CN106810409A - Embedded Subjective and Objective explosive crystal based on gas displacement technology and preparation method thereof - Google Patents
Embedded Subjective and Objective explosive crystal based on gas displacement technology and preparation method thereof Download PDFInfo
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- CN106810409A CN106810409A CN201710054757.2A CN201710054757A CN106810409A CN 106810409 A CN106810409 A CN 106810409A CN 201710054757 A CN201710054757 A CN 201710054757A CN 106810409 A CN106810409 A CN 106810409A
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
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Abstract
The invention provides a kind of preparation method of the embedded Subjective and Objective explosive crystal based on gas displacement technology, the method is with the based solvent compounds of CL 20 as original template, solvate crystal is purged by gas molecule, inducing gas molecule is replaced with the solvent guest molecule in solvate, and packing of molecules rearrangement is carried out, so as to obtain the embedded Subjective and Objective explosive crystal of the embedded gas molecule of structure cell.Method of the present invention preparation process is simple, experiment condition are gentle, without HTHP, by simple gas-solid reaction micro-molecular gas can be made to be embedded in explosive crystal structure cell.Subjective and Objective explosive crystal prepared by the method does not contain other crystal formation crystal, easily amplifies and prepares and popularization and application.The present invention is breached traditionally from molecular structure or the modification explosive by way of component is compound, is improved for explosive combination property and is provided new thinking, and carries out the new way of high explosive performance regulation and control there is provided by being embedded in micro-molecular gas.
Description
The application obtains state natural sciences fund general project (bullets：11472252) subsidy.
Technical field
The present invention relates to a kind of high explosive crystal and preparation method thereof, and in particular to a kind of based on gas displacement technology
Embedded Subjective and Objective explosive crystal and preparation method thereof, belongs to explosive preparing technical field.
Background technology
Energetic material comes as the long-range compacting of realization in weapon warhead, precision strike and the power and power efficiently injured
Source, serves vital to the overall performance and fight capability of armament systems.The weapons and ammunitions of the World War I into
Divide mainly picric acid, but picric acid corrosivity is strong, and accidental explosion easily occurs；Replaced by TNT in World War II, but TNT detonation energies
Amount is relatively low；The high-energy composite explosives with RDX, HMX as Main Ingredients and Appearance are occurred in that later, are greatly improved and are injured power；It is modern military
The requirement of device is then higher, such as precision strike, efficiently injure, failure-survival capability and environment-friendly, cause traditional energetic material
Face a severe challenge.Therefore, the energy limitation of traditional energetic material how is broken through, it is to contain energy at present to prepare energy explosive higher
One of the focus direction in investigation of materials field.
Domestic scholars mainly had following several approach to the research that explosive property improves method in recent years：(1) design synthesis
Novel high-energy single chmical compound explosive.Because most energy-containing compound synthesis conditions are harsh, synthesis cycle is long, it is difficult to obtain in a short time
Break through.(2) Composite Energetic Materials are prepared.Explosive is set to be combined with other materials by physics or chemical method, it is former to improve it
Some physics and chemical property.Such as by the metal powder quick-fried heat of raising is added in explosive formulation, explosive crystal being implanted into polymer
In to disperse impact energy so that the sensitivity for reducing explosive is obtained " insensitive explosives ".(3) containing the preparation of energy eutectic, by tying again
Crystalline substance is piled up the cocrystallized explosive for obtaining by two kinds of single chmical compound explosives again in structure cell, although be expected to take different explosive properties
Benefit long is short, but its performance is generally between the two, it is impossible to the performance of explosive is obtained substantial lifting.If explosive and other
Non- energetic material eutectic, though being possible to improve security, greatly reduces energy density.(4) new ideas energetic material.Metal
Hydrogen, antimatter, full nitrogen energetic material etc., although energy density is high, but is substantially at theoretical calculation and conceptual phase；Although
There is document report to synthesize full nitrogen molecule containing energy, but because it is extremely unstable at normal temperatures, can hardly find practical applications.Additionally,
Mobility can be improved by the improvement to energetic material crystal quality, security is improved.But its range of application is subject to very big
Limitation, such as high-quality explosive improves having little effect for energy or security for nuclear weapon pressed explosives.
To sum up analyze, although having been developed that various methods to improve or regulate and control the performance of explosive at present, but to explosive
The need for the improvement of performance does not still meet practical application.Carry out existing energetic material structure to improve is to lift explosive at present
One feasible and effective way of performance.Hexanitrohexaazaisowurtzitane (CL-20 or HNIW) is the energy being actually applied
One of amount highest single chmical compound explosive, molecular formula is C6H6N12O12, density and energy highest ε-CL-20 explosion velocities reach 9650m.s-1.CL-20 not only has energy very high, it may have good detonation explosion transfer performance.Therefore, it is excellent as base carries out structure with CL-20
Change and performance improvement, it is possible to realize being substantially improved for explosive property.
Based on the Subjective and Objective explosive that supramolecular chemistry thought is constructed, due to the weak interaction between Subjective and Objective molecule, make
Subjective and Objective explosive can stable existence, and have the characteristic of host molecule and guest molecule concurrently so that the property of Subjective and Objective explosive
Can be lifted.Therefore, by the design and preparation of Subjective and Objective explosive, it is capable of achieving that the crystal structure of explosive is improved and optimized,
Then the regulation and control of explosive property are realized.
Domestic and foreign literature (Martin S S, et al, Host-Guest Inclusion Compound from
Nitramine Crystals Exposed to Condensed Carbon Dioxide Chemistry-A European
Journal,2010,16(45):13473-13478；Zhu Kang, etc. supercritical CO2Anti-solvent method prepares CL-20 ultrafine dusts and contains
Can material, 2012,20 (4):445-449.) report and prepare CL-20/CO using the method for high pressure2Subjective and Objective explosive crystal, will
ε-CL-20 crystal is put into pressure vessel, and CO is passed through by compressor2Gases at high pressure, the pressure of gas maintain 15Mpa with
On, while heated pressure container is to 80 DEG C, obtain being embedded in CO after a period of time2The CL-20 base Subjective and Objective explosives of gas.The method
Needs are carried out under high-temperature and high-pressure conditions, and experiment condition is more harsh, and applicable gas molecule limitednumber, for some work
Property gas molecule, be susceptible under high pressure reaction.In addition, CL-20 belongs to high explosive being exploded in closed high-pressure bottle
Risk increase.Therefore, need badly and seek more gentle preparation method and experiment condition.
Patent CN106116993A discloses a kind of Subjective and Objective of the embedded micro-molecular gas based on solution-air cocrystallization technology
Explosive and preparation method thereof, by by N2O gases are continually fed into CL-20 solution, and the method recrystallized using solution makes CL-20
With N2O cocrystallization, so as to obtain CL-20 and N2The Subjective and Objective explosive crystal of O cocrystallization.Although the method overcomes HTHP
Experiment condition, using more gentle solution crystallization mode, but CL-20 belong to polymorphic explosive (had now found that six kinds of α,
β, γ, ε, ζ, δ), mixing crystal formation crystal is easily formed in solution recrystallization process so that mixed in the Subjective and Objective explosive crystalline substance of preparation
There is the CL-20 of other crystal formations, so as to reduce the purity of Subjective and Objective explosive crystal, influence the performances such as its safety, detonation.Therefore, also
Need constantly to explore new Subjective and Objective explosive crystal preparation method.
The content of the invention
It is an object of the present invention to provide a kind of embedded Subjective and Objective explosive crystal based on gas displacement technology
Preparation method, obtains the Subjective and Objective explosive crystal of CL-20 bases, it is expected to lifts the oxygen balance of explosive, increases release quantity, improves detonation
Performance, so as to be that explosive crystal structure optimization and performance regulation and control provide new thinking.
It is another object of the present invention to provide a kind of embedded Subjective and Objective explosive crystal based on gas displacement technology
Preparation method, the method experiment condition is gentle, process is simple, easily realize, is suitable for amplifying and prepares and popularization and application.
To achieve the above object, the invention provides a kind of embedded Subjective and Objective explosive crystal based on gas displacement technology
Preparation method, the method with CL-20 based solvent compounds as original template, by gas molecule purge solvate crystal, lure
Conductive gas molecule is replaced with the solvent guest molecule in solvate, and carries out packing of molecules rearrangement, is embedded so as to obtain structure cell
The embedded Subjective and Objective explosive crystal of gas molecule.
More specifically technical scheme of the invention is as follows：
The preparation method of the embedded Subjective and Objective explosive crystal based on gas displacement technology, mainly includes the following steps that：
Step one：With common CL-20 as raw material, the solvent recrystallization being complexed with CL-20 is selected to, prepares CL-20
Solvate crystal.
Step 2：The solvate crystal tiling dispersion that will be prepared in step one in a reservoir, is passed through gas, to solvation
Thing is persistently purged, and obtains the embedded Subjective and Objective explosive crystal of the embedded gas molecule of structure cell.
The preparation method principle of the above-mentioned embedded Subjective and Objective explosive crystal based on gas displacement technology is：With high explosive
CL-20 is main body, and micro-molecular gas are object, certain way and under the conditions of micro-molecular gas enter into the structure cell of explosive crystal
Inside, forms high-sequential, stronger intermolecular force is formed between the crystal of periodic arrangement, and Subjective and Objective molecule.
In the preparation method of the above-mentioned embedded Subjective and Objective explosive crystal based on gas displacement technology, it is described can be with CL-
The solvent of 20 complexings is selected from dioxane, N,N-dimethylformamide, HMPA, dimethyl carbonate, sulfuric acid diethyl
It is any in ester, sulfolane, 1-METHYLPYRROLIDONE, acetonitrile, γ-fourth lactones, dimethyl sulfoxide (DMSO), trimethyl glyceride, acetone
One kind, but it is not limited to cited solvent.
In the preparation method of the above-mentioned embedded Subjective and Objective explosive crystal based on gas displacement technology, the solvate weight
Method for crystallising includes solvent falling temperature method, solvent-nonsolvent method and solvent evaporated method.
In the preparation method of the above-mentioned embedded Subjective and Objective explosive crystal based on gas displacement technology, the solvate is brilliant
Body needed to be characterized by X-ray powder diffraction before step 2 is carried out, it is determined that all CL-20 solvents of crystal of recrystallization
Compound crystal；If including other crystal in solvate, need according to the method for step one to enter crystallized product again
Row recrystallization.
In the preparation method of the above-mentioned embedded Subjective and Objective explosive crystal based on gas displacement technology, gas in the step 2
Body molecule includes nitrous oxide (N2O), carbon dioxide (CO2), nitrogen dioxide (NO2), nitric oxide (NO), nitric oxide
(NO), nitrogen (N2), hydrogen (H2), ammonia (NH3), oxygen (O2), ozone (O3), fluorine gas (F2), chlorine (Cl2), bromine gas (Br2)、
Methane (CH4), acetylene (C2H2), ethene (C2H4), ethane (C2H6), sulfur dioxide (SO2), nitrogen trioxide (N2O3), four oxidation
Phenodiazine (N2O4), dinitrogen pentoxide (N2O5) in any one, but be not limited to cited gas molecule.
In the preparation method of the above-mentioned embedded Subjective and Objective explosive crystal based on gas displacement technology, in the step 2
Gas is in the lasting purge of solvate, the temperature of gas and solvate is normal temperature (20 DEG C), and the pressure of gas is
Normal pressure (101.3kPa).It should be noted that the condition of gas purging is not limited to cited temperature and pressure, in order to accelerate
The replacement rate of gas can suitably be heated or pressurizeed, that is, lift the temperature of solvate or the pressure of increase gas, general heating
Temperature less than solvate decomposition temperature, preferably gas displacement temperature range between 20 DEG C~80 DEG C, preferably
Gas displacement pressure limit is in normal pressure~20MPa.
In the preparation method of the above-mentioned embedded Subjective and Objective explosive crystal based on gas displacement technology, gas in the step 2
Crystal after body purging is needed to carry out Crystal Structure, and the crystal after determining gas purging is characterized using X-ray powder diffraction
In do not contain solvate, determine that gas molecule has been replaced solvent molecule and entered into crystal lattice using infrared spectrum characterization
In；If purging after crystal in contain solvate, need by crystal proceed gas purge, until gas molecule is complete
Solvent molecule in portion's displacement solvate.
The method of the present invention is based on host-guest chemistry thought, using gas displacement method, by micro-molecular gas and CL-20 bases
The object solvent molecule displacement of solvate, obtains the CL-20 Subjective and Objective explosive crystals of the embedded gas molecule of structure cell.Party's legal system
Standby process is simple, experiment condition are gentle, without HTHP, can be embedded in micro-molecular gas by simple gas-solid reaction
In explosive crystal structure cell, the present invention is breached traditionally from molecular structure or the modification explosive by way of component is compound, is fried
Medicine combination property is improved and provides new thinking, and is opened and carried out the new of high explosive performance regulation and control by embedded micro-molecular gas
Approach.
The present invention is also claimed the preparation by the above-mentioned embedded Subjective and Objective explosive crystal based on gas displacement technology
The embedded Subjective and Objective explosive crystal based on gas displacement technology that method is prepared.
Compared with prior art, one of beneficial effects of the present invention are：The method of the present invention is based on gas displacement technology, with
The solvate of CL-20 is original template, and under the induction metathesis of gas, gas molecule is by dynamic process diffusion
Into in structure cell, so as to obtain the CL-20 base Subjective and Objective explosive crystals that structure cell is embedded in micro-molecular gas.The method preparation technology
Simply, experiment condition is gentle, without HTHP, by simple gas-solid reaction micro-molecular gas can be made to be embedded in explosive brilliant
In body structure cell.Subjective and Objective explosive crystal prepared by the method does not contain other crystal formation crystal, easily amplifies and prepares and popularization and application.
The present invention is breached traditionally from molecular structure or the modification explosive by way of component is compound, is that the improvement of explosive combination property is carried
For new thinking, and the new way of high explosive performance regulation and control is carried out there is provided by being embedded in micro-molecular gas.
Brief description of the drawings
Fig. 1 is the shape appearance figure of CL-20 raw materials.
Fig. 2 is the shape appearance figure of CL-20 solvate crystals.
Fig. 3 is the IR spectrograms of CL-20 raw materials.
Fig. 4 is the IR spectrograms of CL-20.DMC solvates.
Fig. 5 is the XRD spectra of CL-20 raw materials.
Fig. 6 is the XRD spectra of CL-20.DMC solvates.
Fig. 7 is CL-20.CO2The shape appearance figure of Subjective and Objective explosive crystal.
Fig. 8 is CL-20.N2The shape appearance figure of O Subjective and Objective explosive crystals.
Fig. 9 is CL-20.CO2The IR spectrograms of Subjective and Objective explosive crystal.
Figure 10 is CL-20.N2The IR spectrograms of O Subjective and Objective explosive crystals.
Figure 11 is CL-20.CO2The XRD spectra of Subjective and Objective explosive crystal.
Figure 12 is CL-20.N2The XRD spectra of O Subjective and Objective explosive crystals.
Figure 13 is CL-20.CO2The DSC-TG spectrograms of Subjective and Objective explosive crystal.
Figure 14 is CL-20.N2The DSC-TG spectrograms of O Subjective and Objective explosive crystals.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only used to explain the present invention, not
For limiting the present invention.
Detecting instrument：
Field emission scanning electron microscope：Apollo 300CSF-3A, the treatment of test specimen metal spraying, protective gas：Argon gas, electric current：
20mA, time：3min, operating voltage：2KV.
X-ray powder diffraction instrument (XRD)：Bruker D8Advance, diffraction source：CuKαIt is one-dimensional
Detector array：Vantec-1, electric current：40mA, voltage：40kv, sweep limits：5~50 °, sweep speed：0.2s/ is walked, scanning
Step-length：0.02 °/step.
Infra-red sepectrometry (IR)：The Fourier infrared spectrographs of Nicolet 800, KBr compressing tablets, surface sweeping scope：400cm-1~
4000cm-1, resolution ratio：4cm-1。
Means of differential scanning calorimetry-thermal weight loss combined instrument (DSC-TG)：The resistance to 449C types, test scope of speeding of Germany：50~500 DEG C,
Heating rate：10℃.min-1, N2：50ml.min-1。
Embodiment 1
(1) dimethyl carbonate (DMC) solvent of 40ml is measured, is poured into conical flask, then weigh the CL-20 explosives original of 10g
Material is added, and 60 DEG C are heated in water-bath, and explosive is completely dissolved with the speed magnetic agitation of 300r/min；
(2) taper bottleneck is opened wide, the continuous heating at 60 DEG C, is stirred with the speed continuing magnetic force of 300r/min, and put
Put in fume hood, dimethyl carbonate solvent is slowly volatilized, after crystallization 4h, filter, wash, dry；
(3) a small amount of crystallized product is taken, micro- sem observation is carried out, crystal morphology is obtained, while carry out XRD and IR characterize,
Determine all CL-20.DMC solvate crystals of crystallized product；
(4) crystallized product tiled, be dispersed in unlimited glass surface ware；
(5) in fume hood, will be equipped with pure CO2The 8L steel cylinders of gas pass through pressure-reducing valve by stainless steel tube, persistently to molten
Agent compound plane of crystal is purged, and the pressure of purge gas outlet is normal pressure (101.3kPa), and the temperature of gas and sample is
Normal temperature (20 DEG C), after 5h, stops purging；
(6) take the sample after a small amount of purging, carry out micro- sem observation, obtain the pattern of crystal, at the same carry out XRD, IR,
TG-DSC is characterized, and confirms that the sample after purging does not contain solvate crystal, and micro-molecular gas enter in the structure cell of crystal, i.e.,
Obtain CL-20.CO2Subjective and Objective explosive crystal.
Embodiment 2
(1) DMF (DMF) solvent of 40ml is measured, is poured into the there-necked flask of 150ml, then weigh
The CL-20 explosive raw materials of 10g are added, and 80 DEG C are heated in water-bath, make explosive complete with the speed mechanical agitation of 150r/min
Dissolving；
(2) water-bath is stopped heating, makes that the DMF solution of CL-20 is naturally cold in water-bath to be gone, and with 150r/min's
Speed continued mechanical is stirred, and after crystallization 1h, is filtered, washs, is dried；
(3) a small amount of crystallized product is taken, micro- sem observation is carried out, crystal morphology is obtained, while carry out XRD and IR characterize,
Determine all CL-20.DMF solvate crystals of crystallized product；
(4) crystallized product tiled, be dispersed in the pressure bottle with air inlet/outlet, while by pressure bottle in water-bath
It is heated to 80 DEG C；
(5) in fume hood, will be equipped with pure N2The 8L steel cylinders of O gases pass through pressure-reducing valve by stainless steel tube, persistently to molten
Agent compound plane of crystal is purged, and purge gas from air inlet after booster pump is pressurized to 20MPa by entering right in pressure bottle
Gas is purged, and is then discharged from gas outlet, and the temperature of sample maintains 80 DEG C, after 2h, stops purging；
(6) take the sample after a small amount of purging, carry out micro- sem observation, obtain the pattern of crystal, at the same carry out XRD, IR,
TG-DSC is characterized, and confirms that the sample after purging does not contain solvate crystal, and micro-molecular gas enter in the structure cell of crystal, i.e.,
Obtain CL-20.N2O Subjective and Objective explosive crystals.
Embodiment 3
(1) dioxane (DIO) solvent of 30ml is measured as good solvent, is poured into the there-necked flask of 250ml, then weigh
The CL-20 explosive raw materials of 10g are added, and under room temperature (20 DEG C), explosive are completely dissolved with the speed mechanical agitation of 150r/min；
(2) 100ml distilled water is measured as non-solvent, is slowly dropped in CL-20 solution with the speed of 10ml/min, and
With the speed mechanical agitation of 150r/min, under normal temperature (20 DEG C), after stirred crystallization 1h, filter, wash, dry；
(3) a small amount of crystallized product is taken, micro- sem observation is carried out, crystal morphology is obtained, while carry out XRD and IR characterize,
Determine all CL-20.DIO solvate crystals of crystallized product；
(4) crystallized product tiled, be dispersed in the pressure bottle with air inlet/outlet, while pressure bottle is placed on into water-bath
In be heated to 60 DEG C；
(5) in fume hood, will be equipped with pure NO2The 8L steel cylinders of gas pass through pressure-reducing valve by stainless steel tube, persistently to molten
Agent compound plane of crystal is purged, and purge gas from air inlet after booster pump is pressurized to 3MPa by entering in pressure bottle to gas
Body is purged, and is then discharged from gas outlet, and the temperature of sample maintains 60 DEG C, after 3.5h, stops purging；
(6) take the sample after a small amount of purging, carry out micro- sem observation, obtain the pattern of crystal, at the same carry out XRD, IR,
TG-DSC is characterized, and confirms that the sample after purging does not contain solvate crystal, and micro-molecular gas enter in the structure cell of crystal, i.e.,
Obtain CL-20.NO2Subjective and Objective explosive crystal.
Specific examples below 4~20, with embodiment 3, its specific technological parameter is shown in Table 1 to preparation method.
The technological parameter of the embodiment 4~20 of table 1
Solvate crystal scanning electron microscopic picture is as shown in Fig. 2 and raw material obtained in method using embodiment 1 of the invention
CL-20 crystal morphologies (see Fig. 1) are compared, and have obvious difference, and it is bar-shaped to become length by fusiform.It is raw material CL-20 shown in Fig. 3
Infrared spectrum, shown in Fig. 4 be CL-20.DMC solvates infrared spectrum, it can be seen that solvate crystal
Infrared absorption peak it is significantly different with raw material CL-20, and all solvate crystals in crystallized product.With reference to raw material CL-
The XRD spectra of 20 (Fig. 5) and CL-20.DMC solvates (Fig. 6), can prove do not contain raw material CL-20 in crystallized product, entirely
Portion is solvate crystal.CO2The CL-20.CO obtained after gas displacement2The pattern of Subjective and Objective explosive crystal is as shown in fig. 7, hair
With the presence of microstructures such as substantial amounts of crackle and holes, these ducts are exactly micro-molecular gas on the surface of existing Subjective and Objective explosive crystal
Formed during guest molecule in displacement solvate, and Subjective and Objective explosive crystal macro morphology and solvate crystal
It is basically identical.It is CL-20.CO after gas displacement shown in Fig. 92The infrared spectrum of Subjective and Objective explosive, wherein 2279cm-1、2332cm-1、2345cm-1It is CO2Characteristic absorption peak, show CO in sample2Molecule has been embedded in CL-20 structure cells, CL-20 and CO2Deposit
There is no the infrared absorption peak of CL-20.DMC solvates, i.e. gas in stronger intermolecular interaction, and in infrared spectrum
It is replaced.CL-20.CO shown in Figure 112XRD spectra understand, solvate has been free of in sample.It is shown in Figure 13
CL-20.CO2The TG-DSC curves of Subjective and Objective explosive, CO2The weightless temperature range of gas is 177 DEG C~196 DEG C, by CO2Gas
The weight loss of body is calculated CL-20 and CO in crystal2Mol ratio be 2:1.Result above shows, using the side of embodiment 1
Method is embedded in CO in can obtaining structure cell based on gas displacement technology2The CL-20 base Subjective and Objective explosive crystals of gas molecule.
CL-20.N obtained in method using embodiment 2 of the invention2The pattern of O Subjective and Objective explosive crystals as shown in figure 8,
As shown in Figure 10, as shown in figure 12, TG-DSC curves are as shown in figure 14 for XRD spectra for infrared spectrum.It can be seen that CL-
20.N2There is the microstructures such as substantial amounts of crackle and hole in the surface of O Subjective and Objective explosive crystals, there is obvious in infrared spectrum
N2O molecule infrared absorption peaks (2244cm-1、2229cm-1), infrared and XRD spectra display N2O gases are complete by solvate
Replace and be embedded into the structure cell of crystal, N2The weightless temperature range of the gas of O gases is 177 DEG C~189 DEG C, by N2O gases
Weight loss be calculated CL-20 and N in crystal2The mol ratio of O is 2:1, these results suggest that using the method system of embodiment 2
Standby sample is embedded N2The CL-20.N of O molecules2O Subjective and Objective explosive crystals.
As can be seen here, the purpose of the present invention is achieved completely and effectively.Technical scheme is in reality
Apply and shown in example and illustrate, under without departing substantially from the principle, implementation method can make any modification.So, the present invention includes
All variant embodiments based on claim spirit and right.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferably implementation method, embodiments of the present invention are simultaneously not restricted to the described embodiments, it should be appreciated that people in the art
Member can be designed that a lot of other modification and implementation methods, and these modifications and implementation method will fall in principle disclosed in the present application
Within scope and spirit.
Claims (9)
1. a kind of preparation method of the embedded Subjective and Objective explosive crystal based on gas displacement technology, it is characterised in that with CL-20
Based solvent compound is original template, solvate crystal is purged by gas molecule, in inducing gas molecule and solvate
Solvent guest molecule is replaced, and carries out packing of molecules rearrangement, so as to the embedded Subjective and Objective for obtaining the embedded gas molecule of structure cell is fried
Medicine crystal.
2. the preparation method of the embedded Subjective and Objective explosive crystal based on gas displacement technology according to claim 1, its
It is characterised by comprising the following steps：
Step one：With common CL-20 as raw material, the solvent recrystallization being complexed with CL-20 is selected to, prepares the molten of CL-20
Agent compound crystal；
Step 2：The solvate crystal tiling dispersion that will be prepared in step one in a reservoir, is passed through gas, and solvate is held
Continuous purging, obtains the embedded Subjective and Objective explosive crystal of the embedded gas molecule of structure cell.
3. the preparation method of the embedded Subjective and Objective explosive crystal based on gas displacement technology according to claim 2, its
It is characterised by that the solvent that can be complexed with CL-20 in the step one is selected from dioxane, N,N-dimethylformamide, hexamethyl
Phosphoric triamide, dimethyl carbonate, dithyl sulfate, sulfolane, 1-METHYLPYRROLIDONE, acetonitrile, γ-fourth lactones, dimethyl are sub-
Any one in sulfone, trimethyl glyceride, acetone.
4. the preparation method of the embedded Subjective and Objective explosive crystal based on gas displacement technology according to claim 2, its
The solvate recrystallization method being characterised by the step one includes that solvent falling temperature method, solvent-nonsolvent method and solvent steam
Hair method.
5. the preparation method of the embedded Subjective and Objective explosive crystal based on gas displacement technology according to claim 2, its
The solvate crystal being characterised by the step one needed to be characterized by X-ray powder diffraction before step 2 is carried out,
It is determined that all CL-20 solvate crystals of crystal of recrystallization；If in solvate include other crystal, need by
Crystallized product re-starts recrystallization according to the method for step one.
6. the preparation method of the embedded Subjective and Objective explosive crystal based on gas displacement technology according to claim 2, its
Gas molecule includes nitrous oxide, carbon dioxide, nitrogen dioxide, nitric oxide, nitrogen, hydrogen in being characterised by the step 2
Gas, ammonia, oxygen, ozone, fluorine gas, chlorine, bromine gas, methane, acetylene, ethene, ethane, sulfur dioxide, nitrogen trioxide, four oxygen
Change phenodiazine, any one in dinitrogen pentoxide.
7. the preparation method of the embedded Subjective and Objective explosive crystal based on gas displacement technology according to claim 2, its
The gas in step 2 is characterised by the lasting purge of solvate, the temperature of gas and solvate for 20 DEG C extremely
80 DEG C, gas displacement pressure limit is in normal pressure to 20MPa.
8. the preparation method of the embedded Subjective and Objective explosive crystal based on gas displacement technology according to claim 2, its
It is characterised by that the crystal in the step 2 after gas purging needs to carry out Crystal Structure, using X-ray powder diffraction table
Levy determine gas purging after crystal in do not contain solvate, it is molten to determine that gas molecule has been replaced using infrared spectrum characterization
Agent molecule is entered into crystal lattice；If containing solvate in the crystal after purging, need for crystal to proceed gas
Body is purged, the solvent molecule in gas molecule all displacement solvate.
9. the system of the embedded Subjective and Objective explosive crystal of gas displacement technology is based on described in claim 1 to 8 any claim
The embedded Subjective and Objective explosive crystal based on gas displacement technology that Preparation Method is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710054757.2A CN106810409B (en) | 2017-01-24 | 2017-01-24 | Embedded Subjective and Objective explosive crystal based on gas displacement technology and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710054757.2A CN106810409B (en) | 2017-01-24 | 2017-01-24 | Embedded Subjective and Objective explosive crystal based on gas displacement technology and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN110937960A (en) * | 2019-11-07 | 2020-03-31 | 中国工程物理研究院化工材料研究所 | Preparation method of host-guest explosive for in-situ self-assembly of ozone molecules |
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