CN103534011A - 用于油水分离的高亲水并且高疏油的膜 - Google Patents
用于油水分离的高亲水并且高疏油的膜 Download PDFInfo
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- CN103534011A CN103534011A CN201280020116.0A CN201280020116A CN103534011A CN 103534011 A CN103534011 A CN 103534011A CN 201280020116 A CN201280020116 A CN 201280020116A CN 103534011 A CN103534011 A CN 103534011A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000012528 membrane Substances 0.000 title claims abstract description 15
- 238000000926 separation method Methods 0.000 title description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 229920001002 functional polymer Polymers 0.000 claims abstract description 39
- 239000011159 matrix material Substances 0.000 claims abstract description 30
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 18
- 238000007711 solidification Methods 0.000 claims description 17
- 230000008023 solidification Effects 0.000 claims description 17
- -1 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 229920006254 polymer film Polymers 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
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- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000003921 oil Substances 0.000 description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- 239000002033 PVDF binder Substances 0.000 description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 15
- 230000004907 flux Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000009987 spinning Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000000413 hydrolysate Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- FDKXTQMXEQVLRF-ZHACJKMWSA-N (E)-dacarbazine Chemical compound CN(C)\N=N\c1[nH]cnc1C(N)=O FDKXTQMXEQVLRF-ZHACJKMWSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical group FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical compound NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 description 1
- UPJMWRYBLNHWQS-UHFFFAOYSA-N 4-methylbenzenesulfonic acid;toluene Chemical compound CC1=CC=CC=C1.CC1=CC=C(S(O)(=O)=O)C=C1 UPJMWRYBLNHWQS-UHFFFAOYSA-N 0.000 description 1
- VHJFWJXYEWHCGD-UHFFFAOYSA-N 4-nonyl-2-(4-nonylpyridin-2-yl)pyridine Chemical group CCCCCCCCCC1=CC=NC(C=2N=CC=C(CCCCCCCCC)C=2)=C1 VHJFWJXYEWHCGD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- YSRNIQSBBAUXOX-UHFFFAOYSA-N CC(C)C([O])=O Chemical compound CC(C)C([O])=O YSRNIQSBBAUXOX-UHFFFAOYSA-N 0.000 description 1
- IQMFNOYOKCHVEH-UHFFFAOYSA-N CCCCCCCCCC=C.CC(C)(C)Br Chemical compound CCCCCCCCCC=C.CC(C)(C)Br IQMFNOYOKCHVEH-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 229920006373 Solef Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- DCPMPXBYPZGNDC-UHFFFAOYSA-N hydron;methanediimine;chloride Chemical compound Cl.N=C=N DCPMPXBYPZGNDC-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
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- 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
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
-
- 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
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
-
- 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
- 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
- B01D71/34—Polyvinylidene fluoride
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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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
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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
- B01D71/78—Graft polymers
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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
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/08—Thickening liquid suspensions by filtration
- B01D17/085—Thickening liquid suspensions by filtration with membranes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Mechanical Engineering (AREA)
Abstract
本发明涉及一种用于使油与水分离的聚合物膜,所述聚合物膜的孔径为0.005μm至5μm,厚度为50μm至1,000μm,水接触角为0°至60°,油接触角为40°至100°。所述膜包含疏水的基质聚合物以及含疏水骨架和侧链的功能聚合物。每一个所述侧链具有疏油的末端段和亲水的内部段。所述基质聚合物与所述功能聚合物的重量比为99∶1至1∶9。还公开了用于制备上述膜的方法。
Description
背景技术
聚合物膜可用于从水分离液滴体积小于150μm的分散油或乳化油。
例如,使用孔径为0.01~0.1μm的超滤(UF)膜处理含油工业废水。见T.Bilstad和E.Espedal的Membrane Separation of Produced Water,Water Science and Technology34(9),239-246(1996)。UF膜具有严重的膜污染问题。见T.Bilstad和E.Espedal(1996),S.M.Santos和M.R.Wiesner(1997)。在油以降低膜性能的方式沉积在膜表面上或进入膜的孔隙中时,发生膜污染。这是在处理含油废水中广泛使用UF的主要障碍。
需要耐污膜以有效和经济地使油与水分离。
发明简述
本发明本基于对有效使油与水分离而无显著油污染的高亲水并且高疏油的膜的意外发现。
本发明的一个方面涉及下式的聚合物,其可用于制备本发明的膜:
在该式中,W为卤素,m为10至1000(例如,10至500或10至20),n为1至1000(例如,5至500或5至10),x为50至1000(例如,50至500或90至100),y为1至200(例如,1至100或5至10),x1为1至100(例如,5至50或5至10),y1为1至100(例如,5至50或5至10)。
如上式所示,该聚合物包含聚偏氟乙烯(“PVDF”)骨架和聚丙烯酸酯侧链。同样如该式所示,每一个侧链包含疏油的末端段(即,全氟烷基)和亲水的内部段(即,聚乙二醇基团)。
本发明的另一方面涉及包含疏水的基质聚合物和亲水并且疏油的功能聚合物的膜。所述功能聚合物包含疏水骨架和侧链,每一个所述侧链都包含疏油的末端段和亲水的内部段。功能聚合物的实例包括但不限于上式涵盖的聚合物。
上述膜可通过包括以下步骤的方法制备:(i)将基质聚合物和功能聚合物溶解在共混溶剂中以获得共混溶液;(ii)将所述共混溶液脱气以获得脱气溶液;以及(iii)将所述脱气溶液浸入凝固液中以形成聚合物膜。若需要,可通过将脱气溶液挤压进凝固液来实施浸入步骤,以形成中空纤维膜。
本发明的膜优选地具有孔径为0.005μm至5μm(例如,0.05μm至0.5μm或0.1μm至0.3μm),厚度为50μm至1,000μm(例如,100μm至500μm或250μm至350μm),水接触角为0°至60°(例如,5°至55°或10°至50°),以及油接触角为40°至100°(例如,40°至95°或40°至90°)。基质聚合物与功能聚合物的重量比广泛地为99∶1至1∶9(例如,95∶5至6∶4或9∶1至7∶3)。
以下说明书中将给出本文一个或更多个实施方案的细节。通过说明书和权利要求书,本发明的其他特征、主题和优点将变得明显。
发明详述
本发明提供了用于使油与水分离的多孔膜。所述膜高度亲水并且高度疏油,允许水通过而截留油。
所述膜可以是平片、中空纤维或珠,其孔径为0.005~5μm,厚度为50~1000μm。
所述膜的亲水性可用水接触角量化,其优选地为0~60°。另一方面,所述膜的疏油性可用油接触角量化,其优选地为40~100°。
所述膜包含基质聚合物和功能聚合物二者。
疏水的基质聚合物为膜提供支撑。基质聚合物的实例包括但不限于:PVDF、聚四氟乙烯、聚碳酸酯、聚对苯二甲酸乙二酯、聚丙烯、聚酰胺以及这些聚合物中两种或更多种的组合。
作为基质聚合物的PVDF可以是均聚物、共聚物、三元共聚物、高聚物或其组合。其可包含大于70重量%(例如,75重量%或以上)的偏二氟乙烯单元。用作基质聚合物的示例性PVDF共聚物包含71至99重量%的偏二氟乙烯单元和1至29重量%的六氟丙烷单元。可使用的PVDF分子量为1.0×104至1.0×106(优选地1.0×105至1.0×106,更优选地4.0×1o5至8.0×105)。通常市售PVDF的分子量为1×105至1×106。例如,Solvay公司的SolefPVDF的分子量为4.0×105至5.5×105。
对于功能聚合物,其包含疏水骨架和亲水并且疏油的侧链。与其侧链一样,功能聚合物亲水并且疏油。
所述骨架可以是PVDF、聚四氟乙烯、聚碳酸酯、聚对苯二甲酸乙二酯、聚丙烯、聚酰胺或其组合。在一个实施方案中,所述骨架包含分子量1.0×104至1.0×106(优选地5.0×104至5.0×105,更优选地1.0×105至2.5×105)的PVDF。示例的PVDF骨架包含71至99重量%的偏二氟乙烯单元和1至29重量%的氯三氟乙烯单元。
对于侧链,每一个侧链包含疏油的末端段和亲水的内部段。
末端段的一个实例是分子量40至4000(优选地200至2000,更优选地200至400)的全氟烷基。
内部段的实例包括聚乙二醇、聚(N-乙烯吡咯烷酮)、聚丙烯酰胺、聚丙烯酸、聚磺苯乙烯(polystyrenesulfonate)或其组合。这些内部段具有40至4500(优选地200至2500,更优选地220至440)的分子量。
下式涵盖了可用于制备本发明的膜的功能聚合物:
在该式中,W为卤素,即F、Cl、Br和I,m可以为10至1000,n可以为1至1000,x可以为50至1000,y可以为1至200,x1可以为1至100,y1可以为1至100。
这些示例的亲水并且疏油的功能聚合物,每一个都包含PVDF骨架和聚丙烯酸酯侧链。每一个侧链包含全氟烷基末端段和聚乙二醇内部段。
这些功能聚合物可如下得到:
将PVDF(例如,聚(偏二氟乙烯-共-氯三氟乙烯))溶解在溶剂中以得到聚合物溶液。所述溶剂可以是N-甲基-2-吡咯烷酮、二甲基甲酰胺、二甲基乙酰胺、四甲基脲、二甲基亚砜、磷酸三乙酯或其组合。
向PVDF溶液中添加配体和催化剂,之后添加单体。
所述配体可以是1,1,1-三(2-溴异丁酰基氧甲基)乙烷、2-溴异丁酸10-十一烯基酯、2-溴异丁酸2-羟乙酯、4,4′-二壬基-2,2′-联吡啶、双[2-(2′-溴异丁酰基氧)乙基]二硫化物、六(2-溴异丁酸)二季戊四醇酯、2-溴异丁酸十二酯、双(2-溴异丁酸)亚乙酯,1,1,4,7,7-五甲基二亚乙基三胺、2-溴异丁酸十八酯、四(2-溴异丁酸)季戊四醇酯、三(2-吡啶基甲基)胺、三[2-(二甲氨基)乙基]胺或其组合。
所述催化剂可以是铜催化剂,例如,CuCl和CuBr。
所述单体可以是苯乙烯、丙烯酸酯、丙烯酰胺、丙烯腈或其组合,其全部至少包含使生长基团稳定的官能团。在使用丙烯酸酯单体时,其可以是丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸叔丁酯、丙烯酸2-乙基己酯或它们的组合。
将所得混合物加热以得到接枝产物,任选地,将其从混合物中分离或甚至纯化。
然后,将由此得到的接枝产物优选地在升高的温度下在溶剂中用酸水解。所述酸可以是HCl、H2SO4、对甲苯磺酸、三氟乙酸或其组合。所述溶剂可以是甲苯、N-甲基-2-吡咯烷酮、二甲基甲酰胺、二甲基乙酰胺、四甲基脲、二甲基亚砜、磷酸三乙酯或其组合。
将由此得到的水解产物任选地分离/纯化和干燥。
然后在偶联剂和催化剂存在下在溶剂中使水解产物与表面活性剂偶联,得到功能聚合物。所述溶剂的实例包括但不限于:N-甲基-2-吡咯烷酮、二甲基甲酰胺、二甲基乙酰胺、四甲基脲、二甲基亚砜、磷酸三乙酯及其组合
所述表面活性剂是亲水并且疏油的。其可以是含羟基的含氟表面活性剂。
所述偶联剂可以是二环己基碳二亚胺、二异丙基碳二亚胺、乙基-(N’,N’-二甲氨基)丙基碳二亚胺盐酸盐或其组合。
所述催化剂可以是4-(二甲氨基)-吡啶、β,β,β-三溴乙酯、三丁基膦、三氟甲磺酸钪、三氟甲磺酸三甲基硅酯、三氟甲磺酸二苯胺盐、三氟甲磺酸全氟苯胺盐或其组合。
任选地分离/纯化和干燥所述功能聚合物。
可使用由此制备的功能聚合物按照下文所述程序制备本发明的膜:
通过将基质聚合物和功能聚合物(例如,以10至30重量%组合)溶解在共混溶剂中并且任选地搅拌(例如,800rpm)一段时间(例如,2小时),得到共混溶液。优选地,在空气密封容器中制备共混溶液以防止溶剂蒸发。
共混溶剂是可溶解基质聚合物和功能聚合物并且可与凝固液混合的溶剂。共混溶剂的实例包括但不限于:四氢呋喃、甲基乙基酮、二甲基甲酰胺、二甲基乙酰胺、四甲基脲、二甲基亚砜、磷酸三甲酯、N-甲基-2-吡咯烷酮、丁内酯、异佛尔酮、乙酸卡必醇酯(carbitor acetate)或其混合物。若需要,可通过加热随后冷却和过滤得到均匀的聚合物共混溶液。
然后将由此得到的共混溶液脱气(例如,通过将溶液离心),使其中不含有任何气泡。脱气所需时间取决于溶液粘度。
在脱气之后,将聚合物共混溶液优选地在20℃至100℃下、更优选地在60℃至80℃下浸入凝固液中以形成本发明的膜。
凝固液(即,本领域中普遍已知的凝固非溶剂)是可与共混溶剂混合并且添加到共混溶液后中导致形成聚合物膜的液体。凝固液可以是水、甲醇、乙醇、丙醇、异丙醇或其混合物。
若需要,可通过用湿纺设备将共混溶液挤压进凝固液中以形成中空纤维膜来实施共混溶液与凝固液的浸入。例如,通过喷丝头,将共混溶液挤压进凝固液中,同时通过注射泵向由此形成的纤维的内腔中输送相同或不同的凝固液。凝固液表面与喷丝头的出口之间的距离(即,空气间隙)根据待制备的中空纤维膜的孔径和表面粗糙度可以为0至50cm。通常,较大的空气间隙产生具有较低渗透通量和较高溶质分离性能的膜。可通过压缩氮气控制挤压进凝固液中的共混溶液的流速。可通过向喷丝头供应凝固液的注射泵控制通过纤维内腔的凝固液。
本领域技术人员可不需要过多试验来确定本发明膜的制备条件,例如所有反应物的相对浓度、混合/反应的温度、反应/混合/脱气的持续时间、聚合物共混溶液和凝固液的流速、以及过滤器和喷丝头的大小。
以下的特定实施例应解释为仅作示例,而不是以任何方式限制本公开内容的其余部分。无须赘述,相信本领域技术人员可基于本文的描述最大程度地利用本发明。本文引用的全部出版物通过引用整体并入本文。
实施例1:功能聚合物的制备
在用N2净化的气密烧瓶中将聚(偏二氟乙烯-共-氯三氟乙烯)溶解在N-甲基-2-吡比咯烷酮中。将混合物在200至1000rpm下搅拌并且在60至90℃下加热,得到均匀的粘性聚合物溶液。聚合物浓度为10~30重量%。
向上述溶液中添加CuCl(1~5重量%)和五甲基二亚乙基三胺(2~10重量%),之后添加丙烯酸叔丁酯(10至15重量%)。
将所得混合物在50至90℃下加热0.5至4小时。冷却之后,将混合物倒入水中以沉淀出含聚丙烯酸酯侧链的接枝产物,将其用水清洗。
在80至95℃下将接枝产物(1至10克)在对甲苯磺酸甲苯溶液(100mL,10~30重量%)中搅拌4至8小时。冷却之后,将酸性溶液倒入水中,用水清洗,并且在冷冻干燥机中干燥,得到含聚(丙烯酸)侧链的水解产物。
向所述水解产物的二甲基甲酰胺溶液(4~8重量%)中添加ZonylFSN-100含氟表面活性剂(分子量950,2~4重量%)、二环己基碳二亚胺(0.5~1重量%)和4-(二甲氨基)-吡啶(0.01~0.05重量%)。将所得混合物在环境温度下搅拌48~120小时,然后倒入水中,用水清洗,并且在冷冻干燥机中干燥,得到功能聚合物。
实施例2:聚合物共混溶液的制备
在加热至70至100℃的密封容器中,向二甲基甲酰胺中添加PVDF和在实施例1中制备的功能聚合物(10~30重量%组合,PVDF:功能聚合物=7∶3)。将混合物在400至1000rpm下搅拌1~5小时并且冷却至环境温度,得到共混溶液。
将共混溶液在气密的不锈钢掺杂容器中并且通过压缩氮气在2巴压力下加压通过15μm不锈钢过滤器过滤。
通过将溶液在3000至8000rpm下离心5至10分钟,将过滤的共混溶液脱气。
实施例3:中空纤维膜的制作
通过压缩氮气驱动,使用含1.5/0.5的OD/ID的喷丝头的喷丝设备将实施例2的共混溶液挤压进水浴中以形成中空纤维膜。同时,注射泵通过喷丝头内部的孔环向纤维内腔供应水。
空气间隙为0.5cm。用压缩氮气将聚合物共混溶液的流速保持为4mL/分钟。用注射泵将水的流速控制为1mL/分钟。凝固温度为60至80℃。
最后,将由此得到的中空纤维膜在空气中干燥。
实施例4:除油效率的测量
研究在实施例3中制备的中空纤维膜从水中去除乳剂原油的效率。
在死端过滤系统上进行膜过滤实验,用具有提供动力流和压力的泵头(Micropump,170-000)的微量泵(ISMATEC IP65)驱动。用TOC分析器(SHIMADZU,TOC-V)确定油浓度。用与计算机(用于数据收集和渗透通量计算)连接的数字秤测量渗透重量。通过将0.5g十六烷与1L水在均质器(Cole-Parmer,Labgen700)中在14,000rpm下混合20分钟来制备油/水乳剂(500ppm)。
出乎意料的是,如以下结果所示,膜最有效地使油与水分离:
除油效率99%
循环1:
J0 54.93L·m-2·h-1
RFD 49%
RFR 71%
RFR_B 99%
循环2:
J0 54.49L·m-2·h-1
RFD_1 52%
RFR_1 68%
RFR B1 99%
J0是渗透通量,RFD是循环1的相对通量下降,RFR是循环1的相对通量恢复,RFR_B是循环1在反洗30分钟后的相对通量恢复,RFD_1是循环2的相对通量下降,RFR_1循环2的相对通量恢复,RFR_B1是循环2在反洗30分钟后的相对通量恢复。
同样出乎意料地,如通过低相对通量下降和高相对通量恢复证明的,膜显示了对油污的强耐受。
其他实施方案
在本说明书中公开的全部特征可任意组合来合并。本说明书中公开的每一个特征可用起相同、等效或类似目的的可替选特征代替。因此,除非明确指出,否则公开的每一个特征仅是一般系列等效或类似特征的实例。
实际上,为了达到使油与水分离的目的,本领域技术人员可设计包含亲水侧链、疏油侧链和亲水并且疏油侧链的任意组合的膜。另外,可设计这些侧链的比率、长度和密度以允许水通过膜而截留油。
从上文描述中,技术人员可容易地确定本发明的基本特征,并且不脱离其精神和范围可对本发明进行各种改变和修改以使本发明适合于各种用途和条件。因此,其他实施方案也在要求保护的范围之内。
Claims (20)
1.一种下式的聚合物:
其中W是卤素,m是10至1000,n是1至1000,x是50至1000,y是1至200,x1是1至100,y1是1至100。
2.根据权利要求1所述的聚合物,其中m是10至500,n是5至500,x是50至500,y是1至100,x1是5至50,y1是5至50。
3.根据权利要求2所述的聚合物,其中m是10至20,n是5至10,x是90至100,y是5至10,x1是5至10,y1是5至10。
4.一种用于使油与水分离的聚合物膜,所述膜包含:
疏水的基质聚合物,和
功能聚合物,其包含疏水骨架和侧链,每一个所述侧链具有疏油的末端段和亲水的内部段,其中所述膜的孔径为0.005μm至5μm,厚度为50μm至1,000μm,水接触角为0°至60°,油接触角为40°至100°,所述基质聚合物与所述功能聚合物的重量比为99∶1至1∶9。
5.根据权利要求4所述的膜,其中所述膜的孔径为0.05μm至0.5μm,厚度为100μm至500μm,水接触角为5°至55°,油接触角为40°至95°,所述基质聚合物与所述功能聚合物的重量比为95∶5至6∶4。
6.根据权利要求5所述的膜,其中所述膜的孔径为0.1μm至0.3μm,厚度为250μm至350μm,水接触角为10°至50°,油接触角为40°至90°,所述基质聚合物与所述功能聚合物的重量比为9∶1至7∶3。
7.根据权利要求4所述的膜,其中所述基质聚合物是聚偏氟乙烯、聚四氟乙烯、聚碳酸酯、聚对苯二甲酸乙二酯、聚丙烯、聚酰胺或其组合;所述骨架是聚偏氟乙烯、聚四氟乙烯、聚碳酸酯、聚对苯二甲酸乙二酯、聚丙烯、聚酰胺或其组合;所述疏油的末端段是全氟烷基;所述亲水的内部段是聚乙二醇、聚(N-乙烯吡咯烷酮、)基团、聚丙烯酰胺、聚丙烯酸、聚磺苯乙烯或其组合。
8.根据权利要求7所述的膜,其中所述膜的孔径为0.05μm至0.5μm,厚度为100μm至500μm,水接触角为5°至55°,油接触角为40°至95°,所述基质聚合物与所述功能聚合物的重量比为95∶5至6∶4。
9.根据权利要求8所述的膜,其中所述膜的孔径为0.1μm至0.3μm,厚度为250μm至350μm,水接触角为10°至50°,油接触角为40°至90°,所述基质聚合物与所述功能聚合物的重量比为9∶1至7∶3。
10.根据权利要求7所述的膜,其中所述基质聚合物是聚偏氟乙烯,所述功能聚合物是权利要求所述的聚合物。
11.根据权利要求10所述的膜,其中所述膜的孔径为0.05μm至0.5μm,厚度为100μm至500μm,水接触角为5°至55°,油接触角为40°至95°,所述基质聚合物与所述功能聚合物的重量比为95∶5至6∶4。
12.根据权利要求11所述的膜,其中所述膜的孔径为0.1μm至0.3μm,厚度为250μm至350μm,水接触角为10°至50°,油接触角为40°至90°,所述基质聚合物与所述功能聚合物的重量比为9∶1至7∶3。
13.根据权利要求7所述的膜,其中所述基质聚合物是聚偏氟乙烯,所述功能聚合物是权利要求2所述的聚合物。
14.根据权利要求13所述的膜,其中所述膜的孔径为0.05μm至0.5μm,厚度为100μm至500μm,水接触角为5°至55°,油接触角为40°至95°,所述基质聚合物与所述功能聚合物的重量比为95∶5至6∶4。
15.根据权利要求14所述的膜,其中所述膜的孔径为0.1μm至0.3μm,厚度为250μm至350μm,水接触角为10°至50°,油接触角为40°至90°,所述基质聚合物与所述功能聚合物的重量比为9∶1至7∶3。
16.根据权利要求7所述的膜,其中所述基质聚合物是聚偏氟乙烯,所述功能聚合物是权利要求3所述的聚合物。
17.根据权利要求16所述的膜,其中所述膜的孔径为0.05μm至0.5μm,厚度为100μm至500μm,水接触角为5°至55°,油接触角为40°至95°,所述基质聚合物与所述功能聚合物的重量比为95∶5至6∶4。
18.根据权利要求17所述的膜,其中所述膜的孔径为0.1μm至0.3μm,厚度为250μm至350μm,水接触角为10°至50°,油接触角为40°至90°,所述基质聚合物与所述功能聚合物的重量比为9∶1至7∶3。
19.一种用于制备聚合物膜的方法,其包括:
将基质聚合物和功能聚合物溶解在共混溶剂中以获得共混溶液;
将所述共混溶液脱气以获得脱气溶液;以及
将所述脱气溶液浸入凝固液中以形成所述聚合物膜,
其中所述基质聚合物是疏水的,所述功能聚合物包含疏水骨架和亲水的侧链,每一个所述侧链具有疏油的末端段和亲水的内部段。
20.根据权利要求19所述的方法,其中所述浸入步骤是通过将所述脱气溶液挤压进所述凝固液中以形成中空纤维膜来实施的。
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