CN106084281B - 亲水改性的氟化膜(vi) - Google Patents
亲水改性的氟化膜(vi) Download PDFInfo
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- CN106084281B CN106084281B CN201610142913.6A CN201610142913A CN106084281B CN 106084281 B CN106084281 B CN 106084281B CN 201610142913 A CN201610142913 A CN 201610142913A CN 106084281 B CN106084281 B CN 106084281B
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- copolymer
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Abstract
公开了一种适合于亲水改性多孔氟聚合物载体表面的共聚物,例如,式(I)或(II)的共聚物:
Description
背景技术
氟聚合物膜(例如多孔PTFE膜)的性能,包括它们的机械强度,耐化学试剂性或惰性,不粘性,突出的介电性能,高温热稳定性和低摩擦系数,使得它们非常适合于多种应用.然而,对于某些应用来说,在不影响其内在性能的情况下改性PTEF的表面是有益的.为改进用于特定应用的膜的适用性,已努力来改进PTFE膜的表面和化学性能.例如,努力包括表面涂覆,共混,高能表面改性例如宽频紫外辐射或BBUV,其中该膜暴露于波长为250-450nm的UV辐射,和等离子处理,自由基,和臭氧刻蚀,原子层沉积,和改性PTFE类聚合物的合成.然而,大多数的努力集中于高能处理,例如BBUV或等离子.尽管这些表面改性方法的准确机理没有被记载,但是其可能由通过主链键断裂的自由基形成引起,这是因为C-C键的强度已知比F-F键的低约40%.如果大部分自由基得自C-C键断裂或聚合物主链断裂,那么其可能降低PTFE膜的机械和化学稳定性.也已知等离子处理受限于膜表面,其导致在长时间期间这种改性较不稳定.
上述表明存在对于多孔氟聚合物膜或载体的表面改性以提供稳定的亲水氟聚合物多孔膜的未满足的需求,其中该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膜的机械强度.
发明概述
本发明提供一种复合亲水多孔膜,包含多孔氟聚合物载体和涂层,该涂层包含式(I)或(II)的共聚物:
其中式(I)或(II)的共聚物为无规或嵌段共聚物,Rf为全氟取代基团,而Rh为亲水基团或氯,Ra为甲基或乙基,m和n独立地为10-1000,X为烷基,和Y为反应性官能团,其中该涂层共聚物是任选交联的.
本发明的亲水膜具有33达因/cm或更大的临界润湿表面张力(CWST)。该表面改性对随后的用于溶解该涂层材料的常规有机溶剂清洗是稳定的.
本发明进一步提供制备该共聚物的方法和制备亲水改性氟聚合物多孔膜的方法.本发明进一步提供通过这些亲水改性氟聚合物多孔膜来过滤流体的方法。
发明详述
根据一个实施方式,本发明提供一种复合亲水多孔膜,包含多孔氟聚合物载体和含有式(I)或(II)的共聚物的涂层:
其中式(I)或(II)的共聚物为无规或嵌段共聚物,Rf为全氟取代基团,而Rh为亲水基团或氯,Ra为甲基或乙基,m和n独立地为10-1000,X为烷基,和Y为反应性官能团,其中该涂层共聚物是任选交联的.
在实施方式中,n和m表示各个单体的聚合度,并且独立地为约10-约1000,优选约50-约400。
各个单体嵌段可以以任何合适的质量%存在于共聚物中,例如,在一个实施方式中,约99%∶约1%至约50%∶约50%,优选约90%∶约10%至约70%∶约30%,更优选约75%∶约25%.
共聚物可以为任何合适的分子量,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,优选约20kDa至约200kDa,更优选约40kDa至约100kDa.
在一个实施方式中,Y选自氨基、羟基、丙烯酰基、和甲基丙烯酰基.
在任何实施方式中,Rf为全氟取代烷基或链,其中烷基链可以任选在链中包含一个或多个氧原子.例如,Rf为CpF2p+1-(CH2)q(OCH2)r,其中p为1-12,q为0-3,和r为0-2.Rf的特别实例对于式I包括C8F17CH2,C6F13(CH2)2OCH2,C4F9CH2和CF3且对于式II包括CpF2p+1-CH2CH2.
在式(I)的共聚物的一个实施方式中,Rf选自C8F17CH2和C6F13(CH2)2OCH2.
在式(II)的共聚物的一个实施方式中,Rf为C8F17CH2CH2.
在任何实施方式中,Rh选自羟基、烷氧基、氯、烯丙氧基、烷基硫基或烷基硫基丙氧基,其中烷氧基,烷基硫基和烷基硫基丙氧基的烷基部分可以任选被羟基、羧酸、磺酸、膦酸、季铵、烷基砜和/或杂环取代。
在式(II)的共聚物的一个实施方式中,Ra为甲基.
在任何实施方式中,X为甲基.
在任何实施方式中,Y为叔氨基或季铵基,例如,哌啶基,吡啶鎓,二甲基氨基,或二乙基氨基.
式(I)的无规共聚物可以通过涉及取代的环氧化物混合物的阳离子开环聚合方法制备.例如,带有合适取代基的环氧化物单体混合物可以通过使用三烷基铝和具有卤素阴离子和作为抗衡离子的有机阳离子的引发剂盐来聚合.在具有有机阳离子的盐中,作为抗衡阳离子的有机阳离子优选为铵离子或鏻离子,例如双(三芳基亚正膦基)铵离子(bis(triarylphosphoranylidene)ammonium ion),双(三烷基亚正膦基)铵离子(bis(trialkylphosphoranylidene)ammonium ion),和三芳基烷基鏻离子,例如在US2009/0030175A1中所描述的.三芳基烷基鏻离子的实例为[MePPh3]+,其中Me为甲基.因此,单体的混合物,全氟烷基环氧单体和叔丁基缩水甘油醚(TBGE),可以如下面描述地聚合,并且得到的共聚物进一步与酸反应,例如三氟乙酸,以除去侧链的叔丁基基团.
式(I)的嵌段共聚物可以通过涉及含有Rf取代基的环氧化物单体的顺序聚合,接着与另一具有合适取代基例如烷基的环氧单体的开环聚合的方法来制备.因此,例如,在第一步中,制备第一单体的均聚物,用Rf基团取代的环氧化物,并且可以添加具有取代环氧化物的第二单体例如TBGE,并且继续聚合以得到嵌段共聚物.
式(II)的无规共聚物可以通过涉及两种2-取代2-噁唑啉单体混合物的阳离子开环聚合方法制备:一种单体在2-位具有Rf取代基和另一种单体在2-位具有Ra取代基.
式(II)的嵌段共聚物可以通过涉及含有Ra取代基的噁唑啉单体(例如2-甲基-2-噁唑啉)的顺序阳离子开环聚合,接着具有Rf取代基的另一种噁唑啉单体(例如PF8Et-噁唑啉(其中PF8Et为C8F17CH2CH2))的阳离子开环聚合来制备,如下所描述:
供选择地,式(II)的嵌段共聚物可以通过涉及在2-位具有Rf取代基的2-噁唑啉单体的顺序阳离子开环聚合,接着在2-位具有Ra取代基的另一种2-噁唑啉单体的阳离子开环聚合来制备.
该具有Rf取代基的2-噁唑啉单体可以通过3-全氟烷基-丙酸和乙醇胺,或3-全氟烷基-丙腈与乙醇胺的反应制备,如下面所描述:
单体的聚合在合适的溶剂中进行,例如通常用于进行阳离子开环聚合的溶剂.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,正戊烷,己烷和庚烷;脂环烃,例如环己烷;和卤化烃,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,及它们的混合物.
单体浓度可以为1-50wt%,优选2-45wt%,并且更优选3-40wt%.
聚合可以在任何合适的温度下实施,例如,-20至+100℃,优选20至100℃.
为了制备嵌段共聚物,例如,聚合可以实施任何合适的时间以得到合适的每个链段的链长度,其可以为约1分钟至100小时.
聚合物可以通过合适的技术进行分离,例如,用非溶剂沉淀或用合适的淬灭反应混合物浓缩.
共聚物可以通过任何已知的技术表征其分子量和分子量分布.例如,可以应用MALS-GPC技术.该技术通过高压泵使用移动相来洗脱聚合物溶液穿过装载固定相的空白柱.固定相根据链尺寸分离聚合物样品,随后通过三个不同的探测器检测该聚合物.可以应用一系列探测器,例如紫外光探测器(UV-探测器),随后多角度激光散射探测器(MALS-探测器),接着连续的示差折光检测器(RI-探测器).该UV-探测器测量聚合物在254nm波长的光吸收;该MALS-探测器测量聚合物链相对于移动相的散射光.
在一个实施方式中,该共聚物可以进一步以本领域技术人员已知的典型工艺通过侧链烯丙基部分和亲水性硫醇(例如硫代甘油,巯基乙酸)的硫醇-烯反应来改性。
在一个实施方式中,该共聚物可以进一步通过根据本领域技术人员已知的典型工艺的侧链氯甲基部分和亲水性硫醇(例如硫代甘油,巯基乙酸)的亲核取代反应来改性,例如European Polymer Journal vol.43(2007)4516中所描述的.
该共聚物可被进一步改性以使该共聚物在Y处包括可交联反应性官能团.例如,一个或多个羟基可以用丙烯酰基或甲基丙烯酰氯转化为酯基,以提供丙烯酸化的或甲基丙烯酸化的共聚物.或者,一个或多个羟基可以用氨基酸偶联以提供氨基酯官能度.
本发明进一步提供复合亲水多孔膜,包含多孔性氟聚合物和如上面描述的共聚物或聚合物,其中该共聚物是任选交联的.
本发明进一步提供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)在该多孔氟聚合物载体上涂覆包含溶剂和式I或II的共聚物的溶液:
其中式(I)或(II)的共聚物为无规或嵌段共聚物,Rf为全氟取代基团,而Rh为亲水基团或氯,Ra为甲基或乙基,m和n独立地为10-1000,X为烷基,和Y为反应性官能团;
(iii)干燥来自(ii)的涂覆载体以从包含溶剂和共聚物的涂层中除去至少一些溶剂;和任选地
(iv)交联存在于涂层中的共聚物.
当Y具有丙烯酸酯/盐或甲基丙烯酸酯/盐官能度时,交联可以通过例如使用光引发剂和高能辐射例如UV来实施.预期该交联将在膜中提供高度稳定的聚合物网络.
可以使用任何合适的光引发剂,例如类型I和类型II的光引发剂.光引发剂的实例包括樟脑醌、苯甲酮、苯甲酮衍生物、苯乙酮、苯乙酮衍生物、氧化膦及其衍生物、安息香烷基醚(benzoin alkyl ether)、苯偶酰缩酮(benzil ketal)、苯基乙醛酯及其衍生物、二聚苯基乙醛酯、过酸酯、卤代甲基三嗪、六芳基双咪唑/共引发剂体系,二茂铁(ferrocenium)化合物,二茂钛,和它们的组合.
可以改性该表面,例如,如下所示:PTFE多孔载体片在室温下通过用IPA溶剂预润湿膜片和将膜浸渍在涂层聚合物溶液(浓度为0.1质量%-10质量%)中来涂覆.涂覆时间为1分钟至12小时.在浸渍该载体后,在对流烤箱中在100℃-160℃下干燥.干燥时间为10分钟至12小时.
通过测量CWST来确定表面改性中表面张力的变化.该方法依靠某种组合物的一系列溶液.每种溶液具有特定的表面张力.该溶液的表面张力以小的非等价增量从25至92达因/cm.为了测量膜表面张力,将膜放置在白光桌(white light table)顶部上,一滴某一表面张力的溶液施加至膜表面,记录该液滴渗透穿过膜并且变成亮白色(即光穿过薄膜的象征)的时间.当该液滴渗透膜的时间≤10秒时认为是立即润湿.如果时间>10秒,认为该溶液是部分润湿膜.
根据本发明的一个实施方式,亲水氟聚合物膜是多孔膜,例如纳米多孔膜,例如,具有直径在1nm至100nm之间的孔的膜,或具有直径在1μm至10μm之间的孔的微米多孔膜.
根据本发明的实施方式的亲水氟聚合物多孔膜可以用于多种应用,包括例如诊断应用(包括,例如样品制备和/或诊断侧流设备)、喷墨应用、平板印刷术,例如作为HD/UHMWPE基介质的替代、过滤流体用于制药工业、金属去除、超纯水的生产、工业和表面水的处理、过滤流体用于医学应用(包括家庭和/或病人用途,例如静脉内的应用,也包括例如过滤生物流体例如血液(例如除去病毒))、过滤流体用于电子工业(例如,微电子工业和热SPM中过滤光致刻蚀剂流体)、过滤流体用于食品和饮料工业、啤酒过滤、净化、过滤包含抗体和/或蛋白质的流体、过滤包含核酸的流体、细胞检测(包括原位)、细胞收集、和/或过滤细胞培养液.供选择地,或此外,根据本发明实施方式的多孔膜可以用于过滤空气和/或气体,和/或可以用于排放应用(例如使空气和/或气体,不是液体,穿过其中).根据本发明实施方式的多孔膜可以用于多种设备,包括外科设备和产品,例如眼科手术设备.
根据本发明的实施方式,亲水氟聚合物多孔膜可以具有各种结构,包括平面、平板、褶皱、管状、螺旋和中空纤维.
根据本发明实施方式的亲水氟聚合物多孔膜通常放置在外罩中,该外罩包括至少一个入口和至少一个出口和限定入口和出口之间的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跨过流体流动路径以提供过滤器设备或过滤器模块.在一个实施方式中,提供过滤器设备,其包括外罩(该外罩包括入口和第一出口和限定入口和第一出口之间的第一流体流动路径)和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(本发明的膜或包括至少一个本发明的膜的过滤器设置于外罩中跨过第一流体流动路径).
优选地,为了错流应用,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设置在外罩中,该外罩包括至少一个入口和至少两个出口,和限定入口和第一出口之间的至少第一流体流动路径,和入口和第二出口之间的第二流体流动路径,其中本发明的膜或包括至少一个本发明的膜的过滤器跨过第一流体流动路径以提供过滤器设备或过滤器模块.在示意的实施方式中,过滤器设备包括错流过滤器模块,外罩,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和限定入口和第一出口之间的第一流体流动路径,和入口和第二出口之间的第二流体流动路径,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设置跨过第一流体流动路径。
过滤器设备或模块可以是可灭菌的.可以使用任何合适形状和提供入口和一个或多个出口的外罩.
外罩可以用任何合适的刚性的防渗材料制造,包括任何防渗热塑性材料,其与要处理的流体相容.例如,外罩可以用金属,例如不锈钢,或聚合物,例如透明或半透明聚合物,例如丙烯酸,聚丙烯,聚苯乙烯或聚碳酸酯树脂来制备。
根据一个实施方式,亲水氟聚合物多孔膜包括任何合适的多孔氟聚合物载体,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(聚乙烯氯三氟乙烯)、PFPE(全氟聚醚)、PFSA(全氟磺酸)、和全氟聚氧杂环丁烷.多孔载体可以具有任何合适的孔尺寸,例如约2nm至约10微米,优选PTFE和PVDF.
本发明进一步提供由上述方法制备的亲水改性氟聚合物多孔膜.
本发明进一步提供过滤流体的方法,该方法包括使该流体穿过上述亲水氟聚合物多孔膜.
以下实施例进一步描述了本发明,但是当然,不应视为以任何方式限制本发明范围.
实施例1
该实施例描述了根据本发明一个实施方式的式I的共聚物的合成.
氩气净化的40mL具有隔膜的小瓶进料甲基三苯基溴化鏻(37mg;0.1mmol),脱气的六氟苯(12mL),随后进料1,2-环氧-1H,1H,2H,3H,3H-十七氟十一烷(2.83mL;10mmol)和叔丁基缩水甘油醚(6.0mL;40mmol).反应混合物在冰浴中冷却同时剧烈搅拌,随后逐滴添加0.5M的三异丁基铝在己烷中的溶液(2mL;1mmol).搅拌持续24小时同时使该混合物缓慢升温至环境温度.随后通过添加甲醇/水混合物(4∶1,5mL)搅拌30分钟猝灭反应,随后在真空中浓缩.该浓缩物用全氟丁基甲基醚(50mL)稀释,并且通过Celite板过滤.滤液在真空中浓缩以得到3.76g粘性残余物(进料单体的38%).NMR分析(在CDCl3中)显示在得到的聚合物中全氟取代单元的摩尔分率为20%,其通过比较叔丁基信号对C8F17CH2亚甲基质子的信号的积分来计算.
实施例2
该实施例描述了根据本发明一个实施方式的式I的另一共聚物的合成.
如实施例1中描述获得的共聚物(3.7g)溶解在三氟乙酸/水混合物中(95∶5,20mL),并且该溶液在环境温度下搅拌16小时.将反应混合物添加至150mL二乙醚,随后添加150mL己烷.形成的树脂状的沉淀通过倾析分离,用己烷洗涤并且在甲醇中再溶解.通过添加至剧烈搅拌的10体积的二乙醚/己烷1∶1混合物来重复沉淀.树脂状产物通过倾析分离,用己烷清洗并且在真空中干燥,得到0.43g共聚物.通过叔丁基信号完全消失,NMR分析(在DMSO-d6中)确认完全脱保护。元素分析的结果(%C=40.48和%F=22.73)估算共聚物中全氟取代单元的摩尔比率为34%.
实施例3
该实施例描述了根据本发明一个实施方式的式I的又另一共聚物的合成.
氩气净化的40mL具有隔膜的小瓶进料甲基三苯基溴化鏻(37mg;0.1mmol),脱气的无水甲苯(12mL),随后进料1,2-环氧-1H,1H,2H,3H,3H-十七氟十一烷(2.83mL;10mmol)和叔丁基缩水甘油醚(3.0mL;20mmol).然后剧烈搅拌反应混合物,同时添加1.1M的三异丁基铝在甲苯中的溶液(0.9mL;1mmol).观察到轻微的放热反应同时该混合物变浑浊和粘稠.搅拌持续24小时,之后通过添加甲醇/水混合物(4∶1,5mL)来猝灭,然后搅拌30分钟,随后在真空中浓缩.然后该浓缩物用100mL的AK-225溶剂稀释,随后过滤通过Celite板.滤液在真空中浓缩且粘性残余物分散在150mL的甲醇中,随后用全氟己烷液-液萃取(用40mL,3次).全氟己烷层浓缩至干燥得到级分A,同时甲醇层浓缩得到级分B,其通过比较叔丁基信号对C8F17CH2亚甲基质子信号的积分面积来进行NMR分析(在CDCl3中).
级分A-1.20g(进料单体的16%)包含50摩尔%的全氟取代单元.
级分B-5.95g(进料单体的81%)包含36摩尔%的全氟取代单元.
实施例4
该实施例描述了根据本发明一个实施方式的式I的又另一共聚物的合成.
如实施例3中所述获得的级分A(1.19g)溶解在三氟乙酸/水混合物中(95∶5,20mL),并且该溶液在环境温度下搅拌16小时.反应混合物在真空中浓缩,得到的残余物再溶解在最小量的二乙醚中,随后添加10体积的己烷同时剧烈搅拌.形成的树脂状沉淀通过倾析分离,用己烷洗涤并且在真空炉中在50℃下干燥过夜,得到1.01g的最终共聚物.NMR分析(在TFE-d3中)确认侧链叔丁基基团全部移除.元素分析的结果(%C=29.78和%F=55.78)估算共聚物中全氟取代单元的摩尔比率为85%.
实施例5
该实施例描述了根据本发明一个实施方式的式I的又另一共聚物的合成.
如实施例3中所述获得的级分B(5.90g)溶解在三氟乙酸/水混合物中(95∶5,80mL),并且该溶液在环境温度下搅拌16小时.反应混合物在真空中浓缩,残余物再溶解在最小量的二乙醚中,随后添加10体积的己烷同时剧烈搅拌.形成的树脂状沉淀通过倾析分离,用己烷洗涤并且在真空炉中在50℃下干燥过夜,得到5.10g的最终共聚物.NMR分析(在TFE-d3中)确认侧链叔丁基基团的全部移除.元素分析的结果(%C=31.20和%F=49.33)估算共聚物中全氟取代单元的摩尔比率为76%.
实施例6
该实施例描述了根据本发明一个实施方式的式I的又另一共聚物的合成。
氩气净化的40mL具有隔膜的小瓶进料甲基三苯基溴化鏻(37mg;0.1mmol),脱气的无水甲苯(12mL),随后进料3-[2-(全氟己基)乙氧基]-1,2-环氧丙烷(2.80mL;10mmol)和烯丙基缩水甘油醚(2.4mL;20mmol).剧烈搅拌反应混合物,同时添加1.1M的三异丁基铝在甲苯中的溶液(0.9mL;1mmol).搅拌持续24小时,随后通过添加甲醇/水混合物(4∶1,5mL)来猝灭,然后搅拌30分钟,随后在真空中浓缩.得到的浓缩物用100mL的AK-225溶剂稀释,随后过滤通过Celite板.滤液在真空中浓缩和得到的残余物真空干燥以得到5.25g共聚物(单体进料的80%).NMR分析(在CDCl3中)估算全氟取代单元的摩尔比率为40%,通过比较烯丙基亚甲基信号对邻近C6F13部分的亚甲基的信号的积分来计算.
实施例7
该实施例描述了根据本发明一个实施方式的式I的又另一共聚物的合成.
氩气净化的40mL具有隔膜的小瓶进料甲基三苯基溴化鏻(37mg;0.1mmol),脱气的无水甲苯(12mL),随后进料3-[2-(全氟己基)乙氧基]-1,2-环氧丙烷(2.80mL;10mmol)和环氧氯丙烷(1.6mL;20mmol)。剧烈搅拌反应混合物,同时添加1.1M的三异丁基铝在甲苯中的溶液(0.9mL;1mmol).搅拌持续24小时,随后通过添加甲醇/水混合物(4∶1,5mL)来猝灭,然后搅拌30分钟,随后在真空中浓缩.浓缩物用100mL的AK-225溶剂稀释,随后过滤通过Celite板.滤液在真空中浓缩和得到的残余物真空干燥以得到5.58g共聚物(单体进料的92%).NMR分析(在CDCl3中)估算全氟取代单元的摩尔比率为35%,通过比较邻近C6F13部分的亚甲基的信号的积分(2.30-2.50ppm)和保留的质子的积分(3.45-3.80ppm)来计算.
实施例8
该实施例描述了根据本发明一个实施方式的式II的共聚物的中间体的合成.
如Journal of Oleophobic Science vol.59(2010)483中描述的,通过1H,1H,2H,2H-七氟癸基碘化物来合成3-(全氟辛基)-丙腈,并且与稍微过量的乙醇胺在脱水乙酸镉催化剂类似物的存在下反应,如Journal of Polymer Science:Part A Polymer Chemistryvol.32(1994)2187中所述.以71%的产率得到单体并且其结构同时通过1H和19F NMR分析(在CDCl3中)确认,和通过元素分析(计算:%C 30.19;%H 1.56;%N 2.71;%F 62.45;发现%C 30.26;%H 1.57;%N 2.76;%F 60.94)确认其高纯度.
实施例9
该实施例描述了根据本发明一个实施方式的式II的另一共聚物的合成.
氩气净化的40mL具有隔膜的小瓶进料在脱气的1,1,2-三氯乙烷(4mL)中稀释的甲基三氟甲烷磺酸酯(9μL;0.08mmol),随后用注射器添加2-甲基-2-噁唑啉(2.0mL;24mL),剧烈搅拌.小瓶中的内容物在100℃下加热6小时,随后溶解在1,1,2-三氯乙烷(10mL)中的实施例8中描述的全氟取代的噁唑啉单体的溶液(2.07g;4mmol)通过隔膜用注射器逐滴添加.该在100℃下的加热持续16小时,随后通过添加哌啶(0.1mL)终止反应,并且使该反应混合物冷却至环境温度同时特续搅拌过夜.一旦小瓶的内容物逐滴添加至剧烈搅拌的二乙醚(300mL),产生沉淀.该产品通过过滤来收集,用大量的二乙醚清洗,随后在环境温度下真空干燥,得到3.21g(进料单体的78%).1H和19F NMR光谱都确认了期望的结构.用DMF(具有0.05N LiBr)作为移动相实施GPC分析,显示26kDa的Mw(相对于标准PMMA)和1.58的多分散性指数.通过元素分析(%N=12.99;%F=3.18)来估算全氟取代单元的摩尔比率为大约6%.
实施例10
该实施例描述了根据本发明实施方式的共聚物的表面改性性能.
氟聚合物基材,PTFE或PVDF,通过在环境温度下浸泡在该共聚物的溶液(溶剂和浓度显示在下表中)中1小时来浸涂.然后通过短暂的空气干燥(直到样品不再透明),在用于溶解该共聚物的溶剂中大量清洗,然后空气干燥并且通过测量CWST值来测试涂覆膜的润湿性,与未处理的PTFE空白样品(CWST=25达因/cm)或未处理的PVDF空白样品(CWST=44达因/cm)比较。
在此引用的所有引用项目,包括出版物、专利申请以及专利,在此通过引用结合到本申请中,如同指示每个引用项目单独且特定地通过引用并入并且以其全部内容显示.
除非本文说明或者在语境中明确否定,在描述本发明的内容中使用术语“一个”和“一种”和“该”和“至少一个/种”以及类似的指示词(特别是在下文的权利要求书中)被理解为覆盖了单数和复数.除非本文另有指示或在语境中明确否定,使用术语“至少一个/种”和随后一个或多个选项(例如,“A和B的至少一个/种”)应被解释为指的是选自所列选项(A或B)的一个或所列选项中的两个或更多个的任意组合(A和B).除非另有指示,术语“包含”,“具有”,“包括”和“含有”应被解释为开放式选项(即,指的是“包括,但不限于”).除非本文另有指示,本文的值的范围仅仅作为所涉及的落入该范围的每个单个的值的速记方法,并且每一个单个值均引入本申请,就如其在本文中均单独引用.除非本文另有指示或在语境中明确否定,本文描述的方法可以以任何合适的顺序实施.本文使用的任何一个和所有实施例,或示例性语言(例如,“例如”)均仅仅是更好的描述本发明,除非另有声明,其并不是对本发明保护范围的限制.在说明书中的任何语言均不应解释为表示作为本发明的实现所必须的任何非声明要素.
本发明的优选的实施方式在本文中描述,包括对发明人来说实施本发明最佳的模式.这些优选的实施方式的各种变化根据阅读前述说明书后,对本领域技术人员来说可变得显而易见.发明人期望技术人员视情况应用这种变化,并且发明人打算以与本文描述的方法不同的方法来实施本发明.因此,本发明包括后附的为了适用法律所准许的权利要求中引用的主题的所有变形和等价物.进而,除非本文另有指示或在语境中明确否定,上述要素的所有可能变化的任何结合都被本发明所包含。
Claims (18)
1.一种复合亲水多孔膜,包括多孔氟聚合物载体和涂层,所述涂层包含式(I)或(II)的共聚物:
其中式(I)或(II)的共聚物独立地为无规或嵌段共聚物,
Rf为全氟取代烷基,其中烷基链可以任选地在链中含有一个或多个氧原子,
或者,Rf为CpF2p+1-(CH2)q(OCH2)r,其中p为1-12,q为0-3,和r为0-2,其中Rh为亲水基团或氯,Ra为甲基或乙基,m和n独立地为10-1000,X为烷基基团,和Y为反应性官能团,其中所述涂层是任选交联的。
2.根据权利要求1的复合亲水多孔膜,其中Y选自氨基、羟基、丙烯酰基、和甲基丙烯酰基。
3.根据权利要求1的复合亲水多孔膜,其中Rf对于式I独立地选自C8F17CH2,C6F13(CH2)2OCH2,C4F9CH2,和CF3且对于式II独立地选自CpF2p+1-CH2CH2。
4.根据权利要求1的复合亲水多孔膜,其中所述共聚物为式(I),并且Rf选自C8F17CH2和C6F13(CH2)2OCH2。
5.根据权利要求1的复合亲水多孔膜,其中所述共聚物为式(II),并且Rf为C8F17CH2CH2。
6.根据权利要求1或2的复合亲水多孔膜,其中Rh选自羟基、烷氧基、氯、烯丙氧基、烷基硫基或烷基硫基丙氧基,其中烷基可以被羟基、羧酸、磺酸、膦酸、季铵、烷基砜和杂环取代。
7.根据权利要求6的复合亲水多孔膜,其中Rh为羟基。
8.根据权利要求1或2的复合亲水多孔膜,其中Ra是甲基。
9.根据权利要求8的复合亲水多孔膜,其中X为甲基。
10.根据权利要求1或2的复合亲水多孔膜,其中Y为叔氨基或季铵基。
11.根据权利要求10的复合亲水多孔膜,其中所述叔氨基或季铵基选自哌啶基,吡啶鎓,二甲基氨基,和二乙基氨基。
12.根据权利要求1或2的复合亲水多孔膜,其中所述多孔氟聚合物载体选自PTFE、PVDF、聚氟乙烯、聚氯三氟乙烯、氟代乙烯-丙烯、聚乙烯四氟乙烯、聚乙烯氯三氟乙烯、全氟聚醚、全氟磺酸,和全氟聚氧杂环丁烷。
13.一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)用包含溶剂和式(I)或(II)的共聚物的溶液涂覆多孔氟聚合物载体:
其中式(I)或(II)的共聚物独立地为无规或嵌段共聚物,Rf为全氟取代烷基,其中烷基链可以任选地在链中含有一个或多个氧原子,
或者,Rf为CpF2p+1-(CH2)q(OCH2)r,其中p为1-12,q为0-3,和r为0-2,其中Rh为亲水基团或氯,Ra为甲基或乙基,m和n独立地为10-1000,X为烷基基团,和Y为反应性官能团;
(iii)干燥来自(ii)的涂覆载体以从包含溶剂和共聚物的涂层中除去至少一些溶剂;和任选地
(iv)交联存在于涂层中的共聚物。
14.根据权利要求13的方法,其中所述多孔氟聚合物载体选自PTFE、PVDF、聚氟乙烯、聚氯三氟乙烯、氟代乙烯-丙烯、聚乙烯四氟乙烯、聚乙烯氯三氟乙烯、全氟聚醚、全氟磺酸,和全氟聚氧杂环丁烷。
15.权利要求13的方法,其中Rf对于式I选自C8F17CH2,C6F13(CH2)2OCH2,C4F9CH2和CF3且对于式II选自CpF2p+1-CH2CH2。
16.通过权利要求13-15中任一项的方法生产的亲水改性多孔氟聚合物膜。
17.根据权利要求16的亲水改性多孔氟聚合物膜,其中所述多孔氟聚合物载体选自PTFE、PVDF、聚氟乙烯、聚氯三氟乙烯、氟代乙烯-丙烯、聚乙烯四氟乙烯、聚乙烯氯三氟乙烯、全氟聚醚、全氟磺酸,和全氟聚氧杂环丁烷。
18.一种过滤流体的方法,所述方法包括使所述流体穿过权利要求1-12中任一项的复合亲水多孔膜或权利要求16的亲水改性多孔氟聚合物膜。
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JP2017002273A (ja) | 2017-01-05 |
SG10201600623TA (en) | 2016-11-29 |
KR20160129703A (ko) | 2016-11-09 |
US20160317982A1 (en) | 2016-11-03 |
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