CN115304763A - Perfluorobutane polyazide ether and preparation method and application thereof - Google Patents
Perfluorobutane polyazide ether and preparation method and application thereof Download PDFInfo
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- CN115304763A CN115304763A CN202210680837.XA CN202210680837A CN115304763A CN 115304763 A CN115304763 A CN 115304763A CN 202210680837 A CN202210680837 A CN 202210680837A CN 115304763 A CN115304763 A CN 115304763A
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- perfluorobutane
- ether
- polyazide
- aluminum powder
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 280
- 229950003332 perflubutane Drugs 0.000 title claims abstract description 141
- KAVGMUDTWQVPDF-UHFFFAOYSA-N perflubutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)F KAVGMUDTWQVPDF-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 174
- 239000002994 raw material Substances 0.000 claims abstract description 48
- PGRFXXCKHGIFSV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-iodobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)I PGRFXXCKHGIFSV-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000002485 combustion reaction Methods 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012312 sodium hydride Substances 0.000 claims abstract description 19
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 19
- -1 poly-azido glycidyl ether Chemical compound 0.000 claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 139
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 120
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 67
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 54
- 239000007864 aqueous solution Substances 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 24
- 229920002873 Polyethylenimine Polymers 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229920006395 saturated elastomer Polymers 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 17
- 238000004440 column chromatography Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 150000001540 azides Chemical class 0.000 abstract description 67
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 19
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 12
- JSOGDEOQBIUNTR-UHFFFAOYSA-N 2-(azidomethyl)oxirane Chemical compound [N-]=[N+]=NCC1CO1 JSOGDEOQBIUNTR-UHFFFAOYSA-N 0.000 abstract description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012467 final product Substances 0.000 description 32
- 238000002329 infrared spectrum Methods 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 239000005416 organic matter Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000003380 propellant Substances 0.000 description 6
- CDGYSQWAXZZQGE-UHFFFAOYSA-N 2-[azido-[azido(oxiran-2-yl)methoxy]methyl]oxirane Chemical compound N(=[N+]=[N-])C(C1CO1)OC(C1CO1)N=[N+]=[N-] CDGYSQWAXZZQGE-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000004566 IR spectroscopy Methods 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 229940071870 hydroiodic acid Drugs 0.000 description 3
- XXMRTNMIMYSCCI-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,4-decafluorobutane hydroiodide Chemical compound I.FC(F)(F)C(F)(F)C(F)(F)C(F)(F)F XXMRTNMIMYSCCI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000010702 perfluoropolyether Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005530 etching 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
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000010410 layer Substances 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
- 239000000203 mixture Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to perfluorobutane poly azide ether and a preparation method and application thereof, belonging to the technical field of high-energy aluminum powder combustion accelerators. The raw material of the perfluorobutane polyazide is composed of a main raw material and an auxiliary raw material, and the raw material comprises the following components in percentage by mass based on 100% of the total mass of the main raw material: 33-50% of perfluoroiodobutane and 50-67% of poly-azido glycidyl ether; the auxiliary raw material is catalyst sodium hydride. The preparation method of the perfluorobutane poly azide ether comprises the steps of reacting iodine atoms of perfluoroiodobutane with terminal hydroxyl groups of poly glycidyl azide at the temperature of 60-80 ℃ under the action of a catalyst for 6-8 hours to carry out nucleophilic substitution; the perfluorobutane poly azide ether is coated on the surface of aluminum powder to serve as a combustion promoter of the aluminum powder, so that the ignition temperature of the aluminum powder can be effectively reduced, a large amount of energy can be released in the combustion process to promote the combustion of the aluminum powder, the average combustion heat value is 27.9kJ/g, and the combustion heat value is improved by 8.1% compared with pure aluminum powder.
Description
Technical Field
The invention relates to perfluorobutane poly azide ether and a preparation method and application thereof, belonging to the technical field of high-energy aluminum powder combustion accelerators.
Background
The aluminum powder is widely applied to the fields of explosives and propellants because of high combustion heat value, low price and rich energy storage. The pure aluminum powder is easily oxidized by air in the preparation process, an alumina shell with a high melting point (2050 ℃) is formed on the surface of the aluminum powder, and the alumina shell layer can increase the ignition time of the aluminum powder, reduce the combustion efficiency and the combustion speed of the aluminum powder and reduce the energy release of the aluminum powder. In order to reduce the ignition temperature of the aluminum powder, researchers often modify the aluminum powder with a facecoat. The thermal decomposition product of the organic fluoride can perform a pre-ignition reaction with an aluminum oxide shell on the surface of the aluminum powder, so that the energy release rate of the aluminum powder can be greatly increased, and the agglomeration of the aluminum powder in the combustion process can be reduced, therefore, the fluoride is coated on the surface of the aluminum powder to activate the aluminum powder.
In the prior art, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), perfluoropolyether (PFPE), perfluoroiodobutane, fluoride salt or fluororubber are generally used for coating aluminum powder, and then the coated aluminum powder is applied to a propellant to be used as a fuel, but the common fluorides do not contain energy, the energy of the aluminum powder can be reduced after the aluminum powder is coated, and in addition, the compatibility between the aluminum powder coated with the common fluorides and a binder in the propellant is poor, so that the mechanical property and the energy of the propellant are reduced. The fluoride-coated aluminum powder is usually prepared by means of solvent stirring evaporation, ultrasonic dispersion centrifugation and the like, and the fluoride cannot be uniformly distributed on the surface of the aluminum powder and is easy to fall off by virtue of electrostatic acting force between an organic matter and the aluminum powder.
Disclosure of Invention
In order to overcome the defects in the prior art, one of the purposes of the invention is to provide perfluorobutane poly azide ether which contains energy, does not reduce the energy of aluminum powder after coating the aluminum powder, has good compatibility with an adhesive in a propellant, is uniformly coated and is not easy to fall off.
The second purpose of the invention is to provide a preparation method of perfluorobutane polyazide.
The invention also aims to provide application of the perfluorobutane polyazide.
In order to achieve the purpose of the invention, the following technical scheme is provided.
The perfluorobutane poly azide ether (PGAP) is prepared from a main raw material and an auxiliary raw material, wherein the total mass of the main raw material is 100%, and the raw material comprises the following components in percentage by mass: 33-50% of Perfluoroiodobutane (PI) and 50-67% of poly-azido glycidyl ether (GAP); the auxiliary raw material is a catalyst, and the catalyst is sodium hydride.
Preferably, the mass ratio of the catalyst to the polyaziridinyl glycidyl ether is 1.
The invention relates to a preparation method of perfluorobutane polyazide, which comprises the following steps:
the method comprises the following steps:
(1) Dissolving perfluoroiodobutane and polyaziridine glycidyl ether in N, N-Dimethylformamide (DMF) to obtain a mixed solution;
preferably, perfluoroiodobutane and polyaziridine glycidyl ether are dissolved in N, N-dimethylformamide under stirring at a temperature of 40-60 ℃;
preferably, the mass (g) of polyazide glycidyl ether and the volume (mL) of DMF have a ratio of (2-4): (20-40), the molecular weight of the polyaziridinyl glycidyl ether is 480.
(2) Adding a catalyst sodium hydride into the mixed solution obtained in the step (1), heating to 60-80 ℃, condensing, refluxing, and stirring for reacting for 6-8 h;
(3) Cooling the reacted liquid in the step (2) to room temperature, adding ethyl acetate, and then using saturated NaHCO 3 Washing the aqueous solution for 2-4 times, extracting and reserving an organic extraction phase;
preferably, the ratio of the mass (g) of the polyaziridinyl glycidyl ether to the volume (mL) of the ethyl acetate is (2-4): (20-40);
preferably, the mass of the polyaziridinyl glycidyl ether (g)) And saturated NaHCO 3 The proportion relation of the volume (mL) of the aqueous solution is (2-4): (10-20);
(4) And (3) drying the organic extraction phase obtained in the step (3) by using anhydrous magnesium sulfate, removing DMF (dimethyl formamide) by rotary evaporation to obtain a crude product, and purifying by using column chromatography to obtain the perfluorobutane polyazide ether.
Preferably, the mass ratio of the polyaziridine glycidyl ether to anhydrous magnesium sulfate is 1;
preferably, the developing solvent used for the column chromatography purification is a mixed solution of ethyl acetate and hexane, wherein the volume ratio of ethyl acetate to hexane is 1.
The invention relates to an application of perfluorobutane poly azide ether, which is a combustion accelerator coated on the surface of aluminum powder and used as aluminum powder.
Specifically, DMF and hydrofluoric acid aqueous solution with the mass fraction of 2% -3% are uniformly mixed, and aluminum powder is added under the protection of inert gas to form aluminum suspension solution; dissolving perfluorobutane polyazide into DMF to obtain a perfluorobutane polyazide solution; and finally, adding a perfluorobutane polyazide solution into the aluminum suspension, filtering, washing and drying to obtain the perfluorobutane polyazide coated micron aluminum powder.
Advantageous effects
(1) The invention provides perfluorobutane poly azide ether which is an energy-containing organic fluoride, wherein in a main raw material of the perfluorobutane poly azide ether, the mass fraction of perfluoroiodobutane is 33% -50%, and the mass fraction of poly glycidyl azide is 50% -67%; the polyazide glycidyl ether is an energy-containing adhesive, can provide energy and has good compatibility with other components in the propellant; the two ends of the poly (azido-glycidyl ether) contain hydroxyl, the stoichiometric ratio of the perfluoro iodo butane to the poly (azido-glycidyl ether) is 2, the molar ratio can be calculated to be less than 2 according to the mass fraction of the perfluoro iodo butane to the poly (azido-glycidyl ether) in the main raw material component, the mass ratio can retain part of the hydroxyl of the poly (azido-glycidyl ether), and the reactivity of the perfluoro butane poly (azido-glycidyl ether) is endowed; because the glycidyl azide polymer has large steric hindrance, the conventional catalyst, such as NaOH, KCN, RONa and NaSH, is difficult to catalyze the iodine atom of perfluoroiodobutane and the terminal hydroxyl group of the glycidyl azide polymer to carry out nucleophilic substitution reaction, and sodium hydride with strong reducibility is used as the catalyst to efficiently catalyze the nucleophilic substitution reaction.
(2) The invention provides a preparation method of perfluorobutane poly azide ether, which is characterized in that iodine atoms of perfluoroiodobutane and terminal hydroxyl groups of poly glycidyl azide carry out nucleophilic substitution reaction, the poly glycidyl azide has large steric hindrance and is difficult to generate nucleophilic substitution reaction, perfluoroalkyl iodide in perfluoroalkyl halide (chlorine, bromine and iodine) has the strongest reaction activity, the nucleophilic substitution reaction is carried out by utilizing the strong reaction capability of the perfluoroiodobutane and utilizing a strong reducing agent sodium hydride as a catalyst, and the reaction can be finished at 60-80 ℃ for 6-8 h.
(3) The invention provides a preparation method of perfluorobutane poly azide, which is characterized in that DMF with a high boiling point and high polarity is selected as a solvent in step (1), and can be used for simultaneously dissolving poly-azido glycidyl ether and perfluoroiodobutane, wherein the boiling point of the DMF is 153 ℃, and the DMF can be used as the solvent and is applicable to a reaction temperature of 60-80 ℃ without volatilization.
(4) The invention provides a preparation method of perfluorobutane polyazide, which comprises the steps of (1) selecting low-cost ethyl acetate as an organic phase for solvent extraction in order to extract a final product and separate the final product and a byproduct hydroiodic acid; the proportion relation between the mass (g) of the polyaziridine glycidyl ether and the volume (mL) of the ethyl acetate is (2-4): (20-40), too little ethyl acetate cannot completely extract the final product, so that the yield is reduced, and too much ethyl acetate causes waste of ethyl acetate and increases the cost.
(5) The invention provides a preparation method of perfluorobutane poly azide, which adopts saturated NaHCO in step (3) 3 The aqueous solution is used for removing the by-product hydroiodic acid, and the mass of the by-product is determined by the amount of the polyazide glycidyl ether, so that the determination of the polyazide glycidyl ether and saturated NaHCO is required 3 The proportion of the aqueous solution ensures that the by-product is completely reacted; when mass of polyaziridine glycidyl ether (g) and saturated NaHCO 3 The proportion relation of the volume (mL) of the aqueous solution is (2-4): (10-20), the by-product hydroiodic acid can be completely reacted.
(6) The invention provides an application of perfluorobutane poly azide ether, which is a combustion accelerator coated on the surface of aluminum powder and used as aluminum powder; uniformly mixing DMF (dimethyl formamide) and hydrofluoric acid aqueous solution with the mass fraction of 2-3%, and adding aluminum powder under the protection of inert gas to form an aluminum suspension solution; wherein, the etching of the dilute strong acid can remove the oxide shell on the surface of the aluminum powder; dissolving perfluorobutane polyazide ether in DMF to obtain perfluorobutane polyazide ether solution; finally, adding a perfluorobutane poly azide ether solution into the aluminum suspension, coating the perfluorobutane poly azide ether on the surface of the aluminum powder through strong electron acting force between Al-F-C to form a uniform coating layer, and filtering, washing and drying to obtain perfluorobutane poly azide ether coated micron aluminum powder; the perfluorobutane in the perfluorobutane polyazide can enable the aluminum powder to generate a pre-ignition effect (pre-ignition reaction), can effectively reduce the ignition temperature of the aluminum powder, and the average ignition temperature of pure aluminum powder is 850 ℃ and 710 ℃ through the ignition test of the aluminum powder, and is reduced by 140 ℃; the energy-containing poly-azide ether in the perfluorobutane poly-azide ether can release a large amount of energy in the combustion process to promote the combustion of aluminum powder, the average combustion heat value of pure aluminum powder tested by an oxygen elasticity calorimeter is 25.8kJ/g, and the average combustion heat value of perfluorobutane poly-azide ether-coated aluminum powder is 27.9kJ/g, which is improved by 8.1% compared with pure aluminum powder.
Drawings
FIG. 1 is an IR spectrum of perfluoroiodobutane, polyglycidyl ether and the final product prepared in example 1.
Detailed Description
The invention is described in detail below with reference to the drawings and specific examples, but the invention is not limited thereto.
Example 1
The perfluorobutane poly azide ether comprises a raw material and an auxiliary raw material, wherein the raw material comprises the following components in percentage by mass based on 100% of the total mass of the main raw material: 42% of Perfluoroiodobutane (PI) and 58% of polyaziridin glycidyl ether (GAP); the auxiliary raw material is a catalyst, and the catalyst is sodium hydride.
The mass ratio of the catalyst to the polyaziridin glycidyl ether is 1.
A preparation method of perfluorobutane polyazide described in this embodiment includes the following specific steps:
(1) Adding 1.45g of perfluoroiodobutane, 2g of polyazide glycidyl ether and 20mL of DMF (dimethyl formamide) into a three-neck flask, stirring and heating to 55 ℃, and dissolving the perfluoroiodobutane and the polyazide glycidyl ether in the DMF to obtain a mixed solution;
the ratio of the mass (g) of polyazaglycidyl ether to the volume (mL) of DMF was 2:20, the molecular weight of the polyaziridinyl glycidyl ether is 480.
(2) Adding 0.02g of sodium hydride into the mixed solvent obtained in the step (1), heating to 60 ℃, condensing, refluxing, and stirring for reacting for 6 hours;
(3) The liquid after the reaction in step (2) was naturally cooled to room temperature, diluted with 20mL of ethyl acetate, and then diluted with 10mL of saturated NaHCO in total 3 Washing the aqueous solution for 4 times, pouring the aqueous solution into a separating funnel for extraction, and retaining an organic extraction phase;
the ratio of the mass (g) of polyaziridinyl glycidyl ether to the volume (mL) of ethyl acetate was 2:20;
polyazidoglycidyl Ether Mass (g) and saturated NaHCO 3 The proportional relationship of the volume (mL) of the aqueous solution is 2:10;
(4) The organic extract phase from step (3) was dried over 8g anhydrous magnesium sulfate and the DMF was removed by rotary evaporation using a rotary evaporator to give a crude product which was purified by column chromatography to give the final product.
The mass ratio of the polyaziridine glycidyl ether to anhydrous magnesium sulfate is 1;
the developing solvent used for the column chromatography purification is a mixed solution of ethyl acetate and hexane, wherein the volume ratio of ethyl acetate to hexane is 1.
Infrared spectroscopy tests were conducted on the starting materials Perfluoroiodobutane (PI), polyglycidyl ether (GAP) and the final product of example 1, and the results are shown in FIG. 1, wherein the infrared spectrum of the final product of example 1 is only 1241cm higher than that of the polyglycidyl ether -1 At 1199cm -1 The peak at (A) is assigned to the C-F bond of perfluoroiodobutane, and because of the excess of hydroxyl groups in the glycidyl Polyazidoether, the IR spectrum of the final product of example 1 retains 3400cm of the glycidyl Polyazidoether -1 The characteristic peak of hydroxyl radical is 2800-2900 cm -1 Is at CH and CH 2 Characteristic peak of (1) and 2095cm -1 The characteristic peak of the azide group at the position can be used to judge that the final product of example 1 is perfluorobutane polyazide ether (PGAP).
The synthetic route of the method is as follows:
as shown in the synthetic route, the perfluorobutane iodide and the terminal hydroxyl of the polyglycidyl ether can be subjected to nucleophilic substitution reaction to successfully prepare the perfluorobutane polyazide ether.
The application of the perfluorobutane poly azide ether in the embodiment is to coat the surface of aluminum powder to serve as a combustion accelerator of the aluminum powder;
specifically, 20mL of DMF and 4mL of hydrofluoric acid aqueous solution with the mass fraction of 3% are added into a reaction vessel, stirred for 10min to be uniformly mixed, and 2g of micron aluminum powder is added under the protection of nitrogen to obtain an aluminum suspension solution; then 0.2g of perfluorobutane polyazide ether and 20mL of DMF are poured into a beaker and stirred and dissolved at the temperature of 60 ℃ to obtain a perfluorobutane polyazide ether solution; and finally, adding a perfluorobutane polyazide solution into the aluminum suspension, stirring for 5h, filtering the coated Al powder, washing for 3 times by using absolute ethyl alcohol, and drying for 8h in vacuum at the temperature of 80 ℃ to obtain the perfluorobutane polyazide coated micron aluminum powder.
Organic matter coating is observed on the surface of the aluminum powder through a scanning electron microscope, and through an energy spectrometer test, C, N, O and F are found to be uniformly coated on the surface of the aluminum powder, so that the fact that the coated organic matter is perfluorobutane polyazide ether is confirmed.
Ignition tests on pure aluminum powder and the aluminum powder coated with the perfluorobutane polyazide in this embodiment show that the ignition temperature of the pure aluminum powder is 850 ℃, the ignition temperature of the aluminum powder coated with the perfluorobutane polyazide in this embodiment is 710 ℃, and the ignition temperature is 140 ℃ lower than that of the pure aluminum powder, which indicates that the perfluorobutane polyazide can effectively lower the ignition temperature of the aluminum powder.
Oxygen-elasticity calorimeter tests are carried out on pure aluminum powder and the aluminum powder coated with the perfluorobutane poly azide ether, and the results show that the combustion heat of the pure aluminum powder is 25.8kJ/g, the combustion heat of the aluminum powder coated with the perfluorobutane poly azide ether is 27.9kJ/g, and is increased by 8.1% compared with that of the pure aluminum powder, which indicates that the perfluorobutane poly azide ether can effectively promote the combustion of the aluminum powder and improve the energy of the aluminum powder.
Example 2
The perfluorobutane poly azide ether comprises a raw material and an auxiliary raw material, wherein the raw material comprises the following components in percentage by mass based on 100% of the total mass of the main raw material: 33% of Perfluoroiodobutane (PI) and 67% of polyaziridin glycidyl ether (GAP); the auxiliary raw material is a catalyst, and the catalyst is sodium hydride.
The mass ratio of the catalyst to the polyaziridine glycidyl ether is 1.
A preparation method of perfluorobutane polyazide described in this embodiment includes the following specific steps:
(1) Adding 2g of perfluoroiodobutane, 4g of polyazide glycidyl ether and 40mL of DMF (dimethyl formamide) into a three-neck flask, stirring and heating to 40 ℃, and dissolving the perfluoroiodobutane and the polyazide glycidyl ether in the DMF to obtain a mixed solution;
the ratio of the mass (g) of polyazide glycidyl ether to the volume (mL) of DMF is 4:40, the molecular weight of the polyaziridinyl glycidyl ether is 480.
(2) Adding 0.08g of sodium hydride into the mixed solvent obtained in the step (1), heating to 80 ℃, condensing, refluxing, and stirring to react for 8 hours;
(3) The liquid after the reaction in step (2) was naturally cooled to room temperature, diluted with 40mL of ethyl acetate, and then diluted with 20mL of saturated NaHCO in total 3 Washing the aqueous solution for 3 times, pouring the aqueous solution into a separating funnel for extraction, and retaining an organic extraction phase;
the ratio of the mass (g) of polyaziridinyl glycidyl ether to the volume (mL) of ethyl acetate was 4:40;
polyazidoglycidyl Ether Mass (g) and saturated NaHCO 3 The proportional relationship of the volume (mL) of the aqueous solution is 4:20;
(4) The organic extract phase from step (3) was dried over 20g anhydrous magnesium sulfate and the DMF was removed by rotary evaporation using a rotary evaporator to give a crude product which was purified by column chromatography to give the final product.
The mass ratio of the polyaziridine glycidyl ether to anhydrous magnesium sulfate is 1;
the developing solvent used for the column chromatography purification is a mixed solution of ethyl acetate and hexane, wherein the volume ratio of ethyl acetate to hexane is 1.
Infrared spectroscopic measurements of the starting Perfluoroiodobutane (PI), the polyglycidyl ether (GAP) and the end product of example 2 gave similar results to example 1, except that the IR spectrum of the end product of example 2 was 1241cm higher than that of the polyglycidyl ether -1 At 1199cm -1 The peak at (A) is ascribed to the C-F bond of perfluoroiodobutane, and because of the excess of hydroxyl groups in the polyglycidyl ether, the IR spectrum of the final product of example 1 retained 3400cm of the polyglycidyl ether -1 Characteristic peak of hydroxyl group, 2800-2900 cm -1 Is at CH and CH 2 Characteristic peak of (1) and 2095cm -1 The characteristic peak of the azide group at the position can be used to judge that the final product of the example 2 is perfluorobutane polyazide ether (PGAP).
The synthetic route of the method is shown as follows:
as shown in a synthetic route, the perfluorobutane-iodobutane and the terminal hydroxyl of the polyglycidyl ether can be successfully prepared by a nucleophilic substitution reaction method.
The application of the perfluorobutane poly azide ether in the embodiment is to coat the surface of aluminum powder to serve as a combustion accelerator of the aluminum powder;
specifically, adding 20mL of DMF (dimethyl formamide) and 4mL of hydrofluoric acid aqueous solution with the mass fraction of 3% into a reaction container, stirring for 10min to uniformly mix, and adding 2g of micron aluminum powder under the protection of nitrogen to obtain an aluminum suspension solution; then 0.2g of perfluorobutane polyazide ether and 20mL of DMF are poured into a beaker and stirred and dissolved at the temperature of 60 ℃ to obtain a perfluorobutane polyazide ether solution; and finally, adding a perfluorobutane polyazide solution into the aluminum suspension, stirring for 5h, filtering the coated Al powder, washing for 3 times by using absolute ethyl alcohol, and drying for 8h in vacuum at the temperature of 80 ℃ to obtain the perfluorobutane polyazide coated micron aluminum powder.
Organic matter coating on the surface of the aluminum powder is observed through a scanning electron microscope, and through an energy spectrometer test, C, N, O and F are found to be uniformly coated on the surface of the aluminum powder, so that the coated organic matter is proved to be perfluorobutane poly azide ether.
Ignition tests on the aluminum powder coated with the perfluorobutane poly azide ether in the embodiment show that the ignition temperature of the aluminum powder coated with the perfluorobutane poly azide ether in the embodiment is 710 ℃, which is 140 ℃ lower than that of pure aluminum powder, indicating that the perfluorobutane poly azide ether can effectively lower the ignition temperature of the aluminum powder.
Oxygen-elasticity calorimeter tests are carried out on pure aluminum powder and the aluminum powder coated with the perfluorobutane poly azide ether, and the results show that the combustion heat of the pure aluminum powder is 25.8kJ/g, the combustion heat of the aluminum powder coated with the perfluorobutane poly azide ether is 27.8kJ/g, and is improved by 7.8% compared with that of the pure aluminum powder, which indicates that the perfluorobutane poly azide ether can effectively promote the combustion of the aluminum powder and improve the energy of the aluminum powder.
Example 3
The perfluorobutane poly azide ether comprises the following raw materials in percentage by mass based on 100% of the total mass of the main raw materials: 50% of Perfluoroiodobutane (PI) and 50% of polyaziridine glycidyl ether (GAP); the auxiliary raw material is a catalyst, and the catalyst is sodium hydride.
The mass ratio of the catalyst to the polyaziridin glycidyl ether is 1.
A preparation method of perfluorobutane polyazide described in this embodiment includes the following specific steps:
(1) Adding 2g of perfluoroiodobutane, 2g of polyazaglycidyl ether and 20mL of DMF (dimethyl formamide) into a three-neck flask, stirring and heating to 60 ℃, and dissolving the perfluoroiodobutane and the polyazaglycidyl ether in the DMF to obtain a mixed solution;
the ratio of the mass (g) of polyazaglycidyl ether to the volume (mL) of DMF was 2:20, the molecular weight of the polyaziridinyl glycidyl ether is 480.
(2) Adding 0.03g of sodium hydride into the mixed solvent obtained in the step (1), heating to 70 ℃, condensing, refluxing, and stirring for reaction for 7 hours;
(3) The liquid after the reaction in step (2) was naturally cooled to room temperature, diluted with 20mL of ethyl acetate, and then diluted with a total of 15mL of saturated NaHCO 3 Washing the aqueous solution for 4 times, pouring the aqueous solution into a separating funnel for extraction, and retaining an organic extraction phase;
the ratio of the mass (g) of polyaziridinyl glycidyl ether to the volume (mL) of ethyl acetate was 2:20;
polyazidoglycidyl Ether Mass (g) and saturated NaHCO 3 The proportional relationship of the volume (mL) of the aqueous solution is 1:7.5;
(4) Drying the organic extract phase obtained in step (3) with 12g anhydrous magnesium sulfate, removing DMF by rotary evaporation with a rotary evaporator to obtain a crude product, and purifying by column chromatography to obtain a final product;
the mass ratio of the polyaziridine glycidyl ether to anhydrous magnesium sulfate is 1;
the developing solvent used for the column chromatography purification is a mixed solution of ethyl acetate and hexane, wherein the volume ratio of ethyl acetate to hexane is 1.
Infrared spectroscopy of the starting Perfluoroiodobutane (PI), polyglycidyl ether (GAP) and the final product of example 3 gave similar results to example 1, with the final product of example 3 showing an IR spectrum which is 1241cm more than that of the polyglycidyl ether -1 At 1199cm -1 The peak at (A) is ascribed to the C-F bond of perfluoroiodobutane, and because of the excess of hydroxyl groups in the polyglycidyl ether, the IR spectrum of the final product of example 1 retained 3400cm of the polyglycidyl ether -1 The characteristic peak of hydroxyl radical is 2800-2900 cm -1 Is at CH and CH 2 Characteristic peak of (1) and 2095cm -1 The characteristic peak of the azide group at the position can be used to determine that the final product of example 3 is perfluorobutane polyazide ether (PGAP).
The synthetic route of the method is as follows:
as shown in a synthetic route, the perfluorobutane-iodobutane and the terminal hydroxyl of the polyglycidyl ether can be successfully prepared by a nucleophilic substitution reaction method.
The application of the perfluorobutane poly azide ether in the embodiment is to coat the surface of aluminum powder to serve as a combustion accelerator of the aluminum powder;
specifically, 20mL of DMF and 4mL of hydrofluoric acid aqueous solution with the mass fraction of 3% are added into a reaction vessel, stirred for 10min to be uniformly mixed, and 2g of micron aluminum powder is added under the protection of nitrogen to obtain an aluminum suspension solution; then 0.2g of perfluorobutane polyazide ether and 20mL of DMF are poured into a beaker and stirred and dissolved at the temperature of 60 ℃ to obtain a perfluorobutane polyazide ether solution; and finally, adding a perfluorobutane polyazide solution into the aluminum suspension, stirring for 5h, filtering the coated Al powder, washing for 3 times by using absolute ethyl alcohol, and drying for 8h in vacuum at the temperature of 80 ℃ to obtain the perfluorobutane polyazide coated micron aluminum powder.
Organic matter coating on the surface of the aluminum powder is observed through a scanning electron microscope, and through an energy spectrometer test, C, N, O and F are found to be uniformly coated on the surface of the aluminum powder, so that the coated organic matter is proved to be perfluorobutane poly azide ether.
Ignition tests on the aluminum powder coated with the perfluorobutane poly azide ether in the embodiment show that the ignition temperature of the aluminum powder coated with the perfluorobutane poly azide ether in the embodiment is 710 ℃, which is 140 ℃ lower than that of pure aluminum powder, indicating that the perfluorobutane poly azide ether can effectively lower the ignition temperature of the aluminum powder.
Oxygen-elasticity calorimeter tests are carried out on pure aluminum powder and the aluminum powder coated with the perfluorobutane poly azide ether, and the results show that the combustion heat of the pure aluminum powder is 25.8kJ/g, the combustion heat of the aluminum powder coated with the perfluorobutane poly azide ether is 28.0kJ/g, and is increased by 8.5% compared with that of the pure aluminum powder, which indicates that the perfluorobutane poly azide ether can effectively promote the combustion of the aluminum powder and improve the energy of the aluminum powder.
Example 4
The perfluorobutane poly azide ether comprises a raw material and an auxiliary raw material, wherein the raw material comprises the following components in percentage by mass based on 100% of the total mass of the main raw material: 43% of Perfluoroiodobutane (PI) and 57% of polyaziridin glycidyl ether (GAP); the auxiliary raw material is a catalyst, and the catalyst is sodium hydride.
The mass ratio of the catalyst to the polyaziridine glycidyl ether is 1.
A preparation method of perfluorobutane polyazide described in this embodiment includes the following specific steps:
(1) Adding 3g of perfluoroiodobutane, 4g of polyazide glycidyl ether and 20mL of DMF (dimethyl formamide) into a three-neck flask, stirring and heating to 55 ℃, and dissolving the perfluoroiodobutane and the polyazide glycidyl ether in the DMF to obtain a mixed solution;
the ratio of the mass (g) of polyazide glycidyl ether to the volume (mL) of DMF is 4:20, the molecular weight of the polyaziridinyl glycidyl ether is 480.
(2) Adding 0.04g of sodium hydride into the mixed solvent obtained in the step (1), heating to 60 ℃, condensing, refluxing, and stirring to react for 8 hours;
(3) The liquid after the reaction in step (2) was naturally cooled to room temperature, diluted with 20mL of ethyl acetate, and then diluted with 10mL of saturated NaHCO in total 3 Washing the aqueous solution for 3 times, pouring the aqueous solution into a separating funnel for extraction, and keeping an organic extraction phase;
the ratio of the mass (g) of polyaziridinyl glycidyl ether to the volume (mL) of ethyl acetate was 4:20;
polyazidoglycidyl Ether Mass (g) and saturated NaHCO 3 The proportional relationship of the volume (mL) of the aqueous solution is 4:10;
(4) Drying the organic extract phase obtained in the step (3) by using 20g of anhydrous magnesium sulfate, removing DMF by rotary evaporation by using a rotary evaporator to obtain a crude product, and purifying by using column chromatography to obtain a final product;
the mass ratio of the polyaziridine glycidyl ether to anhydrous magnesium sulfate is 1;
the developing solvent used for the column chromatography purification is a mixed solution of ethyl acetate and hexane, wherein the volume ratio of ethyl acetate to hexane is 1.
Infrared spectroscopy of the starting Perfluoroiodobutane (PI), polyglycidyl ether (GAP) and the final product of example 4 gave similar results to example 1, except that the IR spectrum of the final product of example 4 was 1241cm higher than that of the polyglycidyl ether -1 At 1199cm -1 The peak at (A) is assigned to the C-F bond of perfluoroiodobutane, and because of the excess of hydroxyl groups in the glycidyl Polyazidoether, the IR spectrum of the final product of example 1 retains 3400cm of the glycidyl Polyazidoether -1 Characteristic peak of hydroxyl group, 2800-2900 cm -1 Is at CH and CH 2 Characteristic peak of (1) and 2095cm -1 The characteristic peak of the azide group at the position can be used to judge that the final product of the example 4 is perfluorobutane polyazide ether (PGAP).
The synthetic route of the method is as follows:
as shown in a synthetic route, the perfluorobutane-iodobutane and the terminal hydroxyl of the polyglycidyl ether can be successfully prepared by a nucleophilic substitution reaction method.
The application of the perfluorobutane poly azide ether in the embodiment is to coat the surface of aluminum powder to serve as a combustion accelerator of the aluminum powder;
specifically, 20mL of DMF and 4mL of hydrofluoric acid aqueous solution with the mass fraction of 3% are added into a reaction vessel, stirred for 10min to be uniformly mixed, and 2g of micron aluminum powder is added under the protection of nitrogen to obtain an aluminum suspension solution; then 0.2g of perfluorobutane polyazide ether and 20mL of DMF are poured into a beaker and stirred and dissolved at the temperature of 60 ℃ to obtain a perfluorobutane polyazide ether solution; and finally, adding a perfluorobutane polyazide solution into the aluminum suspension, stirring for 5h, filtering the coated Al powder, washing for 3 times by using absolute ethyl alcohol, and drying for 8h in vacuum at the temperature of 80 ℃ to obtain the perfluorobutane polyazide coated micron aluminum powder.
Organic matter coating on the surface of the aluminum powder is observed through a scanning electron microscope, and through an energy spectrometer test, C, N, O and F are found to be uniformly coated on the surface of the aluminum powder, so that the coated organic matter is proved to be perfluorobutane poly azide ether.
Ignition tests on the aluminum powder coated with the perfluorobutane poly azide ether in the embodiment show that the ignition temperature of the aluminum powder coated with the perfluorobutane poly azide ether in the embodiment is 710 ℃, which is 140 ℃ lower than that of pure aluminum powder, indicating that the perfluorobutane poly azide ether can effectively lower the ignition temperature of the aluminum powder.
Oxygen-elasticity calorimeter tests are carried out on pure aluminum powder and the aluminum powder coated with the perfluorobutane poly azide ether, and the results show that the combustion heat of the pure aluminum powder is 25.8kJ/g, the combustion heat of the aluminum powder coated with the perfluorobutane poly azide ether is 27.9kJ/g, and is increased by 8.1% compared with that of the pure aluminum powder, which indicates that the perfluorobutane poly azide ether can effectively promote the combustion of the aluminum powder and improve the energy of the aluminum powder.
Example 5
The perfluorobutane poly azide ether comprises a raw material and an auxiliary raw material, wherein the raw material comprises the following components in percentage by mass based on 100% of the total mass of the main raw material: 40% of Perfluoroiodobutane (PI) and 60% of polyaziridin glycidyl ether (GAP); the auxiliary raw material is a catalyst, and the catalyst is sodium hydride.
The mass ratio of the catalyst to the polyaziridine glycidyl ether is 1.
A preparation method of perfluorobutane polyazide described in this embodiment includes the following specific steps:
(1) Adding 2.7g of perfluoroiodobutane, 4g of polyazide glycidyl ether and 20mL of DMF (dimethyl formamide) into a three-neck flask, stirring and heating to 50 ℃, and dissolving the perfluoroiodobutane and the polyazide glycidyl ether in the DMF to obtain a mixed solution;
the ratio of the mass (g) of polyazide glycidyl ether to the volume (mL) of DMF is 4:20, the molecular weight of the polyaziridinyl glycidyl ether is 480.
(2) Adding 0.05g of sodium hydride into the mixed solvent obtained in the step (1), heating to 80 ℃, condensing, refluxing, and stirring for reacting for 6 hours;
(3) The liquid after the reaction in step (2) was naturally cooled to room temperature, diluted with 25mL of ethyl acetate, and then diluted with 18mL of saturated NaHCO in total 3 Washing the aqueous solution for 4 times, pouring the aqueous solution into a separating funnel for extraction, and keeping an organic extraction phase;
the ratio of the mass (g) of polyazide glycidyl ether to the volume (mL) of ethyl acetate is 1:6.25;
polyazidoglycidyl Ether Mass (g) and saturated NaHCO 3 The proportional relationship of the volume (mL) of the aqueous solution is 1:4.5;
(4) Drying the organic extract phase obtained in the step (3) by using 24g of anhydrous magnesium sulfate, removing DMF by rotary evaporation by using a rotary evaporator to obtain a crude product, and purifying by using column chromatography to obtain a final product;
the mass ratio of the polyaziridine glycidyl ether to anhydrous magnesium sulfate is 1;
the developing solvent used for the column chromatography purification is a mixed solution of ethyl acetate and hexane, wherein the volume ratio of ethyl acetate to hexane is 1.
For raw materials of Perfluoroiodobutane (PI), poly-azido glycidyl ether (PI)GAP) and the final product of example 5, and the infrared spectrum test results are similar to that of example 1, and the infrared spectrum of the final product of example 5 is only 1241cm more than that of poly glycidyl azide -1 At 1199cm -1 The peak at (A) is ascribed to the C-F bond of perfluoroiodobutane, and because of the excess of hydroxyl groups in the polyglycidyl ether, the IR spectrum of the final product of example 1 retained 3400cm of the polyglycidyl ether -1 The characteristic peak of hydroxyl radical is 2800-2900 cm -1 Is at CH and CH 2 Characteristic peak of (1) and 2095cm -1 The characteristic peak of the azide group at the position can be used to judge that the final product of example 5 is perfluorobutane polyazide ether (PGAP).
The synthetic route of the method is as follows:
as shown in a synthetic route, the perfluorobutane-iodobutane and the terminal hydroxyl of the polyglycidyl ether can be successfully prepared by a nucleophilic substitution reaction method.
The application of the perfluorobutane poly azide ether in the embodiment is to coat the surface of aluminum powder to serve as a combustion accelerator of the aluminum powder;
specifically, 20mL of DMF and 4mL of hydrofluoric acid aqueous solution with the mass fraction of 3% are added into a reaction vessel, stirred for 10min to be uniformly mixed, and 2g of micron aluminum powder is added under the protection of nitrogen to obtain an aluminum suspension solution; then 0.2g of perfluorobutane polyazide ether and 20mL of DMF are poured into a beaker and stirred and dissolved at the temperature of 60 ℃ to obtain a perfluorobutane polyazide ether solution; and finally, adding a perfluorobutane polyazide solution into the aluminum suspension, stirring for 5h, filtering the coated Al powder, washing for 3 times by using absolute ethyl alcohol, and drying for 8h in vacuum at the temperature of 80 ℃ to obtain the perfluorobutane polyazide coated micron aluminum powder.
Organic matter coating on the surface of the aluminum powder is observed through a scanning electron microscope, and through an energy spectrometer test, C, N, O and F are found to be uniformly coated on the surface of the aluminum powder, so that the coated organic matter is proved to be perfluorobutane poly azide ether.
Ignition tests on the aluminum powder coated with the perfluorobutane poly azide ether of the embodiment show that the ignition temperature of the aluminum powder coated with the perfluorobutane poly azide ether of the embodiment is 710 ℃, which is 140 ℃ lower than that of pure aluminum powder, indicating that the perfluorobutane poly azide ether can effectively lower the ignition temperature of the aluminum powder.
Oxygen-elasticity calorimeter tests are carried out on pure aluminum powder and the aluminum powder coated with the perfluorobutane poly azide ether in the embodiment, and the results show that the combustion heat of the pure aluminum powder is 25.8kJ/g, the combustion heat of the aluminum powder coated with the perfluorobutane poly azide ether in the embodiment is 27.9kJ/g, and is improved by 8.1% compared with the pure aluminum powder, which indicates that the perfluorobutane poly azide ether can effectively promote the combustion of the aluminum powder and improve the energy of the aluminum powder.
Example 6
The perfluorobutane poly azide ether comprises a raw material and an auxiliary raw material, wherein the raw material comprises the following components in percentage by mass based on 100% of the total mass of the main raw material: perfluoroiodobutane (PI) 50%, polyaziridinyl glycidyl ether (GAP) 50%; the auxiliary raw material is a catalyst, and the catalyst is sodium hydride.
The mass ratio of the catalyst to the polyaziridine glycidyl ether is 1.
The preparation method of the perfluorobutane polyazide ether in the embodiment comprises the following specific steps:
(1) Adding 3g of perfluoroiodobutane, 3g of polyazide glycidyl ether and 20mL of DMF (dimethyl formamide) into a three-neck flask, stirring and heating to 60 ℃, and dissolving the perfluoroiodobutane and the polyazide glycidyl ether in the DMF to obtain a mixed solution;
the ratio of the mass (g) of polyazide glycidyl ether to the volume (mL) of DMF is 3:20, the molecular weight of the polyaziridinyl glycidyl ether is 480.
(2) Adding 0.06g of sodium hydride into the mixed solvent obtained in the step (1), heating to 70 ℃, condensing, refluxing, and stirring for reacting for 6 hours;
(3) Naturally cooling the liquid reacted in the step (2) to room temperature, addingDiluted with 30mL ethyl acetate and then with 30mL saturated NaHCO in total 3 Washing the aqueous solution for 4 times, pouring the aqueous solution into a separating funnel for extraction, and retaining an organic extraction phase;
the ratio of the mass (g) of polyazide glycidyl ether to the volume (mL) of ethyl acetate is 1:10;
polyazidoglycidyl Ether Mass (g) and saturated NaHCO 3 The proportional relationship of the volume (mL) of the aqueous solution is 1:10;
(4) Drying the organic extract phase obtained in the step (3) by using 15g of anhydrous magnesium sulfate, removing DMF by rotary evaporation by using a rotary evaporator to obtain a crude product, and purifying by using column chromatography to obtain a final product;
the mass ratio of the polyaziridine glycidyl ether to anhydrous magnesium sulfate is 1;
the developing solvent used for the column chromatography purification is a mixed solution of ethyl acetate and hexane, wherein the volume ratio of ethyl acetate to hexane is 1.
Infrared spectroscopy of the starting Perfluoroiodobutane (PI), polyglycidyl ether (GAP) and the final product of example 6 gave similar results to example 1, but the IR spectrum of the final product of example 6 was 1241cm higher than that of the polyglycidyl ether -1 At 1199cm -1 The peak at (A) is ascribed to the C-F bond of perfluoroiodobutane, and because of the excess of hydroxyl groups in the polyglycidyl ether, the IR spectrum of the final product of example 6 retained 3400cm of the polyglycidyl ether -1 The characteristic peak of hydroxyl radical is 2800-2900 cm -1 Is at CH and CH 2 Characteristic peak of (1) and 2095cm -1 The characteristic peak of the azide group at the position can be used to judge that the final product of example 6 is perfluorobutane polyazide ether (PGAP).
The synthetic route of the method is as follows:
as shown in the synthetic route, the perfluorobutane iodide and the terminal hydroxyl of the polyglycidyl ether can be subjected to nucleophilic substitution reaction to successfully prepare the perfluorobutane polyazide ether.
The application of the perfluorobutane poly azide ether in the embodiment is to coat the surface of aluminum powder to serve as a combustion accelerator of the aluminum powder;
specifically, 20mL of DMF and 4mL of hydrofluoric acid aqueous solution with the mass fraction of 3% are added into a reaction vessel, stirred for 10min to be uniformly mixed, and 2g of micron aluminum powder is added under the protection of nitrogen to obtain an aluminum suspension solution; then 0.2g of perfluorobutane polyazide ether and 20mL of DMF are poured into a beaker and stirred and dissolved at the temperature of 60 ℃ to obtain a perfluorobutane polyazide ether solution; and finally, adding a perfluorobutane polyazide ether solution into the aluminum suspension, stirring for 5 hours, filtering the coated Al powder, washing for 3 times by using absolute ethyl alcohol, and drying for 8 hours in vacuum at the temperature of 80 ℃ to obtain the perfluorobutane polyazide ether coated micron aluminum powder.
Organic matter coating on the surface of the aluminum powder is observed through a scanning electron microscope, and through an energy spectrometer test, C, N, O and F are found to be uniformly coated on the surface of the aluminum powder, so that the coated organic matter is proved to be perfluorobutane poly azide ether.
Ignition tests on the aluminum powder coated with the perfluorobutane poly azide ether in the embodiment show that the ignition temperature of the aluminum powder coated with the perfluorobutane poly azide ether in the embodiment is 710 ℃, which is 140 ℃ lower than that of pure aluminum powder, indicating that the perfluorobutane poly azide ether can effectively lower the ignition temperature of the aluminum powder.
Oxygen-elasticity calorimeter tests are carried out on pure aluminum powder and the aluminum powder coated with the perfluorobutane poly azide ether in the embodiment, and the results show that the combustion heat of the pure aluminum powder is 25.8kJ/g, the combustion heat of the aluminum powder coated with the perfluorobutane poly azide ether in the embodiment is 27.9kJ/g, and is improved by 8.1% compared with the pure aluminum powder, which indicates that the perfluorobutane poly azide ether can effectively promote the combustion of the aluminum powder and improve the energy of the aluminum powder.
Claims (10)
1. A perfluorobutane polyazide is characterized in that: the raw material of the perfluorobutane polyazide is composed of a main raw material and an auxiliary raw material, and the raw material comprises the following components in percentage by mass based on 100% of the total mass of the main raw material: 33-50% of perfluoroiodobutane and 50-67% of poly-azido glycidyl ether; the auxiliary raw material is catalyst sodium hydride.
2. A perfluorobutane polyazide according to claim 1, wherein: the mass ratio of the catalyst to the polyaziridine glycidyl ether is 1.
3. A process for producing a perfluorobutane polyazidyl ether as claimed in claim 1 or 2, wherein: the method comprises the following steps:
(1) Dissolving perfluoroiodobutane and polyazidine glycidyl ether in N, N-dimethylformamide to obtain a mixed solution;
(2) Adding catalyst sodium hydride into the mixed solution, heating to 60-80 ℃, condensing, refluxing, stirring and reacting for 6-8 h;
(3) The reacted liquid was cooled to room temperature, ethyl acetate was added, and saturated NaHCO was used 3 Washing the water solution for 2-4 times, extracting and reserving an organic extraction phase;
(4) Drying the organic extraction phase by anhydrous magnesium sulfate, carrying out rotary evaporation to obtain a crude product, and purifying by column chromatography to obtain the perfluorobutane polyazide ether.
4. The method for preparing perfluorobutane polyazide ether according to claim 3, wherein: the proportional relation between the mass (g) of the polyazide glycidyl ether and the volume (mL) of the N, N-dimethylformamide is (2-4): (20-40), the molecular weight of the polyaziridine glycidyl ether is 480; perfluoroiodobutane and polyglycidyl ether are dissolved in N, N-dimethylformamide under stirring at a temperature of 40 ℃ to 60 ℃.
5. The method for preparing perfluorobutane polyazide ether according to claim 3, wherein: the proportional relation between the mass (g) of the polyaziridine glycidyl ether and the volume (mL) of the ethyl acetate is (2-4): (20 to 40).
6. The process according to claim 3, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: polyazidoglycidyl Ether Mass (g) and saturated NaHCO 3 The proportion relation of the volume (mL) of the aqueous solution is (2-4): (10-20).
7. The process according to claim 3, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: the mass ratio of the polyaziridine glycidyl ether to the anhydrous magnesium sulfate is 1-1; the developing solvent used for the column chromatography purification is a mixed solution of ethyl acetate and hexane, wherein the volume ratio of ethyl acetate to hexane is 1.
8. The method for preparing perfluorobutane polyazide according to claim 4, wherein: the proportion relation between the mass (g) of the polyaziridine glycidyl ether and the volume (mL) of the ethyl acetate is (2-4): (20-40); polyazidoglycidyl Ether Mass (g) and saturated NaHCO 3 The proportion relation of the volume (mL) of the aqueous solution is (2-4): (10-20); the mass ratio of the polyaziridine glycidyl ether to the anhydrous magnesium sulfate is 1-1; the developing solvent used for the purification by the column chromatography is a mixed solution of ethyl acetate and hexane, wherein the volume ratio of ethyl acetate to hexane is 1.
9. Use of a perfluorobutane polyazide as claimed in claim 1 or 2, wherein: the application is to coat the surface of aluminum powder as a combustion promoter of the aluminum powder.
10. The use of a perfluorobutane polyazide according to claim 9, wherein: uniformly mixing DMF (dimethyl formamide) and hydrofluoric acid aqueous solution with the mass fraction of 2-3%, and adding aluminum powder under the protection of inert gas to form an aluminum suspension solution; dissolving perfluorobutane polyazide ether in DMF to obtain perfluorobutane polyazide ether solution; and finally, adding a perfluorobutane polyazide solution into the aluminum suspension, filtering, washing and drying to obtain the perfluorobutane polyazide coated micron aluminum powder.
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