CN105566884A - Anion-exchange membrane containing xanthene structure and preparation method and application of anion-exchange membrane - Google Patents
Anion-exchange membrane containing xanthene structure and preparation method and application of anion-exchange membrane Download PDFInfo
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- CN105566884A CN105566884A CN201610056375.9A CN201610056375A CN105566884A CN 105566884 A CN105566884 A CN 105566884A CN 201610056375 A CN201610056375 A CN 201610056375A CN 105566884 A CN105566884 A CN 105566884A
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- 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
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
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- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
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- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
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- 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
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
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- C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)
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Abstract
The invention discloses an anion-exchange membrane containing a xanthene structure and a preparation method and application of the anion-exchange membrane. The anion-exchange membrane is a polyarylether compound containing a quaternary ammonium salt side group and the xanthene structure, and the structure of the anion-exchange membrane is shown as a formula (I) (please see the formula in the description). According to the method, an aromatic bisphenol monomer containing the xanthene structure, an aromatic dihalogenation monomer Ar1 containing halogen atoms or/and an aromatic dihalogenation monomer Ar3 containing the halogen atoms and other aromatic bisphenol monomer Ar2 are taken as raw materials to be copolymerized to obtain a polyarylether compound containing the xanthene structure, then bromination and quaternization reactions are performed, and finally membrane coating and anion exchange are performed. The anion-exchange membrane takes polyether sulfone or/and polyether ketone as a framework of the proton exchange membrane, has the higher mechanical property and thermal stability, takes the quaternary ammonium salt group as the side group of the proton exchange membrane, has the good chemical stability and ionic conduction function and can serve as a battery diaphragm to be applied to an alkaline anion-exchange membrane fuel battery and an all-vanadium redox flow battery.
Description
Technical field
The present invention relates to electrochemical field and macromolecule member material field, be specifically related to a kind of polyether compound, anion-exchange membrane and its preparation method and application that contain quaternary ammonium salt side and xanthenes structure.
Background technology
Fuel cell (AFCs) is considered to one of 21st century energy conversion most with prospects.Proton Exchange Membrane Fuel Cells (PEMFCs) is as the one of fuel cell (AFCs), due to energy density and power density is high, environmental friendliness, can at room temperature start fast, the long and advantages of simple structure and simple without electrolyte loss, life-span, develop comparatively rapid in the last few years.PEMFCs is acidic electrolysis plastome, and the ion-exchange membrane used at present is mainly produced with du pont company
series membranes is representative, there is higher ionic conductivity and mechanical property, but it is expensive, add also to there is methanol fuel infiltration while need using the noble metal catalysts such as platinum and intermediate product causes the problems such as poison electrode catalysts, seriously hinder its large-scale marketization application further.In order to overcome these technical problems, researcher also been proposed a kind of fuel cell technology worked under alkaline environment, alkaline anion-exchange membrane fuel cell (AAEMFCs), compared with Proton Exchange Membrane Fuel Cells, have obvious characteristics and advantages: fuel and the oxygenant that effectively can intercept negative and positive the two poles of the earth, methanol permeability is low; Have than speed of response faster in Proton Exchange Membrane Fuel Cells; Poison electrode catalysts can not be caused; Can Ag be used, the transition metal of the earth rich reserves such as Ni, Co, avoid the situation that must use noble metal catalyst, greatly reduce production cost.
As the important component part of AAEMFCs, the performance of performance to battery of anion-exchange membrane has material impact.Anion-exchange membrane in AAEMFCs, needs higher ionic conductivity, high chemical stability and thermostability and good mechanical property etc.At present in alkaline environment, specific conductivity is low is the subject matter that AAEMFCs faces with poor chemical stability.Can prepare containing high OH
-keep suitable swelling capacity while specific conductivity, there is enough physical strengths and chemical stability and can resistance to 80 DEG C and above high temperature be one of significant challenge of facing of AAEMFCs anion-exchange membrane commercialization.The main chain of anion-exchange membrane is generally made up of polyarylether compounds or fatty-chain polymers, and side base is made up of charged quaternary ammonium salt group.Polyether compound has remarkable thermostability, mechanical property and corrosion resistance nature, is applied widely at fuel cell ion exchange membrane Material Field.Therefore, develop that a kind of ionic conductivity is high, thermostability and chemical stability is good and the polyarylether series anion-exchange membrane of low cost has very important Practical significance.
Present specification has higher ionic conductivity, mechanical property, chemical stability and thermal stability based on the anion-exchange membrane comprising xanthenes structure, can be applied in alkaline anion-exchange membrane fuel cell as proton exchange membrane and in all-vanadium flow battery.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of polyether compound and the anion-exchange membrane thereof that comprise xanthenes structure, this anion-exchange membrane has higher ionic conductivity and chemical stability, main chain is made up of polyether compound, has good mechanical property and thermostability.
Technical scheme of the present invention is as follows:
A kind of anion-exchange membrane of xanthenes structure that comprises is for the polyether compound comprising xanthenes structure shown in following formula I:
Wherein x and y represents the polymerization degree, and x is that 1 ~ 200, y is 0 ~ 200 and x/ (x+y) × 100%=5% ~ 100%, y/ (x+y) × 100%=0% ~ 95%, and the relative molecular weight of polymkeric substance is 10000 ~ 100000, R
1can be hydrogen atom, methyl or quaternary ammonium salt group.
Described
respective be independently selected from formula (1) ~ formula (2) any one:
Work as R
1during=hydrogen:
be selected from following formula (3) ~ formula (4) any one:
T is methyl or quaternary ammonium salt group.
Work as R
1when=methyl or quaternary ammonium salt group,
be selected from following formula (5) ~ formula (10) any one:
Preferably, side chain quaternary ammonium salt group can be any one in following substituting group:
Wherein, X is the negatively charged ion of the negative valence charge of band arbitrarily, can be Br
-, Cl
-or OH
-.
According to the present invention, described formula I is random copolymers.
By controlling the ratio that feeds intake, can the ratio of control x and y component, the numerical value of x and y reflects molecular weight and the range of molecular weight distributions thereof of polyether compound.
Another object of the present invention is to provide the above-mentioned preparation method comprising the polyether compound of xanthenes structure.
The inventive method comprises the following steps:
Step (1), be furnished with water trap, thermometer, in the reaction vessel of mechanical stirrer and import and export of nitrogen, adding the aromatic bisphenols monomer containing xanthenes structure, fragrant dihalo monomer A r
1, aromatic bisphenols monomer A r
2, fragrant dihalo monomer A r
3(Ar
1and Ar
3can be same or not same compound) and catalyzer after, add dewatering agent and polar aprotic solvent p again, first be warming up to 140 DEG C of dehydration 3h, after be warming up to 150 ~ 210 DEG C reaction 3 ~ 20h, pour in ethanol and precipitate, use the solution repetitive scrubbing 3 times of ethanol and deionized water (volume ratio is 1:1) afterwards, at 80 DEG C, vacuum-drying 48h obtains polyether compound resin XanPAES.
The described aromatic bisphenols monomer containing xanthenes structure, fragrant dihalo monomer A r
1, aromatic bisphenols monomer A r
2, fragrant dihalo monomer A r
3be 1:1:(0 ~ 19 with the mol ratio of catalyzer): (0 ~ 19): (2.5 ~ 50);
The volume ratio of described dewatering agent and polar aprotic solvent p is (0.4 ~ 1.5): 1;
The described aromatic bisphenols monomer containing xanthenes structure has following formula II constitutional features:
In formula II, R
2=hydrogen atom or methyl.
1. R is worked as
1=R
2during=hydrogen:
The described aromatic bisphenols monomer containing xanthenes structure is structure shown in formula (11):
Described biphenol monomer Ar
2there is following constitutional features:
wherein
be selected from formula (12) ~ formula (13) any one:
Described fragrant dihalo monomer A r
1and Ar
3there is following structure:
Wherein
respective be independently selected from formula (14) ~ (15) any one:
2. R is worked as
2=methyl and R
1when=methyl or quaternary ammonium salt group:
The described aromatic bisphenols monomer containing xanthenes structure has following formula III constitutional features:
Described biphenol monomer Ar
2there is following constitutional features:
wherein
be selected from formula (16) ~ formula (21) any one:
Described fragrant dihalo monomer
be selected from structure shown in same above formula (14) ~ formula (15).
Step (2), the polyether compound XanPAES of preparation in step (1) is dissolved in the enpara kind solvent of certain mass, then appropriate bromizating agent and initiator is added, carry out bromination reaction 5 ~ 8h at a certain temperature, pour in ethanol and precipitate, then use ethanol repetitive scrubbing 3 times, 60 DEG C of vacuum-dryings obtain brominated product B-XanPAES; The mass ratio of described polyether compound XanPAES, enpara kind solvent, bromizating agent and initiator is 1:(24.70 ~ 31.90): (1.27 ~ 2.0304): (0.0583 ~ 0.1033).
Step (3), brominated product B-XanPAES described in step (2) is dissolved in polar aprotic solvent q after, add quaternizing agent, reaction overnight 24h at 50 DEG C, obtains quaternized products; The mass ratio of described brominated product B-XanPAES, polar aprotic solvent q and quaternizing agent is 1:9:(0.16 ~ 10).
Step (4), the quaternized products obtained is coated in prior level-off clean sheet glass above, at 50 DEG C, dry 24h is to make solvent evaporates complete, film is taken off above sheet glass, comprise the anion-exchange membrane Q-XanPAES of xanthenes structure described in obtaining, prepared anion-exchange membrane is assembled in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery respectively and tests correlated performance.
Preferably, the polar aprotic solvent q in the polar aprotic solvent p described in step (1), step (3) is independently N,N-dimethylacetamide separately, N, dinethylformamide, tetramethylene sulfone, the one in N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO).
Preferably, the dewatering agent described in step (1) is toluene.
Preferably, the catalyzer described in step (1) is salt of wormwood, any one in sodium carbonate or cesium carbonate.
Preferably, the polymeric reaction temperature described in step (1) is 150 ~ 210 DEG C.
Preferably, described in step (2), enpara kind solvent is sym.-tetrachloroethane, 1,2-ethylene dichloride, any one in tetracol phenixin.
Preferably, initiator described in step (2) is any one in benzoyl peroxide or Diisopropyl azodicarboxylate.
Preferably, bromizating agent described in step (2) is any one in N-bromo-succinimide or C5H6Br2N2O2.
Preferably, the bromination reaction temperature described in step (2) is 75 ~ 85 DEG C.
Preferably, the quaternizing agent described in step (3) is Trimethylamine 99, N-Methylimidazole, 1,2 dimethylimidazole, any one in pyridine, benzoglyoxaline and triethylene diamine.
Another object of the present invention is to provide the above-mentioned anion-exchange membrane comprising xanthenes structure, and this kind of anion-exchange membrane can be used as proton exchange membrane and be applied in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery.
The anion-exchange membrane comprising xanthenes structure prepared by the present invention also may be used for the other field except all-vanadium flow battery and alkaline anion-exchange membrane fuel cell, comprises electrodialysis, sea water desaltination, sewage treatment area.
Preparation method and application described in the inventive method are the scheme optimized, and reaction monomers of the present invention, temperature, time and other correlated response conditions are the claimed content of this patent, and this patent is claimed is not limited only to this.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention is from Molecular Structure Design and polymer performance angle, has synthesized the anionresin mould material of a series of excellent combination property, and synthesis technique is simple, and raw material is easy to get, and preparation cost is cheap.
(2) alkaline anion-exchange membrane comprising xanthenes structure provided by the invention, main chain is the polyether compound containing xanthenes structure, there is reasonable mechanical property and thermal stability, side base is quaternary ammonium salt group, there is higher ion-exchange performance and chemical stability, the service requirements of anion-exchange membrane in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery can be met.
(3) alkaline anion-exchange membrane comprising xanthenes structure that prepared by the present invention, except can be used for alkaline anion-exchange membrane fuel cell and all-vanadium flow battery China and foreign countries, in electrodialysis, sea water desaltination, sewage disposal, membrane sepn, sensor field, also there is important using value.
Adopt nucleus magnetic resonance
1hNMR carries out analysis and the sign of structure to the prepared anion-exchange membrane comprising xanthenes structure, Zehner (Germany) electrochemical workstation is adopted to measure the ionic conductivity of ion-exchange membrane, adopt back titration method to measure the loading capacity of anion-exchange membrane, adopt high resolution gas chromatography and ultraviolet-visible spectrophotometer respectively to the methyl alcohol in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery and VO
2+-rate of permeation analyze, to and the water-intake rate of anion-exchange membrane and the performance such as swelling capacity and alkaline stability are tested.
Accompanying drawing explanation
Fig. 1 is the resin XanPAES-7 containing xanthenes structure prepared by case study on implementation 7, and brominated product B-XanPAES-7, comprises the nuclear magnetic spectrum of the anion-exchange membrane Q-XanPAES-7 of xanthenes structure.
Fig. 2 is the resin XanPAES-8 containing xanthenes structure prepared by case study on implementation 8, and brominated product B-XanPAES-8, comprises the nuclear magnetic spectrum of the anion-exchange membrane Q-XanPAES-8 of xanthenes structure.
Fig. 3 is the ionic conductivity collection of illustrative plates comprising the anion-exchange membrane of xanthenes structure prepared by case study on implementation 1-6.
Fig. 4 is the thermostability curve comprising the anion-exchange membrane of xanthenes structure prepared by case study on implementation 1-6.
Fig. 5 is the thermostability curve comprising the anion-exchange membrane of xanthenes structure prepared by case study on implementation 7-12.
Embodiment
Be described below in conjunction with the preferred embodiments of the invention, but embodiment of the present invention are not restricted to this.
Embodiment 1
By the aromatic bisphenols monomer (formula II) containing xanthenes structure of 5mmol, the fragrant dihalo monomer A r of 5mmol
1(formula 14), the aromatic bisphenols monomer A r of 5mmol
2(formula 12), the fragrant dihalo monomer A r of 5mmol
3(formula 14), the salt of wormwood of 25mmol, the toluene of 30ml and the tetramethylene sulfone of 50ml join and water trap are housed, thermometer, in the four-hole boiling flask of the 250ml of agitator and import and export of nitrogen, first be warming up to 140 DEG C of reaction 3h, continue to be warming up to 210 DEG C of reaction 3h, polymers soln is poured in ethanol and is precipitated, with ethanol and deionized water repetitive scrubbing 3 times, vacuum-drying 48h at 80 DEG C, obtains fluoropolymer resin XanPAES-1; 1g fluoropolymer resin is dissolved in 1 of 20ml (31.86g), 1,2,2-tetrachloroethane, adds the N-bromo-succinimide of 1.27g and the benzoyl peroxide of 0.086g, reacts 5h and carry out bromination reaction at 85 DEG C, pour in ethanol after being cooled to room temperature and precipitate, with ethanol repetitive scrubbing 3 times, at 60 DEG C, vacuum-drying 24h, obtains brominated product B-XanPAES-1; The brominated product of 1g is dissolved in the tetramethylene sulfone of 9g, add the N-Methylimidazole of 0.20g, 24h is reacted at 50 DEG C, mixture solution is coated on the sheet glass of prior leveling, dry 24h at 50 DEG C, film is taken off from sheet glass, described in obtaining, comprises the anion-exchange membrane Q-XanPAES-1 of xanthenes structure.Prepared anion-exchange membrane is assembled into respectively in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery, test correlated performance.
As shown in Figure 3, at 80 DEG C, Q-XanPAES-1 film ionic conductivity is in deionized water 32.47mS/cm to anion-exchange membrane Q-XanPAES-1 ionic conductance rate curve in deionized water.As shown in Figure 4, the degradation temperature of anion-exchange membrane Q-XanPAES-1 side chain is 310 DEG C to the thermostability curve of anion-exchange membrane Q-XanPAES-1.
Embodiment 2
By the aromatic bisphenols monomer (formula II) containing xanthenes structure of 0.5mmol, the fragrant dihalo monomer A r of 0.5mmol
1(formula 15), the aromatic bisphenols monomer A r of 9.5mmol
2(formula 13), the fragrant dihalo monomer A r of 9.5mmol
3(formula 15), the sodium carbonate of 25mmol, the toluene of 20ml and the N,N-dimethylacetamide of 50ml join and water trap are housed, thermometer, in the four-hole boiling flask of the 250ml of agitator and import and export of nitrogen, be first warming up to 140 DEG C of reaction 3h, continue to be warming up to 165 DEG C of reaction 12h, polymers soln is poured in ethanol and obtain polymkeric substance precipitation, with ethanol and deionized water repetitive scrubbing 3 times, vacuum-drying 48h at 80 DEG C, obtains fluoropolymer resin XanPAES-2; 1g fluoropolymer resin is dissolved in 1 of 20ml (31.86g), 1,2,2-tetrachloroethane, adds the N-bromo-succinimide of 1.27g and the benzoyl peroxide of 0.086g, reacts 5h and carry out bromination reaction at 85 DEG C, be poured in ethanol after being cooled to room temperature and precipitate, with ethanol repetitive scrubbing 3 times, at 60 DEG C, vacuum-drying 24h, obtains brominated product B-XanPAES-2; The brominated product of 1g is dissolved in the N of 9g, N-N,N-DIMETHYLACETAMIDE, add the benzoglyoxaline of 0.18g, 50 DEG C of reaction 24h, mixture solution is coated in prior leveling and on the sheet glass of wash clean, at 50 DEG C, dry 24h, takes off film from sheet glass, comprises the anion-exchange membrane Q-XanPAES-2 of xanthenes structure described in obtaining.Prepared anion-exchange membrane is assembled into respectively in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery, test correlated performance.
As shown in Figure 3, at 80 DEG C, Q-XanPAES-2 film ionic conductivity is in deionized water 44.64mS/cm to the ionic conductance rate curve in deionized water of anion-exchange membrane Q-XanPAES-2.As shown in Figure 4, the degradation temperature of anion-exchange membrane Q-XanPAES-2 side chain is 295 DEG C to the thermostability curve of anion-exchange membrane Q-XanPAES-2.
Embodiment 3
By the aromatic bisphenols monomer (formula II) containing xanthenes structure of 9.5mmol, the fragrant dihalo monomer A r of 9.5mmol
1(formula 14), the aromatic bisphenols monomer A r of 0.5mmol
2(formula 12), the fragrant dihalo monomer A r of 0.5mmol
3(formula 15), the cesium carbonate of 25mmol, the toluene of 25ml and the DMF of 50ml join and water trap are housed, thermometer, in the four-hole boiling flask of the 250ml of agitator and import and export of nitrogen, be first warming up to 140 DEG C of reaction 3h, continue to be warming up to 150 DEG C of reaction 20h, polymers soln is poured in ethanol and obtain polymkeric substance precipitation, with ethanol and deionized water repetitive scrubbing 3 times, vacuum-drying 48h at 80 DEG C, obtains fluoropolymer resin XanPAES-3; 1g fluoropolymer resin is dissolved in 1 of 20ml (24.70g), 2-ethylene dichloride, add the N-bromo-succinimide of 1.27g and the Diisopropyl azodicarboxylate of 0.0583g, react 6h at 80 DEG C and carry out bromination reaction, be poured in ethanol after being cooled to room temperature and precipitate, repetitive scrubbing 3 times, at 60 DEG C, vacuum-drying 24h, obtains brominated product B-XanPAES-3; The brominated product of 1g is dissolved in the N of 9g, dinethylformamide, add the pyridine of 0.17g, 50 DEG C of reaction 24h, mixture solution is coated in prior leveling and on the sheet glass of wash clean, at 50 DEG C, dry 24h, takes off film from sheet glass, comprises the anion-exchange membrane Q-XanPAES-3 of xanthenes structure described in obtaining.Prepared anion-exchange membrane is assembled into respectively in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery, test correlated performance.
As shown in Figure 3, at 80 DEG C, Q-XanPAES-3 film ionic conductivity is in deionized water 3.7mS/cm to the ionic conductance rate curve in deionized water of anion-exchange membrane Q-XanPAES-3.As shown in Figure 4, the degradation temperature of the side chain of anion-exchange membrane Q-XanPAES-3 is 290 DEG C to the thermostability curve of anion-exchange membrane Q-XanPAES-3.
Embodiment 4
By the aromatic bisphenols monomer (formula II) containing xanthenes structure of 5mmol, the fragrant dihalo monomer A r of 5mmol
1(formula 15), the aromatic bisphenols monomer A r of 5mmol
2(formula 13), the fragrant dihalo monomer A r of 5mmol
3(formula 14), the sodium carbonate of 25mmol, the toluene of 30ml and the N-Methyl pyrrolidone of 30ml join and water trap are housed, thermometer, in the four-hole boiling flask of the 250ml of agitator and import and export of nitrogen, first be warming up to 140 DEG C of reaction 3h, continue to be warming up to 200 DEG C of reaction 6h, polymers soln is poured in ethanol and precipitates, with ethanol and deionized water repetitive scrubbing 3 times, vacuum-drying 48h at 80 DEG C, obtains fluoropolymer resin XanPAES-4; 1g fluoropolymer resin is dissolved in the tetracol phenixin of 20ml (31.90g), add the C5H6Br2N2O2 of 2.0304g and the Diisopropyl azodicarboxylate of 0.0583g, react 8h at 75 DEG C and carry out bromination reaction, be poured in ethanol after being cooled to room temperature and precipitate, and with ethanol repetitive scrubbing 3 times, at 60 DEG C, vacuum-drying 24h, obtains brominated product B-XanPAES-4; The brominated product of 1g is dissolved in the N-Methyl pyrrolidone of 9g, add the triethylene diamine of 0.16g, 50 DEG C of reaction 24h, mixture solution is coated in prior leveling and on the sheet glass of wash clean, dry 24h at 50 DEG C, film is taken off from sheet glass, described in obtaining, comprises the anion-exchange membrane Q-PXPPPAES-4 of xanthenes structure.Prepared anion-exchange membrane is assembled into respectively in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery, test correlated performance.
As shown in Figure 3, at 80 DEG C, Q-XanPAES-4 film ionic conductivity is in deionized water 20.25mS/cm to anion-exchange membrane Q-XanPAES-4 ionic conductance rate curve in deionized water.As shown in Figure 4, the degradation temperature of anion-exchange membrane Q-XanPAES-4 side chain is 287 DEG C to the thermostability curve of anion-exchange membrane Q-XanPAES-4, shows good thermostability.
Embodiment 5
By the aromatic bisphenols monomer (formula II) containing xanthenes structure of 10mmol, the fragrant dihalo monomer A r of 10mmol
1(formula 14), the sodium carbonate of 25mmol, the toluene of 30ml and the dimethyl sulfoxide (DMSO) of 20ml join and water trap are housed, thermometer, in the four-hole boiling flask of the 250ml of agitator and import and export of nitrogen, first be warming up to 140 DEG C of reaction 3h, continue to be warming up to 180 DEG C of reaction 10h, polymers soln is poured in ethanol and precipitates, with ethanol and deionized water repetitive scrubbing 3 times, vacuum-drying 48h at 80 DEG C, obtains fluoropolymer resin XanPAES-5; 1g fluoropolymer resin is dissolved in the tetracol phenixin of 20ml (31.90g), add the C5H6Br2N2O2 of 1.9685g and the benzoyl peroxide of 0.072g, react 8h at 75 DEG C and carry out bromination reaction, be poured in ethanol after being cooled to room temperature and precipitate, and with ethanol repetitive scrubbing 3 times, at 60 DEG C, vacuum-drying 24h, obtains brominated product B-XanPAES-5; The brominated product of 1g is dissolved in the dimethyl sulfoxide (DMSO) of 9g, add 1 of 0.18g, 2-methylimidazole, 50 DEG C of reaction 24h, mixture solution is coated in prior leveling and on the sheet glass of wash clean, at 50 DEG C, dry 24h, takes off film from sheet glass, comprises the anion-exchange membrane Q-XanPAES-5 of xanthenes structure described in obtaining.Prepared anion-exchange membrane is assembled into respectively in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery, test correlated performance.
As shown in Figure 3, at 80 DEG C, Q-XanPAES-5 film ionic conductivity is in deionized water 45.25mS/cm to anion-exchange membrane Q-XanPAES-5 ionic conductance rate curve in deionized water.As shown in Figure 4, the degradation temperature of anion-exchange membrane Q-XanPAES-5 side chain is 293 DEG C to the thermostability curve of anion-exchange membrane Q-XanPAES-5.
Embodiment 6
By the aromatic bisphenols monomer (formula II) containing xanthenes structure of 5mmol, the fragrant dihalo monomer A r of 5mmol
1(formula 14), the aromatic bisphenols monomer A r of 5mmol
2(formula 12), the fragrant dihalo monomer A r of 5mmol
3(formula 14), the cesium carbonate of 25mmol, the toluene of 25ml and the tetramethylene sulfone of 40ml join and water trap are housed, thermometer, in the four-hole boiling flask of the 250ml of agitator and import and export of nitrogen, first be warming up to 140 DEG C of reaction 3h, continue to be warming up to 210 DEG C of reaction 3h, polymers soln is poured in ethanol and precipitates, and with ethanol and deionized water repetitive scrubbing 3 times, vacuum-drying 48h at 80 DEG C, obtains fluoropolymer resin XanPAES-6; 1g fluoropolymer resin is dissolved in 1 of 20ml (31.86g), 1,2,2-tetrachloroethane, adds the N-bromo-succinimide of 1.38g and the benzoyl peroxide of 0.092g, reacts 5h and carry out bromination reaction at 85 DEG C, be poured in ethanol after being cooled to room temperature and precipitate, and with ethanol repetitive scrubbing 3 times, at 60 DEG C, vacuum-drying 24h, obtains brominated product B-XanPAES-6; The brominated product of 1g is dissolved in the N of 9g, N-N,N-DIMETHYLACETAMIDE, mixture solution is coated in prior leveling and on the sheet glass of wash clean, dry 24h at 50 DEG C, film is taken off from sheet glass, film bubble being entered 10g massfraction is that in the trimethylamine solution of 30%, 24h fully reacts, and is taken out by film and uses deionized water wash, comprising the anion-exchange membrane Q-XanPAES-6 of xanthenes structure described in obtaining.Prepared anion-exchange membrane is assembled into respectively in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery, test correlated performance.
As shown in Figure 3, at 80 DEG C, Q-XanPAES-6 film ionic conductivity is in deionized water 35.61mS/cm to anion-exchange membrane Q-XanPAES-6 ionic conductance rate curve in deionized water.As shown in Figure 4, the degradation temperature of anion-exchange membrane Q-XanPAES-6 side chain is 302 DEG C to the thermostability curve of anion-exchange membrane Q-XanPAES-6, shows good thermostability.
Table 1, the correlated performance comprising the anion-exchange membrane of xanthenes structure of preparation in embodiment 1 ~ example 6:
Embodiment 7
By the aromatic bisphenols monomer (formula III) containing xanthenes structure of 5mmol, the fragrant dihalo monomer A r of 5mmol
1(formula 14), the aromatic bisphenols monomer A r of 5mmol
2(formula 16), the fragrant dihalo monomer A r of 5mmol
3(formula 14), the salt of wormwood of 25mmol, the toluene of 30ml and the tetramethylene sulfone of 50ml join and water trap are housed, thermometer, in the four-hole boiling flask of the 250ml of agitator and import and export of nitrogen, first be warming up to 140 DEG C of reaction 3h, continue to be warming up to 210 DEG C of reaction 3h, polymers soln is poured in ethanol and is precipitated, with ethanol and deionized water repetitive scrubbing 3 times, vacuum-drying 48h at 80 DEG C, obtains fluoropolymer resin XanPAES-7; 1g fluoropolymer resin is dissolved in 1 of 20ml (31.86g), 1,2,2-tetrachloroethane, adds the N-bromo-succinimide of 1.27g and the benzoyl peroxide of 0.086g, reacts 5h and carry out bromination reaction at 85 DEG C, pour in ethanol after being cooled to room temperature and precipitate, with ethanol repetitive scrubbing 3 times, at 60 DEG C, vacuum-drying 24h, obtains brominated product B-XanPAES-7; The brominated product of 1g is dissolved in the tetramethylene sulfone of 9g, add 1 of 0.20g, 2-methylimidazole, 24h is reacted at 50 DEG C, mixture solution is coated on the sheet glass of prior leveling, at 50 DEG C, dry 24h, takes off film from sheet glass, comprises the anion-exchange membrane Q-XanPAES-7 of xanthenes structure described in obtaining.Prepared anion-exchange membrane is assembled into respectively in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery, test correlated performance.
The resin XanPAES-7 containing xanthenes structure of preparation, brominated product B-XanPAES-7 and comprise xanthenes structure anion-exchange membrane Q-XanPAES-7 nuclear magnetic spectrum as shown in Figure 1, in fluoropolymer resin XanPAES-7 nuclear magnetic spectrogram, 1.5ppm and 1.8ppm place is the proton signal above the aromatic compound containing xanthenes structure on methyl, 7.2ppm with 8.0ppm place is the proton signal on the phenyl ring that is connected with sulfuryl, shows the synthesis of polyethersulfone resin; In the nuclear magnetic spectrogram of brominated product B-XanPAES-7,4.2ppm place becomes methylene radical (-CH for after methyl bromide
2) fignal center; In the nuclear magnetic spectrum of alkaline anion-exchange membrane Q-XanPAES-7,5.3ppm place is the methylene radical (-CH be connected with 1,2 dimethylimidazole
2) signal, 2.2ppm place is the signal of proton on C-2 position in 1,2 dimethylimidazole, and 3.4ppm place is the fignal center of proton on the methyl that is connected with N, shows that 1,2 dimethylimidazole is successfully incorporated into above alkaline anion-exchange membrane.
As shown in Figure 5, the degradation temperature of anion-exchange membrane Q-XanPAES-7 side chain is 296 DEG C to the thermostability curve of anion-exchange membrane Q-XanPAES-7.
Embodiment 8
By the aromatic bisphenols monomer (formula III) containing xanthenes structure of 5mmol, the fragrant dihalo monomer A r of 5mmol
1(formula 15), the aromatic bisphenols monomer A r of 5mmol
2(formula 17), the fragrant dihalo monomer A r of 5mmol
3(formula 15), the sodium carbonate of 25mmol, the toluene of 20ml and the N,N-dimethylacetamide of 50ml join and water trap are housed, thermometer, in the four-hole boiling flask of the 250ml of agitator and import and export of nitrogen, be first warming up to 140 DEG C of reaction 3h, continue to be warming up to 165 DEG C of reaction 12h, polymers soln is poured in ethanol and obtain polymkeric substance precipitation, with ethanol and deionized water repetitive scrubbing 3 times, vacuum-drying 48h at 80 DEG C, obtains fluoropolymer resin XanPAES-8; 1g fluoropolymer resin is dissolved in 1 of 20ml (31.86g), 1,2,2-tetrachloroethane, adds the N-bromo-succinimide of 1.27g and the benzoyl peroxide of 0.086g, reacts 5h and carry out bromination reaction at 85 DEG C, be poured in ethanol after being cooled to room temperature and precipitate, with ethanol repetitive scrubbing 3 times, at 60 DEG C, vacuum-drying 24h, obtains brominated product B-XanPAES-8; The brominated product of 1g is dissolved in the N of 9g, N-N,N-DIMETHYLACETAMIDE, add the N-Methylimidazole of 0.18g, 50 DEG C of reaction 24h, mixture solution is coated in prior leveling and on the sheet glass of wash clean, at 50 DEG C, dry 24h, takes off film from sheet glass, comprises the anion-exchange membrane Q-XanPAES-8 of xanthenes structure described in obtaining.Prepared anion-exchange membrane is assembled into respectively in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery, test correlated performance.
The resin XanPAES-8 containing xanthenes structure of preparation, brominated product B-XanPAES-8 and comprise xanthenes structure anion-exchange membrane Q-XanPAES-8 nuclear magnetic spectrum as shown in Figure 2, in fluoropolymer resin XanPAES-8 nuclear magnetic spectrogram, 1.5ppm and 1.8ppm place is the proton signal above the aromatic compound containing xanthenes structure on methyl, 7.3ppm with 7.8ppm place is the proton signal on the phenyl ring that is connected with carbonyl, shows the synthesis of polyether ketone resin; In the nuclear magnetic spectrogram of brominated product B-XanPAES-8,4.3ppm place becomes methylene radical (-CH for after methyl bromide
2) fignal center; In the nuclear magnetic spectrum of alkaline anion-exchange membrane Q-XanPAES-8,5.2ppm place is the methylene radical (-CH be connected with N-Methylimidazole
2) signal, 3.4ppm place is the fignal center of proton on the methyl that is connected with N above N-Methylimidazole, shows that N-methylimidazole is successfully incorporated in alkaline anion-exchange membrane.
As shown in Figure 5, the degradation temperature of anion-exchange membrane Q-XanPAES-8 side chain is 306 DEG C to the thermostability curve of anion-exchange membrane Q-XanPAES-8.
Embodiment 9
By the aromatic bisphenols monomer (formula III) containing xanthenes structure of 5mmol, the fragrant dihalo monomer A r of 5mmol
1(formula 14), the aromatic bisphenols monomer A r of 5mmol
2(formula 18), the fragrant dihalo monomer A r of 5mmol
3(formula 14), the cesium carbonate of 25mmol, the toluene of 25ml and the DMF of 50ml join and water trap are housed, thermometer, in the four-hole boiling flask of the 250ml of agitator and import and export of nitrogen, be first warming up to 140 DEG C of reaction 3h, continue to be warming up to 150 DEG C of reaction 20h, polymers soln is poured in ethanol and obtain polymkeric substance precipitation, with ethanol and deionized water repetitive scrubbing 3 times, vacuum-drying 48h at 80 DEG C, obtains fluoropolymer resin XanPAES-9; 1g fluoropolymer resin is dissolved in 1 of 20ml (24.70g), 2-ethylene dichloride, add the N-bromo-succinimide of 1.27g and the Diisopropyl azodicarboxylate of 0.0583g, react 6h at 80 DEG C and carry out bromination reaction, be poured in ethanol after being cooled to room temperature and precipitate, repetitive scrubbing 3 times, at 60 DEG C, vacuum-drying 24h, obtains brominated product B-XanPAES-9; The brominated product of 1g is dissolved in the N of 9g, dinethylformamide, add the pyridine of 0.17g, 50 DEG C of reaction 24h, mixture solution is coated in prior leveling and on the sheet glass of wash clean, at 50 DEG C, dry 24h, takes off film from sheet glass, comprises the ion-exchange membrane Q-XanPAES-9 of xanthenes structure described in obtaining.Prepared anion-exchange membrane is assembled into respectively in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery, test correlated performance.
As shown in Figure 5, the degradation temperature of anion-exchange membrane Q-XanPAES-9 side chain is 298 DEG C to the thermostability curve of anion-exchange membrane Q-XanPAES-9.
Embodiment 10
By the aromatic bisphenols monomer (formula III) containing xanthenes structure of 9.5mmol, the fragrant dihalo monomer A r of 9.5mmol
1(formula 14), the aromatic bisphenols monomer A r of 0.5mmol
2(formula 19), the fragrant dihalo monomer A r of 0.5mmol
3(formula 15), the sodium carbonate of 25mmol, the toluene of 30ml and the N-Methyl pyrrolidone of 30ml join and water trap are housed, thermometer, in the four-hole boiling flask of the 250ml of agitator and import and export of nitrogen, first be warming up to 140 DEG C of reaction 3h, continue to be warming up to 200 DEG C of reaction 6h, polymers soln is poured in ethanol and precipitates, with ethanol and deionized water repetitive scrubbing 3 times, vacuum-drying 48h at 80 DEG C, obtains fluoropolymer resin XanPAES-10; 1g fluoropolymer resin is dissolved in the tetracol phenixin of 20ml (31.90g), add the C5H6Br2N2O2 of 2.0304g and the Diisopropyl azodicarboxylate of 0.0583g, react 8h at 75 DEG C and carry out bromination reaction, be poured in ethanol after being cooled to room temperature and precipitate, and with ethanol repetitive scrubbing 3 times, at 60 DEG C, vacuum-drying 24h, obtains brominated product B-XanPAES-10; The brominated product of 1g is dissolved in the N-Methyl pyrrolidone of 9g, add the benzoglyoxaline of 0.19g, 50 DEG C of reaction 24h, mixture solution is coated in prior leveling and on the sheet glass of wash clean, dry 24h at 50 DEG C, film is taken off from sheet glass, described in obtaining, comprises the anion-exchange membrane Q-XanPAES-10 of xanthenes structure.Prepared anion-exchange membrane is assembled into respectively in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery, test correlated performance.
As shown in Figure 5, the degradation temperature of anion-exchange membrane Q-XanPAES-10 side chain is 301 DEG C to the thermostability curve of anion-exchange membrane Q-XanPAES-10.
Embodiment 11
By the aromatic bisphenols monomer (formula III) containing xanthenes structure of 0.5mmol, the fragrant dihalo monomer A r of 0.5mmol
1(formula 15), the aromatic bisphenols monomer A r of 9.5mmol
2(formula 20), the fragrant dihalo monomer A r of 9.5mmol
3(formula 14), the salt of wormwood of 25mmol, the toluene of 30ml and the dimethyl sulfoxide (DMSO) of 20ml join and water trap are housed, thermometer, in the four-hole boiling flask of the 250ml of agitator and import and export of nitrogen, first be warming up to 140 DEG C of reaction 3h, continue to be warming up to 180 DEG C of reaction 10h, polymers soln is poured in ethanol and precipitates, with ethanol and deionized water repetitive scrubbing 3 times, vacuum-drying 48h at 80 DEG C, obtains fluoropolymer resin XanPAES-11; 1g fluoropolymer resin is dissolved in the tetracol phenixin of 20ml (31.90g), add the C5H6Br2N2O2 of 1.9685g and the benzoyl peroxide of 0.072g, react 8h at 75 DEG C and carry out bromination reaction, be poured in ethanol after being cooled to room temperature and precipitate, and with ethanol repetitive scrubbing 3 times, at 60 DEG C, vacuum-drying 24h, obtains brominated product B-XanPAES-11; The brominated product of 1g is dissolved in the dimethyl sulfoxide (DMSO) of 9g, add the triethylene diamine of 0.16g, 50 DEG C of reaction 24h, mixture solution is coated in prior leveling and on the sheet glass of wash clean, dry 24h at 50 DEG C, film is taken off from sheet glass, obtains the anion-exchange membrane Q-XanPAES-11 of described ammonium salt-containing side base and xanthenes structure.Prepared anion-exchange membrane is assembled into respectively in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery, test correlated performance.
As shown in Figure 5, the degradation temperature of anion-exchange membrane Q-XanPAES-11 side chain is 293 DEG C to the thermostability curve of anion-exchange membrane Q-XanPAES-11.
Embodiment 12
By the aromatic bisphenols monomer (formula III) containing xanthenes structure of 3mmol, the fragrant dihalo monomer A r of 3mmol
1(formula 14), the aromatic bisphenols monomer A r of 7mmol
2(formula 21), the fragrant dihalo monomer A r of 7mmol
3(formula 14), the cesium carbonate of 25mmol, the toluene of 25ml and the tetramethylene sulfone of 40ml join and water trap are housed, thermometer, in the four-hole boiling flask of the 250ml of agitator and import and export of nitrogen, first be warming up to 140 DEG C of reaction 3h, continue to be warming up to 210 DEG C of reaction 3h, polymers soln is poured in ethanol and precipitates, and with ethanol and deionized water repetitive scrubbing 3 times, vacuum-drying 48h at 80 DEG C, obtains fluoropolymer resin XanPAES-12; 1g fluoropolymer resin is dissolved in 1 of 20ml (31.86g), 1,2,2-tetrachloroethane, adds the N-bromo-succinimide of 1.38g and the benzoyl peroxide of 0.092g, reacts 5h and carry out bromination reaction at 85 DEG C, be poured in ethanol after being cooled to room temperature and precipitate, and with ethanol repetitive scrubbing 3 times, at 60 DEG C, vacuum-drying 24h, obtains brominated product B-XanPAES-12; The brominated product of 1g is dissolved in the N of 9g, N-N,N-DIMETHYLACETAMIDE, mixture solution is coated in prior leveling and on the sheet glass of wash clean, dry 24h at 50 DEG C, film is taken off from sheet glass, film bubble being entered 10g massfraction is that in the trimethylamine solution of 30%, 24h fully reacts, and is taken out by film and uses deionized water wash, comprising the anion-exchange membrane Q-XanPAES-12 of xanthenes structure described in obtaining.Prepared anion-exchange membrane is assembled into respectively in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery, test correlated performance.
As shown in Figure 5, the degradation temperature of anion-exchange membrane Q-XanPAES-12 side chain is 298 DEG C to the thermostability curve of anion-exchange membrane Q-XanPAES-12.
Embodiment 13
By the aromatic bisphenols monomer (formula III) containing xanthenes structure of 10mmol, the fragrant dihalo monomer A r of 10mmol
1(formula 14), the cesium carbonate of 25mmol, the toluene of 25ml and the tetramethylene sulfone of 40ml join and water trap are housed, thermometer, in the four-hole boiling flask of the 250ml of agitator and import and export of nitrogen, first be warming up to 140 DEG C of reaction 3h, continue to be warming up to 210 DEG C of reaction 3h, polymers soln is poured in ethanol and precipitates, and with ethanol and deionized water repetitive scrubbing 3 times, vacuum-drying 48h at 80 DEG C, obtains fluoropolymer resin XanPAES-13; 1g fluoropolymer resin is dissolved in 1 of 20ml (31.86g), 1,2,2-tetrachloroethane, adds the N-bromo-succinimide of 1.38g and the benzoyl peroxide of 0.092g, reacts 5h and carry out bromination reaction at 85 DEG C, be poured in ethanol after being cooled to room temperature and precipitate, and with ethanol repetitive scrubbing 3 times, at 60 DEG C, vacuum-drying 24h, obtains brominated product B-XanPAES-13; The brominated product of 1g is dissolved in the N of 9g, N-N,N-DIMETHYLACETAMIDE, mixture solution is coated in prior leveling and on the sheet glass of wash clean, dry 24h at 50 DEG C, film is taken off from sheet glass, film bubble being entered 10g massfraction is that in the trimethylamine solution of 30%, 24h fully reacts, and is taken out by film and uses deionized water wash, comprising the anion-exchange membrane Q-XanPAES-13 of xanthenes structure described in obtaining.Prepared anion-exchange membrane is assembled into respectively in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery, test correlated performance.
Table 2, the correlated performance comprising the anion-exchange membrane of xanthenes structure of preparation in embodiment 7 ~ example 13:
Claims (10)
1. comprise an anion-exchange membrane for xanthenes structure, it is characterized in that the polyether compound containing quaternary ammonium salt side and xanthenes structure as shown in formula I:
Wherein x and y represents the polymerization degree, and x is that 1 ~ 200, y is 0 ~ 200 and x/ (x+y) × 100%=5% ~ 100%, y/ (x+y) × 100%=0% ~ 95%, and the relative molecular weight of polymkeric substance is 10000 ~ 100000, R
1for hydrogen atom;
Described
respective be independently selected from formula (1) ~ formula (2) any one:
Described
be selected from following formula (3) ~ formula (4) any one:
T is methyl or quaternary ammonium salt group.
2. comprise an anion-exchange membrane for xanthenes structure, it is characterized in that the polyether compound containing quaternary ammonium salt side and xanthenes structure as shown in formula I:
Wherein x and y represents the polymerization degree, and x is that 1 ~ 200, y is 0 ~ 200 and x/ (x+y) * 100%=5 ~ 100, y/ (x+y) * 100%=0 ~ 95, and the relative molecular weight of polymkeric substance is 10000 ~ 100000, R
1for methyl or quaternary ammonium salt group;
Described
respective be independently selected from formula (1) ~ formula (2) any one:
Described
be selected from following formula (5) ~ formula (10) any one:
3. a kind of anion-exchange membrane comprising xanthenes structure as claimed in claim 1 or 2, is characterized in that R
1when being quaternary ammonium salt group with T, can be in following several substituting group any one:
Wherein X is the negatively charged ion of the negative valence charge of band arbitrarily.
4. comprise a preparation method for the anion-exchange membrane of xanthenes structure, it is characterized in that the method comprises the following steps:
Step (1), water trap is being housed, thermometer, in the reaction vessel of mechanical stirrer and import and export of nitrogen, is adding the aromatic bisphenols monomer containing xanthenes structure, fragrant dihalo monomer A r
1and catalyzer, and add dewatering agent and polar aprotic solvent p, first be warming up to 140 DEG C of dehydration 3h, after be warming up to 150 ~ 210 DEG C reaction 3 ~ 20h, pour in ethanol and precipitate, use the solution repetitive scrubbing 3 times of ethanol and deionized water afterwards, at 80 DEG C, vacuum-drying 48h obtains polyether compound resin XanPAES;
Step (2), the polyether compound XanPAES of preparation in step (1) is dissolved in the enpara kind solvent of certain mass, then appropriate bromizating agent and initiator is added, carry out bromination reaction 5 ~ 8h at a certain temperature, pour in ethanol and precipitate, then use ethanol repetitive scrubbing 3 times, 60 DEG C of vacuum-dryings obtain brominated product B-XanPAES;
Step (3), brominated product B-XanPAES described in step (2) is dissolved in polar aprotic solvent q after, add quaternizing agent, reaction overnight 24h at 50 DEG C, obtains quaternized products;
Step (4), the quaternized products obtained is coated in prior level-off clean sheet glass above, at 50 DEG C, dry 24h is to make solvent evaporates complete, film is taken off above sheet glass, obtains the described anion-exchange membrane Q-XanPAES containing quaternary ammonium salt side and xanthenes structure.
5. a kind of preparation method comprising the anion-exchange membrane of xanthenes structure as claimed in claim 4, is characterized in that:
The aromatic bisphenols monomer containing xanthenes structure described in step (1), fragrant dihalo monomer A r
1be 1:1:(2.5 ~ 50 with the mol ratio of catalyzer);
Water entrainer described in step (1) and the volume ratio of polar aprotic solvent p are (0.4 ~ 1.5): 1;
The mass ratio of the polyether compound XanPAES described in step (2), enpara kind solvent, bromizating agent and initiator is 1:(24.70 ~ 31.90): (1.27 ~ 2.0304): (0.0583 ~ 0.1033);
The mass ratio of the brominated product B-XanPAES described in step (3), polar aprotic solvent q and quaternizing agent is 1:9:(0.16 ~ 10).
6. a kind of preparation method comprising the anion-exchange membrane of xanthenes structure as claimed in claim 4, is characterized in that step (1) can also add aromatic bisphenols monomer A r
2with fragrant dihalo monomer A r
3; The described aromatic bisphenols monomer containing xanthenes structure, fragrant dihalo monomer A r
1, aromatic bisphenols monomer A r
2, fragrant dihalo monomer A r
3be 1:1:(0.01 ~ 19 with the mol ratio of catalyzer): (0.01 ~ 19): (2.5 ~ 50).
7. a kind of preparation method comprising the anion-exchange membrane of xanthenes structure as claimed in claim 4, is characterized in that: the described aromatic bisphenols monomer containing xanthenes structure is as follows:
Described aromatic bisphenols monomer A r
2there is following constitutional features:
wherein
be selected from formula (12) ~ formula (13) any one:
Described fragrant dihalo monomer A r
1and Ar
3there is following structure respectively:
Wherein
with
respective be independently selected from formula (14) ~ (15) any one:
8. a kind of preparation method comprising the anion-exchange membrane of xanthenes structure as claimed in claim 4, is characterized in that: the described aromatic bisphenols monomer containing xanthenes structure is as follows:
Described biphenol monomer Ar
2there is following structure:
wherein
be selected from formula (16) ~ formula (21) any one:
Described fragrant dihalo monomer A r
1and Ar
3there is following structure respectively:
Wherein
respective be independently selected from formula (14) ~ (15) any one:
9. a kind of preparation method comprising the anion-exchange membrane of xanthenes structure as claimed in claim 4, is characterized in that:
Polar aprotic solvent q in polar aprotic solvent p described in step (1), step (3) is independently N separately, N-N,N-DIMETHYLACETAMIDE, DMF, tetramethylene sulfone, the one in N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO);
Dewatering agent described in step (1) is toluene;
Catalyzer described in step (1) is salt of wormwood, any one in sodium carbonate or cesium carbonate;
Polymeric reaction temperature described in step (1) is 150 ~ 210 DEG C;
Described in step (2), enpara kind solvent is sym.-tetrachloroethane, 1,2-ethylene dichloride, any one in tetracol phenixin;
Initiator described in step (2) is any one in benzoyl peroxide or Diisopropyl azodicarboxylate;
Bromizating agent described in step (2) is any one in N-bromo-succinimide or C5H6Br2N2O2;
Bromination reaction temperature described in step (2) is 75 ~ 85 DEG C;
Quaternizing agent described in step (3) is Trimethylamine 99, N-Methylimidazole, 1,2 dimethylimidazole, any one in pyridine, benzoglyoxaline and triethylene diamine.
10. a kind of anion-exchange membrane comprising xanthenes structure can be used as proton exchange membrane and is applied in alkaline anion-exchange membrane fuel cell and all-vanadium flow battery as claimed in claim 1 or 2.
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| CN109232936B (en) * | 2018-09-17 | 2020-11-03 | 福州大学 | Anion exchange membrane for all-vanadium redox flow battery and preparation method thereof |
| CN109438696A (en) * | 2018-11-07 | 2019-03-08 | 沈阳化工大学 | A kind of sulfonation structure containing anthrone polyarylether and preparation method thereof |
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