CN106390782A - 亲水性多孔聚四氟乙烯膜(ii) - Google Patents
亲水性多孔聚四氟乙烯膜(ii) Download PDFInfo
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Abstract
本发明公开了亲水性多孔PTFE膜,其包含PTFE和式(I)的两性共聚物:其中Rf、Rh1、Rh2、Y、m、n和o如本文中所述。还公开了制备亲水性多孔PTFE膜的方法和通过这样的膜过滤流体的方法。
Description
发明背景
多孔PTFE膜的性质,包括其机械强度、化学耐性或惰性、不粘着性、优异的介电性质、在高温下的热稳定性和低摩擦系数使得其对于许多应用而言非常具有吸引力。然而,对于某些应用而言,将会有益的是改进其润湿特性而不影响其内在性质。已进行尝试来改变PTFE膜的一种或多种性质。然而,许多这些尝试导致在PTFE的有吸引力的性质的一种或多种,例如机械强度方面降低。
前文说明存在对于制备具有改进的润湿特性而不明显影响其机械强度的多孔PTFE膜的未满足的需求。
发明简述
本发明提供了包含聚四氟乙烯(PTFE)和式(I)的两性共聚物的亲水性多孔膜:
其中所述两性共聚物为无规或嵌段共聚物,Rf为经全氟取代的基团,而Rh1和Rh2为亲水性基团或氯,m、n和o独立地为0至1000,条件是m+n+o大于或等于10,和Y为羟基。
本发明还提供了制备亲水性多孔PTFE膜的方法,包括:
(i)制备包含PTFE和两性共聚物和任选的润滑剂的共混物:
(ii)将所述共混物挤出成条带;
(iii)将所述条带双轴拉伸,以获得亲水性多孔膜;
任选地
(iv)使所述亲水性多孔膜与试剂反应,以改变所述两性共聚物的化学结构;和任选地
(v)使所述亲水性多孔膜退火;
其中所述两性共聚物具有式(I):
其中所述两性共聚物为均聚物或无规或嵌段共聚物,Rf为经全氟取代的基团,而Rh1和Rh2为亲水性基团或氯,m、n和o独立地为0至1000,条件是m+n+o大于或等于10,和Y为羟基。
所述亲水性多孔膜具有PTFE膜的许多有利之处,例如机械强度,并且同时显示出高水平的水润湿性。
本发明还提供了通过这些亲水性多孔PTFE膜过滤流体的方法。
附图说明
图1展示了于150℃退火的亲水性PTFE膜的表面的光学显微照片。
图2展示了于250℃退火的亲水性PTFE膜的表面的光学显微照片。
图3展示了于350℃退火的亲水性PTFE膜的表面的光学显微照片。
发明详述
根据一个实施方案,本发明提供了包含聚四氟乙烯(PTFE)和式(I)的两性共聚物的亲水性多孔膜:
其中所述两性共聚物为无规或嵌段共聚物,Rf为经全氟取代的基团,而Rh1和Rh2为亲水性基团或氯,m和n独立地为0至1000,条件是m+n+o大于或等于10,和Y为羟基。
在实施方案中,m、n和o表示相应单体的聚合度,并且独立地为从约10至约1000或更大,优选约100至约200。
在其它实施方案中,m、n和o表示所述共聚物中存在的单体的摩尔份额,并且各自可以独立地在0至99摩尔%,优选10至40摩尔%范围内。
各单体嵌段可以以任意合适的质量%存在于嵌段共聚物中,例如在一个实施方案中,从约99%:约1%至约50%:约50%,优选从约90%:约10%至约70%:约30%,且更优选从约75%:约25%。
所述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,从约10kDa至约1000kDa,优选从约75kDa至约500kDa,且更优选从约250kDa至约500kDa的数均或重均分子量(Mn或Mw)。
本发明的两性共聚物可以通过任意合适的方法制备,例如通过氟化的环氧化合物的开环聚合。例如参见US 2009/0030175 A1。所述开环聚合在三烷基铝和具有有机抗衡阳离子的盐存在下如以下所示在两种单体的混合物(全氟烷基环氧化物和叔丁基缩水甘油基醚(TGBE))上进行。使所产生的二嵌段共聚物与酸如三氟乙酸反应,以移除叔丁基并提供全氟化的氧化乙烯与羟甲基氧化乙烯的共聚物:
在一个实施方案中,为了制备三嵌段共聚物,首先制备二嵌段共聚物如由全氟化的氧化乙烯与TGBE获得的二嵌段嵌段共聚物,和可以添加第三单体并继续聚合。
单体的聚合在合适的溶剂,例如氟化的溶剂中进行。所述溶剂可以基于待形成的氟化的聚合物的适当的溶解度选择。合适的溶剂的实例为六氟苯。合适的溶剂的实例包括芳族烃类如苯、甲苯和二甲苯,脂肪烃类如正戊烷、己烷和庚烷,脂环烃类如环己烷,和卤代烃类如二氯甲烷、二氯乙烷、二氯乙烯、四氯乙烷、氯苯、二氯苯和三氯苯,以及其混合物。
单体浓度可以在1至50重量%,优选2至45重量%,且更优选3至40重量%范围内。
可以在任意合适的温度,例如从0至150℃,优选0至80℃进行聚合。
为了制备嵌段共聚物,例如可以使聚合进行任意合适的时间,以获得各嵌段的适当链长度,所述时间可以为从约1分钟至100小时。
可以将催化剂的量选择为任意合适的量。例如,催化剂与单体的摩尔比可以为约1:10至约1:1000,优选约1:50至约1:500,且更优选约1:100至约1:200。例如,催化剂与单体的摩尔比可以是1:n、1:m或1:o,其中n、m和o是平均聚合度。
可以通过合适的技术,例如采用非溶剂沉淀分离所述聚合物。
所述共聚物可以通过任意已知技术表征其分子量和分子量分布。例如可以使用MALS-GPC技术。该技术经由高压泵,使用流动相穿过一堆填充有固定相的柱洗脱聚合物溶液。固定相根据链尺寸分离聚合物样品,随后通过三种不同的检测器检测聚合物。可以连续使用一系列检测器,例如紫外检测器(UV-检测器),随后是多角度激光散射检测器(MALS-检测器),接着又是折射率检测器(RI-检测器)。UV-检测器测量在254nm波长处的聚合物光吸收;MALS-检测器测量聚合物链相对于移动相的散射光。
共聚物的多分散性取决于反应条件。例如,所述共聚物具有1.05至2.5,优选1.1至1.2的Mw/Mn。
两性共聚物的实例、它们的结构和用于形成亲水改性的PTFE膜的代表性制剂列于表1中。
表1.两性共聚物和制剂的实例
本发明还提供了制备亲水性多孔PTFE膜的方法,包括:
(i)制备包含PTFE和两性共聚物和任选的润滑剂的共混物:
(ii)将所述共混物挤出成条带;
(iii)将所述条带双轴拉伸,以获得亲水性多孔膜;
任选地
(iv)使所述亲水性多孔膜与试剂反应,以改变所述两性共聚物的化学结构;和任选地
(v)使所述亲水性多孔膜退火;
其中所述两性共聚物具有式(I):
其中所述两性共聚物为无规或嵌段共聚物,Rf为经全氟取代的基团,而Rh1和Rh2为亲水性基团或氯,m、n和o独立地为0至1000,条件是m+n+o大于或等于10,和Y为羟基。
将需要的量的PTFE粉末与共聚物在合适的溶剂(例如酮溶剂如丙酮或甲基乙基酮)中的溶液混合,以获得共混物,然后将所述共混物与润滑剂如无味溶剂油(例如IsoparG)混合,并使产生的糊剂经受剪切,例如在双辊中,并且在约300psi或更高的压力下成型为原始坯料至少两次,每次约55秒的时间。使产生的原始坯料在室温平衡约12小时或更久。然后将所述原始坯料挤出成期望的形状。例如,在26mm模头间隙尺寸,最大压力和55℃的恒定温度进行挤出,产生管状PTFE条带。接下来,将所述管状条带沿着中心轴切开并围绕移液管(pipette)再次辊轧,产生新的原始坯料(非压缩的)。将所述新的原始坯料在与第一次挤出工艺期间所使用的相同条件下再次挤出。增加该步骤以将有利的横向机械性质提供给PTFE条带。在30℃进行砑光,达到9-10密耳的厚度并切割成4×4英寸。然后将产生的条带在125℃干燥1h,由此从挤出的条带除去所述润滑剂。
然后使所述条带在以下条件伸长:纵向(MD)与横向(TD)的伸长比在300%/秒伸长率的情况下为3。将在伸长炉中的温度设定至150℃。
然后使伸长的条带退火。退火在退火炉中于350℃进行5秒,之后将所述条带冷却。由上述伸长步骤产生的孔隙率在冷却时得以保持。
任选地,使上述获得的多孔膜与酸反应。
根据本发明的一个实施方案,所述亲水性多孔PTFE膜为多孔膜,例如纳米多孔膜,例如具有介于1nm和100nm之间的直径的孔的膜,或具有介于1μm和10μm之间的直径的孔的微米多孔膜。
可以如下测定所产生的多孔膜的表面张力。例如,将PTFE多孔载体的片材在室温通过用IPA溶剂预润湿所述膜片材并将所述膜浸泡在浓度为介于0.1质量%和10质量%之间的涂料聚合物溶液中而涂覆。涂覆时间在(1min至12小时)之间的范围内。在浸泡所述载体之后,将其在对流烘箱中于100℃至160℃干燥。干燥时间在(10分钟至12h)之间。所产生的多孔PTFE膜的润湿特性通过测量临界润湿表面张力来测量。
表面张力方面的表面改性的变化通过测量临界润湿表面张力(CWST)来测量。所述方法依赖于一组某种组成的溶液。每种溶液具有特定的表面张力。所述溶液的表面张力在呈小的非等量增量的25至92达因/cm2的范围内。为了测量膜表面张力,将膜置于白光桌顶部,将一滴某表面张力的溶液施加至所述膜表面,并记录液滴渗透所述膜并且变成亮白色(作为光穿过所述膜的指示)所花费的时间。当液滴渗透所述膜所花费的时间≤10秒时,认为是立即润湿。如果所述时间>10秒,则认为所述溶液部分润湿所述膜。
根据本发明的实施方案的亲水性多孔PTFE膜可以用于多种应用中,包括例如,诊断应用(包括例如,样品制备和/或诊断侧向流动装置),喷墨应用,平版印刷,例如,作为HD/UHMW PE基介质的替代,过滤制药工业的流体,金属去除,生产超纯水,工业和地表水的处理,过滤用于医学应用的流体(包括家用的和/或患者使用的,例如静脉内应用,还包括例如过滤生物流体如血液(例如,病毒清除)),过滤电子工业的流体(例如过滤热SPM和微电子工业中的光致抗蚀剂流体),过滤食品和饮料工业的流体,啤酒过滤,澄清,过滤含抗体和/或含蛋白的流体,过滤含核酸的流体,细胞检测(包括原位),细胞收获,和/或过滤细胞培养液。可选地或额外地,根据本发明的实施方案的多孔膜可以用于过滤空气和/或气体和/或可以用于通气应用(例如,允许空气和/或气体从中通过,但不允许液体从中通过)。根据本发明的实施方案的多孔膜可以用于多种装置,包括外科装置和产品,例如,眼科手术产品。
根据本发明的实施方案,亲水性多孔PTFE膜可以具有多种外形,包括平面、平片、褶皱、管状、螺旋形和中空纤维。
根据本发明的实施方案的亲水性多孔PTFE膜典型地布置在包括至少一个入口和至少一个出口的壳体中,并且所述壳体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所述流体流动路径,以提供过滤器装置或过滤器模块。在一个实施方案中,提供了一种过滤器装置,其包括含有入口和第一出口的壳体,并在所述入口和所述第一出口之间限定第一流体流动路径,以及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,所述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,对于横向流应用,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包括至少一个入口和至少两个出口的壳体中,所述壳体在所述入口和所述第一出口之间至少限定第一流体流动路径,并在所述入口和所述第二出口之间限定第二流体流动路径,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所述第一流体流动路径,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,所述过滤器装置包括横向流过滤器模块,包括入口、包括浓缩物出口的第一出口和包括渗透物出口的第二出口的壳体,并且所述壳体在所述入口和所述第一出口之间限定第一流体流动路径,并在所述入口和所述第二出口之间限定第二流体流动路径,其中横跨所述第一流体流动路径布置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。
所述过滤器装置或模块可以是可消毒的。可以使用合适形状的任意壳体,并提供入口和一个或多个出口。
可以由任意合适的刚性不可渗透性材料,包括与被处理的流体相容的任意不可渗透性热塑性材料生产所述壳体。例如,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生产所述壳体。
本发明还提供了通过上述方法生产的亲水改性的多孔PTFE膜。
本发明还提供了过滤流体的方法,所述方法包括使所述流体通过上述亲水性多孔PTFE膜。
以下实施例进一步阐释了本发明,但是当然不应该被认为是以任意方式限制本发明的范围。
实施例1
本实施例阐释了根据本发明的一个实施方案制备亲水性多孔PTFE膜的方法。
将200g的PTFE树脂粉末FLUON CD123与在丙酮溶剂(25%)和Isopar G润滑剂(50%)中的需要量的共聚物(PF8PO)100-r-(TBGE)200混合,以获得包含5%或10%共聚物的共混物。将所述共混物在双辊中混合。通过施加300psi的压力至少两次,每次55秒的时间将所述共混物成型成原始坯料。使所产生的原始坯料于室温平衡约12小时。然后将所述原始坯料在最大压力和55℃的恒定温度通过26mm模头挤出,产生管状PTFE条带。将所述管状条带沿着中心轴(沿着其长度)切开并围绕移液管辊轧,产生新的原始坯料(非压缩的)。将所述新的原始坯料在与第一次挤出工艺期间所使用的相同条件下挤出。在30℃进行砑光,达到9-10密耳的条带厚度并切割成4×4英寸。将产生的条带在125℃干燥1h,由此从所述条带除去所述润滑剂。使所述条带在MD/TD比例为3的纵向和横向上在300%/秒的伸长率下伸长。将伸长炉的温度设定至150℃。使产生的膜在退火炉中于150℃或350℃如表2中列出那样退火多次。膜性能表征列于表2中,暴露至甲酸(FA)、硫酸(SA)和三氟乙酸(TFA)的结果列于表3中。
表2.膜制备条件和CWST值
表3.膜性能表征
表4.与酸反应的结果
本文引用的所有参考文献,包括出版物、专利申请和专利,在此通过参考以如下相同的程度并入本文中:如同各参考文献单独且明确地表明通过参考且以其整体并入本文中或以其整体列举。
在描述本发明的上下文中(特别是在随后权利要求书的上下文中)的术语“一”和“一个”和“所述(该)”和“至少一个”和相似的术语的使用,除非本文另有说明或通过上下文明显矛盾,将被解释为涵盖单数和复数。跟随一系列一个或多个项目(例如,“A和B中的至少一个”)的术语“至少一个”的使用,除非本文另有说明或通过上下文明显矛盾,将被解释为本意是选自所列出的项目中的一项(A或B)或两个或更多个所列出的项目的任意组合(A和B)。除非另有说明,术语“包含”、“具有”、“包括”和“含有”将被解释为开放式术语(即,意为“包括,但不限于”)。除非本文另有说明,本文数值范围的记载仅意为简记法,其独立地涉及落在该范围内的每个单独的值,且将每个单独的值如同其独立地被记载在本文而并入说明书中。除非本文另有说明或通过上下文明显矛盾,本文描述的所有方法可以以任何合适的顺序实施。除非另有要求,任何和所有实例的使用或本文提供的示例性语言(例如,“例如(如)”)仅旨在更好地说明本发明而不对本发明的范围施加限制。在说明书中没有语言应该被解释为指示任何未要求保护的要素对本发明的实施是必要的。
在本文中描述了本发明优选的实施方案,包括本发明人已知的用于实施本发明的最佳模式。通过阅读上面的描述,这些优选的实施方案的变体对于本领域的普通技术人员可变得显而易见。本发明人预期本领域技术人员视情况而定会使用这些变体,且本发明人意在除了按照本文的具体描述不同地实践本发明。因此,本发明包括所附的权利要求中记载的主题的所有被适用的法律允许的变型和等价物。此外,除非本文另有说明或通过上下文明显矛盾,本发明涵盖了以其所有可能的变体形式的上述要素的任意组合。
Claims (11)
1.亲水性多孔膜,其包含聚四氟乙烯(PTFE)和式(I)的两性共聚物:
其中所述两性共聚物为无规或嵌段共聚物,Rf为经全氟取代的基团,而Rh1和Rh2为亲水性基团或氯,m和n独立地为0至1000,条件是m+n+o大于或等于10,和Y为羟基。
2.根据权利要求1所述的亲水性多孔膜,其中Rf为经全氟取代的烷基,其中烷基链可以在链中任选地含有一个或多个氧原子。
3.根据权利要求1或2所述的亲水性多孔膜,其中Rf为CpF2p+1-(CH2)q(OCH2)r,其中p为1至12、q为0至3和r为0至2。
4.根据权利要求3所述的亲水性多孔膜,其中Rf独立地选自C8F17CH2、C6F13(CH2)2OCH2、C4F9CH2和CF3。
5.根据权利要求4所述的亲水性多孔膜,其中Rf选自C8F17CH2和C6F13(CH2)2OCH2。
6.根据权利要求1-5中任一项所述的亲水性多孔膜,其中Rh1和Rh2独立地选自羟基、酰氧基、三氟乙酰基、烷氧基、氯、烯丙氧基、烷硫基、和烷硫基丙氧基,其中烷硫基和烷硫基丙氧基的烷基部分任选地被羟基、羧酸、磺酸、膦酸、季铵、烷基磺酰基或杂环基取代。
7.根据权利要求6所述的亲水性多孔膜,其中Rh1和Rh2选自羟基和三氟乙酰基。
8.根据权利要求1所述的亲水性多孔膜,其中所述两性共聚物选自:
9.制备亲水性多孔PTFE膜的方法,包括:
(i)制备包含PTFE和两性共聚物和任选的润滑剂的共混物:
(ii)将所述共混物挤出成条带;
(iii)将所述条带双轴拉伸,以获得亲水性多孔膜;
任选地
(iv)使所述亲水性多孔膜与试剂反应,以改变所述两性共聚物的化学结构;和任选地
(v)使所述亲水性多孔膜退火;
其中所述两性共聚物具有式(I):
其中所述两性共聚物为无规或嵌段共聚物,Rf为经全氟取代的基团,而Rh1和Rh2为亲水性基团或氯,m、n和o独立地为0至1000,条件是m+n+o大于或等于10,和Y为羟基。
10.通过根据权利要求9所述的方法制备的亲水性多孔膜。
11.过滤流体的方法,所述方法包括使所述流体通过根据权利要求1-8或10中任一项所述的亲水性多孔膜。
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EP3124102B9 (en) | 2020-10-07 |
US10315168B2 (en) | 2019-06-11 |
CN106390782B (zh) | 2019-03-22 |
US20170028362A1 (en) | 2017-02-02 |
JP2017071755A (ja) | 2017-04-13 |
TWI607023B (zh) | 2017-12-01 |
KR101921701B1 (ko) | 2018-11-26 |
KR20170015138A (ko) | 2017-02-08 |
SG10201604946UA (en) | 2017-02-27 |
EP3124102A1 (en) | 2017-02-01 |
EP3124102B1 (en) | 2020-06-03 |
TW201710302A (zh) | 2017-03-16 |
JP6372520B2 (ja) | 2018-08-15 |
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