CN105859730B - A kind of method that anti-solvent dilution method prepares the round and smooth ε-HNIW crystal of little particle - Google Patents
A kind of method that anti-solvent dilution method prepares the round and smooth ε-HNIW crystal of little particle Download PDFInfo
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- CN105859730B CN105859730B CN201610293585.XA CN201610293585A CN105859730B CN 105859730 B CN105859730 B CN 105859730B CN 201610293585 A CN201610293585 A CN 201610293585A CN 105859730 B CN105859730 B CN 105859730B
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- C07—ORGANIC CHEMISTRY
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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Abstract
The present invention relates to a kind of method that anti-solvent dilution method prepares the round and smooth ε HNIW crystal of little particle, including：HNIW is dissolved completely in recrystallisation solvent, is filtered, filtrate is stand-by；Crystallization kettle is first washed with recrystallisation solvent, after being rinsed again with anti-solvent, anti-solvent is injected in crystallization kettle, it is 25 45 DEG C to adjust water temperature in crystallization kettle chuck, keeps the temperature 5 15min under 50 100 revs/min of stir speed (S.S.), then stir speed (S.S.) is adjusted to 450 600 revs/min, filtrate is added dropwise into anti-solvent, crystal starts to separate out, and after being all added dropwise, continues to stir；After crystal separates out completely, filtering, obtains crystal and mother liquor, crystal washing, drying, obtain the HNIW crystal of ε HNIW content >=95.0%, mother liquor distillation, collects the recrystallisation solvent steamed, filter cut, obtain γ HNIW and anti-solvent.This method has easy to operate, and anti-solvent dosage is few and recyclable, and reaction condition is gentle, securely and reliably, green high-efficient, and the advantages that industrialization easy to implement.
Description
Technical field
The present invention relates to a kind of method that anti-solvent dilution method prepares the round and smooth ε-HNIW crystal of little particle, belong to energetic material
Field.
Background technology
HNIW (Hexanitrohexaazaisowurtzitane, CL-20) is second generation high-explosives, highest as current energy
Explosive, is expected in following alternate application extensive RDX and HMX, becomes the preferably group containing energy of high-energy composite explosives or propellant
Point.It has been generally acknowledged that HNIW has four kinds of crystal forms, i.e. α, beta, gamma and ε at normal temperatures and pressures.Four kinds of crystal forms are contrasted, ε-HNIW have highest
Crystalline density, and stablize the most at normal temperatures and pressures, therefore it becomes high explosive and propellant application is the most favored
Crystal form.But presently commercially available common HNIW crystal comes with some shortcomings, it is poor to be mainly manifested in crystal morphology, with sharp edges
The problems such as angle, mechanical sensitivity is high, limit it and applied in composite explosives and propellant.Therefore carrying out recrystallization to HNIW has
Significance, and prepare that pattern is preferable by recrystallization method, the HNIW products of narrower particle size distribution are primary goals, therefore
It is extremely important to design correct crystallization processes.
At present, the recrystallization method of explosive mainly has evaporative crystallization method, crystallisation by cooling method, solvent-antisolvent crystallisation method, spray
Penetrate crystallisation, crystalization in supercritical fluid.Jet crystallization method and supercritical fluid method are evaporated commonly used to prepare nano-scale particle
Crystallisation and crystallisation by cooling method are used for preparing the solid that solubility with temperature changes greatly.Since HNIW is molten in various solvents
It is not it is obvious that therefore preparing micron order HNIW at present it is preferred that solvent-anti-solvent method, the method work that Xie Du, which is varied with temperature,
Skill is easy to operate, and yield is higher, and process is easy to control, securely and reliably.
M.Ghosh et al. prepares ε-HNIW using solvent-anti-solvent method.Anti-solvent is normal heptane, and used raw material is
α-HNIW, HNIW, ethyl acetate, the ratio of normal heptane is are 1:2:5, by many experiments, recrystallization has reached 500g magnitudes,
But obtained ε-HNIW patterns are double centrums or diamond shape, size distribution is at 150-300 μm.
The method that United States Patent (USP) (U.S.5874574) describes a kind of solvent-anti-solvent recrystallization, anti-solvent selection are
The alkane of aromatic hydrocarbon and short chain, obtains ε-HNIW crystal, but the sample topography obtained is poor, there is sharp corners, size distribution
It is wider.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of anti-solvent dilution method and prepare the round and smooth ε-HNIW crystalline substances of little particle
The method of body, it is contemplated that providing raw material support for composite explosives grain composition, the application study for ε-HNIW provides raw material
Support, this method is in crystallization process, it is not necessary to adds crystal seed and additive.
The technical solution that the present invention solves above-mentioned technical problem is as follows：A kind of round and smooth ε of anti-solvent dilution method preparation little particle-
The method of HNIW crystal, including：
1) HNIW is dissolved completely in recrystallisation solvent, the concentration for making HNIW is 0.27-0.40g/mL, and filtering, filtrate is treated
With；
2) crystallization kettle is first washed with recrystallisation solvent, then after being rinsed with anti-solvent, anti-solvent is injected in crystallization kettle, adjusts knot
Water temperature is 25-45 DEG C in brilliant kettle chuck, keeps the temperature 5-15min under 50-100 revs/min of stir speed (S.S.), then stir speed (S.S.) is adjusted to
450-600 revs/min, the filtrate 1) obtained is added dropwise into anti-solvent, crystal starts to separate out, and after being all added dropwise, continues
Stir 2-4h,
Above-mentioned two anti-solvent is industrial normal octane, industrial normal heptane, industrial dichloromethane, industrial chloroform, work
One or more of mixtures in industry carbon tetrachloride, toluene, benzene and industrial petroleum ether；Wherein, inject anti-molten in crystallization kettle
Agent volume be 1) used in 1-3 times of recrystallisation solvent volume；
3) after crystal separates out completely, filtering, obtains crystal and mother liquor, crystal washing, drying, obtain ε-HNIW content >=95.0%
HNIW crystal, mother liquor distillation, collects the recrystallisation solvent steamed, filters cut, obtains γ-HNIW and anti-solvent, anti-solvent recycling
It is continuing with, γ-HNIW feed intake use as raw material.
Based on the above technical solutions, the present invention can also be improved as follows.
1) and 2) further, in, the recrystallisation solvent is respectively industrial ethyl acetate, industrial acetone, industrial acetic third
One or more of mixtures in ester, industrial acetic methyl esters, are preferably industrial ethyl acetate, 1) recrystallisation solvent and 2) institute used in
It is identical or different with recrystallisation solvent.
Further, in 1), the concentration of the HNIW is 0.30-0.35g/mL.
Further, in 2), two anti-solvents are industrial normal octane.
Further, in 2), water temperature is 20-40 DEG C in the crystallization kettle chuck.
Further, in 2), the drop rate that the filtrate 1) obtained is added dropwise into anti-solvent is 30-50 ml/mins
(mL/min)。
Further, in 3), the distillation is distilled for mother liquor at 80 DEG C.
Further, in 3), the drying is the dry 8-15h in 50 DEG C of baking ovens.
Further, in 3), HNIW contents >=99.9%, HNIW crystalline density >=2.033g/ in the HNIW crystal
cm3, the observation of HNIW crystal appearance is without sharp corners, and crystal face flawless, intergranular is without double team thing, crystal axial ratio≤1.5.
The beneficial effects of the invention are as follows：
1) present invention prepares little particle ε-HNIW crystal using anti-solvent dilution method, by adjusting technique, can obtain grain
Degree is distributed as 50-180 μm of particle, and median is more than 120 μm.The technique has：Easy to operate, anti-solvent dosage is few, can
With recycling, reaction condition is gentle, securely and reliably, green high-efficient, and the advantages that industrialization easy to implement.
2) the method for the present invention first keeps the temperature 10min under low stir speed (S.S.), then heightens stir speed (S.S.), and filter is added dropwise into anti-solvent
Liquid, is because when in HNIW solution injection anti-solvent, stir speed (S.S.) is higher, HNIW solution and anti-solvent using two kinds of stir speed (S.S.)s
Evenly, the crystal grain particle size range separated out is also narrower, and plane of crystal is more smooth for mixing.
3) recrystallisation solvent that mother liquor distills is not discharged into air by the present invention, free from environmental pollution.
Brief description of the drawings
Fig. 1 is the method flow diagram that a kind of anti-solvent dilution method of the present invention prepares the round and smooth ε-HNIW crystal of little particle；
Fig. 2 is raw material ε-HNIW crystal stereoscan photographs；
Fig. 3 is little particle ε-HNIW crystal stereoscan photographs prepared by embodiment 4；
Fig. 4 is little particle ε-HNIW Lens capsule figures prepared by embodiment 4.
Embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
20gHNIW is dissolved in 50mL industrial ethyl acetates, solution is filled into 250mL beakers, three-necked flask is first used
Industrial ethyl acetate washes clean, then rinsed well with industrial normal octane, 125ml works are then added into 500mL three-necked flasks
Industry normal octane, 40 DEG C of waters bath with thermostatic control are in by three-necked flask；Turn on agitator, 10min is preheated under the 100rpm slow-speed of revolution, is being added dropwise
Before HNIW solution, blender speed of agitator is transferred to 550rpm, opens the HNIW solution that filtering is added dropwise into three-necked flask for constant flow pump,
Drop rate is 35mL/min；After being all added dropwise, continue to stir 3h, crystal and mother liquor are separated by filtration, use industry
Ethanol fully washs crystal 2 times, filters again, and dry 10h, weighs in 50 DEG C of baking ovens.Crystal weight is 19.1g, and yield is
95.5%.Through measuring, HNIW content >=99.9%；ε-HNIW content >=95.0%；Density >=2.033g/cm3；Appearance without
Sharp corners, crystal face flawless, intergranular is without double team thing；Crystal axial ratio≤1.5, projected area girth ratio >=0.80；Separate out
Content of the size distribution of crystal between 50-180 μm, accounts for and separates out crystal total amount more than 70%.
Mother liquor distills at 80 DEG C, steams industrial ethyl acetate, and collection is pending, filters cut, obtains γ-HNIW and industry
Normal octane, γ-HNIW and industrial normal octane recycling are continuing with.
Embodiment 2
40gHNIW is dissolved in 120mL industrial acetic methyl esters, solution is filled into 250mL beakers, three-necked flask is first used
Industrial ethyl acetate washes clean, then rinsed well with industrial normal octane, 200mL is then added into 500mL three-necked flasks returns
Normal octane (for mother liquor unification is distilled gained after 1 many experiments of embodiment) is received, three-necked flask is in 35 DEG C of waters bath with thermostatic control；Open
Blender is opened, 10min is preheated under the 100rpm slow-speed of revolution, before HNIW solution is added dropwise, blender speed of agitator is transferred to 500rpm, opens
Open the HNIW solution that filtering is added dropwise into three-necked flask for constant flow pump, drop rate 40mL/min；After being all added dropwise, after
Continuous stirring 3h, crystal and mother liquor are separated by filtration, crystal is fully washed using industrial alcohol 2 times, is filtered again, in 50 DEG C of baking ovens
Middle dry 10h, weighs.Crystal weight is 37.3g, yield 93.25%.Through measuring, HNIW content >=99.9%；ε-
HNIW content >=95.0%；Density >=2.033g/cm3；Appearance is without sharp corners, and crystal face flawless, intergranular is without double team thing；Crystal
Axial ratio≤1.5, projected area girth ratio >=0.80；Content of the size distribution of crystal between 50-180 μm is separated out, is accounted for
Separate out crystal total amount more than 50%.
Mother liquor distills at 80 DEG C, steams industrial acetic methyl esters, collects pending, filters cut, obtains γ-HNIW and just pungent
Alkane, γ-HNIW and normal octane recycling are continuing with.
Embodiment 3
1kg HNIW are dissolved in 3L industrial ethyl acetates, are poured into after solution is filtered in 10L stainless steel barrels, 20L crystallizations
Kettle first uses industrial ethyl acetate washes clean, then is rinsed well with industrial normal octane, and 3L recycling is then being added into crystallization kettle just
Octane (for mother liquor unification is distilled gained after 1 many experiments of embodiment), adjusts 35 DEG C of water temperature in chuck；Turn on agitator,
Preheat 10min under the 50rpm slow-speed of revolution, before HNIW solution is added dropwise, blender speed of agitator is transferred to 450rpm, open constant flow pump to
The HNIW solution of filtering, drop rate 35mL/min are added dropwise in crystallization kettle；After being all added dropwise, continue to stir 3h, will
Crystal is separated by filtration with mother liquor, crystal is fully washed using industrial alcohol 2 times, is filtered again, the dry 10h in 50 DEG C of baking ovens,
Weigh.Crystal weight is 920g, yield 92%.Through measuring, HNIW content >=99.9%；ε-HNIW contents >=
95.0%；Density >=2.033g/cm3；Appearance is without sharp corners, and crystal face flawless, intergranular is without double team thing；Crystal axial ratio≤
1.5, projected area girth ratio >=0.80；Content of the size distribution of crystal between 50-180 μm is separated out, it is total to account for precipitation crystal
Amount more than 60%.
Mother liquor distills at 80 DEG C, steams industrial ethyl acetate, collects pending, filters cut, obtains γ-HNIW and just pungent
Alkane, γ-HNIW and normal octane recycling are continuing with.
Embodiment 4
4kgHNIW is dissolved in 10.0L industrial ethyl acetates, is poured into after solution is filtered in 10L stainless steel barrels, 50L knots
Brilliant kettle first uses industrial ethyl acetate washes clean, then is rinsed well with industrial normal octane, and 20.0L works are then added into crystallization kettle
Industry normal octane, adjusts 37 DEG C of water temperature in chuck；Turn on agitator, 10min is preheated under the 50rpm slow-speed of revolution, and HNIW solution is being added dropwise
Before, blender speed of agitator is transferred to 450rpm, opens the HNIW solution that filtering is added dropwise into crystallization kettle for constant flow pump, and drop rate is
40mL/min；After being all added dropwise, continue to stir 3h, crystal and mother liquor are separated by filtration, fully washed using industrial alcohol
Wash crystal 2 times, filter again, dry 10h, weighs in 50 DEG C of baking ovens.Crystal weight is 3805g, yield 95.12%.Through
Measuring, HNIW content >=99.9%；ε-HNIW content >=95.0%；Density >=2.033g/cm3；As shown in figure 3, this reality
ε-HNIW the appearances of example preparation are applied without sharp corners, crystal face flawless, intergranular is without sandwiching thing, and existing raw material ε-HNIW crystal shapes
Looks are poor, and with sharp corners, mechanical sensitivity is high, and crystal face has crackle, and intergranular has double team thing, sees Fig. 2；Crystal axial ratio≤1.5,
Projected area girth ratio >=0.80；As shown in figure 4, separating out content of the size distribution of crystal between 50-180 μm, precipitation is accounted for
Crystal total amount more than 65%.
Mother liquor distills at 80 DEG C, steams industrial ethyl acetate, and collection is pending, filters cut, obtains γ-HNIW and industry
Normal octane, γ-HNIW and industrial normal octane recycling are continuing with.
Flask used is crystallization kettle in above-described embodiment 1 and 2, and because dosage is different, crystallization kettle title is different, dosage
When few, flask is；When dosage is big, crystallization kettle is, simply volume is had any different, and therefore, flask used in Examples 1 and 2 is not super
Go out the scope of claim.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on, should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of method that anti-solvent dilution method prepares the round and smooth ε-HNIW crystal of little particle, it is characterised in that including：
1) HNIW is dissolved completely in recrystallisation solvent, the concentration for making HNIW is 0.27-0.40g/mL, filtering, and filtrate is stand-by；
2) crystallization kettle is first washed with recrystallisation solvent, then after being rinsed with anti-solvent, anti-solvent is injected in crystallization kettle, adjusts crystallization kettle
Water temperature is 25-45 DEG C in chuck, keeps the temperature 5-15min under 50-100 revs/min of stir speed (S.S.), then stir speed (S.S.) is adjusted to 450-
600 revs/min, the filtrate 1) obtained is added dropwise into anti-solvent, crystal starts to separate out, and after being all added dropwise, continues to stir
2-4h,
Above-mentioned two anti-solvent is industrial normal octane, industrial normal heptane, industrial dichloromethane, industrial chloroform, industry four
One or more of mixtures in chlorination carbon, toluene, benzene and industrial petroleum ether；Wherein, the anti-solvent body in crystallization kettle is injected
Product be 1) used in 1-3 times of recrystallisation solvent volume；
3) after crystal separates out completely, filtering, obtains crystal and mother liquor, crystal washing, drying, obtain ε-HNIW content >=95.0%
HNIW crystal, mother liquor distillation, collects the recrystallisation solvent steamed, filters cut, obtains γ-HNIW and anti-solvent, anti-solvent recycling after
Continuous to use, γ-HNIW feed intake use as raw material.
1) and 2) 2. according to the method described in claim 1, it is characterized in that, in, the recrystallisation solvent is respectively industrial second
One or more of mixtures in acetoacetic ester, industrial acetone, industrial acetic propyl ester, industrial acetic methyl esters, 1) crystallization used is molten
Agent and 2) used in recrystallisation solvent it is identical or different.
3. according to the method described in claim 2, it is characterized in that, the recrystallisation solvent is industrial ethyl acetate.
4. according to the method described in claim 1, it is characterized in that, in 1), the concentration of the HNIW is 0.30-0.35g/
mL。
5. according to the method described in claim 1, it is characterized in that, in 2), two anti-solvents are industrial normal octane.
6. according to the method described in claim 1, it is characterized in that, in 2), water temperature is 20-40 in the crystallization kettle chuck
℃。
7. according to the method described in claim 1, it is characterized in that, in 2), the filtrate that 1) obtains is added dropwise into anti-solvent
Drop rate is 30-50 ml/mins.
8. according to the method described in claim 1, it is characterized in that, in 3), the distillation is distilled for mother liquor at 80 DEG C, institute
It is the dry 8-15h in 50 DEG C of baking ovens to state dry.
9. according to the method described in claim 1, it is characterized in that, in 3), HNIW contents in the HNIW crystal >=
99.9%, HNIW crystalline density >=2.033g/cm3, the observation of HNIW crystal appearance is without sharp corners, crystal face flawless, intergranular without
Sandwich thing, crystal axial ratio≤1.5.
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| CN106317061B (en) * | 2016-08-22 | 2019-02-12 | 北京理工大学 | A kind of method that various concentration method prepares the round and smooth ε-HNIW crystal of bulky grain |
| CN106117229B (en) * | 2016-08-31 | 2018-01-02 | 山西北化关铝化工有限公司 | A kind of preparation method of speciality Hexanitrohexaazaisowurtzitane |
| KR102336825B1 (en) * | 2020-01-07 | 2021-12-09 | 국방과학연구소 | Hniw recrystallization method |
Citations (2)
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|---|---|---|---|---|
| US5973149A (en) * | 1997-10-29 | 1999-10-26 | Snpe | Process for producing the epsilon polymorphic form of hexanitrohexaazaisowurtzitane |
| US20030130503A1 (en) * | 2002-01-09 | 2003-07-10 | Hamilton R. Scott | Crystallization of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.05,903,11]-dodecane |
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2016
- 2016-05-05 CN CN201610293585.XA patent/CN105859730B/en active Active
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|---|---|---|---|---|
| US5973149A (en) * | 1997-10-29 | 1999-10-26 | Snpe | Process for producing the epsilon polymorphic form of hexanitrohexaazaisowurtzitane |
| US20030130503A1 (en) * | 2002-01-09 | 2003-07-10 | Hamilton R. Scott | Crystallization of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.05,903,11]-dodecane |
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