CN114874195B - Insensitive high-energy energetic compound and preparation method thereof - Google Patents
Insensitive high-energy energetic compound and preparation method thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 150000004683 dihydrates Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- -1 2,4, 6-triamino-5-nitropyridine-1, 3-dioxy monohydrate Chemical class 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000004682 monohydrates Chemical class 0.000 claims description 2
- 238000005474 detonation Methods 0.000 abstract description 23
- 239000002360 explosive Substances 0.000 abstract description 8
- 230000002378 acidificating effect Effects 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 40
- 238000012360 testing method Methods 0.000 description 24
- 230000035945 sensitivity Effects 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
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- 150000007514 bases Chemical class 0.000 description 4
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- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012047 saturated solution Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 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 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KQTNLVQDRSXUGW-UHFFFAOYSA-N 1-hydroxy-6-imino-3,5-dinitropyridine-2,4-diamine Chemical compound NC=1C([N+]([O-])=O)=C(N)N(O)C(=N)C=1[N+]([O-])=O KQTNLVQDRSXUGW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B49/00—Use of single substances as explosives
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- Chemical & Material Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an insensitive high-energy energetic compound and a preparation method thereof, wherein the insensitive high-energy energetic compound has the structural formula:the insensitive high-energy energetic compound is non-acidic, does not contain water in crystals, has extremely low solubility in water (the solubility in water is less than 1mg/100mL of water), can be used for a long time, does not corrode a metal shell, and does not pollute a water source. In addition, the insensitive high-energy energetic compound also has the advantages of high detonation energy, high detonation velocity, high detonation pressure and insensitive to impact and friction, and is an insensitive high-energy explosive with great application prospect.
Description
Technical Field
The invention relates to the field of organic energetic materials, in particular to an insensitive high-energy energetic compound and a preparation method thereof.
Background
Insensitive explosives have great utility in the defense and aviation fields, and although insensitive high energy compounds have been rapidly developed over the past decades, insensitive high energy compounds that are truly applicable or have great potential are very rare, mainly because of the following drawbacks of the currently reported insensitive high energy compounds themselves: (1) The high-energy compound is generally high in acidity, and can generate great corrosion to the metal shell during long-term storage and use; (2) The strong acidity makes the high-energy compounds have high solubility in water, and when the high-energy compounds are dissolved in water, the high-energy compounds pollute water sources after penetrating into underground water; (3) The high-energy acid compound can be combined with water to form an energy-containing hydrate in the crystallization process, so that the detonation performance of the high-energy acid compound can be reduced, the water removal process can be removed only by long-time heating in a high-temperature environment, and potential safety hazards are further caused by high-temperature heating; (4) Energetic compound energy and safety are a pair of natural contradictions; (5) The vast majority of energetic compounds reported at present have complex synthesis processes, such as two insensitive high explosive 2,4, 6-triamino-3, 5-dinitropyridine-1-oxide (TADNPyO) and 2, 8-diamino-3, 7-dinitropyrazole triazine fused ring compound (DADNPT), and the manufacturing cost is high because the synthesis steps are more than six steps.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a insensitive high-energy energetic compound and a preparation method thereof, and aims to solve the problems of stronger acidity, higher solubility in water and water content of the existing insensitive high-energy compound.
The technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a insensitive high energy containing compound having the structural formula:
in a second aspect, the present invention provides a method for preparing an insensitive high energy containing compound as described above, comprising the steps of:
adding 4,4', 5' -tetralin-1, 1' -dioxygen dihydrate into a first solvent with a first preset temperature to obtain a first solution;
adding 2,4, 6-triamino-5-nitropyridine-1, 3-dioxy monohydrate into a second solvent with a second preset temperature to obtain a second solution;
and mixing the first solution with the second solution, and reacting to obtain the insensitive high-energy energetic compound.
Optionally, in the first solution, the ratio of the dihydrate 4,4', 5' -bitetrazole-1, 1' -dioxy to the first solvent is (0.05-1000) mmol:100mL.
Optionally, the first preset temperature is 20-100 ℃.
Optionally, the first solvent is at least one selected from water, dimethyl sulfoxide, N-dimethylformamide, acetonitrile, methanol, and ethanol.
Optionally, in the second solution, the ratio of the 2,4, 6-triamino-5-nitropyridine-1, 3-dioxy monohydrate to the second solvent is (0.1 to 30) mmol:100mL.
Optionally, the second preset temperature is 20-100 ℃.
Optionally, the second solvent is at least one selected from water, dimethyl sulfoxide, N-dimethylformamide, acetonitrile, methanol, and ethanol.
Optionally, the molar ratio of the dihydrate 4,4', 5' -bitetrazole-1, 1' -dioxy in the first solution to the monohydrate 2,4, 6-triamino-5-nitropyridine-1, 3-dioxy in the second solution is 1: (0.2-5).
Alternatively, the reaction time is 1s to 2 hours.
The beneficial effects are that: the insensitive high-energy energetic compound provided by the invention has no acidity, no water in crystals and extremely low solubility in water (the solubility in water is less than 1mg/100mL of water), can be used for a long time, does not corrode a metal shell, and does not pollute a water source. In addition, the insensitive high-energy energetic compound also has the advantages of high detonation energy, high detonation velocity, high detonation pressure and insensitive to impact and friction, and is an insensitive high-energy explosive with great application prospect.
Drawings
FIG. 1 is a schematic illustration of a preparation scheme of an insensitive high energy containing compound in an embodiment of the invention.
FIG. 2 (a) shows BTO.2H in the embodiment of the present invention 2 O crystal structure club model, FIG. 2 (b) is TANPDO.H in the embodiment of the invention 2 O crystal structure club model diagram.
FIG. 3 is an infrared spectrum of BTO-TANPDO in example 1 of the present invention.
FIG. 4a isBTO.2H in example 1 of the present invention 2 O Differential Scanning Calorimeter (DSC) results, FIG. 4b is a graph of TANPDO.H in example 1 of the present invention 2 O Differential Scanning Calorimeter (DSC) results, FIG. 4c is a graph showing the Differential Scanning Calorimeter (DSC) results of BTO-TANPDO in example 1 of the present invention.
Detailed Description
The invention provides an insensitive high-energy energetic compound and a preparation method thereof, and the invention is further described in detail below for making the purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Insensitive high-energy compounds in the prior art generally have the problems of high acidity, high solubility in water and water. Currently, TATB is still used as an insensitive high-energy explosive, but the detonation energy of the TATB is only 65% of that of HMX (HMX), which cannot meet the use requirement of the modern insensitive high-energy explosive, and the HMX has very strong detonation energy, but the HMX has high mechanical sensitivity and is easy to cause accidents. Based on the above, the embodiment of the invention provides an acidic-free insensitive high-energy energetic compound with extremely low solubility in water and large detonation energy without water, wherein the insensitive high-energy energetic compound has the structural formula:
in this example, the insensitive high energy containing compound of the structure is named 5,5 '-bitetrazole-1, 1' -dioxo-2, 4, 6-triamino-5-nitropyridine-1, 3-dioxo (wherein 5,5 '-bitetrazole-1, 1' -dioxo is designated BTO,2,4, 6-triamino-5-nitropyridine-1, 3-dioxo is designated TANPDO,5 '-bitetrazole-1, 1' -dioxo-2,4, 6-Triamino-5-nitropyridine-1, 3-dioxy is designated as BTO-TANPDO), which is free of water, has extremely low solubility in water (solubility less than 1mg/100mL of water), is hardly soluble in water, has an acidity of 6.76 (the compound is dissolved in 1L of standard deionized water at 25 ℃ C. To give a saturated solution, the pH of the saturated solution is measured to be 6.76), and has a room temperature density of 1.87 g.cm -3 Impact sensitivity of more than 40J, friction sensitivity of more than 360N, and is insensitive to impact and friction, and is an extremely insensitive compound with explosion velocity of 8611 m.s -1 The detonation pressure is 33.03Gpa (obtained by professional computer software EXPLO 5), the detonation energy is 80 percent of HMX (HMX) (obtained by professional computer software EXPLO 5), and the detonation energy is larger than that of TATB (the detonation energy of which is 65 percent of HMX) which is still used at present. The insensitive high-energy energetic compound provided by the embodiment ensures that the insensitive high-energy energetic compound is insensitive to impact and friction, has high detonation energy, high detonation velocity, high detonation pressure, no acidity, no water and extremely low solubility in water, can be used for a long time, can not corrode a metal shell, can not pollute a water source, and is an insensitive high-energy explosive with great application prospect.
The embodiment of the invention also provides a preparation method of the insensitive high-energy energetic compound, as shown in figure 1, which comprises the following steps:
s1, 4', 5' -bitetrazole-1, 1' -dioxy (BTO.2H) dihydrate 2 O) adding the mixture into a first solvent with a first preset temperature to obtain a first solution;
s2, 4, 6-Triamino-5-nitropyridine-1, 3-Dioxy monohydrate (TANPDO. H) 2 O) adding the mixture into a second solvent with a second preset temperature to obtain a second solution;
s3, mixing the first solution with the second solution, and reacting to obtain the insensitive high-energy energetic compound.
In the present embodiment, BTO.2H 2 O is an acidic energetic compound with excellent performance and contains two symmetrical acidic points, TANPDO.H 2 O is a weakly basic compound with excellent performance and contains two symmetrical alkali points, and the preparation of the two hydratesThe method is extremely simple and has high yield, is suitable for industrial production, but is just due to BTO.2H 2 O and TANPDO.H 2 O is a hydrate and its acidity, so that their respective applications are limited. For example, BTO.2H 2 O has a room temperature density of 1.77 g.cm -3 ,TANPDO·H 2 O has a room temperature density of 1.81 g.cm -3 ，BTO·2H 2 The aqueous solutions of O have acidic pKa acidity values of about 2.2, approaching a medium strong acid, and with metal shells can corrode the metal shell packaging, and they both contain water and have energy densities that do not meet the use requirements. In general, acidic compounds will generally form salts with basic compounds, whereas when the basicity of basic compounds is further reduced, energetic acidic compounds will form strong hydrogen bonds with weakly basic compounds instead of ionic bonds. In particular, the acidic energy-containing hydrate and the weakly basic energy-containing hydrate tend to combine with water to form hydrogen bonds, so the embodiment will have the symmetrical acidic energy-containing hydrate BTO.2H 2 O and basic energetic hydrate TANPDO.H with symmetry 2 O is mixed together, acid points and alkali points are tightly combined with each other through hydrogen bonds, supermolecule self-assembly reaction is carried out, and water molecules in the supermolecule self-assembly reaction are removed, so that a novel energetic compound BTO-TANPDO is generated. In the process of preparing the BTO-TANPDO, water molecules are completely removed, so that the obtained BTO-TANPDO does not contain water, and the problems of high acidity, water of crystallization and low energy density of the existing energetic compound are solved. Furthermore, the inventors have unexpectedly found through extensive studies that BTO.2H is used 2 O and TANPDO.H 2 O is used as a reactant, and the two are matched for use, so that the prepared product BTO-TANPDO has extremely low solubility in water and is hardly dissolved in water, and compared with an insensitive high-energy compound in the prior art, the BTO-TANPDO has very remarkable advantage in the aspect of solubility. Furthermore, due to BTO.2H 2 O and TANPDO.H 2 The energy-containing compound BTO-TANPD with strong hydrogen bond connection prepared by the reaction between O has higher thermal decomposition temperature (250 ℃) and lower sensitivity (impact sensitivity is more than 40J and friction sensitivity is more than 360N).
The preparation method provided by the embodiment is simple, the reaction condition is mild, water can be used as a solvent, the environment is not polluted, the environment protection requirement is completely met, and the yield of the preparation method provided by the embodiment is high and reaches 97%.
In step S1, the BTO.2H 2 The preparation flow of O is as follows:
BTO·2H 2 the preparation method of O is extremely simple and has high yield, thus being very suitable for industrial production.
BTO·2H 2 O is shown in FIG. 2 (a), wherein BTO.2H 2 H in O 2 O is connected with BTO through hydrogen bond, the bond length of the hydrogen bond is
In one embodiment, in the first solution, the BTO.2H 2 The ratio of O to the first solvent is (0.05-1000 mmol): 100mL. For example, the ratio may be 0.05mmol:100mL, 100mmol:100mL, 300mmol:100mL, 500mmol:100mL, 800mmol:100mL, 1000mmol:100mL, etc.
In one embodiment, the first preset temperature is 20 to 100 ℃.
In one embodiment, the first preset temperature is 40 to 100 ℃, for example, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, or the like. The temperature can be such that BTO.2H 2 O dissolves better in the first solvent.
In one embodiment, the first solvent is selected from at least one of water, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), acetonitrile, methanol, ethanol, but is not limited thereto. When the solvent is water, the insensitive high-energy-containing compound is generated in the water, and the preparation process is quite safe. And the product is hardly dissolved in water, so the preparation method provided by the embodiment has high yield which is as high as 97%.
In step S2, whatThe TANPDO.H 2 The preparation flow of O is as follows:
TANPDO·H 2 the preparation method of O is extremely simple and has high yield, thus being very suitable for industrial production.
TANPDO·H 2 O is shown in FIG. 2 (b), wherein TANPDO.H 2 H in O 2 O is connected with TANPDO through hydrogen bond, the bond length of the hydrogen bond is that
In one embodiment, in the second solution, the TANPDO.H 2 The ratio of O to the second solvent is (0.1 to 30) mmol:100mL. For example, the ratio may be 0.1mmol:100mL, 5mmol:100mL, 10mmol:100mL, 15mmol:100mL, 20mmol:100mL, 30mmol:100mL, etc.
In one embodiment, the second preset temperature is 20 to 100 ℃.
In one embodiment, the second preset temperature is 40 to 100 ℃, for example, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, or the like. Due to TANPDO.H 2 O has smaller solubility at room temperature, the solubility of O increases with the temperature, and when the second preset temperature is lower than 40 ℃, TANPDO.H 2 Since the solubility of O is small and the efficiency in synthesizing the compound BTO-TANPDO is low, in this embodiment, TANPDO.H is used 2 O is added into the second solvent at 40-100 ℃ to obtain higher efficiency.
In one embodiment, the second solvent is selected from at least one of water, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), acetonitrile, methanol, ethanol. In the present embodiment, BTO.2H 2 O and TANPDO.H 2 The amount of solvent required for the reaction of the supramolecular self-assembly of O in different solvents is different, for example, in DMSO, the amount of solvent required is smaller due to the greater polarity of DMSOIn the solvents with slightly smaller polarity such as methanol and ethanol, the proportion of the solvents is increased, and the reaction temperature range is basically unchanged.
In step S3, the first solution and the second solution are mixed, and intermolecular strong interaction occurs between the two solutions, so as to perform a supermolecule self-assembly reaction, specifically the following reaction occurs:
symmetrical acid energetic hydrate BTO.2H 2 O and symmetrical basic energetic hydrate TANPDO.H 2 O is mixed together, acid points and alkali points are tightly combined with each other through hydrogen bonds, supermolecule self-assembly reaction is carried out, and water molecules are removed, so that a novel energetic compound BTO-TANPDO is generated. In the process of preparing the BTO-TANPDO, water molecules are completely removed, and the problems of high acidity, crystal water content and low energy density of the existing energetic compound are solved. Furthermore, due to BTO.2H 2 O and TANPDO.H 2 The energy-containing compound BTO-TANPD with strong hydrogen bond connection prepared by the reaction between O has higher thermal decomposition temperature (250 ℃) and lower sensitivity (impact sensitivity is more than 40J and friction sensitivity is more than 360N).
In one embodiment, the BTO.2H in the first solution 2 O and the TANPDO.H in the second solution 2 The molar ratio of O is 1: (0.2-5).
In one embodiment, the BTO.2H in the first solution 2 O and the TANPDO.H in the second solution 2 The molar ratio of O is 1:2.
in one embodiment, the reaction time is 1s to 2 hours.
In one embodiment, the reaction time is 1 to 20 seconds.
The following is a detailed description of specific examples.
Example 1
1mmol of BTO.2H 2 O is added into 5mL of water at 90 ℃ until the completionAfter complete dissolution, an aqueous solution of BTO is obtained;
1mmol of TANPDO.H 2 O is added into 20mL of water at 90 ℃ and is dissolved completely to obtain an aqueous solution of TANPDO;
the BTO aqueous solution is rapidly added into the TANPDO aqueous solution, at the moment of solution mixing, the solution becomes turbid, yellow solid precipitates are generated, the temperature is reduced to room temperature, and the insensitive high-energy containing compound BTO-TANPDO is obtained through filtration, wherein the yield is 95%.
Example 2
1mmol of BTO.2H 2 Adding O into 10mL of water at 90 ℃ and obtaining an aqueous solution of BTO after the O is completely dissolved;
1mmol of TANPDO.H 2 O is added into 30mL of water at 90 ℃ and is dissolved completely to obtain an aqueous solution of TANPDO;
the BTO aqueous solution is rapidly added into the TANPDO aqueous solution, after the BTO aqueous solution is completely dissolved, the solution becomes turbid at the moment of solution mixing, yellow solid precipitates are generated, the temperature is reduced to room temperature, and the insensitive high-energy energetic compound BTO-TANPDO is obtained through filtration, wherein the yield is 92%.
Example 3
1mmol of BTO.2H 2 Adding O into 5mL of DMSO at 90 ℃ and obtaining a DMSO solution of BTO after the O is completely dissolved;
1mmol of TANPDO.H 2 O is added into 20mL of DMSO at 90 ℃ and after the O is completely dissolved, a DMSO solution of TANPDO is obtained;
and rapidly adding the DMSO solution of the BTO into the DMSO solution of the TANPDO, stirring for about 5 seconds, rapidly changing the solution into turbidity, generating yellow solid precipitate, cooling to room temperature, and filtering to obtain the insensitive high-energy energetic compound BTO-TANPDO with the yield of 80 percent.
Example 4
1mmol of BTO.2H 2 Adding O into 5mL of DMF at 90 ℃ and obtaining DMF solution of BTO after the O is completely dissolved;
1mmol of TANPDO.H 2 O is added into 20mL of DMF at 90 ℃ and after the O is completely dissolved, a DMF solution of TANPDO is obtained;
the DMF solution of BTO is rapidly added into DMF solution of TANPDO, stirred for about 10s, the solution becomes turbid rapidly, yellow solid precipitates, the temperature is reduced to room temperature, and the insensitive high-energy energetic compound BTO-TANPDO is obtained by filtration, and the yield is 85%.
Example 5
1mmol of BTO.2H 2 Adding O into 5mL of water at 70 ℃ and obtaining an aqueous solution of BTO after the O is completely dissolved;
1mmol of TANPDO.H 2 O is added into 20mL of DMSO at 90 ℃ and after the O is completely dissolved, a DMSO solution of TANPDO is obtained;
the aqueous solution of BTO is rapidly added into DMSO solution of TANPDO, and the solution is stirred for about 20s, so that the solution becomes turbid rapidly, yellow solid precipitates, the temperature is reduced to room temperature, and the insensitive high-energy containing compound BTO-TANPDO is obtained by filtration, wherein the yield is 95%.
The insensitive high energy compounds prepared in example 1 were tested as follows:
1. an infrared absorption spectrum test was performed, and the infrared absorption spectrum is shown in fig. 3, and specific data are: IR (KBr): v 3359,3238,2983,1683,1642,1551,1506,1405,1312,1205,1160,1108,994,763,731,664,592,45 cm -1 .
Nuclear magnetic resonance testing is carried out, nuclear magnetic data: 1 H NMR(d6-DMSO):δ9.44,9.03,4.37； 13 C NMR(d6-DMSO):148.84,148.02,135.15,105.47ppm。
the infrared spectra and nuclear magnetic test results of the insensitive high energy containing compounds prepared in examples 2-5 are the same as those of example 1 and will not be described in detail here.
2. Three elemental analysis tests were performed, with specific data:
C 10 H 14 N 20 O 10 (574.35) Calcd (calculated) C20.91%, H2.46%, N48.77%;
1st Found (first test value) C20.83%, H2.53%, N49.04%;
2st Found (second test value) C20.90%, H2.44%, N48.86%;
1st Found (first test value) C20.83%, H2.43%, N48.95%.
From this, it was found that the compound contained no water. Elemental analysis test results for the insensitive high energy containing compounds prepared in examples 2-5 are the same as those of example 1 and will not be described in detail herein.
3. Thermal analysis test was performed on BTO.2H in example 1 2 O、TANPDO·H 2 O, BTO-TANPDO was subjected to thermal analysis tests, and the results are shown in FIGS. 4a-4c, respectively, and it can be seen from FIG. 4c that the decomposition temperature of the compound BTO-TANPDO is about 250℃and significantly higher than BTO.2H 2 O (FIG. 4 a), and because BTO-TANPDO is free of water, it is almost insoluble in water, is an ideal high energy density energetic material. And is formed by BTO.2H 2 O、TANPDO·H 2 The DSC thermal decomposition curve of O, BTO-TANPDO shows that the DSC curve of BTO-TANPDO is significantly different from that of BTO.2H 2 O and TANPDO.H 2 Superposition of DSC curves of O demonstrates the formation of the new substance BTO-TANPDO. The consistency of the results of the three elemental analyses further demonstrates the formation of the novel substance BTO-TANPDO.
4. And performing impact sensitivity test, and determining that the impact sensitivity of the compound BTO-TANPDO is more than 40J by using a BAM impact sensitivity tester according to the national army standard test standard of energetic materials through tens of times of tests.
5. And (3) performing friction sensitivity test, and determining that the friction sensitivity of the compound BTO-TANPDO is more than 360N by using a BAM friction sensitivity tester according to the national army standard test standard of the energetic material through tens of tests.
6. The solubility test was performed at room temperature (25 ℃ C.), 2g of BTO-TANPDO was weighed and added to 500mL of water to obtain a supersaturated solution, undissolved BTO-TANPDO was removed by filtration, and undissolved BTO-TANPDO was weighed by drying. Repeating the steps three times, and taking an average value to obtain the solubility of the BTO-TANPDO of less than 1mg/100mL. Far lower than BTO.2H 2 Solubility of O (5.13 g/100 mL) and TANPDO.H 2 Solubility of O (220 mg/100 mL). The BTO-TANPDO provided by the invention has extremely low solubility in water and is almost insoluble in water, so that the BTO-TANPDO has extremely high application value.
7. And (3) performing an acidity test, namely taking 1L of standard deionized water, measuring and calibrating the pH value range of the standard deionized water to be 6.95-7.05, dissolving the compound BTO-TANPDO in 1L of standard deionized water at the room temperature of 25 ℃ to obtain a saturated solution, testing the pH value of the saturated solution for 3 times by adopting a PH meter, and taking an average value of 6.76 to be close to the pH value of pure water (the pH value of the pure water is 7.0, and the pH value range of normal rainwater is 5.0-5.6).
8. The heat of formation of the compound was 540 kJ.mol -1 The room temperature density is 1.86-1.87 g.cm -3 The explosion velocity is 8611 m.s calculated by the software EXPLO5 (6.01 version) in industry -1 The detonation pressure is 33.03Gpa, and the detonation energy is about 80% of HMX after conversion by a related formula.
Thus, the acidity of the compound is extremely low as seen by the acidity test; from elemental analysis, the compound was free of water; the solubility test shows that the compound has extremely low solubility in water; the impact sensitivity test and the friction sensitivity test show that the compound is insensitive to impact and friction and is an insensitive compound; the compound has higher detonation energy obtained by calculation of professional software, and is an insensitive high-energy energetic compound. The test results of BTO-TANPDO obtained in the remaining examples are almost identical to those in example 1.
In summary, the invention provides a insensitive high-energy energetic compound and a preparation method thereof, wherein the insensitive high-energy energetic compound is non-acidic, does not contain water in crystals, has extremely low solubility in water (the solubility in water is less than 1mg/100mL of water), can be used for a long time, does not corrode a metal shell, and does not pollute a water source. In addition, the insensitive high-energy energetic compound also has the advantages of high detonation energy, high detonation velocity, high detonation pressure and insensitive to impact and friction, and is an insensitive high-energy explosive with great application prospect. The preparation method provided by the embodiment is simple, the reaction condition is mild, water can be used as a solvent, the environment is not polluted, the environment protection requirement is completely met, and the yield of the preparation method provided by the embodiment is high and reaches 97%.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (10)
1. A insensitive high energy energetic compound characterized by the structural formula:
2. a method of preparing the insensitive high energy containing compound in accordance with claim 1, comprising the steps of:
adding 4,4', 5' -tetralin-1, 1' -dioxygen dihydrate into a first solvent with a first preset temperature to obtain a first solution;
adding 2,4, 6-triamino-5-nitropyridine-1, 3-dioxy monohydrate into a second solvent with a second preset temperature to obtain a second solution;
and mixing the first solution with the second solution, and reacting to obtain the insensitive high-energy energetic compound.
3. The method according to claim 2, wherein the ratio of the dihydrate 4,4', 5' -bitetrazole-1, 1' -dioxy to the first solvent in the first solution is (0.05-1000) mmol:100mL.
4. The method of claim 2, wherein the first predetermined temperature is 20-100 ℃.
5. The method according to claim 2, wherein the first solvent is at least one selected from the group consisting of water, dimethyl sulfoxide, N-dimethylformamide, acetonitrile, methanol, and ethanol.
6. The method of claim 2, wherein the ratio of 2,4, 6-triamino-5-nitropyridine-1, 3-dioxy monohydrate to the second solvent in the second solution is (0.1 to 30) mmol:100mL.
7. The method of claim 2, wherein the second predetermined temperature is 20-100 ℃.
8. The method according to claim 2, wherein the second solvent is at least one selected from the group consisting of water, dimethyl sulfoxide, N-dimethylformamide, acetonitrile, methanol, and ethanol.
9. The method of claim 2, wherein the molar ratio of the dihydrate 4,4', 5' -bitetrazole-1, 1' -dioxygen in the first solution to the monohydrate 2,4, 6-triamino-5-nitropyridine-1, 3-dioxygen in the second solution is 1: (0.2-5).
10. The method according to claim 2, wherein the reaction time is 1s to 2 hours.
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| CN102304089A (en) * | 2011-07-01 | 2012-01-04 | 中国科学院过程工程研究所 | Synthesis method of 4,4'-5,5'-tetranitro-2,2'-biimidazole |
| CN113444048A (en) * | 2021-05-21 | 2021-09-28 | 哈尔滨工业大学（深圳） | High-energy insensitive energetic compound and preparation method thereof |
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| CN102304089A (en) * | 2011-07-01 | 2012-01-04 | 中国科学院过程工程研究所 | Synthesis method of 4,4'-5,5'-tetranitro-2,2'-biimidazole |
| CN113444048A (en) * | 2021-05-21 | 2021-09-28 | 哈尔滨工业大学（深圳） | High-energy insensitive energetic compound and preparation method thereof |
| CN114315739A (en) * | 2021-12-09 | 2022-04-12 | 哈尔滨工业大学（深圳） | High-energy low-sensitivity energetic compound and preparation method thereof |
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