CN114773517B - Fluorine-containing sulfonic acid resin and preparation method thereof - Google Patents

Fluorine-containing sulfonic acid resin and preparation method thereof Download PDF

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CN114773517B
CN114773517B CN202210364045.1A CN202210364045A CN114773517B CN 114773517 B CN114773517 B CN 114773517B CN 202210364045 A CN202210364045 A CN 202210364045A CN 114773517 B CN114773517 B CN 114773517B
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resin
acid resin
monomer
sulfonic acid
fluorine
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CN114773517A (en
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王杰
刘昊
李道喜
周明正
唐浩林
柴茂荣
王福瑶
刘品阳
干志强
刘飞
方亮
李震康
夏丰杰
刘真
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Wuhan Lvdong Hydrogen Energy Technology Co ltd
Spic Hydrogen Energy Technology Development Co Ltd
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Wuhan Lvdong Hydrogen Energy Technology Co ltd
Spic Hydrogen Energy Technology Development Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/186—Monomers containing fluorine with non-fluorinated comonomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08F2/00—Processes of polymerisation
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • C25B1/04—Hydrogen or oxygen by electrolysis of water
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • 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
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1466—Monomers containing sulfur
    • C08F216/1475—Monomers containing sulfur and oxygen
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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 invention discloses a fluorine-containing sulfonic acid resin and a preparation method thereof, wherein the fluorine-containing sulfonic acid resin is prepared by copolymerizing an acrylic monomer, a perfluoroolefin monomer and a sulfonyl fluoride vinyl ether monomer. According to the fluorine-containing sulfonic acid resin, carboxylic acid groups are introduced into a sulfonic acid resin structure, so that aggregation of a plurality of isolated ion pairs and/or aggregation of isolated ion pairs after water absorption are facilitated, and the isolated ion pairs become ion clusters; meanwhile, the sulfonic acid resin has higher Na and acidification degrees, shortens Na and acidification time, has excellent dissolving capacity and is beneficial to the preparation of solution in the subsequent application process.

Description

Fluorine-containing sulfonic acid resin and preparation method thereof
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a fluorine-containing sulfonic acid resin, and more particularly relates to a preparation method of the fluorine-containing sulfonic acid resin.
Background
Currently, it has been one of the hot directions of current research to solve the balance relationship between the electrical conductivity and mechanical strength of the Proton Exchange Membrane (PEM) in the fuel cell. In contrast, firstly, the enhanced proton exchange membrane is adopted, namely, the perfluorinated sulfonic acid resin and the porous Polytetrafluoroethylene (PTFE) are compounded, so that the PEM can be thinned, the mechanical strength is ensured, the internal resistance of the battery is reduced, the consumption of the sulfonic acid resin can be reduced, and the cost of the battery is reduced while the performance of the battery is improved. However, the porous PTFE reinforced material of the non-proton conductor is introduced into the composite membrane, so that the proton conductivity of the membrane is influenced to a certain degree; yet another way is to increase the proton conductivity of the perfluorosulfonic proton exchange membrane while maintaining the mechanical strength of the crude sulfonic resin. Therefore, it is necessary to study a method for improving the proton transport efficiency of the sulfonic acid resin.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems: the proton transmission channel in the PEM is one of the important factors for improving the proton transmission efficiency, and for the research on the proton transmission channel in the PEM, three models, namely a cluster-network model, a short rod model and a parallel column model, of the proton transmission channel are common, and the cluster-network model proposed by Gierke is most widely recognized among the three models. Hydrophilic sulfonic acid groups in Nafion after water absorption and water molecules form ion clusters with the diameter of about 4nm together, each ion cluster is composed of a certain amount of reverse micelle structures which cover water molecules in sulfonic acid groups, and water channels between the clusters are communicated with each other to form a cluster-network structure for proton transmission. Furthermore, eisenberg proposed a classical ion cluster-cluster (phase) model for ion exchange resins in the non-hygroscopic state: i.e., below a certain "low critical ion content", individual sulfonate ionic groups are present in combination with the counter salt ion as isolated ion pairs; when the ion content exceeds the "low critical ion content", a plurality of isolated ion pairs are aggregated into ion clusters, and when the ion content is further increased to a certain "high critical ion content", the ion clusters are aggregated into a cluster phase for the second time.
For the application of ion exchange resins to proton exchange membranes, hydrophilic single sulfonic acid groups or sulfonic acid-hydrate groups (in this case H) + /H 3 O + As counter-ion) exists as a stand-alone ion pair, with ion content (i.e., ion exchange capacity)) The plurality of isolated ion pairs are gathered and/or the isolated ion pairs absorb water and then are gathered to form ion clusters; the ion clusters further aggregate into cluster phases as the ion content increases; the plurality of cluster phases and the hydrophobic C-F main chain form a cluster-network structure to construct a good proton transmission channel. But the current report of research on reducing the critical ion content to form a cluster phase structure with higher concentration is relatively lacked.
The present invention is directed to solving, at least in part, one of the technical problems in the related art. Therefore, the embodiment of the invention provides the fluorine-containing sulfonic acid resin, and the carboxylic acid group is introduced into the sulfonic acid resin structure, so that a plurality of isolated ion pairs can be aggregated, and/or the isolated ion pairs can be aggregated after absorbing water to form ion clusters; meanwhile, the ion clusters are aggregated into cluster phases along with the increase of the content of the ion clusters, and a plurality of cluster phases and the hydrophobic C-F main chain form a cluster-network structure, so that a good proton transmission channel is constructed, and the proton transmission efficiency is improved.
The molecular structural formula of the fluorosulfonic acid-containing resin provided by the embodiment of the invention is as follows:
Figure BDA0003585140290000021
wherein x, y and z are integers from 1 to 100, m is an integer from 0 to 3, and n is an integer from 0 to 2; r1 is C1-3 alkyl, R2 is aromatic ring or C1-3 alkyl, and Rf is C1-6 perfluorocarbon chain; the end group of the main chain of the fluorine-containing sulfonic acid resin molecule is fluorine-containing alkane, perfluorosulfonyl fluoride and-CF 2 H or perfluoroalkenyl, including straight or branched chain alkanes having 1-6 carbons.
1, in the embodiment of the invention, carboxylic acid groups are introduced into a sulfonic acid resin structure, which is beneficial to aggregation of a plurality of isolated ion pairs and/or aggregation of the isolated ion pairs after water absorption to form ion clusters; meanwhile, the ion clusters are aggregated into cluster phases along with the increase of the content of the ion clusters, and a plurality of cluster phases and the hydrophobic C-F main chain form a cluster-network structure, so that a good proton transmission channel is constructed, and the proton transmission efficiency is improved; 2. the sulfonic acid resin provided by the embodiment of the invention has higher Na conversion and acidification degrees, shortens Na conversion and acidification time, has excellent dissolving capacity, and is beneficial to preparation of a solution in a subsequent application process.
The embodiment of the invention also provides a preparation method of the fluorine-containing sulfonic acid resin, wherein the fluorine-containing sulfonic acid resin is prepared by copolymerizing an acrylic monomer, a perfluoroolefin monomer and a sulfonyl fluoride vinyl ether monomer.
The preparation method of the fluorine-containing sulfonic acid resin provided by the embodiment of the invention has the advantages and technical effects that 1, by copolymerizing acrylic monomers in the process of synthesizing the resin, the method provided by the embodiment of the invention effectively reduces the low critical ion content of isolated ion pairs (namely single sulfonate ion group) aggregated into ion clusters in the sulfonic acid resin and/or the high critical ion content of ion clusters secondarily aggregated into cluster phases, can form ion clusters and/or cluster phases with higher concentration, further constructs and forms a good proton transmission channel, and improves the proton transmission efficiency; 2. according to the method provided by the embodiment of the invention, the acrylic monomer is copolymerized in the resin synthesis process, so that the Na conversion and acidification degrees of the sulfonic acid resin are improved, and the Na conversion and acidification time is shortened; 3. in the method of the embodiment of the invention, the acrylic monomer is copolymerized in the resin synthesis process, so that the dissolving capacity of the sulfonic acid resin in various solvents is improved, and the preparation of the resin solution in the subsequent application process is facilitated.
In some embodiments, the fluorosulfonic acid resin has a mole percentage content of acrylic monomer in a range of 1.0 to 5.0%, a mole percentage content of perfluoroolefin monomer in a range of 60 to 85%, and a mole percentage content of sulfonyl fluoride vinyl ether monomer in a range of 2 to 15% in a molecule.
In some embodiments, the perfluoroolefin monomer is of the formula:
Figure BDA0003585140290000031
wherein Rf is a perfluorocarbon chain having 1 to 6 carbon atoms.
In some embodiments, the acrylic monomer is of the formula:
Figure BDA0003585140290000032
wherein R1 is alkyl containing 1-3 carbon atoms, and R2 is aromatic ring or alkyl containing 1-3 carbon atoms.
In some embodiments, the sulfonyl fluoride vinyl ether monomer is of the formula:
Figure BDA0003585140290000033
wherein m is an integer of 0 to 3, and n is an integer of 0 to 2.
In some embodiments, the acrylic monomer, the perfluoroolefin monomer, and the sulfonyl fluoride vinyl ether monomer are subjected to radical copolymerization at 40-100 ℃ and 1.0-8.0MPa under the initiation of an initiator for 6-48h.
In some embodiments, the copolymerization process is selected from one of emulsion polymerization, solution polymerization, or bulk polymerization.
The embodiment of the invention also provides an ion exchange membrane, which is prepared by adopting the fluorine-containing sulfonic acid resin or the fluorine-containing sulfonic acid resin prepared by the method of the embodiment of the invention. The ion exchange membrane provided by the embodiment of the invention is prepared from the fluorosulfonic acid resin provided by the embodiment of the invention, has all the advantages brought by the fluorosulfonic acid resin provided by the embodiment of the invention, and has excellent mechanical strength, higher proton transmission efficiency and excellent comprehensive performance.
The embodiment of the invention also provides application of the ion exchange membrane in preparation of fuel cells, chlor-alkali electrolytic cells or electrolytic cells for hydrogen production by water electrolysis.
Drawings
Fig. 1 is a TEM image of the ion exchange membrane prepared in example 1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are illustrative and intended to explain the present invention and should not be construed as limiting the present invention.
The molecular structural formula of the fluorosulfonic acid-containing resin provided by the embodiment of the invention is as follows:
Figure BDA0003585140290000041
wherein x, y and z are integers from 1 to 100, m is an integer from 0 to 3, and n is an integer from 0 to 2; r1 is C1-3 alkyl, R2 is aromatic ring or C1-3 alkyl, and Rf is C1-6 perfluorocarbon chain; the end group of the main chain of the fluorine-containing sulfonic acid resin molecule is fluorine-containing alkane, perfluorosulfonyl fluoride and-CF 2 H or perfluoroalkenyl, including straight or branched chain alkanes having 1-6 carbons.
According to the fluorine-containing sulfonic acid resin provided by the embodiment of the invention, carboxylic acid groups are introduced into a sulfonic acid resin structure, so that aggregation of a plurality of isolated ion pairs and/or aggregation of isolated ion pairs after water absorption are facilitated to form ion clusters; meanwhile, the ion clusters are aggregated into cluster phases along with the increase of the content of the ion clusters, and a plurality of cluster phases and the hydrophobic C-F main chain form a cluster-network structure, so that a good proton transmission channel is constructed, and the proton transmission efficiency is improved; the sulfonic acid resin provided by the embodiment of the invention has higher Na conversion and acidification degrees, shortens Na conversion and acidification time, has excellent dissolving capacity, and is beneficial to preparation of a solution in a subsequent application process.
The embodiment of the invention also provides a preparation method of the fluorine-containing sulfonic acid resin, wherein the fluorine-containing sulfonic acid resin is prepared by copolymerizing an acrylic monomer, a perfluoroolefin monomer and a sulfonyl fluoride vinyl ether monomer.
According to the preparation method of the fluorine-containing sulfonic acid resin, the acrylic monomer is copolymerized in the process of synthesizing the resin, so that the low critical ion content of the ion cluster aggregated by isolated ion pairs (namely a single sulfonate ion group) in the sulfonic acid resin and/or the high critical ion content of the ion cluster secondarily aggregated by the ion cluster are effectively reduced, the ion cluster and/or cluster phase with higher concentration can be formed, a good proton transmission channel is further constructed, and the proton transmission efficiency is improved; according to the method provided by the embodiment of the invention, the acrylic monomer is copolymerized in the resin synthesis process, so that the Na conversion and acidification degrees of the sulfonic acid resin are improved, and the Na conversion and acidification time is shortened; in the method of the embodiment of the invention, the acrylic monomer is copolymerized in the resin synthesis process, so that the dissolving capacity of the sulfonic acid resin in various solvents is improved, and the preparation of the resin solution in the subsequent application process is facilitated.
In some embodiments, the fluorosulfonic acid resin has a mole percentage content of acrylic monomer in a range of 1.0 to 5.0%, a mole percentage content of perfluoroolefin monomer in a range of 60 to 85%, and a mole percentage content of sulfonyl fluoride vinyl ether monomer in a range of 2 to 15% in a molecule. In the embodiment of the invention, in the copolymerization process of the fluorine-containing sulfonic acid resin, an acrylic monomer is introduced, and the molar content of the acrylic monomer in the prepared sulfonic acid resin is optimized, if the content of the acrylic monomer is too low, the formation of high-concentration ion clusters and/or cluster phases is not facilitated, so that the proton transmission efficiency is not facilitated to be improved, and if the content of the acrylic monomer is too high, the thermal decomposition temperature of the fluorine-containing sulfonic acid resin is sharply reduced due to the too high content of active carboxylic acid, so that the stability of the subsequently prepared ion exchange membrane in the use process is reduced.
In some embodiments, the perfluoroolefin monomer is of the formula:
Figure BDA0003585140290000051
wherein Rf is a perfluorocarbon chain having 1 to 6 carbon atoms.
In some embodiments, the acrylic monomer is of the formula:
Figure BDA0003585140290000052
wherein R1 is alkyl containing 1-3 carbon atoms, and R2 is aromatic ring or alkyl containing 1-3 carbon atoms.
In some embodiments, the sulfonyl fluoride vinyl ether monomer is of the formula:
Figure BDA0003585140290000053
wherein m is an integer of 0 to 3, and n is an integer of 0 to 2.
In some embodiments, the acrylic monomer, the perfluoroolefin monomer and the sulfonyl fluoride vinyl ether monomer are subjected to radical copolymerization reaction at 40-100 ℃ and 1.0-8.0MPa under the initiation of an initiator, and the reaction time is 6-48h; preferably, the initiator comprises AIBN, N 2 F 2 At least one of a persulfate or a perfluoroalkyl peroxide. Further preferably, the copolymerization method is selected from one of emulsion polymerization, solution polymerization or bulk polymerization.
The three polymerization methods are specifically as follows:
(1) Emulsion polymerization: refers to emulsion copolymerization in the water phase. The method comprises the following specific steps: adding deionized water and an emulsifier into a dry and clean reaction kettle according to the amount of the solvent which is 2-10 times of the total mass of the monomers, adding an acrylic monomer, a perfluoroolefin monomer and a sulfonyl fluoride vinyl ether monomer into the reaction kettle according to the molar ratio of 0.5-5; after the reaction is finished, cooling to room temperature, releasing pressure, evaporating to obtain a monomer for the reaction, recovering the solvent to obtain a powdery product, further carrying out methanol extraction on the powdery product for at least 3 times, and drying at 80-120 ℃ for 8-12h to obtain the fluorine-containing sulfonic acid resin with high proton transmission efficiency.
The emulsifier comprises at least one of perfluoroalkyl acid salt, polyoxyethylene ether or fatty acid salt, wherein the perfluoroalkyl acid salt is ammonium perfluorooctanoate or sodium perfluorooctanoate, the polyoxyethylene ether is polyoxyethylene fatty acid ether or nonylphenol polyoxyethylene ether, and the fatty acid salt is sodium fatty acid.
(2) Solution polymerization: means that the radical copolymerization is carried out in a solvent. The method comprises the following specific steps: adding an acrylic monomer, a perfluoroolefin monomer and a sulfonyl fluoride vinyl ether monomer into a dry and clean reaction kettle according to the molar ratio of 0.5-5; adding a solvent into the reaction kettle according to the proportion that the solvent is 3-10 times of the total mass of the monomers, wherein the solvent comprises at least one of a fluorocarbon solvent or fluorochloroalkane; sealing the reaction kettle, introducing nitrogen to remove oxygen, finally pressurizing to 1.0-8.0MPa, heating to 40-100 ℃, pumping in an initiator, controlling the concentration of the initiator to 0.1-5%, wherein the reaction time is 6-48h, adding the initiator in batches according to 2-10 times, and adding the initiator once every 1h of reaction at intervals until the initiator is completely added; after the reaction is finished, cooling to room temperature, releasing pressure, evaporating to obtain a monomer for the reaction, recovering the solvent to obtain a powdery product, further carrying out methanol extraction on the powdery product for at least 3 times, and drying at 80-120 ℃ for 8-12h to obtain the fluorine-containing ion exchange resin with high proton transmission efficiency.
The fluorocarbon solvent comprises at least one of perfluorodimethylcyclobutane, perfluorocyclohexane and perfluoromethylcyclobutane, and the chlorofluoroalkane is 1, 2-trifluoro-1, 2-trifluoroethane. The initiator may be a perfluoroalkanoyl peroxide compound.
(3) Bulk polymerization: means that the monomers undergo free radical copolymerization only under the action of an initiator. The method comprises the following specific steps: adding an acrylic monomer, a perfluoroolefin monomer and a sulfonyl fluoride vinyl ether monomer into a dry and clean reaction kettle according to the molar ratio of 0.5-5; sealing the reaction kettle, introducing nitrogen to remove oxygen, finally pressurizing to 1.0-8.0MPa, heating to 40-100 ℃, pumping in an initiator, controlling the concentration of the initiator to 0.1-5%, wherein the reaction time is 6-48h, adding the initiator in batches according to 2-10 times, and adding the initiator once every 1h of reaction at intervals until the initiator is completely added; after the reaction is finished, cooling to room temperature, releasing pressure, evaporating to obtain a monomer for the reaction, recovering the solvent to obtain a powdery product, further carrying out methanol extraction on the powdery product for at least 3 times, and drying at 80-120 ℃ for 8-12h to obtain the fluorine-containing ion exchange resin with high proton transmission efficiency.
The initiator comprises AIBN, N 2 F 2 At least one of a persulfate or a perfluoroalkyl peroxide.
The embodiment of the invention also provides an ion exchange membrane, which is prepared by adopting the fluorine-containing sulfonic acid resin or the fluorine-containing sulfonic acid resin prepared by the method of the embodiment of the invention. The ion exchange membrane provided by the embodiment of the invention is prepared from the fluorosulfonic acid resin provided by the embodiment of the invention, has all the advantages brought by the fluorosulfonic acid resin provided by the embodiment of the invention, and has excellent mechanical strength, higher proton transmission efficiency and excellent comprehensive performance.
The embodiment of the invention also provides application of the ion exchange membrane in preparation of fuel cells, chlor-alkali electrolytic cells or electrolytic cells for hydrogen production by water electrolysis.
The present invention will be described in detail below with reference to examples and the accompanying drawings.
EXAMPLE 1 emulsion polymerization
Cleaning and drying the inner wall and the kettle cover of the reaction kettle, weighing 0.4780g of ammonium perfluorooctanoate, adding into 123.41g of deionized water, stirring and emulsifying at 800rpm for 0.5h, and transferring into the reaction kettle; then 2.9632g (0.02 mol) of 3-phenyl-2-propenoic acid (C) were weighed out separately 9 H 8 O 2 ) 27g (0.06 mol) of hexafluoropropylene trimer and 17.84g (0.04 mol) of perfluoro-2- (2-sulfuryl fluoroethyl) propyl vinyl ether (CF) 2 ＝CFOCF 2 CFCF 3 OCF 2 CF 2 CF 2 SO 2 F) Sequentially adding the mixture into a reaction kettle; sealing the reaction kettle, introducing high-purity nitrogen through an air inlet and an air outlet of the reaction kettle to remove oxygen for multiple times, finally pressurizing to 2.5MPa, starting a stirrer to adjust the rotating speed to 500rpm, and heating to 80 ℃; meanwhile, 0.2868g of ammonium persulfate initiator is weighed, stirred and dissolved in 20g of deionized water, after the temperature is stabilized to 80 ℃, 1/4 of initiator solution is pumped into the reaction kettle, and 1/4 of initiator solution is pumped every 1 hour subsequently until the initiator solution is completely added; after the initiator is added, continuing to react for 8 hours; stopping heating, naturally cooling to room temperature, releasing pressure, opening the kettle, transferring the materials into deionized water and absolute ethyl alcohol for soaking and washing, performing suction filtration, transferring into a 100 ℃ oven, and dryingAfter drying for 8 hours, about 17.31g of resin powder was obtained.
Via FTIR and 19 F-NMR joint characterization proves that the polymer has a ternary polymerization structure; meanwhile, other parameters of the polymer are characterized, specifically as follows: in FTIR spectrum, 1744 and 1703cm -1 Free and dimeric C = O extensional vibration absorption peaks, respectively; 1467cm -1 Is the vibration absorption peak of S = O in sulfonyl fluoride; 1200 and 1141cm -1 Is the vibration absorption peak of CF in the skeleton; 980cm -1 Is CF 3 Vibration absorption peak of (1); the thermal decomposition temperature (T) of the polymer was also measured d Temperature point corresponding to 5% mass loss) and melt mass flow rate were 323.5 deg.C (N) 2 Atmosphere, 10 ℃/min) and 27.1g/10min (250 ℃,2.16 Kg).
Of the resin obtained in this example, 3-phenyl-2-propenoic acid (C) 9 H 8 O 2 ) The molar content of the monomer was about 4.3%, the molar content of the hexafluoropropylene trimer monomer was about 81.6%, and the molar content of the perfluoro-2- (2-sulfuryl fluoroethyl) propyl vinyl ether monomer was about 14.1%.
And (3) sodium modification test: weighing 1.5g of the resin prepared in the embodiment and the commercial perfluorosulfonyl fluoride resin respectively, stirring and soaking the resin and the commercial perfluorosulfonyl fluoride resin in 50mL of 1.0mol/L NaOH aqueous solution at 80 ℃, filtering the solution after 12h, soaking and washing the solution with deionized water to be neutral, drying and grinding the solution, and then carrying out KBr tabletting, wherein under the same Na condition, a relatively obvious sulfonyl fluoride characteristic absorption peak (namely 1470 cm) still exists in an infrared spectrogram of the commercial sulfonyl fluoride resin -1 Left and right), and the infrared spectrum of the resin prepared by the implementation does not have the peak; meanwhile, during the Na treatment, the swelling rate and/or swelling degree of the fluorosulfonic acid resin containing carboxylic acid groups of the present example can be observed to be more obvious. The resin prepared in the example was tested to convert it to Na type resin in 1.0mol/L aqueous NaOH for 12h, commercial resin in 1.0mol/L aqueous NaOH for 30h, and commercial resin in 2.0mol/L aqueous NaOH for 16h. It can be seen that this example significantly reduces the transformation time and NaOH concentration of the resin upon sodium modification by introducing carboxylic acid groups.
To make the book solidThe resin powder prepared in the example is slightly stirred and soaked in 1.0mol/L NaOH aqueous solution at 80 ℃ for 12H, then is converted into sodium type resin, filtered, soaked and washed by deionized water to be neutral, and then transferred to 1.0mol/L H 2 SO 4 And stirring and soaking the mixture in the aqueous solution at room temperature for 12 hours to obtain the H-type fluorosulfonic acid resin. The H-type resin is dissolved to prepare an ion exchange membrane, the microstructure of the H-type resin is represented by a TEM after aging for 2 days at room temperature to obtain a TEM image, as shown in FIG. 1, and black particles in the TEM image can be obviously seen to be ion clusters and/or cluster-phase aggregated particles with the diameters of 3-25 nm.
The ion exchange membrane prepared from the resin of this example was subjected to conductivity test (90 ℃, RH 95%) to determine its ionic conductivity to be 183mS cm 1 (ii) a The mechanical property test of the ion exchange membrane is carried out, the tensile strength is 18.2MPa, the tensile strength of the commercial ion exchange membrane is 13.7MPa, and compared with the commercial ion exchange membrane, the tensile strength of the ion exchange membrane prepared by the embodiment is improved by 32.8%.
EXAMPLE 2 solution polymerization
The inner wall and the cover of the reaction kettle are cleaned and dried, and 2.9632g (0.02 mol) of 3-phenyl-2-acrylic acid (C) are weighed 9 H 8 O 2 ) 27g (0.06 mol) of hexafluoropropylene trimer and 17.84g (0.04 mol) of perfluoro-2- (2-sulfurylfluoroethyl) propyl vinyl ether (CF) 2 ＝CFOCF 2 CFCF 3 OCF 2 CF 2 CF 2 SO 2 F) Sequentially adding the mixture into a reaction kettle containing 121g of perfluoromethylcyclobutane; sealing the reaction kettle, introducing high-purity nitrogen through an air inlet and an air outlet of the reaction kettle to remove oxygen for multiple times, finally pressurizing to 2.5MPa, starting a stirrer to adjust the rotating speed to be 500rpm, and heating to 80 ℃; meanwhile, 0.2868g of perfluoropropanoyl peroxide compound initiator is weighed, stirred and dissolved in 20g of perfluoromethylcyclobutane, 1/4 of initiator solution is pumped into the reaction kettle after the temperature is stabilized to 80 ℃, and 1/4 of initiator solution is pumped every 1 hour until the initiator solution is completely added; after the initiator is added, continuing to react for 8 hours; and then stopping heating, naturally cooling to room temperature, releasing pressure, opening the kettle, transferring the materials into deionized water and absolute ethyl alcohol for soaking and washing, performing suction filtration, transferring into a 100 ℃ drying oven, and drying for 8 hours to obtain about 14.1g of resin powder.
Via FTIR and 19 F-NMR joint characterization proves that the polymer has a ternary polymerization structure; at the same time, other parameters of the polymer were characterized: thermal decomposition temperature (T) d Temperature point corresponding to 5% mass loss) and melt mass flow rate were 312.1 deg.C (nitrogen atmosphere, 10 deg.C/min) and 29.4g/10min (250 deg.C, 2.16 Kg), respectively.
Of the resin obtained in this example, 3-phenyl-2-propenoic acid (C) 9 H 8 O 2 ) The molar content of the monomer was 3.9%, the molar content of hexafluoropropylene trimer monomer was 83.2%, and the molar content of perfluoro-2- (2-sulfuryl fluoroethyl) propyl vinyl ether monomer was 12.9%.
An ion exchange membrane prepared from the resin of this example was subjected to conductivity measurement (90 ℃, RH 95%) to determine an ionic conductivity of 178.8mS cm 1 (ii) a The mechanical property test is carried out on the ion exchange membrane, and the tensile strength is 17.9MPa.
Example 3 bulk polymerization
The inner wall and the cover of the reaction vessel were cleaned and dried, and 27g (0.06 mol) of hexafluoropropylene trimer and 17.84g (0.04 mol) of perfluoro-2- (2-sulfuryl fluoroethyl) propyl vinyl ether (CF) were weighed 2 ＝CFOCF 2 CFCF 3 OCF 2 CF 2 CF 2 SO 2 F) And 2.9632g (0.02 mol) of 3-phenyl-2-propenoic acid (C) 9 H 8 O 2 ) Sequentially adding the materials into a reaction kettle in sequence, and then adding 0.2868g of perfluoropropanoyl peroxide compound initiator; sealing the reaction kettle, introducing high-purity nitrogen through an air inlet and an air outlet of the reaction kettle to remove oxygen for multiple times, finally pressurizing to 2.5MPa, starting a stirrer to adjust the rotating speed to 500rpm, and heating to 80 ℃; reacting for 12h; and then stopping heating, naturally cooling to room temperature, releasing pressure, opening the kettle, transferring the materials into deionized water and absolute ethyl alcohol for soaking and washing, carrying out suction filtration, transferring into a 100 ℃ drying oven, and drying for 8 hours to obtain about 14.8g of resin powder.
Via FTIR and 19 F-NMR joint characterization proves that the polymer has a ternary polymerization structure; at the same time, other parameters of the polymer were characterized: thermal decomposition temperature (T) d Corresponding to a mass loss of 5%Temperature point) and melt mass flow rate of 321.3 deg.C (N) 2 Atmosphere, 10 ℃/min) and 29.0g/10min (250 ℃,2.16 Kg).
Of the resin obtained in this example, 3-phenyl-2-propenoic acid (C) 9 H 8 O 2 ) The molar content of the monomer was 4.1%, the molar content of the hexafluoropropylene trimer monomer was 82.3%, and the molar content of the perfluoro-2- (2-sulfuryl fluoroethyl) propyl vinyl ether monomer was 13.6%.
The ion exchange membrane prepared by the resin of the embodiment is subjected to conductivity test (90 ℃, RH95 percent) to obtain the ion conductivity of 180mS cm 1 (ii) a The mechanical property test is carried out on the ion exchange membrane, and the tensile strength is 18.1MPa.
Comparative example 1
The same procedure as in example 1 was conducted, except that the molar content of 3-phenyl-2-propenoic acid units in the resin obtained was 8.0%.
The resin prepared in comparative example 1 was slightly yellowish, FTIR and 19 F-NMR joint characterization proves that the polymer has a ternary polymerization structure; meanwhile, other parameters of the polymer are characterized, specifically: FTIR spectra of 1744 and 1703cm -1 Free and dimeric C = O extensional vibration absorption peaks, respectively; 1467cm -1 Is the vibration absorption peak of S = O in sulfonyl fluoride; 1200 and 1141cm -1 Is the vibration absorption peak of CF in the skeleton; 980cm -1 Is CF 3 Vibration absorption peak of (2); the thermal decomposition temperature (T) of the polymer was also measured d Temperature point corresponding to 5% mass loss) and melt mass flow rate were 248.5 deg.C (N) 2 Atmosphere, 10 ℃/min) and 29.0g/10min (250 ℃,2.16 Kg). Since the thermal decomposition temperature of the resin prepared in comparative example 1 was only 248.5 c, which is significantly lower than 323.5 c of example 1, long-term durability could not be secured after applying it to an ion exchange membrane.
Comparative example 2
The same procedure as in example 1 except that 3-phenyl-2-propenoic acid was not added.
Via FTIR and 19 combined characterization by F-NMR, characteristic of the presence of only sulfonyl fluoride in the infraredAbsorption Peak (i.e. 1467 cm) -1 Is the vibration absorption peak of S = O in sulfonyl fluoride); at the same time, 1200 and 1141cm -1 Is the vibration absorption peak of CF in the skeleton; 980cm -1 Is CF 3 Vibration absorption peak of (1); the thermal decomposition temperature (T) of the polymer was also measured d Temperature point corresponding to 5% mass loss) and the melt mass flow rate were 341.8 deg.C (N) 2 Atmosphere, 10 ℃/min) and 27.0g/10min (250 ℃,2.16 Kg).
The resin powder prepared in comparative example 2 was slightly stirred in 1.0mol/L NaOH aqueous solution at 90 ℃ and soaked for 48 hours, then converted into sodium form, filtered and washed with deionized water to neutrality, and then transferred to 1.0mol/L H 2 SO 4 And stirring and soaking the mixture in the aqueous solution at room temperature for 48 hours to obtain the H-type fluorosulfonic acid resin. Dissolving the H-type resin to prepare an ion exchange membrane, and performing conductivity test (90 ℃, RH 95%) on the membrane to obtain the ion conductivity of 143mS cm 1 (ii) a Meanwhile, the film was subjected to a mechanical property test and the tensile strength was 18.6MPa.
And (3) testing the dissolving capacity:
0.5g of the H-type resin obtained in example 1 and comparative example 2 was taken out, and the resin was left to stand and immersed in 20mL of a water-alcohol (1/1 v/v) (one or more of ethanol, isopropanol and n-butanol) mixed solvent at a constant temperature of 60 ℃ to dissolve the resin in the solvent shown in Table 1.
TABLE 1
Figure BDA0003585140290000101
As can be seen from table 1, in the examples of the present invention, the solubility of the resin is significantly improved by introducing a certain amount of carboxylic acid pendant groups into the resin structure.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A fluorine-containing sulfonic acid resin is characterized in that the molecular structural formula is as follows:
Figure FDA0003585140280000011
wherein x, y and z are integers from 1 to 100, m is an integer from 0 to 3, and n is an integer from 0 to 2; r1 is C1-3 alkyl, R2 is aromatic ring or C1-3 alkyl, and Rf is C1-6 perfluorocarbon chain; the end group of the main chain of the fluorine-containing sulfonic acid resin molecule is fluorine-containing alkane, perfluorosulfonyl fluoride and-CF 2 H or perfluoroalkenyl, said perfluoroalkenyl comprising a linear alkane or a branched alkane containing 1 to 6 carbons.
2. The method for preparing fluorosulfonic acid resin according to claim 1, wherein said fluorosulfonic acid resin is prepared by copolymerizing acrylic monomers, perfluoroolefin monomers, and sulfonyl fluoride vinyl ether monomers.
3. The method for preparing fluorosulfonic acid-containing resin according to claim 2, wherein the molar percentage content of acrylic monomers in the molecules of fluorosulfonic acid-containing resin is 1.0-5.0%, the molar percentage content of perfluoroolefin monomers is 60-85%, and the molar percentage content of sulfonyl fluoride vinyl ether monomers is 2-15%.
4. The method of claim 2, wherein the perfluoroolefin monomer has the structural formula:
Figure FDA0003585140280000012
wherein Rf is a perfluorocarbon chain having 1 to 6 carbon atoms.
5. The method for producing fluorosulfonic acid-containing resin according to claim 2, wherein the acrylic monomer has a structural formula:
Figure FDA0003585140280000013
wherein R1 is alkyl containing 1-3 carbon atoms, and R2 is aromatic ring or alkyl containing 1-3 carbon atoms.
6. The method for preparing fluorosulfonic acid-containing resin of claim 2, wherein said sulfonyl fluoride vinyl ether monomer has a structural formula:
Figure FDA0003585140280000021
wherein m is an integer of 0 to 3, and n is an integer of 0 to 2.
7. The method for preparing fluorosulfonic acid-containing resin of claim 2, wherein the acrylic monomer, perfluoroolefin monomer and sulfonyl fluoride vinyl ether monomer are subjected to radical copolymerization at 40-100 ℃ and 1.0-8.0MPa under the initiation of an initiator for 6-48h.
8. The method of claim 2, wherein the copolymerization method is one selected from emulsion polymerization, solution polymerization, and bulk polymerization.
9. An ion exchange membrane produced by using the fluorosulfonic acid resin according to claim 1 or the fluorosulfonic acid resin produced by the method according to any one of claims 2 to 8.
10. Use of the ion-exchange membrane of claim 9 in the manufacture of a fuel cell, a chlor-alkali cell or a water electrolysis hydrogen production cell.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4357218A (en) * 1974-03-07 1982-11-02 Asahi Kasei Kogyo Kabushiki Kaisha Cation exchange membrane and use thereof in the electrolysis of sodium chloride
CN101693215A (en) * 2009-10-26 2010-04-14 山东东岳神舟新材料有限公司 Preparation and application of fluororesins with low ion exchange capacity
CN101757860A (en) * 2009-11-13 2010-06-30 山东东岳高分子材料有限公司 Ion exchange membrane with interpenetrating network structure and preparation method thereof
CN114213569A (en) * 2021-11-22 2022-03-22 浙江巨化技术中心有限公司 Suspension polymerization preparation method of perfluorosulfonic acid resin

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4357218A (en) * 1974-03-07 1982-11-02 Asahi Kasei Kogyo Kabushiki Kaisha Cation exchange membrane and use thereof in the electrolysis of sodium chloride
CN101693215A (en) * 2009-10-26 2010-04-14 山东东岳神舟新材料有限公司 Preparation and application of fluororesins with low ion exchange capacity
CN101757860A (en) * 2009-11-13 2010-06-30 山东东岳高分子材料有限公司 Ion exchange membrane with interpenetrating network structure and preparation method thereof
CN114213569A (en) * 2021-11-22 2022-03-22 浙江巨化技术中心有限公司 Suspension polymerization preparation method of perfluorosulfonic acid resin

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