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  • 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
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  • 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
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  • B01D71/06—Organic material
  • B01D71/52—Polyethers
  • B01D71/522—Aromatic polyethers
  • B01D71/5221—Polyaryletherketone
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  • 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
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  • B01D71/06—Organic material
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  • B01D71/80—Block polymers
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  • 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
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  • 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
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  • 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
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  • 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
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  • C08G75/23—Polyethersulfones
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  • 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
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  • 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
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  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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  • 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
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  • 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
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  • 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
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  • B01D2323/30—Cross-linking
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  • 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
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  • 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
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  • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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  • 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
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  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M2008/1095—Fuel cells with polymeric electrolytes
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  • H01—ELECTRIC ELEMENTS
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  • H01M2300/0017—Non-aqueous electrolytes
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• • 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
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  • 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 as an alternative to fluorinated cation exchangers such as Nafion® by DuPont.
• Polymers processed into membranes are used in membrane processes, especially 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 according to the invention in accordance with the task, covalent crosslinking is not mandatory.
• the polymer covalently and optionally ionically crosslinked in the present invention in particular covalently and optionally ionically crosslinked polymer, has recurring units of the general formula (1)
• K is a bond, oxygen, sulfur
• radical R is a divalent radical of an aromatic or heteroaromatic compound.
• the present invention relates to polymers with fluorine in the main chain, such as polyvinyl difluoride (PVDF) and polychlorotrifluorethylene and analogs, such as Kel-F® and Neoflon®.
• PVDF polyvinyl difluoride
• Kel-F® and Neoflon® polychlorotrifluorethylene
• Kel-F® and Neoflon® polychlorotrifluorethylene
• the polymers according to the invention become accessible through one or more modification steps of the starting polymers (PI).
• the starting polymers (Pl) are already known. These are polyarylene, 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. They also include polyporroles, polythiophenes, Polyazoles, such as polybenzimidazole, polyanilines, polyazulenes, polycarbazoles, polyindophenines,
• PVDF Polyvinyl difluoride
• polychlorotrifluorethylene and analogues such as Kel-F® and
• the radical R is bonded to P1 via one or more bonds.
• the bond is a covalent bond.
• the radical R can contain functional groups, in particular protonic acids, which interact with other functional groups, in particular bases and anion exchanger groups.
• radicals p independently of one another are a bond or a 1 to 40
• Group containing carbon atoms preferably a branched or unbranched alkyl, cycloalkyl or an optionally alkylated alyl group, which may contain one or more fluorine atoms
• M is hydrogen, a mono- or polyvalent metal cation, preferably Li + , Na + , K + , Rb + , Cs + , or an optionally alkylated ammonium ion and X is a halogen or an optionally alkylated amino group
• the radical R is at least partially substituents of the general formula (3A), (3B), (3C) and / or (3D ) having,
• R 2 , R 3 , R 4 , R 5 independently of one another (2A), (2B), (2C), (2D), (2E), (2F), (2G), (2H), (21), (2J), - (2K), (2L), (2M), (2N), (20), (2P), (2Q) and / or (2R) or a group having 1 to 40 carbon atoms, preferably one are branched or unbranched alkyl, cycloalkyl or an optionally alkylated alyl group which can be fluorinated or partially fluorinated, it being possible for at least two of the radicals R 2 , R and R 4 to be closed to form an optionally aromatic ring, and or the radical R at least
• radical R at least partially has bridges of the general formula (4A), (4B), (4C) and / or (4D),
• R is at least two radicals R, where Y is a 1 to 40 carbon atoms-containing group, preferably a branched or non-branched or non-branched alkyl, cycloalkyl or optionally alkylated aryl group is interconnected, which may be fluorinated oderteüflu ⁇ riert ', Z is. Hydroxyl, a group of the general formula (5)
• the polymer according to the invention and the crosslinked polymer according to the invention show a number of further advantages.
• 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, especially under normal pressure.
• the doped plastic membrane can be produced on an industrial scale.
• the polymer is kovaIent ⁇ -. T e ⁇ efe ⁇ s ⁇ frfalls
• 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
• Dopants 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 (1A), (1B), (IC), (1D); (1E), (IF), ( ⁇ G) .- (IH), (II), (IJ), (IK), (IL), (IM), (IN), (1 ⁇ ), (IP), ( IQ), (1R) 5 (IS) and / or (IT), on: _ 0 -R ⁇ _ (1A)
• 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 C 10 aromatic , a divalent radical of a C 14 aromatic 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 7 , R 8 and R 9 denote single-, four- or three-bonded aromatic or heteroaromatic groups and the radicals U, which are identical within a repeating unit, stand for an oxygen atom, a sulfur atom or an amino group which represents a hydrogen atom, carries 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 Cbpplymere as Victrex ® 720 P and Astrel ®.
• polymers are polyaryl ethers, polyaryl thioethers, polysulfones, polyether ketones, poly pyrroles, polythiophenes, polyazoles, polyphenylenes, polyphenylene vinylenes, polyanilines, polyazulenes, polycarbazoles, polypyrenes, polyindophenines and polyvinyl pyridines, in particular: polyaryl ethers:
• 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), is preferably (1C), (1D), (1E), (IF), (IG), (1H), (II), (IJ), (IK), (IL), (IM), (IN), (10 ), (IP), (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 macromolecule chain. Preferably, however, it has, along a Makromoiekülkette only • • same recurring units of the general formula (1A), (1B), (IC) (1D), (1E), (IF), (IG), (1H), (II) , (IJ), (IK), (IL), (IM), (IN), (10), (IP), (IQ), (1R), (IS) and / or (IT) on .. •
• the resrajmin set has partial substituents of the general formula (2A), (2B), (2C), (2D), (2E), (2F), (2G), (2H), (21), ( 2J), (2K), (2L), (2M), (2N), (20), (2P), (2Q) and / or (2R), preferably of the general formula (2A), (2B), ( 2C), (2D), (2J), (2K), (2L) and / or (2M), suitably of the general formula (2A), (2B), (20), (2J), (2K) and / or (2L), in particular of the general formula (2J) and / or (2K) on:
• R 1 independently of one another denote a bond or a group having 1 to 40 carbon atoms, preferably a branched or unbranched alkyl, cycloalkyl or an optionally alkylated aryl group which optionally contain one or more fluorine atoms.
• R1 is a methylene group (-CH 2 -) and / or a partially or completely fluorinated methylene group (-CFH-) or (-CF 2 -).
• R 1 additionally denotes a bond to the structure determined in the previous sentence.
• M represents hydrogen, a mono- or polyvalent metal cation, preferably Li + , Na + , K + , Rb + , Cs + , Zr 4+ , Ti 4+ , ZrO 2+ or an optionally alkylated ammonium ion, expediently for hydrogen or Li + , especially for hydrogen.
• X is a halogen or an optionally alkylated amino group.
• the radical R has at least partially substituents of the general foils (5A) and or (5B), preferably (5A),
• radical R is at least partially a group of the general formula (5C) and / or (5D), preferably (5C).
• radicals R 2 , R 3 , R 4 and R s independently of one another denote a group having 1 to 40 carbon atoms, of which a branched or unbranched alkyl, cycloalkyl or an optionally alkylated alyl 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 foils (5A-1) and / or (5A-2).
• 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 nucleus.
• R 11 is hydrogen, an alkyl, a cycloalkyl, an aryl or a heteroaryl group or a radical R 10 with the meaning given above, where R 10 and R u can be the same 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 11 are optionally alkylated aniline residues or pyridine residues, preferably alkylated aniline residues are also particularly preferred.
• the radical R at least partially has bridges of the general formula (6)
• 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.
• Z denotes hydroxyl, a group of the general formula
• 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 Bransted 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, N, 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 using 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. However, even extremely thin plastic membranes already have very good mechanical properties and a lower permeability for hydrogen, oxygen and methanol. Therefore . ' They are suitable for use in fuel cells above 80 ° C, expediently above 100 ° C, in particular for use in fuel cells above 120 ° C, without the edge area of the membrane electrode assembly having to be reinforced.
• 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 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 reactant polymer (s) to be used according to the invention can in principle 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), (IJ), (IK), ( IL), (IM), (IN), (10), (IP), (IQ), (1R), (IS) and / or (IT).
• the number of repeating units of the general formula (1 A), (IB), (IC), (ID), (1E), (IF), (IG), (1H), (II), (IJ), ( IK), (IL), (IM), (IN), (10), (IP), (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 lithiating in this way.
• a dried aprotic solvent preferably tetrahydrofuran (THF)
• an inert gas atmosphere preferably argon
• the lithiated polymer is known in a manner known per se with suitable functionalizing agents, preferably with alkylating agents of the general formula
• the introduction of sulfonate groups can also be achieved by the reaction of the lithiated polymer with SO 3 , the introduction of Sulfinate groups also take place through the reaction of the lithiated polymer with SO 2 .
• the degree of functionalization of the starting polymer is preferably in the range from 0.1 to 3 groups per repeating unit, preferably between 0.2 and 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 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. / / ⁇ "
• covalently crosslinked polymer according to the invention Possible fields of use for the covalently crosslinked polymer according to the invention are obvious to the person skilled in the art. It is particularly suitable for all applications which are drawn for cross-linked polymers with low volume resistivities, preferably less than 100 ⁇ cm at 25 ° C. Because of their characteristic properties, they are particularly suitable for applications in electrochemical cells, preferably in secondary batteries, electrolysis cells and in polymer electrolyte membrane fuel cells, in particular in hydrogen and direct methanol fuel cells.
• membrane separation processes preferably in gas separation, pervaporation, perstraction, reverse osmosis, nanofiltration, electrodialysis and diffusion dialysis.
• the volume resistivity R sp of the membranes was determined using. Impedance spectroscopy (IM6 impedance measuring device, Zahner Elektrik) determined in a plexiglass 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 concrete measuring conditions were as follows: 0.5 N HCl 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 PSUS ⁇ 2Li were dissolved in NMP according to Table 2 and filtered.
• the polymer solution was then degassed in vacuo and 1,4-diiodobutane was then added. After that, it was poured onto a glass plate and knife out.
• the glass plate was dried in an oven at 60 ° C for one hour, then at 90 ° C for another hour and finally at 120 ° C under vacuum overnight.
• the plate was cooled to room temperature and placed in a water bath.
• the membrane was separated from the glass plate and stored in 10% HCl at 90 ° C for one day in the oven. It was then conditioned in deionized water at 60 ° C.
• the polymer according to the invention described up to here and also all possible combinations is characterized in that it has at least one substituent from the general formula (2J), (2K), (2L), (2M), (2N), (20), (2P ), (2Q), and / or (2R). If it does not have a substituent from the above group, then it has at least one substituent from the general formula (3C), (3D), (3G), (3H) or that it is crosslinked via a crosslinking bridge from the general formula (4B ). and / or (4C).
• ⁇ up are also polymers which originate exclusively from sulfinated polymers from P1 and the sulfinate group is converted into sulfone groups in the further course of the reactions, which are partially or completely crosslinked ' with a further sulfinated polymer ' via a carbon-containing radical.
• the / ⁇ carbon-containing rest carries the functional groups.
• These can be acids or ⁇ JLU bases.
• 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 sulfinic acid groups which have not yet reacted before the reaction, and the sulfinates are particularly preferred.
• the electrode paste which contains both precursors of polymeric cation exchangers and polymeric sulfinates, to di- or oligohalogen crosslinkers, which may contain functional groups from (2A) to (2R)
• the polymeric sulfinates of the electrode paste react with the free polymeric sulfinates 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 rotation, pervaporation, ''
• 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 (2A) to (21).
• the halogen compound preferably contains the halogens fluorine, chlorine, bromine and / or iodine as a removable anion. Iodide is released at room temperature (25 ° C), bromine at temperatures above 30 ° C and chlorine can only be split off under drastic conditions.
• Fluorine is a leaving group when the fluorine atom is on an aryl group or on a herteroaryl group, a simple example is p-fluorobenzenesulfonate.
• the rest of e.g. (2A) to (21) now carries the desired functional group.
• the acid strength increases considerably due to the upstream sulfone group.
• the proton-releasing group e.g. Sulfonic acid is at least one carbon atom, preference is given to the methylene group -CH2- and the ethylene group -CH2-CH2-.
• the increase in acid strength is clearly detectable up to two carbon atoms in the direct line to the proton-releasing group.
• Membranes made from these polymers according to the invention show better proton conductivity compared to identical polymers in which the proton-releasing group is located directly on the aromatic. If one of the neighboring hydrogen atoms is additionally replaced by fluorine, the acid strength increases again.
• Sulfinated polysulfone PSU-SO 2 -Li 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 ethanesulfonate (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 equivalent amount of bromine ethanesulfonate (sodium salt) is not added, but only half, you get PSU-SO 2 -CH 2 CH 2 -SO 3 " Na + with an IEC of 0.9 meq SO 3 Li / g. And there is still an IEC of 1.0 meq SO 2 Li / g in the same molecule.
• 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.
• polymers which have one of the following groupings:
• P is a polymer as described on pages 9 to 16.
• R 1 is defined as in the description of R 1 for the substituents (2A), (2B), (2C), (2D),
• R55 is one of the substituents from (2A), (2B), (2C), (2D), (2E), (2F), (2G), (2H), (21), (2J), (2K),
• P is a polymer as described on pages 9 to 16.
• R 1 is defined as in the description of R 1 for the substituents (2A), (2B), (2C), (2D),
• R55 is one of the substituents from (2A), (2B), (2C), (2D), (2E), (2F), (2G), (2H), (21), (2J), (2K),
• polymers are sulfinic acids.
• the polymeric sulfamic acid is according to the general formula
• Polysulfone is metalized with butyllithium at -60 ° C according to the prior art, described for example by Guiver et.al. Then the equivalent amount of methyl iodide is added. 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 Cl 2 each at least more than a simply methalized 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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