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    Production Of Monomer, Oligomer And Polymer Phosphonic Acid Esters And Phosphonic And Sulphonic Acids By A Nucleophile Aromatic Substitution
    2.
    发明申请
    Production Of Monomer, Oligomer And Polymer Phosphonic Acid Esters And Phosphonic And Sulphonic Acids By A Nucleophile Aromatic Substitution 审中-公开
    通过亲核取代芳基取代单体，低聚物和聚合物膦酸酯和膦酸和磺酸的生产

    公开(公告)号：US20090221787A1

    公开(公告)日：2009-09-03

    申请号：US11995187

    申请日：2006-07-10

    申请人： Thomas Haring ,  Jochen Kerres ,  Martin Hein ,  Frank Schonberger

    发明人： Thomas Haring ,  Jochen Kerres ,  Martin Hein ,  Frank Schonberger

    IPC分类号： C08G75/00 ,  C07C315/00 ,  C07F9/02 ,  C08G73/24

    CPC分类号： B01D71/52 ,  B01D71/66 ,  B01D71/68 ,  C07C303/02 ,  C07C317/22 ,  C07F9/3834 ,  C07F9/404 ,  C08F8/36 ,  C08F8/40 ,  H01M8/1025 ,  H01M8/1027 ,  H01M8/1032 ,  H01M8/1039 ,  H01M2300/0082 ,  Y02P70/56

    摘要： The invention relates to producing monomer, oligomer and polymer non-fluorinated, partially fluorinated or perfluorinated sulphonic acids by reacting halogenated, low-molecular weight, oligomer or macromolecular arenes with (hydrogen) sulphites, dithionites, sulphides or other reducing sulfur salts, possibly by oxidising sulphur-containing arene intermediates which are formed at a sulphur oxidation degree less than +6 by means of appropriate oxidation agents with formation of corresponding sulphonate functional groups (sulphonic acid, sulfohalogenide, sulphonamide and sulphonic acid ester groups). The invention also relates to a method for producing monomer, oligomer or polymer non-halogenated, partially halogenated or perhalogenated phosphonic acid esters and the derivatives thereof (for example, a free phosphonic acid or a phosphonic acid salt) by a nucleophile aromatic substitution (Michaelis-Becker-reaktion, complete or partial substitution of halogenide functional groups by phosphate functional groups (phosphonic acid esters, phosphonic acid amides, phosphonic acids, phosphonic acid salts, phosphonic acid halogenides). Said invention also relates to a method for producing polymer or ionomer non-halogenated, partially halogenated or perhalogenated containing (CF2)xPO(OR)2— or (CF2)xSO2Me- or (CF2)xSO3Me- side chains, (wherein x=1-20, R=any organic radical, Me=any monovalent cation). A method for carrying out a nucleophile polycondensation of said functionalised (i.e. sulphonated, sulphonated or phosphonated) monomers into oligomers or polymers is also disclosed.

    摘要翻译： 本发明涉及通过卤代，低分子量，低​​聚物或大分子芳烃与（氢）亚硫酸盐，连二亚硫酸盐，硫化物或其它还原硫盐反应制备单体，低聚物和聚合物非氟化的，部分氟化的或全氟化的磺酸，可能通过 通过形成相应的磺酸盐官能团（磺酸，磺基卤化物，磺酰胺和磺酸酯基团）的合适的氧化剂，氧化含硫芳烃中间体，它们以小于+6的硫氧化度形成。 本发明还涉及通过亲核试剂芳香取代产生单体，低聚物或聚合物非卤代，部分卤化或全卤代膦酸酯及其衍生物（例如游离膦酸或膦酸盐）的方法（Michaelis - 磷酸酯官能团（膦酸酯，膦酸酰胺，膦酸，膦酸盐，膦酸卤化物）完全或部分取代卤化物官能团的方法本发明还涉及聚合物或离聚物的制备方法 （CF 2）x SO 2 Me-或（CF 2）x SO 3 Me侧链，（其中x = 1-20，R =任何有机基团，Me =任何 还公开了将所述官能化（即磺化，磺化或膦酸化）单体进行亲核物缩聚成低聚物或聚合物的方法。

    Composites and Composite Membranes
    3.
    发明申请
    Composites and Composite Membranes 审中-公开
    复合材料和复合膜

    公开(公告)号：US20100151352A1

    公开(公告)日：2010-06-17

    申请号：US12636323

    申请日：2009-12-11

    申请人： Thomas Haring ,  Vladimir Linkov ,  Jochen Kerres ,  Andreas Ullrich ,  Chy-Ming Tang ,  Martin Hein ,  Wei Zhang

    发明人： Thomas Haring ,  Vladimir Linkov ,  Jochen Kerres ,  Andreas Ullrich ,  Chy-Ming Tang ,  Martin Hein ,  Wei Zhang

    IPC分类号： H01M8/10 ,  C25C7/04 ,  B01D61/42 ,  C08J5/22 ,  B05D3/02 ,  B01D61/36 ,  C02F1/44 ,  B01D61/02 ,  B01D53/22 ,  H01M6/18

    CPC分类号： B01D67/0093 ,  B01D67/0006 ,  B01D67/0011 ,  B01D69/12 ,  B01D69/141 ,  B01D71/00 ,  B01D71/52 ,  B01D71/62 ,  B01D71/82 ,  B01D2323/30 ,  B01D2325/14 ,  C08J5/2275 ,  C08J2379/06 ,  C25B13/08 ,  H01B1/122 ,  H01M8/1025 ,  H01M8/1027 ,  H01M8/103 ,  H01M8/1032 ,  H01M8/1048 ,  H01M8/1051 ,  H01M8/1081 ,  H01M8/1088 ,  H01M10/05 ,  H01M10/0565 ,  Y02P70/56

    摘要： The invention relates to the following types of composite membranes; composites or composite membranes obtained by adding a metal salt, e.g. from ZrOCl2, to a solvent, especially DMSO, for dissolving one or more polymers in an organic solvent or in aqueous systems, in addition to the subsequent precipitation in the matrix of the thus produced composite-membrane by post-treatment thereof in an acid or in a salt solution, especially phosphoric acid. The invention also relates to composites or composite membranes obtained by subsequent ion exchange of finished polymer membranes with a suitable salt cation, especially ZrO2+, wherein the polymer membrane is, optionally, swollen with an organic solvent or a mixture of organic solvent with water prior to the ion exchange and the subsequent precipitation of a low soluble salt, e.g. from Zr3(PO4)4, in the membrane by post-treatment thereof in an acid or in a salt solution, especially phosphoric acid. The invention further relates to composites or composite membranes obtained by adding nano-scaled Zr3(PO4)4 powder to a polymer solution, composites and composite membranes obtained according to the above-mentioned methods, wherein additional heteropoly acids are also incorporated into the polymer or membrane morphology, in addition to methods for producing said inventive polymers and membranes.

    摘要翻译： 本发明涉及以下类型的复合膜; 复合材料或复合膜，通过加入金属盐， 从ZrOCl 2到溶剂，特别是DMSO中，用于将一种或多种聚合物溶解在有机溶剂或水性体系中，以及随后通过在酸中后处理由此制备的复合膜的基质中的沉淀，或 在盐溶液中，特别是磷酸。 本发明还涉及通过随后使用合适的盐阳离子，特别是ZrO 2 +离子交换成品聚合物膜而获得的复合材料或复合膜，其中聚合物膜任选地在有机溶剂或有机溶剂与水的混合物之前在水中溶胀 离子交换和随后的低溶解盐沉淀，例如 通过在酸或盐溶液，特别是磷酸中后处理，从Zr3（PO4）4中除去。 本发明还涉及通过将纳米级Zr 3（PO 4）4粉末加入到根据上述方法获得的聚合物溶液，复合材料和复合膜中而获得的复合材料或复合膜，其中另外的杂多酸也被引入聚合物或 膜形态，以及用于制备所述本发明聚合物和膜的方法。

    Composites and composite membranes
    4.
    发明申请
    Composites and composite membranes 审中-公开
    复合材料和复合膜

    公开(公告)号：US20060231484A1

    公开(公告)日：2006-10-19

    申请号：US10929648

    申请日：2004-08-30

    申请人： Thomas Haring ,  Vladimir Linkov ,  Jochen Kerres ,  Andreas Ullrich ,  Chy-Ming Tang ,  Martin Hein ,  Wei Zhang

    发明人： Thomas Haring ,  Vladimir Linkov ,  Jochen Kerres ,  Andreas Ullrich ,  Chy-Ming Tang ,  Martin Hein ,  Wei Zhang

    IPC分类号： B01D71/06

    CPC分类号： B01D67/0093 ,  B01D67/0006 ,  B01D67/0011 ,  B01D69/12 ,  B01D69/141 ,  B01D71/00 ,  B01D71/52 ,  B01D71/62 ,  B01D71/82 ,  B01D2323/30 ,  B01D2325/14 ,  C08J5/2275 ,  C08J2379/06 ,  C25B13/08 ,  H01B1/122 ,  H01M8/1025 ,  H01M8/1027 ,  H01M8/103 ,  H01M8/1032 ,  H01M8/1048 ,  H01M8/1051 ,  H01M8/1081 ,  H01M8/1088 ,  H01M10/05 ,  H01M10/0565 ,  Y02P70/56

    摘要： The invention relates to the following types of composite membranes; composites or composite membranes obtained by adding a metal salt, e.g. from ZrOCl2, to a solvent, especially DMSO, for dissolving one or more polymers in an organic solvent or in aqueous systems, in addition to the subsequent precipitation in the matrix of the thus produced composite-membrane by post-treatment thereof in an acid or in a salt solution, especially phosphoric acid. The invention also relates to composites or composite membranes obtained by subsequent ion exchange of finished polymer membranes with a suitable salt cation, especially ZrO2+, wherein the polymer membrane is, optionally, swollen with an organic solvent or a mixture of organic solvent with water prior to the ion exchange and the subsequent precipitation of a low soluble salt, e.g. from Zr3 (PO4)4, in the membrane by post-treatment thereof in an acid or in a salt solution, especially phosphoric acid. The invention further relates to composites or composite membranes obtained by adding nano-scaled Zr3(PO4)4 powder to a polymer solution, composites and composite membranes obtained according to the above-mentioned methods, wherein additional heteropoly acids are also incorporated into the polymer or membrane morphology, in addition to methods for producing said inventive polymers and membranes.

    摘要翻译： 本发明涉及以下类型的复合膜; 复合材料或复合膜，通过加入金属盐， 从一种溶剂，特别是DMSO中，将一种或多种聚合物溶解在有机溶剂或水性体系中，除了随后通过如此制备的复合膜的基质沉淀，由 在酸或盐溶液，特别是磷酸中进行后处理。 本发明还涉及通过随后使用合适的盐阳离子离子交换完成的聚合物膜而获得的复合材料或复合膜，特别是ZrO 2 O + 在离子交换之前用有机溶剂或有机溶剂与水的混合物溶胀，随后沉淀低可溶性盐，例如 通过在酸或盐溶液中，特别是磷酸中后处理，从Zr 3（PO 4）4 S 4 。 本发明还涉及通过将纳米级Zr 3（PO 4）4 N 4）粉末添加到聚合物溶液中获得的复合材料或复合膜，复合材料 以及根据上述方法获得的复合膜，其中除了制备所述本发明聚合物和膜的方法之外，还将其它杂多酸掺入聚合物或膜形态中。

    PHOSPHONIC ACID-CONTAINING BLENDS AND PHOSPHONIC ACID-CONTAINING POLYMERS
    6.
    发明申请
    PHOSPHONIC ACID-CONTAINING BLENDS AND PHOSPHONIC ACID-CONTAINING POLYMERS 有权

    公开(公告)号：US20090220843A1

    公开(公告)日：2009-09-03

    申请号：US12278245

    申请日：2007-02-05

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

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

    IPC分类号： H01M8/10 ,  C08J5/22 ,  C09K3/00 ,  H01M10/00 ,  C25B9/00

    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=Hal, 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 —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 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
    7.
    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。