CN109651447A - One kind being based on the metal energetic compound and preparation method thereof of 3- amino -4- (tetrazolium -5- base) furazan - Google Patents
One kind being based on the metal energetic compound and preparation method thereof of 3- amino -4- (tetrazolium -5- base) furazan Download PDFInfo
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- CN109651447A CN109651447A CN201910060321.3A CN201910060321A CN109651447A CN 109651447 A CN109651447 A CN 109651447A CN 201910060321 A CN201910060321 A CN 201910060321A CN 109651447 A CN109651447 A CN 109651447A
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- Prior art keywords
- furazan
- tetrazolium
- amino
- base
- metal
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- JKFAIQOWCVVSKC-UHFFFAOYSA-N furazan Chemical compound C=1C=NON=1 JKFAIQOWCVVSKC-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 125000003831 tetrazolyl group Chemical group 0.000 title claims abstract description 30
- 150000001875 compounds Chemical class 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005474 detonation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- -1 tetrazole compound Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910014288 N-N Inorganic materials 0.000 description 1
- 229910017852 NH2NH2 Inorganic materials 0.000 description 1
- 229910014320 N—N Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003349 semicarbazides Chemical class 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
-
- 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 Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a kind of metal energetic compounds and its preparation method and application for being based on 3- amino -4- (tetrazolium -5- base) furazan.The structural formula of the metal energetic compound isIts synthetic method are as follows: 3- amino -4- (tetrazolium -5- base) furazan, soluble metallic salt, formylhydrazine are raw material, in appropriate solvent, are reacted 1-1.5 hours at room temperature, and filtering is dried in vacuo to obtain target product.Synthetic method of the present invention is simple, easy to operate, easy to industrialized production.Metal energetic compound based on 3- amino -4- (tetrazolium -5- base) furazan of the invention can be used as a kind of novel energetic material.
Description
Technical field
The invention belongs to energetic material fields, and in particular to one kind is based on the metal of 3- amino -4- (tetrazolium -5- base) furazan
Energetic compound and preparation method thereof.
Background technique
Currently, the design of Nitrogen Heterocyclic Energetic Compounds, synthesis and application are widely concerned by researchers at home and abroad.Its
In, a large amount of C-N, C=N, N-N and N=N key is contained in tetrazole compound, so that its density with higher and positive generation
Enthalpy, and release the nitrogen of no pollution to the environment；Effective unit of the furazan ring as building energetic material, it is flat to can be improved oxygen
Weighing apparatus.Therefore, furazan-tetrazole compound has potential application prospect in the fields such as composite explosives and solid propellant.
With the demand for development of energetic material, the advantages that metal complex is felt immediately due to itself, thermal stability is good, is at home
Rapidly developed outside.In recent years, have various metals energetic compound to be exploited, such as: [Ag16(BTFOF)9]n·[2
(NH4)]n、[Cd2(N2H4)2(N3)4]n(N2H4For hydrazine hydrate), Zn (SCZ)2(H2O)22HTNR (SCZ is semicarbazides, TNR 2,
4,6- trinitroresorein) etc..
2008, Jean ' ne M.Shreeve et al. reported the synthesis of 3- amino -4- (tetrazolium -5- base) furazan for the first time.
3- amino -4- (tetrazolium -5- base) furazan, abbreviation HAFT, which is easy preparation, soluble easily in water, and aqueous solution is in acidity,
In, the presence of furazan ring makes tetrazolium be easy to deprotonation, generate corresponding ion, under certain condition can with metal from
Son synthesizes new high energy richness nitrogen complex at salt.It is a kind of energy-containing compound by people's common concern in recent years, many
Researcher is it has been reported that Cd (NH2NH2)(AFT)2·0.7H2O, Cd (NH2NHCOCONHNH2)1.5(AFT)2·5H2O, Cd
(H2O)2(AFT)2, G (AFT), AG (AFT), DAG (AFT), the synthesis of TAG (AFT) etc., therefore, it is before one kind has application very much
The high-nitrogen energetic materials of scape.
Summary of the invention
For the problems of the prior art, it is high, better heat stability based on 3- amino-that the present invention provides a kind of nitrogen content
The metal energetic compound and preparation method thereof of 4- (tetrazolium -5- base) furazan.
To realize the above technical purpose, the technical scheme is that
One kind being based on the metal energetic compound of 3- amino -4- (tetrazolium -5- base) furazan, the metal energetic compound
Formula is Co (HCONHNH2)2(AFT)2·H2O, shown in result such as formula (I):
The complex is monoclinic system, space group P21/ c, cell parameter a=10.246 (3) nm, b=13.084 (3)
Nm, c=7.1947 (19) nm, β=90.766 (5) °,Z=12, μ=5.070mm-1, F (000)=588, Dc
=2.107gcm-3,R1=0.1040 and wR2=0.1560.
The metal energetic compound the preparation method is as follows:
, as raw material, it is dissolved in it in appropriate solvent using 3- amino -4- (tetrazolium -5- base) furazan, it is anti-with soluble metallic salt
It answers, formylhydrazine is then added, reacts at a certain temperature, filter, be dried in vacuo to obtain purpose product.
3- amino -4- (tetrazolium -5- base) furazan: soluble metallic salt: the molar ratio of formylhydrazine is 1:0.6:1.2.
The soluble metallic salt uses Co (NO3)2·6H2O。
The solvent uses distilled water, and the volume of the solvent and the 3- amino -4- (tetrazolium -5- base) furazan is 1-
10。
The reaction time is 1h.
The certain temperature is 25 DEG C.
The metal energetic compound of 3- amino -4- (tetrazolium -5- base) furazan is as energetic material application.
From the above, it can be seen that the present invention has following advantages:
(1) the metal energetic compound of 3- amino -4- of the invention (tetrazolium -5- base) furazan is the new rich nitrogen of one kind containing energy
Complex can be used for energetic material field.
(2) synthetic method of the present invention is simple, using water as reaction dissolvent, has excellent stability, yield is high, is easy to industry
Productionization.
Detailed description of the invention
Fig. 1 is crystal structure figure of the invention.
Fig. 2 is DSC test chart of the invention.
Fig. 3 is TG-DTG test chart of the invention.
Specific embodiment
In conjunction with Fig. 1, Fig. 2 and Fig. 3, the specific embodiment that the present invention will be described in detail, but right of the invention is not wanted
It asks and does any restriction.
Embodiment 1:
At room temperature, 0.1531g (1mmol) 3- amino -4- (tetrazolium -5- base) furazan is dissolved in 3ml deionized water, is set
It is stirred continuously in 50ml round-bottomed flask, until being completely dissolved, 5ml (NO containing 0.1746g (0.6mmol) Co is added dropwise dropwise3)2·
6H2O aqueous solution reacts 15min, and 5ml is added and contains 0.7207g (1.2mmol) formylhydrazine aqueous solution, and charging is finished, and reacts at room temperature 1h,
Reaction is finished, and filter cake is dried in vacuo by filtering, obtains pink colour target compound.After deionized water washing purification, gained targeted
Object is closed, characterization result is as follows: FT-IR (KBr): 3456,3253,2996,1667,1632,1602,1357,1160,987,877,
634,573,407cm-1。
By gained filtrate in embodiment 1, repeatedly washing and refining and edulcoration, final filtration gained filtrate obtain powder through slow evaporation
Color crystal carries out X- single crystal diffraction test to it.As shown in Figure 1, the crystal belongs to monoclinic system, space group P21/ c, structure cell
Parameter a=10.246 (3) nm, b=13.084 (3) nm, c=7.1947 (19) nm, β=90.766 (5) °,Z
=12, μ=5.070mm-1, F (000)=588, Dc=2.107gcm-3,R1=0.1040 and wR2=0.1560.
By pink colour crystal grind into powder, the DSC and TG-DTG test under 10 DEG C/min of heating rate are carried out.By DSC (figure
2) and TG (Fig. 3) is it is found that the compound thermal behavior is divided into three phases, and the first stage is endothermic process, and 140.2 DEG C of peak temperature, matter
Amount loss about 22.82%.Second stage is exothermic decomposition process, and decomposition peak's temperature is 316.4 DEG C, and mass loss is about
49.08%.Phase III is faint decomposable process, and decomposition peak's temperature is 641.6 DEG C, and mass loss is about 14.37%.From decomposition
Temperature can be seen that the present invention has excellent thermal stability.
Using German IKA C5000 oxygen bomb calorimeter, under adiabatic model to the pink colour crystal (1.2g) in embodiment 1 into
Row constant volume burning Thermal test (ΔcUm).Measuring number is six times, final six ΔscUmAverage value is -1189.80kJmol-1。
According to combustion reaction equation and formula ΔcHm θ=ΔcUm+ Δ nRT calculates to obtain standard molar combustion enthalpy (ΔcHm θ) be-
1171.21kJ·mol-1.Finally according to law of Hess, standard molar formation enthalpy (Δ is calculated to obtainfHm θ) it is -4501.25kJ
mol-1。
According to GJB772A-97, hit using WL-1 type drop-weight meter to by the pink colour crystal (25mg) in embodiment 1
Sensitivity test.Quality of dropping hammer is 10kg, drop height 25cm, the experimental results showed that explosion probability is 56%.Using WM-1 type to reality
It applies pink colour crystal (20mg) in example 1 and carries out friction sensitivity test.Pendulum mass quality is 2700g, and pivot angle is 90 °, implements pressure and is
3.92MPa, the experimental results showed that explosion probability is 60%.According to Kamlet and Jacobs formula:
D=1.01 (NM1/2Q1/2)1/2(1+1.30ρ0)
P=1.55 ρ0 2NM1/2Q1/2
Calculate quick-fried hot (Q), explosion velocity (D) and the detonation pressure (P) of the pink colour crystal in embodiment 1.Obtaining quick-fried heat is 2.912kJg-1, explosion velocity 9.32kms-1, detonation pressure 42.13GPa.
In conclusion the invention has the following advantages that
It is understood that being merely to illustrate the present invention above with respect to specific descriptions of the invention and being not limited to this
Technical solution described in inventive embodiments.Those skilled in the art should understand that still can be carried out to the present invention
Modification or equivalent replacement, to reach identical technical effect；As long as meet use needs, all protection scope of the present invention it
It is interior.
Claims (9)
1. the metal energetic compound that one kind is based on 3- amino -4- (tetrazolium -5- base) furazan, it is characterised in that: the metal contains
Being able to cooperate object chemical formula is Co (HCONHNH2)2(AFT)2·H2O, shown in result such as formula (I):
2. the metal energetic compound according to claim 1 based on 3- amino -4- (tetrazolium -5- base) furazan, feature
Be: the complex is monoclinic system, space group P21/ c, cell parameter a=10.246 (3) nm, b=13.084 (3) nm, c
=7.1947 (19) nm, β=90.766 (5) °,Z=12, μ=5.070mm-1, F (000)=588, Dc=
2.107g·cm-3,R1=0.1040 and wR2=0.1560.
3. the metal energetic compound according to claim 1 based on 3- amino -4- (tetrazolium -5- base) furazan, feature
Be: the metal energetic compound the preparation method is as follows:
, as raw material, it is dissolved in it in appropriate solvent using 3- amino -4- (tetrazolium -5- base) furazan, and soluble metal reactant salt, so
After formylhydrazine is added, react at a certain temperature, filter, be dried in vacuo to obtain purpose product.
4. the metal energetic compound according to claim 3 based on 3- amino -4- (tetrazolium -5- base) furazan, feature
Be: 3- amino -4- (tetrazolium -5- base) furazan: soluble metallic salt: the molar ratio of formylhydrazine is 1:0.6:1.2.
5. the metal energetic compound according to claim 3 based on 3- amino -4- (tetrazolium -5- base) furazan, feature
Be: the soluble metallic salt uses Co (NO3)2·6H2O。
6. the metal energetic compound according to claim 3 based on 3- amino -4- (tetrazolium -5- base) furazan, feature
Be: the solvent uses distilled water, and the volume of the solvent and the 3- amino -4- (tetrazolium -5- base) furazan is 1-10.
7. the metal energetic compound according to claim 3 based on 3- amino -4- (tetrazolium -5- base) furazan, feature
Be: the reaction time is 1h.
8. the metal energetic compound according to claim 3 based on 3- amino -4- (tetrazolium -5- base) furazan, feature
Be: the certain temperature is 25 DEG C.
9. the metal energetic compound according to claim 1 based on 3- amino -4- (tetrazolium -5- base) furazan, feature
Be: the metal energetic compound of 3- amino -4- (tetrazolium -5- base) furazan is as energetic material application.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910060321.3A CN109651447A (en) | 2019-01-22 | 2019-01-22 | One kind being based on the metal energetic compound and preparation method thereof of 3- amino -4- (tetrazolium -5- base) furazan |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910060321.3A CN109651447A (en) | 2019-01-22 | 2019-01-22 | One kind being based on the metal energetic compound and preparation method thereof of 3- amino -4- (tetrazolium -5- base) furazan |
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| Publication Number | Publication Date |
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|---|---|---|---|
| CN201910060321.3A Pending CN109651447A (en) | 2019-01-22 | 2019-01-22 | One kind being based on the metal energetic compound and preparation method thereof of 3- amino -4- (tetrazolium -5- base) furazan |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114907411A (en) * | 2022-04-29 | 2022-08-16 | 闽都创新实验室 | Inorganic-organic hybrid compound crystal, preparation method thereof and application thereof as energetic material |
-
2019
- 2019-01-22 CN CN201910060321.3A patent/CN109651447A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114907411A (en) * | 2022-04-29 | 2022-08-16 | 闽都创新实验室 | Inorganic-organic hybrid compound crystal, preparation method thereof and application thereof as energetic material |
| CN114907411B (en) * | 2022-04-29 | 2024-03-01 | 闽都创新实验室 | Inorganic-organic hybrid compound crystal, preparation method thereof and application thereof as energetic material |
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Application publication date: 20190419 |