CN101624394A - Sphericized hexanitrohexaazaisowurtzitane (HNIW) crystal and preparation method thereof - Google Patents
Sphericized hexanitrohexaazaisowurtzitane (HNIW) crystal and preparation method thereof 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 theGas Anti-Solvent-Process.Prop.Explos.Pyrotech.1999,24:195; People's such as Antoine E.D. Crystallization and Characterization of RDX, HMX, and CL-20.Crystal Growth﹠amp; Design, 2004,4:999; People's such as A.T.Nielsen Flippen-Anderson, Synthesis ofPolyazapolycyclic Caged Polynitramines, Tetrahedron 1998,54:11793.Energy-containing compound crystalline shape has influence on 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.Cyclotrimethylene trinitramine (RDX) and octogen (HMX) spheroidization degree have reached quite high level, and the every performance that improves behind the spheroidization has obtained sign; Have comprehensive performance with PBX (PBX), and obtained using widely based on RDX and HMX.
People's such as document Nicholas B. Ordered Aggregation of Benzamide Crystals InducedUsing a " Motif Capper " Additive.Crystal Growth ﹠amp; Design 2005, the Crystal engineering of polymorph appearance:the case of sulphathiazole.Powder Technol.2001 of 5:467 and BlagdenNicholas, 121:46～52 have been put down in writing use crystal growth control agent and have been gone to control crystalline growth, nucleation and change crystalline habit and pattern.St é hane B é azet and he's colleague (MolecularModeling in Crystal Engineering for Processing of Energetic Materials[J] .Prop.Explos.Pyrotech.2003,28:287～295) has calculated all kinds of SOLVENTS molecule in the ε type hexanitro-six nitrogen mineralizations assorted different 5 alkane (interaction energy on each crystal face of crystal of ε-HNIW) now by molecular dynamics simulation.But hexanitro-six nitrogen mineralizations of spheroidization assorted different 5 alkane (HNIW) crystal now also have not seen reported.
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 by 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 processing step on the basis of changeing brilliant technology, do not need to increase extra security measures yet, ε-the HNIW of the spheroidization that can obtain has premium propertiess such as low sensitivity, high working property energy increasing the product that condition of cost obtains hardly.
Summary of the invention
The 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, its granularity is 20～500 μ m, 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 is achieved by the following technical solutions.
A kind of ε type hexanitro-hexaazaisopen wootz alkyl crystalline method for preparing spheroidization of the present invention, concrete implementation step is as follows:
(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 ethyl acetate, ethyl formate, acetone, methylethylketone, isopropyl acetate, tetrahydrofuran (THF) or its mixture.Anti-solvent is sherwood oil, tetracol phenixin, benzene, octane or hexanaphthene, toluene, dimethylbenzene, methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ether and/or methyl-n-butyl ether etc.The temperature of using in the spheroidization process is 0～60 ℃.The adding speed of anti-solvent does not have special restriction 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 following solvent of/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, on each aufwuchsplate of HNIW crystal because conformation, the intermolecular distance difference of HNIW molecule, the sorptive power of crystal growth control agent molecule on each aufwuchsplate is different, 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, citric acid; Ester, for example butyl butyrate, ethyl butyrate, propyl butyrate, diethyl malonate, propanedioic acid one butyl ester; Alcohol, polyvalent alcohol is tetramethylolmethane, 1,2 for example, and 4-trihydroxybutane, glycerol, molecular weight are the polyvinyl alcohol 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-aminobutyric acid ethyl ester, 2-aminobutyric acid methyl esters, monomethyl maleate or the like, hydroxycarboxylic acid, oxyacetic acid for example, the 1-hydroxy-propionic acid, 2 hydroxy propanoic acid, the 1-hydroxybutyric acid, the 2-hydroxybutyric acid, hydroxy ester, 2 hydroxy propanoic acid ethyl ester for example, the 2 hydroxy propanoic acid methyl esters, the 2-3-hydroxyethyl butyrate, the 2-beta-hydroxymethyl butyrate, amino acid is as Padil, alanine, amino butyl ester, Methionin, arginine, halfcystine, Gelucystine, leucine, Methionin, Xie Ansuan, the 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 and adding toxilic acid, tetramethylolmethane, Padil respectively;
Fig. 2 is α, beta, gamma and ε-HNIW crystalline XRD figure spectrum.
In a specific embodiment of the present invention, ε type hexanitro six azepines different 5 of preparation spheroidization hereby The raw material of alkane crystal can be α-HNIW, β-HNIW, γ-HNIW or its mixture. The solvent that uses is first Acid esters, acetic acid esters or ketone are proper, can be ethyl acetate, Ethyl formate, acetone, MEK, Isopropyl acetate, oxolane or its mixture. Anti-solvent is selected benzinum, carbon tetrachloride, benzene, positive hot Alkane or cyclohexane, toluene, dimethylbenzene, methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ether and/or first Butyl ether etc. The temperature of using in the spheroidization process is 0 to 60 ℃. The adding speed of anti-solvent among the present invention Do not have special restriction, the speed of adding only otherwise affect crystal grows and get final product makes the HNIW raw material of adding 98 % by weight 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 refers to that HNIW solubility therein is molten at least 10/100 milliliters of grams Agent, preferably/100 milliliters of solvents of at least 20 grams, the more preferably solvent of/100 milliliters of solvents of at least 30 grams. This Invent alleged " anti-solvent " and refer to that HNIW solubility therein is 1 gram/100 milliliters below the solvent, excellent Select 0.5 to restrain/100 milliliters below the solvent, more preferably the following solvent of/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 has strong interaction, on each aufwuchsplate of HNIW crystal because conformation, the branch of HNIW molecule Distance is different between son, and the energy of adsorption of crystal growth control agent molecule on each aufwuchsplate is different, therefore at crystalline substance Different to the inhibition speed of each crystal face growth in the bulk-growth process, changed each crystal face of HNIW crystal from face The relative velocity of growth and change the profile of crystal. The crystal growth control agent that uses among the present invention can be carboxylic Acid, polyacid, polyalcohol, acid amides, amino acid, ester etc.
The preferred crystal growth control agent of the present invention is carboxylic acid, for example maleic acid, butenoic acid, butene dioic acid, Caproic acid, adipic acid, phytic acid, citric acid; Ester, for example butyl butyrate, ethyl butyrate, propyl butyrate, third Two diethyl phthalates, malonic acid one butyl ester; Alcohol, polyalcohol for example pentaerythrite, BT, glycerine, Molecular weight is the polyvinyl alcohol of 10-300, and preferred molecular weight is 50-200, and more preferably molecular weight is 70-130, most preferably molecular weight is 80-110; Amino ester, for example, 2-alanine ethyl ester, 2-alanine first Ester, 2-amino-butyric acid ethyl ester, 2-amino-butyric acid methyl esters, monomethyl maleate etc., hydroxycarboxylic acid, for example hydroxyl Guanidine-acetic acid, 1-hydracrylic acid, Lactic acid 1-hydroxybutyric acid, 2-hydroxybutyric acid, hydroxy ester, for example 2-Hydracrylic acid ethyl ester, 2 hydroxy propanoic acid methyl esters, 2-3-hydroxyethyl butyrate, 2-beta-hydroxymethyl butyrate, amino acid, Such as amion acetic acid, alanine, amino butyl ester, lysine, arginine, cysteine, cystine, bright Propylhomoserin, lysine, valine, a-amino-isovaleric acid, tryptophan, vitamin, N-dodecyl alanine, 2-amino-3-glycolic acid, glycine ethyl ester hydrochloride.
In a specific embodiments of the present invention, adopt following steps to prepare the ε type Hexanitrohexaazaisowurtzitane 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 anti-solvent until the HNIW in the solution all disengages the ε that grows into spheroidization-HNIW crystal, the ε of described spheroidization-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 and 26-52 centimetre 5Kg drop impact sensitivity H50。
Wherein the crystal growth control agent also can be with α-HNIW, β-HNIW, and γ-HNIW or its mixture are molten Add before the solvent, also with the cosolvent of the 1-10 volume % that uses solvent that the crystal growth control agent is molten Xie Houzai slowly adds or is added dropwise in the solvent, and cosolvent described herein refers to the crystal growth control agent molten The solvent that Xie Du is bigger, the solubility of preferred crystal growth control agent in cosolvent are 0.1 to 1 gram/100 millis Rise solvent, more preferably the solubility of crystal growth control agent in cosolvent is/100 milliliters of solvents of 0.1 to 2 gram, More preferably the solubility of crystal growth control agent in cosolvent is/100 milliliters of solvents of 0.1 to 3 gram again, optimum Select the solubility of crystal growth control agent in cosolvent be 0.1 to 10 the gram/100 milliliters of solvents, for example ethanol, Formic acid etc.
In specific embodiments of the present invention, the ε type Hexanitrohexaazaisowurtzitane crystal that can prepare a kind 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 preferably50。
In another specific embodiments of the present invention, the ε type Hexanitrohexaazaisowurtzitane crystal that can prepare a kind 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 preferably50。
In another specific embodiments of the present invention, the ε type Hexanitrohexaazaisowurtzitane crystal that can prepare a kind 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 preferably50。
Wherein the crystal growth control agent also can be with α-HNIW, β-HNIW, and γ-HNIW or its mixture are molten Add before the solvent, also with the cosolvent of the 1-10 volume % that uses solvent that the crystal growth control agent is molten Xie Houzai slowly adds or is added dropwise in the solvent, and cosolvent described herein refers to the crystal growth control agent molten The solvent that Xie Du is bigger, the solubility of preferred crystal growth control agent in cosolvent are 0.1 to 1 gram/100 millis Rise solvent, more preferably the solubility of crystal growth control agent in cosolvent is/100 milliliters of solvents of 0.1 to 2 gram, More preferably the solubility of crystal growth control agent in cosolvent is/100 milliliters of solvents of 0.1 to 3 gram again, optimum Select the solubility of crystal growth control agent in cosolvent be 0.1 to 10 the gram/100 milliliters of solvents, for example ethanol, Formic acid etc.
Analyze the chemical purity of each crystal 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 second eyeball/water (60/40, V/V) mobile phase be methanol/water (50/50, V/V), flow velocity is 1mL/min, and sample size is 10uL, The detection wavelength is 230nm, the HPLC purity of mensuration be expressed as target substance the HPLC peak area divided by The percentage method for expressing 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 scans when making quantitative test 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 instrument that drops hammer
50, also measured the H of military HMX simultaneously
50Value as a comparison.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 cms is all got by d representative experiment interval (step-length) drop height and unit at interval.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 by specific 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 ethyl acetate ratios, removal does not have dissolved impurity and then adds in the flask, drip 8 milliliters of trichloromethanes when being ethyl acetate, add crystal seed (about 1 gram), add 8 times of volumes again in the trichloromethane of ethyl 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 ethyl acetate of 20ml the dissolving after-filtration.In ethyl 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 ethyl acetate of 20ml, the dissolving after-filtration, removing does not have dissolved impurity.In ethyl 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 ethyl acetate of 20ml, the dissolving after-filtration, removing does not have dissolved impurity.In ethyl 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 ethyl acetate, add 0.12g crystal growth control agent citric 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 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.Add 0.2g crystal growth control agent polyvinyl alcohol in ethyl acetate, the molecular weight of polyvinyl alcohol 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 ethyl 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 ethyl acetate, add 0.1g crystal growth control agent citric acid, 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 ethyl 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 ethyl 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 (7)
1. the ε type hexanitro-hexaazaisopen wootz alkyl crystal of a spheroidization, described ε-HNIW crystal does not have sharp-pointed corner angle, profile with polyhedron globe, and has the granularity of 20-500 μ m, at least 98% chemical purity of high-performance liquid chromatogram determination, 0.01% to 0.40% porosity and 26-52 centimetre, preferred 30-52 centimetre, 35-52 centimetre 5Kg drop impact sensitivity H most preferably
50
2. ε type hexanitro-hexaazaisopen wootz alkyl crystal according to claim 1, described ε type hexanitro-hexaazaisopen wootz alkyl 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%-99.9% of high-performance liquid chromatogram determination, 0.02% to 0.350% porosity and 26-52 centimetre, preferred 30-52 centimetre, 35-52 centimetre 5Kg drop impact sensitivity H most preferably
50
3. ε type hexanitro-hexaazaisopen wootz alkyl crystal according to claim 1, described ε type hexanitro-hexaazaisopen wootz alkyl crystal, 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%-99.9% 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
4. 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 the HNIW of the continuation anti-solvent of adding in solution all disengages the ε-HNIW crystal that grows into spheroidization, the ε of described spheroidization-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 and 26-52 centimetre, preferred 30-52 centimetre, 35-52 centimetre 5Kg drop impact sensitivity H most preferably
50Use therein solvent is an ethyl acetate, ethyl formate, acetone, methylethylketone, isopropyl acetate, tetrahydrofuran (THF) or its mixture, described anti-solvent is a sherwood oil, tetracol phenixin, benzene, octane, or hexanaphthene, toluene, dimethylbenzene, methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ether, and/or methyl-n-butyl ether, the temperature of using in the spheroidization process is 0 to 60 ℃, anti-solvent added in 4 to 48 hours, described crystal growth control agent molecule has hydroxyl, carboxyl, ester group is or/and amino, crystal growth inhibitor is a toxilic acid, propanedioic acid, butenoic acid, butene dioic acid, caproic acid, hexanodioic acid, Succinic Acid, oxalic acid, phytic acid, citric acid, butyl butyrate, ethyl butyrate, propyl butyrate, diethyl malonate, propanedioic acid one butyl ester, tetramethylolmethane, 1,2, the 4-trihydroxybutane, glycerol, molecular weight is the polyvinyl alcohol of 10-300, the 1-hydroxy-propionic acid, 2 hydroxy propanoic acid, the 1-hydroxybutyric acid, the 2-hydroxybutyric acid, 2-alanine ethyl ester, 2-alanine methyl esters, 2-aminobutyric acid ethyl ester, 2-aminobutyric acid methyl esters, monomethyl maleate, the 2 hydroxy propanoic acid ethyl ester, the 2 hydroxy propanoic acid methyl esters, the 2-3-hydroxyethyl butyrate, the 2-beta-hydroxymethyl butyrate, amino acid is as Padil, alanine, amino butyl ester, Methionin, arginine, halfcystine, Gelucystine, leucine, Methionin, Xie Ansuan, the a-aminoisovaleric acid, tryptophane, Vitamin U, N-dodecyl L-Ala, 2-amino-3-oxyacetic acid, glycine ethyl ester hydrochloride.
5. method according to claim 4, wherein the crystal growth control agent is with α-HNIW, and β-HNIW, γ-HNIW or its mixture add before being dissolved in solvent.
6. method according to claim 4, wherein use the solubility promoter of the 1-10 volume % of solvent slowly to add again after the crystal growth control agent dissolving or to be added dropwise in the solvent, described solubility promoter is meant crystal growth control agent solubleness is preferably/100 milliliters of solvents of 0.1 to 1 gram, more excellent is/100 milliliters of solvents of 0.1 to 2 gram, more preferably 0.1 to 3 restrain/100 milliliters of solvents again, most preferably be the solvent of/100 milliliters of solvents of 0.1 to 10 gram.
7. method according to claim 4, use therein solvent is ethyl acetate, ethyl formate, acetone, tetrahydrofuran (THF) or its mixture, and described anti-solvent is sherwood oil, tetracol phenixin, benzene, octane or hexanaphthene, toluene, dimethylbenzene, methyl alcohol, ethanol.
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