TW201710333A - 親水性多孔聚四氟乙烯膜(i) - Google Patents
親水性多孔聚四氟乙烯膜(i) Download PDFInfo
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- TW201710333A TW201710333A TW105120501A TW105120501A TW201710333A TW 201710333 A TW201710333 A TW 201710333A TW 105120501 A TW105120501 A TW 105120501A TW 105120501 A TW105120501 A TW 105120501A TW 201710333 A TW201710333 A TW 201710333A
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- copolymer
- hydrophilic porous
- ptfe
- membrane
- solution
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- 239000012528 membrane Substances 0.000 title claims abstract description 55
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- 238000000137 annealing Methods 0.000 claims description 6
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
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- BBWBEZAMXFGUGK-UHFFFAOYSA-N bis(dodecylsulfanyl)-methylarsane Chemical compound CCCCCCCCCCCCS[As](C)SCCCCCCCCCCCC BBWBEZAMXFGUGK-UHFFFAOYSA-N 0.000 description 3
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- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/125—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one oxygen atom in the ring
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
- B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本發明揭示一種親水性多孔PTFE膜,其包含PTFE及兩性共聚物,例如下式之共聚物:
□其中m及n於本發明中描述。亦揭示一種製備親水性多孔PTFE膜之方法及經由該膜過濾流體之方法。
Description
本發明關於一種親水性多孔聚四氟乙烯膜。
多孔PTFE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,改善其濕潤特性而不影響其固有性質應為有利的。已努力改質PTFE膜之一或多種性質。然而,大部分努力集中導致一或多種PTFE之有利性質減少,例如,機械強度。
上文展示存在針對以下之尚未滿足的需求:製備具有經改善的濕潤特性而不顯著影響其機械強度之多孔PTFE膜。
本發明提供一種親水性多孔膜,其包含聚四氟乙烯(PTFE)及兩性共聚物之摻合物,其中該兩性共聚物包含重複單元A及B,其中A選自一或多個下列結構:
且B為式或,其中:該兩性共聚物為嵌段共聚物或隨機共聚物;且重複單元A及B之數分別為n及m且範圍在1至約1000,其限制條件為n及m之總和等於或大於10。
該親水性多孔膜享有許多PTFE膜之優勢,例如,機械強度,且同時展示高程度的水可濕性(water wettability)。
本發明進一步提供一種製備親水性多孔膜之方法,其包含:(i)製備包含PTFE及兩性共聚物與視情況的潤滑劑之摻合物;(ii)將該摻合物擠製成帶;(iii)雙軸拉伸該帶以得到親水性多孔膜;視情況地(iv)將該親水性多孔膜與試劑反應以改質該共聚物之化學結構;且視情況地(v)將該親水性多孔膜退火;其中,該兩性共聚物包含重複單元A及B,其中A選自一或多個下列結構:
且B為式或,其中:該兩性共聚物為嵌段共聚物或隨機共聚物;且重複單元A及B之數分別為n及m且範圍在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經由此親水性多孔PTFE膜過濾流體之方法。
圖1A描述拉伸前PTFE預形成物截面之SEM顯微照片,而圖1B描述拉伸後PTFE預形成物截面之SEM顯微照片。
根據一具體實例,本發明提供一種親水性多孔膜,其包含聚四氟乙烯(PTFE)與兩性共聚物的摻合物,其中該兩性共聚物包含重複單元A及B,其中A選自一或多個下列結構:
且B為式或,
其中,該兩性共聚物為嵌段共聚物或隨機共聚物;且重複單元A及B之數分別為n及m且範圍在1至約1000,其限制條件為n及m之總和等於或大於10。
重複單元之化學式上的虛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,兩性共聚物具有下式中之一者:
其中m1+m2=m。
本發明之兩性共聚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於空氣中之穩定性、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)可市售獲得或如下自格拉布氏第二代催化劑(G2)製備:
因此,具有鏈段A的嵌段共聚物選自以下各者:
其可用包含下列步驟之方法製備:(i)在開環複分解聚合(ROMP)催化劑的催化下,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,以獲得均聚物;以及(ii)在ROMP催化劑的催化下,在從(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以獲得具有含有二甲酸的鏈段A的共聚物。
隨機共聚物可以包含下列步驟之方法製備:在ROMP催化劑的催化下,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)在ROMP催化劑的催化下,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-2,3-二甲醯亞胺之混合物。
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,例如用非溶劑沉澱。
該共聚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,藉由高壓泵,經由一組用固定相填充的管柱來沖提聚合物溶液。該固定相根據鏈大小分離聚合物樣品,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。
該共聚物較佳為單分散。舉例而言,共聚物具有1.05至1.5,較佳為1.1至1.2之Mw/Mn。
例如,下式之共聚物:
可用包含下列步驟之方法製備:(i)在開環複分解聚合(ROMP)催化劑的催化下,聚合順-5-氧雜降莰烯-外-2,3-二甲酸酐,以獲得均聚物;以及(ii)在ROMP催化劑的催化下,在從(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:
聚(C2二酸-b-NPF6)可用鹼水溶液水解聚(C2-b-PNF6)來製備,如以下所說明:
聚(C3-b-NPF6)可用包含下列步驟之方法製備:(i)在開環複分解聚合(ROMP)催化劑的催化下,聚合順-5-降莰烯-外-2,3-二甲酸之二甲酯,以獲得均聚物;以及(ii)在ROMP催化劑的催化下,在從(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:
聚(C4-b-NPF6)可用包含下列步驟之方法製備:(i)在ROMP催化劑的催化下,聚合順-5-氧雜降莰烯-外-2,3-二甲酸之二甲酯,以獲得均聚物;以及(ii)在ROMP催化劑的催化下,在從(i)中獲得之均聚物之鏈末端上聚合5-(全氟己基)降莰烯
聚(C3-r-NPF6)可用包含下列步驟之方法製備:在ROMP催化劑的催化下,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。
在上述方法中,聚合可以適合之方式終止,例如,藉由使用諸如乙基乙烯基醚之烷基乙烯基醚終止。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。
本發明進一步提供一種製備親水性多孔PTFE膜之方法,其包含:(i)製備包含PTFE及兩性共聚物與視情況的潤滑劑之摻合物;(ii)將該摻合物擠製成帶;(iii)雙軸拉伸該帶以得到親水性多孔膜;視情況地(iv)將該親水性多孔膜與試劑反應以改質該共聚物之化學結構;且視情況地(v)將該親水性多孔膜退火;
其中,該兩性共聚物包含重複單元A及B,其中A選自一或多個下列結構:
且B為式或,其中:該兩性共聚物為嵌段共聚物或隨機共聚物;且重複單元A及B之數分別為n及m且範圍在1至約1000,其限制條件為n及m之總和等於或大於10。
所需量的PTFE粉末在例如諸如甲醇、乙醇或異丙醇之醇溶劑之適當溶劑中與共聚物溶液混合,以得到摻合物,其隨後與諸如無味礦油精(例如Isopar G)之潤滑劑混合,而對所得到之糊漿施以剪力(例如在雙輥中),且在約300psi或更高的壓力下、至少兩次各約55秒的期間形成坯料。使所產生的坯料在室溫下平衡約12小時或更多。該坯料接著被擠製成所需形狀。例如,在26mm模具間隙大小、最大壓力與55℃恆溫下進行擠製,得到管狀PTFE帶。然後,沿中軸切開該管狀帶並圍繞著吸量管重新輥軋以得到新的坯料(無壓縮)。該新的坯料依第一次擠製程序的相同條件
再度擠製。此步驟係為該PTFE帶提供有利的橫向拉伸機械性質而添加。在30℃進行壓平,目標值為帶的厚度為9-10密耳,且切成4x4”。所得的帶接著在125℃乾燥1小時,藉此將潤滑劑自擠製出的帶中移除。
接著在下列條件拉伸該帶:機械方向(MD)與垂直機械方向(TD)的拉伸比在300%/秒拉伸速率下為3。拉伸烘箱中的溫度設定為150℃。
拉伸後的帶隨後退火。退火以在350℃退火烘箱中5秒進行,隨後冷卻該帶。由上述拉伸產生的孔隙度在冷卻時被保留。
視情況地,將前述所得到的多孔膜與鹼反應以對在共聚物中存在的任何酸酐單元進行開環。鹼可以是胺類或鹼性物質。在一具體實例中,胺類可以是聚醚單胺,諸如聚氧化乙烯單胺、聚氧化丙烯單胺或聚氧化乙烯-共-聚氧化丙烯單胺。聚醚單胺的一個例子為JEFFAMINE® M1000,可自亨斯邁公司獲得,其為具有PO/EO比為3/19、分子量約1000之單胺。可替換地,聚醚胺可為聚醚二胺。聚醚二胺的一個例子為JEFFAMINE® ED176,同樣可自亨斯邁公司獲得,其為主鏈主要為聚氧化乙烯之二胺。
因此,例如,製備在諸如四氫呋喃(THF)的有機溶劑中之約5至10%(w/w)胺溶液。將多孔膜樣品以浸入該胺溶液中一段適當的時間區間,例如,約30分鐘至約2小時,尤其是1小時。胺溶液可以任何適當的溫度與膜接觸,例如,室溫下(20-25℃)。經胺處理後的樣品可以以任何適當的時間區間乾燥,例如,30秒至1分鐘,直到樣品不再透明。所得到的膜在烘箱中溫度約160℃下熱固化約30分鐘的一段時間。所得到的膜浸泡在過量THF中一段適當的時間區間,例如,12-16小時,接著該膜以
新鮮THF沖洗並在約50℃下乾燥約30分鐘的一段時間。
進一步視情況地,所產生的膜可以用1N NaOH溶液處理,隨後以去離子水淋洗再風乾。可替換地,或,除此之外,該膜可以在80℃或更高溫度下與水接觸。
根據本發明之一具體實例,親水性多孔PTFE膜為多孔膜,例如奈米多孔膜,例如,孔隙直徑在1nm至100nm之間的膜,或孔隙直徑在1μm至10μm之間的微多孔膜。
所得多孔膜之表面張力可如下測定。舉例而言,藉由用IPA溶劑預濕潤該膜薄片,且將該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。為了量測膜表面張力,將該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膜表面,且記錄該液滴滲透該膜且如穿過該膜之光所指示變成亮白色所需要的時間。當液滴滲透該膜所需要的時間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膜。
根據本發明之具體實例的親水性多孔PTFE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該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經由此通過)。根據本發明之具體實例之多孔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,親水性多孔PTFE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多孔PTFE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膜或包括至少一種本發明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;及至少一種本發明膜或包含至少一種本發明膜的過濾器,本發明膜或包含至少一種本發明薄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膜或包含至少一種
本發明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,其中本發明膜或包含至少一種本發明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膜或包含至少一種本發明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。
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多孔PTFE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多孔PTFE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,用氬氣沖洗,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且孔徑大小為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偵測器的沃特世(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。
於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):-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。
於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):-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(REF)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,自溶液獲得呈白色沉澱物狀之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-5,6-二甲酸酐(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。將溶液回流持續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×)中沉澱,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:
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×)中沉澱,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)。
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×)中沉澱,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。
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3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)。
此實施例說明根據本發明具體實例製備親水性多孔PTFE膜之方法。
在異丙醇溶劑中混合PTFE樹脂粉末FLUON CD123與2.5重量%之共聚物聚(C2-b-NPF6)溶液以得到PTFE樹脂中含5%聚(C2-b-NPF6)之掺合物。該掺合物與18phr潤滑劑Isopar G混合,且得到的糊漿在雙輥中混合。對掺合物施加300psi之壓力、至少兩次各約55秒的期間使其形成坯料。所得到的坯料在室溫下平衡約12小時。該坯料接著在最大壓力與55℃恆溫下,用26mm模具擠製成管狀PTFE帶。沿中軸(沿長度方向)切開該管狀帶並圍繞著吸量管重新輥軋以得到新的坯料(無壓縮)。該新的坯料依第一次擠製過程的相同條件再度擠製。在30℃進行壓平,目標值為帶的厚度為9-10密耳,且切成4x4”。所得的帶接著在125℃乾燥1小時,藉此將潤滑劑自擠製出的帶中移除。接著在機械方向與垂直機械方向的MD/TD比在300%/秒拉伸速率下為3的條件下拉伸該帶。拉伸烘箱中的溫度設定為150℃。拉伸後的帶隨後退火。退火以在350℃退火烘箱中持續5秒進行。
圖1A描述拉伸前的膜表面的SEM顯微照片,而圖2A描述拉伸後的膜表面的SEM顯微照片。兩個顯微照片的放大率皆為10,000X。經拉伸的膜揭示PTFE區域之間互連之小纖維的數量增加。
使經退火的膜樣品與1N NaOH接觸60秒,隨後以去離子水淋洗。接觸角在膜上量測。所得到的結果如表4所示。
當將由聚(C2-b-NPF6)與PTFE掺合物製備之樣品放置在廣口瓶中之水上時,樣品被水潤濕,而沉到廣口瓶底部,證實其親水性與可濕性。另一方面,將對照組PTFE膜放置在水上時,因其未被潤濕而僅漂浮著。
此實施例說明根據本發明具體實例化學改質親水性多孔PTFE膜之方法。
將根據實施例13所製備但未與NaOH溶液接觸的PTFE膜與JEFFAMINE M1000或JEFFAMINE ED176溶液接觸。淋洗並乾燥所得到的膜且測試其CWST,所得到的結果如表5所示。開環化學改質提昇了CWST。
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。
Claims (7)
- 一種親水性多孔膜,其包含聚四氟乙烯(PTFE)與兩性共聚物之摻合物,其中該兩性共聚物包含重複單元A及B,其中A選自一或多個下列結構:
- 如申請專利範圍第1項所述之親水性多孔膜,其中該兩性共聚物具有選自芳基及烷氧基之鏈末端基。
- 如申請專利範圍第1項或第2項所述之親水性多孔膜,其中該兩性共聚物為下式中之一者:
- 一種製備親水性多孔膜之方法,其包含:(i)製備包含PTFE及兩性共聚物與視情況的潤滑劑之摻合物;(ii)將該摻合物擠製成帶;(iii)雙軸拉伸該帶以得到親水性多孔膜;視情況地(iv)將該親水性多孔膜與試劑反應以改質該共聚物之化學結構;且視情況地(v)將該親水性多孔膜退火;其中,該兩性共聚物包含重複單元A及B,其中A選自一或多個下列結構:
- 如申請專利範圍第4項之方法,其中(iv)中之該試劑為鹼。
- 一種根據申請專利範圍第4項或第5項之方法製成之親水性多孔膜。
- 一種過濾流體的方法,其包含使流體通過如申請專利範圍第1項至第3項或第6項任一項之親水性多孔膜。
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2015
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KR101831267B1 (ko) | 2018-02-22 |
JP6330856B2 (ja) | 2018-05-30 |
JP2017095675A (ja) | 2017-06-01 |
EP3124100B1 (en) | 2018-11-21 |
TWI617602B (zh) | 2018-03-11 |
EP3124100A1 (en) | 2017-02-01 |
US20170028363A1 (en) | 2017-02-02 |
SG10201604718QA (en) | 2017-02-27 |
CN106397742B (zh) | 2018-11-02 |
KR20170015137A (ko) | 2017-02-08 |
US9643131B2 (en) | 2017-05-09 |
CN106397742A (zh) | 2017-02-15 |
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