CN110590565A - Method for preparing highly-sphericized 1,1-diamino-2,2-dinitroethylene crystals - Google Patents
Method for preparing highly-sphericized 1,1-diamino-2,2-dinitroethylene crystals Download PDFInfo
- Publication number
- CN110590565A CN110590565A CN201910908152.4A CN201910908152A CN110590565A CN 110590565 A CN110590565 A CN 110590565A CN 201910908152 A CN201910908152 A CN 201910908152A CN 110590565 A CN110590565 A CN 110590565A
- Authority
- CN
- China
- Prior art keywords
- diamino
- dinitroethylene
- solvent
- crystallization kettle
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a highly-spheroidized 1,1-diamino-2,2-dinitroethylene crystal, which comprises the following steps of 1) adding FOX-7, a mixed solvent and an additive into a crystallization kettle for fully dissolving, wherein the initial temperature of the crystallization kettle is 50 ~ 70 ℃, 2) reducing the temperature of the crystallization kettle while stirring to form a supersaturated solution, then generating and growing crystal nuclei, and preserving heat for 1-3 hours, (3) cooling to room temperature while stirring, and (4) filtering, washing and drying to obtain the highly-spheroidized FOX-7 crystal.
Description
Technical Field
The invention relates to the field of energetic crystal materials, in particular to a preparation method of a highly-sphericized 1,1-diamino-2,2-dinitroethylene crystal.
Background
1,1-diamino-2,2-dinitroethylene with molecular formula C2H4N4O4Structural formula isCommonly known as FOX-7 or DADNE, is a new type of high energy insensitive energetic material. Since the first disclosure of the synthetic route for FOX-7 by Latypov et al (Nikolai V.Latypov, Jan Bergman, Abraham Langlet, et al, Synthesis and reactions of 1,1-diamino-2,2-dinitroethyl, Tetrahedron, 1998, 54(38): 11525-.
FOX-7 belongs to push-pull type olefin, a pi electron conjugated system exists in molecules, strong hydrogen bonds exist in molecules and among molecules, the characteristics of no melting point, high crystal density, good stability, low sensitivity and the like are shown, the FOX-7 has good compatibility with many materials such as common polymers, isocyanate, plasticizers and the like in explosives, and is an ideal candidate and one of components (the crystal structure and the thermal decomposition characteristic of FOX-7 such as Zhouchi, shin New Zeng, week water, and the like, and the fire and explosive report 2007, 30(1): 60-63) which can be used as a formula explosive in the novel blunt (low) sensitive explosives synthesized at present.
In the case of a solid explosive, the physical form of the explosive refers to the size, shape, internal defects, etc. of the explosive. Compared with needle-shaped crystals, the spheroidal crystals with the same average particle size have higher surface area to volume ratio, better free flow characteristic and higher bulk density, and can be prepared into mixed explosives, so that the charge density can be greatly improved, and further the detonation performance of the charges is improved (Zhao Xue, Ruifeng, Feng Shunshan. the influence of the particle morphology of RDX on the performance of RDX-based fusion-cast explosives, Nanjing university of science (Nature science edition), 2011, 35(05): 714-. Moreover, the spherical explosive crystal is compact, has few internal defects, can form a small number of hot spots, and has lower mechanical sensitivity than the common crystal form (Zhao Xue, Ruizhishan, Feng Shun mountain. recrystallization method for preparing spherical RDX, university of Beijing Physician university, 2011, 31(1): 5-7). Therefore, the obtained explosive crystal with uniform granularity, regular appearance and sphericity has important theoretical significance and practical application value for improving the performance of the explosive.
In 2014, Zhouqun et al (Zhouqun, Chenzhiqun, Zheng Kongmin, et al. influence of crystal morphology of FOX-7 on sensitivity, bulletin of explosives and powders, 2014, 37(5): 67-76) in glacial acetic acid, cyclohexanone, acetonitrile, DMSO-H2O、DMF-H2Recrystallizing FOX-7 in O solvent, and performing recrystallization in DMF-H2Obtaining blocky FOX-7 crystals in O; 2016 (Zhouchi, Huangjing, Wangbei, et al.) influence of solvent on phase transition and thermal properties of FOX-7 crystals, bulletin of explosives and powders, 2016, 39 (4): 19-22) in DMSO-H2O、DMF-H2O and NMP-H2O is taken as a solvent to carry out recrystallization, thus obtaining lamellar stacked FOX-7 crystals; liuluo and the like (Liuluo, research on crystallization of high-energy low-sensitivity explosive FOX-7, Mian Yang: southwest university of science and technology, 2018.) select DMF to carry out cooling crystallization to obtain massive crystals of FOX-7, but a few cracks are formed on the surfaces of the crystals, and then DMSO is used as a solvent, and water and ethyl acetate are used as nonsolvents to carry out solvent-nonsolvent crystallization, but ideal FOX-7 crystal forms are not obtained.
In order to obtain the spheroidized FOX-7, the invention provides a simple method for preparing the spheroidized FOX-7 by grinding a mixed solvent by utilizing the principle that the edges and corners of particles are dissolved preferentially and the friction effect generated by mutual collision of the particles in the solvent.
Disclosure of Invention
The invention aims to provide a preparation method of highly-sphericized 1,1-diamino-2,2-dinitroethylene crystals in order to obtain an ideal FOX-7 crystal form. The method has the core content that the FOX-7 raw material in powder form is subjected to a two-step preparation technology of cooling crystallization and solvent grinding, so that the highly-spheroidized FOX-7 crystal is obtained.
The invention is realized by the following technical scheme:
a method for preparing highly spheroidized 1,1-diamino-2,2-dinitroethylene crystals, which comprises the following steps:
1) adding powdery 1,1-diamino-2,2-dinitroethylene, a mixed solvent and an additive into a crystallization kettle for full dissolution, wherein the initial temperature of the crystallization kettle is set to be 50-70 ℃;
2) reducing the temperature of the crystallization kettle while stirring, forming a supersaturated solution, then generating and growing crystal nuclei, and preserving heat for 1-3 hours;
3) after the heat preservation is finished, the temperature of the crystallization kettle is reduced while stirring is continued until the temperature of the crystallization kettle is reduced to room temperature (25 ℃);
4) and filtering, washing and drying the substances in the crystallization kettle to finally obtain the highly-sphericized 1,1-diamino-2,2-dinitroethylene crystal.
Preferably, the concentration of the solution of the powdery 1,1-diamino-2,2-dinitroethylene and the mixed solvent in the step 1) is 0.3 to 0.5 g/mL.
As a preferred technical scheme, the dosage of the additive in the step 1) is 0.01 percent ~ 3 percent of the mass of the powdery 1,1-diamino-2, 2-dinitroethylene.
As a preferable technical scheme, the mixed solvent in the step 1) is composed of a solvent a and a solvent B, the volume ratio of the solvent a to the solvent B is 1:9 ~ 9:1, the solvent a is one of dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, N-diethylformamide and gamma-butyrolactone, and the solvent B is one of water, methanol, ethanol, acetic acid, ethyl acetate, benzene, chlorobenzene, dichloromethane, chloroform, carbon tetrachloride, acetone, dioxane and acetonitrile.
As a preferable technical scheme, the additive in the step 1) is one of span 20, span 80, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 4000, sodium carboxymethylcellulose, beta-cyclodextrin, triton X-100, an emulsifier op-10, sodium dodecyl benzene sulfonate, Tween 20 and Tween 80.
As a preferable technical scheme, the stirring speed of the step 2) and the step 3) is 100-600 r/min.
Preferably, the amount of the additive is 0.1 percent ~ 1.5.5 percent of the mass of the powdery 1,1-diamino-2, 2-dinitroethylene.
Preferably, the volume ratio of the solvent A to the solvent B is 3:7 ~ 4: 1.
As a preferable technical scheme, the cooling rate for reducing the temperature of the crystallization kettle in the step 2) and the step 3) is the same, and is specifically 0.1 ~ 1 ℃/min.
The invention uses a cooling crystallization method, the solution becomes supersaturated by cooling and cooling to separate out crystals, and the highly-sphericized 1,1-diamino-2,2-dinitroethylene crystal is finally obtained by utilizing the principle that the edges and corners of the particles are preferentially dissolved and the friction effect generated by the mutual collision of the particles in the solvent.
Compared with the prior art, the invention has the following beneficial effects:
1) the obtained crystal has extremely high sphericization degree, regular crystal form, smooth surface, less transparent defects in the crystal and good free-running property.
2) The spheroidization process is simple and easy to control, the crystallization mother liquor can be recycled, the pollution of an organic solvent to the environment is favorably reduced, the cost is low, the method is safe and reliable, and the method is suitable for industrial batch production.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is an optical microscopic image of 1,1-diamino-2,2-dinitroethylene in powder form used in the present invention.
FIG. 2 is an optical microscope photograph of highly spheroidized 1,1-diamino-2,2-dinitroethylene crystals prepared by the present invention.
FIG. 3 is a graph showing the particle size distribution of 1,1-diamino-2,2-dinitroethylene in powder form used in the present invention.
FIG. 4 is a graph showing the particle size distribution of highly spheroidized 1,1-diamino-2,2-dinitroethylene crystals prepared by the present invention.
Detailed Description
The invention provides a preparation method of a highly-sphericized 1,1-diamino-2,2-dinitroethylene crystal, which comprises the following steps:
1) adding powdery 1,1-diamino-2,2-dinitroethylene, a mixed solvent and an additive into a crystallization kettle for full dissolution, wherein the initial temperature of the crystallization kettle is set to be 50-70 ℃;
the solvent B is one of water, methanol, ethanol, acetic acid, ethyl acetate, benzene, chlorobenzene, dichloromethane, chloroform, carbon tetrachloride, acetone, dioxane and acetonitrile, the additive is one of span 20, span 80, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 4000, sodium carboxymethylcellulose, beta-cyclodextrin, tween-80, tween-sodium sulfonate, tween-80 and an emulsifier, wherein the concentration of the solution formed by the powdery 1,1-diamino-2,2-dinitroethylene glycol is 0.01% ~% of the mass of the powdery 1,1-diamino-2,2-dinitroethylene, and the mixed solvent is 0.01% of ~%, preferably 0.1% of ~.5% and 0.5% of the additive.
2) Reducing the temperature of the crystallization kettle while stirring, wherein the stirring speed is 100-600 r/min, forming a supersaturated solution, generating and growing crystal nuclei, and preserving heat for 1-3 hours;
3) after the heat preservation is finished, continuously stirring and reducing the temperature of the crystallization kettle at the stirring speed of 100-600 r/min until the temperature of the crystallization kettle is reduced to 25 ℃ at room temperature;
4) and filtering, washing and drying the substances in the crystallization kettle to finally obtain the highly-sphericized 1,1-diamino-2,2-dinitroethylene crystal.
FIG. 1 is an optical microscopic view of a powdery FOX-7 raw material used in the present invention, and FIG. 2 is an optical microscopic view of a spheroidized FOX-7 crystal prepared in the present invention. It can be seen that the FOX-7 obtained after crystallization is changed from powder before crystallization to crystal, and the crystal has high sphericity, smooth surface, transparent interior and few defects. FIG. 3 is a particle size distribution diagram of a powdered FOX-7 raw material used in the present invention, and FIG. 4 is a particle size distribution diagram of a spheroidized FOX-7 prepared in the present invention. By contrast, the median diameter of FOX-7 after crystallization increased from 56.61 μm to 322.91 μm before crystallization. The particles as a whole become several times larger.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described and illustrated with reference to specific embodiments of the present invention. It is to be understood that the embodiments described herein are for purposes of illustration only and are not to be construed as limitations of the present invention, and that equivalent embodiments or modifications thereof, which do not depart from the technical spirit of the present invention, are intended to be included within the scope of the present invention.
Example 1
A method for preparing highly spheroidized 1,1-diamino-2,2-dinitroethylene crystals, which comprises the following steps:
1) weighing 11.66 g of powdery 1,1-diamino-2,2-dinitroethylene, weighing 20mL of dimethyl sulfoxide and 10mL of acetone, and weighing polyethylene glycol 4000 with the weight of 0.1% of that of the 1,1-diamino-2, 2-dinitroethylene; adding dimethyl sulfoxide, acetone and polyethylene glycol 4000 into a crystallization kettle, then adding powdery 1,1-diamino-2,2-dinitroethylene into the crystallization kettle, fully stirring at a stirring speed of 400rpm, heating the crystallization kettle to 60 ℃, fully dissolving the powdery 1,1-diamino-2,2-dinitroethylene, and balancing for 30 min;
2) slowly reducing the temperature of the crystallization kettle while stirring, wherein the stirring speed is 400rpm, the cooling rate is 0.3 ℃/min, cooling to a crystallization point, forming a supersaturated solution, generating and growing crystal nuclei, and preserving heat for 3 hours;
3) after the heat preservation is finished, the temperature of the crystallization kettle is reduced while stirring, the stirring speed is 400rpm, and the cooling rate is 0.3 ℃/min until the temperature of the crystallization kettle is reduced to 25 ℃ at room temperature;
4) and filtering, washing and drying the substances in the crystallization kettle to finally obtain the highly-sphericized 1,1-diamino-2,2-dinitroethylene crystal.
Example 2
A method for preparing highly spheroidized 1,1-diamino-2,2-dinitroethylene crystals, which comprises the following steps:
1) weighing 35g of powdery 1,1-diamino-2,2-dinitroethylene, weighing 30mL of LN-methyl pyrrolidone and 70mL of dichloromethane, and weighing sodium carboxymethylcellulose with the weight of 0.1 percent of that of the 1,1-diamino-2, 2-dinitroethylene; firstly, adding N-methylpyrrolidone, dichloromethane and sodium carboxymethylcellulose into a crystallization kettle, then adding powdery 1,1-diamino-2,2-dinitroethylene into the crystallization kettle, fully stirring at a stirring speed of 300rpm, heating the crystallization kettle to 50 ℃, fully dissolving the powdery 1,1-diamino-2,2-dinitroethylene, and balancing for 30 min;
2) slowly reducing the temperature of the crystallization kettle while stirring, wherein the stirring speed is 300rpm, the cooling rate is 0.7 ℃/min, cooling to a crystallization point, forming a supersaturated solution, generating and growing crystal nuclei, and preserving heat for 2 hours;
3) after the heat preservation is finished, the temperature of the crystallization kettle is reduced while stirring, the stirring speed is 300rpm, and the cooling rate is 0.7 ℃/min until the temperature of the crystallization kettle is reduced to 25 ℃ at room temperature;
4) and filtering, washing and drying the substances in the crystallization kettle to finally obtain the highly-sphericized 1,1-diamino-2,2-dinitroethylene crystal.
Example 3
A method for preparing highly spheroidized 1,1-diamino-2,2-dinitroethylene crystals, which comprises the following steps:
1) weighing 43g of powdery 1,1-diamino-2,2-dinitroethylene, weighing 60 mL of LN, N-dimethylformamide and 40mL of acetonitrile, and weighing Tween 20 with the weight of 1% of that of the 1,1-diamino-2, 2-dinitroethylene; adding N, N-dimethylformamide, acetonitrile and Tween 20 into a crystallization kettle, then adding powdery 1,1-diamino-2,2-dinitroethylene into the crystallization kettle, fully stirring at a stirring speed of 100rpm, heating the crystallization kettle to 60 ℃, fully dissolving the powdery 1,1-diamino-2,2-dinitroethylene, and balancing for 30 min;
2) slowly reducing the temperature of the crystallization kettle while stirring, wherein the stirring speed is 100rpm, the cooling rate is 0.8 ℃/min, cooling to a crystallization point, forming a supersaturated solution, generating and growing crystal nuclei, and preserving heat for 2 hours;
3) after the heat preservation is finished, the temperature of the crystallization kettle is reduced while stirring, the stirring speed is 100rpm, and the cooling rate is 0.8 ℃/min until the temperature of the crystallization kettle is reduced to 25 ℃ at room temperature;
4) and filtering, washing and drying the substances in the crystallization kettle to finally obtain the highly-sphericized 1,1-diamino-2,2-dinitroethylene crystal.
Example 4
A method for preparing highly spheroidized 1,1-diamino-2,2-dinitroethylene crystals, which comprises the following steps:
1) weighing 20g of powdery 1,1-diamino-2,2-dinitroethylene, weighing 40mL of dimethyl sulfoxide and 10mL of ethyl acetate, and weighing span 80 with the weight of 0.3% of that of the 1,1-diamino-2, 2-dinitroethylene; adding dimethyl sulfoxide, ethyl acetate and span 80 into a crystallization kettle, then adding powdery 1,1-diamino-2,2-dinitroethylene into the crystallization kettle, fully stirring at a stirring speed of 500rpm, heating the crystallization kettle to 70 ℃, fully dissolving the powdery 1,1-diamino-2,2-dinitroethylene, and balancing for 30 min;
2) slowly reducing the temperature of the crystallization kettle while stirring, wherein the stirring speed is 500rpm, the cooling rate is 0.5 ℃/min, cooling to a crystallization point, forming a supersaturated solution, generating and growing crystal nuclei, and preserving heat for 3 hours;
3) after the heat preservation is finished, the temperature of the crystallization kettle is reduced while stirring, the stirring speed is 500rpm, and the cooling rate is 0.5 ℃/min until the temperature of the crystallization kettle is reduced to 25 ℃ at room temperature;
4) and filtering, washing and drying the substances in the crystallization kettle to finally obtain the highly-sphericized 1,1-diamino-2,2-dinitroethylene crystal.
Example 5
A method for preparing highly spheroidized 1,1-diamino-2,2-dinitroethylene crystals, which comprises the following steps:
1) weighing 27g of powdery 1,1-diamino-2,2-dinitroethylene, weighing 50mL of gamma-butyrolactone and 40mL of methanol, and weighing beta-cyclodextrin with the weight of 1% of that of the 1,1-diamino-2, 2-dinitroethylene; firstly, adding gamma-butyrolactone, methanol and beta-cyclodextrin into a crystallization kettle, then adding powdery 1,1-diamino-2,2-dinitroethylene into the crystallization kettle, fully stirring at a stirring speed of 600rpm, heating the crystallization kettle to 70 ℃, fully dissolving the powdery 1,1-diamino-2,2-dinitroethylene, and balancing for 30 min;
2) slowly reducing the temperature of the crystallization kettle while stirring, wherein the stirring speed is 600rpm, the cooling rate is 0.1 ℃/min, cooling to a crystallization point, forming a supersaturated solution, generating and growing crystal nuclei, and preserving heat for 1 hour;
3) after the heat preservation is finished, the temperature of the crystallization kettle is reduced while stirring, the stirring speed is 600rpm, and the cooling rate is 0.1 ℃/min until the temperature of the crystallization kettle is reduced to 25 ℃ at room temperature;
4) and filtering, washing and drying the substances in the crystallization kettle to finally obtain the highly-sphericized 1,1-diamino-2,2-dinitroethylene crystal.
Example 6
A method for preparing highly spheroidized 1,1-diamino-2,2-dinitroethylene crystals, which comprises the following steps:
1) weighing 17g of powdery 1,1-diamino-2,2-dinitroethylene, weighing 20mL of LN, N-diethylformamide and 15mL of chloroform, and weighing span 20 with the weight of 1.5 percent of the weight of the 1,1-diamino-2, 2-dinitroethylene; adding N, N-diethylformamide, chloroform and span 20 into a crystallization kettle, then adding powdery 1,1-diamino-2,2-dinitroethylene into the crystallization kettle, fully stirring at a stirring speed of 500rpm, heating the crystallization kettle to 65 ℃, fully dissolving the powdery 1,1-diamino-2,2-dinitroethylene, and balancing for 30 min;
2) slowly reducing the temperature of the crystallization kettle while stirring, wherein the stirring speed is 500rpm, the cooling rate is 1 ℃/min, cooling to a crystallization point, forming a supersaturated solution, generating and growing crystal nuclei, and preserving heat for 3 hours;
3) after the heat preservation is finished, continuously stirring and reducing the temperature of the crystallization kettle at the same time, wherein the stirring speed is 500rpm, and the cooling rate is 1 ℃/min until the temperature of the crystallization kettle is reduced to 25 ℃ at room temperature;
4) and filtering, washing and drying the substances in the crystallization kettle to finally obtain the highly-sphericized 1,1-diamino-2,2-dinitroethylene crystal.
Although the invention has been described herein with reference to illustrative embodiments thereof, it is not intended that each embodiment contain only a single embodiment, but rather that the description be for clarity. It should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the scope and spirit of the principles of this disclosure.
Claims (9)
1. A method for preparing highly-spheroidized 1,1-diamino-2,2-dinitroethylene crystals is characterized by comprising the following steps:
1) adding powdery 1,1-diamino-2,2-dinitroethylene, a mixed solvent and an additive into a crystallization kettle for full dissolution, wherein the initial temperature of the crystallization kettle is set to be 50-70 ℃;
2) reducing the temperature of the crystallization kettle while stirring, forming a supersaturated solution, then generating and growing crystal nuclei, and preserving heat for 1-3 hours;
3) after the heat preservation is finished, the temperature of the crystallization kettle is reduced while stirring is continued until the temperature of the crystallization kettle is reduced to the room temperature;
4) and filtering, washing and drying the substances in the crystallization kettle to finally obtain the highly-sphericized 1,1-diamino-2,2-dinitroethylene crystal.
2. The process for the preparation of highly spherized 1,1-diamino-2,2-dinitroethylene crystals according to claim 1, characterized in that: the concentration of the solution formed by the powdery 1,1-diamino-2,2-dinitroethylene and the mixed solvent in the step 1) is 0.3-0.5 g/mL.
3. The process for producing highly spherical 1,1-diamino-2,2-dinitroethylene crystals according to claim 1, wherein the amount of the additive used in the step 1) is ~ 3% based on 0.01% by mass of the powdery 1,1-diamino-2, 2-dinitroethylene.
4. The process for producing highly spheroidized 1,1-diamino-2,2-dinitroethylene crystals according to claim 1 or 2, wherein the mixed solvent in the step 1) comprises a solvent A and a solvent B, the volume ratio of the solvent A to the solvent B is 1:9 ~ 9:1, the solvent A is one of dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, N-diethylformamide and gamma-butyrolactone, and the solvent B is one of water, methanol, ethanol, acetic acid, ethyl acetate, benzene, chlorobenzene, dichloromethane, chloroform, carbon tetrachloride, acetone, dioxane and acetonitrile.
5. The process for the preparation of highly spherized 1,1-diamino-2,2-dinitroethylene crystals according to claim 1 or 3, characterized in that: the additive in the step 1) is one of span 20, span 80, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 4000, sodium carboxymethylcellulose, beta-cyclodextrin, triton X-100, emulsifier op-10, sodium dodecyl benzene sulfonate, tween 20 and tween 80.
6. The process for the preparation of highly spherized 1,1-diamino-2,2-dinitroethylene crystals according to claim 1, characterized in that: the stirring speed of the step 2) and the step 3) is 100-600 r/min.
7. The process for producing highly spherical 1,1-diamino-2,2-dinitroethylene crystals according to claim 3, wherein the amount of the additive is ~ 1.5.5% by mass of 0.1% by mass of the powdery 1,1-diamino-2, 2-dinitroethylene.
8. The process for producing highly spherical crystals of 1,1-diamino-2,2-dinitroethylene according to claim 4, wherein the volume ratio of the solvent A to the solvent B is 3:7 ~ 4: 1.
9. The method for producing highly spherical 1,1-diamino-2,2-dinitroethylene crystals according to claim 1, wherein the temperature reduction rate for reducing the temperature of the crystallization vessel in the steps 2) and 3) is the same, specifically 0.1 ~ 1 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910908152.4A CN110590565B (en) | 2019-09-25 | 2019-09-25 | Preparation method of highly-spheroidized 1,1-diamino-2,2-dinitroethylene crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910908152.4A CN110590565B (en) | 2019-09-25 | 2019-09-25 | Preparation method of highly-spheroidized 1,1-diamino-2,2-dinitroethylene crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110590565A true CN110590565A (en) | 2019-12-20 |
| CN110590565B CN110590565B (en) | 2023-03-10 |
Family
ID=68862919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910908152.4A Active CN110590565B (en) | 2019-09-25 | 2019-09-25 | Preparation method of highly-spheroidized 1,1-diamino-2,2-dinitroethylene crystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110590565B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358409A (en) * | 2020-11-02 | 2021-02-12 | 天津大学 | M-aminobenzoic acid spherical crystal and preparation method thereof |
| CN114195727A (en) * | 2021-12-27 | 2022-03-18 | 中北大学 | Spherical NTO crystal and preparation method thereof |
| CN116120136A (en) * | 2023-01-03 | 2023-05-16 | 上海交通大学 | Al/GO/AP composite energetic micro-unit material and preparation method thereof |
| CN116239429A (en) * | 2023-03-06 | 2023-06-09 | 中北大学 | Preparation and granularity regulation method of high-quality spherical HATO explosive crystals |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044173A (en) * | 2012-12-06 | 2013-04-17 | 中国工程物理研究院化工材料研究所 | Method for preparing ordered porous energetic crystal material |
| CN106397076A (en) * | 2016-08-30 | 2017-02-15 | 中国工程物理研究院化工材料研究所 | Explosive with both high activity and process stability and preparation method thereof |
| CN106748584A (en) * | 2016-11-29 | 2017-05-31 | 西南科技大学 | The method that emulsion method prepares spheroidization organic molecule monomer or compound |
-
2019
- 2019-09-25 CN CN201910908152.4A patent/CN110590565B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044173A (en) * | 2012-12-06 | 2013-04-17 | 中国工程物理研究院化工材料研究所 | Method for preparing ordered porous energetic crystal material |
| CN106397076A (en) * | 2016-08-30 | 2017-02-15 | 中国工程物理研究院化工材料研究所 | Explosive with both high activity and process stability and preparation method thereof |
| CN106748584A (en) * | 2016-11-29 | 2017-05-31 | 西南科技大学 | The method that emulsion method prepares spheroidization organic molecule monomer or compound |
Non-Patent Citations (3)
| Title |
|---|
| ALOK KUMAR MANDAL ETAL: "Preparation of Spherical Particles of 1,1-Diamino-2,2-dinitroethene (FOX-7) Using a Micellar Nanoreactor", 《ORG. PROCESS RES. DEV.》 * |
| 周群 等: "FOX-7晶体形貌对感度的影响", 《火炸药学报》 * |
| 祁栋梁 等: "溶剂-非溶剂法制备纳米FOX-7及其性能", 《含能材料》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358409A (en) * | 2020-11-02 | 2021-02-12 | 天津大学 | M-aminobenzoic acid spherical crystal and preparation method thereof |
| CN114195727A (en) * | 2021-12-27 | 2022-03-18 | 中北大学 | Spherical NTO crystal and preparation method thereof |
| CN114195727B (en) * | 2021-12-27 | 2023-08-22 | 中北大学 | Spherical NTO crystal and preparation method thereof |
| CN116120136A (en) * | 2023-01-03 | 2023-05-16 | 上海交通大学 | Al/GO/AP composite energetic micro-unit material and preparation method thereof |
| CN116239429A (en) * | 2023-03-06 | 2023-06-09 | 中北大学 | Preparation and granularity regulation method of high-quality spherical HATO explosive crystals |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110590565B (en) | 2023-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110590565B (en) | Preparation method of highly-spheroidized 1,1-diamino-2,2-dinitroethylene crystal | |
| Yang et al. | Fabrication of RDX, HMX and CL-20 based microcapsules via in situ polymerization of melamine–formaldehyde resins with reduced sensitivity | |
| CN102992923B (en) | Preparation method of benzotrifuroxan (BTF) and trinitrotoluene (TNT) cocrystallized explosive | |
| Li et al. | Preparation and growth mechanism of micro spherical ammonium dinitramide crystal based on ultrasound-assisted solvent-antisolvent method | |
| CN111875456B (en) | Preparation method of MTNP/TNAZ eutectic mixture | |
| CN112358370A (en) | CL-20 and NTO eutectic explosive and preparation method thereof | |
| Gao et al. | The facile fabrication and formation mechanism of self-assembled spherical 3, 3′-diamino-4, 4′-azoxyfurazan (DAAF) hierarchical structures | |
| CN105274625A (en) | Spherical NTO (3-nitro-1,2,4-triazol-5-one) crystal with high crystalline density and preparation method | |
| Hou et al. | Facile Preparation and Properties Study of CL‐20/TATB/VitonA Composite Microspheres by a Spray‐Drying Process | |
| CN108299324B (en) | Preparation method of spherical 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt | |
| CN108997238B (en) | Preparation method of fine particle NTO | |
| US9850180B1 (en) | Method for manufacture of amorphous energetics | |
| CN108948604B (en) | Gamma-type polyvinylidene fluoride/polybutylene adipate composite material and preparation method thereof | |
| CN112299931A (en) | Preparation method of multi-scale spherical FOX-7 explosive particles | |
| CN102992924B (en) | Preparation method of benzotrifuroxan (BTF) and 2,4-dinitroanisole (DNAN) cocrystallized explosive | |
| CN106518883B (en) | Six azepine isoamyl of nanometer ε crystal form hexanitro hereby alkane explosive and its batch preparation | |
| CN102992925B (en) | Method for preparing BTF-HNIW (benzotrifuroxan- hexanitrohexaazaisowurtzitane) eutectic explosive | |
| CN103435426A (en) | Preparation method for benzotrifuroxan and m-dinitrobenzene eutectic explosive | |
| CN103641670B (en) | A kind of method of coating RDX and HMX and coating material thereof | |
| CN115677435B (en) | Micro-nano spherical high-energy insensitive CL-20/RDX eutectic explosive and preparation method thereof | |
| An et al. | Different inhibition mechanisms and safety effects of TPU and EVA on thermal decomposition of RDX | |
| CN110698350A (en) | Method for preparing spherical 1,1-diamino-2,2-dinitroethylene crystal by ultrasonic wave assistance | |
| CN103242113B (en) | Polyurethane coated modified potassium chlorate and preparation method and applications thereof | |
| CN113149798A (en) | Preparation method of sea-gall-shaped FOX-7 explosive crystal particles | |
| CN108774328B (en) | Preparation method of nitrified grafted modified nitrocellulose microsphere |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |