CN114085309A - Solution polymerization preparation method of perfluorosulfonic acid resin - Google Patents
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
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- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
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Abstract
The invention discloses a solution polymerization preparation method of perfluorosulfonic acid resin, which comprises the following steps: pre-adding a fluorine-containing solvent and a comonomer into a reactor by taking tetrafluoroethylene A, a monomer B containing a sulfonyl fluoride end group and a monomer C containing a sulfonyl fluoride end group as comonomers, heating to 20-120 ℃, keeping the pressure at 0.2-5 MPa, adding an initiator to initiate a polymerization reaction, and supplementing the comonomer in the reaction process to finally obtain the sulfonyl fluoride type perfluorinated sulfonic acid resin; wherein the structural formula of the monomer B is as follows: CF2＝CFO[CF2CF(CF3)O]a[CF2CF2]bSO2F, wherein a is an integer of 0-1, and b is an integer of 1-2; the structural formula of monomer C:
the perfluorinated sulfonic acid resin disclosed by the invention also comprises a fluorine-containing cyclic monomer unit of a perfluorinated alkoxy group and a sulfonyl fluoride group which simultaneously contain ether bonds, so that the processability in a general solvent is improved, and the perfluorinated sulfonic acid resin is high in conductivity and oxygen permeability. Perfluorosulfonic acid resins that provide low hydrogen permeability for proton exchange membrane applications in fuel cells or high oxygen permeability for electrode applications. The solution polymerization method has low danger and is easy to adjust the molecular weight and molecular weight distribution of the product.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a solution polymerization preparation method of perfluorosulfonic acid resin.
Background
A proton membrane fuel cell is a new type of fuel cell, the electrolyte is a solid organic membrane, the membrane can conduct proton under the humidification condition, it generally uses platinum as catalyst, the working environment temperature is generally 60-80 ℃, it belongs to low temperature fuel cell, the proton exchange membrane fuel cell monomer mainly comprises membrane electrode, sealing ring and flow field plate with air guide channel, the membrane electrode is the core part of the proton exchange membrane fuel cell, the middle is a thin membrane, namely proton exchange membrane, the membrane does not conduct electron, it is the good conductor of hydrogen ion, it not only is used as the channel of electrolyte providing hydrogen ion, but also is used as the diaphragm to separate two pole reaction gas, the two sides of the membrane are gas electrodes, composed of carbon paper and catalyst, the anode is hydrogen electrode, the cathode is oxygen electrode, the flow field plate is generally made of graphite, the proton exchange membrane fuel cell uses hydrogen as fuel, a plurality of battery monomers are connected in series or in parallel according to requirements to form battery packs with different powers.
At present, the proton conducting membrane in the proton membrane fuel cell is mainly perfluorosulfonic acid resin, and relevant patents and reports on research and preparation of perfluorosulfonic acid resin have appeared.
CN101220120A discloses a fluororesin with sulfuryl fluoride and ether end group side groups, which is formed by the ternary copolymerization of alkyl ether end group vinyl ether monomer (A), tetrafluoroethylene (B) and sulfuryl fluoride end group vinyl ether monomer (C), wherein the molecular formula of a polymer chain is as follows, and the product has high ion exchange capacity and maintains physical strength.
Wherein a is an integer of 0 to 3, c is an integer of 0 to 3, b is an integer of 1 to 6, and d is an integer of 1 to 6;
m, n and p are positive integers of 1-100; r is CxH2x+1,x＝1～4。
However, the alkyl ether terminal vinyl ether monomer (A) does not contain a sulfonyl fluoride terminal functional group, and the resin prepared by introducing the sulfonyl fluoride terminal functional group is difficult to improve the electric conductivity and has poor oxygen permeability.
The preparation of the resin generally comprises four methods, namely bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization, and the solution polymerization method adopted by the invention has the advantages of easy temperature control and less danger, but needs subsequent solvent separation.
Disclosure of Invention
The invention aims to provide a solution polymerization preparation method of perfluorosulfonic acid resin, and the prepared perfluorosulfonic acid resin has high conductivity and good oxygen permeability.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing perfluorosulfonic acid resin by solution polymerization comprises the following steps: taking tetrafluoroethylene A, a monomer B containing a sulfonyl fluoride end group and a monomer C containing a sulfonyl fluoride end group as comonomers, pre-adding the comonomers into a reactor, heating to 30-100 ℃, keeping the pressure at 0.5-5 MPa, adding an initiator to initiate polymerization, and supplementing the comonomers in the reaction process to finally obtain the sulfonyl fluoride type perfluorinated sulfonic acid resin;
wherein the structural formula of the monomer B is as follows:
CF2＝CFO[CF2CF(CF3)O]a[CF2CF2]bSO2f, wherein a is an integer of 0-1, and b is an integer of 1-2;
the structural formula of monomer C:
preferably, the sulfonyl fluoride type perfluorosulfonic acid resin has the following structural formula:
preferably, the fluorine-containing solvent is one of 1H-perfluorohexane, dichloropentafluoropropane and 1,1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether or a mixture thereof.
Preferably, when the comonomer is pre-added, the weight ratio of tetrafluoroethylene A: the molar ratio of the (monomer B + the monomer C) is 1: 1-10: 1, preferably 3: 1-6: 1, wherein the molar ratio of the monomer B to the monomer C is 20: 1-1: 2, preferably 10: 1-1: 1.
Preferably, when the comonomers are supplemented, if three comonomers are supplemented, the weight ratio of tetrafluoroethylene A: the molar ratio of the (monomer B + the monomer C) is 20: 1-1: 20, preferably 10: 1-1: 10; the molar ratio of the monomer B to the monomer C is 20: 1-1: 2, preferably 10: 1-1: 1.
Preferably, when the comonomer is supplemented, if only tetrafluoroethylene A is supplemented, the molar ratio of the addition amount of the tetrafluoroethylene A to the initial charging amount is 1: 2-1: 6, preferably 1: 1-1: 4.
Preferably, when the comonomer is supplemented, if only the monomer B and the monomer C are supplemented, the molar ratio of the addition amount to the initial feeding amount is 1: 2-1: 5, and preferably 1: 1-1: 3; the molar ratio of the monomer B to the monomer C is 20: 1-1: 2, preferably 10: 1-1: 1.
Preferably, the initiator is one of a perfluorobutyryl peroxide compound, diisopropyl peroxydicarbonate or a mixture thereof.
Preferably, methanol or cyclohexane is used as chain transfer agent in the copolymerization process, preferably cyclohexane.
Preferably, the method further comprises a post-treatment step of: tabletting sulfonyl fluoride type perfluorinated sulfonic acid resin by using a flat vulcanizing machine at the temperature of 240 ℃, cutting the flaky resin into small particles, placing the small particles into 20 wt% potassium hydroxide solution with the weight being 10 times that of the flaky resin, converting the small particles under the reflux state for 36 hours, taking out the resin, washing the resin to be neutral by using pure water, soaking the resin for 10 times by using 20 wt% nitric acid solution for 1 hour each time, washing the resin to be neutral, drying the resin at the temperature of 100 ℃ for 24 hours to obtain hydrogen type perfluorinated sulfonic acid resin, and placing the hydrogen type perfluorinated sulfonic acid resin into a dryer for cooling.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
in addition to the conventional polymerized monomer units containing tetrafluoroethylene and sulfonyl fluoride groups, the perfluorosulfonic acid resin disclosed by the invention also contains fluorine-containing cyclic monomer units containing perfluoroalkoxy and sulfonyl fluoride groups which simultaneously contain ether bonds, and the five-membered ring and the branched structure contained by the five-membered ring destroy the molecular regularity, so that the whole molecular chain is difficult to crystallize, and the solubility of the copolymer can be improved, thereby improving the processability of the copolymer in a general-purpose solvent. In addition, the fluorine-containing cyclic monomer also has sulfonyl fluoride functional groups, so that the final product has higher conductivity. The fluorine-containing polymer having a dioxolane structure has high affinity with oxygen and is useful for a film requiring high oxygen permeability. Thus the inclusion of dioxolane monomer units also typically provides low hydrogen permeability for proton exchange membrane applications in fuel cells or high oxygen permeability perfluorosulfonic acid resins for electrode applications.
Compared with a bulk polymerization method, the solution polymerization method uses a fluorine-containing solvent as a medium, so that the system has low viscosity, is easy for mass transfer and heat transfer, and is easy to control the system temperature; the monomer concentration is relatively low, and the automatic acceleration effect is not easy to occur when the free radical initiates polymerization, so that the implosion is avoided, and the danger is reduced; local overheating can be avoided, the gel effect is reduced, and the molecular weight distribution of the product are easy to adjust; the addition of a fluorine-containing emulsifier which is required by an emulsion polymerization method and easily causes environmental protection problems is not needed; however, the solvent may generate chain transfer effect to reduce the molecular weight of the polymer, so that the formula and process conditions need to be adjusted according to the characteristics of the solvent to improve the reaction rate and ensure a certain molecular weight. When the organic solvent is used, separation equipment is required to be arranged, the steps of solvent evaporation, recovery, refining and the like are added, the solvent is repeatedly used, washing for removing the emulsifier (emulsion polymerization method) or the suspending agent (suspension polymerization method) is not required, resin impurities are less, and the amount of wastewater is very small.
Drawings
The invention is further illustrated below with reference to the accompanying drawings.
FIG. 1 is an infrared spectrum of a perfluorosulfonic acid resin prepared in example 1.
Detailed Description
The following examples are further illustrative of the present invention, but the present invention is not limited thereto.
Unless otherwise specified, the reaction vessels used in each of the examples and comparative examples were 600mL stainless steel autoclave reactors equipped with a thermometer, a pressure gauge, a heater, a stirring paddle, a liquid metering pump, a feed pipe and a valve, a discharge pipe and a valve, a mass flow meter, and the like.
The perfluorosulfonic acid resins prepared in examples and comparative examples were transformed and tested by the following methods:
pressing sulfonyl fluoride type perfluorinated sulfonic acid resin into a film with the thickness of about 100 mu m by a flat vulcanizing machine, controlling the temperature to be 240 ℃, cutting sheet-shaped resin into small particles, placing the small particles into 20 wt% potassium hydroxide solution with the weight being 10 times of that of the small particles, converting the small particles under a reflux state for 36 hours, taking out the resin, washing the resin to be neutral by pure water, soaking the resin for 10 times by 20 wt% nitric acid solution for 1 hour each time, washing the resin to be neutral, drying the resin at 100 ℃ for 24 hours to obtain hydrogen type perfluorinated sulfonic acid resin, and placing the hydrogen type perfluorinated sulfonic acid resin in a dryer for cooling. Ion exchange Equivalent Weight (EW) was tested with reference to GB/T20042.3 and oxygen permeability was tested with reference to GB/T19789.
Example 1:
and cleaning and drying the reaction kettle, vacuumizing and filling nitrogen for replacement until the water content is below 100ppm and the oxygen content is below 10 ppm. The tetrafluoroethylene monomer was evacuated to 0.1MPa and then to 0.0001MPa, 300mL of 1H-perfluorohexane, 45g of monomer CF2＝CFOCF2CF(CF3)OCF2CF2SO2F、56gCF2＝CFOCF2CF2SO2F and 17g of monomer C are added into a reaction kettle, the temperature is raised to 60 ℃, tetrafluoroethylene is introduced until the pressure reaches 2MPa, and 10mL of perfluorobutyryl peroxide (CF) compound containing 0.02g of perfluorobutyryl peroxide is added by a metering pump3CF2CF2CO-OO-CCF2CF2CF3) Maintaining the reaction pressure at about 2MPa, and continuously adding 45g of monomer CF2＝CFOCF2CF(CF3)OCF2CF2SO2F and 8.5g of monomer C, when the addition amount of the tetrafluoroethylene reaches 100g, stopping adding, allowing the reaction to continue, and when the pressure in the kettle is reduced to 1MPa, stopping the reaction, and recovering the unreacted tetrafluoroethylene monomer. Discharging the materials, transferring the materials into a glass flask, and performing vacuum rotary evaporation to remove unreacted sulfonyl fluoride monomers and solvent to obtain a white powdery product, and simultaneously recovering the unreacted sulfonyl fluoride monomers and the solvent. And further drying the product at 100 ℃ for 24 hours to obtain the dried sulfonyl fluoride type perfluorinated sulfonic acid resin. The resin film after the conversion had an EW value of 1207g/mol and an oxygen gas permeation constant of 2.1cm3/(m·24h·0.1MPa)。
Example 2:
and cleaning and drying the reaction kettle, vacuumizing and filling nitrogen for replacement until the water content is below 100ppm and the oxygen content is below 10 ppm. Vacuumizing to 0.1MPa, vacuumizing to 0.0001MPa, and adding 300mL of dichloropentafluoropropane and 27g of CF monomer2＝CFOCF2CF(CF3)OCF2CF2SO2F and 51g of monomer C are added into a reaction kettle, the temperature is controlled to 20 ℃, tetrafluoroethylene is introduced until the pressure reaches 1MPa, 10mL of initiator solution containing 0.1g of diisopropyl peroxydicarbonate (IPP) is added by a metering pump, the reaction pressure is maintained at about 1MPa, and 90g of monomer CF is continuously supplemented2＝CFOCF2CF(CF3)OCF2CF2SO2F and 0.5g of monomer C, when the addition of the tetrafluoroethylene reaches 100g, stopping adding, allowing the reaction to continue, and when the pressure in the kettle is reduced to 0.2MPa, stopping the reaction, and recovering the unreacted tetrafluoroethylene monomer. Discharging the materials, transferring the materials into a glass flask, and distilling off unreacted sulfonyl fluoride monomer and solvent under vacuum to obtain white powderFurther drying the product at 100 ℃ for 24 hours to obtain the dried sulfonyl fluoride type perfluorinated sulfonic acid resin. The resin film after the transformation had an EW value of 1043g/mol and an oxygen gas permeation constant of 3.2cm3/(m·24h·0.1MPa)。
Example 3:
and cleaning and drying the reaction kettle, vacuumizing and filling nitrogen for replacement until the water content is below 100ppm and the oxygen content is below 10 ppm. Vacuumizing to 0.1MPa, vacuumizing to 0.0001MPa, and adding 1 mL, 1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether and CF (180 g) monomer2＝CFOCF2CF(CF3)OCF2CF2SO2F and 8.5g of monomer C are added into a reaction kettle, the temperature is increased to 120 ℃, tetrafluoroethylene is introduced until the pressure reaches 5MPa, then the addition of the tetrafluoroethylene is stopped, and 10mL of a Compound (CF) containing 0.01g of perfluorobutyryl peroxide is added by a metering pump3CF2CF2CO-OO-CCF2CF2CF3) And 0.01g of methanol in a solution of an initiator and a chain transfer agent, with 4.5g of the CF monomer being continuously added2＝CFOCF2CF(CF3)OCF2CF2SO2F and 21g of the monomer C, and when the pressure in the kettle is reduced to 1MPa, stopping the reaction, and recovering the unreacted tetrafluoroethylene monomer. Discharging the materials, transferring the materials into a glass flask, and performing vacuum rotary evaporation to remove unreacted sulfonyl fluoride monomers and solvent to obtain a white powdery product, and simultaneously recovering the unreacted sulfonyl fluoride monomers and the solvent. And further drying the product at 100 ℃ for 24 hours to obtain the dried sulfonyl fluoride type perfluorinated sulfonic acid resin. The resin film after the conversion had an EW value of 1325g/mol and an oxygen gas permeation constant of 2.3cm3/(m·24h·0.1MPa)。
Example 4:
and cleaning and drying the reaction kettle, vacuumizing and filling nitrogen for replacement until the water content is below 100ppm and the oxygen content is below 10 ppm. Vacuumizing and charging tetrafluoroethylene monomer to 0.1MPa, vacuumizing to 0.0001MPa, and then charging 300mL of 1,1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether and 134g of monomer CF2＝CFOCF2CF(CF3)OCF2CF2SO2F and 42.5g of monomer C were addedIn the reaction vessel, the temperature was raised to 80 ℃ and tetrafluoroethylene was introduced until the pressure reached 3MPa, and 10mL of a perfluorobutyryl peroxide (CF) containing 0.02g was added by a metering pump3CF2CF2CO-OO-CCF2CF2CF3) The initiator solution (2) is prepared by maintaining the reaction pressure at about 3MPa, and when the amount of tetrafluoroethylene added reaches 150g, the reaction is stopped and the unreacted tetrafluoroethylene monomer is recovered. Discharging the materials, transferring the materials into a glass flask, and carrying out vacuum rotary evaporation to remove the unreacted sulfonyl fluoride monomer and the solvent to obtain a white powdery product, and simultaneously recovering the unreacted sulfonyl fluoride monomer and the solvent. And further drying the product at 100 ℃ for 24 hours to obtain the dried sulfonyl fluoride type perfluorinated sulfonic acid resin. The resin film after the conversion had an EW value of 921g/mol and an oxygen permeability constant of 2.7cm3/(m·24h·0.1MPa)。
Example 5:
and cleaning and drying the reaction kettle, vacuumizing and filling nitrogen for replacement until the water content is below 100ppm and the oxygen content is below 10 ppm. Charging tetrafluoroethylene monomer to 0.1MPa by vacuum pumping, further vacuumizing to 0.0001MPa, then charging 100mL of 1H-perfluorohexane, dichloropentafluoropropane and 1,1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether, 84g of monomer CF2＝CFOCF2CF2SO2F and 85g of monomer C are added into a reaction kettle, the temperature is raised to 40 ℃, tetrafluoroethylene is introduced until the pressure reaches 4MPa, 10mL of initiator and chain transfer agent solution containing 0.05g of diisopropyl peroxydicarbonate (IPP) and 0.02g of cyclohexane are added by a metering pump, the reaction pressure is maintained at about 4MPa, and 4.5g of monomer CF is continuously supplemented2＝CFOCF2CF(CF3)OCF2CF2SO2F and 8.5g of monomer C, and when the amount of tetrafluoroethylene added reached 150g, the reaction was stopped and unreacted tetrafluoroethylene monomer was recovered. Discharging the materials, transferring the materials into a glass flask, and performing vacuum rotary evaporation to remove unreacted sulfonyl fluoride monomers and solvent to obtain a white powdery product, and simultaneously recovering the unreacted sulfonyl fluoride monomers and the solvent. And further drying the product at 100 ℃ for 24 hours to obtain the dried sulfonyl fluoride type perfluorinated sulfonic acid resin. The resin film after the conversion had an EW value of 823g/mol and an oxygen gas permeation constant of 4.2cm3/(m·24h·0.1MPa)。
Comparative example 1:
and cleaning and drying the reaction kettle, vacuumizing and filling nitrogen for replacement until the water content is below 100ppm and the oxygen content is below 10 ppm. Vacuumizing and charging tetrafluoroethylene monomer to 0.1MPa, vacuumizing to 0.0001MPa, and then charging 300mL of 1,1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether and 178g of monomer CF2＝CFOCF2CF(CF3)OCF2CF2SO2F is added into a reaction kettle, the temperature is increased to 80 ℃, tetrafluoroethylene is introduced until the pressure reaches 3MPa, and 10mL of perfluorobutyryl peroxide (CF) containing 0.02g is added by a metering pump3CF2CF2CO-OO-CCF2CF2CF3) The reaction pressure of the initiator solution (2) was maintained at about 3MPa, and when the amount of tetrafluoroethylene added reached 150g, the reaction was stopped to recover the unreacted tetrafluoroethylene monomer. Discharging the materials, transferring the materials into a glass flask, and performing vacuum rotary evaporation to remove unreacted sulfonyl fluoride monomers and solvent to obtain a white powdery product, and simultaneously recovering the unreacted sulfonyl fluoride monomers and the solvent. And further drying the product at 100 ℃ for 24 hours to obtain the dried sulfonyl fluoride type perfluorinated sulfonic acid resin. The resin film after the conversion had an EW value of 938g/mol and an oxygen permeability constant of 0.14cm3/(m·24h·0.1MPa)。
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions or modifications made on the basis of the present invention to solve the same technical problems and achieve the same technical effects are all covered in the protection scope of the present invention.
Claims (10)
1. A solution polymerization preparation method of perfluorosulfonic acid resin is characterized by comprising the following steps: taking tetrafluoroethylene A, a monomer B containing a sulfonyl fluoride end group and a monomer C containing a sulfonyl fluoride end group as comonomers, pre-adding a fluorine-containing solvent and the comonomers into a reactor, heating to 20-120 ℃, keeping the pressure at 0.2-5 MPa, adding an initiator to initiate a polymerization reaction, and supplementing the comonomers in the reaction process to finally obtain the sulfonyl fluoride type perfluorinated sulfonic acid resin;
wherein the structural formula of the monomer B is as follows:
CF2＝CFO[CF2CF(CF3)O]a[CF2CF2]bSO2f, wherein a is an integer of 0-1, and b is an integer of 1-2;
the structural formula of monomer C:
2. the method for preparing perfluorosulfonic acid resin according to claim 1, wherein: the structural formula of the sulfonyl fluoride type perfluorinated sulfonic acid resin is as follows:
3. the method for preparing a perfluorosulfonic acid resin according to claim 1, comprising the steps of: the fluorine-containing solvent is one or a mixture of 1H-perfluorohexane, dichloropentafluoropropane and 1,1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether.
4. The method for preparing a perfluorosulfonic acid resin according to claim 1, comprising the steps of: when comonomer is pre-added, tetrafluoroethylene A: the molar ratio of the (monomer B + the monomer C) is 1: 1-10: 1, wherein the molar ratio of the monomer B to the monomer C is 20: 1-1: 2.
5. The method for preparing a perfluorosulfonic acid resin according to claim 1, comprising the steps of: when the comonomer is supplemented, if three comonomers are supplemented, the tetrafluoroethylene A: the molar ratio of the monomer B to the monomer C is 20: 1-1: 20, wherein the molar ratio of the monomer B to the monomer C is 20: 1-1: 2.
6. The method for preparing a perfluorosulfonic acid resin according to claim 1, comprising the steps of: when the comonomer is supplemented, if only the tetrafluoroethylene A is supplemented, the molar ratio of the addition amount of the tetrafluoroethylene A to the initial feeding amount is 1: 2-1: 6.
7. The method for preparing a perfluorosulfonic acid resin according to claim 1, comprising the steps of: when the comonomer is supplemented, if only the monomer B and the monomer C are supplemented, the molar ratio of the addition amount to the initial feeding amount is 1: 2-1: 5, wherein the molar ratio of the monomer B to the monomer C is 20: 1-1: 2.
8. The method for preparing perfluorosulfonic acid resin according to claim 1, wherein: the initiator is one of or a mixture of a perfluorobutyryl peroxide compound and diisopropyl peroxydicarbonate.
9. The method for preparing a perfluorosulfonic acid resin according to claim 1, comprising the steps of: methanol or cyclohexane is used as a chain transfer agent in the copolymerization process.
10. The method for preparing perfluorosulfonic acid resin by solution polymerization according to claim 1, further comprising a post-treatment step of: tabletting sulfonyl fluoride type perfluorinated sulfonic acid resin by using a flat vulcanizing machine at the temperature of 240 ℃, cutting the flaky resin into small particles, placing the small particles into 20 wt% potassium hydroxide solution with the weight being 10 times that of the flaky resin, converting the small particles under the reflux state for 36 hours, taking out the resin, washing the resin to be neutral by using pure water, soaking the resin for 10 times by using 20 wt% nitric acid solution for 1 hour each time, washing the resin to be neutral, drying the resin at the temperature of 100 ℃ for 24 hours to obtain hydrogen type perfluorinated sulfonic acid resin, and placing the hydrogen type perfluorinated sulfonic acid resin into a dryer for cooling.
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| CN114507302A (en) * | 2022-04-19 | 2022-05-17 | 国家电投集团氢能科技发展有限公司 | Sodium conversion liquid of perfluorosulfonyl fluororesin and sodium conversion method of perfluorosulfonyl fluororesin |
| CN115716887A (en) * | 2022-11-29 | 2023-02-28 | 福建海德福新材料有限公司 | Perfluorosulfonic acid resin and preparation method and application thereof |
| CN115850542A (en) * | 2023-02-16 | 2023-03-28 | 苏州润邦半导体材料科技有限公司 | Perfluoro polymer surfactant and preparation method and application thereof |
| CN115948012A (en) * | 2022-11-30 | 2023-04-11 | 华电重工股份有限公司 | Fiber-reinforced proton exchange membrane for hydrogen production by water electrolysis and preparation method thereof |
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| CN114507302A (en) * | 2022-04-19 | 2022-05-17 | 国家电投集团氢能科技发展有限公司 | Sodium conversion liquid of perfluorosulfonyl fluororesin and sodium conversion method of perfluorosulfonyl fluororesin |
| CN115716887A (en) * | 2022-11-29 | 2023-02-28 | 福建海德福新材料有限公司 | Perfluorosulfonic acid resin and preparation method and application thereof |
| CN115716887B (en) * | 2022-11-29 | 2023-08-29 | 福建海德福新材料有限公司 | Perfluorinated sulfonic acid resin and preparation method and application thereof |
| CN115948012A (en) * | 2022-11-30 | 2023-04-11 | 华电重工股份有限公司 | Fiber-reinforced proton exchange membrane for hydrogen production by water electrolysis and preparation method thereof |
| CN115948012B (en) * | 2022-11-30 | 2023-12-19 | 华电重工股份有限公司 | Fiber reinforced proton exchange membrane for hydrogen production by water electrolysis and preparation method thereof |
| CN115850542A (en) * | 2023-02-16 | 2023-03-28 | 苏州润邦半导体材料科技有限公司 | Perfluoro polymer surfactant and preparation method and application thereof |
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