CN110358103B - Insensitive energetic metal organic framework and preparation method thereof - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003446 ligand Substances 0.000 claims abstract description 35
- 239000000725 suspension Substances 0.000 claims abstract description 29
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 20
- 239000012266 salt solution Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910001868 water Inorganic materials 0.000 claims abstract description 15
- DPXYQERJZDYPSS-UHFFFAOYSA-N NC=1N=NC(N=1)=C1N=C(N=N1)N[N+](=O)[O-] Chemical compound NC=1N=NC(N=1)=C1N=C(N=N1)N[N+](=O)[O-] DPXYQERJZDYPSS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 22
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical group [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 7
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 7
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 4
- -1 cesium ions Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 6
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical group O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 159000000006 cesium salts Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- OZFMOFUCCWMYLI-UHFFFAOYSA-N NC(NN1N)=NC1=C1N=NC([N+]([O-])=O)=N1 Chemical compound NC(NN1N)=NC1=C1N=NC([N+]([O-])=O)=N1 OZFMOFUCCWMYLI-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B41/00—Compositions containing a nitrated metallo-organic compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention discloses a chemical formula of [ Cs (ABTNA) H2O]nThe insensitive energetic metal organic framework and the preparation method thereof comprise the following steps: step 1: placing a certain amount of deionized water into a round-bottom flask, suspending a certain amount of 3-amino-3 '-nitramino-5, 5' -bi-1, 2, 4-triazole in the deionized water, and stirring to obtain a uniformly dispersed ligand suspension for later use; step 2: weighing a certain mass of cesium metal salt in a beaker, adding a certain amount of deionized water to prepare a cesium metal salt solution with a certain concentration, and stirring the cesium metal salt solution until the cesium metal salt solution becomes a clear cesium metal salt solution for later use; and step 3: heating the ligand suspension prepared in the step 1 to a certain temperature, slowly dropwise adding the metal cesium salt solution prepared in the step 2 into the ligand suspension, keeping the reaction temperature for a period of time after dropwise adding, naturally cooling, and filtering and drying the generated product crystals to obtain a pure product.
Description
Technical Field
The invention relates to the technical field of energetic composite materials, in particular to an insensitive energetic metal organic framework and a preparation method thereof.
Background
Pyrotechnics generally consist of an oxidizer and a combustible mixed together with an exothermic chemical reaction. Most importantly, the redox reaction must be exothermic, free-standing and independent under certain conditions. Combustible metal powders generally function as the combustible substance in a pyrotechnic. Oxidizers, which cause oxidative combustion of combustibles and produce light and heat, act in fireworks by decomposing oxygen at high temperatures, and commonly used are chlorates, perchlorates, nitrates. In order to increase the strength of the agent, retard the burning rate of the pyrotechnic, enrich the colour of the pyrotechnic agent, small amounts of additives, such as epoxy resins, dextrins, are often used. The colored flame is mainly formed by that alkali metal, alkaline earth metal or transition metal contained in combustible materials and chlorine donor (such as polyvinyl chloride PVC, perchlorate and the like) form metal chloride under high temperature condition. Because the chlorine-containing combustible material produces useful collisions with metal atoms during combustion, chemical reactions occur to form diatomic molecules, and the metal element undergoes useful electronic transitions in the visible region to produce color.
At present, the used firework coloring agent is mainly inorganic alkali metal and alkaline earth metal salt, which has the general property of inorganic salt and is easy to absorb moisture, and perchlorate, chloride and nitrate in the firework coloring agent are water pollutants, and the firework coloring agent has great harm to human health. Therefore, there is a great need and an urgent need to develop novel metal colorants.
Disclosure of Invention
The invention aims to provide an insensitive energetic metal organic frame and a preparation method thereof, and the insensitive energetic nitrogen-containing compound 3-amino-3 '-nitro-amino-5, 5' -bi-1, 2, 4-triazole is used for reacting with different metal cesium salts to prepare a novel moisture-absorption-free energetic metal organic frame material which is a potential firework coloring agent material and meets the requirements of the insensitive energetic material.
In order to achieve the purpose, the invention adopts the following technical scheme:
an insensitive energetic metal organic framework of the formula [ Cs (ABTNA) H2O]nWherein ABTNA is an anionic ligand of 3-amino-3 '-nitramino-5, 5' -bi-1, 2, 4-triazole.
The preparation method for preparing the insensitive energetic metal organic framework comprises the following steps:
step 1: preparation of ligand suspensions
Placing a certain amount of deionized water into a round-bottom flask, suspending a certain amount of 3-amino-3 '-nitramino-5, 5' -bi-1, 2, 4-triazole in the deionized water, and stirring to obtain a uniform ligand suspension for later use;
step 2: preparation of a solution of a cesium salt of a metal
Weighing a certain mass of cesium metal salt in a beaker, adding a certain amount of deionized water to prepare a cesium metal salt solution with a certain concentration, and stirring the cesium metal salt solution until the cesium metal salt solution becomes a clear cesium metal salt solution for later use;
and step 3: containing energetic metal-organic framework [ Cs (ABTNA) H2O]nPreparation of
Heating the ligand suspension prepared in the step 1 to a certain temperature, slowly dropwise adding the metal cesium salt solution prepared in the step 2 into the ligand suspension, keeping the reaction temperature for a period of time after dropwise adding, naturally cooling, and filtering and drying the generated product crystals to obtain a pure product.
Specifically, in some embodiments, in step 2, the metal cesium salt is cesium carbonate or cesium hydroxide or cesium chloride or cesium nitrate.
More preferably, in step 2, the concentration of the metal cesium salt solution is 0.1mol/L to 0.2 mol/L.
More preferably, in the step 2, the molar ratio of the anionic ligand of 3-amino-3 '-nitramino-5, 5' -bi-1, 2, 4-triazole to cesium ions in the metal cesium salt solution in the ligand suspension is 1: 1.
More preferably, in the step 3, the reaction temperature is 30-80 ℃.
The ligand 3-amino-3 '-nitramino-5, 5' -bi-1, 2, 4-triazole (HABTNA) has a nitramine group with an acidic hydrogen ion that readily undergoes metathesis with basic species such as metal carbonates and hydroxides. By utilizing the reaction principle, water and carbon dioxide generated by respectively using hydroxide and carbonate of cesium overflow, so that the reaction is carried out towards the direction of a target product, and therefore the cesium ion-based energetic metal-organic framework material can be obtained. By utilizing the reaction principle, the energy-containing metal organic framework material is prepared, the hydrothermal reaction is not needed, the method is simple and easy to obtain, the reaction is rapid, and the later-stage amplification application is facilitated.
Compared with the prior art, the invention has the beneficial effects that:
insensitive energetic metal organic framework [ Cs (ABTNA) H prepared by the method of the present invention2O]nThe low-temperature-coefficient energy-containing material has good safety and energy-containing performance, good thermal stability, excellent free-running property, can meet the requirements of the low-temperature-coefficient energy-containing material, can be used as a component of a pyrotechnic agent, a propellant and an explosive, and has the impact sensitivity of 80J and the friction sensitivity of 360N. Has better application prospect in the field of firework coloring agent. The preparation method has the advantages of simple process flow, convenient operation, mild reaction conditions, good safety and high product quality.
Drawings
FIG. 1 is a single crystal structure diagram of [ Cs (ABTNA) H2O ] n;
FIG. 2 is a TG-DSC curve of [ Cs (ABTNA) H2O ] n.
Detailed Description
The present invention will be further described with reference to the following examples, which are intended to illustrate only some, but not all, of the embodiments of the present invention. Based on the embodiments of the present invention, other embodiments used by those skilled in the art without any creative effort belong to the protection scope of the present invention.
Example 1
Step 1: preparation of ligand HABTNA suspension
10ml of deionized water was placed in a 50ml round bottom flask, and 0.211g (1mmol) of HABTNA was suspended in the deionized water and vigorously stirred for 30 minutes to obtain a uniform ligand suspension for use.
Step 2: preparation of cesium carbonate solution
1.629g (0.5mmol) of cesium carbonate are weighed into a 25ml beaker, 10ml of deionized water is added to prepare a 0.1mol/L cesium carbonate solution, and the solution is stirred well until it becomes a clear cesium carbonate solution for standby.
And step 3: containing energetic metal-organic framework [ Cs (ABTNA) H2O]nPreparation of
And (2) heating the ligand suspension prepared in the step (1) to 80 ℃, slowly dropwise adding the 0.1mol/L cesium carbonate solution prepared in the step (2) into the ligand suspension, keeping the reaction temperature for 30 minutes after dropwise adding, naturally cooling, and filtering and drying the generated product crystals to obtain a pure product.
Example 2
Step 1: preparation of ligand HABTNA suspension
10ml of deionized water was placed in a 50ml round bottom flask, and 0.211g (1mmol) of HABTNA was suspended in the deionized water and vigorously stirred for 30 minutes to obtain a uniform ligand suspension for use.
Step 2: preparation of Cesium hydroxide solution
1.499g (1mmol) of cesium hydroxide was weighed into a 25ml beaker, 10ml of deionized water was added to prepare a 0.1mol/L cesium hydroxide solution, and the solution was stirred well until it became a clear cesium hydroxide solution for use.
And step 3: containing energetic metal-organic framework [ Cs (ABTNA) H2O]nPreparation of
Heating the ligand suspension prepared in the step 1 to 60 ℃, slowly dropwise adding the 0.2mol/L cesium hydroxide solution prepared in the step 2 into the ligand suspension, keeping the reaction temperature for 60 minutes after dropwise adding, naturally cooling, and filtering and drying the generated product crystals to obtain a pure product.
Example 3
Step 1: preparation of ligand HABTNA suspension
10ml of deionized water was placed in a 50ml round bottom flask, and 0.211g (1mmol) of HABTNA was suspended in the deionized water and vigorously stirred for 30 minutes to obtain a uniform ligand suspension for use.
Step 2: preparation of cesium chloride solution
1.684g (1mmol) of cesium chloride are weighed into a 25ml beaker, 10ml of deionized water is added to prepare a 0.2mol/L cesium chloride solution, and the solution is stirred well until it becomes a clear cesium chloride solution for use.
And step 3: containing energetic metal-organic framework [ Cs (ABTNA) H2O]nPreparation of
Heating the ligand suspension prepared in the step 1 to 60 ℃, slowly dropwise adding the 0.2mol/L cesium chloride solution prepared in the step 2 into the ligand suspension, keeping the reaction temperature for 60 minutes after dropwise adding, naturally cooling, and filtering and drying the generated product crystals to obtain a pure product.
Example 4
Step 1: preparation of ligand HABTNA suspension
10ml of deionized water was placed in a 50ml round bottom flask, and 0.211g (1mmol) of HABTNA was suspended in the deionized water and vigorously stirred for 30 minutes to obtain a uniform ligand suspension for use.
Step 2: preparation of cesium nitrate solution
1.949g (1mmol) of cesium nitrate was weighed into a 25ml beaker, 10ml of deionized water was added to prepare a 0.2mol/L cesium nitrate solution, and the solution was stirred well until it became a clear cesium nitrate solution for use.
And step 3: containing energetic metal-organic framework [ Cs (ABTNA) H2O]nPreparation of
Heating the ligand suspension prepared in the step 1 to 50 ℃, slowly dropwise adding the 0.2mol/L cesium nitrate solution prepared in the step 2 into the ligand suspension, keeping the reaction temperature for 30 minutes after dropwise adding, naturally cooling, and filtering and drying the generated product crystals to obtain a pure product.
TG-DSC test shows that the temperature is 10 ℃ min-1And an energetic metal-organic framework [ Cs (ABTNA) H under a nitrogen atmosphere2O]nAs shown in fig. 1, has a good thermal decomposition temperature, which is as high as 225 deg.c, see fig. 2. Meanwhile, safety performance tests show that the compound shows excellent safety performance in a BAM mechanical sensitivity test system, the impact sensitivity of the compound is more than 80J, and the friction sensitivity of the compound is more than 360N, so that the compound is proved to be an insensitive energetic material.
The insensitive energetic metal organic framework [ Cs (ABTNA) H prepared by the method of the invention2O]nSee table 1 for crystal data:
TABLE 1 is [ Cs (ABTNA) H2O]nCrystal data sheet of
The invention relates to a preparation method of an energy-containing metal organic framework material with 3-amino-3 ' -nitramino-5, 5' -bi-1, 2, 4-triazole as an energy-containing ligand, which is based on 3-amino-3 ' -nitramino-5, 5' -bi-1, 2, 4-triazole (N- (5' -amino-1H,1' H- [3,3' -bi (1,2,4-triazol)]-5-yl) nitramine, HABTNA) and metal cesium metal salt [ cs (abtna) H2O]nIt is first reported in the present invention. Energetic metal organic framework [ Cs (ABTNA) H prepared by the process of the present invention2O]nThe test shows that the material is an insensitive energetic material which has good thermal stability and meets the requirements of the insensitive energetic material, and the impact sensitivity of the material is 80J, and the friction sensitivity of the material is 360N. Therefore, the preparation method of the compound is very important in view of its good characteristics. The invention aims at the compound, designs and develops a reliable, simple and convenient aqueous solution crystallization synthetic route suitable for amplification. The method takes HABTNA and different metal cesium salts as raw materials, and obtains a target product through four simple operations of dissolving, heating, mixing, cooling and the like. The route completes the insensitive energetic metal organic framework material [ Cs (ABTNA) H for the first time2O]nThe preparation method has the advantages that the used raw materials are simple and easy to obtain, and the preparation method is free of organic solvents and environment-friendly.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. An insensitive energy-containing metal-organic framework characterized by the chemical formula [ Cs (ABTNA) H2O]nWherein ABTNA is an anionic ligand of 3-amino-3 '-nitramino-5, 5' -bi-1, 2, 4-triazole.
2. The method for preparing a non-sensitive energetic metal organic framework according to claim 1, characterized in that it comprises the following steps:
step 1: preparation of ligand suspensions
Placing a certain amount of deionized water into a round-bottom flask, suspending a certain amount of 3-amino-3 '-nitramino-5, 5' -bi-1, 2, 4-triazole in the deionized water, and stirring to obtain a uniformly dispersed ligand suspension for later use;
step 2: preparation of a solution of a cesium salt of a metal
Weighing a certain mass of cesium metal salt in a beaker, adding a certain amount of deionized water to prepare a cesium metal salt solution with a certain concentration, and stirring the cesium metal salt solution until the cesium metal salt solution becomes a clear cesium metal salt solution for later use;
and step 3: containing energetic metal-organic framework [ Cs (ABTNA) H2O]nPreparation of
Heating the ligand suspension prepared in the step 1 to a certain temperature, slowly dropwise adding the metal cesium salt solution prepared in the step 2 into the ligand suspension, keeping the reaction temperature for a period of time after dropwise adding, naturally cooling, filtering and drying the generated product crystals to obtain a pure product [ Cs (ABTNA) H2O]n。
3. The method for the preparation of a non-sensitive energy-containing metal-organic framework according to claim 2, wherein in step 2 the metal cesium salt is cesium carbonate or cesium chloride or cesium nitrate.
4. The method of claim 2, wherein in step 2, the concentration of the cesium metal salt solution is 0.1mol/L to 0.2 mol/L.
5. The method for preparing a non-sensitive energy-containing metal-organic framework according to claim 2, wherein in step 2, the molar ratio of the anionic ligand of 3-amino-3 '-nitramino-5, 5' -bi-1, 2, 4-triazole to cesium ions in the metal cesium salt solution in the ligand suspension is 1: 1.
6. The method for preparing a non-sensitive energy-containing metal-organic framework according to claim 2, wherein in step 3, the temperature of the reaction is 30-80 ℃.
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|---|---|---|---|---|
| CN106883423A (en) * | 2017-02-28 | 2017-06-23 | 中国工程物理研究院化工材料研究所 | Alkali metal organic frame containing energy and preparation method thereof |
| CN109096215A (en) * | 2018-10-12 | 2018-12-28 | 中国工程物理研究院化工材料研究所 | Rich nitrogen energetic material 3- amino -3 '-nitramino -5,5 '-connection -1,2,4- triazole and preparation method thereof |
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2019
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883423A (en) * | 2017-02-28 | 2017-06-23 | 中国工程物理研究院化工材料研究所 | Alkali metal organic frame containing energy and preparation method thereof |
| CN109096215A (en) * | 2018-10-12 | 2018-12-28 | 中国工程物理研究院化工材料研究所 | Rich nitrogen energetic material 3- amino -3 '-nitramino -5,5 '-connection -1,2,4- triazole and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 3⁃氨基⁃3′⁃硝胺基⁃5，5′⁃联⁃1H⁃1，2，4⁃三唑的合成与表征;王霆威，李燕，陈东，张祺，朱顺官;《含能材料》;20190329;全文 * |
| Asymmetrically substituted 5,5′-bistriazoles – nitrogen-rich materials with various energetic functionalities;Dippold, Alexander A.; Klapoetke, Thomas M.；Oswald, Michaela;《Dalton Transactions》;20130605;全文 * |
| Study of Six Green Insensitive High Energetic Coordination Polymers Based on Alkali/Alkali-Earth Metals and 4,5-Bis(tetrazol-5-yl)-2H-1,2,3-triazole;Chen Dong，Jing Dong，Zhang Qi,et.al;《Chemistry-An Asian Journal》;20171214;全文 * |
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