CN106398443B - 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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- CN106398443B CN106398443B CN201511036182.9A CN201511036182A CN106398443B CN 106398443 B CN106398443 B CN 106398443B CN 201511036182 A CN201511036182 A CN 201511036182A CN 106398443 B CN106398443 B CN 106398443B
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- coating
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- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 description 3
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Abstract
公开了适用于亲水改性多孔氟聚合物载体表面的聚合物,例如具有下式的共聚物:
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选自
以及B具有下式
其中,n和m为1至约1000,条件是n和m的总和等于或大于10.
本发明进一步提供了复合亲水性多孔薄膜,其包含多孔氟聚合物载体和含有聚合物的涂层,其中该聚合物具有一个或多个连接至聚合物主链的全氟烷基硫基侧基,其中其重复单元具有下式:
其中,*表示全氟烷基硫基侧基的连接点。
该共聚物以及具有全氟烷基硫基侧基的聚合物对多孔氟聚合物载体的表面改性有用.
本发明进一步提供了制备具有全氟烷基硫基侧基的聚合物以及共聚物的方法,以及制备亲水改性氟聚合物多孔薄膜的方法.本发明进一步提供了通过这些多孔薄膜过滤流体的方法。
几个附图视图的简要说明
图1说明了使用根据本发明实施方式的共聚物涂布多孔氟聚合物载体的过程。
图2说明了根据本发明实施方式的交联多孔氟聚合物载体上的涂层的方法。
图3描述了根据本发明实施方式的聚(C4-b-NPF6)共聚物的GPC谱图。
发明详述
根据一个实施方式,本发明提供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选自
以及B具有下式
其中,n和m为1至约1000,条件是n和m的总和等于或大于10.
在本文的式中,重复单元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。
在其它实施方式中,n和m表示存在于共聚物中的单体的摩尔分数,n和m可以独立地为1至99mol%,优选为20至50mol%.
相应单体嵌段可以任意合适质量%存在于嵌段共聚物中,例如在一个实施方式中,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%。
该共聚物可以是嵌段共聚物或无规共聚物.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,例如在一个实施方式中,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。
根据实施方式,本发明的共聚物具有下式中的一种:
在一个实施方式中,本发明的共聚物进一步包含一个或多个下式的重复单元C:
其中,o/(m+n)的比为大于0至约0.25,优选为约0.05至约0.25,以及更优选为约0.10至约0.15mol%.
在一个实施方式中,该共聚物具有下式:
本发明进一步提供了复合亲水性多孔薄膜,其包含多孔氟聚合物载体和含有聚合物的涂层,其中该聚合物具有一个或多个连接至聚合物主链的全氟烷基硫基侧基,该聚合物的重复单元具有式:
其中,*表示全氟烷基硫基侧基的连接点.
在一个实施方式中,该聚合物具有下式:
其中,p+q=m-1.
该全氟烷基硫基侧基可以存在于聚合物的一些或全部重复单元中.因此,例如,全氟烷基硫基侧基的存在量可以是重复单元的大于0至100%,在一个实施方式中,为约1至约50%,或约10至约30%.全氟烷基硫基侧基无规分布于聚合物的主链中.
本发明具有全氟烷基硫基侧基的共聚物和聚合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,例如可使用Grubbs第一代、第二代和第三代催化剂、Umicore、Hoveyda-Grubbs、Schrock和Schrock-Hoveyda催化剂。这样的催化剂的实例包括以下:
在一个实施方式中,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三代催化剂,可以将端基设计成适应任意相容的基团,并且该催化剂可以便利地再循环.该催化剂一个优选实例是:
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:
本发明进一步提供了制备具有全氟烷基硫基侧基的聚合物和共聚物的方法。
因此,本发明提供了一种制备具有链段A的嵌段共聚物的方法,其中链段A选自:
该方法包括:
(i)通过开环易位聚合(ROMP)催化剂催化聚合选自顺式-5-氧杂降冰片烯-外型-2,3-二羧酸酐、顺式-5-降冰片烯-外型-2,3-二羧酸二甲酯、和顺式-5-氧杂降冰片烯-外型-2,3-二羧酸二甲酯的单体,从而获得均聚物;和
(ii)通过ROMP催化剂催化,在由(i)获得的均聚物的链端相继聚合5-(全氟己基)降冰片烯.
由顺式-5-氧杂降冰片烯-外型-2,3-二羧酸酐制备的共聚物(聚(C2-b-PNF6))可以与含水碱反应,从而获得具有含二羧酸的链段A的共聚物.
本发明进一步提供了制备本发明的无规共聚物的方法,其包括:(i)通过ROMP催化剂催化聚合顺式-5-降冰片烯-外型-2,3-二羧酸二甲酯和5-(全氟己基)降冰片烯的混合物;或(ii)通过ROMP催化剂催化聚合顺式-5-氧杂降冰片烯-外型-2,3-二羧酸二甲酯、5-(全氟己基)降冰片烯和N-巯乙基顺式-5-降冰片烯-外型-2,3-二羧基酰亚胺的混合物.
本发明进一步提供了制备具有全氟烷基硫基侧基的聚合物的方法,其包括(i)通过ROMP催化剂催化聚合选自顺式-5-氧杂降冰片烯-外型-2,3-二羧酸酐、顺式-5-降冰片烯-外型-2,3-二羧酸二甲酯和顺式-5-氧杂降冰片烯-外型-2,3-二羧酸二甲酯的单体,从而获得均聚物;和(ii)使得到的均聚物与1H,1H,2H,2H- 全氟癸烷硫醇反应.可以将由顺式-5-氧杂降冰片烯-外型-2,3-二羧酸酐制备并用1H,1H,2H,2H-全氟癸烷硫醇改性的聚合物与含水碱例如,氢氧化钠、氢氧化钾、碳酸钾、碳酸钠等在合适的浓度下例如0.01N至约10N,优选约0.1N至1N下反应,从而获得具有其二羧酸盐的聚合物,其可以使用无机酸例如盐酸、硫酸或硝酸中和,以获得二羧酸的形式,
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。合适溶剂的实例包括芳香烃如苯、甲苯和二甲苯,脂肪烃如正戊烷、己烷和庚烷,脂环烃如环己烷,和卤代烃如二氯甲烷、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%.
聚合可以在任意合适的温度下进行,例如-20至+100℃,优选10至80℃。
为了制备嵌段共聚物,例如,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,催化剂与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,催化剂与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.
聚合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.
本发明的具有全氟烷基硫基侧基的聚合物和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),接着是折射率检测器(RI-检测器).UV-检测器测量聚合物在254nm波长处的光吸收;MALS-检测器测量聚合物链相对于流动相的散射光。
本发明的具有全氟烷基硫基侧基的共聚物和聚合物是高单分散性的。例如,该共聚物的Mw/Mn为1.05至1.5,优选1.1至1.2.
根据一个实施方式,本发明提供了一种制备下式共聚物的方法:
该方法包括:
(i)通过开环易位聚合(ROMP)催化剂催化聚合顺式-5-氧杂降冰片烯-外型-2,3-二羧酸酐,从而获得均聚物;和
(ii)如以下说明,通过ROMP催化剂催化,在由(i)获得的均聚物的链端上聚合5-(全氟己基)降冰片烯:
如以下说明,本发明进一步提供了一种制备聚(C2二酸-b-NPF6)的方法,包含用碱水水解聚(C2-b-PNF6):
本发明进一步提供了一种制备聚(C3-b-NPF6)的方法,包括:
(i)通过ROMP催化剂催化聚合顺式-5-降冰片烯-外型-2,3-二羧酸的二甲酯,从而获得均聚物;和
(ii)如以下说明,通过ROMP催化剂催化,在由(i)获得的均聚物的链端上聚合5-(全氟己基)降冰片烯
本发明进一步提供了一种制备共聚物聚(C4-b-NPF6)的方法,包括:
(i)通过开环易位聚合(ROMP)催化剂催化聚合顺式-5-氧杂降冰片烯-外型-2,3-二羧酸二甲酯,从而获得均聚物;和
(ii)通过ROMP催化剂催化,在由(i)获得的均聚物的链端上聚合5-(全氟己基)降冰片烯。
本发明提供了一种制备共聚物聚(C3-r-NPF6)的方法,包括通过ROMP 催化剂催化聚合顺式-5-降冰片烯-外型-2,3-二羧酸二甲酯和5-(全氟己基)降冰片烯的混合物.
本发明进一步提供了一种制备下式的无规共聚物的方法,包括:
通过ROMP催化剂催化聚合顺式-5-降冰片烯-外型-2,3-二羧酸的二甲酯和5-(全氟己基)降冰片烯和N-巯乙基顺式-5-降冰片烯-外型-2,3-二羧酰亚胺的混合物。
本发明进一步提供了一种制备下式聚合物的方法:
包括如以下所示通过ROMP催化剂催化聚合顺式-5-降冰片烯-外型-2,3-二羧酸的二甲酯和5-(全氟己基)降冰片烯,将得到的聚合物与1H,1H,2H,2H-全氟癸烷硫醇反应:
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。从而,可以提供共聚物的端基的一种。
通过选择适当的ROMP催化剂可以提供其它端基。例如,通过使用在过渡金属上具有苯亚甲基的ROMP催化剂,可以提供苯基端基。
本发明进一步提供了一种如上所述的包含多孔氟聚合物和共聚物或聚合物的复合亲水性多孔薄膜,其中该共聚物或聚合物任选是交联的.
本发明进一步提供了一种亲水改性多孔氟聚合物载体的方法,包括:
(i)提供多孔氟聚合物载体;
(ii)使用包含溶剂和具有上述全氟烷硫基侧基的共聚物或聚合物的溶液涂布该多孔氟聚合物载体;
(iii)干燥来自(ii)的经过涂布的多孔氟聚合物载体,从而从包含所述共聚物或聚合物的溶液中除去至少一些溶剂;以及任选地
(iv)使存在于涂层中的共聚物或聚合物交联。
图1说明使用根据本发明的一个实施方式的共聚物涂布多孔氟聚合物载体的过程.图2说明了根据本发明的一个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、环戊二烯钛及其组合.
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).
根据本发明的一个实施方式,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,或者直径在1μm至10μm之间的孔的微孔薄膜。
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载体浸入浓度为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多孔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多孔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的壳体中,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外壳;以及至少一种本发明的薄膜或包含至少一种本发明的薄膜的过滤器,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,例如由PTFE、PVDF(聚偏氟乙烯)、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制成.多孔载体可以具有合适的孔径,例如约2nm至约10微米,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,该方法包括将该流体通过上述的亲水性氟聚合物多孔薄膜.
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、氯化亚砜、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第二代催化剂、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.通过从三氟化硼中真空蒸馏来纯化环辛二烯(COD),并立即使用.
实施例2
此实施例说明制备二氯[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.
将以上说明的第二代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)搅拌15分钟,获得绿色固体。将混合物在冰箱中冷却24小时,在真空下过滤。使用冷戊烷洗涤得到的G3催化剂,绿色固体,并在真空、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的一个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的一个实施方式制备NPF6单体的方法.
将DCPD(100ml,737mmol)、PF6(168ml,737mmol)加入到Parr高压反应器圆筒容器中并将该圆筒连接至反应器上,加入对苯二酚(2.43g,22.1mmol),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
此实施例说明根据本发明的一个实施方式制备NPF10单体的方法。
将DCPD(24.6ml,183mmol)、PF6(132ml,370mmol)加入到Parr高压反应器圆筒容器中并将该圆筒连接至反应器上,加入对苯二酚(1.08g, 10mmol),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
此实施例说明根据本发明的一个实施方式制备C2单体的方法.
在1个2L装配有磁性搅拌棒的干净圆底烧瓶(RBF)中,将呋喃(390ml,3.35mol)加入到马来酸酐(350g,3.57mol)在1.5L甲苯中的溶液.将混合物在80℃加热6小时.使用甲苯(200mL,3x)进行洗涤并过滤,从溶液中作为白色沉淀获得C2.将白色固体在室温下和真空中干燥24小时.作为纯外型-异构体获得C2,产量为650g,95%。1H-NMR(300MHz,DMSO):δ(ppm)6.6(s,2H),5.4(s,2H),3.15(s,2H).
实施例7
此实施例说明根据本发明的一个实施方式制备C4单体的方法,其中C4是C2单体的二甲酯.
在500ml的RBF中,将外型-7-氧杂降冰片烯-5.6-二羧酸酐(C2)(65g,0.4mol)溶解在甲醇(750ml)中,将亚硫酰氯(25ml)缓慢滴加到C2溶液中,从而形成黄色溶液。将该溶液回流48小时,然后溶剂被除去直到干燥,得到单体.将固体溶解在乙酸乙酯中,用K2CO3溶液(200ml,2x)洗涤,使用去离子水(200ml,2x)洗涤,然后在MgSO4上干燥。将得到的黄色溶液浓缩,从而获得C4单体.1H-NMR(CDCl3):δ(ppm)6.49(s,2H),5.2(s,2H),3.8(s,2H)3.7(s,6H),2.8(s,2H).
实施例8
此实施例说明制备N-2-巯基-乙基-降冰片烯二甲酰亚胺(NHS)的方法.
在500ml的RBF中,将降冰片烯-5.6-二羧酸酐(25g,1.5mol)溶解在甲苯(300ml)中,然后将氨基乙硫醇(14ml,1.83mol)缓慢滴加该溶液中。将Dean-Stark分水器连接至冷凝器上,冷凝器连接至RBF,从而收集反应期间形成的水。将溶液回流24小时,然后将溶剂从黄色溶液中除去直到干燥,获得单体。将得到的固体溶解在乙酸乙酯中,使用K2CO3溶液(200ml,2x)洗涤,使用去离子水(200ml,2x)洗涤,然后在MgSO4上干燥.将得到的黄色溶液浓缩,从而获得单体。
1H-NMR(CDCl3):δ(ppm)6.25(s,2H),5.5(s,2H),3.35(s,2H),3.35(s,2H),3.7(s,6H),2.8(m),1.75(m),1.5(m),1.25(m)。
实施例9
此实施例说明根据本发明的一个实施方式的共聚物聚(C2-b-NPF6)的合成和性能.
在40ml装配有氟聚合物树脂-有机硅隔膜的有孔盖的小瓶中称量Grubbs第三代(G3)催化剂(22mg,0.025mmol).将G3溶解在氩气脱气的THF(60mL)中,并经套管转移到1L装配有搅拌棒的清洁RBF中.使用氩气,对C2单体(3.05g,18.4mmol)在THF(86mL)中的溶液进行脱气,然后转移到G3溶液中,并搅拌30分钟。使用氩气,对NPF6单体(1.03g,2.5mmol)在THF(208mL)中的溶液进行脱气,然后转移到增长的聚(C2)嵌段溶液中,并再搅拌60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终止该反应。将聚合物在MeOH(2L,2x)中沉淀,从而回收纯聚合物的白色固体。过滤得到的聚合物,并在室温和真空条件下进行干燥,产量为(4.0g,98%).
1H-NMR(300MHz,DMSO):δ(ppm)12.25(s),5.5至6.0(m),4.75至5.25(s),4.5至4.75(s),3.75(s),3.3(s),3.25(s).
下表1列出了元素分析数据.
表1.元素分析
将聚(C2-b-NPF6)-1共聚物溶解于THF中,从而提供1wt%的溶液.将PTFE微孔载体(KA-N3P72)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。经涂布的PTFE薄膜的CWST测量为33.41dyne/cm.起始PTFE薄膜的CWST为25.4达因/cm.
实施例10
此实施例说明根据本发明的一个实施方式的另一共聚物聚(C3-b-NPF6)的合成和性能.
在40ml装配有氟聚合物树脂-有机硅隔膜的有孔盖的小瓶中称量Grubbs第三代(G3)催化剂(11mg,0.012mmol)。将G3溶解在氩气脱气的THF(60mL)中,并经套管转移到1L装配有搅拌棒的清洁RBF中.使用氩气,对C3单体(2.5g,12mmol)在THF(86mL)中的溶液进行脱气,然后转移到G3溶液中,并搅拌30分钟。使用氩气,将NPF6单体(0.86g,2.0mmol)在THF(208mL)中的溶液脱气,转移到增长的聚(C3)嵌段溶液中,然后再搅拌60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终止该反应.然后,将聚合物在MeOH(2L,2x)中沉淀,从而回收纯聚合物的白色固体.过滤该得到的聚合物,并在室温和真空下进行干燥,产量为(3.0g,90%).
以下列出1HNMR数据,表2列出元素分析。1H-NMR(300MHz,CDCl3):δ(ppm)5.7至5.2(s宽),3.7至3.5(m宽),3.3至2.8(m宽),2.5至1.75(m宽),1.6(s宽),1.25(s宽)。
表2:聚(C3-b-NPF6)的元素分析
将聚(C3-b-NPF6)-1共聚物溶解于THF中,从而提供1wt%的溶液.将PTFE多孔载体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。经涂布的PTFE薄膜的CWST测量为30达因/cm.起始PTFE载体的CWST为25.4达因/cm。
实施例11
本实施例说明根据本发明的一个实施方式的还另一种共聚物的合成和性能。
按如下所述合成聚(C4-b-NPF6)。在40ml装配有氟聚合物树脂-有机硅隔膜的有孔盖的小瓶中称量Grubbs第三代(G3)催化剂(25mg,0.028mmol)。将G3溶解在氩气脱气的THF(60mL)中,并经套管转移到1L装配有搅拌棒的清洁RBF中。使用氩气,对C4单体(2.5g,11.8mmol)在THF(86mL)中的溶液进行脱气,转移到G3溶液中,并搅拌30分钟.使用氩气,将NPF6单体(0.86g,2.0mmol)在THF(208mL)中的溶液脱气,转移到增长的聚(C4)嵌段溶液中,再搅拌60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终止反应。将聚合物在MeOH(2L,2x)中沉淀,从而回收纯聚合物的白色固体.过滤聚合物,并在室温和真空条件下进行干燥,产量为(3.0g,90%).
1H-NMR(300MHz,CDCl3):δ(ppm)6.85(s宽),5.8(s宽),5.6(s宽),5.2至4.9(s宽),4.8至4.5(s宽),4.4至4.0(m宽)4.0至3.6(m宽)3.2至2.9(m宽),1.4至1.2(m宽).
图3显示共聚物在CH2Cl2中的GPC谱图。该共聚物具有下列性能:Mn=98800,Mw=127200,PDI=1.28.
将聚(C4-b-NPF6)-1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,然后在THF中洗涤30分钟.将该样品再在空气中干燥10分钟.经涂布的PTFE薄膜的CWST测量为39达因/cm.起始PTFE薄膜的CWST为25.4达因/cm.
表3.
实施例12
本实施例说明根据本发明一个实施方式的具有全氟烷硫基侧基的聚合物的合成和性能。
将聚(C2)均聚物(1.0g,6.0mmol)、1H,1H,2H-全氟癸烷硫醇(3.0g,6.0mmol)和AIBN(79.8mg)溶解在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.将获得的沉淀物溶解到THF中,并从庚烷中再次沉淀,从而生成所希望的暗褐色固态聚合物.
1H-NMR(300MHz,CDCl3):δ(ppm)14至13(s宽),5.75(s宽),5.5(s宽),4至5(m宽)3.5至2.5(m宽),1.6(s宽)。
表4.元素分析
将具有全氟烷硫基侧基的聚合物溶解于THF中,从而提供1wt%的溶液。将PTFE微孔载体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。经涂布的PTFE载体的CWST测定为33.41达因/cm(一式三份)(局部35)。起始PTFE载体的CWST为25.4达因/cm.
实施例13
本实施例说明根据本发明的一个实施方式的另一共聚物的合成和性能.
聚(C2二酸-b-NPF6):将聚(C2-b-NPF6)与0.1N的NaOH溶液反应,从而获得聚(C2二酸-b-NPF6)。将聚(C2-b-NPF6)二嵌段共聚物溶解于THF(1质量%)中,从而形成均相溶液.使用0.1N的NaOH水溶液处理该聚合物溶液。将该混合物在环境温度下搅拌1小时,然后在己烷中沉淀。
1H-NMR(300MHz,CDCl3):δ(ppm)14至13(s宽),6.0至5.5(m宽),5.3至4.75(s宽),5.375至4.25(s宽)3.25(s宽),3.3(s宽),3.1(s宽)。
将该聚合物涂布在多孔PTFE载体上,并测量其CWST。表5列出了获得的结果。
表5
实施例14
此实施例说明根据本发明的一个实施方式的又一共聚物聚(C3-r-NPF6)的合成和性能.
在40ml装配有氟聚合物树脂-有机硅隔膜的有孔盖的小瓶中称量Grubbs第三代(G3)催化剂(11mg,0.012mmol).将G3溶解在氩气脱气的DCM(20mL)中,并经套管转移到250ml装配有搅拌棒的清洁RBF中。使用氩气,对溶解在DCM(90ml)中的C3单体(2.5g,12mmol)和NYF6(0.86g,2.0mmol)的混合物进行脱气,转移到G3溶液中,并在室温下搅拌12小时.然后,将乙基乙烯基醚(2mL)加入到无规共聚物的黄色溶液中终止该反应.然后,使该聚合物通过碱性氧化铝、硅胶和硅藻土(Celite)柱,从而除去催化剂。在旋转蒸发器中除去溶剂,得到的聚合物是无色和高粘性的;产量(3.0g,90%)。
1H-NMR(300MHz,CDCl3):δ(ppm)6.0至5.0(s宽),3.7至3.5(m宽),3.3至2.8(m宽),2.5至1.75(m宽),1.6(s宽),1.25(s宽)。
将该聚合物涂布在多孔PTFE载体上,并测量其CWST。表6列出了获得的结果。
表6:数据总结
PI=光引发剂=2-苯甲基-2-(二甲基氨基)-4′-吗啉苯丁酮=BDMB
实施例15
本实施例说明根据本发明的一个实施方式的三嵌段聚合物的合成和性能。
通过ROMP催化剂催化聚合顺式-5-氧杂降冰片烯-外型-2,3-二羧酸的二甲酯、5-(全氟己基)降冰片烯和N-巯乙基顺式-5-降冰片烯-外型-2,3-二羧酰亚胺,合成聚(C4-r-NPF6-r-NHS).
1H-NMR(300MHz,CDCl3):δ(ppm)6(s宽),5.9至5.0(m宽),5.1至4.6(m宽),4.6至4.1(m宽),4.0至3.0(m宽),3.0至2.4(m宽),2.3至1.4(m宽),1.25(s宽).
将该聚合物涂布在多孔PTFE载体上,并测量其CWST。表7列出了获得的结果.
表7.数据总结
PI=光引发剂=2-苯甲基-2-(二甲基氨基)-4′-吗啉苯丁酮=BDMB
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 (20)
1.一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选自:
以及B具有式:
其中,
该共聚物是嵌段共聚物或无规共聚物;并且
重复单元B和A的数量各自是n和m且为1至1000,条件是n和m的总和等于或大于10,
其中该共聚物是任选交联的。
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团。
3.权利要求1或2的复合亲水性多孔薄膜,其中共聚物具有下式中的一种:
4.权利要求1或2的复合亲水性多孔薄膜,其中共聚物进一步包含一个或多个下式的重复单元C:
其中,o/(m+n)的比为大于0到0.25,o是包含在共聚物中的重复单元C的数量。
5.权利要求4的复合亲水性多孔薄膜,其中共聚物是无规共聚物且具有下式:
6.一种复合亲水性多孔薄膜,包含多孔氟聚合物载体和含有聚合物的涂层,其中该聚合物具有一个或多个连接至聚合物主链的全氟烷硫基侧基,该聚合物的重复单元具有式:
其中,*表示全氟烷基硫基侧基的连接点。
7.权利要求6的复合亲水性多孔薄膜,其中该聚合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,其中该聚合物具有下式:
其中p+q=m-1,其中m是权利要求6中所限定的重复单元的总数。
9.一种将多孔氟聚合物载体亲水改性的方法,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选自:
以及B具有式:
其中,
该共聚物是嵌段共聚物或无规共聚物;并且
该重复单元B和A的数量各自是n和m且为1至1000,条件是n和m的总和等于或大于10,
(iii)干燥来自(ii)的经过涂布的氟聚合物载体,从而从包含所述共聚物的溶液中除去至少一部分溶剂;以及任选地
(iv)使存在于涂布的多孔氟聚合物载体中的所述共聚物交联。
10.权利要求9的方法,其中共聚物具有选自芳基和烷氧基的链端基团。
11.权利要求9或10的方法,其中该共聚物具有下式中的一种:
12.权利要求9或10的方法,其中该共聚物进一步包含一个或多个下式的重复单元C:
其中,o/(m+n)的比为大于0到0.25,o是包含在共聚物中的重复单元C的数量。
13.权利要求12的方法,其中共聚物是无规共聚物且具有下式:
14.一种将多孔氟聚合物载体亲水改性的方法,包括:
(i)提供多孔氟聚合物载体;
(ii)使用包含溶剂的溶液和含有聚合物的涂层涂布多孔氟聚合物载体,其中该聚合物具有一个或多个连接至聚合物主链的全氟烷基硫基侧基,其中该聚合物的重复单元具有式:
其中,*表示全氟烷基硫基侧基的连接点;
(iii)干燥来自(ii)的经过涂布的氟聚合物载体,从而从包含该聚合物的溶液中除去至少一部分溶剂;以及任选地
(iv)使存在于涂布的氟聚合物载体中的聚合物交联。
15.权利要求14的方法,其中该聚合物具有选自芳基和烷氧基的链端基团。
16.权利要求14或15的方法,其中该聚合物具有式:
其中,p+q=m-1,其中m是权利要求14中所限定的重复单元的总数。
17.权利要求9、14或15的方法,其中通过将涂层曝露至UV辐射进行涂层的交联。
18.一种通过权利要求9-17中任意一项的方法制备的亲水改性的多孔氟聚合物薄膜。
19.权利要求1、2和5-7中任意一项的复合亲水性多孔薄膜或权利要求18的亲水改性的多孔氟聚合物薄膜,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。
20.一种过滤流体的方法,该方法包括使流体通过权利要求1-8和19中任意一项的复合亲水性多孔薄膜或权利要求18的亲水改性的多孔氟聚合物薄膜。
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CN111836677A (zh) * | 2018-03-22 | 2020-10-27 | 富士胶片株式会社 | 过滤装置、纯化装置、药液的制造方法 |
CN108479414B (zh) * | 2018-04-12 | 2020-12-25 | 南京工业大学 | 一种中空纤维聚合物膜、制备方法及其在盐水精制中的用途 |
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