CN104829548A - 5, 5 '-bistetrazole-1, 1'-dioxo hydroxylammonium salt synthetic method - Google Patents
5, 5 '-bistetrazole-1, 1'-dioxo hydroxylammonium salt synthetic method Download PDFInfo
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- CN104829548A CN104829548A CN201510145693.8A CN201510145693A CN104829548A CN 104829548 A CN104829548 A CN 104829548A CN 201510145693 A CN201510145693 A CN 201510145693A CN 104829548 A CN104829548 A CN 104829548A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
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Abstract
The invention relates to a 5, 5 '-bistetrazole-1, 1'-dioxo hydroxylammonium salt synthetic method, and belongs to organic synthesis technical field. According to the method, glyoxal is used as a raw material, and TKX-50 is obtained by changing of intermediate raw materials, a reaction solvent and technological conditions; the second step is direct preparation of diazido glyoxime by use of one pot method, reaction conditions are mild, the intermediate links are reduced, and the product yield is improved. The third step is direct introduction of HCl gas for preparation of BTO without separation of the high sensitivity diazido glyoxime, BTO salt can be obtained by use of an alkaline solution, later period control of TKX-50 purity is facilitated, product quality can be improved, and the whole reaction overall yield is more than 72%. According to the method, a lot of intermediate operation links can be reduced, the product yield is improved, and the method helps to achieve industrial production.
Description
Technical field
The present invention relates to a kind of 5, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt (TKX-50), belongs to technical field of organic synthesis.
Background technology
5,5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt (TKX-50) is the densification compound of a kind of novel high-energy synthesized by the people such as NikoFischer of Univ Munich Germany in 2012, and its density is 1.918g/cm
3, theoretical quick-fried scooter 9698m/s, impact sensitivity is greater than 20J, friction sensitivity is greater than 120N, and has higher nitrogen content, positive Enthalpies of Formation, to heat and mechanical effect insensitiveness, and not halogen-containing, be a kind of high-energy, low sensitivity, economy, green, the energy-containing compound that over-all properties is splendid.Fabulous application prospect is had in pyrotechnic composition and propelling agent field tool.At present, the TKX-50 synthesis route of bibliographical information is optimized not, and raw material availability is low, and reaction process is complicated.In view of the broad prospect of application of TKX-50 and the complicacy of existing synthetic method, be necessary to improve original synthesis technique, to improve the efficiency of suitability for industrialized production.
Summary of the invention
The object of the invention is to solve the problems of the technologies described above, there is provided a kind of 5, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt (TKX-50), the method has reaction conditions gentleness, operation link is simple, yield is higher, the feature of environmental protection.
The object of the invention is to be achieved through the following technical solutions.
A kind of 5, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt (TKX-50), concrete steps are as follows:
Under step one, room temperature, basic solution is cooled to less than 0 DEG C in ice bath, then adds oxammonium hydrochloride in batches, more slowly drip oxalic dialdehyde the aqueous solution; Oxalic dialdehyde with oxammonium hydrochloride mol ratio be 1:2 ~ 1:3, whole reaction control temperature lower than 10 DEG C, dropwise question response steadily drop back deicing bath slowly rise to room temperature.Filtration, cold water washing, to dry, obtain glyoxime.
Under step 2, room temperature, the glyoxime of step one gained is added dimethyl formamide (DMF), be slowly stirred to glyoxime and dissolve completely, be cooled to after below 0 DEG C and add halogenating agent; The mol ratio of halogenating agent and glyoxime is 2:1 ~ 2.5:1; At 0-10 DEG C, NaN is added after mixing
3, react at least 1 hour, obtain two nitrine glyoximes.
Step 3, by the solution warms to 60 DEG C of two nitrine glyoximes of step 2 gained, then directly pass into excessive sour gas, after 1 hour, stop ventilation.Then add basic solution wherein, adjust ph, to weakly alkaline, obtains 5,5 '-bistetrazole-1,1 '-dioxy (BTO) metal salt precipitate; Filtering-depositing, frozen water wash, it is soluble in water then will to precipitate, and treat that solution is clarified, drip excessive saturated hydrochloric acid aqueous hydroxylamine, obtain TKX-50 precipitation.
Described basic solution comprises LiOH, NaOH, KOH, Mg (OH)
2, Ba (OH)
2, the pH value of adjustment is to 7-13.
Described in step 2, halogenating agent comprises: N-N-halosuccinimides, NaClO, thionyl chloride.
The sour gas that step 3 passes into is HCl gas, acetic acid gas.
The temperature that step 3 passes into gas is 10-80 DEG C, and holding temperature is 10-80 DEG C, and soaking time is 1-12 hour.
Temperature water-soluble for BTO metal-salt is 40-80 DEG C by step 3, and water consumption is BTO salt: water=1:15-40 (mass ratio).
Beneficial effect
1, of the present invention a kind of 5, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt, synthesis dichloroglyoxime uses chlorine as raw material, and whole technique toxicity is large, and gas liquid reaction weak effect, yield is low.The present invention uses N-N-halosuccinimides as chloro agent, and DMF is solvent, has reaction conditions gentleness, environmental protection, has higher product yield.
2, of the present invention a kind of 5, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt, synthesizes two nitrine glyoximes, precursor dichloroglyoxime need be separated, purify, dry.The present invention is then " one kettle way " directly synthesis two nitrine glyoximes, decreases intermediary operation link, greatly reduces costs, be more conducive to suitability for industrialized production.
3, of the present invention a kind of 5, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt, two nitrine glyoximes add in ether by synthesis TKX-50, pass into hydrogenchloride, filter after spending the night.Reaction times is longer, and reaction end should not judge.The present invention does not need two nitrine glyoximes to be separated from solution, directly carries out next step reaction and can improve temperature of reaction.There is reaction times short, feature more safely and efficiently.
4, of the present invention a kind of 5, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt, target product TKX-50, total yield more than 72%, exceeds more than the twice of prior art productive rate, W-response mild condition, can operate, repeatable better, be easy to industry's enlarging production.
Embodiment
Embodiment 1
Of the present invention a kind of 5, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt, concrete steps are as follows:
1) 70g NaOH is dissolved in 150mL water, adds 139g oxammonium hydrochloride at 0 DEG C, drips 128g containing the glyoxal solution of 40%, react the water-bath of 20min recession deicing, overnight at room temperature reaction after stirring and dissolving.After filtration, washing, dry 75.2g glyoxime, productive rate 86%, fusing point 175-176 DEG C.
2) by step 1) the 50g glyoxime that obtains joins in the container that 500mL DMF solvent is housed, and adds 150g N-chlorosuccinimide at 0 DEG C under not stopping agitation condition in batches, reinforced completely removes ice-water bath, slowly rises to room temperature reaction 1h.And then container is put into frozen water, at 0 DEG C, slowly add 74g sodiumazide, reaction 3h, obtains 87.8g bis-nitrine glyoxime.Productive rate 91%, fusing point: 182-184 DEG C.
3) by step 2) the two nitrine glyoxime solution that obtain, HCl gas is directly passed under 60 DEG C of conditions, 1 as a child stopped ventilation, 8h is incubated at 50 DEG C, then revolve and boil off except most of HCl, add saturated NaOH solution wherein, then filtering-depositing, cold water washing, the BTO sodium salt obtained is dissolved in the hot water of 60 DEG C, more slowly instills saturated hydrochloric acid aqueous hydroxylamine, obtain TKX-50 and precipitate 115.6g, count (all counting from glyoxime below) from glyoxime, yield 87%.
Embodiment 2
Of the present invention a kind of 5, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt, concrete steps are as follows:
1) 80g KOH is dissolved in 150mL water, adds 139g oxammonium hydrochloride at 0 DEG C, drips 128g containing the glyoxal solution of 40%, react the water-bath of 20min recession deicing, overnight at room temperature reaction after stirring and dissolving.After filtration, washing, dry 74.3g glyoxime, productive rate 85%, fusing point 175-177 DEG C.
2) by step 1) the 50g glyoxime that obtains joins in the container that 500mL DMF solvent is housed, and adds 202g N-bromo-succinimide at 0 DEG C under not stopping agitation condition in batches, reinforced completely removes ice-water bath, slowly rises to room temperature reaction 1h.And then container is put into frozen water, at 0 DEG C, slowly add 74g sodiumazide, reaction 3h, obtains 83.9g bis-nitrine glyoxime.Productive rate 87%, fusing point: 182-183 DEG C.
3) by step 2) the two nitrine glyoxime solution that obtain, under 60 DEG C of conditions, directly pass into HCl gas, 1 as a child stopped ventilation, at 50 DEG C, be incubated 8h, then revolve and boil off except most of HCl, add saturated KOH solution wherein, then filtering-depositing, cold water washing, the BTO sylvite obtained is dissolved in the hot water of 60 DEG C, slowly instill saturated hydrochloric acid aqueous hydroxylamine again, obtain TKX-50 and precipitate 109g, yield 82%.
Embodiment 3
Of the present invention a kind of 5, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt, concrete steps are as follows:
1) 150g Ba (OH)
2be dissolved in 150mL water, at 0 DEG C, add 139g oxammonium hydrochloride, drip 152g after stirring and dissolving containing the glyoxal solution of 40%, react the water-bath of 20min recession deicing, overnight at room temperature reaction.After filtration, washing, dry 69.9g glyoxime, productive rate 80%, fusing point 175-177 DEG C.
2) by step 1) the 50g glyoxime that obtains joins in the container that 500mL DMF solvent is housed, and adds the NaClO aqueous solution had containing 73.8g at 0 DEG C under not stopping agitation condition in batches, reinforced completely removes ice-water bath, slowly rises to room temperature reaction 1h.And then container is put into frozen water, at 0 DEG C, slowly add 74g sodiumazide, reaction 3h, obtains 64.2g bis-nitrine glyoxime.Productive rate 65%, fusing point: 182-185 DEG C.
3) by step 2) the two nitrine glyoxime solution that obtain, under 60 DEG C of conditions, directly pass into HCl gas, 1 as a child stopped ventilation, was incubated 8h, then revolved and boil off except most of HCl, add saturated Ba (OH) wherein at 50 DEG C
2solution, then filtering-depositing, cold water washing, is dissolved in the BTO barium salt obtained in the hot water of 60 DEG C, more slowly instills saturated hydrochloric acid aqueous hydroxylamine, obtains TKX-50 and precipitates 82.4g, yield 62%.
Embodiment 4
Of the present invention a kind of 5, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt, concrete steps are as follows:
1) 35g LiOH is dissolved in 150mL water, adds 139g oxammonium hydrochloride at 0 DEG C, drips 128g containing the glyoxal solution of 40%, react the water-bath of 20min recession deicing, overnight at room temperature reaction after stirring and dissolving.After filtration, washing, dry 72.6g glyoxime, productive rate 83%, fusing point 175-176 DEG C.
2) by step 1) the 50g glyoxime that obtains joins in the container that 500mL DMF solvent is housed, and in batches adds 67.6g thionyl chloride under not stopping agitation condition at 0 DEG C, reinforced completely removes ice-water bath, slowly rises to room temperature reaction 1h.And then container is put into frozen water, at 0 DEG C, slowly add 74g sodiumazide, reaction 3h, obtains 70.1g bis-nitrine glyoxime.Productive rate 71%, fusing point: 182-184 DEG C.
3) by step 2) the two nitrine glyoxime solution that obtain, acetic acid is added under 60 DEG C of conditions, 8h is incubated at 50 DEG C, then white BTO sodium salt precipitation is obtained after wherein adding saturated LiOH solution, filter and use cold water washing, the BTO lithium salts obtained is dissolved in the hot water of 60 DEG C, more slowly instilling saturated hydrochloric acid aqueous hydroxylamine, obtain TKX-50 and precipitate 54.5g, yield 35%.
Embodiment 5
With case study on implementation 1, the difference is that step 3) temperature that passes into HCl gas is 10 DEG C, obtain 99.71g TKX-50, yield is 75%; The temperature passing into HCl gas is 80 DEG C, and obtaining 98.38g TKX-50 yield is 74%; The temperature passing into HCl gas is 50 DEG C, obtains 114.3g TKX-50, and yield is 86%.
Embodiment 6
With case study on implementation 1, the difference is that step 3) to pass into holding temperature after HCl gas be 10 DEG C, obtain 95.7g TKX-50, yield is 72%; Holding temperature is 80 DEG C, obtains 109g TKX-50, and yield is 82%; Holding temperature is 50 DEG C, obtains 113g TKX-50, and yield is 85%.
Embodiment 7
With case study on implementation 1, the difference is that step 3) soaking time is 1h, obtain 59.8g TKX-50, yield is 45%; Be incubated 12 hours, obtain 115.7g TKX-50, yield is 87%; Be incubated 6 hours, obtain 111.7g TKX-50, yield is 84%.
Embodiment 8
With case study on implementation 1, the difference is that step 3) solution pH value is adjusted to 7, obtain 75.8g TKX-50, yield is 57%; PH value is adjusted to 13, and the yield obtaining 114.4g TKX-50 is 86%; PH value is adjusted to 10, obtains 115.7g TKX-50, and yield is 87%.
Embodiment 9
With case study on implementation 1, the difference is that step 3) BTO sodium salt is dissolved in 40 DEG C of hot water, BTO sodium salt: the consumption of water is 1:40 (mass ratio), obtains 107.7g TKX-50, yield 81%; Be dissolved in 60 DEG C of hot water, BTO sodium salt: the consumption of water is 1:25 (mass ratio), obtains 115.7g TKX-50, and yield is 87%.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to technical characteristic of the present invention.Every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all still belong in the scope of technical scheme of the present invention.
Claims (6)
1. one kind 5, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt, is characterized in that: concrete steps are as follows:
Under step one, room temperature, basic solution is cooled to less than 0 DEG C in ice bath, then adds oxammonium hydrochloride in batches, more slowly drip oxalic dialdehyde the aqueous solution; Oxalic dialdehyde with oxammonium hydrochloride mol ratio be 1:2 ~ 1:3, whole reaction control temperature lower than 10 DEG C, dropwise question response steadily drop back deicing bath slowly rise to room temperature; Filtration, cold water washing, to dry, obtain glyoxime;
Under step 2, room temperature, the glyoxime of step one gained is added dimethyl formamide (DMF), be slowly stirred to glyoxime and dissolve completely, be cooled to after below 0 DEG C and add halogenating agent; The mol ratio of halogenating agent and glyoxime is 2:1 ~ 2.5:1; At 0-10 DEG C, NaN is added after mixing
3, react at least 1 hour, obtain two nitrine glyoximes;
Step 3, by the solution warms to 60 DEG C of two nitrine glyoximes of step 2 gained, then directly pass into excessive sour gas, after 1 hour, stop ventilation; Then add basic solution wherein, adjust ph, to weakly alkaline, obtains 5,5 '-bistetrazole-1,1 '-dioxy (BTO) metal salt precipitate; Filtering-depositing, frozen water wash, it is soluble in water then will to precipitate, and treat that solution is clarified, drip excessive saturated hydrochloric acid aqueous hydroxylamine, obtain TKX-50 precipitation.
2. one 5 as claimed in claim 1, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt, is characterized in that: described basic solution comprises LiOH, NaOH, KOH, Mg (OH)
2, Ba (OH)
2, the pH value of adjustment is to 7-13.
3. one 5 as claimed in claim 1, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt, is characterized in that: described in step 2, halogenating agent comprises: N-N-halosuccinimides, NaClO, thionyl chloride.
4. one 5 as claimed in claim 1, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt, is characterized in that: the sour gas that step 3 passes into is HCl gas, acetic acid gas; The temperature passing into gas is 10-80 DEG C.
5. the one 5 as described in claim 1 or 4, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt, is characterized in that: can also be incubated after step 3 passes into sour gas, and holding temperature is 10-80 DEG C, and soaking time is 1-12 hour.
6. one 5 as claimed in claim 1, the synthetic method of 5 '-bistetrazole-1,1 '-dioxy hydroxylammonium salt, is characterized in that: temperature water-soluble for BTO metal-salt is the mass ratio of 40-80 DEG C, BTO salt and water by step 3 is BTO salt: water=1:15-40.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020040448A1 (en) * | 2018-08-21 | 2020-02-27 | 국방과학연구소 | Method for synthesis of tkx-50 using insensitive intermediate |
| KR20200021909A (en) * | 2018-08-21 | 2020-03-02 | 국방과학연구소 | Synthesis of tkx-50 using insensitive intermediate |
| KR20200021908A (en) * | 2018-08-21 | 2020-03-02 | 국방과학연구소 | Synthesis of tkx-50 using insensitive intermediate |
| KR102102357B1 (en) * | 2019-10-04 | 2020-04-20 | 국방과학연구소 | Synthesis of tkx-50 using protected diazidoglyoxime |
| US11161795B2 (en) | 2018-07-31 | 2021-11-02 | National Chung-Shan Institute Of Science And Technology | Method for preparation of insensitive high explosive |
| KR102459368B1 (en) * | 2022-06-07 | 2022-10-26 | 국방과학연구소 | Method for preparing dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate, thomas klapotke explosive - 50 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0636605A1 (en) * | 1993-07-27 | 1995-02-01 | Junsei Chemical Co., Ltd. | Production method of organic solvent solution of dichloroglyoxime |
| JPH11236362A (en) * | 1998-02-23 | 1999-08-31 | Katayama Chem Works Co Ltd | Production of dichloroglyoxime |
| JP2003012628A (en) * | 2001-07-06 | 2003-01-15 | Katayama Chem Works Co Ltd | Method for producing glyoxime and dichloroglyoxime |
| CN103524444A (en) * | 2013-09-27 | 2014-01-22 | 北京理工大学 | Synthetic method of 5, 5'-bistetrazole-1, 1'-dioxo hydroxyl ammonium salt (TKX-50) |
| US20140171657A1 (en) * | 2011-08-19 | 2014-06-19 | Thomas M. Klapötke | Energetic active composition comprising a dihydroxylammonium salt or diammonium salt of a bistetrazolediol |
| CN104151195A (en) * | 2014-07-23 | 2014-11-19 | 北京理工大学 | Synthesis method of diazidoglyoxime by one-pot process |
| CN104277007A (en) * | 2013-07-10 | 2015-01-14 | 湖北航天化学技术研究所 | Method of synthesizing 5,5'-bistetrazole-1,1'-dioxodihydroxy ammonium salt |
-
2015
- 2015-03-30 CN CN201510145693.8A patent/CN104829548A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0636605A1 (en) * | 1993-07-27 | 1995-02-01 | Junsei Chemical Co., Ltd. | Production method of organic solvent solution of dichloroglyoxime |
| JPH11236362A (en) * | 1998-02-23 | 1999-08-31 | Katayama Chem Works Co Ltd | Production of dichloroglyoxime |
| JP2003012628A (en) * | 2001-07-06 | 2003-01-15 | Katayama Chem Works Co Ltd | Method for producing glyoxime and dichloroglyoxime |
| US20140171657A1 (en) * | 2011-08-19 | 2014-06-19 | Thomas M. Klapötke | Energetic active composition comprising a dihydroxylammonium salt or diammonium salt of a bistetrazolediol |
| CN104277007A (en) * | 2013-07-10 | 2015-01-14 | 湖北航天化学技术研究所 | Method of synthesizing 5,5'-bistetrazole-1,1'-dioxodihydroxy ammonium salt |
| CN103524444A (en) * | 2013-09-27 | 2014-01-22 | 北京理工大学 | Synthetic method of 5, 5'-bistetrazole-1, 1'-dioxo hydroxyl ammonium salt (TKX-50) |
| CN104151195A (en) * | 2014-07-23 | 2014-11-19 | 北京理工大学 | Synthesis method of diazidoglyoxime by one-pot process |
Non-Patent Citations (3)
| Title |
|---|
| PHILLIP L. VAN DER PEET，等: "A Click Chemistry Approach to 5,5′-Disubstituted-3,3′-Bisisoxazoles from Dichloroglyoxime and Alkynes: Luminescent Organometallic Iridium and Rhenium Bisisoxazole Complexes", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
| 王小军，等: "二叠氮基乙二肟合成及表征", 《含能材料》 * |
| 王建龙，等: "N , N′-双(间氯苯基)-3 ,4-二氨基呋咱的合成", 《含能材料》 * |
Cited By (12)
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|---|---|---|---|---|
| US11161795B2 (en) | 2018-07-31 | 2021-11-02 | National Chung-Shan Institute Of Science And Technology | Method for preparation of insensitive high explosive |
| WO2020040448A1 (en) * | 2018-08-21 | 2020-02-27 | 국방과학연구소 | Method for synthesis of tkx-50 using insensitive intermediate |
| KR20200021909A (en) * | 2018-08-21 | 2020-03-02 | 국방과학연구소 | Synthesis of tkx-50 using insensitive intermediate |
| KR20200021710A (en) * | 2018-08-21 | 2020-03-02 | 국방과학연구소 | Synthesis of tkx-50 using insensitive intermediate |
| KR20200021908A (en) * | 2018-08-21 | 2020-03-02 | 국방과학연구소 | Synthesis of tkx-50 using insensitive intermediate |
| KR102128565B1 (en) | 2018-08-21 | 2020-06-30 | 국방과학연구소 | Synthesis of tkx-50 using insensitive intermediate |
| KR102331641B1 (en) | 2018-08-21 | 2021-11-30 | 국방과학연구소 | Synthesis of thp-dag intermediate |
| KR102331642B1 (en) | 2018-08-21 | 2021-11-30 | 국방과학연구소 | Synthesis of tkx-50 using thp-dag |
| US11434209B2 (en) | 2018-08-21 | 2022-09-06 | Agency For Defense Development | Method for synthesis of TKX-50 using insensitive intermediate |
| KR102102357B1 (en) * | 2019-10-04 | 2020-04-20 | 국방과학연구소 | Synthesis of tkx-50 using protected diazidoglyoxime |
| KR102459368B1 (en) * | 2022-06-07 | 2022-10-26 | 국방과학연구소 | Method for preparing dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate, thomas klapotke explosive - 50 |
| WO2023239104A1 (en) * | 2022-06-07 | 2023-12-14 | 국방과학연구소 | Method for preparing dihydroxyammonium 5,5'-bistetrazole-1,1'-diolate |
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Application publication date: 20150812 |