CN116355254A - Preparation method of monovalent selective anion exchange membrane with high permeation flux - Google Patents
Preparation method of monovalent selective anion exchange membrane with high permeation flux Download PDFInfo
- Publication number
- CN116355254A CN116355254A CN202310347622.0A CN202310347622A CN116355254A CN 116355254 A CN116355254 A CN 116355254A CN 202310347622 A CN202310347622 A CN 202310347622A CN 116355254 A CN116355254 A CN 116355254A
- Authority
- CN
- China
- Prior art keywords
- exchange membrane
- anion exchange
- formula
- monomer
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 66
- 230000004907 flux Effects 0.000 title claims description 30
- 238000000034 method Methods 0.000 claims description 53
- 239000000178 monomer Substances 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 31
- NDERTONLGOTDER-UHFFFAOYSA-N 2-(4-hydroxyphenyl)-3h-isoindol-1-one Chemical compound C1=CC(O)=CC=C1N1C(=O)C2=CC=CC=C2C1 NDERTONLGOTDER-UHFFFAOYSA-N 0.000 claims description 23
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 claims description 22
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 14
- 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 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- 238000005266 casting Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 claims description 9
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000003880 polar aprotic solvent Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- AYMUQTNXKPEMLM-UHFFFAOYSA-N 1-bromononane Chemical compound CCCCCCCCCBr AYMUQTNXKPEMLM-UHFFFAOYSA-N 0.000 claims description 5
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 35
- 150000001450 anions Chemical class 0.000 abstract description 20
- 238000000909 electrodialysis Methods 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 50
- 239000003014 ion exchange membrane Substances 0.000 description 17
- 238000002474 experimental method Methods 0.000 description 16
- 238000005342 ion exchange Methods 0.000 description 16
- 230000005012 migration Effects 0.000 description 16
- 238000013508 migration Methods 0.000 description 16
- 238000010561 standard procedure Methods 0.000 description 16
- 230000008961 swelling Effects 0.000 description 16
- 238000010998 test method Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 201000006747 infectious mononucleosis Diseases 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 102000004310 Ion Channels Human genes 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 poly (arylene ether sulfone Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- REUDPRVPPDWOKE-UHFFFAOYSA-N 1,1'-biphenyl;1h-imidazole Chemical group C1=CNC=N1.C1=CC=CC=C1C1=CC=CC=C1 REUDPRVPPDWOKE-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- UQUPIHHYKUEXQD-UHFFFAOYSA-N n,n′-dimethyl-1,3-propanediamine Chemical compound CNCCCNC UQUPIHHYKUEXQD-UHFFFAOYSA-N 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/13—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to the field of polymer high polymer materials, and particularly discloses a preparation method of a monovalent anion exchange membrane with high permeation capacity. The side chain type anion exchange membrane prepared by the invention has the advantages of good ion conductivity, good dimensional stability, higher monovalent anion permeation selectivity and the like, and particularly has wide application prospect in the electrodialysis application field.
Description
Technical Field
The invention relates to the field of polymer high molecular materials, in particular to a preparation method of a monovalent anion exchange membrane with high permeation capacity, and belongs to the technical field of membranes.
Background
The improvement of the ion accurate separation technology level has important significance for the sustainable development of chemical industrial production, and can further meet the requirements of energy conservation and emission reduction, traditional industry transformation and upgrading and the like for important strategic targets of double-carbon countries. Ion accurate separation refers to concentration and return of a certain target ion in a certain specific system. In practical demands, salt preparation by seawater, lithium extraction by salt lake, brine refining in chlor-alkali industry and waste acid/waste alkali recycling in metallurgical industry all require to realize ion separation of the same charge and different valence states. At present, electrodialysis technologies such as common electrodialysis, electrolytic electrodialysis, bipolar membrane electrodialysis, selective electrodialysis and the like are applied to the aspects of material desalination, brine concentration, acid-base concentration, sea water desalination, waste acid-base recovery and the like. Among them, selective electrodialysis has shown unique advantages in applications such as energy conversion, purification of brine in chlor-alkali industry, recycling of high-salt wastewater, recycling of waste acid and waste alkali, extraction of lithium from salt lake, etc., because the primary component mono/divalent ion membrane allows permeation of monovalent ions but prevents permeation of divalent or polyvalent ions. If the traditional ionic membranes in the common electrodialysis membrane stack are partially replaced or added with mono/divalent ionic membranes, selective electrodialysis can be constructed. Currently, the development of mono/divalent ion membrane technology has been greatly improved, but some challenges remain. (1) poor long-period stability. For example, acids or bases generated under the action of an electric field tend to break the structure of the modified layer and weaken the force between the polyelectrolyte skin layer and the base film, so that the charge-repulsive effect on multivalent ions is weakened. (2) lower operating current density. Electrodialysis operation current is selected to be low, which can be attributed to the low limiting current density of mono/divalent ion membranes.
Under the condition of ensuring proper selectivity of the ion membrane, a spiro structure, a fluorenyl Cardo ring structure, a biphenyl imidazole structure and the like are introduced into a main chain, and a twisting folding structure and rigidity are utilized, so that molecules cannot be effectively stacked to prevent loosening of the structure and loss of micropores, free volumes are generated in the polymer membrane to form micro-channels (ion channels), thereby assisting in promoting efficient transmission of monovalent ions, and a type of ion exchange membrane with stable structure, high permeation flux and selectivity is constructed.
Disclosure of Invention
The invention solves the technical problem of providing a method for preparing a side chain type anion exchange membrane with a twisted structure.
In order to solve the technical problems, the invention adopts the following technical scheme:
preparation of monomer (I) in step (1):
the N, N-dimethyl-1, 3-propylene diamine and 3, 3-bis (4-hydroxyphenyl) -3H-isobenzofuranone (phenolphthalein) are subjected to reflux reaction at 160 ℃ in the nitrogen atmosphere to prepare a 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer shown in the formula (I);
step (2) preparation of monomer (II):
bisphenol A is introduced into a methane sulfonic acid to be catalyzed, and is subjected to reflux reaction at 160 ℃ in the nitrogen atmosphere to prepare a 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindan monomer shown in a formula (II);
preparation of the structural main chain in the step (3):
the poly (arylene ether sulfone) with the main chain containing an amino-phenolphthalein structure is obtained by solvent copolycondensation of a 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer shown in the formula (I), a 4,4' -difluoro diphenyl sulfone monomer and a 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindan monomer shown in the formula (II). Wherein the ratio of the total amount of 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone and 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane to the amount of 4,4' -difluorodiphenyl sulfone is 1:1, and the molar ratio of 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer to 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane monomer is x: 100-x=100% -60%: 0% -40%; the number average molecular weight Mn=50000-120000 of the polyarylethersulfone.
Step (4) preparation of an alkyl functionalized and anion exchange membrane of a structural main chain:
dissolving the polyarylethersulfone shown in the formula (III) prepared in the step (3) in an organic solvent, and then according to the mole ratio of 1:1.20 to 1.50 of 1-bromopropane (IV), 1-bromopentane (V), 1-bromoheptane (VI), 1-bromononane (VII), 1, 2-pentafluoro-4-Ding Dianwan (VIII) and 1, 2-tetrahydroperfluorohexane (IX) shown in the following formulas are respectively added and stirred for a certain period of time, and standing and defoaming are carried out to obtain casting solution, wherein the mass volume concentration of polyarylether sulfone in the casting solution is 3 to 8 percent; the organic solvent is one or more of DMF, DMAc, NMP, the obtained casting film liquid is poured on a glass flat plate, in-situ reaction and drying are realized by keeping the casting film liquid at 40-200 ℃ for 12-96 hours, and after cooling, the film is removed from the glass flat plate in water, thus obtaining the alkyl functionalized anion exchange membrane, the structural formula of which is shown in the formula (V), and the thickness of which is 70-150 mu m.
Wherein x:100% -x=100% -60%: 0% -40%;
preferably, step (1) of the present invention is carried out in particular as follows: in a reaction vessel, N-dimethyl-1, 3-propanediamine and 3, 3-bis (4-hydroxyphenyl) -3H-isobenzofuranone (phenolphthalein) are used, heated to reflux under nitrogen atmosphere, kept for 12-48H, cooled to room temperature, slowly poured into an ice-water mixture, then diluted hydrochloric acid is gradually added dropwise, white precipitation appears, the precipitation is washed with water for 5-7 times, and the precipitation is dried in vacuum at 40 ℃ for 48H to obtain the 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer shown in the formula (I).
As a further preferred aspect, in step (1), the molar ratio of N, N-dimethyl-1, 3-propanediamine to 3, 3-bis (4-hydroxyphenyl) -3H-isobenzofuranone (phenolphthalein) is in the range of 1.0-2.5:1, most preferably 1.2:1.
As a further preferred aspect, in step (1), the diluted hydrochloric acid solution is an aqueous hydrochloric acid solution having a ph=0 to 1 (most preferably, ph=0).
As a further preferred aspect, in step (1), the separation and purification is performed as follows: under nitrogen atmosphere, heating to reflux, keeping for 12-48h, cooling to room temperature, slowly pouring into ice-water mixture, then dropwise adding dilute hydrochloric acid, generating white precipitate, washing the precipitate with water for 5-7 times, and vacuum drying the precipitate at 30-80deg.C (more preferably 50deg.C) for 24-48h (more preferably 48 h).
Preferably, step (2) of the present invention is carried out in particular as follows: heating bisphenol A and methane sulfonic acid to reflux in a nitrogen atmosphere in a reaction vessel, keeping for 5-10h, cooling to room temperature, slowly pouring into an ice-water mixture, washing the precipitate with water for 5-7 times, and vacuum drying the precipitate at 50 ℃ for 24h to obtain the 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane monomer shown in the formula (II).
As a further preference, in step (2), the bisphenol A and methanesulfonic acid are fed in a molar ratio of 7-9:1, most preferably 8.4:1.
Preferably, in the step (3), the molar ratio of the 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone to the 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane is 100% -60%: 0% -40%, most preferably 100% -80%: 0% -20%.
Preferably, step (3) of the present invention is carried out in particular as follows: adding 4,4' -difluoro diphenyl sulfone, 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone shown in a formula (I) and 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane shown in a formula (II), a polar aprotic solvent B, a salifying agent potassium carbonate and a water-carrying agent into a reaction container, stirring and reacting for 4-24 hours under the protection of nitrogen at 100-180 ℃, and separating and drying after the reaction is finished to obtain the main chain polyarylethersulfone.
As a further preferred feature, in step (3), the polar aprotic solvent B is at least one of N, N-dimethylacetamide, N-dimethylformamide, and N-methylpyrrolidone.
As a further preference, in step (3), the salt former potassium carbonate is used in a mass amount of 5.0 to 6.5g/20mmol based on the amount of 4,4' -difluorodiphenyl sulfone.
As a further preferable mode, the water-carrying agent is toluene, and the volume ratio of toluene to the polar aprotic solvent B is 0.2-0.7:1.
As a further preferred aspect, in the step (4), the polar solvent C is one or more of Dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and Dimethylsulfoxide (DMSO).
As a further preference, the copolycondensation reaction conditions are: the reaction is carried out at 120-145℃and more preferably 145℃for 3-5 hours (more preferably 4 hours) and then at 145-165℃and more preferably 165℃for 2-4 hours (more preferably 3 hours).
As a further preferred aspect, in step (3), the separation and drying are performed as follows: cooling the reaction liquid to room temperature, slowly pouring the reaction liquid into ethanol, stirring to generate precipitate, filtering, collecting the precipitate, washing the precipitate with ethanol and water for several times, and vacuum drying at 60-120 ℃ for 10-48 h to obtain the main chain polyarylethersulfone.
Preferably, in the step (4), the mass ratio of the polyarylethersulfone to the 1-bromopropane, 1-bromopentane, 1-bromoheptane, 1-bromononane, 1, 2-pentafluoro-4-Ding Dianwan and 1, 2-tetrahydroperfluorohexane-iodoane is 0.4-1.00: 1.
as a further preference, in step (3), the ratio of the amount of poly (arylene ether sulfone) to the amount of 1-bromopropane, 1-bromopentane, 1-bromoheptane, 1-bromononane, 1, 2-pentafluoro-4-Ding Dian, 1, 2-tetrahydroperfluorohexane-iodoane substance is from 0.6 to 1.00, respectively: 1.
preferably, in the step (4), the mass volume concentration of the polyarylethersulfone in the casting solution is 5%.
Preferably, in the step (4), the reaction conditions are: the reaction is carried out for 18 to 36 hours at the temperature of 60 ℃.
As a further preference, in step (3), the reaction conditions are: the reaction was carried out at 60℃for 24h.
The side chain type anion exchange membrane prepared by the invention has the advantages of good ion conductivity, good dimensional stability, higher monovalent anion permeation selectivity and the like, and particularly has wide application prospect in the electrodialysis application field.
Compared with the prior art, the invention has the advantages that:
(1) According to the monovalent anion exchange membrane with high permeation quantity, the lengths of the hydrophobic chain segment, the hydrophilic chain segment and the alkyl linkage in the side chain are regulated, and the hydrophilic and hydrophobic microphase separation is induced in the membrane in a side chain grafting mode to form a continuous ion transmission channel, so that the high-efficiency ion transmission rate and the excellent selective ion transmission channel are formed, and the membrane has good monovalent anion selectivity.
(2) The monovalent anion exchange membrane with high permeation quantity has the advantages that the molecular chains cannot be effectively piled up due to the rigidity and the twisting structure of the membrane containing N-ring QA cations, and a unique ion channel with selective ion transmission is formed, so that the membrane has high flux while good selectivity.
(3) According to the monovalent anion high-permeability anion exchange membrane, proper free volume or micropores are introduced into the membrane, so that the ion conduction resistance in the membrane is reduced, the relatively high conductivity under lower IEC is realized, and the membrane has lower surface resistance; meanwhile, the homogeneous membrane structure formed by chemical bonds between the conductive side chains and the rigid main chain ensures the mechanical stability of the membrane.
Detailed Description
In order to further illustrate the technical scheme of the invention, the following describes the preferred embodiment of the invention with reference to specific examples.
Example 1
Preparation of monomer (I): 100mL (18 mmol) of N, N' -dimethyl-1, 3-propanediamine was weighed into a reaction vessel, 40 g (18 mmol) of 3, 3-bis (4-hydroxyphenyl) -3H-isobenzofuranone (phenolphthalein) was then added, heated to reflux under nitrogen atmosphere, kept for 48 hours, cooled to room temperature, slowly poured into an ice-water mixture, then 0.1M diluted hydrochloric acid was added dropwise to neutralize, white precipitate appeared, the precipitate was washed with water for 6 times, and the precipitate was dried under vacuum at 40℃for 24 hours to give 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer represented by formula (I).
Preparation of monomer (II): 60g (263 mmol) of bisphenol A is weighed into a reaction vessel, 3 g (31 mmol) of methanesulfonic acid is then added, the mixture is heated to reflux under nitrogen atmosphere and kept for 5h, and then cooled to room temperature, and then slowly poured into an ice-water mixture to generate brown precipitate, the precipitate is washed with water for 6 times, and the precipitate is dried in vacuum at 50 ℃ for 24h to obtain the 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane monomer shown in the formula (II).
Preparation of the backbone: 5.0804 g (20 mmol) of 4,4' -difluorodiphenyl sulfone and 8.0498 g (20 mmol) of 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer are introduced into a 250mL three-necked round bottom flask equipped with a water separator in the presence of NMP (80 mL) as solvent, together with 5.5 g of K 2 CO 3 And 45mL toluene were used as catalyst and water carrier, respectively. At N 2 The reaction was carried out at 155℃for 6 hours under an atmosphere and at 165℃for 12 hours. After the solution cooled to room temperature, it was poured into 300mL of ethanol and flocculated under high speed stirring to give a precipitate. The yellow solid is obtained after suction filtration and separation, and is repeatedly washed by ethanol and water for a plurality of times, and is dried in vacuum at 80 ℃ for 24 hours, 10.5 g of polyarylethersulfone with an alternating structure of 4,4' -difluorodiphenyl sulfone and 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone is obtained, and the molecular weight Mn=78200.
Preparation of anion exchange membrane: weighing 5g of polyarylethersulfone, dissolving in 30mL of NMP solvent, magnetically stirring at 80 ℃ until the polyethersulfone is completely dissolved, adding 0.995 g of 1-bromopropane, and stirring to obtain casting solution; and defoaming the casting film liquid, pouring the defoamed casting film liquid into a clean glass die, and drying the glass die at 80 ℃ for 24 hours to form a film, thereby obtaining the polyarylethersulfone anion exchange membrane.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods, see literature report: journal of Membrane Science 574 (2019) 181-195;Journal of Membrane Science 577 (2019) 153-164).
Example 2
Preparation of the monomer: the same procedure as in example 1 was used.
Preparation of the backbone: the same procedure as in example 1 was followed except that 5.0804 g (20 mmol) of 4,4' -difluorodiphenyl sulfone, 7.2448 g (18 mmol) of 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer and 0.6168 g (2 mmol) of 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane monomer were added and reacted to give 10.6 g of polyarylethersulfone having a 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone content of 90% and a molecular weight of 76800 was measured.
Preparation of anion exchange membrane: the same procedure as in example 1 was followed except that 0.9100 g of 1-bromopropane was added, and the resulting mixture was reacted and dried to obtain a polyarylethersulfone anion exchange membrane.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods, see literature report: journal of Membrane Science 574 (2019) 181-195;Journal of Membrane Science 577 (2019) 153-164).
Example 3
Preparation of the monomer: the same procedure as in example 1 was used.
Preparation of the backbone: the same procedure as in example 1 was followed except that 5.0804 g (20 mmol) of 4,4' -difluorodiphenyl sulfone, 6.4398 g (16 mmol) of 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer and 1.2337 g (4 mmol) of 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane monomer were added and reacted to give 10.9 g of polyarylethersulfone having a 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone content of 80% and a molecular weight of 89700 was measured.
Preparation of anion exchange membrane: the same preparation as in example 1 was carried out except that 0.825 g of 1-bromopropane was added, and the resultant was reacted and dried to obtain an anion exchange membrane.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods, see literature report: journal of Membrane Science 574 (2019) 181-195;Journal of Membrane Science 577 (2019) 153-164).
Example 4
Preparation of the monomer: the same procedure as in example 1 was used.
Preparation of the backbone: the same procedure as in example 1 was followed except that 5.0804 g (20 mmol) of 4,4' -difluorodiphenyl sulfone, 5.6348 g (14 mmol) of 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer and 1.851 g (6 mmol) of 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane monomer were added and reacted to give 11.3 g of polyarylethersulfone having a 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone content of 70% and a molecular weight of 89700 was measured.
Preparation of anion exchange membrane: the same preparation as in example 1 was carried out except that 0.73 g of 1-bromopropane was added, and the resultant was reacted and dried to obtain an anion exchange membrane.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods, see literature report: journal of Membrane Science 574 (2019) 181-195;Journal of Membrane Science 577 (2019) 153-164).
Example 5
Preparation of the monomer: the same procedure as in example 1 was used.
Preparation of the backbone: the same procedure as in example 1 was used.
Preparation of anion exchange membrane: the same procedure as in example 1 was followed except that 1.45 g of 1-bromoheptane was added, and the resultant was reacted and dried to obtain an anion exchange membrane.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods, see literature report: journal of Membrane Science 574 (2019) 181-195;Journal of Membrane Science 577 (2019) 153-164).
Example 6
Preparation of the monomer: the same procedure as in example 1 was used.
Preparation of the backbone: the same procedure as in example 1 was used.
Preparation of anion exchange membrane: the same procedure as in example 1 was followed except that 2.22 g of 1, 2-pentafluoro-4-Ding Dianwan was added, and the resulting anion exchange membrane was obtained by reaction and drying.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods see literature report:
Journal of Membrane Science 574(2019)181–195；Journal of Membrane Science 577(2019)153–164)。
example 7
Preparation of the monomer: the same procedure as in example 1 was used.
Preparation of the backbone: the same procedure as in example 1 was used.
Preparation of anion exchange membrane: the same procedure as in example 1 was followed except that 3.03 g of 1, 2-tetrahydroperfluorohexane was added, and reacted and dried to obtain an anion exchange membrane.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods, see literature report: journal of Membrane Science 574 (2019) 181-195;Journal of Membrane Science 577 (2019) 153-164).
Example 8
Preparation of the monomer: the same procedure as in example 1 was used.
Preparation of the backbone: the same procedure as in example 2 was used.
Preparation of anion exchange membrane: the same procedure as in example 1 was followed except that 1.325 g of 1-bromoheptane was added, and the resultant was reacted and dried to obtain an anion exchange membrane.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods, see literature report: journal of Membrane Science 574 (2019) 181-195;Journal of Membrane Science 577 (2019) 153-164).
Example 9
Preparation of the monomer: the same procedure as in example 1 was used.
Preparation of the backbone: the same procedure as in example 2 was used.
Preparation of anion exchange membrane: the same procedure as in example 1 was followed except that 2.025 g of 1, 2-pentafluoro-4-Ding Dianwan was added, and the resulting anion exchange membrane was obtained by reaction and drying.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods, see literature report: journal of Membrane Science 574 (2019) 181-195;Journal of Membrane Science 577 (2019) 153-164).
Example 10
Preparation of the monomer: the same procedure as in example 1 was used.
Preparation of the backbone: the same procedure as in example 2 was used.
Preparation of anion exchange membrane: the same preparation as in example 1 was carried out except that 2.77 g of 1, 2-tetrahydroperfluorohexane iodide was added, and the resultant was reacted and dried to obtain an anion exchange membrane.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods, see literature report: journal of Membrane Science 574 (2019) 181-195;Journal of Membrane Science 577 (2019) 153-164).
Example 11
Preparation of the monomer: the same procedure as in example 1 was used.
Preparation of the backbone: the same procedure as in example 3 was used.
Preparation of anion exchange membrane: the same procedure as in example 1 was followed except that 1.20 g of 1-bromoheptane was added, and the resulting anion exchange membrane was obtained by reaction and drying.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods see literature report:
Journal of Membrane Science 574(2019)181–195；Journal of Membrane Science 577(2019)153–164)。
example 12
Preparation of the monomer: the same procedure as in example 1 was used.
Preparation of the backbone: the same procedure as in example 3 was used.
Preparation of anion exchange membrane: the same procedure as in example 1 was followed except that 1.835 g of 1, 2-pentafluoro-4-Ding Dianwan was added, and the resultant was reacted and dried to obtain an anion exchange membrane.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods, see literature report: journal of Membrane Science 574 (2019) 181-195;Journal of Membrane Science 577 (2019) 153-164).
Example 13
Preparation of the monomer: the same procedure as in example 1 was used.
Preparation of the backbone: the same procedure as in example 3 was used.
Preparation of anion exchange membrane: the same procedure as in example 1 was followed except that 2.505 g of 1, 2-tetrahydroperfluorohexane was added, and reacted and dried to obtain an anion exchange membrane.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods, see literature report: journal of Membrane Science 574 (2019) 181-195;Journal of Membrane Science 577 (2019) 153-164).
Example 14
Preparation of the monomer: the same procedure as in example 1 was used.
Preparation of the backbone: the same procedure as in example 4 was used.
Preparation of anion exchange membrane: the same procedure as in example 1 was followed except that 1.065 g of 1-bromoheptane was added, and the resultant was reacted and dried to obtain an anion exchange membrane.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods, see literature report: journal of Membrane Science 574 (2019) 181-195;Journal of Membrane Science 577 (2019) 153-164).
Example 15
Preparation of the monomer: the same procedure as in example 1 was used.
Preparation of the backbone: the same procedure as in example 4 was used.
Preparation of anion exchange membrane: the same procedure as in example 1 was followed except that 1.63 g of 1, 2-pentafluoro-4-Ding Dianwan was added, and the resulting anion exchange membrane was obtained by reaction and drying.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods, see literature report: journal of Membrane Science 574 (2019) 181-195;Journal of Membrane Science 577 (2019) 153-164).
Example 16
Preparation of the monomer: the same procedure as in example 1 was used.
Preparation of the backbone: the same procedure as in example 4 was used.
Preparation of anion exchange membrane: the same procedure as in example 1 was followed except that 2.225 g of 1, 2-tetrahydroperfluorohexane was added, and reacted and dried to obtain an anion exchange membrane.
The thickness, the ion exchange capacity, the tensile strength and the swelling rate of the prepared monovalent anion selective anion exchange membrane are tested by adopting a national standard method experiment; the surface resistance, migration number, permeation selectivity and ion flux of the ion exchange membrane were tested using a homemade device. The results are shown in Table 1. (for specific test methods, see literature report: journal of Membrane Science 574 (2019) 181-195;Journal of Membrane Science 577 (2019) 153-164).
Table 1.
Claims (10)
1. The preparation method of the monovalent selective anion exchange membrane with high permeation flux is characterized by comprising the following steps:
preparation of monomer (I) in step (1):
the N, N-dimethyl-1, 3-propylene diamine and 3, 3-bis (4-hydroxyphenyl) -3H-isobenzofuranone (phenolphthalein) are subjected to reflux reaction at 160 ℃ in the nitrogen atmosphere to prepare a 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer shown in the formula (I);
step (2) preparation of monomer (II):
bisphenol A is introduced into a methane sulfonic acid to be catalyzed, and is subjected to reflux reaction at 160 ℃ in the nitrogen atmosphere to prepare a 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindan monomer shown in a formula (II);
preparation of the structural main chain in the step (3):
the method comprises the steps of performing solvent copolycondensation on a 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer, a 4,4' -difluoro diphenyl sulfone monomer and a 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindan monomer shown in a formula (II) to obtain polyarylether sulfone with a main chain containing an amino-phenolphthalein structure, wherein the structural formula is shown in a formula (III); wherein the ratio of the total amount of 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone and 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane to the amount of 4,4' -difluorodiphenyl sulfone is 1:1, and the molar ratio of 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer to 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane monomer is x:
100-x=100% -60%: 0% -40%; the number average molecular weight Mn=50000-120000 of the polyarylethersulfone;
step (4) preparation of an alkyl functionalized and anion exchange membrane of a structural main chain:
dissolving the polyarylethersulfone represented by the formula (III) prepared in the step (3) in a polar solvent C, and then according to a molar ratio of 1:1.20 to 1.50 of 1-bromopropane shown in a formula (IV), 1-bromopentane shown in a formula (V), 1-bromoheptane shown in a formula (VI), 1-bromononane shown in a formula (VII), 1, 2-pentafluoro-4-Ding Dian alkane shown in a formula (VIII) and 1, 2-tetrahydroperfluorohexane shown in a formula (IX) are respectively added, and stirring for a certain period of time, standing and defoaming are carried out to obtain a casting solution, wherein the mass volume concentration of polyarylethersulfone in the casting solution is 3 to 8 percent; the organic solvent is one or more of DMF, DMAc, NMP, the obtained casting film liquid is poured on a glass flat plate, in-situ reaction and drying are realized by keeping the casting film liquid at 40-200 ℃ for 12-96 hours, after cooling, the film is removed from the glass flat plate in water, and the alkyl functionalized anion exchange membrane is obtained, the structural formula of which is shown in the formula (V V), and the thickness of which is 70-150 mu m;
wherein x:100% -x=100% -60%: 0% -40%.
2. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 1, wherein: the step (1) is specifically implemented as follows: in a reaction vessel, N-dimethyl-1, 3-propylene diamine and 3, 3-bis (4-hydroxyphenyl) -3H-isobenzofuranone (phenolphthalein) are used, heated to reflux under nitrogen atmosphere, kept for 12-48H, cooled to room temperature, slowly poured into an ice-water mixture, then diluted hydrochloric acid is gradually added dropwise, white precipitation appears, the precipitation is washed with water for 5-7 times, and the precipitation is dried in vacuum at 30-80 ℃ for 24-48H to obtain the 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer shown in the formula (I).
3. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 2, wherein: in the step (1), the feeding mole ratio of the N, N-dimethyl-1, 3-propylene diamine to the 3, 3-bis (4-hydroxyphenyl) -3H-isobenzofuranone (phenolphthalein) is 1.0-2.5:1, and most preferably 1.2:1; the dilute hydrochloric acid solution is an aqueous hydrochloric acid solution with a ph=0-1, and most preferably with a ph=0.
4. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 2, wherein: in step (1), the precipitate is more preferably dried under vacuum at 50℃for 48 hours.
5. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 1, wherein: the step (2) is specifically carried out by heating bisphenol A and methane sulfonic acid to reflux in a reaction vessel under nitrogen atmosphere, maintaining for 5-10h, cooling to room temperature, slowly pouring into an ice-water mixture, washing the precipitate with water for 5-7 times, and vacuum drying the precipitate at 50 ℃ for 24h to obtain the 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane monomer shown in the formula (II).
6. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 5, wherein: in the step (2), the feeding mole ratio of bisphenol A to methane sulfonic acid is as follows
7-9:1, most preferably 8.4:1.
7. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 1, wherein: the step (3) is specifically implemented as follows: adding 4,4' -difluoro diphenyl sulfone, 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone shown in a formula (I) and 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane shown in a formula (II), a polar aprotic solvent B, a salifying agent potassium carbonate and a water-carrying agent into a reaction container, stirring and reacting for 4-24 hours under the protection of nitrogen at 100-180 ℃, and separating and drying after the reaction is finished to obtain the main chain polyarylethersulfone.
8. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 7, wherein: in the step (3), the molar ratio of the 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone to the 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane is preferably 100% -80%: 0% -20%;
the polar aprotic solvent B is at least one of N, N-dimethylacetamide, N-dimethylformamide and N-methylpyrrolidone; the mass dosage of the salifying agent potassium carbonate is 5.0-6.5g/20mmol based on the mass of 4,4' -difluorodiphenyl sulfone; the water-carrying agent is toluene, and the volume ratio of toluene to the polar aprotic solvent B is 0.2-0.7:1;
in the step (3), the mass ratio of the polyarylethersulfone to the 1-bromopropane, 1-bromopentane, 1-bromoheptane, 1-bromononane, 1, 2-pentafluoro-4-Ding Dian and 1, 2-tetrahydroperfluorohexane-iodoane is 0.6-1.00 respectively: 1.
9. the method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 7, wherein: the copolycondensation reaction conditions in the step (3) are as follows: reacting at 120-145 ℃, more preferably 145 ℃ for 3-5 hours, more preferably 4 hours, and further reacting at 145-165 ℃, more preferably 165 ℃ for 2-4 hours, more preferably 3 hours;
in the step (3), the separation and drying are carried out as follows: cooling the reaction liquid to room temperature, slowly pouring the reaction liquid into ethanol, stirring to generate precipitate, filtering, collecting the precipitate, washing the precipitate with ethanol and water for several times, and vacuum drying at 60-120 ℃ for 10-48 h to obtain the main chain polyarylethersulfone.
10. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 1, wherein: in the step (4), the polar solvent C is one or more of Dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO); the mass volume concentration of the polyarylethersulfone in the casting solution is 5%; the reaction conditions are as follows: the reaction is carried out for 18 to 36 hours at the temperature of 60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310347622.0A CN116355254A (en) | 2023-03-29 | 2023-03-29 | Preparation method of monovalent selective anion exchange membrane with high permeation flux |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310347622.0A CN116355254A (en) | 2023-03-29 | 2023-03-29 | Preparation method of monovalent selective anion exchange membrane with high permeation flux |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116355254A true CN116355254A (en) | 2023-06-30 |
Family
ID=86921329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310347622.0A Pending CN116355254A (en) | 2023-03-29 | 2023-03-29 | Preparation method of monovalent selective anion exchange membrane with high permeation flux |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116355254A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117567729A (en) * | 2024-01-19 | 2024-02-20 | 固碳新能源科技(苏州)有限公司 | Ion-conducting polymer and preparation method thereof, ion-conducting cross-linked substance and preparation method thereof, anion exchange membrane and application thereof |
-
2023
- 2023-03-29 CN CN202310347622.0A patent/CN116355254A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117567729A (en) * | 2024-01-19 | 2024-02-20 | 固碳新能源科技(苏州)有限公司 | Ion-conducting polymer and preparation method thereof, ion-conducting cross-linked substance and preparation method thereof, anion exchange membrane and application thereof |
| CN117567729B (en) * | 2024-01-19 | 2024-05-28 | 固碳新能源科技(苏州)有限公司 | Ion-conducting polymer and preparation method thereof, ion-conducting cross-linked substance and preparation method thereof, anion exchange membrane and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Cross-linked hydroxide conductive membranes with side chains for direct methanol fuel cell applications | |
| CN110903449A (en) | Isatin arene copolymer, preparation method and application | |
| CN102504310B (en) | Preparation method of sulfonated polyimide/chitosan composite proton conducting film | |
| JPH1021943A (en) | Polymer electrolytic substance for fuel cell, and fuel cell | |
| Li et al. | Novel side-chain-type sulfonated diphenyl-based poly (arylene ether sulfone) s with a hydrogen-bonded network as proton exchange membranes | |
| CN116355254A (en) | Preparation method of monovalent selective anion exchange membrane with high permeation flux | |
| KR20110066614A (en) | Sulfonated poly(arylene ether)copolymer, method of manufacturing the same, and use thereof | |
| CN107573501A (en) | A kind of cross-linking fluorine-containing sulfonated polyether compound and preparation method thereof | |
| CN110756230A (en) | Preparation method of polyether sulphone anion exchange membrane with homogeneous cross-linked structure | |
| Zhang et al. | Soft template promoted microphase separation in anion exchange membrane of electrodialysis | |
| CN114502623A (en) | Stable anion exchange membrane based on fluorinated aliphatic hydrocarbon and preparation method thereof | |
| Yu et al. | Preparation and research progress of anion exchange membranes | |
| CN110760079B (en) | Preparation method of alkyl side chain type polyarylether sulphone anion exchange membrane with homogeneous cross-linked structure | |
| CN103709379B (en) | aromatic sulfonated polyketone and preparation method thereof | |
| Wang et al. | Ion exchange membrane “ABC”–A key material for upgrading process industries | |
| CN111533913B (en) | Side chain type amphoteric structure polyether sulphone, preparation method thereof and homogeneous phase amphoteric ion exchange membrane | |
| Sarkar et al. | Harnessing imidazole containing crosslinked AEM for HCl resurrection from industrial spent effluent by integrated diffusion dialysis and electrodialysis: Effect of small and macromolecular crosslinker | |
| CN111363152B (en) | Side chain type aromatic main chain embedded aliphatic chain polyarylether sulfone, preparation method thereof and homogeneous phase anion exchange membrane | |
| CN113683805B (en) | Preparation method of cross-linked imidazole functionalized polyether sulphone anion exchange membrane containing benzimidazole structure | |
| KR101710195B1 (en) | Bipolar Membrane for Water-Splitting Electrodialysis Process | |
| CN112457495B (en) | Preparation method of homogeneous anion exchange membrane | |
| CN111530311B (en) | Preparation method of monolithic poly (arylene ether nitrile) bipolar membrane containing corrole water dissociation catalytic group | |
| CN112409593B (en) | Side chain type polyphenylene oxide containing benzimidazole structure, preparation method thereof and homogeneous anion exchange membrane | |
| CN111530298B (en) | Preparation method of monolithic polyarylethersulfone ketone bipolar membrane containing phthalocyanine water dissociation catalytic group | |
| CN108752587B (en) | Sulfonated polyaryletherketone sulfone compound based on binaphthol and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |