Condensed ring type high-heat-resistance explosive and preparation method thereof

Abstract

The invention discloses a fused ring high-heat-resistance explosive and a preparation method thereof, the high-heat-resistance explosive is prepared by a one-pot method, and the fused ring high-heat-resistance explosive has the characteristics of one-step reaction, simple operation, mild conditions and high yield. The room temperature single crystal density of the TNBTP is 1.771 g / cm < 3 >, the TNBTP is insoluble in water and most common solvents, the initial thermal decomposition temperature is up to 388 DEG C, the thermal decomposition peak temperature is 397 DEG C, the actually measured impact sensitivity is 15J, and the friction sensitivity is 360N. The detonation velocity is calculated to be 7745 m / s, the detonation pressure is calculated to be 24.0 GPa, and the detonation velocity is tested to be 7617 m / s and the detonation pressure is tested to be 27.0 GPa by using a small-dose laser ablation method. The invention shows that the TNBTP has higher energy level and safety while having high heat resistance, the comprehensive performance of the TNBTP is superior to that of a typical heat-resistant explosive PYX, and the TNBTP is a high-heat-resistant explosive with great potential.

Description

Technical Field

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

[0002] As the core energy material of national defense weapon systems and civilian blasting equipment, the energy level, safety and thermal stability of explosives are key indicators for evaluating their performance in various aspects such as storage, transportation, assembly, use and execution of functions. In this field, high-heat-resistant explosives - those with a thermal decomposition temperature usually above 350°C - have attracted much attention due to their excellent thermal stability.

[0003] With the rapid development of industries such as defense industry, 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 are difficult to meet 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 process limits their wide application. Therefore, the development of new high heat-resistant explosive materials to meet the ever-changing use needs is of great significance in the fields of national defense, military industry and civilian blasting. Summary of the invention

[0004] The purpose of the present invention is to provide a linked condensed 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" and has 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 fused ring high heat resistant explosive, the high heat resistant explosive compound 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazole[1,5-a]pyridine (TNBTP) has the structural formula:

[0007]

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

[0009]

[0010] The above-mentioned method for preparing a fused-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, adding the ionic salt of 5,5'-bitetrazole to a solvent, adding a catalyst, adding 2-chloro-3,5-dinitropyridine, slowly raising the reaction temperature after the addition, stirring the reaction for 0.5 to 24 hours, and then stopping the heating; after the system temperature returns to room temperature, filtering, washing, and drying in sequence to obtain a crude compound TNBTP;

[0013] Method B, adding 5,5'-bitetrazole to a solvent, adding a base, adding a catalyst, adding 2-chloro-3,5-dinitropyridine, slowly raising the reaction temperature after the addition, stirring the reaction for 0.5 to 24 hours, and then stopping the heating; after the system temperature returns to room temperature, filtering, washing, and drying 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) is added into water and stirred at room temperature for 2 hours or heated and stirred for 1 hour; after the system temperature is cooled to room temperature, it is 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.

[0016] A further solution is that in step 1, the reaction temperature is room temperature to 130° C.; in step 2, the volumetric amount of water used and the mass ratio of the crude TNBTP product fed are (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 volumetric amount of the solvent in step 1 and the mass ratio of the 2-chloro-3,5-dinitropyridine feed are (2-20) mL: 1 g.

[0018] In a further embodiment, the ionic salt of 5,5'-bitetrazole 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.

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

[0022] Another aspect of the present invention also 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 invention discloses a fused ring high heat resistant explosive (6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazole[1,5-a]pyridine) and a preparation method thereof. The preparation of the high heat resistant explosive adopts a "one-pot method" and has the characteristics of one-step reaction, simple operation, mild conditions and high yield. The characteristics of TNBTP are as follows:

[0025] The room temperature single crystal density 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 explosion velocity is 7745 m / s, and the calculated explosion pressure is 24.0 GPa.

[0030] The explosion velocity and explosion pressure obtained by using small-charge laser ablation method are 7617 m / s and 27.0 GPa respectively.

[0031] In summary, TNBTP has high heat resistance, high energy level and safety, and its comprehensive performance is better than that of typical heat-resistant explosive PYX, and it is a high heat-resistant explosive with great potential. The TNBTP of the present invention and its preparation method provide a new type of highly efficient high heat-resistant explosive material for the national defense military industry and civilian blasting fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. 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 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 is the compound TNBTP of the present invention 1 H NMR (in D 2 SO 4 );

[0036] Figure 4 is the compound TNBTP of the present invention 13 C NMR (in D 2 SO 4 ). DETAILED DESCRIPTION

[0037] To make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention.

[0038] Example 1

[0039] At room temperature, add the diammonium salt of 5,5'-biquatrazolium to tetrahydrofuran, then add 2 equivalents of 4-dimethylaminopyridine (DMAP), and then add 2 equivalents of 2-chloro-3,5-dinitropyridine. After the addition is complete, slowly raise the reaction temperature to 65°C, reflux, stir and react for 24 hours, then stop heating. After the system temperature cools to room temperature, filter, wash with a small amount of water and ethanol in turn, and dry to obtain 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazole[1,5-a]pyridine (TNBTP) crude powder. Then add the crude product to water, heat to 50°C and stir for 1 hour, filter, wash with water and ethanol in turn, and dry to obtain 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazole[1,5-a]pyridine (TNBTP) powder. (The yield is about 40%)

[0040] Example 2

[0041] At room temperature, add the diammonium salt of 5,5'-biquatrazolium to dioxane, then add 2 equivalents of 18 crown 6, and then add 2 equivalents of 2-chloro-3,5-dinitropyridine. After the addition is complete, slowly raise the reaction temperature to 105°C, reflux, stir and react for 8 hours, then stop heating. After the system temperature cools to room temperature, filter, wash with a small amount of water and ethanol in turn, and dry to obtain 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazole[1,5-a]pyridine (TNBTP) crude powder. Subsequently, add the crude product to water, heat to 50°C and stir for 1 hour, filter, wash with water and ethanol in turn, and dry to obtain 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazole[1,5-a]pyridine (TNBTP) powder. (The yield is about 58%)

[0042] Example 3

[0043] At room temperature, add 5,5'-biquatrazol to acetonitrile, then add 2 equivalents of potassium hydroxide, then add 2 equivalents of 4-dimethylaminopyridine (DMAP), and then add 2 equivalents of 2-chloro-3,5-dinitropyridine. After the addition is complete, slowly raise the reaction temperature to 80°C, reflux, stir and react for 24 hours, then stop heating. After the system temperature cools to room temperature, filter, wash with a small amount of water and ethanol in turn, and dry to obtain 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazole[1,5-a]pyridine (TNBTP) crude powder. Then add the crude product to water, stir at room temperature for 2 hours, filter, wash with water and ethanol in turn, and dry to obtain 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazole[1,5-a]pyridine (TNBTP) powder. (The yield is about 51%)

[0044] The analytical test results of the above compounds are as follows ( Figure 2-4 ):

[0045] DSC(T onset :388℃, T p :397℃); 1 H NMR (400 MHz, D 2 SO 4 , 25℃) δ (ppm): 10.89 (CH, 2H), 10.35 (CH, 2H); 13 C NMR (100 MHz, D 2 SO 4 , 25℃) δ (ppm): 148.51, 143.09, 141.01, 136.58, 134.12, 131.73; HRMS (C 12 H 3 N 10 O 8 - ·CH 3 OH): theoretical 447.0404, measured 447.0385.

[0046] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can easily think of changes or replacements within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims. It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further explain various possible combinations. In addition, the various different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A fused-ring high heat-resistant explosive and a preparation method thereof, characterized in that: The structural formula of the highly heat-resistant explosive compound 6,6',8,8'-tetranitro-2,2'-bis[1,2,4]triazole[1,5-a]pyridine (TNBTP) is:

2. A fused-ring high heat resistant explosive as claimed in claim 1, characterized in that: The preparation process is as follows:

3. A method for preparing a linked condensed ring high heat resistant explosive as claimed in any one of claims 1 or 2, characterized in that: 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, adding the ionic salt of 5,5'-bitetrazole to a solvent, adding a catalyst, adding 2-chloro-3,5-dinitropyridine, slowly raising the reaction temperature after the addition, stirring the reaction for 0.5 to 24 hours, and then stopping the heating; after the system temperature returns to room temperature, filtering, washing, and drying in sequence to obtain a crude compound TNBTP; Method B, adding 5,5'-bitetrazole to a solvent, adding a base, adding a catalyst, adding 2-chloro-3,5-dinitropyridine, slowly raising the reaction temperature after the addition, stirring the reaction for 0.5 to 24 hours, and then stopping the heating; after the system temperature returns to room temperature, filtering, washing, and drying 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) is added into water and stirred at room temperature for 2 hours or heated and stirred for 1 hour; after the system temperature is cooled to room temperature, it is 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, characterized in that: In the step 1, the reaction temperature is room temperature to 130° C.; in the step 2, the volumetric amount of water used and the mass ratio of the crude TNBTP product fed are (2 to 100) mL: 1 g.

5. The method for preparing a linked condensed ring high heat resistant explosive according to claim 3, characterized in 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; the volumetric amount of the solvent in step 1 and the mass ratio of the 2-chloro-3,5-dinitropyridine feed are (2-20) mL: 1 g.

6. The method for preparing a linked condensed ring high heat resistant explosive according to claim 3, characterized in that: The ionic salt of 5,5'-bitetrazole 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, characterized in 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.

8. The method for preparing a linked condensed ring high heat resistant explosive according to claim 3, characterized in that: 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).

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

10. Use of the linked condensed ring type high heat resistant explosive as claimed in any one of claims 1 to 2 or the linked condensed ring type high heat resistant explosive obtained by the preparation method as claimed in claims 3 to 9.

Images