CN106390778A - 涂覆的ptfe膜 - Google Patents
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- CN106390778A CN106390778A CN201610555725.6A CN201610555725A CN106390778A CN 106390778 A CN106390778 A CN 106390778A CN 201610555725 A CN201610555725 A CN 201610555725A CN 106390778 A CN106390778 A CN 106390778A
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- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 57
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 57
- 239000012528 membrane Substances 0.000 title abstract description 5
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- 238000000576 coating method Methods 0.000 claims description 42
- 239000011248 coating agent Substances 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
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- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 claims description 4
- 238000010422 painting Methods 0.000 claims 1
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- 238000007614 solvation Methods 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- B01D71/36—Polytetrafluoroethene
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Abstract
本发明公开了一种未交联的PFSA涂覆的多孔PTFE膜。
Description
发明背景
PTFE膜,特别是膨胀PTFE(ePTFE)膜,被用于多种不同的液体和气体过滤应用中,包括涉及处理具有挑战性的流体例如腐蚀性或化学活性液体的应用。然而,对于多孔PTFE膜来说存在着这样的需求,其在表现出金属清除或者金属去除效率的同时提供低流动阻力。
本发明的这些和其它的优点将根据下文的描述而变得显而易见。
发明概述
本发明的一种实施方式提供了多孔PTFE膜,其包括具有包含全氟磺酸(PFSA)聚合物的未交联涂层的多孔PTFE基体,其中所述膜的CWST为至少约30达因/cm(约30×10-5N/cm)。
在另一种实施方式中,提供了一种用于过滤包含金属的流体的方法,所述方法包括使包含金属的流体经过多孔PTFE膜和从所述流体去除金属,所述多孔PTFE膜包括具有包含全氟磺酸(PFSA)聚合物的未交联涂层的多孔PTFE基体,其中所述膜的CWST为至少约30达因/cm(约30×10-5N/cm)。
在另一种实施方式中,提供了一种用于过滤硫酸过氧化氢混合物(SPM)流体的方法,所述方法包括使所述流体经过多孔PTFE膜和从所述流体去除颗粒,所述多孔PTFE膜包括具有包含全氟磺酸(PFSA)聚合物的未交联涂层的多孔PTFE基体,其中所述膜的CWST为至少约30达因/cm(约30×10-5N/cm)。
根据本发明的实施方式,还提供了包括所述膜的装置,和制备所述膜的方法。
附图说明
图1为示出根据本发明不同实施方式的PFSA涂覆的PTFE膜与未处理的PTFE膜以及市售UV处理的PTFE膜进行对比的金属吸附图。
图2为示出根据本发明不同实施方式的PFSA涂覆的PTFE膜与未处理的PTFE膜进行对比的金属吸附图,显示出所述吸附是由于涂层,而非筛分。
发明详述
根据本发明的一种实施方式,多孔PTFE膜包括具有包含全氟磺酸(PFSA)聚合物的未交联涂层的多孔PTFE基体,其中所述膜的CWST为至少约30达因/cm(约30×10-5N/cm)。
根据本发明的一种实施方式,用于过滤包含金属的流体的方法包括使包含金属的流体经过多孔PTFE膜和从所述流体去除金属(例如从包含金属的流体去除第2族金属(例如Mg和/或Ca),多价金属和/或过渡金属(例如Cr、Mn、Fe和/或Ni)),所述多孔PTFE膜包括具有包含全氟磺酸(PFSA)聚合物的未交联涂层的多孔PTFE基体,其中所述膜的CWST为至少约30达因/cm(约30×10-5N/cm)。
在另一种实施方式中,提供用于过滤硫酸过氧化氢混合物(SPM)流体的方法,所述方法包括使所述流体经过多孔PTFE膜和从所述流体去除颗粒(例如包含二氧化硅的颗粒),所述多孔PTFE膜包括具有包含全氟磺酸(PFSA)聚合物的未交联涂层的多孔PTFE基体,其中所述膜的CWST为至少约30达因/cm(约30×10-5N/cm)。
在一种实施方式中,提供了制备金属去除膜的方法,所述方法包括使用包含全氟磺酸(PFSA)聚合物的涂层涂覆多孔PTFE基体,和在低于250℃、优选低于约200℃的温度下固化所述涂层。
在又一种实施方式中,提供了制备金属去除膜的方法,所述方法包括使用包含全氟磺酸(PFSA)聚合物的涂层涂覆多孔PTFE基体,其中不使用交联剂,并且所述涂层在室温下制备;和在低于250℃的温度下固化所述涂层。优选地,固化在约25℃至约200℃的温度下执行。
有利地,与其中使用金属试剂、并且所述金属试剂通过后洗涤处理(例如使用HCl)而去除以满足标准(例如在微电子工业中)的某些应用的膜的制备相比,根据本发明的膜可以使用不含金属试剂的涂层来制备。另外地,膜可以根据本发明以有利的制备方法来制备,例如,所述制备可以容易地结合至现有的制备方法中,获得提高的制备速度。
根据本发明的多孔PTFE膜有利地提供了高金属清除或金属去除效率和低流动阻力的结合,同时使正在处理的流体保持为润湿的(即所述膜在处理流体中为未去湿的),并且适用于广泛范围的液体和气体(包括空气)过滤应用,包括无菌过滤应用。示例性的应用例如包括诊断应用(例如包括试样制备和/或诊断侧流设备)、喷墨应用、平版印刷例如作为对于HD/UHMW PE基媒介的替代、过滤制药工业的流体、金属去除、超纯水的制备、工业和地表水的处理、过滤用于医学应用的流体(包括家用和/或患者使用,例如静脉内应用,还例如包括过滤生物流体例如血液(例如病毒去除))、过滤用于电子工业的流体(例如过滤用于微电子中的光致抗蚀剂流体和热的硫酸过氧化氢混合物(SPM)流体)、用于食品和饮料工业的过滤流体、啤酒过滤、净化、过滤含抗体和/或含蛋白质的流体、过滤包含核酸的流体、细胞检测(包括原位检测)、细胞收获和/或过滤细胞培养流体。可替换地,或者另外地,根据本发明实施方式的多孔膜可被用于过滤空气和/或气体和/或可被用于通风应用(例如允许空气和/或气体、但不是液体通过)。根据本发明实施方式的多孔膜可被用于多种不同的设备中,包括外科设备和产品,例如眼外科产品。本发明的膜是尺寸稳定的。在某些实施方式中,多孔PTFE膜可单独地使用,例如作为非支撑膜,并且在其它实施方式中,多孔PTFE膜可与其它多孔元件和/或另一个部件细合使用,从而例如提供例如复合物、过滤元件和/或过滤器的制品。
在制备涂层中使用的合适的PFSA聚合物分散液的一个例子可作为PFSA(例如AQUIVION PFSA D83-24B、AQUIVION PFSA D83-06A和AQUIVION PFSA D79-20BS)购自Solvay Specialty Polymers(Borger,Texas),其基于四氟乙烯和磺酰基氟代乙烯基醚(SFVE)F2C=CF-O-CF2-CF2-SO2F的短侧链(SSC)共聚物。离聚物分散液包含其磺酸形式。合适的PFSA聚合物分散体的另一个例子为DuPontTM PFSA聚合物分散体。
在制备涂层时,涂覆溶液中的PFSA浓度可以根据不同的应用而不同。典型地,浓度范围为约0.1%至约3%,更优选地,为约0.12%至约2.2%。
根据本发明,可以涂覆不同的多孔PTFE基体和膜(包括市售基体和膜)。
膜和基体可以如现有技术已知的进行涂覆,例如但不限于浸涂或喷涂。
膜可以具有任意合适的孔结构,例如孔尺寸(例如由起泡点或者例如在美国专利4,340,479中所描述的KL来证实的,或者由毛细凝聚流动孔隙测量法来证实的)、平均流动孔(MFP)尺寸(例如使用气孔计来表征,例如Porvair Porometer(Porvair plc,Norfolk,UK),或者商标名为POROLUX的气孔计(Porometer.com;Belgium))、孔等级、孔径(例如使用例如在美国专利4,925,572中描述的改进的OSU F2测试来表征)、或者去除等级媒介。所使用的孔结构依赖于待使用的颗粒的尺寸,待处理的流体的组成,和经处理的流体的希望的流出物含量。
典型地,根据本发明的涂覆的多孔PTFE膜的孔等级为约1微米或更小,优选(特别是对于非去湿应用)为约0.05微米至约0.02微米,或更小。例如,所述膜可以是纳米多孔膜,例如,膜具有的孔径为1nm至100nm。
典型地,涂覆的膜具有的厚度范围为约0.2至约5.0密耳(约5至约127微米),优选地,为约0.5至约1.0密耳(约13至约25微米),尽管膜可以比这些数值更厚或者更薄。
多孔膜可以具有任意的希望的临界润湿表面张力(CWST,例如在美国专利4,925,572中所限定的)。CWST可以依赖于一系列特定组成的溶液进行测量。每种溶液具有特定的表面张力。溶液的表面张力以小的不相等的增量由25达因/cm增加至92达因/cm。为了测量膜表面张力,所述膜被置于白光工作台的顶部,将一滴特定表面张力的溶液施加至膜表面,并记录液滴穿过膜并变为亮白色(光线经过所述膜的指示)的时间。当液滴穿透所述膜的时间≤10秒时,认为是立即润湿的。如果所述时间>10秒,那么认为溶液部分地润湿所述膜。CWST可以根据本领域已知进行选择,例如根据另外地例如在美国专利5,152,905、5,443,743、5,472,621和6,074,869中所公开的。
典型地,涂覆的PTFE膜具有的CWST为至少约27达因/cm(约27×10-5N/cm),更优选地,至少约30达因/cm(约30×10-5N/cm),并且在某些实施方式中,至少约35达因/cm(约35×10-5N/cm)。例如,涂覆的PTFE膜具有的CWST可以是约30达因/cm(约30×10-5N/cm)至约40达因/cm(约40×10-5N/cm),或者更大。
包括涂覆的多孔PTFE膜的制品,例如过滤器、过滤元件和/或复合物可以包括附加元件、层或部件,其可以具有不同结构和/或功能,例如如下的任意一个或多个中的至少一个:预过滤、支撑、排泄、间隔和缓冲。说明性地,过滤器还可以包括至少一个附加的元件,例如网和/或筛。
根据本发明的实施方式,膜、过滤元件、复合物和/或过滤器可以具有不同的构型,包括平面的、褶皱的、螺旋的和/或中空圆柱的。
膜、过滤元件、复合物和/或过滤器典型地被置于壳体中,所述壳体包括至少一个入口和至少一个出口,并在所述入口和所述出口之间限定至少一个流体流动路径,其中所述膜横跨流体流动路径,以提供过滤设备。优选地,对于交叉流动应用来说,膜、复合物和/或过滤器被置于壳体中,所述壳体包括至少一个入口和至少两个出口,并在入口和第一出口之间限定至少第一流体流动路径,以及在入口和第二出口之间限定第二流体流动路径,其中所述膜横跨第一流体流动路径以提供过滤设备。所述过滤设备可以是可灭菌的。可以使用具有合适形状并提供至少一个入口和至少一个出口的任何壳体。
所述壳体可以由任意合适的刚性不可渗透材料制得,包括任何不可渗透的热塑性材料,其与待处理的流体相容。例如,所述壳体可以由金属例如不锈钢或者聚合物制得。在一种实施方式中,所述壳体为聚合物,例如丙烯酸类树脂、聚丙烯、聚苯乙烯或者聚碳酸化树脂。
下文的实施例进一步描述了本发明,但是,当然不应当构成为对其范围进行任何方式的限定。
实施例1
本实施例说明了制备根据本发明实施方式的膜的方法。
在甲醇水介质中制备0.25%的PFSA溶液(AQUIVION PFSA 24;D83-24B SolvayPlastics)以获得聚合物溶液。使用所述聚合物溶液浸涂市售PTFE基体((膜)SumitomoElectric Fine Polymer,Inc.,标称孔尺寸50hm)直至完全润湿,从溶液移除并沥水约2分钟,在150℃下保持并干燥10分钟,随后在室温下使用DI水洗涤12小时,进行测试。
结果(与未处理的(对照)PTFE膜和市售UV处理的PTFE膜进行对比)如下:
本实施例示出根据本发明实施方式的CWST增加(由此,膜为未润湿的),流速几乎不下降。
实施例2
本实施例示出根据本发明实施方式的两种PFSA涂覆的PTFE膜(使用不同浓度的PFSA制备)与未处理的(对照)PTFE膜和市售UV处理的PTFE膜进行比较的金属去除效率。
两种PFSA涂覆的PTFE膜根据大体上如在实施例1中所描述的来制备,其中一个膜浸涂于在甲醇水介质中制备的0.25%PFSA溶液(AQUIVION PFSA D83-24B)中,并且另一个膜浸涂于在甲醇水介质中制备的0.5%PFSA溶液(AQUIVION PFSA D83-24B)中。
流体试样分别包含如下的金属:Li、Na、K(第1族金属);Mg、Ca(第2族金属);A1、Pb(第3族金属),和Cr、Mo、Mn、Fe、Ni、Cu、Zn(过渡金属)。
如在图1中所示的,根据本发明的实施方式的膜与未处理的膜和市售UV处理的膜相比,有效地去除了多种不同的第2族金属和多种不同的过渡金属。
实施例3
本实施例示出根据本发明实施方式的两种PFSA涂覆的PTFE膜(使用不同浓度的PFSA制备)的金属去除效率。
两种PFSA涂覆的PTFE膜大体上如在实施例1中所描述的来制备,其中一个膜浸涂于在甲醇水介质中制备的0.25%PFSA溶液(AQUIVION PFSA D83-24B)中,并且另一个膜浸涂于在甲醇水介质中制备的0.5%PFSA溶液(AQUIVION PFSA D83-24B)中。
流体试样分别包含如下的金属:Li、Na、K(第1族金属);Mg、Ca(第2族金属);A1、Pb(第3族金属),和Cr、Mo、Mn、Fe、Ni、Cu、Zn(过渡金属)。
如在图2中所示的,根据本发明的实施方式的膜与未处理的膜相比,更加有效地去除了第2族金属,以及多种不同的第3族金属和多种不同的过渡金属,并且显示出吸附是由于涂层,而非筛分。
实施例4
本实施例示出在PTFE膜上涂覆的PFSA为未交联的,因为涂层并未通过在溶剂中的浸泡而被去除。
PTFE膜使用7位计重秤进行称量。
膜使用24%w/w(原液)PFSA溶液涂覆,大体上如在实施例1中所描述的来制备,以提供未交联的膜。
交联的膜使用24%w/w(原液)PFSA溶液制备,其中所述膜在约260℃干燥。
将干燥的对照、未交联的和交联的膜进行称重。
所述膜在用于制备涂覆的膜的相同的溶剂(甲醇)溶液中浸泡。一系列的涂覆的膜浸泡于室温的溶剂溶液中,另一系列的涂覆的膜浸泡于40℃的溶剂溶液中。使用40℃的溶剂溶液帮助加速任何副产物的溶剂化。
将膜在新鲜溶剂中冲洗3次,干燥,并再次称重。
对照膜的重量以及在室温和40℃的溶剂溶液中浸泡的未交联的涂覆膜的重量与原始重量相等,而在室温和40℃的溶剂溶液中浸泡的交联的涂覆膜的重量小于原始重量,这显示出所述膜为交联的。
本文引用的所有参考文献,包括出版物、专利申请和专利,通过参考并入本文,引用程度如同各参考文献被单独和特别地说明以通过参考并入本文并且以其整体列举。
术语(冠词)“一个(a)”和“一种(an)”和“该(the)”以及类以的用语在描述本发明的上下文中(特别是在下面的权利要求的上下文中)被解释为覆盖单数和复数,除非本文另外说明或上下文明显矛盾。后接一系列的一个或多个项目的术语“至少一种”的(例如,“A和B中的至少一种”)的使用应理解为意味着选自所列项目中的一项(A或B)或两种或多种所列项目的任何组合(A和B),除非在此另外说明或通过上下文看出明显矛盾。术语“包含”,“具有”“包括”和“含有”解释为开放式的术语(意指“包括,但不限于”,),除非另外说明。本文中数值范围仅仅意指用作单独涉及的各个落入范围内的单个数值的简记方法,除非本文另外说明,各个单个的数值被合并到说明书中,如同其被本文单独引用。本文描述的所有方法可以按照任意合适的顺序实施,除非本文另外说明或上下文明显矛盾。任何一个和全部实例的使用,或本文提供的示例性语言(例如“如”、“例如”),仅仅意指更好地阐明发明,而不对发明的范围施加限制,除非另外声明。说明书中没有语言被解释为表明任何未声明的成分是实施本发明必不可少的。
本文描述了本发明的优选实施方式,包括发明人所知的实施发明的最佳模式。这些优选实施方式中的变体对于阅读了前述说明书的普通技术人员来说是显而易见的。发明人预计本领域技术人员适当时会采用这种变体,并且发明人还倾向于与本文详细描述不同地实施的发明。因此,本发明包括适用的法律所允许的本文所附的权利要求中记载的主题的所有改进和等同物。此外,本发明包括上述元素在所有可能的变体中的任意组合,除非本文另外说明或上下文明显矛盾。
Claims (6)
1.用于过滤包含金属的流体的方法,所述方法包括使包含金属的流体经过多孔PTFE膜和由所述流体去除金属,所述多孔PTFE膜包括具有包含全氟磺酸(PFSA)聚合物的未交联涂层的多孔PTFE基体,其中所述膜的CWST为至少约30达因/cm(约30×10-5N/cm)。
2.用于过滤硫酸过氧化氢混合物(SPM)流体的方法,所述方法包括使所述流体经过多孔PTFE膜和由所述流体去除颗粒,所述多孔PTFE膜包括具有包含全氟磺酸(PFSA)聚合物的未交联涂层的多孔PTFE基体,其中所述膜的CWST为至少约30达因/cm(约30×10-5N/cm)。
3.权利要求1或2的方法,其中所述流体为在电子工业中使用的流体。
4.权利要求1-3任一项的方法,包括由所述流体去除第2族金属和/或过渡金属。
5.多孔PTFE膜,包括具有包含全氟磺酸(PFSA)聚合物的未交联涂层的多孔PTFE基体,其中所述膜的CWST为至少约30达因/cm(约30×10-5N/cm)。
6.制备金属去除膜的方法,所述方法包括用包含全氟磺酸(PFSA)聚合物的涂层涂覆多孔PTFE基体;和在低于约200℃的温度下固化所述涂层。
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SG10201603824PA (en) | 2017-02-27 |
JP2017029975A (ja) | 2017-02-09 |
JP6295456B2 (ja) | 2018-03-20 |
EP3130394A1 (en) | 2017-02-15 |
TWI637988B (zh) | 2018-10-11 |
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TW201704306A (zh) | 2017-02-01 |
US20170028359A1 (en) | 2017-02-02 |
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