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    Covalently cross-linked polymers and polymer membranes via sulfinate alkylation
    1.
    发明授权
    Covalently cross-linked polymers and polymer membranes via sulfinate alkylation 失效

    公开(公告)号：US06982303B2

    公开(公告)日：2006-01-03

    申请号：US10173830

    申请日：2002-06-19

    申请人： Jochen Kerres ,  Wei Zhang ,  Chy-Ming Tang ,  Thomas Häring

    发明人： Jochen Kerres ,  Wei Zhang ,  Chy-Ming Tang ,  Thomas Häring

    IPC分类号： C08F283/00 ,  C08G75/00 ,  C08L81/00

    CPC分类号： B01D67/0093 ,  B01D53/228 ,  B01D71/52 ,  B01D71/68 ,  B01D71/82 ,  B01D2323/30 ,  C08G75/00 ,  H01M2/1653 ,  H01M8/1025 ,  H01M8/1027 ,  H01M8/1032 ,  H01M8/1044 ,  H01M8/1051 ,  H01M8/1072 ,  H01M2300/0082 ,  Y02P70/56

    摘要： A covalently cross-linked polymer or polymer membrane consisting of one or more polymers, which can bear the following functional groups (M=Hal(F, Cl, Br, I), OR, NR2; R=alkyl, hydroxyalkyl, aryl; (Me=H, Li, Na, K, Cs, or other metal cations or ammonium ions): a) precursors of cation exchange groups: SO2M and/or POM2 and/or COM b) sulphinate groups SO2Me and which can be covalently cross-linked using the following organic compounds: a) di-, tri- or oligofunctional haloalkanes or haloaromatics, which have been reacted with sulphinate groups SO2Me, whereby the following cross-linking bridges are present in the polymer/in the polymer blend/in the polymer membrane: (Y=cross-linking bridges, X=Hal (F, Cl, Br, I), OR, (CH2)x—; -arylene-; —(CH2)x-arylene-; CH2arylene-CH2—, x=3-12): polymer-SO2Y—SO2-polymer and/or b) compounds containing the following groups: Hal-(CH2)x—NHR, one side of which (Hal-) has been reacted with sulphinate groups SO2ME and the other side (—NHR) with SO2M groups, whereby the following cross-linking bridges are present in the polymer/in the polymer blend/in the polymer membrane: polymer-SO2—(CH2)x—NR—SO2 polymer and/or c) compounds containing the following groups: NHR—(CH2)x—NHR, which have been reacted with sulphinate groups SO2ME, whereby the following cross-linking bridges are present in the polymer/in the polymer blend/in the polymer membrane: polymer-SO2—NR—(CH2)x—NR—SO2-polymer.

    Composites and Composite Membranes
    2.
    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
    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：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。

    Ionically and covalently cross-linked polymers and polymer membranes
    4.
    发明授权
    Ionically and covalently cross-linked polymers and polymer membranes 有权
    离子和共价交联的聚合物和聚合物膜

    公开(公告)号：US06767585B2

    公开(公告)日：2004-07-27

    申请号：US10275854

    申请日：2003-05-12

    申请人： Jochen Kerres ,  Wei Zhang ,  Chy-Ming Tang

    发明人： Jochen Kerres ,  Wei Zhang ,  Chy-Ming Tang

    IPC分类号： B05D302

    CPC分类号： C08F8/44

    摘要： The present invention relates to ionically and covalently cross-linked polymers and polymer membranes having recurrent units of the general formula (1), wherein Q is a link, oxygen, sulfur, (2) or (3) and the R radical is a divalent radical of an aromatic or heteroaromatic compound, and which are characterized in that a) R radical comprises at least partially substituents of general formula (4A), (4B), (4C), (4D), (4E), (4F), (4G) and/or (4H), b) R radical comprises at least partially substituents of the general formula (5A) and/or (5B) and/or the R radical is at least partially a group of the general formula (5C) and/or (5D) and c) the R radical comprises at least partially bridges of the general formula (6) linking at least to R radicals together, R1, R2, R3, R4, R5, M, X, Y, Z and m having the herein-mentioned meanings.

    摘要翻译： 本发明涉及具有通式（1）的复发单元的离子交换和共价交联的聚合物和聚合物膜，其中Q是连接，氧，硫，（2）或（3），R基是二价 芳族或杂芳族化合物的基团，其特征在于a）R自由基至少部分包含通式（4A），（4B），（4C），（4D），（4E），（4F）， （4G）和/或（4H），b）R自由基至少部分包含通式（5A）和/或（5B）的取代基和/或R基团至少部分为通式（5C ）和/或（5D）和c）R基团包含至少部分至少连接至R基团的通式（6）的桥，R 1，R 2，R 3，R 4，R 5，M，X，Y，Z 和m具有这里所述的含义。

    Oligomers and polymers containing sulfonite groups and method for the production thereof
    5.
    发明授权
    Oligomers and polymers containing sulfonite groups and method for the production thereof 有权
    含有亚磺酸基团的低聚物和聚合物及其制备方法

    公开(公告)号：US07202327B2

    公开(公告)日：2007-04-10

    申请号：US10488420

    申请日：2002-09-02

    申请人： Thomas Häring ,  Jochen Kerres ,  Wei Zhang

    发明人： Thomas Häring ,  Jochen Kerres ,  Wei Zhang

    IPC分类号： C08G75/00 ,  C08F28/02 ,  A61K7/06 ,  A61K7/11

    CPC分类号： H01M6/181 ,  C08C19/02 ,  C08F8/04 ,  C08J5/2243 ,  C08J2381/00 ,  H01M8/1023 ,  H01M8/1025 ,  H01M8/1027 ,  H01M8/103 ,  H01M8/1032 ,  H01M8/1039 ,  H01M8/1072 ,  Y02P70/56

    摘要： The invention relates to novel polymers or oligomers containing at least sulfonite groups (P-(SO2)nX, X=1−(n=1), 2−(n=2) or 3−(n=3) valent metal cation or H+ or ammonium ion NR4+ wherein R=alkyl, aryl, H), which are obtained by completely or partially reducing polymers or oligomers containing at least SO2Y-groups (Y=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. 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.

    摘要翻译： 本发明涉及至少含有亚磺酸基团的新型聚合物或低聚物（X-1-（n = 1），2-（ n = 2）或3-（n = 3）价金属阳离子或H +或铵离子NR 4 +其中R =烷基， 芳基，H），其通过完全或部分还原含有至少SO 2 Y-基团（Y = F，Cl，Br，I，OR，NR 2）的聚合物或低聚物而获得， （R =烷基和/或芳基和/或H），N-咪唑基，N-吡唑基），通过合适的还原剂以悬浮液或溶液形式存在。 本发明还涉及聚合物和聚合物（共混物）膜，其通过进一步使得到的硫化聚合物反应而获得，特别是通过亚磺酸基团与单 - 或寡官能亲电体的烷基化。 本发明还涉及用于生产硫化聚合物的方法，以及通过S-烷基化进一步使硫化聚合物与亲电体反应。

    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。