CN111807987A - Method for synthesizing BTAHNAB by taking 3, 5-dichloroaniline as raw material - Google Patents
Method for synthesizing BTAHNAB by taking 3, 5-dichloroaniline as raw material Download PDFInfo
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- hexanitroazobenzene
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- UQRLKWGPEVNVHT-UHFFFAOYSA-N 3,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC(Cl)=C1 UQRLKWGPEVNVHT-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002994 raw material Substances 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- VICLXIGOASSLOA-UHFFFAOYSA-N bis(3,5-dichloro-2,4,6-trinitrophenyl)diazene Chemical compound [O-][N+](=O)C1=C(Cl)C([N+](=O)[O-])=C(Cl)C([N+]([O-])=O)=C1N=NC1=C([N+]([O-])=O)C(Cl)=C([N+]([O-])=O)C(Cl)=C1[N+]([O-])=O VICLXIGOASSLOA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- KQIKZGBRGHRQQR-UHFFFAOYSA-N 5-[(3,5-diamino-2,4,6-trinitrophenyl)diazenyl]-2,4,6-trinitrobenzene-1,3-diamine Chemical compound NC1=C([N+]([O-])=O)C(N)=C([N+]([O-])=O)C(N=NC=2C(=C(N)C(=C(N)C=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O KQIKZGBRGHRQQR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000002360 explosive Substances 0.000 abstract description 11
- 238000005474 detonation Methods 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 abstract description 6
- 238000004458 analytical method Methods 0.000 abstract description 4
- 238000004364 calculation method Methods 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- -1 BTAHNAB Chemical compound 0.000 abstract description 3
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004455 differential thermal analysis Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JDFUJAMTCCQARF-UHFFFAOYSA-N tatb Chemical compound NC1=C([N+]([O-])=O)C(N)=C([N+]([O-])=O)C(N)=C1[N+]([O-])=O JDFUJAMTCCQARF-UHFFFAOYSA-N 0.000 description 2
- CXKCZFDUOYMOOP-UHFFFAOYSA-N 3,5-dichlorobenzoic acid Chemical compound OC(=O)C1=CC(Cl)=CC(Cl)=C1 CXKCZFDUOYMOOP-UHFFFAOYSA-N 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005421 electrostatic potential Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003721 gunpowder Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic energetic materials and preparation thereof, and provides a method for synthesizing a novel heat-resistant energetic material 3,3',5,5' -tetraamino-2, 2',4,4',6,6' -hexanitroazobenzene, namely BTAHNAB, by using 3, 5-dichloroaniline as a raw material. 3, 5-dichloroaniline is added into nitric-sulfuric mixed acid to react to obtain 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene; then mixing with toluene, introducing ammonia gas at a constant speed, stopping introducing ammonia gas after reaction, and continuing the reaction to obtain BTAHNAB. The preparation process is safe and simple, the preparation period is short, the preparation steps are few, and the preparation yield is high. Through calculation and test analysis, the detonation velocity of the BTAHNAB exceeds 8000m/s, the melting point is greater than 330 ℃, and the thermal decomposition temperature is close to 400 ℃, so that the obtained product has good stability and thermal stability, and is a novel heat-resistant explosive with wide application prospect.
Description
Technical Field
The invention belongs to the technical field of organic energetic materials and preparation thereof, and particularly relates to a method for synthesizing a novel heat-resistant energetic material 3,3',5,5' -tetraamino-2, 2',4,4',6,6' -hexanitroazobenzene, namely BTAHNAB, by using 3, 5-dichloroaniline as a raw material.
Background
Energetic materials are widely used in our lives, military and industry. With the development of advanced earth-boring ammunition in recent years, the speed of flying and end-targeting of a projectile body is faster and faster, and the research in the field of penetration is gradually changed from high-speed penetration to high-speed/ultra-high-speed penetration. In the process of ultra-high-speed weapon penetration, the explosive is subjected to continuous load effects such as long-time extrusion, friction, shearing and the like, and the penetration warhead charge needs to bear severe temperature environment and mechanical environment, so that the thermal performance and mechanical performance indexes of the warhead charge are improved to different degrees. The proposal of ammunition systematic engineering requires that the whole ammunition system from gunpowder, explosive and fuze meet the requirement of insensitivity, and a pressure relief design technology, a heat/force buffering technology, a packaging protection technology and the like are gradually applied to the ammunition system.
Therefore, the research on a heat-resistant explosive which meets the application of ultra-high-speed weapons, particularly the requirement of ultra-high-speed penetration ammunition is one of the problems which are urgently needed to be solved at present. Thermal explosives such as TATB, HNS, LLM-105, etc. have been developed in pursuit of thermal properties. By analyzing the current research situation of the existing heat-resistant explosive, the existing heat-resistant explosive has certain defects, for example, the existing commonly used heat-resistant explosive TATB has good heat resistance, but relatively low energy, and can not completely meet the use requirement.
The method for synthesizing the BTAHNAB by taking the BTAHNAB as a novel heat-resistant energetic material and 3, 5-dichlorobenzoic acid as a raw material has certain defects, such as: the preparation process is complex, and the preparation period is long; the preparation steps are excessive, and the waste of raw materials is serious; prepare multi-purpose high-concentration sulfuric acid and dangerous chemicals, react at higher temperature, have certain potential safety hazard.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for synthesizing a novel heat-resistant energetic material 3,3',5,5' -tetraamino-2, 2',4,4',6,6' -hexanitroazobenzene, namely BTAHNAB, by using 3, 5-dichloroaniline as a raw material.
The invention is realized by the following technical scheme: a method for synthesizing a novel heat-resistant energetic material 3,3',5,5' -tetraamino-2, 2',4,4',6,6 '-hexanitroazobenzene (BTAHAB) by taking 3, 5-dichloroaniline as a raw material comprises the steps of putting 3, 5-dichloroaniline into nitric-sulfuric mixed acid, and reacting to obtain 3,3',5,5 '-tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene; 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene is mixed with toluene, ammonia gas is introduced at a constant speed, the introduction of ammonia gas is stopped after the reaction, and the reaction is continued to obtain BTAHNAB.
The method comprises the following specific steps:
(1) preparation of 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene: dripping 98% concentrated sulfuric acid dropwise into 98% concentrated nitric acid in ice water bath under the condition of uniform stirring at 500r/min to prepare mixed acid of nitric acid and sulfur, wherein the temperature in a bottle is ensured not to exceed 20 ℃ in the dripping process. Adding 3, 5-dichloroaniline five times; after the feeding is finished, keeping the stirring speed, heating in a water bath to 60-85 ℃, and reacting for 2 hours; after the reaction is finished, a large amount of reddish yellow foams are contained in the bottle, the bottle is naturally cooled to room temperature, the mixture is poured into 600ml of clean ice water, orange yellow solids are separated out, the mixture is subjected to suction filtration and water washing, and the product 1 is obtained after natural drying, wherein the main component of the product 1 is 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene; heating the product 1 in a mixed solution of acetone and dichloroethane to 60-80 ℃, dissolving, and naturally cooling to separate out pure 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene;
wherein the proportion of the concentrated sulfuric acid, the concentrated nitric acid and the 3, 5-dichloroaniline is as follows: 20-100 ml: 3-20 ml: 0.5-4 g; the proportion of the acetone to the dichloroethane is as follows: 10-40 ml: 40-100 ml;
(2) preparation of 3,3',5,5' -tetraamino-2, 2',4,4',6,6' -hexanitroazobenzene: adding toluene into the purified 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene, keeping the stirring speed at 400r/min to dissolve the raw materials, and heating the mixture to 25-40 ℃ in a water bath. Keeping the temperature and the stirring speed, and introducing ammonia gas at a constant speed for 0.5-4 h under the pressure of 0.1-0.4 MPa to separate out a dark red precipitate. Stopping introducing the ammonia gas, and keeping the temperature and the stirring speed for reaction for 0.5 h. After the reaction is finished, naturally cooling to room temperature, carrying out suction filtration, washing with ethanol and then washing with water to obtain a bright red product with a main component of 3,3',5,5' -tetraamino-2, 2',4,4',6,6' -hexanitroazobenzene;
wherein, the proportion of the 3,3',5,5' -tetraamino-2, 2',4,4',6,6' -hexanitroazobenzene and the toluene is as follows: 0.2-1.5 g: 30-140 ml.
The invention carries out structural characterization on the synthetic product: and carrying out structural characterization on the 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene by utilizing an infrared spectrum, a nuclear magnetic resonance spectrum and differential thermal analysis.
The reaction mechanism for synthesizing BTAHNAB by taking 3, 5-dichloroaniline as a raw material is as follows: the first step is nitration reaction of 3, 5-dichloroaniline, and the reaction mechanism is the positioning group effect of substituent on benzene ring; the second step is that BTCHNAB generates ammonolysis reaction of halogen group under the action of ammonia gas, belonging to nucleophilic substitution reaction. The reaction scheme is shown in FIG. 4.
The invention provides a synthesis method of 3,3',5,5' -tetraamino-2, 2',4,4',6,6 '-hexanitroazobenzene, which has the advantages of safe and simple preparation process, short preparation period and few preparation steps, by using the method for synthesizing 3,3',5,5 '-tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene by 3, 5-dichloroaniline for reference and optimizing the process. The prepared BTAHNAB is a novel heat-resistant explosive with good stability, thermal stability and excellent performance. BTANNAB is structurally characterized by infrared spectrum, nuclear magnetic resonance spectrum and differential thermal analysis.
Through calculation and test analysis, the detonation velocity of the BTAHNAB exceeds 8000m/s, the melting point is greater than 330 ℃, and the thermal decomposition temperature is close to 400 ℃, so that the obtained product has good stability and thermal stability, and is a novel heat-resistant explosive with wide application prospect.
Drawings
The invention is further illustrated with reference to the accompanying drawing, which is an example of a product made.
FIG. 1 is an infrared spectrum of the product BTAHNAB, taken using a PerkinEleer Spctrum100 Fourier transform infrared spectrometer (USA);
FIG. 2 is a nuclear magnetic spectrum of product BTAHNAB, wherein: a is a 1H NMR chart; b is a 13C NMR chart; and testing by using a 500MHz nuclear magnetic resonance spectrometer. Red appearance map display: 3448cm-1、3323 cm-1is-NH2Has an infrared characteristic peak value of 1546cm-1Stretching vibration peak of-N = N-, 1205cm-1Is the C-N stretching vibration peak, 1355cm-1Stretching vibration peak of-C = C-, 1205cm-1is-NO2Characteristic peak of infrared ray of (8), 893cm-1，799cm-1665cm for deformation vibration of benzene ring-1Is an infrared characteristic peak of-Cl. From the 1H NMR chart, 8.38 is the peak for H on the amino group, 3.54 and 2.5 are both solvent peaks for deuterated reagent DMSO. From the 13C NMR chart, 146.97, 140.44, 114.83, 102.24 are four different C peaks in the btahnanab molecule, respectively, and the highest peak with a value of 40 in the chart is the solvent peak of the deuterated reagent DMSO. Determining the product to be 3,5,5 '-tetraamino-2, 2',4,4',6,6' -hexanitroazobenzene;
FIG. 3 is a differential thermal analysis TG-DTA curve of product 2, measured using an HTC-1 type differential thermal micro-computer balance;
FIG. 4 is a flow diagram of the reaction of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples. It should be understood that the following description is intended only to illustrate the present invention and not to limit the contents thereof, and the following examples are intended to obtain the desired products.
Example 1:
preparation of mono, 3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene
Adding 40ml of 98% concentrated sulfuric acid into a 250ml three-neck flask, dropwise adding 8ml of 98% concentrated nitric acid under the conditions of ice-water bath and uniform stirring at 500r/min to prepare the nitric-sulfuric mixed acid, wherein the temperature in the flask is ensured not to exceed 20 ℃ in the dropwise adding process. 2g of 3, 5-dichloroaniline are then added in five portions, the solution being orange-red. After the feeding is finished, the stirring speed is kept, the temperature is raised to 65 ℃ in a water bath, and the reaction is carried out for 2 h. After the reaction is finished, a large amount of reddish yellow foam is filled in the bottle, the bottle is naturally cooled to room temperature, the solution is poured into 600ml of ice water, orange yellow solid is separated out, the solution is subjected to suction filtration and water washing, and the product 1 is obtained after natural drying, wherein the main component of the product 1 is 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene.
Adding 20ml of acetone and 60ml of dichloroethane into a three-neck flask, stirring at a constant speed to fully mix the two solvents, adding the product 1, keeping the stirring speed, heating in a water bath to 70 ℃, fully dissolving the product 3, and enabling the solution to be saturated. And after the dissolution is finished, filtering the clear solution while the clear solution is hot, naturally cooling the clear solution, and filtering and drying the precipitated solid to obtain the purified 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene.
Synthesis of di, 3',5,5' -tetra-amino-2, 2',4,4',6,6' -hexanitroazobenzene
0.7g of 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazo is put into a 100ml three-neck flask, 70ml of toluene is added, the mixture is stirred at a constant speed of 400r/min to dissolve the raw materials, and the temperature is raised to 30 ℃ in a water bath, so that the solution is a clear red liquid. Keeping the temperature and the stirring speed, and introducing ammonia gas at a constant speed for 3h under the pressure of 0.2MPa to separate out a dark red precipitate. Stopping introducing the ammonia gas, and keeping the temperature and the stirring speed for reaction for 0.5 h. And after the reaction is finished, naturally cooling to room temperature, performing suction filtration, washing with ethanol and washing with water to obtain a bright red solid, and naturally drying to obtain a product 2, wherein the main component of the product 2 is 3,3',5,5' -tetraamino-2, 2',4,4',6,6' -hexanitroazobenzene.
Example 2: in the first implementation step, the usage amount of concentrated sulfuric acid is 20ml, the usage amount of nitric acid is 3ml, and the usage amount of 3, 5-dichloroaniline is 0.5g, which is the same as that in the example 1.
Example 3: in the first implementation step, the usage amount of concentrated sulfuric acid is 60ml, the usage amount of nitric acid is 15ml, and the usage amount of 3, 5-dichloroaniline is 3g, which is the same as that in the example 1.
Example 4: in the first implementation step, the usage amount of concentrated sulfuric acid is 100ml, the usage amount of nitric acid is 20ml, and the usage amount of 3, 5-dichloroaniline is 4g, which is the same as that in the example 1.
Example 5: in the first implementation step, after the feeding is finished, the mixed solution is stirred and reacted for 2 hours at the temperature of 60 ℃, and the rest is the same as the example 1.
Example 6: in the first implementation step, after the feeding is finished, the mixed solution is stirred and reacted for 2 hours at 85 ℃, and the rest is the same as the example 1.
Example 7: in the first implementation step, the amount of acetone is 10ml, and the amount of dichloroethane is 40ml, as in example 1.
Example 8: in the first implementation step, the dosage of acetone is 40ml, and the dosage of dichloroethane is 100ml, and the rest is the same as in example 1.
Example 9: in the first embodiment, the recrystallization temperature is 60 ℃, and the rest is the same as in example 1.
Example 10: in the first embodiment, the recrystallization temperature is 80 ℃, and the rest is the same as in example 1.
Example 11: in the second step of this embodiment, the amount of 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene used was 0.2g, and the amount of toluene used was 30ml, as in example 1.
Example 12: in the second step of this embodiment, the amount of 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene used was 1.2g, and the amount of toluene used was 140ml, as in example 1.
Example 13: in the second step, the time period for introducing ammonia gas at constant speed is 0.5h, and the rest is the same as in example 1.
Example 14: in the second step of this embodiment, the time period for introducing ammonia gas at a constant speed is 4 hours, and the rest of the process is the same as that of embodiment 1
Example 15: in the second embodiment, the temperature of the reaction system was 25 ℃ as in example 1.
Example 16: in the second embodiment, the temperature of the reaction system was 40 ℃ as in example 1.
And (4) theoretical density test: calculating molecular volume V of target compound at B3LYP/6-31G x group level by using density functional theorymAnd predicting the theoretical density ρ of the compound using formula 1:
in the formula: vmIs the molar volume of the molecule; m is molecular molal matterAn amount;
is the product of the electrostatic equilibrium coefficient and the total variance of the electrostatic potential. The theoretical density of BTAHNAB is obtained by calculation
。
And (3) detecting the detonation performance: predicting the detonation velocity D and the detonation pressure P of the compound by using a Kamelet-Jacobs equation, and concretely referring to the following formulas 2 and 3:
in the formula: ρ is the density (g/cm) of the compound3) (ii) a N is the amount (mol/g) of gas substances formed by explosion of energy-containing compounds per unit mass;
is the average molar mass (g/mol) of the detonation product gas component; q is the heat of detonation (J/g). The detonation velocity D =8.488km/s and the detonation pressure P =33.296GPa of the BTAHNAB are obtained through calculation.
Melting point: the melting point of the BTAHNAB sample was measured to be greater than 330 deg.C, indicating that it has good heat resistance characteristics.
Thermal performance analysis: thermal performance analysis is carried out on the BTAHNAB under different heating rates, the thermal decomposition peak value is 365 ℃ and the activation energy is 161.6051 when the heating rate is 10 ℃/min, and the peak temperature of the sample is T when the heating rate is close to zeroP0=310.8 ℃, indicating that it has good stability.
Mechanical sensitivity: and (3) performing impact sensitivity test on the BTAHNAB sample by adopting a characteristic falling height method, wherein the test conditions are as follows: the weight of the sample is 3mg, the weight of the drop weight is 5kg, and the impact sensitivity of the BTAHNAB sample is measured to be H50=109.5 cm. The BTAHNAB as a final product is a heat-resistant explosive with excellent performance.
Claims (2)
1. A method for synthesizing a novel heat-resistant energetic material 3,3',5,5' -tetraamino-2, 2',4,4',6,6' -hexanitroazobenzene (BTAHNAB) by taking 3, 5-dichloroaniline as a raw material is characterized in that: 3, 5-dichloroaniline is added into nitric-sulfuric mixed acid to react to obtain 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene; 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene is mixed with toluene, ammonia gas is introduced at a constant speed, the introduction of ammonia gas is stopped after the reaction, and the reaction is continued to obtain BTAHNAB.
2. The method for synthesizing the novel heat-resistant energetic material, namely BTAHNAB, from 3, 5-dichloroaniline as a raw material according to claim 1, wherein the BTAHNAB is prepared from 3,3',5,5' -tetraamino-2, 2',4,4',6,6' -hexanitroazobenzene, and is characterized in that: the method comprises the following specific steps:
(1) preparation of 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene: dripping 98% concentrated sulfuric acid into 98% concentrated nitric acid dropwise under the conditions of ice water bath and uniform stirring at 500r/min to prepare mixed acid of nitric acid and sulfuric acid, ensuring that the temperature in a bottle does not exceed 20 ℃ in the dripping process, and then adding 3, 5-dichloroaniline five times; after the feeding is finished, keeping the stirring speed, heating in a water bath to 60-85 ℃, and reacting for 2 hours; after the reaction is finished, a large amount of reddish yellow foams are contained in the bottle, the bottle is naturally cooled to room temperature, the mixture is poured into 600ml of clean ice water, orange yellow solids are separated out, the mixture is subjected to suction filtration and water washing, and the product 1 is obtained after natural drying, wherein the main component of the product 1 is 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene; heating the product 1 in a mixed solution of acetone and dichloroethane to 60-80 ℃, dissolving, and naturally cooling to separate out pure 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene;
wherein the proportion of the concentrated sulfuric acid, the concentrated nitric acid and the 3, 5-dichloroaniline is as follows: 20-100 ml: 3-20 ml: 0.5-4 g; the proportion of the acetone to the dichloroethane is as follows: 10-40 ml: 40-100 ml;
(2) preparation of 3,3',5,5' -tetraamino-2, 2',4,4',6,6' -hexanitroazobenzene: adding toluene into the purified 3,3',5,5' -tetrachloro-2, 2',4,4',6,6' -hexanitroazobenzene, keeping the temperature at 400r/min, stirring at a constant speed to dissolve the raw materials, and heating to 25-40 ℃ in a water bath; keeping the temperature and the stirring speed, and introducing ammonia gas at a constant speed for 0.5-4 h under the pressure of 0.1-0.4 MPa to separate out a dark red precipitate; stopping introducing ammonia gas, and keeping the temperature and the stirring speed for reaction for 0.5 h; after the reaction is finished, naturally cooling to room temperature, carrying out suction filtration, washing with ethanol and then washing with water to obtain a bright red product with a main component of 3,3',5,5' -tetraamino-2, 2',4,4',6,6' -hexanitroazobenzene;
wherein, the proportion of the 3,3',5,5' -tetraamino-2, 2',4,4',6,6' -hexanitroazobenzene and the toluene is as follows: 0.2-1.5 g: 30-140 ml.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4751289A (en) * | 1986-12-29 | 1988-06-14 | Texas Explosives Co. Inc. | Hexanitrotetrachloroazobenzene and method of preparation |
| DE102011118462A1 (en) * | 2011-11-14 | 2013-05-16 | Maximilian Born | Casing useful for a weapon system, comprises a core comprising secondary explosive material as main charge and primary explosive material, and a sheathing comprising energetic duroplastic- and/or energetic thermoplastic polymers |
| CN109810006A (en) * | 2019-02-21 | 2019-05-28 | 信阳师范学院 | Fluoro- 2,6- dinitroaniline of a kind of castexplosive 3,4,5- tri- and its preparation method and application |
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2020
- 2020-06-22 CN CN202010573611.0A patent/CN111807987A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4751289A (en) * | 1986-12-29 | 1988-06-14 | Texas Explosives Co. Inc. | Hexanitrotetrachloroazobenzene and method of preparation |
| DE102011118462A1 (en) * | 2011-11-14 | 2013-05-16 | Maximilian Born | Casing useful for a weapon system, comprises a core comprising secondary explosive material as main charge and primary explosive material, and a sheathing comprising energetic duroplastic- and/or energetic thermoplastic polymers |
| CN109810006A (en) * | 2019-02-21 | 2019-05-28 | 信阳师范学院 | Fluoro- 2,6- dinitroaniline of a kind of castexplosive 3,4,5- tri- and its preparation method and application |
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| K. PRAEFCKE ET AL.: "Benzenepentarnine - Its Easy Accessibility and Use in Syntheses of Pyrazinoquinoxalines", 《LIEBIGS ANNALEN DER CHEMIE》 * |
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