CN114671896B - Crystal based on triazene bridged azole, preparation method thereof and application of crystal as energetic material - Google Patents
Crystal based on triazene bridged azole, preparation method thereof and application of crystal as energetic material Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 title description 4
- AYNNSCRYTDRFCP-UHFFFAOYSA-N triazene Chemical compound NN=N AYNNSCRYTDRFCP-UHFFFAOYSA-N 0.000 title description 2
- 239000002360 explosive Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 230000000977 initiatory effect Effects 0.000 claims abstract description 13
- 150000001540 azides Chemical class 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 230000035945 sensitivity Effects 0.000 claims description 26
- -1 1-methyltetrazol-5-yl Chemical group 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- 125000004429 atom Chemical group 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical group [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- TZLVRPLSVNESQC-UHFFFAOYSA-N potassium azide Chemical compound [K+].[N-]=[N+]=[N-] TZLVRPLSVNESQC-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 239000003380 propellant Substances 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000004880 explosion Methods 0.000 abstract description 16
- LNAWIXGXVIGLOJ-UHFFFAOYSA-N hydrazine nickel(2+) dinitrate Chemical compound [N+](=O)([O-])[O-].NN.[Ni+2].[N+](=O)([O-])[O-] LNAWIXGXVIGLOJ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 33
- 239000010949 copper Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 9
- 150000004682 monohydrates Chemical class 0.000 description 9
- 229910052573 porcelain Inorganic materials 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- 229910052737 gold Inorganic materials 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005474 detonation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UJMSVOIUWFOQMW-UHFFFAOYSA-N [N+](=O)([O-])N1N(C=2N=[N+](N=CC=2C1)[O-])N=[N+]=[N-] Chemical compound [N+](=O)([O-])N1N(C=2N=[N+](N=CC=2C1)[O-])N=[N+]=[N-] UJMSVOIUWFOQMW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011011 black crystal Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B35/00—Compositions containing a metal azide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic System
- C07F13/005—Compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic System without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
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- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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Abstract
The invention discloses a crystal, a preparation method thereof and application thereof as an energetic material, and belongs to the technical field of energetic materials. The molecular formula of the crystal is M 3 C 8 H 12 N 34 M is a metal element selected from any one of Mn, fe, co, ni, cu, zn, cd. M provided by the invention 3 C 8 H 12 N 34 Has excellent stability and safety, and the required limit dosage of the energy-containing material is 1/2 of that of the current commercial initiating explosive lead azide; compared with the prior commercialized initiating explosive nickel hydrazine nitrate, the required limit dosage is 1/10 of that of the primary explosive nickel hydrazine nitrate, overcomes the defects of serious lead pollution and insufficient explosion performance of the primary explosive nickel hydrazine nitrate, and has important commercial application value in the field of green high-performance energetic materials.
Description
Technical Field
The invention relates to a crystal, a preparation method thereof and application thereof as an energetic material, belonging to the technical field of energetic materials.
Background
The energetic material is mainly applied to the fields of primary explosive, pyrotechnic agent and the like. The primary explosive commercialized at present is mainly lead azide Pb (N 3 ) 2 (LA) Nickel hydrazine nitrate [ Ni (N H)](NO) (NHN) and the like. Although the synthesis of the primary explosive is simple, the explosion products of the primary explosive have serious heavy metal pollution problem, and larger dosage is needed when the primary explosive is detonated due to insufficient output of the explosive force.
Researchers have developed new lead-free and more explosive primary explosive such as 6-nitro-7-azido-pyrazolo [3,4-d ] [1,2,3] triazine-2-oxide (ICM-103), but the synthetic steps are numerous, present a greater risk and are not beneficial to safe production.
Meanwhile, with the development of technology and the improvement of environmental protection requirements, green primary explosive with better performance is required, so that green, high-performance and commercializable primary explosive is explored and becomes an important research direction of energetic materials.
Disclosure of Invention
The method aims at solving the technical problems that the explosion products of the energetic materials in the prior art pollute the environment, the limit drug quantity is larger, the detonating capability is insufficient, the synthesis process is complex and the like. M disclosed in the invention 3 C 8 H 12 N 34 The limit dosage required for initiating the black soljin as the initiating explosive is 1/2 of LA and 1/10 of NHN, overcomes the defects of serious lead pollution and insufficient explosion performance, and has important commercial application value in the field of green high-performance energetic materials.
According to one aspect of the present invention, there is provided a crystal of the formula M 3 C 8 H 12 N 34 M is a metal element selected from any one of Mn, fe, co, ni, cu, zn, cd.
Optionally, the crystal belongs to a monoclinic system.
Optionally, the crystal has a 3-dimensional structure.
Alternatively, the smallest asymmetric structural unit of the 3-dimensional structure comprises three M atoms, two deprotonated 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene ligands, and four azido ions;
the 3M atoms are M1, M2 and M3 respectively;
the M1 is in a 5-coordinate configuration and is respectively coordinated with two N atoms from two deprotonated 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene ligands and 3N atoms on 3 azido groups;
the M2 is in a 4-coordinate configuration and is respectively coordinated with 2N atoms from two deprotonated 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene ligands and 2N atoms on two azido groups;
the M3 is in a 5-coordinate configuration, coordinated to 2N atoms from two deprotonated 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene ligands, 3N atoms on three azido groups, respectively.
Three M (II) atoms connect adjacent deprotonated 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene ligands and N3-anions to form a 1-dimensional chain along the c-axis, adjacent chains being linked by the deprotonated 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene ligands to further build up a 3-dimensional structure.
Optionally, the space group of the crystal is P2 1 /n。
Optionally, the unit cell parameters of the crystal are:
preferably, the method comprises the steps of,
most preferably, the first and second regions are,
according to another aspect of the present invention there is provided a process for the synthesis of the above crystals by reacting a mixture comprising a salt of a metal M, an azide and 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene at a temperature of from 90℃to 180℃for from 24 to 120 hours to give the crystals.
The reaction temperature is independently selected from any value or range of values between any two of 90 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ and 180 ℃.
The reaction time is independently selected from any value or range of values between any two of 24 hours, 36 hours, 48 hours, 100 hours, 120 hours.
Optionally, the molar ratio of the salt of the metal M, the azide and the 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene is (2/5-2): 1 (1/5-2); the molar amount of the salt of metal M is based on the molar amount of M.
Optionally, the mixture further comprises a solvent; preferably, the solvent is at least one of water, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ethanol, acetonitrile and methanol.
Optionally, the mass concentration of the salt of the metal M in the solvent is 0.003-0.111 g/mL, and the mass of the salt of the metal M is calculated by the mass of M.
Alternatively, the salt of metal M is selected from the group consisting of the oxyacid salts of M and the halogen-containing salts of M.
Optionally, the salt of the metal M is nitrate or perchlorate.
Optionally, the azide is at least one selected from sodium azide and potassium azide.
According to still another aspect of the present invention, there is provided an energetic material comprising any of the crystals described above, or comprising crystals obtained by any of the synthetic methods described above.
Optionally, the energetic material has a thermal stability > 200 ℃, an impact sensitivity=1j, a friction sensitivity=5n, and an electrostatic spark sensitivity=40mj.
According to a further aspect of the present invention there is provided the use of an energetic material as described above as an initiating explosive, a propellant energetic additive.
The invention has the beneficial effects that:
m provided by the invention 3 C 8 H 12 N 34 (m= Mn, fe, co, ni, cu, zn, cd) has excellent stability and safety, and is environment-friendly. Experiments show that the thermal stability is higher than 200 ℃, the impact sensitivity is not lower than 1J, the friction sensitivity is not lower than 5N, and the electrostatic spark sensitivity is not lower than 40mJ. The limit dosage required by the energetic material serving as an initiating explosive for initiating the black-cord gold is 15mg, which is 1/2 of that of the currently commercialized lead azide compared with the currently commercialized nickel hydrazine nitrate serving as the initiating explosive, and the limit dosage required by the energetic material serving as the initiating explosive for initiating the black-cord gold is 1/10 of that of the same, overcomes the defects of serious lead pollution and insufficient explosion performance, and has important commercial application value in the field of green high-performance energetic materials.
Drawings
FIG. 1 shows Cu prepared in example 5 of test example 2 according to the present invention 3 C 8 H 12 N 34 (10 mg) photographs of explosion experiments generated by friction sensitivity experiments; wherein, (a) is before the friction test; (b) is in a friction test; (c) is after a rub test; (d) is the explosion of the porcelain plate in which the sample is placed.
FIG. 2 shows the medium Cu of the present invention prepared in test example 2 for example 5 3 C 8 H 12 N 34 (10 mg) experimental photographs of explosions produced by an electrostatic spark sensitivity experiment; wherein, (a) is prior to testing the sample; (b) an explosion in the sample test; (c) is the middle and later stages of the sample test; (d) is near the end of the sample test.
FIG. 3 is a test of the present inventionExample 2 Medium Cu prepared in example 5 3 C 8 H 12 N 34 An experimental chart for testing the limit explosive quantity of the initiating explosive; wherein, (a) is a schematic diagram of an initiating explosive limit dosage testing device; (b-e) detonator of different primary explosive charges breaking 5mm lead plate: (b) 15mg Cu 3 C 8 H 12 N 34 As detonator primary explosive charge, the puncture aperture is 10.91mm; (c) 20mg Cu 3 C 8 H 12 N 34 As detonator primary explosive charge, the puncture aperture is 11.69mm; (d) 30mg of LA is used as primer primary explosive charge, and the breakdown aperture is 6.99mm; (e) 300mg NHN is used as detonator primary explosive charge, and the breakdown aperture is 10.84mm.
FIG. 4 is a Cu film prepared in example 5 3 C 8 H 12 N 34 Is a powder diffraction pattern of (2).
FIG. 5 is Cu prepared in example 5 3 C 8 H 12 N 34 Is a coordination environment diagram of (1).
FIG. 6 is Cu prepared in example 5 3 C 8 H 12 N 34 Is a crystal structure diagram of (a).
Detailed Description
The present invention is described in detail below with reference to examples, but the present invention is not limited to these examples.
Unless otherwise indicated, the starting materials and all materials used in the examples of the present invention were purchased commercially.
As one of the embodiments, the present invention provides a process for preparing a metal M salt, a trinitride, and 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene monohydrate starting materials in a molar ratio M: azide: 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene monohydrate= (2/5-2), wherein the ratio of 1 (1/5-2) is mixed and dispersed in 2-10mL deionized water, and the mixture is placed at the temperature of 90-180 ℃ to react for 24-120 hours, and then cooled to room temperature to obtain the energetic material. The metal salt can be perchlorate, nitrate and other oxygen acid salts, halogen-containing metal salts and the like. The tri-nitride may be sodium azide, potassium azide, etc.
EXAMPLE 1 Compound Mn 3 C 8 H 12 N 34 Is synthesized by (a)
Mn (ClO) 4 ) 2 ·6H 2 O(72.39mg)、NaN 3 (32.5 mg) and 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene monohydrate (136.31 mg) were added to 2mL of deionized water to obtain a mixture, and the mixture was heated to 90 ℃ for 36 hours, then cooled to room temperature, filtered to obtain a large amount of pink crystals, yield: 70%. The chemical formula of the pink crystal is Mn through X-ray single crystal diffraction test 3 C 8 H 12 N 34 。
EXAMPLE 2 Compound Fe 3 C 8 H 12 N 34 Is synthesized by (a)
Fe (ClO) 4 ) 2 ·6H 2 O(217.70mg)、NaN 3 (19.50 mg) and 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene monohydrate (113.6 mg) were added to 5mL of deionized water to obtain a mixture, and the mixture was heated to 130℃for 100 hours, then cooled to room temperature, filtered to obtain a large amount of colorless crystals, yield: 75%. The chemical formula of the colorless crystal is Fe after X-ray single crystal diffraction test 3 C 8 H 12 N 34 A kind of electronic device.
EXAMPLE 3 Compound Co 3 C 8 H 12 N 34 Is synthesized by (a)
Co (ClO) 4 ) 2 ·6H 2 O(146.70mg)、NaN 3 (26.00 mg) and 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene monohydrate (90.88 mg) were added to 6mL of deionized water to obtain a mixture, and the mixture was heated to 120 ℃ for 36 hours, then cooled to room temperature, filtered to obtain a large amount of red crystals, yield: 68%. The chemical formula of the red crystal is Co through X-ray single crystal diffraction test 3 C 8 H 12 N 34 。
EXAMPLE 4 Compound Ni 3 C 8 H 12 N 34 Is synthesized by (a)
Ni (ClO) 4 ) 2 ·6H 2 O(182.85mg)、NaN 3 (32.5 mg) and 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene monohydrate (68.16 mg) were added to 10mL of deionized water to obtain a mixture, and the mixture was heated to 180℃to react 12After 0 hours, the mixture was cooled to room temperature and filtered to obtain a large amount of purple crystals, yield: 73%. The chemical formula of the purple crystal is Ni through X-ray single crystal diffraction test 3 C 8 H 12 N 34 。
EXAMPLE 5 Compound Cu 3 C 8 H 12 N 34 Is synthesized by (a)
Cu (ClO) 4 ) 2 ·6H 2 O(185.27mg)、NaN 3 (32.5 mg) and 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene monohydrate (113.6 mg) were added to 8mL of deionized water to obtain a mixture, and the mixture was heated to 140 ℃ for 48 hours, then cooled to room temperature, filtered to obtain a large amount of black crystals, yield: 37%. The chemical formula of the black crystal is Cu through X-ray single crystal diffraction test 3 C 8 H 12 N 34 。
From FIG. 4, it can be seen that the energetic material Cu provided by the present application 3 C 8 H 12 N 34 The X-ray powder diffraction peak of (2) is consistent with the height of the simulation peak, and has good phase purity.
From fig. 5, it can be appreciated that the chelating ligand exhibits a rich coordination site, and that the chelating ligand links adjacent copper atoms to the bridging azide.
From FIG. 6, it can be seen that the energetic material Cu provided by the present application 3 C 8 H 12 N 34 Has a 3-dimensional structure.
EXAMPLE 6 Compound Zn 3 C 8 H 12 N 34 Is synthesized by (a)
Zn (ClO) 4 ) 2 ·6H 2 O(74.48mg)、NaN 3 (72.39 mg) and 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene monohydrate (136.31 mg) were added to 4mL of deionized water, and all the mixture was heated to 150 ℃ for 36 hours, then cooled to room temperature, filtered to give a large amount of colorless crystals, yield: 67%. The colorless crystal has a chemical formula of Zn by X-ray single crystal diffraction test 3 C 8 H 12 N 34 。
EXAMPLE 7 Compound Cd 3 C 8 H 12 N 34 Is synthesized by (a)
Cd (ClO) 4 ) 2 ·6H 2 O(251.64mg)、NaN 3 (19.50 mg) and 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene monohydrate (22.72 mg) were added to 7mL of deionized water, and all the mixture was heated to 140 ℃ for 24 hours, then cooled to room temperature, filtered to give a large amount of colorless crystals, yield: 55%. The colorless crystal has a chemical formula of Cd through X-ray single crystal diffraction test 3 C 8 H 12 N 34 。
Test example 1
The pink crystals prepared in example 1 were structurally characterized.
The crystal is irradiated by graphite monochromatic Mo-K alphaAfter X-ray single crystal diffraction test (test conditions: 100K) was performed on a Rigaku FR-X micro focus diffractometer, the test was passed through Olex 2 1.2 resolving the structure.
The analysis result of X-ray single crystal diffraction shows that: the structural formula of the crystalline material of the pink crystal is Mn 3 C 8 H 12 N 34 Of P2 belonging to monoclinic system 1 N space groups. The cell parameters are detailed in Table 1.
The crystals prepared in example 2, example 3, example 4, example 5, example 6 and example 7 were respectively subjected to structural characterization by referring to the above methods.
The results of the X-ray single crystal diffraction analysis are shown in Table 1.
Table 1M 3 C 8 H 12 N 34 Related crystallographic parameters of (a)
Test example 2
The crystals prepared in examples 1,2,3, 4, 5, 6 and 7 were subjected to explosion performance test, and the results are shown in table 2.
The testing method comprises the following steps: according to the national army standard test standards GJB 772A-97 and GJB 589.24-2006 of energetic materials, a BAM friction sensitivity tester FSKM-10 produced by the company Czech OZM is adopted, and the corresponding value of 50% firing rate of the compound is determined through tens of tests; according to the electrostatic spark sensitivity test standard of energetic materials, an electrostatic spark sensitivity tester Xspark8 produced by Czech OZM company is adopted, and the value corresponding to the 50% ignition rate of the compound is determined through tens of tests.
The BAM test adopts a weight structure, the loads with different masses are hung at different positions to correspond to corresponding forces, a sample is placed on a disposable porcelain plate, the placement position of the porcelain plate is required to enable stripes of the porcelain plate to be perpendicular to the movement direction of a motor, the sample is pressed by a disposable porcelain head, and the movement speed of the porcelain plate is controlled by a numerical control stepping motor. During testing, the sample is placed at one side of the porcelain plate, which is slightly close to the instrument, and a weight with the required strength is hung on the porcelain plate, so that the porcelain head presses a part of the sample, and the motor is driven. Judging whether the sample is exploded or not according to the smell, the color and the sound. The friction sensitivity value is a threshold value of 50% explosion probability of the sample, and when the scale is adjusted to 1 by using a B1 weight (0.28 Kg), the threshold value of 50% explosion probability is measured to be 5N.
The electrostatic spark sensitivity values of the Xpark8 electrostatic spark sensitivity meter test samples were studied using OZM, and the discharge energy was obtained according to the formula e=0.5cu 2. C represents the capacitance of the capacitor in Farad (F), U represents the charging voltage in volts (V). Static spark sensitivity values measured at 50% firing rate. When c=5nf, u=4kv, e=0.5×c×uζ2=0.5×5×10 (-9) (4×10≡3) ≡2=40 mJ.
Table 2: m is M 3 C 8 H 12 N 34 Performance parameters of (m= Mn, fe, co, ni, cu, zn, cd)
N a =nitrogen content; t (T) dec b =decomposition temperature; IS c Impact sensitivity; FS (FS) d Friction sensitivity; ESD (electro-static discharge) e Electrostatic spark sensitivity
From table 2, it can be known that the energetic material provided by the present application has better stability: the thermal stability is more than 200 ℃, the impact sensitivity is not less than 1J, the friction sensitivity is not less than 5N, the electrostatic spark sensitivity is not less than 40mJ, and the explosion product has little pollution to the environment, thus being an excellent energetic material.
From FIG. 1, it can be seen that the energetic material Cu provided by the present application 3 C 8 H 12 N 34 Has excellent explosion performance and proper friction sensitivity.
From FIG. 2, it can be seen that the energetic material Cu provided in the present application 3 C 8 H 12 N 34 Has excellent explosion performance and proper electrostatic spark sensitivity.
From FIG. 3, it can be seen that the energetic material Cu provided by the present application 3 C 8 H 12 N 34 The detonation cable gold detonating device has excellent detonation capability and strong detonation output capability, and can completely detonate the black cable gold only by 15mg, break through a lead plate with the thickness of 5mm and leave holes with the diameter of 10.91mm on the plate; 20mg of fully detonating black gold, breaking down a lead plate with the thickness of 5mm, and leaving a hole with the diameter of 11.69mm on the plate; under the same test conditions, 30mg of lead azide detonates black gold to break down a lead plate with the thickness of 5mm, and only holes with the diameter of 6.99mm are left on the plate; 300mg of nickel hydrazine nitrate detonates black cable gold, a lead plate with the thickness of 5mm is broken down, and a hole with the diameter of 10.84mm is left on the plate, which is equivalent to the explosion effect achieved by 15mg of the energetic material provided by the application.
While the invention has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the invention, and it is intended that the invention is not limited to the specific embodiments disclosed.
Claims (16)
1. A crystal of the type characterized in that,the chemical formula of the crystal is M 3 C 8 H 12 N 34 M is a metal element selected from any one of Mn, fe, co, ni, cu, zn, cd;
the crystal belongs to a monoclinic system;
the crystal has a 3-dimensional structure;
the smallest asymmetric structural unit of the 3-dimensional structure comprises three M atoms, two deprotonated 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene ligands and four azide ions;
the 3M atoms are M1, M2 and M3 respectively;
the M1 is in a 5-coordinate configuration and is respectively coordinated with two N atoms from two deprotonated 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene ligands and 3N atoms on 3 azido groups;
the M2 is in a 4-coordinate configuration and is respectively coordinated with 2N atoms from two deprotonated 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene ligands and 2N atoms on two azido groups;
the M3 is in a 5-coordinate configuration, coordinated to 2N atoms from two deprotonated 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene ligands, 3N atoms on three azido groups, respectively.
2. The crystal according to claim 1, wherein the space group of the crystal is P2 1 /n。
3. The crystal according to claim 1, wherein the unit cell parameters of the crystal are:
4. the crystal according to claim 1, characterized in thatIn that the method is characterized in that,
5. the crystal according to claim 1, wherein,
6. a process for synthesizing a crystal according to any one of claims 1 to 5, characterized in that a mixture comprising a salt of metal M, azide and 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene is reacted at a temperature of 90℃to 180℃for 24 to 120 hours to obtain the crystal.
7. The method according to claim 6, wherein the molar ratio of the salt of the metal M, the azide, the 1, 3-bis (1-methyltetrazol-5-yl) triaza-1-ene is (2/5-2): 1 (1/5-2); the molar amount of the salt of metal M is based on the molar amount of M.
8. The method according to claim 6, wherein the metal M salt is selected from the group consisting of an oxyacid salt of M and a halogen-containing salt of M.
9. The method according to claim 6, wherein the salt of metal M is nitrate or perchlorate.
10. The method according to claim 6, wherein the azide is at least one selected from the group consisting of sodium azide and potassium azide.
11. The method of claim 6, wherein the mixture further comprises a solvent.
12. The method according to claim 11, wherein the solvent is at least one of water, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, ethanol, acetonitrile, and methanol.
13. The method according to claim 6, wherein the mass concentration of the salt of the metal M in the solvent is 0.003 to 0.111g/mL, and the mass of the salt of the metal M is calculated as the mass of M.
14. An energetic material, characterized in that it comprises a crystal according to any one of claims 1 to 5 or a crystal obtained by a synthesis method according to any one of claims 6 to 13.
15. The energetic material according to claim 14, wherein the energetic material has a thermal stability > 200 ℃, impact sensitivity=1j, friction sensitivity=5n, electrostatic spark sensitivity=40mj.
16. Use of an energetic material according to claim 14 or 15 as an initiating explosive, propellant energetic additive.
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| CN101412736A (en) * | 2008-08-20 | 2009-04-22 | 西北大学 | Energetic coordination complex based on N,N'-bis(tetrazole) ammonium salt |
| JP2010180201A (en) * | 2009-01-07 | 2010-08-19 | Kuraray Co Ltd | Metal complex and method for producing the same |
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| CN107674099A (en) * | 2017-10-26 | 2018-02-09 | 中国科学院福建物质结构研究所 | A kind of energetic material, its preparation method and the application as priming, explosive and pyrotechnic compound |
| CN111153915A (en) * | 2020-01-15 | 2020-05-15 | 中国科学院福建物质结构研究所 | MCHN7Energetic material, preparation method thereof and application thereof as primary explosive, explosive and pyrotechnic agent |
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| CN101412736A (en) * | 2008-08-20 | 2009-04-22 | 西北大学 | Energetic coordination complex based on N,N'-bis(tetrazole) ammonium salt |
| JP2010180201A (en) * | 2009-01-07 | 2010-08-19 | Kuraray Co Ltd | Metal complex and method for producing the same |
| CN102241695A (en) * | 2011-05-16 | 2011-11-16 | 汕头大学 | Akin molecular sieve metal double imidazoles porous coordination polymer and preparation method thereof |
| CN107674099A (en) * | 2017-10-26 | 2018-02-09 | 中国科学院福建物质结构研究所 | A kind of energetic material, its preparation method and the application as priming, explosive and pyrotechnic compound |
| CN111153915A (en) * | 2020-01-15 | 2020-05-15 | 中国科学院福建物质结构研究所 | MCHN7Energetic material, preparation method thereof and application thereof as primary explosive, explosive and pyrotechnic agent |
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