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    • 3. 发明申请
    • PHOSPHONIC ACID-CONTAINING BLENDS AND PHOSPHONIC ACID-CONTAINING POLYMERS
    • 含膦酸的共混物和含膦酸的聚合物
    • WO2007101415A3
    • 2007-12-21
    • PCT/DE2007000260
    • 2007-02-05
    • UNIV STUTTGART INST FUER CHEMIHAERING THOMASKERRES JOCHENSCHOENBERGER FRANKHEIN MARTIN
    • HAERING THOMASKERRES JOCHENSCHOENBERGER FRANKHEIN MARTIN
    • C08J5/00C08G61/00C08G65/00C08G75/00C08G79/00C08J5/20C08J5/22C08L61/00C08L71/00H01M8/00H01M8/10
    • H01M8/1034B01J39/20C08G61/02C08G61/122C08J5/2287C08J2341/00H01M8/1011H01M8/1023H01M8/1025H01M8/1027H01M8/103H01M8/1032H01M8/1039H01M8/1044H01M8/1048H01M8/1072H01M2008/1095H01M2300/0082Y02E60/522Y02E60/523Y02P70/56
    • The invention relates to blends and blend membranes from low-molecular hydroxymethylene-oligo-phosphonic acids R-C(PO 3 H 2 ) 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 SO 2 X, X = HaI, OH, OMe, NR 1 R 2 , OR 1 with Me = any metal cation or ammonium cation, R 1 , R 2 = H or any aryl- or alkyl group, POX 2 , 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(PO 3 H 2 ) 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(PO 3 H 2 ) 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(PO 3 H 2 ) 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 MnO 2 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.
    • 在本发明中,将以下材料都声称:1.共混物和共混物的低分子量的羟基亚甲基的膜低聚膦酸RC(PO 3 ħ 2 )×(OH)ÿ< / SUB>和的聚合物,其中R是任何有机基团和所述聚合物包含以下的官能团:阳离子交换基团或类型的它们的非离子母体SO 2 X,X =哈尔,OH,OME,NO 1 - [R 2 1 我=任何金属阳离子或铵阳离子,R 1 ,R 2 = H或任何的芳基或烷基,POX 2 ,COX和/或碱性基团,例如伯,仲或叔氨基,咪唑基,吡啶基,吡唑等,和/或OH基团 , 这里将低分子量羟基亚低聚膦酸RC(PO 3 ħ 2 )×(OH)ý是优选的,其中x = 2和y = 1。 2.共混物和共混物的低分子量的羟基亚甲基的膜低聚膦酸RC(PO 3 ħ 2 2 (OH) 1 和聚合物,其中所述羟基亚甲基的基团ROligophosphonsäure包含其经历与聚合物或聚合物共混物的酸性基团的离子相互作用的脂族或芳族碱性部分。 3.共混物和共混物的低分子量的羟基亚甲基的膜低聚膦酸RC(PO 3 ħ 2 2 (OH) 1 和聚合物,其中,低分子1-羟基亚甲基-1,1-二膦酸的OH基团被交联彼此并任选地与该聚合物的OH基团共价结合。 4.用1-羟基亚甲基-1,1-二膦酸改性的聚合物,它们是由含羧酸基团或羧酸卤基团-COHal(HAL = F,氯,溴,I)的聚合物的反应制备,其中亚磷酸酯化合物或通过反应 聚合醛或与下胺催化亚磷酸,中间Hydroxyphosphonsäure的氧化与MnO的 2 或其他氧化剂聚合酮基化合物。 还要求保护的方法用于上述材料的制备和使用上述材料中的膜分离过程的膜,特别是在燃料电池中,甚至在> 100℃的温度下
    • 7. 发明申请
    • POLYMERS AND POLYMER MEMBRANES COVALENTLY CROSS-LINKED BY SULPHINATE ALKYLATION
    • 共价交联聚合物和聚合物膜材料VIA SULFINATALKYLIERUNG
    • WO0200773A9
    • 2003-02-13
    • PCT/EP0105826
    • 2001-05-21
    • UNIV STUTTGARTKERRES JOCHENZHANG WEITANG CHY-MINGHAERING THOMAS
    • KERRES JOCHENZHANG WEITANG CHY-MINGHAERING THOMAS
    • B01D53/22B01D61/02B01D61/24B01D61/36B01D61/42B01D67/00B01D71/52B01D71/66B01D71/68B01D71/82C08G75/00C08G81/00C08J5/18C08L87/00C25B13/08H01M2/16H01M8/02H01M8/10H01M10/052H01M10/0565C08J5/22B01D71/06H01B1/12
    • B01D67/0093B01D53/228B01D71/52B01D71/68B01D71/82B01D2323/30C08G75/00H01M2/1653H01M8/1025H01M8/1027H01M8/1032H01M8/1044H01M8/1072H01M8/1081H01M8/1086H01M10/052H01M10/0565H01M2300/0082Y02P70/56
    • The invention relates to 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, Y=(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.
    • 共价交联的聚合物或共价交联的聚合物膜由一种或多种聚合物,其可以携带下列的官能团(M =哈尔(F,氯,溴,I),OR,NR 2; R =烷基,羟烷基,芳基(ME = H,锂,钠,钾,铯,或其它金属阳离子或铵离子);一)阳离子交换基团的前体:SO 2 M和/或POM2和/或COM; b)中的亚磺酸SO2Me,并且其可通过以下的有机化合物的装置被共价交联的:1)二,三或寡官能的卤代烷烃或芳族卤素化合物,已被接触用亚磺酸盐SO2Me到反应中,其中聚合物/聚合物共混物/聚合物膜下面的交联桥本 (Y =交联桥,X =哈尔(F,氯,溴,I),OR,Y = - (CH 2)x - ;亚芳基, - (CH 2)x - 亚芳基; CH2Arylen-CH 2 - ,X = 3-12):聚合物-SO2-Y-SO 2 - 聚合物和/或b)包含以下基团的化合物:Hal-(CH 2)x-NHR,其中(在一侧Hal-)与亚磺酸盐反应SO2Me 过,并且在另一侧(-NHR)与SO 2 M基团,其是存在于聚合物/聚合物共混物/在以下的交联桥的聚合物膜:聚合物-SO 2 - (CH 2)x-NR-SO2-聚合物和/或c )包含以下基团的化合物:NHR(CH 2)x-NHR,已被接触用SO2Me基团进行反应,由此,聚合物/在POLYM erblend /在聚合物膜的交联以下桥都存在:聚合物-SO 2 NR-(CH 2)x-NR-SO2-聚合物。
    • 10. 发明申请
    • COVALENTLY CROSS-LINKED COMPOSITE MEMBRANES
    • 共价交联的复合膜
    • WO03050169A3
    • 2003-08-21
    • PCT/DE0204173
    • 2002-11-04
    • HAERING THOMAS
    • HAERING THOMAS
    • C08J5/22B01D71/68H01M8/02H01M8/10
    • C08J5/2275C08J2371/12C08J2381/06
    • The invention relates to a covalently cross-linked composite and a covalently cross-linked composite polymer membrane consisting of at least one polymer and tectosilicates and/or phyllosilicates. Said tectosilicates and/or phyllosilicates can be both functionalised or non-functionalised. The polymers are characterised in that they can carry 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 exchanger groups SO2M and/or POM2 and/or COM, and b) sulfinate groups SO2Me; and can be covalently cross-linked by means of the following organic compounds: a) difunctional, trifunctional or oligofunctional haloalkanes or haloaromatics which have been reacted with the sulfinate 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, Y=-(CH2)x-; -arylene-; -(CH2)x-arylene-; CH2-arylene-CH2-, x=3-12): polymer-SO2-Y-SO2-polymer; and/or b) compounds containing the groups Hal-(CH2)x-NHR, one side (Hal-) thereof having been reacted with sulfinate groups SO2Me, and the other side (-NHR) having been reacted with SO2Me groups, whereby the following cross-linking bridges are present in the polymer/in the polymer mixture/in the polymer membrane: polymer-SO2-(CH2)x-NR-SO2-polymer; and/or c) compounds containing the groups NHR-(CH2)x-NHR which have been reacted with the SO2Me groups, whereby the following cross-linking bridges are present in the polymer/in the polymer mixture/in the polymer membrane: polymer-SO2-NR-(CH2)x-NR-SO2-polymer.
    • 本发明涉及共价交联的复合材料和包括一种或多种聚合物和支架共价交联的复合聚合物膜,和/或层状硅酸盐。 脚手架和/或层状硅酸盐既可以官能化和本发明的非官能化。 该聚合物的特征在于它们可以携带以下的官能团(M =哈尔(F,氯,溴,I),OR,NR 2; R =烷基,羟烷基,芳基(ME = H,锂,钠,钾 ,铯或其它金属阳离子或铵离子):三 - 一)二 - 或寡官能的卤代烷或卤代芳族:1)阳离子交换基团的前体:SO 2 M和/或POM2和/或COM b)亚磺酸盐SO2Me,并且其可通过以下的有机化合物的装置被共价交联 这已经带来了与亚磺酸盐SO2Me到反应中,从而存在于聚合物/聚合物共混物/聚合物膜下面的交联桥(Y =交联桥,X =哈尔(F,氯,溴,I),OR,Y = - (CH 2 )×;亚芳基 - (CH 2)X - 亚芳基; CH2-CH2-亚芳基,X = 3-12); 聚合物-SO2-Y-SO 2 - 聚合物和/或b)包含以下基团的化合物:Hal-(CH 2)x-NHR,其中(在一侧Hal-)与亚磺酸盐SO2Me到反应反应,和 的另一侧(-NHR)与SO2Me基团,由此,下面的交联桥存在于聚合物/聚合物共混物/聚合物膜:聚合物-SO 2 - (CH 2)x-NR-SO2-聚合物和/或c)的化合物,以下 包含基团:NHR(CH 2)x-NHR,已被接触用SO2Me基团进行反应,从而使下述的交联桥存在于聚合物/聚合物共混物/聚合物膜:聚合物-SO 2 NR-(CH 2)x NR -SO 2聚合物。