EP1481027A1 - Polymeres a chaine principale fonctionnalises - Google Patents

Polymeres a chaine principale fonctionnalises

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Publication number
EP1481027A1
EP1481027A1 EP02796506A EP02796506A EP1481027A1 EP 1481027 A1 EP1481027 A1 EP 1481027A1 EP 02796506 A EP02796506 A EP 02796506A EP 02796506 A EP02796506 A EP 02796506A EP 1481027 A1 EP1481027 A1 EP 1481027A1
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European Patent Office
Prior art keywords
polymer
group
general formula
functional groups
radical
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EP02796506A
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German (de)
English (en)
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Thomas HÄRING
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Individual
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Individual
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/19—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/52—Polyethers
    • B01D71/522—Aromatic polyethers
    • B01D71/5221—Polyaryletherketone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
    • 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
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • C08G75/23—Polyethersulfones
    • 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
    • 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
    • C08J5/2275—Heterogeneous membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions 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; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones
    • 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
    • H01M8/0289—Means for holding the electrolyte
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1034—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having phosphorus, e.g. sulfonated polyphosphazenes [S-PPh]
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • C08G2650/20—Cross-linking
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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

Definitions

  • Functionalized fluorine-free main chain polymers such as sulfonated polyaryl ether ketones and polyether sulfones have been developed in the past by DuPont as an alternative to fluorinated cation exchangers such as Nafion®.
  • Such polymers processed into membranes, are used in membrane processes, in particular in fuel cells.
  • PEM fuel cells polymer electrolyte membrane fuel cells
  • the former convert hydrogen and the latter methanol.
  • Direct methanol fuel cells (DMFC) place higher demands on the membranes than on fuel cells that are operated exclusively with hydrogen.
  • Ionically cross-linked membranes were developed by Kerres et. al. developed. These are acid-base polymer blends and polymer (blend) membranes.
  • An advantage of the ionically crosslinked acid-base blend membranes is the greater flexibility of the ionic bonds and that these polymers / membranes do not dry out so easily at higher temperatures and consequently the membranes do not become brittle as quickly.
  • the ionic bonds have the disadvantage that they start to open at temperatures above 60 ° C., which leads to a strong swelling up to the dissolution of the membrane.
  • the polymer should have the best possible mechanical stability and improved swelling behavior.
  • the swelling behavior based on the dimension (length, width, height), should increase at a temperature of 90 ° C. in deionized water by less than 90% compared to the control value at 30 ° C.
  • Another object was to provide a polymer that can be processed into a membrane and used in fuel cells.
  • the crosslinked polymer should be suitable for use in fuel cells above 80 ° C., in particular above 100 ° C.
  • Membranes made from the polymer are said to be particularly suitable in direct methanol fuel cells.
  • fluorine-free polymeric cation exchangers such as sulfonated polyaryl ether ketones and sulfonated polysulfones
  • a polymeric fluorinated sulfonic acid e.g. Nafion® from DuPont
  • the polymer according to the invention is a polymer with a proton-releasing group, such as sulfonic acid, phosphonic acid and or carboxylic acid, the acid strength of which has been increased in accordance with the invention in accordance with the task, covalent and / or ionic crosslinking is not mandatory.
  • a proton-releasing group such as sulfonic acid, phosphonic acid and or carboxylic acid
  • the uncrosslinked, covalently and / or possibly ionically crosslinked polymer in the present invention has recurring units of the general formula (1)
  • the present invention relates to polymers having fluorine in the main chain, such as polyvinylidene difluoride (PVDF), poly (vinyl fluoride) (PVF) and polychlorotrifluorethylene and analogs, such as Kel-F® and Neoflon®.
  • PVDF polyvinylidene difluoride
  • PVF poly (vinyl fluoride)
  • PVF polychlorotrifluorethylene
  • Kel-F® and Neoflon® such as Kel-F® and Neoflon®.
  • polymers according to the invention are accessible through one or more modification steps of the starting polymers of the general formula (1).
  • Polymers of the general formula (1) are already known. These are polyarylenes, such as polyphenylene and polypyrene, aromatic polyvinyl compounds, such as polystyrene and polyvinylpyridine, polyphenylene vinylene, aromatic polyethers, such as polyphenylene oxide, aromatic thioethers, such as polyphenylene sulfide, polysulfones such as ⁇ Radel R and Ultrason®, and polyether ketones such as PEK, PEEK, PEKK and PEKEKK.
  • polyarylenes such as polyphenylene and polypyrene
  • aromatic polyvinyl compounds such as polystyrene and polyvinylpyridine
  • polyphenylene vinylene aromatic polyethers, such as polyphenylene oxide, aromatic thioethers, such as polyphenylene sulfide, polysulfones such as ⁇ Radel R and
  • polyporroles such as polybenzimidazole, polyanilines, polyazulenes, polycarbazoles, polyindophenines, polyvinylendifluoride (PVDF) and polychlorotrifluorethylenes and analogues, such as Kel-F® and Neoflon®.
  • polyporroles such as polybenzimidazole, polyanilines, polyazulenes, polycarbazoles, polyindophenines, polyvinylendifluoride (PVDF) and polychlorotrifluorethylenes and analogues, such as Kel-F® and Neoflon®.
  • PVDF polyvinylendifluoride
  • Neoflon® such as Kel-F® and Neoflon®.
  • radicals R 1 independently of one another have the general formula (888-1) or (888-2) ß ⁇ .
  • M is independently hydrogen, a mono- or polyvalent cation, preferably Li + , Na + , K + , Rb + , Cs + , TiO 2+ , ZrO 2+ , Ti 4+ , Zr 4+ , Ca 2+ , Mg 2+ or an optionally alkylated ammonium ion and X is a halogen or an optionally alkylated amino group, and wherein R 2 , R 3 , R, R 5 independently of one another are hydrogen, (4A), (4B), (4C), (4D) , (4E), (4F), (4G), (4H), (41), (4J), (4K), (4L), (4M), (4N), (40), (4P), ( 4Q) and / or (4R) or a group having 1 to 40 carbon atoms, preferably a branched or unbranched alkyl, cycloalkyl or an optionally alkylated aryl or heteroaryl group, which can be fluorinated or partially fluorinated
  • radical R optionally has bridges of the general formula (6A), (6B) and or (6C)
  • Y is a group having 1 to 40 carbon atoms, preferably a branched or unbranched alkyl, cycloalkyl or optionally alkylated aryl group
  • Z is hydroxyl, a group of the general formula (7)
  • the doped plastic membranes have a lower volume resistance, preferably less than or equal to 100 Ohm x cm at 20 ° C.
  • the doped plastic membranes have only a low permeability for hydrogen, oxygen and methanol.
  • the doped plastic membrane is suitable for use in fuel cells above 80 ° C, in some cases above 100 ° C and in special cases also above 110 ° C.
  • The. doped plastic membrane is suitable for use in fuel cells above 82 ° C, especially under normal pressure
  • the doped plastic membrane can be produced on an industrial scale. occur both through the formation of covalent and via the formation of ionic bonds.
  • the crosslinked polymer according to the invention is preferably doped with acid.
  • doped polymers refer to those polymers which, owing to the presence of doping agents, have an increased proton conductivity in comparison with the undoped polymers.
  • Dopants for the polymers according to the invention are acids.
  • acids include all known Lewis and Bronsted acids, preferably inorganic Lewis and Bronsted acids. It is also possible to use polyacids, in particular isopolyacids and heterolpolyacids, and also mixtures of different acids.
  • heteropolyacids refer to inorganic polyacids with at least two different central atoms, each consisting of weak, polybasic oxygen acids of a metal (preferably Cr, Mo, V, W) and a non-metal (preferably As, I, P, Se, Si, Te) arise as partially mixed anhydrides.
  • a metal preferably Cr, Mo, V, W
  • a non-metal preferably As, I, P, Se, Si, Te
  • Doping agents which are particularly preferred according to the invention are sulfuric acid and
  • Phosphoric acid A very particularly preferred dopant is phosphoric acid
  • zirconium phosphate and titanium sulfate via methods known to the person skilled in the art are particularly preferred, and modified and unmodified layered and framework silicates are also preferred. Montmorillonite, which is added during membrane production, is particularly preferred in this modification method.
  • the dopants are optionally fixed in the membrane by a calcination process and converted into the strongly Lewis acid form.
  • the calcination of titanium sulfate and zirconium phosphate in the membrane is particularly preferred.
  • the calcination is followed by a new and / or further doping.
  • Phosphoric acid, sulfuric acid and the heteropolyacids mentioned above are particularly preferred as dopants. If necessary, the process can be repeated several times.
  • the temperature range from 60 ° C. to just below the thermal decomposition temperature of the polymer to be doped is suitable as the calcining temperature.
  • the temperature range from 100 ° C. to 300 ° C. is particularly preferred.
  • the calcination fixes some dopants in the membrane for a technically applicable time.
  • the crosslinked polymer according to the invention has recurring units of the general formula (1), in particular recurring units corresponding to the general formulas (IA), (1B), (IC), (ID), (1E), (IF), (1G), ( 1H), (II), (IT), (1K), (1L), (IM), (IN), (10), (1P), (IQ), (1R), (IS) and / or ( IT), on:
  • the radicals R ⁇ are, independently of one another, the same or different 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 4,4'-biphenyl, a divalent radical of a heteroaromatic, a divalent radical of a Cjo aromatic, a divalent radical of a C 14 aromatics and / or a divalent pyrene radical.
  • a C 10 aromatics is naphthalene, for a C 14 aromatics phenanthrene.
  • the substitution pattern of the aromatic and / or heteroaromatic is arbitrary, in the case of phenylene, for example, R 6 can be ortho-, meta- and para-phenylene.
  • radicals R ⁇ R 8 and R 9 denote single-, four- or three-bonded aromatic or heteroaromatic groups and the radicals U, which are the same within a repeating unit, stand for an oxygen atom, a sulfur atom or an amino group, which is a hydrogen atom, a Group having 1-20 carbon atoms, preferably a branched or unbranched alkyl or alkoxy group, or an aryl group as a further radical.
  • polymers having recurring units of the general formula (1) belong to homopolymers and copolymers, for example random copolymers, such as Victrex ® 720 P and Astrel ®.
  • Very particularly preferred polymers are polyaryl ethers, polyaryl thioethers, polysulfones, polyether ketones, poly pyrroles, polythiophenes, polyazoles, polyphenylenes, polyphenylene vinylenes, polyanilines, polyazulenes, polycarbazoles, polypyrenes, polyindiprienines and polyvinylpyridines, in particular:
  • polyaniline polyazulene:
  • Cross-linked polymers with recurring units of the general formula (1A-1), (1B-1), (1C-1), (II-1), (1G-1), (1E-1), (1E-1), ( 1H-1), (11-1), (1F-1), (Ul), (1K-1), (1L-1), (1M-1) and / or (1N : 1).
  • n denotes the number of repeating units along a macromolecule chain of the crosslinked polymer.
  • This number of repeating units of the general formula (1) along a macromolecule chain of the crosslinked polymer is preferably an integer greater than or equal to 10, in particular greater than or equal to 100.
  • the number of repeating units of the general formula (1A), (1B) (1Q , (ID), (1E), (IF), (IG), (1H), (II), (1J), (1K), (1L), (IM), (IN), (lO) > ( 1P), (IQ), (1R), (IS) and / or (IT) along a macromolecule chain of the crosslinked polymer an integer greater than or equal to 10, in particular greater than or equal to 100.
  • the number average molecular weight of the macromolecule chain is greater than 25,000 g / mol, advantageously greater than 50,000 g / mol, in particular greater than 100,000 g / mol.
  • the crosslinked polymer according to the invention can also have different repeating units along a markromolecule chain.
  • 'it has, along a Makromolekiilkette only identical recurring units of the general formula (1A), (1B), (IC), (ID), (1E), (IF), (IG), (1H), (II) , (13), (1K), (1L), (IM), (IN), (10), (1P), (IQ), (1R), (IS) and / or (IT).
  • the radical R has at least partially substituents of the general formula (4A), (4B), (4C), (4D), (4E), (4F), (4G), (4H), (41) , (43), (4K), (4L), (4M), (4N), (40), (4P), (4Q) and / or (4R) preferably of the general formula (4A), (4B), (4C), (4D), (4J), (4K), (4L) and / or (4M), suitably of the general formula (4A), (4B), (4C), (4J), (4K) and / or (4L), in particular of the general formula (4J) and / or (4K).
  • O ox the general formula (4A), (4B), (4C), (4D), (4E), (4F), (4G), (4H), (41) , (43), (4K), (4L), (4M), (4N), (40), (4P), (4Q) and / or (4R) preferably of the general formula (4A), (4B), (4C), (4D), (4J), (4K), (4L) and / or (4M), suit
  • the R 1 radicals independently denote a bond or a 1
  • M stands for hydrogen, a mono- or polyvalent metal cation, preferably Li + , Na + , K + , Rb + , Cs + , Zr 4+ , Ti 4+ , Zr0 2+ or an optionally alkylated ammonium ion, advantageously for hydrogen or Li + , especially for hydrogen.
  • X is a halogen or an optionally alkylated amino group. and / or the radical R is USflS ⁇ partially a group of the general formula (5G) and / or (5Mlor preferably Hfc [Fa ⁇
  • radicals R 2 , R 3 , R 4 and R 5 independently of one another denote a group having 1 to 40 carbon atoms, preferably a branched or unbranched alkyl, cycloalkyl or an optionally alkylated aryl group, at least two of the radicals R 2 , R 3 and R 4 can be closed to form an optionally aromatic ring.
  • R at least partially has substituents of the general formula (5A-1) and / or (5A-2).
  • the radicals R 10 here denotes an optionally alkylated aryl group which has at least one optionally alkylated amino group, or an optionally alkylated heteroaromatic compound which either has at least one optionally alkylated amino group or has at least one nitrogen atom in the heteroaromatic core.
  • R n is hydrogen, an alkyl, a cycl ⁇ alkyl, an aryl, or a heteroaryl group or a radical R 10 with the abovementioned meaning, where R 10 and R 11 can be identical or different.
  • Substituents of the formula (5A-1) in which R 10 is an optionally alkylated aniline residue or pyridine residue, preferably an alkylated aniline residue, are very particularly preferred according to the invention.
  • substituents of the formula (5A-2) in which R 10 and R n are optionally alkylated aniline residues or pyridine residues, preferably alkylated aniline residues are also particularly preferred.
  • the radical R z-ssa ⁇ t partially bridges the general formula (6) on ⁇ / € ⁇ & Ci combine the at least two radicals R, where Y is a group having 1 to 40 carbon atoms, preferably a branched or unbranched alkyl, cycloalkyl or optionally alkylated aryl group, advantageously a linear or branched alkyl group having 1 to 6 carbon atoms.
  • vH polymer according to the invention is preferably doped with acid.
  • doped polymers refer to those polymers which, owing to the presence of doping agents, have an increased proton conductivity in comparison with the undoped polymers.
  • Dopants for the polymers according to the invention are acids.
  • acids include all known Lewis and Br ⁇ nsted acids, preferably inorganic Lewis and Bransted acids. It is also possible to use polyacids, in particular isopolyacids and heteropolyacids, and mixtures of different acids.
  • heteropolyacids denote inorganic polyacids with at least two different central atoms, each of which consists of weak, polybasic oxygen acids of a metal (preferably . Cr, Mo, V, W) and a non-metal (preferably As, I, P, Se , Si, Te) arise as partially mixed anhydrides. They include, among others, 12-molybdate phosphoric acid and 12-tungsten phosphoric acid.
  • Dopants which are particularly preferred according to the invention are sulfuric acid and phosphoric acid.
  • a very particularly preferred dopant is phosphoric acid (H 3 PO 4 ).
  • the conductivity of the plastic membrane according to the invention can be influenced via the degree of doping.
  • the conductivity increases with increasing dopant concentration until a maximum value is reached.
  • the degree of doping is stated as mole of acid per mole of repeating unit of the polymer. In the context of the present invention, a degree of doping between 3 and 15, in particular between 6 and 12, is preferred.
  • Processes for producing doped plastic membranes are known.
  • they are obtained by a polymer according to the invention for a suitable time, preferably 0.5-96 hours, particularly preferably 1-72 hours, at temperatures between room temperature and 100 ° C. and, if appropriate, increased pressure with concentrated acid , preferably wetted with highly concentrated phosphoric acid.
  • the spectrum of properties of the crosslinked polymer according to the invention can be changed by varying its ion exchange capacity.
  • the ion exchange capacity is preferably between 0.5 meq / g and 1.9 meq / g, in each case based on the total mass of the polymer.
  • the polymer according to the invention has a low volume resistivity, preferably of at most 100 ⁇ cm, expediently of at most 50 ⁇ cm, in particular of at most 20 ⁇ cm, in each case at 25 ° C.
  • the properties of the plastic membrane according to the invention can be controlled in part by their overall thickness.
  • the total thickness of the doped plastic membrane according to the invention is preferably between 5 and 100 ⁇ m, advantageously between 10 and 90 ⁇ m, in particular between 20 and 80 ⁇ m.
  • the present invention swells at a temperature of 90 ° C. in deionized water by less than 100%.
  • L is a leaving group, preferably an F, Cl, Br, I, tosylate, and n is an integer greater than or equal to 2, preferably 2.
  • Each reactant polymer preferably has recurring units of the general formula (1). Furthermore, it is expediently not covalently crosslinked.
  • the reaction with the compound (7) can also be used to form Lead bridges of the general formula (8) and / or (9).
  • a polymer mixture is formed 1) at least one starting polymer having functional groups a),
  • a polymer mixture is made from
  • the starting polymer (s) to be used according to the invention can fundamentally have different repeating units of the general formula (1). However, they preferably have only the same recurring units of the general formula (1A), (IB), (IC), (ID), (1E), (IF), (IG), (1H), (II), (U), (1K), ( 1L), (IM), (IN), (10), (1P), (IQ), (1R), (IS) and / or (IT).
  • the number of repeating units of the general formula (1A), (IB), (IC), (ID), (1E), (IF), (IG), (1H), (II), (1J), (1K ), (1L), (IM), (IN), (10), (1P), (IQ), (1R), (IS) and / or (IT) is preferably an integer greater than or equal to 10, preferably at least 100 recurring units.
  • the number average of the molecular weight of the starting polymer or polymers is greater than 25,000 g / mol, advantageously greater than 50,000 g / mol, in particular greater than 100,000 g / mol.
  • the synthesis of the starting polymer having functional groups of the general formula a), b) and / or d) is already known. It can be carried out, for example, by reacting a polymer of the general formula (1) with n-butyllithium in a dried aprotic solvent, preferably tetrahydrofuran (THF), under an inert gas atmosphere, preferably argon, and in this way Iithiating.
  • a polymer of the general formula (1) with n-butyllithium in a dried aprotic solvent, preferably tetrahydrofuran (THF), under an inert gas atmosphere, preferably argon, and in this way Iithiating.
  • THF tetrahydrofuran
  • the lithiated polymer is known in a manner known per se with suitable functionalizing agents, preferably with alkylating agents of the general formula
  • Subst. Is the substituent to be introduced, with ketones and / or aldehydes, which are converted to the corresponding alcoholates, and / or with carboxylic acid residues and / or carboxylic acid halides, which are converted to the corresponding ketones.
  • the introduction of sulfonate groups can also be achieved by the reaction of the lithiated polymer with SO 3 , the introduction of Sulfate groups also occur through the reaction of the lithiated polymer with SO 2 .
  • the degree of functionalization of the precursor polymers is preferably in the range '• from 0.1 to 3 groups per recurring unit, preferably from 0.2 to 2.2 groups per repeating unit.
  • Starting polymers with 0.2 to 0.8 groups a), preferably sulfonate groups, per repeat unit are particularly preferred.
  • reactant polymers with 0.8 to 2.2 groups b) per repeat unit have proven particularly useful.
  • particularly advantageous results are achieved with starting polymers which have 0.8 to 1.3 groups d) per repeating unit.
  • a dipolar aprotic solvent preferably in N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide or sulfolane and react with the halogen compound with stirring.
  • the polymer solution is spread as a film on a base, preferably on a glass plate, a fabric or a nonwoven, and b) the solvent is evaporated, if appropriate at elevated temperature above 25 ° C. and / or reduced pressure below 1000 mbar, and in this way receives a polymer membrane.
  • the properties of the polymer according to the invention can also be improved by treating the polymer a) with an acid in a first step and b) with deionized water in a further step. wherein the polymer is optionally treated with an alkali before the first step.
  • Gas separation, pervaporation, perstraction, reverse osmosis, nanofiltration, electrodialysis and diffusion dialysis can be used in a particularly advantageous manner.
  • the specific volume resistance R sp of the membranes was determined by means of impedance spectroscopy (IM6 impedance measuring device, Zahner electrics) in a Plexiglas unit with gold-coated copper electrodes (electrode area 0.25 cm 2 ). According to the invention, the impedance at which the phase angle between current and voltage was 0 denotes the specific volume resistance.
  • the specific measuring conditions were as follows: 0.5 N HC1 was used, the membrane to be measured was packed between two Nafion 117 membranes, the multi-layer arrangement Nafion 117 / membrane / Nafion 117 membrane was pressed between the two electrodes.
  • the interface resistances between the membrane and the electrode were eliminated by first measuring the multilayer arrangement of all 3 membranes and then the two Nafion 117 membranes alone. The impedance of the Nafion membranes was subtracted from the impedance of all 3 membranes. In the context of the present invention, the specific volume resistances at 25 ° C were determined.
  • Lithium salt of sulfonated polyether ketone PEK Lithium salt of sulfonated polyether ketone PEK
  • PSU Udel ® was first dissolved in dry THF and cooled to -75 ° C under argon. Traces of water in the reaction mixture were removed with 2.5 M n-butyllithium (n-BuLi). The dissolved polymer was then lithiated with 10 M n-BuLi. The reaction was allowed to react for one hour and then pyridine-3-aldehyde or 4,4'-bis (N, N-diethylamino) benzophenone was added. The reaction temperature was then raised to -20 ° C for one hour. For the reaction with SO 2 , the mixture was then cooled again to -75 ° C. and the SO 2 was introduced.
  • n-BuLi n-butyllithium
  • the polymers PEK-SO 3 Li, PSU-P3-SO 2 Li, PSU-EBD-SO 2 Li, PSU-DPK and / or PSUSO2L1 were dissolved in NMP according to Table 2 and filtered. The polymer solution was then degassed in vacuo and then 1,4-diiodobutane was added. After that, it was poured onto a glass plate and knife out. The glass plate was then in an oven at 60 ° C for one hour
  • the polymers according to the invention and the membranes produced therefrom are suitable for producing membrane electrode assemblies. If the sulfinic acid group does not react completely, the electrodes applied to the membrane, e.g. in the form of a paste, ink or via powder coating processes, with reactive groups covalently crosslinked with the membrane via alkylation crosslinkers. Both the membrane and the applied electrodes contain sulfic acid groups which have not yet reacted before the reaction, the sulfinates being particularly preferred.
  • the electrode paste which contains both precursors of polymeric cation exchangers and polymeric sulfinates, di- or oligohalogen crosslinkers, which may contain functional groups from ⁇ ) to ( ⁇ R)
  • the polymeric sulfinates of the electrode paste react with the free polymeric sulfinates of the membrane .
  • the resulting covalent crosslinking solves an existing problem in the insufficient connection of the electrodes to the membrane.
  • polymers according to the invention can be used in other membrane processes, preferably in gas separation, pervaporation, reverse osmosis, nanofiltration, electrodialysis, perstraction and diffusion dialysis.
  • the new polymers can be made by various methods.
  • polymeric sulfinic acids are, inter alia, those described by Guiver et.al. and also by Kerres et.al. described procedures accessible.
  • the polymeric sulfinic acid salt reacts with elimination of Li halide with a mono- or oligohalogen compound with sulfur alkylation or sulfur arylation, which also carry at least one further functional group from ⁇ A.) to (jfirj.
  • the halogen compound preferably contains the halogens fluorine, chlorine, bromine and / or iodine as a removable anion, iodide can be split off at room temperature (25 ° C.), bromine at temperatures above 30 ° C.
  • Sulfinated PSU-SO-Li polysulfone is prepared as described under a-3).
  • the IEC of the protonated form is 1.95 meq SO 2 Li / g. It is dissolved in NMP and an equivalent amount of the sodium salt of bromomethanesulfonate is added. After heating, the following compound is obtained dissolved in NMP PSU-SO 2 -CH 2 -SO 3 " Na + with an IEC of 1.95 meq SO 3 Li / g.
  • bromine-efansulfonate (sodium salt) is reacted with PSU-SO 2 -Li.
  • the reaction proceeds smoothly and after evaporation of the solvent and recrystallization, the pure compound PSU-SO 2 -CH 2 CH 2 -SO 3 " Na + is obtained .
  • the solvent is evaporated in a drying cabinet at a temperature of approx. 80 ° C. until the solution has a concentration of approx. 10-15% by weight. Has.
  • the mixture is then left to cool to room temperature (25 ° C.) and an equivalent amount of diiodobutane is added. The amount of diiodobutane is calculated on the crosslinking of the free sulfinate groups.
  • the solution is then doctored to a membrane on a glass plate and the remaining solvent NMP is evaporated in a drying cabinet. A covalently crosslinked membrane is obtained whose proton-releasing group has a significantly greater acid strength than the control.
  • the membrane is converted into the acid form by an aftertreatment in aqueous mineral acid and water.
  • the salts formed are removed.
  • the following graphic explains an embodiment of the polymers according to the invention.
  • polymers are provided which have one of the following groupings:
  • R 1 is defined as in the description of R 1 for the ⁇ Substituents A),), C), D),
  • ⁇ ⁇ DD is one of your duusi ⁇ u ineiLaus [? F) 3 y D (SL), M),, g), # > ), #Q) or # 1).
  • polymers are sulfinic acids.
  • the polymeric sulfinic acid is according to the general formula
  • Polysulfone is metallized with butyllithium at -60 ° C according to the prior art, described for example by Guiver et al. Then it is mixed with the equivalent amount of methyl iodide. The mixture is allowed to warm to -10 ° C. so that the polysulfone is completely methylated. The methylated polysulfone is cooled again to -60 ° C. and the equivalent amount of butyllithium is added to the metalation. Now you add the equivalent amount of one molecule of SO 2 CI 2 each at least more than a simply methylated methyl group and then you inject iodine dissolved in THF. The procedure is described in detail in the published patent application DE 3636854 AI. The resulting polymer is fluorinated via the well-known Finkelstein reaction via the halogen exchange and freed from the solvent. The polymer is then hydrolyzed in water, acid and / or alkali and the sulfonic acid is released.

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Abstract

La présente invention concerne des polymères à chaîne principale fonctionnalisés tels que des polyaryléther cétones et polyéther sulfones et leur utilisation dans des piles à combustible à membrane à électrolyte polymère.
EP02796506A 2001-11-22 2002-11-22 Polymeres a chaine principale fonctionnalises Withdrawn EP1481027A1 (fr)

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DE10158006 2001-11-22
DE10158006 2001-11-22
DE10208679 2002-02-28
DE10208679 2002-02-28
PCT/DE2002/004414 WO2003060012A1 (fr) 2001-11-22 2002-11-22 Polymeres a chaine principale fonctionnalises

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DE10296292D2 (de) * 2001-11-22 2004-12-23 Thomas Haering Modifizierte kovalent vernetzte Polymere
JP4827044B2 (ja) * 2002-02-28 2011-11-30 ウニヴェルズィテート シュトゥットガルト スルフィナート基を含むオリゴマー及びポリマー、並びにその製造方法
KR100542228B1 (ko) 2004-06-30 2006-01-10 삼성에스디아이 주식회사 연료전지용 고분자 막/전극 접합체 및 이를 포함하는연료전지
WO2006018020A2 (fr) * 2004-08-20 2006-02-23 Universität Stuttgart Ionomeres a groupes ionogenes dans la chaine laterale
JP2007012375A (ja) * 2005-06-29 2007-01-18 Toyota Motor Corp 燃料電池、燃料電池用電極触媒層の製造方法、及び燃料電池の運転方法
WO2007010730A1 (fr) * 2005-07-15 2007-01-25 Jsr Corporation Électrolyte d’électrode pour une utilisation dans une pile à combustible à polymère solide
EP2527156A1 (fr) * 2011-05-25 2012-11-28 RLS Merilna Tehnika D.O.O. Appareil et procédé pour inscrire un motif dans un substrat
GB2552986B (en) 2016-08-17 2020-09-16 Nifco Inc A device for separating oil from a blow-by gas
CN110194838B (zh) * 2019-05-28 2021-07-06 上海大学 1-芘基官能化聚砜材料及其制备方法
US11505671B1 (en) 2021-06-16 2022-11-22 Avanpore LLC Preparation of mesoporous poly (aryl ether ketone) articles and use thereof
US11491464B1 (en) 2021-06-24 2022-11-08 Avanpore LLC Mesoporous poly (aryl ether ketone) hollow fiber membranes and use thereof in mass transfer processes
US11673099B2 (en) 2021-07-14 2023-06-13 Avanpore LLC Composite poly (aryl ether ketone) membranes, their preparation and use thereof
US11511238B1 (en) 2021-07-20 2022-11-29 Avanpore LLC Composite covalent organic framework membranes
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WO2003060012A1 (fr) 2003-07-24
AU2002361930A1 (en) 2003-07-30
US20170095809A1 (en) 2017-04-06
DE10296292D2 (de) 2004-12-23
WO2003060011A3 (fr) 2003-11-13
WO2003060011A2 (fr) 2003-07-24
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US8710175B2 (en) 2014-04-29
US10328425B2 (en) 2019-06-25
US20140155502A1 (en) 2014-06-05
US20170266652A1 (en) 2017-09-21
AU2002363823A8 (en) 2003-07-30
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