CN107602488A - The preparation method of the oxide of 2,6 diaminourea of speciality, 3,5 dinitro pyrazine 1 - Google Patents
The preparation method of the oxide of 2,6 diaminourea of speciality, 3,5 dinitro pyrazine 1 Download PDFInfo
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Abstract
The present invention relates to explosive field, specially a kind of oxide of 2,63,5 dinitro pyrazine of diaminourea of very special quality 1（ANPZO）.Solve using common ANPZO as the technical problem such as the charge process of the casting blasting charge of base is poor, degree of packing is low, powder column sensitivity is high, brisance is low.The speciality ANPZO is using made of following steps：ANPZO is completely dissolved in solvent, solution is made；Under agitation, crystal seed is added, in the range of 80 DEG C ~ 120 DEG C, crystallization is diluted with the solvent aqueous solution of various concentrations；Solution after crystallization is filtered, washed, is dried；Obtain speciality ANPZO；Speciality ANPZO product granularities of the invention are big, purity is high, crystal morphology is in bar-shaped or spherical, crystals and few surface defects, purity is high, spherical crystal is suitable for grain size distribution, improves the performances such as casting blasting charge density, insensitiveness, power and charge process adaptability.
Description
Technical field
The present invention relates to explosive field, specially a kind of speciality 2,6- Diamino-3,5-dinitropyrazine-1-oxides
(ANPZO) preparation method.
Background technology
In heat-resistant explosive of the fusing point more than 300 DEG C, conventional has HNS, PYX, TATB.Wherein photoacoustic spectroscopy
(TATB) energy highest, energy is more than TATB and the insensitive energetic material with good combination property is high Energy Density Materials
(HEDM) main contents of research, and the target of people's diligent pursuit for a long time.U.S.'s lawrence livermore laboratory
2,6- diaminourea -3,5- dinitro pyrazine -1- the oxides (ANPZO) that nineteen ninety-five synthesizes are rated as the one of HEDM research fields
Individual important breakthrough.ANPZO crystalline density is up to 1.913g/cm3, energy higher than TATB by the 20%, heat resistance of output is better than big
Most high explosives, DSC exothermic peaks (354 DEG C) and TATB are almost consistent, comprehensive to shock, spark, friction and shock wave insensitiveness
Close excellent performance.It is expected to turn into the main charge that insensitiveness originates medicine, booster explosive and special Explosive Parts, it is in civilian superelevation fire stons
The field such as oily perforating bullet and military high-energy insensitive explosive has a extensive future.
Synthesis ANPZO prevailing technology is substituted, nitrified, ammonia for reaction initiation material with 2,6 one dichloropyrazines at present
Change, obtain ANPZO after oxidation, see Fig. 3.The method is current yield highest synthetic method, by the Improvement of more than ten years,
Its gross production rate is more than 50%, but really large-scale production application is rarely reported, and 2013, Shanxi Bei Huaguan aluminum chemical industries had
Limit company has synthesized ANPZO using the technique, realizes the industrialization trial production of 20 feather weight.
Small molecule method synthesizes ANPZO using iminodiacetonitrile as raw material, by being cyclized, nitrifying synthesis ANPZO, the technique two
Footwork obtains ANPZO, and the cost of material is low, and process conditions are gentle, and synthesis cycle is short, and the three wastes are few, and Shanxi Bei Huaguan aluminum chemical industries are limited
Company has realized the industrialized production of the technique, and product purity is more than 99%.
The ANPZO granularities that above two technique directly synthesizes are low in 10um or so, bulk density, it is difficult to casting blasting charge and
Directly applied in bonded pelleting PBX explosives.
The content of the invention
The speciality ANPZO of the present invention refers to the physical properties such as outward appearance, granularity, bulk density, surface and internal flaw and is different from
The common ANPZO directly synthesized, fried available for grain size distribution with increasing degree of packing, improvement charge process performance, reducing mixing
Medicine sensitivity, brisance is improved, meet the ANPZO of the very special quality of different application requirement.
Common ANPZO is difficult that the degree of packing that makes composite explosives is put on as cast loading main charge because granularity is small,
Have influence on charge process, anti-overload ability, the intensity of powder column and brisance simultaneously.Speciality ANPZO granularities are big, for granularity
Grading can give full play to the characteristics of ANPZO autologous densities are big, be effectively increased warhead charge density, improve brisance.
The present invention is achieved by the following technical solutions：A kind of speciality 2,6- diaminourea -3,5- dinitro pyrazine -1- oxygen
The preparation method of compound, the speciality 2,6- Diamino-3,5-dinitropyrazine-1-oxides are that ANPZO is to use following step
Made of rapid：
(a), in crystallization kettle, ANPZO is dissolved with solvent, solution is made under the conditions of 80 DEG C~120 DEG C；
(b) crystal seed, is added, in the range of 80 DEG C~120 DEG C, crystallization is diluted with the solvent aqueous solution of various concentrations；
(c), the solution after crystallization is filtered, washs, drain；
(d), target product wet product is dried to moisture under the conditions of 70 DEG C~110 DEG C and is less than 0.1%, that is, is obtained a kind of special
Matter ANPZO.
Further, in step (b) in the range of 80 DEG C~120 DEG C, low concentration is added after first high concentration, uses various concentrations
Solvent aqueous solution be diluted crystallization, fast after crystallization process is first slow, remain a constant speed dilution, and crystallization time control is in 2..5 lab scales
To 4 hours；Counterweight crystalline product, which boil washing, makes product pH value be 6.0~7.5.
The speciality ANPZO physical and chemical indexs of gained of the invention meet table 1 and required, its feature be granularity is big, purity is high,
Crystal morphology is in bar-shaped or spherical；Solvent has excellent solubility property to ANPZO, can be dissolved each other in any proportion with water；Stirring
Under the conditions of, in technology controlling and process scope high temperature range, ANPZO is dissolved completely in solvent solution is made；Add crystal seed
Afterwards, then with the solvent-laden aqueous solution it is diluted, the water content and dilution rate of solvent aqueous solution decide crystallization rate, influence
To the size of product grading, therefore dilution solvent aqueous solution concentration should use from low to high, at the uniform velocity crystallize, crystallization time can not
It is too short；The recrystallization product after washing will be boiled, and to be dried to moisture qualified, that is, obtains speciality ANPZO.Described heating, filtering, drying
Etc. the common knowledge that step is chemical field technical staff, used equipment is also the known normal of those skilled in the art
Know, there can be multiple choices, be easily achieved.
Table 1 lists speciality ANPZO indices of the present invention, have chosen the speciality ANPZO produced in batches three times, right
Its physicochemical property is examined, and qualitative data entirely reaches speciality ANPZO index requests.
The purpose of the present invention is to improve the purity, granularity, crystal morphology of product, meets that the quality in different application field will
Ask.By preferred solvent, different recrystallizing technologies is designed, obtains the crystal of different morphologies, wherein spherical bulk crystalline grain
Footpath can reach 170um, and bulk density is by raw material 0.6g/cm3Bring up to 1.05g/cm3。
Brief description of the drawings
Fig. 1 is that homemade four step rule synthesizes ANPZO crystal microphotos.
Fig. 2 is homemade two step synthetic method ANPZO crystal microphotos.
Fig. 3 is spherical speciality ANPZO crystal microphotos of the present invention.
Fig. 4 is the bar-shaped ANPZO crystal microphoto of speciality of the present invention.
Fig. 5 is the speciality ANPZO production technological process described in embodiment 1.
Embodiment
A kind of speciality 2, the preparation method of 6- Diamino-3,5-dinitropyrazine-1-oxides, the speciality 2,6- diaminos
Base -3,5- dinitro pyrazine -1- oxides are that ANPZO is using made of following steps：
(a), in crystallization kettle, ANPZO is dissolved with solvent, solution is made under the conditions of 80 DEG C~120 DEG C；
(b) crystal seed, is added, in the range of 80 DEG C~120 DEG C, crystallization is diluted with the solvent aqueous solution of various concentrations；
(c), the solution after crystallization is filtered, washs, drain；
(d), target product wet product is dried to moisture under the conditions of 70 DEG C~110 DEG C and is less than 0.1%, that is, is obtained a kind of special
Matter ANPZO.
The selection of recrystallization solvent, rhabdolith are recrystallized with dimethyl sulfoxide (DMSO), and spherical crystal is tied again with sulfuric acid
It is brilliant.
Mass ratio with solvent dissolving ANPZO, ANPZO and solvent is 1:5~15.
Crystal seed is first added before crystallization is diluted, control and the addition of seed size can be according to the granularity requirements of finished product
It is adjusted.
When being diluted crystallization, crystallization is diluted using the solvent aqueous solution of various concentrations, solvent aqueous solution it is dense
Degree is stepped from high to low.
When being diluted crystallization, the dosage of various concentrations solvent aqueous solution is contemplated that residue of mother ANPZO contents, mother liquor
The factors such as cost recovery, utilization rate of equipment and installations, product yield are adjusted, and the concentration control of crystallization Mother liquor is 40%~60%.
It is fast after first slow when being diluted crystallization, stable flow acceleration is kept, knot is controlled by controlling crystallization time
Brilliant speed.
When being diluted crystallization, crystallization time is controlled at 2.5 hours~4 hours.
When being diluted crystallization, solvent aqueous solution can use last consignment of crystalline mother solution to prepare.
After step (c) terminates, counterweight crystalline product boil wash make product pH value be 6.0~7.5 between.
A kind of bar-shaped speciality ANPZO of embodiment 1, by taking 300 liters of reactors as an example, the speciality ANPZO is using following step
Made of rapid：
1st, 100 ㎏ dimethyl sulfoxide (DMSO)s are firstly added, are warming up to 95 DEG C~100 DEG C；
2nd, under stirring condition, the ㎏ ANPZO of 5 ㎏~8 are added, observation ANPZO all dissolves；
3rd, the ㎏ of crystal seed 0 ㎏~0.5 is added.By the order for adding low concentration after first high concentration, two for flowing plus measuring respectively
The methyl sulfoxide aqueous solution, flow acceleration is controlled, it is fast after first slow, add within 2.5~4 hours or so, control crystallization temperature is not less than 80
℃；
5th, 35 DEG C are cooled to, blowing, drains the mother liquor in filtering layer, is repeatedly drained after washing；
6th, crystallized stock is placed in drying cupboard or drying room is dried, under the conditions of 70 DEG C~110 DEG C, be dried to moisture and be less than
0.1%.
Production technological process such as Fig. 5.
Table 1：Speciality ANPZO test data sheets
Claims (10)
1. a kind of speciality 2, the preparation method of 6- Diamino-3,5-dinitropyrazine-1-oxides, it is characterised in that the spy
Matter 2,6- diaminourea -3,5- dinitro pyrazine -1- oxides are that ANPZO is using made of following steps：
（a）, in crystallization kettle, with solvent dissolve ANPZO, solution is made under the conditions of 80 DEG C~120 DEG C；
(b) crystal seed, is added, in the range of 80 DEG C~120 DEG C, crystallization is diluted with the solvent aqueous solution of various concentrations；
(c), the solution after crystallization is filtered, washs, drain；
(d), target product wet product is dried to moisture under the conditions of 70 DEG C~110 DEG C and is less than 0.1%, that is, obtains a kind of speciality
ANPZO。
2. speciality 2 as claimed in claim 1, the preparation method of 6- Diamino-3,5-dinitropyrazine-1-oxides, it is special
Sign is the selection of recrystallization solvent, and rhabdolith is recrystallized with dimethyl sulfoxide (DMSO), and spherical crystal is recrystallized with sulfuric acid.
3. speciality 2 as claimed in claim 1, the preparation method of 6- Diamino-3,5-dinitropyrazine-1-oxides, it is special
Sign is that with solvent dissolving ANPZO, ANPZO and solvent mass ratio be 1:5~15.
4. speciality 2 as claimed in claim 1, the preparation method of 6- Diamino-3,5-dinitropyrazine-1-oxides, it is special
Levy and be first to add crystal seed before crystallization is diluted, control and the addition of seed size can be entered according to the granularity requirements of finished product
Row adjustment.
5. speciality 2 as claimed in claim 1, the preparation method of 6- Diamino-3,5-dinitropyrazine-1-oxides, it is special
Sign is when being diluted crystallization, and crystallization, the concentration of solvent aqueous solution are diluted using the solvent aqueous solution of various concentrations
It is stepped from high to low.
6. the preparation side of the speciality 2,6- diaminourea -3,5- dinitro pyrazine -1- oxides as described in any one of claim 1 ~ 5
Method, it is characterised in that when being diluted crystallization, the dosage of various concentrations solvent aqueous solution is contemplated that residue of mother ANPZO contains
The factor such as amount, disposing mother liquor cost, utilization rate of equipment and installations, product yield is adjusted, the control of crystallization Mother liquor concentration 40%~
60%。
7. the preparation side of the speciality 2,6- diaminourea -3,5- dinitro pyrazine -1- oxides as described in any one of claim 1 ~ 5
Method, it is characterised in that it is fast after first slow when being diluted crystallization, keep stable flow acceleration, by control crystallization time come
Control crystallization rate.
8. the speciality 2 as described in claim 1 or 5, the preparation method of 6- Diamino-3,5-dinitropyrazine-1-oxides, its
It is characterised by when being diluted crystallization, crystallization time is controlled at 2.5 hours~4 hours.
9. the speciality 2 as described in claim 1 or 3, the preparation method of 6- Diamino-3,5-dinitropyrazine-1-oxides, its
It is characterised by when being diluted crystallization, solvent aqueous solution can use last consignment of crystalline mother solution to prepare.
10. the speciality 2 as described in claim 1 or 5, the preparation method of 6- Diamino-3,5-dinitropyrazine-1-oxides,
It is characterized in that step（c）After end, counterweight crystalline product boil wash make product pH value be 6.0~7.5 between.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110981818A (en) * | 2019-12-27 | 2020-04-10 | 山西北化关铝化工有限公司 | Method for reducing loss of 2, 6-diamino-3, 5-dinitropyrazine-1-oxide sulfuric acid recrystallization material |
-
2017
- 2017-09-27 CN CN201710888816.6A patent/CN107602488A/en active Pending
Non-Patent Citations (2)
| Title |
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| ANTHONY J.BELLAMY，等: "Crystal habit of LLM-105", 《NEW TRENDS IN RESEARCH OF ENERGETIC MATERIALS, PROCEEDINGS OF THE SEMINAR, 12TH, PARDUBICE, CZECH REPUBLIC》 * |
| 徐容，等: "重结晶方法对2,6-二氨基-3,5-二硝基吡嗪-1-氧化物晶体特性及性能影响", 《兵工学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110981818A (en) * | 2019-12-27 | 2020-04-10 | 山西北化关铝化工有限公司 | Method for reducing loss of 2, 6-diamino-3, 5-dinitropyrazine-1-oxide sulfuric acid recrystallization material |
| CN110981818B (en) * | 2019-12-27 | 2021-10-22 | 山西北化关铝化工有限公司 | Method for reducing loss of 2, 6-diamino-3, 5-dinitropyrazine-1-oxide sulfuric acid recrystallization material |
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