into a system of orthophosphoric acid and phosphorus pentoxide to react, and prepare 3-hydrazino-5-(5-nitro-1H-pyrazol-3-yl)-4H-1,2,4-triazole-4-amine; Step 2, dissolving the 3-hydrazino-5-(5-nitro-1H-pyrazol-3-yl)-4H-1,2,4-triazole-4-amine obtained in step 1 in dilute hydrochloric acid, adding cyanogen bromide, and reacting at a certain temperature to obtain 6-(5-nitro-1H-pyrazol-3-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diamine; Step 3: The 6-(5-nitro-1H-pyrazol-3-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diamine obtained in step 2 is reacted with an acid to form a salt, thereby obtaining the energetic ion salt with a polyaminotriazole skeleton.

9. The method for preparing an energetic ion salt with a polyaminotriazole skeleton according to claim 8, characterized in that: The acid is at least one of a hydrochloric acid aqueous solution, a nitric acid aqueous solution and a perchloric acid aqueous solution.

10. The method for preparing the energetic ion salt with polyaminotriazole as the skeleton according to claim 9, characterized in that: The concentration of the hydrochloric acid aqueous solution is 1 mol / L, the concentration of the nitric acid aqueous solution is 1 mol / L, and the concentration of the perchloric acid aqueous solution is 1 mol / L.

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