CN1265334A - 离子选择性膜、其制造方法、其用途和装有该膜的仪器 - Google Patents
离子选择性膜、其制造方法、其用途和装有该膜的仪器 Download PDFInfo
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- CN1265334A CN1265334A CN00104174A CN00104174A CN1265334A CN 1265334 A CN1265334 A CN 1265334A CN 00104174 A CN00104174 A CN 00104174A CN 00104174 A CN00104174 A CN 00104174A CN 1265334 A CN1265334 A CN 1265334A
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- Prior art keywords
- selective membrane
- ion selective
- polymer
- membrane
- ion
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Abstract
一种离子选择性膜,是由离子选择性膜形成成分和定形编织物衬底整体形成的。该离子选择性膜形成成分包括一种阳离子聚合物成分和/或一种阴离子聚合物成分以及一种基质成分。每种离子聚合物成分是平均粒径在0.01—10μm的粒状聚合物。该定形编织物衬底具有网状结构。离子选择性膜的生产是通过保持一层涂布制剂与该定形编织物补底紧密接触而形成该膜,涂布制剂中的离子聚合物成分分散于基质在有机溶剂中的溶液或分散体中。该离子选择性膜可用于电解质渗透。也提供了一种装有该离子选择性膜的仪器。
Description
本发明涉及能使电解质通过的、并用定形编织物衬底加固的离子选择性膜,其制造方法,其用途和装有该离子选择性膜的仪器。
阳离子选择性或阴离子选择性膜和电荷镶嵌膜是迄今熟知的。阳离子选择性或阴离子选择性膜(下文中也称为“单一的离子选择性膜”)有阳离子或阴离子的聚合物成分。另一方面,在电荷镶嵌膜中,阳离子聚合物成分和阴离子聚合物成分沿膜厚方向以基本上电子(离子的)连续形式延伸。单一的离子选择性膜具有吸收或渗透抗衡离子,但排斥非抗衡离子的功能,而电荷镶嵌膜具有能透过低分子量电解质,但不能透过或以非常低的渗透速度渗透非电解质的功能。
为制造上述单一离子选择性膜或电荷镶嵌膜,已提出了下列方法:(1)关于单一离子选择性膜,(i)将离子交换树脂和形成基质的热塑性树脂(如聚乙烯或聚氯乙烯)的细粉捏合成均质物,然后在加热条件下形成均质体,(ii)三乙胺、氯磺酸等直接反应在聚乙烯膜、聚氯乙烯膜等,这样就将离子基团引到膜上,(iii)将(甲基)丙烯酸接枝聚合到聚乙烯、聚丙烯等的膜上或将通过苯乙烯或乙烯吡啶的接枝聚合得到的膜进行磺化或季铵化,这样就引入了离子基团;和(2)对于电荷镶嵌膜,使用嵌段共聚物。
使用粗粒度的离子交换树脂的方法(1)(i)易于实施,但难于使可固定离子的浓度更高,因为该树脂颗粒的比表面积小。通过化学反应将离子基团引到膜上的方法(1)(ii)实施起来比较麻烦。另一方面,使用嵌段共聚物的方法(2)本身是非常难于实施的。相反,使用聚合物细粒形式的阳离子成分和/或阴离子成分的方法,其优点在于制造单一离子选择性膜或电荷镶嵌膜非常简单。
在上述使用聚合物细粒的方法中,由于微球体的固有的紧密填充性和各向同性,使用微球体形式的聚合物细粒能更容易制造离子选择性膜。然而,这一方法伴有生产大面积膜的问题,因为膜的成分是离子聚合物,以及如此形成的膜易于在干燥过程中收缩或丧失强度。
作为一种减少上述问题的方法,在日本专利10-87855中提出了使用柔性聚合物成分作为电荷镶嵌膜的基质成分的方法。该方法使大面积电荷镶嵌膜的制造更容易。然而,该方法形成膜需要时间长,而且难于制造厚度均匀的薄膜。在日本专利申请10-232732和10-237708中提出了减小这一问题的方法,使用离子聚合物成分分散于作为基质成分的树脂溶液(如将聚砜类树脂、多芳基化合物树脂或聚氨酯树脂溶于有机溶剂)中的组合物形成膜;和结合使用衬底如机织织物或非机织织物。这些方法能缩短膜形成时间并获得均匀且薄的离子选择性膜以及使加工简单成为可能。
然而,通过结合使用如机织织物或非机织织物衬底制造的离子选择性膜,而且制成适合于实际装置的形状,如平面膜、螺旋状膜、波纹状膜、圆筒形膜或中空的毛细管状,这就牵涉到降低电解质渗透性的问题,因为衬底内开孔的变化和不均匀性,或是因为衬底中开孔周围造成膜厚度的不均匀性而在膜上形成针孔或开裂。因此,强烈的需要解决这一问题。
因此,本发明的目的之一是提供一种使用一种或多种离子聚合物成分和基质成分的离子选择性膜,该膜可在膜的形成或加工过程中抵制发展针孔或开裂,在衬底的开孔周围厚度均匀并有足够的强度。本发明的另一目的是提供一种制造该离子选择性膜的方法。
为了达到上述目的,本发明一方面提供一种由离子选择性膜形成成分和定形编织物衬底的整体形成的离子选择性膜,离子选择性膜形成成分包括一种阳离子聚合物成分和/或阴离子聚合物成分和一种基质成分,在该离子选择性膜中每种离子聚合物成分是0.01-10μm平均粒度范围的粒状聚合物,所述定形编织物衬底具有网状结构;另一方面,提供一种制造该离子选择性膜的方法;更进一步提供了该离子选择性膜的用途;再进一步提供一种装备有该离子选择性膜的仪器。
本发明的离子选择性膜可在形成或加工过程中抵制发展针孔或开裂,在衬底的开孔周围厚度均匀并能保持足够的机械强度。
因此,本发明的离子选择性膜可用于选择性渗透电解质,如用于电解质的运输、分离、浓缩、吸收等。
图1是用于评估在实施例3-5中得到的电荷镶嵌膜和离子选择性膜的仪器的示意性的垂直剖视图;和
图2是表示实施例3的电荷镶嵌膜的透析分离性能的曲线图。
根据本发明的离子选择性膜,其特征在于,由离子选择性膜形成成分-包括作为粒状聚合物或聚合体的阳离子聚合物成分和/或阴离子聚合物成分,和基质成分-以及具有网状结构的定形编织物衬底整体形成的。因此,该离子选择性膜的制造方法的特征在于形成的膜的同时保持一层涂布制剂并与定形编织物衬底紧密接触,其中一种或多种离子聚合物成分是分散于基质成分在有机溶剂中的溶液或分散体系中。顺便说明,每种用于本发明的离子聚合物成分是平均粒径在0.01-10μm、优选0.02-1μm的粒状聚合物。
可用于本发明的离子聚合物成分的实例包括:作为阳离子聚合物成分:含有阳离子基团的聚合物,阳离子基团如伯氨基至叔胺基、季胺基或吡啶基或其盐,和作为阴离子聚合物成分:含有阴离子基团的聚合物,阴离子基团如磺酸基、羧基、硫酸酯基或磷酸酯基或其盐。在将离子基团转化成其盐基团时,可使用一种酸如盐酸、硫酸、磷酸或一种有机酸作为阳离子基团,而碱或碱基可使用如碱金属、氨、胺或链烷醇胺作为阴离子基团。
上述每种离子聚合物成分的制备都可通过先形成非离子粒状聚合物,然后对其进行化学改性如氨化、季铵化、水解、磺化或硫酸化。除了上述例举的之外,化学改性还可用于制备一种或多种离子聚合物成分,只要其可以对这样的非离子聚合物进行阳离子化或阴离子化。
可用于制备离子聚合物成分(每种均含有离子基团或其盐基)单体的一般实例包括阴离子单体如(甲基)丙烯酸、马来酸、富马酸、衣康酸、巴豆酸、苯乙烯磺酸、(甲基)丙烯酰基氧丙基磺酸、(甲基)丙烯酸2-硫代乙基酯、2-(甲基)丙烯酰氨基-2-甲基-1-丙磺酸、2-(甲基)丙烯酰氨基-2-丙磺酸和乙烯磺酸,和它们的盐;4-乙烯吡啶和2-乙烯吡啶,和其季铵化的衍生物;和阳离子单体如(甲基)丙烯酸二甲基氨基乙酯、(甲基)丙烯酸二乙基氨基乙酯、4-乙烯苄基二甲基胺和2-羟基-3-(甲基)丙烯氧丙基二甲基胺、和其盐。
可通过聚合这些阴离子或阳离子单体制备离子聚合物。需要时,在聚合反应时,用这样的离子单体和已知的非离子单体共聚。非离子单体是(甲基)丙烯酸十二烷基酯和(甲基)丙烯酸硬脂酰酯。非离子单体的用量占总单体重量的0-80%。
另一方面,可用于制备非离子聚合物(可通过化学改性转化成离子聚合物)的单体的一般实例包括可化学改性的单体如苯乙烯化合物如苯乙烯、α-甲基苯乙烯、氯甲基苯乙烯和羟甲基苯乙烯;(甲基)丙烯酸酯化合物如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸聚乙二醇酯、(甲基)丙烯酸羟丙酯和(甲基)丙烯酸聚丙二醇酯;(甲基)丙烯酰胺化合物如(甲基)丙烯酰胺、N-甲基(甲基)丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、N-丁氧基甲基(甲基)丙烯酰胺和N,N-二甲基丙烯酰胺;丙烯腈;和乙酸乙酯。聚合上述单体时,可共聚这种化学改性后保持不变的公知非离子单体。这种单体是(甲基)丙烯酸十二烷基酯和(甲基)丙烯酸硬脂酰酯。
尽管并不绝对要求是交联的,使用相应的上述单体等之一制备的每种离子或非离子粒状聚合物优选是交联形式的,因为成膜时使用了有机溶剂。每种粒状聚合物的交联通常是通过在该聚合物等进行聚合时,将上述单体与交联单体共聚而实现的。交联单体是双官能单体如二乙烯苯、亚甲基双(甲基)丙烯酰胺、二甲基丙烯酸乙二醇酯和二甲基丙烯酸1,3-丁二醇酯;三官能单体如三甲基丙烯酸三羟甲基丙酯;和四官能(甲基)丙烯酸酯。这些交联单体优选用量是每100份构成聚合物的单体含该交联单体0.1-30份,更优选0.5-10份。
作为从上述单体和交联单体制备粒状聚合物的一种代表性方法,要提到在水***或非水***中的自由基引发的聚合反应。该聚合反应的示例性方法包括(但不限于)聚合方法如乳液聚合法、无皂乳液聚合法、悬浮聚合法、分散聚合法和反相乳液聚合法。
作为聚合引发剂,用于自由基引发聚合反应中的常规公知的聚合引发剂均可使用。其实例是偶氮化合物如2,2'-偶氮异丁腈、2,2'-偶氮双(异丁酸甲酯)、2,2'-偶氮双(2,4二甲基戊腈)、1,1'-偶氮双(环己烷-1-腈)、2,2'-偶氮双(2-脒基丙烷)二氯化氢、2,2'-偶氮双(2-脒基丙烷)二乙酸酯和2,2'-偶氮双(N,N'-二亚甲基异丁基脒)二氯化氢;有机过氧化物如异丙基苯过氧化氢、过氧化二异丙苯、过氧化苯甲酰和月桂基过氧化物;和过硫酸盐如过硫酸铵和过硫酸钾。
作为本发明离子选择性膜的基质成分,对本发明的目的来说,最优选的基质成分是一种聚合物,该聚合物具有在加热等条件下干燥形成膜的性质,在形成离子选择性膜时,具有优良的物理性质如耐化学性、耐溶剂性和防水性,也具有化学稳定性,并且对水解和氧化降解有极好的耐久性。基质成分的具体实例包括的聚合物如下列通式(1)-(3)的聚砜类树脂、下列通式(4)-(6)的多芳基化合物、下列通式(7)的聚酰胺树脂、下列通式(8)和(9)的聚酰胺-酰亚胺树脂、下列通式(10)和(11)的聚酰亚胺树脂、下列通式(12)和(13)的聚氨酯树脂、下列通式(14)-(16)的氟化树脂、下列通式(17)的硅酮树脂、和二烯烃单体的均聚物或共聚物的氢化产物,所述氢化产物的结构见通式(18)。上述聚合物可单独或结合使用。为了使得到的离子选择性膜具有柔韧性,可向上述聚合物中加入二烯烃聚合物如丁二烯-苯乙烯共聚物或聚烯烃聚合物如聚乙烯、聚乙烯离子交联聚合物、聚丙烯、聚烯烃三聚物或乙烯-乙酸乙酯共聚物。
在上述通式中,n和m代表足够大的数值,以使其相应的树脂分子量约为1,000-500,000。
在本发明中,离子选择性膜的定形编织物衬底材料的实例包括不锈钢、铝、陶瓷、聚酯、尼龙、聚酰胺、聚碳酸酯、聚丙烯、聚乙烯、纤维素、几丁质、聚四氟乙烯、聚氨酯、聚砜、聚氟化的亚乙烯、芳酰胺(aramides)和碳素纤维。在由这些织物制成的定形编织物衬底中,其网状结构的孔大小通常是1-5,000μm,优选范围是10-1,000μm。如果孔小于1μm,当离子选择性膜形成成分(一种或多种离子聚合物成分和基质成分)与定形编织物衬底紧密接触时或当将离子选择性膜切割成预期的形状时或安装在仪器上时,易于发生龟裂。而且,沿衬底的孔周围形成的膜厚度不均匀,因此易于影响电解质的渗透性。另一方面,如果孔大于5,000μm,得到的离子选择性膜易于形成小洞或在其形成或使用过程中开裂。
本发明的离子选择性膜的制造方法的特征在于形成膜的同时保持涂布制剂层与具有网状结构的定形编织物衬底紧密接触。涂布制剂的制备是将粒状聚合物或聚合体分散而制备,即一种或多种离子(阳离子和/或阴离子)聚合物成分分散于至少一种作为基质成分的聚合物在有机溶剂中的溶液或分散体中。所述的至少一种聚合物选自如下:聚砜树脂、多芳基化合物树脂、聚酰胺树脂、聚酰亚胺树脂、聚酰胺-酰亚胺树脂、聚氨酯树脂、氟化树脂、硅酮树脂和二烯烃单体的均聚物或共聚物的氢化产品。
首先,将一种或多种离子聚合物成分混合或分散于基质成分在有机溶剂中的溶液或分散体中来制备涂布制剂。在混合或分散一种或多种离子聚合物成分时,它们是以细粉的形式使用,或者是以预先分散于有机溶剂中的形式使用。尽管对混合或分散一种或多种离子聚合物成分分散于基质成分在有机溶剂中的溶液或分散体的方法并无特殊限制,混合或分散可通过例如在溶解器或均匀混合器中以超声波搅拌或通过搅拌器来进行。关于一种或多种离子聚合物成分和基质成分在离子选择性膜中的所占比例,基质成分相当于这些成分重量总和的2-95%,优选10-80%。
本发明中使用的溶剂是有机溶剂,可溶解或细分散基质的成分。其实例是含氮溶剂如N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-乙烯基-2-吡咯烷酮、N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、N,N-二甲基乙酰胺和N,N-二乙基乙酰胺;醚溶剂如二噁烷和四氢呋喃;酮溶剂如甲乙酮和甲基异丁酮;二甲基亚砜;丙二醇单甲醚;异丙醇;丙二醇单甲醚乙酸酯;二甲苯;二氯乙烯;氯仿;和环己烷。在这些有机溶剂中,对一种或多种离子聚合物成分有极好的分散性和分散稳定性的含氮溶剂是优选的,因为在将一种或多种离子聚合物成分与基质成分混合时,使用的一种或多种离子聚合物成分是微粒或分散于有机溶剂中的形式。其他有机溶剂或水基溶剂也可结合使用,只要得到的分散体系不会变得不稳定。
之后使用如上文得到的涂布制剂来形成离子选择性膜。离子选择性膜的形成可根据已知的涂布方法,将涂布制剂涂布或浇注到适合脱模的基料上,使定形编织物衬底与涂布的表面紧密接触,然后干燥并除去溶剂;或者将涂布制剂涂布或浇注到纺织品形状衬底上或用涂布制剂浸渍定形编织物衬底,然后干燥涂布制剂以去除溶剂。干燥后,如需要可对形成的膜进行处理如热熔化处理、热压处理或季铵化,由此得到本发明的离子选择性膜,其中的离子选择性膜形成成分和定形编织物衬底是整合的。
用于本发明的脱模基料的实例包括玻璃板;铝片和板;如聚四氟乙烯、聚丙烯和聚乙烯形成的塑料片、膜或板;和涂布了硅酮树脂或聚丙烯树脂的脱模纸。用涂布制剂涂布基料或定形编织物衬底的示例方法包括常规已知的涂布方法,如辊涂、刮涂、刀涂、橡皮辊涂布、气刀涂布、凹版涂布、棒涂、喷涂和浸渍。如上所述,通过涂布基料并使定形编织物衬底与涂布后的表面紧密接触得到的预制品在例如滚筒干燥机或鼓风干燥机或在红外线灯下干燥。尽管该厚度根据定形编织物衬底厚度而变化,得到的本发明离子选择性膜厚度范围通常是1-5,000μm,优选10-2,000μm。
如上所述得到的本发明的离子选择性膜具有整体结构,离子选择性膜形成成分(一种或多种离子聚合物成分和基质成分)渗透进定形编织物衬底内。当定形编织物衬底与基料表面紧密接触时,已用离子选择性膜形成成分的分散体涂布的所述表面和离子选择性膜形成成分的膜转移到衬底上,该离子选择性膜形成成分和衬底也至少在其接触面整体结合到一起。为了增加有效膜面积,提高电解质渗透效率和提高耐压性,可通过将本发明的离子选择性膜制成平面膜、螺旋状膜、波纹状膜、圆筒膜或中空毛细管来使用。
当本发明的离子选择性膜是单一的离子选择性膜时,该膜含有阳离子聚合物成分或阴离子聚合物成分作为离子聚合物成分,并且具有吸收或渗透抗衡离子并排斥非抗衡离子的功能。当离子选择性膜是电荷镶嵌膜时,阳离子聚合物成分和阴离子聚合物成分沿膜厚方向以实质上电子连续延伸的形式形成,并且该膜具有能渗透低分子量电解质而不能渗透或只能以非常低的渗透速率渗透非电解质的功能。
因此,根据本发明的单一离子选择性膜可用作电渗析、扩散渗析、电解渗析、电池等的离子交换膜;可用作金属离子的螯合物质;用于消除或净化在电沉积涂漆中的酸、胺或类似的副产品等。特别是,本发明的单一离子选择性膜可在通过海水浓缩、海水脱盐进行的食盐生产中,药品和食品工业中离子成分的分离和纯化中,和在金属提炼或表面处理步骤中的酸分离、废酸回收、电解氧化或还原中用作离子交换膜。也用作吸附隔膜从废水中除去毒性金属离子或从海水中收集有价值的金属。
另一方面,本发明的电荷镶嵌膜可用于电解质的选择性渗透。作为具体的应用实例,它们可用于低分子量电解质如氯化钠、氯化钾、硫酸钠、磷酸钠和氯化钙的脱盐,也可用于盐酸、乙酸和氢氧化钠的去离子化。具体地说,根据本发明的电荷镶嵌膜可在饮用水、工业用水、纯净水、超纯水等的生产中用于水处理中的脱盐;用于化学工业和金属工业中的工业废液的脱盐;用于染色生产工业中染料和颜料的脱盐;用于发酵工业和食品工业中相关生化产品的脱盐、用于药物制剂的脱盐;和吸附染料作为记录介质。
特别是,出于本发明离子选择性膜的电荷镶嵌膜可用于那些迄今为止电渗析还不适用的领域中,例如由于放热导致靶的物质的变性,由于离子吸附等原因的膜污染如蛋白质、DNAs等的脱盐和染料、颜料、表面活性剂等的脱盐。由于有上述膜结构,本发明的电荷镶嵌膜也可在利用膜特性,如电导性或离子渗透性的电渗析、扩散渗析、电解、细胞反应等中用作隔膜等。
现在,通过合成实施例和实施例更具体地描述本发明,除非专门指明,其中的“份”和“%”都是以重量计。
合成实施例1(聚合物A:阳离子粒状聚合物)
4-乙烯吡啶 20.0份
二乙烯苯 2.0份
2,2'-偶氮双(2-脒基丙烷)二氯化氢 0.4份
水 1000份
将上述成分装入烧瓶中并在氮气流下,在80℃下聚合8小时。将得到的聚合物产品冻干,由此得到内部交联的粒状聚合物。作为电子扫描显微镜下测量的结果,发现粒状聚合物的平均粒径大约350nm。
合成实施例2(聚合物B:阳离子粒状聚合物)
氯甲基苯乙烯 200.0份
二乙烯苯 10.0份
过硫酸钾 4.0份
硫代硫酸钠 4.0份
十二烷基硫酸钠 40.0份
水 1000份
将上述成分装入烧瓶中并置于氮气流下,在50℃下聚合12小时。收集得到的粒状聚合物,然后用热水和甲醇充分清洗以除去粒状聚合物表面上的表面活性剂。将该粒状聚合物分散于甲乙酮中,这样就得到分散体。向分散体中加入三乙胺,将得到的混合物在70℃下搅拌12小时,使粒状聚合物转化成季铵盐。该粒状聚合物的平均粒径是约为150nm。
合成实施例3(聚合物C:阴离子粒状聚合物)
苯乙烯 41.6份
丙烯腈 7.1份
甲基丙烯酸羟乙酯 8.1份
二乙烯苯 8.7份
过硫酸钾 0.5份
水 1000份
将上述成分装入烧瓶中并置于氮气流下,在80℃下聚合8小时。得到的聚合物平均粒径大约是180nm。过滤收集粒状聚合物,干燥并粉碎。随后将这样磨碎的粒状聚合物(100份)慢慢加入98%浓硫酸(650份)中,接着在50℃搅拌24小时,然后在80℃搅拌3小时。冷却该反应混合物,然后倒入大量冰水中。随后用碳酸钠中和,过滤收集如此处理过的粒状聚合物,然后用水彻底清洗。红外吸收光谱法、离子色谱法等分析的结果证实,如此得到的粒状聚合物含有磺酸基,引入率大约1个基团/芳香环。该粒状聚合物的平均粒径大约为240nm。
合成实施例4(聚合物D:阴离子粒状聚合物)
苯乙烯磺酸钠 25.0份
苯乙烯 10.0份
丙烯酸丁酯 5.0份
丙烯酰胺 2.8份
二乙烯苯 1.8份
2,2'-偶氮双(2-脒基丙烷)二氯化氢 1.0份
水 1000份
将上述成分装入烧瓶中并置于氮气流下,在75℃下聚合10小时。得到的粒状聚合物通过从丙酮-水中再沉淀进行纯化。得到的粒状聚合物的平均粒径约为100nm。
实施例1
将聚合物A(8.6份)分散于N-甲基-2-吡咯烷酮(20.0份)中。将该分散体和聚砜树脂[化学式(1)]在N-甲基-2-吡咯烷酮中的20%溶液(71.4份)搅拌1小时。将得到的分散体用真空泵进行消泡处理,由此制备出涂布制剂。将该涂布制剂用刀涂机涂布到已涂覆聚丙烯树脂的脱模纸片(下文中简称脱模纸)上。将一块编织的聚酯织物(孔:20μm,孔率:50%,厚度:100μm)与涂布后的表面紧密接触,然后将得到的预制品用热空气干燥。将这样干燥后的预制品在室温下于甲基碘气氛中放置12小时,用稀盐酸进行盐互换,彻底清洗,然后在空气中干燥,借此得到本发明的离子选择性膜。如上所述形成的离子选择性膜的厚度约110μm,无小洞或开裂,并在应用中呈现良好的耐用性和可处理性。
实施例2
将聚合物C(11.0份)分散于N-甲基-2-吡咯烷酮(25.0份)中。将该分散体系和聚砜树脂[化学式(1)]在N-甲基-2-吡咯烷酮中的20%溶液(64.0份)搅拌1小时。将得到的分散体进行消泡处理,由此制备出涂布制剂。将该涂布制剂用刀涂机涂布到脱模纸上。将一块编织的聚酯织物(孔:20μm,孔率:50%,厚度:100μm)与涂布后的表面紧密接触,然后将得到的预制品用热空气干燥。如上所述形成的离子选择性膜的厚度约110μm,无小洞或开裂,并在应用中呈现良好的耐用性和可处理性。
使用实施例1和2中得到的阳离子选择性膜和阳离子选择性膜作为电渗析的离子交换膜,并用于浓缩氯化钠水溶液。证实它们具有良好的渗析性。
实施例3
将聚合物A(2.0份)分散于N-甲基-2-吡咯烷酮(8.0份)中。将该分散体和聚丙烯酸酯[化学式(4)]在N-甲基-2-吡咯烷酮中的10%溶液(66.7份)搅拌1小时。将得到的分散体与另一种由聚合物C(4.7份)和N-甲基-2-吡咯烷酮(18.7份)构成的分散体混合。将如此得到的分散体系进行消泡处理,由此制备出涂布制剂。将该涂布制剂用刀涂机涂布到脱模纸上。将一块编织的聚酯织物(孔:500μm,孔率:50%,厚度:200μm)与涂布后的表面紧密接触,然后将得到的预制品用热空气干燥。将如此得到的膜在室温下于甲基碘气氛中放置12小时,用水清洗,然后在空气中干燥,借此得到本发明的电荷镶嵌膜。如上所述形成的电荷镶嵌膜的厚度约210μm,并且厚度均匀。
(膜的评估)
将0.1mol/L的氯化钾水溶液(100ml)作为电解质和0.1mol/l的葡萄糖水溶液(100ml)作为非电解质放于图1所示的容器A中。另一方面,将去离子水(200ml)加入图1所示的容器B中。用搅拌器1、1分别搅拌容器A、B中的内容物,然后通过上述电荷镶嵌膜2在25℃在环境压力下进行渗析。如图2所示,证明有足够的渗析分离性。
实施例4
将聚合物B(4.6份)分散于N,N-二甲基甲酰胺(25.8份)中。将该分散体和聚醚聚氨酯树脂在N,N-二甲基甲酰胺中的29%溶液(37.6份)搅拌1小时。所得分散体系与另一种由聚合物D(6.4份)和N,N-二甲基甲酰胺(25.5份)构成的分散体混合,由此制备出涂布制剂。将该涂布制剂用刀涂机涂布到脱模纸上。此外,将一块非编织的聚酯织物与涂布后的表面紧密接触,然后将得到的预制品用热空气干燥,由此得到本发明的电荷镶嵌膜。用如实施例3相似的方法评估如上所述获得的电荷镶嵌膜的电解质的渗析分离性。结果实质上可与在实施例3中获得的渗析分离性匹敌,且在其使用时耐用性和可处理性良好。
实施例5
将聚合物A(3.0份)分散于N-二甲基甲酰胺(12.0份)中。将该分散体和丙烯腈-丁二烯共聚树脂的氢化产物[化学式(18)]在N,N-二甲基甲酰胺中的20%(重量)溶液(50份)搅拌1小时。所得分散体与另一种由聚合物C(7.0份)和N,N-二甲基甲酰胺(28.0份)构成的分散体混合,由此制备出涂布制剂。将该涂布制剂用刀涂机涂布到脱模纸上。将一块非机织的聚丙烯织物(孔:300μm,孔率:50%,厚度:200μm)与涂布后的表面紧密接触,然后将得到的预制品用热空气干燥,由此得到本发明的离子选择性膜。用如实施例3相似的方法评估如上所述获得的电荷镶嵌膜的电解质渗析分离性。结果实质上可与在实施例3中获得的渗析分离性匹敌,且在其使用时耐用性和可处理性良好。
Claims (11)
1.一种由形成离子选择性膜成分和定形编织物衬底整体形成的离子选择性膜,离子选择性膜形成成分包括一种阳离子聚合物成分和/或阴离子聚合物成分和一种基质成分,其中每种离子聚合物成分是平均粒度范围是0.01-10μm的粒状聚合物,所述定形编织物衬底具有网状结构。
2.根据权利要求1的离子选择性膜,其中所述粒状聚合物是交联的。
3.根据权利要求1的离子选择性膜,其中所述一种离子聚合物成分和/或多种离子聚合物成分以及基质成分的使用比例是基质成分相当于占所述成分总和的2-95%。
4.根据权利要求1的离子选择性膜,其中所述定形编织织物的衬底有大小在1-5,000μm范围内的孔(线间的间距)。
5.根据权利要求1的离子选择性膜,其中所述基质成分是至少一种聚合物,选自聚砜树脂、多芳基化合物树脂、聚酰胺树脂、聚酰亚胺树脂、聚酰胺-酰亚胺树脂、聚氨酯树脂、氟化树脂、硅酮树脂和二烯烃单体的均聚物或共聚物树脂的氢化产物。
6.如权利要求1定义的离子选择性膜的制备方法,包括在形成膜的同时保持一层涂布制剂与所述定形编织物衬底紧密接触,涂布制剂中所述一种或多种离子聚合物成分分散于所述基质成分在有机溶剂中的溶液或分散体中。
7.根据权利要求6的方法,其中所述有机溶剂是含氮有机溶剂。
8.根据权利要求6的方法,其中通过将所述涂布制剂涂布到脱模基料表面上形成一层涂布层,并且在形成所述膜的同时保持所述涂布层与所述定形编织物衬底紧密接触。
9.一种使用如权利要求1定义的离子选择性膜在渗透电解质中的用途。
10.一种装备有权利要求1定义的离子选择性膜的仪器。
11.根据权利要求10的仪器,其中所述如权利要求1定义的离子选择性膜是平面膜、螺旋状膜、波纹状膜、圆筒形膜或中空毛细管的形式。
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AU (1) | AU769448B2 (zh) |
DE (1) | DE60032956T8 (zh) |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN100448086C (zh) * | 2002-03-06 | 2008-12-31 | 巴斯夫燃料电池有限责任公司 | 包括含乙烯基的膦酸的混合物、含聚乙烯膦酸的聚合物电解质膜及其在燃料电池中的应用 |
CN102557205A (zh) * | 2012-01-21 | 2012-07-11 | 杭州普普科技有限公司 | 一种新型富集与分离污水中金属离子的方法及装置 |
CN103201025A (zh) * | 2010-10-04 | 2013-07-10 | 苏特沃克技术有限公司 | 弹性离子交换膜 |
CN104655609A (zh) * | 2013-11-20 | 2015-05-27 | 北京普析通用仪器有限责任公司 | 激发装置及发射光谱仪 |
CN107037107A (zh) * | 2015-12-08 | 2017-08-11 | 恩德莱斯和豪瑟尔分析仪表两合公司 | 电位传感器 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1381447B1 (en) * | 2001-04-27 | 2007-01-24 | Millipore Corporation | Coated membranes |
US6967232B2 (en) * | 2001-10-04 | 2005-11-22 | Dainichiseika Color & Chemicals Mfg., Co., Ltd. | High-molecular gelling agent precursor for electrolyte |
DE10220818A1 (de) * | 2002-05-10 | 2003-11-20 | Celanese Ventures Gmbh | Verfahren zur Herstellung einer gepfropften Polymerelektrolytmembran und deren Anwendung in Brennstoffzellen |
TW200420506A (en) * | 2003-02-14 | 2004-10-16 | Dainichiseika Color Chem | Method of desalting |
US9365662B2 (en) | 2010-10-18 | 2016-06-14 | Kraton Polymers U.S. Llc | Method for producing a sulfonated block copolymer composition |
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CN106139926B (zh) * | 2016-07-13 | 2019-03-22 | 合肥工业大学 | 聚电解质复合膜、其制备方法与扩散渗析脱盐的方法 |
US10836865B2 (en) * | 2017-02-14 | 2020-11-17 | The Board Of Trustees Of The University Of Alabama | Ionic polyamide and polyamide-imide materials and methods of use |
DE102018118792A1 (de) * | 2017-08-14 | 2019-02-14 | Endress+Hauser Conducta Gmbh+Co. Kg | Verfahren zum Herstellen einer ISE-Halbzelle, ISE-Halbzelle, Sensor und Multiparametersensor |
Family Cites Families (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2965697A (en) | 1956-11-05 | 1960-12-20 | Electric Storage Battery Co | Battery diaphragm |
US3376168A (en) | 1962-08-02 | 1968-04-02 | Yardney International Corp | Metal-containing graft-polymerized product and method of making same |
GB1039444A (en) | 1963-07-24 | 1966-08-17 | Ca Atomic Energy Ltd | Radiation induced graft copolymerization |
US3417459A (en) | 1965-05-06 | 1968-12-24 | Mallory & Co Inc P R | Bonding electrically conductive metals to insulators |
NL6809170A (zh) * | 1968-06-28 | 1969-12-30 | ||
US3673127A (en) | 1969-10-20 | 1972-06-27 | Gen Electric | Ultrafine porous polymer article and method of making |
GB1372225A (en) | 1971-01-07 | 1974-10-30 | Zlehit Pri Ban | Ionically conducting membrane suitable for use as a separator in an alkaline cell |
GB1449814A (en) | 1972-07-18 | 1976-09-15 | Atomic Energy Authority Uk | Method of preparing porous material0synthetic polymer composites |
FR2283167A1 (fr) * | 1974-06-04 | 1976-03-26 | Rhone Poulenc Ind | Utilisation en dialyse selective de membranes a base de polymeres echangeurs d'ions et d'un liant |
JPS568645B2 (zh) | 1974-09-05 | 1981-02-25 | ||
GB1512553A (en) | 1974-09-19 | 1978-06-01 | Mitsubishi Petrochemical Co | Orthopedic material |
GB1538810A (en) | 1976-08-10 | 1979-01-24 | Sumitomo Electric Industries | Hydrophilic porous fluorocarbon structures and process for their production |
US4116889A (en) | 1976-08-19 | 1978-09-26 | Allied Chemical Corporation | Bipolar membranes and method of making same |
US4230463A (en) | 1977-09-13 | 1980-10-28 | Monsanto Company | Multicomponent membranes for gas separations |
USRE31824E (en) | 1977-05-31 | 1985-02-05 | Rai Research Corporation | Separator membranes for electrochemical cells |
EP0004237A1 (fr) | 1978-03-14 | 1979-09-19 | Elf Atochem S.A. | Membranes échangeuses d'ions; leur préparation; leur utilisation dans l'électrolyse du chlorure de sodium |
IT1115166B (it) | 1978-04-07 | 1986-02-03 | Raychem Ltd | Composizioni polimere |
US4258900A (en) | 1979-05-21 | 1981-03-31 | Kamyr Valves, Inc. | Structure maintaining seats against ball valves |
US4346142A (en) | 1979-09-04 | 1982-08-24 | Celanese Corporation | Hydrophilic monomer treated microporous films and process |
FR2505879B1 (fr) | 1981-05-15 | 1985-09-27 | Chloe Chemie | Diaphragme, son procede de preparation et le procede d'electrolyse le mettant en oeuvre |
US4419209A (en) * | 1981-07-20 | 1983-12-06 | Dorr-Oliver Incorporated | Solid polymeric electrolyte |
US4468441A (en) | 1981-10-01 | 1984-08-28 | Rai Research Corp. | Separator membranes for redox-type electrochemical cells |
US4584246A (en) | 1983-11-23 | 1986-04-22 | Chinese Petroleum Corp. | Bipolar membranes |
US4610764A (en) * | 1984-02-07 | 1986-09-09 | Asahi Glass Company Ltd. | Electrolytic cation exchange membrane |
US4969998A (en) | 1984-04-23 | 1990-11-13 | W. L. Gore & Associates, Inc. | Composite semipermeable membrane |
US4613544A (en) | 1984-12-04 | 1986-09-23 | Minnesota Mining And Manufacturing Co. | Waterproof, moisture-vapor permeable sheet material and method of making the same |
US5256503A (en) | 1986-04-07 | 1993-10-26 | Scimat Limited | Process for making a composite membrane |
US4851100A (en) * | 1988-05-02 | 1989-07-25 | Ionics, Incorporated | Novel bipolar membranes and process of manufacture |
GB2250469B (en) * | 1990-12-03 | 1995-03-22 | Aligena Ag | Charged asymmetric mosaic membranes |
DE69330933T2 (de) | 1992-09-25 | 2002-04-04 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Verfahren zur Herstellung geladener Mosaikmembranen |
JP3236754B2 (ja) * | 1995-04-05 | 2001-12-10 | 大日精化工業株式会社 | モザイク荷電膜体、その製造方法、それを用いた脱塩方法及び脱塩装置 |
AU676971B1 (en) | 1995-08-24 | 1997-03-27 | Dainichiseika Color & Chemicals Mfg. Co. Ltd. | Production process of connected microgel particles and articles treated with connected microgel particles |
JP3261047B2 (ja) * | 1996-09-13 | 2002-02-25 | 大日精化工業株式会社 | 荷電モザイク膜、その製造方法、該荷電モザイク膜の使用方法及び該荷電モザイク膜を備えた装置 |
JP3453067B2 (ja) * | 1998-02-25 | 2003-10-06 | 大日精化工業株式会社 | 荷電モザイク膜、荷電モザイク膜の使用方法及び荷電モザイク膜を備えた装置 |
-
2000
- 2000-02-16 DE DE60032956T patent/DE60032956T8/de active Active
- 2000-02-16 EP EP00103173A patent/EP1031598B1/en not_active Expired - Lifetime
- 2000-02-16 ES ES00103173T patent/ES2278555T3/es not_active Expired - Lifetime
- 2000-02-17 MY MYPI20000576 patent/MY123475A/en unknown
- 2000-02-18 AU AU17576/00A patent/AU769448B2/en not_active Ceased
- 2000-02-18 US US09/506,689 patent/US6484887B1/en not_active Expired - Lifetime
- 2000-02-22 KR KR10-2000-0008408A patent/KR100472645B1/ko not_active IP Right Cessation
- 2000-02-22 CN CNB001041746A patent/CN1151865C/zh not_active Expired - Fee Related
- 2000-04-07 TW TW089102885A patent/TW460315B/zh not_active IP Right Cessation
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CN100448086C (zh) * | 2002-03-06 | 2008-12-31 | 巴斯夫燃料电池有限责任公司 | 包括含乙烯基的膦酸的混合物、含聚乙烯膦酸的聚合物电解质膜及其在燃料电池中的应用 |
CN1330045C (zh) * | 2002-06-21 | 2007-08-01 | 格勒诺布尔国立综合理工学院 | 离子导电性增强材料及其在电极和电解质中的应用 |
CN103201025A (zh) * | 2010-10-04 | 2013-07-10 | 苏特沃克技术有限公司 | 弹性离子交换膜 |
CN102557205A (zh) * | 2012-01-21 | 2012-07-11 | 杭州普普科技有限公司 | 一种新型富集与分离污水中金属离子的方法及装置 |
CN104655609A (zh) * | 2013-11-20 | 2015-05-27 | 北京普析通用仪器有限责任公司 | 激发装置及发射光谱仪 |
CN107037107A (zh) * | 2015-12-08 | 2017-08-11 | 恩德莱斯和豪瑟尔分析仪表两合公司 | 电位传感器 |
CN107037107B (zh) * | 2015-12-08 | 2020-10-16 | 恩德莱斯和豪瑟尔分析仪表两合公司 | 电位传感器 |
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CN1151865C (zh) | 2004-06-02 |
AU769448B2 (en) | 2004-01-29 |
DE60032956T8 (de) | 2007-09-13 |
TW460315B (en) | 2001-10-21 |
KR20010014498A (ko) | 2001-02-26 |
AU1757600A (en) | 2000-08-24 |
US6484887B1 (en) | 2002-11-26 |
EP1031598A3 (en) | 2001-03-21 |
EP1031598B1 (en) | 2007-01-17 |
DE60032956D1 (de) | 2007-03-08 |
KR100472645B1 (ko) | 2005-03-07 |
DE60032956T2 (de) | 2007-05-24 |
EP1031598A2 (en) | 2000-08-30 |
MY123475A (en) | 2006-05-31 |
ES2278555T3 (es) | 2007-08-16 |
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