CN108164724B - Aromatic dihydric phenol cross-linked polyaryl ether type anion exchange membrane and preparation method thereof - Google Patents
Aromatic dihydric phenol cross-linked polyaryl ether type anion exchange membrane and preparation method thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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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- 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
- C08G65/38—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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- C08G65/00—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
- C08G65/4093—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 characterised by the process or apparatus used
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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
- C08G65/485—Polyphenylene oxides
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- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
Abstract
The invention discloses an aromatic dihydric phenol cross-linked polyaryl ether type anion exchange membrane and a preparation method thereof. The method comprises the steps of synthesizing polyarylether polymer with active points capable of undergoing chloromethylation reaction through nucleophilic polycondensation, synthesizing quaternized polyarylether polymer through Friedel-crafts alkylation reaction and Moxijin reaction, mixing the quaternized polyarylether polymer and an aromatic dihydric phenol crosslinking agent in proportion, adding heat to crosslink to form a film under semi-closed conditions, and finally alkalizing to obtain the crosslinked anion-exchange membrane. The invention obtains the cross-linking type anion-exchange membranes with different structures by changing the amount of the cross-linking agent. The synthesis process is simple, the ion exchange capacity is controllable, and the prepared anion exchange membrane has a uniform structure and good stability.
Description
Technical Field
The invention belongs to the technical field of anion exchange membranes, and relates to an aromatic dihydric phenol cross-linked polyaryl ether type anion exchange membrane and a preparation method thereof.
Background
In recent decades, Anion Exchange Membrane Fuel Cells (AEMFCs) have received increasing attention as a new type of fuel cell. Anion Exchange Membranes (AEMs) are one of the key components in AEMFCs and serve to isolate fuel from oxidant, transport hydroxide ions from the cathode to the anode and support the electrode reaction catalyst in the fuel cell. An anion exchange membrane is a polymeric membrane with selective permeability, and its properties directly affect the performance, efficiency, lifetime, etc. of the AEMFC. The preparation of anion exchange membranes requires that the following requirements are met: sufficient ionic conductivity, good dimensional stability and mechanical properties, low fuel permeability and reasonable cost. However, no anion exchange membrane can meet the conditions of commercial application, so that the development of an anion exchange membrane with good comprehensive performance becomes a working hotspot in recent years.
Polyarylether is an engineering high molecular material with excellent performance, and a quaternary ammonium type anion exchange Membrane can be prepared after the polyarylether is introduced with quaternary ammonium groups, as shown in a scheme disclosed in document 1(He et al. journal of Membrane Science,2016,504,47-54.), the anion exchange Membrane based on polyarylether has the advantages of high ionic conductivity, good mechanical properties and the like. However, the size stability and alkali resistance stability of the membrane are poor, for example, the IEC of the QPPO membrane is 2.07mmol/g, the size change rate of the membrane is 31.6% under the temperature condition of 25 ℃, the ion conductivity of the membrane is reduced sharply and the alkali resistance stability is poor when the membrane is soaked in 1mol/L KOH solution for treatment at 60 ℃ for 240 hours.
In order to improve the stability of the membrane, the performance of the membrane may be improved by a crosslinking modification method. Crosslinking can effectively inhibit swelling of the membrane and increase the tensile strength of the membrane, while contributing to increase the chemical stability of the membrane, and is one of the most effective methods for improving the stability of anion exchange membranes. The crosslinked high molecular polymer can form a network structure, so that the free volume between main chains is reduced, and unstable cations are difficult to be attacked by hydroxide ions. For example, in document 2(Lu et al solid StateIonics,2013,245-246,8-18.), a cross-linked anion exchange membrane is prepared by using N, N' -tetramethyl-1, 6-hexanediamine as a cross-linking agent, so that the alkali resistance stability of the membrane is improved to a certain extent, but the dimensional change at room temperature is large, the minimum values in the plane and thickness directions reach 13.5% and 10.9%, respectively, and the mechanical strength is poor, and the maximum elongation at break is only 1.9%. Document 3(Lee et al energy & Environmental Science,2017,10,275-285.) a crosslinked anion exchange membrane was prepared using 3-hydroxyphenylacetylene sodium salt as a crosslinking agent. The cross-linked anion exchange membrane is firstly connected with 3-hydroxy phenylacetylene sodium salt at the tail end of a polymer, and then is heated and cross-linked at 180 ℃ to form a cross-linked network structure. The prepared membrane shows good ionic conductivity, battery performance and alkali-resistant stability. However, the cross-linked anion-exchange membrane uses alkyne as a cross-linking agent, and the polymer synthesis conditions are harsh, which is not favorable for realizing large-scale production.
Disclosure of Invention
The invention aims to provide an aromatic dihydric phenol cross-linked polyaryl ether type anion exchange membrane and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows:
the preparation method of the aromatic dihydric phenol cross-linked polyaryl ether type anion exchange membrane comprises the following specific steps:
step 1, preparation of polyarylether polymer:
dissolving bisphenol fluorene (BHPF), Decafluorobiphenyl (DFBP) and biphenyl diphenol (BP) in N, N-Dimethylacetamide (DMAC) to form a 30-35% (w/v) solution, adding potassium carbonate with the mole number of 1.15-1.30 times of that of hydroxyl as a catalyst, adding cyclohexane as an azeotropic water-carrying agent, reacting at 90-95 ℃, slowly pouring into water after the reaction is finished, separating out a white fibrous product, filtering, washing with water, and drying to obtain a polyarylether polymer;
step 2, preparing a chloromethylated polyarylether polymer:
dissolving a dried polyarylether polymer in tetrachloroethane, slowly dropwise adding a mixed solution of chloromethyl ethyl ether, a catalyst of stannic chloride and tetrachloroethane in an ice-water bath, reacting at 30-35 ℃ for 10-12 hours, slowly pouring into ethanol, separating out a flocculent product, filtering, cleaning and drying to obtain a chloromethylated polyarylether polymer;
step 3, preparing the quaternized polyarylether polymer:
dissolving a chloromethylated polyarylether polymer in N, N-Dimethylformamide (DMF) to form a 3-5% (w/v) solution, adding a trimethylamine solution with the mole number being 2.0-2.5 times that of chloromethyl, and stirring for reaction for 48-72 hours to obtain a quaternized polyarylether polymer;
step 4, preparing the cross-linked anion exchange membrane:
the method comprises the following steps of (1) mixing a quaternized polyarylether polymer and an aromatic dihydric phenol crosslinking agent according to a molar ratio of 9-19: 1, filtering and defoaming after mixing, casting, slowly heating to 110-130 ℃, reacting for 6-8 hours, slowly cooling to 60 ℃ after the reaction is finished, drying and forming, stripping, dipping by using 1M sodium hydroxide solution at room temperature, and washing to be neutral to obtain the cross-linked polyarylether anion exchange membrane.
In step 1, the molar ratio of BHPF, DFBP and BP is 3: 4: 1.
in the step 1, the reaction time is 6-8 h.
In step 2, the molar ratio of the polyarylether polymer to chloromethyl ethyl ether is 1: 50, the molar weight ratio of anhydrous stannic chloride to chloromethyl ethyl ether is 0.27: 20. the Ion Exchange Capacity (IEC) is controlled by the reaction time. The theoretical IEC is controlled to be 1.77-1.92 mmol/g.
In the step 4, the cross-linking agent is bisphenol A or 4, 4' - (hexafluoroisopropylidene) bisphenol.
According to the cross-linking type anion-exchange membrane, a high molecular polymer is a polyarylether polymer synthesized by nucleophilic polycondensation, a chloromethyl group is introduced through Friedel-crafts reaction, a quaternary ammonium group is introduced through Menxiu gold reaction to obtain a quaternized polyarylether polymer, then an aromatic dihydric phenol cross-linking agent is reacted with fluorine on a main chain only through a heating method to prepare the cross-linking type anion-exchange membrane, and the membrane material shows excellent stability.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the method is based on nucleophilic polycondensation reaction, Friedel-crafts reaction, Moxiu gold reaction, thermal crosslinking and other methods, and has the characteristics of simple synthesis process, uniform and compact membrane material and the like.
(2) The invention uses a heating method to react the aromatic dihydric phenol cross-linking agent with fluorine on the main chain under the semi-closed condition to prepare the compact and uniform anion exchange membrane, and the prepared cross-linked anion exchange membrane has better stability under the similar IEC level.
The invention can prepare other types of cross-linked anion exchange membranes and meet the requirements of related fields, in particular to the fields of fuel cells, chlor-alkali industry, ion exchange resins, membrane separation, humidity sensors and the like.
Detailed Description
The preparation method of the cross-linking type polyarylether anion exchange membrane of the invention synthesizes polyarylether Polymer (PFAE) by utilizing bisphenol fluorene (BHPF), Decafluorobiphenyl (DFBP) and diphenol (BP) through nucleophilic polycondensation reaction; controlling the degree of substitution of chloromethyl of the polymer by controlling the Friedel-crafts reaction time to obtain a chloromethylated polyarylether polymer (CMPFAE), and then converting the chloromethylated polyarylether polymer into a quaternized polyarylether polymer (QPFAE) by a Menxiu gold reaction; and finally, mixing the aromatic dihydric phenol cross-linking agent with QPFAE according to a ratio, casting to form a film, and preparing the anion exchange membrane through alkaline ion exchange. The method comprises the following specific steps:
step 1, preparation of polyarylether polymer: dissolving bisphenol fluorine (BHPF), Decafluorobiphenyl (DFBP) and biphenyl diphenol (BP) in N, N-Dimethylacetamide (DMAC) to form a 30-35% (w/v) solution, adding potassium carbonate with the mole number of 1.15-1.30 times of that of hydroxyl as a catalyst, using cyclohexane as an azeotropic water-carrying agent, reacting at 90-95 ℃, slowly pouring a product into water after the reaction is finished, separating out a white fibrous product, filtering, washing with water, and drying to obtain the polyarylether polymer PFAE.
The mol ratio of BHPF, DFBP and BP is 3: 4: 1, I is the structural formula of PFAE.
Step 2, preparing a chloromethylated polyarylether polymer: dissolving polyarylether polymer in tetrachloroethane, slowly adding stannic chloride and chloromethyl ethyl ether dissolved in tetrachloroethane under an ice bath condition, reacting at 30-35 ℃ for 10-12 hours, slowly pouring into ethanol, separating out a flocculent product, filtering, cleaning and drying to obtain chloromethyl polyarylether polymer CMPFAE.
The molar ratio of the polyarylether polymer to chloromethyl ethyl ether is 1: 50, the molar weight ratio of anhydrous stannic chloride to chloromethyl ethyl ether is 0.27: 20. the Ion Exchange Capacity (IEC) is controlled by the reaction time. The theoretical IEC is controlled to be 1.77-1.92 mmol/g. II is the structural formula of CMPFAE.
Step 3, preparing the quaternized polyarylether polymer: dissolving a chloromethylated polyarylether polymer in N, N-Dimethylformamide (DMF) to form a 3-5% (w/v) solution, adding a trimethylamine solution with the mole number 2-2.5 times that of chloromethyl, and stirring for reaction for 48-72 hours to obtain the quaternized polyarylether polymer.
III is the structural formula of the quaternized polyarylether polymer.
And 4, preparing the cross-linked anion exchange membrane. The method comprises the following steps of (1) mixing a quaternized polyarylether polymer and an aromatic dihydric phenol crosslinking agent according to a molar ratio of 9-19: 1, filtering and defoaming after mixing, casting, slowly heating to 110-130 ℃, reacting for 6-8 hours, slowly cooling to 60 ℃ after the reaction is finished, drying and forming the membrane, stripping, dipping with 1M sodium hydroxide solution at room temperature, and washing with water to be neutral to obtain the cross-linked polyarylether anion exchange membrane.
The cross-linking agent is bisphenol A or 4, 4' - (hexafluoroisopropylidene) bisphenol, and the molar ratio of the cross-linking agent to the polymer III is 1: 19-1: 9. the cross-linked anion exchange membrane is represented by QPFAE-x-y, wherein x represents the used cross-linking agent, y represents the molar ratio of the cross-linking agent to the QPFAE in the anion exchange membrane, and the non-cross-linked membrane without the cross-linking agent is represented by QPFAE. IV is the structural formula of the cross-linked polyarylether anion exchange membrane.
Example 1 preparation of PFAE Polymer
In a completely dry three-necked flask equipped with a nitrogen inlet and outlet device and a water separator, under a nitrogen blanket, 1.225g of BHPF (3.50mmol), 1.558g of DFBP (4.66mmol), 0.217g of BP (1.17mmol), and 8.5mL of DMAc were added, and after completely dissolving under stirring, 0.7423g of potassium carbonate (6.15mmol) and 8.5mL of cyclohexane were added. The temperature is slowly increased to 90 ℃ for 7 hours, and the water generated by the reaction is removed in the form of a cyclohexane/water azeotrope. After the reaction was complete, heating was stopped and cooling was carried out to 60 ℃. The product was slowly poured into about 500mL of deionized water to precipitate a white fibrous polymer product. The product was washed thoroughly with deionized water and dried in a vacuum oven at 105 ℃ for 24h to give the polymer PFAE.
Example 2 preparation of CMPFAE (1.77) Polymer
Adding into a completely dry three-neck flask equipped with nitrogen inlet and outlet device and oil-water separator1.2g of the polymer PFAE and 18mL of tetrachloroethane are introduced, while 8.2mL of chloromethyl ether, 6mL of tetrachloroethane and 0.3816g of anhydrous SnCl are added to a completely dry dropping funnel4. After the polymer is completely dissolved, slowly introducing nitrogen to keep the nitrogen atmosphere, placing the three-neck flask in an ice bath, slowly dripping the catalyst solution in the dropping funnel into the three-neck flask, returning the temperature to room temperature after dripping, and then heating to 30 ℃ for constant temperature reaction for 10 hours. And after the reaction is finished, pouring the reaction product into excessive ethanol to separate out a white flocculent polymer product, fully soaking and washing the flocculent polymer product by using the ethanol, and drying the flocculent polymer product in a vacuum oven at 60 ℃ for 12 hours to obtain the chloromethylated polymer CMPAEK. As shown in Table 1, the following ingredients1H NMR measurement shows that the chloromethyl content of the prepared CMPAEK is 1.77mmol/g, which is the theoretical ion exchange capacity of the prepared anion exchange membrane.
EXAMPLE 3 preparation of CMPFAE (1.87) Polymer
Similar to the CMPFAE preparation method in example 2, except that the reaction time is 12h at 30 ℃ and the chloromethyl content of the chloromethylated polyarylether polymer obtained by the reaction is 1.87 mmol/g.
Example 4 preparation of CMPFAE (1.92) Polymer
Similar to the CMPFAE preparation method in example 3, except that the isothermal reaction temperature is 35 ℃, the chloromethyl content of the chloromethylated polyarylether polymer obtained by the reaction is 1.92 mmol/g.
Comparative example 1 preparation of CMPFAE (0.95) Polymer
Similar to the preparation method of CMPFAE in example 2, except that the reaction time is 3 hours at 30 ℃, the chloromethyl content of the chloromethylated polyarylether polymer CMPFAE (0.95) obtained by the reaction is 0.95mmol/g, and the lower chloromethyl content can cause the prepared membrane to have too low conductivity and is not suitable for preparing an anion exchange membrane.
Comparative example 2 preparation of CMPFAE (gel) Polymer
Similar to the preparation method of CMPFAE in example 2, except that the reaction time is 14 hours at 30 ℃ and the chloromethylated polyarylether polymer CMPFAE (gel) obtained by the reaction is in a gel state and cannot be prepared into an anion exchange membrane.
EXAMPLE 5 preparation of quaternized polyarylether polymers
Accurately weighing 1.0g of CMPAEK obtained in example 2, dissolving the CMPAEK in 20mL of DMF, slowly adding 0.6mL of TMMA after completely dissolving, sealing and stirring for 48h in dark place to obtain the quaternized polyarylether polymer.
EXAMPLE 6 preparation of anion exchange Membrane QPFAE-BPA-5
Accurately weighing 0.008g of bisphenol A, dissolving in 1mL of DMF, adding 0.01g of anhydrous potassium carbonate, stirring at 60 ℃ for 6 hours to generate activity (-OK) of a terminal phenol group, filtering to remove potassium carbonate particles, adding into the quaternized polymer solution with the theoretical ion exchange capacity of 1.87mmol/g obtained in example 5, stirring, mixing, filtering, defoaming, casting into a clean and flat glass dish, slowly heating to 120 ℃ in a constant-temperature oven, covering, reacting for 6 hours, slowly cooling to 60 ℃, removing the cover, continuously drying for 10 hours, and forming a film. Soaking the membrane in 1M NaOH solution for 72 hours, washing the membrane to be neutral, wiping off surface floating water to obtain a cross-linked anion exchange membrane QPFAE-BPA-5, wherein the molar ratio of the quaternized polyarylether polymer to the bisphenol A is 19: 1.
the performance data are shown in a table 1, the ion exchange capacity actually measured by an acid-base back titration method is 1.51mmol/g, the size change in the thickness direction at the temperature of 30-90 ℃ is 5.7-9.0%, the size change in the plane direction is 6.8-9.1%, and the highest water absorption rate reaches 36.5%; the hydrolytic and antioxidant stabilities are shown in Table 2, and the mass loss after immersion of the membrane in water at 140 ℃ in an autoclave is 6.7% in Fenton's reagent (3% H)2O2，2ppm FeSO4) The mass loss after 1h of treatment at medium 80 ℃ is 6.3%.
EXAMPLE 7 preparation of anion exchange Membrane QPFAE-BPA-10
Similar to the QPFAE-BPA-5 preparation method of example 6, except that the weight of bisphenol A weighed during the film preparation process was 0.016g, and the molar ratio of quaternized polyarylether polymer to bisphenol A was 9: 1.
the performance data is shown in table 1, the actual IEC value is similar to that of other films, the dimension change in the thickness direction is 5.7-9.9% at the temperature of 30-90 ℃, the dimension change in the plane direction is 5.7-8.2%, and the highest water absorption rate reaches 35.4%; the hydrolytic stability and antioxidant stability are shown in table 2, the mass loss after the hydrolytic stability test is 5.8%, and the mass loss after the antioxidant stability test is 5.4%. The stability is slightly better than that of a QPFAE-BPA-5 film, the crosslinking structure is more compact due to the improvement of the crosslinking degree, and the stability is favorably improved.
EXAMPLE 8 preparation of anion exchange Membrane QPFAE-HFBPA-5
Similar to the QPFAE-BPA-5 preparation of example 6, except that the crosslinker used in the film formation was 4,4 '- (hexafluoroisopropylidene) bisphenol, the weighed mass was 0.012g, and the molar ratio of quaternized polyarylether polymer to 4, 4' - (hexafluoroisopropylidene) bisphenol was 19: 1.
the performance data is shown in table 1, the actual IEC value is similar to that of other films, the dimension change in the thickness direction is 5.2-8.8% at the temperature of 30-90 ℃, the dimension change in the plane direction is 5.9-8.7%, and the highest water absorption rate reaches 35.1%; the hydrolytic stability and antioxidant stability are shown in table 2, the mass loss after the hydrolytic stability test is 6.4%, and the mass loss after the antioxidant stability test is 5.3%. The stability is slightly better than QPFAE-BPA-5 film because 4, 4' - (hexafluoroisopropylidene) bisphenol has 6 more fluorine atoms than bisphenol A, which can improve the hydrophobicity of the film and thus the stability of the film.
EXAMPLE 9 preparation of anion exchange Membrane QPFAE-HFBPA-10
Similar to the QPFAE-HFBPA-5 preparation of example 8, except that the mass of 4,4 '- (hexafluoroisopropylidene) bisphenol weighed during the film formation was 0.024g, the molar ratio of quaternized polyarylether polymer to 4, 4' - (hexafluoroisopropylidene) bisphenol was 9: 1.
the performance data is shown in table 1, the actual IEC value is similar to that of other films, the dimension change in the thickness direction is 5.3-9.8% at the temperature of 30-90 ℃, the dimension change in the plane direction is 5.9-8.4%, and the highest water absorption rate reaches 34.3%; the hydrolytic stability and antioxidant stability are shown in table 2, the mass loss after the hydrolytic stability test is 5.0%, and the mass loss after the antioxidant stability test is 4.7%. The stability of the membrane is best due to the combination of a cross-linking agent containing multiple fluorines and a higher degree of cross-linking.
Comparative example 3 preparation of Cross-Linked anion exchange Membrane
Similar to the QPFAE-BPA-5 preparation method in example 6, except that the temperature was directly raised from 60 ℃ to 120 ℃ during the film formation, the obtained film was uneven and uniform, and wrinkles appeared.
Comparative example 4 preparation of anion exchange Membrane QPFAE
The quaternary ammonium polyarylether polymer solution with the theoretical ion exchange capacity of 1.77mmol/g obtained in the example 5 is filtered and defoamed, cast in a clean and flat glass dish, dried in a constant temperature oven at 60 ℃ for 12 hours and then formed into a film. And soaking the membrane in a 1M NaOH solution for 72 hours, washing the membrane to be neutral, and wiping off surface floating water to obtain the non-crosslinked anion exchange membrane QPFAE.
The performance data is shown in table 1, the actual IEC value is similar to that of other films, the dimensional change in the thickness direction at 30-90 ℃ is 5.4-10.1%, the dimensional change in the plane direction is 6.0-8.8%, and the highest water absorption rate reaches 38.1%; the mass loss after the hydrolytic stability test was 5.0%, and the mass loss after the antioxidant stability test was 4.7%. Compared with the cross-linked membrane, the stability of the uncrosslinked membrane is poor, which shows that the cross-linked membrane prepared by using the aromatic dihydric phenol cross-linking agent can effectively improve the stability of the membrane.
TABLE 1 basic Properties of Cross-Linked polyarylether anion exchange membranes
a: warp beam1Theoretical values for H NMR measurements;b: actual value determined by acid-base back titration;c: a dimensional change in the film thickness direction;d: the size of the film surface changes;e: water absorption.
TABLE 2 chemical stability of crosslinked polyarylether anion exchange membranes
a: mass loss after treatment in water at 140 ℃ for 24 h;b: in Fenton's reagent (3% H)2O2，2ppm FeSO4) The mass loss after 1h of treatment at medium 80 ℃.
Claims (6)
1. The preparation method of the aromatic dihydric phenol crosslinked polyaryl ether type anion exchange membrane is characterized by comprising the following specific steps:
step 1, preparation of polyarylether polymer:
dissolving bisphenol fluorene, decafluorobiphenyl and biphenol in N, N-dimethylacetamide to form a 30-35% w/v solution, adding potassium carbonate with the mole number of 1.15-1.30 times of that of hydroxyl as a catalyst, adding cyclohexane as an azeotropic water-carrying agent, reacting at 90-95 ℃, slowly pouring into water after the reaction is finished, separating out a white fibrous product, filtering, washing with water and drying to obtain a polyarylether polymer;
step 2, preparing a chloromethylated polyarylether polymer:
dissolving a dried polyarylether polymer in tetrachloroethane, slowly dropwise adding a mixed solution of chloromethyl ethyl ether, a catalyst of stannic chloride and tetrachloroethane in an ice-water bath, reacting at 30-35 ℃ for 10-12 hours, slowly pouring into ethanol, separating out a flocculent product, filtering, cleaning and drying to obtain a chloromethylated polyarylether polymer;
step 3, preparing the quaternized polyarylether polymer:
dissolving a chloromethylated polyarylether polymer in N, N-dimethylformamide to form a 3-5% w/v solution, adding a trimethylamine solution with the mole number of 2.0-2.5 times that of chloromethyl, and stirring for reaction for 48-72 hours to obtain a quaternized polyarylether polymer;
step 4, preparing the cross-linked anion exchange membrane:
the method comprises the following steps of (1) mixing a quaternized polyarylether polymer and an aromatic dihydric phenol crosslinking agent according to a molar ratio of 9-19: 1, filtering and defoaming after mixing, casting, slowly heating to 110-130 ℃, reacting for 6-8 hours, slowly cooling to 60 ℃ after the reaction is finished, drying and forming, stripping, dipping by using 1M sodium hydroxide solution at room temperature, and washing to be neutral to obtain the cross-linked polyarylether anion exchange membrane.
2. The preparation method according to claim 1, wherein in step 1, the molar ratio of bisphenol fluorene, decafluorobiphenyl and biphenol is 3: 4: 1.
3. the preparation method according to claim 1, wherein in the step 1, the reaction time is 6-8 h.
4. The method of claim 1, wherein in step 2, the molar ratio of polyarylether polymer to chloromethyl ethyl ether is 1: 50, the molar weight ratio of anhydrous stannic chloride to chloromethyl ethyl ether is 0.27: 20.
5. the method of claim 1, wherein in step 4, the crosslinking agent is bisphenol a or 4, 4' - (hexafluoroisopropylidene) bisphenol.
6. The aromatic dihydric phenol crosslinked polyaryl ether anion exchange membrane prepared by the preparation method according to any one of claims 1 to 5.
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