CN110117212B - Energy-containing crystal material self-assembled by melamine nitrogen oxide and oxidant and preparation method thereof - Google Patents
Energy-containing crystal material self-assembled by melamine nitrogen oxide and oxidant and preparation method thereof Download PDFInfo
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- CN110117212B CN110117212B CN201910458044.1A CN201910458044A CN110117212B CN 110117212 B CN110117212 B CN 110117212B CN 201910458044 A CN201910458044 A CN 201910458044A CN 110117212 B CN110117212 B CN 110117212B
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0008—Compounding the ingredient
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/66—Derivatives of melamine in which a hetero atom is directly attached to a nitrogen atom of melamine
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Abstract
The invention discloses a preparation method of an energy-containing crystal material self-assembled by melamine nitrogen oxide and an oxidant, which comprises the following steps: step 1, preparation of melamine oxynitride: adding enough melamine into a proper amount of trifluoroacetic acid, dissolving, dripping aqueous hydrogen peroxide solution, reacting, and filtering to obtain white precipitate. Dissolving the white precipitate in a proper amount of water, adding alkali to neutralize until the pH value is 7, and filtering to obtain melamine nitrogen oxide; step 2, preparing the energetic crystal material: dissolving melamine nitrogen oxide with aqueous hydrogen peroxide solution, nitric acid or perchloric acid respectively, and obtaining the energy-containing crystal material self-assembled by the melamine nitrogen oxide and an oxidant through a series of operations. In the invention, the melamine nitrogen oxide and the energetic crystal material self-assembled by the melamine nitrogen oxide, the hydrogen peroxide, the nitric acid and the perchloric acid have the advantages of simple preparation process, low raw material cost, high density, high detonation performance, proper sensitivity and the like, and are high-energy explosives with great potential application values.
Description
Technical Field
The invention relates to an energetic material and a preparation method thereof, in particular to an energetic crystal material prepared by self-assembling melamine oxynitride, hydrogen peroxide, nitric acid and perchloric acid and a preparation method thereof.
Background
The energetic crystal material is a compound or a mixture which is composed of an oxidant and a combustible and can perform a violent oxidation-reduction chemical reaction by self-oxygen supply and do work externally.
Typical high energy energetic compounds, such as hexanitrohexaazaisowurtzitane (CL-20) and 1,3,5, 7-tetranitro-1, 3,5, 7-tetraazacyclooctane (HMX), have high raw material costs, complicated preparation processes, and oxidizing agents (e.g., nitro) and combustible components (e.g., -CH)2Skeleton) components are usually integrated in one molecule, and the defects that the contradiction between energy and sensitivity is difficult to effectively reconcile exist. Therefore, it is not suitable for some fields where strict requirements are imposed on energy, sensitivity, etc.
Disclosure of Invention
The invention overcomes the defects of the prior art, provides the energy-containing crystal material formed by self-assembling melamine oxynitride and an oxidant and the preparation method thereof, and provides a new method for developing a novel energy-containing crystal material.
The invention is realized in such a way that:
a preparation method of an energetic crystal material self-assembled by melamine nitrogen oxide and an oxidant comprises the following steps:
step 1, preparation of melamine oxynitride
Adding enough melamine into proper amount of trifluoroacetic acid, dissolving at 25-70 ℃, dripping enough hydrogen peroxide aqueous solution, reacting for 6-24 hours, and filtering to obtain white precipitate. Dissolving the white precipitate in a proper amount of water, adding alkali to neutralize until the pH value is 7, and filtering to obtain melamine nitrogen oxide;
step 2, preparation of energetic crystal material
1) Preparation of self-assembled energetic crystal material of melamine oxynitride and hydrogen peroxide
Adding a proper amount of aqueous hydrogen peroxide solution into melamine nitrogen oxide, fully stirring, filtering to obtain a saturated solution, standing in a constant-temperature oven, volatilizing a solvent, sequentially forming crystal nuclei, growing crystal grains, forming crystals, filtering, and drying to obtain the self-assembled energetic crystal material of melamine nitrogen oxide and hydrogen peroxide.
2) Preparation of self-assembled energetic crystal material of melamine oxynitride and nitric acid
Dissolving melamine nitrogen oxide in a proper amount of nitric acid, completely dissolving at 25-70 ℃, volatilizing the solvent in a dry ventilation environment, filtering, and drying to obtain the self-assembled energetic crystal material of the melamine nitrogen oxide and the nitric acid.
3) Preparation of self-assembled energetic crystal material of melamine oxynitride and perchloric acid
Under the heating condition of 25-70 ℃, dissolving melamine nitrogen oxide in a proper amount of perchloric acid, naturally cooling to room temperature after complete dissolution, filtering, and drying to obtain the self-assembled energetic crystal material of melamine nitrogen oxide and perchloric acid.
The further scheme is as follows:
the concentration of the aqueous hydrogen peroxide solution is 30-50%.
The further scheme is as follows:
the alkali added in the step 1 is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate.
The further scheme is as follows:
the mass fraction of the nitric acid is 30-97.5%.
The further scheme is as follows:
the mass concentration of perchloric acid is 30-70%.
The invention also claims the related substances prepared by the above preparation method, in particular:
melamine oxynitride having the structure:
the self-assembly energetic crystal material of melamine nitrogen oxide and hydrogen peroxide has the following structure:
the self-assembly energetic crystal material of melamine oxynitride and nitric acid has the following structure:
the self-assembly energetic crystal material of melamine oxynitride and perchloric acid has the following structure:
according to the invention, a cheap chemical raw material melamine is used, the melamine nitrogen oxide is firstly prepared by adopting nitrogen oxidation reaction, and a series of novel self-assembly energetic compounds are prepared by utilizing the efficient self-assembly of the melamine nitrogen oxide and an oxidant. The self-assembled energetic crystal material formed by the hydrogen peroxide, the nitric acid and the perchloric acid molecules has better adjustability in energy and safety because the oxidizing component and the combustible component are distributed in different molecules.
Compared with the prior art, one of the beneficial effects of the invention is that the melamine nitrogen oxide and the energetic crystal material self-assembled with the hydrogen peroxide, the nitric acid and the perchloric acid have the advantages of simple preparation process, low cost of raw materials, high density, high detonation performance, proper sensitivity and the like, and are high-energy explosives with great potential application value.
Drawings
FIG. 1 shows the crystal structure of melamine oxynitride hydrate
FIG. 2 shows the crystal structure of a self-assembled energetic crystal material of melamine oxynitride and hydrogen peroxide
FIG. 3 shows the crystal structure of a self-assembled energetic crystal material of melamine oxynitride and nitric acid
FIG. 4 shows the crystal structure of self-assembled energy-containing crystal material of melamine oxynitride and perchloric acid
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Trifluoroacetic acid was added to a three-necked flask at 30 c, then sufficient melamine was added with stirring, dissolved, and sufficient 30% hydrogen peroxide was slowly added dropwise. After 6 hours of reaction, a white precipitate was obtained by filtration. Dissolving the white precipitate in appropriate amount of water, adding sodium bicarbonate to neutralize until pH is 7, and filtering to obtain melamine nitrogen oxide, wherein the crystal structure of melamine nitrogen oxide hydrate is shown in figure 1.
Example 2
Trifluoroacetic acid was added to a three-necked flask at 60 c, then sufficient melamine was added with stirring, dissolved, and sufficient 30% hydrogen peroxide was slowly added dropwise. After 24 hours of reaction, a white precipitate was obtained by filtration. Dissolving the white precipitate in a proper amount of water, adding sodium hydroxide to neutralize the solution until the pH value is 7, and filtering the solution to obtain the melamine nitrogen oxide.
Example 3
Hydrochloric acid was added to a three-necked flask at 50 c, then sufficient melamine was added with stirring, dissolved, and sufficient 30% hydrogen peroxide was slowly added dropwise. After 6 hours of reaction, a white precipitate was obtained by filtration. Dissolving the white precipitate in a proper amount of water, adding sodium carbonate to neutralize until the pH value is 7, and filtering to obtain the melamine nitrogen oxide. The reaction route is as follows:
example 4
Trifluoroacetic acid was added to a three-necked flask at 60 c, then sufficient melamine was added with stirring, dissolved, and sufficient 50% hydrogen peroxide was slowly added dropwise. After 6 hours of reaction, a white precipitate was obtained by filtration. Dissolving the white precipitate in a proper amount of water, adding potassium bicarbonate to neutralize until the pH value is 7, and filtering to obtain the melamine nitrogen oxide.
Example 5
10ml of 30% strength hydrogen peroxide are added to a beaker at 25 ℃ and sufficient melamine nitroxide is added with stirring, dissolved and filtered. Standing in a constant temperature oven at 30 deg.C, evaporating filtrate solvent, precipitating crystal, and drying to obtain self-assembled energetic crystal of melamine nitrogen oxide and hydrogen peroxide, wherein the crystal structure is shown in figure 2.
Example 6
10ml of 50% strength hydrogen peroxide are added to a beaker at 25 ℃ and sufficient melamine nitroxide is then added with stirring, dissolved and filtered. Standing the filtrate in a constant-temperature oven at 50 ℃, evaporating the solvent, separating out crystals, and drying to obtain the self-assembled energetic crystals of the melamine oxynitride and the hydrogen peroxide.
Example 7
10ml of white fuming nitric acid was added to the beaker at 25 ℃ and sufficient melamine nitroxide was added with stirring to dissolve completely. Evaporating the solvent in the ventilation position, separating out crystals, and drying to obtain the self-assembly energetic crystal material of the melamine nitrogen oxide and the nitric acid, wherein the crystal structure of the self-assembly energetic crystal material is shown as the attached figure 3.
Example 8
10ml of a 30% strength aqueous nitric acid solution are added to a beaker at 50 ℃ and sufficient melamine nitroxide is added with stirring to dissolve. And (3) evaporating the solvent at a ventilated position, separating out crystals, and drying to obtain the self-assembled energy-containing crystal material of the melamine nitrogen oxide and the nitric acid.
Example 9
10ml of 70% strength perchloric acid are added to a beaker at 60 ℃ and sufficient melamine nitroxide is added with stirring to dissolve completely. And (3) placing the solution in a beaker, standing in a thermostat at 30 ℃, evaporating the solvent, separating out crystals, and drying to obtain the self-assembled energetic crystal material of the melamine nitrogen oxide and the perchloric acid, wherein the crystal structure of the self-assembled energetic crystal material is shown in figure 4.
The melamine nitrogen oxide prepared in the embodiment of the invention and the energetic crystal material (the code numbers are 1, 1H, 1N and 1P in sequence) self-assembled with hydrogen peroxide, nitric acid and perchloric acid have the specific relevant performance data shown in the following table.
Although the invention has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure. More specifically, various variations and modifications may be made to the component parts and/or arrangements of the subject combination arrangement within the scope of the disclosure herein. In addition to variations and modifications in the component parts and/or arrangements, other uses will also be apparent to those skilled in the art.
Claims (9)
1. A preparation method of an energetic crystal material self-assembled by melamine nitrogen oxide and an oxidant is characterized by comprising the following steps:
step 1, preparation of melamine oxynitride
Adding sufficient melamine into a proper amount of trifluoroacetic acid, dissolving at 25-70 ℃, dripping sufficient aqueous hydrogen peroxide solution, reacting for 6-24 hours, and filtering to obtain white precipitate; dissolving the white precipitate in a proper amount of water, adding alkali to neutralize until the pH value is 7, and filtering to obtain melamine nitrogen oxide;
step 2, preparation of energetic crystal material
1) Preparation of self-assembled energetic crystal material of melamine oxynitride and hydrogen peroxide
Adding a proper amount of aqueous hydrogen peroxide solution into melamine nitrogen oxide, fully stirring, filtering to obtain a saturated solution, standing in a constant-temperature oven, volatilizing a solvent, sequentially forming crystal nuclei, growing crystal grains, forming crystals, filtering and drying to obtain a self-assembled energetic crystal material of the melamine nitrogen oxide and the hydrogen peroxide;
or
2) Preparation of self-assembled energetic crystal material of melamine oxynitride and nitric acid
Dissolving melamine nitrogen oxide in a proper amount of nitric acid, completely dissolving at 25-70 ℃, volatilizing the solvent in a dry ventilation environment, filtering, and drying to obtain a self-assembled energetic crystal material of the melamine nitrogen oxide and the nitric acid;
or
3) Preparation of self-assembled energetic crystal material of melamine oxynitride and perchloric acid
Under the heating condition of 25-70 ℃, dissolving melamine nitrogen oxide in a proper amount of perchloric acid, naturally cooling to room temperature after complete dissolution, filtering, and drying to obtain the self-assembled energetic crystal material of melamine nitrogen oxide and perchloric acid.
2. The method of claim 1 for the preparation of an energetic crystalline material of melamine nitroxide self-assembled with an oxidizing agent, characterized in that:
the concentration of the aqueous hydrogen peroxide solution is 30-50%.
3. The method of claim 1 for the preparation of an energetic crystalline material of melamine nitroxide self-assembled with an oxidizing agent, characterized in that:
the alkali added in the step 1 is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate.
4. The method of claim 1 for the preparation of an energetic crystalline material of melamine nitroxide self-assembled with an oxidizing agent, characterized in that:
the mass fraction of the nitric acid is 30-97.5%.
5. The method of claim 1 for the preparation of an energetic crystalline material of melamine nitroxide self-assembled with an oxidizing agent, characterized in that:
the mass concentration of perchloric acid is 30-70%.
6. Melamine oxynitride, obtainable by a process according to any one of claims 1 to 5, characterized by the following structure:
7. the self-assembly energy-containing crystal material of melamine oxynitride and hydrogen peroxide is prepared by the preparation method of any one of claims 1 to 5, and is characterized by having the following structure:
8. the self-assembly energetic crystal material of melamine oxynitride and nitric acid is prepared by the preparation method of any one of claims 1 to 5 and is characterized by having the following structure:
9. the self-assembled energetic crystal material of melamine oxynitride and perchloric acid is prepared by the preparation method of any one of claims 1 to 5, and is characterized by having the following structure:
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| CN110746368A (en) * | 2019-12-03 | 2020-02-04 | 西北大学 | 2,4, 6-triamino-1, 3, 5-triazine-1, 3-dioxide, preparation method and application thereof |
| CN111153864B (en) * | 2020-01-17 | 2021-06-29 | 西北大学 | Nitrogen-rich heat-resistant insensitive energetic compound and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008047210A2 (en) * | 2006-10-17 | 2008-04-24 | Kemon S.P.A. | Compounds derived from 1 -ethyl-4,5-diamino-pyrazole and their use for oxidative dyeing of keratin fibres |
| CN107935940A (en) * | 2017-11-28 | 2018-04-20 | 中国工程物理研究院化工材料研究所 | The preparation method of 2,4,6 triamido of energy-containing compound, 5 nitro-pyrimidine, 1,3 dioxide |
| CN108314597A (en) * | 2018-05-09 | 2018-07-24 | 中国工程物理研究院化工材料研究所 | 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide and nitric acid self-assembled crystal and preparation method thereof |
| CN108586169A (en) * | 2018-05-09 | 2018-09-28 | 中国工程物理研究院化工材料研究所 | 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide and hydrogen peroxide self-assembled crystal and preparation method |
| CN109438366A (en) * | 2018-12-03 | 2019-03-08 | 中国工程物理研究院化工材料研究所 | 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide and perchloric acid the self assembly crystalline material containing energy |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008047210A2 (en) * | 2006-10-17 | 2008-04-24 | Kemon S.P.A. | Compounds derived from 1 -ethyl-4,5-diamino-pyrazole and their use for oxidative dyeing of keratin fibres |
| CN107935940A (en) * | 2017-11-28 | 2018-04-20 | 中国工程物理研究院化工材料研究所 | The preparation method of 2,4,6 triamido of energy-containing compound, 5 nitro-pyrimidine, 1,3 dioxide |
| CN108314597A (en) * | 2018-05-09 | 2018-07-24 | 中国工程物理研究院化工材料研究所 | 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide and nitric acid self-assembled crystal and preparation method thereof |
| CN108586169A (en) * | 2018-05-09 | 2018-09-28 | 中国工程物理研究院化工材料研究所 | 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide and hydrogen peroxide self-assembled crystal and preparation method |
| CN109438366A (en) * | 2018-12-03 | 2019-03-08 | 中国工程物理研究院化工材料研究所 | 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide and perchloric acid the self assembly crystalline material containing energy |
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