CN110358103B - Insensitive energetic metal organic framework and preparation method thereof - Google Patents
Insensitive energetic metal organic framework and preparation method thereof Download PDFInfo
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- CN110358103B CN110358103B CN201910642539.XA CN201910642539A CN110358103B CN 110358103 B CN110358103 B CN 110358103B CN 201910642539 A CN201910642539 A CN 201910642539A CN 110358103 B CN110358103 B CN 110358103B
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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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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 |
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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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