CN103781810A - 在含水介质中制备的阳离子交换材料 - Google Patents
在含水介质中制备的阳离子交换材料 Download PDFInfo
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Abstract
本申请描述了一种制备聚合物的方法,所述方法包括:在包含水和水溶性醇的含水溶液中混合以下:具有磺酸官能团的基于乙烯基的单体、双官能的基于乙烯基的交联剂和聚合引发剂,以形成反应溶液,其中所述单体和交联剂可溶于反应溶液中;和使单体和交联剂聚合,以形成所述聚合物。本申请还描述了一种聚合物,所述聚合物包括包含磺酸官能团的聚合物骨架;和包含醇官能团的交联。
Description
领域
总体而言,本公开涉及阳离子交换材料。
背景
制备标准阳离子交换材料采用非聚合的高沸点溶剂,用于使含磺酸基的乙烯基单体和二乙烯基交联剂在自由基引发剂存在下聚合。在若干情况下,在溶剂中溶解单体和交联剂必须经长时间高温混合和使用抑制剂来抑制在高温混合制备期间单体的过早聚合。另外,阳离子交换材料的后处理涉及处理在危险废物流中高达30-35重量%的溶剂,提高废物处置的成本。
MacDonald的美国专利号4,617,321公开了阳离子交换材料的制备,其中含磺酸基的乙烯基单体与丙烯酰胺和N-羟甲基丙烯酰胺聚合,使用水作为非聚合溶剂。MacDonald教导将单体在80℃下聚合2小时。
本领域已知用于生产阳离子交换膜的过程涉及在非含水介质中制备阳离子交换膜(和/或前体),和使膜磺化,以得到磺酸基。使用这些原料涉及的成本,以及将该过程放大至工业级的成本,增加与膜生产过程相关的成本。
发明概述
期望提供一种较低成本溶剂系统和/或更环保的溶剂系统用于制备阳离子交换材料。
期望简化用于制备阳离子交换材料的过程,例如通过使用比起在先前已知的过程中所需的温度(例如当使用NMP来溶解AMPS时所需的温度)更接近环境温度的温度下可溶解单体(例如AMPS)的溶剂。
期望使用导致在制备后废物流中降低量的有机溶剂的溶剂系统,从而降低废物处理和处置成本。
本公开的一个目的是消除或减轻先前的阳离子交换材料和它们的生产方法的至少一个缺点。
在第一方面,本公开提供了一种制备聚合物的方法,所述方法包括:在包含水和水溶性醇的含水溶液中混合:具有磺酸或磺酸盐官能团的基于乙烯基的单体、双官能的基于乙烯基的交联剂和聚合引发剂,以形成反应溶液,其中所述单体和交联剂可溶于反应溶液中;和使单体和交联剂聚合,以形成所述聚合物。
在一些方法中,所述单体和交联剂可以0.50:1-2.0:1(单体:交联剂)的摩尔比混合;所述聚合引发剂可以0.0025:1-0.02:1(聚合引发剂的摩尔数:单体和交联剂的总摩尔数)的摩尔比加入;和所述含水溶液可包括1.0:1-3.0:1(水:水溶性醇)重量比的水和水溶性醇。
在具体的方法中,所述单体和交联剂可共计为反应溶液的50-80重量%;其中所述剩余重量%包含具有1.0:1-3.0:1重量比的水:醇的含水溶液。
所述基于乙烯基的单体可为基于丙烯酸的单体、基于苯乙烯的单体或基于烯丙基的单体。
所述单体可为2-丙烯酰胺基丙基甲磺酸(AMPS),所述交联剂可为甘油二甲基丙烯酸酯(GDMA),并且所述水溶性醇可为1-丙醇。
所述方法还可包括在真空下混合反应溶液。
所述方法还可包括将所述聚合物放置在背衬布上,以形成聚合物片材;干燥所述聚合物片材;和将磺酸基转化为磺酸盐官能团,以形成阳离子交换膜片材。可将聚合物片材在60℃-90℃温度下干燥30-120分钟。碳酸氢钠饱和溶液可用于将磺酸基转化为磺酸盐官能团。所述背衬布可选自丙烯酸、聚丙烯(prolyene)和聚酯布。
在另一方面,本公开提供了一种聚合物,所述聚合物包括包含磺酸官能团的聚合物骨架;和包含醇官能团的交联。
所述聚合物骨架可包括式I的单体结构单元:
式I。
所述交联可包括式II的交联剂:
式II。
预期的具体聚合物可根据式III:
式III。
结合附图,检阅以下具体实施例的描述,本公开的其它方面和特征对于本领域普通技术人员变得显而易见。
附图简述
图1说明用于形成交联聚合物的聚合反应。
图2为说明用于合成交联聚合物的方法的流程图。
图3为说明使用所述交联聚合物用于制备阳离子交换膜的方法的流程图。
发明详述
总的来说,本公开提供了用于在含水介质中制备阳离子交换材料的过程。更具体地,本公开涉及在含水介质中制备的与甘油二甲基丙烯酸酯交联的聚(2-丙烯酰胺基丙基甲磺酸)。
用于合成聚合物的过程通过图2的流程图说明,并且包括:以0.5:1-2.0:1摩尔比(单体:交联剂)将基于乙烯基的单体和基于乙烯基的交联剂的50-80重量%的混合物混合;剩余重量%包含具有1.0:1-3.0:1重量比的水:醇的含水溶液,其中所述聚合引发剂可以0.0025:1-0.02:1的摩尔比(聚合引发剂的摩尔数:单体和交联剂的总摩尔数)加入。
在各种实例中,基于乙烯基的单体和基于乙烯基的交联剂可组成反应溶液的50-55、55-60、60-65、65-70、70-75或75-80重量%。在其它实例中,基于乙烯基的单体和基于乙烯基的交联剂可组成反应溶液的50-60、60-70或70-80重量%。
在各种实例中,含水溶液可具有0.5:1-1.0:1、1.0:1-1.5:1、1.5:1-2.0:1、2.0:1-2.5:1或2.5:1-3.0:1重量比的水:醇。在其它实施例中,含水溶液可具有0.5:1-1.5:1、1.5:1-3.0:1重量比的水:醇。
在特定实施例中,基于乙烯基的单体和基于乙烯基的交联剂可组成反应溶液的60-70重量%并且可溶解于水和水溶性醇的含水溶液中,该含水溶液组成反应溶液的剩余部分,所述含水溶液具有1.5:1-3.0:1重量比的水:醇和0.7-0.85重量%的聚合引发剂。
基于乙烯基的单体和基于乙烯基的交联剂可溶于水和水溶性醇的含水溶液中。基于乙烯基的单体可为基于丙烯酸的单体、基于苯乙烯的单体或基于烯丙基的单体。单体可为例如2-丙烯酰胺基丙基甲磺酸(AMPS)、苯乙烯磺酸钠、甲基烯丙基磺酸钠、乙烯基磺酸钠、烯丙基磺酸钠、2-丙烯酰胺基-2-甲基丙磺酸、2-磺基乙基甲基丙烯酸钠或2-磺基丁基甲基丙烯酸钠。优选的单体为AMPS。
基于乙烯基的交联剂可为基于丙烯酸的交联剂、基于苯乙烯的交联剂或基于烯丙基的交联剂。基于乙烯基的交联剂可为例如甘油二甲基丙烯酸酯(GDMA)、N-(丙烯酰胺基甲基)甲基丙烯酰胺、乙二醇二甲基丙烯酸酯、甘油二甲基丙烯酸酯、聚(乙二醇)二甲基丙烯酸酯和亚甲基双丙烯酰胺。优选的基于乙烯基的交联剂为GDMA。
所述水溶性醇为能增溶所述单体和交联剂的水溶性溶剂。优选,水溶性醇为高沸点、低成本、低毒性溶剂。在特定的实施方案中,水溶性醇为丙醇或丁醇。在特定的实施方案中,水溶性醇为1-丙醇。
单体和交联剂的聚合可使用可溶于含水溶剂的聚合引发剂热引发或光化学引发,例如使用2,2'-偶氮二(2-甲基丙脒)二盐酸盐(工业上称为V-50);2,2'-偶氮二[2-(2-咪唑啉-2-基)丙烷]二盐酸盐(VA-044);脱水2,2'-偶氮二[2-(2-咪唑啉-2-基)丙烷]二硫酸盐(VA-046B);水合2,2'-偶氮二[N-(2-羧乙基)-2-甲基丙脒](VA-057);2,2'-偶氮二{2-[1-(2-羟乙基)-2-咪唑啉-2-基]丙烷}二盐酸盐(VA-060);2,2'-偶氮二[2-(2-咪唑啉-2-基)丙烷](VA-061);2,2'-偶氮二(1-亚氨基-1-吡咯烷-2-乙基丙烷)二盐酸盐(VA-067);2,2'-偶氮二{2-甲基-N-[1,1-双(羟甲基)-2-羟乙基]丙酰胺}(VA-080);或2,2'-偶氮二[2-甲基-N-(2-羟乙基)丙酰胺](VA-086)。在特定实例中,聚合引发剂可为例如2,2'-偶氮二(2-甲基丙脒)二盐酸盐。
可期望使用引发温度低于50℃的聚合引发剂,以促进在温和条件下膜固化。使用在较低温度(例如,50℃)下引发聚合/固化的引发剂可帮助避免在较高温度下固化涉及的能量成本。
在聚合反应中的链封端通过不同的机理发生,例如通过两个活性聚合部位重组或通过活性聚合部位与抑制剂相互作用。如果期望较长链,聚合引发剂浓度和聚合抑制剂浓度应比期望较短链情况下的浓度低。取决于聚合物的期望长度,可期望聚合在不含或基本上不含聚合抑制剂的反应条件下发生,所述聚合抑制剂例如氧、硝基苯、丁基化的羟基甲苯或二苯基苦基偕肼(DPPH)。
生产的聚合材料可用于生产例如阳离子交换树脂或阳离子交换膜。用于生产阳离子交换膜的示例性过程通过图3的流程图说明。在这样的方法中,单体、交联剂和聚合引发剂的混合物用于润湿膜背衬布,例如丙烯酸、聚酯或聚丙烯。将混合物夹在玻璃板之间以除去过量的试剂和随后通过干燥固化,例如在60-90℃温度的烘箱中30-120分钟。应理解的是,当与在较高温度(例如,90℃)下固化相比时,在较低温度(例如,60℃)下固化需要更长的固化时间。
取决于所用的单体,固化的膜可转化为阴离子官能团,例如通过在碳酸氢钠饱和溶液中处理膜达一定的时间(例如,10-20小时,取决于膜的尺寸),以将磺酸基转化为磺酸钠官能团。膜可例如用去离子水漂洗1天,以得到阳离子交换膜。
在一个具体的实例中,交联的聚合物由2-丙烯酰胺基丙基甲磺酸(AMPS)和甘油二甲基丙烯酸酯(GDMA)在水/丙醇溶液存在下聚合而生产,并且使用2,2'-偶氮二(2-甲基丙脒)二盐酸盐(V-50)引发,如在图1中说明的,并且在实施例1、3、5、7、9和12中举例说明。在实施例1、3、5、7、9和12中所用的试剂和溶剂的量汇总于下表1,并且试剂和溶剂的相应重量%以及AMPS:GDMA和水:丙醇的摩尔比和重量比汇总于表2。
表1
表2
以下实施例教导本申请(实施例1、3、5、7、9和12)预期的不同聚合物的合成,并且教导使用不同的聚合物生产阳离子交换膜的不同方式和报道膜所得到的性质(实施例2、4、6、8、10、11和13)。
实施例1 单体、交联剂和聚合引发剂的示例性混合物
将AMPS (34.8 g)溶解于水(24 g)中并且搅拌35分钟。将GDMA (27.5 g)溶解于1-丙醇(13 g)中并且搅拌15分钟。将GDMA溶液缓慢加入到AMPS溶液中,将所得到的溶液搅拌15分钟。最后,将V-50催化剂(0.73 g)加入到烧瓶中,将溶液搅拌另外的20分钟。将溶液转移至圆底烧瓶,并且在真空下脱气45分钟。
实施例2 生产示例性阳离子交换膜
如在实施例1中所述生产的脱气的单体混合物用于湿润丙烯酸背衬布。将丙烯酸布(0.44958 mm厚)放置在聚酯薄膜片材上,进而将该片材放置在干净的玻璃板上,并且将如实施例1中所述的单体溶液倒在背衬布上。将第二聚酯薄膜片材放置在湿丙烯酸背衬布上,并且将过量的单体混合物从布排出。将两个聚酯薄膜片材和丙烯酸(acylic)布夹在玻璃板之间,并且使用粘合夹具夹紧。夹入的片材通过在85℃的烘箱中加热40分钟而固化。将已固化的夹入片材在烘箱外面冷却15分钟,移除玻璃板。将聚酯薄膜片材与丙烯酸(acylic)/聚合物膜分离,将膜在碳酸氢钠饱和溶液中浸泡10-14小时,以将AMPS的磺酸基转化为磺酸钠官能团。膜用去离子水漂洗1天或直到分析级别,以得到阳离子交换膜。
由AMPS和GDMA的聚合生产的阳离子交换膜对各种溶液(例如2 N氯化钠和1 N氢氧化钠)防漏并且稳定,并且理论离子交换容量为2.5 mEq/g(干重),水含量为33重量%。
由AMPS和GDMA的共聚生产的阳离子交换膜的测量的离子交换容量为2.31 meq/g(干重);水含量为46.7%;厚度为0.56 mm,并且面电阻为10.96 Ohm-cm2。
实施例3 单体、交联剂和聚合引发剂的示例性混合物
将AMPS (33.54 g)溶解于水(22 g)中并且搅拌35分钟。将GDMA (28.4 g)溶解于1-丙醇(13 g)中并且搅拌15分钟。将GDMA溶液缓慢加入到AMPS溶液中,将所得到的溶液搅拌15分钟。最后,将V-50催化剂(0.71 g)加入到烧瓶中,将溶液搅拌另外的20分钟。将溶液转移至圆底烧瓶,并且在真空下脱气45分钟。
实施例4 生产示例性阳离子交换膜
如如在实施例3中所述生产的脱气的单体混合物用于湿润丙烯酸背衬布。将丙烯酸布(0.44958 mm厚)放置在聚酯薄膜片材上,进而将该片材放置在干净的玻璃板上,并且将如实施例3中所述的单体溶液倒在背衬布上。将第二聚酯薄膜片材放置在湿丙烯酸背衬布上,并且将过量的单体混合物从布排出。将两个聚酯薄膜片材和丙烯酸(acylic)布夹在玻璃板之间,并且使用粘合夹具夹紧。夹入的片材通过在85℃的烘箱中加热40分钟而固化。将已固化的夹入片材在烘箱外面冷却15分钟,移除玻璃板。将聚酯薄膜片材与丙烯酸(acylic)/聚合物膜分离,将膜在碳酸氢钠饱和溶液中浸泡10-14小时,以将AMPS的磺酸基转化为磺酸钠官能团。膜用去离子水漂洗1天或直到分析级别,以得到阳离子交换膜。
由AMPS和GDMA的聚合生产的阳离子交换膜对各种溶液(例如2 N氯化钠和1 N氢氧化钠)防漏并且稳定,并且理论离子交换容量为2.4 mEq/g(干重),溶剂(水+丙醇)含量为33重量%。
实施例5 单体、交联剂和聚合引发剂的示例性混合物
将AMPS (30.6 g)溶解于水(18 g)中并且搅拌35分钟。将GDMA (30.6 g)溶解于1-丙醇(15 g)中并且搅拌15分钟。将GDMA溶液缓慢加入到AMPS溶液中,将所得到的溶液搅拌15分钟。最后,将V-50催化剂(0.71 g)加入到烧瓶中,将溶液搅拌另外的20分钟。将溶液转移至圆底烧瓶,并且在真空下脱气45分钟。
实施例6 生产示例性阳离子交换膜
如如在实施例5中所述生产的脱气的单体混合物用于湿润丙烯酸背衬布。将丙烯酸布(0.44958 mm厚)放置在聚酯薄膜片材上,进而将该片材放置在干净的玻璃板上,并且将如实施例5中所述的单体溶液倒在背衬布上。将第二聚酯薄膜片材放置在湿丙烯酸布上,并且将过量的单体混合物从布排出。将两个聚酯薄膜片材和丙烯酸(acylic)布夹在玻璃板之间,并且使用粘合夹具夹紧。夹入的片材通过在85℃的烘箱中加热40分钟而固化。将已固化的夹入片材在烘箱外面冷却15分钟,移除玻璃板。将聚酯薄膜片材与丙烯酸(acylic)/聚合物膜分离,将膜在碳酸氢钠饱和溶液中浸泡10-14小时,以将AMPS的磺酸基转化为磺酸钠官能团。膜用去离子水漂洗1天或直到分析级别,以得到阳离子交换膜。
由AMPS和GDMA的聚合生产的阳离子交换膜对各种溶液(例如2 N氯化钠和1 N氢氧化钠)防漏并且稳定,并且理论离子交换容量为2.2 mEq/g(干重),溶剂(水+丙醇)含量为33重量%。
实施例7 单体、交联剂和聚合引发剂的示例性混合物
将AMPS (33 g)溶解于水(20g)中并且搅拌35分钟。将GDMA (28.1 g)溶解于1-丙醇(13 g)中并且搅拌15分钟。将GDMA溶液缓慢加入到AMPS溶液中,将所得到的溶液搅拌15分钟。最后,将V-50催化剂(0.71 g)加入到烧瓶中,将溶液搅拌另外的20分钟。将溶液转移至圆底烧瓶,并且在真空下脱气45分钟。
实施例8 生产示例性阳离子交换膜
如如在实施例7中所述生产的脱气的单体混合物用于湿润丙烯酸背衬布。将丙烯酸布(0.44958 mm厚)放置在聚酯薄膜片材上,进而将该片材放置在干净的玻璃板上,并且将如实施例7中所述的单体溶液倒在背衬布上。将第二聚酯薄膜片材放置在湿丙烯酸布上,并且将过量的单体混合物从布排出。将两个聚酯薄膜片材和丙烯酸(acylic)布夹在玻璃板之间,并且使用粘合夹具夹紧。夹入的片材通过在85℃的烘箱中加热35分钟而固化。将已固化的夹入片材在烘箱外面冷却15分钟,移除玻璃板。将聚酯薄膜片材与丙烯酸(acylic)/聚合物膜分离,将膜在碳酸氢钠饱和溶液中浸泡10-14小时,以将AMPS的磺酸基转化为磺酸钠官能团。膜用去离子水漂洗1天或直到分析级别,以得到阳离子交换膜。
由AMPS和GDMA的聚合生产的阳离子交换膜对各种溶液(例如2 N氯化钠和1 N氢氧化钠)防漏并且稳定,并且理论离子交换容量为2.4 mEq/g(干重),溶剂(水+丙醇)含量为33重量%。
由AMPS和GDMA的聚合生产的阳离子交换膜的测量的离子交换容量为2.06 meq/g(干重),水含量为41.8%,厚度为0.59 mm,并且面电阻为12.00 Ohm-cm2。
实施例9 单体、交联剂和聚合引发剂的示例性混合物
在室温下将AMPS (33 g)溶解于水(20g)中并且搅拌30分钟。将GDMA (28.5 g)溶解于1-丙醇(13 g)中,并且缓慢加入到AMPS溶液中。将所得到的溶液搅拌20分钟。最后,将V-50催化剂(0.71 g)加入到烧瓶中,将溶液搅拌另外的20分钟。将溶液转移至圆底烧瓶,并且在真空下脱气45分钟。
实施例10 生产示例性阳离子交换膜
如如在实施例9中所述生产的脱气的单体混合物用于湿润丙烯酸背衬布。将丙烯酸布(0.44958 mm厚)放置在聚酯薄膜片材上,进而将该片材放置在干净的玻璃板上,并且将如实施例9中所述的单体溶液倒在背衬布上。将第二聚酯薄膜片材放置在湿丙烯酸布上,并且将过量的单体混合物从布排出。将两个聚酯薄膜片材和丙烯酸(acylic)布夹在玻璃板之间,并且使用粘合夹具夹紧。夹入的片材通过在85℃的烘箱中加热40分钟而固化。将已固化的夹入片材在烘箱外面冷却15分钟,移除玻璃板。将聚酯薄膜片材与丙烯酸(acylic)/聚合物膜分离,将膜在碳酸氢钠饱和溶液中浸泡10-14小时,以将AMPS的磺酸基转化为磺酸钠官能团。膜用去离子水漂洗1天或直到分析级别,以得到阳离子交换膜。
由AMPS和GDMA的聚合生产的阳离子交换膜对各种溶液(例如2 N氯化钠和1 N氢氧化钠)防漏并且稳定,并且理论离子交换容量为2.4 mEq/g(干重),溶剂(水+丙醇)含量为33重量%。
由AMPS和GDMA的聚合生产的阳离子交换膜的测量的离子交换容量为2.25 meq/g(干重),水含量=45.1%,厚度为0.56 mm,面电阻为10.95 Ohm-cm2。
实施例11 生产示例性阳离子交换膜
如如在实施例9中所述生产的脱气的单体混合物用于湿润丙烯酸背衬布。将丙烯酸布(0.44958 mm厚)放置在聚酯薄膜片材上,进而将该片材放置在干净的玻璃板上,并且将如实施例9中所述的单体溶液倒在背衬布上。将第二聚酯薄膜片材放置在湿丙烯酸布上,并且将过量的单体混合物从布排出。将两个聚酯薄膜片材和丙烯酸(acylic)布夹在玻璃板之间,并且使用粘合夹具夹紧。夹入的片材通过在85℃的烘箱中加热40分钟而固化。将已固化的夹入片材在烘箱外面冷却15分钟,移除玻璃板。将聚酯薄膜片材与丙烯酸(acylic)/聚合物膜分离,将膜在碳酸氢钠饱和溶液中浸泡10-14小时,以将AMPS的磺酸基转化为磺酸钠官能团。膜用去离子水漂洗1天或直到分析级别,以得到阳离子交换膜。
由AMPS和GDMA的聚合生产的阳离子交换膜对各种溶液(例如2 N氯化钠和1 N氢氧化钠)防漏并且稳定,并且理论离子交换容量为2.4 mEq/g(干重),溶剂(水+丙醇)含量为33重量%。
由AMPS和GDMA的聚合生产的阳离子交换膜的测量的离子交换容量为1.98 meq/g(干重),水含量为39.2 %,厚度为0.54 mm,并且面电阻为16.76 Ohm-cm2。
实施例12 单体、交联剂和聚合引发剂的示例性混合物
将AMPS (33 g)溶解于水(20g)中并且搅拌10分钟。将1-丙醇(10g)加入到溶液中,将其搅拌10分钟。将GDMA (28.1 g)加入到溶液中,随后搅拌10分钟。最后,将V-50催化剂(0.85 g)加入到烧瓶中,将溶液搅拌另外的15分钟。将溶液转移至圆底烧瓶,并且在真空下脱气30分钟。
实施例13 生产示例性阳离子交换膜
如如在实施例12中所述生产的脱气的单体混合物用于湿润丙烯酸背衬布。将丙烯酸、聚丙烯或聚酯布放置在聚酯薄膜片材上,进而将该片材放置在干净的玻璃板上,并且将如实施例12中所述的单体溶液倒在背衬布上。将第二聚酯薄膜片材放置在丙烯酸、聚丙烯或聚酯布上,并且将过量的单体混合物从丙烯酸、聚丙烯或聚酯布排出。将两个聚酯薄膜片材和丙烯酸、聚丙烯或聚酯布夹在玻璃板之间,并且使用粘合夹具夹紧。夹入的片材通过在75℃、80℃或85℃的烘箱中干燥30、45或60分钟而固化。将已固化的夹入片材在烘箱外面冷却15分钟,移除玻璃板。将聚酯薄膜片材与所得的膜分离,将膜在碳酸氢钠饱和溶液中浸泡10-14小时,以将AMPS的磺酸基转化为磺酸钠官能团。膜用去离子水漂洗1天或直到分析级别,以得到阳离子交换膜。
由如在实施例12中所述的AMPS和GDMA的聚合生产的阳离子交换膜对各种溶液(例如2 N氯化钠和1 N氢氧化钠)防漏并且稳定。生产的阳离子交换膜:离子交换容量为2.2-2.3 mEq/g(干重),水含量为40-45重量%,并且面电阻为10-13 Ohm cm2。
实施例14 用于测定离子交换容量和水含量的实验方案
使用模具切割各自为3”×0.75”尺寸的两个膜条,并且放置在锥形瓶(250 ml)中。将100 ml 1N盐酸加入到烧瓶中,将烧瓶振动30分钟。1N HCl随后用100 mL去离子(DI)水替代,将烧瓶振动15分钟。将去离子水洗涤重复3次,或直至溶液pH为4.0。将膜在1N NaCl溶液中浸泡,并且振动30分钟。将条从烧瓶移除,并且用去离子水漂洗至烧瓶中。使用吸收纸将膜表面上的过量水吸干,记录膜的湿重 (W湿)。随后将膜在120℃的烘箱中干燥至少30分钟。将膜从烘箱移除,立即测量干重(W干)。在酚酞指示剂存在下,将得自锥形瓶的1N NaCl溶液用0.1N NaOH溶液(在滴定管中)滴定。0.1N NaOH溶液的初始和最终体积(滴定管读数)分别记录为Vi和Vf。随后根据以下等式计算膜的离子交换容量和水含量:
IEC (以meq/g计)=[(0.1N NaOH的滴定体积)×(NaOH的当量浓度)/(W干-布背衬重量)]×1000
水含量(以%计)=[(W湿-W干)/(W湿-布背衬重量)]×100
实施例15 用于测量厚度和面电阻的实验方案
将膜条切割成为3”×0.75”尺寸,并且放置在100 ml塑料瓶中。将80 ml 1N NaCl加入到瓶中,将瓶振动30分钟。将溶液弃置,将膜在80 mL去离子(DI)水中洗涤3次。随后将膜在瓶中在0.01N NaCl溶液中浸泡,并且振动至少30分钟。随后使用厚度量规测量厚度。通过将膜放置在与传导率/电阻率计连接的两个铂电极之间测量电阻。将记录的电阻乘以电极的面积,以得到面电阻。
上述实施例旨在仅为说明性。在不偏离本发明的范围的情况下,本领域技术人员可以对具体的实施例实施变更、修改和变化,本发明的范围仅由所附权利要求限定。
Claims (13)
1. 一种制备聚合物的方法,所述方法包括:
在包含水和水溶性醇的含水溶液中混合以下:
具有磺酸官能团的基于乙烯基的单体,
双官能的基于乙烯基的交联剂,和
聚合引发剂,
以形成反应溶液,其中所述单体和交联剂可溶于所述反应溶液中;和
使所述单体和交联剂聚合,以形成所述聚合物。
2. 权利要求1的方法,其中:
所述单体和交联剂以0.5:1-2.0:1(单体:交联剂)的摩尔比混合;
所述聚合引发剂以0.0025:1-0.02:1(聚合引发剂的摩尔数:单体和交联剂的总摩尔数)的摩尔比加入;和
所述含水溶液包含1.0:1-3.0:1(水:水溶性醇)重量比的水和水溶性醇。
3. 权利要求2的方法,其中所述反应溶液包含:
所述单体和交联剂共计为所述反应溶液的50-80重量%;和
所述含水溶液组成所述反应溶液的剩余重量%。
4. 权利要求1的方法,其中所述单体为2-丙烯酰胺基丙基甲磺酸(AMPS),所述交联剂为甘油二甲基丙烯酸酯(GDMA),并且所述水溶性醇为1-丙醇。
5. 权利要求1的方法,所述方法还包括在真空下混合所述反应溶液。
6. 权利要求1的方法,所述方法还包括:
将所述聚合物放置在背衬布上,以形成聚合物片材;
干燥所述聚合物片材;和
将所述磺酸基转化为磺酸盐官能团,以形成阳离子交换膜片材。
7. 权利要求6的方法,其中将所述聚合物片材在60℃-90℃温度下固化30-120分钟。
8. 权利要求6的方法,其中使用碳酸氢钠饱和溶液将所述磺酸基转化为磺酸盐官能团。
9. 权利要求6的方法,其中所述背衬布选自丙烯酸、聚丙烯(prolyene)和聚酯布。
10. 一种聚合物,所述聚合物包含:
包含磺酸官能团的聚合物骨架;和
包含醇官能团的交联。
11. 权利要求10的聚合物,其中所述聚合物骨架包含式I的单体结构单元:
式I。
13. 权利要求10的聚合物,其中所述聚合物根据式III:
式III。
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