CN110372902B - Side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membrane - Google Patents
Side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membrane Download PDFInfo
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 73
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 53
- 239000011737 fluorine Substances 0.000 title claims abstract description 53
- 229920002098 polyfluorene Polymers 0.000 title claims abstract description 50
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 45
- 150000003863 ammonium salts Chemical group 0.000 title claims abstract description 35
- -1 ether compound Chemical class 0.000 claims abstract description 42
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims abstract description 13
- 238000005266 casting Methods 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 239000003880 polar aprotic solvent Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000502 dialysis Methods 0.000 claims description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 5
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 40
- 150000001875 compounds Chemical class 0.000 description 19
- 229920000090 poly(aryl ether) Polymers 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 150000001768 cations Chemical group 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ONUFSRWQCKNVSL-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4,5,6-pentafluorophenyl)benzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1F ONUFSRWQCKNVSL-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- QCHSEDTUUKDTIG-UHFFFAOYSA-L dipotassium clorazepate Chemical compound [OH-].[K+].[K+].C12=CC(Cl)=CC=C2NC(=O)C(C(=O)[O-])N=C1C1=CC=CC=C1 QCHSEDTUUKDTIG-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
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- C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
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- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
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Abstract
The invention relates to a side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membrane. The invention obtains side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether compound by one-step reaction of fluorine-containing polyfluorene ether compound containing dimethylamine side chain and brominated alkyl quaternary ammonium salt compound, and then prepares the anion exchange membrane by a solution casting method. The anion exchange membrane has excellent mechanical property and thermal stability, and the bromine ion conductivity of the anion exchange membrane is obviously improved compared with that of a fluorine-containing polyfluorene ether anion exchange membrane containing a single quaternary ammonium salt side chain.
Description
Technical Field
The invention relates to a side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membrane, belonging to the field of ion exchange membrane materials.
Background
The anion exchange membrane is a polymer film which contains positively charged groups on a chemical structure and has the function of selectively permeating anions in a solution, and is widely applied to the fields of electrodialysis, diffusion dialysis, water electrolysis, all-vanadium flow batteries, alkaline fuel batteries and the like. Due to the characteristics of high vanadium resistance, low fuel permeability and the like, the anion exchange membrane has great application potential in all-vanadium flow batteries and alkaline fuel cells, and the research and development and performance optimization of novel anion exchange membrane materials are concerned by the scientific and industrial fields. However, the anion exchange membranes on the market at present generally have the problems of low conductivity, poor stability and the like, and are difficult to realize large-scale commercial application.
Traditional quaternary ammonium salt anion exchange membranes are prepared mainly by reacting a quaternizing agent with specific functional groups on a polymer backbone to introduce cationic groups. For example, Mendon et al (Chinese patent CN102516526B and Int. J. Hydrogen Energy, 2012, 37, 16168-16176) disclose a polyarylether anion exchange membrane containing quaternary ammonium salt side groups and fluorenyl groups, which has a chloride ion conductivity of 3.3 mS cm-1 at room temperature and sufficient mechanical strength to meet the application requirements of alkaline fuel cells and all-vanadium flow batteries. The method introduces cationic groups into specific positions of the polymer skeleton through one-step reaction to prepare the anion exchange membrane, and has simple process and mild reaction conditions. However, the cation groups of the obtained anion exchange membrane are directly connected to the main chain or are connected to the main chain through shorter aliphatic chains, so that the ion mobility is low, the aggregation of quaternary ammonium salt ions is not facilitated, an effective anion transmission channel is formed, and the anion conductivity is improved. In addition, the ionic groups are closer to the polymer backbone, reducing the chemical stability of the membrane to some extent.
Therefore, the double quaternary ammonium ion flexible side chain is introduced to the fluorine-containing polyfluorene ether to synthesize the side chain double quaternary ammonium ion type fluorine-containing polyfluorene ether anion exchange membrane, which is beneficial to improving the activity and aggregation degree of cationic groups in the ion exchange membrane so as to obtain the anion exchange membrane with excellent ion transmission performance and chemical stability, and has important significance for the research and development of anion exchange membrane materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and a side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membrane is synthesized by introducing a biquaternary ammonium ion flexible side chain on fluorine-containing polyfluorene ether. The side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membrane has the advantages of simple process, high ionic conductivity, good mechanical property, high chemical stability and the like, and has important application prospect in the field of ion exchange membranes.
In order to achieve the purpose, the invention adopts the following technical scheme:
a side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membrane consists of a side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether compound with the following structural formula:
wherein X is any anion, m is 1-400, n is 10-400, and y is 1-4.
The preparation method of the side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membrane specifically comprises the following steps:
(1) preparing a side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether compound: dissolving a fluorine-containing polyfluorene ether compound containing a dimethylamine side chain in a polar aprotic solvent to prepare a solution A; then, dissolving 0.5-1.5 times molar weight of brominated alkyl quaternary ammonium salt compound Br-y-QA of the dimethylamine group in a polar aprotic solvent to prepare a solution B; then, slowly dropwise adding the solution B into the solution A under the protection of argon, and continuously stirring for 10-50 h at 20-80 ℃ after dropwise adding; finally, putting the reactant into a dialysis bag, dialyzing in deionized water for 3-10 days, and dewatering and drying at 80-120 ℃ for 10-40 hours to obtain a side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether compound;
(2) preparing an anion exchange membrane: dissolving the side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether compound in the step (1) in a polar aprotic solvent to prepare a solution of 1-8 wt.%, casting the solution on a horizontally placed glass plate, drying the glass plate in a common oven at 40-100 ℃ for 10-50 hours, and drying the glass plate in a vacuum oven at 60-150 ℃ for 10-50 hours to obtain the side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membrane.
The chemical structure of the fluorine-containing polyfluorene ether compound containing dimethylamine side chain in the step (1) is as follows:
wherein m is 1 to 400, and n is 10 to 400;
the chemical structure of the brominated alkyl quaternary ammonium salt compound Br-y-QA is as follows:
wherein y is 1 to 4.
In the step (1), the concentration of the solution A is 1-10 wt.%, and the concentration of the solution B is 5-10 wt.%.
In the step (1), the speed of dripping the solution B into the solution A is 1-5 mL/min.
The thickness of the anion exchange membrane prepared in the step (2) is 40-80 μm. In order to better practice the invention, the polar aprotic solvent in the above step comprisesN,N-dimethylacetamide,N,N-dimethylformamide,NAny one of methyl pyrrolidone, dimethyl sulfoxide and 1, 3-dimethyl-2-imidazolidinone.
The side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membrane obtained by the invention can be used as a battery diaphragm material.
The preparation scheme of the invention is a preferable scheme, and reasonable temperature, time and other reaction conditions which can be expected by a person skilled in the art are all protected by the invention and are not limited to the reaction conditions.
The invention obtains side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether compound by one-step reaction of fluorine-containing polyfluorene ether compound containing dimethylamine side chain and brominated alkyl quaternary ammonium salt compound, and then prepares the anion exchange membrane by a solution casting method.
Compared with the prior art, the invention has the following effects:
(1) the raw materials adopted by the invention are common chemical raw materials, are low in price and are easy to obtain;
(2) the quaternary ammonium salt group is introduced through the reaction of the dimethylamine group and the bromine group, the reaction condition is mild, and the ion exchange capacity of the membrane can be controlled by adjusting the content of the dimethylamine group in the polymer.
(3) According to the invention, the flexible biquaternary ammonium salt cation side chain and the fluorine-containing aromatic main chain are adopted, so that mutual aggregation of side chain cation groups in a film forming process is facilitated, and the side chain cation groups are separated from the main chain to form an ion transmission channel, and therefore, the obtained anion exchange membrane has excellent bromide ion conductivity and oxidation stability.
Drawings
FIG. 1 shows the hydrogen nuclear magnetic resonance spectrum of the side chain bis-quaternary ammonium salt ionic fluorene-containing polyarylether compound DQA-PFE-40-C3 prepared in example 4 of the present invention.
FIG. 2 is an infrared spectrum of a side chain bis-quaternary ammonium salt ionic fluorene-containing polyarylether compound DQA-PFE-40-C3 prepared in example 4 of the present invention.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of a side chain bis-quaternary ammonium salt ionic fluorene-containing polyarylether compound DQA-PFE-40-C6 prepared in example 6 of the present invention.
FIG. 4 is an infrared spectrum of a side chain bis-quaternary ammonium salt ionic fluorene-containing polyarylether compound DQA-PFE-40-C6 prepared in example 6 of the present invention.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
EXAMPLE 1 preparation of fluorine-containing polyfluorene ether Compound PFE-40
Fluorine-containing polyfluorene ether compound PFE-40 was prepared by the method described in the reference (int. J. Hydrogen Energy, 2012, 37, 16168-16176). Fluorenyl bisphenol DABPF 0.7434 g (1.6 mmol), bisphenol fluorene 0.8410 g (2.4 mmol) and decafluorobiphenyl 1.3500 g (4.04 mmol) containing dimethylamino groups were dissolved in 12 mLN-To methyl pyrrolidone was added 1.2g (8 mmol) cesium fluoride and 0.5 g (12 mmol) calcium hydride, followed by reaction at room temperature for 24 h under protection of argon. And after the reaction is finished, pouring the product into 500 mL of deionized water to separate out a precipitate, filtering, collecting the precipitate, dissolving the precipitate in dichloromethane again, pouring the obtained product into methanol to separate out the precipitate, filtering, collecting the precipitate, and drying the precipitate in a vacuum oven at 80 ℃ for 24 hours to obtain the fluorine-containing polyfluorene ether compound PEF-40. Yield: 98 percent.
EXAMPLE 2 preparation of fluorine-containing polyfluorene ether Compound PFE-20
The experimental procedure was the same as in example 1, except for the amounts of fluorenylbisphenol DABPF containing dimethylamine groups and bisphenol fluorene. In this example, the charge amount of fluorenylbisphenol DABPF containing dimethylamine groups was 0.3717 g (0.80 mmol) and the charge amount of bisphenol fluorene was 1.1213 g (3.2 mmol). The fluorine-containing polyfluorene ether compound PFE-20 is obtained by reaction. Yield: 97 percent.
EXAMPLE 3 preparation of a side-chain Mono-quaternary ammonium salt ionic fluorene-containing polyarylether Compound QA-PFE-40
Synthesis of side chain quaternary ammonium salt ion fluorene-containing polyarylether Compound QA-PFE-40 reference (int. J. hydrogen Energy, 2012, 37, 16168-. 1.00 g (1.16 mmol) of the fluorine-containing polyfluorene ether compound PFE-40 obtained in example 1 was dissolved in 20 mL of a solventN-To a solution of 5 wt.% in methyl pyrrolidone, 0.1 mL (1.8 mmol) of methyl iodide was slowly added dropwise to the reaction system, and after the addition, the reaction was carried out under argon protection at room temperature for 20 hours in the absence of light. And after the reaction is finished, pouring the product into 200 mL of deionized water to separate out a precipitate, then filtering and collecting the precipitate, washing for 3-5 times by using acetone, and carrying out vacuum drying for 12 h at 80 ℃ to obtain the side chain quaternary ammonium salt ion fluorene-containing polyarylether compound QA-PFE-40.
Example 4 preparation of side chain bis-quaternary ammonium salt ionic fluorene-containing polyarylether compound DQA-PFE-40-C3
1.00 g (1.16 mmol) of the fluorine-containing polyfluorene ether compound PFE-40 obtained in example 1 was dissolved in 20 mL of a solventN- A 5 wt.% solution was made in methyl pyrrolidone, while 0.45 g (1.74 mmol) of the brominated alkyl quaternary ammonium salt compound Br-1-QA was dissolved in 4.5 mLN-The methyl pyrrolidone is prepared into a 10 wt% solution, and the brominated alkyl quaternary ammonium salt compound Br-1-QA is prepared by the method in the reference literature (J. Mater. chem. A, 2016, 4, 13938-. And then, slowly dropwise adding the bromoalkyl quaternary ammonium salt compound solution into the fluorine-containing polyfluorene ether solution at the speed of 5 mL/min under the protection of argon, and reacting for 40 hours at 40 ℃ under the protection of argon after dropwise adding. After the reaction was completed, the product was filled into a dialysis bag and dialyzed in deionized water for 5 days, during which the deionized water was changed twice a day. The product was then dried by air blowing at 80 ℃ for 12 hours and then dried under vacuum at 80 ℃Obtaining a side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether compound DQA-PFE-40-C3 after 12 hours; yield: 96 percent. The data of the nuclear magnetic resonance hydrogen spectrum of the compound are as follows:1H NMR (400 MHz, DMSO-d6) 7.94 (s,1H), 7.44 (d, 2H), 7.27 (d, 1H), 7.06 (d, 2H), 6.96 (s,1H), 4.75 (s,1H), 3.15 (m, 1H), 3.04 (t, 1H), 2.20 (s, 1H). Infrared data are: FT-IR (cm)-1) υ 3413, 3039,2923, 2850, 1647, 1599, 1487, 1240, 1207, 1171, 1070, 982, 816, 729. The hydrogen spectrum of nuclear magnetic resonance of the prepared side chain biquaternary ammonium salt ionic fluorene-containing polyarylether compound DQA-PFE-40-C3 is shown in figure 1, and the infrared spectrum is shown in figure 2.
Example 5 preparation of side chain bis-quaternary ammonium salt ionic fluorene-containing polyarylether compound DQA-PFE-20-C3
The procedure was as in example 4, except that the fluorine-containing polyfluorene ether raw material PFE-40 was changed to the fluorine-containing polyfluorene ether compound PFE-20 of example 2 in an amount of 1.55 g (2.32 mmol). The side chain biquaternary ammonium salt ionic polyarylether compound DQA-PFE-20-C3 is obtained through reaction. Yield: 98 percent.
Example 6 preparation of side chain bis-quaternary ammonium salt ionic fluorene-containing polyarylether compound DQA-PFE-40-C6
The experimental procedure was as in example 4 except that Br-4-QA was used instead of the brominated alkyl quaternary ammonium salt compound as the starting material, and the charge amount was 0.53 g (1.74 mmol). The reaction is carried out to obtain the side chain biquaternary ammonium salt ionic fluorene-containing polyarylether compound DQA-PFE-40-C6. Yield: 96 percent. The data of the nuclear magnetic resonance hydrogen spectrum of the compound are as follows:1H NMR (400 MHz, DMSO-d6)7.95 (s,1H), 7.42 (d, 2H),7.34(s, 2H), 7.14 (s,1H), 4.71 (d, 1H), 3.09 (s,2H), 1.71 (d, 1H), 1.33 (s, 1H). The infrared data are: FT-IR (cm)-1) υ 3413, 3066, 3037,2927, 2862, 2819, 2757, 1649, 1602, 1487, 1205, 1170, 1070, 981, 816, 746, 729. The nuclear magnetic resonance hydrogen spectrogram and the infrared spectrogram of the prepared side chain biquaternary ammonium salt ionic fluorene-containing polyarylether compound DQA-PFE-40-C6 are shown in figure 3 and figure 4 respectively.
Example 7 preparation of side chain bis-quaternary ammonium salt ionic fluorene-containing polyarylether compound DQA-PFE-20-C6
The experimental procedure was as in example 4, except that 1.00 g (1.50 mmol) of the fluorine-containing polyfluorene ether compound PFE-20 and the bromoalkyl quaternary ammonium salt compound Br-4-QA in example 2 were used as starting materials in an amount of 0.68 g (2.25 mmol). The reaction is carried out to obtain the ionic fluorene-containing polyarylether compound DQA-PFE-20-C6 containing 20 mol percent of long side chain biquaternary ammonium salt. Yield: 97 percent.
Example 8 preparation of anion exchange Membrane based on the above Quaternary ammonium salt Ionic fluorene-containing polyarylether Compound
Dissolving 0.5 g of the above-mentioned side chain monoquaternary ammonium salt ion type and side chain diquaternary ammonium salt ion type fluorine-containing polyfluorene ether compound in 10 mLN-Preparing a 5 wt% solution in methyl pyrrolidone, casting on a horizontally placed flat glass, drying in a constant temperature oven at 80 ℃ for 12 hours, and then drying in a vacuum oven at 80 ℃ for 12 hours to obtain a film-shaped product in a glass plate shape. And (3) removing the membrane from the glass plate, and then soaking the membrane in deionized water to prepare the target side chain mono-quaternary ammonium salt ionic and side chain bis-quaternary ammonium salt ionic fluorene-containing polyarylether anion exchange membrane product.
Example 9 testing of the Performance of the side chain Mono-Quaternary ammonium salt type and side chain BiQuaternary ammonium salt type fluorine-containing polyfluoroether anion exchange membranes
Ion exchange capacity was measured by titration, bromide conductivity by AC impedance, tensile properties by Universal testing machine, 1M (VO)2)2SO4The solution was soaked at room temperature for 2 weeks to test oxidation stability. The characterization shows that the performances of the side chain single quaternary ammonium salt ionic type and the side chain double quaternary ammonium salt ionic type fluorine-containing polyfluorene ether anion-exchange membrane are shown in the following table:
TABLE 1 Performance of side chain monoquaternary ammonium salt ionic and side chain diquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membranes
The test data in Table 1 show that compared with the side chain single quaternary ammonium salt ionic anion exchange membrane QA-PFE-40, the side chain double quaternary ammonium salt ionic anion exchange membrane DQA-PFE-20-C3 and DQA-PFE-20-C6 have similar ion exchange capacities, but the bromine ion conductivity is remarkably improved, and the adjustment and control of the distribution of the ionic groups in the anion exchange membrane have obvious beneficial effects. The conductivity of the bromide ions was further improved by virtue of the higher ion exchange capacity of DQA-PFE-40-C3 and DQA-PFE-40-C6 compared to the other samples.
Claims (5)
1. A side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membrane is characterized by consisting of a side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether compound with the following structural formula:
wherein X is any anion, m is 1-400, n is 10-400, and y is 1-4;
the preparation method of the side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membrane specifically comprises the following steps:
(1) preparing a side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether compound: dissolving a fluorine-containing polyfluorene ether compound containing a dimethylamine side chain in a polar aprotic solvent to prepare a solution A; then, dissolving 0.5-1.5 times molar weight of brominated alkyl quaternary ammonium salt compound Br-y-QA of the dimethylamine group in a polar aprotic solvent to prepare a solution B; then, slowly dropwise adding the solution B into the solution A under the protection of argon, and continuously stirring for 10-50 h at 20-80 ℃ after dropwise adding; finally, putting the reactant into a dialysis bag, dialyzing in deionized water for 3-10 days, and dewatering and drying at 80-120 ℃ for 10-40 hours to obtain a side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether compound;
(2) preparing an anion exchange membrane: dissolving the side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether compound in the step (1) in a polar aprotic solvent to prepare a solution of 1-8 wt%, then casting the solution on a horizontally placed glass plate, drying the solution for 10-50 hours in a common oven at 40-100 ℃, and then drying the solution for 10-50 hours in a vacuum oven at 60-150 ℃ to obtain the side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membrane;
the chemical structure of the fluorine-containing polyfluorene ether compound containing dimethylamine side chain in the step (1) is as follows:
wherein m is 1 to 400, and n is 10 to 400;
the chemical structure of the brominated alkyl quaternary ammonium salt compound Br-y-QA is as follows:
wherein y is 1 to 4.
2. The side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membrane according to claim 1, wherein the concentration of the solution A in the step (1) is 1-10 wt.%, and the concentration of the solution B in the step (1) is 5-10 wt.%.
3. The side chain biquaternary ammonium salt ionic fluorine-containing polyfluorene ether anion exchange membrane according to claim 1, wherein the speed of dripping the solution B into the solution A in the step (1) is 1-5 mL/min.
4. The side chain biquaternary ammonium salt ionic fluorine-containing polyfluoroether anion exchange membrane according to claim 1, wherein the thickness of the anion exchange membrane prepared in the step (2) is 40-80 μm.
5. The membrane of claim 1 wherein the polar aprotic solvent comprises a polar aprotic solventN,N-dimethylacetamide,N,N-dimethylformamide,NAny one of methyl pyrrolidone, dimethyl sulfoxide and 1, 3-dimethyl-2-imidazolidinone.
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