CN115260422B - Preparation method of sulfonated polyether-ether-ketone, sulfonated polyether-ether-ketone membrane and application - Google Patents
Preparation method of sulfonated polyether-ether-ketone, sulfonated polyether-ether-ketone membrane and application Download PDFInfo
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 171
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 171
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000012528 membrane Substances 0.000 title abstract description 41
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 17
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000446 fuel Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 24
- 238000004090 dissolution Methods 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 6
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 5
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229940090668 parachlorophenol Drugs 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000005374 membrane filtration Methods 0.000 claims description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 39
- 239000000843 powder Substances 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 18
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 9
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 125000000542 sulfonic acid group Chemical group 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- HKCNCNXZAZPKDZ-UHFFFAOYSA-N (4,4-difluorocyclohexa-1,5-dien-1-yl)-phenylmethanone Chemical compound C1=CC(F)(F)CC=C1C(=O)C1=CC=CC=C1 HKCNCNXZAZPKDZ-UHFFFAOYSA-N 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003519 biomedical and dental material Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000007791 dehumidification Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 210000002540 macrophage Anatomy 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- -1 sulfonic acid compound Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
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- 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
- C08J5/18—Manufacture of films or sheets
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- 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
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
-
- 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
Abstract
The application relates to a preparation method of sulfonated polyether-ether-ketone, which comprises the steps of dissolving polyether-ether-ketone in an organic solvent to prepare polyether-ether-ketone solution, and then adding a sulfonating agent to carry out sulfonation reaction, wherein the organic solvent comprises p-chlorophenol and o-dichlorobenzene. The application also relates to a sulfonated polyether-ether-ketone membrane which has good proton conductivity and hydrophilicity. The application also relates to application of the sulfonated polyether-ether-ketone in preparing membrane filter materials, fuel cells or biomedical materials.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a preparation method of sulfonated polyether-ether-ketone, a sulfonated polyether-ether-ketone membrane and application thereof, and particularly relates to application of the sulfonated polyether-ether-ketone membrane as a proton exchange membrane.
Background
The sulfonation reaction can introduce a sulfonic acid group into an organic molecule, a sulfur atom of the sulfonic acid group is connected with a carbon atom in the organic molecule, and the obtained product is a sulfonic acid compound. Advantages of introducing sulfonic acid groups include the following: (1) After sulfonic acid groups are introduced into organic molecules, the organic molecules can have various surface activities such as emulsification, wetting, foaming and the like, and can be widely applied to the synthesis of surfactants; (2) Sulfonation can also impart water solubility and acidity to the organic matter by utilizing the hydrolyzability of the sulfonic acid group; (3) selective sulfonation is often used to separate isomers; (4) introducing a sulfonic acid group to obtain a series of intermediate products.
Polyether ether ketone (PEEK) is a high polymer formed by repeating units containing one ketone bond and two ether bonds in a main chain structure, and sulfonated polyether ether ketone is a modified polymer prepared by taking polyether ether ketone as a raw material and performing sulfonation reaction. The sulfonated polyether-ether-ketone has good proton conductivity and hydrophilicity, can improve the ion exchange capacity, improve the separation performance and the permeability, is more suitable for the technical field of membrane separation, and can be used for preparing membrane materials such as ultrafiltration, nanofiltration, reverse osmosis, gas dehumidification, proton exchange membranes and the like.
However, the preparation of sulfonated polyether-ether-ketone requires excessive sulfonating agent (sulfonating agent is used as reaction solvent at the same time), which not only increases the production cost, but also makes it difficult to control the sulfonation degree, resulting in the loss of polymer performance.
Based on the above, it is necessary to provide a method for preparing sulfonated polyether ether ketone with low cost and controllable sulfonation degree.
Disclosure of Invention
Based on the above, the purpose of the application is to provide a preparation method of sulfonated polyether-ether-ketone, which has controllable sulfonation degree, is easy to separate and purify, and is suitable for industrial production.
In a first aspect, the present application provides a method for preparing sulfonated polyetheretherketone, comprising the steps of: dissolving polyether-ether-ketone in an organic solvent to prepare a polyether-ether-ketone solution; the organic solvent comprises p-chlorophenol and o-dichlorobenzene;
and adding a sulfonating agent into the polyether-ether-ketone solution to carry out sulfonation reaction to obtain sulfonated polyether-ether-ketone.
In some embodiments of the present application, in the method for preparing sulfonated polyetheretherketone, the organic solvent is a mixture of p-chlorophenol and o-dichlorobenzene;
the volume ratio of the parachlorophenol to the orthodichlorobenzene is (0.1-10): 1.
in some embodiments of the present application, the conditions under which the polyetheretherketone is dissolved in the organic solvent in the method of preparing the sulfonated polyetheretherketone include one or more of the following:
the dissolution temperature is 23-250 ℃;
the dissolution pressure is 0.1MPa to 10MPa.
In some embodiments of the present application, the sulfonated polyetheretherketone has a melt index of 5g/10min to 300g/10min.
In some embodiments of the present application, the sulfonation reaction is carried out at a reaction temperature of 10 ℃ to 250 ℃ for a reaction time of 4 to 48 hours.
In some embodiments of the present application, the method for preparing sulfonated polyetheretherketone has at least one of the following features:
the mass concentration of the polyether-ether-ketone in the polyether-ether-ketone solution is 0.01-0.1 g/mL;
in the step of adding a sulfonating agent into the polyether-ether-ketone solution for sulfonation reaction, adding the sulfonating agent into the polyether-ether-ketone solution at a rate of 1-20 mL/min;
the sulfonation reaction is carried out under the protection of protective gas;
the sulfonating agent is one or more selected from concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide and sulfamic acid.
In some embodiments of the present application, in the method for preparing sulfonated polyetheretherketone, the sulfonating agent is concentrated sulfuric acid;
the mass volume ratio of the polyether-ether-ketone to the sulfonating agent is (0.01-0.5): 1.
in some embodiments of the present application, the method for preparing sulfonated polyetheretherketone further comprises the following steps after the sulfonation reaction: standing for layering to obtain top-layer liquid and bottom-layer liquid, and mixing the bottom-layer liquid and water to separate out solid.
In a second aspect the present application provides a sulfonated polyetheretherketone membrane, obtainable according to the method of the first aspect of the present application.
In a third aspect of the present application there is provided the use of a sulfonated polyetheretherketone membrane of the second aspect of the present application in the preparation of a membrane filtration material, a fuel cell or a biomedical material.
The traditional preparation of sulfonated polyether-ether-ketone requires the use of excessive sulfonating agent as a reaction solvent, the sulfonation degree is uncontrollable, polymer molecules are easy to break, and great reagent waste is caused. In the preparation method, the mixed organic solvent can play a good synergistic effect, and the polyether-ether-ketone can be completely dissolved in the solvent, so that the sulfonation reaction can be carried out. Meanwhile, the sulfonating agent is mainly used for providing sulfonate groups in the reaction process and is not used as a solvent as in the traditional scheme, so that the production cost is greatly saved, the adding amount of the sulfonating agent is controllable, and excessive sulfonation can be avoided.
The sulfonated polyether-ether-ketone prepared by the preparation method is simple in post-treatment, easy to purify and suitable for industrial production.
The sulfonated polyether-ether-ketone can be used for preparing membrane materials such as a hydrophilic filtering membrane, a proton exchange membrane and the like, can also be used for preparing biomedical materials such as 3D printing bionic bone materials, has elastic modulus matched with normal cartilage, and can regulate and control polarization capacity of macrophages.
Detailed Description
The present application is further illustrated below in conjunction with the embodiments, examples. It should be understood that these examples are illustrative only of the present application and are not intended to limit the scope of the present application. Furthermore, it is to be understood that various changes and modifications may be made by one skilled in the art after reading the teachings of this application, and such equivalents are intended to fall within the scope of the claims appended hereto.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Terminology
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
herein, "preferred", "better", etc. are merely embodiments or examples that describe better results, and it should be understood that they do not limit the scope of protection of the present application.
In this application, "further," "still further," "particularly," and the like are used for descriptive purposes and are not to be construed as limiting the scope of the present application.
In this application, the terms "first," "second," "third," "fourth," and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of a technical feature being indicated. Moreover, the terms "first," "second," "third," "fourth," and the like are used for non-exhaustive list description purposes only, and are not to be construed as limiting the number of closed forms.
In the present application, the technical features described in an open manner include a closed technical scheme composed of the listed features, and also include an open technical scheme including the listed features.
In this application, reference is made to a numerical interval (i.e., a numerical range), where the optional numerical distribution is considered continuous, and includes two numerical endpoints (i.e., a minimum value and a maximum value) of the numerical range, and each numerical value between the two numerical endpoints, unless otherwise indicated. When a numerical range merely points to integers within the numerical range, both end integers of the numerical range are included, as well as each integer between the two ends, unless expressly stated otherwise. Further, when a plurality of range description features or characteristics are provided, these ranges may be combined. In other words, unless otherwise indicated, the ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The temperature parameter in the present application is not particularly limited, and may be a constant temperature treatment or may vary within a predetermined temperature range. It should be appreciated that the constant temperature process described allows the temperature to fluctuate within the accuracy of the instrument control. Allows for fluctuations within a range such as + -5 ℃, + -4 ℃, + -3 ℃, + -2 ℃, + -1 ℃.
In the present application, the weight may be a mass unit known in the chemical industry such as mu g, mg, g, kg.
The polyether-ether-ketone has excellent thermal stability and chemical stability, and the sulfonated polyether-ether-ketone (sulfonated polyether-ether-ketone) not only maintains the good performance of the polyether-ether-ketone, but also has higher proton conductivity and hydrophilicity, and simultaneously improves the example exchange capacity of the polymer, thereby having excellent application prospects in the fields of fuel cells, membrane exchange and biomedical materials. At present, polyether-ether-ketone and excessive sulfonating agent are generally mixed for sulfonation reaction to prepare sulfonated polyether-ether-ketone, the sulfonation rate is uncontrollable, the reagent is not recyclable, and the cost is high.
In a first aspect of the present application, a method for preparing sulfonated polyetheretherketone is provided, wherein polyetheretherketone is dissolved in a suitable mixed organic solvent (such as a mixed solvent containing parachlorophenol and o-dichlorobenzene), and reaction products are easily separated and purified under a suitable sulfonation reaction condition (temperature, time, pressure and the like), so that raw materials are recyclable, and reagent waste and environmental pollution are avoided.
In a first aspect, the present application provides a method for preparing sulfonated polyetheretherketone, comprising the steps of:
dissolving polyether-ether-ketone in an organic solvent to prepare a polyether-ether-ketone solution; the organic solvent comprises p-chlorophenol and o-dichlorobenzene;
and adding a sulfonating agent into the polyether-ether-ketone solution to perform sulfonation reaction to obtain sulfonated polyether-ether-ketone.
In some embodiments, the organic solvent is a mixture of p-chlorophenol and o-dichlorobenzene. Further, the volume ratio of the parachlorophenol to the orthodichlorobenzene is (0.1-10): 1, further may be (1 to 5): 1, such as, for example, 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 8:1, 10:1, etc.
In some embodiments, in the step of dissolving the polyetheretherketone in the organic solvent, the polyetheretherketone is dissolved in the organic solvent at a dissolution temperature and a dissolution pressure. In some embodiments, the dissolution temperature is 23 ℃ to 250 ℃, and further may be 150 ℃ to 250 ℃, for example, 23 ℃, 50 ℃, 80 ℃, 100 ℃,150 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 230 ℃, 250 ℃, and the like. In some embodiments, the dissolution pressure is 0.1MPa to 10MPa, and further may be 1MPa to 10MPa, such as 0.1MPa, 0.5MPa, 1MPa, 2MPa, 5MPa, 8MPa, 10MPa, etc. In some embodiments, the dissolution time is from 0.5h to 48h, further may be from 1h to 2h, such as, for example, 0.5h, 0.8h, 1h, 2h, 5h, 12h, 24h, 48h, etc.
In some embodiments, the dissolution time, dissolution pressure, and dissolution temperature are in the following relationship: the higher the dissolution temperature and the higher the dissolution pressure, the shorter the dissolution time required. In some preferred embodiments, the dissolution temperature is 150 ℃ to 250 ℃, the dissolution pressure is 1MPa to 10MPa, and the dissolution time is 1h to 2h.
In some embodiments, the melt index of the polyetheretherketone is 5g/10min to 30g/10min, further 100g/10min to 300g/10min, such as 5g/10min, 10g/10min, 20g/10min, 50g/10min, 100g/10min, 150g/10min, 200g/10min, 300g/10min, etc.
In some embodiments, in the step of adding a sulfonating agent to the polyetheretherketone solution to perform sulfonation, the reaction temperature is 10℃to 250℃and may further be 25℃to 30℃such as 10℃to 20℃to 30℃to 50℃to 100℃to 150℃to 180℃to 200℃to 230℃to 250 ℃. Lower reaction temperatures facilitate control of the sulfonation rate. In some embodiments, the reaction temperature is room temperature, further may be 25 ℃ to 30 ℃.
In some embodiments, in the step of adding the sulfonating agent to the polyetheretherketone solution to perform the sulfonation reaction, the reaction time is 4 to 48 hours, and further may be 12 to 24 hours, such as 4 hours, 10 hours, 12 hours, 15 hours, 18 hours, 22 hours, 24 hours, 30 hours, 35 hours, 40 hours, 45 hours, 48 hours, for example. The lower the reaction temperature, the longer the reaction time required. In some preferred embodiments, the reaction temperature is 25-30 ℃ and the reaction time is 24-48 h, so that uncontrollable sulfonation degree caused by overhigh temperature can be avoided, and the performance of the material is influenced by overhigh sulfonation degree.
In some embodiments, the mass concentration of polyetheretherketone in the polyetheretherketone solution is 0.01 to 0.1g/mL.
In some embodiments, the sulfonating agent is added to the polyetheretherketone solution at a rate of 1 to 20mL/min during the step of adding the sulfonating agent to the polyetheretherketone solution to perform the sulfonation reaction.
In some embodiments, in the step of adding a sulfonating agent to the polyetheretherketone solution to perform sulfonation, the sulfonating agent is added to the polyetheretherketone solution under stirring; preferably the stirring is at a rate of 100 to 300RPM.
In some embodiments, the sulfonation reaction is conducted under protective gas shielding conditions, further the protective gas is selected from one or both of nitrogen and argon.
In some embodiments, the sulfonating agent is selected from one or more of concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide and sulfamic acid, and further can be one or two of fuming sulfuric acid and chlorosulfonic acid.
In some embodiments, in the step of adding a sulfonating agent to the polyetheretherketone solution to perform the sulfonation reaction, the sulfonating agent is a liquid, and the volume of the added sulfonating agent is 6% -22% of the total volume of the polyetheretherketone solution and the sulfonating agent.
In the application, after the sulfonation reaction is finished, obvious layering can be found, the top layer is an organic solvent layer (containing p-chlorophenol and o-dichlorobenzene), and the bottom layer is a sulfonating agent layer (containing product sulfonated polyether-ether-ketone). The product at the bottom layer and the organic solvent at the top layer can be collected by a simple liquid separation method, the recovered organic solvent can be reused, the cost is saved, and the solvent pollution is avoided.
In some embodiments, after the step of adding a sulfonating agent to the polyetheretherketone solution to perform the sulfonation reaction, the method further comprises the steps of: standing for layering to obtain top layer liquid and bottom layer liquid, and mixing the bottom layer liquid and water to separate out solid.
In some embodiments, after mixing the underlying liquid and water to precipitate a solid, the solid is washed with an alcohol solution and dried.
In some embodiments, in the step of mixing the primer liquid and water to precipitate a solid, the primer liquid and water are mixed at 0-5 ℃.
In some embodiments, the alcohol solution is a mixed solution of ethanol and water, and the volume ratio of ethanol to water may be (75-100): 1.
In some embodiments, the solid is washed with an alcohol solution and dried at a temperature of 100 ℃ to 140 ℃, and further 110 ℃ to 130 ℃, such as 110 ℃, 120 ℃, 130 ℃, and the like. In some embodiments, the solid is washed with an alcohol solution and dried for a period of time ranging from 8 hours to 12 hours, and further ranging from 9 hours to 11 hours, such as 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, etc. In some preferred embodiments, the drying temperature is 120 ℃ and the drying time is 8 to 12 hours.
In some embodiments, the step of adding a sulfonating agent to the polyetheretherketone solution to perform sulfonation, and allowing the solution to stand to obtain a top liquid and a bottom liquid which are opposite to each other, further comprises the following solvent recovery step: standing the top liquid, pouring out or sucking out to obtain a recovered organic solvent; the recovered organic solvent comprises p-chlorophenol and o-dichlorobenzene, and can be reused for dissolving polyether-ether-ketone.
In some embodiments, the recovered organic solvent can be used for preparing a polyether-ether-ketone solution, and further, a sulfonating agent is added into the polyether-ether-ketone solution for sulfonation reaction to prepare sulfonated polyether-ether-ketone.
In some embodiments, a method of preparing sulfonated polyetheretherketone comprises the steps of:
dissolving polyether-ether-ketone into an organic solvent I to prepare a polyether-ether-ketone solution;
continuously introducing inert gas, and dropwise adding a sulfonating agent into the polyether-ether-ketone solution under the stirring condition to carry out sulfonation reaction; preferably, the stirring condition is 100-300 RPM, and the dropping speed of the sulfonating agent is 1-20 mL/min;
standing and layering to obtain a top-layer liquid and a bottom-layer liquid which are opposite, recovering an organic solvent I in the top-layer liquid, pouring the bottom-layer liquid into ice water, and separating out solids;
breaking the solid, washing the solid with ethanol and deionized water until the solid is neutral, and drying the solid to obtain sulfonated polyether-ether-ketone powder.
The second aspect of the application provides sulfonated polyether-ether-ketone which has excellent performances of high temperature resistance, chemical corrosion resistance and the like, and also has good proton conductivity and hydrophilicity. The sulfonated polyetheretherketone of the present application may be prepared by the preparation method of the first aspect of the present application.
In some embodiments, the sulfonated polyetheretherketone consists of the following units:
in some embodiments, n is an integer between 1000 and 2000000, further may be an integer between 5000 and 1000000, such as 1000, 5000, 10000, 30000, 100000, 500000, 800000, 1000000, etc.
In some embodiments, the sulfonated polyetheretherketone is a powdered solid.
In a third aspect of the present application, there is provided the use of a sulfonated polyetheretherketone in the preparation of a membrane filtration material, a fuel cell or a biomedical material. The proton exchange membrane (Proton Exchange Membrane, PEM) is the core component of a proton exchange membrane fuel cell (Proton Exchange Membrane Fuel Cell, PEMFC), serving as a barrier and proton conducting function, critical to cell performance. The membrane material prepared from the sulfonated polyether-ether-ketone has high temperature resistance, chemical corrosion resistance and strong proton conduction capacity, and can be used for preparing proton exchange membranes.
In the membrane filter material, the filter membrane used for water body filtration and gas dehumidification needs to have good hydrophilicity, and the membrane material prepared from the sulfonated polyether-ether-ketone has high temperature resistance, chemical corrosion resistance and strong hydrophilicity, and can be used for preparing a hydrophilic filter membrane.
In some embodiments, the membrane material is an ultrafiltration, nanofiltration, reverse osmosis, gas-dehumidifying membrane.
In some embodiments, the membrane material (sulfonated polyetheretherketone membrane) is prepared by a process comprising: dissolving sulfonated polyether-ether-ketone in an organic solvent II, and preparing a sulfonated polyether-ether-ketone membrane by a tape casting method; preferably, the organic solvent II is N, N-dimethylacetamide.
In some embodiments, the concentration of sulfonated polyetheretherketone in organic solvent ii is 1% to 50%, preferably 10% to 30%, for example 1%, 5%, 10%, 15%, 20%, 25%, 30%, 50%, etc.
The following are some specific examples.
The experimental parameters not specified in the following specific examples are preferentially referred to the guidelines given in the application document, and may also be referred to the experimental manuals in the art or other experimental methods known in the art, or to the experimental conditions recommended by the manufacturer.
The starting materials and reagents referred to in the following specific examples may be obtained commercially or may be prepared by known means by those skilled in the art.
In the examples below, sulfur content may be tested using instrumentation and testing methods known in the art, such as by including an elemental analyzer.
Example 1
Step one, preparing polyether-ether-ketone
Into a 500mL flange flask equipped with an argon inlet and a torque stirrer were charged 4, 4-difluorobenzophenone (BDF) (0.52 mol,113.4 g), hydroquinone (HQ) 57.8g and diphenyl sulfone (DPS) (1.1 mol,244 g). The flask was purged with argon for 30 minutes. The mixture was then heated to 160℃and 57.8g of sodium carbonate and 0.31g of potassium carbonate were added to the reaction mixture. The temperature was raised to 315 c per minute at 1 c and maintained at that temperature until the desired torque rise was reached. The required torque rise is determined from a calibration curve of torque rise versus RV. The reaction mixture was then poured into foil trays, cooled, ground and washed with 2L of acetone, then warm water (40-50 ℃) until the conductivity of the wastewater reached < 2. Mu.. Epsilon. The obtained polymer powder was dried in an air oven at 150℃for 8 hours to obtain polyether-ether-ketone powder.
Step two, preparing polyether-ether-ketone solution
31.2g of polyether-ether-ketone powder with the melt index of 100g/10min, 125 g mL p-chlorophenol and 375mL o-dichlorobenzene are weighed in a 2000mL pressure dissolution kettle, the preparation temperature is 150 ℃, the pressure is 5Mpa, and the mixture is stirred for 1h, so that 500mL of polyether-ether-ketone solution with uniform dispersion is formed.
Step three, preparing sulfonated polyether-ether-ketone
After restoring to normal temperature and pressure, a sulfonating agent (fuming sulfuric acid, 150 mL) is dripped into the polyether-ether-ketone solution at 25 ℃ for sulfonation reaction, wherein the reaction time is 24 hours. And standing for layering after the reaction is finished, slowly pouring the thick slurry at the bottom into ice water, precipitating solids, smashing the obtained solids, and repeatedly washing with ethanol and deionized water to be neutral to obtain powdery sulfonated polyether ketone.
Step four, preparing sulfonated polyether-ether-ketone membrane
And (3) baking the sulfonated polyether-ether-ketone powder at 120 ℃ for 12 hours to constant weight, weighing 20g of dried sulfonated polyether-ether-ketone powder, dissolving in 200mL of N, N-dimethylacetamide, and preparing the sulfonated polyether-ether-ketone film by a tape casting method.
Example 2
The sulfonated polyether-ether-ketone membrane is prepared by adopting the preparation method basically same as that of the example 1, wherein in the third step, fuming sulfuric acid (150 mL) is dripped into the dispersion liquid at 40 ℃ to carry out sulfonation reaction after the normal temperature and the normal pressure are restored; the remaining parameters and operation steps were the same as in example 1.
Example 3
The sulfonated polyether ether ketone membrane was prepared using substantially the same preparation method as in example 1, except that the sulfonating agent in step three was chlorosulfonic acid; the remaining parameters and operation steps were the same as in example 1.
Example 4
The sulfonated polyether ether ketone membrane was prepared by the same preparation method as in example 1, except that in the third step, the sulfonation reaction time was 8 hours; the remaining parameters and operation steps were the same as in example 1.
Example 5
A sulfonated polyether ether ketone membrane was prepared by substantially the same preparation method as in example 1, except that in the third step, the time of sulfonation was 24 hours; the remaining parameters and operation steps were the same as in example 1.
Comparative example 1
The same method as in the step one of example 1 was used to prepare a polyether-ether-ketone powder, 31.2g of the polyether-ether-ketone powder was weighed and put into a 2000mL pressure dissolution vessel, 650mL of a sulfonating agent (fuming sulfuric acid) was added, the temperature was set at 150℃and the pressure was 5MPa, and sulfonation was carried out for 24 hours. And standing for layering after the reaction is finished, slowly pouring the thick slurry at the bottom into ice water, precipitating solids, smashing the obtained solids, and repeatedly washing with ethanol and deionized water to be neutral to obtain powdery sulfonated polyether-ether-ketone. Baking sulfonated polyether-ether-ketone powder at 120 ℃ for 12 hours to constant weight; 20g of dried sulfonated polyether-ether-ketone powder is weighed, dissolved in 200mL of N, N-dimethylacetamide, and a casting method is used for preparing the sulfonated polyether-ether-ketone membrane.
Comparative example 2
Step one, preparing polyether-ether-ketone
Into a 500mL flange flask equipped with an argon inlet and a torque stirrer were charged 4, 4-difluorobenzophenone (BDF) (0.52 mol,113.4 g), hydroquinone (HQ) 57.8g and diphenyl sulfone (DPS) (1.1 mol,244 g). The flask was purged with argon for 30 minutes. The mixture was then heated to 160℃and 57.8g of sodium carbonate and 0.31g of potassium carbonate were added to the reaction mixture. The temperature was raised to 315 c per minute at 1 c and maintained at that temperature until the desired torque rise was reached. The required torque rise is determined from a calibration curve of torque rise versus RV. The reaction mixture was then poured into foil trays, cooled, ground and washed with 2L of acetone, then warm water (40-50 ℃) until the conductivity of the wastewater reached < 2. Mu.. Epsilon. The obtained polymer powder was dried in an air oven at 150℃for 8 hours to obtain polyether-ether-ketone powder.
Step two, preparing polyether-ether-ketone solution
31.2g of polyether-ether-ketone powder with the melt index of 100g/10min, 75 g mL p-chlorophenol and 425mL of o-dichlorobenzene are weighed in a 2000mL pressure dissolution kettle, the temperature is set to 150 ℃, the pressure is 5Mpa, the stirring is carried out for 1h, the polyether-ether-ketone powder is not dissolved, the swelling phenomenon is generated, and the polyether-ether-ketone solution can not be prepared like a colloid.
Step three, preparing sulfonated polyether-ether-ketone
After the normal temperature and the normal pressure are restored, a sulfonating agent (fuming sulfuric acid, 150 mL) is dripped into the polyether-ether-ketone colloid for sulfonation reaction at 25 ℃ for 24 hours. Standing for layering after the reaction is finished, slowly pouring the thick colloid at the bottom into ice water, smashing, and repeatedly cleaning with ethanol and deionized water to be neutral to obtain powdery solid.
Step four, preparing sulfonated polyether-ether-ketone membrane
Baking the powdery solid obtained in the third step at 120 ℃ for 12 hours to constant weight; 20g of the dried powder was weighed and mixed with 200mL of N, N-dimethylacetamide, and the preparation failed in the third step, and thus it was found that the sulfonated polyether ether ketone film could not be prepared.
Comparative example 3
Step one, preparing polyether-ether-ketone
Into a 500mL flange flask equipped with an argon inlet and a torque stirrer were charged 4, 4-difluorobenzophenone (BDF) (0.52 mol,113.4 g), hydroquinone (HQ) 57.8g and diphenyl sulfone (DPS) (1.1 mol,244 g). The flask was purged with argon for 30 minutes. The mixture was then heated to 160℃and 57.8g of sodium carbonate and 0.31g of potassium carbonate were added to the reaction mixture. The temperature was raised to 315 c per minute at 1 c and maintained at that temperature until the desired torque rise was reached. The required torque rise is determined from a calibration curve of torque rise versus RV. The reaction mixture was then poured into foil trays, cooled, ground and washed with 2L of acetone, then warm water (40-50 ℃) until the conductivity of the wastewater reached < 2. Mu.. Epsilon. The obtained polymer powder was dried in an air oven at 150℃for 8 hours to obtain polyether-ether-ketone powder.
Step two, preparing polyether-ether-ketone solution
31.2g of polyether-ether-ketone powder with the melt index of 100g/10min and 500mL of o-dichlorobenzene are weighed in a 2000mL pressure dissolution kettle, the preparation temperature is 150 ℃, the pressure is 5Mpa, and the stirring is carried out for 1h, so that the polyether-ether-ketone powder is not dissolved and still is in a powder state, and the polyether-ether-ketone solution can not be prepared.
Step three, preparing sulfonated polyether-ether-ketone
After the normal temperature and the normal pressure are restored, a sulfonating agent (fuming sulfuric acid, 150 mL) is dripped into the polyether-ether-ketone powder for sulfonation reaction at 25 ℃ for 24 hours. Standing for layering after the reaction is finished, pouring the polyether-ether-ketone powder at the bottom into ice water, and repeatedly cleaning with ethanol and deionized water until the mixture is neutral to obtain powdery solid.
Step four, preparing sulfonated polyether-ether-ketone membrane
Baking the powdery solid obtained in the third step at 120 ℃ for 12 hours to constant weight; 20g of the dried powder was weighed and mixed with 200mL of N, N-dimethylacetamide, and the preparation failed in the third step, and thus it was found that the sulfonated polyether ether ketone film could not be prepared.
Comparative example 4
Step one, preparing polyether-ether-ketone
Into a 500mL flange flask equipped with an argon inlet and a torque stirrer were charged 4, 4-difluorobenzophenone (BDF) (0.52 mol,113.4 g), hydroquinone (HQ) 57.8g and diphenyl sulfone (DPS) (1.1 mol,244 g). The flask was purged with argon for 30 minutes. The mixture was then heated to 160℃and 57.8g of sodium carbonate and 0.31g of potassium carbonate were added to the reaction mixture. The temperature was raised to 315 c per minute at 1 c and maintained at that temperature until the desired torque rise was reached. The required torque rise is determined from a calibration curve of torque rise versus RV. The reaction mixture was then poured into foil trays, cooled, ground and washed with 2L of acetone, then warm water (40-50 ℃) until the conductivity of the wastewater reached < 2. Mu.. Epsilon. The obtained polymer powder was dried in an air oven at 150℃for 8 hours to obtain polyether-ether-ketone powder.
Step two, preparing polyether-ether-ketone solution
31.2g of polyether-ether-ketone powder with the melt index of 100g/10min and 500mL of diphenyl sulfone are weighed into a 2000mL pressure dissolution kettle, the preparation temperature is 150 ℃, the pressure is 5Mpa, and the mixture is stirred for 1h, and the polyether-ether-ketone powder is not dissolved and still in a powder state, so that the polyether-ether-ketone solution can not be prepared.
Step three, preparing sulfonated polyether-ether-ketone
After the normal temperature and the normal pressure are restored, a sulfonating agent (fuming sulfuric acid, 150 mL) is dripped into the polyether-ether-ketone powder for sulfonation reaction at 25 ℃ for 24 hours. Standing for layering after the reaction is finished, pouring the polyether-ether-ketone powder at the bottom into ice water, and repeatedly cleaning with ethanol and deionized water until the mixture is neutral to obtain powdery solid.
Step four, preparing sulfonated polyether-ether-ketone membrane
Baking the powdery solid obtained in the third step at 120 ℃ for 12 hours to constant weight; 20g of the dried powder was weighed and mixed with 200mL of N, N-dimethylacetamide, and the preparation failed in the third step, and thus it was found that the sulfonated polyether ether ketone film could not be prepared.
Performance testing
The sulfonated polyether ether ketone membranes of the examples and comparative examples were each tested for sulfur content. The test results are shown in the following Table (Table 1)
TABLE 1 Sulfur content of several sulfonated polyetheretherketones
Table 1 is a comparison table of sulfur content test results of elemental analysis methods for different sulfonated polyether ether ketone preparation methods, and the mass fraction of sulfur directly reflects the content of sulfonic acid groups in the polymer, so that the sulfonation degree of the polymer can be determined by measuring the content of sulfur in the polymer. In Table 1, "-" means that the sulfur content could not be tested due to failure to make the product.
According to the table 1, the sulfonation degree of the sulfonated polyether-ether-ketone prepared by the preparation method is controllable, and the sulfonated polyether-ether-ketone film can be prepared and has good application prospect.
All documents mentioned in this application are incorporated by reference in this application as if each were individually incorporated by reference. Unless otherwise conflict with the purpose and/or technical solution of the present application, the present application relates to the cited documents which are incorporated by reference in their entirety for all purposes. When reference is made to a cited document in this application, the definitions of the relevant technical features, terms, nouns, phrases, etc. in the cited document are also incorporated by reference. Examples of the relevant technical features and preferred modes to be cited in the present application when the cited documents are referred to in the present application are incorporated by reference in the present application, but are not limited to being able to implement the present application. It should be understood that when a reference is made to the description herein, it is intended to control or adapt the present application in light of the description herein.
The technical features of the above-described embodiments and examples may be combined in any suitable manner, and for brevity of description, all of the possible combinations of the technical features of the above-described embodiments and examples are not described, however, as long as there is no contradiction between the combinations of the technical features, they should be considered to be within the scope described in the present specification.
The above examples merely represent a few embodiments of the present application and are not to be construed as limiting the scope of the claims. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. Further, it will be understood that various changes or modifications may be made to the present application by those skilled in the art after reading the foregoing teachings, and equivalents thereof will be within the scope of the present application. It should also be understood that those skilled in the art, based on the technical solutions provided in the present application, can obtain technical solutions through logical analysis, reasoning or limited experiments, all fall within the protection scope of the claims attached to the present application. The scope of the patent is, therefore, indicated by the appended claims, and the description may be used to interpret the contents of the claims.
Claims (10)
1. The preparation method of the sulfonated polyether-ether-ketone is characterized by comprising the following steps of: dissolving polyether-ether-ketone in an organic solvent to prepare a polyether-ether-ketone solution; the organic solvent comprises p-chlorophenol and o-dichlorobenzene; the mass concentration of the polyether-ether-ketone in the polyether-ether-ketone solution is 0.01-0.1 g/mL;
and adding a sulfonating agent into the polyether-ether-ketone solution to carry out sulfonation reaction to obtain sulfonated polyether-ether-ketone.
2. The method for preparing sulfonated polyether ether ketone according to claim 1, wherein said organic solvent is a mixture of p-chlorophenol and o-dichlorobenzene;
the volume ratio of the parachlorophenol to the orthodichlorobenzene is 1:3-10:1.
3. The method of preparing sulfonated polyether ether ketone according to claim 1, wherein the conditions under which said polyether ether ketone is dissolved in said organic solvent include one or more of the following:
the dissolution temperature is 23-250 ℃;
the dissolution pressure is 0.1-10 MPa.
4. The method for preparing sulfonated polyether-ether-ketone according to claim 1, wherein the melt index of the polyether-ether-ketone is 5g/10 min-300 g/10min.
5. The method for preparing sulfonated polyether-ether-ketone according to claim 1, wherein the reaction temperature of the sulfonation reaction is 10-250 ℃ and the reaction time is 4-48 h.
6. The method for preparing sulfonated polyether ether ketone according to claim 1, wherein said method comprises at least one of the following features:
in the step of adding a sulfonating agent into the polyether-ether-ketone solution for sulfonation reaction, adding the sulfonating agent into the polyether-ether-ketone solution at a rate of 1-20 mL/min;
the sulfonation reaction is carried out under the protection of protective gas;
the sulfonating agent is one or more selected from concentrated sulfuric acid, chlorosulfonic acid, sulfur trioxide and sulfamic acid.
7. The method for preparing sulfonated polyether ether ketone according to claim 5, wherein said sulfonating agent is concentrated sulfuric acid;
the mass volume ratio of the polyether-ether-ketone to the sulfonating agent is (0.01-0.5): 1.
8. the method for preparing sulfonated polyether ether ketone according to claim 1, further comprising the following steps after said sulfonation reaction: standing for layering to obtain top-layer liquid and bottom-layer liquid, and mixing the bottom-layer liquid and water to separate out solid.
9. A sulfonated polyetheretherketone, characterized in that it is prepared according to the preparation method of any one of claims 1 to 8.
10. Use of the sulfonated polyetheretherketone of claim 9 for the preparation of membrane filtration materials, fuel cells or biomedical materials.
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| KR20100116483A (en) * | 2009-04-22 | 2010-11-01 | 성균관대학교산학협력단 | Cross-linkable poly(ether ether ketone) with pendent sulfonation groups, polymer electrolyte membrane for fuel cell prepared therewith and preparation method thereof |
| CN102352004A (en) * | 2011-07-11 | 2012-02-15 | 大连理工大学 | Chloromethylated polyetheretherketone (PEEK) and synthetic method thereof |
| CN112852101A (en) * | 2021-01-22 | 2021-05-28 | 中国石油大学(北京) | Sulfonated polyether ether ketone based proton exchange membrane and preparation method and application thereof |
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| CN102352004A (en) * | 2011-07-11 | 2012-02-15 | 大连理工大学 | Chloromethylated polyetheretherketone (PEEK) and synthetic method thereof |
| CN112852101A (en) * | 2021-01-22 | 2021-05-28 | 中国石油大学(北京) | Sulfonated polyether ether ketone based proton exchange membrane and preparation method and application thereof |
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