CN118165162A - Breathable fluorine-containing ion exchange resin dispersion liquid and preparation method thereof - Google Patents

Breathable fluorine-containing ion exchange resin dispersion liquid and preparation method thereof Download PDF

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CN118165162A
CN118165162A CN202410230517.3A CN202410230517A CN118165162A CN 118165162 A CN118165162 A CN 118165162A CN 202410230517 A CN202410230517 A CN 202410230517A CN 118165162 A CN118165162 A CN 118165162A
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ion exchange
resin dispersion
fluorine
resin
exchange resin
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张永明
王丽
张恒
邹业成
丁涵
李志勇
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Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
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Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
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    • 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

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Abstract

The invention belongs to the field of high polymer materials, and relates to a breathable fluorine-containing ion exchange resin dispersion liquid and a preparation method thereof, wherein the micelle particle size of the resin dispersion liquid is 145-210 nm, the uniform and stable advantage is achieved, and the use temperature of a catalytic layer prepared by the dispersion liquid can be expanded from-30 ℃ to 85 ℃ to-30 ℃ to 150 ℃. The fluorine-containing ion exchange resin structure introduces a part of heterocycle, and the heterocycle has larger steric hindrance, so that the crystallinity of the polymer is reduced, the air permeability is increased, the fluorine-containing ion exchange resin is particularly suitable for being applied to catalyst coating resin, the impedance of a catalytic layer can be effectively reduced, and the performance of a fuel cell is improved.

Description

Breathable fluorine-containing ion exchange resin dispersion liquid and preparation method thereof
The application is a divisional application based on application with application number 202211276153.X (application date 2022-10-18, the name of which is breathable fluorine-containing ionic polymer and a preparation method thereof).
Technical Field
The invention belongs to the field of fluorine-containing high polymer materials, and relates to a breathable fluorine-containing ion exchange resin dispersion liquid and a preparation method thereof.
Background
The perfluorosulfonic acid ion exchange resin was successfully developed from dupont in the seventies of the last century, and has high chemical stability in strong acid and strong alkali, and can conduct ions, thus being applied to the fields of chlor-alkali industry and proton exchange membrane fuel cells. An extensive report of the properties of perfluorosulfonic acid ion exchange resins is found in the DuPont's earlier patents, such as U.S. Pat. No. 3, 4433082A, which is a synthetic process employing the copolymerization of tetrafluoroethylene monomer with perfluorovinyl ether containing sulfonyl fluoride. Other vinyl ether monomers with sulfonyl fluoride are also used for copolymerization, for example, the preparation of fluorosulfonic resins by copolymerizing a short-side perfluorosulfonyl fluoride monomer with a fluorovinyl monomer such as tetrafluoroethylene is reported in US4358545A by DOW chemical company. The polymerization process and the post-treatment process of this perfluorosulfonic acid ion exchange resin polymer are described in more detail in U.S. Pat. No. 3, 8680209B2, incorporated by Dain Kogyo and Asahi Kabushiki Kaisha.
When perfluorosulfonic acid ion exchange resins are used as fuel cells, one of the key requirements of membrane electrodes formed from ion exchange membranes and catalyst layers is chemical stability and resistance of the electrode catalyst to carbon monoxide (CO) poisoning. Currently, most fuel cell membrane electrodes operate at temperatures between 25 and 80 c and poisoning of the catalyst layer of the membrane electrode occurs in environments where CO levels reach 10 ppm. In order to solve the difficulties existing in the membrane electrode of the current fuel cell, such as improving the activity and the utilization rate of the catalyst, enhancing the CO poisoning resistance of the catalyst layer of the membrane electrode, etc., an effective solution is to increase the working temperature of the fuel cell, and when the working temperature exceeds 100 ℃, the tolerance of the catalyst in the membrane electrode to CO can be increased to about 1000 ppm. However, after the working temperature of the existing fuel cell membrane is increased to be more than 100 ℃, the water retention of the membrane is greatly reduced, and the proton conductivity is obviously reduced, for example, when the working temperature is high at 120 ℃, the proton conductivity is far lower than 0.01S/cm, and the requirement of ion conduction cannot be met. The development of the high-temperature proton exchange membrane can better improve the efficiency of the fuel cell, reduce the cost of a cell system and be more suitable for the commercialization requirement of the fuel cell.
At present, related patent reports about ion exchange membranes in membrane electrodes of high-temperature fuel cells exist, for example, chinese patent CN101768236A reports that perfluorinated ion exchange resins are prepared by multi-component copolymerization of tetrafluoroethylene, sulfonyl fluoride olefin ether monomers with short side groups with two different structures and phosphonate side group olefin ether monomers, and have higher high-temperature proton conduction, but the high-temperature catalyst coating resin matched with the perfluorinated ion exchange resins does not meet the air permeability required by catalyst coatings.
Disclosure of Invention
The invention aims to solve the problems that the prior perfluorosulfonic acid resin is difficult to keep water and further difficult to conduct protons due to high temperature when the temperature of the prior perfluorosulfonic acid resin is higher than 100 ℃, and the resin still has proton conductivity under high temperature is required to be provided for widening the service temperature of the perfluorosulfonic acid resin. The invention also aims to solve the problem that the prior perfluorinated sulfonic acid resin has poor air permeability when used for a catalyst coating.
The above object of the present invention is achieved by the following technical scheme:
a high-permeability fluorine-containing ionic polymer containing ion exchange groups has the following structural formula:
Wherein a, b, c are each independently an integer from 1 to 20, a ', b ', c ' are each independently an integer from 1 to 3, k is an integer from 1 to 3, f is an integer from 1 to 4, preferably k=1, f=1; t is an integer from 1 to 3, v is an integer from 1 to 4, preferably t=1 to 2, v=1; x/(x+y+z) =0.1 to 0.8, y/(x+y+z) =0.1 to 0..7,z/(x+y+z) =0.2 to 0.8, where R is- (OCF 2)i(CF2) jX, X is Cl or F, i=0 to 1, j=0 to 1; p is 2 or 3. Preferably R is F, cl or CF 3.
R1 isR f1 is/>
Wherein m and n are integers of 0 to 4, and m and n are not 0 at the same time.
The high-permeability fluorine-containing ion-exchange group-containing polymer is formed by quaternary copolymerization of fluorine-containing olefin monomer, long-chain perfluoro vinyl ether monomer with phosphonate, long-chain perfluoro vinyl ether monomer with sulfonyl fluoride and perfluoro heterocyclic olefin monomer, wherein the long-chain perfluoro vinyl ether monomer with phosphonate is selected from but not limited to the structures and derivatives thereof shown in the following formula (I):
where k is an integer from 1 to 3, f is an integer from 1 to 4, preferably k=1, f=1, p=1-2.
Preferably, the process for preparing a highly breathable fluoropolymer containing ion exchange groups wherein the perfluorovinyl ether monomer bearing sulfonyl fluoride is selected from, but not limited to, the structures listed in the following figure (II) and derivatives thereof:
Where t is an integer from 1 to 3 and v is an integer from 1 to 4, preferably t=1 to 2 and v=1.
Preferably, the method for preparing the high gas permeability type fluorine-containing ionic polymer containing ion exchange groups, wherein the perfluorinated heterocyclic olefin monomer is a perfluorinated heterocyclic olefin monomer with sulfonyl fluoride groups and is selected from but not limited to the structures listed in formula (III) and derivatives thereof:
wherein R 11 is CF 2 =c <, or-cf=cf-; r f1 is Wherein m and n are integers of 0 to 4, and m and n are not 0 at the same time.
The fluorine-containing ionic polymer obtained by the invention comprises the following components in percentage by mole: 50-80% of fluorine-containing olefin units, 20-10% of long-chain perfluoro vinyl ether polymer units with phosphonate, 20-5% of long-chain perfluoro vinyl ether polymer units with sulfonyl fluoride and 10-5% of perfluoro heterocyclic olefin polymer units.
A high-permeability fluorine-containing ionic polymer containing ion exchange groups can be prepared by solution polymerization, emulsion polymerization and dispersion polymerization. Comprises the steps of carrying out copolymerization reaction on fluoroolefin monomer, phosphonate long-chain perfluorinated vinyl ether monomer, sulfonyl fluoride long-chain perfluorinated vinyl ether monomer and sulfonyl fluoride group-containing perfluorinated heterocyclic olefin monomer under the action of an initiator, wherein the reaction time of the polymerization reaction is 1-24 hours, the reaction temperature is 20-90 ℃, and the reaction pressure is 0.1-10 MPa; preferably, the reaction time of the polymerization reaction is 6 to 12 hours, the reaction temperature is 30 to 60 ℃, and the reaction pressure is 0.2 to 0.6MPa.
Preferably, the initiator is selected from oil-soluble initiators, and one or more of N 2F2, peroxides, perfluoroalkyl peroxides, azo compounds and redox initiation systems can be selected.
Further preferably, the perfluoroalkyl peroxide is a perfluoropropionyl peroxide, a 3-chlorofluoropropionyl peroxide, a perfluoromethoxy acetyl peroxide,-H-perfluorobutyryl peroxide,/>-SO 2 F-perfluoro-2, 5, 8-trimethyl-3, 6, 9-trioxa-undecyl peroxide 、CF3CF2CF2CO-OO-COCF2CF2CF3、CF3CF2CF2OCFCF3CO-OO-COCFCF3OCF2CF2CF3、CF3CF2CH2CO-OO-COCH2CF2CF3 or CF 3OCF2CF2CO-OO-COCF2CF2OCF3.
The preparation method comprises a solution polymerization preparation method, wherein the mass percentage concentration of a fluorine-containing solvent in a polymerization system is 80-90%, the mass percentage concentration of a long-chain perfluorinated vinyl ether monomer with phosphonate in the solvent is 1-10%, the mass percentage concentration of a long-chain perfluorinated vinyl ether monomer with sulfonyl fluoride in the solvent is 1-20%, and the mass percentage concentration of a perfluorinated heterocyclic olefin monomer in the solvent is 1-10%.
The preparation method comprises the step of performing emulsion polymerization reaction in a water phase, wherein in the step of emulsion polymerization reaction, the mass percentage concentration of an emulsifier in water is 0.01-5%, the mass percentage concentration of a perfluoro vinyl ether monomer with long chain sulfonyl fluoride in the water phase is 1-10%, the mass percentage concentration of a perfluoro vinyl ether monomer with phosphonate in the water phase is 1-35%, the mass percentage concentration of a perfluoro heterocyclic olefin monomer in the water phase is 1-5%, and fluorine-containing olefin monomers and derivatives are continuously introduced in a gas phase state.
In the emulsion polymerization step, the emulsifier is selected from anionic emulsifiers, including, for example, sodium fatty acid, sodium lauryl sulfate, sodium alkyl sulfonate, sodium alkylaryl sulfonate; nonionic emulsifiers, for example alkylphenol polyether alcohols, such as one or more of nonylphenol polyoxyethylene ether, polyoxyethylene fatty acid ether; and reactive self-emulsifying agents perfluorosulfonates, perfluorophosphates or perfluorocarboxylates, such as potassium perfluorovinyl ether sulfonate, ammonium perfluorovinyl ether phosphonate, and the like. Sodium dodecyl benzene sulfonate and nonylphenol polyoxyethylene ether NP-10 are preferred.
The invention also provides a sulfonic acid resin which has high proton conductivity and high gas permeability at high and low temperatures, is suitable for the field of fuel cells, and is particularly suitable for catalyst coating resins.
The structural formula is as follows:
Wherein a, b, c are integers from 1 to 20, a ', b ', c ' are integers from 1 to 3, k is an integer from 0 to 3, f is an integer from 1 to 4, preferably k=1, f=2; t is an integer from 0 to 3, v is an integer from 1 to 4, preferably t=1, v=2.
X/(x+y+z) =0.1 to 0.8, y/(x+y+z) =0.1 to 0.7, and z/(x+y+z) =0.2 to 0.8, wherein R is- (OCF 2)i(CF2)j X, X
Is Cl or F, i is 0-2, j is 0-2; preferably R is F, cl or CF 3.
R 1 isR f is/>
Wherein m and n are integers of 0 to 4, and m and n are not 0 at the same time.
The sulfonic acid resin (V) is obtained by chemically treating the fluorine-containing ionic polymer shown in the formula (IV), wherein the chemical treatment method is to firstly convert sulfonyl fluoride and phosphonate groups of the fluorine-containing ionic polymer shown in the formula (IV) into alkali groups by alkali, and then react with strong acid to convert into hydrogen-type ionic groups.
Preferably, the alkali can be alkali metal salt, weak base or organic base, and the strong acid is nitric acid, sulfuric acid, hydrochloric acid and other common strong acid or mixed solution of strong acids. Preferably, the concentration of the strong acid used is 5 to 30%.
Further preferably, when alkali metal salt is selected as alkali metal salt, it may be lithium hydroxide, sodium hydroxide or potassium hydroxide, preferably the alkali metal salt is present in the solution in a concentration of 1 to 50% by mass, more preferably it may be heated during the transformation, and even more preferably the heating temperature is 25 to 95 ℃.
Preferably, when the alkali is weak base or organic base, it may be ammonia water, ferric hydroxide, copper hydroxide, sodium methoxide, potassium ethoxide, etc., preferably the weak base is 1-30% by mass concentration in the solution, more preferably it may be heated during transformation, and even more preferably the heating temperature is 25-95 ℃.
More preferably, the reaction time of the transformation reaction is 24 to 96 hours. Wherein the alkali treatment time is 6-48, and the acid treatment time is 48-96 hours.
The invention provides a gas permeable fluorine-containing ion exchange resin dispersion liquid, which aims to improve the speed of gas reaching internal catalyst particles and improve the utilization efficiency of a catalyst.
The above object of the present invention is achieved by the following technical scheme:
the invention provides a breathable fluorine-containing ion exchange resin dispersion liquid, which comprises a breathable fluorine-containing ion exchange resin (formula V), water and an organic solvent.
The organic solvent is one or more of proton organic solvents such as methanol, ethanol, N-propanol, isopropanol, butanol, glycerin and the like or aprotic solvents such as N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), N-methylpyrrolidine copper and the like. When the organic solvent is mixed in a plurality of kinds, the organic solvents may be mixed in any ratio.
The total content of the fluorine-containing ion exchange resin in the resin dispersion is 2% to 50%, more preferably 5% to 40%, still more preferably 10% to 30%; particularly preferably 15 to 25%.
The total content of pure water in the resin dispersion is 5% to 95%, preferably 15% to 75%.
The total content of organic solvents in the resin dispersion is 2.5% to 87.5%, preferably 5% to 75%. Particularly preferably 20 to 50%.
The mass ratio of the organic solvent to water in the resin dispersion is 1:15-15:1, preferably 1:10-10:1, more preferably 1:8-8:1. Most preferably 1:5 to 5:1. More preferably 1:1 to 2.
The invention provides a preparation method of the perfluorosulfonic acid phosphoric acid resin dispersion liquid, which comprises the steps of firstly adding a mixed solvent of water and an organic solvent under the condition that the concentration of total solid components is 2% -50% to obtain a composition; heating and stirring for 1-12 hours at 50-250 ℃ under the conditions of an autoclave and inert gas environment to obtain ionomer solution, and concentrating the ionomer solution to obtain resin dispersion liquid with target composition.
Preferably, the inert gas is selected from one of nitrogen, argon or xenon, more preferably nitrogen.
Preferably, the pressure is 1-10MPa. Preferably, the temperature is 170 to 230 ℃.
Preferably, the concentration method includes a method of evaporating the solvent by heating, concentrating under reduced pressure, and the like.
The catalytic layer prepared from the perfluorinated sulfonic acid resin dispersion liquid has high proton conductivity, high exchange capacity and high air permeability, and effectively improves the utilization efficiency of a catalyst.
One or more technical schemes provided by the specific embodiments of the invention have at least the following beneficial effects:
1. The invention adopts fluoroolefin monomer, long-chain perfluorovinyl ether monomer with phosphonate, long-chain perfluorovinyl ether monomer with sulfonyl fluoride and fluoroheterocycle olefin monomer for quaternary copolymerization, wherein the fluoroolefin monomer forms a polymer main chain to provide stability under severe environment, and the phosphoric acid type ionic group and two sulfonic acid type ionic groups are combined to provide ion conductivity and gas permeability at different temperatures. By means of the combination of the four monomers, the high-temperature proton conductivity of the resin is particularly improved, so that the polymer is particularly suitable for catalyst coating resin in the field of fuel cells, particularly suitable for catalyst coating matched with a high-temperature proton exchange membrane, and particularly suitable for proton exchange membranes reported by CN 101768236A.
2. The perfluorinated ion exchange resin has wide working area, the use temperature of the ion exchange resin commonly used in the prior art is between-30 and 85 ℃, and the perfluorinated ion exchange resin expands the temperature from-30 to 85 ℃ to-30 to 150 ℃.
3. The invention provides a breathable fluorine-containing ion exchange resin dispersion liquid, and the use temperature of a catalytic layer prepared by the dispersion liquid can be expanded from-30 ℃ to 85 ℃ to-30 ℃ to 150 ℃. The fluorine-containing ion exchange resin structure introduces a part of heterocycle, and the heterocycle has larger steric hindrance, so that the crystallinity of the polymer is reduced, the air permeability is increased, the fluorine-containing ion exchange resin is particularly suitable for being applied to catalyst coating resin, the impedance of a catalytic layer can be effectively reduced, and the performance of a fuel cell is improved. The micelle particle size of the resin dispersion is 145-210 nm, and the resin dispersion is uniform and stable.
Drawings
Embodiments of the present invention will be described in detail below with reference to the attached drawings:
FIG. 1 is a Fourier transform infrared spectrum of the F-1 polymer prepared in example 1;
FIG. 2 is a Fourier transform infrared spectrum of the F-2 polymer prepared in example 2;
FIG. 3 is a Fourier transform infrared spectrum of the F-3 polymer prepared in example 3;
FIG. 4 is a Fourier transform infrared spectrum of the F-4 polymer prepared in example 4;
FIG. 5 is a nuclear magnetic F-spectrum of the F-1 polymer prepared in example 1;
FIG. 6 is a nuclear magnetic F-spectrum of the F-2 polymer prepared in example 2;
FIG. 7 is a nuclear magnetic F-spectrum of the F-3 polymer prepared in example 3;
FIG. 8 is a nuclear magnetic F-spectrum of the F-4 polymer prepared in example 4;
Fig. 9 is a membrane electrode polarization curve.
Detailed Description
The following examples are further illustrative of the invention, which is not limited thereto. The reaction kettles used in the examples were all 10L stainless steel high-pressure reaction kettles, equipped with temperature sensors, pressure sensors, heating circulation systems, cooling circulation systems, stirring motors, internal cooling water pipes, liquid metering pumps, gas feed valves, liquid feed valves, and material discharge valves in the reaction kettles, unless otherwise specified.
The ion exchange capacity is the result of measurement of the sulfonic acid resin (formula V) which is converted from sulfonyl fluoride to sulfonic acid and from phosphonate to phosphoric acid unless otherwise specified in the examples below.
The embodiment is not specifically described, and the percentage content is mass percentage.
The perfluoroalkyl initiators used in the synthesis of the present invention can be prepared according to techniques known in the art, the preparation methods recommended in the present invention are described in j. Org. Chem.,1982, 47 (11): 2009-2013.
The perfluorinated vinyl ether monomers with phosphonate used in the synthesis process of the present invention may be prepared according to techniques known in the art, the preparation methods recommended in the present invention are described in Yamabe M,Akiyama K,Akatsuka Y,et al.Novel phosphonated perfluorocarbon polymers[J].European Polymer Journal,2000,36(5):1035-1041 and Danilich M J,Burton D J,Marchant R E.Infrared study of perfluorovinylphosphonic acid,perfluoroallylphosphonic acid,and pentafluoroallyldiethylphosphonate[J].1995,9(3):229-234.
The perfluorinated heterocyclic olefin monomers used in the synthesis process of the present invention may be found in the preparation methods of US20060099476A1, US20090048424 and US 7799468. The potassium persulfate, ammonium persulfate, N 2F2 gas and FC-40 adopted in the synthesis process can be all purchased. The comonomer fluorine-containing alkene adopted in the synthesis process is purchased from Shandong the Eastern Mountain high molecular material Co., ltd; the perfluorovinyl ether sulfonyl fluoride monomer adopts Chinese patent application number: CN 201810798170.7, a process for the preparation.
Example 1
The structural formula of the perfluorocyclopentene monomer (C 5O4F8 S) is:
The reaction kettle is cleaned, 5.0L of deionized water, 100g of sodium dodecyl benzene sulfonate and 125g of nonylphenol polyoxyethylene ether NP-10 emulsifier are added, a stirring device is started, high-purity nitrogen is pumped into vacuum to replace for three times, and after the oxygen content in the reaction kettle is tested to be below 1ppm, the vacuum is pumped. 980g of the long-chain perfluorovinyl ether monomer (CF 2CFOCF2CF3CFOCF2SO2 F) having a sulfonyl fluoride, 325g of the long-chain perfluorovinyl ether monomer (CF 2CFOCF2CFCF3OCF2PO(OC2H3)2) having a phosphonate, and 3) 200g of the perfluorocyclopentene monomer (C 5O4F8 S) were added to the reaction through a liquid feed valve. Tetrafluoroethylene monomer is filled into a reaction kettle until the pressure is 1.6MPa, the temperature is raised to 30 ℃, 3.5g of perfluorobutyryl peroxide compound (CF 3CF2CF2COOOCOCF2CF2CF3) is added by a metering pump to initiate polymerization, tetrafluoroethylene (CF 2＝CF2) monomer is continuously introduced to keep the reaction pressure at 1.6MPa, and 0.85g of initiator is added into the system every 15 min. After 2 hours of reaction, the initiator addition was stopped, and after allowing the reaction to proceed for 15 minutes, the tetrafluoroethylene monomer addition was stopped.
Cooling the reaction kettle through a cooling circulation system, recovering unreacted tetrafluoroethylene monomer through a recovery system, placing milky white slurry in the kettle into a post-treatment system through a discharging valve, demulsifying and condensing through high-speed shearing or other well-known demulsification modes, filtering and separating to obtain white polymer powder, and drying in a 100 ℃ oven to obtain the perfluorinated ion polymer simultaneously provided with sulfonyl fluoride and phosphonate side groups, wherein the perfluorinated ion polymer is marked as F-1. The perfluorovinyl ether monomer with sulfonyl fluoride, perfluorovinyl ether monomer with phosphonate and perfluorocyclopentene monomer in the filtrate are recycled after being recovered by a recovery system.
Polymer data: the total ion exchange capacity of the resin is: 1.44mmol/g dry resin.
IR spectrogram: the S=O vibration absorption peak in sulfonyl fluoride exists in the range of 1468cm -1; the two strongest absorptions of 1200 and 1148cm -1 were caused by CF vibration; P=O stretching vibration is approximately overlapped with C-F absorption peak at 1260-1250cm -1, and P-O-C has absorption peak at 1034cm -1.
The mole percent of tetrafluoroethylene monomer units in the polymer structure is 70.2%, the mole percent of sulfonyl fluoride vinyl ether monomer units containing cyclic structures is 7.2%, the mole percent of phosphonate vinyl ether monomer units is 15%, and the mole percent of sulfonyl fluoride perfluorovinyl ether monomer units is 7.6% determined by the residual amount of reactants and nuclear magnetic integration.
Example 2
The structural formula of the perfluorocyclopentene monomer (C 6O6F10S2) is:
The reaction kettle is cleaned, 5.0L of deionized water, 125g of sodium dodecyl benzene sulfonate and 80g of nonylphenol polyoxyethylene ether NP-10 emulsifier are added, a stirring device is started, high-purity nitrogen is pumped into vacuum to replace for three times, and after the oxygen content in the reaction kettle is tested to be below 1ppm, the vacuum is pumped. After adding (1) 800g of a long-chain perfluorovinyl ether sulfonyl fluoride monomer (CF 2CFO(CF2CF3CFO)2CF2SO2 F), (2) 400g of a long-chain perfluorovinyl ether monomer with phosphonate (CF 2CFOCF2CFCF3OCF2PO(OC2H3)2) and (3) 30g of a perfluorocyclopentene monomer (C 6O6F10S2) to the reaction vessel through a liquid feed valve, the reaction vessel was charged with a tetrafluoroethylene monomer to a pressure of 3.5MPa. Heating to 70 ℃, adding 35g of 10% ammonium persulfate aqueous solution into the mixture by a metering pump to initiate polymerization, continuously introducing chlorotrifluoroethylene to keep the reaction pressure at 3.5MPa, and stopping adding the initiator after reacting for 2 hours. After allowing the reaction to proceed for 15 minutes, the addition of chlorotrifluoroethylene monomer was stopped.
Cooling the reaction kettle through a cooling circulation system, recovering unreacted trifluoro vinyl chloride monomer through a recovery system, placing milky slurry in the kettle into a post-treatment system through a discharging valve, performing demulsification and condensation through high-speed shearing or other well-known demulsification modes, filtering and separating to obtain white polymer powder, and drying in a 100 ℃ oven to obtain the perfluoro ion exchange resin with sulfonyl fluoride and phosphonate side groups at the same time, wherein the mark is F-2. The long-chain perfluorovinyl ether monomer with sulfonyl fluoride and the long-chain perfluorovinyl ether monomer with phosphonate and the perfluorocyclopentene monomer in the filtrate are recycled after being recovered by a recovery system.
Polymer data: the total ion exchange capacity of the resin is: 1.3mmol/g dry resin.
IR spectrogram: the S=O vibration absorption peak in sulfonyl fluoride exists in the range of 1468cm -1; the two strongest absorptions of 1200 and 1148cm -1 were caused by CF vibration; P=O stretching vibration is approximately overlapped with C-F absorption peak at 1260-1250cm -1, and P-O-C has absorption peak at 1034cm -1.
The mole percent of the trifluoro vinyl chloride monomer unit in the polymer structure is 69.2%, the mole percent of the sulfonyl fluoride vinyl ether monomer unit containing the cyclic structure is 9.4%, the mole percent of the phosphonate vinyl ether monomer unit is 15.8% and the mole percent of the sulfonyl fluoride perfluoro vinyl ether monomer unit is 5.6% determined by the residual reactant amount and the nuclear magnetic integral.
Example 3
The structural formula of the perfluorocyclopentene monomer (C 5O4F8 S) is as follows:
Cleaning the reaction kettle, adding 5.0L FC-40 fluorinated solution (fluorine-containing solvent), adding (1) 200g of long-chain perfluorovinyl ether monomer with sulfonyl fluoride (CF 2CFO(CF2CF3CFO)2CF2SO2 F) and (2) 325g of long-chain perfluorovinyl ether monomer with phosphonate (CF 2CFOCF2CFCF3OCF2PO(OC3H6)2 and (2) 50g of perfluorocyclopentene monomer (C 5O4F8 S), starting a stirring device, introducing flowing nitrogen for about 30 minutes to deoxidize, filling hexafluoropropylene monomer into the reaction kettle until the pressure is 2.9MPa after the oxygen content in the reaction kettle is tested to be less than 1ppm, heating to 40 ℃, adding 10g of perfluoropropoxypropyl peroxide compound (CF3CF2CF2OCF(CF3)CO-OO-COCF(CF3)OCF2CF2CF3) by a metering pump to initiate polymerization, continuously introducing hexafluoropropylene monomer to keep the reaction pressure at 2.9MPa, adding 2.0g of initiator into the system every 20min, stopping adding the initiator after the reaction for 2.5h, and keeping the reaction for 20min, stopping the monomer added, cooling the reaction kettle through a cooling circulation system, and drying the obtained solution in a 100 ℃ oven to obtain the perfluoropropyl resin marked with sulfonyl fluoride and carboxylic acid ester groups at the same time as F-3.
Polymer data: the total ion exchange capacity of the resin is: 1.6mmol/g dry resin. IR spectrogram: the S=O vibration absorption peak in sulfonyl fluoride exists in the range of 1468cm -1; the two strongest absorptions of 1200 and 1148cm -1 were caused by CF vibration; P=O stretching vibration is approximately overlapped with C-F absorption peak at 1260-1250cm -1, and P-O-C has absorption peak at 1034cm -1.
The mole percent of hexafluoropropylene monomer units in the polymer structure is 69.8 percent, the mole percent of sulfonyl fluoride vinyl ether monomer units containing a cyclic structure is 9.8 percent, the mole percent of vinyl ether monomer units containing phosphonate is 14.9 percent, and the mole percent of sulfonyl fluoride perfluoro vinyl ether monomer units is 5.5 percent.
Example 4
The preparation method of example 1 is adopted, and the main difference from example 1 is that: (2) Is a long-chain perfluoro vinyl ether monomer (CF 2CFOCF2CFCF3OCF2CF2PO(OC2H3)2) with phosphonate.
The reaction kettle is cleaned, 5.0L of deionized water, 100g of sodium dodecyl benzene sulfonate and 125g of nonylphenol polyoxyethylene ether NP-10 emulsifier are added, a stirring device is started, high-purity nitrogen is pumped into vacuum to replace for three times, and after the oxygen content in the reaction kettle is tested to be below 1ppm, the vacuum is pumped. 980g of the long-chain perfluorovinyl ether monomer (CF 2CFOCF2CF3CFOCF2SO2 F) having a sulfonyl fluoride, 325g of the long-chain perfluorovinyl ether monomer (CF 2CFOCF2CFCF3OCF2CF2PO(OC2H3)2) having a phosphonate, and 3) 200g of the perfluorocyclopentene monomer (same as in example 1) were charged into the reaction through a liquid feed valve. Tetrafluoroethylene monomer is filled into a reaction kettle until the pressure is 1.6MPa, the temperature is raised to 30 ℃, 3.5g of perfluorobutyryl peroxide compound (CF 3CF2CF2COOOCOCF2CF2CF3) is added by a metering pump to initiate polymerization, tetrafluoroethylene (CF 2＝CF2) monomer is continuously introduced to keep the reaction pressure at 1.6MPa, and 0.85g of initiator is added into the system every 15 min. After 2 hours of reaction, the initiator addition was stopped, and after allowing the reaction to proceed for 15 minutes, the tetrafluoroethylene monomer addition was stopped.
Cooling the reaction kettle through a cooling circulation system, recovering unreacted tetrafluoroethylene monomer through a recovery system, placing milky white slurry in the kettle into a post-treatment system through a discharging valve, demulsifying and condensing through high-speed shearing or other well-known demulsifying modes, filtering and separating to obtain white polymer powder, and drying in a 100 ℃ oven to obtain the perfluorinated ion exchange resin simultaneously provided with sulfonyl fluoride and phosphonate side groups, wherein the perfluorinated ion exchange resin is marked as F-4. The perfluorovinyl ether monomer with sulfonyl fluoride, perfluorovinyl ether monomer with phosphonate and perfluorocyclopentene monomer in the filtrate are recycled after being recovered by a recovery system.
Polymer data: the total ion exchange capacity of the resin is: 1.32mmol/g dry resin.
IR spectrogram: the S=O vibration absorption peak in sulfonyl fluoride exists in the range of 1468cm -1; the two strongest absorptions of 1200 and 1148cm -1 were caused by CF vibration; P=O stretching vibration is approximately overlapped with C-F absorption peak at 1260-1250cm -1, and P-O-C has absorption peak at 1034cm -1.
The mole percent of tetrafluoroethylene monomer units in the polymer structure is 72.2 percent, the mole percent of sulfonyl fluoride vinyl ether monomer units containing a cyclic structure is 9.6 percent, the mole percent of phosphonate vinyl ether monomer units is 13 percent, and the mole percent of sulfonyl fluoride perfluoro vinyl ether monomer units is 5.2 percent.
Chemical treatment of the polymers obtained by polymerization of examples 1-4 to prepare perfluorosulfonic acid resins.
The fluorine-containing ionic polymer containing sulfonyl fluoride and phosphonate groups is added into sodium hydroxide solution with the mass fraction of 15 percent, and is soaked for 15 hours, wherein the soaking temperature is 80 ℃. Then placing the treated resin in a container, washing the resin with pure water to pH=7, washing the resin at 45 ℃, and drying the resin at 80 ℃ to obtain the alkali type fluorine-containing ion exchange resin. Soaking an alkali type fluorine-containing ion exchange resin in nitric acid with the mass fraction of 20%, heating to 85 ℃, and changing the acid for 10-20 times to obtain the fluorine-containing ion polymer with sulfonic acid and phosphoric acid type ionic groups. Marked as fluorine-containing sulfonic acid resin H-1, H-2, H-3 and H-4 respectively.
Examples 1-4 chemical treatment of resins obtained by polymerization a fluorine-containing ionic polymer containing sulfonyl fluoride and phosphonate groups was added to 18% mass fraction aqueous ammonia and immersed for 30 hours at 50 ℃. Then placing the treated resin in a container, washing the resin with pure water to pH=7, washing the resin at 50 ℃, and drying the resin at 90 ℃ to obtain the alkali type fluorine-containing ion exchange resin. Soaking the alkali type fluorine-containing ion exchange resin in sulfuric acid with the mass fraction of 20%, heating to 85 ℃, and changing the acid for 10-20 times to obtain the fluorine-containing ion polymer with sulfonic acid and phosphoric acid type ionic groups. Marked as fluorine-containing sulfonic acid resin H-1 ', H-2 ', H-3 ', respectively.
Comparative example one
The amounts of each monomer added (1) 200g of the long-chain perfluorovinyl ether monomer having sulfonyl fluoride (CF 2CFOCF2CF3CFOCF2SO2 F), (2) 100g of the long-chain perfluorovinyl ether monomer having phosphonate (CF 2CFOCF2CFCF3OCF2PO(OC2H3)2) and (3) 50g of the perfluorocyclopentene monomer (C 6O4F10 S) were adjusted in the same manner as in example 1.
The resulting polymer had tetrafluoroethylene units of 89% of the total mole fraction of the copolymer, the polymer with phosphonate long chain perfluorovinyl ether of 6.7% of the total mole fraction of the copolymer, the polymer with sulfonyl fluoride long chain perfluorovinyl ether of about 3% of the total mole fraction of the copolymer, and the perfluoroheterocycloalkene polymer of about 1.3% of the total mole fraction of the copolymer, and the polymer of comparative example 1 was converted to the corresponding resin, designated D1, in the manner described in example 5.
Comparative example two
The polymer obtained according to the method described in example 1 of patent CN101768236a was transformed into a resin according to the method described in example 5 and denoted as D2. Hydrogen permeation coefficient of 0.42×10 -13cm3·cm/(cm2 ·s·pa), oxygen permeation coefficient of 0.16×10 -13cm3·cm/(cm2 ·s·pa), and resistivity at 120 ℃ or higher is significantly higher than that of the resin obtained by the present invention. The synergistic promotion effect of each group in the invention also improves the proton conductivity of the resin under high-temperature environment, especially above 120 ℃. Specific resin resistivity tests were performed according to GBT20042.3-2009.
The gas permeability test method is to use a permeation cell for permeation, and then to measure the permeation amount by gas chromatography, and the specific test method is according to GBT20042.3-2009.
Table 1: the resins of examples and comparative examples have resistivity and gas permeability coefficients at different temperatures
The hydrogen permeability coefficient of the resin obtained by the invention is 5.7-5.85 multiplied by 10 -13cm3·cm/(cm2 s Pa, and the oxygen permeability coefficient is 3-3.15 multiplied by 10 -13cm3·cm/(cm2 s Pa); the resistivity at 105 ℃ is 43-45 omega cm, and the resistivity at 125 ℃ is 30-33 omega cm; the resistivity at 155 ℃ is 17-21 Ω cm.
Example 5:
2kg of a mixed solution of water and DMF (the mass ratio of water to DMF is 1:1) was prepared, 300g of the resin obtained in example 1 was added to the mixed solution, and the mixture was transferred to an autoclave, and after the replacement of the internal air with nitrogen, the mixture was heated and stirred at an internal temperature of 180℃and 1.9MPa for 10 hours, thereby obtaining an ionomer solution, and the ionomer solution was concentrated by heating at 80℃to obtain a resin dispersion.
The resulting dispersion had a perfluorinated ion exchange resin content of 20.87%, a water content of 37.43% and a DMF content of 41.7%.
3G of carbon-supported platinum catalyst powder having a Pt content of 40% was mixed with 61g of n-propanol, 15g of water and 6.4g of a resin solution to prepare a catalyst ink, the catalyst ink was thoroughly mixed by ball milling, and then a mold was coated on Polytetrafluoroethylene (PTFE) to obtain a catalyst layer having a platinum loading of 0.3mg/cm 2. The coated surfaces of 2 sheets of PTFE were faced to each other with an electrolyte membrane interposed therebetween, and then transfer-bonding was performed by hot pressing under conditions of 1MPa at 120℃to remove the PTFE sheets, thereby obtaining a membrane electrode MEA. Methods of manufacturing MEA's are conventional in the art and reference is made to Journal of appled electrochemlstry (applied electrochemically), 22 (1992) 1-7 for details. And transferring the catalyst layer to the surface of a composite proton exchange membrane (commercial DMR100 membrane) to obtain the membrane electrode.
Example 6:
2kg of a mixed solution of water, ethanol, DMAC and butanol (the mass ratio of water, ethanol, DMAC and butanol is 25:10:1:2) was prepared, 350g of the resin obtained in example 2 was added to the mixed solution, and the mixture was transferred to an autoclave, and after the inside air was replaced with nitrogen, the mixture was heated and stirred at an internal temperature of 220℃and 2.3MPa for 4 hours. Thereby obtaining an ionomer solution. The ionomer solution described above was concentrated under reduced pressure.
The resulting dispersion had a perfluorinated ion exchange resin content of 23.37%, a water content of 49.21%, an ethanol content of 20.85%, a DMAC content of 2.3% and a butanol content of 4.27%.
The preparation method of the membrane electrode was as described in example 5, and the addition amount of the resin solution was 5.5g, with other parameters unchanged.
Example 7:
2kg of a mixed solution of water, n-propanol and isopropanol (the mass ratio of water, n-propanol and isopropanol is 2:1:1) was prepared, 210g of the resin obtained in example 3 was added to the mixed solution, and the mixture was transferred to an autoclave, and after the inside air was replaced with nitrogen, the mixture was heated and stirred at an internal temperature of 170℃and 1.7MPa for 6 hours. Thereby obtaining an ionomer solution. The ionomer solution was concentrated under reduced pressure to give a resin solution having an ionomer solids content of about 15%.
The resulting dispersion had a perfluorinated ion exchange resin content of 15.84%, a water content of 42.34%, an n-propanol content of 24.47% and an isopropanol content of 17.35%.
Method for preparing membrane electrode referring to example 5, the other parameters were unchanged, and the addition amount of the resin solution was 8.1g.
Comparative example 1
2Kg of a mixed solution of water and ethanol (the mass ratio of water to n-propanol: 1:1) was prepared, and 320g of a perfluorosulfonic acid resin (structure: 1.2 mmol/g)Molecular weight 22 ten thousand) was added to the above mixed solution, which was then transferred to an autoclave, and after the replacement of the internal controller with nitrogen, the mixture was heated and stirred at an internal temperature of 200℃and a pressure of 2.1MPa for 5 hours. Thereby obtaining an ionomer solution. The ionomer solution was concentrated under reduced pressure to obtain a resin solution having an ionomer solid content of about 20%.
The resulting dispersion had a perfluorinated ion exchange resin content of 20.21%, a water content of 44.37% and an n-propanol content of 35.42%.
Method for preparing membrane electrode referring to example 5, the other parameters were unchanged, and the addition amount of the resin solution was 6.4g.
Comparative example 2
2Kg of a mixed solution of water, isopropanol and DMF (the mass ratio of water, isopropanol and DMF is 2:2:1) was prepared, and 320g of a perfluorosulfonic acid resin having an exchange capacity of 1.2mmol/g (structureMolecular weight 23 ten thousand) was added to the above mixed solution, which was then transferred to an autoclave, and after the replacement of the internal controller with nitrogen, the mixture was heated and stirred at an internal temperature of 250℃and a pressure of 2.5MPa for 5 hours. Thereby obtaining an ionomer solution. The ionomer solution was concentrated by heating at 80 ℃ until a resin solution with an ionomer solids content of about 10% was obtained.
The resulting dispersion had a perfluorinated ion exchange resin content of 11.53%, a water content of 39.42%, an isopropyl alcohol content of 32.17% and a DMF content of 16.88%.
Method for preparing membrane electrode referring to example 5, the other parameters were unchanged, and the addition amount of the resin solution was 11.2g.
The solid content of the resin dispersion liquid is tested by adopting a halogen analysis tester, and the micelle size is tested by adopting a Brookhaven particle size analyzer. The smaller the ionomer micelle particle size in the resin dispersion liquid is, the porosity of the electrode is increased, more reaction sites are exposed, the gas transmission channels are increased, and the electrochemical performance of the membrane electrode is more excellent.
Each performance index of the membrane electrode is detected by adopting the following method:
Porosity: testing by adopting a mercury porosimeter according to GB/T21650.1-2008;
Total hole area: the test was performed using a mercury porosimeter according to GB/T21650.1-2008.
Manufacturing a single fuel cell: the fuel cell was constructed by stacking the same gas diffusion layer, bipolar plate, and support plate (the gas diffusion layer of the maillard GDS 3260, the group of serpentine flow channel bipolar plates) on both electrodes of the membrane electrode obtained in the example or the comparative example.
Membrane electrode polarization performance test: the fuel cell unit was set in Scribner Series 890e test stand, and polarization performance curve test was performed. The test conditions were as follows: the cell temperature was 75 ℃,40% rh humidified, the pressure was 100KPa, the voltage was swept from 0.9V to 0.2V, every 0.05V, and the cell was stabilized for 3min under this voltage condition.
The results of the sample tests are summarized in Table 2, and the polarization curve results are shown in FIG. 9.
TABLE 2 resin solutions and membrane electrode performance data for examples 5-7 and comparative examples 1-2
Fig. 9 is a graph showing polarization properties of the membrane electrode prepared in examples and comparative examples, and it can be seen that introduction of heterocycle in the structure of fluorine-containing ion exchange resin reduces crystallinity of the polymer, increases air permeability, exposes more reaction sites, increases gas transmission channels, increases voltage in turn under the same current density, and has more excellent electrochemical properties.

Claims (10)

1. A gas-permeable fluorine-containing ion exchange resin dispersion, characterized in that it comprises a gas-permeable fluorine-containing ion exchange resin, water and an organic solvent; the total content of the breathable fluorine-containing ion exchange resin in the resin dispersion liquid is 2% -50%, the total content of pure water is 5% -95%, and the total content of the organic solvent is 2.5% -87.5%;
the structural formula of the breathable fluorine-containing ion exchange resin is as follows:
Wherein a, b and c are integers of 1-20, a ', b ', c ' are integers of 1-3, k is an integer of 0-3, and f is an integer of 1-4; t is an integer of 0 to 3, v is an integer of 1 to 4, X/(x+y+z) =0.1 to 0.8, y/(x+y+z) =0.1 to 0.7, z/(x+y+z) =0.2 to 0.8, wherein R is- (OCF 2)i(CF2)j X, X is Cl or F, i is 0 to 2, and j is 0 to 2;
R 1 is R f is/>Or (b)Wherein m and n are integers of 0 to 4, and m and n are not 0 at the same time.
2. The resin dispersion according to claim 1, wherein k=1, f=2; t=1, v=2; r is F, cl or CF 3.
3. The resin dispersion according to claim 1, wherein the organic solvent is selected from the group consisting of protic organic solvents and aprotic organic solvents;
The proton organic solvent is one or more selected from methanol, ethanol, n-propanol, isopropanol, butanol or glycerin; the aprotic organic solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidine copper.
4. The resin dispersion according to claim 1, wherein the total content of the gas-permeable fluorine-containing ion exchange resin in the resin dispersion is from 5% to 40%, preferably from 10% to 30%.
5. The resin dispersion according to claim 1, wherein the total content of the gas-permeable fluorine-containing ion exchange resin in the resin dispersion is 15 to 25%; the total content of pure water in the resin dispersion liquid is 15% -75%; the total content of the organic solvent in the resin dispersion is 20-50%.
6. The resin dispersion according to claim 1, wherein the mass ratio of organic solvent to water in the resin dispersion is 1:15-15:1, preferably 1:5-5:1, further preferably 1:1-2.
7. The method for producing a resin dispersion according to any one of claims 1 to 6, wherein the breathable fluorine-containing ion exchange resin, water and an organic solvent are mixed to obtain a composition having a total solid content of 2% to 50%; heating and stirring the composition for 1-12 hours at 50-250 ℃ in an autoclave and an inert gas environment to obtain an ionomer solution, and concentrating the ionomer solution to obtain a resin dispersion liquid with a target composition.
8. The method of claim 7, wherein the inert gas is selected from one of nitrogen, argon or xenon, more preferably nitrogen.
9. The method according to claim 7, wherein the pressure is 1-10MPa and the temperature is 170-230 ℃.
10. The method according to claim 7, wherein the concentration method comprises evaporating the solvent by heating and concentrating under reduced pressure.
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