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    PHOSPHONIC ACID-CONTAINING BLENDS AND PHOSPHONIC ACID-CONTAINING POLYMERS
    3.
    发明申请
    PHOSPHONIC ACID-CONTAINING BLENDS AND PHOSPHONIC ACID-CONTAINING POLYMERS 审中-公开

    公开(公告)号：US20140213672A1

    公开(公告)日：2014-07-31

    申请号：US14165456

    申请日：2014-01-27

    申请人： Thomas Häring

    发明人： Thomas Häring ,  Jochen Kerres ,  Frank Schönberger ,  Martin Hein

    IPC分类号： H01M8/10

    CPC分类号： H01M8/1034 ,  B01J39/20 ,  C08G61/02 ,  C08G61/122 ,  C08J5/2287 ,  C08J2341/00 ,  H01M8/1011 ,  H01M8/1023 ,  H01M8/1025 ,  H01M8/1027 ,  H01M8/103 ,  H01M8/1032 ,  H01M8/1039 ,  H01M8/1044 ,  H01M8/1048 ,  H01M8/1072 ,  H01M2008/1095 ,  H01M2300/0082 ,  Y02E60/522 ,  Y02E60/523 ,  Y02P70/56

    摘要： The invention relates to blends and blend membranes from low-molecular hydroxymethylene-oligo-phosphonic acids R—C(PO3H2)x(OH)y and polymers, the group R representing any organic group and the polymers containing the following functional groups: cation exchanger groups or their nonionic precursors of the type SO2X, X═HaI, OH, OMe, NR1R2, OR1 with Me=any metal cation or ammonium cation, R1, R2=H or any aryl- or alkyl group, POX2, COX and/or basic groups such as primary, secondary or tertiary amino groups, imidazole groups, pyridine groups, pyrazole groups etc. and/or OH groups. Low molecular hydroxymethylene-oligo-phosphonic acids R—C(PO3H2)x(OH)y are preferred in which x=2 and y=1. The invention also relates to low-molecular hydroxymethylene-oligo-phosphonic acids R—C(PO3H2)2(OH)1 and polymers, wherein the group R of the hydroxymethylene-oligophosphonic acid contains an aliphatic or aromatic basic group which ionically interacts with the acidic groups of the polymer or of the polymer mixture. The invention further relates to blends and blend membranes from low-molecular hydroxymethylene-oligo-phosphonic acids R—C(PO3H2)2(OH)1 and polymers, wherein the OH groups of the low-molecular hydroxymethylene-1,1-bisphosphonic acid are covalently cross-linked with each other or optionally with OH groups of the polymer. The invention also relates to polymers that are modified with the 1-hydroxymethylene-1,1-bisphosphonic acid group. The polymers are produced by reacting polymers which contain carboxylic acid groups or carboxylic halide groups —COHaI (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 MnO2 or any other oxidant. The invention finally relates to methods for producing the aforementioned materials and to the use of membranes of the aforementioned materials in membrane processes and especially in fuel cells, even at temperatures of >100° C.

    Phosphonic acid-containing blends and phosphonic acid-containing polymers
    4.
    发明授权
    Phosphonic acid-containing blends and phosphonic acid-containing polymers 有权
    含膦酸的共混物和含膦酸的聚合物

    公开(公告)号：US08637174B2

    公开(公告)日：2014-01-28

    申请号：US12278245

    申请日：2007-02-05

    申请人： Thomas Häring ,  Jochen Kerres ,  Frank Schönberger ,  Martin Hein

    发明人： Thomas Häring ,  Jochen Kerres ,  Frank Schönberger ,  Martin Hein

    IPC分类号： H01M8/10

    CPC分类号： H01M8/1034 ,  B01J39/20 ,  C08G61/02 ,  C08G61/122 ,  C08J5/2287 ,  C08J2341/00 ,  H01M8/1011 ,  H01M8/1023 ,  H01M8/1025 ,  H01M8/1027 ,  H01M8/103 ,  H01M8/1032 ,  H01M8/1039 ,  H01M8/1044 ,  H01M8/1048 ,  H01M8/1072 ,  H01M2008/1095 ,  H01M2300/0082 ,  Y02E60/522 ,  Y02E60/523 ,  Y02P70/56

    摘要： Various blends and blend membranes from low-molecular hydroxymethylene-oligo-phosphonic acids R—C(PO3H2)x(OH)y and polymers, the group R representing any organic group, the polymers containing cation exchanger groups or their nonionic precursors of the type SO2X, X being a halogen, OH, OMe, NR1R2, OR1 with Me being any metal cation or ammonium cation, R1, R2 being H or any aryl- or alkyl group, PDX2, 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 —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 MnO2 or another oxidant.

    摘要翻译： 来自低分子羟基亚甲基 - 寡聚膦酸RC（PO 3 H 2）x（OH）y和聚合物的各种共混物和共混膜，R代表任何有机基团，含有阳离子交换剂基团的聚合物或其SO 2 X型非离子前体， X是卤素，OH，OMe，NR1R2，OR1，其中Me是任何金属阳离子或铵阳离子，R1，R2是H或任何芳基或烷基，POX2，COX和/或碱性基团如伯，仲或叔 氨基，咪唑基，吡啶基，吡唑基等和/或OH基。 这样的膜还可以包括用1-羟基亚甲基-1,1-二膦酸基团改性的聚合物。 聚合物可以通过使含有羧酸基团或羧酸卤化物-COHal（Hal = F，Cl，Br，I）的聚合物与亚磷酸酯化合物或通过使聚合醛或聚合酮化合物与亚磷酸酯反应同时进行胺 催化，中间体羟基膦酸与MnO2或另一种氧化剂的氧化。

    CROSS-LINKED HIGH STABLE ANION EXCHANGE BLEND MEMBRANES WITH POLYETHYLENEGLYCOLS AS HYDROPHILIC MEMBRANE PHASE
    6.
    发明申请
    CROSS-LINKED HIGH STABLE ANION EXCHANGE BLEND MEMBRANES WITH POLYETHYLENEGLYCOLS AS HYDROPHILIC MEMBRANE PHASE 审中-公开

    公开(公告)号：US20200023348A1

    公开(公告)日：2020-01-23

    申请号：US16312975

    申请日：2017-06-22

    申请人： Thomas HÄRING ,  between Lizenz GmbH ,  UNIVERSITÄT STUTTGART

    发明人： Jochen KERRES

    IPC分类号： B01J41/13 ,  B01J41/14 ,  C08J5/22 ,  H01M8/1025 ,  C25B13/08 ,  H01M8/1032 ,  H01M8/18 ,  B01D71/28 ,  B01D71/52 ,  B01D71/68 ,  B01D69/02

    摘要： 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).