Bipyrazole-based heat-resistant explosive and perchlorate and synthesis method thereof

Abstract

The invention discloses a bipyrazole-based heat-resistant explosive as well as perchlorate and a synthesis method of the bipyrazole-based heat-resistant explosive. The preparation method comprises the following steps: (1) carrying out oxidation reaction on 5, 5 '-dimethyl-4, 4'-dinitro-2H, 2 'H-3, 3'-bipyrazole under the action of potassium hydroxide and potassium permanganate; and (2) carrying out cyclization reaction on the reaction product in the step (1) and diaminoguanidine hydrochloride in a polyphosphoric acid system to obtain the target product heat-resistant explosive, and (3) carrying out acid-base neutralization reaction on the heat-resistant explosive to generate related energetic ionic salt. The heat-resistant explosive and the energetic ionic salt synthesized in the invention have excellent thermal stability and detonation performance, and have application prospects in the field of heat-resistant explosives. The synthesis process is simple and convenient, no by-product is generated, the target product with high purity can be obtained without purification, and industrial production can be carried out.

Description

Technical Field

[0001] The invention relates to a bipyrazole-based heat-resistant explosive, belonging to the field of organic energetic materials. Background Art

[0002] With the development of aerospace industry and the exploitation of underground resources such as oil and natural gas, there is a demand for an explosive that is resistant to high pressure (or low pressure) and high temperature, referred to as heat-resistant explosive. Heat-resistant explosive refers to a type of explosive that can maintain appropriate mechanical sensitivity and reliably detonate after being subjected to a high temperature environment for a long time. In addition to the good detonation performance of commonly used explosives, this type of explosive must also have a high melting point and a high thermal decomposition temperature (over 250°C). Heat-resistant explosives are widely used in the fields of nuclear weapons, spacecraft, and separation of various levels of spacecraft. With the development of the times, they also have broad application prospects in the exploitation of deep-sea oil and gas resources, natural gas drilling, and space exploration. For example, the perforating guns currently used in the exploitation of deep-sea and deep-well resources widely use hexanitropine (HNS, T d =318°C) and 2,6-bis(picrylamino)-3,5-dinitropyridine (PYX, T d =360℃) etc. as its main charge.

[0003] As the difficulty of obtaining deep-sea resources continues to increase, as well as the depth of deep-sea mining and drilling, the heat resistance requirements of heat-resistant explosives are also constantly increasing. For example, the well temperature at a drilling depth of 6 km is 230°C, and when the depth extends to 7 km, the temperature can rise to 300-350°C. Traditional explosives such as cyclotrimethylene trinitrile (RDX, T d =204℃) and 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (octogenin, HMX, T d =280℃) are commonly used in shallow wells and medium-deep wells with a depth of no more than 4km. As the well depth continues to increase, RDX and HMX can no longer meet the actual application needs. People use hexanitropine (HNS, T d =318°C) and 2,6-bis(picrylamino)-3,5-dinitropyridine (PYX, T d =360℃) to replace RDX and HMX. However, the density and energy of HNS and PYX are relatively low. For example, the density of HNS is 1.75g / cm 3 , the detonation velocity is 7612m / s; the density of PYX is 1.76g / cm 3 , with an explosion velocity of 7757m / s. Their energy and density cannot meet the growing demand for practical applications. Summary of the Invention

[0004] In order to overcome the shortcomings of existing heat-resistant explosives, the purpose of the present invention is to provide a heat-resistant explosive 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) and its perchlorate with excellent thermal stability, and provide their preparation methods.

[0005] The technical solution for achieving the purpose of the present invention is: the bipyrazole-based heat-resistant explosive of the present invention is named 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine), and its structural formula is shown in (I):

[0006]

[0007] The perchlorate based on bipyrazole heat-resistant explosives of the present invention is named 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine)-diperchlorate, and its structural formula is shown in (II):

[0008]

[0009] The synthesis method of bipyrazole-based heat-resistant explosives according to the present invention comprises:

[0010] (1) subjecting 5,5'-dimethyl-4,4'-dinitro-2H,2'H-3,3'-bipyrazole I to oxidation reaction under the action of potassium hydroxide and potassium permanganate to obtain 4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-dicarboxylic acid II,

[0011]

[0012] (2) In the presence of a polyphosphoric acid system H3PO4 / P2O5, 4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-dicarboxylic acid II is cyclized with diaminoguanidine hydrochloride to obtain the target product, based on the step of bipyrazole heat-resistant explosive III.

[0013]

[0014] Preferably, in step (1), the molar ratio of 5,5'-dimethyl-4,4'-dinitro-2H,2'H-3,3'-bipyrazole I to KOH is 1:2-8.

[0015] Preferably, in step (1), the molar ratio of 5,5'-dimethyl-4,4'-dinitro-2H,2'H-3,3'-bipyrazole I to potassium permanganate is 1:4-10.

[0016] Preferably, in step (1), the solvent used in the reaction system is deionized water.

[0017] Preferably, in step (1), the reaction temperature is 80-100° C., and the reaction time is 12-24 h.

[0018] Preferably, in step (2), the ratio of H3PO4 to P2O5 in the polyphosphoric acid system is 1 g: 1-5 mL, wherein the concentration of H3PO4 is 85 wt%.

[0019] Preferably, in step (2), the molar ratio of 4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-dicarboxylic acid II to diaminoguanidine hydrochloride is 1:4-16.

[0020] Preferably, in step (2), the reaction temperature is 110-140° C. and the reaction time is 12-24 h.

[0021] The synthesis method of the perchlorate based on bipyrazole heat-resistant explosive of the present invention comprises the steps of: subjecting bipyrazole heat-resistant explosive III to an acid-base neutralization reaction with perchloric acid to prepare the target product, the perchlorate based on bipyrazole heat-resistant explosive IV;

[0022]

[0023] Preferably, the molar ratio of the bipyrazole-based heat-resistant explosive III to perchloric acid is 1:1-8.

[0024] Preferably, the reaction solvent is one or more of methanol, ethanol, and acetonitrile.

[0025] Preferably, the reaction time is 2 to 24 hours; and the reaction temperature is 65°C to 80°C.

[0026] Compared with the prior art, the present invention has the following advantages:

[0027] (1) The 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) compound of the present invention has excellent thermal stability, and its initial thermal decomposition temperature reaches 346°C, which is much higher than the currently commonly used heat-resistant explosive HNS (318°C). At the same time, the 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) compound of the present invention has the characteristics of high density, and its density is 1.78g / cm3 , significantly better than HNS (1.75g / cm 3 Most importantly, the 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) compound of the present invention has a high detonation velocity of 8675 m / s, which is significantly better than HNS (7612 m / s) and PYX (7757 m / s).

[0028] (2) The 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine)-diperchlorate compound of the present invention has excellent thermal stability, and its initial thermal decomposition temperature reaches 328°C, which is much higher than the currently commonly used heat-resistant explosive HNS (318°C). At the same time, the 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine)-diperchlorate compound of the present invention has the characteristics of high density, and its density is 1.92g / cm 3 , significantly better than HNS (1.75g / cm 3 Most importantly, the 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine)-diperchlorate compound of the present invention has a high detonation velocity of 8604 m / s, which is significantly better than HNS (7612 m / s) and PYX (7757 m / s).

[0029] (3) The synthesis method of the 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) compound and the 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine)-diperchlorate compound provided by the present invention is simple, no side reactions occur during the preparation process, high-purity compounds can be obtained without purification, and industrial production can be carried out. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a single crystal image of 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine).

[0031] Figure 2This is the TG / DSC curve of 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine).

[0032] Figure 3 This is a single crystal image of 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine)-diperchlorate.

[0033] Figure 4 This is the TG / DSC curve of 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine)-diperchlorate. DETAILED DESCRIPTION

[0034] The present invention will be further described below in conjunction with the embodiments and drawings.

[0035] 5,5'-Dimethyl-4,4'-dinitro-2H,2'H-3,3'-bipyrazole I was prepared according to the reference [Y. Tang, C. He, GH Imler, DA Parrishb, JM Shreeve, AC–C bonded 5,6-fused bicyclic energetic molecule: exploring an advanced energetic compound with improved performance. Chemical Communications, 2018, 54(75): 10566-10569.].

[0036] The specific synthesis route of 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) or its perchlorate of the present invention is as follows:

[0037]

[0038] Example 1:

[0039] At room temperature, add 100 mL of deionized water to a 250 mL three-necked flask, followed by 11.2 g (20.0 mmol) of KOH. Stir to dissolve, then slowly add 12.6 g (5.0 mmol) of 5,5'-dimethyl-4,4'-dinitro-2H,2'H-3,3'-bipyrazole I. Raise the temperature to 65°C, and slowly add 94.8 g (0.6 mol) of potassium permanganate to the reaction system in batches, keeping the reaction temperature below 80°C. After the addition is complete, raise the temperature to 100°C and react for 12 hours. After the reaction, the mixture was cooled to room temperature, manganese dioxide was removed by filtration, and the filter cake was washed with 300 mL of deionized water. The filtrate was collected and adjusted to pH 2 with 20% dilute hydrochloric acid. The filtrate was extracted with ethyl acetate (50 mL × 3), and the organic phase was washed with saturated brine (20 mL × 3), dried over anhydrous magnesium sulfate, and the solvent was evaporated to obtain white 4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-dicarboxylic acid II (14.02 g, 90.2%).

[0040] 1 H NMR (500MHz, DMSO-d6): δ = 8.39 (s, 2H), 8.10 (s, 2H) ppm. 13 C NMR (125MHz, DMSO-d6): δ = 159.9, 140.3, 1341, 130.5ppm. IR (KBr): Elemental analysis for C8H6N8O6 (310.18): C 30.98, H 1.95, N 36.12%. Found: C 30.72, H 2.20, N 36.09%.

[0041] Example 2:

[0042] At room temperature, add 100 mL of deionized water to a 250 mL three-necked flask, followed by 11.2 g (20.0 mmol) of KOH. Stir to dissolve, then slowly add 12.6 g (5.0 mmol) of 5,5'-dimethyl-4,4'-dinitro-2H,2'H-3,3'-bipyrazole I. Raise the temperature to 65°C, and slowly add 31.6 g (0.2 mol) of potassium permanganate to the reaction system in batches, keeping the reaction temperature below 80°C during addition. After the addition is complete, raise the temperature to 100°C and react for 12 hours. After the reaction, the mixture was cooled to room temperature, manganese dioxide was removed by filtration, and the filter cake was washed with 300 mL of deionized water. The filtrate was collected and adjusted to pH 2 with 20% dilute hydrochloric acid. The filtrate was extracted with ethyl acetate (50 mL × 3), and the organic phase was washed with saturated brine (20 mL × 3), dried over anhydrous magnesium sulfate, and the solvent was evaporated to obtain white 4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-dicarboxylic acid II (4.16 g, 26.8%).

[0043] Example 3:

[0044] At room temperature, add 100 mL of deionized water to a 250 mL three-necked flask, followed by 11.2 g (20.0 mmol) of KOH. Stir to dissolve, then slowly add 12.6 g (5.0 mmol) of 5,5'-dimethyl-4,4'-dinitro-2H,2'H-3,3'-bipyrazole I. Raise the temperature to 65°C, and slowly add 126.4 g (0.8 mol) of potassium permanganate to the reaction system in batches, keeping the reaction temperature below 80°C. After the addition is complete, raise the temperature to 100°C and react for 12 hours. After the reaction, the mixture was cooled to room temperature, manganese dioxide was removed by filtration, and the filter cake was washed with 300 mL of deionized water. The filtrate was collected and adjusted to pH 2 with 20% dilute hydrochloric acid. The filtrate was extracted with ethyl acetate (50 mL × 3), and the organic phase was washed with saturated brine (20 mL × 3), dried over anhydrous magnesium sulfate, and the solvent was evaporated to obtain white 4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-dicarboxylic acid II (12.46 g, 80.2%).

[0045] Example 4:

[0046] At room temperature, add 100 mL of deionized water to a 250 mL three-necked flask, followed by 11.2 g (20.0 mmol) of KOH. Stir to dissolve, then slowly add 12.6 g (5.0 mmol) of 5,5'-dimethyl-4,4'-dinitro-2H,2'H-3,3'-bipyrazole I. Raise the temperature to 65°C, and slowly add 79.0 g (0.7 mol) of potassium permanganate to the reaction system in batches, keeping the reaction temperature below 80°C. After the addition is complete, raise the temperature to 100°C and react for 12 hours. After the reaction, the mixture was cooled to room temperature, manganese dioxide was removed by filtration, and the filter cake was washed with 300 mL of deionized water. The filtrate was collected and adjusted to pH 2 with 20% dilute hydrochloric acid. The filtrate was extracted with ethyl acetate (50 mL × 3), and the organic phase was washed with saturated brine (20 mL × 3), dried over anhydrous magnesium sulfate, and the solvent was evaporated to obtain white 4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-dicarboxylic acid II (10.48 g, 67.4%).

[0047] Example 5:

[0048] At room temperature, phosphorus pentoxide (20.0 g, 15.0 mmol) was slowly dissolved in a 250 mL three-necked flask containing 85 wt% orthophosphoric acid (70.0 g, 60.0 mmol). The mixture was heated to 80°C and stirred for half an hour. A uniform mixture of 4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-dicarboxylic acid II (15.6 g, 50.0 mmol) and diaminoguanidine hydrochloride (102.15 g, 400 mmol) was then added. After the addition was complete, the system was heated to 120°C and stirred for 12 hours. After the reaction, the mixture was poured into ice water to quench, and the pH was adjusted to 7 with 2M sodium hydroxide solution. The precipitate was filtered, washed with cold water, and dried to obtain a yellow solid 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) III (17.95 g, 86.2%).

[0049] 1 H NMR (500MHz, DMSO-d6): δ = 6.15 (s, 2H), 5.51 (s, 2H) ppm; 13 C NMR (125MHz, DMSO-d6): δ = 156.09, 141.09, 135.88, 133.06, 131.52ppm; IR (KBr): Elemental analysis for C 10 H 10 N16 O4(418.30): C 28.71, H 2.41, N 53.58%; found: C28.74, H2.40, N 53.56%.

[0050] Example 6:

[0051] At room temperature, slowly dissolve phosphorus pentoxide (20.0 g, 15.0 mmol) in a 250 mL three-necked flask containing 85% orthophosphoric acid (70.0 g, 60.0 mmol). The mixture was heated to 80°C and stirred for half an hour. A uniform mixture of 4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-dicarboxylic acid II (15.6 g, 50.0 mmol) and diaminoguanidine hydrochloride (127.69 g, 500 mmol) was then added. After the addition was complete, the system was heated to 120°C and stirred for 12 hours. After the reaction, the mixture was poured into ice water to quench, and the pH was adjusted to 7 with 2M sodium hydroxide solution. The precipitate was filtered, washed with cold water, and dried to obtain a yellow solid 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) III (15.2 g, 73%).

[0052] Example 7:

[0053] At room temperature, slowly dissolve phosphorus pentoxide (20.0 g, 15.0 mmol) in a 250 mL three-necked flask containing 85% orthophosphoric acid (70.0 g, 60.0 mmol). The mixture was heated to 80°C and stirred at this temperature for half an hour. A uniform mixture of 4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-dicarboxylic acid II (15.6 g, 50.0 mmol) and diaminoguanidine hydrochloride (51.08 g, 200 mmol) was then added. After the addition was complete, the system was heated to 120°C and stirred at this temperature for 12 hours. After the reaction, the mixture was poured into ice water to quench, and the pH was adjusted to 7 with 2M sodium hydroxide solution. The precipitate was filtered, washed with cold water, and dried to obtain a yellow solid 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) III (13.50 g, 64.8%).

[0054] Example 8:

[0055] At room temperature, slowly dissolve phosphorus pentoxide (20.0 g, 15.0 mmol) in a 250 mL three-necked flask containing 85% orthophosphoric acid (70.0 g, 60.0 mmol). The mixture was heated to 80°C and stirred for half an hour. A homogeneous mixture of 4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-dicarboxylic acid II (15.6 g, 50.0 mmol) and diaminoguanidine hydrochloride (178.77 g, 700 mmol) was then added. After the addition was complete, the system was heated to 120°C and stirred for 12 hours. After the reaction, the mixture was poured into ice water to quench, and the pH was adjusted to 7 with 2M sodium hydroxide solution. The precipitate was filtered, washed with cold water, and dried to obtain a yellow solid 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) III (9.52 g, 61.3%).

[0056] Example 9:

[0057] At room temperature, 0.84 g (2.0 mmol) of 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) III was dissolved in 10 mL of acetonitrile. 1.72 g (12.0 mmol) of a 70% perchloric acid solution was then added dropwise. The mixture was heated to 80°C and stirred until the solution became clear. This temperature was maintained for 2 hours. The mixture was then cooled to room temperature, filtered, and air-dried to yield 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) diperchlorate IV (1.15 g, 92.7%).

[0058] 1 H NMR (500MHz, DMSO-d6): δ = 8.58 (s, 2H), 5.99 (s, 2H) ppm; 13 C NMR (125MHz, DMSO-d6): δ = 152.00, 141.63, 133.05, 132.18, 130.52ppm; IR (KBr): Elemental analysis for C 10 H 12 Cl2N 16 O 12 (619.21): C 19.40, H 1.95, N 36.19%; found: C 19.43, H1.93, N 36.18%.

[0059] Example 10:

[0060] At room temperature, 0.84 g (2.0 mmol) of 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) III was dissolved in 10 mL of acetonitrile. 1.15 g (8.0 mmol) of a 70% perchloric acid solution was then added dropwise. The mixture was heated to 80°C and stirred until the solution became clear. This temperature was maintained for 2 hours. The mixture was then cooled to room temperature, filtered, and air-dried to yield 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) diperchlorate IV (0.93 g, 75.0%).

[0061] Example 11:

[0062] At room temperature, 0.84 g (2.0 mmol) of 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) III was dissolved in 10 mL of acetonitrile. 2.87 g (20.0 mmol) of a 70% perchloric acid solution was then added dropwise. The mixture was heated to 80°C and stirred until the solution became clear. The temperature was maintained for 2 hours. The mixture was then cooled to room temperature, filtered, and air-dried to yield 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) diperchlorate IV (0.53 g, 42.7%).

[0063] The obtained 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) III was subjected to relevant performance tests, and the single crystal image is shown in FIG. Figure 1 As shown, the TG / DSC curve is as follows Figure 2 As shown, the relevant performance is as follows:

[0064] 1. Measured density: 1.78g / cm 3 ;

[0065] 2. Thermal decomposition temperature: no melting point, initial thermal decomposition temperature is 346℃;

[0066] 3. Sensitivity performance: impact sensitivity>40J, friction sensitivity>360N;

[0067] 4. Detonation performance: Detonation velocity is 8675m / s (EXPLO5 v6.01), and explosion pressure is 29.62GPa (EXPLO5 v6.01).

[0068] The obtained 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine)-diperchlorate IV was subjected to relevant performance tests, and the single crystal image is shown in FIG. Figure 3 As shown, the TG / DSC curve is as follows Figure 4 As shown, the relevant performance is as follows:

[0069] 1. Measured density: 1.92g / cm 3 ;

[0070] 2. Thermal decomposition temperature: no melting point, initial thermal decomposition temperature is 328℃;

[0071] 3. Sensitivity performance: impact sensitivity 32J, friction sensitivity>360N;

[0072] 4. Detonation performance: Detonation velocity is 8604m / s (EXPLO5 v6.01), and explosion pressure is 33.79GPa (EXPLO5 v6.01).

[0073] The synthesized heat-resistant explosive 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine) and its perchlorate 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine)-diperchlorate have better thermal conductivity than the traditional heat-resistant explosive HNS (ρ=1.75g / cm 3 , D v =7612m / s) and PYX (ρ = 1.76g / cm 3 , D v =7757m / s) higher density and energy.

[0074] The above-described specific embodiments describe the present invention in detail, but the scope of the present invention is not limited by these specific embodiments. Those skilled in the art of energetic materials may devise numerous other modifications and embodiments based on the present invention without departing from the spirit and scope of the present invention. Therefore, all such modifications and embodiments are intended to be within the scope of the appended claims.

Claims

1. Based on bipyrazole heat-resistant explosives, characterized in that, It is named 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine), and its structural formula is shown in (I):

2. Perchlorate based on bipyrazole heat-resistant explosive, characterized in that, It is named 5,5'-(4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-diyl)bis(4H-1,2,4-triazole-3,4-diamine)-diperchlorate, and its structural formula is shown in (II):

3. A synthesis method based on bipyrazole heat-resistant explosives, characterized in that: include: (1) subjecting 5,5'-dimethyl-4,4'-dinitro-2H,2'H-3,3'-bipyrazole I to oxidation reaction under the action of potassium hydroxide and potassium permanganate to obtain 4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-dicarboxylic acid II, (2) In the presence of a polyphosphoric acid system H3PO4 / P2O5, 4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-dicarboxylic acid II is cyclized with diaminoguanidine hydrochloride to obtain the target product, based on the step of bipyrazole heat-resistant explosive III.

4. The method according to claim 3, wherein In step (1), the molar ratio of 5,5'-dimethyl-4,4'-dinitro-2H,2'H-3,3'-bipyrazole I to KOH is 1:2-8; the molar ratio of 5,5'-dimethyl-4,4'-dinitro-2H,2'H-3,3'-bipyrazole I to potassium permanganate is 1:4-10.

5. The method according to claim 3, wherein In step (1), the solvent used in the reaction system is deionized water; the reaction temperature is 80-100° C., and the reaction time is 12-24 h.

6. The method according to claim 3, wherein In step (2), the ratio of H3PO4 to P2O5 in the polyphosphoric acid system is 1 g: 1-5 mL, wherein the concentration of H3PO4 is 85 wt%.

7. The method according to claim 3, wherein In step (2), the molar ratio of 4,4'-dinitro-2H,2'H-[3,3'-bipyrazole]-5,5'-dicarboxylic acid II to diaminoguanidine hydrochloride is 1:4-16; the reaction temperature is 110-140°C; and the reaction time is 12-24 hours.

8. A method for synthesizing perchlorate of bipyrazole heat-resistant explosives, characterized in that: include: The step of reacting the bipyrazole heat-resistant explosive III described in claim 1 with perchloric acid to form a salt to prepare the target product, bipyrazole heat-resistant explosive perchlorate IV, 9. The method according to claim 8, wherein The molar ratio of bipyrazole-based heat-resistant explosive III to perchloric acid is 1:1-8; the reaction solvent is one or more of methanol, ethanol, and acetonitrile; the reaction time is 2-24 hours; and the reaction temperature is 65-80°C.

10. Use of the bipyrazole-based heat-resistant explosive or the perchlorate of the bipyrazole-based heat-resistant explosive as claimed in claim 1 or 2 as a heat-resistant explosive.

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