CN116693464A - Energetic ionic salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole and preparation method thereof - Google Patents
Energetic ionic salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole and preparation method thereof Download PDFInfo
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- NFNKXKGHQWFZNE-UHFFFAOYSA-N 3-hydrazinyl-1h-1,2,4-triazol-5-amine Chemical compound NNC1=NNC(N)=N1 NFNKXKGHQWFZNE-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 150000003839 salts Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- -1 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride Chemical compound 0.000 claims abstract description 84
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000002360 explosive Substances 0.000 claims abstract 2
- 239000003380 propellant Substances 0.000 claims abstract 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 20
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000012954 diazonium Substances 0.000 claims description 13
- 150000001989 diazonium salts Chemical class 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 235000010288 sodium nitrite Nutrition 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 235000011150 stannous chloride Nutrition 0.000 claims description 8
- 239000001119 stannous chloride Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006193 diazotization reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 4
- 229950002929 trinitrophenol Drugs 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 16
- 238000003756 stirring Methods 0.000 abstract description 16
- 238000005474 detonation Methods 0.000 abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 11
- 230000035945 sensitivity Effects 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 7
- 239000000015 trinitrotoluene Substances 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 2
- LZLKDWBQTGTOQY-UHFFFAOYSA-N trinitramide Inorganic materials O=N(=O)N(N(=O)=O)N(=O)=O LZLKDWBQTGTOQY-UHFFFAOYSA-N 0.000 description 2
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 1
- BSNCOPOPGMQUNL-UHFFFAOYSA-N 1-hydroxytetrazole Chemical compound ON1C=NN=N1 BSNCOPOPGMQUNL-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- NDYLCHGXSQOGMS-UHFFFAOYSA-N CL-20 Chemical compound [O-][N+](=O)N1C2N([N+]([O-])=O)C3N([N+](=O)[O-])C2N([N+]([O-])=O)C2N([N+]([O-])=O)C3N([N+]([O-])=O)C21 NDYLCHGXSQOGMS-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- HTQVYCDIDXGOGD-UHFFFAOYSA-N methanol;2,4,6-trinitrophenol Chemical compound OC.OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O HTQVYCDIDXGOGD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- HURPOIVZCDCEEE-UHFFFAOYSA-N n-(2h-tetrazol-5-yl)nitramide Chemical compound [O-][N+](=O)NC=1N=NNN=1 HURPOIVZCDCEEE-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- JDFUJAMTCCQARF-UHFFFAOYSA-N tatb Chemical compound NC1=C([N+]([O-])=O)C(N)=C([N+]([O-])=O)C(N)=C1[N+]([O-])=O JDFUJAMTCCQARF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses an energetic ionic salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole and a preparation method thereof, belonging to the technical field of energetic materials. An energetic ionic salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole, the synthesis steps of which comprise: synthesizing 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride; stirring and reacting 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride with metal salt or alkali and acid in a solvent, filtering, washing and drying to obtain the energetic ionic salt of 3-hydrazino-5-amino-1H-1, 2, 4-triazole. The invention has simple synthetic route and high yield, and the target energetic ion salt is easy to purify and has high purity. The nitrogen-rich energetic ion salt prepared by the invention has excellent detonation performance, the preparation method is simple and feasible, is convenient for industrial safe production, and can be widely applied to the fields of novel high-energy insensitive explosive, low characteristic signals, insensitive propellant and the like.
Description
Technical Field
The invention discloses an energetic ionic salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole and a preparation method thereof, belonging to the technical field of energetic materials.
Background
Conventional energetic compounds such as: TNT, RDX, HMX, TATB, PETN, CL-20, etc., the energy released is mainly derived from the cleavage of the backbone ring, and-NO 2 、-N 3 、-ONO 2 、-NNO 2 The energy release of the isoblast group has irreconcilable contradiction between the energy characteristic and the sensitivity characteristic, the sensitivity is often higher as the energy is higher, and the environmental pollution caused by the gas generated by the explosion is larger. The azole compounds have been widely studied as the core structure of nitrogen-rich materials. According to the number of nitrogen atoms in the structure, the nitrogen content is improved to be beneficial to the increase of detonation performance, but the insensitive requirement cannot be met, so that the pursuit of the balance of high energy and low sensitivity becomes the main trend of the development of energetic materials.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses an energetic ionic salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole and a preparation method thereof, which solve the problem that an energetic material has high detonation performance and can meet the requirements on the insensitivity.
Specifically, the purpose of the invention can be achieved by the following technical scheme:
an inorganic energetic ionic salt of 3-hydrazino-5-amino-1H-1, 2, 4-triazole, which has the structure:
wherein A is - Is perchlorate anions or nitrate anions.
The preparation method of the 3-hydrazino-5-amino-1H-1, 2, 4-triazole inorganic energetic ion salt comprises the following steps:
(1) Under an acidic condition, diazotizing 3, 5-diamino-1, 2,4 triazole and sodium nitrite to generate diazonium salt; stannous chloride reacts with the diazonium salt to prepare 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride;
wherein a is 3, 5-diamino-1, 2, 4-triazole, b is diazonium salt, c is 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride;
(2) Reacting the 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride with silver nitrate or silver perchlorate to prepare 3-hydrazino-5-amino-1H-1, 2, 4-triazole inorganic energetic ion salt,
wherein A is - Is perchlorate anions or nitrate anions.
Further, the concentration of hydrochloric acid in the diazotization reaction is 1 to 20mol/L.
Further, the molar ratio of the 3, 5-diamino-1, 2,4 triazole to the sodium nitrite is 1:0.5-4.0.
Further, the reaction temperature in the step (1) is-20 to 20 ℃.
Further, the molar ratio of the 3, 5-diamino-1, 2,4 triazole to stannous chloride is 1:0.5-2.0.
Further, the molar ratio of the 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride to silver nitrate or silver perchlorate is 1:0.5-2.0.
Further, the reaction system solvent of the step (2) comprises any one or more of water, methanol and ethanol.
Further, the reaction temperature in the step (2) is-20-100 ℃.
An organic energetic ionic salt of 3-hydrazino-5-amino-1H-1, 2, 4-triazole, which has the structure:
wherein A is - Comprises any one of 5-nitryl amino tetrazole anion, 5-nitryl tetrazole anion, 3-nitryl-1, 2, 4-triazole-5-ketone, mononitrophenol anion, dinitrophenol anion, trinitrophenol anion, mononitroresorcinol anion, dinitroresorcinol anion, trinitroresorcinol anion and trinitrophloroglucinol anion.
The preparation method of the 3-hydrazino-5-amino-1H-1, 2, 4-triazole organic energetic ionic salt comprises the following steps:
(1) Under an acidic condition, diazotizing 3, 5-diamino-1, 2,4 triazole and sodium nitrite to generate diazonium salt; stannous chloride reacts with the diazonium salt to prepare 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride;
wherein a is 3, 5-diamino-1, 2, 4-triazole, b is diazonium salt, c is 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride;
(2) Reacting the 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride with lithium hydroxide to prepare 3-hydrazino-5-amino-1H-1, 2, 4-triazole; and then reacting the 3-hydrazino-5-amino-1H-1, 2, 4-triazole with an acidic energetic compound to prepare the 3-hydrazino-5-amino-1H-1, 2, 4-triazole organic energetic ionic salt.
Wherein, acid represents an acidic energetic compound.
Further, the concentration of hydrochloric acid in the diazotization reaction is 1 to 20mol/L.
Further, the molar ratio of the 3, 5-diamino-1, 2,4 triazole to the sodium nitrite is 1:0.5-4.0.
Further, the reaction temperature in the step (1) is-20 ℃.
Further, the molar ratio of the 3, 5-diamino-1, 2,4 triazole to stannous chloride is 1:0.5-2.0.
Further, the reaction temperature in the step (2) is 10-100 ℃.
Further, the molar ratio of the 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride to the lithium hydroxide is 1:2.
Further, the step (2) de reaction system solvent comprises any one or a mixture of more of water, methanol and ethanol.
The invention has the beneficial effects that:
(1) The invention prepares the nitrogen-enriched energetic ion salt by carrying out double decomposition reaction or acid-base neutralization reaction on the 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride and metal salt or acid, and has the advantages of less required instruments and equipment, simple synthetic route, high yield, easy purification of the target energetic ion salt and high purity.
(2) Energetic ionic salts based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole are novel energetic compounds with high energy density, wherein the detonation performance of most energetic ionic salts is equivalent to RDX (cyclotrimethylene trinitro-amine), partial detonation performance is superior to RDX, mechanical sensitivity is lower than RDX, detonation parameters are far higher than TNT (trinitrotoluene), and industrial production and transportation are safe.
Drawings
FIG. 1 is a single crystal plot of 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride of example 1.
FIG. 2 is a single crystal plot of 3-hydrazino-5-amino-1H-1, 2, 4-triazole nitrate in example 1.
FIG. 3 is a single crystal plot of 3-hydrazino-5-amino-1H-1, 2, 4-triazole perchlorate in example 2.
FIG. 4 is a single crystal plot of 3-hydrazino-5-amino-1H-1, 2, 4-triazole 2,4, 6-trinitrophloroglucinol salt of example 5.
FIG. 5 is a single crystal plot of 3-hydrazino-5-amino-1H-1, 2, 4-triazole 5-nitroaminotetrazole salt of example 7.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation route of the energetic ion salt is shown as follows:
specific examples of the present invention are provided below.
Example 1
A preparation method of energetic ion salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole, which comprises the following steps:
step 1: 10g (100.1 mmol) of 3, 5-diamino-1, 2, 4-triazole are weighed into a three-necked round bottom flask, 200ml of 10mol/L hydrochloric acid are added, stirred and dissolved, and the ice bath is cooled to 0 ℃. 7.5g (110 mmol) of sodium nitrite are weighed out and dissolved in 25ml of water. And (3) dropwise adding the sodium nitrite solution into the hydrochloric acid solution of the 3, 5-amino-1, 2,4 triazole under stirring for a period of time not exceeding 1.5h, and carrying out diazotization reaction. The reaction was continued with stirring at 0℃for 1h. 22.6g (100 mmol) of stannous chloride dihydrate was weighed and added to the reaction solution in a period of not less than 0.5h to conduct reduction reaction of diazonium salt. After the addition is finished, stirring and reacting for 1-2 hours, heating to 80 ℃, carrying out hot filtration on the reaction liquid, cooling, precipitating white solid, carrying out suction filtration, washing with absolute ethyl alcohol and absolute methyl alcohol in sequence, and drying a filter cake to obtain white powder of 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride, wherein the yield is 62%, and the crystal structure diagram is shown in figure 1.
3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride:
EA theory: c is 12.84%, H is 4.31%, N is 44.93%; EA experimental value: c is 12.79%, H is 4.38%, and N is 45.01%.
IR(KBr,cm -1 )：υ＝3316,3096,2956,2671,1922,1707,1686,1643,1566,1499,1324,1219,1189,1113,989。
MS(ESI + ):m/z＝115.07[C 2 H 7 N 6 + ]；MS(ESI - ):m/z＝35.00[Cl - ]。
Step 2: 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride (0.374 g,2 mmol) was dissolved in 10mL of water, then an aqueous solution of silver nitrate (0.68 g,4 mmol) was added thereto, stirring was continued for 1 hour at room temperature, the reaction solution was filtered to precipitate AgCl, and the filtrate was dried by spin-drying to give a white powder solid, yield 81% and the crystal structure diagram was shown in FIG. 2.
3-hydrazino-5-amino-1H-1, 2, 4-triazole nitrate:
EA theory: 10.00% C, 3.36% H, 46.66% N; EA experimental value: c10.11%, H3.30%, N46.73%.
IR(KBr,cm -1 )：υ＝3355,3203，1790,1689,1641,1489,1384,1213,1177,1087,1052,836cm -1 。
MS(ESI + ):m/z＝115.07[C 2 H 7 N 6 + ]；MS(ESI - )：m/z＝61.99[NO 3 - ]。
Example 2
A preparation method of energetic ion salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole, which comprises the following steps:
step 1: step 1 as in example 1;
step 2: 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride (0.374 g,2 mmol) was dissolved in 10mL of water, then an aqueous solution of silver perchlorate (0.83 g,4 mmol) was added thereto, stirring was continued for 1 hour at room temperature, the reaction solution was filtered to precipitate AgCl, and the filtrate was dried by spin-drying to give a white powder solid, yield 78%, and the crystal structure diagram was shown in FIG. 3.
3-hydrazino-5-amino-1H-1, 2, 4-triazole perchlorate:
EA theory: c is 7.21%, H is 3.03%, and N is 25.23%; EA experimental value: c7.29%, H2.89%, N25.31%.
IR(KBr,cm -1 )：υ＝3184,3095,2954,2829,2670，1705,1641,1530,1496,1417,1216，1112，1089，1058，989cm -1 。
MS(ESI + )：m/z＝115.07[C 2 H 7 N 6 + ]；MS(ESI - )：m/z＝98.95[ClO 4 - ]。
Example 3
A preparation method of energetic ion salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole, which comprises the following steps:
step 1: step 1 as in example 1;
step 2: 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride (0.374 g,2 mmol) is dissolved in 10mL of water, liOH (0.096 g,4 mmol) is added in batches at room temperature, after stirring and reacting for 15min, the temperature is raised to 45 ℃,4mmol of 2,4, 6-trinitrophenol methanol solution (10 mL) is added, stirring and reacting for 30min, yellow precipitate is separated out, suction filtration is carried out, filter cake is washed with water and dried, and yellow powder solid is obtained, and the yield is 77%.
3-amino-5-hydrazino-1, 2, 4-triazole 2,4, 6-trinophenolate:
EA theory: 27.64% C, 2.65% H, and 27.63% N; EA experimental value: c27.71%, H2.30%, N27.73%.
IR(KBr，cm -1 )：υ＝3363，3232，3083,2748，1702,1634，1563，1480，1427，1328，1275,1231,1164，1087，1022，920cm -1 。
MS(ESI + )：m/z＝114.99[C 2 H 7 N 6 + ]；MS(ESI - )：m/z＝227.99[C 6 H 2 N 3 O 7 - ]。
Example 4
A preparation method of energetic ion salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole, which comprises the following steps:
step 1: step 1 as in example 1;
step 2: 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride (0.374 g,2 mmol) is dissolved in 10mL of water, liOH (0.096 g,4 mmol) is added in batches at room temperature, after stirring and reacting for 15min, the temperature is raised to 45 ℃,4mmol of 2,4, 6-trinitroresorcinol methanol solution (10 mL) is added, stirring and reacting for 30min, yellow precipitate is separated out, suction filtration is carried out, filter cake is washed with water and dried, yellow powder solid is obtained, and the yield is 72%.
3-hydrazino-5-amino-1H-1, 2, 4-triazole 2,4, 6-trinitroresorcinol salt:
EA theory: 27.82% C, 2.00% H, and 27.81% N; EA experimental value: 27.74% C, 2.06% H and 27.90% N.
IR(KBr，cm -1 )：υ＝3421，3226，2919，1693，1642，1517，1479，1414，1336，1241，1103，1047，1009，896cm -1 。
MS(ESI + )：m/z＝114.99[C 2 H 7 N 6 + ]；MS(ESI - )：m/z＝243.89[C 6 H 2 N 3 O 8 - ]。
Example 5
A preparation method of energetic ion salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole, which comprises the following steps:
step 1: step 1 as in example 1;
step 2: 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride (0.374 g,2 mmol) is dissolved in 10mL of water, liOH (0.096 g,4 mmol) is added in batches under the condition of room temperature, after stirring and reacting for 15min, the temperature is raised to 45 ℃,4mmol of 2,4, 6-trinitro-phloroglucinol methanol solution (10 mL) is added, stirring and reacting for 30min, yellow precipitation is carried out, suction filtration is carried out, filter cakes are washed with water and dried, yellow powder solid is obtained, the yield is 71%, and the crystal structure is shown in figure 4.
3-hydrazino-5-amino-1H-1, 2, 4-triazole 2,4, 6-trinitro-phloroglucinol salt:
EA theory: c is 25.61%, H is 2.42%, N is 33.60%; EA experimental value: c25.51%, H2.33%, N33.67%.
IR(KBr，cm -1 )：υ＝3408，3276，3173，2916，1706,1648，1551，1453，1296，1203，1048，1109，903cm -1 。
MS(ESI + )：m/z＝114.99[C 2 H 7 N 6 + ]；MS(ESI - )：m/z＝259.89[C 6 H 2 N 3 O 9 - ]。
Example 6
A preparation method of energetic ion salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole, which comprises the following steps:
step 1: step 1 as in example 1;
step 2: 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride (0.374 g,2 mmol) is dissolved in 10mL of water, liOH (0.096 g,4 mmol) is added in batches under the condition of room temperature, stirring is carried out for 15min, the temperature is raised to 45 ℃, 3-nitro-1, 2, 4-triazole-5-ketone (0.374 g,2 mmol) is added in batches, stirring is carried out for 30min, then rotary evaporation is carried out for concentration until powder is just separated out, then cooling is carried out, suction filtration is carried out, filter cake is dried, and white powder solid is obtained, and the yield is 78%.
3-hydrazino-5-amino-1H-1, 2, 4-triazole 3-nitro-1, 2, 4-triazol-5-one salt:
EA theory: c is 19.68%, H is 3.30%, N is 57.36%; EA experimental value: c19.63%, H3.35%, N57.42%.
IR(KBr，cm -1 )：υ＝3372，3266，3032，2883，2813,2661，1715，1593，1545，1473，1296，1218，1126，1049，950cm -1 。MS(ESI + )：m/z＝114.99[C 2 H 7 N 6 + ]；MS(ESI - )：m/z＝128.89[C 2 HN 4 O 3 - ]。
Example 7
A preparation method of energetic ion salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole, which comprises the following steps:
step 1: step 1 as in example 1;
step 2: 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride (0.374 g,2 mmol) is dissolved in 10mL of water, liOH (0.096 g,4 mmol) is added in batches under the condition of room temperature, stirring is carried out for 15min, the temperature is raised to 45 ℃, 5-nitroaminotetrazole (0.374 g,2 mmol) is added in batches for stirring and reacting for 30min, then the mixture is concentrated by rotary evaporation until powder is separated out, then the mixture is cooled, suction filtration is carried out, a filter cake is dried, white powder solid is obtained, the yield is 79%, and the crystal structure diagram is shown in figure 5.
3-hydrazino-5-amino-1H-1, 2, 4-triazole 5-nitroamino tetrazolium salt:
EA theory: 14.76% C, 3.30% H, 68.84% N; EA experimental value: c is 17.69%, H is 3.36%, and N is 68.94%.
IR(KBr，cm -1 )：υ＝3362，3177，3112，1717，1659，1532，1438，1326，1241，1152，1110，1054,1010，990cm -1 。
MS(ESI + )：m/z＝115.07[C 2 H 7 N 6 + ]；MS(ESI - )：m/z＝129.02[CHN 6 O 2 - ]。
IR in the examples means infrared spectrum, MS means mass spectrum, EA means organic element analysis.
Enthalpy of formation of 3-hydrazino-5-amino-1H-1, 2, 4-triazole energetic ionic salts was calculated based on the method described in literature Lal S, staples R J, shreeve J N M. Design and synthesis of phenylene-bridged isoxazole and tetrazole-1-ol based energetic materials of low sensitivity [ J ]. Dalton Transactions,2023,52 (11): 3449-3457; calculating parameters such as detonation velocity, detonation pressure and the like by adopting an EXPLO5 (V6.04) program; the thermal decomposition temperature of the energetic ionic salt was determined by DSC-TGA simultaneous thermal analyzer from Bruker, germany; the mechanical sensitivity of the hydraulic pump is tested by adopting a drop hammer impact sensitivity tester and a friction sensitivity tester of the Czech OZM company; the structure of the energetic ion salts was characterized by means of an APEX II SmartX-ray single crystal diffractometer, CE-440Elemental Analyzer elemental analyzer, agilent 500-MS mass spectrometer, nicolet fourier transform infrared spectrometer, etc. from Bruker, germany.
The properties of the energetic ionic salts obtained in the examples are shown in Table 1 below.
TABLE 1
The properties of the TNT and RDX known in the prior art are shown in Table 2 below.
TABLE 2
Note that: t (T) d -a thermal decomposition temperature; ρ -density; delta f H-enthalpy of formation; d-detonation velocity; p-detonation pressure; FS-friction feel; IS-crash sensitivity.
As can be seen from comparing table 1 with table 2:
1. the detonation velocity and detonation pressure of the energetic ionic salt are far higher than TNT, and the energetic ionic salt shows high detonation performance;
2. the energetic ion salt has high nitrogen content, impact sensitivity far higher than TNT and RDX, friction feeling better than TNT, mechanical sensitivity with excellent insensitive performance and transportation safety;
3. the invention has simple synthetic route and simple and feasible purification method, and is convenient for industrial production.
The foregoing embodiments have described the technical solutions and advantageous effects of the present invention in detail, and it should be understood that the foregoing embodiments are merely specific examples of the present invention, and are not intended to limit the present invention. Any modifications, additions, and equivalent substitutions made within the principle of the invention should be included in the protection scope of the invention.
Claims (10)
1. An energetic ionic salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole, which is characterized in that the energetic ionic salt is named as an inorganic energetic ionic salt of 3-hydrazino-5-amino-1H-1, 2, 4-triazole, and the structural formula of the inorganic energetic ionic salt is as follows:
wherein A is - Is perchlorate anions or nitrate anions.
2. A process for the preparation of energetic ionic salts based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole, characterized in that it comprises the following steps:
(1) Under an acidic condition, diazotizing 3, 5-diamino-1, 2,4 triazole and sodium nitrite to generate diazonium salt; stannous chloride reacts with the diazonium salt to prepare 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride;
wherein a is 3, 5-diamino-1, 2, 4-triazole, b is diazonium salt, c is 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride;
(2) Reacting the 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride with silver nitrate or silver perchlorate to prepare 3-hydrazino-5-amino-1H-1, 2, 4-triazole inorganic energetic ion salt,
wherein A is - Is perchlorate anions or nitrate anions.
3. The method according to claim 2, wherein the concentration of hydrochloric acid in the diazotization reaction is 1 to 20mol/L; the molar ratio of the 3, 5-diamino-1, 2,4 triazole to the sodium nitrite is 1:0.5-4.0.
4. The method according to claim 2, wherein the reaction temperature in the step (1) is-20 to 20 ℃; the molar ratio of the 3, 5-diamino-1, 2,4 triazole to stannous chloride is 1:0.5-2.0.
5. The preparation method according to claim 2, wherein the molar ratio of the 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride to silver nitrate or silver perchlorate is 1:0.5-2.0.
6. The method according to claim 2, wherein the reaction system solvent of step (2) comprises a mixture of any one or more of water, methanol and ethanol; the reaction temperature in the step (2) is between-20 and 100 ℃.
7. An energetic ionic salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole, which is characterized in that the energetic ionic salt is named as an organic energetic ionic salt of 3-hydrazino-5-amino-1H-1, 2, 4-triazole, and the organic energetic ionic salt has a structural formula:
wherein A is - Comprises any one of 5-nitryl amino tetrazole anion, 5-nitryl tetrazole anion, 3-nitryl-1, 2, 4-triazole-5-ketone, mononitrophenol anion, dinitrophenol anion, trinitrophenol anion, mononitroresorcinol anion, dinitroresorcinol anion, trinitroresorcinol anion and trinitrophloroglucinol anion.
8. A preparation method of energetic ion salt based on 3-hydrazino-5-amino-1H-1, 2, 4-triazole, which is characterized by comprising the following steps:
(1) Under an acidic condition, diazotizing 3, 5-diamino-1, 2,4 triazole and sodium nitrite to generate diazonium salt; stannous chloride reacts with the diazonium salt to prepare 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride;
wherein a is 3, 5-diamino-1, 2, 4-triazole, b is diazonium salt, c is 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride;
(2) Reacting the 3-hydrazino-5-amino-1H-1, 2, 4-triazole hydrochloride with lithium hydroxide to prepare 3-hydrazino-5-amino-1H-1, 2, 4-triazole; then the 3-hydrazino-5-amino-1H-1, 2, 4-triazole reacts with an acidic energetic compound to prepare 3-hydrazino-5-amino-1H-1, 2, 4-triazole organic energetic ionic salt,
wherein, acid represents an acidic energetic compound.
9. The method according to claim 8, wherein the concentration of hydrochloric acid in the diazotization reaction is 1 to 20mol/L; the molar ratio of the 3, 5-diamino-1, 2,4 triazole to the sodium nitrite is 1:0.5-4.0; the reaction temperature in the step (1) is-20 ℃; the molar ratio of the 3, 5-diamino-1, 2,4 triazole to stannous chloride is 1:0.5-2.0; the reaction temperature in the step (2) is 10-100 ℃; the reaction system solvent of the step (2) comprises any one or a mixture of more of water, methanol and ethanol.
10. Use of the energetic ionic salt according to claim 1 or 7 for research into novel high energy insensitive explosives, low signature and insensitive propellants.
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