WO2010076911A1 - Copolymères post-sulfonés contenant des groupes perfluorocyclobutane et leur procédé de préparation et leur utilisation - Google Patents

Copolymères post-sulfonés contenant des groupes perfluorocyclobutane et leur procédé de préparation et leur utilisation Download PDF

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WO2010076911A1
WO2010076911A1 PCT/KR2009/000174 KR2009000174W WO2010076911A1 WO 2010076911 A1 WO2010076911 A1 WO 2010076911A1 KR 2009000174 W KR2009000174 W KR 2009000174W WO 2010076911 A1 WO2010076911 A1 WO 2010076911A1
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membrane
copolymer
polymer
group
formula
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Korean (ko)
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김정훈
장봉준
이수복
박재완
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한국화학연구원
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06—Polysulfones; Polyethersulfones

Definitions

  • the present invention relates to a later-fonned copolymer comprising a perfluorocyclobutane group, a preparation method thereof, and a use thereof.
  • Fuel cell is an energy conversion system that converts chemical energy into electrical energy, and is actively researched due to its environmentally friendly features, which require the development of alternative energy due to the explosive increase in electric demand, high energy efficiency and low pollutant emission.
  • Fuel cells are classified according to the electrolyte material or operating temperature used. Among them, polymer electrolyte membrane fuel cells (PEMFCs) can be used for small combined cycle power generation that supplies power and heat simultaneously. Compared to the battery, it has excellent energy conversion characteristics and power density characteristics, can operate at low temperature, and has many advantages such as stability against mechanical shock, and thus, has been in the spotlight as a power source for automobiles and electronic components.
  • PEMFCs polymer electrolyte membrane fuel cells
  • Such polymer electrolyte membranes require high ionic conductivity, safety against redox, high mechanical strength, and the like.
  • Commercially available fuel cell membranes include, for example, Nafion TM from Dupont, an Allex-based ion exchange membrane, and Asiplex TM from Asahi Chemical.
  • these all-fluorine-based polymer electrolyte membranes have a problem of high cost and excellent efficiency compared to excellent performance.
  • DMFC direct methanol fuel cell
  • methanol crossover there is a problem that methanol is ejected from the anode to the cathode through the membrane (methanol crossover).
  • various researches are being conducted to replace the perfluorinated layer with a non-fluorine-based or partial fluorine-based layer.
  • US Patent No. 5,602, 185 discloses a process for preparing a polymer electrolyte membrane by copolymerizing a partially fluorine-based trifluorostyrene derivative.
  • the above method uses a palladium catalyst in the manufacturing process, the production cost of the monomer increases, the mechanical properties decrease due to the rigid structure of the polystyrene itself, and the distribution, position, and number of sulfonic acid groups in the polymer skeleton are controlled.
  • the water content of the membrane is increased as the sulfonic acid group increases, the physical properties of the electrolyte membrane is lowered.
  • U.S. Patent No. 6,090,895 also discloses a crosslinking process of sulfonated polymers such as sulfonated polyetherketones, sulfonated polyethersulfones and sulfonic acid polystyrenes.
  • sulfonated polymers such as sulfonated polyetherketones, sulfonated polyethersulfones and sulfonic acid polystyrenes.
  • sulfonated polymers such as sulfonated polyetherketones, sulfonated polyethersulfones and sulfonic acid polystyrenes.
  • European Patent Publication No. 1,113,517 A2 discloses a block copolymer polymer electrolyte membrane having a sulfonic acid group and a sulfonic acid group.
  • the sulfonated aromatic block using sulfuric acid is a block copolymer composed of an aliphatic block and an aromatic block, but there is a problem in that the aliphatic polymer bond is chemically decomposed during the sulfonation process.
  • US Patent Publication No. 2004-186262 discloses a method for producing a multiblock copolymer polymer electrolyte membrane in which hydrophobic blocks made of hydrocarbons and hydrophilic blocks are alternately made. Due to the low solubility of the multiblock copolymer, the -SO 3 K type copolymer was converted to -SO 2 Cl using thionyl chloride to impart hydrogen ion conductivity to the polymer membrane.
  • the method has a problem in that the manufacturing process is complicated, there is a problem of toxicity during the manufacturing process, and the mechanical integrity of the polymer thin film does not reach the level required for driving the fuel cell.
  • the present inventors have made efforts to improve the problem of the polymer used in the conventional electrolyte membrane, as a result, a copolymer from a high sulfonation activity monomer and a low sulfonation activity monomer containing a perfluorovinyloxy group in the sock end
  • the phonation described later can not only easily prepare the sulfonated copolymer, but also modify the polymer membrane including the copolymer through various processes such as fuel cell membrane, ion exchange membrane, dehumidification membrane, humidification membrane, and the like. It has been found that the use can be used and the present invention has been completed.
  • Another object of the present invention is to provide a method for preparing the above-mentioned fonned copolymer.
  • Still another object of the present invention is to provide a polymer membrane including the later-fonned copolymer of Formula 1 above.
  • Another object of the present invention is to provide a use of the polymer membrane comprising the copolymerized later described in the formula (1).
  • Another object of the present invention to provide a method for producing a polymer film comprising a copolymerized later described in the formula (1).
  • the present invention provides a later-fonned copolymer represented by the formula (1):
  • the present invention is to prepare a copolymer compound (4) having a perfluorocyclobutane ring by polymerizing a monomer compound (2) having a low sulfonation activity and a monomer compound (3) having a high sulfonation activity (Ste 1); And a perfluorocyclobutane group comprising a perfluorocyclobutane group comprising the copolymer compound (4) prepared in step 1 to be later fonned using a sulfonating agent to prepare a copolymer of Formula 1 (step 2). It provides a process for the preparation of the copolymer.
  • the present invention provides a polymer film including a copolymer fonned later, including a perfluorocyclobutane group represented by Chemical Formula 1.
  • the present invention provides a variety of uses for use in fuel cell membranes, ion exchange membranes, dehumidification membranes, humidification membranes and the like of a polymer membrane comprising a copolymerized later described in the formula (1).
  • the present invention is to dissolve the below-coated copolymer of the formula (1), and to coat it on a suitable support or solid surface used for film coating to form a film, and then under atmospheric pressure or vacuum in the temperature range of 50-250 °C It provides a method for producing a polymer membrane comprising a copolymerized later described in the formula (1) comprising the step of drying for 10 minutes to 48 hours.
  • the later-fonned copolymer including the perfluorocyclobutane group of Formula 1 according to the present invention can be easily prepared in solution or in a molten state, and the polymer membrane including the same exhibits excellent hydrogen ion conductivity and excellent mechanical properties.
  • it is not only chemically stable but also controls the distribution, position, number, and the like of sulfonic acid groups in the polymer skeleton, and does not involve deterioration of membrane properties due to the increase of sulfonic acid groups. It is processed into various types of composite membranes, flat membranes, hollow fiber membranes, and tube membranes, and can be usefully used in fuel cell membranes, ion exchange membranes, dehumidification membranes, humidification membranes, and the like.
  • FIG. 1 is a graph showing the results of measuring the hydrogen ion conductivity of the polymer membrane prepared in Examples 1 to 3 of the present invention and the polymer membrane of Comparative Example (Nafion 115).
  • the present invention provides a later-fonned copolymer comprising a perfluorocyclobutane group represented by the following formula (1).
  • R is an inert organic compound which contains at least one benzene ring but does not induce a chemical reaction and has a low sulfonation activity, wherein when R comprises two benzene rings, the benzene rings are directly connected to each other or- Connected via any one selected from the group consisting of (CO)-,-(SO 2 )-,-(SO)-,-(PO)-, and-(C (CF 3 ) 2 )-;
  • R ′ is an aromatic compound having a high sulfonation activity including at least one benzene ring, wherein when R ′ includes two benzene rings, the benzene rings are directly connected to each other or -O-, -S-,- (CH 2 )-,-(C (CH 3 ) 2 )-,-(PO)-,-(Si (CH 3 ) 2 )-,-(Si (C 6 H 5 ) 2 )-, -NH- , -NR 1 -and -R 2 -are connected via any one selected from the group consisting of, wherein R 1 is alkyl or aryl having 1 to 25 carbon atoms, R 2 is alkylene having 1 to 25 carbon atoms Or arylene;
  • R ′′ is a form in which R ′ is fonned below by introducing —SO 3 H into R ′;
  • N, m 1 and m 2 are integers, where m 1 is 0 when all R's are later fonned, and 10 ⁇ n + m 1 + m 2 ⁇ 100,000.
  • R is , , , , And so on.
  • R ' is , , , , , , , , , , And so on.
  • a sulfonating agent to prepare a copolymer of the formula (1) described later comprising the perfluorocyclobutane group comprising a step (step 2)
  • Step 1 is a step of preparing a copolymer compound (4) having a perfluorocyclobutane ring by polymerizing a monomer compound (2) having a low sulfonation activity and a monomer compound (3) having a high sulfonation activity. to be.
  • the monomer compound having low sulfonation activity (2) and the monomer compound having high sulfonation activity (3) used as starting materials have a perfluorovinyloxy group at both ends in common.
  • the perfluorovinyloxy group undergoes a cyclization reaction to form a perfluorocyclobutane ring.
  • the polymerization reaction of step 1 according to the present invention is preferably carried out in an inert gas atmosphere.
  • inert gas nitrogen or argon atmosphere is mentioned, for example.
  • step 1 is preferably carried out in a molten state or a solution state by heating for 30 minutes to 72 hours in the temperature range of 130-450 °C. If the reaction temperature is less than 130 ° C., the cyclobutane cyclization reaction does not occur or occurs very slowly. On the other hand, when the reaction temperature exceeds 450 °C there is a problem that the copolymer is decomposed.
  • the reaction solvent is not particularly limited as long as it is a solvent capable of appropriately dissolving the reactants and the product.
  • aprotic polar solvents such as dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF) and dimethylacetamide (DMAC) are used, or diphenyl ether
  • DMSO dimethyl sulfoxide
  • NMP N-methyl-2-pyrrolidone
  • DMF dimethylformamide
  • DMAC dimethylacetamide
  • diphenyl ether A solvent having a breaking point of 130 ° C. or higher can be used, such as (DPE) and 1,3,5-trimethylbenzene.
  • Step 2 is a step of preparing a copolymer of Chemical Formula 1 by fonning the copolymer compound (4) prepared in Step 1 later using a sulfonating agent.
  • the above-mentioned fonning may be performed by using a known method, and as the sulfonating agent that can be used, there is no particular limitation as long as it is a material capable of introducing -SO 3 H into the polymer.
  • the sulfonating agent that can be used
  • chlorosulfonic acid, sulfur trioxide, sulfuric acid, fuming sulfuric acid, acyl sulfate and the like can be used.
  • Step 2 is a hydrophobic moiety that maintains the mechanical density of the thin film by sulfonating a monomer (R ') moiety having a high sulfonation activity of the copolymer compound (4) prepared in step 1, and imparts ion conductivity to the thin film. Ensure that the hydrophilic moieties are alternately linked by chemical bonds.
  • the later-fonned copolymer according to the production method according to the present invention is characterized in that the sulfonated activity monomer (2) and the sulfonated activity monomer (3) are bonded to each other and then later fonned. Therefore, by adjusting the ratio of the compound (2) and compound (3), it is possible to easily control the distribution and number of sulfonic acid groups in the polymer skeleton.
  • the present invention provides a polymer membrane comprising a later-fonned copolymer comprising a perfluorocyclobutane group represented by the formula (1).
  • the polymer membrane may be used by various processing in the form of a polymer blend membrane, a polymer crosslinked membrane, a polymer composite membrane, a hollow fiber membrane, a tube membrane and the like by a processing method commonly used in the art.
  • polymer membrane according to the present invention can be used for applications such as fuel cell membrane, ion exchange membrane, dehumidification membrane, humidification membrane.
  • Experimental Example 1 in which the polymer membranes of Examples 1 to 3 for the polymer membrane according to the present invention were measured for hydrogen ion conductivity in comparison with Nafion 115, which has been used as a conventional polymer membrane, has a hydrogen ion conductivity of the polymer membrane according to the present invention. It is much improved than Nafion 115, showing at least an equivalent degree of hydrogen ion conductivity (see FIG. 1 ).
  • the polymer membrane according to the present invention not only includes perfluorocyclobutane groups known as chemically stable materials having excellent mechanical properties, but also regulates the proportion of monomers during polymerization, such as the number, distribution and position of sulfonic acid groups in the polymer skeleton. It is possible to control the characteristics of the membrane property is prevented from being deteriorated with the increase of sulfonic acid groups.
  • the polymer membrane according to the present invention can be usefully used as electrolyte membranes such as fuel cell membranes and ion exchange membranes, dehumidification membranes, humidification membranes and the like.
  • the present invention provides a method for producing the polymer membrane.
  • the method for producing a polymer membrane according to the present invention comprises the following steps:
  • fonned copolymers containing the perfluorocyclobutane group represented by the formula (1) include dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF) and dimethylacetamide
  • DMSO dimethyl sulfoxide
  • NMP N-methyl-2-pyrrolidone
  • DMF dimethylformamide
  • step A-2 Coating the polymer solution prepared in step A-1 on a glass, metal, porous polymer support (ceramic, polysulfone, polyisamide, etc.) or a solid surface used for film coating to form a film (step A-2 );
  • step A-3 Drying the film formed in step A-2 for 10 minutes to 48 hours at atmospheric pressure or vacuum in the temperature range of 50-250 ° C (step A-3).
  • the copolymer was dissolved in dichloroethane at a concentration of 1 wt% under a nitrogen atmosphere, and then chlorosulfonic acid was slowly added dropwise to 4 moles of the biphenyl repeating unit, and then fonned later for 7 hours. The solvent of the mixture was removed and washed several times with distilled water to prepare a later-fonned copolymer of Chemical Formula 1.
  • 4,4'-bis (2-trifluorovinyloxy) diphenyl sulfide (4,4'-Bis (2-trifluorovinyloxy) diphenyl sulfide) which is a monomer having high sulfonation activity and a monomer having low sulfonation activity
  • 4, 4'-bis (2-trifluorovinyloxy) benzophenone (4,4'-Bis (2-trifluorovinyloxy) benzophenone) in a weight ratio of 1: 1, 1: 5, and 1:10, respectively, was added to diphenyl ether. 20 wt% was added, followed by heating at 200 ° C. under nitrogen for one day, and then slowly cooling to room temperature.
  • the obtained polymer solution was slowly added dropwise into excess methanol, precipitated, filtered, and dried to obtain a copolymer corresponding to compound (4).
  • acetylsulfate acetic anhydride / condensed sulfuric acid, 1.5 mol / 1 mol
  • the solvent of the mixture was removed and washed several times with distilled water to prepare a later-fonned copolymer of Chemical Formula 1.
  • Trifluorovinyloxy) tetrafluorobenzene (1,4-Bis (trifluorovinyloxy) tetrafluorobenzene) was added at a weight ratio of 1: 1, 1: 5, and 1:10, respectively, in 20 wt% of diphenyl ether, followed by nitrogen It was heated at 200 °C for one day and then slowly cooled to room temperature.
  • the obtained polymer was slowly added dropwise into excess methanol, precipitated, filtered, and dried to obtain a copolymer of Compound (4).
  • the copolymer was dissolved in dichloroethane at 1 wt% under a nitrogen atmosphere, and then chlorosulfonic acid was slowly added dropwise to 4 moles of the biphenyl repeating unit, and then fonned later for 7 hours.
  • the solvent of the mixture was removed and washed several times with distilled water to prepare a later-fonned copolymer of Chemical Formula 1.
  • the hydrogen ion conductivity of the polymer membrane in which the monomer having a high sulfonation activity and the monomer having a low sulfonation activity was adjusted in a weight ratio of 1: 1 by a potentiostatic potential 2 probe It was measured by the (potentiostatic two-probe) method.
  • 1 x 1 cm 2 and 1.5 x 1.5 cm 2 carbon paper electrodes are placed on each side of the specimen with an area of 2 x 2 cm 2 at a constant pressure, and an ultra-pure water is allowed to flow out of it. A frequency of MHz-100 Hz was applied.
  • Example 1 Temperature (°C) Hydrogen ion conductivity (S / cm) Example 1
  • Example 2 Example 3 Nafion 115 30 0.0880 0.0810 0.0580 0.0650 40 0.0940 0.0850 0.0630 0.0730 50 0.1050 0.0920 0.0720 0.0860 60 0.1150 0.1090 0.0830 0.0900 70 0.1300 0.1120 0.0870 0.0930 80 0.1410 0.1230 0.0900 0.0960 90 0.1510 0.1400 0.1040 0.1200 100 0.1670 0.1450 0.1210 0.1100
  • sulfonic acid groups in the polymer skeleton because it does not involve deterioration of membrane properties due to the increase of sulfonic acid groups, polymer blend membranes, polymer crosslinked membranes, and polymers It is processed in various forms of a composite membrane, a flat membrane, a hollow fiber membrane, and a tube membrane, so that it can be usefully used in fuel cell membranes, ion exchange membranes, dehumidification membranes, humidification membranes, and the like.

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Abstract

La présente invention concerne des copolymères post-sulfonés contenant des groupes perfluorocyclobutane, un procédé de préparation et leur utilisation. Les polymères contenant des groupes perfluorocyclobutane selon la présente invention permettent une préparation facile dans une solution et à l'état fondu. La membrane électrolytique préparée présente une conductivité de protons améliorée, des propriétés mécaniques résistantes et une stabilité chimique. Il est possible de contrôler la distribution, la localisation, et le nombre de groupes d'acide sulfonique dans le squelette du polymère, et empêcher la réduction de propriétés physiques de la membrane entraînée par l'accroissement des groupes d'acide sulfonique. Ainsi, le membrane électrolytique peut être traitée dans des formes diverses telles que sous la forme d'une membrane de mélange homogène de polymères, d'une membrane de polymère réticulé, d'une membrane composite polymère, d'une membrane plate, d'une membrane fibre creuse, et d'une membrane tubulaire et peut être utilisé pour une membrane de pile à combustible, une membrane d'échange d'ions, une membrane de déshydratation, et une membrane d'humidification, et analogues.
PCT/KR2009/000174 2008-12-30 2009-01-13 Copolymères post-sulfonés contenant des groupes perfluorocyclobutane et leur procédé de préparation et leur utilisation WO2010076911A1 (fr)

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CN115164282A (zh) * 2022-08-08 2022-10-11 西南科技大学 一种真空膜除湿暖通空调系统及运行控制方法

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KR101307482B1 (ko) * 2011-12-28 2013-09-11 한국화학연구원 퍼플루오로사이클로부탄기를 포함하는 브랜치된 후술폰화 멀티블록 공중합체, 이의 제조방법 및 이를 이용한 전해질막
KR101403481B1 (ko) * 2012-03-13 2014-06-11 한국화학연구원 퍼플루오로사이클로부탄기로 연결되는 블록 공중합체 및 이의 제조방법
CN103819316B (zh) * 2014-03-13 2015-11-18 中国科学院上海有机化学研究所 可固化的聚芴及其作为耐热材料的应用

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CN114381026A (zh) * 2022-01-18 2022-04-22 董天都 一种磺化全氟聚苯质子交换膜及其制备方法
CN115164282A (zh) * 2022-08-08 2022-10-11 西南科技大学 一种真空膜除湿暖通空调系统及运行控制方法

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