CN106009020A - 亲水改性的氟化薄膜 - Google Patents
亲水改性的氟化薄膜 Download PDFInfo
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- CN106009020A CN106009020A CN201511035780.4A CN201511035780A CN106009020A CN 106009020 A CN106009020 A CN 106009020A CN 201511035780 A CN201511035780 A CN 201511035780A CN 106009020 A CN106009020 A CN 106009020A
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- copolymer
- following formula
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- repetitive
- porous membrane
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Abstract
公开了用于亲水改性多孔氟聚合物载体的共聚物。该共聚物的实例为:
Description
发明背景
氟聚合物薄膜例如多孔PTFE薄膜的性能,包括它们的机械强度、耐化学性或惰性、不粘着性、优异的介电性、高温热稳定性和低摩擦系数使得它们对于许多应用具有非常大的吸引力。然而,对于某些应用,在不影响其内在性质的情况下对PTFE的表面进行改性是有益的。为了改善该薄膜对于专门应用的适用性,人们已经努力地对PTFE薄膜的表面和化学性能进行改性。例如,该努力包括表面涂布、共混、高能表面改性,例如宽谱带紫外线辐射或BBUV,其中该薄膜被暴露于波长为250-450nm的紫外线辐射,及等离子体处理、自由基和臭氧蚀刻、原子层沉积,以及该改性PTFE类聚合物的合成。然而,大多数努力聚焦在高能处理上,例如BBUV和等离子体。尽管并没有报导这些表面改性方法的确切机理,但是由于已知C-C键强度比F-F键强度低约40%,因此,很可能由键的断裂导致形成自由基。如果大部分自由基得自于C-C断裂或聚合物主链断裂,则可能降低PTFE薄膜的机械和化学稳定性。同样已知的是等离子体处理被限制于薄膜的表面,这使得其在长时间段的情况下不太稳定。
上述情况表明仍然存在着未得到满足的需求,即对多孔氟聚合物薄膜或载体进行表面改性以提供稳定的亲水性氟聚合物多孔薄膜,其中该表面改性不会显著影响该多孔氟聚合物载体或得到的复合多孔薄膜的机械强度。
发明概述
本发明提供了一种复合亲水性多孔薄膜,包含多孔氟聚合物载体和含有共聚物的涂层,其中该共聚物包含重复单元A和B,其中A具有下式:
以及B具有下式:
其中,该共聚物是嵌段共聚物或无规共聚物;x是3至约10;
该共聚物中存在的重复单元A和B的数目n和m为1至约1000,条件是n和m的总和等于或大于10,其中该共聚物任选为交联的。
本发明还提供了具有离子交换或螯合官能团的共聚物。
本发明的共聚物可用于多孔氟聚合物薄膜或载体的表面改性。
本发明进一步提供了制备共聚物的方法以及制备亲水改性的氟聚合物多孔薄膜的方法。
多个附图视图的简要说明
图1说明了本发明实施方式的亲水性多孔薄膜的建议性的交联结构。
图2描述了根据本发明实施方式的聚(NTEG)均聚物和聚(NTEG-b-NPF6)共聚物的FTIR。
图3说明了使用本发明实施方式的共聚物涂布多孔氟碳载体的方法。
图4说明了涂布和测量根据本发明实施方式的亲水性多孔薄膜的CWST粘结条件的方法。
图5描述了聚(NTEG-r-NPF10)的GPC谱图。
图6描述了聚(NTEG-b-NPF10)的GPC谱图。
发明详述
根据实施方式,本发明提供了一种复合亲水性多孔薄膜,包含多孔氟聚合物载体和含有共聚物的涂层,其中该共聚物包含重复单元A和B,其中A具有下式:
以及B具有下式:
其中,该共聚物是嵌段共聚物或无规共聚物;x是3至约10;
该共聚物中存在的重复单元A和B的数目n和m为1至约1000,条件是n和m的总和等于或大于10,其中该共聚物任选为交联的。
本文式中,重复单元的式中虚线表示该共聚物可以是嵌段共聚物或无规共聚物。嵌段共聚物通过圆括号:(重复单元)表示。无规共聚物通过方括号[重复单元]表示。
在实施方式中,n和m表示相应单体的聚合度,并且独立为约10至约1000,优选为约20至约50。
在其他的实施方式中,n和m表示存在于共聚物中的单体的摩尔分数,n和m可以独立为1至99mol%,优选为20至50mol%。
根据实施方式,本发明的共聚物具有下式中的一种:
在实施方式中,本发明进一步提供了一种复合亲水性多孔薄膜,其包含多孔氟聚合物载体和含有共聚物的涂层,其中该共聚物包含重复单元A和B以及一种或多种连接于一个或多个重复单元A上的螯合或离子交换官能团,其中A具有下式:
以及B具有下式:
其中,*是螯合或离子交换官能团的连接点;
该共聚物是嵌段共聚物或无规共聚物;x是3至约10;
该共聚物中存在的重复单元A和B的数目n和m为1至约1000,条件是n和m的总和等于或大于10,
其中所述共聚物任选为交联的。
在实施方式中,该螯合或离子交换官能团选自羧基烷硫基、磺化烷硫基和甘油基硫基,及其组合。
上述实施方式的共聚物的实例包括:
本发明的共聚物可以是嵌段共聚物或无规共聚物。该嵌段共聚物可以是二嵌段(A-B),三嵌段(A-B-A或B-A-B),或多嵌段共聚物((A-B)x)。任选地,该共聚物可以具有第3链段C,例如三嵌段共聚物或无规共聚物例如A-B-C。
该共聚物可以具有任意合适的分子量,例如在实施方式中,数均或重均分子量(Mn或Mw)为约10kDa至约1000kDa,优选为约75kDa至约500kDa,更优选为约250kDa至约500kDa。
相应单体嵌段可以任意合适质量%存在于嵌段共聚物中,例如在实施方式中,为从约99%:约1%至约50%:约50%,优选为从约90%:约10%至约70%:约30%,更优选为约75%:约25%。
本发明的共聚物可以通过任意合适的方法制备,例如通过环状单体的开环易位聚合(ROMP)。通常,包含碳烯配体的过渡金属催化剂调节了该易位反应。
可以使用任意合适的ROMP催化剂,例如Grubbs’一代、二代和三代催化剂,且也可以使用Umicore、Hoveyda-Grubbs、Schrock和Schrock-Hoveyda催化剂。该催化剂的实例包括以下:
在实施方式中,由于Grubbs’三代催化剂的优点,例如在空气中的稳定性,对多官能团的耐受性和/或快速聚合引发和增长速率,因此是特别合适的。此外,使用Grubbs’三代催化剂,可以将端基设计成适合任意相容的基团,并且该催化剂可以便利地再循环。这样的催化剂的优选实例是:
上述三代Grubbs催化剂(G3)可以从商业上获得或者如下所述由Grubbs二代催化剂(G2)制备:
单体的聚合在合适的溶剂,例如通常用于进行ROMP聚合的溶剂中进 行。合适的溶剂的实例包括芳香烃,例如苯、甲苯和二甲苯,脂肪烃,例如正戊烷、己烷和庚烷,脂环烃,例如环己烷,和卤代烃,例如二氯甲烷、二氯乙烷、二氯乙烯、四氯乙烷、氯苯、二氯苯和三氯苯及其混合物。
单体的浓度可以为1至50wt%,优选2至45wt%,和更优选3至40wt%。
聚合反应可以在任意合适的温度下进行,例如-20至+100℃,优选10至80℃。
聚合反应可以在任意适合于获得适当链长的各个嵌段的时间内进行,其可以是约1分钟至100小时。
催化剂的量可以选择任意合适的量。例如,催化剂和单体的摩尔比可以是约1∶10至约1∶1000,优选约1∶50至1∶500,更优选约1∶100至约1∶200。例如,催化剂和单体的摩尔比可以是1∶n和1∶m,其中n和m是平均聚合度。
该共聚物可以通过合适的技术进行分离,例如使用非溶剂进行沉淀。
可以通过任意已知技术来表征本发明共聚物的分子量和分子量分布。例如,可以使用MALS-GPC技术。该技术使用流动相,经由高压泵,通过填充有固定相的多个柱洗脱聚合物溶液。固定相按照链尺寸分离聚合物样品,随后通过3个不同的检测器检测聚合物。可以使用一系列检测器,例如紫外线检测器(UV-检测器),随后是多角度激光散射检测器(MALS-检测器),接着按顺序是折射率检测器(RI-检测器)。UV-检测器测量聚合物在254nm波长的光吸收;MALS-检测器测量聚合物链相对于流动相的散射光。
本发明的共聚物是高度单分散的。例如,该共聚物的Mw/Mn为1.05至1.5,优选1.1至1.2。
根据实施方式,本发明提供了一种制备共聚物聚(NTEG-b-NPF6)或聚(NTEG-b-NPF10)的方法,其包括:
(i)通过开环易位聚合(ROMP)催化剂催化聚合5-(单甲氧基三甘醇)降冰片烯(NTEG),从而获得均聚物聚NTEG;和
(ii)接着,通过ROMP催化剂催化,在由(i)获得的5-(全氟己基)降冰片烯或5-(全氟癸基)降冰片烯均聚物的链端上聚合。
以下说明该方法:
根据实施方式,本发明提供了一种制备无规共聚物聚(NTEG-r-NPF6)的方法,包括通过ROMP催化剂催化,聚合NTEG和5-(全氟己基)降冰片烯的混合物。
如下说明,5-(全氟癸基)降冰片烯可由环戊二烯和1H,1H,2H-全氟-10-癸烯制备。
本发明进一步提供了制备具有如上所述离子交换或螯合官能团的共聚物的方法,其包含提供包含重复单元A和B的共聚物,其中A具有下式:
以及B具有下式:
然后,将该共聚物与巯基乙酸、巯乙基磺酸盐或硫代甘油反应。
例如,共聚物聚(NTEG-b-PNF6)MAcOH、聚(NTEG-b-PNF6)MeSNa或聚(NTEG-b-PNF6)硫代甘油可以通过以下方法制备,即使聚(NTEG-b-PNF6)与巯基乙酸盐阴离子、巯乙基磺酸盐阴离子或硫代甘油反应:
本发明进一步提供了一种包含多孔氟聚合物载体和如上所述共聚物的复合亲水性多孔薄膜,其中该共聚物是任选交联的。
本发明进一步提供了一种亲水改性多孔氟碳化合物载体的方法,包括:
(i)提供多孔氟聚合物载体;
(ii)使用包含溶剂和如上所述共聚物的溶液涂布多孔氟聚合物载体;
(iii)干燥来自(ii)的涂布的载体,以从溶液中除去至少一些溶剂;以及任选地
(iv)交联存在于涂布的薄膜中的共聚物。
如下可以确定得到的多孔薄膜的表面张力。例如,通过在室温下,使用IPA溶剂使薄膜片材预润湿,并将该薄膜浸入浓度为约0.1质量%至10质量%的聚合物溶液中,从而涂布PTFE薄膜片材。PTFE片材的涂布时间为约1分钟到12小时。在浸渍该薄膜之后,将该薄膜在100℃-160℃的对流烘箱中干燥。干燥时间介于约10分钟到12小时之间。通过测量临界润湿表面张力,测定PTFE薄膜的润湿特性。
通过测量临界润湿表面张力(CWST),测量在表面改性中表面张力的变化。该方法依靠特定组成的一系列溶液。各溶液均具有比表面张力。该 溶液的表面张力为25到92达因/厘米,按非等同的小量增加。为了测量薄膜表面张力,将其放置到白色光的桌子上,将1滴具有一定表面张力的溶液施加到薄膜表面,并记录流体穿透薄膜并作为光通过了薄膜的指示而变为亮白色所花费的时间。当液滴渗透该薄膜所花费的时间≤10秒时,则认为是立即润湿。如果时间大于10秒,则认为该溶液是部分润湿该薄膜。
可通过任意合适的方法进行交联,例如,通过使用光引发剂或高能辐射,例如紫外线。可预期交联将在薄膜中提供高度稳定的聚合物网络。图1说明这样的交联薄膜的建议结构。
交联可以按照如下进行。使用IPA任选地预润湿聚合物涂布了的PTFE片材,然后使用在其中制备光引发剂的溶剂进行洗涤,从而用该溶剂交换IPA。然后,将该片材浸入到一定浓度的光引发剂溶液中一定时间,随后暴露于紫外线照射下。在光引发剂溶液中的浸泡时间为1分钟到24小时。紫外线照射时间为30秒至24小时。然后,测量薄膜临界润湿表面张力(CWST)、性能表征和/或SPM测试。本文中“SPM”是指在120℃-180℃的热硫酸过氧化氢混合物(H2SO4(96%)∶H2O2(30%)的体积比为80∶20)。
根据本发明的实施方式,该亲水性氟聚合物薄膜是多孔薄膜,例如纳米多孔薄膜,例如孔直径在1纳米至100纳米之间的薄膜,或者孔直径在1μm至10μm之间的微米多孔薄膜。
根据本发明实施方式的亲水性氟聚合物多孔薄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/或诊断的侧向流动设备)、喷墨应用、平版印刷、例如,作为HD/UHMW PE基介质的替代品、过滤用于制药工业中的流体、金属脱除、生产超纯水、处理工业和地表水、过滤用于医学应用中的流体(包括家用和/或患者用,例如静脉内应用,还包括例如过滤生物学流体,例如血(例如病毒去除))、过滤用于电子工业的流体(例如过滤微电子工业中的光刻胶流体和热SPM)、过滤用于食品和饮料工业的流体、啤酒过滤、澄清、过滤含抗体和/或蛋白质的流体、过滤含核酸的流体、细胞检测(包括原位)、细胞收集和/或过滤细胞培养液。
可替代地或另外地,根据本发明实施方式的多孔薄膜可以用于过滤空气和/或气体和/或可以用于通风应用(例如允许空气和/或气体,而不是 液体从其中通过)。根据本发明实施方式的薄膜可以用于多种设备,包括外科设备和产品,例如眼外科产品。
根据本发明的实施方式,该亲水性的氟聚合物多孔薄膜可以具有多种结构,包括平面的、平板的、褶皱的、管状的、螺旋状的和空心的纤维。
根据本发明实施方式的亲水性氟聚合物多孔薄膜通常布置在壳体中,其包含至少一个入口和至少一个出口,且在入口和出口之间限定了至少一个流体流动路径,其中至少一种本发明的薄膜或包含至少一种本发明薄膜的过滤器横跨该流体流动路径,从而提供了一种过滤器设备或过滤器模块。在一个实施方式中,提供一种过滤器设备,其包含含有一个入口和第一出口且在入口和第一出口之间限定了第一流体流动路径的壳体;以及至少一种本发明的薄膜或包含至少一种本发明薄膜的过滤器,本发明的薄膜或包含至少一种本发明薄膜的过滤器被布置在壳体中并横跨第一流体流动路径。
优选地,对于交叉流动应用,将至少一种本发明的多孔薄膜或包含至少一种本发明的多孔薄膜的过滤器布置在壳体中,该壳体包含至少一个入口和至少两个出口且在入口和第一出口之间限定了至少一个第一流体流动路径,以及在入口和第二出口之间限定第二流体流动路径,其中将本发明的多孔薄膜或包含至少一种本发明薄膜的过滤器横跨第一流体流动路径,以提供过滤器设备或过滤器模块。在一个说明性的实施方式中,过滤器设备包含交叉流动过滤器模块,壳体包含入口、包含浓缩物出口的第一出口、和包含渗透物出口的第二出口,并且在入口和第一次出口之间限定了第一流体流动路径,在入口和第二出口之间确定了第二流体流动路径,其中至少一种本发明薄膜或包含至少一种本发明薄膜的过滤器被布置成横跨第一流体流动路径。
过滤设备或模块可以是可消毒的。可以使用具有合适形状且提供入口和一个或多个出口的任意壳体。
该壳体可以由任意合适的刚性不渗透性材料构成,包括任意不渗透性热塑性材料,其与处理的流体相容。例如,该壳体可以由金属,例如不锈钢制成,或由聚合物,例如透明或半透明的聚合物,例如丙烯酸类聚合物、聚丙烯、聚苯乙烯或聚碳酸酯树脂制成。
根据实施方式,该亲水性氟聚合物多孔薄膜包含任意合适的多孔载体,例如微孔的氟聚合物载体,例如该载体可以由以下制成:PTFE、PVDF(聚偏二氟乙烯)、PVF(聚氟乙烯)、PCTFE(聚氯三氟乙烯)、FEP(氟化乙烯-丙烯)、ETFE(聚乙烯四氟乙烯)、ECTFE(聚乙烯氯代三氟乙烯)、PFPE(全氟聚醚)、PFSA(全氟磺酸)和全氟聚氧杂环丁烷。该多孔载体可以具有任意合适的孔径,例如约10nm到约10μm,优选PTFE和PVDF。
本发明进一步提供了一种通过如上所述方法制备的亲水改性的氟聚合物薄膜。
本发明进一步提供了一种过滤流体的方法,该方法包含将该流体通过如上所述的薄膜。
下列实施例将进一步说明本发明,但是当然不应当将其认为是以任何方式限制其范围。
实施例1
材料:购买并原样使用下列材料。
5-降冰片烯-2,3-二羧酸二甲酯(C3)购自Alfa Aesar。
将二氯甲烷(DCM)储存在活性氧化铝上,并在使用之前使用氩气吹扫,异丙醇(IPA)、二环戊二烯(DCPD)、1H,1H,2H-全氟-1-辛烯(PF6)、1H,1H,2H-全氟-1-十二烯(PF10)、甲苯、氯化亚砜、乙酸乙酯、二甲基甲酰胺(DMF)、马来酰亚胺、呋喃、二异丙基偶氮二羧酸酯(DIAD)、三苯基膦(Ph3P)、1-十六醇、四氢呋喃(THF)、乙酸乙酯、N-苯基马来酰亚胺、乙腈、甲醇、Grubbs二代催化剂、3-溴吡啶和戊烷由Sigma-Aldrich Co.获得,在不进行进一步处理的情况下使用。二氯戊烷也由Sigma-Aldrich Co.获得并在使用前使用碱性氧化铝处理。
实施例2
此实施例说明制备二氯[1,3-二(2,4,6-三甲基苯基)-2-咪唑啉亚基](苯亚甲基)二(3-溴吡啶)钌(II)(G3)催化剂。
将上述说明的二代Grubbs催化剂(G2)(1.0g,1.18mmol)与3-溴吡啶(1.14mL,11.8mmol)在50mL的烧瓶中混合。在室温下搅拌5分钟后,红色混合物转变为亮绿色。加入戊烷(40mL)并搅拌15分钟,得到绿色固体。将该混合物在冰箱中冷却24小时,然后在真空下过滤。使用冷戊烷清洗得到的G3催化剂绿色固体,然后在真空、室温下干燥,从而获得0.9g的产量,产率为88%。
实施例3
此实施例说明本发明实施方式的均聚物和共聚物的凝胶渗透色谱表征。
通过MALS-GPC技术在下列条件下表征获得的均聚物和嵌段共聚物的分子量和分子量分布性能:
流动相:二氯甲烷(DCM)。
流动相温度:30℃。
UV波长:245nm。
所使用的柱:3个PSS SVD Lux分析柱(苯乙烯-二乙烯基苯共聚物网络),该柱的固定态相珠直径为5μm,孔径为1000A,100,000A和1,000,000A,以及保护柱。
流动速率:1mL/min。
GPC系统:具有UV和RI检测器的水HPLC alliance e2695系统
MALS系统:DAWN HELEOS 8系统,其具有8个按664.5nm运行激光的检测器。
实施例4
此实施例说明根据本发明一个实施方式制备NPF6单体的过程。
将DCPD(100ml,737mmol)、PF6(168ml,737mmol)和氢醌(2.43g,22.1mmol)装入到Parr高压反应器圆柱体容器中,将该圆柱体连接至反应器上,加热到170℃进行72小时。将反应内容物溶解于150mlDCM中,并转移到500ml圆底烧瓶中,从而通过真空蒸镏纯化该单体。
1H-NMR(CDCl3):δ(ppm)6.2-6.0(2H),3.2(1H),3.0(1H),2.8(1H),2.0(1H),1.5(1H),和1.2-1.4(2H).19F-NMR(CDCl3):δ-89.9(s),-112.6(m),-123.8至-121.3(m),-127.1至-125.3(m).
实施例5
此实施例说明根据本发明一个实施方式制备NPF10单体的过程。
将DCPD(24.6ml,183mmol)、PF6(132ml,370mmol)和氢醌(1.08g,10mmol)装入到Parr高压反应器圆柱体容器中,并将该圆柱体连接至反应器上,加热到170℃进行72小时。将反应内容物溶解于150mlDCM中,并转移到500ml圆底烧瓶中,从而通过真空蒸馏纯化该单体。
1H-NMR(CDCl3):δ(ppm)6.2-6.0(2H),3.2(1H),3.0(1H),2.8(1H), 2.0(1H),1.5(1H),和1.2-1.4(2H).19F-NMR(CDCl3):δ-80.9(s),-112.6(m),-123.8至-121.4(m),-127.2至-125.5(m).
实施例6
此实施例说明制备三甘醇单甲醚甲苯磺酸盐(TEG-OTs)的过程。
三甘醇单甲醚甲苯磺酸盐(TsTEG):
将50g三甘醇单甲醚加入175ml THF中,并将该内容物在冰水浴中冷却。将在175ml水中的氢氧化钠(36.5g)加入该冷却的溶液中。然后,使用滴液漏斗,经过30分钟,缓慢加入在125ml THF中的甲苯磺酰氯(75g)。在加入后,将内容物加热至环境温度并搅拌过夜。在完成该反应后,收集分离的有机层,然后使用二乙醚(4x100ml)萃取该含水层。使用10%的氢氧化钠溶液,接着使用饱和盐水以及水洗涤合并的有机层。将其在无水硫酸钠上干燥,过滤并浓缩,从而获得呈粘性液体的纯产品(82.3g,85%的产率)。
三甘醇基降冰片烯单体(NTEG):
在氩气气氛下,将5-降冰片烯-2-甲醇(15g)滴加到NaH(4.5g)在600mL干DMF中的悬浮液中。将该混合物在室温下搅拌10分钟,并在60℃搅拌1小时。在室温下,加入溶解在75mLDMF中的TsTEG(58.5g)。在室温下,将得到的混合物搅拌10分钟,然后在60℃搅拌12小时,之后,加入750mL0.1M的NaCl溶液,然后分离该层。使用乙酸乙酯萃取该含水层,使用10%的NaHCO3和盐水洗涤该合并的有机层,在MgSO4上干燥,然后在真空下浓缩。通过柱色谱法,将获得的残基在硅胶(庚烷∶乙酸乙酯=3∶1)上纯化,已提供无色油(18.62g,产率为57%)。
1HNMR(CDCl3,400MHz):δ(ppm)=6.10-5.90(m,2H),3.65-3.52,3.19-3.03(m,14H),3.36(s,3H),2.88-2.73(m,2H),2.33,1.68(brs, 1H),2.35-2.32,1.10-1.05(m,1H),1.28-1.20(m,2H),0.49-0.44(m,1H)。
实施例7
本实施例说明根据本发明实施方式的共聚物的合成和性能。
聚(NTEG-b-NPF6):将Grubbs二代(G2)催化剂(18mg,0.021mmol)和三苯基膦(277mg,1.06mmol)称入40ml装有氟聚合物树脂-有机硅隔膜的有孔盖的小瓶中。将该催化剂溶解于用氩气脱气的二氯甲烷(DCM)(40mL)中,并经由套管转移到1L装配有搅拌棒的干净的RBF中。使用氩气,对第一单体NTEG(2.0g,7.4mmol)在DCM(100mL)中的溶液进行脱气,然后转移到催化剂溶液中,并搅拌30分钟。30分钟后,取1-2mL由第一单体形成的均聚物等分试样进行分子量表征。使用氩气,对第二单体NPF10(1.55g,2.54mmol)在DCM(200mL)中的溶液进行脱气,然后转移到RBF中正在生成的均聚物溶液中,然后将该烧瓶中的内容物搅拌另外180分钟。然后,将乙基乙烯基醚(2mL)加入到二嵌段共聚物的黄色溶液中,从而终止该聚合反应。将得到的聚合物在甲醇(2L,2X)中沉淀,从而采收呈白色固体的纯聚合物。过滤该聚合物,并在室温,真空条件下进行干燥;产量(9.2g,98%)。
1H-NMR(300MHz,CDCl3):δ(ppm)6.0至6.35(s,宽),5.5至6.0(s,宽),4.5至5.2(s,宽),4.3至4.5(s,宽),3.5至3.8(m,宽),3.0至3.3(s,宽,2.0至2.4(s,宽),1.5至1.7(s,宽),1.0至1.3(s).
图2显示聚(NTEG)、聚NPF6和聚(NTEG-b-NPF6)的FTIR。下表1列出了元素分析数据。
表1.元素分析
图3说明使用本发明的共聚物涂布氟碳多孔载体的顺序。
将聚(NTEG-b-NPF6)共聚物溶解于THF中,以提供1wt%的溶液。将PTFE微孔薄膜样品浸入聚合物溶液中1小时。将该PTFE样品在160℃干燥10分钟,然后在THF中洗涤30分钟。将该样品在160℃再干燥10分钟。经涂布的PTFE薄膜的CWST测量为33.4达因/厘米(CWST1)。起始PTFE薄膜的CWST为25达因/厘米。该洗涤后的CWST为31.3达因/厘米(CWST2),在使用硫酸和过氧化氢(SPM)的热混合物处理后,该CWST为31.3达因/厘米(CWST6)。
实施例8
此实施例说明UV交联根据本发明一个实施方式的聚(NTEG-b-NPF6)共聚物的方法及该共聚物性能。
图4说明该过程。涂层由1质量%的共聚物溶液形成,并且使用Irgacure 2959(0.25%)的DI水溶液进行交联。
表2列出CWST数据。
表2.CWST数据
聚合物 | CWST涂层 | CWST交联 | CWST后SPM |
聚(NTEG-b-NPF6) | 33 | 33 | 30 |
聚(NTEG-b-NPF6) | 33 | 33 | 30 |
聚(NTEG-b-NPF10) | 33 | 33 | 30 |
实施例9
本实施例说明根据本发明实施方式的另一种共聚物的合成和性能。
如下说明,通过对单体混合物使用ROMP活性聚合反应,合成无规共聚物。
上述制备无规共聚物的方法的优点是单体和溶剂不必要是高度纯的。
将溶解在氩气吹扫的DCM(25ml)中的G3催化剂(15mg,0.017mmol)经由套管转移到250ml清洁的经过火焰干燥的装配有搅拌棒的RBF中,然后将独立小瓶中的NTEG单体(3.0g,11.1mmol)和NPF6(1.14g,2.78mmol)在DCM(125ml)中的溶液加入到搅拌的G3催化剂绿色溶液中,从而由浅黄绿色转变到浅棕色。继续搅拌总计15小时,然后加入过量的乙烯基乙基醚,从而终止该聚合反应。使该聚合物溶液通过碱性氧化铝、硅胶和硅藻土(Celite)柱以除去催化剂。通过旋转蒸发器(rotavap)除去溶剂,聚合物是无色和高粘性的,在冷却时转变为固体。产量(4.0g,92%)。 1H-NMR(300MHz,CDCl3):δ(ppm)5.7至5.0(m,宽),3.8至3.4(m,宽),3.4至2.9(m,宽),2.9至2.45(m,宽),2.45至1.3(m,宽),1.3至1.0.6(m,宽)。
图5显示共聚物在二氯甲烷中的GPC谱图。Mn=74KDa,Mw=84KDa,Mw/Mn=1.14。表2列出元素分析数据。
表2.元素分析
将聚(NTEG-r-NPF6)共聚物溶解于THF中,从而提供1wt%的溶液。 将PTFE微孔薄膜样品浸入聚合物溶液中1小时。将该PTFE样品在空气中干燥10分钟,然后再在100℃烘干10分钟,接着在THF中洗涤30分钟。将该样品在空气中再干燥10分钟,并在100℃烘干10分钟。在使用该共聚物处理后,经涂布的PTFE薄膜的CWST增加。
起始PTFE薄膜的CWST为25达因/厘米。该洗涤后的CWST为31.3达因/厘米(CWST2),在使用硫酸和过氧化氢(SPM)的热混合物处理后,CWST为31.3达因/厘米(CWST6)。下表3列出了CWST值。当在相同的涂布溶剂中处理和洗涤该薄膜时,该PTFE的CWST从25.4达因/厘米增加到39-40达因/厘米。
表3.PTFE薄膜的CWST值
实施例10
此实施例说明在本发明实施方式的氟聚合物薄膜内交联共聚物聚(NTEG-r-NPF6)的方法。图4描述了该涂布过程。表4列出了获得的结果。
表4
光引发剂=Irgacure 2959
实施例11
本实施例说明根据本发明实施方式的另一种共聚物的合成和性能。
聚(NTEG-b-NPF10)
如下说明,通过对单体混合物使用ROMP活性聚合反应,合成嵌段共聚物:
如下所述,通过Diels-Alder反应,制备5-(全氟癸基)降冰片烯单体:
制备聚(NTEG-b-NPF10)的合成过程:将Grubbs二代(G2)催化剂(18mg,0.021mmol)和三苯基膦(277mg,1.06mmol)称入40ml装配有氟聚合物树脂-有机硅隔膜的有孔盖的小瓶中。将该催化剂溶解于用氩气脱气的二氯甲烷(DCM)(40mL)中,并经由套管转移到1L装配有搅拌棒的干净的RBF中。使用氩气,对第一单体NTEG(2.0g,7.4mmol)在DCM(100mL)中的溶液进行脱气,然后转移到催化剂溶液中,并搅拌30分钟。30分钟后,取1-2mL的由第一单体形成的均聚物的等分试样进行分子量表征。使用氩气,对第二单体NPF10(1.55g,2.54mmol)在DCM(200mL)中的溶液进行脱气,然后转移到RBF中正在生成的均聚物溶液中,然后将该烧瓶中的内容物搅拌另外180分钟。然后,将乙基乙烯基醚(2mL)加入到二嵌段共聚物的黄色溶液中,从而终止该聚合反应。将得到的聚合物在甲醇(2L,2X)中沉淀,以回收呈白色固体的纯聚合物。过滤该聚合物,并在室温、真空条件下进行干燥;产量(9.2g,98%)。
1H-NMR(300MHz,CDCl3):δ(ppm)6.0至6.35(s,宽),5.5至6.0(s,宽),4.5至5.2(s,宽),4.3至4.5(s,p宽),3.5至3.8(m,宽),3.0至3.3(s,宽,2.0至2.4(s,宽),1.5至1.7(s,宽),1.0至1.3(s).
图5描述了聚(NTEG-b-NPF10)的GPC谱图。
将聚(NTEG-b-NPF10)共聚物溶解于THF中,以提供1wt%的溶液。将PTFE微孔薄膜样品浸入聚合物溶液中1小时。将该PTFE样品在空气中干燥10分钟,然后在THF中洗涤30分钟。将该样品再在空气中干燥10分钟。在使用该共聚物处理后,经涂布的PTFE薄膜的CWST增加。
当在相同的涂布溶剂中处理和洗涤该薄膜时,该PTFE的CWST从25.4 达因/厘米增加到33.41达因/厘米。聚合物的两种单体之间的进料单体摩尔比[NTEG]∶[NPF10]=90∶10mol%,其可以对PTFE薄膜提供强力的粘性。表5列出了CWST值。
表5
表5的数据说明NPF6和NPF10在二嵌段共聚物中贡献的对比,在NPF10含量较低的情况下(10%的NPF10相比20%的NPF6),可以得到更高的CWST。
实施例12
此实施例说明化学改性聚(NTEG-b-NPF6)共聚物的方法,以便提供根据本发明实施方式的螯合和/或离子交换性能。
使用MAcOH对聚(NTEG-b-NPF6)进行硫醇烯反应改性:将聚(NTEG-b-NPF6)(0.99g)、硫代乙醇酸(MAcOH,0.9g)和AIBN(79.8mg)溶解于33ml的THF中,并在氮气下,在55℃下反应26小时。将反应混合物倒入水中。将获得的沉淀再溶解到THF中,并从庚烷中再次沉淀,从而生成暗褐色固体。
使用MeSNa对聚(NTEG-b-NPF6)进行硫醇烯反应改性:将聚(NTEG-b-NPF6)(0.99g)、2-巯基乙烷巯基磺酸钠(MeSNa,1.6g)和AIBN(79.8mg)溶解于33ml的THF中,并在氮气下,在55℃,反应26小时。将反应混合物倒入水中。将获得的沉淀再溶解到THF中,并从庚烷中再次沉淀,从而生成淡黄色的固体。
使用硫代甘油对聚(NTEG-b-NPF6)进行硫醇烯反应改性::将聚(NTEG-b-NPF6)(0.99g)、1-硫代甘油(1.05g)和AIBN(79.8mg)溶解于33ml的THF中,并在氮气下,在55℃,反应26小时。将反应混合物倒入水中。将获得的沉淀再溶解到THF中,并从庚烷中再次沉淀,以产生 黄白色固体。
1H-NMR(300MHz,CDCl3):δ(ppm)5.7至5.0(m,宽),3.8至3.6(m,宽),3.6至3.4(m宽),3.4至3.3(s),2.9至2.3(m,宽),2.3至1.75(m,宽),1.3至0.8(m,宽).
将官能化的共聚物溶解于THF中,以提供1wt%的溶液。将PTFE微孔薄膜样品浸入聚合物溶液中1小时。将该PTFE样品在160℃,在测定CWST1的条件下,干燥10分钟。随后,在THF中洗涤30分钟,并测量CWST2。然后,再在160℃下,将该样品干燥10分钟,并测量CWST6。表6列出CWST数据。
表6
在此引入的包括出版物、专利申请和专利的全部参考内容在此以相同的程度引入,就如同各个参考内容被独立地和具体地指明以参考的方式引入,并且在此完整列出。
除非本文另外指明或明显与上下文内容矛盾,本发明内容中公开使用的“一个(a)”、“一个(an)”、“该(the)”和“至少一种”和类似指示物(特别是下列权利要求书的内容中)均解释为包含单个或多个。除非本文另外指明或明显与上下文相矛盾,使用术语“至少一种”后跟一系列的一种或多种项目(例如“至少一种A和B”)应解释为是指选自所列项目(A或B)中的一项,或两个或多个所列项目(A和B)的任意组合。除非另处指明,术语“包含、“具有”、“包括”和“含有”应被认为是开放式的术语(即,是指“包括,但不局限于”)。本文列举的数值范围仅仅是作 为单独提及落入该范围内的各个离散值的速记方法,除非本文另外指明,每个离散值就像是在本文中被单独列举一样被引入到说明书中。除非本文另处指明或与上下文明显矛盾,本文描述的所有方法均可以任意合适的次序进行。除非另外声明,本文提供的任意和全部实施例或示范性语言(例如“例如”)的使用仅仅是为了更好地说明本发明,并不是对本发明的范围进行限制。说明书中没有措辞应当认为是对本发明实践必不可少的任意未主张的部分。
本文描述的本发明优选的实施方式包括发明人已知的实施本发明最好的方式。通过阅读上述说明书,那些优选的实施方式的变形对本领域技术人员来讲变得显而易见。本发明人希望本领域技术人员根据情况来采用这些变形,因此本发明人希望实践与本文具体描述的不同的发明。因此,本发明包括所有本文适用法律允许的附加的权利要求所描述的主题的改进或等同物。此外,除非本文另外指明或与上下文明显矛盾,本发明包含上述部分的所有可能变化的任意组合。
Claims (17)
1.一种复合亲水性多孔薄膜,其包含多孔氟聚合物载体和含有共聚物的涂层,其中该共聚物包含重复单元A和B,其中A具有下式:
以及B具有式:
其中,该共聚物是嵌段共聚物或无规共聚物;x是3至约10;该共聚物中存在的重复单元A和B的数目n和m为1至约1000,条件是n和m的总和等于或大于10,其中该共聚物任选为交联的。
2.权利要求1的复合亲水性多孔薄膜,其中该共聚物具有选自芳基和烷氧基的链端基。
3.权利要求1或2任意一项的复合亲水性多孔薄膜,其中该共聚物具有下式中的一种:
4.权利要求3的复合亲水性多孔薄膜,其中该嵌段共聚物具有下式:
5.权利要求3的复合亲水性多孔薄膜,其中该无规共聚物具有下式:
6.一种复合亲水性多孔薄膜,其包含多孔氟聚合物载体和含有共聚物的涂层,其中该共聚物包含重复单元A和B以及一种或多种连接至一个或多个重复单元A上的螯合或离子交换官能团,其中A具有下式:
以及B具有下式:
其中,*是螯合或离子交换官能团的连接点;
该共聚物是嵌段共聚物或无规共聚物;x是3至约10;
该共聚物中存在的重复单元A和B的数目n和m为1至约1000,条件是n和m的总和等于或大于10;
其中该共聚物任选为交联的。
7.权利要求6的复合亲水性多孔薄膜,其中该共聚物具有选自芳基和烷氧基的链端基。
8.权利要求6或7的复合亲水性多孔薄膜,其中该螯合或离子交换官能团选自羧基烷硫基、磺酰基烷硫基和甘油基硫基,及其组合。
9.权利要求6-8任意一项的复合亲水性多孔薄膜,其中该共聚物具有下式:
10.一种多孔氟聚合物载体的亲水改性方法,包括:
(i)提供多孔氟聚合物载体;
(ii)使用包含溶剂和共聚物的溶液涂布该多孔氟聚合物载体,其中该共聚物包含重复单元A和B,其中A具有下式:
以及B具有下式:
其中,该共聚物是嵌段共聚物或无规共聚物;x是3至约10;
该共聚物中存在的重复单元A和B的数目n和m为1至约1000,条件是n和m的总和等于或大于10,
(iii)干燥来自(ii)的涂布的载体,以从包含所述共聚物的溶液中除去至少一些溶剂;以及任选地
(iv)交联存在于涂布的薄膜中的所述共聚物。
11.权利要求10的方法,其中该共聚物具有下式:
12.一种多孔氟聚合物载体的亲水改性方法,包括:
(i)提供多孔氟聚合物载体;
(ii)使用包含溶剂和共聚物的溶液涂布该多孔氟聚合物载体,其中该共聚物包含重复单元A和B,以及一种或更多种连接至一个或多个重复单元A的螯合或离子交换官能团,其中A具有下式:
以及B具有下式:
其中,*是螯合或离子交换官能团的连接点;该共聚物是嵌段共聚物或无规共聚物;x是3至约10,;该共聚物中存在的重复单元A和B的数目n和m为1至约1000,条件是n和m的总和等于或大于10;
(iii)干燥来自(ii)的经涂布的氟聚合物载体,以从包含所述共聚物的溶液中除去至少一些溶剂;以及任选地
(iv)交联存在于涂布的薄膜中的所述共聚物。
13.权利要求12的方法,其中该共聚物具有下式:
14.一种通过权利要求10-13任意一项的方法生产的亲水性多孔薄膜。
15.权利要求1-9任意一项的复合亲水性多孔薄膜或权利要求14的亲水改性多孔氟聚合物薄膜,其中该多孔氟聚合物载体选自PTFE、PVDF、PVF(聚氟乙烯)、PCTFE(聚氯三氟乙烯)、FEP(氟化乙和丙烯)、ETFE(聚乙烯四氟乙烯)、ECTFE(聚乙烯氯代三氟乙烯)、PFPE(全氟聚醚)、PFSA(全氟磺酸)和全氟聚氧杂环丁烷。
16.一种过滤流体的方法,该方法包括将该流体通过权利要求1-9、14或15任意一项的亲水性多孔薄膜。
17.权利要求1-9、14或15任意一项的复合亲水性多孔薄膜,其构造为平面、平板、褶皱的、管状、螺旋状或空心的纤维结构。
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TWI585132B (zh) | 2017-06-01 |
KR101780380B1 (ko) | 2017-09-21 |
EP3075763B1 (en) | 2017-12-13 |
US20160288059A1 (en) | 2016-10-06 |
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