CN102686621A - 可固化组合物和膜 - Google Patents
可固化组合物和膜 Download PDFInfo
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- CN102686621A CN102686621A CN2010800568823A CN201080056882A CN102686621A CN 102686621 A CN102686621 A CN 102686621A CN 2010800568823 A CN2010800568823 A CN 2010800568823A CN 201080056882 A CN201080056882 A CN 201080056882A CN 102686621 A CN102686621 A CN 102686621A
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- MFPWEWYKQYMWRO-UHFFFAOYSA-N tert-butyl carboxy carbonate Chemical compound CC(C)(C)OC(=O)OC(O)=O MFPWEWYKQYMWRO-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
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- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- LMRVIBGXKPAZLP-UHFFFAOYSA-N trimethyl-[2-methyl-2-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(C)(C)NC(=O)C=C LMRVIBGXKPAZLP-UHFFFAOYSA-N 0.000 description 1
- GHVWODLSARFZKM-UHFFFAOYSA-N trimethyl-[3-methyl-3-(prop-2-enoylamino)butyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCC(C)(C)NC(=O)C=C GHVWODLSARFZKM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Abstract
一种可固化组合物,包含:(i)2.5-50wt%的包含至少两个丙烯酰胺基团的交联剂;(ii)12-65wt%的包含烯键式不饱和基团和阳离子基团的可固化离子化合物;(iii)10-70wt%的溶剂;(iv)0-10wt%的自由基引发剂;以及(v)非固化盐;其中,(i)与(ii)的摩尔比>0.10。该组合物用于制备离子交换膜。
Description
技术领域
本发明涉及可固化组合物、它们在膜制备中的应用以及这种膜在离子交换工艺中的应用。
背景技术
离子交换膜用于许多应用,包括在例如流过式电容器(FTC)中用于净化水的电去离子(EDI)、连续电去离子(CEDI)、电渗析(ED)、反向电渗析(EDR)和电容去离子;用于例如氟化物去除或酸回收的唐南(Donnan)或扩散渗析(DD);用于有机溶剂脱水的渗透蒸发;燃料电池;水电解(EL)或用于氯碱生产;以及其中通过离子渗透膜将两股盐浓度不同的液流分开来发电的逆电渗析(RED)。
电去离子(EDI)是其中采用膜及电势影响离子迁移而从含水液体中除去离子的水处理工艺。其与诸如常规离子交换的其他净水技术的不同之处在于其不需要使用诸如酸或苛性钠的化学物质。EDI可以用于生产超纯水。
电渗析(ED)和反向电渗析(EDR)是从水和其他流体中除去离子和其他带电物质的电化学分离工艺。ED和EDR采用少量电运送这些物质通过由离子交换材料组成的膜从而产生分离的纯化液流和浓缩液流。借助直流电(DC)电压使离子穿过膜转移,由于电流驱使离子穿过膜以除去待处理的液流中的盐分,因此离子被从供给流体中去除。ED和EDR是适合用于生产饮用水的技术。离子交换膜还用于零排放脱盐技术(ZDD)。
膜电极组件(MEA)适用于多种应用,诸如电解、传感器,尤其是燃料电池。
流过式电容器(FTC)是采用带电碳电极除去离子而不使用化学物质的减少总溶解固体(TDS)的有效装置。
离子交换膜的生产中的一个重要问题是如何提供具有最小缺陷的薄膜。期望的是,膜具有良好的选择渗透性和低电阻。另外,期望膜具有强度,同时具有柔韧性。柔韧性是用于缠绕成紧密圆周结构的膜所必需的。膜还需要在较长时间内保持其物理完整性。期望的是,用于制备膜的方法不会导致过多卷曲。还期望膜能够耐受它们可能接触到的化学物质,例如,抗水解性。
膜使用者要求获得最低价格,这意味着用于膜的生产工艺是理论上便宜的并且膜应当能够很容易地进行大量生产。
US 5,037,858描述了由高pH的N,N’-亚甲基双丙烯酰胺的浓溶液制备阴离子选择性膜。在实施例1中使用的组合物的pH为约13.5并且该组合物不包含非固化盐。
US 2004/0203149描述了包含支撑性大孔凝胶的复合材料。在实施例1中,使包括交联剂(N,N’-亚甲基双丙烯酰胺交联剂)、可固化离子化合物((3-丙烯酰胺丙基)三甲基氯化铵)、溶剂和光引发剂的组合物交联以形成大孔凝胶。该凝胶被描述为机械性能极弱。该组合物不包含非固化盐。
发明内容
除了用于制备膜的快速工艺和通过该工艺制备的膜,以及这些膜的应用外,本发明还致力于提供适合用于制备膜的组合物。
根据本发明的第一方面,提供了可固化组合物,包括:
(i)2.5-50wt%的包含至少两个丙烯酰胺基团的交联剂;
(ii)12-65wt%的包含烯键式不饱和基团和阳离子基团的可固化离子化合物;以及
(iii)10-70wt%的溶剂;
(iv)0-10wt%的自由基引发剂;以及
(v)非固化盐;
其中,(i)与(ii)的摩尔比>0.10。
本发明的组合物具有良好的贮存稳定性,而且由此生产的膜还具有良好的选择渗透性和抗水解性,甚至是在碱性条件下。这种贮存稳定性尤其适用于膜的连续生产,其中组合物的大储存罐可以处于生产线上一段时间,或处于等待替换几乎耗尽了的罐的储存状态。此外,该组合物不易于腐蚀膜生产设备,诸如罐和管道。许多膜的破裂强度也很好。
在一个实施方案中,组合物的pH为1-12,更优选1.5-11,尤其为2-10,更尤其为3-9,特别是4-8,例如4-5或5-7。在另一实施方案中,组合物的pH不为1-12。
在一个实施方案中,组合物不包含自由基引发剂,或还包含0.005-10wt%的光引发剂。
交联剂优选以3-45wt%、更优选4-35wt%、尤其是5-25wt%或5-35wt%的量存在于组合物中。相对高的交联剂含量通常导致高选择渗透性并具有高电阻,而对于相对低的交联剂含量来说,形成的膜结构更开阔,导致稍微降低的选择渗透性。相对低的交联剂含量容许更高含量的可固化离子化合物和更高的溶胀度,这两者都可以用于获得具有低电阻的膜。根据得到的膜的所需性质(其反过来取决于膜的预期应用),选择交联剂与可固化离子化合物的比例。
当期望膜具有低电阻时,组合物中所用的可固化离子单体的量优选为高,而为了容纳较高量的可固化离子单体,则要降低交联剂的量。因而,为了制备具有低电阻的膜,优选的交联剂含量为4-20wt%,更优选6-18wt%,尤其是7-15wt%,更尤其是约10wt%。采用该量的交联剂,仍可以获得具有良好选择渗透性而不会过度溶胀的适当强度的膜。当期望膜具有极高选择渗透性时,通常在组合物中选择较高的交联剂的量,优选以8-48wt%,更优选10-35wt%,例如12-30wt%的量存在。
交联剂优选具有两个或三个丙烯酰胺基团,更优选两个丙烯酰胺基团。
交联剂的分子量优选满足方程式:
(Y×m)>交联剂的分子量
其中,m是交联剂中丙烯酰胺基团的个数;以及
Y是120,优选105,更优选90,尤其优选85或77。
优选上述Y的较低值,因为得到的交联剂比Y较大时更有效地交联。此外,具有上述Y的较低值的交联剂具有较低的分子量,为较高量的可固化离子化合物留下空间,从而在相同程度的交联和选择渗透性的情况下达到更低的电阻。
交联剂优选具有分子式(1):
其中:
R1和R2每一个独立地是H或甲基;
R3和R4每一个独立地是H、烷基,R3和R4与它们所连接的N基团以及Y一起形成任意取代的6元环或7元环;以及
Y是任意取代和任意间隔的亚烃基基团。
当R3或R4是烷基时,优选是C1-4-烷基。
当R3和R4与它们所连接的N基团以及Y一起形成任意取代的6元环或7元环时,它们优选形成哌嗪环、高哌嗪环或三嗪环。
可以在Y中出现的任意间隔优选是醚基基团,或者更优选是氨基基团。Y优选具有式-(CnH2n)-,其中n是1、2或3。
作为合适的交联剂的实例,可以是:N,N’-亚甲基双(甲基)丙烯酰胺、N,N’-亚乙基双(甲基)丙烯酰胺、N,N’-亚丙基双(甲基)丙烯酰胺、N,N’-亚丁基双(甲基)丙烯酰胺、N,N’-(1,2-二羟基亚乙基)双(甲基)丙烯酰胺、1,4-二丙烯酰基哌嗪(1,4-diacryoyl piperazine)、1,4-双(丙烯酰基)高哌嗪、三丙烯酰基-三(2-氨基乙基)胺、三丙烯酰基二亚乙基三胺、四丙烯酰基三亚乙基四胺、1,3,5-三丙烯酰基六氢-1,3,5-三嗪和/或1,3,5-三甲基丙烯酰基六氢-1,3,5-三嗪。术语“(甲基)”是缩写,意为“甲基”是可选的,例如N,N’-亚甲基双(甲基)丙烯酰胺是N,N’-亚甲基双丙烯酰胺和N,N’-亚甲基双甲基丙烯酰胺的缩写。
更优选地,R3和R4都是H,并且Y是任意取代的C1-3-亚烃基基团或任意取代的-(C1-3-亚烃基-N(R5)-C1-3-亚烃基)-基团,其中R5是H或C1-4-烷基。尤其优选的交联剂是N,N’-亚甲基双(甲基)丙烯酰胺、N,N’-亚乙基双(甲基)丙烯酰胺、N,N’-亚丙基双(甲基)丙烯酰胺、N,N’-(1,2-二羟基亚乙基)双(甲基)丙烯酰胺、三丙烯酰基-三(2-氨基乙基)胺和三丙烯酰基二亚乙基三胺。
组合物中存在的非固化盐有助于溶解溶解性差的交联剂并且提供出乎意料稳定的组合物,即使是对于诸如N,N’-亚甲基双(甲基)丙烯酰胺的溶解性差的交联剂。
非固化盐可以是在用于使组合物固化的条件下不能与交联剂形成共价键的任何盐。通常,非固化盐包含由酸(尤其是无机酸)衍生的阴离子基团和阳离子基团(尤其是无机阳离子基团)。非固化盐在25℃水中的溶解度优选是至少250g/L,更优选是至少400g/L。优选的非固化盐是无机盐,例如锂、钠、钾、铵、镁和钙的无机盐以及包含这些盐中的两种或两种以上的混合物。
在一个实施方案中,可固化组合物不包含锂盐和钙盐。在另一实施方案中,可固化组合物包含锂盐和/或钙盐。
优选的非固化盐包括氯化锂、溴化锂、硝酸锂、碘化锂、氯酸锂、硫氰酸锂、高氯酸锂、四氟硼酸锂、六氟磷酸锂、六氟砷酸锂、硫氰酸铵、氯化铵、碘化铵、硝酸铵、氯化钠、溴化钠、硝酸钠、硫氰酸钠、硝酸钙、硫氰酸钙、溴化钙、氯酸钙、高氯酸钙、碘化钙、四氟硼酸钙、六氟磷酸钙、六氟砷酸钙、氯化镁、溴化镁、硝酸镁、硫氰酸镁、硫氰酸钾、氯酸钾,以及包含这些盐中的两种或两种以上的混合物。更优选是氯化锂、溴化锂、硝酸锂、硝酸铵、硝酸钠、硝酸钙以及包含这些盐中的两种或更多种的混合物。
非固化盐优选包含离液序列高的阴离子(即,弱水合阴离子),而阳离子优选是“结构生成”的(kosmotropic)。优选的离液序列高的阴离子是霍夫迈斯特序(Hofmeister series)中排序低的那些,霍夫迈斯特序可以通过实验方法按照从包含珠状形式的环氧氯丙烷交联葡聚糖凝胶(例如G-10)的填充柱洗脱的速率的顺序来确定,如J.Biol.Chem.,261,12477-12485(1986)中详细描述的。优选的离液序列高的阴离子是洗脱慢于或等于氯化物的那些,例如硫氰酸盐、氯酸盐、高氯酸盐、亚氯酸盐、碘化物、溴化物、硝酸盐、氯化物和亚硝酸盐。阴离子优选不是硫酸盐、亚硫酸盐、磷酸盐和氟化物。
非固化盐优选具有相对低的分子量,例如低于200,更优选低于150,尤其是低于110,更尤其是低于90,甚至更尤其是低于70。当计算非固化盐的分子量时,不考虑任何结晶水(当存在时)。
可固化组合物优选包含2-50wt%、更优选2-30wt%的非固化盐。因而在优选的实施方案中,组合物包含上面指定份数的(i)、(iii)和(iv)、20-65wt%的组分(ii)和2-30wt%的组分(v)。
在许多情况下,组合物中非固化盐的存在还可以改进由其制造的膜的选择渗透性。当交联剂在溶剂中具有低溶解度(例如,溶解度小于2wt%)时,组合物优选以3-40wt%、更优选4-30wt%、尤其是7-25wt%(例如约10wt%或15-35wt%)的量包含非固化盐。优选的量在一定程度上取决于非固化盐的分子量和组合物中存在的交联剂的量。
优选地,作为非固化盐的一部分的阳离子的摩尔数与组合物(包括交联剂和任选的其他可固化单体)中(甲基)丙烯酰胺键的总摩尔数的比率是0.3-1.1,更优选0.4-1.05,尤其是0.7-1.02,例如是约0.9。令人惊奇的是,即使当交联剂在溶剂中具有良好的溶解性时,非固化盐的存在也可以给组合物带来优势,例如,改进的选择渗透性和更结实的膜。
优选地,交联剂在20℃下的10wt%的LiNO3水溶液中的溶解度为至少2wt%。
可固化离子化合物优选以20-65wt%或25-65wt%、更优选35-60wt%、尤其是40-57wt%、更尤其是45-55wt%的量存在于组合物中。一般地,可固化离子化合物的量尽可能高以尽量增大膜中的电荷密度。
组分(i)与组分(ii)的摩尔比优选是至少0.15,更优选至少0.2,尤其至少0.25。在一个实施方案中,组分(i)与组分(ii)的摩尔比优选小于5.0,更优选小于4.0,尤其小于1.5,更尤其小于1.0。在另一实施方案中,组分(i)与组分(ii)的摩尔比优选小于1.5,更优选小于1.0,尤其小于0.7,更尤其小于0.5。优选的可固化离子化合物包含季铵基团。这些化合物的实例包括(3-丙烯酰胺基丙基)三甲基氯化铵、(3-甲基丙烯酰胺基丙基)三甲基氯化铵、苄乙基三甲基氯化铵、(2-(甲基丙烯酰氧基)乙基)三甲基氯化铵、[3-(甲基丙烯酰基氨基)丙基]三甲基氯化铵、(2-丙烯酰胺基-2-甲基丙基)三甲基氯化铵、3-丙烯酰胺基-3-甲基丁基三甲基氯化铵、丙烯酰基氨基-2-羟基丙基三甲基氯化铵、N-(2-氨基乙基)丙烯酰胺三甲基氯化铵及包含其中两种或两种以上的混合物。
当交联剂在20℃的10wt%的LiNO3水溶液中的溶解度小于2wt%时,组分(i)和组分(ii)相对于组合物总重量的总重量分数(wt%)优选为30-90wt%,更优选30-88wt%或30-90wt%,尤其是35-80wt%,更尤其是40-80wt%,例如约50wt%或约55wt%。
当交联剂在20℃的10wt%的LiNO3水溶液中的溶解度是至少2wt%时,组分(i)和组分(ii)的总wt%优选是40-85wt%,更优选是45-80wt%,尤其是55-80wt%,例如约60wt%或约65wt%。如果想要避免膜溶胀和较低的选择渗透性,组分(i)和组分(ii)的总wt%优选大于30wt%。
可固化组合物可以包含一种或一种以上的作为组分(i)的交联剂。在这种情况下,上述溶解度是指整个交联剂混合物的溶解度。在特别优选的实施方案中,组分(i)由(一种或多种)具有两个丙烯酰胺基团的交联剂组成,组分(ii)由(一种或多种)具有一个烯键式不饱和基团和一个或多个阳离子基团的可固化离子化合物组成。优选地,组分(ii)中的烯键式不饱和基团是(甲基)丙烯酰胺基团,因为这可以使膜具有特别良好的抗水解性。最优选的可固化离子化合物是3-丙烯酰胺基丙基三甲基氯化铵。
通常,组分(i)为膜提供耐溶胀性,而潜在地降低柔韧性。
当组分(ii)仅具有一个烯键式不饱和基团(例如,一个H2C=CHCON<基团)时,它不能够交联。但是,它能够与组分(i)反应。仅具有一个烯键式不饱和基团的组分(ii)可以为最终得到的膜提供所需的柔韧度,其特别适用于需要紧密缠绕的膜的应用。组分(ii)还通过提供阳离子基团帮助膜将带不同电荷的离子区分开。
在一个实施方案中,组合物包含小于10wt%、更优选小于5wt%的除了组分(i)和(ii)以外的烯键式不饱和化合物。在优选的实施方案中,组合物不包含除了组分(i)和(ii)以外的烯键式不饱和化合物。
组合物的溶剂含量优选是实现均相溶液形式的组合物所必需的最小值,或者比最小值大5%以下,但是同时溶剂含量至少是15wt%。
优选极性溶剂,尤其是含水溶剂,因为这些溶剂特别适合溶解可固化离子化合物。优选地,至少一半的溶剂是水,其余包含有机溶剂。有机溶剂可以用于提供组合物的所有组分的均相溶液。包含有机溶剂还可能在制备膜的工艺中具有优势,因为许多有机溶剂有效地降低组合物的粘性和/或表面张力,使得制造工艺在某些方面更容易。优选地,溶剂包含至少40wt%的水,更优选至少60wt%的水。优选地,组合物包含15-55wt%、更优选16-45wt%、尤其是20-40wt%、更尤其是22-35wt%的溶剂。
溶剂优选是水或者是包含水和水溶性有机溶剂的混合物。由于存在水溶性有机溶剂,也可以接受少量水不溶溶剂使得整个溶剂混合物是混溶的。
当溶剂包含水和有机溶剂时,水与有机溶剂的重量比优选大于2∶3,更优选介于10∶1和1∶1之间,更优选介于10∶1和1∶2之间,尤其介于5∶1和1∶1之间,更尤其介于3∶1和2∶1之间。
有机溶剂是任选的一种有机溶剂,或两种或两种以上的有机溶剂的组合。
优选的有机溶剂包括C1-4醇(例如,甲醇、乙醇和异丙醇)、二醇(例如,乙二醇和丙二醇)、三醇(例如,丙三醇)、碳酸酯(例如,碳酸亚乙酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、二碳酸二叔丁酯和碳酸甘油酯)、二甲基甲酰胺、丙酮、N-甲基-2-吡咯烷酮,以及包含它们中的两种或两种以上的混合物。特别优选的有机溶剂是异丙醇。
在一个实施方案中,有机溶剂具有低沸点,例如,沸点小于100℃。可以通过蒸发容易地除去低沸点溶剂,避免为除去溶剂所需的洗涤步骤。
可固化组合物的最佳溶剂含量在一定程度上取决于溶剂、(一种或多种)可固化化合物和交联剂之间的相互作用,并且对于每种组合都可以通过简单的实验进行测定。
当组合物含有0%的自由基引发剂时,可以采用电子束照射进行固化。
优选地,组合物包含0.01-10wt%、更优选0.01-5wt%、尤其是0.01-2wt%、更尤其是0.05-2wt%的自由基引发剂。优选的自由基引发剂是光引发剂。
可固化组合物可以包含一种或一种以上作为组分(iv)的自由基引发剂。
对于丙烯酰胺、双丙烯酰胺和更高丙烯酰胺,优选I型光引发剂。I型光引发剂的实例如WO 2007/018425,第14页第23行至第15页第26行所述,其内容结合于此作为参考。尤其优选的光引发剂包括α-羟基烷基苯甲酮,例如,2-羟基-2-甲基-1-苯基丙烷-1-酮和2-羟基-2-甲基-1-(4-叔丁基)苯基丙烷-1-酮;以及酰基膦氧化物,例如,2,4,6-三甲基苯甲酰基-二苯基氧化膦和双(2,4,6-三甲基苯甲酰基)-苯基氧化膦。
可固化组合物任选地包含0-10wt%、优选0-5wt%的除了(i)之外的具有一个以上烯键式不饱和基团且无离子基团的(一种或多种)可固化化合物(vi)。
可固化组合物任选地包含0-20wt%、优选0-10wt%的具有一个烯键式不饱和基团且无离子基团的(一种或多种)可固化化合物(vii)。
当组合物中存在自由基引发剂时,优选地,还包括阻聚剂。其用于在例如储存期间防止组合物的过早固化。合适的阻聚剂包括对苯二酚、对苯二酚单甲基醚、2,6-二叔丁基-4-甲基苯酚、4-叔丁基邻苯二酚、吩噻嗪、4-氧代-2,2,6,6-四甲基-1-哌啶醇氧(piperidinoloxy)自由基、4-羟基-2,2,6,6-四甲基-1-哌啶醇氧自由基、2,6-二硝基-仲丁基苯酚、三(N-亚硝基-N-苯基羟胺)铝盐、OmnistabTM IN 510以及包含它们中的两种或两种以上的混合物。
可固化组合物可以包含其他组分,例如酸、pH控制剂、防腐剂、粘度调节剂、稳定剂、分散剂、消泡剂、有机/无机盐、阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂和/或两性表面活性剂、缓冲剂等。
缓冲剂可以用于减少由于酸性和碱性化合物浓度变化引起的pH值的波动。
当然,可固化组合物可能包含上面未具体提及或未包括的其他组分。
可以通过在可固化组合物中包括胺类增效剂提高固化速率。合适的胺类增效剂是例如游离的烷基胺,例如三乙胺或三乙醇胺;芳香胺,例如2-乙基己基-4-二甲基氨基苯甲酸酯、4-二甲氨基苯甲酸乙酯;也可以是聚合胺,如聚丙烯胺及其衍生物。
可固化胺类增效剂,诸如烯键式不饱和胺(例如,丙烯酸胺)是优选的,因为由于它们具有通过固化结合到膜中的能力,它们的使用会产生较小的气味,还因为它们可以包含能够用于最终(阴离子可渗透)膜中的碱性基团。
使用时,胺类增效剂的量优选是基于组合物中可聚合组分的总重量的0.1-10wt%,更优选0.3-3wt%。
鉴于前述内容,特别优选的组合物包括可固化组合物,该可固化组合物包括:
(i)4-35wt%的包含至少两个丙烯酰胺基团的交联剂;
(ii)35-60wt%的包含烯键式不饱和基团和阳离子基团的可固化离子化合物;以及
(iii)16-45wt%的溶剂;
(iv)0.01-2wt%的光引发剂;
(v)2-30wt%的非固化盐;
其中,(i)与(ii)的摩尔比为至少0.15,优选小于1.5。更优选地,(i)与(ii)的摩尔比介于0.2和1.0之间。
在可选的实施方案中,可固化组合物包含:
(i)5-35wt%的包含至少两个丙烯酰胺基团的交联剂;
(ii)20-65wt%的包含烯键式不饱和基团和阳离子基团的可固化离子化合物;以及
(iii)16-45wt%的溶剂;
(iv)0.01-2wt%的光引发剂;
(v)3-40wt%的非固化盐;
其中,(i)与(ii)的摩尔比介于0.10和5之间。优选地,(i)与(ii)的摩尔比介于0.15和1.5之间;更优选地,(i)与(ii)的摩尔比介于0.2和1.0之间。
所有组分的最佳量在一定程度上取决于所选择的单个组分的性质以及组合物的预期用途。
优选地,该组合物的pH为1.5至11。
优选地,烯键式不饱和基团是(甲基)丙烯酰胺基团。
优选地,上述可固化组合物中(i)、(ii)、(iii)、(iv)和(v)的份数总计为100。这并不排除存在其他不同的组分,但仅设定上述组分相对于这些组分的总量的比率。
优选地,可固化组合物不包含或基本上不包含甲基丙烯酸化合物(例如,甲基丙烯酸酯和甲基丙烯酰胺化合物),即,组合物包含至多10wt%的不包含丙烯酸基团而包含一个或多个甲基丙烯酸基团的化合物。
优选地,可固化组合物不包含或基本上不包含二乙烯苯。
优选地,可固化组合物不包含或基本上不包含苯乙烯。
优选地,可固化组合物不包含或基本上不包含染料和色素。这是因为组合物中不需要包含染料和色素。
因此,优选的可固化组合物不包含或基本上不包含二乙烯苯、染料、色素、苯乙烯、甲基丙烯酸化合物以及具有磺基基团的化合物。
根据本发明的第二方面,提供了用于制备膜的工艺,该工艺包括以下步骤:
(i)将可固化组合物涂覆至支撑体;以及
(ii)固化组合物以形成膜;
其中,可固化组合物如本发明的第一方面所限定的。
到目前为止,通常以缓慢且能源密集的工艺(通常具有许多阶段)来制造这种膜。本发明能够以简单工艺制造膜,这种简单工艺可以长时间连续地运行从而相对便宜地大量生产膜。
任选地,该工艺包括分离固化后的组合物和支撑体的另一步骤,但是需要时,可以省略该另一步骤,因而生产出包含固化后的组合物和多孔支撑体的复合膜。
膜优选是阳离子交换膜。
膜(包括支撑体)的厚度优选小于250μm,更优选介于10μm和200μm之间,最优选介于20μm和150μm之间。
基于膜、任何多孔支撑体以及与得到的膜保持接触的任何多孔强化材料的总干重,膜的离子交换能力优选为至少0.1meq/g,更优选为至少0.3meq/g,尤其大于0.6meq/g,更尤其大于1.0meq/g。可以通过如Djugoleckiet al,J.of Membrane Science,319(2008),第217页所述的滴定法测量离子交换能力。
优选地,膜对小阴离子(例如Cl-)的选择渗透性大于80%,尤其大于85%或更尤其大于90%,例如大于95%。
优选地,膜的电阻小于10ohm.cm2,更优选小于5ohm.cm2,最优选小于3ohm.cm2。对于某些应用,高电阻可以是可接受的,尤其是当选择渗透性非常高,例如90%或更高时。可以通过下面实施例部分中描述的方法来测定电阻。
优选地,膜在水中的溶胀小于100%,更优选小于75%,最优选小于60%。溶胀度可以通过交联剂的量、非固化盐的量以及通过在固化步骤中选择适当的参数并进一步通过多孔支撑体的性质进行控制。
可以通过Djugolecki et al,J.,Membrane Science,319(2008),第217-218页所述的方法测量电阻、选择渗透性和水中的溶胀百分比。
通常,离子交换膜是基本上无孔的,例如,孔小于标准扫描电子显微镜(SEM)的检测限。因而,采用Jeol JSM-6335F场发射SEM(应用加速电压2kV,焦距4mm,光圈4,样品涂有厚度为1.5nm的Pt,放大倍数100,000x,3°倾斜视野),平均孔径通常小于5nm,优选小于2nm。
得到的膜优选具有低透水性,从而离子可以通过膜而水分子不通过膜。优选地,膜的透水性小于1.10-7m3/m2.s.kPa,更优选小于1.10-8m3/m2.s.kPa,最优选小于5.10-9m3/m2.s.kPa,尤其小于1.10-9m3/m2.s.kPa。对透水性的要求取决于膜的预期用途。
需要时,组合物中可以包括作为润湿剂或用于调整表面张力的表面活性剂或表面活性剂的组合。可以使用可商购的表面活性剂,包括可照射固化表面活性剂。适合用于组合物中的表面活性剂包括非离子表面活性剂、离子表面活性剂、两性表面活性剂及它们的组合。
优选地,对可固化组合物的组分进行选择使得固化步骤期间不发生相分离。通过这种方式,降低了在得到的膜中具有大孔结构的可能性。
在一定程度上,通过(一种或多种)交联剂和可固化化合物的特性以及它们的功能性(例如每分子所包含的可交联基团的数量)来确定膜的网状结构。
在固化工艺期间,可固化组合物可以在支撑体顶部上形成层,或者其可以全部地或部分地渗入支撑体的孔径,并因此形成浸渍复合膜。还可以将可固化组合物涂覆到支撑体的两面以实现对称的复合膜。在优选的实施方案中,将支撑体用组合物进行饱和,然后通过EB或UV照射使饱和支撑体固化。
需要时,本发明的工艺可以包括其他步骤,例如,洗涤和/或干燥得到的膜。
例如为了提高支撑体的润湿性和粘着性,在将可固化组合物涂覆到支撑体的表面之前,可以对支撑体进行电晕放电处理、等离子体辉光放电处理、火焰处理、紫外线照射处理、化学处理等。
还可以对支撑体进行处理以将其表面能修改为例如70mN/m以上的值。
虽然采用固定支撑体分批制备膜是可能的,但是,为了发挥本发明的全部优势,更优选采用移动支撑体连续制备膜。支撑体可以是连续展开的辊的形式或者支撑体可以停留在连续的传动带上(或这些方法的组合)。采用这些技术,可以连续地对支撑体涂覆可固化组合物或者可以大批量地涂覆可固化组合物。
可以通过任何合适的方法例如通过淋涂、刮刀涂布、气刀涂布、罗拉刮刀涂布、斜板式涂布、轧辊涂布、正转辊涂布、逆转辊涂布、微辊涂布、浸涂、轧染涂布(foulard coating)、吻合涂布、刮棒式涂布(rod bar coating)或喷雾涂布对支撑体涂覆可固化组合物。可以同时或连续地完成多层的涂布。当涂布多层时,可固化组合物可以是相同或不同的。对于同时涂布多层,优选淋涂、斜板式涂布和狭缝式涂布。可以将可固化组合物涂覆到支撑体的一面或涂覆到支撑体的两面。
在一个实施方案中,例如同时或连续地对支撑体涂覆至少两种可固化组合物,它们可以是相同的或不同的。可以将可固化组合物涂覆到支撑体的同一面或不同面上。因而,可以不止一次地执行涂覆步骤,每次涂覆之间既可以实施固化也可以不实施固化。当对不同面进行涂覆时,得到的复合膜可以是对称的或不对称的,并且可固化组合物层可以具有相同或不同的厚度。当对同一面进行涂覆时,可以形成包括至少一个顶层和至少一个底层的复合膜,其中底层比顶层更接近于支撑体。在该实施方案中,顶层、底层连同任何中介层组成膜,并且多孔支撑体为得到的复合膜提供强度。
因此在优选工艺中,将可固化组合物连续地涂覆至移动支撑体,更优选借助于制造单元进行涂覆,该制造单元包括一个或多个可固化组合物涂覆工作台、用于固化组合物的一个或多个照射源、膜收集工作台以及用于将支撑体从可固化组合物涂覆工作台移动到照射源和膜收集工作台的装置。
(一个或多个)可固化组合物涂覆工作台可以位于相对于(一个或多个)照射源的上游位置,而(一个或多个)照射源位于相对于膜收集工作台的上游位置。
为了生产可充分流动的可固化组合物从而通过高速涂布机涂覆,优选地,可固化组合物的粘度小于5000mPa.s(在35℃下测量),更优选为1-1500mPa.s(在35℃下测量)。最优选地,可固化组合物的粘度为2-500mPa.s(在35℃下测量)。对于诸如斜板式液滴涂布(slide bead coating)的涂布方法,优选的粘度为2-150mPa.s(在35℃下测量)。
采用合适的涂布技术,可以将可固化组合物涂覆至以以下速度移动的支撑体:超过5m/min,优选超过10m/min,更优选超过15m/min,例如大于20m/min,或甚至更高的速度,诸如60m/min、120m/min或可以高达400m/min。
优选地,通过自由基聚合反应,优选采用电磁照射实施固化。照射源可以是提供固化组合物所必需的照射波长和照射强度的任何源。用于固化的UV光源的典型实例是由Fusion UV Systems供应的输出量为600瓦/英寸(240W/cm)的D-灯泡。备选物是来自同一供应商的V-灯泡和H-灯泡。
当可固化组合物中未包含光引发剂时,可以通过电子束曝光,例如采用50-300keV曝光来固化组合物。还可以通过等离子体或电晕曝光来实现固化。
在固化期间,组分(i)和(ii)发生聚合以形成聚合膜。可以通过任何合适的方式,例如通过照射和/或加热引起固化。优选地,快速地发生固化足以在30秒内形成膜。需要时,在结束之后可以实施进一步固化,但是通常不需要这样。
优选用热方法(例如,通过采用红外线照射),或更优选通过使用紫外线或电子束照射组合物来实现固化。
对于热固化,可固化组合物优选包含一种或多种热反应自由基引发剂,优选以0.01-5份/100份可固化组合物的量存在,其中所有份数均是按重量计算。
热反应自由基引发剂的实例包括有机过氧化物,例如过氧乙醚和/或过氧化苯甲酰;氢过氧化物,例如甲基过氧化氢;偶姻,例如苯偶姻;某些偶氮化合物,例如α,α’-偶氮二异丁腈和/或γ,γ’-偶氮双(γ-氰基戊酸);过硫酸酯;过醋酸酯,例如过醋酸甲酯和/或过醋酸叔丁酯;过氧草酸酯,例如,过氧草酸二甲酯和/或过氧草酸二(叔丁基)酯;二硫化物,例如,二硫化二甲基秋兰姆;和酮过氧化物,例如过氧化甲乙酮。红外线固化通常使用在约30℃至约150℃范围内的温度。在大多数情况下,使用在约40℃至约110℃范围内的温度。
优选地,可固化组合物的固化在已将组合物涂覆到支撑体之后的3分钟内,更优选在60秒内开始。
优选地,通过照射可固化组合物少于30秒、更优选少于10秒、尤其少于3秒、更尤其少于2秒来实现固化。在连续工艺中,连续进行照射,可固化组合物穿过辐射束的速度是决定固化时间的主要因素。
优选地,固化采用紫外线。假设波长与包含在可固化组合物中的任何光引发剂的吸收波长相匹配,举例来说,合适的波长是UV-A(390至320nm)、UV-B(320至280nm)、UV-C(280至200nm)和UV-V(445至395nm)。
合适的紫外光源是汞弧灯、碳弧灯、低压汞灯、中压汞灯、高压汞灯、旋流等离子弧灯、金属卤化物灯、氙灯、钨灯、卤素灯、激光器和紫外线发光二极管。特别优选中压或高压汞蒸气类型的紫外线发射灯。在大多数情况下,最大发射在200和450nm之间的灯是特别合适的。
照射源的能量输出优选为20-1000W/cm,优选40-500W/cm,但是只要可以实现所需的曝光剂量,其可以更高或更低。曝光强度是可以用于控制影响膜的最终结构的固化程度的参数之一。优选地,如通过高能量UV辐射计(UV PowerMapTM,购自EIT,Inc)在该仪器指示的UV-A和UV-B范围内所测量的,曝光剂量为至少40mJ/cm2,更优选介于40和1500mJ/cm2之间,最优选介于70和900mJ/cm2之间。可以自由选择曝光时间,但是优选短曝光时间,通常小于10秒,更优选小于5秒,尤其小于3秒,更尤其小于2秒,例如介于0.1和1秒之间。
为了在高涂布速率下达到所需的曝光剂量,可以使用多于一盏UV灯,从而不止一次地照射可固化组合物。当使用两盏或多盏灯时,所有的灯可以给出同等剂量或者每一盏灯都可以具有单独的设置。例如,第一盏灯可以给出比第二盏灯和其余各灯更高的剂量,或者第一盏灯的曝光强度可以较低。改变每盏灯的曝光剂量可能影响聚合物基质结构和最终的交联密度。在优选的实施方案中,通过采用两个或更多个照射源,例如两盏灯(每面各一盏)同时从相对面照射来固化组合物。两个或更多个照射源优选采用相同强度照射组合物。通过采用这种对称配置,可以实现较高的交联效率并且可以降低或防止膜的卷曲。
如上所述,在可固化组合物中可以包含光引发剂,其在采用UV或可见光照射进行固化时通常是必需的。合适的光引发剂是本领域中已知的那些。优选在20℃和60℃之间实施采用UV或电子束照射的固化。虽然可以使用更高的温度,但因为它们可以导致更高的制造成本而不是优选的。
优选的支撑体是多孔支撑体,例如,它们可以是纺布或无纺布混合纤维,例如,聚乙烯、聚丙烯、聚丙烯腈、聚氯乙烯、聚酯、聚酰胺和它们的共聚物;或基于例如聚砜、聚醚砜、聚亚苯基砜、聚亚苯基硫醚、聚酰亚胺、聚醚酰亚胺(polyethermide)、聚酰胺、聚酰胺酰亚胺、聚丙烯腈、聚碳酸酯、聚丙烯酸酯、醋酸纤维素、聚丙烯、聚(4-甲基-1-戊烯)、聚偏二氟乙烯、聚四氟乙烯、聚六氟丙烯、聚三氟氯乙烯和它们的共聚物的多孔膜。
各种多孔支撑体是可商购获得的,例如,购自Freudenberg FiltrationTechnologies(Novatexx materials)和Sefar AG。
令人惊奇的是,具有阳离子基团的离子交换膜在选择渗透性和传导性方面可以显示出良好的性质,与此同时,通过本发明的工艺进行制造又不会太过昂贵。
本工艺实现制备具有所需柔韧程度(不是过于柔韧或者过于刚性)的膜。溶剂的存在改进了可固化组合物的涂布性能并且可以提供具有少量缺陷、不易卷曲同时在使用中保持良好耐用性的薄膜。
根据本发明的第三方面,提供了通过根据本发明第二方面的工艺获得的膜。
根据本发明第三方面的膜还可以用于需要具有阳离子基团的膜的其他应用。
根据本发明第三方面的膜优选具有上述有关本发明的第二方面的性质。
本发明的膜特别适用于ED、(C)EDI、EDR、ZDD、FTC、DD、EL和RED,但是它们还可以用于其他目的(例如渗透蒸发、燃料电池)。
根据本发明的第四方面,提供了根据本发明第三方面的膜用于水净化或用于发电的用途。
根据本发明的第四方面,提供了包含一个或多个根据本发明第三方面的膜的电渗析或逆电渗析单元、电去离子模块或流过式电容器。电去离子模块优选是连续电去离子模块。
优选地,电渗析或逆电渗析单元或电去离子模块或流过式电容器包括至少一个阳极、至少一个阴极和一个或多个根据本发明第三方面的膜。此外,装置优选地包括用于沿着根据本发明的膜的第一面提供盐度相对高的水流的进口和用于沿着膜的第二面提供盐度不太高的流水的进口,使得离子从膜的第一面穿过到达膜的第二面。优选地,装置的一个或多个膜包括具有阳离子的根据本发明第三方面的膜以及具有阴离子的另一个膜。
在优选的实施例中,装置包括至少3个、更优选至少5个(例如36个、64个或高达500个)根据本发明第三方面的膜,膜的数量取决于应用。举例来说,膜可以用于板框式或层叠盘式结构或螺旋缠绕设计中。可选地,具有阳离子基团的根据本发明的连续第一膜可以以波纹管式(或Z字形)方式折叠,而具有阴离子基团(即,与第一膜带有相反电荷)的第二膜可以插入皱褶之间以形成多个通道,流体可以沿着该多个通道通过并且该多个通道具有作为侧壁的交替的阴离子膜和阳离子膜。
具体实施方式
现通过非限制性实施例举例说明本发明,除非另有规定,其中所有份数和百分比均按重量计算。
在实施例中,通过下面描述的方法测量以下性质。
一般测试方法
选择渗透性通过采用静态膜电位测量法进行测量。用待研究的膜将两个电解槽(cell)分开。在测量之前,膜在0.1M NaCl溶液中平衡至少12小时。在待研究的膜的相对面上,具有不同NaCl浓度的两股液流通过电解槽。一股液流的浓度为0.1M NaCl(购自Sigma Aldrich,最低纯度99.5%),而另一股液流的浓度是0.5M NaCl。两股液流的流速都是0.90dm3/min。将两个甘汞参比电极(购自Metrohm AG,瑞士)连接至插入每个电解槽中的Haber-Luggin毛细管并且用于测量膜电势差。有效膜面积是3.14cm2,温度是25℃。
当达到稳态时,测量膜电势(ΔVmeas)。
根据公式计算膜的选择渗透性(α(%)):
α(%)=ΔVmeas/ΔVtheor×100%。
理论膜电势(ΔVtheor)是采用能斯特方程计算的100%选择性渗透膜的电势。为了弥补日常测量波动,所有的α(%)测量包括内标以校准结果。使用的内标是α(%)值为92%的AMX膜(购自Tokuyama Soda)。
电阻(“ER”)通过Djugolecki et al,J.of Membrane Science,319(2008)第217-218页描述的方法进行测量,并对该方法做了如下修改:
·辅助膜是CMX和AMX,购自Tokuyama Soda,日本;
·对于四个外室,使用购自Watson Marlow(型号504S/50)的双头蠕动泵,而对于两个中央室,使用具有易加载II型77200-62齿轮泵的Cole Parmer masterflex控制台驱动(77521-47);
·每股液流的流速是475ml/min,通过Porter Instrument流量计(型号150AV-B250-4RVS)和Cole Parmer流量计(型号G-30217-90)控制;
·膜的有效面积是3.14cm2。
成分
MBA是N,N′-亚甲基双丙烯酰胺(MW=154),购自Sigma Aldrich。
BAHP是1,4-双(丙烯酰基)高哌嗪,如WO 2010/106356中所述合成。
ATMAC是3-丙烯酰胺基丙基三甲基氯化铵,购自Kohjin。
HDMAP是2-羟基-2-甲基-1-苯基-丙烷-1-酮,光引发剂,购自Cytec。
MeHQ是对苯二酚单甲醚,阻聚剂,购自Merck。
IPA是异丙醇,购自Shell。
MeOH和EtOH分别是甲醇和乙醇(96%),购自Sigma Aldrich。
LiNO3、LiBr和LiCl是锂盐,购自Sigma Aldrich。
NovatexxTM 2597是无纺布聚酰胺材料,购自Freudenberg FiltrationTechnologies。
NovatexxTM 2426是无纺布聚对苯二甲酸乙二酯材料,购自FreudenbergFiltration Technologies。
当计算溶剂含量时,包括在任何成分中存在的任何溶剂的量(例如,将任何结晶水作为溶剂处理)。
实施例1至15和对比实施例1和2
在80℃下,通过混合表1中所示的成分(以wt%表示)制备根据本发明的可固化组合物CC1至CC15和对比可固化组合物CE1和CE2。
表1
表1(续)
*水包括MeHQ阻聚剂(约1000ppm)。
在手动约5m/min的速度下,采用150μm的钢丝缠绕棒对铝地下载体涂覆可固化组合物,然后采用钢丝缠绕刮棒式涂布机水平地涂覆无纺布支撑体(NovatexxTM 2597)至4微米的厚度。可固化组合物的温度是50℃。通过采用速度为30m/min(单程)、在100%强度下运转的配备有D-灯泡的Light Hammer LH6(购自Fusion UV Systems)固化经涂布的支撑体来制备膜。曝光时间是0.47秒。在固化之后,将膜在0.1M NaCl溶液中储存至少12个小时。
得到的膜的选择渗透性(α(%))和电阻(ER)如表1所示。
实施例16至19
使用表2所列的成分通过与实施例1至15类似的方式混合所示成分来制备根据本发明的可固化组合物CC16至CC19。
表2
*水包括MeHQ阻聚剂(约1000ppm)。
通过实施例1描述的方法对NovatexxTM 2426支撑体涂覆CC16至CC19。
得到的膜的选择渗透性(α(%))和电阻(ER)如上面表2所示。
Claims (24)
1.一种可固化组合物,包含:
(i)2.5-50wt%的交联剂,所述交联剂包含至少两个丙烯酰胺基团;
(ii)12-65wt%的可固化离子化合物,所述可固化离子化合物包含烯键式不饱和基团和阳离子基团;
(iii)10-70wt%的溶剂;
(iv)0-10wt%的自由基引发剂;以及
(v)非固化盐;
其中,(i)与(ii)的摩尔比>0.10。
2.根据权利要求1所述的组合物,其中,(i)与(ii)的摩尔比小于5。
3.根据前述权利要求中任一项所述的组合物,其中,组分(i)和组分(ii)相对于所述组合物的总重量的总wt%是30-88wt%。
4.根据前述权利要求中任一项所述的组合物,包括2-50wt%的作为组分(v)的非固化盐。
5.根据前述权利要求中任一项所述的组合物,其中,(i)与(ii)的摩尔比为至少0.15,并且,所述组合物包含20-65wt%的组分(ii)和2-30wt%的组分(v)。
6.根据前述权利要求中任一项所述的组合物,其中,所述溶剂包含水和水溶性有机溶剂。
7.根据前述权利要求中任一项所述的组合物,包含0.005-10wt%的作为组分(iv)的光引发剂。
8.根据前述权利要求中任一项所述的组合物,除了组分(i)和组分(ii)外,不包含烯键式不饱和化合物。
9.根据前述权利要求中任一项所述的组合物,其中,所述烯键式不饱和基团是丙烯酰胺基团或甲基丙烯酰胺基团。
10.根据前述权利要求中任一项所述的组合物,包含:
(i)5-35wt%的交联剂,所述交联剂包含至少两个丙烯酰胺基团;
(ii)20-65wt%的可固化离子化合物,所述可固化离子化合物包含烯键式不饱和基团和阳离子基团;以及
(iii)16-45wt%的溶剂;
(iv)0.01-2wt%的光引发剂;以及
(v)3-40wt%的非固化盐;
其中,(i)与(ii)的摩尔比为至少0.15。
11.根据前述权利要求中任一项所述的组合物,其中,(i)与(ii)的摩尔比为至少0.15且小于1.5。
12.一种用于制备膜的工艺,包括以下步骤:
(i)将可固化组合物涂覆至支撑体;以及
(ii)固化所述组合物以形成膜;
其中,所述可固化组合物是如权利要求1至11中任一项所限定的。
13.根据权利要求12所述的工艺,其中,采用电子束或UV照射实施所述固化。
14.根据权利要求12或13所述的工艺,其中,通过采用电子束或UV光照射小于30秒的时间来固化所述组合物。
15.根据权利要求12至14中任一项所述的工艺,其中,借助于制造单元将所述可固化组合物连续地涂覆至移动支撑体,所述制造单元包括可固化组合物涂覆工作台、用于固化所述组合物的照射源、膜收集工作台以及用于将所述支撑体从所述可固化组合物涂覆工作台移动至所述照射源和所述膜收集工作台的装置。
16.根据权利要求12至15中任一项所述的工艺,其中,将所述可固化组合物涂覆至以超过5m/min的速度移动的支撑体。
17.根据权利要求12至16中任一项所述的工艺,包括分离固化后的组合物和支撑体的另一步骤。
18.通过权利要求12至17中任一项所述的工艺获得的或可获得的膜。
19.权利要求18所述的膜作为离子交换膜在用于水净化、脱盐、废水处理、电解、渗透蒸发或发电的离子交换工艺中的用途。
20.一种电渗析或逆电渗析单元,包含一个或多个根据权利要求18所述的膜。
21.一种流过式电容器器件,包含一个或多个根据权利要求18所述的膜。
22.一种燃料电池,包括一个或多个根据权利要求18所述的膜。
23.一种扩散渗析装置,包括一个或多个根据权利要求18所述的膜。
24.一种膜电极组件,包括一个或多个根据权利要求18所述的膜。
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PCT/GB2010/052063 WO2011073641A1 (en) | 2009-12-16 | 2010-12-09 | Curable compositions and membranes |
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CN (1) | CN102686621B (zh) |
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CN104437090A (zh) * | 2013-09-24 | 2015-03-25 | 韩国能源研究技术研究所 | 反向电透析装置用离子交换膜及包含它的反向电透析装置 |
CN107849275A (zh) * | 2015-07-14 | 2018-03-27 | 富士胶片制造欧洲有限公司 | 离子交换膜 |
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US20120248029A1 (en) | 2012-10-04 |
GB0921951D0 (en) | 2010-02-03 |
CN102686621B (zh) | 2015-03-18 |
US9259685B2 (en) | 2016-02-16 |
US9539548B2 (en) | 2017-01-10 |
CA2782733C (en) | 2015-02-24 |
JP2013514423A (ja) | 2013-04-25 |
CA2782733A1 (en) | 2011-06-23 |
EP2361270B1 (en) | 2013-05-01 |
US20160207008A1 (en) | 2016-07-21 |
EP2350150A1 (en) | 2011-08-03 |
JP2013514420A (ja) | 2013-04-25 |
US20120248030A1 (en) | 2012-10-04 |
EP2361271A1 (en) | 2011-08-31 |
JP5648066B2 (ja) | 2015-01-07 |
JP5648065B2 (ja) | 2015-01-07 |
EP2361270A1 (en) | 2011-08-31 |
WO2011073640A1 (en) | 2011-06-23 |
EP2361271B1 (en) | 2013-07-03 |
US20150129428A1 (en) | 2015-05-14 |
WO2011073641A1 (en) | 2011-06-23 |
WO2011073638A1 (en) | 2011-06-23 |
US8968965B2 (en) | 2015-03-03 |
EP2350150B1 (en) | 2012-08-22 |
US8956783B2 (en) | 2015-02-17 |
US20120248028A1 (en) | 2012-10-04 |
JP5697687B2 (ja) | 2015-04-08 |
US8968964B2 (en) | 2015-03-03 |
JP2013514422A (ja) | 2013-04-25 |
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