CN110590481B - Rapid preparation method of HMX large single crystal - Google Patents
Rapid preparation method of HMX large single crystal Download PDFInfo
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- CN110590481B CN110590481B CN201910966243.3A CN201910966243A CN110590481B CN 110590481 B CN110590481 B CN 110590481B CN 201910966243 A CN201910966243 A CN 201910966243A CN 110590481 B CN110590481 B CN 110590481B
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- 239000013078 crystal Substances 0.000 title claims abstract description 149
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 50
- 239000011549 crystallization solution Substances 0.000 claims abstract description 49
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000002360 explosive Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 35
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 abstract description 102
- 238000002425 crystallisation Methods 0.000 abstract description 11
- 230000008025 crystallization Effects 0.000 abstract description 11
- 239000000028 HMX Substances 0.000 description 79
- 238000009826 distribution Methods 0.000 description 16
- 230000007547 defect Effects 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000003517 fume Substances 0.000 description 12
- 230000001788 irregular Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002076 thermal analysis method Methods 0.000 description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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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
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
- C30B7/06—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using non-aqueous solvents
Abstract
The invention discloses a rapid preparation method of a HMX large single crystal, which comprises the following steps: dissolving common HMX crystals in DMSO to form a high-concentration crystallization solution; standing the high-concentration crystallization solution at 0-30 ℃ for 12-24 h; adding an organic micromolecule poor solvent into the high-concentration crystallization solution after standing to obtain a solution to be crystallized; standing the solution to be crystallized at 0-30 ℃, naturally volatilizing the solvent, crystallizing for 3-20 d, filtering, washing and drying to obtain the single explosive HMX large-size single crystal. According to the method, the organic micromolecule poor solvent is added into the HMX high-concentration crystallization solution, natural volatilization of the solvent and natural driving force of crystal growth are utilized, and the large-size polyhedral beta-HMX single crystal with the grain size of 2-5 mm is prepared through crystallization.
Description
Technical Field
The invention belongs to the field of energetic crystal materials, and particularly relates to a rapid preparation method of a HMX large single crystal.
Background
In recent years, a great deal of research shows that the crystal quality (such as purity, density, crystal form, granularity, defects and the like) of the elementary explosive can be improved by a crystallization technology, and the application performance and the safety performance of the elementary explosive are improved. By adopting the technologies of programmed cooling crystallization, solvent-non-solvent crystallization, ultrasonic-assisted crystallization and the like at home and abroad, the crystallization process for improving the quality of the single-substance explosive crystals such as hexogen, octogen and the like through the crystallization technology is researched, and the improved explosive crystals with various crystal qualities of different grades and obtained to different degrees are obtained. However, most of the crystallization processes tend to prepare micron/nanometer-sized fine-particle HMX crystals, and the preparation of large-size single crystals is not involved, so that the requirements of new research and application at present cannot be met. Aiming at the problem, the invention researches a rapid preparation method of the HMX large-size single crystal, and the large-size polyhedral beta-HMX single crystal with the grain diameter of 2-5 mm can be rapidly prepared by the method, thereby meeting the requirements of new research and application.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for rapidly preparing a large single crystal of HMX, comprising the steps of:
dissolving a common HMX crystal in DMSO to form a high-concentration crystallization solution;
step two, standing the high-concentration crystallization solution at the temperature of 0-30 ℃ for 12-24 h;
adding an organic micromolecule poor solvent into the high-concentration crystallization solution after standing to obtain a solution to be crystallized;
and step four, standing the solution to be crystallized at the temperature of 0-30 ℃, naturally volatilizing the solvent, crystallizing for 3-20 days, filtering, washing and drying to obtain the single-substance explosive HMX large-size single crystal.
Preferably, in the first step, the mass fraction of HMX in the high-concentration crystallization solution is 20% to 41%.
Preferably, the organic small molecule poor solvent is one or a mixture of ethanol, isopropanol, n-propanol, n-butanol, n-pentanol or ethyl acetate.
Preferably, in the third step, the mass fraction of the poor organic small-molecule solvent in the solution to be crystallized is 1-20%.
Preferably, the following process is further included between the third step and the fourth step: and carrying out ultrasonic treatment on the solution to be crystallized for 10-15 min.
Preferably, the frequency of the ultrasound is 50-120 kHz, the power density of the ultrasonic is 2000-3000W/L, the ultrasound adopts intermittent irradiation, and the intermittent time during the intermittent irradiation is 20-30 s/10-15 s.
Preferably, in the fourth step, in the middle process of crystallizing for 3d to 20d, the solution to be crystallized is placed in a pulsed magnetic field, the intensity, frequency and temperature of the pulsed magnetic field are adjusted, and the solution to be crystallized is treated for 10 to 15 min.
Preferably, the pulse magnetic field intensity is 0.5-3.5 Tesla, the frequency is 2-5 times/min, and the temperature is 0-30 ℃.
The invention at least comprises the following beneficial effects: according to the invention, by adding the poor organic micromolecule solvent into the HMX high-concentration crystallization solution, the natural driving force of natural volatilization of the solvent and crystal growth is utilized, and the large-size polyhedral beta-HMX single crystal with the particle size of 2-5 mm is prepared through crystallization, so that new research and application requirements are met. In addition, the method for preparing the beta-HMX large-size single crystal has the advantages of simple process flow, mild conditions and safe process, and is suitable for industrial 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.
Description of the drawings:
FIG. 1 is a photograph of a product of beta-HMX crystals prepared in example 1 of the present invention;
FIG. 2 is a photograph of a product of beta-HMX crystals prepared in example 2 of the present invention;
FIG. 3 is a photograph of a product of beta-HMX crystals prepared in example 3 of the present invention;
FIG. 4 is a photograph of a product of beta-HMX crystals prepared in example 4 of the present invention;
FIG. 5 is a photograph of a product of beta-HMX crystals prepared in example 5 of the present invention;
FIG. 6 is a photograph of a product of beta-HMX crystals prepared in example 6 of the present invention;
FIG. 7 is an infrared spectrum of the β -HMX crystal prepared in example 1 and a raw material common HMX crystal;
FIG. 8 is a thermal analysis (DSC) curve of the β -HMX crystals prepared in example 1;
FIG. 9 is a thermal analysis (DSC) curve of a starting conventional HMX crystal;
fig. 10 is a microscopic view of a raw material common HMX crystal.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof; and the common HMX crystals used are not limited to the commercial HMX crystals given in the examples.
Example 1:
a rapid preparation method of HMX large single crystal comprises the following steps:
step one, dissolving 45.00g of common HMX crystal in 100g of analytical pure DMSO to form a high-concentration crystallization solution; the adopted common HMX crystal is industrial HMX, is powdery, has a beta-crystal form, is irregular in appearance and has multiple defects, and the particle size distribution is 10-100 mu m; fig. 10 shows a microscope image (magnification 500 times) of a normal HMX crystal;
transferring the high-concentration crystallization solution into a crystallizer, placing the crystallizer in a fume hood, and standing for 24 hours at the temperature of 21-30 ℃;
step three, slowly and uniformly adding 15.0mL of absolute ethyl alcohol into the high-concentration crystallization solution after standing to obtain a solution to be crystallized;
step four, standing the solution to be crystallized at 21-30 ℃, naturally volatilizing the solvent, crystallizing for 15d, then filtering, washing with deionized water, and drying in vacuum to obtain 42.79g of beta-HMX large-size polyhedral single crystal with the particle size distributed between 2mm and 5mm, wherein the yield is 95.09%; FIG. 1 shows the product of example 1, in which the crystals are transparent or semitransparent polyhedrons, and part of the crystals are opaque due to the adhesion symbiosis of the part of the crystals caused by the generation of a large number of nuclei in the early stage or the shaking of the crystallization liquid in the early stage of crystallization; the particle size is distributed between 2mm and 5mm and is beta-HMX crystal; FIG. 7 is an infrared spectrum of the β -HMX crystal prepared in example 1 and a raw material common HMX crystal; as can be seen from the figure, the infrared spectrogram of the prepared single crystal HMX is completely coincident with the infrared spectrogram of the raw material beta-HMX, and the positions of absorption peaks are completely consistent, thus proving that the two are the same substance; fig. 8 thermal analysis (DSC) curves of the β -HMX crystals prepared in example 1 and the starting normal HMX crystals. As can be seen from FIG. 8, the melting endothermic peak of the single-crystal HMX produced disappeared, the decomposition starting temperature was 179.6 ℃ and the decomposition peak temperature was 282.7 ℃, the decomposition starting temperature and the decomposition peak temperature were slightly advanced as compared with the starting material HMX, and the decomposition peak width was slightly narrower than that of the starting material HMX, indicating that the thermal decomposition of the single-crystal HMX was more rapid than that of the starting material HMX.
Example 2:
a rapid preparation method of HMX large single crystal comprises the following steps:
step one, dissolving 4.34g of common HMX crystal in 15.66g of analytically pure DMSO to form a high-concentration crystallization solution; the adopted common HMX crystal is industrial HMX, is powdery, has a beta-crystal form, is irregular in appearance and has multiple defects, and the particle size distribution is 10-100 mu m;
transferring the high-concentration crystallization solution into a crystallizer, placing the crystallizer in a fume hood, and standing for 24 hours at the temperature of 21-28 ℃;
step three, slowly and uniformly adding 0.35g of n-amyl alcohol into the high-concentration crystallization solution after standing to obtain a solution to be crystallized;
step four, standing the solution to be crystallized at 21-28 ℃, naturally volatilizing the solvent, crystallizing for 5d, then filtering, washing with deionized water, and drying in vacuum to obtain 4.10g of beta-HMX large-size polyhedral single crystal with the particle size distributed in 2-5 mm, wherein the yield is 94.47%. FIG. 2 shows the product of example 2, the crystals are transparent gem-like polyhedra containing a small number of intergrown crystals, the particle size distribution is 2mm to 5mm, and the crystals are beta-HMX crystals.
Example 3:
a rapid preparation method of HMX large single crystal comprises the following steps:
step one, dissolving 4.34g of common HMX crystal in 15.66g of analytically pure DMSO to form a high-concentration crystallization solution; the adopted common HMX crystal is industrial HMX, is powdery, has a beta-crystal form, is irregular in appearance and has multiple defects, and the particle size distribution is 10-100 mu m;
transferring the high-concentration crystallization solution into a crystallizer, placing the crystallizer in a fume hood, and standing for 24 hours at the temperature of 21-28 ℃;
step three, slowly and uniformly adding 0.45g of isopropanol into the high-concentration crystallization solution after standing to obtain a solution to be crystallized;
step four, standing the solution to be crystallized at 21-28 ℃, naturally volatilizing the solvent, crystallizing for 5d, then filtering, washing with deionized water, and drying in vacuum to obtain 3.96g of beta-HMX large-size polyhedral single crystal crystals with the particle size distributed in 2-3 mm, wherein the crystals are transparent and gem-like polyhedrons and contain a small amount of crystals with rhombohedral crystal faces; the yield was 91.24%. FIG. 3 is a graph showing the product of example 3, the crystals being transparent gem-like polyhedrons, crystals containing a small number of rhombohedral faces, and β -HMX crystals.
Example 4:
a rapid preparation method of HMX large single crystal comprises the following steps:
step one, dissolving 4.34g of common HMX crystal in 15.66g of analytically pure DMSO to form a high-concentration crystallization solution; the adopted common HMX crystal is industrial HMX, is powdery, has a beta-crystal form, is irregular in appearance and has multiple defects, and the particle size distribution is 10-100 mu m;
transferring the high-concentration crystallization solution into a crystallizer, placing the crystallizer in a fume hood, and standing for 24 hours at the temperature of 21-28 ℃;
step three, slowly and uniformly adding 0.74g of absolute ethyl alcohol into the high-concentration crystallization solution after standing to obtain a solution to be crystallized;
step four, standing the solution to be crystallized at 21-28 ℃, naturally volatilizing the solvent, crystallizing for 5d, then filtering, washing with deionized water, and drying in vacuum to obtain 4.19g of beta-HMX large-size polyhedral single crystal with the particle size distributed in 2-5 mm, wherein the crystal is a transparent gem-like polyhedron and tends to be spherical and contains a small amount of symbiotic crystals; the yield was 96.54%. FIG. 4 shows the product of example 4, crystals that are transparent gem-like polyhedra, trending spherical, containing a small number of intergrown crystals, and having a particle size distribution of 2mm to 5mm, as β -HMX crystals. FIG. 5 shows the product of example 5, in which the crystals are transparent gem-like polyhedra, oriented spherical, and have a particle size distribution of 2mm to 5mm, and are beta-HMX crystals. The grains with the grain diameter of 2 mm-4 mm are more, and contain a small amount of crystal with rhombohedral faces.
Example 5:
a rapid preparation method of HMX large single crystal comprises the following steps:
step one, dissolving 4.34g of common HMX crystal in 15.66g of analytically pure DMSO to form a high-concentration crystallization solution; the adopted common HMX crystal is industrial HMX, is powdery, has a beta-crystal form, is irregular in appearance and has multiple defects, and the particle size distribution is 10-100 mu m;
transferring the high-concentration crystallization solution into a crystallizer, placing the crystallizer in a fume hood, and standing for 24 hours at the temperature of 21-28 ℃;
step three, slowly and uniformly adding 1.18g of absolute ethyl alcohol into the high-concentration crystallization solution after standing to obtain a solution to be crystallized;
step four, standing the solution to be crystallized at 21-28 ℃, naturally volatilizing the solvent, crystallizing for 5d, then filtering, washing with deionized water, and drying in vacuum to obtain 3.62g of beta-HMX large-size polyhedral single crystal crystals with the particle size distributed in 2-3 mm, wherein the crystals are transparent polyhedrons and tend to be spherical, the number of particles with the particle size of 2-3 mm is large, and the crystals contain a small number of rhombic crystals; the yield was 83.41%.
Example 6:
a rapid preparation method of HMX large single crystal comprises the following steps:
step one, dissolving 5.71g of common HMX crystal in 14.29g of analytically pure DMSO to form a high-concentration crystallization solution; the adopted common HMX crystal is industrial HMX, is powdery, has a beta-crystal form, is irregular in appearance and has multiple defects, and the particle size distribution is 10-100 mu m;
transferring the high-concentration crystallization solution into a crystallizer, placing the crystallizer in a fume hood, and standing for 24 hours at the temperature of 21-28 ℃;
step three, slowly and uniformly adding 3.11g of ethyl acetate into the high-concentration crystallization solution after standing to obtain a solution to be crystallized;
step four, standing the solution to be crystallized at 21-28 ℃, naturally volatilizing the solvent, crystallizing for 5d, then filtering, washing with deionized water, and drying in vacuum to obtain 5.62g of beta-HMX large-size polyhedral single crystal crystals with the particle size distributed in 2-5 mm, wherein the crystals are transparent polyhedrons, the number of particles with the particle size of 2-3 mm is large, and the crystals contain a small number of rhombic crystal faces; the yield was 98.42%. FIG. 6 is the product of example 6, the crystals are transparent polyhedrons with a particle size distribution of 2mm to 5mm, and are β -HMX crystals. The grains with the grain diameter of 2 mm-3 mm are more, and contain a small amount of crystal with rhombohedral faces.
Example 7:
a rapid preparation method of HMX large single crystal comprises the following steps:
step one, dissolving 4.34g of common HMX crystal in 15.66g of analytically pure DMSO to form a high-concentration crystallization solution; the adopted common HMX crystal is industrial HMX, is powdery, has a beta-crystal form, is irregular in appearance and has multiple defects, and the particle size distribution is 10-100 mu m;
transferring the high-concentration crystallization solution into a crystallizer, placing the crystallizer in a fume hood, and standing for 24 hours at the temperature of 21-28 ℃;
step three, slowly and uniformly adding 0.35g of n-amyl alcohol into the high-concentration crystallization solution after standing to obtain a solution to be crystallized; carrying out ultrasonic treatment on the solution to be crystallized for 12 min; the frequency of the ultrasonic wave is 60kHz, the power density of the ultrasonic wave is 3000W/L, the ultrasonic wave adopts intermittent irradiation, the intermittent time during the intermittent irradiation is 20s/10s, namely the ultrasonic wave is stopped for 10s in 20s during the ultrasonic process, and the ultrasonic wave is sequentially carried out;
and step four, standing the solution to be crystallized at the temperature of 21-28 ℃, naturally volatilizing the solvent, crystallizing for 5d, then filtering, washing with deionized water, and drying in vacuum to obtain 4.25g of beta-HMX large-size polyhedral single crystal crystals with the particle size distributed in 3-4 mm, wherein the yield is 97.93%.
Example 8:
a rapid preparation method of HMX large single crystal comprises the following steps:
step one, dissolving 4.34g of common HMX crystal in 15.66g of analytically pure DMSO to form a high-concentration crystallization solution; the adopted common HMX crystal is industrial HMX, is powdery, has a beta-crystal form, is irregular in appearance and has multiple defects, and the particle size distribution is 10-100 mu m;
transferring the high-concentration crystallization solution into a crystallizer, placing the crystallizer in a fume hood, and standing for 24 hours at the temperature of 21-28 ℃;
step three, slowly and uniformly adding 0.35g of n-amyl alcohol into the high-concentration crystallization solution after standing to obtain a solution to be crystallized;
step four, standing the solution to be crystallized at 21-28 ℃, naturally volatilizing the solvent, crystallizing for 2.5d, then placing the solution to be crystallized in a pulsed magnetic field, adjusting the intensity of the pulsed magnetic field to be 1.5 Tesla, the frequency to be 2 times/min and the temperature to be 21-28 ℃, treating the solution to be crystallized for 10min, then continuously standing for crystallizing for 2.5d, then filtering, washing with deionized water and drying in vacuum to obtain 4.2g of beta-HMX large-size polyhedral single crystal with the particle size distributed in 3-5 mm, wherein the crystal is a transparent gem-like polyhedron and tends to be spherical; the yield was 96.77%.
Example 9:
a rapid preparation method of HMX large single crystal comprises the following steps:
step one, dissolving 4.34g of common HMX crystal in 15.66g of analytically pure DMSO to form a high-concentration crystallization solution; the adopted common HMX crystal is industrial HMX, is powdery, has a beta-crystal form, is irregular in appearance and has multiple defects, and the particle size distribution is 10-100 mu m;
transferring the high-concentration crystallization solution into a crystallizer, placing the crystallizer in a fume hood, and standing for 24 hours at the temperature of 21-28 ℃;
step three, slowly and uniformly adding 0.45g of isopropanol into the high-concentration crystallization solution after standing to obtain a solution to be crystallized; carrying out ultrasonic treatment on the solution to be crystallized for 15 min; the frequency of the ultrasonic wave is 80kHz, the power density of the ultrasonic wave is 2500W/L, the ultrasonic wave adopts intermittent irradiation, the intermittent time during the intermittent irradiation is 30s/15s, namely the ultrasonic wave is stopped for 15s in the ultrasonic process, and the ultrasonic wave is sequentially carried out;
step four, standing the solution to be crystallized at 21-28 ℃, naturally volatilizing the solvent, crystallizing for 5d, then filtering, washing with deionized water, and drying in vacuum to obtain 4.20g of beta-HMX large-size polyhedral single crystal with the particle size distributed in 3-4 mm, wherein the crystal is a transparent gem-like polyhedron; the yield was 96.77%.
Example 10:
a rapid preparation method of HMX large single crystal comprises the following steps:
step one, dissolving 4.34g of common HMX crystal in 15.66g of analytically pure DMSO to form a high-concentration crystallization solution; the adopted common HMX crystal is industrial HMX, is powdery, has a beta-crystal form, is irregular in appearance and has multiple defects, and the particle size distribution is 10-100 mu m;
transferring the high-concentration crystallization solution into a crystallizer, placing the crystallizer in a fume hood, and standing for 24 hours at the temperature of 21-28 ℃;
step three, slowly and uniformly adding 0.45g of isopropanol into the high-concentration crystallization solution after standing to obtain a solution to be crystallized;
step four, standing the solution to be crystallized at 21-28 ℃, naturally volatilizing the solvent, crystallizing for 2.5d, then placing the solution to be crystallized in a pulsed magnetic field, adjusting the intensity of the pulsed magnetic field to be 2 Tesla, the frequency to be 3 times/min and the temperature to be 21-28 ℃, treating the solution to be crystallized for 12min, then continuously standing for crystallizing for 2.5d, then filtering, washing with deionized water and drying in vacuum to obtain 4.22g of beta-HMX large-size polyhedral single crystal with the particle size distributed between 3mm and 4mm, wherein the crystal is a transparent and gemform polyhedron; the yield was 97.24%.
Example 11:
a rapid preparation method of HMX large single crystal comprises the following steps:
step one, dissolving 4.34g of common HMX crystal in 15.66g of analytically pure DMSO to form a high-concentration crystallization solution; the adopted common HMX crystal is industrial HMX, is powdery, has a beta-crystal form, is irregular in appearance and has multiple defects, and the particle size distribution is 10-100 mu m;
transferring the high-concentration crystallization solution into a crystallizer, placing the crystallizer in a fume hood, and standing for 24 hours at the temperature of 21-28 ℃;
step three, slowly and uniformly adding 0.35g of n-amyl alcohol into the high-concentration crystallization solution after standing to obtain a solution to be crystallized; carrying out ultrasonic treatment on the solution to be crystallized for 12 min; the frequency of the ultrasonic wave is 60kHz, the power density of the ultrasonic wave is 3000W/L, the ultrasonic wave adopts intermittent irradiation, the intermittent time during the intermittent irradiation is 20s/10s, namely the ultrasonic wave is stopped for 10s in 20s during the ultrasonic process, and the ultrasonic wave is sequentially carried out;
step four, standing the solution to be crystallized at 21-28 ℃, naturally volatilizing the solvent, crystallizing for 2.5d, then placing the solution to be crystallized in a pulsed magnetic field, adjusting the intensity of the pulsed magnetic field to be 1.5 Tesla, the frequency to be 2 times/min and the temperature to be 21-28 ℃, treating the solution to be crystallized for 10min, then continuously standing for crystallizing for 2.5d, then filtering, washing with deionized water and drying in vacuum to obtain 4.30g of beta-HMX large-size polyhedral single crystal with the particle size distributed in 4-5 mm, wherein the crystal is a transparent gem-like polyhedron and tends to be spherical; the yield was 99.08%.
Example 12:
a rapid preparation method of HMX large single crystal comprises the following steps:
step one, dissolving 4.34g of common HMX crystal in 15.66g of analytically pure DMSO to form a high-concentration crystallization solution; the adopted common HMX crystal is industrial HMX, is powdery, has a beta-crystal form, is irregular in appearance and has multiple defects, and the particle size distribution is 10-100 mu m;
transferring the high-concentration crystallization solution into a crystallizer, placing the crystallizer in a fume hood, and standing for 24 hours at the temperature of 21-28 ℃;
step three, slowly and uniformly adding 0.45g of isopropanol into the high-concentration crystallization solution after standing to obtain a solution to be crystallized; carrying out ultrasonic treatment on the solution to be crystallized for 15 min; the frequency of the ultrasonic wave is 80kHz, the power density of the ultrasonic wave is 2500W/L, the ultrasonic wave adopts intermittent irradiation, the intermittent time during the intermittent irradiation is 30s/15s, namely the ultrasonic wave is stopped for 15s in the ultrasonic process, and the ultrasonic wave is sequentially carried out;
step four, standing the solution to be crystallized at 21-28 ℃, naturally volatilizing the solvent, crystallizing for 2.5d, then placing the solution to be crystallized in a pulsed magnetic field, adjusting the intensity of the pulsed magnetic field to be 2 Tesla, the frequency to be 3 times/min and the temperature to be 21-28 ℃, treating the solution to be crystallized for 12min, then continuously standing for crystallizing for 2.5d, then filtering, washing with deionized water and drying in vacuum to obtain 4.27g of beta-HMX large-size polyhedral single crystal with the particle size distributed in 4-5 mm, wherein the crystal is a transparent and gemform polyhedron; the yield was 98.39%.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (1)
1. A rapid preparation method of HMX large single crystal is characterized by comprising the following steps:
dissolving a common HMX crystal in DMSO to form a high-concentration crystallization solution;
step two, standing the high-concentration crystallization solution at the temperature of 0-30 ℃ for 12-24 h;
adding an organic micromolecule poor solvent into the high-concentration crystallization solution after standing to obtain a solution to be crystallized;
step four, standing the solution to be crystallized at the temperature of 0-30 ℃, naturally volatilizing the solvent, crystallizing for 3-20 days, filtering, washing and drying to obtain the single explosive HMX large-size single crystal, wherein the particle size of the single explosive HMX large-size single crystal is 2-5 mm;
in the first step, the mass fraction of HMX in the high-concentration crystallization solution is 20-41%;
the organic micromolecule poor solvent is one or a mixture of isopropanol, normal propyl alcohol, normal butanol, normal amyl alcohol or ethyl acetate;
in the third step, the mass fraction of the poor organic small molecule solvent in the solution to be crystallized is 1-20%;
the following processes are also included between the third step and the fourth step: carrying out ultrasonic treatment on the solution to be crystallized for 10-15 min;
the frequency of the ultrasonic is 50-120 kHz, the power density of the ultrasonic is 2000-3000W/L, the ultrasonic adopts intermittent irradiation, and the intermittent time during the intermittent irradiation is 20-30 s/10-15 s;
in the fourth step, in the middle process of crystallizing for 3d to 20d, the solution to be crystallized is placed in a pulsed magnetic field, the intensity, the frequency and the temperature of the pulsed magnetic field are adjusted, and the solution to be crystallized is treated for 10 to 15 min;
the pulse magnetic field intensity is 0.5-3.5 Tesla, the frequency is 2-5 times/min, and the temperature is 0-30 ℃.
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| US4785094A (en) * | 1986-09-26 | 1988-11-15 | Morton Thiokol, Inc. | Crystallization of beta HMX |
| CN103936534A (en) * | 2014-05-09 | 2014-07-23 | 北京理工大学 | Idiosyncratic refined HMX (cyclotetramethylene tetranitramine) crystal 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4785094A (en) * | 1986-09-26 | 1988-11-15 | Morton Thiokol, Inc. | Crystallization of beta HMX |
| CN103936534A (en) * | 2014-05-09 | 2014-07-23 | 北京理工大学 | Idiosyncratic refined HMX (cyclotetramethylene tetranitramine) crystal 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 |
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