Other

Thomas Haring and Rima Haring

Micronas Gmbh

Universitãt Stuttgart

Universitaet Stuttgart

Universit&auml;t Stuttgart

Thomas Häring

Rima Häring

Universitat Stuttgart Lehrstuhl Und Institut Fur Chemische Verfahrenstechnik

Universtitat Stuttgart

Haring, Thomas

Haring, Rima

Universität Stuttgart Institut Für Chemische Verfahrenstechnik

Linkov, Vladimir

Jochen Kerres

Wei Cui

Wei Zhang

Martin Hein

Werner Schnurnberger

Andreas Ullrich

Chy-Ming Tang

Gilbert Alexander Erdler

Holger Reinecke

Mirko Frank

Claas Mueller

Claas Müller

W Zhang

Thomas H&auml;ring

C Tang

Frank Schönberger

Vladimir Linkov

Thomas Haring

Norbert Nicoloso

Günther Schäfer

The invention relates to:—anion exchange blend membranes consisting the following blend components:—a halomethylated polymer (a polymer with —(CH2)x—CH2—Hal groups, Hal=F, Cl, Br, I; x=0-12), which is quaternised with a tertiary or a n-alkylated/n-arylated imidazole, an N-alkylated/N-arylated benzimidazole or an N-alkylated/N-arylated pyrazol to form an anion exchanger polymer. - an inert matrix polymer in which the anion exchange polymer is embedded and which is optionally covalently crosslinked with the halomethylated precursor of the anion exchanger polymer,—a polyethyleneglycol with epoxide or halomethyl terminal groups which are anchored by reacting with N—H-groups of the base matrix polymer using convalent cross-linking—optionally an acidic polymer which forms with the anion-exchanger polymer an ionic cross-linking (negative bound ions of the acidic polymer forming ionic cross-linking positions relative to the positive cations of the anion-exchanger polymer)—optionally a sulphonated polymer (polymer with sulphate groups —SO2Me, Me=any cation), which forms with the halomethyl groups of the halomethylated polymer convalent crosslinking bridges with sulfinate S-alkylation. The invention also relates to a method for producing said membranes, to the use of said membranes in electrochemical energy conversion processes (e.g. Redox-flow batteries and other flow batteries, PEM-electrolyses, membrane fuel cells), and in other membrane methods (e.g. electrodialysis, diffusion dialysis).

Cross-linked high stable anion exchange blend membranes with polyethyleneglycols as hydrophilic membrane phase

The invention relates to: &#x2014;anion exchange blend membranes consisting the following blend components: &#x2014;a halomethylated polymer (a polymer with &#x2014;(CH)&#x2014;CH&#x2014;Hal groups, Hal=F, Cl, Br, I; x=0-12), which is quaternised with a tertiary or a n-alkylated/n-arylated imidazole, an N-alkylated/N-arylated benzimidazole or an N-alkylated/N-arylated pyrazol to form an anion exchanger polymer. &#x2014;an inert matrix polymer in which the anion exchange polymer is embedded and which is optionally covalently crosslinked with the halomethylated precursor of the anion exchanger polymer, &#x2014;a polyethyleneglycol with epoxide or halomethyl terminal groups which are anchored by reacting with N&#x2014;H-groups of the base matrix polymer using covalent cross-linking&#x2014;optionally an acidic polymer which forms with the anion-exchanger polymer an ionic cross-linking (negative bound ions of the acidic polymer forming ionic cross-linking positions relative to the positive cations of the anion-exchanger polymer)&#x2014;optionally a sulphonated polymer (polymer with sulphate groups &#x2014;SOMe, Me=any cation), which forms with the halomethyl groups of the halomethylated polymer covalent crosslinking bridges with sulfinate S-alkylation. The invention also relates to a method for producing said membranes, to the use of said membranes in electrochemical energy conversion processes (e.g. Redox-flow batteries and other flow batteries, PEM-electrolyses, membrane fuel cells), and in other membrane methods (e.g. electrodialysis, diffusion dialysis).

The invention relates to a composite or a composite membrane consisting of an ionomer and of an inorganic optionally functionalized phyllosilicate. The isomer can be: (a) a cation exchange polymer; (b) an anion exchange polymer; (c) a polymer containing both anion exchanger groupings as well as cation exchanger groupings on the polymer chain; or (d) a blend consisting of (a) and (b), whereby the mixture ratio can range from 100% (a) to 100% (b). The blend can be ionically and even covalently cross-linked. The inorganic constituents can be selected from the group consisting of phyllosilicates or tectosilicates.

Composites and composite membranes

Ionomers and ionomer membranes, consisting of a non-fluorinated or partly fluorinated non-, partly or fully-aromatic main chain and a non- or partly-fluorinated side chain with ionic groups or their non-ionic precursors, have a positive impact on the proton conductivity of the ionomers. Various processes produce these polymeric proton conductors. The membranes are useful for fuel cell applications.

Ionomers with ionic groups in the side chain

Ionomers and ionomer membranes, consisting of a non-fluorinated or partly fluorinated non-, partly or fully-aromatic main chain and a non- or partly-fluorinated side chain with ionic groups or their non-ionic precursors, have a positive impact on the proton conductivity of the ionomers. Various processes produce these polymeric proton conductors.

Various blends and blend membranes from low-molecular hydroxymethylene-oligo-phosphonic acids R&#x2014;C(POH)(OH)and polymers, the group R representing any organic group, the polymers containing cation exchanger groups or their nonionic precursors of the type SOX, X being a halogen, OH, OMe, NRR, ORwith Me being any metal cation or ammonium cation, R, Rbeing H or any aryl- or alkyl group, PDX, COX and/or basic groups such as primary, secondary or tertiary amino groups, imidazole groups, pyridine groups, pyrazole groups etc. and/or OH groups. Such membranes may also include polymers that are modified with the 1-hydroxymethylene-1,1-bisphosphonic acid group. The polymers may be formed by reacting polymers which contain carboxylic acid groups or carboxylic halide groups &#x2014;COHal (Hal=F, Cl, Br, I) with phosphite compounds or by reacting polymeric aldehydes or polymeric keto compounds with phosphite esters while carrying out an amine catalysis, an oxidation of the intermediary hydroxyphosphonic acid with MnOor another oxidant.

Phosphonic acid-containing blends and phosphonic acid-containing polymers

In a method for producing a proton-conductive, structured electrolyte membrane, particularly for a fuel cell, a coating, which comprises at least one ion-conductive cross-linking component having at least one acid group and at least one photoactive substances interacting therewith, is applied onto a solid body surface. The coating is optically masked in that at least one region of the coating, in which the electrolyte membrane is supposed to be, is exposed such that the cross-linking component cross-links with the photoactive substances to form a polymer and/or copolymer network adhering to the solid body surface. At least one unexposed region of the coating is removed in order to structure the electrolyte membrane.

Method for producing a proton-conducting, structured electrolyte membrane

The invention relates to novel organic/inorganic hybrid membranes which have the following composition: a polymer acid containing &#x2014;SOH, POH, &#x2014;COOH or B(OH)groups, a polymeric ease (optional), which contains primary, secondary or tertiary amino groups, pyridine groups, imidazole, benzimidazole, triazole, benzotriazole, pyrazole or benzopyrazole groups, either in the side chain or in the main chain; an additional polymeric base (optional) containing the aforementioned basic groups; an element or metal oxide or hydroxide, which has been obtained by hydrolysis and/or sol-gel reaction of an elementalorganic and/or metalorganic compound during the membrane forming process and/or by a re-treatment of the membrane in aqueous acidic, alkaline or neutral electrolytes. The invention also relates to methods for producing said membranes and to various uses for membranes of this type.

Polymer membranes

The invention relates to novel polymers or oligomers containing at least sulfinate groups (P&#x2014;(SO2)nX, X=1-(n=1), 2-(n=2) or 3-(n=3) valent metal cation or H+ or ammonium ion NR4+ where R=alkyl, aryl, H), which are obtained by completely or partially reducing polymers or oligomers containing at least SO2Y-groups (Y&#x2550;F, Cl, Br, I, OR, NR2 (R=alkyl and/or aryl and/or H), N-imidazolyl, N-pyrazolyl) by means of suitable reducing agents in a suspension or in a solution form. Polymer and polymer(blend)membranes which are obtained by further reacting the received sulfinated polymers, especially by alkylation of the sulfinate groups with mono- di- or oligo functional electrophiles. The invention further relates to methods for producing the sulfinated polymers and for further reacting the sulfinated polymers with electrophiles by S-alkylation.

Oligomers and polymers containing sulfinate groups and method for the production thereof

The invention relates to organic/inorganic hybrid polymer blends and hybrid polymer blend membranes that are composed of: one polymer acid halide containing SOX, POXor COX groups (X&#x2550;, Cl, Br, I); one elemental or metallic oxide or hydroxide, obtained by the hydrolysis and/or the sol/gel reaction of an elemental and/or organometallic compound during the membrane forming process and/or by subsequently treating the membrane in aqueous acidic, alkaline or neutral electrolytes. The invention further relates to hybrid blends and hybrid blend membranes containing polymers that carry SOH, POHand/or COOH groups, obtained by aqueous, alkaline or acidic hydrolysis of the polymer acid halides contained in the polymer blend or the polymer blend membrane. The invention also relates to methods for producing the inventive hybrid blends and hybrid blend membranes.

Organic-inorganic membranes

The invention relates to novel organic/inorganic hybrid membranes which have the following composition: a polymer acid containing &#x2014;SOH, &#x2014;POH, &#x2014;COOH or B(OH)groups, a polymeric ease (optional), which contains primary, secondary or tertiary amino groups, pyridine groups, imidazole, benzimidazole, triazole, benzotriazole, pyrazole or benzopyrazole groups, either in the side chain or in the main chain; an additional polymeric base (optional) containing the aforementioned basic groups; an element or metal oxide or hydroxide, which has been obtained by hydrolysis and/or sol-gel reaction of an elementalorganic and/or metalorganic compound during the membrane forming process and/or by a re-treatment of the membrane in aqueous acidic, alkaline or neutral electrolytes. The invention also relates to methods for producing said membranes and to various uses for membranes of this type.

The invention relates to polymers obtained by S-alkylation of sulfinated polymers with alkylation agents, and AB-cross-linked polymers obtained by reacting polymers containing alkylation groups with low-molecular sulfinates, under S-alkylation, or AB-cross-linked polymers obtained by S-alkylation of sulfinated polymers with polymers containing alkylation groups.

Oligomers and polymers containing sulfinate groups, and method for producing the same

The invention relates to novel polymers or oligomers containing at least sulfonite groups (P-(SO)X, X=1&#x2212;(n=1), 2&#x2212;(n=2) or 3&#x2212;(n=3) valent metal cation or Hor ammonium ion NRwherein R=alkyl, aryl, H), which are obtained by completely or partially reducing polymers or oligomers containing at least SOY-groups (Y=F, Cl, Br, I, OR, NR(R=alkyl and/or aryl and/or H), N-imidazolyl, N-pyrazolyl) by means of suitable reducing agents in a suspension or in a solution form. The invention also relates to polymers and polymer(blend) membranes which are obtained by further reacting the obtained sulfinated polymers, especially by alkylation of the sulfinate groups with mono- di- or oligo functional electrophiles. The invention further relates to methods for producing the sulfinated polymers and for further reacting the sulfinated polymers with electrophiles by S-alkylation.

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Ostfildern, Germany

Jochen Kerres