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    PROTONENLEITENDE KERAMIK-POLYMER-KOMPOSITMEMBRAN FÜR DEN TEMPERATURBEREICH BIS 300 oC
    2.
    发明授权
    PROTONENLEITENDE KERAMIK-POLYMER-KOMPOSITMEMBRAN FÜR DEN TEMPERATURBEREICH BIS 300 oC 有权
    质子传导陶瓷聚合物复合材料用于温度范围高达300摄氏度

    公开(公告)号：EP1181327B1

    公开(公告)日：2010-02-24

    申请号：EP00925253.7

    申请日：2000-05-02

    申请人： Häring, Thomas ,  Häring, Rima

    发明人： KERRES, Jochen ,  NICOLOSO, Norbert ,  SCHÄFER, Günther

    IPC分类号： C08J5/22 ,  B01D69/12

    CPC分类号： B82Y30/00 ,  B01D69/141 ,  B01J31/0244 ,  B01J31/06 ,  B01J31/08 ,  B01J35/065 ,  C08J5/2275 ,  C08J2371/12 ,  C08K9/02 ,  C08K2201/011 ,  H01M2/166 ,  H01M8/04197 ,  H01M8/1011 ,  H01M8/1025 ,  H01M8/1027 ,  H01M8/1032 ,  H01M8/1048 ,  H01M8/1067 ,  H01M8/1081 ,  H01M2300/0068 ,  H01M2300/0082 ,  H01M2300/0091 ,  Y02E60/523 ,  Y02P70/56

    摘要： The invention relates to a composite membrane that consists of organic functional polymers and ceramic nanoparticles (1 - 100 nm), except for phyllosilicates and tectosilicates, with intercalating water and/or a high surface concentration in acidic/alkaline groups (for example hydroxyl) and water. The use of such particles allows a sufficiently high mechanical stability of the composite material and a stabilization of the proton concentration in the membrane that is necessary for the conductivity up to an operating temperature of 300 °C. The inventive composite material is characterized by the interfaces that are formed in the microheterogeneous mixture between the polymer and the ceramic powder. Said interfaces, if formed in a sufficiently high quantity (high phase share of nanoscale particles) allow a transport of the protons at a low pressure and at temperatures of more than 100 °C. If the polymer/ceramic particle boundary layer is modified by means of boundary groups that have different polarities, preferably at the polymer skeleton, the local establishment of equilibrium and thus the binding strength of the proton charge carriers is influenced. This effect can be used, for example for alcohol/water mixtures as a fuel, to reduce the MeOH passage (Me = CH3, C2H5, C3H7, ...) across the membrane, which is especially important for the development of efficient direct methanol fuel cells. In addition to its use in fuel cells, the inventive membrane can also be used in the field of energy and process technology, in which water vapor is produced or required in addition to electric current or in which (electro)chemically catalyzed reactions are carried out at increased temperatures at a pressure that ranges from the atmospheric pressure to elevated working pressures or that are carried out in a water vapor atmosphere. The invention further relates to a method for producing and processing such a composite membrane.

    MODIFIZIERTES POLYMER UND MODIFIZIERTE POLYMERMEMBRAN
    3.
    发明授权
    MODIFIZIERTES POLYMER UND MODIFIZIERTE POLYMERMEMBRAN 有权
    改性聚合物和改性聚合物膜

    公开(公告)号：EP1076674B1

    公开(公告)日：2010-06-02

    申请号：EP99927652.0

    申请日：1999-03-26

    申请人： Häring, Thomas ,  Häring, Rima

    发明人： KERRES, Jochen ,  CUI, Wei

    IPC分类号： C08G65/48 ,  C08L71/00 ,  B01D71/82 ,  B01D71/68 ,  H01M8/02 ,  H01M8/10

    CPC分类号： H01M8/1044 ,  B01D71/52 ,  B01D71/66 ,  B01D71/68 ,  C08G61/12 ,  C08G65/48 ,  C08G75/0295 ,  C08G75/20 ,  C08G75/23 ,  C08J5/2256 ,  C08J2381/02 ,  C08J2381/06 ,  C08L81/02 ,  C08L81/06 ,  H01M8/1023 ,  H01M8/1025 ,  H01M8/1027 ,  H01M8/1032 ,  Y02P70/56

    摘要： The invention relates to a method for producing nitrated and optionally sulphonated and aminated and optionally sulphonated aryl main chain polymers, in addition to aryl main chain polymers thus modified. Aryl main chain polymers (e.g. (1)) are nitrated by dissolving them in expensive, toxic and environmentally damaging solvents. Aryl main chain polymers which are selectively and simultaneously nitrated and sulphonated were not previously known in literature. The inventive method makes it possible to produce low-cost nitrated (and optionally sulphonated (2)) or post-reduction aminated (and optionally sulphonated) aryl main chain polymers without any organic solvents. Nitration (and optionally additional sulphonation) of the aryl main chain polymers occurs by dissolving them in concentrated sulphuric acid and by adding desired amounts of nitric acid at different temperatures and with different agitating times. The reaction can be carried out (a) as a two-step process: nitration followed by isolation of the polymer, then optional sulphonation and (b) as a single-step process: simultaneous nitration and sulphonation (2). The nitrated (or additionally sulphonated) polymers can then be reduced to form aminated (or additionally sulphonated) polymer. The polymers can be reacted with other polymers to form polymer blends. The polymers and polymer blends can be used as ion conducting membranes in electro membrane processes.

    KOMPOSITE UND KOMPOSITMEMBRANEN
    4.
    发明授权
    KOMPOSITE UND KOMPOSITMEMBRANEN 有权

    公开(公告)号：EP1177247B1

    公开(公告)日：2007-08-01

    申请号：EP00934975.4

    申请日：2000-05-02

    申请人： Häring, Thomas ,  Häring, Rima

    发明人： KERRES, Jochen ,  HÄRING, Thomas ,  HÄRING, Rima

    IPC分类号： C08J5/22 ,  B01D69/12

    CPC分类号： B01D67/0041 ,  B01D69/141 ,  B01D71/00 ,  B01D71/024 ,  B01D71/62 ,  B01D71/68 ,  B01D2325/18 ,  B01D2325/26 ,  B01J21/16 ,  B01J31/10 ,  B01J31/1633 ,  B01J35/065 ,  C08J5/2275 ,  C08J2383/02 ,  H01M8/0289 ,  H01M8/1023 ,  H01M8/103 ,  H01M8/1032 ,  H01M8/1051 ,  H01M8/1081 ,  Y02E60/523 ,  Y02P70/56 ,  Y10T428/249953 ,  Y10T428/249969

    摘要： 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 exchanger polymer; (b) an anion exchanger polymer; (c) a polymer containing both anion exchanger groupings as well as cation exchanger groupings on the polymer chain; (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 of the phyllosilicates or tectosilicates. The use of bentonites and zeolites are generally preferred in special montomorillonite. The mixture ratio isomer:bentonite ranges from 99:1 to 30:70. The invention also relates to the application of the composites/composite membranes: as proton conductors in membrane fuel cells (H2 fuel cells PEFC, direct methanol fuel cells DMFC) at temperatures greater than 100 °C; in (electro)membrane separation methods such as dialysis, diffusion dialysis, gas separation, pervaporation, perstraction and in microfiltration and ultrafiltration, particularly due to their antifouling properties, and; as catalytic membranes in catalytic membrane reactors.

    摘要翻译： 热稳定的质子传导复合材料包含酸和/或有机碱和层状/骨架硅酸盐。 质子传导复合材料包含1-99重量％的酸和/或有机碱和99-1重量％的层状/骨架硅酸盐，并且在高达400℃下是热稳定的。 还包括以下独立权利要求：（i）通过将如下定义的离聚物（前体）的溶液与层状和/或骨架硅酸盐混合并蒸发溶剂来生产复合材料和复合共混膜; 和（ii）用于膜和膜分离方法得到的离子非导电复合材料和由20-98重量％的下述碱性聚合物和2-80重量％的层状/骨架硅酸盐获得的复合共混膜。

    PHOSPHONSÄURE-HALTIGE BLENDS UND PHOSPHONSÄURE-HALTIGE POLYMERE
    7.
    发明公开
    PHOSPHONSÄURE-HALTIGE BLENDS UND PHOSPHONSÄURE-HALTIGE POLYMERE 审中-公开
    PHOSPHONSUREURE HALTIGE聚合物中的PHOSPHONSUREURE HALTIGE BLENDS

    公开(公告)号：EP1984430A2

    公开(公告)日：2008-10-29

    申请号：EP07711177.1

    申请日：2007-02-05

    申请人： Universität Stuttgart - Institut für Chemische Verfahrenstechnik ,  Häring, Thomas

    发明人： HÄRING, Thomas ,  KERRES, Jochen ,  SCHÖNBERGER, Frank ,  HEIN, Martin

    IPC分类号： C08J5/00 ,  C08J5/20 ,  C08J5/22 ,  C08L61/00 ,  C08L71/00 ,  H01M8/00 ,  H01M8/10 ,  C08G61/00 ,  C08G65/00 ,  C08G75/00 ,  C08G79/00

    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 = 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 -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.

    摘要翻译： 由羟基亚甲基 - 寡聚膦酸RC（PO 3 H 2）x（OH）y和基团R是任何有机基团x和y的聚合物形成的共混物或混合膜是整数，羟基亚甲基 - 低聚 - 膦酸 是涉及碳酸，碳酸卤化物或碳酸酐的反应的产物，并且所述聚合物包括选自（i）适合的阳离子交换基团或其非离子前体的官能团，和（ii ）适合的基本组。