WO2024096603A1 - Procédé de production d'un polymère à base de fluor anionique contenant un groupe acide perfluoro sulfonique, et membrane polymère produite à partir de celui-ci - Google Patents

Procédé de production d'un polymère à base de fluor anionique contenant un groupe acide perfluoro sulfonique, et membrane polymère produite à partir de celui-ci Download PDF

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WO2024096603A1
WO2024096603A1 PCT/KR2023/017334 KR2023017334W WO2024096603A1 WO 2024096603 A1 WO2024096603 A1 WO 2024096603A1 KR 2023017334 W KR2023017334 W KR 2023017334W WO 2024096603 A1 WO2024096603 A1 WO 2024096603A1
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monomer
batch
vdf
anionic
polymer
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PCT/KR2023/017334
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Korean (ko)
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손은호
허현준
소원욱
박인준
이명숙
장봉준
강홍석
김주현
백지훈
오명석
이상구
육신홍
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한국화학연구원
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Application filed by 한국화학연구원 filed Critical 한국화학연구원
Publication of WO2024096603A1 publication Critical patent/WO2024096603A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/34—Polymerisation in gaseous state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C08F8/38—Sulfohalogenation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0239—Organic resins; Organic polymers

Definitions

  • the present invention relates to a method for producing an anionic fluorine-based polymer containing perfluorosulfate groups with excellent dispersibility in general-purpose solvents and a polymer membrane prepared therefrom.
  • a fuel cell is a power generation source that directly converts the chemical energy of chemical fuel into electrical energy, using the electrochemical reaction of hydrogen and oxygen, which is the reverse reaction of the electrolysis of water. Since it does not require a combustion process to burn fuel, it has the advantage of high thermal efficiency and no emission of pollutants such as dust or chemicals.
  • fuel cells can be manufactured with various capacities and are easy to install within power demand areas, so they can reduce transmission and substation facilities, making it a useful cutting-edge technology in terms of power system operation.
  • Fuel cells are broadly classified into phosphoric acid type (PAFC), molten carbonate type (MCFC), solid electrolyte type (SOFC), and solid polymer type (PEMFC) depending on the type of electrolyte.
  • PAFC phosphoric acid type
  • MCFC molten carbonate type
  • SOFC solid electrolyte type
  • PEMFC solid polymer type
  • solid polymer fuel cells have a high current density and are being actively developed, including being used in automobiles, a representative means of transportation.
  • the fuel cell power generation system can be divided into fuel cell main body technology and system technology, and each sector consists of unit cell element technology (MEA) manufacturing technology, material technology such as the essential electrolyte, unit cell stacking technology, It is divided into stack configuration technology and stack performance measurement technology.
  • MEA unit cell element technology
  • System technology consists of the development of peripheral devices (reformers, inverters, waste heat recovery devices), which are system configuration technologies, and system comprehensive technologies such as system design and operation.
  • VDF vinylidene fluoride
  • TFE ethylene tetrafluoride
  • the purpose of the present invention is as follows.
  • the object is to provide a method for producing an anionic fluoropolymer containing a perfluorosulfuric acid group.
  • the object is to provide an anionic fluoropolymer containing a perfluorosulfuric acid group prepared by the above production method.
  • the object is to provide a polymer membrane made of the anionic fluoropolymer.
  • the object is to provide a polymer film made from the anionic fluoropolymer.
  • the object is to provide a solid polymer fuel cell (Proton-Exchange Membrane Fuel Cell, PEMFC) including the polymer membrane.
  • PEMFC Solid Polymer Fuel Cell
  • VDF Vinylidene Fluoride
  • TFE Tetrafluoroethylene
  • CTFE Chlorotrifluoroethylene
  • the polymerization step is polymerized at a temperature of 52 °C to 58 °C,
  • a method for producing an anionic fluoropolymer containing perfluorosulfuric acid groups is provided:
  • CF 2 CF-O-[CF 2 -CF(CF 3 )-O] m -[CF 2 ] n -SO 2 F
  • n is an integer from 2 to 4.
  • the present invention provides an anionic fluoropolymer containing a perfluorosulfuric acid group prepared by the above production method.
  • the present invention provides a polymer membrane made of the anionic fluoropolymer.
  • the present invention provides a polymer film made from the anionic fluoropolymer.
  • the present invention provides a solid polymer fuel cell (Proton-Exchange Membrane Fuel Cell, PEMFC) including the polymer membrane.
  • PEMFC Solid Polymer Fuel Cell
  • a fluorine-based anionic resin containing perfluorinated sulfate groups is manufactured using distilled water without using a fluorine-based solvent, so it is environmentally friendly and has the advantage of being able to control the physical properties by variously adjusting the anionic part.
  • the present invention has excellent dispersibility in general-purpose solvents such as methyl ethyl ketone (MEK) and acetone. It has the characteristics of very high efficiency and usability.
  • MEK methyl ethyl ketone
  • Figure 1 is a conceptual diagram showing a reaction system for producing an anionic fluoropolymer containing perfluorinated sulfate groups according to the present invention.
  • Figure 2 The left side of Figure 2 is a photograph made by dissolving the fluoropolymer containing the -SO 2 F group prepared in Figure 1 in a solvent and applying it to a glass substrate, and the right side is a photograph of the anionic fluoropolymer containing sulfate groups obtained after conversion of the -SO 3 H end group. This is a photo showing the film.
  • Figure 3 is a photograph showing the inside of a reactor in which the product state in the comparative example is a precipitate, that is, the products are leached after the reaction and aggregated into a lump inside the reactor.
  • Figure 4 is a photograph showing the inside of the reactor in which the product state is an emulsion in the example, that is, the products are well dispersed in the reaction medium after the reaction.
  • Figure 5 shows 19 F-NMR data for example samples (3-1, 3-2, 3-3) in Table 3.
  • Figure 6 is a photograph showing the SO 2 F type film (left and middle photos) and the acid treatment process and the film after acid treatment (right photo) for the sample of Example 3-1 in Table 3.
  • VDF Vinylidene Fluoride
  • TFE Tetrafluoroethylene
  • CTFE Chlorotrifluoroethylene
  • the polymerization step is polymerized at a temperature of 52 °C to 58 °C,
  • a method for producing an anionic fluoropolymer containing perfluorosulfuric acid groups is provided:
  • CF 2 CF-O-[CF 2 -CF(CF 3 )-O] m -[CF 2 ] n -SO 2 F
  • n is an integer from 2 to 4.
  • n is preferably an integer of 0 to 2; It may be an integer of 1 to 2. In one embodiment, m is 1. In Formula 1, n is preferably an integer of 2 to 3. In one embodiment n is 2.
  • the conversion rate of the first monomer may be within 60%, but is preferably 65% or more, but is not limited thereto.
  • the manufacturing method includes a first monomer containing a perfluorosulfuric acid group represented by Formula 1, vinylidene fluoride (VDF), tetrafluoroethylene (TFE), and chlorotrifluoroethylene, and polymerizing a second monomer, which is at least one selected from the group consisting of (CTFE).
  • a perfluorosulfuric acid group represented by Formula 1, vinylidene fluoride (VDF), tetrafluoroethylene (TFE), and chlorotrifluoroethylene
  • CTFE chlorotrifluoroethylene
  • the second monomer may be selected from VDF alone or CTFE alone, or a mixture of VDF and CTFE. This is because when TFE is the second monomer, a freon-based solvent or a fluorine-based solvent is generally used as the reaction solvent, causing environmental and economic problems due to the nature of the reaction using 1.5 to 2 times more reaction solvent than the monomer. Because you can.
  • the second monomer may be VDF alone or a mixture of VDF and CTFE, and more preferably, the second monomer may be VDF alone.
  • the polymerization temperature in the polymerization step is very important in the production of anionic fluoropolymers containing perfluorosulfuric acid groups. This is because if the polymerization temperature in the polymerization step is 50°C or lower, the reaction time is too long and precipitates form in the product state. There is a problem that this occurs, and if the polymerization temperature in the polymerization step is 60°C or higher, the reaction time is shortened, but there is also a problem that precipitates are generated in the product state.
  • the polymerization temperature in the polymerization step is selected in a range that has the advantage of solving the problem of precipitates occurring in the product state and providing an appropriate reaction time, which is 52°C to 58°C.
  • the polymerization temperature in the polymerization step is preferably 53°C to 57°C; It may be 54°C to 56°C, and in one embodiment, the polymerization temperature in the polymerization step is 55°C.
  • the manufacturing method may additionally include the step of supplying a gaseous second monomer into a reactor containing a liquid raw material containing the first monomer before the polymerization step.
  • the reactor is preferably a high pressure reactor, and the material of the reactor may include stainless steel, but is not limited thereto.
  • a stirrer may be installed inside the reactor, and the type of the stirrer is not limited, but in one embodiment, it is a turbine-type high-speed stirrer.
  • the ratio of the diameter (d) of the stirrer to the diameter (D) of the reactor is 0.4 to 0.8; 0.5 to 0.7; It may be 0.55 to 0.65, and in one embodiment, the ratio of the diameter (d) of the stirrer to the diameter (D) of the reactor is 0.58 to 0.62; 0.59 to 0.61; It is 0.6.
  • the manufacturing method can be performed through a reaction system, and the reaction system includes the reactor; and a gaseous phase supply device that supplies the second monomer in the gaseous phase.
  • the reactor includes a liquid raw material containing a first monomer, and the liquid raw material may include a first monomer, water (specifically, distilled water), and a surfactant (specifically, a fluorine-based surfactant).
  • the pressure of the supplied vapor phase second monomer is 10 to 40 atmG; 15 to 30 atmG; It may be 19 to 25 atmG. If the pressure of the supplied second monomer in the gas phase is less than 10 atmG, the speed of the polymerization reaction may slow down and the yield may decrease, and if the pressure of the second monomer in the supplied gas phase is more than 30 atmG, the reaction temperature An increase in may cause problems in controlling the reaction speed.
  • the liquid raw material containing the first monomer includes the first monomer and may additionally include a reaction solvent and a surfactant.
  • the production method is an emulsion (emulsion) using a reaction solvent to produce a liquid raw material containing a first monomer. It may include an emulsion step.
  • the reaction solvent may preferably be a water-soluble liquid or water (H 2 O), and in one embodiment, the liquid is water, specifically distilled water.
  • water is not affected by environmental problems and economic limitations, can be used by adjusting various ratios, and has the advantage of being able to change the physical properties of the final product depending on reactivity, production amount, concentration, etc. There is.
  • the emulsion may be performed using a surfactant, preferably using a fluorine-based surfactant.
  • a surfactant preferably using a fluorine-based surfactant.
  • the use of fluorine-based surfactant is not essential, but it is desirable to supply it in small quantities to ensure dispersion stability of the final product.
  • the fluorine-based surfactant includes perfluorooctanoic acid (APFO), perfluorooctanesulfonic acid (PFOS), etc., and may be a fluorine-based nonionic surfactant.
  • the fluorine-based nonionic surfactant is Zonyl FS- It could be 300. In one example, APFO was used as the fluorine-based surfactant.
  • the weight of the fluorine-based surfactant supplied in the above production method is 0.01 to 5% by weight based on the total weight of the reaction solvent and the fluorine-based surfactant; 0.03 to 4% by weight; 0.05 to 3% by weight; It may be 0.1 to 2% by weight.
  • the second monomer when the second monomer is CTFE alone, a mixture of CTFE and VDF, or a mixture of CTFE and TFE, even if the supply amount of fluorine-based surfactant is significantly reduced compared to other cases, the final product, that is, an anionic product containing a perfluorosulfuric acid group, It can maintain high dispersibility in reaction solvents of fluoropolymers, especially water.
  • the weight of the fluorine-based surfactant is 0.01 to 4% by weight when the second monomer is CTFE alone, a mixture of CTFE and VDF, or a mixture of CTFE and TFE; 0.02 to 3% by weight; 0.03 to 2% by weight; It may be 0.05 to 0.3% by weight.
  • the weight of the fluorine-based surfactant is 0.02 to 5% by weight when the second monomer does not include CTFE; 0.04 to 4% by weight; It may be 0.2 to 3% by weight.
  • the above manufacturing method can be performed in a batch, semi-batch, or continuous manner.
  • Continuous means a process in which influents and discharges flow continuously
  • semi-batch means a process in which only some of the influents and discharges flow continuously
  • batch means only at the beginning of the process. This refers to a process in which all influents are introduced, the reactor is blocked, reacted for a certain period of time without inflow or discharge, and then the effluents are discharged.
  • the manufacturing method may be performed in a batch or semi-batch manner, and in one embodiment, the manufacturing method is performed in a batch manner.
  • the batch method may be a constant volume batch or a constant pressure batch.
  • the batch method is a constant volume batch, which means that the pressure is lowered according to the reaction and the monomer ratio is the same ( This is because even if monomers (second monomer/first monomer) are added, an anionic fluoropolymer containing perfluorosulfuric acid groups with a lower equivalent value (g/mol) can be produced.
  • the batch method may be a method in which the second monomer is not additionally supplied during the polymerization step.
  • the anionic fluoropolymer containing a perfluorosulfuric acid group to be prepared in the above production method may have an equivalent value of 1300 g/mol or less, preferably 100 to 1300 g/mol; 200 to 1300 g/mol; 300 to 1200 g/mol; 400 to 1200 g/mol; 500 to 1200 g/mol; 600 to 1200 g/mol; 700 to 1200 g/mol; 800 to 1200 g/mol; It may be 900 to 1200 g/mol, and in one embodiment, the equivalent value of the anionic fluoropolymer is 1000 to 1100 g/mol.
  • the weight ratio of the polymerized second monomer and the first monomer may be 0.3 to 0.8 in order to prepare an anionic fluoropolymer characterized by the above-described equivalent value.
  • the weight ratio of the polymerized second monomer and the first monomer means the weight ratio of the second monomer and the first monomer used in the polymerization reaction, [(second monomer used in the polymerization reaction)/((the weight ratio used in the polymerization reaction) 1st monomer)].
  • the weight ratio of the polymerized second monomer and the first monomer is 0.35 to 0.7; It may be 0.35 to 0.65, and in one embodiment, the weight ratio of the polymerized second monomer and the first monomer is 0.38 to 0.62; 0.39 to 0.61; It is 0.4 to 0.6.
  • the polymerization step may be performed using a polymerization initiator, preferably using a radical initiator.
  • the radical initiator may be selected from compounds with excellent solubility in the reaction solvent.
  • the reaction solvent is water, ammonium persulfate (APS), potassium persulfate (KPS), sodium persulfate (SPS), etc.
  • the radical initiator is sodium persulfate.
  • the manufacturing method is additionally performed after the polymerization step.
  • the step of preparing a polymer dispersion containing the SO 2 F group may include dispersing the polymer prepared in the polymerization step in an organic solvent.
  • the polymer content is 1 to 60% by weight based on the weight of the polymer and organic solvent; 10 to 50% by weight; It may be 20 to 40% by weight. In one embodiment, the polymer content is 20 to 30% by weight based on the weight of the polymer and organic solvent; 22 to 28% by weight; It is 25% by weight.
  • Organic solvents for dispersing polymers include, but are not limited to, acetone, methyl ethyl ketone, dimethyl formamide, and N-methyl-2-pyrrolidone. In addition to the organic solvents listed above, various general-purpose solvents can be selected. possible. In one embodiment, the organic solvent for dispersing the polymer is methyl ethyl ketone.
  • the step of manufacturing the polymer film is
  • It may include a final drying step of the underwater desorbed substrate.
  • the substrate is a glass substrate in one embodiment.
  • the thickness of the film produced in the step of manufacturing the polymer film can be adjusted depending on the solid content of the polymer dispersion and the thickness of the humidity film. That is, the thickness of the film is not limited, but ranges from 5 to 45; It may be 10 to 40 ⁇ m and in one embodiment the thickness of the film is 15 to 35 ⁇ m.
  • the polymer dispersion in the step of preparing the polymer film is the same as the description of the polymer dispersion described above in the step of preparing the polymer dispersion containing the SO 2 F group.
  • the polymer dispersion may use acetone, methyl ethyl ketone, dimethyl formamide, N-methyl-2-pyrrolidone, etc. as a solvent.
  • the polymer dispersion is methyl ethyl ketone.
  • the drying temperature In the step of drying the coated substrate and the final drying step of the substrate desorbed in water, the drying temperature must take into account the boiling point of the polymer dispersion solvent and the polymer decomposition temperature. This is because at temperatures higher than the boiling point of the polymer dispersion solvent, the solvent boils and dries, making it difficult to obtain a film with a uniform surface.
  • the polymer dispersion solvent is methyl ethyl ketone
  • its boiling point is 79.6 ° C
  • the decomposition temperature of the prepared polymer is 395.5 ° C. That is, for example, when dried at 80°C, the methyl ethyl ketone solvent boils and dries, making it difficult to obtain a film with a uniform surface.
  • the drying temperature is 40 to 79 °C; 45 to 75°C; It may be 50 to 70 °C, and in one embodiment, the drying temperature is 55 to 65 °C; 57 to 63°C; 59 to 61°C; It is 60°C.
  • the step of introducing the SO 3 - K + ion group is
  • It may include the step of carrying out a hydrolysis substitution reaction through stirring.
  • the potassium hydroxide/methanol solution refers to a methanol solution to which potassium hydroxide has been added.
  • the weight of potassium hydroxide i.e., the weight of potassium hydroxide relative to methanol
  • the concentration of potassium hydroxide in the potassium hydroxide/methanol solution is 1.5 wt%.
  • the polymer film Compared to the potassium hydroxide/methanol solution, the polymer film contains 0.12 to 0.32 wt%; It may be 0.17 to 0.27 wt%. In one example, the polymer film content is 0.22 wt% compared to the potassium hydroxide/methanol solution.
  • the stirring speed is 50 to 700 rpm; 100 to 600 rpm; 200 to 500 rpm; It may be 200 to 400 rpm. In one embodiment, the stirring speed is 250 to 350 rpm; It is 300 rpm.
  • the reaction time in the step of hydrolytic substitution reaction through stirring is 12 to 48 hours; It may be 18 to 36 hours, and in one embodiment, the reaction time in the step of hydrolytic substitution reaction through stirring is 20 to 30 hours; 22 to 27 hours; 23 to 25 hours; It's 24 hours.
  • the step of converting and synthesizing the SO 3 H group is
  • It may include the step of performing a cation exchange reaction by stirring the immersed fluorine-based polymer film.
  • the compound immersed in the step of immersing the fluorine-based polymer film into which the SO 3 - K + group is introduced is an aqueous sulfuric acid solution.
  • the weight of sulfuric acid (i.e., the weight of sulfuric acid relative to water) in the sulfuric acid aqueous solution is 9.6 to 11.6 wt%; It may be 10.1 to 11.1 wt%. In one embodiment, the concentration of sulfuric acid in the aqueous sulfuric acid solution is 10.6 wt%.
  • the weight percent of the polymer film relative to the sulfuric acid aqueous solution is 0.07 to 0.27 weight percent; It may be 0.12 to 0.22% by weight. In one embodiment, the weight percent of the polymer film compared to the sulfuric acid aqueous solution is 0.17 weight percent.
  • the reaction temperature may vary depending on the type of sample, but ranges from room temperature to 150°C, 50 to 130°C; It may be 80 to 120°C, and in one embodiment, the reaction temperature is 90 to 110°C; 95 to 105°C; It is 100°C.
  • the stirring speed is 50 to 700 rpm; 100 to 600 rpm; 200 to 500 rpm; It may be 200 to 400 rpm. In one embodiment, the stirring speed is 250 to 350 rpm; It is 300 rpm.
  • the reaction time is 12 to 48 hours; It may be 18 to 36 hours, and in one embodiment, the reaction time is 20 to 36 hours; 22 to 30 hours; 23 to 27 hours; It's 24 hours.
  • the present invention provides an anionic fluoropolymer containing a perfluorosulfuric acid group prepared by the above production method.
  • the present invention provides a polymer membrane made of the anionic fluoropolymer.
  • the present invention provides a polymer film made from the anionic fluoropolymer.
  • the present invention provides a solid polymer fuel cell (Proton-Exchange Membrane Fuel Cell, PEMFC) including the polymer membrane.
  • PEMFC Solid Polymer Fuel Cell
  • anionic fluoropolymer the polymer membrane, the polymer film, and the solid polymer fuel cell are the same as those described in the manufacturing method.
  • a reactor with a volume of 2 L was prepared, the interior of which was electropolished under vacuum, and the turbine-type stirrer and baffle were removable.
  • an initiator aqueous solution containing 1.117 g of initiator (Sodium Persulfate (SPS)) dissolved in 20 g of distilled water is added, followed by VDF or VDF/CTFE mixture to reach the set pressure. do. After the reaction proceeded for about 3 hours, the temperature was lowered, the remaining VDF or VDF/CTFE mixed gas was transferred to a storage tank, and the reaction was terminated.
  • SPS sodium Persulfate
  • the product was separated using precipitation or centrifugation, washed several times with distilled water and ethanol, and vacuum dried to obtain solid content.
  • the polymer was dispersed in an organic solvent to prepare a dispersion.
  • the polymer content was 25% by weight of the total, and methyl ethyl ketone was used as the organic solvent.
  • the polymer dispersion was coated on a glass substrate and a film was produced through drying, desorption in water, and final drying processes. At this time, the thickness of the film can be adjusted depending on the solid content of the polymer dispersion and the thickness of the humidity film.
  • the thickness of the film prepared in Step 2 was 25 ( ⁇ 10) ⁇ m.
  • the boiling point of the polymer dispersion solvent and the decomposition temperature of the polymer must be taken into consideration. At temperatures higher than the boiling point of the solvent, the solvent boils and dries, making it difficult to obtain a film with a uniform surface.
  • Example 2 the solvent for the polymer dispersion is methyl ethyl ketone, its boiling point is 79.6 °C, and the decomposition temperature of the prepared polymer is 395.5 °C. That is, when drying at a temperature higher than the boiling point of the polymer dispersion solvent, Example 2. In Step 2, for example, 80° C., the polymer dispersion solvent, methyl ethyl ketone, boils and dries, making it difficult to obtain a film with a uniform surface. Therefore, in Step 2 of Example 2, it was dried at 60°C.
  • a fluorine-based polymer containing a SO 2 F group was replaced with a group containing an ion (-SO 3 - K + ) through a hydrolysis reaction using a potassium hydroxide/methanol solution .
  • a film of a fluorine-based copolymer or terpolymer containing a SO 2 F group (the weight of the film compared to the potassium hydroxide/methanol solution is 0.22 wt%) is immersed in a potassium hydroxide/methanol solution (the weight of the potassium hydroxide compared to methanol is 1.5 wt%). , and stirred at 300 rpm at room temperature to perform a hydrolysis substitution reaction for 24 hours.
  • an ionomer film with hydrogen ion conductivity is prepared by replacing the -SO 3 - K + group with -SO 3 - H + through a cation exchange reaction using an aqueous sulfuric acid solution.
  • a fluorine-based polymer film containing SO 3 - K + group (the weight of the polymer film compared to the aqueous sulfuric acid solution is 0.17 wt%) is immersed in an aqueous sulfuric acid solution (the weight of the sulfuric acid relative to water is 10.6 wt%) and heated at 300 rpm at 100 o C. Stir and perform a cation exchange reaction for 24 hours.
  • An ionomer film was prepared through steps 1 to 4 of Example 1 and Example 2.
  • the second monomer type, second monomer supply method, second monomer/first monomer mass composition ratio, and reaction temperature were varied, and in Examples 2-1 to 2-4, the second monomer/first monomer mass composition ratio was particularly different. It is 0.3 to 0.8, and the reaction temperature is 52 °C to 58 °C.
  • An ionomer film was prepared through steps 1 to 4 of Example 1 and Example 2.
  • the second monomer type, second monomer supply method, second monomer/first monomer mass composition ratio, and reaction temperature were varied, and in Comparative Examples 2-1 to 2-9, the second monomer/first monomer mass composition ratio was particularly is not 0.3 to 0.8, or the reaction temperature is not 52°C to 58°C.
  • the second monomer type, second monomer supply method, second monomer/first monomer composition ratio, and reaction temperature of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-9 are as follows.
  • the reaction time from the start of adding raw materials until the reaction was completed was measured, and the state of the product produced after the reaction was confirmed.
  • the state of the product was categorized into emulsion, precipitate, and large amount of precipitate.
  • the ion exchange capacity and ion equivalent weight of the ionomer with hydrogen ion conductivity were measured using the acid-base titration method.
  • 25 - 35 mg of the ionomer film whose side chain terminal was substituted with -SO 3 - H + was immersed in 200 mL of 1M NaCl solution and stirred at 300 rpm at 40 o C for 48 hours to convert the H + ions of the ionomer film into Na on the NaCl solution.
  • Cation exchange was performed with + .
  • the temperature is preferably room temperature - 80 o C
  • the stirring speed is 100 - 500 rpm
  • the time is preferably 48 hours or more.
  • Ion exchange capacity (Equation 1) and ion equivalent weight (Equation 2) can be calculated using the volume (V) and concentration (C) of the NaOH solution used for titration and the weight (W) of the ionomer film until pH 7 is reached. there is.
  • the ion equivalent, or equivalent value is a value calculated from 19F-NMR and obtained assuming that all -SO 2 F groups are converted to -SO 3 H.
  • the conditions representing the optimal reaction time (1 h to 4 h), the optimal product state (emulsion), and the optimal equivalent value (EW, 1300 g/mol or less) are the temperature conditions. It was confirmed that the conditions were 52°C to 58°C. In addition, it was confirmed that the mass composition ratio of the second monomer/first monomer also affects the equivalent value (EW, g/mol), and it was confirmed that a polymer with the desired equivalent value could be manufactured when the mass composition ratio was 0.3 to 0.8. did.
  • reaction temperature was confirmed to be the most important variable because it determines whether a smooth reaction can occur.
  • the temperature conditions were 52 °C to 58 °C
  • the temperature conditions were 50 °C, 60 °C, and 65 °C
  • the production method disclosed herein can produce an optimal product when the reaction temperature condition is 52°C to 58°C.
  • the goal herein is to produce a polymer with an equivalent value of 1300 g/mol or less, and it was confirmed that the mass composition ratio of the second monomer/first monomer has an effect on achieving this goal. Specifically, it was confirmed that a polymer of the corresponding equivalent value could be manufactured when the mass composition ratio was 0.3 to 0.8.
  • An ionomer film was prepared through steps 1 to 4 of Example 1 and Example 2.
  • the total amount (mol) of monomers was fixed at 0.7, the amount of initiator (sodium persulfate, SPS) was set at 1.117 g, the amount of surfactant APFO was also set at 2 g, and Examples 3-1 to 3-3 were batch type. VDF was supplied in batch.
  • An ionomer film was prepared through steps 1 to 4 of Example 1 and Example 2.
  • the total amount (mol) of monomers was fixed at 0.7, the amount of initiator (sodium persulfate, SPS) was set to 1.117 g, the amount of surfactant APFO was also set to 2 g, and Comparative Examples 3-1 to 3-3 were used in half.
  • -VDF was supplied in a semi-batch manner.
  • Example 3-1 is a batch type even though the monomer mass composition ratio is the same.
  • Example 3-3 showed equivalent values of 1407 and 782, and showed lower values than the equivalent values of 1792 and 1145 in semi-batch Comparative Examples 3-1 and 3-2. In other words, it was confirmed that when the monomer mass composition ratio is the same, the batch method can produce a polymer with an equivalent value closer to the target value than the semi-batch method.
  • Example 3-3 and Comparative Example 3-3 showing similar equivalent values a monomer mass composition ratio of 0.4 is sufficient in the batch method to produce a polymer with an equivalent value of 780, but in the semi-batch method, a monomer mass composition ratio of 0.2 is required. You can confirm that it is necessary. In other words, it can be seen that in the semi-batch method, more of the first monomer, which is relatively cost-consuming, must be used compared to the second monomer, and it was confirmed that the manufacturing method presented herein is more suitable for the batch method than the semi-batch method.
  • the semi-batch type is a method of controlling the input amount by maintaining the pressure of the VDF, that is, the vapor phase second monomer, while the batch type allows a pressure drop according to the consumption of the VDF, that is, the vapor phase second monomer, and adjusts the input amount through this. means method. In other words, these results are interpreted as results achieved through pressure drop under the same reaction conditions.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne un procédé de production d'un polymère fluoré anionique contenant un groupe acide perfluoro sulfonique, le procédé comprenant : la polymérisation d'un premier monomère, contenant un groupe acide perfluoro sulfonique représenté par la formule chimique 1, et d'un second monomère, qui est au moins un monomère choisi dans le groupe constitué par le fluorure de vinylidène, le tétrafluoroéthylène et le chlorotrifluoroéthylène. <Formule chimique 1> CF2=CF-O-[CF2-CF(CF3)-O]m-[CF2]n-SO2F, où m est un nombre entier de 0 à 3, et n est un nombre entier de 2 à 4.
PCT/KR2023/017334 2022-11-02 2023-11-02 Procédé de production d'un polymère à base de fluor anionique contenant un groupe acide perfluoro sulfonique, et membrane polymère produite à partir de celui-ci WO2024096603A1 (fr)

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KR20220144252 2022-11-02
KR10-2022-0144252 2022-11-02
KR1020230149035A KR20240063036A (ko) 2022-11-02 2023-11-01 과불소 황산기 포함 음이온성 불소계 고분자의 제조방법 및 이로부터 제조된 고분자막
KR10-2023-0149035 2023-11-01

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5608022A (en) * 1993-10-12 1997-03-04 Asahi Kasei Kogyo Kabushiki Kaisha Perfluorocarbon copolymer containing functional groups and a method for producing it
KR20010040945A (ko) * 1998-02-13 2001-05-15 메리 이. 보울러 플루오르화 이오노머 및 그의 용도
KR101643794B1 (ko) * 2009-03-24 2016-07-28 더블유.엘. 고어 앤드 어소시에이트스, 인코포레이티드 팽창성 관능성 ｔｆｅ 공중합체 미세 분말, 그로부터 수득된 팽창된 관능성 생성물 및 팽창된 생성물의 반응
WO2022031585A1 (fr) * 2020-08-03 2022-02-10 The Chemours Company Fc, Llc Pastille de résine, son procédé de fabrication et produit moulé à base de cette dernière
KR20220091725A (ko) * 2020-12-24 2022-07-01 경상국립대학교산학협력단 과불화술폰산 이오노머가 그래프트된 그래핀 옥사이드를 포함하는 양이온 교환막 및 이를 이용한 용도

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5608022A (en) * 1993-10-12 1997-03-04 Asahi Kasei Kogyo Kabushiki Kaisha Perfluorocarbon copolymer containing functional groups and a method for producing it
KR20010040945A (ko) * 1998-02-13 2001-05-15 메리 이. 보울러 플루오르화 이오노머 및 그의 용도
KR101643794B1 (ko) * 2009-03-24 2016-07-28 더블유.엘. 고어 앤드 어소시에이트스, 인코포레이티드 팽창성 관능성 ｔｆｅ 공중합체 미세 분말, 그로부터 수득된 팽창된 관능성 생성물 및 팽창된 생성물의 반응
WO2022031585A1 (fr) * 2020-08-03 2022-02-10 The Chemours Company Fc, Llc Pastille de résine, son procédé de fabrication et produit moulé à base de cette dernière
KR20220091725A (ko) * 2020-12-24 2022-07-01 경상국립대학교산학협력단 과불화술폰산 이오노머가 그래프트된 그래핀 옥사이드를 포함하는 양이온 교환막 및 이를 이용한 용도

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