CN108409676A - A method of control NTO crystal morphologies and granularity - Google Patents
A method of control NTO crystal morphologies and granularity Download PDFInfo
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- CN108409676A CN108409676A CN201810324150.6A CN201810324150A CN108409676A CN 108409676 A CN108409676 A CN 108409676A CN 201810324150 A CN201810324150 A CN 201810324150A CN 108409676 A CN108409676 A CN 108409676A
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- nto
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/14—Nitrogen atoms
Abstract
The present invention relates to a kind of methods of control NTO crystal morphologies and granularity, belong to material crystals pattern and granularity control field.The present invention can prepare large, medium and small (D50~500 μm, D50~250 μm, D50~100 μm) three kinds of varigrained spherical NTO crystal.The present invention provides a comparatively safe external environment, this, which is other granularity control methods such as ball milling, to give using cooling recrystallization technology to NTO explosives；In addition, recrystallization process need not be spray-dried, the equipment of complex precise needed for supercritical fluid technique, sol-gal process etc..The present invention uses water (D50~500 μm, D50~250 μm of spherical NTO crystal), water-ethanol mixed solvent (D50~250 μm of spherical NTO crystal) and ethyl alcohol (D50~100 μm of spherical NTO crystal) as the solvent recrystallized, more economical and environmentally friendly.
Description
Technical field
The present invention relates to a kind of methods of control NTO crystal morphologies and granularity, belong to material crystals pattern and are controlled with granularity
Field.
Background technology
The crystal morphology of single chmical compound explosive has tremendous influence to its performance, is directly related to the application of single chmical compound explosive.It is past
Smaller toward major diameter, the explosive being spherical is more bigger than major diameter, low in the explosive sensitivity of needle prick shape, with more practical valence
Value, and it is also more safe in produce reality.Therefore, the crystal morphology control in single chmical compound explosive production process just seems especially
It is important.In addition, the granularity of explosive crystal directly affects its application performance, shows the every aspects such as powder charge, explosion velocity, sensitivity, be
The important qualifying point of another in single chmical compound explosive production process.
3- nitros -1,2,4- triazole -5- ketone (3-nitro-1,2,4-triazol-5-one, NTO) be by Manchot and
What Loll took the lead in being synthesized in 1905, with the attention to high-energy insensitive single chmical compound explosive, NTO is increasingly closed by people
Note.Directly the NTO crystal made from reaction is typical zigzag class crystalline rods, is easy to assemble, has seriously affected answering for it
With.Therefore, it is necessary to seek a kind of process for purification of NTO crystal spheroidization.
Recrystallization is given birth to as a kind of simple common substance purification and crystal morphology and granularity control method in modern industry
It is largely used in production.The recrystallization process carried out using the dissolution-crystallization principle of solute provides one relatively to explosive purification
The external environment of safety, this, which is ball milling equigranular control methods, to give；In addition, recrystallization process need not spray it is dry
The equipment of complex precise needed for dry, supercritical fluid technique, sol-gel method etc..Therefore, the present invention is recrystallized using cooling
Method be prepared for large, medium and small (D50~500 μm, D50~250 μm, D50~100 μm) three kinds of varigrained spherical NTO are brilliant
Body does technical foundation for the application of next step NTO.
Invention content
The object of the present invention is to provide a kind of method of control NTO crystal morphologies and granularity, this method is tied again using cooling
Crystal technique prepares large, medium and small (D50~500 μm, D50~250 μm, D50~100 μm) three kinds of varigrained spherical NTO crystal,
Technical foundation is done in application for next step NTO.
The purpose of the present invention is what is be achieved through the following technical solutions.
A method of control NTO crystal morphologies and granularity are as follows：
Step 1：In a solvent by NTO dissolvings, solution A is obtained；
The solvent is：Prepare D50~500 μm of spherical NTO crystal, solvent is water；Prepare D50~250 μm spherical
NTO crystal, solvent is water or volume ratio is 1:1 water-ethanol mixed solvent；Prepare D50~100 μm of spherical NTO crystal, it is molten
Agent is ethyl alcohol.
The material of the NTO (g) and solvent (mL), which compares, is：Prepare D50~500 μm and D50~250 μm of spherical NTO crystal
When, material is than being 1:6~1:10；Prepare D50When~100 μm of spherical NTO crystal, material is than being 1:13~1:27.
Step 2：Continue under stirring, the solution A obtained by step 1 is slowly heated up, until solute all dissolves；This
When, then constant temperature 20~40 minutes is slowly dropped to room temperature, crystal is gradually precipitated during this；It filters, wash, is dry, obtaining crystalline substance
Body；
Step 3：The dissolution of crystals that step 2 is obtained is in ethyl acetate, the material ratio of crystal (g) and ethyl acetate (mL)
It is 1:1；30min is stirred in 25 DEG C of speed with 200~400r/min；Again with the speed of 2~3 DEG C/min by above-mentioned mixed system
60 DEG C are warming up to, constant temperature stirs 2~4h with the speed of 300~500r/min；With the speed of 1~2 DEG C/min by the above mixture
System is down to 25 DEG C；It filters, wash, obtain large, medium and small (D after drying50~500 μm, D50~250 μm, D50~100 μm) three kinds not
The spherical NTO crystal of one-size.
Mixing speed described in step 2 is：Prepare D50~500 μm of spherical NTO crystal, mixing speed are 90~100r/
min；Prepare D50~250 μm and D50~100 μm of spherical NTO crystal, mixing speed are 200~300r/min；
The cooling rate that room temperature is down to described in step 2 is：Prepare D50~500 μm and D50~250 μm of spherical NTO is brilliant
Body, cooling rate are 1.0~2.5 DEG C/min；Prepare D50~100 μm of spherical NTO crystal, cooling rate be 3.5~7.0 DEG C/
min。
Advantageous effect
1, the method for a kind of control NTO crystal morphologies and granularity of the invention, can prepare large, medium and small (D50~500 μm,
D50~250 μm, D50~100 μm) three kinds of varigrained spherical NTO crystal.
2, the method for a kind of control NTO crystal morphologies and granularity of the invention, is commonly tied again using modern industrial production
Crystal technique realizes the control to NTO crystal morphologies and granularity.The cooling carried out using the dissolution-crystallization principle of solvent solute is tied again
Brilliant process provides a comparatively safe external environment to explosive, this, which is ball milling equigranular control methods, to give；This
Outside, cooling recrystallization process need not be spray-dried, complex precise needed for supercritical fluid technique, sol-gel method etc.
Equipment.
3, the method for a kind of control NTO crystal morphologies and granularity of the invention, using water (D50~500 μm, D50~250 μm
Spherical NTO crystal), water-ethanol mixed solvent (D50~250 μm of spherical NTO crystal) and ethyl alcohol (D50~100 μm spherical
NTO crystal) as the solvent recrystallized, more economical and environmentally friendly.
Description of the drawings
Fig. 1 is big granularity (D50~500 μm) spherical NTO crystal optical microscopy map；
Fig. 2 is small grain size (D50~100 μm) spherical NTO crystal optical microscopy map.
Specific implementation mode
With reference to embodiment, the present invention will be further described with attached drawing.
Embodiment 1
A method of control NTO crystal morphologies and granularity are as follows：
Step 1：1gNTO is dissolved in 8.5mL water, solution is obtained；
Step 2：Under the lasting stirring of 90r/min, the solution obtained by step 1 is slowly heated up, until solute is whole
Dissolving；At this point, constant temperature 30 minutes, is then slowly dropped to room temperature with the speed of 2 DEG C/min, crystal is gradually precipitated during this；It takes out
Filter, washing, drying, obtain crystal；
Step 3：The dissolution of crystals that step 2 is obtained is in ethyl acetate, the material ratio of crystal (g) and ethyl acetate (mL)
It is 1:1；30min is stirred in 25 DEG C of speed with 300r/min；Above-mentioned mixed system is warming up to 60 with the speed of 3 DEG C/min again
DEG C, heat preservation stirs 3h with the speed of 400r/min；The above mixed system is down to 25 DEG C with the speed of 2 DEG C/min；It filters, wash
Wash, dry after obtain the spherical NTO crystal of big granularity.
Characterization of The Products：The pattern and granularity of the NTO crystal of acquisition are carried out using light microscope and laser particle analyzer
Characterization.Fig. 1 is the optical microscopy map of the spherical NTO crystal of big granularity.The test result of laser particle analyzer shows in the product
It is worth grain size D50About 500 μm.
Embodiment 2
A method of control NTO crystal morphologies and granularity are as follows：
Step 1：1gNTO is dissolved in 9mL water, solution is obtained；
Step 2：Under the lasting stirring of 250r/min, the solution obtained by step 1 is slowly heated up, until solute is whole
Dissolving；At this point, constant temperature 35 minutes, is then slowly dropped to room temperature with the speed of 2 DEG C/min, crystal is gradually precipitated during this；It takes out
Filter, washing, drying, obtain crystal；
Step 3：The dissolution of crystals that step 2 is obtained is in ethyl acetate, the material ratio of crystal (g) and ethyl acetate (mL)
It is 1:1；30min is stirred in 25 DEG C of speed with 300r/min；Above-mentioned mixed system is warming up to 60 with the speed of 2 DEG C/min again
DEG C, heat preservation stirs 3h with the speed of 400r/min；The above mixed system is down to 25 DEG C with the speed of 2 DEG C/min；It filters, wash
Wash, dry after obtain the spherical NTO crystal of middle granularity.
Characterization of The Products：The pattern and granularity of the NTO crystal of acquisition are carried out using light microscope and laser particle analyzer
Characterization.The test result of laser particle analyzer shows the median particle diameter D of the product50About 250 μm.
Embodiment 3
A method of control NTO crystal morphologies and granularity are as follows：
Step 1：1gNTO is dissolved in 20mL ethyl alcohol, solution is obtained；
Step 2：Under the lasting stirring of 250r/min, the solution obtained by step 1 is slowly heated up, until solute is whole
Dissolving；At this point, constant temperature 40 minutes, is then slowly dropped to room temperature with the speed of 5 DEG C/min, crystal is gradually precipitated during this；It takes out
Filter, washing, drying, obtain crystal；
Step 3：The dissolution of crystals that step 2 is obtained is in ethyl acetate, the material ratio of crystal (g) and ethyl acetate (mL)
It is 1:1；30min is stirred in 25 DEG C of speed with 300r/min；Above-mentioned mixed system is warming up to 60 with the speed of 3 DEG C/min again
DEG C, heat preservation stirs 3h with the speed of 400r/min；The above mixed system is down to 25 DEG C with the speed of 2 DEG C/min；It filters, wash
Wash, dry after obtain the spherical NTO crystal of small grain size.
Characterization of The Products：The pattern and granularity of the NTO crystal of acquisition are carried out using light microscope and laser particle analyzer
Characterization.Fig. 2 is the optical microscopy map of the spherical NTO crystal of small grain size.The test result of laser particle analyzer shows in the product
It is worth grain size D50About 100 μm.
Embodiment 4
NTO cooling recrystallization scale-ups
According to the requirement of NTO granule sizes, carries out NTO cooling recrystallization scale-ups in coordinative solvent respectively, prepare
Go out the spherical NTO samples of large, medium and small three kinds of different grain size ranks, characterization result such as following table：
1 large, medium and small three kind of varigrained spherical NTO sample characterizations result of table
Above-described specific descriptions have carried out further specifically the purpose, technical solution and advantageous effect of invention
It is bright, it should be understood that the above is only a specific embodiment of the present invention, the protection model being not intended to limit the present invention
It encloses, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the present invention
Protection domain within.
Claims (3)
1. a kind of method of control NTO crystal morphologies and granularity, it is characterised in that：It is as follows：
Step 1：In a solvent by NTO dissolvings, solution A is obtained；
The solvent is：Prepare D50~500 μm of spherical NTO crystal, solvent is water；Prepare D50~250 μm of spherical NTO is brilliant
Body, solvent is water or volume ratio is 1:1 water-ethanol mixed solvent；Prepare D50~100 μm of spherical NTO crystal, solvent is second
Alcohol；
The material of the NTO (g) and solvent (mL), which compares, is：Prepare D50~500 μm and D50When~250 μm of spherical NTO crystal, ratio is expected
It is 1:6~1:10；Prepare D50When~100 μm of spherical NTO crystal, material is than being 1:13~1:27；
Step 2：Continue under stirring, the solution A obtained by step 1 is slowly heated up, until solute all dissolves；At this point,
Constant temperature 20~40 minutes, is then slowly dropped to room temperature, and crystal is gradually precipitated during this；It filters, wash, is dry, obtaining crystal；
Step 3：For the dissolution of crystals that step 2 is obtained in ethyl acetate, it is 1 that the material of crystal (g) and ethyl acetate (mL), which compares,:
1；30min is stirred in 25 DEG C of speed with 200~400r/min；Above-mentioned mixed system is heated up with the speed of 2~3 DEG C/min again
To 60 DEG C, constant temperature stirs 2~4h with the speed of 300~500r/min；The above mixed system is dropped with the speed of 1~2 DEG C/min
To 25 DEG C；It filters, wash, obtain large, medium and small three kinds varigrained spherical NTO crystal after drying.
2. the method for a kind of control NTO crystal morphologies and granularity as described in claim 1, it is characterised in that：Described in step 2
Mixing speed be：Prepare D50~500 μm of spherical NTO crystal, mixing speed are 90~100r/min；Prepare D50~250 μm
And D50~100 μm of spherical NTO crystal, mixing speed are 200~300r/min.
3. the method for a kind of control NTO crystal morphologies and granularity as described in claim 1, it is characterised in that：Described in step 2
The cooling rate for being down to room temperature is：Prepare D50~500 μm and D50~250 μm of spherical NTO crystal, cooling rate be 1.0~
2.5℃/min；Prepare D50~100 μm of spherical NTO crystal, cooling rate are 3.5~7.0 DEG C/min.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875455A (en) * | 2020-07-23 | 2020-11-03 | 西安近代化学研究所 | Manufacturing method of NTO-based PBX explosive modeling powder |
| CN113336610A (en) * | 2021-05-20 | 2021-09-03 | 北京理工大学 | Novel crystal form NTO elementary substance explosive and preparation method thereof |
| CN114195727A (en) * | 2021-12-27 | 2022-03-18 | 中北大学 | Spherical NTO crystal and preparation method thereof |
| CN114315745A (en) * | 2021-12-27 | 2022-04-12 | 中北大学 | Nano-scale NTO crystal and preparation method thereof |
| CN115142117A (en) * | 2022-06-06 | 2022-10-04 | 北京理工大学 | Spherical single crystal 3-nitro-1,2, 4-triazole-5-ketone and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875455A (en) * | 2020-07-23 | 2020-11-03 | 西安近代化学研究所 | Manufacturing method of NTO-based PBX explosive modeling powder |
| CN113336610A (en) * | 2021-05-20 | 2021-09-03 | 北京理工大学 | Novel crystal form NTO elementary substance explosive and preparation method thereof |
| CN114195727A (en) * | 2021-12-27 | 2022-03-18 | 中北大学 | Spherical NTO crystal and preparation method thereof |
| CN114315745A (en) * | 2021-12-27 | 2022-04-12 | 中北大学 | Nano-scale NTO crystal and preparation method thereof |
| CN114315745B (en) * | 2021-12-27 | 2023-08-18 | 中北大学 | Nanoscale NTO crystal and preparation method thereof |
| CN114195727B (en) * | 2021-12-27 | 2023-08-22 | 中北大学 | Spherical NTO crystal and preparation method thereof |
| CN115142117A (en) * | 2022-06-06 | 2022-10-04 | 北京理工大学 | Spherical single crystal 3-nitro-1,2, 4-triazole-5-ketone and preparation method thereof |
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