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WO2010096027A1 - Ionomères fluorochloro - Google Patents

Ionomères fluorochloro Download PDF

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Publication number
WO2010096027A1
WO2010096027A1 PCT/US2008/073505 US2008073505W WO2010096027A1 WO 2010096027 A1 WO2010096027 A1 WO 2010096027A1 US 2008073505 W US2008073505 W US 2008073505W WO 2010096027 A1 WO2010096027 A1 WO 2010096027A1
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Prior art keywords
ionomers
fluorochloro
membrane
group
perfluorochloro
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Application number
PCT/US2008/073505
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English (en)
Inventor
Huey-Shen Wu
Original Assignee
Huey-Shen Wu
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Priority to PCT/US2008/073505 priority Critical patent/WO2010096027A1/fr
Publication of WO2010096027A1 publication Critical patent/WO2010096027A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • 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
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • 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
    • H01M8/1039—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
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being 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
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
    • 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
    • H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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

Definitions

  • This invention relates to fluorochloro ionomcrs, and specifically to fluorochloro iononicrs of high ionic conductivity, low methanol crossover rate, relatively low hydration and that can be processed into thin films.
  • the fluorochloro ionomcrs arc preferably fluorochloro compounds suitable for applications where reasonably high ionic conductivity in low humidity environments and good barrier properties at high humidity is desirable.
  • One major application is in solid polymer electrolyte fuel cells.
  • Another major application is for protective covering against noxious liquids and gases.
  • perfluorosulfonic acid membrane structures are preferred, structural improvements are still needed to accommodate the increasing demands of fuel cell systems for specific applications. Higher performance, lower cost, greater durability, better water management, the capability to perform at higher temperatures, and flexibility in operating with a wide range of fuels arc some of the challenges that need to be overcome before widespread commercial adoption of the technology can be implemented.
  • Tlic membrane electrolyte in PEM fuel cells plays two critical roles: effectively separating both fuel and oxidant, preventing mixing: and transporting protons from the anode to the cathode to complete the redox reaction chemistry.
  • the membrane electrolyte should provide strong mechanical, chemical, and electrochemical stability and low gas permeability over a wide range of operating conditions.
  • membranes arc required to have high proton conductivity at low to medium temperatures (sub-zero to 9O 0 C).
  • an ionic conductivity of 90-100 mS/cm is an acceptable and useful range for several applications in the portable, stationary, and mobile classifications, with membrane thicknesses ranging from 20 micron to 200 micron.
  • PFSA membranes are the membranes of choice for PEM fuel cell systems, since their robustness, durability, and well-balanced physicochcmicaJ properties top general PEM requirements.
  • PEM membranes fluorinatcd and non-fiuorinated
  • Nafion membrane has been considered the benchmark material against which most results arc compared.
  • PFSA membranes Tlic development of PFSA membranes has a long and rich history dating to the discovery of poly(tetrafluoroeth ⁇ lene) (PTFE) in 1938.
  • PTFE poly(tetrafluoroeth ⁇ lene)
  • Nafion membrane was originally developed for chlor-alkali applications in early 1962, and later the functional group of the side chain was modified from a weaker acid to a stronger acid to suit fuel cell applications.
  • its first use in a fuel cell was in 1966 with its successful demonstration in NASA ' s space program. ⁇
  • Nafion resin is a copolymer of TFE (tctrafluoroethylenc) and vinyl ether
  • the pcrfluorinatcd backbone imparts superior chemical and thermal stability to non-fluorinated polymers.
  • the pendant sulfonic acid (-SO3H) group imparts super acidic characteristics for facile proton transport.
  • the acid capacity or membrane equivalent weight (EW), of the membrane is determined by the composition of the vinyl ether and can be typically produced from 0.67-1.25 milli-equivalents per gram, corresponding to 1500-800 EW.
  • the proton conductivity of the membrane is strongly dependent on the water content in the membrane structure.
  • the acid capacity strongly affects the water uptake; therefore, the conductivity of the final membrane, as shown in Table 1 (published in WO 00/52060 PCT Patent application).
  • An EW range from 800- 1 100 is preferred for all the practical fuel cell applications considered today because it produces the maximum ionic conductivity.
  • Sclcct membrane which is a micro-reinforced composite structure of expanded PTFE and perfluorosulfonic acid ionomcr.
  • Asahi Glass Co. introduced a thin, flat PTFE fibril-reinforced PFSA membrane with good mechanical strength and performance.
  • a continuous-film production facility has been established that uses a newly developed process.
  • a large number of research groups arc actively engaged in modifying existing PFSA membrane structures to further improve membrane functionality and durability while retaining the base membrane properties. Both physical and chemical modifications have been explored.
  • PFSA membranes with phosphoric and sulfuric acids: inorganic materials, namely, zirconium (hydrogen) phosphate and silica; and the development of blend composite membranes such as ionically cross-linked acid-base membranes, PFSA/polybcnzimidazolc, and perfluorinated composite membrane structures.
  • inorganic materials namely, zirconium (hydrogen) phosphate and silica
  • blend composite membranes such as ionically cross-linked acid-base membranes, PFSA/polybcnzimidazolc, and perfluorinated composite membrane structures.
  • Tlic instant invention relates to fluorochloro ionomcrs made from copolymerization of fluorochloro monomers, which form polymeric backbone, and comonomcrs consisting of ionic groups or precursors which can be converted to ionic groups such as acid groups or amines or quaternary amine groups.
  • the said fluorochloro monomers are preferably perfluorochloroethyelene.
  • Chlorotrifluorocthylenc is most preferred, because of its case and safe of handling far superior to tctrafluorocthylcne which is dangerously explosive.
  • poly(chlorotrifluoroethylene) PCTFE has been demonstrated as the best barrier polymer against permeation of organics including methanol, far better than any known perfluorinated polymers.
  • the barrier properties of PCTFE are 10 to 100 times better than those of PTFE or FEP for oxygen. CO2 and HCl.
  • the most famous brand of such PCTFE barrier membrane has been Honeywell (now GE Plastics) AclonC ⁇ barrier membrane, wherein oxygen, moisture and organics all have the lowest crossover rate compared to any known plastic films.
  • PCTFE membrane electrolyte based on PCTFE backbone could exhibit superior barrier property against methanol crossover than PTFE backbone.
  • PCTFE has also been demonstrated far stronger than PTFE in mechanical strength, which is also critical for control of undesirable membrane swollen with better water management.
  • the combination of fluorine and chlorine in the polymeric backbone makes surprising improvement over PFSA ionomers and other ionomers.
  • PCTFE maintains its useful service temperatures over a very broad temperature range (-100° C to 200° C).
  • PCTFE has comparable mechanical strength and durability to Nylon and possesses excellent impact resistance at ambient and sub-ambient temperature. PCTFE also possesses low flame spread and low smoke generation characteristics.
  • Direct methanol fuel cells offer high energy, compact power that is required to power numerous electronic devices for extended mission times.
  • DMFC technology would benefit greatly with the advent of a PEM that maintains high proton conductivity under conditions of low humidity while also inhibiting methanol permeability. Swelling of the PEM due to high solvent uptake can compromise mechanical integrity and promote methanol diffusion through the membrane. A PEM that is a good proton conductor under conditions of low humidity would help to minimize these effects.
  • Our PCTFE based polymer electrolytes unexpectedly have the advantage of improved internal water management and ion conductivity and reduced methanol crossover. Internal water balance within the PCTFE based polymer electrolyte membrane could enhance water management, and alleviate the need to recycle water formed at the cathode.
  • the acid form of an ionomcr means that substantially all the ion exchange groups, e.g., -SO3H sulfonic groups, -COOH carboxylic acid groups, and phosphonic acid groups are protonated.
  • One important parameter used to characterize ionomcrs is the equivalent weight.
  • the equivalent weight is defined to be the weight of the polymer in acid form required to neutralize one equivalent of NaOH.
  • Lower EW means that there are more active ionic species (e.g., protons) present. If it takes more NaOH to neutralize the ionomcrs, there must be more active ionic species within the polymer. Because the ionic conductivity is generally proportional to the number of active ionic species in the polymer, one would therefore like to lower the EW in order to increase conductivity.
  • PFSA ionomer membranes there is a limit to the amount of water or solvent such that PFSA ionomer membranes can contain. If too much water is present, the film may lose much of its physical integrity, becoming gel-like with little rigidity and may completely disintegrate. In addition, depending un the polymer composition, low EW PFSA ionomers may even partially or completely dissolve in water Furthermore, even if the films were mechanically stable, too high a hydration would tend to dilute the number of ions present for conduction, thereby lowering the ionic conductivity. Thus, there is an optimal degree of hydration that is high enough to provide the highest conductivity, while not so high that the films become mechanically unstable when hydrated.
  • chlor-alkali electrolytic cell membranes for the electrolysis of sodium chloride, for example, in U.S. Patent number: 4,358,545, 4,417,969, 4,478,695 and 6, 156.451.
  • this generic class of polymers described as fluoropolymer ionomers, has been proposed for use as coatings as described in US. Pat. No. 4,661,41 1: as wire insulation such as in WO 90/15828; as replacements for acid catalysts, primarily in organic synthesis as described in "Pcrfluorinatcd Resin sulfonic Acid (Nafion-H ⁇ ) Catalysis in Synthesis", by Olah, G. A.. Iyer P. S.
  • DuPont Nafion® perfluoro ionomer films have also been demonstrated as a good barrier to chemical agents (US Patent No. 4,515,761 ); however, it has not been commercial for protective covering application due to its extremely high cost.
  • ionomers ion conducting polymers
  • PEM fuel cells When ionomers (ion conducting polymers) arc used as the electrolyte in PEM fuel cells, they conduct protons from one electrode to the other.
  • contaminants such as carbon monoxide tend to poison the catalysts used in the MEA. These contaminants can interfere with the flow of ions between the electrodes and thus degrade the performance of the fuel cell.
  • One way to reduce the effect of carbon monoxide is to operate the fuel cell at an elevated temperature. This reduces the formation and/or increases the destruction rate of potential contaminants and thereby allows more efficient electrode performance.
  • the problem with running at high temperatures, however, is that it vaporizes liquid water within the fuel cell, and in so doing, tends to reduce the degree of hydration in the membrane.
  • an ionomcr with relatively low hydration and acceptably high ionic conductivity would require less ambient water to function as the electrolyte in PEM fuel cells. It could function efficiently both in lower humidity environments at lower temperatures, as well as at temperatures closer to and even potentially above the boiling point of water.
  • the first embodiment of the invention is pcrfluorochloro ionomcrs having ( I) equivalent weight between 600 and 1500. preferably between 800 and 1200, and most preferably between 900 and 1100; (2) chlorine content between 8% and 30% by weight.
  • the chlorine content can be determined by elemental analysis.
  • These ionomers are capable of being processed into thin films or membranes (from 5 micrometer thick to 200 micrometer) and are extremely well suited for low humidity or high temperature fuel cell applications and for chemical protective covering materials.
  • the second embodiment of the invention is partially fluorochloro ionomcrs having (1) moisture vapor permeability rate > 3000 gram H2 ⁇ /m 2 /day (about Vi mil thick film); (2) chlorine content of between 10% and 39% by weight.
  • These ionomers can be processed into thin films or membranes (from 5 micrometer thick to 200 micrometer) and are suited for some fuel cell applications and more preferably for breathable protective covering materials.
  • the third embodiment of the invention is process of producing these fluorochloro ionomcrs by radical copolymerization of at least one fluorochloro monomer and at least one comonomer consisting of ionic groups or precursors that can be converted to ionic groups such as acid groups or amines or quaternary amine groups.
  • Fluorochloro ionomers means polymers containing significant amount of fluorine and chlorine atoms on the polymer backbone and carrying ionic groups (anionic or cationic) on the polymer pendant side chain. These fluorochloro ionomers are made by copolymerization of at least one fluorochloro monomer and at least one comonomer that carrying ionic group or earn ing precursor group which can be converted to ionic groups.
  • the first preferred class of fluorochloro ionomers is perfluorochloro ionomers wherein the entire polymer backbone is substituted fully by fluorine and chlorine atoms and the polymer side chain carrying ionic groups.
  • the perfluorochloro ionomers have ( 1) equivalent weight between 600 and 1500, preferably between 800 and 1200, and most preferably between 900 and 1 100; (2) chlorine content between 8% and 30% by weight. The chlorine content can be determined by elemental analysis.
  • the perfluorochloro ionomers arc made by copolymerization of at least one perfluorochloro monomers and at least one functional monomers substantially fluorinated with at least one moiety that is ionic group or convertible to ionic groups.
  • Example of the functional monomers includes, but not limited to, compounds of the following molecular structure:
  • CF2 CF -(O -CF2 -CF)n -O -(CF)-(CF)a -(CF2)h -Y CF2X Rf Ri wherein X is F, Cl or mixtures; n is an integer 0. 1 or 2; Rf is selected from F. Cl, pcrfluoroalkyl radical, and chloropcrfluoroalkyl radical; a is an integer of 0 or 1; b is an integer of 1, 2. or 3.
  • Y is a functional group convertible to an ionic group.
  • Example of Y include, but not limited to. sulfonyl halide (-SO2W); ester (-COOR); wherein W is F or Cl. and R is an alkyl group with carbon number from 1 to 12.
  • Functional group Y can be converted to certain ionic groups Z by chemical treatment.
  • the resulting perfluorochloro ionomers have the following pendant side chain:
  • Z is a functional group with ionic character.
  • Z as an anionic group includes, but not limited to, sulfonic acid -SO3H, or its salt form -SO3M.
  • Z as an cationic group includes, but not limited to. sulfonamide amine -SO2N(-R-)2 NR, sulfonamide imidazole, sulfonamide quaternary amine, and the like.
  • the pcrfluorochloro ionomers arc most suited for fuel cell applications, including hydrogen or methanol fuel cell applications. These ionomers arc capable of being processed into thin films or membranes (from 5 micrometer thick to 200 micrometer) and arc extremely well suited for low humidity or high temperature fuel cell applications and for breathable chemical protective covering materials.
  • "'breathable" means the protective covering allows sufficient moisture vapor permeability, which is important for the comfort of human body.
  • the second preferred class of fluorochloro ionomers is partially fluorochloro ionomers wherein polymer backbone is partially substituted by fluorine and chlorine atoms and the polymer side chain earn ing ionic groups.
  • the partially fluorochloro ionomers have (1) moisture vapor permeability rate > 3000 gram H2 ⁇ /m 2 /day (about Vi mil thick film); (2) chlorine content of between 10% and 39% by weight. The chlorine content can be determined by elemental analysis. These ionomers arc suited for certain fuel cell applications but more suited for breathable protective covering materials.
  • the partially fluorochloro ionomers are made by copolymerization of at least one fluorochloro monomer and at least one functional monomer carrying at least one moiety that is ionic group or convertible to ionic groups.
  • Example of the functional monomer includes, but not limited to, acrylic acid, tcrt-butyl acrylatc, mcthacrylic acid, malcic anhydride, malcic acid, itaconic acid, itaconic anhydride, styrcne, methylstyrenc, 2-acrylamido-2- mcthyl-1-propancsulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, allyl chloride, allyl bromide, vinyl imidazole, vinylpyridine, O-acrylamidopropyOtrimethylammonium chloride, and the like.
  • alkcncs include but not limited to ethylene, propylene, butylcncs, and vinyl acetate and the like.
  • alkcncs including but not limited to ethylene, propylene, butylcncs, and vinyl acetate and the like.
  • tcrt-butyl acrylate monomer the tert-butyl group can be hydrolyzed by a base or thermally hydrolyzed into carboxylic acid group.
  • styrcne or methylstyrenc is used, the aromatic ring can be acidified by sulfur trioxide or concentrated sulfuric acid to create pendant sulfonic acid group onto aromatic ring.
  • the halidc group can be converted to quaternary amine group by reacting with a tertiary amine. This is simply to demonstrate that some precursors which have no ionic character can be converted to ionic group by chemical treatment.
  • These partially fluorochloro ionomcrs are capable of being processed into thin films or membranes (from 5 micrometer thick to 200 micrometer) and are extremely well suited for fuel cell applications and for breathable chemical protective covering applications.
  • the reaction can occur in an aqueous system or in a solvent system.
  • the functional comonomcrs are less water soluble, the copolymerization reaction is preferred to be in aqueous emulsions, mini-emulsions, or micro-emulsions.
  • solvent system for copolymcrization. wherein all monomers arc soluble in the selected solvent system before polymerization.
  • the temperature of copolymcrization in cither case is ranged from 0 to 150° C, preferably 40 to 100° C.
  • Initiators for polymerization include free-radical initiators, such as pcrsulfatcs, azo initiators, peroxides, or photo initiators, of which free radicals can be generated by heat, chemical, ultraviolet or gamma rays. Amount of initiators present can range between 0.01 and 3 percent by weight based on the final polymer content.
  • the fluoiochloro monomers are introduced to the reactor mostly from vapor phase. Sufficient mixing between liquid and vapor phases is important to encourage adequate mass transfer.
  • Tlic product made from the copolymcrization may be precursors of ion conducting polymers. Further chemical treatment is required to convert precursors to ionomcrs. Since most applications arc for coating or extrusion, film fomiation quality is critical. It is possible to do the coating or extrusion application using precursor polymers or ionomcrs directly. Either coating or extrusion application would allow the ionomers to be processed into thin films, either alone or in composite forms with other porous substrates to form a composite membrane.
  • the said other porous substrates can be a support of woven or non-woven porous material preferably microporous membranes, including but not limited to. microporous Nylon (polyamidc).
  • PVDF microporous polyvinylidcne fluoride
  • PTFE microporous polytetrafluoroethylene
  • bipolar membrane ie. a double layers of membrane wherein each layer of ionomcr has opposite charge to the other layer.
  • This can be done by double coating or co-extrusion of two fluorochloro ionomers of opposite charged ionomers.
  • this invented fluorochloro ionomers can be applied as double layers structure wherein one layer is fluorochloro sulfonic acid ionomer and the other layer is fluorochloro carboxylic acid ionomer.
  • Such double layer membrane can be made by double coating or co-extrusion.
  • Another aspect of this invention is to make one monolithic layer of fluorochloro sulfonyl fluoride membrane first, following by chemical treatment to convert one side of fluorochloro sulfonyl fluoride membrane into carboxylic acid membrane and the other side to become fluorochloro sulfonic acid membrane. This would avoid the traditional challenging need for laminating sulfonic acid and carboxylic acid membrane together for chlor-alkali industry application.
  • a sample of 1 cm x 1.5 cm in size was cut from a membrane and placed in a vacuum oven at 120" C for 24 hours at about 60 mm Hg using a nitrogen bleed to maintain the pressure. Then, the sample was removed, and weighed when cool in I minute to obtain the dry weight. The sample was then placed in de-ionized water for 2 hours at 21 ⁇ 25" C. The sample was then removed from water, patted dry with a paper cloth, and immediately weighed to obtain the hydratcd weight. The degree of hydration in percent is calculated as
  • Equivalent weight determination is based on the method of WO 00/52060 PCT patent application.
  • the conductivity determination is based on the method of Doyle ct al, WO 98/20573 PCT patent application.
  • Moisture vapor permeability rate determination is based on ASTM-E96-66BW test method.
  • BW test is an inverted cup test, wherein water is in direct contact with each sample.
  • Chemical agent permeation rate determination is based on method described in US Patent No. 6,395,383.
  • the resulting copolymer (IA) is further converted to sulfonic acid of pcrfluorochloro ionomcrs (IB), carboxylic acid of pcrfluorochloro ionomcrs (1C), sulfonamide amine of fluorochloro ionomers (ID), bi- layer of (1 B)/( 1C), composite membrane of (I B)/(1C), composite bipolar membrane of ( 1B)/(1D).
  • Example 2 the synthesis of copolymer of chlorotrifluorocthylcnc (CFCNCF2) and tcrt- butyl acrylatc. The resulting copolymer is further converted to carboxylic acid sodium salt partially fluorochloro ionomcrs.
  • the resulting copolymer has the following structure:
  • the sulfonic acid of perfluorochloro ionomers ( IB) can form uniform thin film (after drying from 5 micrometer thick up to 200 micrometer) by removing volatile solvent in an hot air circulated oven at 160° C for 3 minutes.
  • Degree of hydration and chemical agent permeation rate of our invented perfluorochloro sulfonic acid ionomer membrane arc all better than Nafion® perfluoro ionomer membrane when compared with that of similar equivalent weight, while ionic conductivity remains the same for the ionomers with similar equivalent weight.
  • Some copolymer ( IA) is also converted to carboxylic acid perfluorochloro ionomers with the same chemical reaction methods taught by M. Seko. H. Miyauchi, J. Ohmura, and K. Kimoto, in '" Modem Chlor-Alkali Technology (C. Jackson, ed.). Vol. 3, p. 76, Ellis Horwood, Chichcstcr (1983).
  • the resulting carboxylic acid perfluoro ionomers have the following structure:
  • copolymer ( IA) is processed into thin film of about 2-mil thick.
  • One side of ( IA) is treated with the chemical method of (IB) and the other side is treated with the chemical method of ( 1C).
  • the resulting membrane has one side of sulfonic acid pcrfluorochloro ionomcr and the other side of carboxylic acid pcrfluorochloro ionomcr.
  • Such film with two layers of ionomcrs without lamination is very suitable for chlor-alkali industrial applications.
  • perfluorochloro ionomcrs with sulfonic acid group (I B) is coated onto one side of microporous 0.2 micron PVDF membrane (1 Vi mil thick) and the other side of the PVDF membrane is coated with pcrfluorochloro ionomcrs with carboxylic acid group ( 1C).
  • the resulting composite membrane (1B)/(1C) is useful for chlor-alkali industrial application.
  • perfluorochloro ionomers with sulfonic acid group ( IB) is coated onto one side of microporous 0.2 micron PVDF membrane ( 1 Yi mil thick) and the other side of the PVDF membrane is coated with pcrfluorochloro ionomcrs with sulfonamide amine group ( I D).
  • the resulting bipolar membrane ( 1 B)/( 1 D) has moisture vapor permeability rate > 3,000 gram/nr/day.
  • the bipolar membrane has unusually low chemical agent permeability rate easily satisfying specifications and low methanol crossover rate, which shows the membrane is very useful for many industrial applications as well as breathable protective covering applications.
  • Example 1 of this invention is repeated, except that PSEPVE is replaced by tert- butyl acrylatc.
  • the copolymer is then treated with sodium hydroxide NaOH(aq) at 95° C for 6 hours to obtain carboxylic acid sodium salt ionomcrs as follows:
  • the partially fluorochloro ionomcrs are coated onto one side of microporous 0.2 micron Nylon membrane (about 2-mil thick) and dried at 130° C for 2 minutes.
  • the add-on weight to the microporous Nylon membrane is about 20 gram/m 2 .
  • This partially fluorochloro ionomer coating thickness is about '/ ⁇ > mil.
  • the coated membrane has moisture vapor permeability rate > 3.000 gram/nr/day.
  • the coated membrane has low chemical agent permeability rate satisfying specifications, which means the invented fluorochloro ionomers have unusually good barrier properties for breathable protective covering applications.
  • Example 6 of US Patent number 6.228.963 is repeated, except that PPVE is not used and TFE is replaced by CTFE (Chlorotrifluoroethylene).
  • CTFE Chlorotrifluoroethylene
  • Tlic copolymer is further ionized by ammonia NH4 ⁇ H(aq) at 95° C for 6 hours to become
  • copolymer is further ionized, with the method taught in Example 1 of US Patent number 6, 156,451, by potassium hydroxide KOH(aq) to become
  • Example 3 of this invention is repeated except that malcic anhydride is replaced by acrylic acid.
  • the copolymer made is shown below:
  • the copolymer is further ionized by NaOH(aq) at 95° C for 6 hours to become sodium salt of carboxylic acid of fluorochloro ioiiomcrs.
  • Tlic partially fluorochloro ionomcrs arc coated onto one side of microporous 0.2 micron Nylon membrane (about 2-mil thick) and dried at 130 C for 2 minutes.
  • the add-on weight to the microporous Nylon membrane is about 16 gram/m 2 .
  • This partially fluorochloro ionomer coating thickness is about ' ⁇ mil.
  • the coated membrane has moisture vapor permeability rate > 3,000 gram/m 2 /day.
  • the coated membrane has low chemical agent permeability rate satisfying specifications, which means the invented fluorochloro ionomers have unusually good barrier properties for breathable protective covering applications.
  • Example 4 of this invention is repeated, except that malcic anhydride is replaced by acrylic acid.
  • the copolymer is shown below:
  • the copolymer is further ionized by LiOH(aq) at 100° C for 6 hours to become
  • Example 1 of US Patent number 6, 153,697 is repeated except that 785 grams CHHPM is replaced by 236 grams styrene and isobutylene is not used.
  • the copolymer made is shown below:
  • the copolymer is further ionized by sulfur trioxidc SOs at 1 10° C for 6 hours to become sulfonic acid of fluorochloro ionomers.
  • the partially fluorochloro ionomers arc coated onto one side of microporous 0.2 micron PVDF membrane (about 1 Vi mil thick) and dried at 130 ° C for 2 minutes.
  • the add-on weight to the microporous PVDF membrane is about 18 gram/m 2 .
  • This partially fluorochloro ionomer coating thickness is about Vi mil.
  • the coated membrane has moisture vapor permeability rate > 3,000 gram/m 2 /day.
  • the coated membrane has unusually low chemical agent permeability rate satisfying specifications, which means the invented fluorochloro ionomers have unusually good barrier properties for breathable protective covering applications.

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Abstract

La présente invention concerne de nouveaux ionomères fluorochloro et des procédés de production de ceux-ci. Le premier mode de réalisation préféré de l'invention concerne des ionomères perfluorochloro ayant (1) un poids équivalent compris entre 600 et 1500, de préférence entre 800 et 1200, et de manière préférée entre toutes entre 900 et 1100 ; et (2) une teneur en chlore comprise entre 8 % et 30 % en poids. Ces ionomères sont perméables à l'air et d'excellents matériaux de barrière, peuvent être traités en films ou membranes minces et sont adaptés pour des applications de pile à combustible à faible humidité ou à température élevée et pour des matériaux de couverture protectrice chimique. Le deuxième mode de réalisation préféré de l'invention concerne des ionomères partiellement fluorochloro ayant (1) un taux de perméabilité de vapeur d'eau > 3000 grammes de H2O/m²/jour (film d'environ 1/2 mil d'épaisseur) ; et (2) une teneur en chlore comprise entre 10 % et 39 % en poids. Ces ionomères sont perméables à l'air et d'excellent matériaux de barrière qui peuvent également être traités en films ou membranes minces et sont adaptés pour certaines applications de pile à combustible et plus préférablement pour des applications de couverture protectrice perméable à l'air. Les membranes peuvent être des films monolithiques ou des films multicouches, ou des films composites, ou des membranes bipolaires. Ces nouveaux ionomères fluorochloro sont fabriqués par copolymérisation radicalaire d'au moins un monomère fluorochloro et au moins un comonomère constitué d'au moins un groupe ionique ou au moins un précurseur qui peut être converti en groupes ioniques tels que des groupes acides ou des amines ou des groupes d'amine quaternaire. Ledit monomère fluorochloro contenant au moins un atome de fluor et au moins un atome de chlore est polymérisable par voie radicalaire comprenant le chlorotrifluoroéthylène (CFCl=CF2) et le dichlorodifluoroéthylène (CFCl=CFCl).
PCT/US2008/073505 2009-02-18 2009-02-18 Ionomères fluorochloro WO2010096027A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014502300A (ja) * 2010-11-26 2014-01-30 ソルヴェイ・スペシャルティ・ポリマーズ・イタリー・エッセ・ピ・ア フッ素化イオン交換ポリマーの液体組成物
WO2016128315A1 (fr) 2015-02-11 2016-08-18 Solvay Specialty Polymers Italy S.P.A. Nouveau fluoropolymère pouvant être traité thermiquement

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KR20010040945A (ko) * 1998-02-13 2001-05-15 메리 이. 보울러 플루오르화 이오노머 및 그의 용도
US6902676B2 (en) * 2001-02-26 2005-06-07 Ausimont S.P.A. Porous hydrophilic membranes
US20050182215A1 (en) * 2001-12-06 2005-08-18 Wu Huey S. Low equivalent weight ionomer
US20060223894A1 (en) * 2005-03-17 2006-10-05 Solvay Solexis S.P.A. Ionomeric membrane
US20060241261A1 (en) * 2001-12-06 2006-10-26 Wu Huey S Low equivalent weight ionomer
US20070066691A1 (en) * 2005-03-17 2007-03-22 Solvay Solexis S.P.A. Composite ionomeric membrane
US20090053576A1 (en) * 2007-08-20 2009-02-26 Huey-Shen Wu Fluorochloro Ionomers

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Publication number Priority date Publication date Assignee Title
KR20010040945A (ko) * 1998-02-13 2001-05-15 메리 이. 보울러 플루오르화 이오노머 및 그의 용도
US6902676B2 (en) * 2001-02-26 2005-06-07 Ausimont S.P.A. Porous hydrophilic membranes
US20050182215A1 (en) * 2001-12-06 2005-08-18 Wu Huey S. Low equivalent weight ionomer
US20060241261A1 (en) * 2001-12-06 2006-10-26 Wu Huey S Low equivalent weight ionomer
US20060223894A1 (en) * 2005-03-17 2006-10-05 Solvay Solexis S.P.A. Ionomeric membrane
US20070066691A1 (en) * 2005-03-17 2007-03-22 Solvay Solexis S.P.A. Composite ionomeric membrane
US20090053576A1 (en) * 2007-08-20 2009-02-26 Huey-Shen Wu Fluorochloro Ionomers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014502300A (ja) * 2010-11-26 2014-01-30 ソルヴェイ・スペシャルティ・ポリマーズ・イタリー・エッセ・ピ・ア フッ素化イオン交換ポリマーの液体組成物
WO2016128315A1 (fr) 2015-02-11 2016-08-18 Solvay Specialty Polymers Italy S.P.A. Nouveau fluoropolymère pouvant être traité thermiquement
CN107250178A (zh) * 2015-02-11 2017-10-13 索尔维特殊聚合物意大利有限公司 新颖的可热加工的氟聚合物
CN107250178B (zh) * 2015-02-11 2020-11-13 索尔维特殊聚合物意大利有限公司 新颖的可热加工的氟聚合物

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