CN113773326B - 3, 6-dinitrametes triazolo triazole and ionic salt, preparation method and application thereof - Google Patents
3, 6-dinitrametes triazolo triazole and ionic salt, preparation method and application thereof Download PDFInfo
- Publication number
- CN113773326B CN113773326B CN202111227423.3A CN202111227423A CN113773326B CN 113773326 B CN113773326 B CN 113773326B CN 202111227423 A CN202111227423 A CN 202111227423A CN 113773326 B CN113773326 B CN 113773326B
- Authority
- CN
- China
- Prior art keywords
- triazole
- triazolo
- dinitramine
- salt
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000003839 salts Chemical class 0.000 title claims abstract description 10
- AFWHQLQLEUKQAH-UHFFFAOYSA-N triazolo[4,5-d]triazole Chemical compound N1=NC2=NN=NC2=N1 AFWHQLQLEUKQAH-UHFFFAOYSA-N 0.000 title description 2
- -1 dinitrate triazole Chemical compound 0.000 claims abstract description 59
- 150000003852 triazoles Chemical class 0.000 claims abstract description 24
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentoxide Inorganic materials [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000035945 sensitivity Effects 0.000 abstract description 37
- 238000012360 testing method Methods 0.000 abstract description 9
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical group O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 abstract description 6
- 150000001450 anions Chemical class 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 48
- FQSLYAYRGHPRJT-UHFFFAOYSA-N 3h-[1,2,4]triazolo[4,3-b][1,2,4]triazole Chemical compound C1=NN2CN=NC2=N1 FQSLYAYRGHPRJT-UHFFFAOYSA-N 0.000 description 22
- 238000005474 detonation Methods 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 16
- 238000000354 decomposition reaction Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 8
- 230000005311 nuclear magnetism Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- IVKALSRVPPOGQU-UHFFFAOYSA-N 3h-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,6-diamine Chemical compound NC1=NN2C(N)N=NC2=N1 IVKALSRVPPOGQU-UHFFFAOYSA-N 0.000 description 5
- 150000002429 hydrazines Chemical class 0.000 description 5
- KPTSBKIDIWXFLF-UHFFFAOYSA-N 1,1,2-triaminoguanidine Chemical class NN=C(N)N(N)N KPTSBKIDIWXFLF-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- JGGFDEJXWLAQKR-UHFFFAOYSA-N 1,2-diaminoguanidine Chemical class NNC(N)=NN JGGFDEJXWLAQKR-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 description 3
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical class NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 description 3
- 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 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000028 HMX Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003349 semicarbazides Chemical class 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OJUDFURAIYFYBP-UHFFFAOYSA-N (dihydrazinylmethylideneamino)azanium;chloride Chemical compound Cl.NNC(NN)=NN OJUDFURAIYFYBP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UBDZFAGVPPMTIT-UHFFFAOYSA-N 2-aminoguanidine;hydron;chloride Chemical compound [Cl-].NC(N)=N[NH3+] UBDZFAGVPPMTIT-UHFFFAOYSA-N 0.000 description 1
- UJTTUOLQLCQZEA-UHFFFAOYSA-N 9h-fluoren-9-ylmethyl n-(4-hydroxybutyl)carbamate Chemical compound C1=CC=C2C(COC(=O)NCCCCO)C3=CC=CC=C3C2=C1 UJTTUOLQLCQZEA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SCIZLHIMZCLSND-UHFFFAOYSA-N diamino(carbamimidoyl)azanium;chloride Chemical compound Cl.NN(N)C(N)=N SCIZLHIMZCLSND-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229960000789 guanidine hydrochloride Drugs 0.000 description 1
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical group N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention relates to 3, 6-dinitramine [1,2,4]]Triazolo [4,3 ]b][1,2,4]Triazole and ionic salt thereof, and a preparation method and application thereof. 3, 6-dinitramine [1,2,4]]Triazolo [4,3 ]b][1,2,4]The N5-position nitramine group vertical to the condensed ring framework is removed from the molecular structure of the triazole, so that a completely planar large conjugated system is formed when the nitramine group is converted into anions, pi-pi interaction between layers is enhanced, and the thermal stability and sensitivity of the dinitrate triazole energetic ion salt are improved. The energetic ion salt in the invention is tested by using a BAM impact sensitivity instrument to find that the impact sensitivity is between 7 and 10J; friction sensitivity was found to be between 140-220N using a BAM friction sensitivity meter test.
Description
Technical Field
The invention relates to the field of energetic materials, in particular to a novel high-energy energetic compound, especially 3, 6-dinitramine [1,2,4] triazolo [4,3-b ] [1,2,4] triazole, an ionic salt thereof, a preparation method and application thereof.
Background
The nitramine explosives generally have excellent detonation properties, such as traditional single-ring nitramine explosives, namely cyclotrimethylene trinitro (commonly known as Hemsojin, RDX) and cyclotetramethylene tetranitramine (commonly known as octogen, HMX), which are about 1.5-1.8 times the equivalent mass of 2,4, 6-trinitrotoluene (TNT).
The energy of conventional mono-or bi-cyclic nitramines is almost exclusively derived from the oxidation of the carbon skeleton. The nitrogen-enriched condensed ring type nitrate explosive has another part of energy source, namely high positive formation enthalpy and larger ring tension caused by a large amount of energy-containing N-N and C-N single/double bonds contained in the molecular structure. More importantly, the method comprises the steps of,after the nitramine group of the compound is changed into nitramine anion, stable large conjugate plane anion can be formed with the nitrogen-rich condensed ring skeleton, and then the stable large conjugate plane anion is paired with proper nitrogen-rich cation, so that the high-energy low-inductance energetic material with good oxygen balance, high formation enthalpy, high density and good thermal stability is hopefully obtained. For example, 3, 6-dinitramine [1,2,4]]Triazole [4,3-b ]][1,2,4,5]The diammonium salt of tetrazine is a novel energetic salt with excellent comprehensive performance and has the density of 1.84g cm -3 The decomposition temperature is 213 ℃, and the detonation velocity is 9301 and 9301m s -1 Explosion pressure 35.4Gpa, impact sensitivity 32J and friction sensitivity more than 360N.
Therefore, the invention selects [1,2,4] triazolo [4,3-b ] [1,2,4] triazole as a plane framework, introduces two nitramine groups, synthesizes 3, 6-dinitrano [1,2,4] triazolo [4,3-b ] [1,2,4] triazole with high yield through only one-step reaction, converts the 3, 6-dinitrano [1,2,4] triazole into completely coplanar anions, and is paired with nitrogen-rich cations to form energetic ion salts. The potential value of the material as an energetic material is studied and evaluated by characterization of its structure and thermal analysis. This is the first synthetic route for the compound, and no related report has been found before.
Disclosure of Invention
The invention aims to provide a novel high-energy energetic compound, in particular to 3, 6-dinitramine [1,2,4] triazolo [4,3-b ] [1,2,4] triazole, an ionic salt thereof, a preparation method and application thereof, and provides a novel method for synthesizing and amplifying research of novel energetic materials.
The invention is realized by the following technical scheme: 3, 6-dinitrano [1,2,4] triazolo [4,3-b ] [1,2,4] triazole (hereinafter referred to as dinitrano triazole) has the structural formula:
the invention further provides a preparation method of the 3, 6-dinitrano [1,2,4] triazolo [4,3-b ] [1,2,4] triazole, which comprises the following steps: dissolving 3, 6-diamino [1,2,4] triazolo [4,3-b ] [1,2,4] triazole in sulfuric acid, dropwise adding nitric acid, reacting for 2-4h, adding the reaction solution into crushed ice, quenching, filtering to obtain yellow solid, and drying to obtain 3, 6-dinitram [1,2,4] triazolo [4,3-b ] [1,2,4] triazole.
As a further improvement of the technical scheme of the preparation method, the system temperature is kept below 0 ℃ in the whole preparation process.
As a further improvement of the technical scheme of the preparation method, the sulfuric acid is concentrated sulfuric acid with the mass fraction of 98% or fuming sulfuric acid with the mass fraction of 20%, and the nitric acid is fuming nitric acid or anhydrous nitric acid.
As a further improvement of the technical scheme of the preparation method, the volume ratio of sulfuric acid to nitric acid is 3:1-4:1.
As a further improvement to the preparation process of the present invention, at least 1.2g of sulfuric acid is required per 1mmol of 3, 6-diamino [1,2,4] triazolo [4,3-b ] [1,2,4] triazole.
The invention further provides application of the 3, 6-dinitrano [1,2,4] triazolo [4,3-b ] [1,2,4] triazole as an energetic material.
The invention also provides a 3, 6-dinitramine [1,2,4] triazolo [4,3-b ] [1,2,4] triazole energetic ion salt, which has the structural formula:
wherein,
the invention further provides a preparation method of the 3, 6-dinitramine [1,2,4] triazolo [4,3-b ] [1,2,4] triazole energetic ion salt, which comprises the following steps:
(1) When (when)3, 6-dinitramine [1,2,4]]Triazolo [4,3-b ]][1,2,4]The triazole reacts with ammonia water or hydrazine hydrate for 3 to 4 hours, and the crude product is recrystallized after the reaction liquid is concentrated to obtain the corresponding energetic ion salt;
(2) When (when)3, 6-dinitramine [1,2,4]]Triazolo [4,3-b ]][1,2,4]And (3) mixing triazole with sodium hydroxide solid, reacting with corresponding hydrochloride in a solvent for 3-4 hours, concentrating the reaction solution, and recrystallizing the crude product to obtain the corresponding energetic ion salt.
The invention also provides a synthetic route of the 3, 6-dinitramine [1,2,4] triazolo [4,3-b ] [1,2,4] triazole energetic ion salt, and the specific synthetic route is shown as follows:
the invention further provides application of the 3, 6-dinitramine [1,2,4] triazolo [4,3-b ] [1,2,4] triazole energetic ion salt as an energetic material.
Compared with the prior art, the invention has the following beneficial effects:
1) Compared with 3,6, 7-trinitro [1,2,4] triazolo [4,3-b ] [1,2,4] triazole (trinitro-trinitro) series energetic compounds, the invention eliminates the N5-position nitro-amine group vertical to the condensed ring framework in the molecular structure of the dinitrate triazole, so that a complete plane large conjugated system is formed when the dinitrate is converted into anions, pi-pi interaction between layers is enhanced, and the thermal stability and sensitivity of the dinitrate triazole energetic ion salt are improved. For example: the decomposition temperature of hydrazine salt of dinitrate triazolo triazole is raised by 8 ℃, the impact sensitivity is reduced by 1J, and the friction sensitivity is reduced by 40N.
2) The decomposition temperature of the obtained 7 dinitrate triazolo triazole energetic ion salts is 170-230 ℃; has higher density of 1.70-1.79g/cm 3 。
3) The theoretical detonation velocity of the energetic ion salt obtained by calculation of EXPLO5 (v 6.01) software is 8272-9138m/s, and the detonation pressure is 25.7-33.5GPa. Wherein the detonation velocity of the ammonium salt and the aminoguanidine salt is equivalent to that of RDX, and the detonation velocity of the hydrazine salt, the diaminoguanidine salt and the triaminoguanidine salt is superior to that of RDX.
4) The energetic ion salt in the invention is tested by using a BAM impact sensitivity instrument (BFH-10) to find that the impact sensitivity is between 7 and 10J; friction sensitivity was found to be between 140 and 220N using a BAM friction sensitivity meter (FSKM-10) test. In combination with the detonation performance and sensitivity, the detonation performance of the hydrazine salt is equivalent to RDX, the sensitivity is superior to RDX, and the comprehensive performance is optimal.
4) The salt synthesis method is simple, mild in condition, high in yield, and environment-friendly, and deionized water is mostly used as a reaction solvent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a single crystal structure diagram of energetic ion salt semicarbazide salt 8.
FIG. 2 is a DSC-TG schematic of the energetic ion salt, triaminoguanidine salt 7.
FIG. 3 is a hydrogen spectrum of the energetic ion salt diaminoguanidine salt 6.
FIG. 4 is a carbon spectrum of the energetic ion salt diaminoguanidine salt 6.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. 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.
In the invention, the 3, 6-dinitrano [1,2,4] triazolo [4,3-b ] [1,2,4] triazole has the structural formula:
the invention provides a specific example of a preparation method of 3, 6-dinitrano [1,2,4] triazolo [4,3-b ] [1,2,4] triazole, which comprises the following steps: dissolving 3, 6-diamino [1,2,4] triazolo [4,3-b ] [1,2,4] triazole in sulfuric acid, dropwise adding nitric acid, reacting for 2-4h, adding the reaction solution into crushed ice, quenching, filtering to obtain yellow solid, and drying to obtain 3, 6-dinitram [1,2,4] triazolo [4,3-b ] [1,2,4] triazole.
In specific application, the system temperature is kept below 0 ℃ in the whole preparation process.
In the invention, the sulfuric acid is concentrated sulfuric acid with the mass fraction of 98% or fuming sulfuric acid with the mass fraction of 20%, and the nitric acid is fuming nitric acid or anhydrous nitric acid.
In the present invention, when sulfuric acid and nitric acid are of the above-mentioned types, the volume ratio of sulfuric acid to nitric acid is 3:1 to 4:1.
In addition, at least 1.2g of sulfuric acid is required per 1mmol of 3, 6-diamino [1,2,4] triazolo [4,3-b ] [1,2,4] triazole.
The invention also provides application of the 3, 6-dinitrano [1,2,4] triazolo [4,3-b ] [1,2,4] triazole as an energetic material.
The invention further provides a 3, 6-dinitramine [1,2,4] triazolo [4,3-b ] [1,2,4] triazole energetic ion salt which has the structural formula:
wherein,
the invention further provides a preparation method of the 3, 6-dinitramine [1,2,4] triazolo [4,3-b ] [1,2,4] triazole energetic ion salt, which comprises the following steps:
(1) When (when)3, 6-dinitramine [1,2,4]]Triazolo [4,3-b ]][1,2,4]Triazole and ammonia water or hydrazine hydrateAfter 3-4 hours, concentrating the reaction solution, and recrystallizing the crude product to obtain the corresponding energetic ionic salt (acid-base neutralization reaction);
(2) When (when)
3, 6-dinitramine [1,2,4]]Triazolo [4,3-b ]][1,2,4]And (3) mixing triazole with sodium hydroxide solid, reacting with corresponding hydrochloride in a solvent for 3-4 hours, concentrating the reaction solution, and recrystallizing the crude product to obtain the corresponding energetic ion salt (displacement reaction).
In the present invention, it is preferable that in the step (1), the molar ratio of the 3, 6-dinitrano [1,2,4] triazolo [4,3-b ] [1,2,4] triazole to ammonia water or hydrazine hydrate is 1:1. In the step (2), the molar ratio of the 3, 6-dinitrano [1,2,4] triazolo [4,3-b ] [1,2,4] triazole to sodium hydroxide is 1:1, and the molar ratio of the 3, 6-dinitrano [1,2,4] triazolo [4,3-b ] [1,2,4] triazole to the hydrochloride is 1:1.
Specifically, in the step (1), the reaction solvent may be water, methanol or ethanol, and the reaction temperature is 30-60 ℃; in the step (2), the reaction solvent is water and the reaction temperature is 40-80 ℃.
The invention also provides application of the 3, 6-dinitramine [1,2,4] triazolo [4,3-b ] [1,2,4] triazole energetic ion salt as an energetic material.
In order to describe the technical scheme of the invention in more detail, the following examples are provided.
EXAMPLE 1 Synthesis of Dinitroaminotriazol (1)
1.39g of 3, 6-diamino [1,2,4] previously ground and pulverized are added to 15g of oleum]Triazolo [4,3-b ]][1,2,4]Triazole (10 mmol) was dissolved completely by sonication, followed by slow addition of 4mL fuming nitric acid at a temperature not exceeding-5 ℃. The reaction was carried out for 3.5 hours, and the temperature was maintained at-5 ℃. Then quenched with 40g crushed ice and filtered to give a yellow solid in CaCl 2 After drying overnight, the product was obtained (yield 78%).
In the present invention, the 3, 6-diamino [1,2,4] triazolo [4,3-b ] [1,2,4] triazole is prepared in a laboratory homemade manner, see C.Bian, Q.Lei, J.Zhang, et al, polyhedron,2021,201,115158.
And (3) structural identification of the product:
decomposition temperature: 121 ℃ (DSC, melting point and decomposition temperature are both peak temperatures referred to below).
Nuclear magnetism 1 H NMR([D 6 ]DMSO,100MHz,25℃,TMS):δ＝7.17(s,br)ppm. 13 C NMR([D 6 ]DMSO,600MHz,25℃):δ＝158.96,150.08,138.72ppm.
Mass spectrum (ESI) 228.0 (M-H) -.
Infrared spectrum (KBr): 3339,1670,1582,1483,1424,1371,1312,1256,1160,1071,1014,987,921,865,824,763,721,670,625,480,456, 426 cm -1 。
Elemental analysis: molecular formula C 3 H 3 N 9 O 4 Theoretical C,15.73; h,1.32; n,55.02. Measured value C,15.70; h,1.36; n,55.00.
The above structural identification data confirm that the resulting material is indeed dinitroaminotriazol (compound 1).
EXAMPLE 2 Synthesis of Dinitroaminotriazol (1)
1.98g of 3, 6-diamino [1,2,4] previously ground and pulverized were added to 17.1g of concentrated sulfuric acid]Triazolo [4,3-b ]][1,2,4]Triazole (14.2 mmol) was dissolved completely by sonication, then 3.8mL of anhydrous nitric acid was slowly added to react for 2.5h while maintaining the temperature at-5℃and keeping the temperature at-2 ℃. Quenching with 56g crushed ice, filtering, compacting to obtain yellow solid, and adding CaCl 2 Intermediate dried overnight, washed with a suitable amount of acetonitrile, filtered and the resulting filter cake was placed in an oven at 50 ℃ for 2h under vacuum to give 2.73g of dinitroaminotriazolo triazole (84% yield).
EXAMPLE 3 Synthesis of ammonium salt of dinitrate triazolo triazole (2)
458mg of dinitrate triazolo triazole (compound 1,2 mmol) was dispersed in 20mL of water, 136mg of concentrated aqueous ammonia (mass fraction 25%) was added thereto, the temperature was kept at 50℃and stirred for 4 hours. After cooling, the mixture was concentrated and filtered to give a beige solid product (yield 80%).
Structural identification, density detection, detonation performance calculation and sensitivity test of the product:
the decomposition temperature was 190 ℃.
Nuclear magnetism 1 H NMR([D 6 ]DMSO,100MHz,25℃,TMS):δ＝13.71(s,br),7.14(s)ppm. 13 C NMR([D 6 ]DMSO,600MHz,25℃):δ＝160.54,148.31,141.35ppm.
Infrared spectrum (KBr): 3735,3465,3210,3034,1790,1668,1623,1571,1479,1453,1367,1307,1270,1218,1162,1072,1007,981,915,859,823,769,713,642,601,457cm -1 。
Elemental analysis: molecular formula C 3 H 6 N 10 O 4 Theoretical C,14.64; h,2.46; n,56.90. Measured value C,14.65; h,2.48; n,56.87.
Density 1.76g/cm 3 。
Calculate detonation velocity (EXPLO 5 software): 8767m/s, burst pressure 30.8Gpa.
Impact sensitivity 11J, friction sensitivity 240N.
The above structural identification data confirm that the resulting material is indeed an ammonium salt of dinitroaminotriazol (compound 2).
EXAMPLE 4 Synthesis of hydrazine salt of Dinitroaminotriazol (3)
458mg of dinitrate triazolo triazole (compound 1,2 mmol) was dispersed in 10mL of water, to which 100mg of hydrazine hydrate (99% by mass) was added, keeping the temperature at 40℃and stirring for 4 hours. After cooling, the mixture was concentrated, filtered and recrystallized from methanol to give a beige solid product (yield 78%).
Structural identification, density detection, detonation performance calculation and sensitivity test of the product:
decomposition temperature: 191 ℃.
Nuclear magnetism 1 H NMR([D6]DMSO,100MHz,25℃,TMS):δ＝7.59(s,br)ppm. 13 C NMR([D 6 ]DMSO,600MHz,25℃):δ＝1661.52,149.18,141.31ppm.
Infrared spectrum (KBr): 3488,3066,1661,1576,1538,1485,1417,1270,1064,966,903,856,821,766,711,637,594,45 cm -1 。
Elemental analysis: molecular formula C 3 H 7 N 11 O 4 Theoretical value C,13.80; h,2.70; n (N),59.00. Measured value C,13.78; h,2.71; n,59.02.
Density 1.79g/cm 3 。
Calculate detonation velocity (EXPLO 5 software): 9138m/s, burst pressure 33.5Gpa.
Impact sensitivity 9J, friction sensitivity 220N.
The above structural identification data confirm that the material is indeed the hydrazine salt of the dinitroaminotriazol (compound 3).
EXAMPLE 5 Synthesis of guanidine salt of Dinitrotriazolo triazole (4)
458mg of dinitrate triazolo triazole (compound 1,2 mmol) was dispersed in 30mL of water, 80mg of sodium hydroxide (2 mmol) was added thereto, and after stirring at room temperature for 20min, 191mg of guanidine hydrochloride (2 mmol) was added thereto, and the temperature was kept at 70℃and stirred for 4h. After cooling, the mixture was concentrated, filtered and recrystallized from hot water to give yellow brown solid product (yield 93%).
Structural identification, density detection, detonation performance calculation and sensitivity test of the product:
decomposition temperature: 173 ℃.
Nuclear magnetism 1 H NMR([D 6 ]DMSO,100MHz,25℃,TMS):δ＝13.85(s,br),12.94(s,br),6.98(s)ppm. 13 C NMR([D6]DMSO,600MHz,25℃):δ＝160.51,158.35,148.19,141.30ppm.
Infrared spectrum (KBr): 3853,3735,3399,3324,3264,2360,1685,1569,1481,1295,1217,1166,1074,980,914,865,825,767,716,696,641,535,460cm -1 。
Density 1.70g/cm 3 。
Elemental analysis: molecular formula C 4 H 8 N 12 O 4 Theoretical C,16.67; h,2.80; n,58.32. Measured value C,16.68; h,2.83; n,58.30.
Calculate detonation velocity (EXPLO 5 software): 8272m/s, burst pressure 25.7GPa.
Impact sensitivity 7J, friction sensitivity 180N.
The above structural identification data confirm that the material is indeed the guanidine salt of the dinitrate triazolo triazole (compound 4).
EXAMPLE 6 Synthesis of aminoguanidine salt of dinitrate triazolo triazole (5)
458mg of dinitrate triazolo triazole (compound 1,2 mmol) was dispersed in 30mL of water, 80mg of sodium hydroxide (2 mmol) was added thereto, and after stirring at room temperature for 20min, 221mg of aminoguanidine hydrochloride (2 mmol) was added thereto, and the temperature was kept at 70℃and stirred for 4h. After cooling, the mixture was concentrated, filtered and recrystallized from hot water to give a yellow solid product (yield 94%).
Structural identification, density detection, detonation performance calculation and sensitivity test of the product:
decomposition temperature: 203 ℃.
Nuclear magnetism 1 H NMR([D 6 ]DMSO,100MHz,25℃,TMS):δ＝13.85(s),12.90(s,br),8.59(s),7.28(s),6.77(s),4.71(s)ppm. 13 C NMR([D 6 ]DMSO,600MHz,25℃):δ＝160.53,159.21,148.20,141.31ppm.
Infrared spectrum (KBr): 3551,3448,3411,3351,3271,3217,2710,1611,1569,1481,1447,1422,1373,1341,1308,1249,1211,1150,1087,1063,1010,983,933,914,860,823,771,713,632,596,503,463cm -1 。
Elemental analysis: molecular formula C 4 H 9 N 13 O 4 Theoretical value C,15.85; h,2.99; n,60.06. Measured value C,15.84; h,3.01; n,60.04.
Density 1.77g/cm 3 。
Calculate detonation velocity (EXPLO 5 software): 8789m/s and burst pressure 29.2Gpa.
Impact sensitivity 8J, friction sensitivity 180N.
The above structural identification data confirm that the material is indeed an aminoguanidine salt of dinitroaminotriazol (compound 5).
EXAMPLE 7 Synthesis of diaminoguanidine salt of Dinitrotriazolo triazole (6)
458mg of dinitroaminotriazolo triazole (compound 1,2 mmol) was dispersed in 30mL of water, 80mg of sodium hydroxide (2 mmol) was added thereto, and after stirring at room temperature for 20min, 251mg of diaminoguanidine hydrochloride (2 mmol) was added thereto, and the temperature was kept at 70℃and stirred for 4h. After cooling, the mixture was concentrated, filtered and recrystallized from hot water to give a yellow solid product (92% yield).
Structural identification, density detection, detonation performance calculation and sensitivity test of the product:
decomposition temperature: 173 ℃.
Nuclear magnetism 1 H NMR([D 6 ]DMSO,100MHz,25℃,TMS):δ＝13.85(d,br),8.56(s),7.16(s),4.61(s)ppm. 13 C NMR([D 6 ]DMSO,600MHz,25℃):δ＝160.58,160.18,148.15,141.33ppm.
Infrared spectrum (KBr): 3730,3335,3255,3082,2706,2645,1674,1617,1514,1460,1397,1343,1241,1223,1177,1111,1084,1051,1019,997,972,916,863,844,777,759,733,629,596,518,461,423cm -1 。
Elemental analysis: molecular formula C 4 H 10 N 14 O 4 Theoretical value C,15.10; h,3.17; n,61.62. Measured value C,15.08; h,3.16; n,62.65.
Density 1.78g/cm 3 。
Calculate detonation velocity (EXPLO 5 software): 9030m/s, burst pressure 31.0Gpa.
Impact sensitivity 8J, friction sensitivity 200N.
The above structural identification data confirm that the material is indeed the diaminoguanidine salt of dinitroaminotriazol (compound 6).
EXAMPLE 8 Synthesis of Triaminoguanidine salt of Dinitrotriazolo triazole (7)
458mg of dinitrate triazolo triazole (compound 1,2 mmol) was dispersed in 30mL of water, 80mg of sodium hydroxide (2 mmol) was added thereto, and after stirring at room temperature for 20min, 281mg of triaminoguanidine hydrochloride (2 mmol) was added thereto, and the temperature was kept at 60℃and stirred for 4h. After cooling, the mixture was concentrated, filtered and recrystallized from hot water to give a yellow solid product (yield 88%).
Structural identification, density detection, detonation performance calculation and sensitivity test of the product:
decomposition temperature: 170 ℃.
Nuclear magnetism 1 H NMR([D 6 ]DMSO,100MHz,25℃,TMS):δ＝13.73(s,br),8.61(s),4.52(s)ppm. 13 C NMR([D 6 ]DMSO,600MHz,25℃):δ＝160.59,159.50,148.32,141.34ppm.
Infrared spectrum (KBr): 3585,3320,3213,1685,1622,1568,1530,1479,1458,1414,1375,1333,1303,1245,1212,1186,1146,1074,1018,982,917,856,836,769,717,635,601cm -1 。
elemental analysis: molecular formula C 4 H 11 N 15 O 4 Theoretical value C,14.42; h,3.33; n,63.05. Actual measurement C,14.41; h,3.36; n,63.03.
Density 1.73g/cm 3 。
Calculate detonation velocity (EXPLO 5 software): 8963m/s, burst pressure 30.2Gpa.
Impact sensitivity 8J, friction sensitivity 230N.
The above structural identification data confirm that the material is indeed the triaminoguanidine salt of dinitroaminotriazol (compound 7).
EXAMPLE 9 Synthesis of semicarbazide salt of Dinitrotriazolo triazole (8)
458mg of dinitrate triazolo triazole (compound 1,2 mmol) was dispersed in 30mL of water, 80mg of sodium hydroxide (2 mmol) was added thereto, and after stirring at room temperature for 20min, 223mg of semicarbazide hydrochloride (2 mmol) was added thereto, and the temperature was kept at 60℃and stirred for 4h. After cooling, the mixture was concentrated, filtered and recrystallized from hot water to give a yellow solid product (yield 86%).
Structural identification, density detection, detonation performance calculation and sensitivity test of the product:
decomposition temperature: 186 deg.c.
Nuclear magnetism 1 H NMR([D 6 ]DMSO,100MHz,25℃,TMS):δ＝8.61(s),6.58(s)ppm. 13 C NMR([D 6 ]DMSO,600MHz,25℃):δ＝160.47,158.26,148.24,141.25ppm.
Infrared spectrum (KBr): 3745,3517,3371,3281,3212,3057,2932,2792,2708,2022,1710,1679,1619,1547,1484,1451,1422,1378,1274,1214,1166,1085,981,914,868,828,768,723,600,521,459cm -1 。
Elemental analysis: molecular formula C 4 H 8 N 12 O 5 Theoretical value C,15.79; h,2.65; n,55.26. Measured value C,15.80; h,2.67; n,55.26.
Density 1.76g/cm 3 。
Calculate detonation velocity (EXPLO 5 software): 8568m/s, burst pressure 28.7Gpa.
Impact sensitivity 10J, friction sensitivity 190N.
The above structural identification data confirm that the resulting material is indeed a semicarbazide salt of the dinitroaminotriazol (compound 8).
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1.3,6-dinitramine [1,2,4]]Triazolo [4,3 ]b][1,2,4]Triazole, its structural formula is:
。
2. the 3, 6-dinitramine [1,2,4] of claim 1]Triazolo [4,3 ]b][1,2,4]The preparation method of triazole is characterized by comprising the following steps: 3, 6-diamino [1,2,4]]Triazolo [4,3 ]b][1,2,4]Dissolving triazole in sulfuric acid, dropwise adding nitric acid, reacting 2-4h, adding the reaction solution into crushed ice, quenching, suction filtering to obtain yellow solid, and drying to obtain 3, 6-dinitramine [1,2,4]]Triazolo [4,3 ]b][1,2,4]Triazole.
3.3, 6-dinitramine [1,2,4] according to claim 2]Triazolo [4,3 ]b][1,2,4]A process for preparing triazole, characterized in that the system temperature is kept below 0 ℃ throughout the preparation.
4. 3, 6-dinitramine [1,2,4] according to claim 2]Triazolo [4,3 ]b][1,2,4]A process for producing triazole, characterized in that the sulfuric acid is 98% by mass of concentrated sulfuric acid or 20% by mass of concentrated sulfuric acidFuming sulfuric acid, and nitric acid is fuming nitric acid or anhydrous nitric acid.
5. 3, 6-dinitramine [1,2,4] according to claim 4]Triazolo [4,3 ]b][1,2,4]The preparation method of the triazole is characterized in that the volume ratio of sulfuric acid to nitric acid is 3:1-4:1.
6. 3, 6-dinitramine [1,2,4] according to claim 2]Triazolo [4,3 ]b][1,2,4]A process for preparing triazole, characterized in that 1mmol of 3, 6-diamino [1,2,4]]Triazolo [4,3 ]b][1,2,4]Triazole requires at least 1.2g sulfuric acid.
7.3,6-dinitramine [1,2,4]]Triazolo [4,3 ]b][1,2,4]Triazole energetic ion salt has a structural formula:
，
wherein,。
8. the 3, 6-dinitramine [1,2,4] of claim 7]Triazolo [4,3 ]b][1,2,4]The preparation method of the triazole energetic ion salt is characterized by comprising the following steps:
(1) When (when)3, 6-dinitramine [1,2,4]]Triazolo [4,3 ]b][1,2,4]After triazole reacts with ammonia water or hydrazine hydrate for 3-4 h, concentrating a reaction solution, and recrystallizing a crude product to obtain corresponding energetic ion salt;
(2) When (when)3, 6-dinitramine [1,2,4]]Triazolo [4,3 ]b][1,2,4]After triazole and sodium hydroxide solid are mixed and then react with corresponding hydrochloride in a solvent for 3 to 4h,and concentrating the reaction solution, and recrystallizing the crude product to obtain the corresponding energetic ionic salt.
9. The 3, 6-dinitramine [1,2,4] of claim 7]Triazolo [4,3 ]b][1,2,4]Use of triazole energetic ion salts as energetic materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111227423.3A CN113773326B (en) | 2021-10-21 | 2021-10-21 | 3, 6-dinitrametes triazolo triazole and ionic salt, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111227423.3A CN113773326B (en) | 2021-10-21 | 2021-10-21 | 3, 6-dinitrametes triazolo triazole and ionic salt, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113773326A CN113773326A (en) | 2021-12-10 |
| CN113773326B true CN113773326B (en) | 2023-11-17 |
Family
ID=78873314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111227423.3A Active CN113773326B (en) | 2021-10-21 | 2021-10-21 | 3, 6-dinitrametes triazolo triazole and ionic salt, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113773326B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115991680B (en) * | 2022-12-07 | 2024-04-12 | 西南科技大学 | Bis (1, 2, 4-triazole) triazene cationic nitrogen-rich energetic ion salt, and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4300962A (en) * | 1979-10-18 | 1981-11-17 | The United States Of America As Represented By The United States Department Of Energy | Ammonium nitrate explosive systems |
| US5256792A (en) * | 1989-12-14 | 1993-10-26 | The United States Of America As Represented By The United States Department Of Energy | Amine salts of nitroazoles |
| US5466821A (en) * | 1981-03-18 | 1995-11-14 | Zeneca Limited | Heterocyclic compounds |
| US20070155737A1 (en) * | 2005-05-20 | 2007-07-05 | Alantos Pharmaceuticals, Inc. | Heterobicyclic metalloprotease inhibitors |
| CN101578282A (en) * | 2007-01-16 | 2009-11-11 | Snpe巨能材料公司 | Furazane derivatives, preparation thereof and energetic compositions containing them |
| CN103641834A (en) * | 2013-12-12 | 2014-03-19 | 沈阳药科大学 | Pyrrolobenzodiazepine compounds, and preparation method and application thereof |
| CN104016932A (en) * | 2014-06-19 | 2014-09-03 | 西安近代化学研究所 | Method for synthesizing 5,5'-dinitroamino-3,3'-co-1,2,4-triazole carbohydrazide |
| CN104447762A (en) * | 2014-12-08 | 2015-03-25 | 北京理工大学 | Energetic ionic salts of 7-nitryl-4-ketone-4,8-dihydro-[1,2,4] triazole [5,1-d] [1,2,3,5] tetrazine-2-oxide and preparation method of energetic ionic salt |
| CN105017290A (en) * | 2015-07-30 | 2015-11-04 | 中北大学 | [Ag(C12H10N4)].(ClO4) complex assembled by benzotriazole ligand and Ag(I) as well as preparation method and application thereof |
| CN106414409A (en) * | 2014-02-27 | 2017-02-15 | 先正达参股股份有限公司 | Polymorphs of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide |
| CN110386938A (en) * | 2019-08-23 | 2019-10-29 | 中北大学 | Trintriamine triazol triazole and its ion salt containing energy and preparation |
-
2021
- 2021-10-21 CN CN202111227423.3A patent/CN113773326B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4300962A (en) * | 1979-10-18 | 1981-11-17 | The United States Of America As Represented By The United States Department Of Energy | Ammonium nitrate explosive systems |
| US5466821A (en) * | 1981-03-18 | 1995-11-14 | Zeneca Limited | Heterocyclic compounds |
| US5256792A (en) * | 1989-12-14 | 1993-10-26 | The United States Of America As Represented By The United States Department Of Energy | Amine salts of nitroazoles |
| US20070155737A1 (en) * | 2005-05-20 | 2007-07-05 | Alantos Pharmaceuticals, Inc. | Heterobicyclic metalloprotease inhibitors |
| CN101578282A (en) * | 2007-01-16 | 2009-11-11 | Snpe巨能材料公司 | Furazane derivatives, preparation thereof and energetic compositions containing them |
| CN103641834A (en) * | 2013-12-12 | 2014-03-19 | 沈阳药科大学 | Pyrrolobenzodiazepine compounds, and preparation method and application thereof |
| CN106414409A (en) * | 2014-02-27 | 2017-02-15 | 先正达参股股份有限公司 | Polymorphs of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide |
| CN104016932A (en) * | 2014-06-19 | 2014-09-03 | 西安近代化学研究所 | Method for synthesizing 5,5'-dinitroamino-3,3'-co-1,2,4-triazole carbohydrazide |
| CN104447762A (en) * | 2014-12-08 | 2015-03-25 | 北京理工大学 | Energetic ionic salts of 7-nitryl-4-ketone-4,8-dihydro-[1,2,4] triazole [5,1-d] [1,2,3,5] tetrazine-2-oxide and preparation method of energetic ionic salt |
| CN105017290A (en) * | 2015-07-30 | 2015-11-04 | 中北大学 | [Ag(C12H10N4)].(ClO4) complex assembled by benzotriazole ligand and Ag(I) as well as preparation method and application thereof |
| CN110386938A (en) * | 2019-08-23 | 2019-10-29 | 中北大学 | Trintriamine triazol triazole and its ion salt containing energy and preparation |
Non-Patent Citations (3)
| Title |
|---|
| "4-氨基-1,2,4-三唑苦味酸盐的合成与性能";夏云霞等;《精细化工》;第25卷(第05期);第445-448页 * |
| "High-performing and thermally stable energetic 3,7-diamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole derivatives";Yongxing Tang等;《J. Mater. Chem. A》;第5卷;第6100–6105页 * |
| "基于有机阴离子的含能离子盐研究进展";黄海丰;《火炸药学报》;第35卷(第03期);第1-10页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113773326A (en) | 2021-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Klapötke et al. | Thermal stabilization of energetic materials by the aromatic nitrogen-rich 4, 4′, 5, 5′-tetraamino-3, 3′-bi-1, 2, 4-triazolium cation | |
| Wang et al. | Synthesis of 1-(2 H-tetrazol-5-yl)-5-nitraminotetrazole and its derivatives from 5-aminotetrazole and cyanogen azide: a promising strategy towards the development of C–N linked bistetrazolate energetic materials | |
| Zhang et al. | Towards improved explosives with a high performance: N-(3, 5-dinitro-1 H-pyrazol-4-yl)-1 H-tetrazol-5-amine and its salts | |
| Thottempudi et al. | Azo substituted 1, 2, 4-oxadiazoles as insensitive energetic materials | |
| Wu et al. | 3, 4-Diamino-1, 2, 4-triazole based energetic salts: synthesis, characterization, and energetic properties | |
| Domasevitch et al. | Facile and selective polynitrations at the 4-pyrazolyl dual backbone: straightforward access to a series of high-density energetic materials | |
| Yadav et al. | Facile fabrication of functionalized pyrimidine derivatives: constructing a new family of high performance and less sensitive energetic compounds | |
| Xiong et al. | Combinations of furoxan and 1, 2, 4-oxadiazole for the generation of high performance energetic materials | |
| Liu et al. | Green primary energetic materials based on N-(3-nitro-1-(trinitromethyl)-1 H-1, 2, 4-triazol-5-yl) nitramide | |
| Klapötke et al. | 5, 5′‐Hydrazinebistetrazole: An Oxidation‐stable Nitrogen‐rich Compound and Starting Material for the Synthesis of 5, 5′‐Azobistetrazolates | |
| CN113773326B (en) | 3, 6-dinitrametes triazolo triazole and ionic salt, preparation method and application thereof | |
| Sun et al. | Tetracyclic pyrazine-fused furazans as insensitive energetic materials: syntheses, structures, and properties | |
| Kumar et al. | Resolving synthetic challenges faced in the syntheses of asymmetric N, N′-ethylene-bridged energetic compounds | |
| Ma et al. | Synthesis and thermal behavior of a fused, tricyclic pyridine-based energetic material: 4-amino-5-nitro-[1, 2, 5] oxadiazolo [3, 4-e] tetra-zolo [1, 5-a] pyridine-3-oxide | |
| CN110386938B (en) | Trinitroamine triazolotriazole, energetic ionic salt thereof and preparation method thereof | |
| Yadav et al. | Dianionic nitrogen-rich triazole and tetrazole-based energetic salts: synthesis and detonation performance | |
| Tao et al. | Novel insensitive energetic-cocrystal-based BTO with good comprehensive properties | |
| Aizikovich et al. | The nitration pattern of energetic 3, 6-diamino-1, 2, 4, 5-tetrazine derivatives containing azole functional groups | |
| Deblitz et al. | Explosive Werner-type cobalt (III) complexes | |
| Klapötke et al. | N-Functionalisation of 5, 5′-bistetrazole providing 2, 2′-di (azidomethyl) bistetrazole: a melt-castable metal-free green primary explosive | |
| Kofen et al. | 1, 5-Dimethyltetrazole as a ligand in energetic 3d5 to 3d10-metal coordination compounds | |
| Joo et al. | Polynitramino compounds outperform PETN | |
| Parakhin et al. | Linking polynitro hexaazaisowurtzitane cages via an N, N'-methylene bridge: a promising strategy for designing energetic ensembles of CL-20 derivatives and adjusting their properties | |
| Xue et al. | Exploring Application of 1, 2, 4‐Triazole Energetic Salts: Gas Generating Agent, Propellant and Explosive Compositions | |
| Habert et al. | Synthesis and reactivity of 5-hydrazino-3-nitro-1, 2, 4-triazole (HNT): an amphoteric energetic platform |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |