[go: up one dir, main page]

US20100063168A1 - Ionomers with ionogenic groups in the sidechain - Google Patents

Ionomers with ionogenic groups in the sidechain Download PDF

Info

Publication number
US20100063168A1
US20100063168A1 US11/573,982 US57398205A US2010063168A1 US 20100063168 A1 US20100063168 A1 US 20100063168A1 US 57398205 A US57398205 A US 57398205A US 2010063168 A1 US2010063168 A1 US 2010063168A1
Authority
US
United States
Prior art keywords
poly
hal
ionomeres
solvents
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11/573,982
Inventor
Haring Thomas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of US20100063168A1 publication Critical patent/US20100063168A1/en
Priority to US13/330,614 priority Critical patent/US8742021B2/en
Priority to US14/293,904 priority patent/US9403162B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/19—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—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
    • 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
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • 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
    • 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

  • Ionomer membranes containing phosphoric acid or phosphonic acid have received in recent years a growing interest because the phosphoric and phosphonic acid groups show water-free proton conductivity, in that phosphoric acid groups or phosphonic acid groups can act as proton donator as well as as proton acceptor.
  • This water-free proton conductivity of phosphoric acids is especially interesting for fuel cells in the temperature range between 100° C. and 200° C., because in this temperature range in fuel cells the vapour pressure of water is very low so that sulfonic acid containing ionomer membranes do not work anymore, because they need water molecules as proton acceptors. From the literature several membrane types are known, whose proton conductivity is generated from phosphoric acid or phosphonic acids.
  • the aim of the invention is to provide ionomers and ionomer membranes with the ionic group on a flexible side chain which has a positive impact on the proton conductivity of the ionomers.
  • the aim is furthermore to provide processes for the production of these polymeric proton conductors.
  • FIG. 1 Ionomers according to the invention are shown in FIG. 1 .
  • the method 1 is depicted in FIG. 2 .
  • the method 2 is depicted in FIG. 3 .
  • the side chain halogenated polymers can be converted via Michaelis-Arbusov reaction or related reactions and subsequent hydrolysis towards polymers with the phosphonic acid group in the side chain. This reaction is depicted in FIG. 4 .
  • main chains all kinds of polymers are possible. Preferred as main chains are however:
  • (Het)aryl main chain polymers like:
  • Suitable reagents for the deprotonation of the aryl polymer are n-butyllithium, sec-butyllithium, tert. butyllithium, methyllithium, phenyllithium, Grignard compounds like phenylmagnesiumhalide and other Grignard compounds, lithium diisopropylamide, and other lithium amides, sodium naphtalide, potassium naphtalide, zinc organic compounds (“Rieke metals”)
  • Suitable solvents for the metal organic reaction are ether solvents like THF, diethylether, glyme, diglyme, triglyme, dioxane and other ether solvents as well as hydrocarbon solvents C n H 2n+2 , cyclohexane, benzene, toluene, xylole and other C—H— aromatic solvants and any other mixtures thereof and with ether solvents.
  • the compounds with nucleophilically substitutable halogens and ionogenic groups may contain as halogene F, Cl, Br, or I. Preferred are Cl, Br and I. Also mixtures of organic compounds with different halgenes and different alkyl chain lengths can be used.
  • the dihalogen alcanes according to the invention method 2 can be also mixed dihalogen alcanes, that is compounds like Br—(C(R 1 ) 2 ) x —I, where both halogen atoms have different reactivity to assure that no cross-linking takes place during method 2 . If for example the compound I—(CH 2 )—Cl is reacted with lithiated PSU, I is preferred to be exchanged nucleophilically. Thereby Cl, Br and I are preferred.
  • mixtures of dihalogene compounds with different halgenes and different alkyl chain lengths can be used. Also compounds like Hal-(C(R 1 ) 2 ) x -Aryl-Hal are possible. According to the invention also Hal-(C(R 1 ) 2 ) x —Z-Aryl-Hal are possible.
  • halogenated hetaromates can be used. Some of these hetaromates are shown in FIG. 6 .
  • the hetaromates may contain in addition organic rests which do not react with the reactands of the process according to the invention.
  • Suitable nucleophilic groups for the reaction with the side chain halogenated polymers are shown in FIG. 7 .
  • sulfinate groups SO 2 M are especially preferred.
  • the sulfinates react with the halogenes preferred by S-Alkylation, as depicted in FIG. 8 for the reaction of a side-chain halogenated polymer with lithium sulfinatophenylphosphonic acid dialkylester.
  • membranes with a proton conducting functional group at the end of an alkyl-, aryl- or alkylaryl side chain can be made according to the following process:
  • Suitable solvents for the reaction of the side-chain halogenated polymers with compounds containing a nucleophilic group and the ionic group or their non-ionic precursor are ether solvents as described above, hydrocarbon solvents (aliphatic or aromatic, as described above), dipolar-aprotic solvents such as NMP, DMAc, DMF, DMSO, Sulfolan, protic solvents such as alcoholes C n H 2n+1 , water or any other mixtures of these solvents with each other.
  • the reaction temperature for the metal organic reaction is from ⁇ 100° C. to +100° C. Preferred is the temperature range from ⁇ 80 to 0° C.
  • the reaction temperature for the reaction of the deprotonated polymer with the organic compound containing a halogen atom and one or more ionic groups or their non-ionic precursors is from ⁇ 100° C. to +100° C. Preferred is the temperature range from ⁇ 80 to 0° C.
  • the reaction temperature for the reaction of the deprotonated polymer with the dihalogen compounds is from ⁇ 100° C. to +100° C. Preferred is the temperature range from ⁇ 80 to 0° C.
  • the reaction temperature for the reaction of the side-chain halogenated polymer with nucleophilic groups and ionic groups or their non-ionic precursors is from ⁇ 100° C. to +200° C. Preferred is the temperature range from ⁇ 80 to +150° C.
  • Suitable solvents for the Michaelis-Arbusov-reaction of the side-chain halogenated polymers are ether solvents as described above, hydrocarbon solvents (aliphatic or aromatic, as described above), dipolar-aprotic solvents such as NMP, DMAc, DMF, DMSO, Sulfolan, protic solvents such as alcoholes C n H 2n+1 , water or any other mixture of these solvents with each other.
  • dipolar-aprotic solvents especially preferred is DMSO.
  • Suitable catalyst systems for the Michaelis-Arbusov-reaction are NiCl 2 (with use of Triethylphosphite as phosphonation agent) or Pd(PPh 3 ) 4 /triethylamine (with use of (EtO) 2 POH as phosphonation agent). Preferred is Pd(PPh 3 ) 4 /triethylamine as catalyst system.
  • reaction temperature for the Michaelis-Arbusov-reaction of the side-chain halogenated polymer with nucleophilic groups and ionic groups or their non-ionic precursors is from ⁇ 100° C. to +200° C. Preferred is the temperature range from 0 to +150° C.
  • Suitable conditions for hydrolysis of the proton-conducting groups are:
  • the reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to ⁇ 60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on.
  • the precipitated polymer is dried at 60° C. From the product, the following analyses are prepared: 1 H—, 13 C and 31 P-NMR, elemental analysis.
  • the reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to ⁇ 60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of Chlormethanphosphonklaichloride (2-fold excess) is added into the reaction mixture as fast as possible.
  • the solution changes colour at once to black and in a few minutes back to yellow-orange.
  • the reaction mixture is stirred for 6 h at ⁇ 40° C., increases the temperature for 24 h to ⁇ 20° C., then for 12 h to 0° C.
  • the polymer is precipitated from the solution with 4 l demineralised water. The polymer soon forms a yellow cake in the upper THF layer, which is separated and digested with methanol for 12 h.
  • the thus purified polymer is dried at 60° C. From the product, the following analyses are prepared: 1 H—, 13 C and 31 P-NMR, elemental analysis.
  • the reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to ⁇ 60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of dibromhexane is added into the reaction mixture as fast as possible.
  • reaction mixture is stirred for 12 h at ⁇ 20° C., the temperature is increased to 0° C. for 4 h.
  • the solution is hydrolysed with 10 ml MeOH, precipitated in 2 l MeOH, digested in MeOH and washed on the filter twice.
  • the thus purified polymer is dried at 25° C. under vacuum.
  • the reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to ⁇ 60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of dibrombutane is added into the reaction mixture as fast as possible.
  • reaction mixture is stirred for 12 h at ⁇ 20° C., the temperature is increased to 0° C. for 4 h.
  • the solution is hydrolysed with 10 ml MeOH, precipitated in 2 l MeOH, digested in MeOH and washed on the filter twice.
  • the thus purified polymer is dried at 25° C. under vacuum.
  • the reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to ⁇ 60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of dibromdodecane is added into the reaction mixture as fast as possible.
  • reaction mixture is stirred for 12 h at ⁇ 20° C., the temperature is increased to 0° C. for 4 h.
  • the solution is hydrolysed with 10 ml MeOH, precipitated in 2 l MeOH, digested in MeOH and washed on the filter twice.
  • the thus purified polymer is dried at 25° C. under vacuum.
  • the reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to ⁇ 60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of diiodbutane is added into the reaction mixture as fast as possible.
  • reaction mixture is stirred for 12 h at ⁇ 20° C., the temperature is increased to 0° C. for 4 h.
  • the solution is hydrolysed with 10 ml MeOH, precipitated in 2 l MeOH, digested in MeOH and washed on the filter twice.
  • the thus purified polymer is dried at 25° C. under vacuum.
  • the reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to ⁇ 60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of diioddecane is added into the reaction mixture as fast as possible.
  • reaction mixture is stirred for 12 h at ⁇ 20° C., the temperature is increased to 0° C. for 4 h.
  • the solution is hydrolysed with 10 ml MeOH, precipitated in 2 l MeOH, digested in MeOH and washed on the filter twice.
  • the thus purified polymer is dried at 25° C. under vacuum.
  • the solvent is evaporated in a ventilated or vacuum drying ovenat increased temperature of 50 to 140° C.
  • a ventilated or vacuum drying ovenat increased temperature of 50 to 140° C.
  • the sulfinate-S-alkylation of the sulfinato-benzolphosphonic acid ester and the diiodbutane takes place and the membrane cross-links.
  • the membrane is posttreated to saponificate the phosphonic acid ester with 48% HBr or concentrated HCl under reflux.

Landscapes

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

Abstract

The invention relates to ionomeric membranes, comprising a non- or partly-fluorinated, non-, partly- or fully-aromatic backbone and a non- or partly-fluorinated sidechain with ionogenic groups, or the non-ionic precursors thereof and a method for production of said ionomeric membranes.

Description

    SUMMARY
  • It is claimed:
      • Ionomer membranes, consisting of a non-fluorinated or partly fluorinated non-, partly or fully-aromatic main chain and a non- or partly-fluorinated side chain with ionic groups or their non-ionic precursors
      • Process for the production of the above mentioned ionomer membranes
    STATE-OF-THE-ART
  • Ionomer membranes containing phosphoric acid or phosphonic acid have received in recent years a growing interest because the phosphoric and phosphonic acid groups show water-free proton conductivity, in that phosphoric acid groups or phosphonic acid groups can act as proton donator as well as as proton acceptor. This water-free proton conductivity of phosphoric acids is especially interesting for fuel cells in the temperature range between 100° C. and 200° C., because in this temperature range in fuel cells the vapour pressure of water is very low so that sulfonic acid containing ionomer membranes do not work anymore, because they need water molecules as proton acceptors. From the literature several membrane types are known, whose proton conductivity is generated from phosphoric acid or phosphonic acids.
  • There are for example:
      • blend membranes made of polybenzimidazole (PBI) and phosphoric acid with 5 to 6 phosphoric acid molecules per PBI repeating unit1,2. These membranes work at temperatures greater than 100° C. in the fuel cell very well, however phosphoric acid can be transported below 100° C. out of the membrane resulting in a decrease of conductivity and corrosion problems. 1 Wainright, J. S.; Wang, J.-T.; Weng, D.; Savinell, R. F.; Litt, M. H., J. Electrochem. Soc. 1995, 142, L1212 Calundann, G., Sansone, M., Benicewicz, B., Choe, E. W., Uensal, Oe., Kiefer, J., DE 10246459 A1, 2004
      • Phosphonated poly(phosphazene) obtained by reaction of brominated poly(bisphenoxyphosphazene) with t-butyllithium, followed by reaction with chloro-phosphoric acid diphenylester and finally partial hydrolysis of the formed phosphonic acid diphenylester to the free phosphonic acid3. A disadvantage of this reaction is that only a part of the lithiated groups reacts with the chlorophosphoric acid ester, and only a part of the formed phosphonic acid ester groups reacts to the free phosphonic acid group. 3 H. R. Allcock, M. A. Hofmann. R. M. Wood, Macromolecules 2001, 34, 6915-6921
      • Phosphonated poly(ethersulfon)e from brominated poly(ethersulfon)e by the Michaelis-Arbusov reaction4. A disadvantage of these polymers is, that the phosphonic acid groups are directly attached to the aromatic main chain, which has a negative impact on the proton conductivity, because the aryl main chain polymers are very stiff polymers and also with this method only a very limited number of phosphonic acid groups can be attached to the aromatic main chain polymer, which results in a great distance between the proton conducting groups and in turn in a low proton conductivity. 4 K. Jakoby et al, DE Offen 101 48 131 A1
  • For sulfonated ionomers it ha been shown, that the arrangement of the sulfonic acid groups in the side chain results in an increase in proton conductivity above 100° C. as compared with sulfonated ionomers with the sulfonic acid groups in the aromatic main chain. In a specific example the proton conductivities of sulfonated PEEK (sPEEK) and of poly(carbonylphenoxy)phenylene (“Poly-X 2000”) at 120° C. have been compared5. The Poly-X 2000 polymer was at 120° C. much more proton conducting than sPEEK. Disadvantages of this polymer are the expensive production process and the great stiffness of the polymer main chain and side chain. 5N. Ogato, M. Rikukawa, WO 94/24717
    • Purpose
  • The aim of the invention is to provide ionomers and ionomer membranes with the ionic group on a flexible side chain which has a positive impact on the proton conductivity of the ionomers. The aim is furthermore to provide processes for the production of these polymeric proton conductors.
  • Ionomers according to the invention are shown in FIG. 1.
    • DESCRIPTION
  • Surprisingly it has been found that ionomers and ionomer membranes with ionic groups or their non-ionic precursors at the end of a flexible side chain can be obtained by method 1 with the following steps:
    • 1a: the starting polymer is deprotonated by a metal organic reaction;
    • 1b: the deprotonated polymer is reacted with an aliphatic halogen compound, which has preferentially a halogen atom at one end and a non-ionic precursor of the ionic group at the other, wherein the halogen is exchanged nucleophilically;
    • 1c: the non-ionic form of the ionic group is hydrolysed, whereby the protonic form of the cation exchange group is liberated.
  • The method 1 is depicted in FIG. 2.
  • Surprisingly it has been found that also method 2 leads to ionomers and ionomer membranes with a proton conducting group in the side chain:
    • 2a: the starting polymer is deprotonated by a metal organic reaction;
    • 2b: the deprotonated polymer is reacted with an excess of an aliphatic dihalogen compound or a mixture of different dihalogen compounds (different halogenes and/or different chain lengths of the dihalogen compound(s) are possible), which carry preferentially the halogen compounds at the end of the molecule, whereby a part of the halogen atoms of the dihalogen compound(s) are exchanged nucleophilically: Ar—Li+Hal-((C(R2)2)x-Hal→Ar—((C(R2)2)x-Hal
    • 2c: the polymers carrying the nucleophilically exchangable halogens in the side chain are reacted with a compound carrying a nucleophilic group Nu and one or more ionic group(s) or their non-ionic form Y. In doing so the remaining halogens are exchanged nucleophilically;
    • 2d: the non-ionic form of the ionic group is hydrolysed, whereby the protonic form of the cation exchange group is liberated.
  • The method 2 is depicted in FIG. 3.
  • Surprisingly it has been found that the side chain halogenated polymers can be converted via Michaelis-Arbusov reaction or related reactions and subsequent hydrolysis towards polymers with the phosphonic acid group in the side chain. This reaction is depicted in FIG. 4.
  • As polymer main chains all kinds of polymers are possible. Preferred as main chains are however:
      • polyolefines like polyethylene, polypropylene, polyisobutylene, polynorbornene, polymethylpentene, poly(1,4-isoprene), poly(3,4-isoprene), poly(1,4-butadiene), poly(1,2-butadiene) and block copolymers, alternating copolymer or statistical copolymers of polydienes polybutadiene and polyisoprene with styrole,
      • styrole(co)polymers like polystyrole, poly(methylstyrole), poly(α,β,β-trifluorstyrole), poly(pentafluorostyrole)
      • perfluorinated ionomers like Nafion® or the SO2Hal-precursor of Nafion® (Hal=F, Cl, Br, I), Dow®-Membrane, GoreSelect®-Membrane.
      • partly fluorinated polymers like polyvinylidenfluoride, polyvinylfluoride and their copolymers with polyolefines or with aryl main chain polymersfrom FIG. 5 (see below)
      • N-basic polymers like polyvinylcarbazole, polyethylenimine, poly(2-vinylpyridine), poly(3-vinylpyridine), poly(4-vinylpyridine)
      • (Het)aryl main chain polymers, containing the building block depicted in FIG. 5.
  • Particularly preferred are (Het)aryl main chain polymers like:
      • Polyetherketones like polyetherketone PEK Victrex®, polyetheretherketone
      • PEEK Victrex®, polyetheretherketoneketone PEEKK, polyetherketoneetherketone ketone PEKEKK Ultrapek®
      • Polyethersulfones like polysulfone Udel®, polyphenylsulfone Radel R®, Polyetherethersulfone Radel A®, polyethersulfone PES Victrex®
      • Poly (Benz) imidazole like PBI Celazol® and others the (Benz) imidazole-group containing oligomers and polymer, in which the (Benz) imidazole group can be available in the main chain or in the side chain
      • Polyphenyleneether like poly(2,6-dimethyloxyphenylene), poly(2,6-diphenyloxyphenylene)
      • Polyphenylenesulfide and copolymers
      • Poly(1,4-phenylene) or Poly (1,3-phenylene), which can be modified in the lateral group if necessary with benzoyl, naphtoyl or o-phenyloxy-1,4-benzoyl group, m-phenyloxy-1,4-benzoyl group or p-phenyloxy-1,4-benzoyl group.
      • Poly(benzoxazole) and copolymers
      • Poly(benzthiazole) and copolymers
      • Poly(phtalazinone) and copolymers
      • Polyaniline and copolymers
      • Polythiazole
      • Polypyrrole
  • Suitable reagents for the deprotonation of the aryl polymer are n-butyllithium, sec-butyllithium, tert. butyllithium, methyllithium, phenyllithium, Grignard compounds like phenylmagnesiumhalide and other Grignard compounds, lithium diisopropylamide, and other lithium amides, sodium naphtalide, potassium naphtalide, zinc organic compounds (“Rieke metals”)
  • Suitable solvents for the metal organic reaction are ether solvents like THF, diethylether, glyme, diglyme, triglyme, dioxane and other ether solvents as well as hydrocarbon solvents CnH2n+2, cyclohexane, benzene, toluene, xylole and other C—H— aromatic solvants and any other mixtures thereof and with ether solvents.
  • Some of the suitable compounds with nucleophilically substitutable halogens and ionogenic groups or their non-ionic precursors for the reaction with the deprotonated polymers are depicted in FIG. 2. Particularly preferred are compounds of the typ Hal-(CH2)x—Y (Y see FIG. 2, x=1−20).
  • The compounds with nucleophilically substitutable halogens and ionogenic groups may contain as halogene F, Cl, Br, or I. Preferred are Cl, Br and I. Also mixtures of organic compounds with different halgenes and different alkyl chain lengths can be used.
  • Suitable dihalogene compounds for the reaction with the deprotonated polymers are: Hal-(C(R1)2)x-Hal Cl, Br, I; R1=H, F, CnH2n+1, aryl). The dihalogen alcanes according to the invention method 2 can be also mixed dihalogen alcanes, that is compounds like Br—(C(R1)2)x—I, where both halogen atoms have different reactivity to assure that no cross-linking takes place during method 2. If for example the compound I—(CH2)—Cl is reacted with lithiated PSU, I is preferred to be exchanged nucleophilically. Thereby Cl, Br and I are preferred. Also mixtures of dihalogene compounds with different halgenes and different alkyl chain lengths can be used. Also compounds like Hal-(C(R1)2)x-Aryl-Hal are possible. According to the invention also Hal-(C(R1)2)x—Z-Aryl-Hal are possible.
  • Also in another embodiment of the invention halogenated hetaromates can be used. Some of these hetaromates are shown in FIG. 6. The hetaromates may contain in addition organic rests which do not react with the reactands of the process according to the invention.
  • Suitable nucleophilic groups for the reaction with the side chain halogenated polymers are shown in FIG. 7.
  • Hereby sulfinate groups SO2M are especially preferred. There the sulfinates react with the halogenes preferred by S-Alkylation, as depicted in FIG. 8 for the reaction of a side-chain halogenated polymer with lithium sulfinatophenylphosphonic acid dialkylester.
  • Surprisingly it has been found, that membranes with a proton conducting functional group at the end of an alkyl-, aryl- or alkylaryl side chain can be made according to the following process:
  • In a suitable solvent (see below), whereby dipolar-aprotic solvents are preferred, the following components are mixed:
      • (1) polymer containing at least sulfinate groups SO2M;
      • (2) low molecular di- or oligohalogenalcane (Hal-(C(R1)2)x-Hal (Hal=F, Cl, Br, I; R1=H, F, CnH2n+1, Aryl), Hal-(C(R1)2)x-Aryl-Hal or Hal-(C(R1)2)x—Z-Aryl-Hal)
      • (3) low molecular aromatic, aliphatic or aromatic-aliphatic compound, containing at least a sulfinate group and the non-ionic form of a cation exchange group.
  • If from the solution of these components a thin film is casted and then the solvent at increased temperature and if necessary reduced pressure is evaporated, covalently cross-linked membranes are formed, which contain the non-ionic form of the cation exchange group in the polymer side chain.
  • Suitable solvents for the reaction of the side-chain halogenated polymers with compounds containing a nucleophilic group and the ionic group or their non-ionic precursor are ether solvents as described above, hydrocarbon solvents (aliphatic or aromatic, as described above), dipolar-aprotic solvents such as NMP, DMAc, DMF, DMSO, Sulfolan, protic solvents such as alcoholes CnH2n+1, water or any other mixtures of these solvents with each other.
  • The reaction temperature for the metal organic reaction is from −100° C. to +100° C. Preferred is the temperature range from −80 to 0° C.
  • The reaction temperature for the reaction of the deprotonated polymer with the organic compound containing a halogen atom and one or more ionic groups or their non-ionic precursors is from −100° C. to +100° C. Preferred is the temperature range from −80 to 0° C.
  • The reaction temperature for the reaction of the deprotonated polymer with the dihalogen compounds is from −100° C. to +100° C. Preferred is the temperature range from −80 to 0° C.
  • The reaction temperature for the reaction of the side-chain halogenated polymer with nucleophilic groups and ionic groups or their non-ionic precursors is from −100° C. to +200° C. Preferred is the temperature range from −80 to +150° C.
  • Suitable solvents for the Michaelis-Arbusov-reaction of the side-chain halogenated polymers are ether solvents as described above, hydrocarbon solvents (aliphatic or aromatic, as described above), dipolar-aprotic solvents such as NMP, DMAc, DMF, DMSO, Sulfolan, protic solvents such as alcoholes CnH2n+1, water or any other mixture of these solvents with each other. Preferred are dipolar-aprotic solvents, especially preferred is DMSO.
  • Suitable catalyst systems for the Michaelis-Arbusov-reaction are NiCl2 (with use of Triethylphosphite as phosphonation agent) or Pd(PPh3)4/triethylamine (with use of (EtO)2POH as phosphonation agent). Preferred is Pd(PPh3)4/triethylamine as catalyst system.
  • Possible is also the use of sodium dialkylphosphite in THF as phosphonation agent. Also other processes known from the literature for this reaction are possible.
  • The reaction temperature for the Michaelis-Arbusov-reaction of the side-chain halogenated polymer with nucleophilic groups and ionic groups or their non-ionic precursors is from −100° C. to +200° C. Preferred is the temperature range from 0 to +150° C.
  • Suitable conditions for hydrolysis of the proton-conducting groups are:
    • Acid ester:
    • —PO(OR2)2, —COOR2, —SO(OR2)2: Me3SiBr/CCl4, 48% HBr, BBr3, NaOH, HCl
    • Acid halides:
    • —POHal2, COHal, SO2Hal: 10% NaOH/90° C., 10% HCl/90° C., H2O/90° C.
    • Acid amides:
      concentrated aqueous acids or bases
    EXAMPLES Reaction of Lithiated PSU with Diethyl-2-Bromethylphosphonate Chemicals:
  • 11.05 g PSU Udel P 1800 (0.025 mol) dried
    1000 ml THF anhydrous
    5 ml n-BuLi 10 N (0.05 mol)
    24.51 g (0.1 mol) Diethyl-2-Bromethylphosphonate (M=245.06 g/mol, δ=1.348 g/cm3)≈18.2 ml
  • Figure US20100063168A1-20100311-C00001
    • Procedure:
  • The reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to −60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on.
  • Then within 10 min the 10N n-BuLi is syringed in.
  • The stirring is continued for 2 hours. Then the solution of diethylbromethylphosphonate is added into the reaction mixture as fast as possible. Subsequently, the reaction mixture is stirred for 6 h at −60° C. Then, 100 ml solution is removed from the reaction mixture, which is hydrolyzed in methanol (EA and NMR), the temperature is increased to −40° C./24 h, subsequently to −20° C. and 0° C., under respective hydrolysis of 100 ml solution. Methanol is used as precipitant.
  • The precipitated polymer is dried at 60° C. From the product, the following analyses are prepared: 1H—, 13C and 31P-NMR, elemental analysis.
    • Addendum: The methanol-dissolved fractions from −60 to −20° C. are precipitated in methanol>very fine, mucous>not filterable: salting out with saturated table salt solution.
      • The biggest fraction at 0° C. is precipitated in water and filtered over 3 days (G2), washed with water and dried.
  • Relating to phosphorus content 1.37 groups per repeat unit are bound.
  • Reaction of Dilithiated PSU with Cl—CH2—POCl2
    • Chemicals:
    • 11.05 g PSU Udel P 1800 (0.025 mol) dried
    • 1000 ml THF anhydrous
    • 5 ml n-BuLi 10 N (0.05 mol)
    • 16.7 g (0.1 mol) Chlormethanphosphonsäuredichlorid (M=167.36 g/mol, δ=1.638 g/cm3)≈
    • 10.2 ml, SdP.: 78° C./10 mm
  • Figure US20100063168A1-20100311-C00002
    • Procedure:
  • The reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to −60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of Chlormethanphosphonsäuredichloride (2-fold excess) is added into the reaction mixture as fast as possible. The solution changes colour at once to black and in a few minutes back to yellow-orange. Subsequently, the reaction mixture is stirred for 6 h at −40° C., increases the temperature for 24 h to −20° C., then for 12 h to 0° C. The polymer is precipitated from the solution with 4 l demineralised water. The polymer soon forms a yellow cake in the upper THF layer, which is separated and digested with methanol for 12 h.
  • The thus purified polymer is dried at 60° C. From the product, the following analyses are prepared: 1H—, 13C and 31P-NMR, elemental analysis.
  • Relating to phosphorus content 0.31 groups per repeat unit are bound.
  • Because the reaction at −60° C. is very fast, cool after addition of butyl lithium to −80° C., keep 12 h at −80° C., then follow the instructions as above from −60° C. to room temperature.
  • Reaction of Dilithiated PSU with Dibromhexane
    • Chemicals:
    • 4.42 g PSU Udel P 1800 (0.01 mol) dried
    • 300 ml THF anhydrous
    • 2 ml n-BuLi 10 N (0.02 mol)
    • 19.52 g Dibromhexane (0.08 mol, 243.98 g/mol)
  • Figure US20100063168A1-20100311-C00003
    • Procedure:
  • The reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to −60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of dibromhexane is added into the reaction mixture as fast as possible. Subsequently, the reaction mixture is stirred for 12 h at −20° C., the temperature is increased to 0° C. for 4 h. The solution is hydrolysed with 10 ml MeOH, precipitated in 2 l MeOH, digested in MeOH and washed on the filter twice.
  • The thus purified polymer is dried at 25° C. under vacuum.
  • Relating to bromine content 0.87 groups per repeat unit are bound.
  • Reaction of Dilithiated PSU with Dibrombutane
    • Chemicals:
    • 4.42 g PSU Udel P 1800 (0.01 mol) dried
    • 300 ml THF anhydrous
    • 2 ml n-BuLi 10 N (0.02 mol)
    • 21.59 g Dibrombutane (0.1 mol, 215.9 g/mol)
  • Figure US20100063168A1-20100311-C00004
    • Procedure:
  • The reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to −60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of dibrombutane is added into the reaction mixture as fast as possible. Subsequently, the reaction mixture is stirred for 12 h at −20° C., the temperature is increased to 0° C. for 4 h. The solution is hydrolysed with 10 ml MeOH, precipitated in 2 l MeOH, digested in MeOH and washed on the filter twice.
  • The thus purified polymer is dried at 25° C. under vacuum.
  • Relating to bromine content 0.98 groups per repeat unit are bound.
  • Reaction of Dilithiated PSU with Dibromdodecane
    • Chemicals:
    • 4.42 g PSU Udel P 1800 (0.01 mol) dried
    • 300 ml THF anhydrous
    • 2 ml n-BuLi 10 N (0.02 mol)
    • 23.4 g Dibromdodecane (0.071 mol, 328.14 g/mol)
  • Figure US20100063168A1-20100311-C00005
    • Procedure.
  • The reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to −60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of dibromdodecane is added into the reaction mixture as fast as possible. Subsequently, the reaction mixture is stirred for 12 h at −20° C., the temperature is increased to 0° C. for 4 h. The solution is hydrolysed with 10 ml MeOH, precipitated in 2 l MeOH, digested in MeOH and washed on the filter twice.
  • The thus purified polymer is dried at 25° C. under vacuum.
  • Relating to bromine content 0.3 groups per repeat unit are bound.
  • Reaction of Dilithiated PSU with Diiodbutane
    • Ansatz:
    • 4.42 g PSU Udel P 1800 (0.01 mol) dried
    • 300 ml THF anhydrous
    • 2 ml n-BuLi 10 N (0.02 mol)
    • 62 g Diiodbutane (0.2 mol, 309.92 g/mol)
  • Figure US20100063168A1-20100311-C00006
    • Procedure:
  • The reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to −60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of diiodbutane is added into the reaction mixture as fast as possible. Subsequently, the reaction mixture is stirred for 12 h at −20° C., the temperature is increased to 0° C. for 4 h. The solution is hydrolysed with 10 ml MeOH, precipitated in 2 l MeOH, digested in MeOH and washed on the filter twice.
  • The thus purified polymer is dried at 25° C. under vacuum.
  • Relating to iodine content 1.51 groups per repeat unit are bound.
  • Reaction of Dilithiated PSU with Diioddecane
  • Chemicals:
    • 4.42 g PSU Udel P 1800 (0.01 mol) dried
    • 300 ml THF anhydrous
    • 2 ml n-BuLi 10 N (0.02 mol)
    • 38 g diioddecane (0.096 mol, 394.08 g/mol)
  • Figure US20100063168A1-20100311-C00007
    • Procedure:
  • The reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to −60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of diioddecane is added into the reaction mixture as fast as possible. Subsequently, the reaction mixture is stirred for 12 h at −20° C., the temperature is increased to 0° C. for 4 h. The solution is hydrolysed with 10 ml MeOH, precipitated in 2 l MeOH, digested in MeOH and washed on the filter twice.
  • The thus purified polymer is dried at 25° C. under vacuum.
  • Relating to iodine content 0.56 groups per repeat unit are bound.
    • Production of a Covalently Cross-Linked Ionomomer Membrane
  • 3 g PSU(SO2Li)2 (2 sulfinate groups per PSU repeating unit, sulfinate-IEC=3.4 meq SO2Li/g polymer) are dissolved in 17 g NMP. 2.7 mmol meta-LiO2S-benzolphosphonic acid dioctylester (obtained by lithiation of benzolphosphonic acid dioctylester under Argon in THF and subsequent reaction with SO2) and 0.4 mmol 1,4-Diiodbutan are added to the solution and let to homogenise. Then the polymer solution is casted on a support (glas plate or metal plate and/or cloth/vlies/mocroporous membrane). The solvent is evaporated in a ventilated or vacuum drying ovenat increased temperature of 50 to 140° C. Hereby the sulfinate-S-alkylation of the sulfinato-benzolphosphonic acid ester and the diiodbutane takes place and the membrane cross-links. After solvent evaporation the membrane is posttreated to saponificate the phosphonic acid ester with 48% HBr or concentrated HCl under reflux.
    • CITED NON-PATENT LITERATURE
    • 1 Wainright, J. S.; Wang, J.-T.; Weng, D.; Savinell, R. F.; Lift, M. H., J. Electrochem. Soc. 1995, 142, L121
    • 3 H. R. Allcock, M. A. Hofmann, R. M. Wood, Macromolecules 2001, 34, 6915-6921

Claims (13)

1. Polymeric ionomers and ionomer membranes, characterised in that they are composed of a non- or partly-fluorinated, partly or fully aromatic main chain and a non- or partly fluorinated side chain with ionic groups or their non-ionic precursor and if are necessary covalently cross-linked.
2. Polymeric ionomers and ionomer membranes according to claim 1, characterised in that they contain the following structure:
Figure US20100063168A1-20100311-C00008
3. Polymeric ionomers and ionomer membranes according to claim 1, characterised in that as polymer main chain the following polymers are possible:
Polyolefines like Polyethylen, Polypropylen, Polyisobutylen, Polynorbornen, Polymethylpenten, Poly(1,4-isopren), Poly(3,4-isopren), Poly(1,4-butadien), Poly(1,2-butadien) and Block-, alternating or statistical copolymers of polydiene, polybutadiene and polyisoprene with styrole
styrol(co)polymere like polystyrole, poly(methylstyrole), poly(α,β,β-trifluorstyrole), poly(pentafluorostyrole)
perfluorinated ionomeres like Nafion® or the SO2Hal-precursor of Nafion® (Hal=F, Cl, Br, I), Dow®-Membrane, GoreSelect®-Membrane.
partly-fluorinated polymeres like polyvinylidenfluoride, polyvinylfluoride and their copolymeres with polyolefines or with arylmain chain polymers of FIG. 5 (see below) N-basic polymeres like polyvinylcarbazole, polyethylenimine, poly(2-vinylpyridine), poly(3-vinylpyridine), poly(4-vinylpyridine)
(Het)aryl main chain polymers containing the construction units of FIG. 5.
4. Polymeric ionomeres and ionomer membranes according to claim 1, characterised in that as polymer main chain the following polymers are preferred:
polyetherketones like polyetherketone PEK Victrex®, polyetheretherketone PEEK Victrex®, polyetheretherketoneketone PEEKK, polyetherketonetherketone-ketone PEKEKK Ultrapek®
polyethersulfone like polysulfone Udel®, polyphenylsulfone Radel R®, polyetherethersulfone Radel A®, polyethersulfone PES Victrex®
poly(benz)imidazole like PBI Celazol® and other oligomers and polymers containing the (Benz)imidazole unit, whereby the (Benz)imidazole group can be in main chain or in the polymer side chain polyphenylenether like Poly(2,6-dimethyloxyphenylen), Poly(2,6-diphenyloxyphenylen)
polyphenylensulfide and copolymeres
poly(1,4-phenylene) or poly(1,3-phenylene), which are modified in the side chain if necessary with benzoyl-, naphtoyl- or o-phenyloxy-1,4-benzoylgroups, m-phenyloxy-1,4-benzoylgroup or p-phenyloxy-1,4-benzoylgroups.
poly(benzoxazole) and copolymers
poly(benzthiazole) and copolymers
poly(phtalazinone) and copolymers
polyanilin and copolymers
polythiazoles
polypyrroles
5. Process to produce polymeric ionomeres and ionomer membranes according to claim 1, characterised in that as reagents for the Arylpolymer-Deprotonation the following reagents are used:
n-Butyllithium, sec-Butyllithium, tert. Butyllithium, Methyllithium, Phenyllithium, Grignard reagents as phenylmagnesiumhalogenide and other Grignard reagents, lithiumdiisopropylamide, and other lithium amides, sodium naphtalide, potassium naphtalide, zinc organic compounds (“Rieke metals”).
6. Process to produce polymeric ionomeres and ionomer membranes according to claim 1, characterised in that as solvents for the deprotonation reaction the following solvents are used:
ether solvents like THF, diethylether, glyme, diglyme, triglyme, dioxane and other ether solvents as well as hydrocarbon solvents CnF2n+2, cyclohexane, benzene, toluene, xylole and other C—H— aromatic solvants and any other mixtures thereof and with ether solvents, wherein ether solvents are preferred and THF is especially preferred.
7. Process to produce polymeric ionomeres and ionomer membranes according to claim 1, characterised in that as compounds with nucleophilically substitutable halogene atoms and ionic groups compounds with the following structure are used:

Hal-C(R1)x—Y,
wherein Y and R1 are defined in FIG. 2.
8. Process to produce polymeric ionomeres and ionomer membranes according to claim 7, characterised in that as compounds with nucleophilically substitutable halogene atoms and ionic groups compounds with the following structure are preferred: Hal-(CH2)x—Y, wherein Y and R1 are defined in FIG. 2.
9. Process to produce polymeric ionomeres and ionomer membranes according to claim 7, characterised in that as halogen atoms iodine and bromine are preferred.
10. Process to produce polymeric ionomeres and ionomer membranes according to claim 2, characterised in that the following dihalogene compounds are used in the reaction with the deprotonated polymers:

Hal-(C(R1)2)x-Hal (Hal=F,Cl,Br,I; R1═H,F,CnH2n+1, Aryl)

Br—(C(R1)2)x—I

Hal-(C(R1)2)x-Aryl-Hal

Hal-(C(R1)2)x—Z-Aryl-Hal, wherein Z is defined in FIG. 5.
11. Process to produce polymeric ionomeres and ionomer membranes according to claim 2, characterised in that the following nucleophilic compounds are used in the reaction with the side-chain halogenated polymers:
Figure US20100063168A1-20100311-C00009
12. Process to produce polymeric ionomeres and ionomer membranes according to claims 2 and 11, characterised in that for the reaction with side-chain halogenated polymers, compounds with a sulfinate group are preferred as nucleophilic compounds, which react by S-Alkylation with the halogenated polymers.
13. Process to produce polymeric ionomeres and ionomer membranes according to claims 2 and 11, characterised in that as solvents for the reaction of the side-chain halogenated polymers with compounds containing a nucleophilic group and the ionic group or their non-ionic precursor are ether solvents as described above, hydrocarbon solvents (aliphatic or aromatic, as described above), dipolar-aprotic solvents such as NMP, DMAc, DMF, DMSO, Sulfolan, protic solvents such as alcoholes CnH2n+1, water or any other mixtures of these solvents with each other are used.
US11/573,982 2004-08-20 2005-08-20 Ionomers with ionogenic groups in the sidechain Abandoned US20100063168A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US13/330,614 US8742021B2 (en) 2004-08-20 2011-12-19 Ionomers with ionic groups in the side chain
US14/293,904 US9403162B2 (en) 2004-08-20 2014-11-12 Ionomers with ionic groups in the side chain

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102004041336.3 2004-08-20
DE102004041336 2004-08-20
PCT/DE2005/001504 WO2006018020A2 (en) 2004-08-20 2005-08-20 Ionomers with ionogenic groups in the sidechain

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2005/001504 A-371-Of-International WO2006018020A2 (en) 2004-08-20 2005-08-20 Ionomers with ionogenic groups in the sidechain

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/330,614 Continuation US8742021B2 (en) 2004-08-20 2011-12-19 Ionomers with ionic groups in the side chain

Publications (1)

Publication Number Publication Date
US20100063168A1 true US20100063168A1 (en) 2010-03-11

Family

ID=35907773

Family Applications (3)

Application Number Title Priority Date Filing Date
US11/573,982 Abandoned US20100063168A1 (en) 2004-08-20 2005-08-20 Ionomers with ionogenic groups in the sidechain
US13/330,614 Expired - Fee Related US8742021B2 (en) 2004-08-20 2011-12-19 Ionomers with ionic groups in the side chain
US14/293,904 Expired - Fee Related US9403162B2 (en) 2004-08-20 2014-11-12 Ionomers with ionic groups in the side chain

Family Applications After (2)

Application Number Title Priority Date Filing Date
US13/330,614 Expired - Fee Related US8742021B2 (en) 2004-08-20 2011-12-19 Ionomers with ionic groups in the side chain
US14/293,904 Expired - Fee Related US9403162B2 (en) 2004-08-20 2014-11-12 Ionomers with ionic groups in the side chain

Country Status (5)

Country Link
US (3) US20100063168A1 (en)
EP (1) EP1786544A2 (en)
JP (3) JP2008510845A (en)
DE (1) DE112005002051A5 (en)
WO (1) WO2006018020A2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1987081B1 (en) * 2006-02-16 2012-09-12 Basf Se Oligomeric and polymeric aromatic phosphonic acids, their blends, processes for preparing them and uses as polyelectrolytes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6723757B1 (en) * 1998-04-18 2004-04-20 Universitat Stuttgart Lehrstuhl Engineering ionomeric blends and engineering ionomeric blend membranes
US7288599B2 (en) * 2002-02-28 2007-10-30 Jochen Kerres Oligomers and polymers containing sulfinate groups, and method for producing the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
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 (en) * 1995-04-12 1996-10-29 Dainippon Ink & Chem Inc Method for producing ionomer of polyphenylene sulfide copolymer
KR19990028586A (en) * 1995-06-30 1999-04-15 악커만,야코비 Polyarylene sulfides having polymer-bonded phosphonium salts and methods for preparing the same
JP3561250B2 (en) * 2001-09-21 2004-09-02 株式会社日立製作所 Fuel cell
AU2002363823A1 (en) * 2001-11-22 2003-07-30 Haring, Rima Modified covalently cross-linked polymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6723757B1 (en) * 1998-04-18 2004-04-20 Universitat Stuttgart Lehrstuhl Engineering ionomeric blends and engineering ionomeric blend membranes
US7288599B2 (en) * 2002-02-28 2007-10-30 Jochen Kerres Oligomers and polymers containing sulfinate groups, and method for producing the same

Also Published As

Publication number Publication date
WO2006018020A3 (en) 2006-05-18
JP5766655B2 (en) 2015-08-19
US20150064609A1 (en) 2015-03-05
JP2012224856A (en) 2012-11-15
JP2014221896A (en) 2014-11-27
US20120245237A1 (en) 2012-09-27
JP2008510845A (en) 2008-04-10
EP1786544A2 (en) 2007-05-23
WO2006018020A2 (en) 2006-02-23
US9403162B2 (en) 2016-08-02
US8742021B2 (en) 2014-06-03
DE112005002051A5 (en) 2008-08-28

Similar Documents

Publication Publication Date Title
Date et al. Synthesis and morphology study of SEBS triblock copolymers functionalized with sulfonate and phosphonate groups for proton exchange membrane fuel cells
JP4051736B2 (en) Polymer electrolyte, polymer electrolyte membrane, and fuel cell
EP2147947B1 (en) Process for preparing an aromatic polyether sulfone blockcopolymer
Bock et al. Arylphosphonic acid‐functionalized polyelectrolytes as fuel cell membrane material
EP1248313B1 (en) Polymer electrolyte and process for producing the same
US8637174B2 (en) Phosphonic acid-containing blends and phosphonic acid-containing polymers
JP4754214B2 (en) POLYPHENYLENE TYPE POLYMER, METHOD FOR PREPARING THE SAME, MEMBRANE, AND FUEL CELL DEVICE INCLUDING THE MEMBRANE
KR20030077413A (en) Aromatic polymer, method for producing the same and uses thereof
JP2011026592A (en) Step-by-step alkylation of polymeric amine
Rusanov et al. Proton-conducting polymers and membranes carrying phosphonic acid groups
CN102186905A (en) Polymer electrolyte synthesis method, polymer electrolyte membrane, and solid polymer fuel cell
WO2005001969A1 (en) Polymer electrolyte, polymer electrolyte membrane therefrom, membrane electrode assembly and polymer electrolyte fuel cell
JP5454853B2 (en) Sulfonated poly (arylene) as a hydrolytically and thermally oxidatively stable polymer
US8058383B2 (en) Arylene-fluorinated-sulfonimide ionomers and membranes for fuel cells
US8022165B2 (en) Catalytic process for the phosphonylation of high-temperature polymers
US20120296065A1 (en) Polyarylene ionomers membranes
US9403162B2 (en) Ionomers with ionic groups in the side chain
KR101417139B1 (en) Oligomer and polymer Aromatic phosphonic acid, combination thereof, process for their preparation and use as polymer electrolyte
TWI527842B (en) Polymer of fluorine-containing sulfonated poly(arylene ether)s and method of menufacturing the same
JP6819047B2 (en) Diphenylsulfone compounds for polymer electrolytes, polymer electrolytes, methods for producing polymer electrolytes, membrane electrode assemblies, and polymer electrolyte fuel cells.
US7838594B2 (en) Bridged arylene fluorinated sulfonimide compositions and polymers
WO2011082158A1 (en) Polyarylene ionomers
JP6202422B2 (en) Method for producing polymer electrolyte
KR20070005002A (en) Polymers with oxocarbon groups and uses thereof
DE102004063204A1 (en) Polymeric ionomers and ionomer membranes with an optionally fluorinated, optionally aromatic main chain and optionally fluorinated side chains carrying ionic groups, used e.g. in membranes for fuel cells

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION