TW201815852A - 氟聚合物及包含氟聚合物(ii)的膜 - Google Patents
氟聚合物及包含氟聚合物(ii)的膜 Download PDFInfo
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- TW201815852A TW201815852A TW106126555A TW106126555A TW201815852A TW 201815852 A TW201815852 A TW 201815852A TW 106126555 A TW106126555 A TW 106126555A TW 106126555 A TW106126555 A TW 106126555A TW 201815852 A TW201815852 A TW 201815852A
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- Prior art keywords
- copolymer
- porous
- monomer unit
- vinylpyridine
- coating
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 65
- 229920002313 fluoropolymer Polymers 0.000 title description 7
- 239000004811 fluoropolymer Substances 0.000 title description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 55
- 239000012530 fluid Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 28
- -1 vinylphenyl Chemical group 0.000 claims abstract description 26
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 21
- 229920001400 block copolymer Polymers 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical group C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 16
- 229920005604 random copolymer Polymers 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 6
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 6
- 239000010702 perfluoropolyether Substances 0.000 claims description 6
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 5
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920002098 polyfluorene Polymers 0.000 claims description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 238000004377 microelectronic Methods 0.000 abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 239000012634 fragment Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
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- FIKKDQZDISQACH-UHFFFAOYSA-N 1-ethenyl-3-(1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctan-2-yloxymethyl)benzene Chemical compound FC(C(F)(F)F)(OCC=1C=C(C=C)C=CC1)C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F FIKKDQZDISQACH-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LMRVYUVOZMATLH-UHFFFAOYSA-N FC(=C(C(SC(C(F)(F)F)(F)F)(F)F)C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)C1=C(C(=C(C(=C1F)F)F)F)F Chemical compound FC(=C(C(SC(C(F)(F)F)(F)F)(F)F)C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)C1=C(C(=C(C(=C1F)F)F)F)F LMRVYUVOZMATLH-UHFFFAOYSA-N 0.000 description 4
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- GZQZKLFXWPAMFW-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(1,2,2-trifluoroethenyl)benzene Chemical group FC(F)=C(F)C1=C(F)C(F)=C(F)C(F)=C1F GZQZKLFXWPAMFW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920001780 ECTFE Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- KQNZLOUWXSAZGD-UHFFFAOYSA-N benzylperoxymethylbenzene Chemical compound C=1C=CC=CC=1COOCC1=CC=CC=C1 KQNZLOUWXSAZGD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- URJIJZCEKHSLHA-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecane-1-thiol Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCS URJIJZCEKHSLHA-UHFFFAOYSA-N 0.000 description 1
- QEHNHXICRMUWGA-UHFFFAOYSA-N 3-(1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctan-2-yloxy)prop-1-enylbenzene Chemical group FC(C(F)(F)F)(OCC=CC1=CC=CC=C1)C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F QEHNHXICRMUWGA-UHFFFAOYSA-N 0.000 description 1
- DPZYLEIWHTWHCU-UHFFFAOYSA-N 3-ethenylpyridine Chemical compound C=CC1=CC=CN=C1 DPZYLEIWHTWHCU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
-
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
-
- 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
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Abstract
本發明揭示一種共聚物、由該共聚物製備之多孔膜及一種使用該等多孔膜將金屬離子例如自微電子行業中產生之流體移除來處理流體的方法,其中該共聚物包括單體單元I及單體單元II,其中單體單元I具有式A-X-CH2-B,其中A為Rf-(CH2)n,Rf為式CF3-(CF2)x-之全氟烷基,其中x為3-12,n為1-6,X為O或S,且B為乙烯基苯基,且單體單元II為乙烯基吡啶。
Description
正考慮將包含氟聚合物之膜用於過濾多種流體,例如用於自微電子流體移除痕量金屬雜質。一些此等膜之特徵為低表面能值或臨界潤濕表面張力(CWST)值及/或對有機溶劑及侵蝕性化學物質之抵抗性高。儘管此等膜存在一或多種優勢,但仍需要具有諸如低CWST值及/或對有機溶劑及/或侵蝕性化學物質之抵抗性提高之改良特性的氟聚合物及包含此類氟聚合物之膜。
本發明提供具有低CWST值之氟聚合物及由該等氟聚合物製備之膜。在一具體實例中,本發明提供包含聚合單體單元I及聚合單體單元II之共聚物,其中單體單元I具有下式:A-X-CH2-B,其中A為Rf-(CH2)n,Rf為式CF3-(CF2)x-之全氟烷基,其中x為3-12,n為1-6,X為O或S,且B為乙烯基苯基,且單體單元II為乙烯基吡啶。
共聚物為超疏水聚合物且可用於賦予材料表面疏油特性,亦即低於25達因/公分之表面張力。本發明亦提供一種製備多孔膜之方法,該 多孔膜包含安置於多孔載體上之共聚物。本發明進一步提供一種過濾流體,尤其微電子流體之方法。舉例而言,多孔膜適合於移除存在於微電子裝置中產生之流體中之金屬雜質,至低於1ppb,較佳低於0.005或低於大多數儀器之偵測極限的濃度。
根據一具體實例,本發明提供一種包含聚合單體單元I及聚合單體單元II之共聚物,其中單體單元I具有式A-X-CH2-B,其中A為Rf-(CH2)n,Rf為式CF3-(CF2)x-之全氟烷基,其中x為3-12,n為1-6,X為O或S,且B為乙烯基苯基,且單體單元II為乙烯基吡啶。
在共聚物之一具體實例中,n=2、3或4,尤其為2。
在以上具體實例中之任一者中,x=4、5、6、7或8,尤其為6。
在以上具體實例中之任一者中,乙烯基吡啶可為2-乙烯基吡啶、3-乙烯基吡啶或4-乙烯基吡啶,尤其4-乙烯基吡啶。
全氟烷基可在任何合適位置-鄰位、間位或對位,較佳間位或對位位置存在於B之苯環上,或可使用鄰位異構體、間位異構體及/或對位異構體之混合物。在本文中,「p/m」表明對位及間位異構體之混合物。
在以上具體實例中之任一者中,共聚物為嵌段共聚物,例如二嵌段、三嵌段或多嵌段共聚物,或無規共聚物。
在一具體實例中,單體單元I包含選自由以下組成之群之單體:2-(全氟己基)乙醇、2-(全氟辛基)乙基硫醇、2-(全氟辛基)乙醇、2-(全氟己基)乙基硫醇、對位及/或間位取代之[[(全氟己基伸乙基)氧基]甲基]-苯乙烯以及對位及/或間位取代之[[(全氟己基伸乙基)硫基]甲基]-苯乙烯。
在一具體實例中,共聚物選自由以下組成之群:聚[對/間-[[(全氟己基伸乙基)硫基]甲基]-苯乙烯與聚乙烯吡啶之共聚物及聚[對/間-[[(全氟己基伸乙基)氧基]甲基]-苯乙烯與聚乙烯吡啶之共聚物。在另一具體實例中,共聚物選自由以下組成之群:聚[對/間-[[(全氟辛基伸乙基)硫基]甲基]-苯乙烯與聚乙烯吡啶之共聚物;及聚[對/間-[[(全氟辛基伸乙基)氧基]甲基]-苯乙烯與聚乙烯吡啶之共聚物。
在以上具體實例中之任一者中,共聚物包括至少35體積%之氟化鏈。在另一具體實例中,無規共聚物包含50%或更少之全氟-苯乙烯基團之體積比。
共聚物可藉由任何合適技術來製備。舉例而言,嵌段共聚物可如流程1或流程2中所說明製備。
活性自由基聚合可用於製備嵌段共聚物,且AIBN可用於製備無規共聚物。全氟己基乙基硫基甲基苯乙烯嵌段有利地提供與底層基板相互作用以形成自組裝結構之凡得瓦爾力(van der Waals forces)。此特徵可用於膜形成,用於膜改質,以及用於製備中空纖維膜。由全氟己基乙基硫 基甲基苯乙烯嵌段提供之凡得瓦爾力促進由於兩個片段(疏油及更加親水之乙烯基吡啶嵌段)在選擇性溶劑中之不相容性而引起的相分離,進而允許界定之孔形成且使得個別嵌段自組裝為界定之形態及有序疇。
在嵌段共聚物呈現具有低至例如20達因/公分之表面張力的疏油特徵(表明排斥烴)的同時,其亦呈現具有與親水性溶劑一樣高達58達因/公分之表面張力的親水特徵。在另一方面,無規共聚物為疏油的,表面張力低至例如20達因/公分。
嵌段共聚物藉由4-乙烯基吡啶(4VP)之順序聚合來合成。隨後在40小時之後添加全氟己基乙基硫基甲基苯乙烯(pfotms)。簡言之,4-乙烯基吡啶(2.63g,2.4mL氯苯中25mmol)、再結晶過氧化苯甲基(0.061g,0.25mmol)與TEMPO(0.05g,0.32mmol)之溶液裝入圓底燒瓶。在冰水浴中脫氣20分鐘之後,反應混合物在95℃之加熱浴溫下加熱3h以完全分解BPO,且在125℃下加熱40h以允許進行聚合。反應混合物隨後冷卻至室溫,且添加pfotms(6.2g,1.6mL氯苯中12.5mmol)。混合物如前所述脫氣。反應在130℃下進行40h。在用氯仿(100mL)稀釋,自己烷沈澱及乾燥之後獲得嵌段共聚物。1H NMR結果展示1/0.55之4vp/pfotms比率。DSC結果表明嵌段共聚物具有兩個Tg(49℃及140℃)。
聚[對/間-[[(全氟己基伸乙基)硫基]甲基]-苯乙烯或聚[對/間-[[(全氟己基伸乙基)氧基]甲基]-苯乙烯與4-乙烯基吡啶之無規共聚物可藉由以下合成:將1當量之4-乙烯基吡啶與1當量之於THF中合適濃度之對位或對/間-[[(全氟己基伸乙基)硫基]甲基]-苯乙烯,例如66%濃度之對/間-[[(全氟己基伸乙基)硫基]甲基]-苯乙烯混合。隨後添加3莫耳%之偶氮二異 丁腈(AIBN)且混合物脫氣20分鐘,然後反應混合物在合適溫度,例如60℃下攪拌約14小時,之後反應冷卻且於異丙醇中沈澱。隨後將溶劑傾析且沈澱物再溶解於丙酮中。丙酮中之產物於新鮮甲醇中再沈澱,使用粗燒結漏斗過濾,用異丙醇洗滌且在真空烘箱中乾燥隔夜。
無規共聚物亦可使用其他自由基聚合方法合成,例如,用於有機反應之所有熱活化及UV活化自由基引發劑可用於達成此目的。
單體比率為1:1之無規共聚物,例如聚(pfotms-ran-4vp)產出可溶於丙酮之共聚物且尤其適合於膜塗佈。
使用(2,2,6,6-四甲基哌啶-1-基)氧基(TEMPO)用於嵌段聚合允許聚合物鏈之緩慢增長率及較短鏈之再結合,從而產生具有1.2-1.5之狹窄分子量分佈之嵌段共聚物。
在一具體實例中,無規共聚物之數目平均分子量為約5KDa至約100KDa,尤其10KDa至約60KDa,[驗證]且更尤其約50KDa。數目平均分子量藉由GPC確定。
無規共聚物之平均分子量為約50kDa,而嵌段共聚物之分子量視聚合反應之持續時間而定。
嵌段共聚物可藉由任何合適方法合成,包括例如原子轉移自由基聚合(ATRP)、碘轉移聚合(ITP)、陰離子聚合及氮氧化物介導之自由基聚合(NMP)之其他形式。
嵌段共聚物之數目平均分子量為約10KDa至約400KDa,尤其50KDa至約200KDa,且更尤其約150KDa。當嵌段共聚物之分子量將視聚合之持續時間而定時,對於進行86小時而言,嵌段之平均分子量為約 400KDa。
本發明進一步提供一種包含上述共聚物中之任一者的多孔膜,其中該多孔膜係獨立的或安置於多孔載體,例如多孔聚合載體上。
在一具體實例中,多孔聚合載體係選自PVC/PAN、聚碸、聚醚碸、HDPE、PET、PPS、PPSU(聚苯碸)、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。
多孔膜可為疏油性的,尤其為具有約23達因/公分或更少,例如21達因/公分或22達因/公分之CWST之疏油膜。多孔膜可為例如按功能製備之膜,其包含用於製備多孔膜及共聚物之聚合物;或其可為塗佈有共聚物之多孔膜。
CWST可藉由合適方法量測。在一具體實例中,方法依賴於一組某種組成之溶液。各溶液具有特定表面張力。溶液表面張力以較小非相等增量處於15達因/公分至92達因/公分之範圍內。為量測膜表面張力,將其位於白光台之頂部上,將一滴某一表面張力之溶液塗覆於多孔膜表面,且記錄液滴滲透多孔膜且變為亮白色(表明光穿過多孔膜)所花費之時間。當液滴滲透多孔膜所花費之時間10秒時,視為即刻潤濕。若時間>10秒,則溶液視為將多孔膜部分潤濕。
根據本發明之一具體實例,多孔膜為多孔膜,例如奈米多孔膜,例如孔直徑在1nm與100nm之間的多孔膜或孔直徑在1μm與10μm之間的微孔膜。
多孔膜亦可為包含一或多個官能基之官能化膜。多孔膜可為例如帶電膜。多孔膜之官能化可產生達至約50達因/公分之CWST。官能基可包括例如陽離子、陰離子、極性基團,其可藉由熟習此項技術者已知之技術在形成共聚物之後引入至吡啶環上。
本發明進一步提供一種製備包含如上文所述之共聚物之多孔膜的方法,在一具體實例中,該方法包含:(i)使該共聚物溶解於溶劑中以獲得包含該共聚物之溶液;(ii)澆鑄來自(i)之該溶液以獲得塗層;(iii)使該溶劑自該塗層蒸發;以及視情況(iv)洗滌該塗層以獲得該多孔膜。
在另一具體實例中,本發明提供一種製備包含如上文所述之共聚物之多孔膜的方法,該方法包含:(i)使該共聚物及第二聚合物溶解於溶劑中以獲得包含該共聚物及該第二聚合物之溶液;(ii)使來自(i)之該溶液與造孔粉末混合以獲得混合物;(iii)澆鑄來自(ii)之混合物以獲得塗層;(iv)使該溶劑自該塗層蒸發;(v)洗滌該塗層以移除該造孔粉末;及(vi)乾燥該所得膜。
多孔膜可例如藉由以下製備:使共聚物(例如聚(pftoms-co-vp))及第二聚合物(例如PVC-AN)溶解於合適溶劑或溶劑之混合物,例如THF中且以600rpm攪拌60分鐘,隨後將實現所需孔徑之可溶 性顆粒,諸如NaHCO3顆粒加入溶液中且以1500rpm攪拌120分鐘。此混合物隨後澆鑄至玻璃板上諸如PET之基板上。在室溫下緩慢蒸發溶劑之後,將多孔膜浸沒於稀HCl溶液中隔夜以移除可溶性顆粒。視溶劑之沸點而定,所得膜於烘箱中在合適溫度,例如40℃至100℃,尤其80℃下乾燥合適時間,例如60分鐘以移除溶劑。
合適第二聚合物亦包括HDPE、PET、PPS、PPSU(聚苯碸)、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。
可用於以上方法之合適可溶性粒子包括碳酸鉀、沸石、纖維素、可溶性纖維、矽石粒子及奈米粒子;例如氧化鋅。
多孔膜可以許多方式之一包含共聚物。舉例而言,多孔膜可包括包含共聚物之塗層。多孔膜可藉由將2%共聚物溶解於合適溶劑,例如丙酮中來製備且將多孔載體,諸如PTFE浸漬於聚合物溶液2秒。經塗佈之載體於烘箱中在80℃下乾燥20分鐘,且產物浸沒於IPA中2小時,於烘箱中在80℃下乾燥30分鐘以獲得多孔膜。PTFE載體及塗佈在該載體上之多孔膜之表面的SEM顯微圖分別描繪於圖1-圖2中。
氟化鏈必須以按聚合物之體積計,至少35%存在以便賦予多孔膜疏油性。另外,為使聚合物可溶於非氟化溶劑,無規共聚物中之全氟-苯乙烯嵌段之體積比不可超過50%。
有利地,共聚物可賦予諸如多孔膜之材料以疏油特性,在材料上提供23達因或更少之表面張力而不需要後處理。包括共聚物之多孔膜 在酸、鹼、有機溶劑、氧化劑中為穩定的且在高溫下及對γ照射穩定。可在多孔膜中實現高水突破壓力及空氣流動速率,且其可易於諸如用陽離子及陰離子基團官能化。
多孔膜亦可用於自許多應用,諸如微電子行業中之水及有機流體移除諸如以下之痕量金屬:Li、Na、K(及其他第1族金屬);Mg、Ca(及其他第2族金屬);Al(及其他第3族金屬)、Pb(及其他第4族金屬)、Sb、Bi(及其他第5族金屬)以及Cd、Cr、Mo、Pd、Ag、W、V、Mn、Fe、Ni、Cu、Zn(及其他過渡金屬),例如使其降至0.005ppb之水準或低於儀器之偵測極限。
本發明包括以下具體實例,但不限於:
1)包含片段A及片段A之無規共聚物,其中片段A為聚[對/間-[[(全氟己基伸乙基)硫基]甲基]-苯乙烯或聚[對/間-[[(全氟己基伸乙基)氧基]甲基]-苯乙烯;且片段B為4-乙烯基吡啶;
2)包含片段A及片段B之嵌段共聚物,其中片段A為聚[對/間-[[(全氟己基伸乙基)硫基]甲基]-苯乙烯或聚[對/間-[[(全氟己基伸乙基)氧基]甲基]-苯乙烯;且片段B為4-乙烯基吡啶;
3)多孔膜,其包含親水性、疏水性或帶電膜及包含無規共聚物之塗層,該無規共聚物包含片段A及片段B,其中片段A為聚[對/間-[[(全氟己基伸乙基)硫基]甲基]-苯乙烯或聚[對/間-[[(全氟己基伸乙基)氧基]甲基]-苯乙烯;且片段B為4-乙烯基吡啶;其中當塗佈有共聚物時,該多孔膜為具有23達因/公分或更少之表面張力之疏油膜。
4)包含塗層之多孔PTFE膜,該塗層包含嵌段共聚物,該嵌段共聚 物包含片段A及片段B,其中片段A為聚[對/間-[[(全氟己基伸乙基)硫基]甲基]-苯乙烯或聚[對/間-[[(全氟己基伸乙基)氧基]甲基]-苯乙烯;且片段B為4-乙烯基吡啶;其中當塗佈時,該PTFE膜在烴中具有23達因/公分或更少之表面張力且在氫鍵鍵結溶劑中為親水性的,具有約58達因/公分或更少之表面張力;
5)包含嵌段共聚物之自組裝膜,該嵌段共聚物包含片段A及片段B;其中片段A為聚[對/間-[[(全氟己基伸乙基)硫基]甲基]-苯乙烯或聚[對/間-[[(全氟己基伸乙基)氧基]甲基]-苯乙烯;且片段B為4-乙烯基吡啶;根據本發明之具體實例,多孔膜可具有多種組態,包括平面、平板、摺疊、管狀、螺旋形及中空纖維。在一個具體實例中,多孔膜為中空纖維膜。
根據本發明之具體實例之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,提供一種過濾裝置,其包含: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器模組。在一說明性具體實例中,過濾裝置包含交叉流過濾模組、殼體,殼體包含入口、包含濃縮物出口之第一出口及包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。可採用具有合適形狀且提供一入口及一或多個出口之任何殼體。
殼體可由任何合適剛性不可滲透之材料製造,包括任何不可滲透之熱塑性材料,其與處理中之流體相容。舉例而言,殼體可由以下製造:金屬,諸如不鏽鋼;或聚合物,例如透明或半透明聚合物,諸如丙烯酸樹脂、聚丙烯樹脂、聚苯乙烯樹脂或聚碳酸酯樹脂。
根據本發明之具體實例之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、生產超純水、處理工業用水及表層水、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(例如移除病毒))、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(包括原位)、細胞捕獲及/或過濾細胞培養物流體。可替代地或另外,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/或氣體通過但不允許液體通過)。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。
本發明進一步提供一種過濾流體之方法,該方法包含使流體通過上述多孔膜中之任一者。舉例而言,痕量金屬雜質在下一代半導體及微電子材料製造中不斷引起問題。本發明之一個具體實例包含一種自流體,尤其微電子流體移除金屬之方法,其係藉由使含金屬流體通過包括共聚物之多孔膜且自流體移除金屬。在一個具體實例中,本發明方法包括使含金屬流體通過包括共聚物及官能基之官能化多孔膜且自流體移除金屬。官能化膜可將約99%之大多數痕量金屬自流體移除。
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疇。
實施例1
此實施例說明根據本發明之一具體實例製備全氟己基乙基硫醇與乙烯基吡啶之嵌段共聚物或聚(pfotms-嵌段-4vp)。
在40小時之後添加4-乙烯基吡啶(4VP)及全氟己基乙基硫基甲基苯乙烯(pfotms)。將4VP(2.63g,2.4mL氯苯中25mmol)、再結晶過氧化苯甲基(0.061g,0.25mmol)與TEMPO(0.05g,0.32mmol)之溶液裝入圓底燒瓶中。在冰水浴中脫氣20分鐘之後,反應混合物在95℃下加熱3h以完全分解BPO,且在125℃下加熱40h以允許進行聚合。反應混合物隨後冷卻至室溫,且添加pfotms(6.2g,1.6mL氯苯中12.5mmol)。混合物如前所述脫氣。反應在130℃下進行40h。在用氯仿(100mL)稀釋,自 己烷沈澱及乾燥之後獲得嵌段共聚物。NMR結果展示1/0.55之4vp/pfotms比率。DSC結果表明嵌段共聚物具有兩個Tg(49℃及140℃)。
實施例2
此實施例說明根據本發明之一具體實例製備全氟己基乙基硫醇與乙烯基吡啶之無規共聚物或聚(pfotms-ran-4vp)。
在60℃下使全氟己基乙基硫醇甲基苯乙烯(10mmol)溶解於含有乙醇(10mL)之250mL圓底燒瓶中,且添加4-乙烯基吡啶(10mmol)。反應混合物用氮氣淨化20分鐘且隨後添加AIBN(360mg,0.989mmol,10莫耳%),且再繼續淨化5分鐘。然後,反應混合物在60℃下攪拌16小時。使所獲得之產物冷卻至室溫,且用水及丙酮依序沖洗,且在真空烘箱中用P2O5乾燥隔夜。
全氟辛基乙基硫醇與乙烯基吡啶之無規共聚物或聚(pfdtms-ran-4vp)使用相同步驟合成。
實施例3
多孔膜藉由以下製備:將聚(pftoms-共-vp)與PVC-AN在THF中混合且以600rpm攪拌60分鐘,添加NaHCO3顆粒,且以1500rpm攪拌120分鐘。此混合物澆鑄至玻璃板上之PET基板上。在室溫下緩慢蒸發THF之後,將所得澆鑄物浸沒於稀HCl溶液中隔夜以移除碳酸氫鈉顆粒。將所得膜於烘箱中在80℃下乾燥60分鐘。
實施例4
此實施例說明無規共聚物及多孔膜之一些特性。表1闡述共聚物及均聚物之玻璃轉移溫度
表2說明經塗佈之膜之表面張力量測及空氣流/水突破特性化。
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,其引用程度就如同個別及特定地指示各參考文獻以引用之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),應將術語「一(a/an)」及「該(the)」及「至少一個(at least one)」及類似涉及對象之使用解釋為涵蓋單數與複數兩者。除非本文另外指示或與上下文明顯矛盾,否則使用術語「至少一個」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)」)應解釋為意謂選自所列舉項目之一個項目(A或B)或所列舉項目之兩個或超過兩個之任何組合(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)」應解釋為開放式術語(亦即,意謂「包括但不限於(including, but not limited to,)」)。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另外與上下文明顯矛盾,否則本文所述之所有方法可以任何合適順序進行。除非另外主張,否則使用本文所提供之任何及所有實例或例示性語言(例如「諸如」)僅意欲更好地闡明本發明而非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示實施本發明所必需之任何未主張要素。
本文描述本發明之較佳具體實例,其包括本發明者已知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技術者而言可變得顯而易見。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描述之其他方式來實施本發明。因此,在適用法律允許下,本發明包括隨附於本文之申請專利範圍中所敍述之主題的所有修改及同等物。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呈其所有可能變化形式之任何組合。
圖1描繪PTFE載體之SEM顯微圖。
圖2描繪根據本發明之一具體實例的塗佈在PTFE載體上之共聚物之表面的SEM顯微圖。
Claims (13)
- 一種包含聚合單體單元I及聚合單體單元II之共聚物,其中單體單元I具有式A-X-CH 2-B,其中A為Rf-(CH 2)n,Rf為式CF 3-(CF 2) x-之全氟烷基,其中x為3-12,n為1-6,X為O或S,且B為乙烯基苯基,且單體單元II為乙烯基吡啶。
- 如申請專利範圍第1項之共聚物,其中n=2。
- 如申請專利範圍第1項或第2項之共聚物,其中x=4-8。
- 如申請專利範圍第1項至第3項中任一項之共聚物,其中該乙烯基吡啶為4-乙烯基吡啶。
- 如申請專利範圍第1項至第4項中任一項之共聚物,該共聚物為嵌段共聚物。
- 如申請專利範圍第1項至第4項中任一項之共聚物,該共聚物為無規共聚物。
- 一種多孔膜,其包含安置於多孔載體上之如申請專利範圍第1項至第6項中任一項之共聚物。
- 如申請專利範圍第7項之多孔膜,其中該多孔載體為多孔聚合載體。
- 如申請專利範圍第8項之多孔膜,其中該多孔聚合載體係選自PVC/PAN、聚碸、聚醚碸、HDPE、PET、PPS、PPSU(聚苯碸)、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。
- 一種製備包含共聚物之多孔膜之方法, 其中該共聚物包含聚合單體單元I及聚合單體單元II,其中單體單元I具有式A-X-CH 2-B,其中A為Rf-(CH 2)n,Rf為式CF 3-(CF 2) x-之全氟烷基,其中x為3-12,n為1-6,X為O或S,且B為乙烯基苯基,且單體單元II為乙烯基吡啶;該方法包含:(i)使該共聚物溶解於溶劑中以獲得包含該共聚物之溶液;(ii)澆鑄來自(i)之該溶液以獲得塗層;(iii)使該溶劑自該塗層蒸發;以及視情況(iv)洗滌該塗層以獲得該多孔膜。
- 一種製備包含共聚物之多孔膜之方法,其中該共聚物包含聚合單體單元I及聚合單體單元II,其中單體單元I具有式A-X-CH 2-B,其中A為Rf-(CH 2)n,Rf為式CF 3-(CF 2) x-之全氟烷基,其中x為3-12,n為1-6,X為O或S,且B為乙烯基苯基,且單體單元II為乙烯基吡啶;該方法包含:(i)使該共聚物及第二聚合物溶解於溶劑中以獲得包含該共聚物及該第二聚合物之溶液;(ii)將來自(i)之該溶液與造孔粉末混合以獲得混合物;(iii)澆鑄來自(ii)之該混合物以獲得塗層;(iv)使該溶劑自該塗層蒸發;(v)洗滌該塗層以移除該造孔粉末;及(vi)乾燥該所得膜。
- 一種多孔膜,其藉由如申請專利範圍第10項或第11項之方法製備。
- 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7項至第9項或第12項中任一項之多孔膜。
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