TWI574841B - 經親水性改質之氟化薄膜(i) - Google Patents
經親水性改質之氟化薄膜(i) Download PDFInfo
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- TWI574841B TWI574841B TW104138731A TW104138731A TWI574841B TW I574841 B TWI574841 B TW I574841B TW 104138731 A TW104138731 A TW 104138731A TW 104138731 A TW104138731 A TW 104138731A TW I574841 B TWI574841 B TW I574841B
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- Prior art keywords
- copolymer
- polymer
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- fluoropolymer
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- 239000012528 membrane Substances 0.000 title description 4
- 229920000642 polymer Polymers 0.000 claims description 74
- 229920001577 copolymer Polymers 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 48
- 229920002313 fluoropolymer Polymers 0.000 claims description 47
- 239000004811 fluoropolymer Substances 0.000 claims description 45
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 16
- 239000012530 fluid Substances 0.000 claims description 16
- 229920001400 block copolymer Polymers 0.000 claims description 11
- 229920005604 random copolymer Polymers 0.000 claims description 11
- -1 polychlorotrifluoroethylene Polymers 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 5
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- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 4
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 4
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000010702 perfluoropolyether Substances 0.000 claims description 3
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- 239000005977 Ethylene Substances 0.000 claims description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 4
- 125000003118 aryl group Chemical group 0.000 claims 4
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
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- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 10
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- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
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Description
本發明係關於複合親水性多孔薄膜及經親水性改質之多孔氟化聚合物薄膜,包含其聚合物組成物的合成及親水性改質氟化聚合物與過濾流體的方法。
氟聚合物薄膜(例如,多孔PTFE薄膜)之性質包括其機械強度、化學抗性或惰性、非黏著性、極佳介電性質、在高溫下的熱穩定性及低摩擦係數,使其對各種應用極具有吸引力。然而,對於某些應用,改質PTFE之表面而不影響其固有性質應為有利的。已努力改質PTFE薄膜之表面及化學性質,以便改良薄膜對於特定應用之適合性。舉例而言,努力包括表面塗層、摻合、高能表面改質(例如,寬波段紫外輻射或BBUV,其中將薄膜曝露於波長250-450nm之UV輻射)及電漿處理、自由基及臭氧蝕刻、原子層沉積以及合成經改質之類PTFE聚合物。然而,大部分努力集中於高能處理,諸如BBUV及電漿。雖然此等表面改質方法之確切機制未經報導,但其可能藉由鍵斷裂來引起自由基形成,因為已知C-C鍵強度比F-F鍵低約40%。若大部分自由基由C-C斷裂或聚合物主鏈斷裂所產生,則其可降低PTFE薄膜之機械及化學穩定性。亦已知電漿處理限於薄膜之表面,此使得其在較長時間段期間較不穩定。
前文展示存在針對以下之尚未滿足的需求:表面改質多孔氟聚合物薄膜或載體以提供穩定的親水性氟聚合物多孔薄膜,且其中該表面改質不顯著影響多孔氟聚合物載體或所得複合多孔薄膜之機械強度。
本發明提供一種複合親水性多孔薄膜,其包含多孔氟聚合物載體及包含共聚物的塗層,其中該共聚物包含重複單元A及B,其中A選自
且B具有式或,其中n及m為1至約1000,其限制條件為n及m之總和等於或大於10。
本發明進一步提供一種複合親水性多孔薄膜,其包含多孔氟聚合物載體及包含聚合物的塗層,該聚合物具有一或多個連接至該聚合物之主鏈的全氟烷硫基側基,該聚合物之重複單元具有下式:
其中*指示該全氟烷硫基側基之連接點。
具有全氟烷硫基側基的共聚物及聚合物適用於改質多孔氟聚合物載體之表面。
本發明進一步提供製備具有全氟烷硫基側基的共聚物及聚合物之方法以及製備經親水性改質之氟聚合物多孔薄膜之方法。本發明進一步提供經由此等多孔薄膜過濾流體之方法。
根據一具體實例,本發明提供一種複合親水性多孔薄膜,其包含多孔氟聚合物載體及包含共聚物的塗層,其中該共聚物包含重複單元A及B,其中A選自:
且B具有式或,其中n及m為1至約1000,其限制條件為n及m之總和等於或大於10。
在本文中的化學式中,重複單元之化學式上的點線指示共聚物可為嵌段共聚物或隨機共聚物。嵌段共聚物利用圓括號指示:(重複單元)。隨機共聚物利用方括號指示:[重複單元]。
在具體實例中,n及m表示對應單體之聚合程度,且獨立地為約10至約1000,較佳為約20至約50。
在其他具體實例中,n及m表示共聚物中存在的單體之莫耳分率,且n及m可獨立地在介於1至99莫耳%、較佳20至50莫耳%之間的範圍內。
對應的單體嵌段可以任何適合之質量%存在於嵌段共聚物中,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%。
共聚物可為嵌段共聚物或隨機共聚物。嵌段共聚物可為二嵌段(A-B)、三嵌段(A-B-A或B-A-B)或多嵌段共聚物((A-B)x)。共聚物視情況可具有第三鏈段C,例如三嵌段共聚物或隨機共聚物,諸如A-B-C。
共聚物可具有任何適合之分子量,例如在一具體實例中,數
目或重量(Mn或Mw)平均分子量為約10kDa至約1000kDa,較佳為約75kDa至約500kDa,且更佳為約250kDa至約500kDa。
根據一具體實例,本發明之共聚物具有下式中之一者:
在一具體實例中,本發明之共聚物進一步包含一或多個具有下式之重複單元C:
其中比率o/(m+n)為大於0至約0.25莫耳%,較佳為約0.05至約0.25莫耳%,且更佳為約0.10至約0.15莫耳%。
在一具體實例中,共聚物具有下式:
本發明進一步提供一種複合親水性多孔薄膜,其包含多孔氟聚合物載體及包含聚合物的塗層,其中該聚合物具有一或多個連接至該聚合物之主鏈的全氟烷硫基側基,該聚合物之重複單元具有下式:
其中*指示該全氟烷硫基側基之連接點。
在一具體實例中,聚合物具有下式:
其中p+q=m-1。
全氟烷硫基側基可存在於聚合物之一些或所有重複單元中。因此,舉例而言,全氟烷硫基側基可以大於0至100%、且在具體實例中約1至約50%或約10至約30%重複單元之量存在。全氟烷硫基側基隨機地位於聚合物之主鏈中。
具有本發明之全氟烷硫基側基的共聚物及聚合物可利用任何適合之方法製備,例如經由環狀單體之開環複分解聚合(ring opening metathesis polymerization;ROMP)製備。典型地,含有碳烯配位體之過渡金屬催化劑促成該複分解反應。
可使用任何適合之ROMP催化劑,例如可採用格拉布氏(Grubbs')第一代、第二代及第三代催化劑、優美科(Umicore)、胡偉達-格拉布(Hoveyda-Grubbs)、施羅克(Schrock)及施羅克-胡偉達(Schrock-Hoveyda)催化劑。該等催化劑之實例包括以下各者:
在一具體實例中,格拉布氏第三代催化劑由於其諸如空氣中之穩定性、對多種官能基具有耐受性及/或較快聚合起始及增長速率之優點而尤其適合。此外,用格拉布氏第三代催化劑,末端基可經工程改造以容納任何相容基團,且該催化劑可易於回收。該催化劑之一較佳實例為:
以上第三代格拉布氏催化劑(G3)可市售獲得或自格拉布氏第二代催化劑(G2)如下製備:
本發明進一步提供一種製備具有全氟烷硫基側基的共聚物及聚合物之方法。
因此,本發明提供一種製備具有選自以下各者之鏈段A的嵌段共聚物之方法:
該方法包含:(i)利用開環複分解聚合(ROMP)催化劑催化,聚合選自順-5-氧雜降莰烯-外-2,3-二甲酸酐、順-5-降莰烯-外-2,3-二甲酸之二甲酯及順-5-氧雜降莰烯-外-2,3-二甲酸之二甲酯的單體,獲得均聚物;以及(ii)利用ROMP催化劑催化,在(i)中獲得之均聚物之鏈末端上依序聚合5-(全氟己基)降莰烯。
自順-5-氧雜降莰烯-外-2,3-二甲酸酐(聚(C2-b-PNF6))製備
的共聚物可與鹼水溶液反應,獲得鏈段A具有二甲酸的共聚
物。
本發明進一步提供一種製備本發明之隨機共聚物之方法,其包含利用ROMP催化劑催化,聚合(i)順-5-降莰烯-外-2,3-二甲酸之二甲酯及5-(全氟己基)降莰烯之混合物,或(ii)利用ROMP催化劑催化,聚合順-5-氧雜降莰烯-外-2,3-二甲酸之二甲酯、5-(全氟己基)降莰烯及N-巰基乙基順-5-降莰烯-外-2,3-二羧基亞胺之混合物。
本發明進一步提供一種製備具有全氟烷硫基側基的聚合物之方法,其包含(i)利用ROMP催化劑催化,聚合選自以下之單體:順-5-氧雜降莰烯-外-2,3-二甲酸酐、順-5-降莰烯-外-2,3-二甲酸之二甲酯及順-5-氧雜降莰烯-外-2,3-二甲酸之二甲酯,獲得均聚物;以及(ii)使所得均聚物與1H,1H,2H,2H-全氟癸硫醇反應。自順-5-氧雜降莰烯-外-2,3-二甲酸酐製備且用1H,1H,2H,2H-全氟癸硫醇改質的聚合物可與鹼水溶液(例如,氫氧化鈉、氫氧化鉀、碳酸鉀、碳酸鈉及其類似鹼)在適合之濃度(例如,0.01N至約10N,且較佳約0.1N至1N)下反應,獲得具有其二甲酸鹽之聚合物,其可用諸如鹽酸、硫酸或硝酸之無機酸中和成二甲酸形式,
單體之聚合在適合之溶劑中進行,例如通常用於進行ROMP聚合的溶劑。適合之溶劑的實例包括: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;以及鹵化烴,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50重量%,較佳2至45重量%,且更佳3至40重量%範圍內。
聚合可在任何適合之溫度下進行,例如-20至+100℃,較佳10至80℃。
為了製備嵌段共聚物,例如聚合可持續任何適合於獲得各嵌
段之適當鏈長的時間進行,該時間可為約1分鐘至100小時。
可以任何適合之量選擇催化劑之量。舉例而言,催化劑比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,催化劑比單體之莫耳比可為1:n及1:m,其中n及m為平均聚合程度。
聚合物可利用適合之技術進行分離,例如用非溶劑沈澱。
本發明之具有全氟烷硫基側基的共聚物及聚合物可利用任何已知技術對其分子量及分子量分佈進行鑑定。舉例而言,可採用MALS-GPC技術。該技術使用移動相,經由高壓泵,聚合物溶液經由一組用固定相填充的管柱來沖提。該固定相根據鏈尺寸分離聚合物樣品,接著利用三種不同偵測器偵測該聚合物。可採用一系列偵測器,例如紫外線偵測器(UV偵測器),後面為多角度雷射光散射偵測器(MALS偵測器),其後面又為折射率偵測器(RI偵測器)成一列。UV偵測器量測聚合物在254nm波長下的光吸收;MALS偵測器量測相對於移動相來自聚合物鏈的散射光。
本發明之具有全氟烷硫基側基的共聚物及聚合物高度單分散。舉例而言,共聚物之Mw/Mn為1.05至1.5,較佳為1.1至1.2。
根據一具體實例,本發明提供一種製備具有下式之共聚物的方法:
該方法包含:(i)利用開環複分解聚合(ROMP)催化劑催化,聚合順-5-氧雜降莰烯-外-2,3-二甲酸酐,獲得均聚物;以及(ii)利用ROMP催化劑催化,在(i)中獲得之均聚物之鏈末端上聚合5-(全氟己基)降莰烯,如以下所說明:
本發明進一步提供一種製備聚(C2二酸-b-NPF6)的方法,其包含用鹼水溶液水解聚(C2-b-PNF6),如以下所說明:
本發明進一步提供一種製備聚(C3-b-NPF6)之方法,其包含:(i)利用開環複分解聚合(ROMP)催化劑催化,聚合順-5-降莰烯-外-2,3-二甲酸之二甲酯,獲得均聚物;以及(ii)利用ROMP催化劑催化,在(i)中獲得之均聚物之鏈末端上聚合5-(全氟己基)降莰烯,如以下所說明:
本發明進一步提供一種製備共聚物聚(C4-b-NPF6)之方法,其包含:(i)利用ROMP催化劑催化,聚合順-5-氧雜降莰烯-外-2,3-二甲酸之二甲酯,獲得均聚物;以及(ii)利用ROMP催化劑催化,在(i)中獲得之均聚物之鏈末端上聚合5-(全氟己基)降莰烯
本發明進一步提供一種製備共聚物聚(C3-r-NPF6)之方法,其包含利用ROMP催化劑催化,聚合順-5-降莰烯-外-2,3-二甲酸之二甲酯及5-(全氟己基)降莰烯之混合物。
本發明進一步提供一種製備具有下式之隨機共聚物的方法:
其包含利用ROMP催化劑催化,聚合順-5-氧雜降莰烯-外-2,3-二甲酸之二甲酯、5-(全氟己基)降莰烯及N-巰基乙基順-5-降莰烯-外-2,3-二羧基亞胺之混合物。
本發明進一步提供一種製備具有下式之聚合物的方法:
其包含利用ROMP催化劑催化,聚合順-5-降莰烯-外-2,3-二甲酸之二甲酯及5-(全氟己基)降莰烯,且使所得聚合物與1H,1H,2H,2H-全氟癸硫醇反應,如以下所說明:
在上述方法中,聚合可以適合之方式終止,例如藉由使用烷基乙烯基醚,諸如乙基乙烯基醚終止。因此,可提供共聚物之末端基中之一者。
可藉由選擇適當ROMP催化劑來提供末端基中之另一者。舉例而言,可藉由使用在過渡金屬上的具有亞苄基的ROMP催化劑來提供苯基端基。
本發明進一步提供包含多孔氟聚合物及如上所述之共聚物或聚合物之複合親水性多孔薄膜,其中該共聚物或聚合物視情況交聯。
本發明進一步提供一種親水性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)用包含溶劑及如上所述之具有全氟烷硫基側基之共聚物或聚合物的溶液塗佈該多孔氟聚合物載體;(iii)乾燥來自(ii)之該經塗佈之多孔氟聚合物載體,以自包含該共聚物或聚合物的溶液移除至少一些溶劑;且視情況(iv)使存在於該塗層中的共聚物或聚合物交聯。
圖1說明用根據本發明之一具體實例之共聚物塗佈多孔氟聚合物載體的方法。圖2說明使根據本發明之一具體實例之多孔氟聚合物載體上之塗層交聯的方法。
交聯可利用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)進行。預期該交聯將在薄膜中提供高度穩定聚合物網狀結構。
可使用任何適合之光引發劑,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/共起始劑系統、二茂鐵化合物、二茂鈦及其組合。
交聯可如下進行。經聚合物塗佈之PTFE薄片視情況用IPA預濕潤,接著用溶劑(光引發劑用該溶劑製備以使IPA與該溶劑交換)洗滌該等薄片。接著將薄片在具有特定濃度之光引發劑之溶液中浸泡特定時
間,接著曝露於UV照射。在光引發劑溶液中的浸泡時間在1分鐘至24小時範圍內。UV照射時間在30秒至24小時範圍內。接著量測薄膜臨界濕潤表面張力(critical wetting surface tension;CWST)、效能鑑定及/或SPM測試。「SPM」意謂在120℃至180℃下熱硫酸過氧化氫混合物(按體積計H2SO4(96%):H2O2(30%)為80:20)。
根據本發明之一具體實例,親水性氟聚合物薄膜為多孔薄膜,例如奈米孔薄膜,例如孔隙直徑在1nm至100nm之間的薄膜,或孔隙直徑在1μm至10μm之間的微孔薄膜。
所得多孔薄膜之表面張力可如下測定。舉例而言,藉由用IPA溶劑預濕潤該薄膜薄片,且將該薄膜浸泡於濃度範圍在0.1質量%至10質量%之間的塗佈聚合物溶液中來在室溫下塗佈PTFE多孔載體之薄片。塗佈時間介於(1分鐘至12小時)之間的範圍內。在浸泡載體之後,將其在對流烘箱中在100℃至160℃下乾燥。乾燥時間在介於(10分鐘至12小時)之間的範圍內。藉由量測臨界濕潤表面張力來量測所得多孔PTFE薄膜的濕潤特性。
表面改質在表面張力方面的改變藉由量測臨界濕潤表面張力(CWST)來量測。該方法依賴於一組具有特定組成之溶液。各溶液具有比表面積張力。溶液的表面張力在25至92達因/公分範圍內,呈小幅非等量遞增形式。為了量測薄膜表面張力,將該薄膜置放在白光台之頂部上,將一滴具有特定表面張力之溶液塗覆至該薄膜表面,且記錄該液滴滲透該薄膜且如穿過該薄膜之光所指示變成亮白色所需要的時間。當液滴滲透該薄膜所需要的時間10秒時,視為即時濕潤。若時間>10秒,則溶液視為部
分地濕潤該薄膜。
根據本發明之具體實例的親水性氟聚合物多孔薄膜可用於各種應用,包括例如診斷應用(包括例如樣品製備及/或診斷側向流動裝置)、噴墨應用、微影術(例如,作為基於HD/UHMW PE之介質的替代物)、供醫藥產業用之過濾流體、金屬移除、製備超純水、處理工業及地表水、用於醫療應用之過濾流體(包括供家庭及/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))、供電子工業用之過濾流體(例如,在微電子產業及熱SPM中之過濾光阻流體)、供食品及飲料產業用之過濾流體、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(包括於臨場)、細胞收集及/或過濾細胞培養物流體。或者,或此外,根據本發明之具體實例之多孔薄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經由此通過)。根據本發明之具體實例之多孔薄膜可用於各種裝置中,包括外科裝置及產品,諸如,眼科外科產品。
根據本發明之具體實例,親水性氟聚合物多孔薄膜可具有各種組態,包括平面形、平坦薄片、褶狀、管狀、螺旋形及中空纖維。
根據本發明之具體實例的親水性氟聚合物多孔薄膜典型地安置於包含至少一個入口及至少一個出口且在該入口與該出口之間界定至少一個流體流動路徑的外殼中,其中至少一種本發明薄膜或包括至少一種本發明薄膜的過濾器橫越該流體流動路徑,從而提供過濾裝置或過濾模組。在一具體實例中,提供一種過濾裝置,其包含:外殼,其包含入口及第一出口,且在該入口與該第一出口之間界定第一液體流動路徑;及至少
一種本發明薄膜或包含至少一種本發明薄膜的過濾器,本發明薄膜或包含至少一種本發明薄膜的過濾器橫越該第一液體流動路徑安置於該外殼中。
對於交叉流動應用,至少一種本發明多孔薄膜或包含至少一種本發明薄膜的過濾器較佳安置於外殼中,該外殼包含至少一個入口及至少兩個出口,且在該入口與該第一出口之間界定至少一個第一液體流動路徑,且在該入口與該第二出口之間界定第二液體流動路徑,其中本發明薄膜或包含至少一種本發明薄膜的過濾器橫越該第一液體流動路徑,從而提供過濾裝置或過濾模組。在一說明性具體實例中,過濾裝置包含交叉流動過濾模組,外殼包含入口、包含濃縮物出口的第一出口及包含滲透物出口的第二出口,且在該入口與該第一出口之間界定第一液體流動路徑,且在該入口與該第二出口之間界定第二液體流動路徑,其中至少一種本發明薄膜或包含至少一種本發明薄膜的過濾器橫越該第一液體流動路徑安置。
過濾裝置或模組可為可滅菌的。可採用具有適合之形狀且提供入口及一或多個出口之任何外殼。
外殼可自任何適合之硬質不透水材料製造,包括任何不透水的熱塑性材料,其與所處理之流體相容。舉例而言,外殼可由以下各者製造:金屬,諸如不鏽鋼;或聚合物,例如透明或半透明聚合物,諸如丙烯酸、聚丙烯、聚苯乙烯或聚碳酸酯樹脂。
根據一具體實例,親水性氟聚合物多孔薄膜包含任何適合之多孔氟聚合物載體,例如由以下各者製備的載體: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。該多孔載體可具有任何適合之孔徑,例如約2nm至約10微米,較佳PTFE及PVDF。
本發明進一步提供利用上文所述之方法製備的經親水性改質之氟聚合物多孔薄膜。
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通過上文所述之親水性氟聚合物多孔薄膜。
以下實施例進一步說明本發明,但當然不應解釋為以任何方式限制其範圍。
材料:購買且按原樣使用以下材料。
5-降莰烯-2,3-二甲酸二甲酯(C3)購自Alfa Aesar。
將二氯甲烷(dichloromethane;DCM)以活性氧化鋁儲存,且在使用之前,用氬氣淨化,異丙醇(isopropyl alcohol;IPA)、二環戊二烯(dicyclopentadiene;DCPD)、1H,1H,2H-全氟-1-辛烯(1H,1H,2H-Perflouro-1-octene;PF6)、1H,1H,2H-全氟-1-十二烯(1H,1H,2H-Perflouro-1-dodecene;PF10)、甲苯、亞硫醯氯、乙酸乙酯、二甲基甲醯胺(DMF)、順丁烯二醯亞胺、呋喃、偶氮二甲酸二異丙酯(DIAD)、三苯膦(Ph3P)、1-十六醇、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,且在無進一步處理之情況下使用。亦獲自Sigma-Aldrich公司的二氯戊烷在使用之前用鹼性氧化鋁處理。環辛二烯(COD)自硼三氟化物藉由真空蒸餾純化,且新鮮使用的。
此實施例說明製備二氯[1,3-雙(2,4,6-三甲基苯基)-2-亞咪唑啶基](亞苄基)雙(3-溴吡啶)釕(II)(G3)催化劑。
將以上所說明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)在50mL燒瓶中混合。在室溫下攪拌5min後,紅色混合物變為亮綠色。在攪拌下持續15分鐘添加戊烷(40mL),且獲得綠色固體。將混合物在冷凍器中冷卻24h,且在真空下過濾。將所得G3催化劑、綠色固體用冷戊烷洗滌,且在真空下在室溫下乾燥,得到0.9g之產量,88%產率。
此實施例說明對根據本發明之一具體實例的均聚物及共聚物進行凝膠滲透層析法鑑定。
所獲得之均聚物及嵌段共聚物利用MALS-GPC技術在以下條件下對其分子量及分子量分佈性質進行鑑定:移動相:二氯甲烷(DCM)。
移動相溫度:30℃。
UV波長:245nm。
所使用之管柱:三個PSS SVD Lux分析管柱(苯乙烯-二乙
烯苯共聚物網狀結構)、具有直徑5μm且孔徑為1000A、100,000A及1,000,000A之珠粒作為固定相之管柱以及保護管柱。
流動速率:1mL/min。
GPC系統:具有UV及RI偵測器的waters HPLC alliance e2695系統。
MALS系統:具有8個在664.5nm下操作雷射之偵測器的DAWN HELEOS 8系統。
此實施例說明製備根據本發明之一具體實例的NPF6單體之程序。
Parr高壓反應器圓柱容器裝入DCPD(100ml,737mmol)、PF6(168ml,737mmol),且將該圓柱連接至該反應器,且裝入對苯二酚(2.43g,22.1mmol),加熱至170℃後持續72小時。將反應內含物溶解至150ml DCM中,且轉移至500ml圓底燒瓶中,藉由真空蒸餾純化該單體。
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),及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)。
此實施例說明製備根據本發明之一具體實例的NPF10單體之程序。
Parr高壓反應器圓柱容器裝入DCPD(24.6ml,183mmol)、PF6(132ml,370mmol),且將該圓柱連接至該反應器,且裝入對苯二酚(1.08g,10mmol),加熱至170℃後持續72小時。將反應內含物溶解至150ml DCM中,且轉移至500ml圓底燒瓶中,藉由真空蒸餾純化該單體。
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),及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)。
此實施例說明製備根據本發明之一具體實例的C2單體之程序。
在裝備有磁性攪拌棒的乾淨2L圓底燒瓶(RBF)中,將呋喃(390ml,3.35mol)添加至順丁烯二酸酐(350g,3.57mol)於1.5L甲苯中之溶液中。在80℃下加熱混合物6h。在用甲苯(200mL,3×)洗滌,且過濾後,自溶液獲得呈白色沈澱物狀之C2。在真空下在室溫下乾燥白色固體24h。獲得呈純外異構體形式之C2,產量為650g,95%。1H-NMR(300MHz,DMSO):δ(ppm)6.6(s,2H),5.4(s,2H),3.15(s,2H)。
此實施例說明製備根據本發明之一具體實例之C4單體的程序,該C4單體為C2單體之二甲酯。
向500ml RBF中,將外-7-氧雜降莰烯-5.6-二羧酸酐(C2)(65g,0.4mol)溶解於甲醇(750ml)中,將亞硫醯氯(25ml)緩慢逐滴添加至C2溶液中,形成黃色溶液。將溶液迴流持續48小時,之後移除溶劑直至乾燥,且獲得單體。將固體溶解於乙酸乙酯中,用K2CO3溶液(200ml,
2×)洗滌,用DI水(200ml,2×)洗滌,且經MgSO4乾燥。濃縮所得黃色溶液,得到C4單體。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)。
此實施例說明製備N-2-巰基-乙基-降莰烯-二甲醯亞胺(NHS)之程序。
向500ml RBF中,將降莰烯-5.6-二羧酸酐(25g,1.5mol)溶解於甲苯(300ml)中,將胺基乙硫醇(14ml,1.83mol)緩慢逐滴添加至溶液中。將迪恩-斯塔克分水器(Dean-Stark trap)連接至與RBF連接的冷凝器,以收集反應期間所形成之水。將溶液迴流持續24小時,之後自黃色溶液移除溶劑直至乾燥,且獲得單體。將所得固體溶解於乙酸乙酯中,用K2CO3溶液(200ml,2×)洗滌,用DI水(200ml,2×)洗滌,且經MgSO4乾燥。濃縮所得黃色溶液,得到單體。
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)。
此實施例說明根據本發明之一具體實例的共聚物聚(C2-b-NPF6)之合成及性質。
在裝備有氟聚合物樹脂-聚矽氧頂部開口隔膜的40mL瓶中稱量格拉布氏第3代(G3)催化劑(22mg,0.025mmol)。將G3溶解於經氬氣脫氣的THF(60mL)中,且經由套管轉移至裝備有攪拌棒的乾淨1L RBF中。C2單體(3.05g,18.4mmol)於THF(86mL)中之溶液用氬氣脫氣,且轉移至G3溶液中,且攪拌30分鐘。NPF6單體(1.03g,2.5mmol)於THF(208mL)中之溶液用氬氣脫氣,且轉移至聚合中的聚(C2)嵌段溶液,且再攪拌60分鐘。接著將乙基乙烯基醚(2mL)添加至二嵌段共聚物之黃色溶液中以終止反應。將聚合物在MeOH(2L,2×)中沈澱,以回收純聚合物之白色固體。將所得聚合物過濾,且在真空下在室溫下乾燥,產量(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)。
元素分析資料列舉於以下表1中。
將聚(C2-b-NPF6)-1共聚物溶解於THF中,得到1重量%溶液。將PTFE微孔載體(KA-N3P72)樣品浸沒於聚合物溶液中1小時。將PTFE樣品風乾10分鐘,接著在THF中洗滌30min。將樣品再次風乾10分鐘。經塗佈之PTFE薄膜之CWST經量測為33.41達因/公分。初始PTFE薄膜之CWST為25.4達因/公分。
此實施例展現根據本發明之一具體實例之另一共聚物聚(C3-b-NPF6)的合成及性質。
在裝備有氟聚合物樹脂-聚矽氧頂部開口隔膜的40mL瓶中
稱量格拉布氏第3代(G3)催化劑(11mg,0.012mmol)。將G3溶解於經氬氣脫氣的THF(60mL)中,且經由套管轉移至裝備有攪拌棒的乾淨1L RBF中。C3單體(2.5g,12mmol)於THF(86mL)中之溶液用氬氣脫氣,且轉移至G3溶液中,且攪拌30分鐘。NPF6單體(0.86g,2.0mmol)於THF(208mL)中之溶液用氬氣脫氣,且轉移至聚合中的聚(C3)嵌段溶液,且再攪拌60分鐘。接著將乙基乙烯基醚(2mL)添加至二嵌段共聚物之黃色溶液中以終止反應。接著將聚合物在MeOH(2L,2×)中沈澱,以回收純聚合物之白色固體。將所得聚合物過濾,且在真空下在室溫下乾燥,產量(3.0g,90%)。
1H NMR資料列舉如下,且元素分析列舉於表2中。1H-NMR(300MHz,CDCl3):δ(ppm)5.7至5.2(s寬峰),3.7至3.5(m寬峰),3.3至2.8(m寬峰),2.5至1.75(m寬峰),1.6(s寬峰),1.25(s寬峰)。
將聚(C3-b-NPF6)-1共聚物溶解於THF中,得到1重量%溶液。將PTFE多孔載體樣品浸沒於聚合物溶液中1小時。將PTFE樣品風乾10分鐘,接著在THF中洗滌30min。將樣品再次風乾10分鐘。經塗佈之PTFE薄膜之CWST經量測為30達因/公分。初始PTFE載體之CWST為25.4達因/公分。
此實施例展現根據本發明之一具體實例之又一共聚物的合成及性質。
聚(C4-b-NPF6)如下合成。在裝備有氟聚合物樹脂-聚矽氧頂部開口隔膜的40mL瓶中稱量格拉布氏第3代(G3)催化劑(25mg,0.028mmol)。將G3溶解於經氬氣脫氣的THF(60mL)中,且經由套管轉移至裝備有攪拌棒的乾淨1L RBF中。C4單體(2.5g,11.8mmol)於THF(86mL)中之溶液用氬氣脫氣,且轉移至G3溶液中,且攪拌30分鐘。NPF6單體(0.86g,2.0mmol)於THF(208mL)中之溶液用氬氣脫氣,且轉移至聚合中的聚(C4)嵌段溶液,且再攪拌60分鐘。接著將乙基乙烯基醚(2mL)添加至二嵌段共聚物之黃色溶液中以終止反應。將聚合物在MeOH(2L,2×)中沈澱,以回收純聚合物之白色固體。將聚合物過濾,且在真空下在室溫下乾燥,產量(3.0g,90%)。
1H-NMR(300MHz,CDCl3):δ(ppm)6.85(s寬峰),5.8(s寬峰),5.6(s寬峰),5.2至4.9(s寬峰),4.8至4.5(s寬峰),4.4至4.0(m寬峰)4.0至3.6(m寬峰)3.2至2.9(m寬峰),1.4至1.2(m寬峰)。
在CH2Cl2中之共聚物之GPC圖形展示於圖3中。共聚物具有以下性質:Mn=98800,Mw=127200,PDI=1.28。
將聚(C4-b-NPF6)-1共聚物溶解於THF中,得到1重量%溶液。將PTFE微孔薄膜樣品浸沒於聚合物溶液中1小時。將PTFE樣品風乾10分鐘,接著在THF中洗滌30min。將樣品再次風乾10分鐘。經塗佈之PTFE薄膜之CWST經量測為39達因/公分。初始PTFE薄膜之CWST為25.4達因/公分。
此實施例展現根據本發明之一具體實例之具有全氟烷硫基側基之聚合物的合成及性質。
將聚(C2)均聚物(1.0g,6.0mmol)、1H,1H,2H-全氟癸硫醇(3.0g,6.0mmol)及AIBN(79.8mg)溶解於33ml THF中,且允許在55℃下在氮氣下反應26h。將反應混合物傾入水中。將所獲得之沈澱物溶解於THF中,且再次自庚烷沈澱,得到想要之深褐色固體聚合物。
1H-NMR(300MHz,CDCl3):δ(ppm)14至13(s寬峰),5.75(s寬峰),5.5(s寬峰),4至5(m寬峰)3.5至2.5(m寬峰),1.6(s寬峰)。
將具有全氟烷硫基側基之聚合物溶解於THF中,得到1重量%溶液。將PTFE微孔載體樣品浸沒於聚合物溶液中1小時。將PTFE樣品風乾10分鐘,接著在THF中洗滌30min。將樣品再次風乾10分鐘。經塗佈之PTFE載體之CWST經量測為33.41達因/公分(一式三份)(35部分)。初始PTFE載體之CWST為25.4達因/公分。
此實施例展現根據本發明之一具體實例之另一共聚物的合成及性質。
聚(C2二酸-b-NPF6):使聚(C2-b-NPF6)與0.1N NaOH溶液反
應,獲得聚(C2二酸-b-NPF6)。將聚(C2-b-NPF6)二嵌段共聚物溶解於THF(1質量%)中,形成均相溶液。用0.1N NaOH水溶液處理聚合物溶液。將混合物在環境溫度下攪拌1h,接著在己烷中沉澱。
1H-NMR(300MHz,CDCl3):δ(ppm)14至13(s寬峰),6.0至5.5(m寬峰),5.3至4.75(s寬峰),5.375至4.25(s寬峰)3.25(s寬峰),3.3(s寬峰),3.1(s寬峰)。
將聚合物塗佈在多孔PTFE載體上,且量測其CWST。所獲得之結果列舉於表5中。
此實施例展現根據本發明之一具體實例之又一共聚物聚(C3-r-NPF6)的合成及性質。
在裝備有氟聚合物樹脂-聚矽氧頂部開口隔膜的40mL瓶中稱量格拉布氏第3代(G3)催化劑(11mg,0.012mmol)。將G3溶解於經氬氣脫氣的DCM(20mL)中,且經由套管轉移至裝備有攪拌棒的乾淨250ml RBF中。將C3單體(2.5g,12mmol)及NYF6(0.86g,2.0mmol)混合物溶解於DCM(90ml)中之溶液用氬氣脫氣,且轉移至G3溶液中,且在室溫下攪拌12小時。接著將乙基乙烯基醚(2mL)添加至隨機共聚物之黃色溶液中以終止反應。接著使聚合物通過鹼性氧化鋁、矽膠及矽藻土之管柱以移除催化劑。在旋轉蒸發儀中移除溶劑,且所得聚合物為無色且高度黏性的;產量(3.0g,90%)。
1H-NMR(300MHz,CDCl3):δ(ppm)6.0至5.0(s寬峰),3.7至3.5(m寬峰),3.3至2.8(m寬峰),2.5至1.75(m寬峰),1.6(s寬峰),1.25(s寬峰)。
將聚合物塗佈在多孔PTFE載體上,且量測其CWST。所獲得之結果列舉於表6中。
此實施例展現根據本發明之一具體實例之三嵌段聚合物的合成及性質。
利用ROMP催化劑催化,藉由聚合順-5-氧雜降莰烯-外-2,3-二甲酸之二甲酯、5-(全氟己基)降莰烯及N-巰基乙基順-5-降莰烯-外-2,3-二羧基亞胺之混合物來合成聚(C4-r-NPF6-r-NHS)。
1H-NMR(300MHz,CDCl3):δ(ppm)6(s寬峰),5.9至5.0(m寬峰),5.1至4.6(m寬峰),4.6至4.1(m寬峰),4.0至3.0(m寬峰),3.0至2.4(m寬峰),2.3至1.4(m寬峰),1.25(s寬峰)。
將聚合物塗佈在多孔PTFE載體上,且量測其CWST。所獲得之結果列舉於表7中。
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)均以引用的方式併入本文中,該引用程度就如同各參考文獻分別地
且特定地指示為以引用的方式併入且全文闡述於本文中一般。
除非本文中另外指示或明顯與上下文矛盾,否則在描述本發明之上下文中(尤其在隨附申請專利範圍的上下文中),使用術語「一種(a/an)」及「該(the)」及「至少一種(at least one)」及類似指示物應理解為涵蓋單數及複數兩者。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」)之術語「至少一」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以及B)。除非另外說明,否則術語「包含」、「具有」、「包括」及「含有」均解釋為開放式術語(亦即,意謂「包括(但不限於)」)。除非本文中另外指示,否則本文中值範圍之列舉僅意欲充當單獨提及屬於該範圍內之各獨立值的簡寫方法,且各獨立值併入本說明書中,如同在本文中單獨地敍述一般。除非本文中另外指示或上下文明顯矛盾,否則本文中所描述的所有方法均可以任何適合次序進行。除非另外主張,否則使用本文所提供之任何及所有實例或例示性語言(例如,「諸如」)僅意欲更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解釋為指示任何未主張之要素對於實踐本發明而言必不可少。
本文描述本發明之較佳具體實例,包括本發明人已知的用於進行本發明之最佳模式。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該等變化,且本發明人意欲以不同於本文中特定所述之方式實踐本發明。因此,本發明包括如由適用法律所准許之在此隨附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以
其他方式與上下文明顯矛盾,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說明用根據本發明之一具體實例的共聚物塗佈多孔氟聚合物載體之方法。
圖2說明在根據本發明之一具體實例的多孔氟聚合物載體上交聯塗層之方法。
圖3描繪根據本發明之一具體實例之共聚物聚(C4-b-NPF6)的GPC圖形。
Claims (20)
- 一種複合親水性多孔薄膜,其包含多孔氟聚合物載體及包含共聚物的塗層,其中該共聚物包含重複單元A及B,其中A選自
- 如申請專利範圍第1項之複合親水性多孔薄膜,其中該共聚物具有選自芳基及烷氧基的鏈末端基。
- 如申請專利範圍第1項或第2項之複合親水性多孔薄膜,其中該共聚物具有下式中之一者:
- 如申請專利範圍第1項或第2項之複合親水性多孔薄膜,其中該共聚物進一步包含一或多個具有下式之重複單元C:
- 如申請專利範圍第4項之複合親水性多孔薄膜,其中該共聚物為隨機共聚物,且具有下式:
- 一種複合親水性多孔薄膜,其包含多孔氟聚合物載體及包含聚合物的塗層,該聚合物具有一或多個連接至該聚合物之主鏈的全氟烷硫基側基,該聚合物重複單元具有下式:
- 如申請專利範圍第6項之複合親水性多孔薄膜,其中該聚合物具有選自芳基及烷氧基的鏈端基。
- 如申請專利範圍第6項或第7項之複合親水性多孔薄膜,其中該聚合物具有下式:
- 一種親水性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)用包含溶劑及共聚物的溶液塗佈該多孔氟聚合物載體,其中該共聚物包含重複單元A及B,其中A選自
- 如申請專利範圍第9項之方法,其中該共聚物具有選自芳基及烷氧基的鏈端基。
- 如申請專利範圍第9項或第10項之方法,其中該共聚物具有下式中之一者:
- 如申請專利範圍第9項或第10項之方法,其中該共聚物進一步包含一或多個具有下式之重複單元C:
- 如申請專利範圍第12項之方法,其中該共聚物為隨機共聚物,且具有下式:
- 一種親水性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)用包含溶劑及及包含聚合物的塗料之溶液塗佈該多孔氟聚合物載體,該聚合物具有一或多個連接至該聚合物之主鏈的全氟烷硫基側基,該聚合物之重複單元具有下式:
- 如申請專利範圍第14項之方法,其中該聚合物具有選自芳基及烷氧基之鏈端基。
- 如申請專利範圍第14項或第15項之方法,其中該聚合物具有下式:
- 如申請專利範圍第9項或第10項之方法,其中該塗層之交聯藉由將該 塗層曝露於UV輻射來進行。
- 一種經親水性改質之多孔氟聚合物載體,其利用如申請專利範圍第9項、第10項、第14項及第15項中任一項之方法製備。
- 如申請專利範圍第1項、第2項、第6項及第7項中任一項之複合親水性多孔薄膜,其中該多孔氟聚合物載體係選自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通過如申請專利範圍第1項、第2項、第6項及第7項中任一項之複合親水性多孔薄膜。
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US6126825A (en) * | 1996-12-02 | 2000-10-03 | Fuji Photo Film Co., Ltd. | Microporous membrane and process for the production thereof |
CN101490126A (zh) * | 2006-07-21 | 2009-07-22 | 三井化学株式会社 | 开环复分解聚合物、其加氢物及其制造方法、以及其用途 |
CN103415335A (zh) * | 2011-03-14 | 2013-11-27 | 日本戈尔有限公司 | 水处理过滤器用滤材及其制造方法 |
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KR101745515B1 (ko) | 2017-06-09 |
US9636641B2 (en) | 2017-05-02 |
KR20160117140A (ko) | 2016-10-10 |
US10213750B2 (en) | 2019-02-26 |
CN106398443B (zh) | 2019-02-05 |
JP6060449B2 (ja) | 2017-01-18 |
TW201634254A (zh) | 2016-10-01 |
US20160288061A1 (en) | 2016-10-06 |
CN106398443A (zh) | 2017-02-15 |
EP3075765A1 (en) | 2016-10-05 |
JP2016196625A (ja) | 2016-11-24 |
US20170197184A1 (en) | 2017-07-13 |
EP3075765B1 (en) | 2018-01-10 |
SG10201509646VA (en) | 2016-10-28 |
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