CN106810409B - 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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- CN106810409B CN106810409B CN201710054757.2A CN201710054757A CN106810409B CN 106810409 B CN106810409 B CN 106810409B CN 201710054757 A CN201710054757 A CN 201710054757A CN 106810409 B CN106810409 B CN 106810409B
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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 preparation method of the present invention provides a kind of embedded Subjective and Objective explosive crystal based on gas displacement technology, this method is using 20 based solvent compounds of CL 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, to obtain the embedded Subjective and Objective explosive crystal that structure cell embeds gas molecule.Method preparation process of the invention is simple, experiment condition is mild, is not necessarily to high temperature and pressure, micro-molecular gas can be made to be embedded in explosive crystal structure cell by simple gas-solid reaction.Subjective and Objective explosive crystal prepared by this method does not contain other crystal form crystal, is easy amplification and prepares and promote and apply.The present invention breaches traditionally from molecular structure or by the compound mode modification explosive of component, provides new thinking for the improvement of explosive comprehensive performance, and provide the new way that high explosive performance regulation and control are carried out by embedded micro-molecular gas.
Description
The application obtains state natural sciences fund general project (project number：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 with the power and power efficiently injured
Source, overall performance and fight capability to weapon system serve vital.The weapons and ammunitions of the World War I at
Divide mainly picric acid, but picric acid corrosivity is strong, and accidental explosion easily occurs；Replaced in World War II by TNT, but TNT detonation energies
It measures relatively low；Occur, with high-energy composite explosives RDX, HMX as the main component, greatly improving and injuring power later；It is modern military
The requirement of device then higher, such as precision strike, efficiently injure, failure-survival capability and environmental-friendly, cause traditional energetic material
It faces a severe challenge.Therefore, the energy limit for how breaking through traditional energetic material, it is to contain energy at present to prepare the higher explosive of energy
One of the hot spot direction in investigation of materials field.
Domestic scholars were mainly the following approach to the research of explosive property improvement method in recent years：(1) design synthesis
Novel high-energy single chmical compound explosive.Since most energy-containing compound synthesis conditions are harsh, synthesis cycle is long, it is difficult to obtain in a short time
It breaks through.(2) Composite Energetic Materials are prepared.Explosive is set to be combined with other materials by physics or chemical method, to improve its original
Some physics and chemical property.Quick-fried heat such as is improved by adding metal powder into explosive formulation, explosive crystal is implanted into polymer
In to disperse impact energy, the sensitivity to reduce explosive obtains " insensitive explosives ".(3) preparation of the eutectic containing energy, by tying again
The cocrystallized explosive that crystalline substance is accumulated two kinds of single chmical compound explosives again in structure cell, although being expected to that different explosive properties is made to take
Long benefit is short, but its performance is generally between the promotion that the performance of explosive between the two, can not be made to obtain substance.If explosive with it is other
Non- energetic material eutectic greatly reduces energy density though being possible to improve safety.(4) new concept energetic material.Metal
Hydrogen, antimatter, full nitrogen energetic material etc., although energy density is high, are substantially at theoretical calculation and conceptual phase；Although
There is document report to synthesize full nitrogen molecule containing energy, but since it is extremely unstable at normal temperatures, can hardly find practical applications.In addition,
It can improve mobility by the improvement to energetic material crystal quality, improve safety.But its application range is by prodigious
Limitation improves having little effect for energy or safety if high-quality explosive is for nuclear weapon pressed explosives.
It to sum up analyzes, although having been developed that a variety of methods to improve or regulate and control the performance of explosive, to explosive at present
The improvement of performance does not still meet the needs of practical application.It is current promotion explosive to carry out structure improvement to existing energetic material
One feasible and effective way of performance.Hexanitrohexaazaisowurtzitane (CL-20 or HNIW) is the energy being actually applied
Measure one of highest single chmical compound explosive, molecular formula C6H6N12O12, density and the highest ε-CL-20 explosion velocities of energy reach 9650m.s-1.CL-20 not only has very high energy, it may have good detonation explosion transfer performance.Therefore, excellent using CL-20 as base progress structure
Change and performance improvement, it is possible to realize being substantially improved for explosive property.
Made due to the weak interaction between Subjective and Objective molecule based on the Subjective and Objective explosive that supramolecular chemistry thought is constructed
Obtaining Subjective and Objective explosive can be stabilized, and have both the characteristic of host molecule and guest molecule so that the property of Subjective and Objective explosive
It can be promoted.Therefore, crystal structure improvement and optimization, it can be achieved that explosive are designed with preparation by Subjective and Objective explosive,
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
Energy material, 2012,20 (4):It 445-449.) reports and prepares 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 compressor2High pressure gas, the pressure of gas maintain 15Mpa with
On, while heated pressure container obtains embedded CO to 80 DEG C, after a period of time2The CL-20 base Subjective and Objective explosives of gas.This method
It needs to carry out under high-temperature and high-pressure conditions, experiment condition is more harsh, and applicable gas molecule type is limited, for some work
Property gas molecule, is easy to happen reaction under high pressure.It explodes in closed high-pressure bottle in addition, CL-20 belongs to high explosive
Risk increase.Therefore, there is an urgent need for seek more mild preparation method and experiment condition.
Patent CN106116993A discloses a kind of Subjective and Objective of the insertion 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, make CL-20 using the method that solution recrystallizes
With N2O cocrystallization, to obtain CL-20 and N2The Subjective and Objective explosive crystal of O cocrystallization.Although this method overcomes high temperature and pressure
Experiment condition, the more mild solution crystallization mode of use, but CL-20 belong to polymorphic explosive (had now found that six kinds of α,
β, γ, ε, ζ, δ), it is easy to form mixing crystal form crystal in solution recrystallization process so that mix in the Subjective and Objective explosive crystalline substance of preparation
The CL-20 for having other crystal forms influences the performances such as its safety, detonation to reduce the purity of Subjective and Objective explosive crystal.Therefore, also
It needs constantly to explore new Subjective and Objective explosive crystal preparation method.
Invention content
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 promote the oxygen balance of explosive, increase release quantity, improves detonation
Performance, to provide new thinking for explosive crystal structure optimization and performance regulation and control.
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, this method experiment condition is mild, simple for process, easy to implement, be suitable for amplification prepare and promote and apply.
To achieve the above object, the present invention provides a kind of embedded Subjective and Objective explosive crystal based on gas displacement technology
Preparation method, this method using CL-20 based solvents compound 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, embedded to obtain structure cell
The embedded Subjective and Objective explosive crystal of gas molecule.
The more specific technical solution of the present invention is as follows：
The preparation method of embedded Subjective and Objective explosive crystal based on gas displacement technology, mainly includes the following steps that：
Step 1：Using common CL-20 as raw material, the solvent recrystallization that selection can be complexed with CL-20 prepares CL-20
Solvate crystal.
Step 2：In a reservoir by the solvate crystal prepared in step 1 tiling dispersion, it is passed through gas, to solvation
Object persistently purges, and obtains the embedded Subjective and Objective explosive crystal that structure cell embeds gas molecule.
The preparation method principle of the above-mentioned embedded Subjective and Objective explosive crystal based on gas displacement technology is：With high explosive
Based on CL-20, micro-molecular gas is object, certain way and under the conditions of micro-molecular gas enter the structure cell of explosive crystal
Inside, formed high-sequential, periodic arrangement crystal, and stronger intermolecular force is formed between 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, hexamethylphosphoramide, dimethyl carbonate, sulfuric acid diethyl
It is arbitrary in ester, sulfolane, N-Methyl pyrrolidone, 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 needs to characterize by X-ray powder diffraction before carrying out step 2, determines all CL-20 solvents of crystal of recrystallization
Compound crystal；If comprising other crystal in solvate, need by crystallized product according to step 1 method again into
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), ethylene (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 room 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 suitably can be heated or be pressurizeed, that is, promoted the temperature of solvate or increased the pressure of gas, general to heat
Temperature is less than the decomposition temperature of solvate, and preferable gas displacement temperature range is 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
The purged crystal of body needs to carry out Crystal Structure, is characterized using X-ray powder diffraction and determines the purged crystal of gas
In do not contain solvate, determine that gas molecule has replaced solvent molecule and enters crystal lattice using infrared spectrum characterization
In；If containing solvate in purged crystal, need crystal continuing gas purging, until gas molecule is complete
Replace the solvent molecule in solvate in portion.
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 of solvate is replaced, and the CL-20 Subjective and Objective explosive crystals that structure cell embeds gas molecule are obtained.Party's legal system
For simple for process, experiment condition is mild, it is not necessarily to high temperature and pressure, micro-molecular gas can be made to be embedded in by simple gas-solid reaction
In explosive crystal structure cell, the present invention breaches traditionally from molecular structure or by the compound mode modification explosive of component, is fried
Medicine comprehensive performance, which is improved, provides new thinking, and opens and carry out the new of high explosive performance regulation and control by embedded micro-molecular gas
Approach.
The preparation of the embedded Subjective and Objective explosive crystal based on gas displacement technology by above-mentioned is also claimed in the present invention
The embedded Subjective and Objective explosive crystal based on gas displacement technology that method prepares.
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 is spread
Into in structure cell, to obtain the CL-20 base Subjective and Objective explosive crystals that structure cell is embedded in micro-molecular gas.This method preparation process
Simply, experiment condition is mild, is not necessarily to high temperature and pressure, micro-molecular gas can be made to be embedded in explosive by simple gas-solid reaction brilliant
In body structure cell.Subjective and Objective explosive crystal prepared by this method does not contain other crystal form crystal, is easy amplification and prepares and promote and apply.
The present invention breaches traditionally from molecular structure or by the compound mode modification explosive of component, is carried for the improvement of explosive comprehensive performance
For new thinking, and provide the new way that high explosive performance regulation and control are carried out by embedded micro-molecular gas.
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 implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.
Detecting instrument：
Field emission scanning electron microscope：Apollo 300CSF-3A, the processing 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, scanning range：5~50 °, sweep speed：0.2s/ is walked, scanning
Step-length：0.02 °/step.
Infra-red sepectrometry (IR)：800 Fourier infrared spectrographs of Nicolet, KBr tablettings, surface sweeping range：400cm-1~
4000cm-1, resolution ratio：4cm-1。
Differential scanning calorimetry-thermal weight loss combined instrument (DSC-TG)：The resistance to 449C types of speeding of Germany, test scope：50~500 DEG C,
Heating rate：10℃.min-1, N2：50ml.min-1。
Embodiment 1
(1) dimethyl carbonate (DMC) solvent for measuring 40ml, is poured into conical flask, then weighs the CL-20 explosive originals of 10g
Material is added, and 60 DEG C are heated in water-bath, so that explosive is completely dissolved with the rate magnetic agitation of 300r/min；
(2) taper bottleneck is opened wide, the continuous heating at 60 DEG C, is stirred with the rate continuing magnetic force of 300r/min, and put
It sets in draught cupboard, dimethyl carbonate solvent is made slowly to volatilize, after crystallizing 4h, be filtered, washed, dry；
(3) a small amount of crystallized product is taken, micro- sem observation is carried out, obtains crystal morphology, is carried out at the same time XRD and IR characterizations,
Determine all CL-20.DMC solvate crystals of crystallized product；
(4) crystallized product tiled, be dispersed in open glass surface ware；
(5) in draught cupboard, pure CO will be housed2The 8L steel cylinders of gas pass through stainless steel tube by pressure reducing valve, 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
Room temperature (20 DEG C) after 5h, stops purging；
(6) take a small amount of purged sample, carry out micro- sem observation, obtain the pattern of crystal, be carried out at the same time XRD, IR,
TG-DSC is characterized, and confirms that purged sample does not contain solvate crystal, and micro-molecular gas enters in the structure cell of crystal, i.e.,
Obtain CL-20.CO2Subjective and Objective explosive crystal.
Embodiment 2
(1) n,N-Dimethylformamide (DMF) solvent for measuring 40ml, is poured into the three-necked flask of 150ml, then weigh
The CL-20 explosive raw materials of 10g are added, and are heated to 80 DEG C in water-bath, keep explosive complete with the rate mechanical agitation of 150r/min
Dissolving；
(2) water-bath is stopped heating, makes the DMF solution of CL-20 is naturally cold in water-bath to go, and with 150r/min's
Rate continued mechanical stirs, and after crystallizing 1h, is filtered, washed, dries；
(3) a small amount of crystallized product is taken, micro- sem observation is carried out, obtains crystal morphology, is carried out at the same time XRD and IR characterizations,
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 draught cupboard, pure N will be housed2The 8L steel cylinders of O gases pass through stainless steel tube by pressure reducing valve, persistently to molten
Agent compound plane of crystal is purged, purge gas be pressurized to after 20MPa by booster pump enter from air inlet it is 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 a small amount of purged sample, carry out micro- sem observation, obtain the pattern of crystal, be carried out at the same time XRD, IR,
TG-DSC is characterized, and confirms that purged sample does not contain solvate crystal, and micro-molecular gas enters 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 three-necked flask of 250ml, then weigh
The CL-20 explosive raw materials of 10g are added, and under room temperature (20 DEG C), so that explosive is completely dissolved with the rate mechanical agitation of 150r/min；
(2) 100ml distilled water is measured as non-solvent, is slowly dropped in CL-20 solution with the rate of 10ml/min, and
It after stirred crystallization 1h, is filtered, washed, dries under room temperature (20 DEG C) with the rate mechanical agitation of 150r/min；
(3) a small amount of crystallized product is taken, micro- sem observation is carried out, obtains crystal morphology, is carried out at the same time XRD and IR characterizations,
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 water-bath
In be heated to 60 DEG C；
(5) in draught cupboard, pure NO will be housed2The 8L steel cylinders of gas pass through stainless steel tube by pressure reducing valve, persistently to molten
Agent compound plane of crystal is purged, and purge gas, which is pressurized to by booster pump after 3MPa, to be entered in pressure bottle from air inlet 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 a small amount of purged sample, carry out micro- sem observation, obtain the pattern of crystal, be carried out at the same time XRD, IR,
TG-DSC is characterized, and confirms that purged sample does not contain solvate crystal, and micro-molecular gas enters in the structure cell of crystal, i.e.,
Obtain CL-20.NO2Subjective and Objective explosive crystal.
Following specific examples 4~20, preparation method are shown in Table 1 with embodiment 3, specific technological parameter.
The technological parameter of 1 embodiment 4~20 of table
Solvate crystal scanning electron microscopic picture is as shown in Fig. 2, and raw material made from method of the present invention using embodiment 1
CL-20 crystal morphologies are compared (see Fig. 1), there is apparent difference, and it is rodlike to become length by fusiform.It is raw material CL-20 shown in Fig. 3
Infrared spectrum, shown in Fig. 4 is the infrared spectrum of CL-20.DMC solvates, it can be seen from the figure that solvate crystal
Infrared absorption peak and raw material CL-20 it is significantly different, and all solvate crystals in crystallized product.In conjunction with raw material CL-
The XRD spectra of 20 (Fig. 5) and CL-20.DMC solvates (Fig. 6) can prove and 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 a large amount of crackle and holes, these ducts are exactly micro-molecular gas on the surface of existing Subjective and Objective explosive crystal
It is formed by when replacing the guest molecule in solvate, and the macro morphology and solvate crystal of Subjective and Objective explosive crystal
It is almost the same.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 CO2It deposits
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.The CL-20.CO shown in Figure 112XRD spectra it is found that being free of solvate in sample.It is shown in Figure 13
CL-20.CO2The TG-DSC curves of Subjective and Objective explosive, CO2The temperature range of gas weightlessness is 177 DEG C~196 DEG C, passes through CO2Gas
CL-20 and CO in crystal is calculated in the weight loss of body2Molar ratio be 2:1.The above result shows that using the side of embodiment 1
Method is based on being embedded in CO in the available structure cell of gas displacement technology2The CL-20 base Subjective and Objective explosive crystals of gas molecule.
CL-20.N made from method of the present invention using embodiment 22The patterns of O Subjective and Objective explosive crystals as shown in figure 8,
Infrared spectrum is as shown in Figure 10, and XRD spectra is as shown in figure 12, and TG-DSC curves are as shown in figure 14.It can be seen from the figure that CL-
20.N2There are the microstructures such as a large amount of crackle and hole on the surface of O Subjective and Objective explosive crystals, have in infrared spectrum apparent
N2O molecule infrared absorption peaks (2244cm-1、2229cm-1), infrared and XRD spectra shows N2O gases are complete by solvate
It replaces and is embedded into the structure cell of crystal, N2The temperature range of the gas weightlessness of O gases is 177 DEG C~189 DEG C, passes through N2O gases
Weight loss CL-20 and N in crystal is calculated2The molar ratio of O is 2:1, it these results suggest that the method system using embodiment 2
Standby sample is embedded N2The CL-20.N of O molecules2O Subjective and Objective explosive crystals.
It can be seen that the purpose of the present invention is achieved completely and effectively.Technical scheme of the present invention is in reality
It applies and is shown and illustrated in example, under without departing substantially from the principle, embodiment can make arbitrary 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 preferable embodiment, embodiment of the present invention are not limited by the above embodiments, it should be appreciated that people in the art
Member can be designed that a lot of other modification and implementations, these modifications and implementations will be fallen in principle disclosed in the present application
Within scope and spirit.
Claims (6)
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, and the embedded Subjective and Objective that gas molecule is embedded to obtain structure cell is fried
Medicine crystal；Include the following steps：
Step 1：Using common CL-20 as raw material, the solvent recrystallization that selection can be complexed with CL-20 prepares the molten of CL-20
Agent compound crystal；
Step 2：In a reservoir by the solvate crystal prepared in step 1 tiling dispersion, it is passed through gas, solvate is held
Continuous purging obtains the embedded Subjective and Objective explosive crystal that structure cell embeds gas molecule；
Solvate crystal in the step 1 needs to characterize by X-ray powder diffraction before carrying out step 2, determines
The all CL-20 solvate crystals of crystal of recrystallization；If needing to crystallize comprising other crystal in solvate
Product re-starts recrystallization according to the method for step 1；
The purged crystal of gas needs to carry out Crystal Structure in the step 2, is characterized using X-ray powder diffraction true
Determine not containing solvate in the purged crystal of gas, determines that gas molecule has replaced solvent point using infrared spectrum characterization
Son enters in crystal lattice；If containing solvate in purged crystal, need crystal continuing gas to blow
It sweeps, the solvent molecule in gas molecule all displacement solvate.
2. the preparation method of the embedded Subjective and Objective explosive crystal according to claim 1 based on gas displacement technology,
It is characterized in that in the step 1 that dioxane, N,N-dimethylformamide, hexamethyl can be selected from the solvent that CL-20 is complexed
Phosphoric triamide, dimethyl carbonate, dithyl sulfate, sulfolane, N-Methyl pyrrolidone, acetonitrile, γ-fourth lactones, dimethyl are sub-
Any one in sulfone, trimethyl glyceride, acetone.
3. the preparation method of the embedded Subjective and Objective explosive crystal according to claim 1 based on gas displacement technology,
The solvate recrystallization method being characterized in that in the step 1 includes that solvent falling temperature method, solvent-nonsolvent method and solvent steam
Hair method.
4. the preparation method of the embedded Subjective and Objective explosive crystal according to claim 1 based on gas displacement technology,
It is characterized in that in the step 2 that gas molecule includes nitrous oxide, carbon dioxide, nitrogen dioxide, nitric oxide, nitrogen, hydrogen
Gas, ammonia, oxygen, ozone, fluorine gas, chlorine, bromine gas, methane, acetylene, ethylene, ethane, sulfur dioxide, nitrogen trioxide, four oxygen
Change any one in phenodiazine, dinitrogen pentoxide.
5. the preparation method of the embedded Subjective and Objective explosive crystal according to claim 1 based on gas displacement technology,
The gas in step 2 is characterized in that in the lasting purge of solvate, the temperature of gas and solvate be 20 DEG C extremely
80 DEG C, gas displacement pressure limit is in normal pressure to 20MPa.
6. the system of the embedded Subjective and Objective explosive crystal based on gas displacement technology described in claim 1 to 5 any claim
The embedded Subjective and Objective explosive crystal based on gas displacement technology that Preparation Method prepares.
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| CN107827835B (en) * | 2017-11-22 | 2021-09-28 | 中国工程物理研究院化工材料研究所 | Simple preparation method of explosive solvate |
| CN107814671B (en) * | 2017-11-22 | 2019-12-24 | 中国工程物理研究院化工材料研究所 | Method for refining hexanitrohexaazaisowurtzitane alkyl host-guest explosive crystals |
| CN109096022A (en) * | 2018-09-17 | 2018-12-28 | 中国工程物理研究院化工材料研究所 | A kind of HNIW base composite explosives and preparation method thereof that heat-resistant crystalline substance becomes |
| CN110937960B (en) * | 2019-11-07 | 2021-04-06 | 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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