EP1786544A2 - Ionomeres a groupes ionogenes dans la chaine laterale - Google Patents

Ionomeres a groupes ionogenes dans la chaine laterale

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Publication number
EP1786544A2
EP1786544A2 EP05778891A EP05778891A EP1786544A2 EP 1786544 A2 EP1786544 A2 EP 1786544A2 EP 05778891 A EP05778891 A EP 05778891A EP 05778891 A EP05778891 A EP 05778891A EP 1786544 A2 EP1786544 A2 EP 1786544A2
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European Patent Office
Prior art keywords
poly
polymers
compounds
solvents
ionomers
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EP05778891A
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German (de)
English (en)
Inventor
Thomas HÄRING
Jochen Kerres
Martin Hein
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HAERING, THOMAS
Universitaet Stuttgart
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Universitaet Stuttgart
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Publication of EP1786544A2 publication Critical patent/EP1786544A2/fr
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    • 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
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • 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
    • B01D71/82—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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    • 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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    • 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
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    • 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
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0286—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
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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
    • 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
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • 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
    • H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
    • 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
    • H01M8/103—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]
    • 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
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • 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
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. in situ polymerisation or in situ crosslinking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/16—Membrane materials having positively charged functional groups
    • 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
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • C08J2365/02—Polyphenylenes
    • 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
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • Ionomermembranen consisting of a non- or partially fluorinated non-, partially or fully aromatic main chain and a non- or partially fluorinated side chain with ionogenic groups or their nonionic precursors
  • Phosphoric or phosphonic acid-containing ionomer membranes have received increasing attention in recent years because the phosphoric or phosphonic acid groups exhibit anhydrous proton conductivity because phosphorous or phosphonic acid groups can function both as a proton donor and as a proton acceptor.
  • This anhydrous proton conductivity of phosphoric acids is particularly interesting in fuel cells in the temperature range between 100 0 C and 200 ° C, since in this temperature range in fuel cells only a very low water vapor is present, and thus sulfonic acid ionomer membranes no longer work, since they rely on water molecules as proton acceptor are. From the literature various types of membranes are known whose proton conductivity is generated by phosphoric or phosphonic acids. For example:
  • PBI Polybenzimidazole
  • phosphoric acid blend membranes containing 5-6 phosphoric acid molecules per PBI repeating unit 1 , 2 . These membranes work very well at T> 100 ° C in the fuel cell, but at T ⁇ 100 ° C, the phosphoric acid can be discharged from the membrane, which leads to conductivity reduction and corrosion problems.
  • Phosphonated poly phosphazenes
  • brominated poly bisphenoxyphosphazene
  • chlorophosphorus diphenyl ester reaction with chlorophosphorus diphenyl ester and subsequent partial hydrolysis of the resulting phosphonic acid diphenyl ester to the free phosphonic acid 3 .
  • the object of the invention is to provide ionomers and ionomer membranes in which the ionogenic group sits on a flexible side chain, which has a positive effect on the ionic conductivity of the ionomers.
  • the object is also to provide methods to access these polymeric Hf ⁇ -Leitern.
  • the ionomers according to the invention are shown in FIG.
  • ionomers and ionomer membranes with the ionogenic groups or their nonionogenic precursors can be synthesized at the end of a flexible side chain according to the following method 1 in the following stages:
  • the base polymer is deprotonated by means of organometallic reaction
  • Ib the deprotonated polymer is reacted with an aliphatic halogen compound which preferably carries the halogen atom at one end and a nonionic precursor of the ionic group at the other end, whereby the halogen is nucleophilicly exchanged;
  • Ic the nonionic form of the ionic group is hydrolyzed, releasing the H + -FoHn of the cation exchange moiety.
  • a method 2 also leads to ionomers and ionomer membranes having the H.sup. -Conducting group in the side chain: 2a: the base polymer is deprotonated by means of an organometallic reaction; 2b: the deprotonated polymer is reacted excessively with an aliphatic dihalogen compound or a mixture of different dihalogen compounds (different halogens and / or different chain lengths of the dihalogen compound (s) are possible), which preferably carries the halogen atoms at the ends of the molecule a part of the halogen atoms of the dihalo compound (s) is nucleophilicly exchanged: Ar-Li + Hal - ((C (R 2 ) 2 ) X- Hal -> Ar - ((C (R 2 ) 2 ) X- Hal 2c: the In the side chain nucleophil exchangeable halogen-containing polymers are reacted with a compound
  • side-chain halogenated polymers can be converted into polymers with the phosphonic acid group in the side chain by Michaelis-Arbusov reaction or related reactions and subsequent hydrolysis. This reaction is shown schematically in Fig. 4.
  • Polyolefms such as polyethylene, polypropylene, polyisobutylene, polynorbornene,
  • Styrene (co) polymers such as polystyrene, poly (methylstyrene), poly ( ⁇ , ⁇ , ⁇ -trifluorostyrene),
  • N-basic polymers such as polyvinylcarbazole, polyethyleneimine, poly (2-vinylpyridine),
  • aryl main chain polymers such as:
  • Polyether ketones such as polyether ketone PEK Victrex®, polyether ether ketone PEEK Victrex®, polyether ether ketone ketone PEEKK, polyether ketone ether ketone PEKEKK Ultrapek®
  • Polyethersulfones such as Polysulfone Udel®, Polyphenylsulfone Radel R®, Polyetherethersulfone Radel A®, Polyethersulfone PES Victrex® Poly (benz) imidazoles such as PBI Celazol® and others the (benz) imidazole
  • (Benz) imidazole group may be present in the main chain or in the polymer side chain
  • Polyphenylene ethers such. Poly (2,6-dimethyloxyphenylene), poly (2,6-diphenyloxyphenylene)
  • 1,4-benzoyl groups or p-phenyloxy-l, 4-benzoyl groups may be modified.
  • Suitable reagents for the aryl polymer deprotonation are n-butyllithium, sec-butyllithium, tert. Butyllithium, methyllithium, phenyllithium, Grignard compounds such as phenylmagnesium halide and other Grignard compounds, lithium diisopropylamide, and other lithium amides, sodium naphtalide, potassium naphtalide, zinc organic compounds ("Rieke metals”)
  • Suitable solvents for the organometallic reaction are ether solvents such as THF, diethyl ether, glyme, diglyme, triglyme, dioxane and other ethereal solvents as well as hydrocarbon solvents C n H 2n +! , Cyclohexane, benzene, toluene, xylene and other CH aromatics and any mixtures thereof and with ether solvents.
  • ether solvents such as THF, diethyl ether, glyme, diglyme, triglyme, dioxane and other ethereal solvents as well as hydrocarbon solvents C n H 2n +! , Cyclohexane, benzene, toluene, xylene and other CH aromatics and any mixtures thereof and with ether solvents.
  • the compounds having nucleophilically substitutable halogen atoms and ionogenic groups may contain, as halogen, F, Cl, Br, or I. In this case, Cl, Br, and I are preferred. It is also possible to use mixtures of organic compounds with different halogens and different alkyl chain lengths.
  • dihaloalkanes can also be mixed dihaloalkanes, ie compounds of the type Br- (C (RO 2 VI), where the two halogen atoms have different reactivity to ensure that no crosslinking occurs in the reaction of Method 2. If for example, if the compound I- (CH 2 ) X- C1 is reacted with lithiated PSU, it is preferable to exchange the nucleophile I. It is preferable to use Cl, Br, and I.
  • halogenated heteroaromatics can be used. Some of these heteroaromatics are shown in Fig. 6.
  • the heteroaromatics may additionally contain organic radicals which do not react with the reactants of the process according to the invention.
  • Sulfinate groups SO 2 M are particularly preferred.
  • the sulfinates react with the halogens preferably under S-alkylation, as shown in Fig. 8 for the reaction of a side-chain halogenated polymer with Lithiumulfonatophenylphosphonkladialkylester.
  • the membranes, at the end of an alkyl, aryl or Alkylarylchargeoli have a H + type functional group can also be prepared by the following method: hi a suitable solvent (see below) 5 while a dipolar-aprotic solvent preferably , the following components are mixed together: (1) a polymer containing at least sulfato groups SO 2 M;
  • Suitable solvents for the reaction of the side chain halogenated polymers with the compounds containing a nucleophilic group and the ionogenic moieties or their nonionic precursors are ethereal solvents. as listed above, hydrocarbon solvents (aliphatic or aromatic, as listed above), dipolar aprotic solvents such as NMP, DMAc, DMF, DMSO, sulfolane, protic solvents such as alcohols C n H 2n + 1 , water or any mixtures of the listed solvents with one another.
  • the reaction temperatures for the organometallic reactions are in the range -100 ° C to + 100 ° C. Preference is given to a temperature range of -80 to 0 ° C.
  • reaction temperatures for the reaction of the deprotonated polymer with a halogen atom, and one or more ionic groups or their non-ionic precursors containing organic compound are in the range -100 0 C to +100 0 C. Preferred is a temperature range of -80 to 0 ° C. ,
  • reaction temperatures for the reactions of the deprotonated polymer with the dihalo compounds are in the range -100 ° C to +100 0 C. Preferred is a temperature range of -80 to 0 ° C.
  • reaction temperatures for the reaction of the side chain halogenated polymer with nucleophilic moieties and ionogenic moieties or their nonionic precursors containing compounds are in the range -100 ° C to + 200 ° C. Preference is given to a temperature range of -80 to + 150 ° C.
  • Suitable solvents for the Michaelis-Arbusov reaction of the side chain halogenated polymers are ethereal solvents as listed above, hydrocarbon solvents (aliphatic or aromatic as listed above), dipolar aprotic solvents such as NMP, DMAc, DMF, DMSO, sulfolane, protic solvents such as alcohols C "H 2n + i, water or any mixtures of the listed solvents with one another. Preference is given here to dipolar aprotic solvents, particularly preferably DMSO.
  • Suitable catalyst systems for the Michaelis-Arbusov reaction are NiCl 2 (using triethylphosphite as a phosphonating agent) or Pd (PPh 3 ) 4 / triethylamine (using (EtO) 2 POH as the phosphonating agent). In this case, Pd (PPh 3 ) 4 / triethylamine is preferred as the catalyst system. Also possible is the use of sodium dialkyl phosphite in THF as a phosphonating agent. Other literature known methods are possible.
  • reaction temperatures for the Michaelis-Arbusov reaction of the sokettenhalogen seeking polymers are in the range -100 ° C to + 200 ° C. Preference is given to a temperature range of 0 to 15O 0 C.
  • Suitable hydrolysis conditions for the hydrolysis of the nonionic precursors of the proton-conducting groups are:
  • the THF is poured into the reaction vessel under protective gas. Thereafter, the dried polymer is added to the reaction vessel with stirring and vigorous purging with argon. After the polymer has dissolved, it is cooled down to -60 ° C under a strong stream of argon. Now titrate the polymer solution with n-BuLi (14 ml of 2.5 N n-BuLi, barrel) until a slight yellow / orange color indicates that the reaction mixture is now anhydrous. Thereafter, the IO N n-BuLi is injected within 10 minutes. You leave 2h stir long. Thereafter, the solution of diethylbromethylphosphonate is added to the reaction solution as quickly as possible.
  • the THF is poured into the reaction vessel under protective gas. Thereafter, the dried polymer is added to the reaction vessel with stirring and vigorous purging with argon. After the polymer has dissolved, it is cooled down to -60 ° C under a strong stream of argon. Now titrate the polymer solution with n-BuLi (14 ml of 2.5 N n-BuLi, barrel) until a slight yellow / orange color indicates that the reaction mixture is now anhydrous. Thereafter, the 10 N n-BuLi is injected within 10 min. Leave to stir for 2 hours. Thereafter, the solution of chloromethanephosphonic dichloride (2-fold excess) is added to the reaction solution as quickly as possible.
  • the solution suddenly turns black and turns yellow-orange within a few minutes. Thereafter, the reaction mixture is stirred for 6 h at -4O 0 C, the temperature is increased to - 20 0 C / 24 h, then to 0 0 CJIl h.
  • the polymer solution is precipitated in 41% distilled water. The polymer forms after a short phase in the upper THF layer of a yellowish cake, which is skimmed off and digested with methanol for 12 h.
  • the thus purified polymer is dried at 60 ° C.
  • the following analyzes are performed on the product: 1 H, 13 C, and 31 P NMR, elemental analysis.
  • the THF is poured into the reaction vessel under protective gas. Thereafter, the dried polymer is added to the reaction vessel with stirring and vigorous purging with argon. After the polymer has dissolved, it is cooled down to -60 ° C under a strong stream of argon. Now titrate the polymer solution with 2.5 N n-BuLi until a slight yellow / orange color indicates that the reaction mixture is now anhydrous. Thereafter, the IO N n-BuLi is injected within 10 minutes. Leave to stir for 2 hours. Then add the dibromohexane to the reaction solution as fast as possible. Thereafter, the reaction mixture is stirred for 12 h at -20 ° C, the temperature is raised to 0 ° C / 4 h. It is hydrolyzed with 10 ml MeOH, precipitated in 2 1 MeOH, digested in MeOH and washed again on the frit 2 times.
  • the thus purified polymer is dried at 25 0 C in a vacuum.
  • the THF is poured into the reaction vessel under protective gas. Thereafter, the dried polymer is added to the reaction vessel with stirring and vigorous purging with argon. After the polymer has dissolved, it is cooled down to -60 ° C under a strong stream of argon. Now titrate the polymer solution with 2.5 N n-BuLi until a slight yellow / orange color indicates that the reaction mixture is now anhydrous. Thereafter, the 10 N n-BuLi is injected within 10 min. Leave to stir for 2 hours. Then add the dibromobutane to the reaction solution as quickly as possible. Thereafter, the reaction mixture is stirred for 12 h at -20 ° C, the temperature is raised to 0 ° C / 4 h. It is hydrolyzed with 10 ml MeOH, precipitated in 2 1 MeOH, digested in MeOH and washed again on the frit 2 times.
  • the thus purified polymer is dried at 25 0 C in a vacuum.
  • the THF is poured into the reaction vessel under protective gas. Thereafter, the dried polymer is added to the reaction vessel with stirring and vigorous purging with argon. After the polymer is dissolved, it is cooled down to -60 0 C, under vigorous stream of argon. Now titrate the polymer solution with 2.5 N n-BuLi until a slight yellow / orange color indicates that the reaction mixture is now anhydrous. Thereafter, the 10 N n-BuLi is injected within 10 min. Leave to stir for 2 hours. Then add the dibromodecane as fast as possible to the reaction solution. Thereafter, the reaction mixture is stirred for 12 h at -20 ° C, the temperature is raised to 0 ° C / 4 h. It is hydrolyzed with 10 ml MeOH, precipitated in 2 1 MeOH 5 digested in MeOH and washed again on the frit 2 times.
  • the thus purified polymer is dried at 25 ° C in a vacuum.
  • the THF is poured into the reaction vessel under protective gas. Thereafter, the dried polymer is added to the reaction vessel with stirring and vigorous purging with argon. After the polymer is dissolved, it is cooled down to -60 0 C, under vigorous stream of argon. Now titrate the polymer solution with 2.5 N n-BuLi until a slight yellow / orange color indicates that the reaction mixture is now anhydrous. Thereafter, the IO N n-BuLi is injected within 10 minutes. Leave to stir for 2 hours. Then add the diiodobutane to the reaction solution as fast as possible. Thereafter, the reaction mixture is stirred for 12 h at -20 ° C, the temperature is raised to 0 0 C / 4 h. It is hydrolyzed with 10 ml MeOH, precipitated in 2 1 MeOH 5 digested in MeOH and washed again on the frit 2 times.
  • the thus purified polymer is dried at 25 0 C in a vacuum. Based on the iodine content, 1.51 groups per formula unit are attached!
  • the THF is poured into the reaction vessel under protective gas. Thereafter, the dried polymer is added to the reaction vessel with stirring and vigorous purging with argon. After the polymer has dissolved, it is cooled down to -60 ° C under a strong stream of argon. Now titrate the polymer solution with 2.5 N n-BuLi until a slight yellow / orange color indicates that the reaction mixture is now anhydrous. Thereafter, the IO N n-BuLi is injected within 10 minutes. Leave to stir for 2 hours. Then add the diiododecane to the reaction solution as soon as possible. Thereafter, the reaction mixture is stirred for 12 h at -20 ° C, the temperature is raised to 0 0 C / 4 h. It is hydrolyzed with 10 ml MeOH, precipitated in 2 1 MeOH, digested in MeOH and washed again on the frit 2 times.
  • the thus purified polymer is dried at 25 0 C in a vacuum.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Electrochemistry (AREA)
  • Sustainable Energy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne des membranes ionomères constituées d'une chaîne principale non ou partiellement fluorée et non, partiellement ou entièrement aromatique et d'une chaîne latérale non ou partiellement fluorée présentant des groupes ionogènes ou leurs précurseurs non ioniques. Cette invention concerne également un procédé de production des membranes ionomères susmentionnées.
EP05778891A 2004-08-20 2005-08-20 Ionomeres a groupes ionogenes dans la chaine laterale Withdrawn EP1786544A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004041336 2004-08-20
PCT/DE2005/001504 WO2006018020A2 (fr) 2004-08-20 2005-08-20 Ionomeres a groupes ionogenes dans la chaine laterale

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EP1786544A2 true EP1786544A2 (fr) 2007-05-23

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US (3) US20100063168A1 (fr)
EP (1) EP1786544A2 (fr)
JP (3) JP2008510845A (fr)
DE (1) DE112005002051A5 (fr)
WO (1) WO2006018020A2 (fr)

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KR101417139B1 (ko) * 2006-02-16 2014-07-16 바스프 에스이 소중합체 및 중합체 방향족 포스폰산, 이들의 배합물, 이들의 제조 방법 및 고분자 전해질로서의 용도

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Publication number Priority date Publication date Assignee Title
US4598137A (en) * 1984-11-30 1986-07-01 Canadian Patents And Development Limited Polyarylene polyethersulfone ionomers
JPH08283413A (ja) * 1995-04-12 1996-10-29 Dainippon Ink & Chem Inc ポリフェニレンスルフィド共重合体アイオノマーの製法
JP3946252B2 (ja) * 1995-06-30 2007-07-18 ペメアス・ゲーエムベーハー ポリマーの結合したホスホニウム塩を有するポリアリーレンスルフィド及びその製造法
DE19817374A1 (de) * 1998-04-18 1999-10-21 Univ Stuttgart Lehrstuhl Und I Engineering-Ionomerblends und Engineering-Ionomermembranen
JP3561250B2 (ja) * 2001-09-21 2004-09-02 株式会社日立製作所 燃料電池
DE10296292D2 (de) * 2001-11-22 2004-12-23 Thomas Haering Modifizierte kovalent vernetzte Polymere
DE10390721D2 (de) * 2002-02-28 2005-02-10 Univ Stuttgart Sulfinatgruppen enthaltende Oligomere und Polymere und Verfahren zu ihrer Herstellung

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WO2006018020A2 (fr) 2006-02-23
US20150064609A1 (en) 2015-03-05
JP5766655B2 (ja) 2015-08-19
DE112005002051A5 (de) 2008-08-28
JP2012224856A (ja) 2012-11-15
US8742021B2 (en) 2014-06-03
WO2006018020A3 (fr) 2006-05-18
US9403162B2 (en) 2016-08-02
JP2014221896A (ja) 2014-11-27
JP2008510845A (ja) 2008-04-10
US20100063168A1 (en) 2010-03-11
US20120245237A1 (en) 2012-09-27

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