CN111909419B - 具有氟化的共聚物作为表面处理的多孔膜 - Google Patents
具有氟化的共聚物作为表面处理的多孔膜 Download PDFInfo
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- CN111909419B CN111909419B CN202010385224.4A CN202010385224A CN111909419B CN 111909419 B CN111909419 B CN 111909419B CN 202010385224 A CN202010385224 A CN 202010385224A CN 111909419 B CN111909419 B CN 111909419B
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
公开了多孔膜,其包括多孔载体和涂层,该涂层包含具有单体单元A和B以及任选的单体单元C的共聚物,其中,A为不同于四氟乙烯的卤化的乙烯基单体,卤化的烷基乙烯基醚,或式CnH2n的烯烃,其中n为1‑6;B为全氟(烷基乙烯基)醚化合物、全氟烷基乙烯基化合物或全氟烷氧基烷基乙烯基醚化合物,每个化合物具有一个或更多个磺酸基团或其盐、一个或更多个磺酰氟基团、一个或更多个磺酰胺基团或一个或更多个磺酸酯基团;和C为偏氟乙烯。还公开了制备这样的多孔膜的方法和通过使用这些膜处理流体的方法。
Description
背景技术
含氟聚合物膜,例如多孔PTFE膜的性质,包括它们的机械强度、耐化学性或惰性、非粘性、优异的介电性质、在高的温度的热稳定性和低摩擦系数,使得它们对于许多应用而言非常具有吸引力。然而,对于某些应用将会有益的是,将PTFE的表面改性而不影响其固有性质。已经做出努力来改变PTFE膜的表面和化学性质,从而改进该膜对特定应用的适用性。例如,已做出的努力包括表面涂布,共混,高能表面改性,例如宽谱带紫外线辐射(BBUV),其中将膜暴露至波长250-450nm的UV辐射,和等离子体处理,自由基,和臭氧蚀刻,原子层沉积以及合成改性类PTFE聚合物。然而,当暴露至极其腐蚀性的流体,如热硫酸(如微电子学中遇到的那些)或氧化性流体时,大多数这些努力都无法获得令人满意的膜性质。
上述表明存在对耐腐蚀性或氧化性流体的多孔含氟聚合物膜的未满足的需求。
发明内容
本发明提供了多孔膜,其包括多孔的氟化的聚合物载体和涂层,所述涂层包含第一共聚物,
该第一共聚物包含聚合的单体单元A和B,和任选的聚合的单体单元C;
其中,A为不同于四氟乙烯的卤化的乙烯基单体,卤化的烷基乙烯基醚,或式CnH2n的烯烃,其中n为1-6;B为全氟(烷基乙烯基)醚化合物,全氟烷基乙烯基化合物或全氟烷氧基烷基乙烯基醚化合物,每个化合物具有一个或更多个磺酸基团或其盐、一个或更多个磺酰氟基团、一个或更多个磺酰胺基团或一个或更多个磺酸酯基团,和C为偏氟乙烯;
如果C存在的话,则其以在A、B和C之和的最多约30mol%的范围存在;
和,该第一共聚物具有按每个磺酸基团或其盐计约1200至约3000的当量重量。
本发明另外提供了制备多孔膜的方法,所述多孔膜包括多孔的氟化的聚合物载体和涂层,所述涂层包含第一共聚物,
该第一共聚物包含聚合的单体单元A和B,和任选的聚合的单体单元C;其中:A为不同于四氟乙烯的卤化的乙烯基单体,卤化的烷基乙烯基醚,或式CnH2n的烯烃,其中n为1-6;B为全氟(烷基乙烯基)醚化合物,全氟烷基乙烯基化合物或全氟烷氧基烷基乙烯基醚化合物,每个化合物具有一个或更多个磺酸基团或其盐、一个或更多个磺酰氟基团、一个或更多个磺酰胺基团或一个或更多个磺酸酯基团,和C为偏氟乙烯;
如果C存在的话,则其以在最多约30mol%的范围存在;
和,该第一共聚物具有按每个磺酸基团计约1200至约3000的当量重量;该方法包括:
提供多孔的氟化的聚合物载体和将该多孔的氟化的聚合物载体用第一共聚物涂布;和当B为具有一个或更多个磺酰氟基团或磺酸酯基团的全氟(烷基乙烯基)醚时,将磺酰氟基团或磺酸酯基团的一个或更多个用碱水解。
本发明另外提供了通过使用这些多孔膜处理或过滤流体的方法。
多孔膜的实施方案的有利之处在于,该膜在热的浓硫酸中在150℃至200℃范围内的温度具有长期稳定性。
具体实施方式
根据一个实施方案,本发明提供了多孔膜,其包括多孔的氟化的聚合物载体和涂层,所述涂层包含第一共聚物,
该第一共聚物包含聚合的单体A和B,和任选的聚合的单体C;
其中,A为不同于四氟乙烯的卤化的乙烯基单体,卤化的烷基乙烯基醚,或式CnH2n的烯烃,其中n为1-6;
B为全氟(烷基乙烯基)醚化合物,全氟烷基乙烯基化合物或全氟烷氧基烷基乙烯基醚化合物,每个化合物具有一个或更多个磺酸基团或其盐、一个或更多个磺酰氟基团、一个或更多个磺酰胺基团或一个或更多个磺酸酯基团,和C为偏氟乙烯;
如果C存在的话,则其以在A、B和C之和的最多约30mol%的范围存在;
和,该第一共聚物具有按每个磺酸基团或其盐计约1200至约3000的当量重量。
本发明另外提供了制备多孔膜的方法,所述多孔膜包括多孔的氟化的聚合物载体和涂层,所述涂层包含第一共聚物,
该第一共聚物包含聚合的单体单元A和B,和任选的聚合的单体单元C;其中:A为不同于四氟乙烯的卤化的乙烯基单体,卤化的烷基乙烯基醚,或式CnH2n的烯烃,其中n为1-6;B为全氟(烷基乙烯基)醚化合物,全氟烷基乙烯基化合物或全氟烷氧基烷基乙烯基醚化合物,每个化合物具有一个或更多个磺酸基团或其盐、一个或更多个磺酰氟基团、一个或更多个磺酰胺基团或一个或更多个磺酸酯基团,和C为偏氟乙烯;
如果C存在的话,则其以在最多约30mol%的范围存在;
和,该第一共聚物具有按每个磺酸基团计约1200至约3000的当量重量;该方法包括:
提供多孔的氟化的聚合物载体和将该多孔的氟化的聚合物载体用第一共聚物涂布;和当B为具有一个或更多个磺酰氟基团或磺酸酯基团的全氟(烷基乙烯基)醚时,将磺酰氟基团或磺酸酯基团的一个或更多个用碱水解。
根据一个实施方案,A选自氯三氟乙烯、溴三氟乙烯、六氟丙烯、三氟乙烯、H2C=CHCF3、H2C=CFCF3、CHF=CHCF3、H2C=CFCl、H2C=CFBr、CF2=CFOCF3、CF2=CFOC3F7、CF2=CFOC2H4C6F13、CH2=CHOC2H4C6F13、CF2=CFOC2H4Br、乙烯、丙烯及其任意组合。在特别的实施方案中,A为氯三氟乙烯。
根据任意上述实施方案,B选自CF2=CFOCF2CF(CF3)OC2F4SO2F、CF2=CFOCF2CF(CF3)OC2F4SO3H、CF2=CFOC2F4SO2F、CF2=CFOC2F4SO3H、CF2=CFC2F4SO2F、CF2=CFC2F4SO3H、CF2=CFOC4F8SO2F、CF2=CFOC4F8SO3H及其任意组合。在特别的实施方案中,B为CF2=CFOCF2CF(CF3)OC2F4SO2F。在另一实施方案中,B为CF2=CFOCF2CF(CF3)OC2F4SO3H。
根据任意上述实施方案,如果C存在的话,其可以以A、B和C之和的最多约30mol%,最多约20mol%,最多约10mol%,约5至约30mol%,约5至约20mol%,约10至约30mo%,约10至约20mol%,约2至10mol%或约1至约5mol%的量存在。根据本发明的实施方案,当C以如本文中描述的低的量存在的话,多孔膜对热的碱性氧化性溶液更稳定,例如在暴露至热的碱性氧化性溶液时,重量方面的损失明显更小。热的碱性氧化性溶液是本领域已知的;例如参见美国专利5,928,792号,实施例13。
共聚物可以为无规共聚物或嵌段共聚物。
根据任意上述实施方案,多孔膜包括任意合适的多孔含氟聚合物载体,例如由下述制成的载体:PTFE(聚四氟乙烯)、PVDF(聚偏氟乙烯)、PFA(全氟烷氧基乙烯基聚合物)、PMA(全氟烷氧基乙烯基聚合物)、PVF(聚氟乙烯)、PCTFE(聚氯三氟乙烯)、FEP(氟化的乙烯-丙烯聚合物)、ETFE(聚乙烯四氟乙烯)、ECTFE(聚乙烯-氯三氟乙烯)、PFPE(全氟聚醚)、FKM(聚氯三氟乙烯-偏氟乙烯)和全氟聚氧杂环丁烷。多孔载体优选为PTFE、FEP、PFA或PCTFE,并且最优选为PTFE。多孔载体可以具有任意合适的孔径,例如约2nm至约10微米。
共聚物可以具有任意合适的分子量,例如在一个实施方案中,约10kDa至约1000kDa,20kDa至约600kDa,优选约75kDa至约500kDa,并且更优选约100kDa至约500kDa的数均或重均(Mn或Mw)分子量。
可以通过任意合适的方法,例如通过自由基聚合来制备共聚物。可以使用任意合适的自由基引发剂。合适的自由基引发剂的实例包括2,2′-偶氮双(2-甲基丙腈)(AIBN)、4,4'-偶氮双(4-氰基戊酸)(ACPA)、过氧化氢、叔丁基过氧化物、过氧苯甲酸叔丁酯、过氧苯甲酸叔戊酯、过辛酸叔丁酯、过辛酸叔戊酯、过氧化新戊酸叔丁酯、二叔丁基过氧化物、过氧化二碳酸叔丁基环己酯、叔戊基过氧化氢、过氧化二苯甲酰、过硫酸铵、过硫酸钾、过硫酸钠、甲基乙基酮过氧化物和全氟-3-乙基-2,4-二甲基-3-戊基持续自由基。
可以以本体方式,即在不存在溶剂的情况下,或优选在溶剂中进行聚合。用于进行聚合的合适的溶剂的实例包括水,碳酸二甲酯,乙腈,乙酸甲酯,芳族烃如苯、甲苯和二甲苯,脂族烃如正戊烷、己烷和庚烷,脂环烃如环己烷和卤化的溶剂如二氯甲烷、二氯乙烷、二氯乙烯、四氯乙烷、氯苯、二氯苯、三氯苯、1,1,1,3,3-五氟丁烷、甲氧基九氟丁烷(7100)和FC75(全氟(丁基四氢呋喃))以及其混合物。
可以在任意合适的温度,例如-20至+100℃或更优选地10℃至80℃,特别是45℃至80℃进行聚合。
可以通过合适的技术,例如采用非溶剂沉淀或凝固而分离聚合物。
“SPM”意指在120℃至180℃的温度的热的硫酸过氧化氢混合物(按体积计70:30、75:25或80:20的H2SO4(96%):H2O2(30%))。
根据本发明的一个实施方案,多孔膜具有介于1nm与100nm之间,介于100nm与1000nm之间的直径的孔,或介于1μm与10μm之间的直径的孔。
可以通过将PTFE多孔载体的片材用异丙醇润湿,然后将载体用磺酸或磺酸盐形式的聚合物的0.1重量%-10重量%溶液涂布而制备多孔膜。涂布时间在介于1秒与1小时之间的范围内。在浸泡载体之后,将其在60℃至160℃干燥。干燥时间在介于10分钟与96h之间的范围内。替代地,可以通过将PTFE多孔载体的片材用磺酰氟形式的聚合物的0.1重量%-10重量%溶液涂布而制备多孔膜。涂布时间在介于1秒与1小时之间的范围内。在浸泡载体之后,将其在60℃至160℃干燥。干燥时间在介于10分钟与96h之间的范围内。然后可以将经涂布的多孔载体通过浸泡在碱性溶液中而将磺酰氟基团水解成磺酸根基团。任选地随后可以通过浸泡在酸性溶液,如5%HCl中而将磺酸根基团转变成磺酸基团。
关于表面张力的表面改性方面的改变可以通过测量临界表面张力(CWST)来进行测量。该方法依赖于一定组成的一系列溶液。每个溶液具有特定的表面张力。溶液的表面张力以小的非等量增量处在25至92达因/cm范围内。为了测量膜表面张力,将膜定位至白光台面顶部上,将一滴一定表面张力的溶液施加至膜表面并且记录液滴渗过该膜并且变成亮白色而作为光穿过膜的指示所花费的时间。当液滴渗过膜所花费的时间≤10秒时,认为立即润湿。如果该时间>10秒,则认为溶液部分地润湿该膜。
可以将根据本发明的实施方案的多孔膜用于各种应用,包括例如过滤电子工业的流体(例如过滤微电子工业中的光致抗蚀剂流体、热的硫酸和热的SPM)和用于处理含有离子材料的流体,例如作为离子交换膜。
根据本发明的实施方案,多孔膜可以具有各种形状,包括平面状、平坦的片状、褶皱状、管状、螺旋状和中空纤维状。
将根据本发明的实施方案的多孔膜典型地布置在壳体中,所述壳体包括至少一个入口和至少一个出口,并且限定入口与出口之间的至少一个流体流动路径,其中至少一个本发明的膜或包括至少一个本发明的膜的过滤器横跨流体流动路径,以提供过滤器装置或过滤器模块。在一个实施方案中,提供了过滤器装置,其包括:壳体,该壳体包括入口和第一出口,并且限定入口与第一出口之间的第一流体流动路径;和至少一个本发明的膜或包括至少一个本发明的膜的过滤器,将本发明的膜或包括至少一个本发明的膜的过滤器布置在壳体中横跨第一流体流动路径。
优选地,对于错流应用,将至少一个本发明的多孔膜或包括至少一个本发明的膜的过滤器布置在壳体中,所述壳体包括至少一个入口和至少两个出口,并且至少限定在入口与第一出口之间的第一流体流动路径,以及入口与第二出口之间的第二流体流动路径,其中本发明的膜或包括至少一个本发明的膜的过滤器横跨第一流体流动路径,以提供过滤器装置或过滤器模块。在一个示例性实施方案中,过滤器装置包括错流过滤器模块,壳体包括入口、第一出口和第二出口,所述第一出口包括浓缩物出口,所述第二出口包括渗余物出口,并且所述壳体限定入口与第一出口之间的第一流体流动路径以及入口与第二出口之间的第二流体流动路径,其中将至少一个本发明的膜或包括至少一个本发明的膜的过滤器横跨第一流体流动路径布置。
过滤器装置或模块是无菌的。可以使用合适形状并且提供入口和一个或更多个出口的任意壳体。
壳体可以由任意合适的刚性不渗透性材料制造,包括任意不渗透性热塑性材料,其与被处理的流体相容。例如,壳体可以由金属,如不锈钢或由聚合物,例如透明或半透明聚合物,如丙烯酸系、聚丙烯、聚苯乙烯或聚碳酸酯树脂制造。
本发明另外提供了过滤或处理流体的方法,该方法包括使流体通过上文描述的多孔膜。
以下实施例进一步阐释本发明,但当然不应被解释为以任何方式限制其范围。
实施例1-16
这些实施例说明了根据本发明的实施方案的通过自由基引发的共聚制备共聚物的方法。
PFSVE与不同单体的自由基共聚在配备有防爆盘、Bourdon压力计以及入口和出口阀的Hastelloy Parr高压釜(50mL、100mL或300mL)中进行。电子装置控制和调节高压釜的加热和搅拌二者。将容器封闭并且用30巴压力的氮气吹扫2分钟和10x 10-3毫巴的真空15分钟,进行3次。经由紧密连接至入口阀的漏斗引入自由基引发剂、PFSVE和溶剂(如果可用的话)。将高压釜冷冻至-90℃并且通过双重称重转移气体(例如氯三氟乙烯,CTFE)。然后将高压釜加热至需要的温度。在搅拌18h之后,将高压釜冷却至室温。在放气以去除未反应的单体之后,开启高压釜。将反应混合物在真空烘箱(10mbar)中在80℃放置48h。以重力测量法测定反应的收率(获得共聚物的质量/转移至高压釜中的单体的质量)。
表1和2列出了进行的聚合中的反应物和获得的产物的组成,如从元素分析或19FNMR计算。
表1.共聚物1-12和1C-3C的组成和聚合条件。
表1(续表)
表2.共聚物13-16和4C的组成和聚合条件
实施例 | VDF,g | HFP,g | TrFE,g | PMVE,g | CTFE,g | PFSVE,g | 引发剂,g | 溶剂,g | 温度,℃ |
13 | 5 | 24 | 10 | KPS 0.034 | H<sub>2</sub>O 30 | 70 | |||
14 | 5 | 15 | 23 | KPS 0.030 | H<sub>2</sub>O 30 | 70 | |||
15 | 8 | 11 | KPS 0.017 | H<sub>2</sub>O 30 | 70 | ||||
16 | 2 | 40 | 30 | P16S 1.80 | 无 | 60 | |||
4C | 5 | 8.7 | KPS 0.013 | H<sub>2</sub>O 30 | 70 |
表2(续表)
上文使用的缩写为如下:
VDF:偏氟乙烯
CTFE:氯三氟乙烯
HFP:六氟丙烯
TrFE:三氟乙烯
PMVE:全氟甲基乙烯基醚
PFSVE:全氟(4-甲基-3,6-二氧杂辛-7-烯)磺酰氟
PPFR:全氟-3-乙基-2,4-二甲基-3-戊基持续自由基
APS:过硫酸铵
KPS:过硫酸钾
DMC:碳酸二甲酯
T121:过氧-2-乙基己酸叔戊酯。
P16S:过氧二碳酸叔丁基环己酯。
实施例17-30
这些实施例说明了根据本发明的实施方案的膜表面处理在暴露至热的浓硫酸时的稳定性。
将一片由Pall公司制造的具有在<10nm量级的孔径的PTFE膜在实施例1-10、12-14、1C或2C的聚合物的溶液中浸没60秒并且从溶液移除。将样品在60℃干燥15分钟。然后将样品在氢氧化钾在50/50IPA/水中的0.1M溶液中浸没1小时。然后将样品在60/40IPA/水中浸没15分钟,然后在水中浸泡1小时,进行3次。将样品在60℃干燥20分钟。通过滴加已知表面张力的溶液和记录完全润湿样品的最高表面张力,测量CWST。将新鲜样品在异丙醇中浸入5分钟,然后在水中浸入10分钟,并且再次在水中浸入1小时。将样品浸没在水中过夜。将样品在浓硫酸中在150℃浸没2小时。将样品从酸中移除并且在水中若干次地每次浸没至少1小时。将样品在60℃干燥20分钟。通过滴加已知表面张力的溶液和记录完全润湿样品的最高表面张力,测量CWST。
在下表3中列出的结果显示了经涂布的膜具有比未处理的膜更高的CWST值以及经涂布的膜在热的浓硫酸中是稳定的。
表3.暴露至热的浓硫酸的表面处理的稳定性。
实施例32-40
这些实施例说明了制备本发明的膜的另一方法以及表面处理在热的浓硫酸中的稳定性。
将12%四甲基氢氧化铵在1:1的水:IPA中的溶液添加至实施例2、6、7和2C的聚合物在6:172DE:7100中的1%溶液。添加10当量的碱,并且使溶液搅拌约8小时,偶尔摇晃。添加水(~0.5-1体积),通过过滤收集产物,将其用水洗涤并且干燥。
将12%四甲基氢氧化铵在1:1的水:IPA中的溶液添加至实施例1、3-5和8的聚合物在6:172DE:7100中的1%溶液,使用1.9当量的碱。使溶液搅拌约8小时,偶尔摇晃。然后在旋转蒸发仪上去除约2/3的溶剂。将样品用约3体积的水萃取,和通过在旋转蒸发仪上去除溶剂而回收所得的产物。
将一片由Pall公司制造的在<10nm量级的PTFE膜在水解的聚合物的溶液中浸没60秒并且从溶液移除。将样品在60℃干燥15分钟并且称重。通过滴加已知表面张力的溶液和记录完全润湿样品的最高表面张力,测量CWST。将新鲜样品在异丙醇中浸入5分钟,然后在水中浸入10分钟,并且再次在水中浸入1小时。将样品浸没在水中过夜。将样品在浓硫酸中在150℃浸没2小时。将样品从酸中移除并且将样品在水中若干次地每次浸没至少1小时。将样品在60℃干燥20分钟。通过滴加已知表面张力的溶液和记录完全润湿样品的最高表面张力,测量CWST。表4中的结果显示,经涂布的膜具有比未处理的膜更高的CWST值以及经涂布的膜在热的浓硫酸中是稳定的。
表4.经表面处理的膜的CWST值
C,例如在此在2C中,是指对比实施例。
实施例41-47
这些实施例说明了当共聚物的分子量越高时,PTFE膜对共聚物的吸收越高。
将PTFE微滤膜的片在实施例3-7或2C的聚合物的2%重量/体积溶液中浸没60秒并且从溶液中移除。将样品在60℃干燥15分钟。然后将样品在氢氧化钾在50/50IPA/水中的0.1M溶液中浸没1小时。然后将样品在60/40IPA/水中浸没15分钟,然后在水中浸泡1小时,进行3次。将样品在60℃干燥20分钟。然后将样品放置在IPA浴中在75℃过夜。将样品在60℃干燥20分钟并且称重。表5中列出结果并且显示,随着样品具有的分子量越高,聚合物吸收越高。
表5.经表面处理的膜的CWST值
实施例 | 聚合物实施例 | Mn,kDa | 重量增加,% |
41 | 4 | 38 | 8.1 |
42 | 3 | 35 | 6.6 |
43 | 3 | 35 | 5.1 |
44 | 5 | 28 | 5.9 |
45 | 1C | 19 | 3.6 |
46 | 6 | 15 | 3.6 |
47 | 7 | 15 | 2.9 |
C是指对比实施例。
实施例48-57
这些实施例说明了当使采用根据本发明的实施方案的共聚物涂布的PTFE膜在热的异丙醇中经历洗涤时,以更大的量保留具有较高当量重量的共聚物。
将PTFE微滤膜的片在实施例1-5、8、2C-4C的聚合物的2%重量/体积溶液或D521中浸没60秒并且从溶液中移除。将样品在60℃干燥15分钟。然后将样品在氢氧化钾在50/50IPA/水中的0.1M溶液中浸没1小时。然后将样品在60/40IPA/水中浸没15分钟,然后在水中浸泡1小时,进行3次。将样品在70/30IPA/H2O中短暂浸没,用水冲洗,然后在5%HCl中浸没2小时。在用水充分冲洗之后,将样品在60℃干燥20分钟并且称重。用涂布的样品不用HCl处理。然后将样品放置在IPA浴中在75℃过夜。将样品在60℃干燥20分钟并且称重。显示的大多数数据是两个或更多个实验的平均值。表6中列出的结果显示,具有1300以上的当量重量的共聚物的保留率,例如保留的份额大于具有更低的当量重量的样品的保留率。
表6.载体的共聚物在洗涤之后的保留率
实施例 | 聚合物实施例 | 当量重量 | 保留的份额 |
48 | 1 | 3130 | 0.97 |
49 | 4 | 2040 | 0.98 |
50 | 2 | 1960 | 1.01 |
51 | 5 | 1920 | 0.92 |
52 | 3 | 1670 | 1.02 |
53 | 8 | 1300 | 0.98 |
54 | 1C | 1220 | 0.77 |
55 | Nafion D521 | 1090 | 0.86 |
56 | 2C | 940 | 0.68 |
57 | 3C | 790 | 0.82 |
C是指对比实施例。
实施例58-71
这些实施例说明了当使采用根据本发明的实施方案的共聚物涂布的PTFE膜在碱性氧化性溶液中经历洗涤时,以更大的量保留具有较低偏氟乙烯(VDF)含量的共聚物。
将一片由Pall公司制造的在<10nm量级的PTFE膜在实施例2、3、5-13、1C、3C或4C的聚合物的溶液中浸没60秒并且从溶液移除。将样品在60℃干燥15分钟。然后将样品在氢氧化钾在50/50IPA/水中的0.1M溶液中浸没1小时。然后将样品在60/40IPA/水中浸没15分钟,然后在水中浸泡1小时,进行3次。将样品在60℃干燥20分钟并且称重。将新鲜样品在异丙醇中浸入5分钟,然后在水中浸入10分钟,并且再次在水中浸入1小时。将样品浸没在水中过夜。将样品浸没在热的碱性氧化性溶液中。将样品从溶液中移除,然后将样品在水中若干次地每次浸没至少1小时。将样品在60℃干燥20分钟并且重新称重。表7中列出的结果显示,具有更小含量的VDF的共聚物与具有更大VDF含量的样品相比更稳定并且损失更少的重量。
表7.VDF含量对份额损失的影响
实施例 | 聚合物实施例 | VDF mol% | 份额损失 |
58 | 4C | 87 | 0.69 |
59 | 12 | 53 | 0.61 |
60 | 13 | 51 | 0.80 |
61 | 8 | 36 | 0.59 |
62 | 9 | 34 | 0.90 |
63 | 10 | 34 | 0.35 |
64 | 11 | 20 | 0.55 |
65 | 3 | 17 | 0.41 |
66 | 5 | 18 | 0.47 |
67 | 3C | 11 | 0.42 |
68 | 2 | 0 | 0.03 |
69 | 6 | 0 | 0.00 |
70 | 7 | 0 | 0.19 |
71 | 2C | 0 | 0.05 |
C是指对比实施例。
本文引用的所有参考文献,包括出版物、专利申请和专利在此均通过引用并入本文,其程度如同每篇参考文献被单独地和具体地指出通过引用并入并且在本文中完整地阐述一样。
在描述本发明的上下文中(特别是在之前权利要求的上下文中)使用术语“一种”和“一个”和“该”和“至少一个”以及类似的指示物将被解释为除非本文另有指示或明确与上下文相矛盾,否则涵盖单数和复数。除非本文另有指示或明确与上下文相矛盾,否则使用术语“至少一个/种”跟随一个或更多个项目的列表(例如,“A和B中的至少一个/种”)应被解释为表示从列出的项目中选择的一个项目(A或B)或所列项目(A和B)中的两个或更多个的任意组合。除非另有注明,否则术语“包含”、“具有”、“包括”和“含有”应被解释为开放式术语(即,意味着“包括但不限于”)。除非本文另有指示,否则本文中对数值范围的描述仅旨在用作单独提及落入该范围内的每个单独的值的简写方法,并且将每个单独的值并入本说明书中,如同其在本文中单独引用一样。除非本文另有指示或上下文另外明显矛盾,否则本文所述的所有方法均可以任意合适的顺序进行。除非另外声明,否则本文提供的任何和所有实例或示例性语言(例如,“如”)的使用仅旨在更好地阐明本发明,而不是对本发明的范围进行限制。本说明书中的任何语言都不应被解释为表明任何未要求保护的要素对于本发明的实施是必不可少的。
本文描述了本发明的优选实施方案,包括本发明人已知的实施本发明的最佳方式。在阅读上述描述时,那些优选实施方案的变型对于本领域普通技术人员而言可以变得显而易见。本发明人预期本领域技术人员适当地采用这些变型,并且本发明人预期本发明以不同于本文具体描述的方式实施。因此,本发明包括适用法律所允许的待批准的权利要求中所述主题的所有变型和等效方案。此外,除非本文另有指示或上下文另外明显矛盾,否则本发明涵盖上述要素的所有可能变型的任意组合。
Claims (15)
1.多孔膜,其包括多孔的氟化的聚合物载体和涂层,所述涂层包含第一共聚物,
所述第一共聚物包含聚合的单体单元A、B和C;其中:
A选自氯三氟乙烯、溴三氟乙烯、六氟丙烯、三氟乙烯、H2C=CHCF3、H2C=CFCF3、CHF=CHCF3、H2C=CFCl和H2C=CFBr,卤化的烷基乙烯基醚,或式CnH2n的烯烃,其中n为2-6;
B为全氟(烷基乙烯基)醚化合物、全氟烷基乙烯基化合物或全氟烷氧基烷基乙烯基醚化合物,所述化合物的每个具有一个或更多个磺酸基团或其盐、一个或更多个磺酰氟基团、一个或更多个磺酰胺基团或一个或更多个磺酸酯基团;和
C为偏氟乙烯;和C以在A、B和C之和的最多30mol%的范围存在;和
所述第一共聚物具有按每个磺酸基团或其盐、磺酰氟基团、磺酰胺基团或磺酸酯基团计1200至3000的当量重量。
2.根据权利要求1所述的多孔膜,其中A选自氯三氟乙烯、溴三氟乙烯、六氟丙烯和三氟乙烯及其任意组合。
3.根据权利要求1或2所述的多孔膜,其中A为氯三氟乙烯。
4.根据权利要求1所述的多孔膜,其中B选自CF2=CFOCF2CF(CF3)OC2F4SO2F、CF2=CFOCF2CF(CF3)OC2F4SO3H、CF2=CFOC2F4SO2F、CF2=CFOC2F4SO3H、CF2=CFC2F4SO2F、CF2=CFC2F4SO3H、CF2=CFOC4F8SO2F、CF2=CFOC4F8SO3H及其任意组合。
5.根据权利要求4所述的多孔膜,其中B为CF2=CFOCF2CF(CF3)OC2F4SO3H。
6.根据权利要求1所述的多孔膜,其中所述第一共聚物由以下物质产生:包含聚合的单体单元A、B’和C的第二共聚物,
其中B’为全氟(烷基乙烯基)醚化合物、全氟烷基乙烯基化合物或全氟烷氧基烷基乙烯基醚化合物,每个化合物具有一个或更多个磺酰氟基团或磺酸酯基团,
和用碱性溶液水解所述第二共聚物的一个或更多个磺酰氟基团或磺酸酯基团。
7.根据权利要求1或6所述的多孔膜,其中所述共聚物为无规共聚物或嵌段共聚物。
8.根据权利要求1或6所述的多孔膜,其中氟化的聚合物载体选自聚四氟乙烯、氟化的乙烯-丙烯共聚物(FEP)、全氟烷氧基乙烯基聚合物(PFA)、聚氯三氟乙烯(PCTFE)及其任意组合。
9.根据权利要求1或6所述的多孔膜,其中所述氟化的聚合物载体为聚四氟乙烯。
10.根据权利要求1所述的多孔膜,其中A在所述第一共聚物中以50至95mol%的范围存在,B在所述第一共聚物中以5至20mol%的范围存在和C在所述第一共聚物中以5至30mol%的范围存在,且A、B和C之和为100mol%。
11.制备多孔膜的方法,所述多孔膜包括多孔的氟化的聚合物载体和涂层,所述涂层包含第一共聚物,
所述第一共聚物包含聚合的单体单元A、B和C;其中:
A选自氯三氟乙烯、溴三氟乙烯、六氟丙烯、三氟乙烯、H2C=CHCF3、H2C=CFCF3、CHF=CHCF3、H2C=CFCl和H2C=CFBr,卤化的烷基乙烯基醚,或式CnH2n的烯烃,其中n为2-6;
B为全氟(烷基乙烯基)醚化合物,全氟烷基乙烯基化合物或全氟烷氧基烷基乙烯基醚化合物,每个化合物具有一个或更多个磺酸基团或其盐、一个或更多个磺酰氟基团、一个或更多个磺酰胺基团或一个或更多个磺酸酯基团,
和C为偏氟乙烯;
其中C以在最多30mol%的范围存在;
和所述第一共聚物具有按每个磺酸基团计1200至3000的当量重量;所述方法包括:
提供多孔的氟化的聚合物载体,和
将所述多孔的氟化的聚合物载体用所述第一共聚物涂布;和当B为具有一个或更多个磺酰氟基团的全氟(烷基乙烯基)醚时,将所述磺酰氟基团的一个或更多个用碱水解。
12.根据权利要求11所述的方法,其中A在所述第一共聚物中以50至95mol%的范围存在,B在所述第一共聚物中以5至20mol%的范围存在和C在所述第一共聚物中以5至30mol%的范围存在,且A、B和C之和为100mol%。
13.过滤腐蚀性流体的方法,包括使所述腐蚀性流体经过根据权利要求1-10任一项所述的多孔膜。
14.根据权利要求13所述的方法,其中所述腐蚀性流体包括浓硫酸。
15.从流体中去除离子材料的方法,包括使所述流体经过根据权利要求1-10任一项所述的多孔膜。
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CN102421831A (zh) * | 2009-04-06 | 2012-04-18 | 恩特格里斯公司 | 非去湿性多孔膜 |
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