TWI593725B - 經親水性改質之氟化膜(v) - Google Patents
經親水性改質之氟化膜(v) Download PDFInfo
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- TWI593725B TWI593725B TW104135568A TW104135568A TWI593725B TW I593725 B TWI593725 B TW I593725B TW 104135568 A TW104135568 A TW 104135568A TW 104135568 A TW104135568 A TW 104135568A TW I593725 B TWI593725 B TW I593725B
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- porous membrane
- composite hydrophilic
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- coating
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D147/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Coating compositions based on derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0095—Drying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/106—Membranes in the pores of a support, e.g. polymerized in the pores or voids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Description
多孔含氟聚合物膜,例如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、原子層沈積及經改質PTFE樣聚合物之合成。然而,大多數努力集中於高能量處理,諸如BBUV及電漿。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鍵結強度低於F-F鍵約40%,故其可使得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,由此使其在較長時段內較不穩定。
上文展示並未滿足對表面改質多孔含氟聚合物載體以提供
親水性含氟聚合物膜之需要,該等膜穩定,且其中表面改質並不會明顯影響含氟聚合物載體或所得膜之機械強度。
本發明提供一種複合親水性多孔膜,其包含多孔含氟聚合物載體及包含交聯聚合物網路之塗層,其中該複合親水性膜藉由以下產生:以包含溶劑、交聯劑、光引發劑及遙螯聚合物之塗層組成物塗佈多孔含氟聚合物載體,該遙螯聚合物包含由聚合1,5-環辛二烯重複單元製成之主鏈,其中重複單元中之至少一者包含連接於其上之側位親水性基團且重複單元中之另一者包含連接於其上之側位氟化疏水性基團,及使所得塗層就地交聯。
共聚物及經改質之均聚物適用於改質含氟聚合物膜之表面。
本發明進一步提供製備遙螯共聚物之方法及製備經親水性改質之含氟聚合物膜之方法。
根據一具體實例,本發明提供一種複合親水性多孔膜,其包含多孔含氟聚合物載體及包含交聯聚合物網路之塗層,其中該複合親水性
膜藉由以下產生:以包含溶劑、交聯劑、光引發劑及遙螯聚合物之塗層組成物塗佈多孔含氟聚合物載體,該遙螯聚合物包含由聚合1,5-環辛二烯重複單元製成之主鏈,其中該等重複單元中之至少一者包含連接於其上之側位親水性基團且該等重複單元中之另一者包含連接於其上之側位氟化疏水性基團,及使所得塗層就地交聯。
遙螯聚合物之末端基團可為疏水性及/或親水性末端。在一具體實例中,末端基團為疏水性的。在另一具體實例中,末端基團為親水性的。
根據一具體實例,遙螯聚合物包含重複單元B及C中之至少一者,及視情況存在之一或多個重複單元A,其中重複單元A至C具有下式:
其中R為親水性基團。
在上述具體實例中,親水性基團R選自羧基烷基、磺酸烷基及羥基烷基。
在本發明之具體實例中,單元A、B及/或C可以任何適合之方式,例如以嵌段或隨機分佈之嵌段之方式存在。
在一具體實例中,遙螯聚合物包含單元A、B及C。舉例而言,遙螯聚合物具有下式:
其中x及m獨立地為n+m+x之0至35莫耳%,其中n+m+x=10至1000,n及m獨立地為約10至約1000,且R為親水性基團。
在一具體實例中,遙螯聚合物包含親水性末端基團。舉例而言,親水性末端基團包含聚羥烷基醚基團。
在一具體實例中,遙螯聚合物具有下式:
其中R為親水性基團,例如羧基烷基、磺酸烷基或羥基烷基,且n為約10至約1000,其中P為能夠引發聚合之基團。
在一具體實例中,遙螯聚合物具有下式:
或
其中P為能夠引發聚合之基團,x及m獨立地為n+m+x之0至35莫耳%,其中n+m+x=10至1000,且R為親水性基團。
遙螯聚合物可藉由任何適合之交聯劑,較佳藉由二硫醇或多硫醇交聯。
可利用任何適合之光引發劑,例如選自以下之光引發劑: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、苯基乙醛酯及其衍生物、二聚苯基乙醛酯、過酸酯、鹵甲基三、六芳基雙咪唑/共引發劑系統、二茂鐵、二茂鈦及其組合。
任何適合之多孔含氟聚合物載體可經親水性改質,例如多孔含氟聚合物載體可選自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。
根據一具體實例,塗層之交聯藉由使塗層曝露於UV照射來實現。
本發明進一步提供一種下式之遙螯聚合物:
或
其中P為能夠引發聚合之基團,x及m獨立地為n+m+x之0至35莫耳%,其中n+m+x=10至1000,且R為親水性基團。
本發明進一步提供一種親水性改質多孔含氟聚合物載體之
方法,其包含:(i)提供多孔含氟聚合物載體;(ii)以包含溶劑、交聯劑、光引發劑及如上文所述遙螯聚合物之溶液塗佈該多孔含氟聚合物載體;(iii)乾燥來自(ii)之經塗佈含氟聚合物載體以自經塗佈溶液移除至少一些溶劑;及(iv)使塗層中存在之該遙螯聚合物交聯。
本發明進一步提供一種藉由上述方法產生之經親水性改質之含氟聚合物膜。
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述複合親水性多孔膜中之任一者。
遙螯聚合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75kDa至約500kDa,且更佳約250kDa至約500kDa。
本發明之遙螯聚合物可藉由任何適合之方法製備,例如經由1,5-環辛二烯(COD)之開環複分解聚合。典型地,含有碳烯配位體之過渡金屬催化劑介導複分解反應。
可使用任何適合之ROMP催化劑,例如可利用格拉布氏(Grubbs')第一、第二及第三代催化劑、優美科(Umicore)、荷維達-格拉布氏(Hoveyda-Grubbs)、施羅克(Schrock)及施羅克-荷維達(Schrock-Hoveyda)催化劑。此類催化劑之實例包括以下:
在一具體實例中,格拉布氏第三代催化劑因其諸如空氣穩定性、耐受多個官能基及/或快速聚合起始及傳播速率之優勢而尤其適合。此外,在格拉布氏第三代催化劑之情況下,可對末端基團進行工程改造以容納任何相容基團,且可容易回收催化劑。此類催化劑之較佳實例為:
以上第三代格拉布氏催化劑(G3)可購得或可如下由格拉布氏第二代催化劑(G2)製得:
單體之聚合在適合溶劑中實施,例如一般用於實施ROMP聚合之溶劑。適合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%之範圍內。
聚合可在任何適合之溫度,例如-20℃至+100℃,較佳10℃至80℃下進行。
聚合可進行任何適合於獲得適當鏈長之聚合物之時間,其可為約1分鐘至100小時。
催化劑之量可經選擇在任何適合之量內。舉例而言,催化劑與單體之莫耳比可為約1:10至約1:1000,較佳約1:50至1:500,且更佳約1:100至約1:200。舉例而言,催化劑與單體之莫耳比可為1:n及1:m,其中n及m為平均聚合度。
聚合物可藉由適合技術,例如用非溶劑沈澱來分離。
可藉由任何已知技術使聚合物之分子量及分子量分佈特性化。舉例而言,可利用MALS-GPC技術。該技術經由高壓泵使用流動相通過一組充填固定相之管柱來洗提聚合物溶液。固定相根據鏈大小分離聚合物樣品,隨後藉由三個不同偵測器偵測聚合物。可利用一系列偵測器,例如紫外線偵測器(UV-偵測器),隨後多角度雷射光散射偵測器(MALS-偵測器),隨後又為折射率偵測器(RI-偵測器)成一排。UV-偵測器量測254nm
波長之聚合物光吸收;MALS-偵測器量測相對於流動相來自聚合物鏈之散射光。
本發明之共聚物高度單分散。舉例而言,共聚物之Mw/Mn為1.05至1.5,較佳1.1至1.2。
根據一具體實例,聚環辛二烯(聚(COD)或PCOD)可藉由如下所示由ROMP催化劑使COD聚合,隨後終止聚合而獲得:
在上述方法中,聚合可以適合方式終止,例如藉由使用烷基乙烯醚,諸如乙基乙烯醚。
根據另一具體實例,可如下所示使用ROMP製備遙螯聚COD:
可進一步改質遙螯聚(COD)以提供具有多個羥基之遙螯聚(COD)。舉例而言,可如下所示使以上遙螯聚(COD)與羥基甲基環氧乙烷反應以獲得具有多個羥基之遙螯聚(COD):
為黏著於多孔含氟聚合物載體,例如PTFE,由與氟化硫醇反應提供親氟部分。A可經由親水性單硫醇添加親水性官能基。反應如下所示:
其中m+x=n。
根據另一具體實例,遙螯聚(COD)可如下改質:
其中m+x=y+1(XIII)。
以上結構由改質超分支P(gly-COD-gly)系統產生且在交聯步
驟期間於膜上就地產生。
或者,本發明提供一種下式之經改質線性樹枝狀聚(COD):
其中n+m+x=y+1(VII)。
超分支PCOD首先與縮水甘油反應,且反應產物藉由引入親水性與氟化側鏈進行改質。硫醇烯反應將親水性與氟側鏈引入PCOD主鏈中。氟側鏈與PCOD、隨後與親水性組分反應之依序反應或兩者之混合物與PCOD反應以同時引入兩者。
調整PCOD系統之分子量以便為硫醇烯官能基以及交聯提供足夠雙鍵。
本發明進一步提供一種複合親水性膜,其包含多孔含氟聚合物及共聚物或如上文所述經改質均聚物,其中該共聚物或經改質均聚物視情況交聯。
所得多孔膜之表面張力可如下確定。舉例而言,在室溫下藉由視情況用IPA溶劑預潤濕膜薄片及將膜浸泡於濃度在0.1質量%與10質量%之間的範圍內之聚合物溶液中來塗佈PTFE膜薄片。PTFE薄片塗佈時間在1分鐘與12小時之間的範圍內。在浸泡膜之後,於對流烘箱中在100
℃至160℃下將膜乾燥。乾燥時間在10分鐘與12小時之間的範圍內。PTFE膜潤濕特徵藉由量測臨界潤濕表面張力來量測。塗佈及交聯方法示於圖1中。圖2圖示一種使根據本發明之一具體實例之多孔含氟聚合物載體上之塗層交聯之方法。
關於表面張力之表面改質之變化藉由研發用於量測多孔膜表面張力而非固體表面之方法來量測。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。溶液表面張力以小非等效增量處於25至92達因/公分之範圍內。為量測位於白光台之頂部上之膜的表面張力,將一滴某一表面張力之溶液塗覆於膜表面上,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。
交聯可藉由任何適合之方法進行,例如藉由使用光引發劑及高能輻射,例如UV。交聯意欲在膜中提供高度穩定之聚合物網路。
交聯可如下進行。經聚合物塗佈之PTFE薄片用IPA預潤濕,接著用製備光引發劑之溶劑洗滌薄片以用彼溶劑交換IPA。接著將薄片浸沒於某一濃度之光引發劑之溶液中一定時間,隨後曝露於UV照射。在光引發劑溶液中之浸泡時間在1分鐘至24小時之範圍內。UV照射時間在30秒至24小時之範圍內。接著量測膜臨界潤濕表面張力(CWST)、性能特性化及/或SPM測試。「SPM」意謂120℃至180℃下熱硫酸過氧化氫混合物(以體積計80:20之H2SO4(96%):H2O2(30%))。
根據本發明之一具體實例,親水性含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含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。或者,或另外,根據本發明之具體實例之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膜可用於多種裝置中,包括手術裝置及產品,諸如例如,眼科手術產品。
根據本發明之具體實例,親水性含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、螺旋形及中空纖維。
根據本發明之具體實例之親水性含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。可利用具有適合形狀且提供至少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,親水性含氟聚合物多孔膜包含任何適合之多孔含氟聚合物載體,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之孔徑,例如約10奈米至約10微米,較佳為PTFE及PVDF。
本發明進一步提供一種藉由上述方法產生之經親水性改質之含氟聚合物膜。
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述親水性含氟聚合物膜。
以下實施例進一步說明本發明,但當然不應將其解釋為以任何方式限制其範圍。
材料:購買以下材料且按原樣使用。
5-降冰片烯-2,3-二甲酸二甲酯(C3)購自Alfa Aesar,
將二氯甲烷(DCM)儲存於活性氧化鋁上且在使用之前用吹氬氣掃,異丙醇(IPA)、二環戊二烯(DCPD)、四氫呋喃(THF)、乙酸乙酯、N-苯基順丁烯二醯亞胺、乙腈、甲醇、格拉布氏第二代催化劑、3-溴吡啶及戊烷獲自Sigma-Aldrich公司,且未經進一步處理即使用。亦獲自Sigma-Aldrich公司之二氯戊烷在使用之前用鹼性氧化鋁處理。藉由真空蒸餾自三氟化硼純化1,5-環辛二烯(COD)且新鮮使用。
此實施例說明二氯[1,3-雙(2,4,6-三甲基苯基)-2-亞咪唑啶基](苯亞甲基)雙(3-溴吡啶)釕(II)(G3)催化劑之製備。
使上文所示之第二代格拉布氏催化劑(G2)(1.0g,1.18mmol)與3-溴吡啶(1.14mL,11.8mmol)於50mL燒瓶中混合。在室溫下攪拌5min時,紅色混合物變為亮綠色。在攪拌下添加戊烷(40mL)維持15分鐘且獲得綠色固體。於冷藏器中冷卻混合物24h且真空過濾。將所得G3催化劑,一種綠色固體,用冷戊烷洗滌且在室溫下真空乾燥,得到產量0.9g,產率88%。
此實施例說明根據本發明之一具體實例之均聚物及共聚物之凝膠滲透層析特性化。
藉由MALS-GPC技術在以下條件下使獲得之均聚物及嵌段共聚物之分子量及分子量分佈特性特性化:
流動相:二氯甲烷(DCM)。
流動相溫度:30℃。
UV波長:245nm。
所用管柱:三個PSS SVD Lux分析型管柱(苯乙烯-二乙烯苯共聚物網路)、具有直徑5μm之固定相珠粒及1000A、100,000A及1,000,000A之孔徑之管柱、及保護管柱。
流動速率:1mL/min。
GPC系統:具有UV及RI偵測器之waters HPLC alliance e2695系統
MALS系統:操作664.5nm下之雷射的具有8個偵測器之DAWN HELEOS 8系統。
此實施例說明根據本發明之一具體實例之聚環辛二烯(P-COD)之合成。
在裝備有攪拌棒之50ml圓底燒瓶中,組合格拉布氏第二代催化劑(3.0mg,0.004mmol)、2-丁烯-1,4-二醇(10.0mg,0.12mmol)及1,5-環辛二烯(490mg,4.54mmol)且用氬氣脫氣5min且轉移至40℃之油浴。持續加熱1h,隨後將於5ml DCM中之剩餘1,5-環辛二烯(4.5mg,4.2mmol)添加至混合物中且再持續加熱6h。藉由於甲醇中沈澱來分離羥基封端之聚合物(P-COD)。1H-NMR(300MHz,CDCl3):δ(ppm)5.3至5.5(s,寬峰,1H),1.75至2.5(s,寬峰)。
此實施例說明根據本發明之一具體實例之合成具有式(X)之縮水甘油基末端基的遙螯聚合物聚(gly-hb-COD-hb-gly)之方法。
在裝備有攪拌棒之50ml圓底燒瓶中,在90℃至100℃下將遙螯聚環辛二烯(羥基封端)(1.0g)溶解於二乙二醇二甲醚中。在攪拌下用CaH2(0.5g)活化羥基1h。經30min將縮水甘油(10.0g,135mmol)逐滴添加至混合物中。反應持續加熱12h。藉由於己烷中沈澱來分離聚合物。1H-NMR(CDCl3):δ(ppm)5.6(s 1H),5.45至5.3(m寬峰),2.4(s 2H),2.2
至1.9(m寬峰)。
此實施例說明用含氟試劑官能化聚環辛二烯及其超分支嵌段共聚物之方法。
在光引發劑存在下在UV照射下遵循實質上相同之方法將PCOD均聚物或式A之共聚物用1H,1H,2H,2H-全氟癸硫醇後官能化。舉例而言,將PCOD(1.0g)溶解於含有至多15質量%Irgacure 2959光引發劑(1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙-1-酮)之四氫呋喃中。使溶液曝露於UV照射(300-480nm,150-250mWatt,60至180秒)。將反應混合物用於PTFE塗佈及交聯方法中。
此實施例說明PTFE多孔載體上PCOD及聚(gly-hb-COD-hb-gly)之塗佈及交聯程序。
氟化PCOD或氟化聚(甘胺酸-hb-鱈魚-hb-gly)超分支嵌段聚丙三醇之塗佈及交聯程序實質上相同。以下實施例基於氟化PCOD。
多孔PTFE膜藉由將膜浸泡於含有以下之溶液中用經由硫醇烯反應改質之氟化PCOD來塗佈:於THF中之氟化PCOD(1至10質量%濃度)、光引發劑(Irgacure,1至15質量%)、3-巰基乙磺酸之鈉鹽(1至15質量%,於THF水溶液中用稀HCl溶液(1N)中和,直至形成於THF中之均勻溶液),在UV照射(300-480nm,150-250mWatt,60秒至180秒)下使膜與此混合物交聯。接著用去離子水洗滌膜且在100℃下乾燥10min。
PCOD及P(gly-hb-COD-hb-gly)之GPC跡線描繪於圖3中。
在光引發劑(Irgacure 2959,10%)存在下在UV照射(90秒)下使P(gly-hb-COD-hb-gly)就地與1H,1H,2H,2H-全氟癸硫醇反應。所得聚合物混合物用以塗佈PTFE膜且遵循如上文所述之相同方法來量測CWST。PTFE及經處理PTFE表面之CWST示表1於。
本文所引用之所有參考文獻(包括公開案、專利申請案及專利)均以引用的方式併入本文中,該引用程度就如同各參考文獻個別及特定指示以引用的方式併入且全文闡述於本文一般。
除非本文中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的上下文中),應將術語「一(a/an)」及「等(the)」及「至少一個(at least one)」及類似指示物的使用理解為涵蓋單數個與複數個。除非本文中另外指示或與上下文明顯矛盾,否則使用後接一或多個項目之清單(例如「A及B中之至少一者(at least one of A and B)」)之術語「至少一者(at least one)」應理解為意謂選自所列舉項目之一個項目(A或B)或所列舉項目中之兩者或兩者以上的任何組合(A及B)。除非另外指示,否則術語「包含(comprising)」、「具有(having)」、「包括(including)」及「含有(containing)」應解釋為開放式術語(亦即,意謂「包含(但不限於)(including,but not imited to)」)。除非本文另外指示,否則本文中數值範圍之列舉僅意欲充當個別提及屬於該範圍內之各獨立值之簡寫
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與上下文明顯矛盾,否則本文所述之所有方法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具體實例或例示性語言(例如「諸如(such as)」)僅意欲較好地闡明本發明而不對本發明之範圍造成限制。本說明書中之語言不應理解為指示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,否則本發明涵蓋上述要素在其所有可能變化中之任何組合。
圖1圖示根據本發明之一具體實例之親水性氟化聚合物之塗佈方法。
圖2圖示根據本發明之一具體實例之親水性氟化聚合物之塗佈及交聯方法。
圖3描述CH2Cl2中之聚(COD)及聚(gly-hb-COD-hb-gly)之GPC跡線。
Claims (17)
- 一種複合親水性多孔膜,其包含多孔含氟聚合物載體及包含交聯聚合物網路之塗層,其中該複合親水性膜藉由以下產生:以包含溶劑、交聯劑、光引發劑及遙螯聚合物之塗層組成物塗佈該多孔含氟聚合物載體,該遙螯聚合物包含由聚合1,5-環辛二烯重複單元製成之主鏈,其中該等重複單元中之至少一者包含連接於其上之側位親水性基團且該等重複單元中之另一者包含連接於其上之側位氟化疏水性基團,及使所得塗層就地交聯。
- 如申請專利範圍第1項之複合親水性多孔膜,其中該遙螯聚合物包含疏水性及/或親水性末端基團。
- 如申請專利範圍第1項之複合親水性多孔膜,其中該遙螯聚合物包含重複單元B及C中之至少一者及視情況存在之一或多個重複單元A,其中重複單元A-C具有下式:
- 如申請專利範圍第3項之複合親水性多孔膜,其中R選自羧基烷基、磺酸烷基及羥基烷基。
- 如申請專利範圍第1項至第4項中任一項之複合親水性多孔膜,其包含重複單元A、B及C。
- 如申請專利範圍第1項至第4項中任一項之複合親水性多孔膜,其具有疏水性末端基團。
- 如申請專利範圍第1項至第4項中任一項之複合親水性多孔膜,其中該遙螯聚合物具有下式:
- 如申請專利範圍第1項至第4項中任一項之複合親水性多孔膜,其中該遙螯聚合物包含疏水性末端基團。
- 如申請專利範圍第8項之複合親水性多孔膜,其中該遙螯聚合物具有下式:
- 如申請專利範圍第9項之複合親水性多孔膜,其中R選自羧基烷基、磺酸烷基及羥基烷基。
- 如申請專利範圍第1項至第4項中任一項之複合親水性多孔膜,其中該交聯劑為二硫醇或多硫醇。
- 如申請專利範圍第9項之複合親水性多孔膜,其中該遙螯聚合物具有下式:
- 如申請專利範圍第1項至第4項中任一項之複合親水性多孔膜,其中該光引發劑選自樟腦醌、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、苯基乙醛酯及其衍生物、二聚苯基乙醛酯、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。
- 如申請專利範圍第1項至第4項中任一項之複合親水性多孔膜,其中該多孔含氟聚合物載體選自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1項至第4項中任一項之複合親水性多孔膜,其中該塗層之交聯藉由使該塗層曝露於UV照射來實現。
- 一種親水性改質多孔含氟聚合物載體之方法,其包含:(i)提供多孔含氟聚合物載體;(ii)以包含溶劑、交聯劑、光引發劑及下式之遙螯聚合物之溶液塗佈該多孔含氟聚合物載體:
- 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15項中任一項之複合親水性多孔膜。
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