CN103204854A - Tetranitroglycoluril preparation method - Google Patents
Tetranitroglycoluril preparation method Download PDFInfo
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- CN103204854A CN103204854A CN2012105475385A CN201210547538A CN103204854A CN 103204854 A CN103204854 A CN 103204854A CN 2012105475385 A CN2012105475385 A CN 2012105475385A CN 201210547538 A CN201210547538 A CN 201210547538A CN 103204854 A CN103204854 A CN 103204854A
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- glycoluril
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- nitrosonitric acid
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Abstract
The invention discloses a tetranitroglycoluril preparation method. The method comprises the following steps: dissolving glycoluril in fuming nitric acid at 0-10DEG C to obtain a glycoluril-fuming nitric acid solution, adding the glycoluril-fuming nitric acid solution to a ZnCl2 dissolved acetic anhydride solution at 0-5DEG C, and carrying out a nitrating reaction of the obtained mixed solution at 0-5DEG C for 4-5h to obtain a white product tetranitroglycoluril, wherein the weight ratio of tetranitroglycoluril to ZnCl2 is 20:1-10:1, and the feeding weight ratio of glycoluril to fuming nitric acid is 1:40-1:120. The method which adopts an acetic acid catalyst system is simple and safe to operate, has a good process reappearance, and allows the stable white solid to be obtained.
Description
Technical field
The present invention relates to a kind of synthetic method that contains energy explosive tetranitro glycoluril, this material has thermostability and higher explosion velocity preferably, can be used as high energy component or the synthetic intermediate of these high energy components of high explosive, propelling agent and pyrotechnic composition.
Background technology
The tetranitro glycoluril has thermostability preferably, generally at 100 ℃ (in air) 24 hours weightlessness＜1%, under the situation of low humidity, tetranitro glycoluril (through 80 ℃ of vacuum heating treatment some hours) normal temperature is placed in open containers and was not changed in 1 month, store (10*10 millimeter powder column) 16 months losss of weight 0.5%, powder column outward appearance no change in the airtight Glass Containers.20 ℃, density is 1.98g/cm
3, being higher than octogen and hexogen, theoretical explosion velocity is very high, is at least 9100m/s, might substitute hexogen and octogen as explosive.
The hydrolysis of tetranitro glycoluril can obtain sodium salt, sylvite, lithium salts etc.Tetranitro amine tetra-na salt is a kind of promising new high-density, high-power and stable explosive.The Theoretical Calculation detonation parameter is 42.7GPa, and explosion velocity is 10.9km/s, and detonation energy reaches 7081kJ/mol, be known contain can material in one of the highest compound of energy.Because it has positive oxygen balance and gratifying machine security performance, thereby can be used as the solid rocket propellant that high energy oxidizer is used for the advanced person.
Known patent US4487938 has introduced the synthetic method of tetranitro glycoluril, a kind of is indirect nitrofication process, namely be that the raw material nitric acid nitrating is the dinitrobenzene glycoluril with the glycoluril, then the dinitrobenzene glycoluril separated purification, carry out the nitrated tetranitro glycoluril that obtains of second step with nitrosonitric acid.Another kind is direct nitrofication process, i.e. glycoluril direct nitrated final product that obtains in nitrosonitric acid.Used nitrosonitric acid is the miscellany of nitric acid and nitrogen pentoxide in the patent, and nitrogen pentoxide content is at 5-50%, and is not moisture.
" war industry's journal " introduced in interim " study on the synthesis of tetranitro glycoluril and hydrolysate thereof " literary composition in glycoluril-salpeter solution and dripped the method that aceticanhydride synthesizes the tetranitro glycoluril, 8 hours reaction times in 1980 the 3rd.
Summary of the invention
The objective of the invention is to overcome the preparation method that the deficiencies in the prior art provide a kind of tetranitro glycoluril, this method safety simple to operate, technology favorable reproducibility also obtain stable white solid.
Technical solution of the present invention is (except explanation was arranged, the ratio that adopts among the present invention was weight proportion):
Glycoluril is dissolved in nitrosonitric acid, be added under 0-5 ℃ and be dissolved with ZnCl
2Solution of acetic anhydride in, the nitration reaction by mixed solution obtains white products tetranitro glycoluril.
Glycoluril of the present invention: zinc chloride weight ratio=20:1-10:1, weight ratio=the 1:40-1:120 that feeds intake of glycoluril and nitrosonitric acid, glycoluril dissolves in nitrosonitric acid, and its solvent temperature is 0-10 ℃ and gets glycoluril-nitrosonitric acid solution that glycoluril-nitrosonitric acid solution is added at 0-5 ℃ and is dissolved with ZnCl
2Solution of acetic anhydride in carry out nitration reaction, the nitration reaction temperature is 0-5 ℃, the time is 4-5 hour.
ZnCl of the present invention
2Solution of acetic anhydride be formulated as zinc chloride: diacetyl oxide weight ratio=1:300-1:100.
Nitrosonitric acid consumption of the present invention is its 30 times of theoretical consumption weight, and diacetyl oxide is half of nitric acid dosage (volume).
Temperature control in the present invention's reaction is all cooled off with ice bath.
The present invention joins glycoluril among the reaction flask A that nitrosonitric acid is housed fast, and solvent temperature is cooled to 0-10 ℃ in the reaction flask A, is stirred to glycoluril and dissolves fully, pours in the constant pressure funnel its solution stand-by; Aceticanhydride is joined in another reaction flask B that zinc chloride is housed, when the solution among the reaction flask B is cooled to 0-10 ℃, drip glycoluril-nitrosonitric acid solution in reaction flask B, and control makes temperature of reaction be lower than 5 ℃, glycoluril-nitrosonitric acid solution dropwises back 10min and begins to have precipitation to produce, precipitation capacity constantly increased with the reaction times, react 4-5 hour precipitation fully, miscellany in the bottle is poured out filtration, wash until neutrality with anhydrous methylene chloride, dry under 65 ℃ then, obtain white solid.
The present invention compared with prior art beneficial effect is.
(1) the present invention has used the nitrated system different with patent US4487938, this nitrated system safe in experimentation, and experimental implementation is simple.
(2) compare with article " study on the synthesis of tetranitro glycoluril and hydrolysate thereof ", the present invention has used zinc chloride as catalyzer, has shortened the reaction times, has improved product yield.
(3) mode that has adopted glycoluril-salpeter solution to drip in the aceticanhydride solution, compare with dropping mode in the prior art " study on the synthesis of tetranitro glycoluril and hydrolysate thereof ", temperature of reaction is easier to control, the security that has improved experimental implementation in the dropping process.
Embodiment
The present invention is described in detail below in conjunction with embodiment.
Embodiment 1
(1) the 120ml nitrosonitric acid is placed stirring-head is housed, temperature is taken into account in the four-hole boiling flask 1 of reflux condensing tube, and with ice bath solution in the flask is chilled to 0-5 ℃;
(2) join in the reaction flask 1 the little branch of 5g glycoluril is a spot of, and solution temperature in the reaction flask 1 is remained on 0-10 ℃;
(3) the 0.25g zinc chloride is joined stirring-head is housed, temperature is taken into account in the four-hole boiling flask 2 of reflux condensing tube;
(4) the 60ml aceticanhydride is joined in the reaction flask 2, and solution in the reaction flask 2 is cooled to 0-5 ℃;
(5) will dissolve good glycoluril-nitrosonitric acid solution is poured in the constant pressure funnel;
(6) when solution temperature is lower than 5 ℃ in the reaction flask 2, in reaction flask 2, drip glycoluril-nitrosonitric acid solution, the temperature of solution remains on 0-5 ℃ in the reaction flask 2;
(7) 10min began to have precipitation to produce after glycoluril-nitrosonitric acid solution dropwised, and precipitation capacity constantly increased with the reaction times, in the nitration reaction process temperature of reaction was remained on 0-5 ℃, the complete stopped reaction of 5h postprecipitation;
(8) miscellany in the bottle is poured out filtration, until neutrality, dry under 65 ℃ then with the anhydrous methylene chloride flushing, obtain white solid 8.7g, transformation efficiency 80%.
Product is white powder, density 1.98g/cm
3
Embodiment 2
(1) the 120ml nitrosonitric acid is placed stirring-head is housed, temperature is taken into account in the four-hole boiling flask 1 of reflux condensing tube, and with ice bath solution in the flask is chilled to 0-5 ℃;
(2) join in the reaction flask 1 the little branch of 5g glycoluril is a spot of, and solution temperature in the reaction flask 1 is remained on 0-10 ℃;
(3) the 0.35g zinc chloride is joined stirring-head is housed, temperature is taken into account in the four-hole boiling flask 2 of reflux condensing tube;
(4) the 60ml aceticanhydride is joined in the reaction flask 2, and solution in the reaction flask 2 is cooled to 0-5 ℃;
(5) will dissolve good glycoluril-nitrosonitric acid solution is poured in the constant pressure funnel;
(6) when solution temperature is lower than 5 ℃ in the reaction flask 2, in reaction flask 2, drip glycoluril-nitrosonitric acid solution, the temperature of solution remains on 0-5 ℃ in the reaction flask 2;
(7) 10min began to have precipitation to produce after glycoluril-nitrosonitric acid solution dropwised, and precipitation capacity constantly increased with the reaction times, in the nitration reaction process temperature of reaction was remained on 0-5 ℃, the complete stopped reaction of 4.5h postprecipitation;
(8) miscellany in the bottle is poured out filtration, until neutrality, dry under 65 ℃ then with the anhydrous methylene chloride flushing, obtain white solid 8.9g, transformation efficiency 82%.
Product is white powder, density 2.001g/cm
3
Embodiment 3
(1) the 120ml nitrosonitric acid is placed stirring-head is housed, temperature is taken into account in the four-hole boiling flask 1 of reflux condensing tube, and with ice bath solution in the flask is chilled to 0-5 ℃;
(2) join in the reaction flask 1 the little branch of 5g glycoluril is a spot of, and solution temperature in the reaction flask 1 is remained on 0-10 ℃;
(3) the 0.5g zinc chloride is joined stirring-head is housed, temperature is taken into account in the four-hole boiling flask 2 of reflux condensing tube;
(4) the 60ml aceticanhydride is joined in the reaction flask 2, and solution in the reaction flask 2 is cooled to 0-5 ℃;
(5) will dissolve good glycoluril-nitrosonitric acid solution is poured in the constant pressure funnel;
(6) when solution temperature is lower than 5 ℃ in the reaction flask 2, in reaction flask 2, drip glycoluril-nitrosonitric acid solution, the temperature of solution remains on 0-5 ℃ in the reaction flask 2;
(7) 10min began to have precipitation to produce after glycoluril-nitrosonitric acid solution dropwised, and precipitation capacity constantly increased with the reaction times, in the nitration reaction process temperature of reaction was remained on 0-5 ℃, and the 4h postprecipitation is complete, stopped reaction;
(8) miscellany in the bottle is poured out filtration, until neutrality, dry under 65 ℃ then with the anhydrous methylene chloride flushing, obtain white solid 9.1g, transformation efficiency 85%.
Product is white powder, density 2.006g/cm
3
Embodiment 4
(1) the 120ml nitrosonitric acid is placed stirring-head is housed, temperature is taken into account in the four-hole boiling flask 1 of reflux condensing tube, and with ice bath solution in the flask is chilled to 0-5 ℃;
(2) join in the reaction flask 1 the little branch of 5g glycoluril is a spot of, and solution temperature in the reaction flask 1 is remained on 0-10 ℃;
(3) the 60ml aceticanhydride is joined another is equipped with stirring-head, temperature is taken into account in the four-hole boiling flask 2 of reflux condensing tube, and solution in the reaction flask 2 is cooled to 0-5 ℃;
(4) will dissolve good glycoluril-nitrosonitric acid solution is poured in the constant pressure funnel;
(5) when solution temperature is lower than 5 ℃ in the reaction flask 2, in reaction flask 2, drip glycoluril-nitrosonitric acid solution, the temperature of solution remains on 0-5 ℃ in the reaction flask 2;
(6) in reaction flask, add the 0.5g zinc chloride after glycoluril-nitrosonitric acid solution dropwises;
(7) begin to have precipitation to produce behind the reaction 30min, precipitation capacity constantly increased with the reaction times, in the nitration reaction process temperature of reaction was remained on 0-5 ℃, and the 4.5h postprecipitation is complete, stopped reaction;
(8) miscellany in the bottle is poured out filtration, until neutrality, dry under 65 ℃ then with the anhydrous methylene chloride flushing, obtain white solid 8.9g, transformation efficiency 82%.
Product is white powder, density 2.002g/cm
3
Claims (6)
1. the preparation method of a tetranitro glycoluril is characterized in that: glycoluril is dissolved in nitrosonitric acid, be added under 0-5 ℃ and be dissolved with ZnCl
2Solution of acetic anhydride in, the nitration reaction by mixed solution obtains white products tetranitro glycoluril.
2. according to the preparation method of the described tetranitro glycoluril of claim 1, it is characterized in that: glycoluril: zinc chloride weight ratio=20:1-10:1, weight ratio=the 1:40-1:120 that feeds intake of glycoluril and nitrosonitric acid, glycoluril dissolves in nitrosonitric acid, its solvent temperature is 0-10 ℃ and gets glycoluril-nitrosonitric acid solution that glycoluril-nitrosonitric acid solution is added at 0-5 ℃ and is dissolved with ZnCl
2Solution of acetic anhydride in carry out nitration reaction, the nitration reaction temperature is 0-5 ℃, the time is 4-5 hour.
3. according to the preparation method of claim 1 or 2 described tetranitro glycolurils, it is characterized in that: described ZnCl
2Solution of acetic anhydride be formulated as zinc chloride: diacetyl oxide weight ratio=1:300-1:100.
4. according to the preparation method of claim 1 or 2 described tetranitro glycolurils, it is characterized in that: described diacetyl oxide is half of nitrosonitric acid volumetric usage.
5. according to the preparation method of claim 1 or 2 described tetranitro glycolurils, it is characterized in that: the temperature control in the reaction is all cooled off with ice bath.
6. according to the preparation method of claim 1 or 2 described tetranitro glycolurils, it is characterized in that: glycoluril is joined fast among the reaction flask A that nitrosonitric acid is housed, solvent temperature is cooled to 0-10 ℃ in the reaction flask A, is stirred to glycoluril and dissolves fully, pours in the constant pressure funnel its solution stand-by; Aceticanhydride is joined in another reaction flask B that zinc chloride is housed, when the solution among the reaction flask B is cooled to 0-10 ℃, in reaction flask B, drip glycoluril-nitrosonitric acid solution, and control makes temperature of reaction be lower than 5 ℃, after glycoluril-nitrosonitric acid solution dropwises, begin to have precipitation to produce, precipitation capacity constantly increased with the reaction times, reacted 4-5 hour precipitation fully, miscellany in the bottle is poured out filtration, until neutrality, dry under 65 ℃ then with the anhydrous methylene chloride flushing, obtain white solid.
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| CN2012105475385A CN103204854A (en) | 2012-12-17 | 2012-12-17 | Tetranitroglycoluril preparation method |
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| CN2012105475385A CN103204854A (en) | 2012-12-17 | 2012-12-17 | Tetranitroglycoluril preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108863839A (en) * | 2018-08-06 | 2018-11-23 | 湖北文理学院 | Alkali metal salt, preparation method and the high energy material of tenitramine base ethane |
| CN115850271A (en) * | 2022-12-15 | 2023-03-28 | 南京理工大学 | Method for preparing tetranitrodiketopiperazine by catalytic nitration of zinc chloride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4487938A (en) * | 1973-07-24 | 1984-12-11 | Societe Nationale Des Poudres Et Explosifs | Tetranitroglycoluril and method of preparation thereof |
| US5336784A (en) * | 1993-06-07 | 1994-08-09 | The Regents Of The University Of California | Synthesis of 1,3,3-trinitroazetidine |
| CN101235035A (en) * | 2008-01-31 | 2008-08-06 | 侯忠德 | Method for preparing tetramethoxymethylglycoluril |
-
2012
- 2012-12-17 CN CN2012105475385A patent/CN103204854A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4487938A (en) * | 1973-07-24 | 1984-12-11 | Societe Nationale Des Poudres Et Explosifs | Tetranitroglycoluril and method of preparation thereof |
| US5336784A (en) * | 1993-06-07 | 1994-08-09 | The Regents Of The University Of California | Synthesis of 1,3,3-trinitroazetidine |
| CN101235035A (en) * | 2008-01-31 | 2008-08-06 | 侯忠德 | Method for preparing tetramethoxymethylglycoluril |
Non-Patent Citations (1)
| Title |
|---|
| 彭忠吉，等: "四硝基甘脲及其水解产物的合成研究", 《兵工学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108863839A (en) * | 2018-08-06 | 2018-11-23 | 湖北文理学院 | Alkali metal salt, preparation method and the high energy material of tenitramine base ethane |
| CN108863839B (en) * | 2018-08-06 | 2021-03-26 | 湖北文理学院 | Alkali metal salt of tetranitraminoethane, preparation method thereof and high-energy material |
| CN115850271A (en) * | 2022-12-15 | 2023-03-28 | 南京理工大学 | Method for preparing tetranitrodiketopiperazine by catalytic nitration of zinc chloride |
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Application publication date: 20130717 |