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DE10024575A1 - Covalently crosslinked polymer or membrane, used e.g. in fuel cells, batteries or separation processes, comprises reacting polymers with chlorosulphonyl or sulfinate groups with bifunctional crosslinker, e.g. dihalo-alkane - Google Patents

Covalently crosslinked polymer or membrane, used e.g. in fuel cells, batteries or separation processes, comprises reacting polymers with chlorosulphonyl or sulfinate groups with bifunctional crosslinker, e.g. dihalo-alkane

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Publication number
DE10024575A1
DE10024575A1 DE10024575A DE10024575A DE10024575A1 DE 10024575 A1 DE10024575 A1 DE 10024575A1 DE 10024575 A DE10024575 A DE 10024575A DE 10024575 A DE10024575 A DE 10024575A DE 10024575 A1 DE10024575 A1 DE 10024575A1
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Germany
Prior art keywords
polymer
groups
membrane
hal
polymers
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.)
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DE10024575A
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German (de)
Inventor
Jochen Kerres
Wei Zhang
Chy-Ming Tang
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.)
Universitaet Stuttgart
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Universitaet Stuttgart
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Publication date
Application filed by Universitaet Stuttgart filed Critical Universitaet Stuttgart
Priority to DE10054233A priority Critical patent/DE10054233A1/en
Priority claimed from DE10054233A external-priority patent/DE10054233A1/en
Priority to IL14772601A priority patent/IL147726A0/en
Priority to CNB018018637A priority patent/CN100354344C/en
Priority to JP2002505894A priority patent/JP2004502008A/en
Priority to KR1020027000826A priority patent/KR100925846B1/en
Priority to CA2379962A priority patent/CA2379962C/en
Priority to PCT/EP2001/005826 priority patent/WO2002000773A2/en
Priority to AU93695/01A priority patent/AU784360B2/en
Priority to EP01974075A priority patent/EP1290069A2/en
Priority to BR0106652-8A priority patent/BR0106652A/en
Publication of DE10024575A1 publication Critical patent/DE10024575A1/en
Priority to ZA200201339A priority patent/ZA200201339B/en
Priority to US10/173,830 priority patent/US6982303B2/en
Priority to AU2006202592A priority patent/AU2006202592A1/en
Priority to JP2012066401A priority patent/JP5937856B2/en
Priority to JP2015106831A priority patent/JP2015212386A/en
Withdrawn legal-status Critical Current

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • B01D71/52—Polyethers
    • B01D71/522—Aromatic polyethers
    • B01D71/5222—Polyetherketone, polyetheretherketone, or polyaryletherketone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
    • 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
    • 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
    • H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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
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    • Y02E60/30—Hydrogen technology
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Composite Materials (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

A covalently crosslinked polymer or membrane comprises polymers with precursors of cation exchange groups (e.g. SO2Cl) and/or sulfinate groups (e.g. SO2Li), crosslinked with reactive polyhalo-compounds (e.g. alpha ,w-dihaloalkanes), alpha -halo-w-amino-alkanes or alpha ,w-diaminoalkanes. A covalently crosslinked polymer or polymer membrane (I) comprises polymer(s) with the following functional groups (a) precursors of cation exchange groups, i.e. SO2M, POM2 and/or COM, and/or (b) sulfinate (SO2Me), covalently crosslinked with (a') di-, tri- or oligo-functional haloalkanes or haloaromatics which react with sulfinate groups to form a crosslinking bridge of formula polymer-SO2-Y-SO2-polymer and/or (b') compounds of formula Hal-(CH2)x-NHR which react on one side (Hal) with sulfinate groups and on the other (NHR) with SO2M groups to form a bridge of formula polymer-SO2-(CH2)x-NR-SO2-polymer, and/or (c') compounds of formula RNH-(CH2)x-NHR which react with SO2M groups to form a bridge of formula polymer-SO2-NR-(CH2)x-NR-SO2-polymer. In these formulae, M = Hal, OR or NR2; Hal = F, Cl, Br or I; R = alkyl, hydroxyalkyl or aryl; Me = H, Li, Na, K, Cs, other metal cations or ammonium ions; Y = -(CH2)x-, arylene, -(CH2)x-arylene- or -CH2-arylene-CH2-; and x = 3-12. An Independent claim is also included for the production of (I) (including polymer blends) by dissolving the polymers in a dipolar aprotic solvent (dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide or sulfolane) adding the crosslinker, homogenizing, filtering, degassing, spreading the solution as a thin film on a substrate (glass, metal, woven or non-woven fabric etc.), removing the solvent by heating at 80-130 deg C and/or applying reduced pressure, or by using a fan oven, and optionally stripping the film from the substrate. The film is then subjected to further treatment as follows (one or more of these stages may be omitted): (a) 1-50 wt% aqueous sodium hydroxide solution at room temperature (RT) to 95 deg C, (b) fully dematerialized water at RT-95 deg C, (c) 1-50 wt% aqueous mineral acid at RT-95 deg C, (d) stage (b) again as above.

Description

Stand der TechnikState of the art

Der Autor dieser Patentanmeldung hat ein neues Verfahren zur Herstellung von kovalent vernetzten Ionomermembranen entwickelt, das beruht auf einer Alkylierungsreaktion von Sulfinatgruppen enthaltenden Polymeren, Polymerblends und Polymer(blend)membranen (J. Kerres, W. Cui, W. Schnurnberger: "Vernetzung von modifizierten Engineering Thermoplasten", Deutsches Patent 196 22 337.7 (Anmeldung vom 4. 6. 1996), Deutsches Patentamt (1997) "Reticulation de Materiaux Thermoplastiques Industriels Modifies", Französisches Patent F 97 06706 vom 30.05.1997). Vorteil des kovalenten Netzwerks ist seine Hydrolysebeständigkeit auch bei höheren Temperaturen. Nachteil der in der obigen Erfindung beschriebenen ionenleitfähigen, kovalent vernetzten Polymere und Polymerblends ist es, daß bei der Alkylierung der Sulfinatgruppen während der Membranbildung ein hydrophobes Netzwerk entsteht, das mit der ionenleitfähigen Polymer(blend)komponente, beispielsweise einem sulfonierten Polymer Polymer-SO3Me z. T. unverträglich ist, so daß eine inhomogene Polymer(blend)morphologie generiert wird, die die mechanische Stabilität herabsetzt (Versprödung bei Austrocknung!) und die auch eine vollständige Vernetzung wegen partieller Entmischung von Sulfinatphase und Sulfonatphase verhindert.The author of this patent application has developed a new process for the preparation of covalently crosslinked ionomer membranes which is based on an alkylation reaction of polymers containing sulfinate groups, polymer blends and polymer (blend) membranes (J. Kerres, W. Cui, W. Schnurnberger: "Crosslinking of modified Engineering Thermoplastics ", German Patent 196 22 337.7 (application dated June 4, 1996), German Patent Office (1997)" Reticulation de Materiaux Thermoplastiques Industriels Modifies ", French Patent F 97 06706 dated May 30, 1997). The advantage of the covalent network is its resistance to hydrolysis even at higher temperatures. The disadvantage of the ion-conductive, covalently crosslinked polymers and polymer blends described in the above invention is that during the alkylation of the sulfinate groups during the membrane formation, a hydrophobic network is formed which is combined with the ion-conductive polymer (blend) component, for example a sulfonated polymer polymer-SO 3 Me e.g. T. is incompatible, so that an inhomogeneous polymer (blend) morphology is generated, which reduces the mechanical stability (embrittlement when drying out!) And also prevents complete crosslinking due to partial separation of the sulfinate phase and sulfonate phase.

Beschreibungdescription

Somit ist es Aufgabe der Erfindung, neue kovalent vernetzte Polymere/Membranen bereitzustellen, bei denen die kovalent vernetzte Polymer(blend)komponente mit der ionenleitfähigen Polymer(blend)komponente gut verträglich ist.It is therefore an object of the invention to develop new covalently crosslinked polymers / membranes To provide, in which the covalently crosslinked polymer (blend) component with the ion-conductive polymer (blend) component is well tolerated.

Diese Aufgabe wird durch die Bereitstellung von Membranen gemäß Anspruch 1 gelöst. Weiterhin trägt das erfindungsgemäße Verfahren zur Lösung dieser Aufgabe bei. Hierbei wird eine Polymerlösung hergestellt, welche Polymere enthält, die folgende funktionelle Gruppen enthalten:
This object is achieved by the provision of membranes according to claim 1. Furthermore, the method according to the invention contributes to solving this problem. Here, a polymer solution is produced that contains polymers that contain the following functional groups:

  • - Sulfinatgruppen -SO2Me- sulfinate groups -SO 2 Me
  • - Sulfochloridgruppen und/oder andere Vorstufen von Kationenaustauschergruppen.- Sulfochloride groups and / or other precursors of cation exchange groups.

Außerdem wird der Polymerlösung ein bi- oder oligofunktioneller Alkylierungsvernetzer (typischerweise ein α,ω-Dihalogenalkan) und gegebenenfalls ein sek. Diaminvernetzer NHR- (CH2)x-NHR zugesetzt. Die Ausbildung der kovalenten Vernetzungsbrücken erfolgt während der Membranbildung bei der Abdampfung des Lösungsmittels durch Alkylierung der Sulfinatgruppen und gegebenenfalls Sulfonamidbildung via Reaktion der im Polymer vorhandenen Sulfohalogenidgruppen mit den sek. Aminogruppen des Diaminvernetzers. Während der an die Membranbildung anschließenden sauren und/oder basischen und/oder neutral wässrigen Nachbehandlung der Membranen werden die Vorstufen der Kationenaustauschergruppierungen zu Kationenaustauschergruppen hydrolysiert.In addition, the polymer solution is a bi- or oligo-functional alkylation crosslinker (typically an α, ω-dihaloalkane) and optionally a sec. Diamine crosslinker NHR- (CH 2 ) x -NHR added. The covalent crosslinking bridges are formed during the membrane formation during evaporation of the solvent by alkylation of the sulfinate groups and optionally sulfonamide formation via reaction of the sulfohalide groups present in the polymer with the sec. Amine groups of the diamine crosslinker. During the acidic and / or basic and / or neutral aqueous aftertreatment of the membranes following the membrane formation, the precursors of the cation exchanger groups are hydrolyzed to cation exchanger groups.

In Abb. 1 ist die Ausbildung der kovalenten Vernetzungsbrücken bei Blends aus sulfochloriertem Polymer und sulfiniertem Polymer schematisch dargestellt, in Abb. 2 die Ausbildung der kovalenten Vernetzungsbrücken bei einem Polymer, das sowohl Sulfinat- als auch Sulfochloridgruppen enthält. Fig. 1 schematically shows the formation of the covalent cross-linking bridges in blends of sulfochlorinated polymer and sulfinated polymer, in Fig. 2 the formation of the covalent cross-linking bridges in a polymer which contains both sulfinate and sulfochloride groups.

Die erfindungsgemäßen Composites bestehen aus Polymeren mit folgenden funktionellen Gruppen:The composites according to the invention consist of polymers with the following functional Groups:

Nach der Membranherstellung, vor der Hydrolyse:
After membrane production, before hydrolysis:

  • - -SO2M und/oder POM2 und/oder -COM (M = Hal (F, Cl, Br, I), OR, NR2; R = Alkyl, Hydroxyalkyl, Aryl)- -SO 2 M and / or POM 2 and / or -COM (M = Hal (F, Cl, Br, I), OR, NR 2 ; R = alkyl, hydroxyalkyl, aryl)
  • - Vernetzungsbrücken:
    • a) Polymer-SO2-Y-SO2-Polymer
      gegebenenfalls:
    • b) Polymer-SO2-Y'-NR-SO2-Polymer
    • c) Polymer-SO2-NR-Y"-NR-SO2-Polymer
    - Network bridges:
    • a) Polymer-SO 2 -Y-SO 2 polymer
      possibly:
    • b) Polymer-SO 2 -Y'-NR-SO 2 polymer
    • c) Polymer-SO 2 -NR-Y "-NR-SO 2 polymer

Nach der Hydrolyse:
After hydrolysis:

  • - -SO3M-, -PO3M2-, -COOM-Gruppen- -SO 3 M-, -PO 3 M 2 -, -COOM groups
  • - o. g. Vernetzungsbrücken- o. G. Networking bridges

Durch die kovalente Vernetzung der Sulfinatpolymere im Gemisch mit Vorstufen von Kationenaustauscherpolymeren wird eine bessere Vermischung der Blendphasen und damit auch ein höherer Vernetzungsgrad erreicht, was sich in einer besseren mechanischen Stabilität des resultierenden Polymerfilms äußert, verglichen mit kovalent vernetzten Polymer(blend)filmen aus Kationenaustauscherpolymeren und polymeren Sulfinaten. Durch die gezielte Einbeziehung einer aminogruppenhaltigen Vernetzungskomponente, die mit den Vorstufen der Kationenaustauschergruppen reagiert, in das Polymernetzwerk wird eine weitere Verbesserung der mechanischen Eigenschaften erzielt. Through the covalent crosslinking of the sulfinate polymers in a mixture with precursors of Cation exchange polymers will mix better with the blend phases and thus also achieved a higher degree of crosslinking, which translates into better mechanical stability of the resulting polymer film, compared to covalently crosslinked Polymer (blend) films from cation exchange polymers and polymeric sulfinates. Through the targeted inclusion of a crosslinking component containing amino groups, which is linked to the Precursors of the cation exchange groups react, another becomes in the polymer network Improvement in mechanical properties achieved.  

AnwendungsbeispieleExamples of use

Im folgenden soll die Erfindung durch zwei Beispiele näher erläutert werden. Die Massen/Volumina der eingesetzten Komponenten sind in der Tabelle 1 aufgeführt.In the following the invention will be explained in more detail by two examples. The Masses / volumes of the components used are listed in Table 1.

1. Vorschrift zur Membranherstellung1. Regulation for membrane production

Sulfochloriertes PSU Udel® (IEC = 1,8 meq SO2Cl/g) und PSUSO2Li (IEC = 1,95 meq SO2Li/g) (Polymerstrukturen siehe Abb. 2) werden in N-Methylpyrrolidinon (NMP) aufgelöst. Danach wird zur Lösung der Vernetzer α,ω-Diiodbutan gegeben. Man rührt 15 Minuten. Danach wird die Lösung filtriert und entgast. Ein dünner Film der Polymerlösung wird auf einer Glasplatte ausgerakelt. Die Glasplatte wird in einen Vakuumtrockenschrank gelegt, und bei Temperaturen von 80-130°C wird das Lösungsmittel bei einem Unterdruck von 700 bis schließlich 15 mbar abgezogen. Der Film wird dem Trockenschrank entnommen und abgekühlt. Der Polymerfilm wird unter Wasser von der Glasplatte abgelöst und zuerst in 10%iger Salzsäure und dann in vollentsalztem Wasser bei Temperaturen von 60 bis 90°C für jeweils 24 Stunden hydrolysiert/nachbehandelt.Sulfochlorinated PSU Udel® (IEC = 1.8 meq SO 2 Cl / g) and PSUSO 2 Li (IEC = 1.95 meq SO 2 Li / g) (polymer structures see Fig. 2) are dissolved in N-methylpyrrolidinone (NMP) . Then the crosslinking agent α, ω-diiodobutane is added to the solution. Stir for 15 minutes. The solution is then filtered and degassed. A thin film of the polymer solution is scraped out on a glass plate. The glass plate is placed in a vacuum drying cabinet and the solvent is drawn off at temperatures of 80-130 ° C. at a negative pressure of 700 to finally 15 mbar. The film is removed from the drying cabinet and cooled. The polymer film is detached from the glass plate under water and first hydrolyzed / aftertreated in 10% hydrochloric acid and then in deionized water at temperatures from 60 to 90 ° C. for 24 hours.

2. Eingesetzte Mengen der Reaktanten und Charakterisierungsergebnisse2. Amounts of reactants used and characterization results

Tabelle 1 Table 1

Eingesetzte Mengen der Reaktanten und Charakterisierungsergebnisse Amounts of reactants used and characterization results

Claims (14)

1. Kovalent vernetztes Polymer oder kovalent vernetzte Polymermembran, bestehend aus einem oder mehreren Polymeren, die die folgenden funktionellen Gruppen tragen können (M = Hal (F, Cl, Br, I), OR, NR2; R = Alkyl, Hydroxyalkyl, Aryl; (Me = H, Li, Na, K, Cs oder andere Metallkationen oder Ammoniumionen):
  • a) Vorstufen von Kationenaustauschergruppen: SO2M und/oder POM2 und/oder COM
  • b) Sulimatgruppen SO2Me
und die mittels folgenden organischen Verbindungen kovalent vernetzt sein können:
  • a) di- tri- oder oligofunktionellen Halogenalkanen oder Halogenaromaten, die mit Sulfinatgruppen SO2Me zur Reaktion gebracht worden waren, wodurch im Polymer/im Polymerblend/in der Polymermembran folgende Vernetzungsbrücken vorhanden sind (Y = Vernetzungsbrücke, X = Hal (F, Cl, Br, I), OR, Y = -(CH2)x-; -Arylen-; -(CH2)x-Arylen-; CH2-Arylen-CH2-, x = 3-12): Polymer-SO2-Y-SO2-Polymer
und/oder
  • 1. Verbindungen, die folgende Gruppen enthalten: Hal-(CH2)x-NHR, die auf der einen Seite (Hal-) mit Sulfinatgruppen SO2Me zur Reaktion gebracht worden waren, und auf der anderen Seite (-NHR) mit SO2M-Gruppen, wodurch im Polymer/im Polymerblend/in der Polymermembran folgende Vernetzungsbrücken vorhanden sind: Polymer-SO2-(CH2)X-NR- SO2-Polymer.
und/oder
  • 1. Verbindungen, die folgende Gruppen enthalten: NHR-(CH2)x-R NHR, die mit SO2Me- Gruppen zur Reaktion gebracht worden waren, wodurch im Polymer/im Polymerblend/in der Polymermembran folgende Vernetzungsbrücken vorhanden sind: Polymer-SO2-NR-(CH2)x- NR-SO2-Polymer.
1. Covalently cross-linked polymer or covalently cross-linked polymer membrane, consisting of one or more polymers which can carry the following functional groups (M = Hal (F, Cl, Br, I), OR, NR 2 ; R = alkyl, hydroxyalkyl, aryl ; (Me = H, Li, Na, K, Cs or other metal cations or ammonium ions):
  • a) Precursors of cation exchange groups: SO 2 M and / or POM 2 and / or COM
  • b) Sulimate groups SO 2 Me
and which can be covalently crosslinked using the following organic compounds:
  • a) di- or oligofunctional haloalkanes or haloaromatics which have been reacted with sulfinate groups SO 2 Me, whereby the following crosslinking bridges are present in the polymer / in the polymer blend / in the polymer membrane (Y = crosslinking bridge, X = Hal (F, Cl , Br, I), OR, Y = - (CH 2 ) x -; -arylene-; - (CH 2 ) x -arylene-; CH 2 -arylene-CH 2 -, x = 3-12): polymer SO 2 -Y-SO 2 polymer
and or
  • 1. Compounds containing the following groups: Hal- (CH 2 ) x -NHR, which had been reacted on one side (Hal-) with sulfinate groups SO 2 Me and on the other side (-NHR) with SO 2 M groups, as a result of which the following crosslinking bridges are present in the polymer / in the polymer blend / in the polymer membrane: Polymer-SO 2 - (CH 2 ) X -NR- SO 2 polymer.
and or
  • 1. Compounds which contain the following groups: NHR- (CH 2 ) x -R NHR which had been reacted with SO 2 Me groups, as a result of which the following crosslinking bridges are present in the polymer / in the polymer blend / in the polymer membrane: SO 2 -NR- (CH 2 ) x - NR-SO 2 polymer.
2. Kovalent vernetzter Polymerblend oder Polymerblendmembran nach Anspruch 1, dadurch gekennzeichnet, daß er aus folgenden Polymeren zusammengesetzt ist:
  • a) einem Polymer mit wenigstens SO2M-Gruppen
  • b) einem Polymer mit wenigstens SO2Me-Gruppen.
2. Covalently cross-linked polymer blend or polymer blend membrane according to claim 1, characterized in that it is composed of the following polymers:
  • a) a polymer with at least SO 2 M groups
  • b) a polymer with at least SO 2 Me groups.
3. Kovalent vernetzter Polymerblend oder Polymerblendmembran nach den Ansprüchen 1 bis 2, dadurch gekennzeichnet, daß er aus einem Polymer besteht, das folgende Gruppen enthält: SO2M-Gruppen und SO2Me-Gruppen.3. Covalently cross-linked polymer blend or polymer blend membrane according to claims 1 to 2, characterized in that it consists of a polymer which contains the following groups: SO 2 M groups and SO 2 Me groups. 4. Kovalent vernetzter Polymerblend oder Polymerblendmembran nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß das die funktionellen Gruppen tragende Grundpolymer oder die die funktionellen Gruppen tragenden Grundpolymere ausgewählt sind aus der Gruppe der Polyethersulfone, Polysulfone, Polyphenylsulfone, Polyetherethersulfone, Polyetherketone, Polyetheretherketone, Polyphenylenether, Polydiphenylphenylenether, Polyphenylensulfide oder Copolymere sind, die mindestens eine dieser Komponenten enthalten.4. Covalently cross-linked polymer blend or polymer blend membrane according to claims 1 to 3, characterized in that the base polymer carrying the functional groups  or the base polymers bearing the functional groups are selected from the group of polyether sulfones, polysulfones, polyphenyl sulfones, polyether ether sulfones, Polyether ketones, polyether ether ketones, polyphenylene ethers, polydiphenylphenylene ethers, Polyphenylene sulfides or copolymers are at least one of these components contain. 5. Kovalent und ionisch vernetzter Polymerblend oder Polymerblendmembran nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß als Grundpolymere folgende Polymere bevorzugt sind: Polysulfone, Polyphenylenether oder andere lithiierbare Polymere.5. Covalently and ionically crosslinked polymer blend or polymer blend membrane according to the Claims 1 to 4, characterized in that the following polymers as base polymers preferred are: polysulfones, polyphenylene ethers or other lithiable polymers. 6. Kovalent vernetzter Polymerblend oder Polymerblendmembran nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß als Vernetzer bevorzugt werden: Hal-(CH2)x-Hal oder Hal-CH2-Phenylen-CH2-Hal (x = 3-12, Hal = F, Cl, Br, I).6. Covalently crosslinked polymer blend or polymer blend membrane according to claims 1 to 5, characterized in that preferred crosslinkers are: Hal (CH 2 ) x -Hal or Hal-CH 2 -phenylene-CH 2 -Hal (x = 3-12 , Hal = F, Cl, Br, I). 7. Kovalent vernetzter Polymerblend oder Polymerblendmembran nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß die SO2M- und/oder POM2- und/oder COM-Gruppen des Polymers/der Polymer(blend)membran durch folgende Nachbehandlung(en) zu den jeweiligen Kationenaustauschergruppen SO3Me und/oder PO3Me2 und/oder COOMe (Me = H, Li, Na, K, Cs oder andere Metallkationen oder Ammoniumionen) hydrolysiert werden:
  • a) in 1 bis 50 gew.-%iger wässriger Lauge bei T = RT-95°C
  • b) in vollentsalztem Wasser bei T = RT-95°C
  • c) in 1 bis 50 gew.-%iger wässriger Mineralsäure bei T = RT-95°C
  • d) in vollentsalztem Wasser bei T = RT-95°C
Dabei kann ggf. einer oder mehrere der Nachbehandlungsschritte ausgelassen werden.7. Covalently cross-linked polymer blend or polymer blend membrane according to claims 1 to 6, characterized in that the SO 2 M and / or POM 2 - and / or COM groups of the polymer / the polymer (blend) membrane by the following aftertreatment (s) to the respective cation exchange groups SO 3 Me and / or PO 3 Me 2 and / or COOMe (Me = H, Li, Na, K, Cs or other metal cations or ammonium ions) are hydrolyzed:
  • a) in 1 to 50 wt .-% aqueous alkali at T = RT-95 ° C.
  • b) in deionized water at T = RT-95 ° C
  • c) in 1 to 50 wt .-% aqueous mineral acid at T = RT-95 ° C.
  • d) in deionized water at T = RT-95 ° C
If necessary, one or more of the post-treatment steps can be omitted. 8. Verfahren zur Herstellung von kovalent vernetzten Polymeren, Polymerblends oder Polymer(blend)membranen nach den Ansprüchen 1-7, dadurch gekennzeichnet, daß die Polymere gleichzeitig oder nacheinander in einem dipolar-aprotischen Lösungsmittel, das ausgewählt ist aus N,N-Dimethylformamid (DMF), N,N-Dimethylacetamid (DMAc), N- Methylpyrrolidinon (NMP), Dimethylsulfoxid (DMSO) oder Sulfolan, aufgelöst werden, danach der Vernetzer zugegeben wird, danach der Vernetzer durch Rühren in der Polymerlösung homogen verteilt wird, danach die Polymerlösung filtriert wird, danach die Polymerlösung entgast wird, danach die Polymerlösung als dünner Film auf einer Unterlage (Glasplatte, Metallplatte, Gewebe, Vlies etc.) gespreitet wird, danach das Lösungsmittel durch Erhitzen auf 80 bis 130°C und/oder durch Anlegen von Unterdruck oder im Umlufttrockner entfernt wird, danach der Polymerfilm gegebenenfalls von der Unterlage abgelöst wird, danach der Polymerfilm folgendermaßen nachbehandelt wird:
  • a) in 1 bis 50 gew.-%iger wässriger Lauge bei T = RT bis 95°C
  • b) in vollentsalztem Wasser bei T = RT bis 95°C
  • c) in 1 bis 50 gew.-%iger wässriger Mineralsäure bei T = RT bis 95°C
  • d) in vollentsalztem Wasser bei T = RT bis 95°C
Dabei kann ggf. einer oder mehrere der Nachbehandlungsschritte ausgelassen werden.8. A process for the preparation of covalently crosslinked polymers, polymer blends or polymer (blend) membranes according to claims 1-7, characterized in that the polymers simultaneously or successively in a dipolar aprotic solvent which is selected from N, N-dimethylformamide ( DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidinone (NMP), dimethyl sulfoxide (DMSO) or sulfolane, are dissolved, then the crosslinker is added, then the crosslinker is homogeneously distributed in the polymer solution by stirring, then the polymer solution is filtered, then the polymer solution is degassed, then the polymer solution is spread as a thin film on a support (glass plate, metal plate, fabric, fleece, etc.), then the solvent by heating to 80 to 130 ° C and / or by applying negative pressure or is removed in a circulating air dryer, after which the polymer film, if appropriate, is detached from the base, after which the polymer film follows as follows delt is:
  • a) in 1 to 50 wt .-% aqueous alkali at T = RT to 95 ° C.
  • b) in deionized water at T = RT to 95 ° C
  • c) in 1 to 50 wt .-% aqueous mineral acid at T = RT to 95 ° C.
  • d) in deionized water at T = RT to 95 ° C
If necessary, one or more of the post-treatment steps can be omitted. 9. Verwendung der Membranen nach denAnsprüchen 1-8 zur Gewinnung von Energie auf elektro-chemischem Weg.9. Use of the membranes according to claims 1-8 for the production of energy electro-chemical way. 10. Verwendung der Membranen nach den Ansprüchen 1-8 als Bestandteil von Membranbrennstoffzellen (H2- oder Direktmethanol-Brennstoffzellen) bei Temperaturen von 0 bis 180°C.10. Use of the membranes according to claims 1-8 as a component of membrane fuel cells (H 2 - or direct methanol fuel cells) at temperatures from 0 to 180 ° C. 11. Verwendung der Membranen nach den Ansprüchen 1-8 in elektrochemischen Zellen.11. Use of the membranes according to claims 1-8 in electrochemical cells. 12. Verwendung der Membranen nach nach den Ansprüchen 1-8 in sekundären Batterien.12. Use of the membranes according to claims 1-8 in secondary batteries. 13. Verwendung der Membranen nach den Ansprüchen 1-8 in Elektrolysezellen.13. Use of the membranes according to claims 1-8 in electrolytic cells. 14. Verwendung der Membranen nach den Ansprüchen 1-8 in Membrantrennprozessen wie Gastrennung, Pervaporation, Perstraktion, Umkehrosmose, Elektrodialyse, und Diffusionsdialyse.14. Use of the membranes according to claims 1-8 in membrane separation processes such as Gas separation, pervaporation, perstraction, reverse osmosis, electrodialysis, and Diffusion dialysis.
DE10024575A 2000-05-19 2000-05-19 Covalently crosslinked polymer or membrane, used e.g. in fuel cells, batteries or separation processes, comprises reacting polymers with chlorosulphonyl or sulfinate groups with bifunctional crosslinker, e.g. dihalo-alkane Withdrawn DE10024575A1 (en)

Priority Applications (15)

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DE10054233A DE10054233A1 (en) 2000-05-19 2000-11-02 Covalently cross-linked composite membranes
BR0106652-8A BR0106652A (en) 2000-05-19 2001-05-21 The invention relates to a covalently cross-linked polymer or polymeric membrane consisting of one or more polymers
PCT/EP2001/005826 WO2002000773A2 (en) 2000-05-19 2001-05-21 Polymers and polymer membranes covalently cross-linked by sulphinate alkylation
EP01974075A EP1290069A2 (en) 2000-05-19 2001-05-21 Polymers and polymer membranes covalently cross-linked by sulphinate alkylation
JP2002505894A JP2004502008A (en) 2000-05-19 2001-05-21 Covalently crosslinked polymers and polymer membranes via sulfinate alkylation
KR1020027000826A KR100925846B1 (en) 2000-05-19 2001-05-21 Polymers and Polymer Membranes Covalently Crosslinked by Sulfinate Alkylation
CA2379962A CA2379962C (en) 2000-05-19 2001-05-21 Covalently cross-linked polymers and polymer membranes via sulfinate alkylation
IL14772601A IL147726A0 (en) 2000-05-19 2001-05-21 Polymers and polymer membranes covalently cross-linked by sulphinate alkylation
AU93695/01A AU784360B2 (en) 2000-05-19 2001-05-21 Polymers and polymer membranes covalently cross-linked by sulphinate alkylation
CNB018018637A CN100354344C (en) 2000-05-19 2001-05-21 Covalently cross-linked polymers and polymer membranes by sulfinate alkylation
ZA200201339A ZA200201339B (en) 2000-05-19 2002-02-18 Polymers and polymer membranes covalently cross-linked by sulphinate alkylation.
US10/173,830 US6982303B2 (en) 2000-05-19 2002-06-19 Covalently cross-linked polymers and polymer membranes via sulfinate alkylation
AU2006202592A AU2006202592A1 (en) 2000-05-19 2006-06-17 Polymers and polymer membranes covalently cross-linked by sulphinate alkylation
JP2012066401A JP5937856B2 (en) 2000-05-19 2012-03-22 Covalently crosslinked polymers and polymer membranes via sulfinate alkylation
JP2015106831A JP2015212386A (en) 2000-05-19 2015-05-11 Covalently crosslinked polymers and polymer membranes via sulfinate alkylation

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DE10024575A1 (en) * 2000-11-02 2001-11-22 Univ Stuttgart Covalently crosslinked polymer or membrane, used e.g. in fuel cells, batteries or separation processes, comprises reacting polymers with chlorosulphonyl or sulfinate groups with bifunctional crosslinker, e.g. dihalo-alkane
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DE10024575A1 (en) * 2000-11-02 2001-11-22 Univ Stuttgart Covalently crosslinked polymer or membrane, used e.g. in fuel cells, batteries or separation processes, comprises reacting polymers with chlorosulphonyl or sulfinate groups with bifunctional crosslinker, e.g. dihalo-alkane
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