CN103172476A - Preparation method of submicron particle 1-oxo-diamino-3, 5-dinitropyrazine explosive - Google Patents
Preparation method of submicron particle 1-oxo-diamino-3, 5-dinitropyrazine explosive Download PDFInfo
- Publication number
- CN103172476A CN103172476A CN2013101176919A CN201310117691A CN103172476A CN 103172476 A CN103172476 A CN 103172476A CN 2013101176919 A CN2013101176919 A CN 2013101176919A CN 201310117691 A CN201310117691 A CN 201310117691A CN 103172476 A CN103172476 A CN 103172476A
- Authority
- CN
- China
- Prior art keywords
- explosive
- preparation
- diamino
- oxygen
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention provides a preparation method of a submicron particle 1-oxo-diamino-3, 5-dinitropyrazine (or 2. 6-diamino-3, 5-dinitropyrazine-1-oxide, called as LLM-105). The preparation method comprises the steps of: jetting of a crystallization device, non-solvent preparation, preparation of an explosive solution, ultrasonic jet for crystallization, pretreatment of a crystallization solution, separation of the crystallization solution, washing and purifying, drying, storage and the like. The preparation method can be used for preparing submicron particle LLM-105 at high efficiency and low cost; and the product performance can reach the using requirements of slapper plate detonators.
Description
Technical field
The invention belongs to military Loading Materials for Initiating Explosive Devices technical field, be specifically related to a kind of submicron particles 1-oxygen-diamino-3,5-dinitrobenzene pyrazine (or 2,6-diamino-3,5-dinitrobenzene pyrazine-1-oxide compound, code name LLM-105, following content represents with code name LLM-105) preparation method of explosive, the present invention is applicable to the preparation that safety type impacts the sheet primary explosive of detonator.
Background technology
After the explosive super-refinement, explosion energy discharges faster, and detonation wave is propagated more stable, detonation critical diameter decrease, and powder charge intensity increases substantially, and therefore ultra-fine explosive just more and more is used for impacting the sheet charging explosive in detonator.And the severity of battlefield surroundings has proposed the requirement of high safety, high reliability to the impact sheet charging explosive in detonator of priming system: namely high to short pulse stimulation sensitivity and output energy, and good to the relative insensitiveness of mechanical stimulus and resistance toheat.In using non-sensitive type safe initiation medicine, HNS-IV(submicron particles hexanitro-Stilbene) though good short pulse sensitivity and safety performance are arranged.But medicament output energy (explosion velocity is 7060m/s only) on the low side is restricted its range of application.Although and submicron particles LLM-105 short pulse sensitivity is slightly poorer than HNS-IV, but its safety performance is better, output energy (explosion velocity 8560m/s) is higher by 21% than HNS-IV, thereby the medicament detonating capability is improved significantly, and good application prospect is arranged in extraordinary advanced technology weapon.
LLM-105 is U.S. Lao Lunsilifu mole laboratory, the heat-resisting high-energy insensitive explosive of a kind of high comprehensive performance that nineteen ninety-five synthesizes.For many years, synthesis technique, structure properties and the booster explosive formulating of this explosive have mainly been carried out both at home and abroad.And super-refinement prepares and the research of the medicine that is applied to start about LLM-105 is carried out, unprecedented report.
Explosive is carried out general grinding/ball milled or the dropping liquid of adopting of super-refinement preparation carry out chemicrystallization in non-solvent.Studies confirm that: grind or the ball milling Explosive Refining can be brought more mechanical impurity into, and fine particle can occur again when refineing to a certain degree and reunite, therefore be difficult to obtain the fines product.And chemicrystallization is the dissolving liquid to be disperseed to join generate the refinement crystal in non-solvent, and two kinds of the crystallization process of dropping and jet crystallization methods are arranged usually.Drip crystallization process because drop is large, easily reunite during local crystallize out in non-solvent, and feed time is long, can't obtain the submicron order blasting explosive granules.And the jet crystallization method is that explosive liquid is mixed with the non-solvent rapid stirring under the high dispersing state, so crystallization of refinement is effective, can obtain submicron and even nano level blasting explosive granules.But because LLM-105 is the heat resistant type explosive, only just be dissolved in the minority strong solvent under heating condition, adopt simple jet crystallization method, the phenomenon that a large amount of medicine of a warm nature liquid are ejected into the explosive dust that namely atomizes out in air very easily appears in course of injection, thereby only have minority explosive solution can be in non-solvent the crystallization explosive crystal, can't obtain equally distributed tiny LLM-105 crystal.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of submicron particles 1-oxygen-diamino-3, the preparation method of 5-dinitrobenzene pyrazine explosive, and the submicron particles blasting explosive granules of acquisition is even, and particle size distribution range is narrow, can be used as the medicine that starts and uses.
A kind of submicron particles 1-oxygen-diamino-3 of the present invention, 5-dinitrobenzene pyrazine explosive preparation method is characterized in comprising the following steps successively:
A) preparation of non-solvent measures the mixing solutions of distilled water and dispersion agent, after evenly mixing in container, puts into the refrigerator-freezer precooling;
B) preparation of explosive solution takes 1-oxygen-diamino-3, and 5-dinitrobenzene pyrazine explosive and solvent are put into container, is heated with stirring to entirely molten;
C) jet crystallization is put into pool type ultrasonic oscillation device with the non-solvent solution of step a preparation; With 1-oxygen-diamino-3 of step b, 5-dinitrobenzene pyrazine explosive hot solution is poured in the jet crystallization device, and the jet crystallization device is fixed on traversing carriage; By the micropore on the spray tube of jet crystallization bottom of device, explosive solution is vertically sprayed into pool type ultrasonic oscillation device liquid level; In course of injection, control traversing carriage and move back and forth, Explosive jet efflux is evenly distributed spurt into pool type ultrasonic oscillation device liquid level, until fried liquid medicine jet is complete; Continue ultrasonic concussion 1h ~ 3h;
D) crystal solution is separated employing centrifugation or sand core funnel suction strainer separate mode, isolates the explosive crystal in the step c) crystal solution;
E) wash 1-oxygen-diamino-3 that purifying obtains steps d, 5-dinitrobenzene pyrazine explosive crystal washs purifying, drying, storage with cleaning solvent.
Described jet crystallization device comprises that the molten medicine of constant temperature sprays still, spray tube and air pressure system.Its mode of connection is: after the molten medicine of constant temperature sprays the still lower end and spray tube is connected, and the unsettled pool type ultrasonic oscillation device top of being placed in, the molten medicine of constant temperature sprays the still while and is connected with air pressure system.
It is that sandwich-type injects the heating bath heating that the molten medicine of described constant temperature sprays still, and the molten medicine of constant temperature sprays still and is provided with cover plate, and cover plate is provided with charging opening and the control valve that is connected air pressure system, and the kettle bottom is provided with the medicine liquid outlet control valve.
Described spray tube adopts right angle crankle shape structure, is divided into two parts of vertical section and horizontal section; The interior pond width of spray tube horizontal section length and pool type ultrasonic oscillation device adapts, and the horizontal section downside is provided with a plurality of micropores, and micropore is arranged in a linear.
In the preparation of the described non-solvent of step a), by 5～20 times of mixing solutionss that measure distilled water and dispersion agent of required explosive solution body accumulated amount, wherein the mass ratio of distilled water and dispersion agent is 5000:0.5～5;
The described dispersion agent of step a) adopts that tween, this dish, the acid of two-ethylhexyl succinate semi-annular jade pendant are received, the acid of hexadecyl benzene semi-annular jade pendant is received, a kind of in hexadecyl trimethyl ammonium bromide.
In the preparation of step b) explosive solution, take 1-oxygen-diamino-3,5-dinitrobenzene pyrazine explosive and solvent according to the ratio of 1:20;
The described solvent of step b) is a kind of in dimethyl formamide, METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO).
The described cleaning solvent of step e) is one or more in methyl alcohol, ethanol, dioxane, acetone, tetrahydrofuran (THF), vinyl acetic monomer, water.
The preparation method of submicron particles LLM-105 explosive of the present invention is comprised of the ultrasonic crystallization of refinement of explosive solution, crystal solution separation, purifying, dry technology.The explosive hot solution is ejected at condition of high voltage generates uniform micro crystal in non-solvent medium under ultrasonic concussion, utilize the high frequency oscillation ultrasonic wave to remove residual solvent in the refinement crystal.Weak property solvent and strong solvent are arranged in pairs or groups mutually, form and have certain washing effect and don't make ultra-fine grain form the composite cleaning solvent of hard gathering, and the Uniform Dispersion medicine is rolled into a ball in cleaning solvent, increase effectively washing area, make the purifying of submicron particles LLM-105 and the anti-gathering of ultra-fine grain be in all the time the optimised process point of mutually taking into account.Dry by the dispersion of being association of activity and inertia, accelerate the residual cleaning solvent evaporation rate in ultra-fine grain, extenuate to greatest extent ultra-fine grain and assemble, thereby make ultra-fine LLM-105 explosive property reach the utilisation technology requirement.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of product of the present invention;
Fig. 2 is the scanning electron microscope (SEM) photograph of product of the present invention;
Fig. 3 is the jet crystallization device schematic diagram that the present invention adopts;
In figure: 1. the air pressure system 2. pneumatics inlet control valve 3. heating bath liquid outlet 4. medicine liquid outlet control valve 5. pool type ultrasonic oscillation device 6. charging opening 7. heating bath liquid entrance 8. spray tube 9. molten medicines of constant temperature spray still 10. cover plates.
Embodiment
The invention will be further described below in conjunction with example.
A kind of submicron particles 1-oxygen-diamino-3 of the present invention, 5-dinitrobenzene pyrazine explosive preparation method comprises the following steps successively:
A) preparation of non-solvent measures the mixing solutions of distilled water and dispersion agent, after evenly mixing in container, puts into the refrigerator-freezer precooling;
B) preparation of explosive solution takes 1-oxygen-diamino-3, and 5-dinitrobenzene pyrazine explosive and solvent are put into container, is heated with stirring to entirely molten;
C) jet crystallization non-solvent solution that step a) is prepared is put into pool type ultrasonic oscillation device 5; With step b) 1-oxygen-diamino-3,5-dinitrobenzene pyrazine explosive hot solution is poured in the jet crystallization device, the jet crystallization device is fixed on traversing carriage; The micropore of the spray tube 8 by the jet crystallization bottom of device vertically sprays into explosive solution the liquid level of pool type ultrasonic oscillation device 5; In course of injection, control traversing carriage and move back and forth, Explosive jet efflux is evenly distributed spurt into the liquid level of pool type ultrasonic oscillation device 5, until fried liquid medicine jet is complete; Continue ultrasonic concussion 1h ~ 3h;
D) crystal solution separate to adopt centrifugation or sand core funnel suction strainer separate mode, isolates step c) explosive crystal in crystal solution;
E) the washing purifying is with steps d) 1-oxygen-diamino-3 of obtaining, 5-dinitrobenzene pyrazine explosive crystal washs purifying, drying, storage with cleaning solvent.
Described jet crystallization device comprises that the molten medicine of constant temperature sprays still 9, spray tube 8 and air pressure system 1.Its mode of connection is: after the molten medicine of constant temperature sprays still 9 lower ends and spray tube 8 is connected, and the unsettled top that is placed in pool type ultrasonic oscillation device 5, the molten medicine of constant temperature sprays the still while and is connected with air pressure system 1.
The molten medicine of described constant temperature sprays still 9 and injects the heating bath heating for sandwich-type, and the kettle outside that the molten medicine of constant temperature sprays still 9 is respectively arranged with heating bath liquid entrance 7 and heating bath liquid exports 3.The molten medicine injection still of constant temperature 9 tops are provided with cover plate 10, cover plate 10 adopts demountable structure, be provided with charging opening 6 on cover plate 10, charging opening 6 adopts the cap-rotating type sealed structures, and air pressure system is communicated with by the internal space on the explosive solution of pneumatics control valve 2, cover plate 10 and the molten medicine injection of constant temperature still 9; The kettle bottom is provided with medicine liquid outlet control valve 4.
Described spray tube 8 adopts right angle crankle shape structure, is divided into two parts of vertical section and horizontal section; The wide degree in interior pond of spray tube 8 horizontal section lengths and pool type ultrasonic oscillation device 5 adapts, and the horizontal section downside is provided with a plurality of micropores, and micropore is arranged in a linear.
In the preparation of the described non-solvent of step a), by 5～20 times of mixing solutionss that measure distilled water and dispersion agent of required explosive solution body accumulated amount, wherein the mass ratio of distilled water and dispersion agent is 5000:0.5～5;
The described dispersion agent of step a) adopts that tween, this dish, the acid of two-ethylhexyl succinate semi-annular jade pendant are received, the acid of hexadecyl benzene semi-annular jade pendant is received, a kind of in hexadecyl trimethyl ammonium bromide.
In the preparation of step b) explosive solution, take 1-oxygen-diamino-3,5-dinitrobenzene pyrazine explosive and solvent according to the ratio of 1:20;
The described solvent of step b) is a kind of in dimethyl formamide, METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO).
The described cleaning solvent of step e) is one or more in methyl alcohol, ethanol, dioxane, acetone, tetrahydrofuran (THF), vinyl acetic monomer, water.
The present invention adopts jet crystallization device shown in Figure 3 according to the characteristic of LLM-105 high temperature powder, carries out the ultrasonic crystallization of refinement of LLM-105.By pool type ultrasonic oscillation device power and interior pond length and width, determine to add the non-solvent amount in pool type ultrasonic oscillation device and spray amount of liquid medicine.
Submicron particles LLM-105 explosive preparation process of the present invention is as follows:
(ⅰ) preparation of non-solvent
Non-solvent is intended to reduce explosive solution degree of supersaturation in crystallization, impel explosive to generate fast fine crystals.Therefore the non-solvent of selecting must not dissolve explosive, and purity is high, and temperature is low, and is good with the solvent mutual solubility, in order to rapid diffusion.As select water, ethanol, acetonitrile or several mixed solvent to do non-solvent.The consumption principle: the explosive solution amount is large, and temperature is high, the corresponding increase of non-solvent consumption.For eliminating surface tension between crystallize out and liquid medium, impelling crystal to spread, prevent crystal accumulation in crystal solution, also must select suitable dispersion agent, its consumption principle: be directly proportional to the explosive charging capacity.
Take the water of 10g explosive charging capacity/dispersion agent proportioning (mL/g) as example:
Distilled water 1000～4000
Dispersion agent (chemical pure) 0.1～4
Mixing in container is configured to non-solvent solution with water and dispersion agent, precooling in refrigerator-freezer.
(ⅱ) preparation of explosive solution
Select the solvent strong to the LLM-105 solvability, as dimethyl sulfoxide (DMSO) (DMSO), METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF) etc., and heating increases solubleness.Because all kinds of SOLVENTS there are differences LLM-105 solubleness, so under specified temp, the solvent for use amount is different.The solvent that solubleness is high, consumption is few, and molten medicine temperature is low; The solvent that solubleness is low, consumption is large, and molten medicine temperature is high.The concrete quantity of solvent of using is advisable can all dissolve explosive under proper temperature.
Certain proportioning (W
Explosive/ V
Solvent=g/mL) under, LLM-105 and DMSO, NMP, the solubility property of DMF is as follows:
LLM-105(purity 〉=99%) 10
DMSO (chemical pure)～200, molten medicine temperature (75～80) ℃
NMP (chemical pure)～300, molten medicine temperature (105～110) ℃
DMF (chemical pure)～450, molten medicine temperature～115 ℃
The solubility property demonstration, the solute effect of LLM-105 in DMSO is best, and be normal first-selected for experiment, specifically expects than increasing and decreasing according to charging capacity.
(ⅲ) explosive solution/crystal water ratio (volume ratio mL/L)=1/5 ~ 20(by pool type ultrasonic oscillation device power with its in pond size determine material than)
(ⅳ) jet crystallization
To add the hot explosive liquid of LLM-105 in the molten medicine injection of constant temperature still, under the sealing pneumatics, from spray tube below arrangement micropore, be ejected into crystallization of refinement in the water at low temperature of strong ultrasonic concussion, back and forth parallel is laid the traversing carriage that the molten medicine of constant temperature sprays still, until fried liquid medicine jet is complete, continue ultrasonic concussion 10min ~ 3h.
(ⅴ) crystal solution is separated
The LLM-105 crystal solution is separated to solid-liquid limpid in supercentrifuge, outwells liquid phase, take out solid materials to be purified, or adopt sand core funnel to filter.
(the vi) washing purifying of LLM-105 refinement crystal
With residual solvent and dispersion agent in suitable cleaning solvent eccysis LLM-105 refinement crystal, and keep as far as possible in last handling process superfine crystal not grow up;
(the vii) preparation of cleaning solvent (volume ratio)
The solvent that cleaning function is strong, purified crystals is effective, but easily causes ultrafine particle to assemble; The solvent that wash-out is weak, though be difficult for causing gathering, purification effect is poor.Therefore, when using separately methyl alcohol, ethanol, dioxane, tetrahydrofuran (THF), vinyl acetic monomer, acetone, water washing, all kinds of SOLVENTS be should consider to the microsolubility of ultra-fine LLM-105, consumption and supersound washing time determined; Or with the composite use of strong, weak property cleaning solvent, have complementary advantages, be mixed with a kind of purifying and anti-cleaning solvent of assembling dual-use function taken into account, as: acetone/water=5/5, tetrahydrofuran (THF)/water=6/4, methanol/water=8/2, ethanol/water=9/1.
(viii) wash purification process
Feed intake by every 10g LLM-105, use the 1000mL cleaning solvent, with isolated LLM-105 " clay " shape medicine piece, evenly spread in cleaning solvent, solvent and dispersion agent wherein removed in washing, then isolates the washing slip, and repeated washing operates repeatedly.
(ⅶ) disperse drying and storage procedures
After isolated pure damp-resolving medicinal piece is air-dry, namely change rapid dispersion in special dispersion cutting machine (protective shield isolated operation) over to, then thin layer is spread in dish out, dry in vacuum drying oven.
A kind of submicron particles LLM-105 explosive preparation method provided by the invention, its technical characteristics is: the crystal solution pre-treatment, abolish emulsification and particle aggregation, accelerate centrifugation.Epistasis forms with weak property solvent interworking and mixes suitable cleaning solvent, and is good and bad complementary, makes LLM-105 purifying and ultra-fine grain prevent assembling, and is in all the time the optimised process point of mutually taking into account.Isolated submicron particles LLM-105 clay shape medicine piece needs uniform subdivision loose in cleaning solvent, improves purification efficiency.Submicron particles LLM-105 washing slip is shaken processing, the gathering that improves the purifying effect and alleviate superfine crystal particle.The dispersion of being association of activity and inertia is dried in the shade, and can increase the volatilization area of ultra-fine grain, makes the ultra-fine LLM-105 in drying process, and under in good time dynamic disturbance, particle aggregation is extenuated, and then obtains good drying.The sem test product cut size is 0.1 μ m～0.4 μ m approximately, and purity reaches 99%, and performance satisfies impacts the requirement of sheet blasting cap initiation.
12000mL distilled water and 12g polysorbas20 are added the made of square plastic bucket, after mixing in refrigerator precooling stand-by;
30g LLM-105 and 600mL DMSO are added the there-necked flask that is easy to observe dissolved state, stir be warming up to 80 ℃ make explosive complete molten after, add constant temperature to spray in still, capping links pressure line, starts air compressor machine stand-by;
Quantitative precooling water at low temperature, add pool type ultrasonic oscillation device, start ultrasonic concussion, adjusting the micropore spray tube lies across above the concussion liquid level, the opening pressure valve make explosive liquid be ejected into the concussion water surface below straight tube micropore spray tube, and back and forth parallel is laid the support that the molten medicine of constant temperature sprays still, until sprayed explosive liquid, ultrasonic concussion washing explosive crystal solution 10min;
Crystal solution is all measured added centrifugal bottle, be separated to solid-liquid with the 10000r/min rotating speed limpid in whizzer, discard liquid phase, take out solid substances to be purified;
Continuous 5 composite washing solns of use (5/5 acetone/water) approximately after 3000mL Uniform Dispersion material, ultrasonic concussion, are separated to solid-liquid with the 10000r/min rotating speed limpid in whizzer.Discard liquid phase, take out the solid piece of purifying mass, disperse air-dry extremely half-dried degree in dish, redispersion becomes powder, drying products.And with the powder bottling (or bag) that parches, the sealing lucifuge is deposited.
In the made of square plastic bucket, add 4500mL distilled water and 1.3g Si dish 60 mixings, precooling is stand-by;
Add 20g LLM-105 and 400mL DMSO in there-necked flask, stirring is warming up to 80 ℃ makes explosive entirely molten, adds constant temperature to spray in still;
Quantitative precooling water at low temperature, add pool type ultrasonic oscillation device, start ultrasonic concussion, adjusting the micropore spray tube lies across above the concussion liquid level, the opening pressure valve, make explosive liquid be ejected into the concussion water surface below straight tube micropore spray tube, and back and forth parallel is laid the support that the molten medicine of constant temperature sprays still, until sprayed explosive liquid;
Adopt sand core funnel filtering for crystallizing liquid, take out solid substances to be purified;
Continuous 3 use approximately after 2500mL distilled water Uniform Dispersion material, ultrasonic concussion, adopt sand core funnel to filter out unnecessary liquid, take out the solid piece of purifying mass, disperse air-dryly to half-dried degree in dish, and redispersion becomes powder, drying products.
Add 5000mL pure water and 1.6g two-ethylhexyl succinate semi-annular jade pendant acid sodium mixing in the made of square plastic bucket, be chilled in advance 2 ℃ stand-by;
Add 10g LLM-105 and 200mL DMSO in there-necked flask, stir lower heating in water bath to 80 and ℃ make explosive complete molten stand-by;
Quantitative precooling water at low temperature, add pool type ultrasonic oscillation device, start ultrasonic concussion, adjusting the micropore spray tube lies across above the concussion liquid level, the opening pressure valve make explosive liquid be ejected into the concussion water surface below straight tube micropore spray tube, and back and forth parallel is laid the support that the molten medicine of constant temperature sprays still, until sprayed explosive liquid, ultrasonic concussion washing explosive crystal solution 2h;
Crystal solution is all measured added centrifugal bottle, be separated to solid-liquid with the 10000r/min rotating speed limpid in whizzer, discard liquid phase, take out solid substances to be purified;
Continuous 3 composite washing solns of use (9/1 ethanol/water) approximately after 3000mL Uniform Dispersion material, ultrasonic concussion, are separated to solid-liquid with the 10000r/min rotating speed limpid in whizzer.Discard liquid phase, take out the solid piece of purifying mass, disperse air-dry extremely half-dried degree in dish, redispersion becomes powder, drying products.And with the powder bottling (or bag) that parches, the sealing lucifuge is deposited.
Embodiment 4
Add 6800mL pure water and the acid of 2.2g hexadecyl benzene semi-annular jade pendant to receive mixing in the made of square plastic bucket, be chilled in advance-10 ℃ stand-by;
Add 30g LLM-105 and 650mL DMSO in there-necked flask, stir lower heating in water bath to 80 and ℃ make explosive complete molten stand-by;
Jet crystallization and aftertreatment are with embodiment 1.
Quantitative precooling water at low temperature, add pool type ultrasonic oscillation device, start ultrasonic concussion, adjusting the micropore spray tube lies across above the concussion liquid level, the opening pressure valve make explosive liquid be ejected into the concussion water surface below straight tube micropore spray tube, and back and forth parallel is laid the support that the molten medicine of constant temperature sprays still, until sprayed explosive liquid, ultrasonic concussion washing explosive crystal solution 20min;
Crystal solution is all measured added centrifugal bottle, be separated to solid-liquid with the 10000r/min rotating speed limpid in whizzer, discard liquid phase, take out solid substances to be purified;
Approximately 3000mL Uniform Dispersion material washing of continuous 3 composite washing solns of use (8/2 methanol/water) adopts sand core funnel to filter out unnecessary liquid, takes out the solid piece of purifying mass, disperses air-dry extremely half-dried degree in dish, and redispersion becomes powder, drying products.And with the powder bottling (or bag) that parches, the sealing lucifuge is deposited.
Add 800mL distilled water and 0.1g hexadecyl trimethyl ammonium bromide mixing in the 1000mL beaker, be chilled in advance 3 ℃ stand-by;
Add 2g LLM-105 and 40mL DMSO in there-necked flask, stir lower heating in water bath to 80 and ℃ make explosive complete molten stand-by;
Quantitative precooling water at low temperature, add pool type ultrasonic oscillation device, start ultrasonic concussion, adjusting the micropore spray tube lies across above the concussion liquid level, the opening pressure valve make explosive liquid be ejected into the concussion water surface below straight tube micropore spray tube, and back and forth parallel is laid the support that the molten medicine of constant temperature sprays still, until sprayed explosive liquid, ultrasonic concussion washing explosive crystal solution 10min;
Crystal solution is added in sand core funnel, and suction filtration is removed unnecessary liquid, takes out solid substances to be purified;
Approximately 200mL Uniform Dispersion material washing of continuous 3 composite washing solns of use (8/2 methanol/water) adopts sand core funnel to filter out unnecessary liquid, takes out the solid piece of purifying mass, disperses air-dry extremely half-dried degree in dish, and redispersion becomes powder, drying products.And with the powder bottling (or bag) that parches, the sealing lucifuge is deposited.
Adopt the present invention can efficiently prepare in batches the submicron particles LLM-105 of particle diameter 0.1 μ m～0.4 μ m, product performance reach the blasting cap initiation requirement.The submicron particles LLM-105 of preparation, purity 〉=99%, granule-morphology are seen Fig. 1 and Fig. 2.
Claims (9)
1. submicron particles 1-oxygen-diamino-3, the preparation method of 5-dinitrobenzene pyrazine explosive is characterized in that comprising the following steps successively:
A) preparation of non-solvent measures the mixing solutions of distilled water and dispersion agent, after evenly mixing in container, puts into the refrigerator-freezer precooling;
B) preparation of explosive solution takes 1-oxygen-diamino-3, and 5-dinitrobenzene pyrazine explosive and solvent are put into container, is heated with stirring to entirely molten;
C) jet crystallization is put into pool type ultrasonic oscillation device with the non-solvent solution of step a preparation; With 1-oxygen-diamino-3 of step b, 5-dinitrobenzene pyrazine explosive hot solution is poured in the jet crystallization device, and the jet crystallization device is fixed on traversing carriage; By the micropore on the spray tube (8) of jet crystallization bottom of device, explosive solution is vertically sprayed into pool type ultrasonic oscillation device (5) liquid level; In course of injection, control traversing carriage and move back and forth, Explosive jet efflux is evenly distributed spurt into pool type ultrasonic oscillation device liquid level, until fried liquid medicine jet is complete; Continue ultrasonic concussion 1h ~ 3h;
D) crystal solution is separated employing centrifugation or sand core funnel suction strainer separate mode, isolates the explosive crystal in step c crystal solution;
E) wash 1-oxygen-diamino-3 that purifying obtains steps d, 5-dinitrobenzene pyrazine explosive crystal washs purifying, drying, storage with cleaning solvent.
2. a kind of submicron particles 1-oxygen-diamino-3 according to claim 1,5-dinitrobenzene pyrazine explosive preparation method is characterized in that: described jet crystallization device comprises that the molten medicine of constant temperature sprays still (9), spray tube (8) and air pressure system (1); Its mode of connection is: after the molten medicine of constant temperature sprays the still lower end and spray tube (8) is connected, and the unsettled pool type ultrasonic oscillation device top of being placed in, the molten medicine of constant temperature sprays still (9) while and is connected with air pressure system.
3. a kind of submicron particles 1-oxygen-diamino-3 according to claim 2,5-dinitrobenzene pyrazine explosive preparation method, it is characterized in that: the molten medicine of described constant temperature sprays still (9) and injects the heating bath heating for sandwich-type, the molten medicine of constant temperature sprays still and is provided with cover plate (10), cover plate is provided with charging opening (6) and the control valve that is connected air pressure system (1) (2), and the kettle bottom is provided with medicine liquid outlet control valve (4).
4. a kind of submicron particles 1-oxygen-diamino-3 according to claim 2,5-dinitrobenzene pyrazine explosive preparation method is characterized in that: described spray tube (8), adopt right angle crankle shape structure, be divided into two parts of vertical section and horizontal section; The interior pond width of spray tube (8) horizontal section length and pool type ultrasonic oscillation device (5) adapts, and the horizontal section downside is provided with a plurality of micropores, and micropore is arranged in a linear.
5. a kind of submicron particles 1-oxygen-diamino-3 according to claim 1,5-dinitrobenzene pyrazine explosive preparation method, it is characterized in that: in the preparation of the described non-solvent of step a), by 5～20 times of mixing solutionss that measure distilled water and dispersion agent of required explosive solution body accumulated amount, wherein the mass ratio of distilled water and dispersion agent is 5000:0.5～5.
6. a kind of submicron particles 1-oxygen-diamino-3 according to claim 1,5-dinitrobenzene pyrazine explosive preparation method is characterized in that: the described dispersion agent of step a) adopts that tween, this dish, the acid of two-ethylhexyl succinate semi-annular jade pendant are received, the acid of hexadecyl benzene semi-annular jade pendant is received, a kind of in hexadecyl trimethyl ammonium bromide.
7. a kind of submicron particles 1-oxygen-diamino-3 according to claim 1,5-dinitrobenzene pyrazine explosive preparation method, it is characterized in that: in the preparation of step b) explosive solution, take 1-oxygen-diamino-3,5-dinitrobenzene pyrazine explosive and solvent according to the ratio of 1:20.
8. a kind of submicron particles 1-oxygen-diamino-3 according to claim 1,5-dinitrobenzene pyrazine explosive explosive preparation method is characterized in that: the described solvent of step b) is a kind of in dimethyl formamide, METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO).
9. a kind of submicron particles 1-oxygen-diamino-3 according to claim 1,5-dinitrobenzene pyrazine explosive preparation method is characterized in that: the described cleaning solvent of step e) is one or more in methyl alcohol, ethanol, dioxane, acetone, tetrahydrofuran (THF), vinyl acetic monomer, water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101176919A CN103172476A (en) | 2013-04-08 | 2013-04-08 | Preparation method of submicron particle 1-oxo-diamino-3, 5-dinitropyrazine explosive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101176919A CN103172476A (en) | 2013-04-08 | 2013-04-08 | Preparation method of submicron particle 1-oxo-diamino-3, 5-dinitropyrazine explosive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103172476A true CN103172476A (en) | 2013-06-26 |
Family
ID=48632750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013101176919A Pending CN103172476A (en) | 2013-04-08 | 2013-04-08 | Preparation method of submicron particle 1-oxo-diamino-3, 5-dinitropyrazine explosive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103172476A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467217A (en) * | 2013-09-24 | 2013-12-25 | 中国工程物理研究院化工材料研究所 | Preparation method of cubic short rod-like 1-oxygen-diamido-3,5-dinitro pyrazine explosive |
| CN104193564A (en) * | 2014-09-09 | 2014-12-10 | 中国工程物理研究院化工材料研究所 | Fine-particle high-energy low-sensitivity explosive compound and preparation method thereof |
| CN105503750A (en) * | 2016-01-28 | 2016-04-20 | 中国工程物理研究院化工材料研究所 | 2,6-diamino-3,5-dinitropyrazine-1-oxide synthetic method |
| CN105753613A (en) * | 2016-01-26 | 2016-07-13 | 中国工程物理研究院化工材料研究所 | High-quality explosive crystals prepared by self-assembling and preparation method thereof |
| CN106543091A (en) * | 2016-10-28 | 2017-03-29 | 西安近代化学研究所 | A kind of preparation method of 2,6 diaminourea of fine grained, 3,5 dinitro pyrazine, 1 oxide |
| CN106748583A (en) * | 2016-11-28 | 2017-05-31 | 中国工程物理研究院化工材料研究所 | The preparation method of the LLM 105 of three-dimensional classification micron spherical structure is built into by nanometer rods |
| CN106748594A (en) * | 2017-03-16 | 2017-05-31 | 中国工程物理研究院化工材料研究所 | Monodispersed oxidate microspheres explosive of 2,6 diaminourea, 3,5 dinitro pyrazine 1 and preparation method thereof |
| CN106946635A (en) * | 2017-04-24 | 2017-07-14 | 中国工程物理研究院化工材料研究所 | The preparation method of single dispersing Hexanitrohexaazaisowurtzitane micrometre hollow sphere |
| CN106986845A (en) * | 2017-04-11 | 2017-07-28 | 中国工程物理研究院化工材料研究所 | The spheroidal crystal preparation method of the explosives of LLM 105 |
| CN113024474A (en) * | 2021-03-11 | 2021-06-25 | 中国工程物理研究院化工材料研究所 | Channel type continuous crystallization method of LLM-105 |
| CN116903425A (en) * | 2023-08-02 | 2023-10-20 | 北京理工大学 | LLM-105/HNS jet blending crystal preparation device and preparation method |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0277386A2 (en) * | 1987-01-21 | 1988-08-10 | Bofors Explosives AB | A method for the production of HNS II |
| CN2394949Y (en) * | 1999-10-29 | 2000-09-06 | 江阴市飞龙电化设备有限公司 | Pulp moulding and forming machine |
| EP1256558A2 (en) * | 2001-05-11 | 2002-11-13 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for producing crystals from propellants, explosives and oxidizers dissolved in a solvent |
| US20040216822A1 (en) * | 2001-07-03 | 2004-11-04 | Heinz Hofmann | Process for the production of a pressed insensitive explosive mixture |
| US6841016B1 (en) * | 2000-03-02 | 2005-01-11 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Process for the production of crystalline energetic materials |
| CN1796008A (en) * | 2004-12-31 | 2006-07-05 | K.C.科技株式会社 | Substrate treatment equipment and treatment method thereof |
| CN101636223A (en) * | 2007-03-19 | 2010-01-27 | 普罗索尼克斯有限公司 | The method for preparing crystal |
| CN101888744A (en) * | 2009-05-14 | 2010-11-17 | 东京化工机株式会社 | Surface treatment apparatus for substrate material |
| CN102149438A (en) * | 2008-07-18 | 2011-08-10 | 普罗索尼克斯有限公司 | Process for improving crystallinity |
| CN102320903A (en) * | 2011-06-16 | 2012-01-18 | 中国工程物理研究院化工材料研究所 | Method for preparing high-quality energetic crystal material fine particles |
| CN102872612A (en) * | 2012-10-15 | 2013-01-16 | 中国工程物理研究院化工材料研究所 | Ultrasonic crystallizer |
-
2013
- 2013-04-08 CN CN2013101176919A patent/CN103172476A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0277386A2 (en) * | 1987-01-21 | 1988-08-10 | Bofors Explosives AB | A method for the production of HNS II |
| CN2394949Y (en) * | 1999-10-29 | 2000-09-06 | 江阴市飞龙电化设备有限公司 | Pulp moulding and forming machine |
| US6841016B1 (en) * | 2000-03-02 | 2005-01-11 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Process for the production of crystalline energetic materials |
| EP1256558A2 (en) * | 2001-05-11 | 2002-11-13 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for producing crystals from propellants, explosives and oxidizers dissolved in a solvent |
| US20040216822A1 (en) * | 2001-07-03 | 2004-11-04 | Heinz Hofmann | Process for the production of a pressed insensitive explosive mixture |
| CN1796008A (en) * | 2004-12-31 | 2006-07-05 | K.C.科技株式会社 | Substrate treatment equipment and treatment method thereof |
| CN101636223A (en) * | 2007-03-19 | 2010-01-27 | 普罗索尼克斯有限公司 | The method for preparing crystal |
| CN102149438A (en) * | 2008-07-18 | 2011-08-10 | 普罗索尼克斯有限公司 | Process for improving crystallinity |
| CN101888744A (en) * | 2009-05-14 | 2010-11-17 | 东京化工机株式会社 | Surface treatment apparatus for substrate material |
| CN102320903A (en) * | 2011-06-16 | 2012-01-18 | 中国工程物理研究院化工材料研究所 | Method for preparing high-quality energetic crystal material fine particles |
| CN102872612A (en) * | 2012-10-15 | 2013-01-16 | 中国工程物理研究院化工材料研究所 | Ultrasonic crystallizer |
Non-Patent Citations (7)
| Title |
|---|
| JINGYU WANG,ET AL.,: "Study on Ultrasound- and Spray-Assisted Precipitation of CL-20", 《PROPELLANTS EXPLOS. PYROTECH.》, vol. 37, no. 6, 31 December 2012 (2012-12-31) * |
| 李敏娜等: "MgO 超细颗粒水分散体系的稳定性研究", 《应用化工》, vol. 41, no. 4, 28 April 2012 (2012-04-28), pages 625 - 630 * |
| 李海波等: "LLM-105重结晶与性能研究", 《含能材料》, vol. 16, no. 6, 15 December 2008 (2008-12-15) * |
| 李黎瑛等: "不同分散剂对超细镍粉分散性能的影响", 《电子元件与材料》, vol. 31, no. 6, 30 June 2012 (2012-06-30), pages 52 - 55 * |
| 江伟辉等: "表面活性剂对硅酸锆超细粉体分散性的影响", 《中国陶瓷》, vol. 148, no. 12, 5 December 2012 (2012-12-05), pages 17 - 20 * |
| 王友兵等: "细颗粒LLM-105的制备及其热性能", 《含能材料》, vol. 19, no. 5, 25 October 2011 (2011-10-25), pages 523 - 526 * |
| 魏丽丽等: "表面活性剂对超细银粉分散性能的影响", 《中国有色金属学报》, vol. 19, no. 3, 15 March 2009 (2009-03-15), pages 596 - 600 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467217B (en) * | 2013-09-24 | 2015-08-19 | 中国工程物理研究院化工材料研究所 | The preparation method of cube corynebacterium 1-oxygen-diamino-3,5-dinitrobenzene pyrazine explosive |
| CN103467217A (en) * | 2013-09-24 | 2013-12-25 | 中国工程物理研究院化工材料研究所 | Preparation method of cubic short rod-like 1-oxygen-diamido-3,5-dinitro pyrazine explosive |
| CN104193564A (en) * | 2014-09-09 | 2014-12-10 | 中国工程物理研究院化工材料研究所 | Fine-particle high-energy low-sensitivity explosive compound and preparation method thereof |
| CN105753613A (en) * | 2016-01-26 | 2016-07-13 | 中国工程物理研究院化工材料研究所 | High-quality explosive crystals prepared by self-assembling and preparation method thereof |
| CN105503750A (en) * | 2016-01-28 | 2016-04-20 | 中国工程物理研究院化工材料研究所 | 2,6-diamino-3,5-dinitropyrazine-1-oxide synthetic method |
| CN105503750B (en) * | 2016-01-28 | 2018-03-02 | 中国工程物理研究院化工材料研究所 | The synthetic method of the oxide of 2,6 diaminourea, 3,5 dinitro pyrazine 1 |
| CN106543091A (en) * | 2016-10-28 | 2017-03-29 | 西安近代化学研究所 | A kind of preparation method of 2,6 diaminourea of fine grained, 3,5 dinitro pyrazine, 1 oxide |
| CN106748583A (en) * | 2016-11-28 | 2017-05-31 | 中国工程物理研究院化工材料研究所 | The preparation method of the LLM 105 of three-dimensional classification micron spherical structure is built into by nanometer rods |
| CN106748594A (en) * | 2017-03-16 | 2017-05-31 | 中国工程物理研究院化工材料研究所 | Monodispersed oxidate microspheres explosive of 2,6 diaminourea, 3,5 dinitro pyrazine 1 and preparation method thereof |
| CN106748594B (en) * | 2017-03-16 | 2019-01-15 | 中国工程物理研究院化工材料研究所 | Monodispersed 2,6- diamino -3,5- dinitro pyrazine -1- oxidate microspheres explosive and preparation method thereof |
| CN106986845B (en) * | 2017-04-11 | 2019-07-19 | 中国工程物理研究院化工材料研究所 | The spheroidal crystal preparation method of LLM-105 explosive |
| CN106986845A (en) * | 2017-04-11 | 2017-07-28 | 中国工程物理研究院化工材料研究所 | The spheroidal crystal preparation method of the explosives of LLM 105 |
| CN106946635A (en) * | 2017-04-24 | 2017-07-14 | 中国工程物理研究院化工材料研究所 | The preparation method of single dispersing Hexanitrohexaazaisowurtzitane micrometre hollow sphere |
| CN106946635B (en) * | 2017-04-24 | 2019-07-19 | 中国工程物理研究院化工材料研究所 | The preparation method of monodisperse Hexanitrohexaazaisowurtzitane micrometre hollow sphere |
| CN113024474A (en) * | 2021-03-11 | 2021-06-25 | 中国工程物理研究院化工材料研究所 | Channel type continuous crystallization method of LLM-105 |
| CN113024474B (en) * | 2021-03-11 | 2023-03-10 | 中国工程物理研究院化工材料研究所 | Channel type continuous crystallization method of LLM-105 |
| CN116903425A (en) * | 2023-08-02 | 2023-10-20 | 北京理工大学 | LLM-105/HNS jet blending crystal preparation device and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103172476A (en) | Preparation method of submicron particle 1-oxo-diamino-3, 5-dinitropyrazine explosive | |
| CN103977593B (en) | The method and device of preparation nanometer eutectic energetic material | |
| CN102581272B (en) | Method for preparing nanometer aluminum composite powder coated with nitro-cotton | |
| CN104193564B (en) | Fine-particle high-energy low-sensitivity explosive compound and preparation method thereof | |
| CN107304150B (en) | A kind of high-voltage electrostatic spraying prepares boron/potassium nitrate/nitrocellulose complex microsphere method | |
| CN107324637B (en) | Recycle the chemical industry equipment of production glass that discarded glass recycles | |
| CN106563399B (en) | A kind of method that supercritical fluid prepares " shell-core " structure nano microcapsules | |
| CN106116995B (en) | A kind of method that aqueous suspension prepares press fitting aluminum composition modeling powder | |
| Han et al. | Fabrication of microspherical Hexanitrostilbene (HNS) with droplet microfluidic technology | |
| CN112089797A (en) | Preparation method of superfine gastrodia elata powder and vacuum freeze-drying preparation of superfine gastrodia elata powder | |
| EP1469938A1 (en) | Apparatus and process for preparing crystalline particles | |
| CN103467217A (en) | Preparation method of cubic short rod-like 1-oxygen-diamido-3,5-dinitro pyrazine explosive | |
| CN110526790A (en) | A kind of boron of core-shell structure/potassium nitrate preparation method | |
| CN107400033A (en) | A kind of energetic material complex microsphere and its preparation method and application | |
| CN104248938A (en) | Preparation equipment of pelletizing particles in aqueous medium | |
| CN108997238B (en) | Preparation method of fine particle NTO | |
| CN103342618B (en) | The batch preparation of a kind of submicron hexanitro-six azepine isoamyl hereby alkane explosive | |
| CN102718187B (en) | Hollow ultrafine ammonium perchlorate and preparation method thereof | |
| CN106518883B (en) | Six azepine isoamyl of nanometer ε crystal form hexanitro hereby alkane explosive and its batch preparation | |
| CN108299324B (en) | Preparation method of spherical 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt | |
| CN108976176A (en) | 3,3 '-diamino -4, the thinning method of 4 '-azoxy furazan explosive crystals | |
| CN108997126A (en) | A kind of synthesis technology of the Barium trinitroresorcinate based on block Flow Technique | |
| CN101844955B (en) | Method for sensitizing microporous smokeless firework explosive | |
| EP0994829A1 (en) | Thermally-stabilized prilled ammonium dinitramide particles, and process for making the same | |
| US4529321A (en) | Device for the preparation of dispersions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130626 |