TWI613086B - 親水改質氟化薄膜（ｖｉ） - Google Patents
親水改質氟化薄膜（ｖｉ） Download PDFInfo
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- TWI613086B TWI613086B TW105102438A TW105102438A TWI613086B TW I613086 B TWI613086 B TW I613086B TW 105102438 A TW105102438 A TW 105102438A TW 105102438 A TW105102438 A TW 105102438A TW I613086 B TWI613086 B TW I613086B
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Abstract
本發明揭示適用於親水改質多孔氟聚合物載體表面之共聚物，例如式(I)或(II)共聚物：
Description
本發明關於複合親水性多孔膜，其包含多孔氟聚合物載體及包含共聚物之塗層，親水改質多孔氟聚合物載體之方法，親水改質多孔氟聚合物膜及經由該複合親水性多孔膜或該親水改質多孔氟聚合物膜過濾流體之方法。
氟聚合物膜，例如多孔PTFE膜之特性，包括其機械強度、耐化學性或化學惰性、非黏附性、極佳介電特性、高溫熱穩定性及低摩擦係數使其對各種應用極具吸引力。然而，對於某些應用，有益的是改質PTFE之表面而不影響其固有特性。已努力改質PTFE膜之表面及化學特性以改良該膜對於特定應用之適用性。舉例而言，努力包括表面塗佈、摻合、高能量表面改質(例如寬頻紫外輻射或BBUV(其中膜曝露於波長250-450nm之UV照射)及電漿處理)、自由基及臭氧蝕刻、原子層沉積及經改質之類PTFE聚合物之合成。然而，大多數努力集中於高能量處理，諸如BBUV或電漿。儘管並未報導此等表面改質途徑之精確機制，但因為已知C-C鍵結強度比F-F鍵低約40%，故其可能起因於藉由鍵斷裂形成自由基。若大多數自由基由C-C斷裂或主聚合物鏈斷裂產生，則其可降低PTFE膜之機械及化學穩定性。亦已知電漿處理限於膜之表面，使得此類改質在較長時間段期
間為較不穩定的。
上文展示並未滿足對表面改質多孔氟聚合物膜或載體以提供穩定之親水性氟聚合物多孔膜之需要，且其中表面改質並不會明顯影響多孔氟聚合物載體或所得複合多孔膜之機械強度。
本發明提供複合親水性多孔膜，其包含多孔氟聚合物載體及包含式(I)或(II)共聚物之塗層：
本發明之親水性膜具有33達因/公分或大於33達因/公分之臨界濕潤表面張力(CWST)。表面改質為對於利用用於溶解塗佈材料之常用有機溶劑之後續洗滌為穩定的。
本發明進一步提供製備共聚物之方法及製備經親水改質之氟聚合物多孔膜之方法。本發明進一步提供經由此等經親水改質之氟聚合
物多孔膜過濾流體之方法。
根據一具體實例，本發明提供複合親水性多孔膜，其包含多孔氟聚合物載體及包含式(I)或(II)共聚物之塗層：
在具體實例中，n及m表示各別單體之聚合度，且獨立地為約10至約1000，較佳為約50至約400。
各別單體嵌段可以任何適合之質量%存在於共聚物中，例如在一具體實例中，約99%：約1%至約50%：約50%，較佳約90%：約10%至約70%：約30%，且更佳約75%：約25%。
共聚物可具有任何適合之分子量，例如，在一具體實例中，
數量或重量(Mn或Mw)平均分子量為約10kDa至約1000kDa，較佳約20kDa至約200kDa，且更佳約40kDa至約100kDa。
在一具體實例中，Y選自胺基、羥基、丙烯醯基及甲基丙烯醯基。
在具體實例之任一者中，Rf為經全氟取代之烷基或鏈，其中烷基鏈可視情況在該鏈中含有一或多個氧原子。舉例而言，Rf為CpF2p+1-(CH2)q(OCH2)r，其中p為1至12，q為0至3，且r為0至2。Rf之特定實例包括針對式I之C8F17CH2、C6F13(CH2)2OCH2、C4F9CH2和CF3及針對式II之CpF2p+1-CH2CH2。
在式(I)共聚物之一具體實例中，Rf選自C8F17CH2及C6F13(CH2)2OCH2。
在式(II)共聚物之一具體實例中，Rf為C8F17CH2CH2。
在具體實例之任一者中，Rh選自羥基、烷氧基、氯、烯丙氧基、烷硫基或烷硫基丙氧基，其中烷氧基、烷硫基及烷硫基丙氧基之烷基部分可視情況經羥基、羧酸、磺酸、膦酸、四級銨、烷基碸及/或雜環取代。
在式(II)共聚物之一具體實例中，Ra為甲基。
在具體實例之任一者中，X為甲基。
在具體實例之任一者中，Y為三級胺基或四級銨基團，例如哌啶基、吡啶陽離子(pyridinium)、二甲胺基或二乙胺基。
式(I)之無規共聚物可藉由涉及經取代之環氧化物之混合物之陽離子開環聚合的方法製備。舉例而言，帶有適合的取代基之環氧單
體之混合物可藉由使用三烷基鋁及具有鹵素陰離子及有機陽離子作為相對離子之引發劑鹽來聚合。具有有機陽離子作為相對陽離子之鹽中之有機陽離子較佳為銨離子或鏻離子，諸如雙(三芳基亞正膦基)銨離子、雙(三烷基亞正膦基)銨離子及三芳基烷基鏻離子，如例如US2009/0030175 A1中所描述。三芳基烷基鏻離子之實例為[MePPh3]+，其中Me為甲基。因此，單體、全氟烷基環氧基單體及第三丁基縮水甘油醚(TBGE)之混合物可如以下所說明聚合，且使所得共聚物與諸如三氟乙酸之酸進一步反應以移除側接第三丁基。
式(I)之嵌段共聚物可藉由涉及具有Rf取代基之環氧單體之連續聚合，繼而具有適合的取代基(例如烷基)之另一環氧單體之開環聚合的方法製備。因此，舉例而言，在第一步驟中，可產生第一單體(經Rf基團取代之環氧化物)之均聚物，且可添加具有經取代之環氧化物(諸如TBGE)之第二單體，且持續聚合以獲得嵌段共聚物。
式(II)之無規共聚物可藉由涉及以下兩個經2取代之2-
唑啉單體之混合物之陽離子開環聚合的方法製備：一個單體在2-位置處具有Rf取代基且另一單體在2-位置處具有Ra取代基。
式(II)之嵌段共聚物可藉由涉及具有Ra取代基之
唑啉單體(諸如2-甲基-2-
唑啉)之連續陽離子開環聚合，繼而具有Rf取代基之另一
唑啉單體(例如PF8Et-
唑啉(其中PF8Et為C8F17CH2CH2))之陽
離子開環聚合的方法製備，如以下所說明：
替代地，式(II)之嵌段共聚物可藉由涉及在2-位置處具有Rf取代基之2-
唑啉單體之連續陽離子開環聚合，繼而在2-位置處具有Ra取代基之另一2-
唑啉單體之陽離子開環聚合的方法製備。
具有Rf取代基之2-
唑啉單體可藉由3-全氟烷基-丙酸及乙醇胺或3-全氟烷基-丙腈與乙醇胺之反應製備，如以下所說明：
於適合的溶劑，例如通常用於進行陽離子開環聚合之溶劑中進行單體之聚合。適合的溶劑之實例包括芳族烴，諸如苯、甲苯及二甲苯；脂族烴，諸如正戊烷、己烷及庚烷；脂環烴，諸如環己烷；及鹵化烴，諸如二氯甲烷、二氯乙烷、二氯乙烯、四氯乙烷、氯苯、二氯苯及三氯苯；以及其混合物。
單體濃度可在1至50wt%，較佳2至45wt%，且更佳3至40wt%範圍內。
聚合可在任何適合的溫度，例如-20℃至+100℃，較佳20℃
至100℃下進行。
為了製備嵌段共聚物，例如聚合可進行適合於獲得各嵌段之適當鏈長之任何時間，其可為約1分鐘至100小時。
聚合物可藉由適合的技術，例如利用非溶劑之沉澱或藉由適當淬滅之反應混合物之濃縮來分離。
可藉由任何已知技術使共聚物之分子量及分子量分佈特性化。舉例而言，可採用MALS-GPC技術。該技術經由高壓泵使用移動相通過一組充填固定相之管柱來溶離(elute)聚合物溶液。固定相根據鏈大小分離聚合物樣品，繼而藉由三個不同偵測器偵測聚合物。可採用一系列偵測器，例如紫外線偵測器(UV-偵測器)，繼而多角度雷射光散射偵測器(MALS-偵測器)，之後繼而成一列之折射率偵測器(RI-偵測器)。UV-偵測器量測254nm波長之聚合物光吸收；MALS-偵測器量測相對於移動相來自聚合物鏈之散射光。
在一具體實例中，可根據熟習此項技術者已知之典型的程序，藉由側接烯丙基部分與親水性硫醇(例如硫代甘油、巰基乙酸)之硫醇-烯反應來進一步改質共聚物。
在一具體實例中，根據熟習此項技術者已知之典型的程序，例如如European Polymer Journal第43卷(2007)4516中所描述，可藉由側接氯甲基部分與親水性硫醇(例如硫代甘油、巰基乙酸)之親核取代反應來進一步改質共聚物。
共聚物可進一步改質以使得共聚物在Y處包括可交聯反應性官能基。舉例而言，可用丙烯醯氯或甲基丙烯醯氯將一或多個羥基轉換
成酯基以提供丙烯酸化或甲基丙烯酸化共聚物。替代地，一或多個羥基可與胺基酸偶合以提供胺酯官能團。
本發明進一步提供一種複合親水性多孔膜，其包含多孔氟聚合物及如上文所描述之共聚物或聚合物，其中該共聚物視情況交聯。
本發明進一步提供一種親水改質多孔氟聚合物載體之方法，其包含：(i)提供多孔氟聚合物載體；(ii)用包含溶劑及式I或II共聚物之溶液塗佈該多孔氟聚合物載體：
其中式(I)或(II)共聚物為無規或嵌段共聚物，Rf為經全氟取代之基團，而Rh為親水性基團或氯，Ra為甲基或乙基，m及n獨立地為10至1000，X為烷基，且Y為反應性官能基；(iii)乾燥來自(ii)之經塗佈之載體以自包含溶劑及共聚物之塗層中移除至少一些溶劑；及視情況(iv)使塗層中所存在之共聚物交聯。
當Y具有丙烯酸酯或甲基丙烯酸酯官能團時，可例如藉由
使用光引發劑及高能量輻射，例如UV來進行交聯。交聯意欲在膜中提供高度穩定之聚合物網路。
可使用任何適合的光引發劑，例如I型及II型光引發劑。光引發劑之實例包括樟腦醌、二苯甲酮、二苯甲酮衍生物、苯乙酮、苯乙酮衍生物、膦氧化物及衍生物、安息香烷基醚二苯基乙二酮縮酮、苯乙醛酸酯及其衍生物、二聚苯乙醛酸酯、過酸酯、鹵甲基三
、六芳基雙咪唑/共引發劑系統、二茂鐵化合物、二茂鈦及其組合。
表面可例如經如下改質：在室溫下藉由用IPA溶劑預濕潤膜薄片及在濃度範圍在0.1質量%與10質量%之間的塗佈聚合物溶液中浸泡該膜來塗佈PTFE多孔載體之薄片。塗佈時間在(1分鐘至12小時)之間的範圍內。在浸泡載體之後，於對流烘箱中在100℃至160℃下將其乾燥。乾燥時間在(10分鐘至12小時)之間的範圍內。
藉由量測CWST來量測就表面張力而言之表面改質的變化。該方法依賴於一組某些組成物之溶液。各溶液具有特定表面張力。溶液之表面張力以小非等效增量(small non-equivalent increments)處於25至92達因/公分範圍內。為了量測膜表面張力，將膜安置於白光台頂部上，將一滴具有某一表面張力之溶液施加至膜表面上，且記錄液滴滲透通過膜且變為亮白色(作為光穿過膜之指示)所花費之時間。當液滴滲透膜所花費之時間
10秒時視為即刻潤濕。若時間>10秒，則溶液視為將膜部分潤濕。
根據本發明之一具體實例，親水性氟聚合物膜為多孔膜，例如奈米多孔膜，例如孔直徑在1nm與100nm之間的膜，或孔直徑在1μm與10μm之間的微孔膜。
根據本發明之具體實例之親水性氟聚合物多孔膜可用於多種應用中，包括例如診斷應用(包括例如樣品製備及/或診斷性側流裝置)、噴墨應用、微影術(例如替代基於HD/UHMW PE之介質)、過濾用於醫藥行業之流體、金屬移除、製造超純水、處理工業及表面水、過濾用於醫學應用之流體(包括用於家庭及/或患者使用，例如靜脈內應用，亦包括例如，過濾生物流體，諸如血液(例如病毒移除))、過濾用於電子行業之流體(例如過濾微電子行業中之光阻流體及熱SPM)、過濾用於食品及飲料行業之流體、啤酒過濾、澄清、過濾含抗體及/或蛋白質之流體、過濾含核酸之流體、細胞偵測(包括就地)、細胞捕獲及/或過濾細胞培養物流體。替代地，或另外，根據本發明之具體實例之多孔膜可用於過濾空氣及/或氣體，及/或可用於排氣應用(例如允許空氣及/或氣體但不允許液體穿過其間)。根據本發明之具體實例之多孔膜可用於多種裝置中，包括手術裝置及產品，諸如眼科手術產品。
根據本發明之具體實例，親水性氟聚合物多孔膜可具有多種構型，包括平面、平坦薄片、摺疊、管狀、螺旋形及空心纖維。
根據本發明之具體實例之親水性氟聚合物多孔膜典型地安置於包含至少一個入口及至少一個出口且界定入口與出口之間的至少一個流體流動路徑之殼體中，其中至少一個本發明膜或包括至少一個本發明膜之過濾器跨越流體流動路徑，以提供過濾裝置或過濾模組。在一具體實例中，提供包含以下之過濾裝置：包含入口及第一出口且界定入口與第一出口之間的第一流體流動路徑的殼體；及至少一個本發明膜或包含至少一個本發明膜之過濾器，本發明膜或包含至少一個本發明膜之過濾器跨越第一
流體流動路徑安置於殼體中。
較佳地，對於交叉流應用，至少一個本發明多孔膜或包含至少一個本發明膜之過濾器安置於包含至少一個入口及至少兩個出口且界定入口與第一出口之間的至少一個第一流體流動路徑及入口與第二出口之間的第二流體流動路徑之殼體中，其中本發明膜或包含至少一個本發明膜之過濾器跨越第一流體流動路徑以提供過濾裝置或過濾模組。在說明性具體實例中，過濾裝置包含交叉流過濾模組、殼體，該殼體包含入口、含濃縮物出口之第一出口及含滲透物出口之第二出口且界定入口與第一出口之間的第一流體流動路徑及入口與第二出口之間的第二流體流動路徑，其中至少一個本發明膜或包含至少一個本發明膜之過濾器跨越第一流體流動路徑安置。
過濾裝置或模組可滅菌。可採用具有適合的形狀且提供一個入口及一或多個出口之任何殼體。
殼體可由任何適合的剛性不透水材料製造，該材料包括任何不透水之熱塑性材料，其與處理中之流體相容。舉例而言，殼體可由金屬，諸如不鏽鋼或由聚合物，例如透明或半透明聚合物，諸如丙烯酸樹脂、聚丙烯樹脂、聚苯乙烯樹脂或聚碳酸酯樹脂製造。
根據一具體實例，親水性氟聚合物多孔膜包含任何適合的多孔氟聚合物載體，例如由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/氯三氟乙烯))、PFPE(全氟聚醚)、PFSA(全氟磺酸)及全氟聚氧代環丁烷製成之載體。多孔載體可具有任何適合的孔徑，例如約2
nm至約10微米，較佳為PTFE及PVDF。
本發明進一步提供一種藉由上文所描述之方法產生之經親水改質之氟聚合物多孔膜。
本發明進一步提供一種過濾流體之方法，該方法包含使該流體穿過上文所描述之親水性氟聚合物多孔膜。
以下實施例進一步說明本發明，但不應解釋為以任何方式限制其範疇。
此實施例說明根據本發明一具體實例之式I共聚物之合成。
向經氬氣淨化之具有隔片之40mL小瓶中裝入溴化甲基三苯基鏻(37mg；0.1mmol)、經脫氣之六氟苯(12mL)，繼而裝入1,2-環氧基-1H,1H,2H,3H,3H-十七氟十一烷(2.83mL；10mmol)及第三丁基縮水甘油醚(6.0mL；40mmol)。在劇烈攪拌的同時於冰浴中冷卻反應混合物，繼而逐滴添加三異丁基鋁於己烷中之0.5M溶液(2mL；1mmol)。持續攪拌24小時，同時使混合物緩慢升溫至環境溫度。之後，藉由添加甲醇/水混合物(4：1，5mL)淬滅反應，攪拌30分鐘，繼而真空濃縮。濃縮物用全氟丁基甲基醚(50mL)稀釋且經由矽藻土墊過濾。真空濃縮濾液，得到3.76g黏性殘餘物(所饋入單體之38%)。NMR分析(於CDCl3中)指示，在所得聚合物中，經全氟取代之單元之莫耳分數為20%，其係藉由比較第三丁基信號與C8F17CH2亞甲基質子信號之整合而計算得到。
此實施例說明根據本發明一具體實例之式I之另一共聚物
之合成。
使如實施例1中所描述獲得之共聚物(3.7g)溶解於三氟乙酸/水混合物(95：5，20mL)中，且在環境溫度下攪拌溶液16小時。將反應混合物添加至150mL二乙醚中，繼而添加150mL己烷。藉由傾析分離所形成之樹脂沉澱物，用己烷洗滌且再溶解於甲醇中。藉由添加至經劇烈攪拌之10體積二乙醚/己烷1：1混合物中來重複沉澱。藉由傾析分離樹脂產物，用己烷洗滌且真空乾燥，產生0.43g共聚物。NMR分析(於DMSO-d6中)藉由第三丁基信號完全消失來確證完全去保護。元素分析結果(%C=40.48及%F=22.73)估算共聚物中經全氟取代之單元之莫耳比為34%。
此實施例說明根據本發明一具體實例之式I之又一共聚物之合成。
向經氬氣淨化之具有隔片之40mL小瓶中裝入溴化甲基三苯基鏻(37mg；0.1mmol)、經脫氣之無水甲苯(12mL)，繼而裝入1,2-環氧基-1H,1H,2H,3H,3H-十七氟十一烷(2.83mL；10mmol)及第三丁基縮水甘油醚(3.0mL；20mmol)。隨後劇烈攪拌反應混合物，同時添加三異丁基鋁於甲苯中之1.1M溶液(0.9mL；1mmol)。觀測到略微放熱反應，同時混合物變得渾濁及黏性的。持續攪拌24小時，繼而藉由添加甲醇/水混合物(4：1，5mL)淬滅，隨後攪拌30分鐘，繼而真空濃縮。濃縮物隨後用100mLAK-225溶劑稀釋，繼而經由矽藻土墊過濾。真空濃縮濾液且使黏性殘餘物分散於150mL甲醇中，繼而用全氟己烷(3次40mL)進行液-液萃取。使全氟己烷層濃縮至乾燥得到溶離份A，同時濃縮甲醇層產生溶離份B，其藉
由NMR(於CDCl3中)，藉由比較第三丁基信號與C8F17CH2亞甲基質子信號之整合區域來分析。
溶離份A-1.20g(所饋入單體之16%)含有50莫耳%經全氟取代之單元。
溶離份B-5.95g(所饋入單體之81%)含有36莫耳%經全氟取代之單元。
此實施例說明根據本發明一具體實例之式I之又一共聚物之合成。
使如實施例3中所描述獲得之溶離份A(1.19g)溶解於三氟乙酸/水混合物(95：5，20mL)中，且在環境溫度下攪拌溶液16小時。真空濃縮反應混合物，使所得殘餘物再溶解於少量二乙醚中，繼而在攪拌劇烈的同時添加10體積己烷。藉由傾析分離所形成之樹脂沉澱物，用己烷洗滌且在真空烘箱中在50℃下乾燥隔夜，產生1.01g最終共聚物。NMR分析(於TFE-d3中)確證完全移除側接第三丁基。元素分析結果(%C=29.78及%F=55.78)估算共聚物中經全氟取代之單元之莫耳比為85%。
此實施例說明根據本發明一具體實例之式I之又一共聚物之合成。
使如實施例3中所描述獲得之溶離份B(5.90g)溶解於三氟乙酸/水混合物(95：5，80mL)中，且在環境溫度下攪拌溶液16小時。真空濃縮反應混合物，使殘餘物再溶解於少量二乙醚中，繼而在劇烈攪拌的
同時添加10體積己烷。藉由傾析分離所形成之樹脂沉澱物，用己烷洗滌且在真空烘箱中在50℃下乾燥隔夜，產生5.10g最終共聚物。NMR分析(於TFE-d3中)確證完全移除側接第三丁基。元素分析結果(%C=31.20及%F=49.33)估算共聚物中經全氟取代之單元之莫耳比為76%。
此實施例說明根據本發明一具體實例之式I之又一共聚物之合成。
向經氬氣淨化之具有隔片之40mL小瓶中裝入溴化甲基三苯基鏻(37mg；0.1mmol)、經脫氣之無水甲苯(12mL)，繼而裝入3-[2-(全氟己基)乙氧基]-1,2-環氧丙烷(2.80mL；10mmol)及烯丙基縮水甘油醚(2.4mL；20mmol)。劇烈攪拌反應混合物，同時添加三異丁基鋁於甲苯中之1.1M溶液(0.9mL；1mmol)。持續攪拌24小時，繼而藉由添加甲醇/水混合物(4：1，5mL)淬滅，隨後攪拌30分鐘，繼而真空濃縮。所得濃縮物用100mL AK-225溶劑稀釋，繼而經由矽藻土墊過濾。真空濃縮濾液且真空乾燥所得殘餘物，產生5.25g共聚物(所饋入單體之80%)。NMR分析(於CDCl3中)估算經全氟取代之單元之莫耳比為40%，如藉由比較烯丙基亞甲基信號與靠近C6F13部分之亞甲基信號之整合所計算。
此實施例說明根據本發明一具體實例之式I之又一共聚物之合成。
向經氬氣淨化之具有隔片之40mL小瓶中裝入溴化甲基三苯基鏻(37mg；0.1mmol)、經脫氣之無水甲苯(12mL)，繼而裝入3-[2-(全
氟己基)乙氧基]-1,2-環氧丙烷(2.80mL；10mmol)及環氧氯丙烷(1.6mL；20mmol)。劇烈攪拌反應混合物，同時添加三異丁基鋁於甲苯中之1.1M溶液(0.9mL；1mmol)。持續攪拌24小時，繼而藉由添加甲醇/水混合物(4：1，5mL)淬滅，繼而攪拌30分鐘，繼而真空濃縮。濃縮物用100mL AK-225溶劑稀釋，繼而經由矽藻土墊過濾。真空濃縮濾液且真空乾燥所得殘餘物，產生5.58g共聚物(所饋入單體之92%)。NMR分析(於CDCl3中)估算經全氟取代之單元之莫耳比為35%，如藉由比較靠近C6F13部分之亞甲基信號之整合(2.30-2.50ppm)與其餘質子之整合(3.45-3.80ppm)所計算。
此實施例說明中間物至根據本發明一具體實例之式II共聚物之合成。
由如Journal of Oleophobic Science第59卷(2010)483中所描述之1H,1H,2H,2H-七氟癸基碘化物合成3-(全氟辛基)-丙腈，且在類似地如Journal of Polymer Science：Part A Polymer Chemistry第32卷(1994)2187中所描述之乙酸鎘去水催化劑存在下使其與略微過量乙醇胺反應。以71%產率獲得單體，且其結構藉由1H及19F NMR分析(於CDCl3中)兩者確證，且其高純度藉由元素分析(計算值：%C 30.19、%H 1.56、%N 2.71、%F 62.45；實驗值：%C 30.26、%H 1.57、%N 2.76、%F 60.94)確證。
此實施例說明根據本發明一具體實例之式II之另一共聚物之合成。
向經氬氣淨化之具有隔片之40mL小瓶中裝入於經脫氣之
1,1,2-三氯乙烷(4mL)中稀釋之三氟甲烷磺酸甲酯(9μL；0.08mmol)，繼而在劇烈攪拌下用注射器添加2-甲基-2-
唑啉(2.0mL；24mL)。在100℃下加熱小瓶之內含物6小時，之後經由隔片，用注射器逐滴添加溶解於1,1,2-三氯乙烷(10mL)中之實施例8中所描述之經全氟取代之
唑啉單體(2.07g；4mmol)之溶液。在100℃下持續加熱16小時，繼而藉由添加哌啶(0.1mL)終止反應，且使反應混合物冷卻至環境溫度，同時持續攪拌隔夜。將小瓶之內含物逐滴添加至經劇烈攪拌之二乙醚(300mL)中，隨後出現沉澱。藉由過濾收集產物，用大量二乙醚洗滌，繼而在環境溫度下真空乾燥，產生3.21g(所饋入之單體之78%)。1H及19F NMR光譜均符合預期結構。用DMF(具有0.05N LiBr)作為移動相進行之GPC分析指示26kDa(相對於PMMA標準物)之Mw與1.58之多分散指數。自元素分析(%N=12.99；%F=3.18)估算經全氟取代之單元之莫耳比為約6%。
此實施例說明根據本發明之具體實例之共聚物之表面改質特性。
藉由在環境溫度下在共聚物溶液(溶劑及下表中所指示之濃度)中浸泡1小時來浸漬塗佈氟聚合物基板(PTFE或PVDF)。之後短暫風乾(直至樣品不再透明為止)，在用於共聚物溶解之溶劑中廣泛洗滌，繼而風乾且相比於未經處理之PTFE對照(CWST=25達因/公分)或未經處理之PVDF對照(CWST=44達因/公分)，藉由量測CWST值來測試經塗佈之膜之可濕性。
本文中所引用之所有參考文獻(包括公開案、專利申請案及專利)均以引用之方式併入本文中，該引用程度就如同各參考文獻個別地且特定地指示以引用之方式併入且全文闡述於本文中。
除非本文另外指示或與上下文明顯矛盾，否則在描述本發明之上下文中(尤其在以下申請專利範圍之上下文中)使用術語「一(a/an)」及「該(the)」及「至少一個(at least one)」及類似參照物應解釋為涵蓋單數及複數兩者。除非本文另外指示或與上下文明顯矛盾，否則應將後接一或多個項目之清單(例如「A及B中之至少一者」)之術語「至少一個」的使用理解為意謂選自所列項目之一個項目(A或B)或所列項目中之兩者或兩者以上之任何組合(A及B)。除非另外指出，否則術語「包含(comprising)」、「具有(having)」、「包括(including)」及「含有(containing)」應理解為開放術語(亦即，意謂「包括(但不限於)」)。除非本文另外指示，否則本文中數值範圍之敍述僅意欲充當個別提及屬於該範圍內之各獨立值之速記方法，且各獨立值併入本說明書中，如同在本文中個別敍述一般。除非本文另外指示或上下文另外明顯矛盾，否則本文所描述之所有方法均可以任何適合順序進行。除非另外主張，否則使用本文所提供之任何及所有實施例或例示性語言(例如「諸如」)僅意欲較好地闡明本發明且不對本發明之範疇造成限制。本說明書中之語言不應理解為指明任何未主張之要
素對於實踐本發明而言必不可少。
本發明之較佳具體實例描述於本文中，包括本發明人已知之進行本發明的最佳模式。在閱讀前文描述之後，彼等較佳具體實例之變化對於一般熟習此項技術者可變得顯而易見。本發明人期望熟習此項技術者適當時採用此類變化，且本發明人意欲以不同於本文中特定所描述之方式來實踐本發明。因此，若適用法律允許，則本發明包括隨附於本文之申請專利範圍中所敍述之標的物的所有修改及等效物。此外，除非本文另外指示或另外與上下文明顯矛盾，否則本發明涵蓋上文所描述要素在其所有可能變化中之任何組合。
Claims (21)
- 一種複合親水性多孔膜，其包含多孔氟聚合物載體及包含式(I)或(II)共聚物之塗層：
- 如申請專利範圍第1項之複合親水性多孔膜，其中Y選自胺基、羥基、丙烯醯基及甲基丙烯醯基。
- 如申請專利範圍第1項或第2項之複合親水性多孔膜，其中Rf為經全氟取代之烷基，其中烷基鏈可視情況在該鏈中含有一或多個氧原子。
- 如申請專利範圍第1項或第2項之複合親水性多孔膜，其中Rf為CpF2p+1-(CH2)q(OCH2)r，其中p為1至12，q為0至3，且r為0至2。
- 如申請專利範圍第4項之複合親水性多孔膜，其中Rf獨立地選自針對式I之C8F17CH2、C6F13(CH2)2OCH2、C4F9CH2及CF3及針對式II之 CpF2p+1-CH2CH2。
- 如申請專利範圍第1項之複合親水性多孔膜，其中該共聚物具有式(I)且Rf選自C8F17CH2及C6F13(CH2)2OCH2。
- 如申請專利範圍第1項之複合親水性多孔膜，其中該共聚物具有式(II)且Rf為C8F17CH2CH2。
- 如申請專利範圍第1項或第2項之複合親水性多孔膜，其中Rh選自羥基、烷氧基、氯、烯丙氧基、烷硫基或烷硫基丙氧基，其中烷基可經羥基、羧酸、磺酸、膦酸、四級銨、烷基碸及雜環取代。
- 如申請專利範圍第8項之複合親水性多孔膜，其中Rh為羥基。
- 如申請專利範圍第1項或第2項之複合親水性多孔膜，其中Ra為甲基。
- 如申請專利範圍第10項之複合親水性多孔膜，其中X為甲基。
- 如申請專利範圍第1項或第2項之複合親水性多孔膜，其中Y為三級胺基或四級銨基團。
- 如申請專利範圍第12項之複合親水性多孔膜，其中該三級胺基或四級銨基團選自哌啶基、吡啶陽離子(pyridinium)、二甲胺基及二乙胺基。
- 一種親水改質多孔氟聚合物載體之方法，其包含：(i)提供多孔氟聚合物載體；(ii)用包含溶劑及式(I)或(II)共聚物之溶液塗佈該多孔氟聚合物載體：
- 如申請專利範圍第14項之方法，其中，該共聚物之該Rf為經全氟取代之烷基，其中烷基鏈可視情況含有氧原子。
- 如申請專利範圍第14項或第15項之方法，其中該共聚物之該Rf為CpF2p+1-(CH2)q(OCH2)r，其中p為1至12，q為0至3，且r為0至2。
- 如申請專利範圍第16項之方法，其中Rf選自針對式I之C8F17CH2、C6F13(CH2)2OCH2、C4F9CH2及CF3及針對式II之CpF2p+1-CH2CH2。
- 一種經親水改質之多孔氟聚合物膜，其由如申請專利範圍第14項至第17項中任一項之方法產生。
- 如申請專利範圍第1項或第2項之複合親水性多孔膜，其中該多孔氟 聚合物載體選自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/氯三氟乙烯))、PFPE(全氟聚醚)、PFSA(全氟磺酸)及全氟聚氧代環丁烷。
- 如申請專利範圍第18項之經親水改質之多孔氟聚合物膜，其中該多孔氟聚合物載體選自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/氯三氟乙烯))、PFPE(全氟聚醚)、PFSA(全氟磺酸)及全氟聚氧代環丁烷。
- 一種過濾流體之方法，該方法包含使該流體穿過如申請專利範圍第1項至第13項中任一項之複合親水性多孔膜或如申請專利範圍第18項之經親水改質之多孔氟聚合物膜。
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- 2016-01-27 SG SG10201600623TA patent/SG10201600623TA/en unknown
- 2016-01-27 EP EP16152959.9A patent/EP3088071B1/en active Active
- 2016-01-27 TW TW105102438A patent/TWI613086B/zh active
- 2016-01-27 JP JP2016013576A patent/JP6217992B2/ja active Active
- 2016-01-29 CN CN201610142913.6A patent/CN106084281B/zh active Active
- 2016-01-29 KR KR1020160011254A patent/KR101786873B1/ko active IP Right Grant
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721579A (zh) * | 2013-12-24 | 2014-04-16 | 巨化集团技术中心 | 一种含氟微孔膜表面亲水改性方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US9849428B2 (en) | 2017-12-26 |
| KR20160129703A (ko) | 2016-11-09 |
| JP2017002273A (ja) | 2017-01-05 |
| CN106084281B (zh) | 2019-08-20 |
| SG10201600623TA (en) | 2016-11-29 |
| CN106084281A (zh) | 2016-11-09 |
| EP3088071A1 (en) | 2016-11-02 |
| TW201637836A (zh) | 2016-11-01 |
| KR101786873B1 (ko) | 2017-10-18 |
| JP6217992B2 (ja) | 2017-10-25 |
| EP3088071B1 (en) | 2019-07-24 |
| US20160317982A1 (en) | 2016-11-03 |
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