CN105418524B - A kind of preparation method of speciality 3- nitros -1,2,4- triazole -5- ketone - Google Patents
A kind of preparation method of speciality 3- nitros -1,2,4- triazole -5- ketone Download PDFInfo
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- CN105418524B CN105418524B CN201511000135.9A CN201511000135A CN105418524B CN 105418524 B CN105418524 B CN 105418524B CN 201511000135 A CN201511000135 A CN 201511000135A CN 105418524 B CN105418524 B CN 105418524B
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- triazole
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention discloses a kind of preparation methods of 31,2,4 triazole of nitro of speciality, 5 ketone, include the following steps：There is provided 31,2,4 triazole of nitro 5 ketone solution；Crystallisation by cooling is carried out to 3 nitro, 1,2,4 triazole, the 5 ketone solution by cooling down medium, obtains 31,2,4 triazole of nitro of speciality, 5 ketone.Method provided by the invention improves single chmical compound explosive crystalline density using recrystallization technology, reduces matter crystal internal defect, eliminates surface blemish, and surface is smooth closely knit, controls crystal shape and granularity, so as to improve single chmical compound explosive quality, meets processability.
Description
Technical field
The present invention relates to explosive field, more particularly to a kind of speciality 3- nitros -1,2, the preparation method of 4- triazole -5- ketone.
Background technology
3- nitros -1,2,4- triazole -5- ketone (NTO) is a kind of energy close to cyclotrimethylene trinitramine, and sensitivity is close to three
The high-energy insensitive explosive of amino trinitrobenzen.Since the 1980s, both at home and abroad to 3- nitros -1,2,4- triazole -5- ketone
Synthesis, performance, structure and composite explosives formula have carried out extensive research, research shows that 3- nitros -1,2,4- triazole -5- ketone
Detonation property and sensitivity size and crystal morphology are in close relations.
3- nitros -1,2, there are two kinds of crystal forms for 4- triazole -5- ketone：α and β, alpha-crystal form are stable anorthic system, and alpha-crystal form is
Unstable anorthic system, typical crystal is in rodlike, and is easily reunited, and the grain size of product is big, and crystal defect is more, causes to feel
Degree improves, and limits use scope.
3- nitros -1,2 that synthetic reaction process directly obtains, 4- triazole -5- ketone are in typical club shaped structure, and draw ratio is about
It is 3: 1, shock wave is sensitive, and processability is poor, and the viscosity when that can lead to powder charge in casting blasting charge increases, and is unfavorable for casting,
In 3- nitros -1,2,4- triazole -5- ketone in use, must solve due to 3- nitros -1,2,4- triazole -5- ketone crystallization shapes are led
The problem of difficult forming of cause.
Invention content
The purpose of the present invention is to provide a kind of speciality 3- nitros -1,2, the preparation method of 4- triazole -5- ketone, the present invention carries
Speciality 3- nitros -1,2 that the preparation method of confession obtains, 4- triazole -5- ketone granularities are big, plane of crystal is round and smooth, without apparent water chestnut.
The present invention provides a kind of speciality 3- nitros -1,2, the preparation method of 4- triazole -5- ketone includes the following steps：
3- nitros -1,2,4- triazole -5- ketone solution are provided；
By cooling down medium to the 3- nitros -1,2,4- triazole -5- ketone solution carries out crystallisation by cooling, obtains speciality 3- nitre
Base -1,2,4- triazole -5- ketone.
Preferably, the cooling medium is alcohols solvent.
Preferably, the cooling medium is ethylene glycol or ethyl alcohol.
Preferably, the temperature of the cooling medium is -20 DEG C~-27 DEG C.
Preferably, the cooldown rate of the crystallisation by cooling is 6 DEG C/min~8 DEG C/min.
Preferably, the cooldown rate from low to high during the crystallisation by cooling.
Preferably, the initial temperature of the crystallisation by cooling is 60 DEG C~68 DEG C, and the final temperature of the crystallisation by cooling is less than 0
℃。
Preferably, the 3- nitros -1,2, the mass concentration of 4- triazole -5- ketone solution is 7%~8%.
Preferably, the 3- nitros -1,2, the solvent in 4- triazole -5- ketone solution are N-Methyl pyrrolidone.
Preferably, it is further included after the crystallisation by cooling：
The material that the crystallisation by cooling is obtained carries out separation of solid and liquid.
The present invention provides a kind of speciality 3- nitros -1,2, the preparation method of 4- triazole -5- ketone includes the following steps：It carries
For 3- nitros -1,2,4- triazole -5- ketone solution；By cooling down medium to the 3- nitros -1,2,4- triazole -5- ketone solution carries out
Crystallisation by cooling obtains speciality 3- nitros -1,2,4- triazole -5- ketone.The present invention is by cooling down medium to 3- nitros -1,2,4- tri-
Azoles -5- ketone solution carries out crystallisation by cooling, improves single chmical compound explosive crystalline density using recrystallization technology, reduces matter crystal internal defect,
Surface blemish is eliminated, surface is smooth closely knit, controls crystal shape and granularity, so as to improve single chmical compound explosive quality, meets mouldability
Energy.Embodiment the experimental results showed that, obtained speciality 3- nitros -1,2,4- triazoles -5- ketone particle size is up to 180 microns, pattern
Spherical in shape, circularities are up to 0.9, and reduction shock sensitivity is low, and ratio of long axis to short axis is 1.05~1.1, and plane of crystal is smooth, corner angle
It is few, it is spherical to advantageously reduce explosive sensitivity.
Description of the drawings
Fig. 1 is 3- nitros -1,2 that the embodiment of the present invention 1 is used, and 4- triazole -5- ketone prepares raw material micro-structure diagram；
Speciality 3- nitros -1,2 that Fig. 2 is provided for the embodiment of the present invention 1,4- triazole -5- ketone micro-structure diagrams.
Specific embodiment
The present invention provides a kind of speciality 3- nitros -1,2, the preparation method of 4- triazole -5- ketone includes the following steps：
3- nitros -1,2,4- triazole -5- ketone solution are provided；
By cooling down medium to the 3- nitros -1,2,4- triazole -5- ketone solution carries out crystallisation by cooling, obtains speciality 3- nitre
Base -1,2,4- triazole -5- ketone..
Method provided by the invention, by cooling down medium to 3- nitros -1,2,4- triazole -5- ketone solution carries out cooling knot
Crystalline substance improves single chmical compound explosive crystalline density using recrystallization technology, reduces matter crystal internal defect, eliminates surface blemish, and surface is smooth
It is closely knit, crystal shape and granularity are controlled, so as to improve single chmical compound explosive quality, meets processability.
For the present invention using cooling medium to 3- nitros -1,2,4- triazole -5- ketone solution carries out crystallisation by cooling.In the present invention
In, the 3- nitros -1,2, the solvent in 4- triazole -5- ketone solution preferably includes N-Methyl pyrrolidone, more preferably N- first
Base pyrrolidone solution.The present invention does not have special limit to the 3- nitros -1,2, the preparation method of 4- triazole -5- ketone solution
System, the solution preparation technique scheme that who knows using those skilled in the art.The embodiment of the present invention, using N- methylpyrroles
Alkanone aqueous dissolution 3- nitros -1,2,4- triazole -5- ketone specifically under conditions of stirring, accelerate dissolving 3- nitros -1,2,4-
The dissolving of triazole -5- ketone.In the present invention, the volume of N-Methyl pyrrolidone and water in the N-Methyl pyrrolidone aqueous solution
Than preferably (0.8~1.5): 3, further preferably 1: 3；Heretofore described solution temperature is preferably 60 DEG C~70 DEG C, into
One step is preferably 65 DEG C~68 DEG C.
In the present invention, the 3- nitros -1,2, the mass fraction of 4- triazole -5- ketone solution is preferably 7%~8%, into
One step is preferably 7.2%~7.5%.
Be provided 3- nitros -1,2, after 4- triazole -5- ketone solution, the present invention by cool down medium to the 3- nitros -
1,2,4- triazole -5- ketone solution carries out crystallisation by cooling, obtains speciality 3- nitros -1,2,4- triazole -5- ketone.In the present invention, institute
It is preferably alcohols solvent, further preferably ethylene glycol or ethyl alcohol to state cooling medium.It is preferred that medium usage amount is cooled down in the present invention
For 150~200L, more preferably 165~185L.
In the present invention, preferably -20 DEG C~-27 DEG C of the temperature of the cooling medium, more preferably -22 DEG C~25 DEG C,
The temperature that medium is cooled down in the present invention is preferably controlled by cooling device, does not have particular/special requirement to the cooling device, using this
Cooling device known to field technology personnel uses Yu Hua Instrument Ltd. of Henan Gongyi City in the embodiment of the present application
The glass kettle of the model SL-20L of production；In embodiments herein, the temperature of the cooling medium can be specially -21
DEG C, -23 DEG C, -24 DEG C or -26 DEG C.
In the present invention, the cooldown rate of the crystallisation by cooling is preferably 6 DEG C/min~8 DEG C/min, more preferably 6.5
DEG C/min~7.5 DEG C/min；In embodiments herein, the cooldown rate can be specially 6 DEG C/min, 7 DEG C/min or 8
℃/min。
In the present invention, the preferred cooldown rate from low to high of crystallisation by cooling process passes through in of the invention and cooling is controlled to be situated between
The temperature of matter controls cooldown rate, and the crystallisation by cooling time is preferably 10min~15min in the embodiment of the present invention, further excellent
It is selected as 11min~13min.
In the present invention, the initial temperature of the crystallisation by cooling is preferably 60 DEG C~68 DEG C, more preferably 62 DEG C~65 DEG C；Institute
The final temperature for stating crystallisation by cooling be preferably 0 DEG C hereinafter, more preferably -10 DEG C~-4 DEG C, cool down in the embodiment of the present application and terminate
Temperature can be specially -8 DEG C, -5 DEG C or -4 DEG C.
In the present invention, crystallisation by cooling process is preferably using double-deck coiled pipe crystallization kettle, to the appearance of the double-deck coiled pipe crystallization kettle
Measure no particular/special requirement, the capacity of double-deck coiled pipe crystallization kettle is preferably 200L in the embodiment of the present application.The bilayer that the present invention uses
Coiled pipe crystallization kettle body shape is hemispherical, has the condenser pipe of snakelike disk-like structure, and crystallisation by cooling area is more than 0.5m2,
Material caused by since autoclave body draw ratio is excessive can be mitigated during crystallisation by cooling and distributes the problem of uneven；Mixing speed adjusting selecting
It is stirred with three leaf push types, mass transfer between radially, axially of material in double-deck coiled pipe crystallization kettle, heat transfer can be promoted；Double-deck snake
Pipe crystallization kettle inner wall is highly polished；Be conducive to crystal uniform growth during crystallisation by cooling, obtain the preferable crystal of face shaping,
Effective Control granularity growth rate, improves size distribution situation.
After completing the crystallization, the material after the crystallization is preferably carried out separation of solid and liquid by the present invention, obtains speciality 3- nitre
Base -1,2,4- triazole -5- ketone.The present invention does not have the method for the separation of solid and liquid special limitation, using people in the art
Who technical solution of separation of solid and liquid for knowing of member；In the present invention, the separation of solid and liquid preferably filters, and is more selected as taking out
Filter.
After the separation of solid and liquid, the present invention preferably distills obtained liquid phase part, removes the water in the liquid phase part
Point, N-Methyl pyrrolidone is obtained, realizes the recycling of N-Methyl pyrrolidone；Distillation process in the embodiment of the present invention
In, remaining 3- nitros -1,2 are obtained, 4- triazole -5- ketone is preferably reused.The distillation of obtained liquid phase part is gone in the present invention
After moisture removal, because solubility changes, 3- nitros -1,2,4- triazole -5- ketone is precipitated, and suspension is formed with N-Methyl pyrrolidone,
Using filter method, 3- nitros -1,2,4- triazole -5- ketone is filter cake, and N-Methyl pyrrolidone is filtrate, realizes the two separation.
After completing the separation of solid and liquid, the present invention preferably dries obtained solid fraction, obtains speciality 3- nitros -1,2,
4- triazole -5- ketone.In the present invention, the drying carries out preferably in drying cupboard, and the present invention does not have particular/special requirement to drying cupboard,
Using drying cupboard well-known to those skilled in the art.In the present invention, the temperature of the drying is preferably 60 DEG C~70
DEG C, further preferably 65 DEG C~68 DEG C；In embodiments herein, the temperature of the drying can be specially 62 DEG C, 64 DEG C,
66 DEG C or 69 DEG C.The present invention is dried filter cake to obtain 3- nitros -1,2,4- triazole -5- ketone dry products, 3- nitros -1,2,4- tri-
The moisture of azoles -5- ketone dry products is preferably shorter than 0.1%.
The present invention provides a kind of 3- nitros -1,2, the preparation method of 4- triazole -5- ketone includes the following steps：3- is provided
Nitro -1,2,4- triazole -5- ketone solution；By cooling down medium to the 3- nitros -1,2,4- triazole -5- ketone solution is cooled down
Crystallization, obtains speciality 3- nitros -1,2,4- triazole -5- ketone.The present invention is by cooling down medium to 3- nitros -1,2,4- triazoles -5-
Ketone solution carries out crystallisation by cooling, improves single chmical compound explosive crystalline density using recrystallization technology, reduces matter crystal internal defect, eliminates
Surface blemish, surface is smooth closely knit, controls crystal shape and granularity, so as to improve single chmical compound explosive quality, meets processability.It is real
Apply example the experimental results showed that, obtained speciality 3- nitros -1,2, for 4- triazoles -5- ketone particle size up to 180 microns, pattern is in ball
Shape, circularities are up to 0.9, and reduction shock sensitivity is low, and ratio of long axis to short axis is 1.05~1.1, and plane of crystal is smooth, and corner angle are few, class
Spherical shape advantageously reduces explosive sensitivity.
In order to further illustrate the present invention, with reference to embodiment to speciality 3- nitros -1,2 provided by the invention, 4- tri-
The preparation method of azoles -5- ketone is described in detail, but cannot they be interpreted as limiting the scope of the present invention.
Embodiment 1：
The ethylene glycol of 170L is placed in cooling medium in advance, the temperature of cooling equipment is set by SL-20L cooling devices
Difference ± 2 DEG C of -25 DEG C of coolant temperature of control；Double-deck coiled pipe crystallization kettle of the capacity for 200L is used, under room temperature in bilayer
9.3L water and 3.1LN- methyl pyrrolidones are added in coiled pipe crystallization kettle crystallization kettle, is dissolved under the conditions of 65 DEG C；Stirring bar
Under part, add in 1kgNTO (for microstructure as shown in Figure 1, raw material 3- nitros -1,2,4- triazole -5- ketone is in typical club shaped structure,
Its draw ratio is about 3: 1), NTO empties the hot water in crystallization kettle chuck after all dissolving；Cooling medium is poured into double-deck snake immediately
Carry out crystallisation by cooling in pipe crystallization kettle internal cooling coil pipe and in double-deck coiled pipe crystallization kettle chuck, control rate of temperature fall for 6 DEG C/
Min~8 DEG C/min, from low to high；15min temperature is down to -5 DEG C by 68 DEG C, obtains crystallization 3- nitros -1,2,4- triazole -5- ketone；
Filtering carries out filtrate distillation and removes moisture removal, recycles remaining 3- nitros -1,2,4- triazole -5- ketone and N-Methyl pyrrolidone,
It will obtain filter cake and filter cake is placed in drying cupboard drying, and under the conditions of 65 DEG C, be dried to moisture less than 0.10%, obtain speciality 3- nitre
Base -1,2,4- triazole -5- ketone.
Speciality 3- nitros -1,2 that the present invention will obtain, 4- triazole -5- ketone carries out microstructure detection, as a result such as Fig. 2 institutes
Show, Fig. 2 is speciality 3- nitros -1,2 for being prepared of the embodiment of the present invention, the microstructure of 4- triazole -5- ketone, can be with by Fig. 2
Find out, feature 3- nitros -1,2 that the present embodiment obtains, the crystal of 4- triazole -5- ketone is close to spherical shape, and surface is smooth closely knit；It obtains
3- nitros -1,2, up to 180 microns, pattern is spherical in shape for the crystallization of 4- triazole -5- ketone, and circularities reduce shock sensitivity up to 0.9
Low, ratio of long axis to short axis is 1.05~1.1, and plane of crystal is smooth, and corner angle are few, spherical to advantageously reduce explosive sensitivity.
Embodiment 2
Speciality 3- nitros -1,2 are prepared using the technical solution of embodiment 1,4- triazole -5- ketone, unlike, this reality
It applies in example, cooling medium is ethyl alcohol, and the temperature for cooling down medium is 23 DEG C ± 2 DEG C, 3- nitros -1,2,4- triazole -5- ketone solution
Mass fraction is 8%.
Speciality 3- nitros -1,2 that the present embodiment obtains, the crystal of 4- triazole -5- ketone is close to spherical shape, and surface is smooth closely knit；
Obtained 3- nitros -1,2, up to 180 microns, pattern is spherical in shape for the crystallization of 4- triazole -5- ketone, and circularities reduce shock wave up to 0.9
Sensitivity is low, and ratio of long axis to short axis is 1.05~1.1, and plane of crystal is smooth, and corner angle are few, spherical to advantageously reduce explosive sensitivity.
Embodiment 3
Speciality 3- nitros -1,2 are prepared using the technical solution of embodiment, 4- triazole -5- ketone, unlike, this reality
It applies in example, cooling medium is ethyl alcohol, and usage amount is that the temperature of 180L cooling media is 24 DEG C ± 2 DEG C, and the time of crystallisation by cooling is
10min。
Speciality 3- nitros -1,2 that the present embodiment obtains, the crystal of 4- triazole -5- ketone is close to spherical shape, and surface is smooth closely knit；
Obtained 3- nitros -1,2, up to 180 microns, pattern is spherical in shape for the crystallization of 4- triazole -5- ketone, and circularities reduce shock wave up to 0.9
Sensitivity is low, and ratio of long axis to short axis is 1.05~1.1, and plane of crystal is smooth, and corner angle are few, spherical to advantageously reduce explosive sensitivity.
The property of each obtained feature NTO various performance parameters of embodiment such as speciality NTO that 1 embodiment of the present invention of table obtains
It can test result；The crystal morphology of each obtained feature NTO of embodiment is as shown in table 2.
The performance test results of speciality NTO that 1 embodiment of the present invention of table obtains
The crystal appearance for the speciality NTO that 2 embodiment of the present invention of table obtains
| Lot number | Solution temperature | Coolant temperature | Rate of temperature fall | Crystal morphology |
| Embodiment 1 | 66.5℃ | - 24 DEG C~-27 DEG C | 6.5℃/min | The relatively round axial ratio of crystal form is 1.05 |
| Embodiment 2 | 67℃ | - 24 DEG C~-27 DEG C | 6.5℃/min | The relatively round axial ratio of crystal form is 1.08 |
| Embodiment 3 | 67℃ | - 24 DEG C~-27 DEG C | 6.5℃/min | The relatively round axial ratio of crystal form is 1.02 |
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of speciality 3- nitros -1,2, the preparation method of 4- triazole -5- ketone, include the following steps：
3- nitro -1,2,4- triazole -5- ketone solution is provided；
By cooling down medium to the 3- nitros -1,2,4- triazole -5- ketone solution carries out crystallisation by cooling, obtain speciality 3- nitros -
1,2,4- triazole -5- ketone；
The cooldown rate of the crystallisation by cooling is 6 DEG C/min~8 DEG C/min；
Cooldown rate from low to high during the crystallisation by cooling；
The initial temperature of the crystallisation by cooling is 60 DEG C~68 DEG C, and the final temperature of the crystallisation by cooling is less than 0 DEG C.
2. preparation method according to claim 1, which is characterized in that the cooling medium is alcohols solvent.
3. preparation method according to claim 2, which is characterized in that the cooling medium is ethylene glycol or ethyl alcohol.
4. preparation method according to claim 1, which is characterized in that the temperature of the cooling medium is -20 DEG C~-27
℃。
5. preparation method according to claim 1, which is characterized in that the 3- nitros -1,2,4- triazole -5- ketone solution
Mass concentration is 7%~8%.
6. preparation method according to claim 1, which is characterized in that the 3- nitros -1,2, in 4- triazole -5- ketone solution
Solvent be N-Methyl pyrrolidone.
7. preparation method according to claim 1, which is characterized in that further included after the crystallisation by cooling：
The material that the crystallisation by cooling is obtained carries out separation of solid and liquid.
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