Classifications

• • 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]
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
  • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
  • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
• • 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
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
  • C08J3/243—Two or more independent types of crosslinking for one or more 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
  • C08J3/246—Intercrosslinking of at least two 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
  • 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
  • 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
  • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08L71/12—Polyphenylene oxides
  • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
• • 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
  • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/14—Membrane materials having negatively charged functional groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/42—Ion-exchange membranes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
• • 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
  • C08J2481/00—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
  • C08J2481/06—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
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M2008/1095—Fuel cells with polymeric electrolytes
• • 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

• the present invention relates to covalently and ionically crosslinked polymers, in particular covalently and ionically crosslinked polymers having repeating units of the general formula
• the radical R is a divalent radical of an aromatic or heteroaromatic compound.
• the present invention describes a method for producing the covalently and ionically crosslinked polymers and their use, in particular in fuel cells.
• Polymers with repeating units of the general formula (1) are already known. They include, for example, polyarylenes such as polyphenylene and polypyrene, aiOmatische polyvinyl compounds such as polystyrene and polyvinyl pyridine, polyphenylene vinylene, aiOmatische polyethers such as polyphenylene oxide, aromatic polythioethers such as polyphenylene sulfide, polysulfones, such as Radel R ®, and polyether ketones such as PEK. Furthermore, they also include polypyrroles, polythiophenes, polyazoles, such as polybenzimidazole, polyanilines, polyazulenes, polycarbazoles and polyindophenines.
• polyarylenes such as polyphenylene and polypyrene
• aiOmatische polyvinyl compounds such as polystyrene and polyvinyl pyridine
• polyphenylene vinylene aiOmatische polyethers
• membranes are doped with concentrated phosphoric acid or sulfuric acid and serve as proton conductors in so-called polyelectrolyte membrane fuel cells (PEM fuel cells).
• PEM fuel cells polyelectrolyte membrane fuel cells
• MEE membrane electrode assembly
• a disadvantage of these membranes is their mechanical instability with a low modulus of elasticity, a low tensile strength and a low upper flow limit, and their relatively high permeability to hydrogen, oxygen and methanol.
• covalently cross-linked ionomer membranes which is based on an alkylation reaction of polymers containing sulfinate groups, polymer blends and polymer (blend) membranes.
• the covalent network has good resistance to hydrolysis even at higher temperatures.
• WO 99/02756 and WO 99/02755 disclose ionically crosslinked acid-base polymer blends and polymer (blend) membranes.
• An advantage of the ionically crosslinked acid-base blend membranes is that the ionic bonds are flexible, the polymers / membranes do not dry out so easily even at higher temperatures because of the hydrophilicity of the acid-base groups, and therefore the polymers / membranes also do not become brittle at higher temperatures.
• the ionically crosslinked ionomer (membrane) systems described in these documents have the disadvantage that the ionic bonds are in the temperature range dissolve between 60 and 90 ° C and the polymers / membranes begin to swell exorbitantly from this temperature range. Therefore, these membranes are also not very suitable for applications in fuel cells, especially at higher temperatures above 80 ° C.
• the polymer according to the invention should have a low volume resistivity, preferably less than or equal to 100 ⁇ cm at 25 ° C., and a low permeability for hydrogen, oxygen and methanol.
• Another object was to provide a cross-linked polymer that can be used in fuel cells.
• the crosslinked polymer should be suitable for use in fuel cells above 80 ° C., in particular above 100 ° C.
• the object of the invention was also to provide a process for producing the crosslinked polymer which can be carried out in a simple manner, inexpensively and on an industrial scale.
• radicals R 1 independently of one another are a bond or a group having 1 to 40 carbon atoms, preferably a branched or unbranched alkyl, cycloalkyl or an optionally alkylated aryl group
• M is hydrogen, a metal cation, preferably Li + , Na + , K + , Rb + , Cs + , or an optionally alkylated ammonium ion
• X is a halogen or an optionally alkylated amino group
• the radical R at least partially has substituents of the general formula (5A) and / or (5B),
• R 2 , R 3 , R 4 and R 5 are independently 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, and or the radical R is at least partially a group of the general formula (5C) and / or (5D)
• the radical R at least partially has bridges of the general formula (6), 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, Z is hydroxyl, a group of the general formula
• the crosslinked polymer according to the invention shows a number of further advantages. These include:
• Volume resistance preferably less than or equal to 100 ⁇ cm at 25 ° 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, especially under normal pressure.
• the doped plastic membrane is simple, large-scale and inexpensive to manufacture.
• the polymer is ionically and covalently cross-linked.
• crosslinked polymers refer to those polymers whose linear or branched macromolecules present in the collective are linked to one another to form three-dimensional polymeric networks. Networking can be done via the
• 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), (1F), (IG), (IG), ( 1H), (II), (1J), (1K), (1L), (IM), (IN), (1O), (1P), (IQ), (1R), (IS) and / or ( IT), on:
• the radicals R 6 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 the same within a repeating unit, represent 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 Copofymere 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, 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 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 cross-linked polymer according to the invention can in principle also have different repeating units along a macromolecule chain. However, it preferably has only the same repeating units of the general formula (1A), (1B), (IC), (1D), (1E), (IF), (IG), (IH), (II) along a macromolecule chain, (IJ), (IK), (IL), (IM), (IN), (10), (IP), (IQ), (IR), (IS) and / or (IT).
• the radical R preferably has at least partially substituents of the general formula (4A), (4B), (4C), (4D), (4E), (4F), (4G) and / or (4H) of the general formula (4A), (4B), (4C) and / or (4D), advantageously of the general formula (4A), (4B) and / or (4C), in particular of the general formula (4A):
• R 1 independently 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. In the context of a very particularly preferred embodiment of the present invention, R 1 is a bond.
• M represents hydrogen, a metal cation, preferably Li + , Na + , K + , Rb + , Cs + , or an optionally alkylated ammonium ion, advantageously hydrogen or Li + , in particular hydrogen.
• X is a halogen or an optionally alkylated amino group.
• the radical R according to the invention has at least partially substituents of the general formula (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 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).
• R 10 here denotes an optionally alkylated aryl group which has at least one optionally alkylated amino group, or an optionally alkylated heteroaioate which either has at least one optionally alkylated amino group or has at least one nitrogen atom in the heteroaiomatic core.
• R 11 is hydrogen, an alkyl, a cycloalkyl, 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 11 are optionally alkylated aniline residues or pyridine residues, preferably alkylated aniline residues are also particularly preferred.
• the radical R at least partially has brackets 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, especially 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 invention can be determined by the degree of doping
• Plastic membrane are affected.
• 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.
• a degree of doping between 3 and 15, in particular between 6 and 12, is preferred.
• Processes for producing doped plastic membranes are known. In a preferred embodiment of the present invention, 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.
• extremely thin plastic membranes already have very good mechanical properties and a lower permeability for hydrogen, oxygen and methanol. They are therefore 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 region of the membrane electrode unit 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%.
• Methods for producing the crosslinked polymer according to the invention are obvious to the person skilled in the art.
• a procedure has proven to be very particularly suitable in which one or more reactant polymers, the one or more or all of the functional groups a), b) and d) have, where d) sulfinate groups of the general formula (6)
• 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 of 1) at least one starting polymer having functional groups a) and b) and 2) at least one starting polymer having functional groups d) is used.
• 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 repeating units of the general formula (1A), (1B), (IC), (1D), (1E), (IF), (IG), (IH), (II), (IJ) , (IK), (IL), (IM), (IN), (10), (IP), (IQ), (IR), (IS) and / or (IT).
• the number of repeating units of the general formula (1A), (1B), (IC), (1D), (1E), (IF), (IG), (IH), (II), (IJ), (IK ), (IL), (IM), (IN), (10), (IP), (IQ), (IR), (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 formulas 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 in a manner known per se with suitable functionalizing agents, preferably with alkylating agents of the general formula
• Sulfonate groups can also be introduced by reacting the lithiated polymer with SO 3
• sulfonate groups can also be introduced by reacting 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-methylpyiTolidone, 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, if appropriate at elevated temperature above 25 ° C. and / or reduced pressure evaporates less than 1000 mbar and in this way receives a polymer membrane.
• the properties of the polymer according to the invention can also be improved by changing the polymer a) treated with an acid in a first step and b) treated with deionized water in a further step. wherein the polymer is optionally treated with an alkali before the first step.
• Electrolysis cells and in polymer electrolyte membrane fuel cells, in particular in hydrogen and direct methanol fuel cells are also present.
• membrane separation processes preferably in gas separation, pervaporation, perstraction, reverse osmosis, nanofiltration, electrodialysis and diffusion dialysis.
• IEC ion exchange capacity
• the specific volume resistance R sp of the membranes was determined by means of impedance spectroscopy (IM6 impedance measuring device, Zahner electrics) 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 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
• IEC ion exchange capacity
• 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). Then the dissolved polymer 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.

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