CN106397805A - 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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- CN106397805A CN106397805A CN201511036181.4A CN201511036181A CN106397805A CN 106397805 A CN106397805 A CN 106397805A CN 201511036181 A CN201511036181 A CN 201511036181A CN 106397805 A CN106397805 A CN 106397805A
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- Prior art keywords
- copolymer
- film
- porous
- following formula
- carrier
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Abstract
公开了用于亲水改性氟聚合物薄膜的共聚物。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、耐化学性或化学惰性、不粘性、优异的介电性质、在高温下的热稳定性和低摩擦系数使得它们对于多种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.为了改善该薄膜用于特定应用的适用性,人们已经努力对PTFE薄膜的表面和化学性能进行改性.例如,该努力包括表面涂层、共混、高能表面改性,例如宽谱带紫外线辐射或BBUV,其中将薄膜暴露于波长为250-450nm的UV辐射,以及等离子体处理、自由基和臭氧蚀刻、原子层沉积,以及合成改性的PTFE类聚合物.然而,大多数努力集中在高能处理上例如BBUV和等离子体.尽管没有报道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~40%,因此其很可能由键的断裂导致形成自由基.如果大多数的基团由C-C断裂或聚合物主链断裂导致,则可能降低PTFE薄膜的机械和化学稳定性.同样已知等离子体处理限制于薄膜的表面,这使得其在长时间段内不太稳定.
上述内容表明对多孔氟聚合物薄膜或载体的表面进行改性以提供稳定的亲水性氟聚合物多孔薄膜存在着未满足的需求,其中表面改性不显著影响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:该共聚物可以是嵌段共聚物或无规共聚物;
该共聚物中存在的重重单元A和B的值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.
本发明的共聚物对多孔氟聚合物薄膜或载体的表面改性有用.
本发明进一步提供了制备共聚物的方法以及制备亲水性改性的氟聚合物薄膜的方法.
多个附图视图的简要说明
图1描述了本发明实施方式的聚(iM6Ac-b-NPF6)和聚(iM6Ac)的GPC色谱。
图2说明了使用本发明实施方式的共聚物涂布多孔氟聚合物载体并测量经涂布的薄膜的表面张力的过程.
图3说明了使用本发明实施方式的共聚物涂布多孔氟聚合物载体、交联共聚物并测量经涂布的薄膜的表面张力的过程.
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,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重单元A和B,其中A具有下式:
以及B具有式:
其中:该共聚物可以是嵌段共聚物或无规共聚物;
该共聚物中存在的重重单元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,其中该共聚物为任选交联的.
在本文的式中,重复单元的式上的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,并且独立地为约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%.
该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%.
该共聚物可以具有任意合适的链端基,例如该链端基选自芳基和烷氧基,优选苯基和乙氧基.
该阴离子可以是任意合适的阴离子,例如氟离子、氯离子、溴离子或碘离子、甲苯磺酸根、甲磺酸根、苯磺酸根(besylate)、磺酸根、硫酸根、磷酸根或膦酸根.
根据一个实施方式,该共聚物具有下式中的一种:
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介导该易位反应.
可以使用任意合适的ROMP催化剂,例如Grubbs第一代、第二代和第三代催化剂,且也可以使用Umicore、Hoveyda-Grubbs、Schrock和Schrock-Hoveyda催化剂。这样的催化剂的实例包括以下:
在实施方式中,由于Grubbs第三代催化剂的优点例如在空气中的稳定性,对多种官能团的耐受性和/或快速聚合引发和增长速率,因此特别合适.此外,使用Grubbs第三代催化剂,可将端基设计成适应任意可相容的基团,并且该催化剂可便利地再循环.这样的催化剂优选的实例是:
上述第三代Grubbs催化剂(G3)可以从商业上获得或者由Grubbs第二代催化剂(G2)如下制备:
单体的聚合反应在合适的溶剂中进行,例如通常用于进行ROMP聚合的溶剂.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.
单体浓度可以为1至50wt%,优选2至45wt%,和更优选3至40wt%.
聚合可以在任意合适的温度下进行,例如-20至+100℃,优选10至80℃.
聚合可以在任意适合于获得各个嵌段的适当链长的时间内进行,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.
本发明共聚物可以通过任意已知技术对它们的分子量和分子量分布进行表征.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.固定相根据链长分离聚合物样品,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),接着又是折射度检测器(RI-检测器).UV-检测器测量聚合物在254nm波长时的光吸收;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.
本发明进一步提供了一种制备本发明实施方式的共聚物的方法,其包括:
(i)通过开环易位聚合(ROMP)催化剂催化聚合(a)N-羟乙乙基外型-7-氧杂降冰片烯5,6-二甲酰亚胺(iM6)、(b)N-乙酰氧乙基外型-7-氧杂降冰片烯5,6-二甲酰亚胺(AciM6)或(c)N-甲氧基乙基外型-7-氧杂降冰片烯5,6-二甲酰亚胺(M11),以获得均聚物聚(iM6)、聚(AciM6)或聚(M11);和
(ii)通过ROMP催化剂依次在由(i)获得的均聚物的链端催化聚合5-(全氟-正己基)降冰片烯或二环(2-2-1)庚-2-烯单全氟己烷或5-(全氟-正辛基)降冰片烯或二环[2-2-1]庚-2-烯单全氟辛烷。
本发明进一步提供了制备本发明另一个实施方式的共聚物的方法,其包括:
(i)通过ROMP催化剂催化聚合N-(单甲氧基三环氧乙烷)二甲基铵外型-7-降冰片烯5,6-二甲酰亚胺(QNTEG)盐或N-(磺酰基丙基)二甲基铵外型-7-降冰片烯5,6-二甲酰亚胺(Sulfobetaine Zwitterionic NorBornene,SZNB)以获得均聚物;和
(ii)通过ROMP催化剂依次在由(i)获得的均聚物的链端催化聚合5-(全氟-正己基)降冰片烯或二环(2-2-1)庚-2-烯单全氟己烷或5-(全氟-正辛基)降冰片烯或二环[2-2-1]庚-2-烯单全氟辛烷.
以下说明了QNTEG和SZNB单体可以从降冰片烯-甲醛开始制备.中心中 间体是通过5-降冰片烯-2-甲醛(与例如二甲胺)的还原性烷基化合成的叔胺(NMDMA).然后,使用1,3-丙烷磺内酯(对于SZNB)或使用三乙二醇单甲基醚的甲磺酸酯进行烷基化。此外,通过使用例如β-丙内酯或溴乙酸(或其酯,接着酯水解)的烷基化可以合成羧基甜菜碱单体(CZNB).
在上述方法中,可以以合适的方式终止聚合反应,例如通过使用烷基乙烯基醚例如乙基乙烯基醚.
本发明进一步提供了一种包含多孔氟聚合物载体和含有如上所述共聚物的涂层的复合亲水性薄膜,其中该共聚物可以任选进行交联.
本发明进一步提供了一种亲水改性氟聚合物载体的方法,其包含:
(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,以从包含所述共聚物或均聚物的溶液中除去至少一些溶剂;以及任选地
(iv)使涂布的载体中的所述共聚物交联.
在实施方式中,在使用包含溶剂和共聚物的溶液涂布多孔氟聚合物载体之前,使用溶剂例如异丙醇预润湿该载体.
在实施方式中,将该涂布的载体在100℃-160℃的温度下进行干燥.
图2说明使用根据本发明实施方式的共聚物涂布该多孔氟聚合物载体的过程.图3说明根据本发明实施方式交联多孔氟聚合物载体上的涂层的方法.
可以通过任意合适的方式进行交联,例如通过使用光引发剂或高能辐射,例如紫外线.注意到交联在薄膜中提供高度稳定的聚合物网络.
可以使用任意合适的光引发剂,例如I型和II型光引发剂.光引发剂的实例包括樟脑醌、二苯甲酮、二苯甲酮衍生物、苯乙酮、苯乙酮衍生物、氧化膦和衍生物、安息香烷基醚联苯甲酰缩酮、苯基乙醛酸酯及其衍生物、二聚苯基乙醛酸酯、过酸酯、卤代甲基三嗪、六芳基二咪唑/共引发剂体系、二茂铁化合物、环戊二烯钛及其结合.
交联可以按照如下进行.使用IPA任选地预润湿聚合物涂布的PTFE片材,然后使用溶剂进行洗涤,在溶剂中制备光引发剂,以用该溶剂交换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.光引发剂溶液中的浸入时间为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.“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,例如具有直径在1纳米至100纳米之间的孔的薄膜,或者具有直径在1μm至10μm之间的孔的微米多孔薄膜.
可以如下确定得到的多孔薄膜的表面张力.例如,在室温下,通过使用IPA溶剂预润湿薄膜片材和将该多孔薄膜浸入浓度为0.1质量%至10质量%的涂层聚合物溶液中来涂布PTFE多孔载体片材.涂布时间为(1分钟到12小时).在浸泡该载体之后,将其在100℃-160℃的对流烘箱中干燥.干燥时间介于(10分钟到12小时)之间.通过测量临界润湿表面张力,测量得到的多孔PTFE薄膜的润湿特性.
通过测量临界润湿表面张力(CWST)来测量在表面改性中表面张力的变化.该方法依赖于某种组成的一系列溶液.每种溶液具有特定的表面张力.该溶液的表面张力范围为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顶,将1滴具有一定表面张力的溶液施加到薄膜表面,记录液体穿透薄膜并作为光穿过薄膜的指示而发亮白色所花费的时间。当液滴穿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>10秒,则认为该溶液是部分润湿该薄膜.
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.可选地或额外地,根据本发明的实施方式的薄膜可以用于过滤空气和/或气体和/或可以用于排气应用(例如允许空气和/或气体通过,但不允许液体通过).根据本发明的实施方式的薄膜可用于各种装置,包括手术装置和产品,例如眼科手术产品。
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构造,包括平面的、平板的、褶皱的、管状的、螺旋状的和中空的纤维.
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括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,将至少一种本发明薄膜或包含至少一种本发明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,从而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,过滤器设备包含一个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限定了第 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制造,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,例如不锈钢制造,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造。
根据实施方式,该亲水性氟碳多孔薄膜包含任意合适的氟聚合物载体,例如PTFE、PVDF(聚偏氟乙稀)、PVF(聚氟乙烯)、PCTFE(聚氯三氟乙烯)、FEP(氟化乙烯-丙稀)、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,优选PTFE和PVDF.
本发明进一步提供了一种通过上述方法制备的亲水改性的氟聚合物多孔薄膜.
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上述的多孔薄膜.
下列实施例将进一步举例说明本发明,但是自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AlfaAesar.
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进行吹扫,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、亚硫酰氯、乙酸乙酯、二甲基甲酰胺(DMF)、马来酰亚胺、呋喃、偶氮二羧酸二异丙酯(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. 通过从在四氢呋喃中的硼烷中真空蒸馏来纯化环辛二烯(COD),并立即使用。
实施例2
此实施例说明二氯[1,3-二(2,4,6-三甲基苯基)-2-亚咪唑烷基](苯亚甲基)二(3-溴吡啶)钌(II)(G3)催化剂的制备.
将以上说明的二代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,并在真空下过滤.使用冷戊烷清洗得到的G3催化剂绿色固体,并在真空,室温下干燥,从而提供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技术在如下条件下对获得的均聚物和嵌段共聚物用它们的分子量和分子量分布性能表征:
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),该柱的静态相珠直径为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waters HPLC alliance e2695系统
MALS系统:DAWN HELEOS 8系统,具有8个于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)和对苯二酚(2.43g,22.1mmol)加入到Parr高压反应器圆筒容器中,将该圆筒连接至反应器上,加热到170℃进行72小时.将反应内容物溶解于150ml DCM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-89.9(s),-112.6(m),-123.8至-121.3(m),-127.1至-125.3(m)。
实施例5
本实施例说明根据本发明实施方式的iM6和iM6Ac的合成.
在500ml的RBF中,将降冰片烯-5.6-二羧酸的酸酐(25g,1.5mol)溶解在MeOH/THF(300ml)的混合物中,然后将氨基乙醇(9ml,1.5mol)缓慢滴入该溶液中.将收集水的stark-dean分水器连接至与RBF连接的冷凝器上.将溶液回流24小时,之后将溶剂从黄色溶液中除去,直到干燥,并获得该单体.将该固体溶解在乙酸乙酯中,使用K2CO3溶液(200ml,2x)洗涤,使用DI水(200ml,2x)洗涤,然后在MgSO4上干燥.将黄色溶液浓缩以提供单体并通过从MeOH结晶而进行纯化.
1H-NMR(CDCl3):δ(ppm)6.5(s,2H),5.25(s,2H),3.6至3.9(m,4H),2.29(s,2H),2.3至2.6(s,宽,H).
将iM6(25g,120mmol)、乙酸酐(14ml,240mmol,0.18ml)进行混合.将该混合物回流3小时.完成之后,将反应混合物用10%的碳酸氢钠(15ml)进行稀释,并用CH2Cl2(3×20mL)进行萃取。将合并的有机层在MgSO4上干燥,通过蒸发除去溶剂,从而提供乙酰化的化合物iM6-Ac.
实施例6
此实施例说明根据本发明实施方式的聚(iM6-b-NPF6)的合成.
将Grubbs二代(G2)催化剂(16mg,0.018mmol)和三苯基膦(245mg,0.94mmol)称入40ml装配有氟聚合物树脂-有机硅隔膜有孔盖的小瓶中.将该催化剂溶解于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iM6-Ac(2.0g,6.42mmol)在DCM(100mL)中的溶液进行脱气,转移到催化剂溶液中,并搅拌30分钟.30分钟后,取1-2mL等分的由第一单体形成的均聚物进行分子量表征.使用氩气,对第二单体NPF6(1.2g,2.81mmol)在DCM(200mL)中的溶液进行脱气,转移到RBF中正在生成的均聚物溶液中,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,从而将该纯聚合物作为白色固体回收.过滤该聚合物,并在室温,真空条件下进行干燥;产率(9.2g,98%).图1中描述了聚(iM6Ac-b-NPF6)和聚(iM6Ac)的GPC色谱.
通过两种方法,将聚(iM6Ac-b-NPF6)水解,从而产生聚(iM6-b-NPF6).第 一种是使用前述的标准涂布方法将聚(iM6Ac-b-NPF6)涂布在PTFE薄膜上,然后将薄膜浸泡于IPA中的KOH的醇溶液中,从而将乙酰基脱保护,并原位产生聚(iM6-b-NPF6).第二种方法包括使用含水KOH的碱性浴在溶液中进行脱保护,同时将聚合物溶解在THF中,从而产生聚(iM6-b-NPF6)的聚合物沉淀.
1H-NMR(300MHz,CDCl3):δ(ppm)6.5至6.0(s,宽),5.75至5.6(m,宽),5.65至5.2(m,宽),5.0至4.4(m,宽),4.5至4.0(m,宽),4.0至3.6(s,宽),3.5至2.9(m,宽),2.5至1.3(m,宽).
如图2所示,通过以下方式测试该共聚物吸附至氟聚合物基底的能力,即将PTFE薄膜在1%(w/v)的溶液中浸涂1小时,通过测量薄膜表面的瞬时临界润湿表面张力(CWST)测试经涂布的薄膜的湿润能力.由于溶剂能够溶解聚(iM6-b-NPF6)二嵌段共聚物,选择DMAC和TFE/DCM(1∶1)混合物用于涂布实验,这是因为二者均润湿“原生”PTFE薄膜.
如图3所示,为了进一步稳定该共聚物层,将涂布的薄膜浸入0.25%的光引发剂(Irgacure 2959)水溶液中5分钟,然后UV照射60秒进行交联处理.
将经交联步骤后的样品在140℃下使用80/20的浓硫酸和过氧化氢的混合物考验3小时(“热SPM”),然后进行12小时的去离子水滴流洗涤并干燥.
表1总结了各个步骤之后的湿润性结果.
表1
使用共聚物提高了PTFE薄膜的表面能,如CWST’s所示为33-40,而未 处理的“原生”PTFE薄膜是25.4达因/cm.
实施例7
此实施例说明根据本发明一个实施方式的聚(SZNB-NPF6)的合成和性能.合成多种聚(SZNB-NPF6)共聚物(聚(SZNB-r-NPF6)、聚(SZNB-b-NPF6)-1、聚(SZNB)均聚物和聚(SZNB-b-NPF6)).通过NMR光谱学已经证实了它们的通用结构.元素分析特别是N/F比的结果和沉淀共聚物的回收率已经用于评估他们的最终组成.
NMDMA:
使用2M二甲胺的THF溶液稀释5-降冰片烯-2-甲醛(20mL;约149mmol),同时在环境温度下激烈搅拌30min.在10分钟内逐份加入固体三乙酰氧基硼氢化钠(40g;约180mmol)在此期间观察到放热反应.此时,使用无水1,2-二氯乙烷(50mL)稀释该混合物,然后继续搅拌16小时.通过倒入过量的饱和碳酸氢钠溶液将反应混合物猝灭,然后使用二氯甲烷(150mL)萃取.将底部的有机层进行分离,使用饱和碳酸氢盐溶液、盐水进行萃取,然后在无水硫酸镁上干燥。在倾析之后,使用2个体积的戊烷稀释该有机相并过滤出不溶性物质,接着通过旋转蒸发进行浓缩,同时真空不超过30托,浴温度不超过50℃.通过NMR,认为得到的褐色液体(18.2g,相应于81%的粗产率)足够纯,从而原样继续进行烷基化步骤.
SZNB:
使用无水THF(80mL)稀释12.5gNMDMA下描述的叔胺,接着在环境温度下,在保持强烈搅拌的同时,在15分钟内滴加1,3-丙烷磺内酯(12.5g;约1.2当量)溶解在无水THF(30mL)中的溶液.通过形成的沉淀的量的增加可以看出反应的进程.在24小时之后,过滤出固体,并多次使用无水THF且最后一次使用乙醚洗涤.在真空管道(house vacuum)中,在60℃下干燥得到的产品过夜,最终获得单体SZNB,产率12.8g(59%).通过NMR(在重水中)和LCMS证实预期的结构,其中观察到274.4的希望的分子峰.通过元素分析证实满足ROMP聚合方案的纯度.(计算C57.11,H8.48,N5.12,S11.93:发现C56.07,H9.37,N4.85,S11.15).
通常的聚合方案:
在氩气的正压下,在储存的溶剂中,ROMP在碱性氧化铝上进行ROMP反应,并使用氩气进行广泛吹扫。通过套管插入法,将溶液在烧瓶之间转移.全部操作均在环境温度下进行.通常,将第三代Grubbs引发剂(G3)称入氩气吹扫的圆底烧瓶中,然后使用合适的溶剂溶解,然后依次(用于嵌段共聚物合成)或作为混合物(用于无规共聚物)加入单体溶液.在合适的时间之后,通过以下方式终止该聚合反应,即通过添加过量的乙基乙烯基醚(EVE),搅拌30分钟,最后滴加约10倍体积的合适的非溶剂进行沉淀。除去上清液之后,使用非溶剂多次洗涤固体,然后溶解(通常在TFE中)以转移到配衡烧瓶(tarred flask)中以在真空下旋转蒸发至恒重.
聚(SZNB-r-NPF6):
将一起溶解在TFE(40mL)中的SZNB(1.7g)和NPF6(0.64g)的混合物加入到G3(14mg)在TFE(10mL)的溶液中,保持搅拌16小时,接着EVE猝灭并在甲醇中沉淀.回收2.05g(总单体进料的85%).元素分析-发现C44.38,H6.19,F25.41,N2.46,S5.90.
聚(SZNB-b-NPF6)-1:
将SZNB(3.16g)在TFE(60mL)中的溶液加入到G3(26mg)在TFE(10mL)的溶液中,然后搅拌2小时.接着,加入NPF6(1.19g)在TFE(10mL)中的溶液.不久之后,反应混合物变浑浊,开始形成沉淀.在再一个30分钟和EVE猝灭之后,将沉淀滤出,使用甲醇洗涤,然后通过分析确定其主要是NPF6的均聚 物.将合并了甲醇洗涤物的滤液中所形成的沉淀分离.回收3.15g(总单体进料的72%).元素分析-发现C45.84,H7.25,F14.37,N3.45,S8.27.
聚(SZNB)的均聚物:
将SZNB(1.05g)在TFE(20mL)中的溶液加入到G3(9mg)在DCM(15mL)的溶液中,然后搅拌1小时.然后,加入NPF6(0.4g)溶解在DCM(5mL)中的溶液,保持搅拌30分钟,然后EVE猝灭并在甲醇中沉淀.回收0.84g(总单体进料的58%).元素分析-发现C50.17,H9.62,F1.11,N4.24,S10.28.
聚(SZNB-b-NPF6)-2:
将SZNB(3.21g)在1∶1的TFE/DCM混合物(80mL)中的溶液加入到G3(26mg)在1∶1的TFE/DCM混合物(20mL)的溶液中,然后搅拌2小时.然后,加入NPF6(1.21g)在1∶1的TFE/DCM混合物(20mL)中的溶液,保持搅拌30分钟,然后EVE猝灭并在乙醚中沉淀.使用温热的甲醇(100mL)萃取该沉淀16小时,接着干燥至恒重.回收1.83g(总单体进料的41%).元素分析-发现C48.02,H6.98,F17.11,N3.31,S7.41.
通过以下方式测试该共聚物吸附至氟聚合物基底的能力,即将PTFE薄膜在1%(w/v)的溶液中浸涂1小时,通过测量薄膜表面的瞬时CWST测试经涂布的薄膜的湿润性.选择2,2,2-三氟乙醇(TFE)作为溶剂,因为其同时具有溶解SZNB-衍生的共聚物和润湿“原生”PTFE薄膜的能力.
为了进一步稳定共聚物层,将涂布的薄膜通过浸入光引发剂含水溶液中5分钟,然后UV照射60秒进行交联处理.所采用的具体条件列于下表中.
然后,将经交联步骤后的样品在140℃下下使用80∶20的浓硫酸和过氧化氢的混合物考验3小时(所谓的“热SPM”),然后进行12小时的去离子水滴流洗涤并干燥.
下表2总结了各个步骤之后的湿润性结果.
共聚物明显提高了PTFE薄膜的表面能,如CWST在33-48范围,而未处理的“原生”PTFE薄膜是25.4达因/cm.
表2
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 (12)
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具有下式:
其中:共聚物是嵌段共聚物或无规共聚物;
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的复合多孔薄膜,其中共聚物具有下式的一种:
4.权利要求3的复合亲水性多孔薄膜,其中该共聚物具有下式的一种:
5.权利要求3的复合亲水性多孔薄膜,其中该共聚物具有下式的一种:
6.一种亲水改性多孔氟聚合物载体的方法,包括:
(i)提供一种多孔氟聚合物载体;
(ii)使用包含溶剂和共聚物的溶液涂布多孔氟聚合物载体,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;
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,从而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)使存在于涂布的载体中的所述共聚物交联。
7.权利要求6的方法,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的方法,其中该共聚物具有下式的一种:
9.一种通过权利要求6-8任一项的方法制备的亲水改性的多孔氟聚合物薄膜。
10.权利要求1-5任一项的复合亲水性多孔薄膜或权利要求10的亲水改性的多孔氟聚合物薄膜,其中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。
11.一种过滤流体的方法,该方法包含将该流体通过权利要求1-5、9或10中任一项的多孔薄膜。
12.权利要求1-5、9或10任一项的亲水性多孔薄膜,其可以构造为平面、平板、褶皱、管状、螺旋状或中空纤维结构。
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US20160288062A1 (en) | 2016-10-06 |
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CN106397805B (zh) | 2019-02-01 |
KR20160117139A (ko) | 2016-10-10 |
US9643130B2 (en) | 2017-05-09 |
SG10201509681RA (en) | 2016-10-28 |
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