CN106422817B - 自润湿多孔膜 - Google Patents
自润湿多孔膜 Download PDFInfo
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- CN106422817B CN106422817B CN201610490968.6A CN201610490968A CN106422817B CN 106422817 B CN106422817 B CN 106422817B CN 201610490968 A CN201610490968 A CN 201610490968A CN 106422817 B CN106422817 B CN 106422817B
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Abstract
本发明公开了自润湿多孔膜，其包含芳族疏水性聚合物如聚砜和润湿剂，所述润湿剂包含式A‑B或A‑B‑A的共聚物，其中A为包括式(I)CH2＝C(R1)(R2)的聚合的单体的亲水性片段，其中R1和R2如本文所述，和B为聚醚砜，其中，片段B和A通过氧原子连接。本发明还公开了制备自润湿膜的方法，包括流延含有芳族疏水性聚合物和润湿剂的溶液，然后使流延溶液经受相转化。所述自润湿多孔膜用于血液透析、微滤和超滤。
Description
背景技术
芳族疏水性聚合物如聚砜和聚醚砜处于以下原因的一个或多个而作为成膜聚合物是有吸引力的：高玻璃化转变温度、无定形玻璃态、热和氧化稳定性、优异的强度和柔韧性、耐极端pH，和即使在升高的温度下的低蠕变性。然而，这些聚合物本身是疏水性的，并且因此由这些聚合物制得的多孔膜不被水润湿。
已尝试通过多种方法改进由这样的聚合物制得的多孔膜的表面润湿性，所述方法包括涂覆和交联亲水性聚合物，通过电子束、γ辐射或紫外线或其它辐射接枝亲水性单体，表面氧化，表面引发自由基接枝，与亲水性添加剂，如聚乙烯吡咯烷酮(PVP)、PVP的共聚物、聚乙烯醇(PVA)、PVA的共聚物、聚氧化乙烯(PEO)、PEO与聚氧化丙烯的共聚物共混，和亲水单体的原位聚合。
上述所尝试的方法的一种或多种伴随有缺陷。例如，采用涉及共混亲水性添加剂的方法中，添加剂在水性环境中长时间使用时倾向于浸出多孔膜。涉及涂覆和交联亲水性聚合物的方法倾向于收缩或改变膜孔，从而限制了膜的有用性.
前述表明存在以下未满足的需求：由会产生水可润湿表面的芳族疏水性聚合物制备多孔膜和在延长的使用期中表面润湿性稳定。
发明简述
本发明提供了自润湿多孔膜，其包含芳族疏水性聚合物和润湿剂，所述润湿剂包含式A-B或A-B-A的共聚物，其中A为包括聚合的单体或单体混合物的亲水性片段，其中所述单体具有式(I)：
CH2＝C(R1)(R2) (I)，
其中R1为氢或烷基，和R2选自经取代的或未取代的杂环基、经取代的或未取代的杂芳基、甲酰基氨基、甲酰基氨基烷基、氨基羰基、烷基羰氧基、和氨基羰基烷基，其被两性离子基团取代，和B为聚醚砜，其中片段B和A通过氧原子连接.本发明还提供了制备这种自润湿多孔膜的方法。
本发明的自润湿多孔膜具有通过71达因/cm2的高临界润湿表面张力(CWST)证实的高的水可润湿性。润湿添加剂具有与芳族疏水性聚合物的高相容性，因此不会浸出或仅最低限度浸出。润湿添加剂本身也均匀地分布在所述多孔膜中。所述多孔膜具有高水渗透性，例如在330-620LMH范围内。该多孔膜还具有通过低污染性表明的低的非特异性蛋白结合(BSA)。
附图说明
图1描述了作为由WE3润湿剂(PVP-共-PVAc)制备的PES膜和由根据本发明实施方案的具有51mol％的PVP的实施例3的共聚物制备的自湿润膜的BSA流量的函数的通量。
图2描述了作为时间的函数的图1中所描述的膜的BSA通量。
发明详述
在一个实施方案中，本发明提供了自润湿多孔膜，其包含芳族疏水性聚合物和润湿剂，所述润湿剂包含式A-B或A-B-A的共聚物，其中A为包括聚合单体或单体混合物的亲水性片段，其中所述单体具有式(I)：
CH2＝C(R1)(R2) (I)，
其中R1为氢或烷基，和R2选自经取代的或未取代的杂环基、经取代的或未取代的杂芳基、甲酰基氨基、甲酰基氨基烷基、氨基羰基、烷基羰氧基、和氨基羰基烷基，其被两性离子基团取代，和B为聚醚砜，其中片段B和A通过氧原子连接。“A”还包括端基。
本文中所使用的术语“杂环基”是指单环杂环基团或双环杂环基团。所述单环杂环是三元、四元、五元、六元或七元环，其含有至少一个独立地选自O、N、N(H)和S的杂原子。所述三元或四元环包含零个或一个双键和杂原子选自O、N、N(H)及S。所述五元环包含零个或一个双键，和一个、二个或三个选自O、N、N(H)及S的杂原子。所述六元环包含零个、一个或两个双键和一个、二个或三个选自O、N、N(H)及S的杂原子。所述七元环包含零个、一个、二个或三个双键和一个、二个或三个选自O、N、N(H)及S的杂原子。所述单环杂环可以是未取代的或经取代的和通过任何可取代的碳原子或包含在所述单环杂环内的任何可取代的氮原子连接到母体分子部分。
杂环基的实例包括吡啶基、哌啶基、哌嗪基、吡嗪基、吡咯基、吡喃基、四氢吡喃基、四氢噻喃基、吡咯烷基、吡咯烷酮基、呋喃基、四氢呋喃基、噻吩基、四氢噻吩基、嘌呤基、嘧啶基、噻唑基、噻唑烷基、噻唑啉基、噁唑基、三唑基、四唑基、四嗪基、苯并噁唑基、吗啉基、硫代磷杂环戊烯基(thiophorpholinyl)、喹啉基和异喹啉基。
术语“杂芳基”是指具有五个至十个环原子的环状芳族基团，所述环原子的至少一个原子是O、S或N，且其余原子是碳。杂芳基的实例包括吡啶基、吡嗪基、嘧啶基、吡咯基、吡唑基、咪唑基、噻唑基、噁唑基、异噁唑基、噻二唑基、噁二唑基、噻吩基、呋喃基、喹啉基、和异喹啉基。
杂环基或杂芳基结构部分上的取代基可以是烷基、卤代、羟基、硝基、羧基、酮基、氧代、氨基、磺酸氧基、磺酰基、磺酰氧基、磷酰基(phospho)、膦酰基或它们的任意组合。例如，环CH2基团可以被C＝O基团替代。取代可以是在碳原子上或在杂原子如环氮上，例如，在环氮上的烷基提供季铵基团。
根据一个实施方案中，所述烷基优选为C1-C6烷基。烷基的实例包括甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、异戊基、正己基等。
两性离子基团包括带正电荷的基团和带负电荷的基团，其通过合适的间隔原子分开，所述间隔原子如碳、氧或硫，或结构部分如烷基结构部分。带正电荷的基团的实例包括铵基团和季铵基团。带负电荷的基团的实例包括羧酸根、磺酸根和膦酸根。
在一个实施方案中，R1为氢或甲基，和R2选自吡咯烷酮基、吡啶基、咪唑基、N-甲基咪唑基、甲酰基氨基、甲酰基氨基甲基、氨基羰基、甲基羰氧基、和氨基羰基丙基，其被两性离子基团取代.
在一个具体的实施方案中，A为包括聚合的单体或单体混合物的亲水性片段，所述单体或单体混合物选自1-乙烯基吡咯烷-2-酮、N-[3-(二甲氨基)丙基]甲基丙烯酰胺、乙酸乙烯酯、1-乙烯基咪唑、1-乙烯基-3-烷基咪唑鎓、1-乙烯基-2-吡啶、1-乙烯基-4-吡啶、丙烯酰胺、N-乙烯基甲酰胺和N-烯丙基甲酰胺和3-(甲基丙烯酰氨基丙基)二甲基(3-磺基丙基)铵内盐。
形成膜的芳族疏水性聚合物可以选自聚砜(PSU)、聚苯醚砜(PPES)、聚醚砜(PES)、聚碳酸酯(PC)、聚醚醚酮(PEEK)、二氮杂萘酮联苯聚芳醚砜酮(poly(phthalazinone ethersulfone ketone))(PPESK)、聚苯硫醚(PPS)、聚苯醚(PPE)、聚氧化亚苯基(PPO)和聚醚酰亚胺(PEI)，其具有以下结构：
芳族疏水性聚合物可以具有任何合适的分子量，例如，约25kDa至约250kDa，优选约50kDa至约100kDa的数均分子量。芳族疏水性聚合物中的“n”的值可以为约30至约300，优选约50至约250。
共聚物的芳族疏水性聚合物片段B为被一个或优选两个酚结构部分封端的聚醚砜。如本领域技术人员已知那样，这样的酚取代的结构部分可以通过在相对于双(4-氯苯基)砜(或其氟同系物)过量的双酚S存在下进行缩聚而引入。
每个上述芳族疏水性片段B内的重复单元的数量n可以为约10至约250，优选约20至约200，并且更优选约30至约100。
嵌段共聚物的数均分子量为约5,000至约50,000克/摩尔，优选约10,000至约40,000克/摩尔的范围。
根据一个实施方案，所述共聚物具有式(Ia)或(Ib)：
其中A’为亲水性单体的聚合物片段，T为端基，和Y为氯或氟。
共聚物的具体实例包括：
其中，m1或m2为约5至约80，且优选约20至约60，和n为约20至约200，并且优选约30至约100。
A-B型的二嵌段共聚物可以由具有一个末端羟基的聚合物片段B制备，和A-B-A型的三嵌段共聚物可以由具有两个末端羟基的聚合物片段B制备。
例如，所述1-乙烯基吡咯烷-2-酮单体可以聚合在预形成的聚合物片段B上。商购可得的聚合物片段B的实例是Solvay的双遥爪聚醚砜VW-10700RP，其具有末端羟基.1-乙烯基吡咯烷-2-酮如下所示聚合在聚合物上：
可以使用任何合适的自由基引发剂，例如，偶氮异丁腈(AIBN)、过氧化苯甲酰、过氧化乙酰、过氧化月桂酰、叔丁基过氧化物、过氧化异丙苯、过乙酸叔丁酯、和叔丁基氢过氧化物。
因此，该共聚物的末端基团(式(Ia)或(Ib)中的T)的性质可以根据所使用的引发剂而变化。本发明的式中存在的2-甲基丙腈端基源自与AIBN产生的自由基共聚的终止。其它端基的实例为苯甲酸酯、乙酸酯、月桂酸酯、叔丁氧基、异丙苯氧基等。
本发明还提供了制备自润湿多孔膜的方法，包括：(i)将溶液流延成期望形状，所述溶液包含溶剂、芳族疏水性聚合物和式A-B-A的共聚物，其中，A为包括聚合的单体或单体混合物的亲水性片段，其中所述单体具有式(I)：
CH2＝C(R1)(R2) (I)，
其中R1为氢或烷基，和R2选自经取代的或未取代的杂环基、经取代的或未取代的杂芳基、甲酰基氨基、甲酰基氨基烷基、氨基羰基、烷基羰氧基、和氨基羰基烷基，其被两性离子基团取代，和B为聚醚砜，其中片段B和A通过氧原子连接；
(ii)使流延溶液经受相转化，以形成自润湿多孔膜；和
(iii)任选地用水冲洗所述自润湿多孔膜。
本发明还提供了通过上述方法制备的自润湿多孔膜。
根据本发明的一个实施方案，所述自润湿多孔膜是以下多孔膜，例如纳米多孔膜，例如具有1nm和100nm之间的直径的孔的膜，或具有1μ和10μm之间的直径的孔的微孔膜。
形成膜的聚合物溶液通过将聚合物溶于溶剂或溶剂混合物中制备。许多聚合物适合用作本发明中的形成膜的聚合物，并且是本领域已知的。合适的聚合物可以包括聚合物，例如，聚砜(PSU)、聚醚砜(PES)、聚苯醚(PPE)、聚苯醚砜(PPES)、聚氧化亚苯基(PPO)、聚碳酸酯(PC)、二氮杂萘酮联苯聚芳醚砜酮(PPESK)、聚醚醚酮(PEEK)、聚醚酮酮(PEKK)、聚醚酰亚胺(PEI)和它们的共混物。
除了一种或多种聚合物，典型的聚合物溶液包含至少一种溶剂，并且可以进一步包含至少一种非溶剂。合适的溶剂包括例如，N，N-二甲基甲酰胺(DMF)；N，N-二甲基乙酰胺(DMAC)；N-甲基吡咯烷酮(NMP)；二甲基亚砜(DMSO)，甲基亚砜，以及它们的混合物。合适的非溶剂包括例如，水；各种聚乙二醇(PEG；例如PEG-200、PEG-300、PEG-400、PEG-1000)；各种聚丙二醇；各种醇，例如甲醇、乙醇、异丙醇(IPA)、戊醇、己醇、庚醇和辛醇。
典型地，本发明的共聚物A-B-A以从约3至约20重量％的范围，优选在约4至约15重量％的范围的量包括在膜流延溶液中。
膜流延溶液典型地包括约10至约30重量％的芳族疏水性聚合物，约0至约10重量％的添加剂如PEG，最多至约90重量％的量的极性溶剂或溶剂混合物如NMP、DMF和/或DMAc。也可包括非溶剂如水和/或醇。
在自润湿膜的形成中可以使用的典型骤冷浴包括但不限于，含有非溶剂如水、醇等，无论是其本身，还是与一种或多种极性溶剂组合的浴。
溶液的合适组分是本领域已知的。包括聚合物和示例性溶剂和非溶剂的示例性溶液包括公开于例如美国专利4,340,579；4,629,563；4,900,449；4,964,990，5,444,097；5,846,422；5,906,742；5,928,774；6,045,899；6,146,747和7,208,200中的那些。
将所述芳族疏水性聚合物，所述共聚物和所述溶剂和其它添加剂首先混合在一起，然后在约55至约75℃，优选约60至约65℃的温度加热，直至形成均匀的溶液。
可以在合适的基材如玻璃上通过使用刮刀流延具有合适厚度例如约0.005至约0.006英寸的厚度的膜而制备平片膜。将流延膜在骤冷浴中凝固，并在水中洗涤一段时间，所述时间足以浸出不直接结合到疏水基聚合物的任何材料。通过本领域技术人员已知的方法干燥所述膜。
除了制备平片膜，可以使用本领域中公知的方法将本发明的自润湿膜成型为褶皱膜、中空纤维膜、管状膜等。
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所述自润湿多孔膜。
根据本发明的实施方案的自润湿多孔膜可以用于多种应用中，包括例如，血液透析、微滤和超滤应用。此外，还发现它们可以用于诊断应用(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，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，自润湿多孔膜可以具有多种构造，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自润湿多孔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。
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。
原料和方法：起始原料是Solvay的双遥爪聚醚砜VW-10700RP，据描述，通过滴定测定，其具有密度为0.187毫当量的OH/每克树脂的末端酚结构部分。通过在DMAc中的GPC分析(使用PS标准)测定，该聚合物具有Mw＝21332。所有引用数据由制造商的分析证明提供。在具有0.05N LiBr的DMF中并以PMMA为标准进行内部(In-house)分析得到Mw＝31578和PDI＝1.62。
将乙烯基单体进行真空蒸馏或通过包含抑制剂去除剂的柱。
实施例
实施例1
本实施例阐释根据实施方案制备共聚物A-B-A的通用规程。
将VW-10700RP溶于无水NMP，然后添加乙烯基单体和作为自由基引发剂的AIBN。将产生的混合物用氩气在环境温度吹扫至少2-5min，然后在80℃加热16-24小时。在该时间之后，将反应混合物对空气开放，并添加过量剧烈搅拌的非溶剂，通常为至少10体积的2-丙醇。将产生的沉淀物滤出(或在某些情况下离心)，用2-丙醇充分冲洗，并在真空烘箱中于70℃干燥过夜。将获得的原料通过GPC(具有0.05N LiBr的DMF，并用PMMA的分子量标准校准)分析，并通过1H-NMR分析(在DMSO-d6)和元素分析测定该组合物。
实施例2
本实施例阐释根据本发明的实施方案制备PVP-b-PES-b-PVP的方法，其中(m1+m2)/n＝0.35：
将VW-10700RP(0.5g；0.093mmol的OH)，1-乙烯基吡咯烷-2-酮(1.0mL；9mmol)和AIBN(8mg；0.047mmol)溶于无水NMP(3mL)，并根据所述通用规程共聚，生成0.39g产物。
如通过比较在7.80-8.20ppm之间(PES单元，4H)和在1.20-2.40ppm之间(VP单元，6H)的信号的积分测定，1H NMR分析表明35摩尔％的VP单元。元素分析(％N＝2.46；％S＝10.71)表明34摩尔％的VP单元。GPC：Mw＝31370；PDI＝1.55.
实施例3
本实施例阐释根据本发明的实施方案制备PVP-b-PES-b-PVP的方法，其中(m1+m2)/n＝0.50。
将VW-10700RP(0.5g；0.093mmol的OH)，1-乙烯基吡咯烷-2-酮(2.0mL；18mmol)和AIBN(16mg；0.094mmol)溶于无水NMP(2mL)，并根据上述通用规程共聚，生成0.66g产物。
如通过比较在7.80-8.20ppm之间(PES单元，4H)和在1.20-2.40ppm之间(VP单元，6H)的信号的积分的测定，1H NMR分析表明50摩尔％的VP单元。元素分析(％N＝4.09；％S＝8.56)表明52摩尔％的VP单元。GPC：Mw＝32600；PDI＝1.58。
实施例4
本实施例阐释根据本发明的实施方案制备PVAc-b-PES-b-PVAc的方法，其中(m1+m2)/n＝0.16。
将VW-10700RP(0.5g；0.093mmol的OH)，乙酸乙烯酯(1.75mL；18.7mmol)和AIBN(15mg；0.092mmol)溶于无水NMP(3mL)，并且除将甲醇作为非溶剂用于沉淀以外，根据所述通用规程共聚并清洗产物(0.57g)。
如通过比较在7.80-8.20ppm之间(PES单元，4H)和在4.60-4.80ppm之间(VAc单元，1H)的信号的积分测定，1H NMR分析表明16摩尔％的VAc单元。GPC：Mw＝30225；PDI＝1.59。
实施例5
本实施例阐释根据本发明的实施方案制备P4VP-b-PES-b-P4VP的方法，其中(m1+m2)/n＝0.11。
将VW-10700RP(0.5g；0.093mmol的OH)，4-乙烯基吡啶(1.1mL；10.2mmol)和AIBN(15mg；0.092mmol)溶于无水NMP(3mL)，并且根据上述通用规程，使用甲醇作为非溶剂共聚，生成0.41g产物。
如通过比较在7.20-7.30ppm之间(PES单元，4H)和在6.50-6.70ppm之间(4-VP单元，2H)的信号的积分测定，1H NMR分析表明11摩尔％的4-VP单元。元素分析(％N＝1.11；％S＝12.90)表明16摩尔％的4-VP单元。GPC：MW＝32080；PDI＝1.60。
实施例6
本实施例阐释根据本发明的实施方案制备自润湿膜的方法。
将5g包含30重量％的PES E6020、65重量％的DMF和5重量％的NMP的聚合物溶液与12.5g的40重量％的悬浮在DMF中的160nm Li掺杂的HMDS处理的二氧化硅微粒(由Harton等另外描述)合并。向该混合物中连续添加PEG1000(0.23g)、PVP-K90(0.06g)和实施例3中描述的PVP-b-PES-b-PVP(0.12g)，随后在30,000rpm均质化5min和在200mbar脱气30min。使用压延流延棒将所产生的混合物流延到预成型的PVOH薄膜(由10％的储备溶液在玻璃板上在80℃下干燥2h制备)上，在烘箱中于60℃放置8min，然后立即在水浴中于80℃放置1h。最后，将所述膜在1N的HCl中浸泡30min，用水洗涤，和在10％的KOH水溶液中浸泡过夜。将产生的膜用水洗涤2h，然后于70℃干燥1h。
为了对比，使用包含WE3(Ashland’s PlasdoneTM S-630 copovidone) 代替本发明的共聚物的配方制备薄膜作为标准物。在润湿性、水流量、颗粒保留和BSA溶液流量和通量方面比较样品。结果示于表1中.
表1膜的性质
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 (6)
1.一种自润湿多孔膜，其包含芳族疏水性聚合物和润湿剂，所述润湿剂为式(Ia)或(Ib)的共聚物：
其中A’为选自4-乙烯基吡啶和乙酸乙烯酯的单体的亲水性聚合物；
T为选自2-甲基丙腈、苯甲酸酯、乙酸酯、叔丁氧基和异丙苯氧基的端基，
Y为氯或氟，
m1或m2的每一个为5至80，且n为20至200。
2.根据权利要求1所述的自润湿多孔膜，其中所述润湿剂为下式的共聚物：
其中，m1或m2的每一个为5至80，且n为20至200。
3.根据权利要求1或2所述的自润湿多孔膜，其中所述芳族疏水性聚合物选自聚砜、聚醚砜、聚苯醚、聚苯醚砜、聚氧化亚苯基、聚碳酸酯、二氮杂萘酮联苯聚芳醚砜酮、聚醚酮、聚醚醚酮、聚醚酮酮、聚酰亚胺、聚醚酰亚胺和聚酰胺酰亚胺。
4.根据权利要求3所述的自润湿多孔膜，其中所述芳族疏水性聚合物为聚砜或聚醚砜。
5.一种制备根据权利要求1或2所述的自润湿多孔膜的方法，包括：
(i)将溶液流延成期望形状，所述溶液包含溶剂、芳族疏水性聚合物和所述润湿剂；
(ii)使流延溶液经受相转化，以形成自润湿多孔膜；和
(iii)任选地用水冲洗所述自润湿多孔膜。
6.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或2所述的自润湿多孔膜。
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| CN108671774B (zh) * | 2018-06-05 | 2020-10-09 | 中国石油大学(华东) | 一种油水分离网膜及其制备方法与应用 |
| KR20220044209A (ko) * | 2019-08-06 | 2022-04-06 | 솔베이 스페셜티 폴리머즈 유에스에이, 엘.엘.씨. | 막 및 이의 제조를 위한 중합체 |
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| TWI648319B (zh) | 2019-01-21 |
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| AU2016202722A1 (en) | 2017-01-19 |
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