EP1984430A2 - Mélanges contenant de l'acide phosphonique et polymères contenant de l'acide phosphonique - Google Patents

Mélanges contenant de l'acide phosphonique et polymères contenant de l'acide phosphonique

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Publication number
EP1984430A2
EP1984430A2 EP07711177A EP07711177A EP1984430A2 EP 1984430 A2 EP1984430 A2 EP 1984430A2 EP 07711177 A EP07711177 A EP 07711177A EP 07711177 A EP07711177 A EP 07711177A EP 1984430 A2 EP1984430 A2 EP 1984430A2
Authority
EP
European Patent Office
Prior art keywords
groups
hydroxymethylene
polymers
polymer
acid
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.)
Pending
Application number
EP07711177A
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German (de)
English (en)
Inventor
Thomas HÄRING
Jochen Kerres
Frank SCHÖNBERGER
Martin Hein
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.)
HAERING, THOMAS
Institut fuer Chemische Verfahrenstechnik Universitaet Stuttgart
Original Assignee
Institut fuer Chemische Verfahrenstechnik Universitaet Stuttgart
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Application filed by Institut fuer Chemische Verfahrenstechnik Universitaet Stuttgart filed Critical Institut fuer Chemische Verfahrenstechnik Universitaet Stuttgart
Publication of EP1984430A2 publication Critical patent/EP1984430A2/fr
Pending legal-status Critical Current

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    • 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
    • H01M8/1034—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having phosphorus, e.g. sulfonated polyphosphazenes [S-PPh]
    • 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
    • B01J39/20—Macromolecular compounds obtained 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • 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
    • C08J5/2287—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—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
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    • 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
    • H01M8/1041—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
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
    • 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. insitu polymerisation or insitu crosslinking
    • 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
    • C08J2341/00—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 bond to sulfur or by a heterocyclic ring containing sulfur; Derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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
    • 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
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • 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

  • perfluorinated sulfonic acid-based ionomer membranes can operate at temperatures below 100 0 C in electrochemical cells, particularly fuel cells are used, and in this temperature range show good H + - conductivity and high (electro) chemical stability. However, they are not usable at temperatures above 100 0 C, since they then dry out and therefore their proton conductivity decreases by several orders of magnitude 1 , 2 . However, it is useful to operate fuel cells at temperatures above 100 0 C, since in this temperature range, the CO tolerance of the fuel cell reaction due to faster electrode kinetics is significantly greater than below 100 0 C 3 .
  • micrometer to nanometer size microporous particles which may be inorganic hydroxides, oxides or salts, or inorganic / organic hybrid compounds, such as SiO 2 , 5 , 6 , TiO 2 , ZrO 2 7 , or layer phosphates or zirconium sulfophenyl phosphonates , wherein the layer phosphates such as zirconium or
  • Zirconiumsulfophenylphosphonat also have a Eigenprotonenleitrange,.
  • Another approach is the incorporation of phosphoric acid into basic polybenzimidazole membranes, with the phosphoric acid acting as the proton conductor, since phosphoric acid can function both as a proton donor and as a proton acceptor.
  • Non-fluorinated arylphosphonic acids are generally only medium-strength acids (pKs «
  • Polymeric phosphonic acids have poor film-forming properties (are very brittle)
  • Phosphonic acids tend to condense at temperatures around 12O 0 C, which is their
  • the object of the present invention consists in the preparation of 1-hydroxymethylene-l, l-bisphosphonic acid-containing polymer blends having the following properties:
  • Another object of the invention are processes for preparing the polymer mixtures containing phosphonic acid groups (blends).
  • the object of the invention is the use of polymer mixtures containing phosphonic acid groups (blends) in membrane processes such as gas separation, pervaporation, perstraction, PEM electrolysis and secondary batteries such as PEM and direct methanol fuel cells, in particular under conditions of reduced humidification (0
  • the object of the invention can be achieved by: 1. Preparation of optionally physically, ionically or covalently crosslinked Blen ⁇ s and blend membranes of low molecular weight hydroxymethylene-oligophosphonic RC (POsH 2 ) x (OH) y with polymers which contain the following functional groups:
  • Basic groups such as primary, secondary or tertiary amino groups, imidazole groups, pyridine groups, pyrazole groups etc. and / or
  • Phosphonic acids for example, produced from carboxylic acids by reaction with
  • PCl 3 ZH 3 PO 3 and subsequent hydrolysis with H 2 O 23 ' 24 ' 25 '26 " 27 are shown in Figure 1. Further, preferred low molecular weight according to the invention.
  • a particular embodiment of these blends consists in the fact that ionic crosslinking sites can exist between the polymers and the low molecular weight phosphonic acids, for example between the cation exchange groups of the polymer with a basic group (eg pyridine radical) of the low molecular weight phosphonic acid compound, see Figure 8.
  • a basic group eg pyridine radical
  • the binding of the low molecular weight Hydroxymethylenphosphonkla to the polymers consists in covalent crosslinking, such as by crosslinking of the OH group of the phosphonic acid compound with an OH group of the polymer by means of an ⁇ , ⁇ -Dihalogenalkans, see Figure 9.
  • Further possible crosslinking reactions for the OH group of l-hydroxymethylene-l, l-bisphosphonic acid grouping and optionally with OH groups of polymers according to the invention are:
  • the covalent cross-linking prevents outdiffusion of the phosphonic acid compound from the polymer and improves the mechanical stability of the blend films.
  • interpenetrating networks of very different structure and composition.
  • IPN interpenetrating networks
  • a dipolar aprotic solvent such as N-methylpyrrolidinone (NMP), N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO): a polymer having sulfochloride groups, a crosslinker for Sulfochlorid phenomenon such.
  • NMP N-methylpyrrolidinone
  • DMAc N, N-dimethylacetamide
  • DMF N-dimethylformamide
  • DMSO dimethyl sulfoxide
  • 4,4'-Diaminodiphenylsulfon 40 a bifunctional l-hydroxymethylene-l, l-bisphosphonic acid such as l, 4-bis (l-hydroxymethylene l, l-bisphosphonic) benzene and a crosslinker for the OH groups of the 1- Hydroxymethylene 1,1-bisphosphonic acid groups such.
  • glutaraldehyde After a homogeneous solution of all components has been prepared, the solution is spread out on a pad and the solvent is evaporated.
  • HPN hybrid polymer network
  • Glutaraldehyde 36 After a homogeneous solution of all components has been prepared, the solution is doctored on a pad and the solvent is evaporated. The resulting HPN can still be post-treated as follows: 1. Post-treatment in mineral acid (H 2 SO 4 from 0.1 to 80% concentration, HCl from 0.1 to 37% concentration or phosphoric acid from 0.1 to 85% concentration) and optionally 2. subsequent storage in water to remove excess mineral acid.
  • mineral acid H 2 SO 4 from 0.1 to 80% concentration, HCl from 0.1 to 37% concentration or phosphoric acid from 0.1 to 85% concentration
  • the resulting HPN consists of the covalent network of the polymer having the sulfinate and sulfonate groups 42 , the sulfinate groups having been cross-linked by S-alkylation using the 1,4-diiodobutane, and the network of 3- (l-hydroxy-l, l-bisphosphonic acid) pyridine and glutaraldehyde.
  • ionic interactions between the two networks additionally exist via the pyridine moiety of 3- (1-hydroxy-1,1-bisphosphonic acid) -pyridine and the sulfonate moieties of the sulfonated polymer.
  • the 1,4-diiodobutane crosslinker can also crosslink a portion of the pyridine groups by alkylation, whereby mixed crosslinking bridges between sulfinate groups and pyridine groups can arise 43 .
  • Polyolefins such as polyethylene, polypropylene, polyisobutylene, polynorbornene,
  • Styrene (co) polymers such as polystyrene, poly (methylstyrene), poly ( ⁇ , ß, ß-trifluorstyiOl),
  • Poly (4-vinylpyridine), poly (2-vinylpyridine) and their copolymers perfluorinated ionomers such as Nafion® or the SO 2 Hal precursor of Nafion® (HaI F,
  • Het aryl backbone polymers such as:
  • Polyether ketones such as polyether ketone PEK Victrex®, polyetheretherketone
  • Polyethersulfones such as Polysulfone Udel®, Polyphenylsulfone Radel R®,
  • (Benz) imidazole group may be present in the main chain or in the polymer side chain
  • Polyphenylene ethers such. Poly (2,6-dimethyloxyphenylene), poly (2,6-diphenyloxyphenylene)
  • 1,4-benzoyl groups or p-phenyloxy-l, 4-benzoyl groups can.
  • aryl main chain polymers are possible as base polymers for the polymers and polymer mixtures according to the invention.
  • All possible block copolymers of the polymeric, in particular aryl main chain, polymers are also possible, the following types of block copolymers being preferred:
  • Block copolymers composed of blocks containing basic groups and of unmodified blocks; while the choice of basic groups is not limited, but there are heterocyclic or heteroaromatic, z.
  • Block copolymers of acidic (cation exchange group-containing) blocks and blocks containing basic groups
  • Block copolymers with blocks containing OH groups and blocks containing acid groups Block copolymers with blocks containing OH groups and blocks containing acid groups
  • Block copolymers with OH-containing blocks and blocks containing basic groups Block copolymers with OH-containing blocks and blocks containing basic groups.
  • Method via metallation first metallation (eg with n-butyllithium) 3 then reaction with an S-electrophile (SO 2 , SO 3 , SOCl 2 , SO 2 Cl 2 ), then optionally conversion to
  • Monomers are polymerized / polycondensed, such as. In McGrath et al., 53 , 54 , 55 .
  • One possible method is the metallation of the polymer and the subsequent reaction of the metalated polymer with a halogenated phosphoric or phosphonic esters (examples: Chlorphosphorklarediaryl 16 - or alkyl ester, 2- Bromethanphosphonklaredialkylester, 3-dialkyl phosphonate -Brompropan etc.).
  • carboxylation of the polymers all common methods can be used. Likely here are the carboxylation of polymers via lithiated intermediates, for example the lithiation of polysulfone PSU Udel or the lithiation of polyphenylene oxide with subsequent reaction of the lithiated intermediate with solid or gaseous CO 2 56 '57 .
  • the corresponding acid chloride can be prepared from the polymeric carboxylic acid by reaction with thionyl chloride (for further reaction with, for example, tris (timethylsilyl) phosphite to give the corresponding 1-hydroxymethylene-1,1-bisphosphonic acid).
  • methyl aromatics can be reacted with potassium permanganate to the corresponding aromatic carboxylic acids, for example, the 2-, 3- or 4-methylpyridines.
  • Aliphatic carboxylic acids are also accessible by oxidation of aliphatic alcohols or aldehydes.
  • Arylene main chain polymer (general regulation)
  • caustic alkali metal such as NaOH, KOH 5 LiOH etc.
  • alkaline earth liquor such as Ba (OH) 25 Ca (OH) 2
  • aqueous ammonia or aqueous primary, secondary or tertiary amines or quaternary ammonium salts at temperatures from O to 10O 0 C for 1 to 480 hours;
  • a polymer containing OH groups is dissolved in a dipolar aprotic or in a protic solvent, for example in DMSO.
  • the low molecular weight aryl-l-hydroxymethylene-l, l-bisphosphonic acid is dissolved in the same solvent, either in the H form or in the Na + form.
  • Glutaraldehyde is then added to the solution of the low molecular weight 1-hydroxymethylene-1,1-bisphosphonic acid, specifically per mole of OH groups of the low molecular weight aryl-1-hydroxymethylene-1,1-bisphosphonic acid, Vi mole of glutaraldehyde.
  • the combined solution is doctored onto a glass plate to a thin film.
  • the DMSO at temperatures of 50 to 150 0 C and optionally reduced pressure of 800-1 Ombar removed by evaporation.
  • the glass plate is removed with the polymer film under water from the glass plate.
  • the polymer film is aftertreated as follows:
  • caustic alkali, such as NaOH, KOH, LiOH etc.
  • alkaline earth liquor such as Ba (OH) 25 Ca (OH) 2
  • aqueous ammonia or aqueous primary, secondary or tertiary amines or quaternary ammonium salts at temperatures from 0 to 100 ° C for 1 to 480 hours;
  • Carboxylated PSU with 2 carboxylic acid groups per repeat unit is prepared after 5 ⁇ .
  • the PSU diacid chloride To prepare the PSU diacid chloride, the PSU dicarboxylic acid is dissolved in a 9-fold excess of thionyl chloride, based on the mass of the polymer. A small amount of N, N-dimethylformamide is added to this mixture and refluxed for 72 hours. The PSU diacid chloride is precipitated in a large excess of isopropanol and excess thionyl chloride is washed out. The PSU-di-acid chloride is dried to zw constant weight.

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  • Fuel Cell (AREA)

Abstract

L'invention concerne des mélanges et des membranes faites de mélanges d'acides oligophosphoniques d'hydroxyméthylène à bas poids moléculaire R-C(PO<SUB>3</SUB>H<SUB>2</SUB>)x(OH)<SUB>y</SUB> et de polymères, le radical R étant un radical organique quelconque et les polymères contenant les groupes suivants : des groupes échangeurs de cations ou leurs précurseurs non ioniques du type SO<SUB>2</SUB>X, X=HaI, OH OMe, NR<SUB>1</SUB>R<SUB>2</SUB>, OR<SUB>1</SUB> où Me est un cation métallique quelconque ou un cation d'ammonium, R<SUB>1</SUB>, R<SUB>2 </SUB>est<SUB/>H ou un radical aryle ou alkyle quelconque, POX<SUB>2</SUB>, COX et/ou des groupes basiques tels que des groupes amino primaires, secondaires ou tertiaires, des groupes imidazol, des groupes pyridine, des groupes pyrazol etc. et/ou des groupes OH. Selon l'invention, il s'agit de préférence d'acides oligophosphoniques d'hydroxyméthylène à bas poids moléculaire R-C(PO<SUB>3</SUB>H<SUB>2</SUB>)x(OH)<SUB>y</SUB> pour lesquels x=2 et y=1. L'invention concerne aussi des mélanges et des membranes faites de mélanges d'acides oligophosphoniques d'hydroxyméthylène à bas poids moléculaire R-C(PO<SUB>3</SUB>H<SUB>2</SUB>)<SUB>2</SUB>(OH)<SUB>1</SUB> et de polymères, le radical R des acides oligophosphoniques d'hydroxyméthylène contenant un groupement aliphatique ou aromatiques qui entre en interaction ionique avec les groupes acides du polymères ou du mélange de polymères. L'invention a également pour objet des mélanges et des membranes faites de mélanges d'acides oligophosphoniques d'hydroxyméthylène à bas poids moléculaire R-C(PO<SUB>3</SUB>H<SUB>2</SUB>)<SUB>2</SUB>(OH)<SUB>1</SUB> et de polymères, les groupes OH des acides I-hydroxyméthylène-II-biphosphoniques à bas poids moléculaire étant réticulés entre eux de façon covalente et éventuellement avec des groupes OH du polymère. L'invention se rapporte également à des polymères modifiés avec les groupes acide I-hydroxyméthylène-II-biphosphonique, ceux-ci étant préparés par réaction avec des polymères qui contiennent des groupes acide carboxylique ou des groupes halogénure d'acide carboxylique -COHal (Hal=F, Cl, Br, I), avec des composés de phosphite, ou par réaction d'aldéhydes polymères ou de composés céto polymères avec des esters d'acide phosphoreux sous catalyse aminée, sous oxydation des acides hydroxyphosphoniques intermédiaires avec MnO<SUB>2</SUB> ou un autre agent d'oxydation. L'invention concerne aussi des procédés pour préparer les substances mentionnées ci-dessus et l'utilisation de membranes faites des substances mentionnées ci-dessus, dans le cadre de processus membranaires et en particulier dans des piles à combustible, même à des températures >100°C.
EP07711177A 2006-02-03 2007-02-05 Mélanges contenant de l'acide phosphonique et polymères contenant de l'acide phosphonique Pending EP1984430A2 (fr)

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DE102006005782 2006-02-03
PCT/DE2007/000260 WO2007101415A2 (fr) 2006-02-03 2007-02-05 Mélanges contenant de l'acide phosphonique et polymères contenant de l'acide phosphonique

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US (3) US8637174B2 (fr)
EP (1) EP1984430A2 (fr)
JP (3) JP2009525360A (fr)
DE (1) DE112007000280A5 (fr)
WO (1) WO2007101415A2 (fr)

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DE112007000280A5 (de) 2008-10-30
WO2007101415A3 (fr) 2007-12-21
US20090220843A1 (en) 2009-09-03
US20140213672A1 (en) 2014-07-31
JP2016145351A (ja) 2016-08-12
US20170170505A1 (en) 2017-06-15
JP2009525360A (ja) 2009-07-09
JP2013177598A (ja) 2013-09-09
US8637174B2 (en) 2014-01-28
WO2007101415A2 (fr) 2007-09-13

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