A fused ring high heat-resistant explosive and a preparation method thereof

Abstract

The application discloses a kind of high heat-resisting explosive of condensed ring and preparation method thereof, the preparation of the high heat-resisting explosive uses "one pot method", with the characteristics of one-step reaction, simple operation, mild condition, high yield.6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazole[1,5-a]pyridine (TNBTP) room temperature single crystal density is 1.771g / cm 3 , insoluble in water and most common solvents, initial thermal decomposition temperature is as high as 388℃, thermal decomposition peak temperature is 397℃, actual impact sensitivity is 15J, friction sensitivity is 360N. Calculated detonation velocity is 7745m / s, calculated detonation pressure is 24.0GPa, detonation velocity is 7617m / s and detonation pressure is 27.0GPa using small amount of laser ablation method. It shows that TNBTP has high heat resistance, high energy level and safety, and the comprehensive performance is better than typical heat-resistant explosive PYX, which is a high heat-resistant explosive with great potential.

Description

Technical Field

[0001] The present invention relates to the technical field of energetic materials, in particular to a linked condensed ring high heat-resistant explosive and a preparation method thereof. Background Art

[0002] Explosives are core energy materials used in defense weapon systems and civilian blasting equipment. Their energy level, safety, and thermal stability are key indicators for evaluating their performance in various stages, including storage, transportation, assembly, use, and functional execution. Within this field, high-heat explosives—those with a thermal decomposition temperature typically exceeding 350°C—are attracting significant attention due to their exceptional thermal stability.

[0003] With the rapid development of industries such as defense, aerospace, and energy mining, as well as the continuous advancement of technology, the requirements for the heat resistance of explosives are also increasing. At present, although traditional explosives such as RDX and HMX are widely used, they do not have high heat resistance and cannot meet the more demanding application environments. On the other hand, although high-heat-resistant explosives such as TACOT and PYX have shown good heat resistance, their complex preparation processes limit their widespread application. Therefore, the development of new high-heat-resistant explosive materials to meet the ever-changing application needs is of great significance in both the defense and military industries and the civilian blasting fields. Summary of the Invention

[0004] The purpose of the present invention is to provide a linked fused ring high heat-resistant explosive and a preparation method thereof in order to solve the above problems. The preparation of the high heat-resistant explosive adopts a "one-pot method" with the characteristics of one-step reaction, simple operation, mild conditions and high yield, and can efficiently prepare 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazolo[1,5-a]pyridine (TNBTP).

[0005] The present invention achieves the above-mentioned purpose through the following technical solutions:

[0006] A high-heat-resistant explosive of the fused-ring type, wherein the structural formula of the high-heat-resistant explosive compound 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazolo[1,5-a]pyridine (TNBTP) is:

[0007]

[0008] A further solution is that the preparation process is as follows:

[0009]

[0010] The method for preparing the above-mentioned linked condensed ring high heat-resistant explosive comprises the following steps:

[0011] Step 1: Synthesis of compound 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazolo[1,5-a]pyridine (TNBTP):

[0012] Method A: Add the ionic salt of 5,5'-bitetrazole to a solvent, add a catalyst, and add 2-chloro-3,5-dinitropyridine. After the addition is complete, slowly increase the reaction temperature and stir the reaction for 0.5 to 24 hours. Then stop heating. After the system temperature returns to room temperature, filter, wash, and dry in sequence to obtain a crude compound TNBTP.

[0013] Method B: Add 5,5'-bitetrazole to a solvent, add a base, add a catalyst, and add 2-chloro-3,5-dinitropyridine. After the addition is complete, slowly increase the reaction temperature and stir the reaction for 0.5 to 24 hours. Then stop heating. After the system temperature returns to room temperature, filter, wash, and dry in sequence to obtain a crude product.

[0014] Step 2, purification of 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazolo[1,5-a]pyridine (TNBTP):

[0015] The crude product of 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazolo[1,5-a]pyridine (TNBTP) was added to water and stirred at room temperature for 2 hours or heated and stirred for 1 hour. After the system temperature was cooled to room temperature, it was filtered, washed, and dried in sequence to obtain an orange-yellow 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazolo[1,5-a]pyridine (TNBTP) powder.

[0016] A further solution is that in step 1, the reaction temperature is room temperature to 130° C.; in step 2, the volume ratio of water to the feed mass of crude TNBTP is (2 to 100) mL: 1 g.

[0017] A further scheme is that the solvent in step 1 is selected from one or more of water, methanol, ethanol, isopropanol, ethylene glycol, DMF, DMSO, THF, acetonitrile, dichloromethane, chloroform, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycerol, acetone, triethanolamine, pyridine, benzene, toluene, and xylene; and the volume ratio of the solvent used in step 1 to the mass ratio of the 2-chloro-3,5-dinitropyridine feed is (2-20) mL: 1 g.

[0018] In a further embodiment, the ionic salt of 5,5'-tetrazole in method A in step 1 includes one or more of ammonium salts, hydrazine salts, hydroxylamine salts, guanidine salts, aminoguanidine salts, triethylamine salts, methylamine salts, dimethylamine salts, trimethylamine salts, lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, and manganese salts.

[0019] A further embodiment is that the base in method B in step 1 includes an organic base, one or more of an alkali metal hydroxide, carbonate, and bicarbonate; the organic base includes ammonia water, hydrazine hydrate, hydroxylamine, guanidine, aminoguanidine, triethylamine, methylamine, dimethylamine, or trimethylamine.

[0020] In a further embodiment, the catalyst in step 1 is a nucleophilic catalyst, including one or more of betaine, crown ether compounds such as 18-crown 6, and 4-dimethylaminopyridine (DMAP).

[0021] A further scheme is that in the method A of step 1, the ratio of the amount of the ionic salt of 5,5'-tetrazole, the catalyst, and 2-chloro-3,5-dinitropyridine is 1:(1-3):(2-3); in the method B of step 1, the ratio of the amount of the 5,5'-tetrazole, the base, the catalyst, and 2-chloro-3,5-dinitropyridine is 1:1:(1-3):(2-3).

[0022] Another aspect of the present invention further provides the use of the above-mentioned linked condensed ring type high heat resistant explosive or the linked condensed ring type high heat resistant explosive obtained by the above-mentioned preparation method.

[0023] The beneficial effects of the present invention are:

[0024] The present invention discloses a high-heat-resistant fused-ring explosive (6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazolo[1,5-a]pyridine) and a preparation method thereof. The high-heat-resistant explosive is prepared using a one-pot process, characterized by a one-step reaction, simple operation, mild conditions, and high yield. The characteristics of TNBTP are as follows:

[0025] The single crystal density at room temperature is 1.771g / cm3. It is insoluble in water and most common solvents and has excellent chemical stability.

[0026] The initial thermal decomposition temperature is as high as 388 °C, and the thermal decomposition peak temperature is 397 °C, indicating that it has high heat resistance.

[0027] The measured impact sensitivity is 15J and the friction sensitivity is 360N. These indicators show that TNBTP has relatively high safety while maintaining high heat resistance.

[0028] The detonation performance of TNBTP is as follows:

[0029] The calculated detonation velocity is 7745 m / s, and the calculated detonation pressure is 24.0 GPa.

[0030] The detonation velocity obtained by using the small-charge laser ablation method is 7617m / s and the detonation pressure is 27.0GPa.

[0031] In summary, TNBTP not only possesses high heat resistance, but also possesses high energy levels and safety, with overall performance superior to the typical heat-resistant explosive PYX, making it a highly promising high-heat-resistant explosive. The TNBTP of the present invention and its preparation method provide a new, highly efficient, high-heat-resistant explosive material for both national defense, military, and civilian blasting applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the practical drawings required in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0033] Figure 1 The crystal structure of 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazolo[1,5-a]pyridine (TNBTP) of the present invention;

[0034] Figure 2 This is the DSC chart of 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazolo[1,5-a]pyridine (TNBTP) of the present invention.

[0035] Figure 3 The compound TNBTP of the present invention 1 H NMR (in D2SO4);

[0036] Figure 4 The compound TNBTP of the present invention 13 C NMR (in D2SO4). DETAILED DESCRIPTION

[0037] To make the objectives, technical solutions, and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other implementations obtained by those of ordinary skill in the art without inventive effort are within the scope of protection of the present invention.

[0038] Example 1

[0039] The di-ammonium salt of 5,5'-diazotetrazole was added to tetrahydrofuran at room temperature, followed by the addition of 2 equivalents of 4-dimethylaminopyridine (DMAP), then 2 equivalents of 2-chloro-3,5-dinitropyridine. After the addition was complete, the reaction temperature was slowly increased to 65°C and the reaction was stirred at reflux for 24 hours. The heating was then stopped. After the temperature of the system had cooled to room temperature, the product was filtered, washed with small amounts of water and ethanol, and dried to obtain a crude powder of 6,6',8,8'-tetranitro-2,2'-bis[l,2,4]triazolo[l,5-a]pyridine (TNBTP). The crude product was then added to water and stirred at 50°C for 1 hour. The product was filtered, washed with water and ethanol, and dried to obtain a powder of 6,6',8,8'-tetranitro-2,2'-bis[l,2,4]triazolo[l,5-a]pyridine (TNBTP). (Yield of approximately 40%).

[0040] Example 2

[0041] The di-ammonium salt of 5,5'-diazotetrazole was added to tetrahydrofuran at room temperature, followed by the addition of 2 equivalents of 4-dimethylaminopyridine (DMAP), then 2 equivalents of 2-chloro-3,5-dinitropyridine. After the addition was complete, the reaction temperature was slowly increased to 65°C and the reaction was stirred at reflux for 24 hours. The heating was then stopped. After the temperature of the system had cooled to room temperature, the product was filtered, washed with small amounts of water and ethanol, and dried to obtain a crude powder of 6,6',8,8'-tetranitro-2,2'-bis[l,2,4]triazolo[l,5-a]pyridine (TNBTP). The crude product was then added to water and stirred at 50°C for 1 hour. The product was filtered, washed with water and ethanol, and dried to obtain a powder of 6,6',8,8'-tetranitro-2,2'-bis[l,2,4]triazolo[l,5-a]pyridine (TNBTP). (Yield of approximately 40%).

[0042] Example 3

[0043] The di-ammonium salt of 5,5'-diazotetrazole was added to tetrahydrofuran at room temperature, followed by the addition of 2 equivalents of 4-dimethylaminopyridine (DMAP), then 2 equivalents of 2-chloro-3,5-dinitropyridine. After the addition was complete, the reaction temperature was slowly increased to 65°C and the reaction was stirred at reflux for 24 hours. The heating was then stopped. After the temperature of the system had cooled to room temperature, the product was filtered, washed with small amounts of water and ethanol, and dried to obtain a crude powder of 6,6',8,8'-tetranitro-2,2'-bis[l,2,4]triazolo[l,5-a]pyridine (TNBTP). The crude product was then added to water and stirred at 50°C for 1 hour. The product was filtered, washed with water and ethanol, and dried to obtain a powder of 6,6',8,8'-tetranitro-2,2'-bis[l,2,4]triazolo[l,5-a]pyridine (TNBTP). (Yield of approximately 40%).

[0044] The results of the analytical tests on the above compound are as follows: Figure 2-4

[0045] DSC(T onset :388℃, T p :397℃); 1 H NMR (400 MHz, D2SO4, 25℃) δ (ppm): 10.89 (C-H, 2H), 10.35 (C-H, 2H); 13 C NMR (100 MHz, D2SO4, 25℃) δ (ppm): 148.51, 143.09, 141.01, 136.58, 134.12, 131.73; HRMS (C 12 H3N 10 O8 - ·CH3OH): Theoretical 447.0404, Found 447.0385.

[0046] The above merely describes the specific embodiments of the present application, but the protection scope of the present application is not limited thereto, any skilled person in the art can easily think of the changes or replacements within the technical range disclosed by the present application, which should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims. In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction, in order to avoid unnecessary repetition, the present application will not further describe various possible combination manners. Furthermore, the various different embodiments of the present application can also be combined in any manner, as long as it does not deviate from the idea of the present application, it should also be considered as the disclosed content of the present application.​

Claims

1. A high heat resistant explosive of the fused ring type, characterized in that: The structural formula of the high heat-resistant explosive compound 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazolo[1,5-a]pyridine (TNBTP) is: 。 2. A method for preparing a linked condensed ring high heat resistant explosive, characterized in that: The preparation process is as follows: 。 3. The method for preparing a linked condensed ring high heat resistant explosive according to claim 2, wherein: The following steps are involved: Step 1: Synthesis of compound 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazolo[1,5-a]pyridine (TNBTP): Method A: Add the ionic salt of 5,5'-bitetrazole to a solvent, add a catalyst, and add 2-chloro-3,5-dinitropyridine. After the addition is complete, slowly increase the reaction temperature and stir the reaction for 0.5 to 24 hours. Then stop heating. After the system temperature returns to room temperature, filter, wash, and dry in sequence to obtain a crude compound TNBTP. Method B: Add 5,5'-bitetrazole to a solvent, add a base, add a catalyst, and add 2-chloro-3,5-dinitropyridine. After the addition is complete, slowly increase the reaction temperature and stir the reaction for 0.5 to 24 hours. Then stop heating. After the system temperature returns to room temperature, filter, wash, and dry in sequence to obtain a crude product. Step 2: Purification of 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazolo[1,5-a]pyridine (TNBTP): The crude product of 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazolo[1,5-a]pyridine (TNBTP) was added to water and stirred at room temperature for 2 hours or heated and stirred for 1 hour. After the system temperature was cooled to room temperature, it was filtered, washed, and dried in sequence to obtain orange-yellow 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazolo[1,5-a]pyridine (TNBTP) powder.

4. The method for preparing a linked condensed ring high heat resistant explosive according to claim 3, wherein: In the step 1, the reaction temperature is room temperature to 130° C.; in the step 2, the volume ratio of water to the crude TNBTP is (2 to 100) mL: 1 g.

5. The method for preparing a linked condensed ring high heat resistant explosive according to claim 3, wherein: The solvent in step 1 is selected from one or more of water, methanol, ethanol, isopropanol, ethylene glycol, DMF, DMSO, THF, acetonitrile, dichloromethane, chloroform, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycerol, acetone, triethanolamine, pyridine, benzene, toluene, and xylene; and the volume ratio of the solvent used in step 1 to the mass ratio of the 2-chloro-3,5-dinitropyridine feed is (2-20) mL: 1 g.

6. The method for preparing a linked condensed ring high heat resistant explosive according to claim 3, wherein: The ionic salt of 5,5'-tetrazole in method A in step 1 includes one or more of ammonium salt, hydrazine salt, hydroxylamine salt, guanidine salt, aminoguanidine salt, triethylamine salt, methylamine salt, dimethylamine salt, trimethylamine salt, lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt, magnesium salt, and manganese salt.

7. The method for preparing a linked condensed ring high heat resistant explosive according to claim 3, wherein: The base in method B in step 1 includes an organic base, one or more of an alkali metal hydroxide, carbonate, and bicarbonate; the organic base includes ammonia water, hydrazine hydrate, hydroxylamine, guanidine, aminoguanidine, triethylamine, methylamine, dimethylamine, or trimethylamine.

8. The method for preparing a linked condensed ring high heat resistant explosive according to claim 3, wherein: The catalyst in step 1 is a nucleophilic catalyst selected from one or more of betaine, a crown ether compound of 18-crown-6, and 4-dimethylaminopyridine (DMAP).

9. The method for preparing a linked condensed ring high heat resistant explosive according to claim 3, wherein: In the method A of step 1, the molar ratio of the ionic salt of 5,5'-tetrazole, the catalyst, and 2-chloro-3,5-dinitropyridine is 1:(1-3):(2-3); in the method B of step 1, the molar ratio of 5,5'-tetrazole, the base, the catalyst, and 2-chloro-3,5-dinitropyridine is 1:1:(1-3):(2-3).

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