CN117866132A - Fluorine-containing resin dispersion liquid and preparation method and application thereof - Google Patents

Fluorine-containing resin dispersion liquid and preparation method and application thereof Download PDF

Info

Publication number
CN117866132A
CN117866132A CN202410033647.8A CN202410033647A CN117866132A CN 117866132 A CN117866132 A CN 117866132A CN 202410033647 A CN202410033647 A CN 202410033647A CN 117866132 A CN117866132 A CN 117866132A
Authority
CN
China
Prior art keywords
resin
fluorine
vinyl ether
temperature
sulfonyl fluoride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202410033647.8A
Other languages
Chinese (zh)
Inventor
张永明
张恒
邹业成
苏璇
史翔
赵淑会
张卫东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
Original Assignee
Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong Dongyue Future Hydrogen Energy Materials Co Ltd filed Critical Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
Publication of CN117866132A publication Critical patent/CN117866132A/en
Pending legal-status Critical Current

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Fuel Cell (AREA)

Abstract

The invention belongs to the technical field of fluorine-containing high polymer materials, and particularly relates to a fluorine-containing resin dispersion liquid, a preparation method and application thereof. The dispersion liquid comprises resin, organic solvent and water; wherein the resin is fluorine-containing resin. The fluorine-containing resin dispersion liquid is uniform in dispersion, has no white incompletely dissolved resin residue, and is good in storage stability, and a film material prepared from the dispersion liquid has high chemical stability and high ion exchange capacity.

Description

Fluorine-containing resin dispersion liquid and preparation method and application thereof
The present application is a divisional application based on application number 202211272311.4 (application date 2022-10-18, entitled "copolymer containing perfluorobutyl ethyl ether", fluorine-containing resin and preparation method).
Technical Field
The invention belongs to the technical field of fluorine-containing high polymer materials, and particularly relates to a fluorine-containing resin dispersion liquid, a preparation method and application thereof.
Background
A fuel cell is an electrochemical power generation device that operates on the principle of directly converting chemical energy stored in a fuel and an oxidant into electrical energy. The Proton Exchange Membrane Fuel Cell (PEMFC) is used as one of fuel cells, has the characteristics of high power density, high energy conversion efficiency, environmental protection, no pollution, low heat radiation, low emission, no noise and the like, not only becomes the optimal energy source of the future pure electric vehicle, a small fixed base station and portable electric equipment, but also has wide market prospect. The proton exchange membrane fuel cell is composed of a proton exchange membrane, an electrode and a flow field plate.
Proton exchange membranes are prepared from perfluorinated, partially fluorinated, or non-fluorinated sulfonic acid type resins. The perfluorosulfonic acid proton exchange membrane developed based on long-chain perfluorosulfonic acid resin is the most widely developed, and the resin is obtained by copolymerizing tetrafluoroethylene and perfluorovinyl ether sulfonic acid monomer, has a polytetrafluoroethylene skeleton and a perfluoroside chain structure with hydrophilic sulfonic acid at the end connected by ether bonds, and has higher ion conductivity and good chemical stability.
The working temperature of the existing fuel cell is usually 25-80 ℃, and belongs to low-temperature PEMFC. Compared with the low-temperature PEMFC, the high-temperature PEMFC (100-120 ℃) greatly simplifies the water heat management system of the cell stack, overcomes a plurality of difficulties which are difficult to solve by the low-temperature PEMFC, such as improving the activity and the utilization rate of the catalyst, enhancing the carbon monoxide (CO) poisoning resistance of the electrode catalyst and the like.
The high-temperature PEMFC has higher requirements on mechanical stability and film forming property of the perfluorinated sulfonic acid resin, a mode of a composite film is adopted in the prior art to compound a plurality of films with different ion exchange capacities, the inner film has a low IEC value and bears the function of mechanical strength, the outer film has a high IEC value and plays a role in ion transfer, but the composite film still cannot meet the requirements of the high-temperature PEMFC on the uniformity and the improvement of the electric conductivity of ion transfer. And the proton conduction and physical and chemical properties of sulfonic acid groups are limited, and the perfluorinated sulfonic acid proton membrane of perfluorinated sulfonic acid resin is difficult to conduct protons at the temperature of more than 100 ℃ so as to influence the working efficiency of the perfluorinated sulfonic acid proton membrane at high temperature.
The phosphonic acid doped aromatic heterocyclic polymer proton membrane can improve high-temperature proton conductivity, but has the defects of low-temperature working efficiency, incapability of quick starting, poor stability, short service life and the like.
Disclosure of Invention
The present invention aims to provide a fluororesin dispersion and a method for producing the same, which address the above-described drawbacks. The fluorine-containing resin dispersion liquid is uniform in dispersion, has no white incompletely dissolved resin residue, and is good in storage stability, and a film material prepared from the dispersion liquid has high chemical stability and high ion exchange capacity.
The technical scheme of the invention is as follows:
a fluorine-containing resin dispersion comprising a resin, an organic solvent and water; wherein the repeating unit of the resin is represented by the following formula:
wherein k is an integer of 0 to 3, and f is an integer of 1 to 4;
a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x/(x+y+z)＝0.1～0.8，y/(x+y+z)＝0.05～0.5，z/(x+y+z)＝0.1～0.6；
wherein R is- (OCF) 2 ) m (CF 2 ) n X, wherein X is Cl or F; m and n are integers from 0 to 3.
Further, the mass percent of the fluorine-containing resin in the fluorine-containing resin dispersion liquid is 5% -50%, the mass percent of the organic solvent is 5% -60%, and the mass percent of the water is 20% -75%.
Preferably, the fluorine-containing resin dispersion liquid comprises 10-45% of fluorine-containing resin by mass, 15-50% of organic solvent by mass and 30-50% of water by mass.
Further, the organic solvent in the fluorine-containing resin dispersion liquid is one or more of ethanol, glycol, dimethylformamide, N-propanol, isopropanol, acetone, glycerol, butanediol, diethylamine, dimethylacetamide, acetaldehyde, propylene glycol, cyclohexane or N-methylpyrrolidine (NMP).
The preparation method of the fluorine-containing resin dispersion liquid comprises the following steps:
(1) Firstly, preparing a mixed solvent consisting of water and an organic solvent, and then adding the fluorine-containing resin into the mixed solvent and transferring the mixed solvent into an autoclave;
(2) Under the protection of inert gas, mechanically stirring, controlling the temperature to be 100-260 ℃ and the pressure to be 2-5MPa, dissolving for 2-15 hours, stopping heating and stirring, cooling to room temperature and recovering to normal pressure to obtain a mixed solution;
(3) Transferring the mixed solution into a separating funnel, extracting and separating the mixed solution by carbon tetrachloride at normal temperature and normal pressure, and taking the lower layer solution to obtain the resin dispersion liquid with uniform dispersion, high chemical stability and high exchange capacity.
Further, the inert gas is one of nitrogen, argon or xenon.
Further, the dissolution temperature is 160-250 ℃ and the dissolution time is 4-10 hours.
The fluorine-containing resin dispersion liquid can be used in fields of polytetrafluoroethylene surface hydrophilic treatment, catalyst coating, electrochemical sensor production and other electrolytic devices, electrochemical devices, electrodialysis devices and the like and other same or similar fields.
The fluorine-containing resin dispersion liquid is uniform in dispersion, has no white resin residue which is not completely dissolved, is good in storage stability, and has high chemical stability and high ion exchange capacity.
In order to improve the uniformity and conductivity of ion conduction of the ion exchange membrane, the dispersion liquid is used for casting membrane, and has the advantages of good membrane forming performance, high mechanical stability, excellent chemical corrosion resistance of a medium, high ion conductivity in a wide temperature range, and the ion exchange membrane prepared by the dispersion liquid can be used for fuel cell membranes, especially high-temperature fuel cell membranes.
A perfluorobutyl ethyl ether-containing multipolymer has the following repeating units:
wherein k is an integer of 0 to 3, f is an integer of 1 to 4, and p is an integer of 1 to 3;
a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x/(x+y+z)＝0.1～0.8，y/(x+y+z)＝0.05～0.5，z/(x+y+z)＝0.1～0.6；
wherein R is- (OCF) 2 ) m (CF 2 ) n X, wherein X is Cl or F; m and n are integers from 0 to 3.
The multipolymer contains straight-chain sulfonyl fluoride side groups, branched-chain sulfonyl fluoride side groups and phosphonate side groups, so that the multipolymer endows the multipolymer with excellent melt processing performance and high-temperature proton conductivity through the coordination of sulfonic acid groups and phosphonic acid groups with straight-chain and branched-chain structures.
Further, the multipolymer containing the perfluoro butyl ethyl ether is formed by copolymerizing fluoroolefin/fluorovinyl ether monomer, sulfonyl fluoride-containing straight-chain vinyl ether monomer, sulfonyl fluoride-containing branched-chain vinyl ether monomer and phosphonate-containing vinyl ether monomer;
wherein, the structural formula of the fluoroolefin/fluoroolefin ether monomer is as follows: CF (compact flash) 2 ＝CF-(OCF 2 ) m (CF 2 ) n X, X is Cl or F, m and n are independent integers of 0-3;
preferably, m=0, n=0, x is Cl or F;
preferably, m=1, n=2, x is F;
preferably, m=1, n=0, and x is F;
the structural formula of the sulfonyl fluoride-containing linear vinyl ether monomer is as follows: CF (compact flash) 2 ＝CF-OCF 2 CF 2 CF 2 CF 2 SO 2 F；
The structural formula of the sulfonyl fluoride-containing branched vinyl ether monomer is as follows: CF (compact flash) 2 ＝CF-OCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 F；
The structural formula of the phosphonate vinyl ether monomer is as follows:
wherein k is an integer of 0 to 3, f is an integer of 1 to 4, and p is an integer of 1 to 3;
preferably, k=1, f=2, p=2.
Further, the copolymer containing perfluorobutyl ethyl ether comprises 45-90% of fluoroolefin/fluorovinyl ether monomer polymerized units by mole, 4-35% of sulfonyl fluoride-containing straight-chain vinyl ether monomer polymerized units by mole, 1-35% of sulfonyl fluoride-containing branched-chain vinyl ether monomer polymerized units by mole, and 5-45% of phosphonate-containing vinyl ether monomer polymerized units by mole.
Further optimizing, the fluoroolefin/fluorovinyl ether monomer polymerized units in the perfluorobutyl ethyl ether-containing multipolymer account for 60-80% of the mole content, the sulfonyl fluoride-containing straight-chain vinyl ether monomer polymerized units account for 5-20% of the mole content, the sulfonyl fluoride-containing branched-chain vinyl ether monomer polymerized units account for 5-15% of the mole content, and the phosphonate-containing vinyl ether monomer polymerized units account for 10-25% of the mole content.
A fluorine-containing resin obtained by a transformation reaction of the multipolymer; the repeating unit of the resin is represented by the following formula:
wherein k is an integer of 0 to 3, and f is an integer of 1 to 4;
a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x/(x+y+z)＝0.1～0.8，y/(x+y+z)＝0.05～0.5，z/(x+y+z)＝0.1～0.6；
wherein R is- (OCF) 2 ) m (CF 2 ) n X, wherein X is Cl or F; m and n are integers from 0 to 3.
The preparation method of the multipolymer comprises the steps of carrying out dispersion polymerization reaction on fluoroolefin/fluorovinyl ether monomer, sulfonyl fluoride-containing linear vinyl ether monomer, sulfonyl fluoride-containing branched vinyl ether monomer and phosphonate-containing vinyl ether monomer under the action of an initiator;
wherein the reaction time is 3-12 hours, the reaction temperature is 30-100 ℃, and the reaction pressure is 0.1-8 MPa;
preferably, the reaction temperature is 40-80 ℃ and the reaction pressure is 1.5-4.5 MPa.
Further, the preparation method of the multipolymer comprises the following steps of: sulfonyl fluoride containing linear vinyl ether monomer: sulfonyl fluoride containing branched vinyl ether monomer: phosphonate containing vinyl ether monomer: the initiator is (3-12): 1-8): 2-10): 5-15): 0.001-0.05;
the initiator is selected from the group consisting of peroxides, perfluoroalkyl peroxides, N 2 F 2 One or more of azo compounds, persulfates or redox systems formed by persulfates and sodium thiosulfate;
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, CF 3 CF 2 CF 2 CO-OO-COCF 2 CF 2 CF 3 、CF 3 CF 2 CF 2 OCFCF 3 CO-OO-COCFCF 3 OCF 2 CF 2 CF 3 、CF 3 CF 2 CH 2 CO-OO-COCH 2 CF 2 CF 3 Or CF (CF) 3 OCF 2 CF 2 CO-OO-COCF 2 CF 2 OCF 3 ；
The persulfate is selected from ammonium persulfate salt, alkali metal sulfide or alkali earth metal persulfate;
further preferably, the persulfate is selected from ammonium persulfate and potassium persulfate.
The dispersion stabilizer adopted in the dispersion polymerization reaction is one or more of a cationic stabilizer, an anionic stabilizer, a nonionic stabilizer, a reactive stabilizer and a nano inorganic stabilizer;
preferably, the anionic stabilizer comprises sodium fatty acid, sodium dodecyl sulfate, sodium alkyl sulfonate, sodium alkylaryl sulfonate;
the nonionic stabilizer comprises alkylphenol polyether alcohols, such as one or more of nonylphenol polyoxyethylene ether, polyoxyethylene fatty acid and polyoxyethylene fatty acid ether;
the reactive stabilizer includes perfluorosulfonates, perfluorophosphates or perfluorocarboxylates, such as potassium perfluorovinyl ether sulfonate, ammonium perfluorovinyl ether phosphonate.
More preferably, the dispersion stabilizer is CF 3 CF 2 (CF 2 OCF(CF 3 )) 2 COONH 4 ；
The dispersion medium of the dispersion polymerization reaction is deionized water;
the mass percentage of the dispersion stabilizer in water is 0.5-8%.
Further, the preparation method of the multipolymer comprises the following specific steps:
(1) Firstly, adding a dispersing medium and a dispersing agent into a reaction kettle, and stirring;
then, filling nitrogen, enabling the oxygen content in the reaction kettle to be less than 5ppm, and vacuumizing;
(2) Firstly, adding all sulfonyl fluoride-containing branched vinyl ether monomers and all phosphonate-containing vinyl ether monomers into a reaction kettle at one time; adding an initial amount of short alkenyl ether monomer containing sulfonyl fluoride, wherein the initial amount is 50% -80% of the total addition amount of the short alkenyl ether monomer containing sulfonyl fluoride;
then, filling fluoroolefin/fluorovinyl ether monomer into the reaction kettle until the pressure in the kettle is 0.1-8 MPa, heating to 30-100 ℃, and adding an initiator to initiate dispersion polymerization;
continuously introducing fluoroolefin/fluoroolefin ether monomer in the reaction process, keeping the pressure at 0.1-8 MPa, and adding the residual addition of sulfonyl fluoride-containing short-chain olefin ether monomer into the reaction system at intervals of 45-60 min; simultaneously adding an initiator into the system every 20-25 min;
finally, after the reaction is finished, filtering, separating and drying to obtain the multipolymer containing sulfonyl fluoride.
The preparation method of the fluorine-containing resin comprises the step of carrying out transformation reaction on the multipolymer or the multipolymer prepared by the preparation method; the method comprises the following steps:
(1) The multipolymer and alkali liquor are subjected to transformation reaction for 8 to 24 hours at the temperature of between 40 and 100 ℃ under the atmosphere of nitrogen protection;
(2) And after the reaction is finished, filtering, washing with water to be neutral, and then carrying out acid washing to obtain the fluorine-containing resin.
Further, the multi-component copolymer in the step (1) of the preparation method of the fluorine-containing resin: the mass ratio of the alkali liquor is 1 (15-45);
the mass percentage concentration of the alkali liquor is 3-25%;
the alkali liquor is any one or more aqueous solutions of sodium hydroxide, potassium hydroxide, sodium bicarbonate, ammonia water and sodium carbonate;
the mass percentage concentration of the pickling solution adopted in the step (2) is 3-20%; the pickling time is 12-48 hours;
the pickling solution is one or more of nitric acid, sulfuric acid or hydrochloric acid;
the number average molecular weight of the fluorine-containing resin prepared by the preparation method is 20-40 ten thousand.
The fluorine-containing resin or the fluorine-containing resin prepared by the preparation method is used for the high-temperature proton exchange membrane.
The beneficial effects of the invention are as follows:
the copolymer contains three group structures of a straight-chain sulfonyl fluoride side group, a branched-chain sulfonyl fluoride side group and a phosphonate side group, and the fluorine-containing resin prepared from the copolymer has lower resistivity under high temperature conditions through the cooperation among the straight-chain sulfonyl fluoride side group, the branched-chain sulfonyl fluoride side group and the phosphonate side group, so that the ion exchange membrane prepared from the fluorine-containing resin has higher conductivity under high temperature conditions, and is beneficial to developing high-temperature PEMFC.
The fluorine-containing resin provided by the invention is composed of fluoroolefin/fluorovinyl ether monomer polymerization units, sulfonyl fluoride-containing linear vinyl ether monomer polymerization units, sulfonyl fluoride-containing branched vinyl ether monomer polymerization units and phosphonate-containing vinyl ether monomer polymerization units, wherein the perfluorobutyl ethyl ether structure in the sulfonyl fluoride-containing linear vinyl ether monomer polymerization units is matched with other two structures to provide more physical crosslinking points, so that the film forming performance of the resin is greatly improved, and the mechanical property after film forming is processed.
Meanwhile, the resin structure is regulated by the addition amount of the monomer and the reaction condition, so that the exchange capacity of the resin is regulated in a larger range, the synergistic effect of the three is exerted, and the ion conductivity is improved.
The ion exchange capacity of the resin prepared by the multipolymer of the invention is 1.35-1.75mmol/g; the melt index is 7.5-11.0g/10min, the tensile strength is 29.5-32.5MPa, and the elongation at break is 180-215%.
The resin has a resistivity of 40.0-41.5 Ω & cm at 110deg.C, 28.0-30 Ω & cm at 130deg.C, and 17.0-18.5 Ω & cm at 150deg.C.
Drawings
FIG. 1 is an infrared spectrum of a perfluorobutyl ethyl ether-containing multipolymer obtained in example 1 of the present invention.
FIG. 2 is an infrared spectrum of a perfluorobutyl ethyl ether-containing multipolymer obtained in comparative example 1 of the present invention.
FIG. 3 is a graph showing the comparison of storage stability of the fluororesin dispersions obtained in examples 1 to 3 of the present invention.
Detailed Description
The technical scheme of the invention is described in detail below with reference to the accompanying drawings.
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 determined from the conversion of sulfonyl fluoride to sulfonic acid and the conversion of phosphonate to phosphinic acid unless otherwise specified in the examples below.
The potassium persulfate adopted in the synthesis process of the invention can be purchased through national drug groups.
Tetrafluoroethylene monomer adopted in the synthesis process is purchased from Shandong Dongyue polymer material limited company; the sulfonyl fluoride-containing branched vinyl ether monomer adopts a preparation method described in Chinese patent CN 201810798170.7; the phosphonate vinyl ether monomer-containing monomer adopts the preparation method described in Chinese patent CN 200910230218.5. The sulfonyl fluoride-containing linear vinyl ether is prepared by the method described in Chinese patent CN200910229444.1, CN200910229446.0 and CN 200910230218.5.
Example 1
After the reaction vessel was cleaned, 5.0L of deionized water and 125g of a fluorosurfactant CF were added 3 CF 2 (CF 2 OCF(CF 3 )) 2 COONH 4 Starting the stirring device, vacuumizing, filling high-purity nitrogen for three times, and vacuumizing after the oxygen content in the reaction kettle is tested to be below 5 ppm.
56g of a sulfonyl fluoride-containing linear vinyl ether CF were added to the reaction vessel via a liquid feed valve 2 ＝CF-OCF 2 CF 2 CF 2 CF 2 SO 2 F,180g of branched vinyl ether monomer CF containing sulfonyl fluoride 2 ＝CF-OCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 F and 160g of phosphonate containing vinyl ether monomer fc=cf-OCF 2 CF(CF 3 )O-CF 2 CF 2 -PO(C 2 H 5 ) 2 After that, the processing unit is configured to,
tetrafluoroethylene monomer is filled into a reaction kettle until the pressure is 3.6MPa, the temperature is raised to 82 ℃, and 450mg of potassium persulfate is added by a metering pump to initiate polymerization.
Continuously introducing tetrafluoroethylene monomer, keeping the reaction pressure at 3.6MPa, and adding 5g of sulfonyl fluoride-containing linear vinyl ether CF into the system every 60min 2 ＝CF-OCF 2 CF 2 CF 2 CF 2 SO 2 And F, adding 20mg of an initiator into the system every 30min, stopping adding the initiator and the sulfonyl fluoride-containing linear vinyl ether after reacting for 4h, and stopping adding the tetrafluoroethylene monomer after the reaction is continued for 30 min.
Cooling the reaction kettle through a cooling circulation system, recovering unreacted tetrafluoroethylene monomer through a recovery system, placing the milky white slurry in the kettle into a post-treatment system through a discharging valve, shearing at high speed, filtering and separating to obtain white polymer powder, and drying in a 100 ℃ oven to obtain the multipolymer with sulfonyl fluoride and phosphonate.
By measuring the elemental content of sulfur and phosphorus in the polymer and combining the nuclear magnetic spectrum diagram, the mole percent of tetrafluoroethylene monomer units in the polymer structure is 75.6%, the mole percent of sulfonyl fluoride-containing linear vinyl ether monomer units is 3.5%, the mole percent of sulfonyl fluoride-containing branched vinyl ether monomer units is 9.4%, and the mole percent of phosphonate-containing vinyl ether monomer units is 11.5%.
The preparation method of the ion exchange resin is characterized in that the ion exchange resin is obtained by carrying out transformation reaction on the multi-component copolymer containing sulfonyl fluoride; the method comprises the following specific steps:
(1) Hot-press vulcanizing the multipolymer powder obtained in the embodiment by a flat vulcanizing machine, wherein the temperature of an upper heating plate and a lower heating plate of the flat vulcanizing machine is set to 230 ℃ to obtain a transparent sheet with the thickness of 1-3mm, and shearing the transparent sheet material to prepare transparent multipolymer precursor resin granules with the length of 3-5 mm;
(2) 15g of sheared granules are taken and placed in 200g of sodium hydroxide aqueous solution with the mass percentage concentration of 8%, and the granules are continuously stirred for 24 hours at 70 ℃ under the protection of nitrogen for transformation reaction;
(3) And after the transformation reaction is finished, filtering the obtained resin, washing the resin to be neutral by deionized water, stirring the resin in hydrochloric acid solution with the mass percent concentration of 8% for 48 hours, and filtering out solid resin, namely the fluorine-containing resin.
GPC revealed that the number average molecular weight of the fluorine-containing resin was 37.5 ten thousand.
Infrared spectrogram analysis: 1479cm -1 Is provided with a vibration absorption peak of sulfonyl fluoride group of 1287.0cm -1 The strong absorption peak is a telescopic vibration absorption peak of phosphonate group P=0, 713cm -1 And 598cm -1 Characteristic peaks of (C) are attributed to CF after tetrafluoroethylene copolymerization 2 CF 2 Repeat units 2900-3050cm -1 The hydrocarbon vibration absorption peak of ethyl in phosphate is shown.
The resin prepared in example 1 was prepared as a resin dispersion, comprising the following steps:
(1) Preparing 1.3kg of mixed solvent consisting of water and n-propanol, wherein the mass ratio of the water to the n-propanol is 1:2.9; 283g
The resin obtained in example 1 was added to the mixed solvent and transferred into an autoclave;
(2) Sealing the autoclave, introducing nitrogen for protection, stirring, heating to 175 ℃, keeping the temperature at 2.2MPa for 8.5 hours, cooling to room temperature, recovering the pressure to normal pressure, and taking out the mixed solution;
(3) Transferring the mixed solution into a separating funnel, extracting and separating by carbon tetrachloride at normal temperature and normal pressure, and taking the lower layer solution to obtain a resin dispersion liquid containing 22.06wt% of the resin obtained in the example 1, 20.86wt% of water and 57.08wt% of normal propyl alcohol.
The obtained resin dispersion is coated into a film by a wire rod, and the proton exchange film with the thickness of 12 mu m is obtained after the solvent is volatilized by heating.
Example 2
After the reaction vessel was cleaned, 5.0L of deionized water and 144g of fluorosurfactant CF were added 3 CF 2 (CF 2 OCF(CF 3 )) 2 COONH 4 Starting the stirring device, vacuumizing, filling high-purity nitrogen for three times, and vacuumizing after the oxygen content in the reaction kettle is tested to be below 5 ppm.
56g of a sulfonyl fluoride-containing linear vinyl ether CF were added to the reaction vessel via a liquid feed valve 2 ＝CF-OCF 2 CF 2 CF 2 CF 2 SO 2 F,210g of a branched vinyl ether monomer CF containing sulfonyl fluoride 2 ＝CF-OCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 F and 250g of phosphonate containing vinyl ether monomer fc=cf-OCF 2 CF(CF 3 )O-CF 2 CF 2 -PO(C 2 H 5 ) 2 After that, the processing unit is configured to,
charging tetrafluoroethylene monomer into a reaction kettle until the pressure is 3.7MPa, heating to 85 ℃, adding 450mg of potassium persulfate by a metering pump to initiate polymerization, continuously charging tetrafluoroethylene monomer to keep the reaction pressure at 3.7MPa, and adding 6g of sulfonyl fluoride-containing linear vinyl ether CF into the system every 60min 2 ＝CF-OCF 2 CF 2 CF 2 CF 2 SO 2 F, adding 20mg of initiator into the system every 20min, stopping adding the initiator after reacting for 3h, and stopping adding tetrafluoroethylene monomer after the reaction is continued for 30 min.
Cooling the reaction kettle through a cooling circulation system, recovering unreacted tetrafluoroethylene monomer through a recovery system, placing the milky white slurry in the kettle into a post-treatment system through a discharging valve, shearing at high speed, filtering and separating to obtain white polymer powder, and drying in a 100 ℃ oven to obtain the multipolymer with sulfonyl fluoride and phosphonate.
By measuring the elemental content of sulfur and phosphorus in the polymer and combining the nuclear magnetic spectrum diagram, the mole percent of tetrafluoroethylene monomer units in the polymer structure is 64.8%, the mole percent of sulfonyl fluoride-containing linear vinyl ether monomer units is 3.9%, the mole percent of sulfonyl fluoride-containing branched vinyl ether monomer units is 15.4%, and the mole percent of phosphonate-containing vinyl ether monomer units is 15.9%.
GPC revealed that the number average molecular weight of the fluorine-containing resin was 33.2 ten thousand.
The resin prepared in example 2 was prepared as a resin dispersion, comprising the following steps:
(1) Preparing 2.5kg of mixed solvent consisting of water and isopropanol, wherein the mass ratio of the water to the isopropanol is 4:3.8; 544g
The resin obtained in example 2 was added to the mixed solvent and transferred into an autoclave;
(2) Sealing the autoclave, introducing nitrogen for protection, stirring, heating to 220 ℃, keeping the temperature for 5 hours after the pressure reaches 4MPa, cooling to room temperature, recovering the pressure to normal pressure, and taking out the mixed solution;
(3) The mixed solution was transferred to a separating funnel, and after extraction and separation by carbon tetrachloride at normal temperature and normal pressure, the lower layer solution was taken out to obtain a resin dispersion containing 21.89wt% of the resin obtained in example 2, 40.45wt% of water, and 37.66wt% of isopropyl alcohol.
The resulting resin dispersion was film-formed by bar coating onto a polytetrafluoroethylene-reinforced mesh (2 layers, porosity 80%, grammage 3.2 g/m) 2 ). The solvent is heated and volatilized to obtain the proton exchange membrane with the thickness of 15 mu m.
Example 3
After the reaction vessel was cleaned, 5.0L of deionized water and 125g of a fluorosurfactant CF were added 3 CF 2 (CF 2 OCF(CF 3 )) 2 COONH 4 Starting the stirring device, vacuumizing, filling high-purity nitrogen for three times, and vacuumizing after the oxygen content in the reaction kettle is tested to be below 5 ppm.
58g of a sulfonyl fluoride-containing linear vinyl ether CF were added to the reaction vessel via a liquid feed valve 2 ＝CF-OCF 2 CF 2 CF 2 CF 2 SO 2 F,160g of branched vinyl ether monomer CF containing sulfonyl fluoride 2 ＝CF-OCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 F and 305g of phosphonate-containing vinyl ether monomer fc=cf-OCF 2 CF(CF 3 )O-CF 2 CF 2 -PO(C 2 H 5 ) 2 After that, the processing unit is configured to,
tetrafluoroethylene monomer is filled into a reaction kettle until the pressure is 4.1MPa, the temperature is raised to 82 ℃, and 450mg of potassium persulfate is added by a metering pump to initiate polymerizationContinuously introducing tetrafluoroethylene monomer, keeping the reaction pressure at 4.1MPa, and adding 5g of sulfonyl fluoride-containing linear vinyl ether CF into the system every 60min 2 ＝CF-OCF 2 CF 2 CF 2 CF 2 SO 2 And F, adding 20mg of initiator into the system every 30min, stopping adding the initiator after reacting for 5h, and stopping adding tetrafluoroethylene monomer after the reaction is continued for 30 min.
Cooling the reaction kettle through a cooling circulation system, recovering unreacted tetrafluoroethylene monomer through a recovery system, placing the milky white slurry in the kettle into a post-treatment system through a discharging valve, shearing at high speed, filtering and separating to obtain white polymer powder, and drying in a 100 ℃ oven to obtain the multipolymer with sulfonyl fluoride and phosphonate.
By measuring the elemental content of sulfur and phosphorus in the polymer and combining the nuclear magnetic spectrum diagram, the mole percent of tetrafluoroethylene monomer units in the polymer structure is 67.2%, the mole percent of sulfonyl fluoride-containing linear vinyl ether monomer units is 3.1%, the mole percent of sulfonyl fluoride-containing branched vinyl ether monomer units is 8.9%, and the mole percent of phosphonate-containing vinyl ether monomer units is 20.8%.
GPC revealed that the number average molecular weight of the fluorine-containing resin was 28.7 million.
The resin prepared in example 3 was prepared as a resin dispersion, comprising the following steps:
(1) 1.2kg of a mixed solvent consisting of water, ethylene glycol and n-propanol is prepared, wherein the water is as follows: ethylene glycol: the mass ratio of the n-propanol is 2.5:0.63:4.7; 262g of the resin obtained in example 3 was added to the mixed solvent and transferred into an autoclave;
(2) Sealing the autoclave, introducing nitrogen for protection, stirring, heating to 280 ℃, keeping the temperature for 7 hours after the pressure reaches 4.3MPa, cooling to room temperature, recovering the pressure to normal pressure, and taking out the mixed solution;
(3) The mixed solution was transferred to a separating funnel, and after extraction and separation by carbon tetrachloride at normal temperature and normal pressure, the lower layer solution was taken out to obtain a resin dispersion containing 22.12% by weight of the resin obtained in example 3, 25.19% by weight of water, 6.2% by weight of ethylene glycol and 46.49% by weight of n-propanol.
The resulting resin dispersion was applied to a polytetrafluoroethylene-reinforced net by spraying to form a film (2 layers, porosity 80%, grammage 3.2 g/m) 2 ). The solvent was heated to evaporate to give a 14 μm proton exchange membrane.
Example 4
After the reaction vessel was cleaned, 5.0L of deionized water and 135g of a fluorosurfactant CF were added 3 CF 2 (CF 2 OCF(CF 3 )) 2 COONH 4 Starting the stirring device, vacuumizing, filling high-purity nitrogen for three times, and vacuumizing after the oxygen content in the reaction kettle is tested to be below 5 ppm.
58g of a sulfonyl fluoride-containing linear vinyl ether CF were added to the reaction vessel via a liquid feed valve 2 ＝CF-OCF 2 CF 2 CF 2 CF 2 SO 2 F,170g of branched vinyl ether monomer CF containing sulfonyl fluoride 2 ＝CF-OCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 F and 250g of phosphonate containing vinyl ether monomer fc=cf-OCF 2 CF(CF 3 )O-CF 2 CF 2 -PO(C 2 H 5 ) 2 After that, the processing unit is configured to,
charging tetrafluoroethylene monomer into a reaction kettle until the pressure is 3.8MPa, heating to 85 ℃, adding 400mg of potassium persulfate by a metering pump to initiate polymerization, continuously charging tetrafluoroethylene monomer to keep the reaction pressure at 3.8MPa, and adding 5g of sulfonyl fluoride-containing linear vinyl ether CF into the system every 60min 2 ＝CF-OCF 2 CF 2 CF 2 CF 2 SO 2 And F, adding 20mg of initiator into the system every 20min, stopping adding the initiator after reacting for 3h, and stopping adding tetrafluoroethylene monomer after the reaction is continued for 30 min.
Cooling the reaction kettle through a cooling circulation system, recovering unreacted tetrafluoroethylene monomer through a recovery system, placing the milky white slurry in the kettle into a post-treatment system through a discharging valve, shearing at high speed, filtering and separating to obtain white polymer powder, and drying in a 100 ℃ oven to obtain the multipolymer with sulfonyl fluoride and phosphonate.
By measuring the elemental content of sulfur and phosphorus in the polymer and combining the nuclear magnetic spectrum diagram, the mole percent of tetrafluoroethylene monomer units in the polymer structure is 71.8%, the mole percent of sulfonyl fluoride-containing linear vinyl ether monomer units is 3.2%, the mole percent of sulfonyl fluoride-containing branched vinyl ether monomer units is 8.9%, and the mole percent of phosphonate-containing vinyl ether monomer units is 16.1%.
GPC revealed that the number average molecular weight of the fluorine-containing resin was 31.1 ten thousand.
The resin prepared in example 4 was prepared as a resin dispersion, comprising the following steps:
(1) 2kg of a mixed solvent composed of water, ethylene glycol and isopropanol is prepared, wherein the water is as follows: ethylene glycol: the mass ratio of the isopropanol is 4.4:0.7:2.8; 435g of the resin obtained in example 4 was added to the mixed solvent and transferred into an autoclave;
(2) Sealing the autoclave, introducing nitrogen for protection, stirring, heating to 280 ℃, keeping the temperature for 7 hours after the pressure reaches 4.6MPa, cooling to room temperature, recovering the pressure to normal pressure, and taking out the mixed solution;
(3) The mixed solution was transferred to a separating funnel, and after extraction and separation by carbon tetrachloride at normal temperature and normal pressure, the lower layer solution was taken out to obtain a resin dispersion containing 21.93wt% of the resin obtained in example 4, 43.66wt% of water, 6.7wt% of ethylene glycol, and 27.71% of isopropyl alcohol.
The resulting resin dispersion was film-formed by bar coating onto a polytetrafluoroethylene-reinforced mesh (3 layers, porosity 80%, grammage 3.2 g/m) 2 ). The solvent was heated to evaporate to give a 13 μm proton exchange membrane.
Comparative example 1
After the reaction vessel was cleaned, 5.0L of deionized water and 125g of a fluorosurfactant CF were added 3 CF 2 (CF 2 OCF(CF 3 )) 2 COONH 4 Starting the stirring device, vacuumizing, filling high-purity nitrogen for three times, and vacuumizing after the oxygen content in the reaction kettle is tested to be below 5 ppm. 96g of a sulfonyl fluoride-containing linear vinyl ether CF were added to the reaction vessel through a liquid feed valve 2 ＝CF-OCF 2 CF 2 CF 2 CF 2 SO 2 F,240g of branched vinyl ether monomer CF containing sulfonyl fluoride 2 ＝CF-OCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 F and 35g of phosphonate-containing vinyl ether monomer fc=cf-OCF 2 CF(CF 3 )O-CF 2 CF 2 -PO(C 2 H 5 ) 2 Then, tetrafluoroethylene monomer is filled into a reaction kettle until the pressure is 3.1MPa, the temperature is raised to 80 ℃, 450mg of potassium persulfate is added by a metering pump to initiate polymerization, the tetrafluoroethylene monomer is continuously introduced to keep the reaction pressure at 3.1MPa, and 3g of sulfonyl fluoride-containing linear vinyl ether CF is added into the system every 60min 2 ＝CF-OCF 2 CF 2 CF 2 CF 2 SO 2 F, adding 20mg of initiator into the system every 25min, stopping adding the initiator after reacting for 4h, and stopping adding tetrafluoroethylene monomer after the reaction is continued for 30 min. Cooling the reaction kettle through a cooling circulation system, recovering unreacted tetrafluoroethylene monomer through a recovery system, placing the milky white slurry in the kettle into a post-treatment system through a discharging valve, shearing at high speed, filtering and separating to obtain white polymer powder, and drying in a 100 ℃ oven to obtain the multipolymer with sulfonyl fluoride and phosphonate.
By measuring the elemental content of sulfur and phosphorus in the polymer and combining the nuclear magnetic spectrum diagram, the mole percent of tetrafluoroethylene monomer units in the polymer structure is 74.1%, the mole percent of sulfonyl fluoride-containing linear vinyl ether monomer units is 8.1%, the mole percent of sulfonyl fluoride-containing branched vinyl ether monomer units is 15.3%, and the mole percent of phosphonate-containing vinyl ether monomer units is 2.5%.
GPC revealed that the number average molecular weight of the fluorine-containing resin was 39.2 ten thousand.
Infrared spectrogram analysis 1479cm -1 Is provided with a vibration absorption peak of sulfonyl fluoride group of 1290.0cm -1 The strong absorption peak is a telescopic vibration absorption peak of phosphonate group P=0, 1000cm -1 ～1148cm -1 The two strongest absorptions are caused by fluorocarbon vibration, 728cm -1 And 601cm -1 Characteristic peaks of (C) are attributed to CF after tetrafluoroethylene copolymerization 2 CF 2 Repeat units 2900-3050cm -1 The hydrocarbon vibration absorption peak of ethyl in phosphate is shown.
The resin prepared in comparative example 1 was prepared as a resin dispersion, and the specific steps were as follows:
(1) 2kg of a mixed solvent consisting of water and isopropanol is prepared, wherein the water is as follows: the mass ratio of the isopropanol is 5.4:2.5; 420g of the resin obtained in comparative example 1 was added to the mixed solvent and transferred into an autoclave;
(2) Sealing the autoclave, introducing nitrogen for protection, stirring, heating to 200 ℃, keeping the temperature for 7 hours after the pressure reaches 3MPa, cooling to room temperature, recovering the pressure to normal pressure, and taking out the mixed solution;
(3) Transferring the mixed solution into a separating funnel, extracting and separating the mixed solution by carbon tetrachloride at normal temperature and normal pressure, and taking the lower layer solution to obtain the resin 22.03 weight percent, the water 53.78 weight percent and the isopropanol 24.19 weight percent of the resin obtained in the comparative example 1.
The resulting resin dispersion was knife coated to form a film. The solvent is heated and volatilized to obtain the proton exchange membrane with the thickness of 15 mu m.
Comparative example 2
The copolymer of the comparative example is formed by the multi-component copolymerization of tetrafluoroethylene, two short side group sulfonyl fluoride vinyl ether monomers with different structures and a phosphonate side group vinyl ether monomer, and the repeating unit is shown as the following formula:
M + is hydrogen ion, n=0.
The preparation method of the multipolymer of the comparative example comprises the following specific steps:
the reaction vessel was washed and charged with 5.0L of deionized water, 500ml of a solution containing 105g of sodium phosphonate pendant vinyl ether monomer (F) 2 C＝
CF-O-CF 2 CF 2 -PO 3 2- 2Na + ) 150g of nonylphenol polyoxyethylene ether NP-10, starting a stirring device, vacuumizing, filling high-purity nitrogen for replacement for three times, vacuumizing after the oxygen content in the reaction kettle is tested to be below 1ppm, and adding 500g of sulfonyl fluoride side-group vinyl ether monomer (F) into the reaction kettle through a liquid feeding valve 2 C＝CF-O-CF 2 CF 2 -SO 2 F) 405g of sulfonyl fluoride side-group vinyl ether monomer (F) 2 C＝CF-O-CF 2 CF 2 CF 2 CF 2 -SO 2 F) Then, tetrafluoroethylene monomer was charged into the reaction vessel to a pressure of 2.9MPa, the temperature was raised to 35℃and 8.0g of perfluoropropoxypropyl peroxide (CF) was added by a metering pump 3 CF 2 CF 2 OCF(CF 3 )CO-OO-CCF(CF 3 )OCF 2 CF 2 CF 3 ) The polymerization was initiated and tetrafluoroethylene (CF) 2 ＝CF 2 ) The monomer keeps the reaction pressure at 2.9MPa, 2.4g of initiator is added into the system every 25min, after 2.5h of reaction, the initiator is stopped to be added, and after the reaction is continued for 25min, the tetrafluoroethylene monomer is stopped to be added.
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, shearing at high speed, filtering and separating to obtain white polymer powder, and drying in a 100 ℃ oven to obtain the functional perfluorinated resin with short side group sulfonyl fluoride and sodium phosphonate side groups. The sulfonyl fluoride vinyl ether monomer and sodium phosphonate side group vinyl ether monomer in the filtrate are recycled after being recovered by a recovery system.
The copolymer structure of this comparative example has 73.8 mole percent of tetrafluoroethylene monomer units, sulfonyl fluoride side-group vinyl ether monomer (F 2 C＝CF-O-CF 2 CF 2 -SO 2 F) 15 mole percent, sulfonyl fluoride side-group vinyl ether monomer (F) 2 C＝
CF-O-CF 2 CF 2 CF 2 CF 2 -SO 2 F) The mole percent is 9 percent, and the mole percent of sodium phosphonate side group vinyl ether monomer is 2.2 percent.
The ion exchange resin prepared by the multipolymer of the comparative example has the ion exchange capacity of 0.95mmol/g, the melt index of 4.2g/10min, poor film forming performance, the tensile strength of 23.1MPa, the elongation at break of 148 percent, and the resistivity at high temperature, particularly the resistivity at the temperature of more than or equal to 130 ℃ is higher than that of the examples 1-4. The resin of this comparative example was found to have a high melt viscosity, a low melt index, unfavorable processing, and uneven distribution with trace crystallization. Both tensile strength and elongation at break were lower than in examples 1-4.
GPC measured that the number average molecular weight of the resin was 20 ten thousand.
The resin prepared in comparative example 2 was prepared as a resin dispersion, and the specific steps were as follows:
(1) 2kg of a mixed solvent composed of water and glycol is prepared, wherein the water is as follows: the mass ratio of the glycol is 2:1; 590g of the resin obtained in comparative example 2 was added to the mixed solvent and transferred into an autoclave;
(2) Sealing the autoclave, introducing nitrogen for protection, stirring, heating to 180 ℃, keeping the temperature for 5 hours after the pressure reaches 1.9MPa, cooling to room temperature, recovering the pressure to normal pressure, and taking out the mixed solution;
(3) Transferring the mixed solution into a separating funnel, extracting and separating the mixed solution by carbon tetrachloride at normal temperature and normal pressure, and taking the lower layer solution to obtain the resin containing 29.98wt% of resin obtained in comparative example 2, 46.73wt% of water and 23.29wt% of glycol.
The resulting resin dispersion was applied to a polyethylene reinforcing mesh by spraying to form a film (3 layers, porosity 83%, grammage 3.0 g/m) 2 ). The solvent was heated to volatilize to give a 16 μm proton exchange membrane.
The micelle particle diameter of the resin dispersion obtained in this comparative example was 274nm, and the tensile strength of the proton exchange membrane produced from the resin dispersion was 30.0MPa and the dimensional change rate was 19.2%.
1. Performance testing was performed on the resins prepared in examples 1-4 and comparative examples 1-2:
1. ion exchange capacity test method: the test was performed using GB/T30296-2013.
1. Melt index: the melt index was measured using a MFI-1322 model and GB/T3682-2000.
3. Tensile strength and elongation at break: and mechanical property test is carried out on the ion exchange resin prepared by using GB 13022-91. The test temperature is 25-30 ℃, the type II test sample is 115mm long, the distance between clamps is 80mm, and the stretching speed is 50mm/min.
4. Resin resistivity: the method for testing the resistivity of the ion exchange resin comprises the following steps: the resistance R of the sample is tested by adopting a two-electrode method, an instrument is adopted as an electrochemical workstation Autolab PGSTA302, the frequency interval is 106Hz-10Hz, and the resistivity is calculated by a calculation formula: ρ=rs/L, where: l is the thickness (cm) of the membrane, R is the resistance (Ω) of the membrane, ρ is the resistivity (Ω·cm) of the sample, and S is the area (cm) of the test portion of the sample 2 )。
The specific results of the above tests are detailed in table 1.
TABLE 1
From the comparison of the above data, the high temperature resistivity was not lowered when the monomer was polymerized as described in comparative example 1.
2. Performance testing was performed on proton exchange membranes prepared using the resin dispersions described in examples 1-4 and comparative examples 1-2:
1. ion exchange capacity: treating a target product for more than 12 hours by adopting a Fenton reagent under the water bath condition of 80 ℃, carrying out ion exchange by using a NaCl aqueous solution with the concentration of 1M, collecting the ion exchanged solution, titrating by using a 0.1M NaOH standard solution by taking phenolphthalein as an indicator until the solution turns pink, wherein the Ion Exchange Capacity (IEC) value of the target product can be calculated according to the following formula:
IEC＝(V NaOH ×C NaOH )/m
wherein: v (V) NaOH The volume of the NaOH standard solution consumed, mL,
C NaOH the molar concentration of NaOH standard solution, mmol/mL,
m-mass of dry target product, g.
2. Micelle particle size: the test was performed using a Brookhaven particle size analyzer.
3. Tensile strength: the test is carried out by using a GB/T1040-92 method.
4. Dimensional change rate: tested using the GB/T20042.3-2009 method.
5. Conductivity at 120 ℃): the temperature of the test condition is 120 ℃ measured by an electrochemical impedance tester.
The specific results of the above tests are detailed in Table 2.
TABLE 2 Performance index of proton exchange membranes prepared with resin dispersions of examples 1-4 and comparative examples 1-2
/>

Claims (9)

1. A fluorine-containing resin dispersion liquid, characterized by comprising a resin, an organic solvent and water; wherein the resin is a fluorine-containing resin, and the repeating unit of the fluorine-containing resin is shown as the following formula:
wherein k is an integer of 0 to 3, and f is an integer of 1 to 4;
a. b and c are independent integers of 1 to 20, a ', b ' and c ' are independent integers of 1 to 3;
x/(x+y+z)＝0.1～0.8，y/(x+y+z)＝0.05～0.5，z/(x+y+z)＝0.1～0.6；
wherein R is- (OCF) 2 ) m (CF 2 ) n X, wherein X is Cl or F; m and n are integers from 0 to 3.
2. The fluororesin dispersion according to claim 1, wherein the mass percentage of the fluororesin is 5 to 50%, the mass percentage of the organic solvent is 5 to 60%, and the mass percentage of the water is 20 to 75%.
3. The fluororesin dispersion according to claim 2, wherein the mass percentage of the fluororesin is 10% to 45%, the mass percentage of the organic solvent is 15% to 50%, and the mass percentage of the water is 30% to 50%.
4. The fluororesin dispersion according to claim 1, wherein the organic solvent is one or more of ethanol, ethylene glycol, dimethylformamide, N-propanol, isopropanol, acetone, glycerol, butanediol, diethylamine, dimethylacetamide, acetaldehyde, propylene glycol, ethylene oxide or N-methylpyrrolidine .
5. A process for preparing a fluororesin dispersion according to any one of claims 1 to 4, comprising the steps of:
(1) Firstly, preparing a mixed solvent consisting of water and an organic solvent, and then adding the fluorine-containing resin into the mixed solvent and transferring the mixed solvent into an autoclave;
(2) Under the protection of inert gas, mechanically stirring, controlling the temperature to be 100-260 ℃ and the pressure to be 2-5MPa, dissolving for 2-15 hours, stopping heating and stirring, cooling to room temperature and recovering to normal pressure to obtain a mixed solution;
(3) Transferring the mixed solution into a separating funnel, extracting and separating the mixed solution by carbon tetrachloride at normal temperature and normal pressure, and taking the lower layer solution to obtain the resin dispersion liquid with uniform dispersion, high chemical stability and high exchange capacity.
6. The method for producing a fluororesin dispersion according to claim 5, wherein the inert gas in the step (2) is one of nitrogen, argon or xenon.
7. The method for producing a fluororesin dispersion according to claim 5, wherein the dissolution temperature in step (2) is 160℃to 250℃and the dissolution time is 4 to 10 hours.
8. Use of the fluororesin dispersion according to any one of claims 1 to 4 or the fluororesin dispersion produced by the production process according to any one of claims 5 to 7 in polytetrafluoroethylene surface hydrophilization treatment, catalyst coating, electrochemical sensors and electrodialysis devices.
9. A high temperature fuel cell film characterized by being cast from the fluororesin dispersion according to any one of claims 1 to 4 or the fluororesin dispersion produced by the production method according to any one of claims 5 to 7.
CN202410033647.8A 2021-10-18 2022-10-18 Fluorine-containing resin dispersion liquid and preparation method and application thereof Pending CN117866132A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN2021112091919 2021-10-18
CN202111209191 2021-10-18
CN202211272311.4A CN115991829A (en) 2021-10-18 2022-10-18 Multi-copolymer containing perfluorobutyl ethyl ether, fluorine-containing resin and preparation method

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN202211272311.4A Division CN115991829A (en) 2021-10-18 2022-10-18 Multi-copolymer containing perfluorobutyl ethyl ether, fluorine-containing resin and preparation method

Publications (1)

Publication Number Publication Date
CN117866132A true CN117866132A (en) 2024-04-12

Family

ID=85993147

Family Applications (31)

Application Number Title Priority Date Filing Date
CN202211270056.XA Active CN115991825B (en) 2021-10-18 2022-10-17 Fluorine-containing ionic membrane and preparation method thereof
CN202211269110.9A Active CN115991821B (en) 2021-10-18 2022-10-17 Proton exchange membrane containing phosphonic acid structural unit and preparation method thereof
CN202211268613.4A Active CN115991816B (en) 2021-10-18 2022-10-17 High-temperature-resistant proton exchange membrane and preparation method thereof
CN202211269114.7A Active CN115991823B (en) 2021-10-18 2022-10-17 Mixed perfluorinated proton exchange membrane and preparation method thereof
CN202211268626.1A Active CN115991818B (en) 2021-10-18 2022-10-17 Multipolymer ion exchange membrane and preparation method thereof
CN202211270059.3A Active CN115991826B (en) 2021-10-18 2022-10-17 Perfluorinated phosphonic acid ion exchange membrane and preparation method thereof
CN202211269764.1A Active CN115991824B (en) 2021-10-18 2022-10-17 Proton exchange membrane containing annular structural unit and preparation method thereof
CN202211268637.XA Active CN115991819B (en) 2021-10-18 2022-10-17 Phosphonic acid sulfonic acid composite proton exchange membrane and preparation method thereof
CN202211269108.1A Active CN115991820B (en) 2021-10-18 2022-10-17 Polymeric phosphonic acid ionic membrane and preparation method thereof
CN202211269112.8A Pending CN115991822A (en) 2021-10-18 2022-10-17 Ionic polymer membrane containing perfluorobutyl ethyl ether and preparation method thereof
CN202211268622.3A Active CN115991817B (en) 2021-10-18 2022-10-17 Phosphonic acid sulfonic acid copolymer ion exchange membrane and preparation method thereof
CN202211276230.1A Active CN115991835B (en) 2021-10-18 2022-10-18 Wide-temperature-zone polymerized phosphonic acid resin and preparation method thereof
CN202211272311.4A Pending CN115991829A (en) 2021-10-18 2022-10-18 Multi-copolymer containing perfluorobutyl ethyl ether, fluorine-containing resin and preparation method
CN202410033647.8A Pending CN117866132A (en) 2021-10-18 2022-10-18 Fluorine-containing resin dispersion liquid and preparation method and application thereof
CN202211276153.XA Active CN115991833B (en) 2021-10-18 2022-10-18 Breathable fluorine-containing ionic polymer and preparation method thereof
CN202211272307.8A Pending CN115991828A (en) 2021-10-18 2022-10-18 Perfluorinated sulfonic acid resins containing phosphonic acid structural units
CN202410230517.3A Pending CN118165162A (en) 2021-10-18 2022-10-18 Breathable fluorine-containing ion exchange resin dispersion liquid and preparation method thereof
CN202410035268.2A Pending CN117946314A (en) 2021-10-18 2022-10-18 Multipolymer ion exchange resin dispersion liquid, preparation method and application thereof
CN202211276307.5A Active CN115991836B (en) 2021-10-18 2022-10-18 Phosphonic acid sulfonic acid copolymer ion resin and preparation method thereof
CN202211272342.XA Active CN115991832B (en) 2021-10-18 2022-10-18 Mixed fluorine-containing ion resin
CN202311638556.9A Pending CN117683166A (en) 2021-10-18 2022-10-18 High-temperature-resistant fluorine-containing ion exchange resin dispersion liquid and preparation method thereof
CN202410230518.8A Pending CN118165163A (en) 2021-10-18 2022-10-18 Mixed fluorine-containing ion resin dispersion liquid and preparation method thereof
CN202410252886.2A Pending CN118184855A (en) 2021-10-18 2022-10-18 Phosphonic acid sulfonic acid copolymer ion resin dispersion liquid and preparation method thereof
CN202311634040.7A Pending CN117700598A (en) 2021-10-18 2022-10-18 Fluorine-containing resin dispersion liquid containing cyclic structure and preparation method thereof
CN202211272339.8A Active CN115991831B (en) 2021-10-18 2022-10-18 Fluorine-containing resin containing cyclic structure and preparation method thereof
CN202410035282.2A Pending CN117866133A (en) 2021-10-18 2022-10-18 Perfluorinated sulfonic acid resin dispersion containing phosphonic acid structural units, and preparation method and application thereof
CN202211276154.4A Active CN115991834B (en) 2021-10-18 2022-10-18 Fluorine-containing sulfonic acid phosphonic acid resin with high oxygen permeability and high temperature proton conductivity and preparation method thereof
CN202211272321.8A Active CN115991830B (en) 2021-10-18 2022-10-18 High temperature resistant functional polymer
CN202410243495.4A Pending CN118184854A (en) 2021-10-18 2022-10-18 High-oxygen-permeability fluorine-containing phosphoric acid-sulfonic acid resin dispersion liquid and preparation method thereof
CN202211272292.5A Pending CN115991827A (en) 2021-10-18 2022-10-18 Multi-copolymer containing sulfonyl fluoride, ion exchange resin and preparation method
CN202311588777.XA Pending CN117700597A (en) 2021-10-18 2022-10-18 Polymeric phosphonic acid resin dispersion liquid and preparation method and application thereof

Family Applications Before (13)

Application Number Title Priority Date Filing Date
CN202211270056.XA Active CN115991825B (en) 2021-10-18 2022-10-17 Fluorine-containing ionic membrane and preparation method thereof
CN202211269110.9A Active CN115991821B (en) 2021-10-18 2022-10-17 Proton exchange membrane containing phosphonic acid structural unit and preparation method thereof
CN202211268613.4A Active CN115991816B (en) 2021-10-18 2022-10-17 High-temperature-resistant proton exchange membrane and preparation method thereof
CN202211269114.7A Active CN115991823B (en) 2021-10-18 2022-10-17 Mixed perfluorinated proton exchange membrane and preparation method thereof
CN202211268626.1A Active CN115991818B (en) 2021-10-18 2022-10-17 Multipolymer ion exchange membrane and preparation method thereof
CN202211270059.3A Active CN115991826B (en) 2021-10-18 2022-10-17 Perfluorinated phosphonic acid ion exchange membrane and preparation method thereof
CN202211269764.1A Active CN115991824B (en) 2021-10-18 2022-10-17 Proton exchange membrane containing annular structural unit and preparation method thereof
CN202211268637.XA Active CN115991819B (en) 2021-10-18 2022-10-17 Phosphonic acid sulfonic acid composite proton exchange membrane and preparation method thereof
CN202211269108.1A Active CN115991820B (en) 2021-10-18 2022-10-17 Polymeric phosphonic acid ionic membrane and preparation method thereof
CN202211269112.8A Pending CN115991822A (en) 2021-10-18 2022-10-17 Ionic polymer membrane containing perfluorobutyl ethyl ether and preparation method thereof
CN202211268622.3A Active CN115991817B (en) 2021-10-18 2022-10-17 Phosphonic acid sulfonic acid copolymer ion exchange membrane and preparation method thereof
CN202211276230.1A Active CN115991835B (en) 2021-10-18 2022-10-18 Wide-temperature-zone polymerized phosphonic acid resin and preparation method thereof
CN202211272311.4A Pending CN115991829A (en) 2021-10-18 2022-10-18 Multi-copolymer containing perfluorobutyl ethyl ether, fluorine-containing resin and preparation method

Family Applications After (17)

Application Number Title Priority Date Filing Date
CN202211276153.XA Active CN115991833B (en) 2021-10-18 2022-10-18 Breathable fluorine-containing ionic polymer and preparation method thereof
CN202211272307.8A Pending CN115991828A (en) 2021-10-18 2022-10-18 Perfluorinated sulfonic acid resins containing phosphonic acid structural units
CN202410230517.3A Pending CN118165162A (en) 2021-10-18 2022-10-18 Breathable fluorine-containing ion exchange resin dispersion liquid and preparation method thereof
CN202410035268.2A Pending CN117946314A (en) 2021-10-18 2022-10-18 Multipolymer ion exchange resin dispersion liquid, preparation method and application thereof
CN202211276307.5A Active CN115991836B (en) 2021-10-18 2022-10-18 Phosphonic acid sulfonic acid copolymer ion resin and preparation method thereof
CN202211272342.XA Active CN115991832B (en) 2021-10-18 2022-10-18 Mixed fluorine-containing ion resin
CN202311638556.9A Pending CN117683166A (en) 2021-10-18 2022-10-18 High-temperature-resistant fluorine-containing ion exchange resin dispersion liquid and preparation method thereof
CN202410230518.8A Pending CN118165163A (en) 2021-10-18 2022-10-18 Mixed fluorine-containing ion resin dispersion liquid and preparation method thereof
CN202410252886.2A Pending CN118184855A (en) 2021-10-18 2022-10-18 Phosphonic acid sulfonic acid copolymer ion resin dispersion liquid and preparation method thereof
CN202311634040.7A Pending CN117700598A (en) 2021-10-18 2022-10-18 Fluorine-containing resin dispersion liquid containing cyclic structure and preparation method thereof
CN202211272339.8A Active CN115991831B (en) 2021-10-18 2022-10-18 Fluorine-containing resin containing cyclic structure and preparation method thereof
CN202410035282.2A Pending CN117866133A (en) 2021-10-18 2022-10-18 Perfluorinated sulfonic acid resin dispersion containing phosphonic acid structural units, and preparation method and application thereof
CN202211276154.4A Active CN115991834B (en) 2021-10-18 2022-10-18 Fluorine-containing sulfonic acid phosphonic acid resin with high oxygen permeability and high temperature proton conductivity and preparation method thereof
CN202211272321.8A Active CN115991830B (en) 2021-10-18 2022-10-18 High temperature resistant functional polymer
CN202410243495.4A Pending CN118184854A (en) 2021-10-18 2022-10-18 High-oxygen-permeability fluorine-containing phosphoric acid-sulfonic acid resin dispersion liquid and preparation method thereof
CN202211272292.5A Pending CN115991827A (en) 2021-10-18 2022-10-18 Multi-copolymer containing sulfonyl fluoride, ion exchange resin and preparation method
CN202311588777.XA Pending CN117700597A (en) 2021-10-18 2022-10-18 Polymeric phosphonic acid resin dispersion liquid and preparation method and application thereof

Country Status (1)

Country Link
CN (31) CN115991825B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115991825B (en) * 2021-10-18 2023-12-22 山东东岳未来氢能材料股份有限公司 Fluorine-containing ionic membrane and preparation method thereof

Family Cites Families (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4810806A (en) * 1987-07-31 1989-03-07 E. I. Du Pont De Nemours And Company Halogenated 1,3-dioxolanes and derivatives
JPH09188795A (en) * 1995-12-29 1997-07-22 Asahi Glass Co Ltd Liquid composition of perfluorocarbon polymer containing fluorosulfonyl group
JPH11307108A (en) * 1998-04-23 1999-11-05 Asahi Glass Co Ltd Manufacture of electrode-membrane joined body for solid high polymer electrolyte fuel cell
US6087032A (en) * 1998-08-13 2000-07-11 Asahi Glass Company Ltd. Solid polymer electrolyte type fuel cell
JP4406984B2 (en) * 1999-12-22 2010-02-03 旭硝子株式会社 COATING LIQUID FOR ELECTROLYTE FOR SOLID POLYMER ELECTROLYTE FUEL CELL AND METHOD FOR PRODUCING ELECTRODE FOR SOLID POLYMER ELECTROLYTE FUEL CELL
JP5028711B2 (en) * 2000-02-15 2012-09-19 旭硝子株式会社 Polymer electrolyte fuel cell
ATE480878T1 (en) * 2003-01-20 2010-09-15 Asahi Glass Co Ltd PRODUCTION METHOD FOR ELECTROLYTE MATERIAL FOR SOLID POLYMER FUEL CELLS AND MEMBRANE ELECTRODE ARRANGEMENT FOR SOLID POLYMER FUEL CELLS
CN100530442C (en) * 2003-04-28 2009-08-19 旭硝子株式会社 Solid polymer electrolyte material, production method thereof and membrane electrode assembly for solid polymer electrolyte fuel cell
EP1734603B1 (en) * 2004-04-02 2010-01-06 Asahi Glass Company, Limited Electrolyte material for polymer electrolyte fuel cells, electrolyte membrane and membrane- electrode assembly
JP4788267B2 (en) * 2004-10-26 2011-10-05 旭硝子株式会社 Polymer having fluorosulfonyl group and 1,3-dioxolane structure and use thereof
JP4810868B2 (en) * 2005-04-19 2011-11-09 旭硝子株式会社 ELECTROLYTE MEMBRANE FOR SOLID POLYMER FUEL CELL, METHOD FOR PRODUCING THE SAME, MEMBRANE ELECTRODE ASSEMBLY FOR SOLID POLYMER TYPE FUEL CELL, AND METHOD FOR OPERATING THE SAME
JP5011662B2 (en) * 2005-07-01 2012-08-29 旭硝子株式会社 Method for producing electrolyte membrane for polymer electrolyte fuel cell
JP4867843B2 (en) * 2007-08-09 2012-02-01 旭硝子株式会社 Fluorosulfonyl group-containing monomer and polymer thereof, and sulfonic acid group-containing polymer
JP5316413B2 (en) * 2007-09-12 2013-10-16 信越化学工業株式会社 Solid polymer electrolyte membrane, method for producing solid polymer electrolyte membrane, and fuel cell
US7989566B2 (en) * 2008-01-22 2011-08-02 Dupont Performance Elastomers Llc Process for producing fluoropolymers
CN101320818B (en) * 2008-07-15 2010-06-09 山东东岳神舟新材料有限公司 Fibre reinforced multi-layer fluorine-contained ionic exchange film
CN101721922B (en) * 2008-07-22 2011-12-28 山东华夏神舟新材料有限公司 Microporous film enhanced multilayer fluorine-containing crosslinked ion-doped film and preparation method thereof
EP2436705B1 (en) * 2009-05-29 2018-01-24 Asahi Glass Company, Limited Electrolyte material, liquid composite, and membrane electrode assembly for solid polymer fuel cells
US20110027687A1 (en) * 2009-07-31 2011-02-03 Asahi Glass Company, Limited Electrolyte material, liquid composition and membrane/electrode assembly for polymer electrolyte fuel cell
FR2951729B1 (en) * 2009-10-22 2011-12-23 Commissariat Energie Atomique COPOLYMERS COMPRISING PHOSPHONATE GROUPS AND / OR PHOSPHONIC ACID USEFUL FOR CONSTITUTING FUEL CELL MEMBRANES
CN101768235B (en) * 2009-12-03 2010-12-29 山东东岳神舟新材料有限公司 Functional high-exchange-capacity ion exchange resin and preparation method thereof
CN101768234B (en) * 2009-12-03 2010-12-29 山东东岳神舟新材料有限公司 Fluoric polymer and preparing method thereof
CN101775095B (en) * 2009-12-03 2010-12-29 山东东岳神舟新材料有限公司 Functional perfluoro resin and preparation method thereof
CN101773792B (en) * 2009-12-07 2012-11-14 山东华夏神舟新材料有限公司 Inorganic metal ion mixing with fluorine proton exchange membrane and preparing method thereof
CN101777658A (en) * 2009-12-07 2010-07-14 山东东岳神舟新材料有限公司 Fluorine-containing proton exchange membrane for fuel cell
CN101728549B (en) * 2009-12-10 2011-05-04 山东东岳神舟新材料有限公司 High-temperature proton exchange compound film
EP2511311B1 (en) * 2009-12-11 2013-11-27 Shandong Huaxia Shenzhou New Material Co., Ltd. Perfluorinated ion exchange resin, preparation method and use thereof
CN101709101B (en) * 2009-12-15 2011-09-07 山东东岳神舟新材料有限公司 Perfluorinated ion exchange resin with high exchange capacity, preparation method and application thereof
CN101709102B (en) * 2009-12-15 2012-11-14 山东华夏神舟新材料有限公司 Perfluorinated resin with high exchange capacity as well as preparation method and application thereof
JP5486693B2 (en) * 2009-12-15 2014-05-07 シャンドン・フアシャ・シェンゾウ・ニュー・マテリアル・カンパニー・リミテッド High exchange capacity perfluorinated ion exchange resin, method for its preparation and use
CN101768236B (en) * 2009-12-25 2012-02-08 山东华夏神舟新材料有限公司 Perfluorinated ion exchange resin as well as preparation method and application thereof
WO2011075877A1 (en) * 2009-12-25 2011-06-30 山东东岳神舟新材料有限公司 Perfluorinated ion exchange resin, preparation method and use thereof
CN102008905B (en) * 2010-06-18 2013-09-25 山东华夏神舟新材料有限公司 Proton exchange film as well as preparation method and application thereof
CN102024958B (en) * 2010-06-18 2013-09-25 山东华夏神舟新材料有限公司 Proton exchange membrane and preparation method and application thereof
WO2011156937A1 (en) * 2010-06-18 2011-12-22 山东东岳神舟新材料有限公司 Fluorine containing ionomer composite with ion exchange function, preparation method and use thereof
CN102522576B (en) * 2011-12-24 2013-12-04 山东东岳高分子材料有限公司 Fuel cell membrane with high tolerance and its preparation method
CN104134812B (en) * 2013-05-02 2017-02-08 山东东岳高分子材料有限公司 Fiber-net-reinforced polymer electrolyte membrane and preparation method thereof
CN104134813B (en) * 2013-05-02 2016-12-28 山东东岳高分子材料有限公司 A kind of long-life polyelectrolyte film and preparation method thereof
CN103864979A (en) * 2014-03-06 2014-06-18 山东华夏神舟新材料有限公司 Fluorine-containing polymer and preparation method thereof
JP6524835B2 (en) * 2015-07-27 2019-06-05 Ａｇｃ株式会社 Method for producing fluorosulfonyl group-containing monomer, fluorosulfonyl group-containing polymer, sulfonic acid group-containing polymer, liquid composition and membrane electrode assembly
EP3910711B1 (en) * 2019-01-08 2023-08-09 Agc Inc. Catalyst layer, catalyst layer forming liquid and membrane electrode assembly
CN112436168A (en) * 2020-11-30 2021-03-02 山东东岳未来氢能材料股份有限公司 Long-life enhanced perfluorinated proton membrane and preparation method thereof
CN115991825B (en) * 2021-10-18 2023-12-22 山东东岳未来氢能材料股份有限公司 Fluorine-containing ionic membrane and preparation method thereof

Also Published As

Publication number Publication date
CN117700598A (en) 2024-03-15
CN115991833A (en) 2023-04-21
CN115991833B (en) 2024-04-12
CN115991825A (en) 2023-04-21
CN115991821B (en) 2023-12-22
CN115991834A (en) 2023-04-21
CN115991822A (en) 2023-04-21
CN115991834B (en) 2024-04-12
CN115991820A (en) 2023-04-21
CN115991825B (en) 2023-12-22
CN118165162A (en) 2024-06-11
CN115991823A (en) 2023-04-21
CN118184855A (en) 2024-06-14
CN115991829A (en) 2023-04-21
CN115991816B (en) 2024-01-23
CN115991824B (en) 2023-12-22
CN117683166A (en) 2024-03-12
CN115991835B (en) 2024-01-05
CN115991836A (en) 2023-04-21
CN115991830A (en) 2023-04-21
CN115991817B (en) 2024-01-23
CN115991832B (en) 2024-04-12
CN115991819B (en) 2024-05-03
CN115991827A (en) 2023-04-21
CN115991820B (en) 2024-01-05
CN115991817A (en) 2023-04-21
CN118184854A (en) 2024-06-14
CN115991826B (en) 2023-12-22
CN115991831B (en) 2024-01-12
CN115991824A (en) 2023-04-21
CN117946314A (en) 2024-04-30
CN115991818B (en) 2024-05-14
CN115991830B (en) 2024-01-05
CN115991826A (en) 2023-04-21
CN115991828A (en) 2023-04-21
CN115991819A (en) 2023-04-21
CN115991818A (en) 2023-04-21
CN118165163A (en) 2024-06-11
CN117866133A (en) 2024-04-12
CN115991821A (en) 2023-04-21
CN115991836B (en) 2024-04-12
CN115991816A (en) 2023-04-21
CN117700597A (en) 2024-03-15
CN115991832A (en) 2023-04-21
CN115991823B (en) 2023-12-29
CN115991831A (en) 2023-04-21
CN115991835A (en) 2023-04-21

Similar Documents

Publication Publication Date Title
WO2011069281A1 (en) Perfluorinated ion exchange resin, preparation method and use thereof
CN117866132A (en) Fluorine-containing resin dispersion liquid and preparation method and application thereof
EP2514773B1 (en) High exchange capacity perfluorinated ion exchange resin, preparation method and use thereof
CN113861327A (en) Perfluorosulfonic acid resin binder with high proton conductivity and mechanical properties and preparation method thereof
WO2011075877A1 (en) Perfluorinated ion exchange resin, preparation method and use thereof
CN113121764A (en) Branched polyarylether ion exchange membrane and preparation method thereof
CN117264107A (en) Ion exchange resin and preparation method thereof, and ion exchange resin film and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination