CN101624394B - Preparation method of sphericized hexanitrohexaazaisowurtzitane (HNIW) crystal - Google Patents
Preparation method of sphericized hexanitrohexaazaisowurtzitane (HNIW) crystal Download PDFInfo
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Abstract
The invention provides a sphericized epsilon type hexanitrohexaazaisowurtzitane (HNIW) crystal and a preparation method thereof. The preparation method of the sphericized epsilon type hexanitrohexaazaisowurtzitane (HNIW) crystal comprises the following steps: a) dissolving alpha-HNIW, beta-HNIW and gamma-HNIW or mixture of the alpha-HNIW, the beta-HNIW and the gamma-HNIW into a solvent to form a saturated solution of the alpha-HNIW, the beta-HNIW and the gamma-HNIW or the mixture of the alpha-HNIW, the beta-HNIW and the gamma-HNIW; b) adding a crystal growth control agent to the saturated solution and adding an anti-solvent to form a supersaturated solution; and c) adding epsilon-HNIW seed crystals to the supersaturated solution and continuously adding the anti-solvent until all HNIW in the supersaturated solution is released to grow a sphericized epsilon-HNIW crystal. The sphericized epsilon-HNIW crystal does not have sharp edges and corners but has a multi-faceted spherical shape, particle size of 20 to 500 um, chemical purity of 98 to 99.9 percent determined by high performance liquid chromatography, porosity of 0.01 percent to 0.40 percent and 5Kg drop hammer impact sensitivity H50 of 26 to 52 centimeters.
Description
Technical field
The present invention relates to a kind of hexanitro-hexaazaisopen wootz alkyl (HNIW) crystal of spheroidization, also relate to the hexanitro-hexaazaisopen wootz alkyl crystalline method for preparing this spheroidization, belong to fiery explosive field.
Background technology
Energy-containing compound crystalline granularity, shape and its subsurface defect are important performance perameters; Described in following document: people's such as Teipel Ulrich Crystallization of HMX-Particles by Using the Gas Anti-Solvent-Prop.Explos.Pyrotech.1999,24:195; People's such as Antoine E.D. Crystallization and Characterization of RDX, HMX, and CL-20.Crystal Growth &Design, 2004,4:999; People's such as A.T.Nielsen Flippen-Anderson, Synthesis of Polyazapolycyclic Caged Polynitramines, Tetrahedron 1998,54:11793.Energy-containing compound crystalline shape affects is to sensitivity and tap density thereof, and the spheric crystal has good processing characteristics in being processed into the process of energetic material, and has security preferably, and the product of processing has better blast performance and low sensitivity.RDX (RDX) and HMX (HMX) spheroidization degree have reached quite high level, and each item performance that improves behind the spheroidization has obtained sign; PBX (PBX) with based on RDX and HMX has comprehensive performance, and has obtained using widely.
People's such as document Nicholas B. Orderd Aggregation of Benzamide Crystals Induced Using a " Motif Capper " Additive.Crystal Growth & Design 2005; The Crystal engineering of polymorph appearance:the case of sulphathiazole.Powder Technol.2001 of 5:467 and Blagden Nicholas, 121:46～52 have been put down in writing the use crystal and have been generated the growth of control agent district control crystalline, nucleation and change crystalline habit and pattern.St é hane B é azet and his colleague (Molecular Modeling in Crystal Engineering for Processing Materials [J] .Prop.Explos.Pyrotech.2003,28:287～295) through the analog calculation of molecule power property all kinds of SOLVENTS molecule in the ε type hexanitro-hexaazaisopen wootz alkyl crystal (interaction energy on each crystal face of crystal of ε-HNIW).But the ε of spheroidization (HNIW) crystal was not also met report.
There is α at normal temperatures and pressures in HNIW, four kinds of crystal formations of beta, gamma and ε, and wherein ε-the HNIW thermostability is best, density is the highest, is the crystal formation of using in the reality.Usually the α that obtains after nitrated, β or γ type HNIW must be prepared into ε-HNIW through changeing crystalline substance.
The present invention adds the crystal growth control agent in changeing brilliant process, make non-ε grow into the ε-HNIW crystal of spheroidization.This crystal growing process does not increase other process step on the basis of changeing brilliant technology; Need not increase extra security measures yet; ε-the HNIW of the spheroidization that can obtain has premium propertiess such as low sensitivity, high working property ability increasing the product that condition of cost obtains hardly.
Summary of the invention
The present invention provides ε type hexanitro-hexaazaisopen wootz alkyl crystal of a kind of spheroidization and preparation method thereof; Prepared ε-HNIW crystal does not have sharp-pointed corner angle; Its profile is a polyhedron globe, and its granularity is 20～500 μ m, and its purity of high-performance liquid chromatogram determination is 98-99.9%; Its porosity is 0.01%～0.40%, 26-52 centimetre 5Kg drop impact sensitivity H
50
The present invention also provides a kind of ε type hexanitro-hexaazaisopen wootz alkyl crystalline method for preparing spheroidization.
The present invention realizes through following technical scheme.
A kind of ε type hexanitro-hexaazaisopen wootz alkyl crystalline method for preparing spheroidization of the present invention, the practical implementation step is following:
(1) with α-HNIW, β-HNIW, γ-HNIW or its mixture are dissolved in and form its saturated solution in the solvent;
(2) in the saturated solution of (1) preparation, add the crystal growth control agent, and add anti-solvent, form the supersaturated solution of the solute that is added in (1);
(3) in the supersaturated solution of (2) preparation, add ε-HNIW crystal seed, and the HNIW of anti-solvent in solution that continue to add in (2) disengage all, grow into the ε-HNIW crystal of spheroidization.
Above-mentioned solvent is manthanoate, acetic ester or ketone, is ETHYLE ACETATE, ethyl formate, acetone, methylethylketone, isopropyl acetate, THF or its mixture.Anti-solvent is sherwood oil, tetracol phenixin, benzene, octane or hexanaphthene, toluene, YLENE, methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ether and/or methyl-n-butyl ether etc.The temperature of in the spheroidization process, using is 0～60 ℃.The adding speed of anti-solvent does not have special limitation among the present invention; The speed that adds only otherwise influencing crystal growth gets final product; Make 98 weight % of the HNIW raw material of adding disengage the anti-solvent that comes and in 4～48h, add, preferably in 6～24h, add, more preferably in 8～16h, add.
Solvent of the present invention is meant that HNIW solubleness therein is/100 milliliters of solvents of at least 10 grams, preferably/100 milliliters of solvents of at least 20 grams, the more preferably solvent of/100 milliliters of solvents of at least 30 grams.Alleged " the anti-solvent " of the present invention is meant that HNIW solubleness therein is 1 gram/100 milliliters below the solvent, and/100 milliliters of preferred 0.5 grams are below the solvent, more preferably the solvent below/100 milliliters of solvents of 0.1 gram.
Crystal growth control agent molecule of the present invention has hydroxyl, carboxyl, ester group, amino etc.; They and HNIW molecule have strong interaction; Conformation, intermolecular distance owing to the HNIW molecule on each aufwuchsplate of HNIW crystal are different; The sorptive power of crystal growth control agent molecule on each aufwuchsplate is different, and be therefore different to the inhibition speed of each crystal face growth in crystal growing process, changed the speed of relative movement of each crystal face growth of HNIW crystal and changed the crystalline profile from face.The crystal growth control agent that uses among the present invention can be carboxylic acid, polyprotonic acid, polyvalent alcohol, acid amides, amino acid, ester etc.
The preferred crystal growth control agent of the present invention is a carboxylic acid, for example toxilic acid, butenoic acid, butene dioic acid, caproic acid, hexanodioic acid, phytic acid, Hydrocerol A; Ester, for example butyl butyrate, ethyl n-butyrate, propyl butyrate, ethyl malonate, propanedioic acid one butyl ester; Alcohol, polyvalent alcohol is tetramethylolmethane, 1,2 for example, and 4-trihydroxybutane, USP Kosher, molecular weight are the Z 150PH of 10-300, and preferred molecular weight is 50-200, and more preferably molecular weight is 70-130, and most preferably molecular weight is 80-110; Amino ester, for example, 2-alanine ethyl ester, 2-alanine methyl esters, 2-propalanine ethyl ester, 2-propalanine methyl esters, monomethyl maleate or the like; Hydroxycarboxylic acid; Oxyacetic acid for example, 1-hydroxy-propionic acid, 2 hydroxy propanoic acid; The 1-hydroxybutyric acid; The 2-hydroxybutyric acid, ester OH, for example 2 hydroxy propanoic acid ethyl ester, 2 hydroxy propanoic acid methyl esters, 2-3-hydroxyethyl butyrate, 2-beta-hydroxymethyl butyrate; Amino acid is like Padil, alanine, amino butyl ester, Methionin, l-arginine, halfcystine, Gelucystine, leucine, Methionin, Xie Ansuan, a-aminoisovaleric acid, tryptophane, Vitamin U, N-dodecyl L-Ala, 2-amino-3-oxyacetic acid, glycine ethyl ester hydrochloride.
Beneficial effect
ε-HNIW the crystal of the spheroidization of the present invention's preparation does not have sharp-pointed corner angle; Its profile is a polyhedron globe, and its granularity is 20～500 μ m, its purity of high-performance liquid chromatogram determination be 98% and more than; Its porosity is 0.01%～0.40%, 26-52 centimetre 5Kg drop impact sensitivity H
50
Description of drawings
Fig. 1 is that the crystal growth control agent changes ε-HNIW crystalline pattern that crystalline substance obtains for not adding the crystal growth control agent with adding toxilic acid, tetramethylolmethane, Padil respectively;
Fig. 2 is α, beta, gamma and ε-HNIW crystalline XRD figure spectrum.
In an embodiment of the present invention, the ε type hexanitro-hexaazaisopen wootz alkyl crystalline raw material of preparation spheroidization can be α-HNIW, β-HNIW, γ-HNIW or its mixture.The solvent that uses is proper as manthanoate, acetic ester or ketone, can be ETHYLE ACETATE, ethyl formate, acetone, methylethylketone, isopropyl acetate, THF or its mixture.Anti-solvent is selected sherwood oil, tetracol phenixin, benzene, octane or hexanaphthene, toluene, YLENE, methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ether and/or methyl-n-butyl ether etc.The temperature of in the spheroidization process, using is 0 to 60 ℃.The adding speed of anti-solvent does not have special limitation among the present invention; The speed that adds only otherwise influencing crystal growth gets final product; Make 98 weight % of the HNIW raw material of adding disengage the anti-solvent that comes and in 4 to 48 hours, add, preferably in 6-24 hour, add, more preferably in 8-16 hour, add.
Alleged " solvent " of the present invention is meant that HNIW solubleness therein is/100 milliliters of solvents of at least 10 grams, preferably/100 milliliters of solvents of at least 20 grams, the more preferably solvent of/100 milliliters of solvents of at least 30 grams.Alleged " the anti-solvent " of the present invention is meant that HNIW solubleness therein is 1 gram/100 milliliters below the solvent, and/100 milliliters of preferred 0.5 grams are below the solvent, more preferably the solvent below/100 milliliters of solvents of 0.1 gram.
Crystal growth control agent molecule of the present invention has hydroxyl, carboxyl, ester group, amino etc.; They and HNIW molecule have strong interaction; Conformation, intermolecular distance owing to the HNIW molecule on each aufwuchsplate of HNIW crystal are different; The sorptive power of crystal growth control agent molecule on each aufwuchsplate is different, and be therefore different to the inhibition speed of each crystal face growth in crystal growing process, changed the speed of relative movement of each crystal face growth of HNIW crystal and changed the crystalline profile from face.The crystal growth control agent that uses among the present invention can be carboxylic acid, polyprotonic acid, polyvalent alcohol, acid amides, amino acid, ester etc.
The preferred crystal growth control agent of the present invention is a carboxylic acid, for example toxilic acid, butenoic acid, butene dioic acid, caproic acid, hexanodioic acid, phytic acid, Hydrocerol A; Ester, for example butyl butyrate, ethyl n-butyrate, propyl butyrate, ethyl malonate, propanedioic acid one butyl ester; Alcohol, polyvalent alcohol is tetramethylolmethane, 1,2 for example, and 4-trihydroxybutane, USP Kosher, molecular weight are the Z 150PH of 10-300, and preferred molecular weight is 50-200, and more preferably molecular weight is 70-130, and most preferably molecular weight is 80-110; Amino ester, for example, 2-alanine ethyl ester, 2-alanine methyl esters, 2-propalanine ethyl ester, 2-propalanine methyl esters, monomethyl maleate or the like; Hydroxycarboxylic acid; Oxyacetic acid for example, 1-hydroxy-propionic acid, 2 hydroxy propanoic acid; The 1-hydroxybutyric acid; The 2-hydroxybutyric acid, ester OH, for example 2 hydroxy propanoic acid ethyl ester, 2 hydroxy propanoic acid methyl esters, 2-3-hydroxyethyl butyrate, 2-beta-hydroxymethyl butyrate; Amino acid is like Padil, alanine, amino butyl ester, Methionin, l-arginine, halfcystine, Gelucystine, leucine, Methionin, Xie Ansuan, a-aminoisovaleric acid, tryptophane, Vitamin U, N-dodecyl L-Ala, 2-amino-3-oxyacetic acid, glycine ethyl ester hydrochloride.
In a specific embodiments of the present invention, adopt following steps to prepare the ε type hexanitro-hexaazaisopen wootz alkyl crystal of spheroidization:
A) with α-HNIW, β-HNIW, γ-HNIW or its mixture are dissolved in and form its saturated solution in the solvent,
B) in above solution, add the crystal growth control agent, and add anti-solvent with the formation supersaturated solution,
C) in above-mentioned supersaturated solution, add ε-HNIW crystal seed; And continue to add the HNIW of anti-solvent in solution and all disengage the ε-HNIW crystal that grows into spheroidization, the ε of said spheroidization-HNIW crystal does not have sharp-pointed corner angle, has the profile of polyhedron globe; And has the granularity of 20-500 μ m; The chemical purity of the 98-99.9% of high-performance liquid chromatogram determination, 0.01% to 0.40% porosity and 26-52 centimetre 5Kg drop impact sensitivity H
50
Wherein the crystal growth control agent also can be with α-HNIW; β-HNIW; γ-HNIW or its mixture add before being dissolved in solvent; Also will slowly add after with the dissolving of crystal growth control agent again or be added dropwise in the solvent with the solubility promoter of the 1-10 volume % that uses solvent, solubility promoter described herein be meant that to the bigger solvent of crystal growth control agent solubleness the solubleness of preferred crystal growth control agent in solubility promoter is/100 milliliters of solvents of 0.1 to 1 gram; More preferably the solubleness of crystal growth control agent in solubility promoter is/100 milliliters of solvents of 0.1 to 2 gram; More preferably the solubleness of crystal growth control agent in solubility promoter is/100 milliliters of solvents of 0.1 to 3 gram again, and most preferably the solubleness of crystal growth control agent in solubility promoter is 0.1 to 10 gram/100 milliliters of solvents, for example ethanol, formic acid etc.
In specific embodiments of the present invention, can prepare a kind of ε type hexanitro-hexaazaisopen wootz alkyl crystal of spheroidization according to the present invention, described ε-HNIW crystal does not have sharp-pointed corner angle; Profile with polyhedron globe; And has the granularity of 20-500 μ m, the chemical purity of the 98-99.9% of high-performance liquid chromatogram determination, 0.01% to 0.40% porosity; With 26-52 centimetre, preferred 30-52 centimetre, 35-52 centimetre 5Kg drop impact sensitivity H most preferably
50
In another specific embodiments of the present invention, can prepare a kind of ε type hexanitro-hexaazaisopen wootz alkyl crystal of spheroidization according to the present invention, described ε-HNIW crystal does not have sharp-pointed corner angle; Profile with polyhedron globe; And has the granularity of 50-450 μ m, the chemical purity of the 98-99.8% of high-performance liquid chromatogram determination, 0.02% to 0.350% porosity; With 26-52 centimetre, preferred 30-52 centimetre, 35-52 centimetre 5Kg drop impact sensitivity H most preferably
50
In another specific embodiments of the present invention, can prepare a kind of ε type hexanitro-hexaazaisopen wootz alkyl crystal of spheroidization according to the present invention, described ε-HNIW crystal does not have sharp-pointed corner angle; Profile with polyhedron globe; And has the granularity of 80-250 μ m, the chemical purity of the 98-99.8% of high-performance liquid chromatogram determination, 0.03% to 0.30% porosity; With 26-52 centimetre, preferred 30-52 centimetre, 35-52 centimetre 5Kg drop impact sensitivity H most preferably
50
Wherein the crystal growth control agent also can be with α-HNIW; β-HNIW; γ-HNIW or its mixture add before being dissolved in solvent; Also will slowly add after with the dissolving of crystal growth control agent again or be added dropwise in the solvent with the solubility promoter of the 1-10 volume % that uses solvent, solubility promoter described herein be meant that to the bigger solvent of crystal growth control agent solubleness the solubleness of preferred crystal growth control agent in solubility promoter is/100 milliliters of solvents of 0.1 to 1 gram; More preferably the solubleness of crystal growth control agent in solubility promoter is/100 milliliters of solvents of 0.1 to 2 gram; More preferably the solubleness of crystal growth control agent in solubility promoter is/100 milliliters of solvents of 0.1 to 3 gram again, and most preferably the solubleness of crystal growth control agent in solubility promoter is 0.1 to 10 gram/100 milliliters of solvents, for example ethanol, formic acid etc.
Analyze each crystalline chemical purity with HPLC, instrument adopts Water 996 type high performance liquid chromatographs, chromatographic condition: 300mm*4.6mm Hyper ODS2C18 chromatographic column; 25 ℃ of column temperatures, solvent are that (60/40, V/V) moving phase is methanol (50/50 to second eyeball/water; V/V), flow velocity is 1mL/min, and sample size is 10uL; The detection wavelength is 230nm, and the HPLC purity of mensuration is expressed as the area at the HPLC peak of target substance and representes method divided by the percentage ratio of the area at all HPLC peaks.
The XRD quantitative analysis method is according to Quantitative determination of ε-phase inpolymorphic HNIW using X-ray diffraction patterns of Chen Huaxiong etc.; Propellants Explos Pyrotech; The 33rd volume, the described method of 467-471 page or leaf is measured the content that changes ε phase HNIW in the brilliant product.Adopt the XRD figure spectrum of the automatic X-ray diffractometer working sample of X ' Pert HighScore type, the instrument application graphite monochromator, the step-length that when making quantitative test, scans is adjusted to 0.02 °/s.Sample mix adopts warm therapy to mix, and thick matter HNIW sample is milled in the non-solvent trichloromethane.The XRD figure spectrum of measuring is removed the back of the body end and to specifying the peak to advance into area integral, is carried out quantitative Analysis then with the JADE data processing software.
The sensitivity test method is pressed GJB 772A-97 defined method, surveys the characteristic drop height H of HNIW by lifting and lowering method with the Cast appearance that drops hammer
50, also measured the H of military HMX simultaneously
50Value is as comparing.The quality of dropping hammer is 5 ± 0.005Kg, and medicine is 50 ± 1mg.Measuring temperature is 15～26 ℃, and humidity is 20%～22%.Test seasonal h representative beginning experimental level, make i represent the experimental level number, the logarithmic value that on behalf of experiment interval (step-length) drop height and unit at interval, d all get cms.When processing data, should note removing invalid test number (TN).Total test number (TN) is no less than 20 times.
Embodiment
Embodiment
In the present invention, unless stated otherwise, the per-cent described in the present invention is weight percentage.Below come example the present invention through concrete embodiment, be not to be used for limiting the present invention.
The comparative example
10g γ-HNIW (g) is dissolved in there-necked flask with 20 milliliters of ETHYLE ACETATE ratios; Removal does not have dissolved impurity and then adds in the flask, drips 8 milliliters of trichloromethanes when being ETHYLE ACETATE, adds crystal seed (about 1 restrains); Add 8 times of volumes again in the trichloromethane of ETHYLE ACETATE; Trichloromethane added at 18 hours, and dissolved HNIW is all disengaged, and changeing brilliant temperature is 20-25 ℃.The ε that makes-HNIW crystal has sharp-pointed corner angle, and its profile is pyramid the more, and mean particle size is 120 μ m, and its purity of high-performance liquid chromatogram determination is 98.7%, and its porosity is 0.90%, 5Kg drop impact sensitivity H
50It is 19 centimetres.
Embodiment 1
In there-necked flask, 10g γ-HNIW is joined in the ETHYLE ACETATE of 20ml the dissolving after-filtration.In ETHYLE ACETATE, add 0.1 gram toxilic acid, stir and make its dissolving.Add 1g ε-HNIW crystal seed after dripping the 8ml trichloromethane, add the 160ml trichloromethane again, trichloromethane added at 21 hours, and dissolved HNIW is all disengaged, and changeing brilliant temperature is 20～25 ℃.Changeing the brilliant ε-HNIW crystal that makes does not have sharp-pointed corner angle, and its profile is a polyhedron globe, and its mean particle size is 160 μ m, its purity of high-performance liquid chromatogram determination be 99.2% and more than, its porosity is 0.02%, 5Kg drop impact sensitivity H
50It is 41 centimetres.
In there-necked flask, 10g γ-HNIW is joined in the ETHYLE ACETATE of 20ml, the dissolving after-filtration, removing does not have dissolved impurity.In ETHYLE ACETATE, add the 0.12g tetramethylolmethane, stir and make its dissolving.Add 1g ε-HNIW crystal seed after dripping the 8ml trichloromethane, add the 160ml trichloromethane again, trichloromethane added at 20 hours, and dissolved HNIW is all disengaged, and changeing brilliant temperature is 20～25 ℃.Changeing the brilliant ε-HNIW crystal that makes does not have sharp-pointed corner angle, and its profile is a polyhedron globe, and its mean particle size is 150 μ m, its purity of high-performance liquid chromatogram determination be 99.1% and more than, its porosity is 0.02%, 5Kg drop impact sensitivity H
50It is 31 centimetres.
Embodiment 3
In there-necked flask, 10g γ-HNIW is joined in the ETHYLE ACETATE of 20ml, the dissolving after-filtration, removing does not have dissolved impurity.In ETHYLE ACETATE, add 0.15g crystal growth control agent Padil, stir and make its dissolving.Add 1g ε-HNIW crystal seed after dripping the 8ml trichloromethane, add the 160ml trichloromethane again, trichloromethane added at 20 hours, and dissolved HNIW is all disengaged, and changeing brilliant temperature is 20～25 ℃.Changeing the brilliant ε-HNIW crystal that makes does not have sharp-pointed corner angle, and its profile is a polyhedron globe, and its mean particle size is 130 μ m, its purity of high-performance liquid chromatogram determination be 99.2% and more than, its porosity is 0.03%, 5Kg drop impact sensitivity H
50It is 30 centimetres.
Embodiment 4
In there-necked flask, 10g γ-HNIW is joined in the ethyl formate of 20ml, the dissolving after-filtration, removing does not have dissolved impurity.In ETHYLE ACETATE, add 0.12g crystal growth control agent Hydrocerol A, stir and make its dissolving.Add 1g ε-HNIW crystal seed after dripping the 8ml trichloromethane, add the 160ml trichloromethane again, trichloromethane added at 24 hours, and dissolved HNIW is all disengaged, and changeing brilliant temperature is 25～30 ℃.Changeing the brilliant ε-HNIW crystal that makes does not have sharp-pointed corner angle, and its profile is a polyhedron globe, and its mean particle size is 290 μ m, its purity of high-performance liquid chromatogram determination be 99.3% and more than, its porosity is 0.01%, 5Kg drop impact sensitivity H
50It is 41 centimetres.
Embodiment 5
In there-necked flask, 10g γ-HNIW is joined in the ethyl formate of 20ml, the dissolving after-filtration, removing does not have dissolved impurity.In ETHYLE ACETATE, add 0.2g crystal growth control agent Z 150PH, the molecular weight of Z 150PH is 10～300, stirs to make its dissolving.Add 1g ε-HNIW crystal seed after dripping the 8ml trichloromethane, add the 160ml trichloromethane again, trichloromethane added at 30 hours, and dissolved HNIW is all disengaged, and changeing brilliant temperature is 30～35 ℃.Changeing the brilliant ε-HNIW crystal that makes does not have sharp-pointed corner angle, and its profile is a polyhedron globe, and its mean particle size is 320 μ m, its purity of high-performance liquid chromatogram determination be 99.1% and more than, its porosity is 0.01%, 5Kg drop impact sensitivity H
50It is 45 centimetres.
Embodiment 6
In there-necked flask, 10g γ-HNIW is joined in the ethyl formate of 20ml, the dissolving after-filtration, removing does not have dissolved impurity.In ETHYLE ACETATE, add the amino butyl ester of 0.18g crystal growth control agent, stir and make its dissolving.Add 1g ε-HNIW crystal seed after dripping the 8ml trichloromethane, add the 160ml trichloromethane again, trichloromethane added at 22 hours, and dissolved HNIW is all disengaged, and changeing brilliant temperature is 20～25 ℃.Changeing the brilliant ε-HNIW crystal that makes does not have sharp-pointed corner angle, and its profile is a polyhedron globe, and its mean particle size is 190 μ m, its purity of high-performance liquid chromatogram determination be 99.2% and more than, its porosity is 0.02%, 5Kg drop impact sensitivity H
50It is 46 centimetres.
Embodiment 7
In there-necked flask, 10g β-HNIW is joined in the ethyl formate of 20ml, the dissolving after-filtration, removing does not have dissolved impurity.In ETHYLE ACETATE, add 0.1g crystal growth control agent Hydrocerol A, stir and make its dissolving.Add 1g ε-HNIW crystal seed after dripping the 8ml sherwood oil, add the 160ml sherwood oil again, sherwood oil added at 20 hours, and dissolved HNIW is all disengaged, and changeing brilliant temperature is 20～25 ℃.Changeing the brilliant ε-HNIW crystal that makes does not have sharp-pointed corner angle, and its profile is a polyhedron globe, and its mean particle size is 190 μ m, its purity of high-performance liquid chromatogram determination be 99.1% and more than, its porosity is 0.03%, 5Kg drop impact sensitivity H
50It is 36 centimetres.
Embodiment 8
In there-necked flask, 10g β-HNIW is joined in the ethyl formate of 20ml, the dissolving after-filtration, removing does not have dissolved impurity.In ETHYLE ACETATE, add 0.12g crystal growth control agent tetramethylolmethane, stir and make its dissolving.Add 1g ε-HNIW crystal seed after dripping the 8ml sherwood oil, add the 160ml sherwood oil again, sherwood oil added at 21 hours, and dissolved HNIW is all disengaged, and changeing brilliant temperature is 20～25 ℃.Changeing the brilliant ε-HNIW crystal that makes does not have sharp-pointed corner angle, and its profile is a polyhedron globe, and its mean particle size is 190 μ m, its purity of high-performance liquid chromatogram determination be 99.1% and more than, its porosity is 0.02%, 5Kg drop impact sensitivity H
50It is 39 centimetres.
Embodiment 9
In there-necked flask, 10g β-HNIW is joined in the ethyl formate of 20ml, the dissolving after-filtration, removing does not have dissolved impurity.In ETHYLE ACETATE, add 0.15g crystal growth control agent Padil, stir and make its dissolving.Add 1g ε-HNIW crystal seed after dripping the 8ml sherwood oil, add the 160ml sherwood oil again, sherwood oil added at 18 hours, and dissolved HNIW is all disengaged, and changeing brilliant temperature is 20～25 ℃.Changeing the brilliant ε-HNIW crystal that makes does not have sharp-pointed corner angle, and its profile is a polyhedron globe, and its mean particle size is 140 μ m, its purity of high-performance liquid chromatogram determination be 99.1% and more than, its porosity is 0.03%, 5Kg drop impact sensitivity H
50It is 39 centimetres.
Claims (3)
1. ε type hexanitro-hexaazaisopen wootz alkyl crystalline method for preparing spheroidization, it comprises:
A) with α-HNIW, β-HNIW, γ-HNIW or its mixture are dissolved in and form its saturated solution in the solvent,
B) in above solution, add the crystal growth control agent, and add anti-solvent with the formation supersaturated solution,
C) in above-mentioned supersaturated solution, add ε-HNIW crystal seed, and continue to add the HNIW of anti-solvent in solution and all disengage the ε-HNIW crystal that grows into spheroidization,
Said α-HNIW, β-HNIW, γ-HNIW, ε-HNIW crystal have the XRD crystalline structure shown in the accompanying drawing 2; The ε of spheroidization-HNIW crystal does not have sharp-pointed corner angle; Have the profile of polyhedron globe, and have the granularity of 20-500 μ m, the chemical purity of the 98%-99.9% of high-performance liquid chromatogram determination; 0.01% to 0.40% porosity and 26-52 centimetre 5Kg drop impact sensitivity H
50Use therein solvent is ETHYLE ACETATE, ethyl formate, acetone, methylethylketone, isopropyl acetate, THF or its mixture; Said anti-solvent is sherwood oil, tetracol phenixin, benzene, octane, hexanaphthene, toluene, YLENE, ether and/or methyl-n-butyl ether; The temperature of in the spheroidization process, using is 0 to 60 ℃, and anti-solvent added in 4 to 48 hours, and said crystal growth control agent molecule has hydroxyl, carboxyl, ester group or/and amino; Crystal growth inhibitor is toxilic acid, propanedioic acid, butene dioic acid, hexanodioic acid, Succinic Acid, oxalic acid, Hydrocerol A, tetramethylolmethane, 1; 2,4-trihydroxybutane, USP Kosher, molecular weight are the Z 150PH of 10-300, Padil, alanine, Methionin, l-arginine, halfcystine, Gelucystine, leucine, Methionin, Xie Ansuan.
2. method according to claim 1 wherein uses the solubility promoter of the 1-10 volume % of solvent slowly to add in the solvent after the crystal growth control agent dissolving again, and described solubility promoter is meant that to crystal growth control agent solubleness be/100 milliliters of solvents of 0.1 to 1 gram.
3. method according to claim 1, use therein solvent are ETHYLE ACETATE, ethyl formate, acetone, THF or its mixture, and said anti-solvent is sherwood oil, tetracol phenixin, benzene, octane, hexanaphthene, toluene or YLENE.
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| CN101973950A (en) * | 2010-09-17 | 2011-02-16 | 北京理工大学 | Method for preparing HMX by dynamic material ratio technology |
| CZ2011608A3 (en) * | 2011-09-29 | 2013-03-06 | Univerzita Pardubice | Process for preparing epsilon-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane with reduced sensitivity to impact |
| CN102898429B (en) * | 2012-09-18 | 2016-01-13 | 北京理工大学 | The recrystallization method of a kind of control ε-HNIW crystalline form and narrow size-grade distribution |
| CN103145512B (en) * | 2013-03-13 | 2014-12-10 | 中国工程物理研究院化工材料研究所 | High-gurney-energy low-vulnerability PBX explosive and preparation method thereof |
| CN103360185B (en) * | 2013-03-28 | 2016-03-09 | 北京理工大学 | A kind of round and smooth treatment unit of CL-20 particle and slip processing method |
| CN103497070B (en) * | 2013-09-17 | 2016-03-02 | 中国工程物理研究院化工材料研究所 | The method of hexanitro-six azepine isoamyl hereby alkane explosive spheroidization |
| CN103539800B (en) * | 2013-10-18 | 2015-07-29 | 中国工程物理研究院化工材料研究所 | The preparation method of macrobead Hexanitrohexaazaisowurtzitane explosive |
| CN104592277B (en) * | 2015-02-12 | 2017-03-08 | 西安近代化学研究所 | A kind of cuprous spheroidization preparation method of decahydro ten tetraethylammonium borate |
| CN105418619B (en) * | 2015-12-29 | 2017-12-12 | 山西北化关铝化工有限公司 | A kind of preparation method of speciality Hexanitrohexaazaisowurtzitane |
| CN106117229B (en) * | 2016-08-31 | 2018-01-02 | 山西北化关铝化工有限公司 | A kind of preparation method of speciality Hexanitrohexaazaisowurtzitane |
| CN107796907A (en) * | 2017-09-27 | 2018-03-13 | 山西北化关铝化工有限公司 | The purity analysis methods of speciality CL 20 |
| CN109485531A (en) * | 2018-12-13 | 2019-03-19 | 南京理工大学 | Superfine spherical CL-20 Composite Energetic Materials and preparation method thereof |
| CN112466413B (en) * | 2020-12-04 | 2024-04-12 | 南通海智医药科技有限公司 | Molecular regulation and control method for specific crystal form of small molecular medicine |
| CN113214271A (en) * | 2021-04-25 | 2021-08-06 | 西南科技大学 | Continuous preparation method of micron granular CL-20/HMX eutectic |
| CN115959955B (en) * | 2022-12-27 | 2024-05-10 | 西安近代化学研究所 | CL-20-based aluminum-containing explosive recycling process |
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