CN105367778A - 亲水嵌段共聚物和由其制备的膜 - Google Patents
亲水嵌段共聚物和由其制备的膜 Download PDFInfo
- Publication number
- CN105367778A CN105367778A CN201510536472.3A CN201510536472A CN105367778A CN 105367778 A CN105367778 A CN 105367778A CN 201510536472 A CN201510536472 A CN 201510536472A CN 105367778 A CN105367778 A CN 105367778A
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- Prior art keywords
- group
- alkanethiol
- formula
- segmented copolymer
- hydrophobic polymer
- Prior art date
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- Granted
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- 239000012528 membrane Substances 0.000 title abstract description 17
- 229920001400 block copolymer Polymers 0.000 title abstract description 12
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 50
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 36
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 36
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 31
- -1 1,2-dihydroxypropyl group Chemical group 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims description 48
- 239000000126 substance Substances 0.000 claims description 45
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 14
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 13
- 239000004697 Polyetherimide Substances 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- 125000003368 amide group Chemical group 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 229920001601 polyetherimide Polymers 0.000 claims description 13
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 13
- 125000002252 acyl group Chemical group 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 10
- 229920002530 polyetherether ketone Polymers 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- 239000004417 polycarbonate Substances 0.000 claims description 8
- 229920000515 polycarbonate Polymers 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 125000004423 acyloxy group Chemical group 0.000 claims description 7
- 125000004647 alkyl sulfenyl group Chemical group 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000007766 curtain coating Methods 0.000 claims description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 6
- 229920001721 polyimide Polymers 0.000 claims description 6
- 239000004962 Polyamide-imide Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 5
- 229920001652 poly(etherketoneketone) Polymers 0.000 claims description 5
- 229920002312 polyamide-imide Polymers 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- 125000003282 alkyl amino group Chemical group 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 2
- 235000018417 cysteine Nutrition 0.000 claims description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- 229960001708 magnesium carbonate Drugs 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000012530 fluid Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- 238000005266 casting Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 229960003761 propamidine Drugs 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 0 CC*C(C*1*(C)C1)COCC=C*CCN(C)C Chemical compound CC*C(C*1*(C)C1)COCC=C*CCN(C)C 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012434 nucleophilic reagent Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- CSJDJKUYRKSIDY-UHFFFAOYSA-N 1-sulfanylpropane-1-sulfonic acid Chemical compound CCC(S)S(O)(=O)=O CSJDJKUYRKSIDY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006596 Alder-ene reaction Methods 0.000 description 1
- KVSIREVXWGXZOV-UHFFFAOYSA-N CC(C)Oc(cc1)ccc1-c1ccccc1 Chemical compound CC(C)Oc(cc1)ccc1-c1ccccc1 KVSIREVXWGXZOV-UHFFFAOYSA-N 0.000 description 1
- COTOUBYYTMGCGA-UHFFFAOYSA-N CN(C)[S] Chemical compound CN(C)[S] COTOUBYYTMGCGA-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XOGTZOOQQBDUSI-UHFFFAOYSA-M Mesna Chemical compound [Na+].[O-]S(=O)(=O)CCS XOGTZOOQQBDUSI-UHFFFAOYSA-M 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 229920002556 Polyethylene Glycol 300 Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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Abstract
公开了一种式A-B-A(I)或者A-B(II)的嵌段共聚物,其中嵌段A是:(i)烯丙基缩水甘油醚的聚合物;或者(ii)烯丙基缩水甘油醚的聚合物,其中所述烯丙基中的一个或多个被1,2-二羟基丙基或式-(CH2)a-S-(CH2)b-X的基团代替,其中a、b和X如本文所定义。发现了所述嵌段共聚物在由芳族疏水性聚合物如聚醚砜制备多孔膜中作为湿润剂的用途。还公开了这种嵌段共聚物的制备方法和由其制备的多孔膜。
Description
发明背景
芳族聚合物,如聚砜、聚醚砜、聚(酞嗪醚砜酮)、聚(对苯硫醚)、聚醚酰亚胺、聚酰亚胺、聚氧化亚苯基(polyphenyleneoxide)、聚苯醚(polyphenyleneether)、聚醚醚酮,由于它们的化学稳定性、可加工性、机械强度、柔韧性和热稳定性,可用于制备多孔膜。因为这些聚合物通常是疏水性的,由这些聚合物制备的膜是疏水性的,因此缺乏所需的表面性质,如润湿性、低蛋白质吸附、抗血栓和受控表面化学反应。
已经进行了尝试来改进由芳族聚合物制成的膜的一种或多种表面性质。例如,已用高能辐射或等离子体处理膜以赋予亲水性。在其他实例中,已将亲水性单体接枝到疏水性膜的表面。也已经进行了尝试来用水溶性聚合物如聚乙二醇或聚乙烯吡咯烷酮涂覆疏水性膜。然而,以上改进性质、特别是亲水性的尝试具有一个或多个缺点,如缺乏再现性、缺乏改性稳定性和/或孔堵塞。
上述表明,对于由芳族疏水性聚合物形成的亲水性膜以及对于赋予由芳族疏水性聚合物形成的膜以亲水性的方法,存在未能满足的需要。
发明概述
本发明提供了一种亲水性嵌段共聚物,其可用于赋予由芳族疏水性聚合物形成的膜以亲水性。
本发明提供式A-B-A(I)或者A-B(II)的嵌段共聚物,其中嵌段A是:(i)烯丙基缩水甘油醚的聚合物,所述聚合物具有烯丙基;或者(ii)烯丙基缩水甘油醚的聚合物,其中所述烯丙基中的一个或多个被1,2-二羟基丙基或式-(CH2)a-S-(CH2)b-X的基团代替,其中a为3且b为1至3,并且X选自酸性基团、碱性基团、阳离子、阴离子、两性离子、卤素、羟基、酰基、酰氧基、烷基硫基、烷氧基、醛基、酰氨基、氨基甲酰基、脲基、氰基、硝基、环氧基、式-C(H)(COOH)(NH2)的基团和式-C(H)(COOH)(NHAc)的基团或其盐;并且嵌段B是芳族疏水性聚合物链段。
本发明还提供一种制备嵌段共聚物的方法,包括:(i)提供具有一种或多种末端官能团的芳族疏水性聚合物链段;和(ii)在碱的存在下,在所述芳族疏水性聚合物链段上进行烯丙基缩水甘油醚的开环聚合。任选地,烯丙基中的一个或多个被亲水性基团代替,以产生亲水性共聚物。
本发明还提供包含如上所述的芳族疏水性聚合物和嵌段共聚物的多孔膜,和制备这种多孔膜的方法。
本发明具有以下优点中的一个或多个。它提供了用于调节多孔膜中期望的亲水性程度的简便方法。不同亲水性程度的嵌段共聚物由芳族疏水性聚合物制备。该嵌段共聚物的组成可容易地通过公知的技术表征。使用该嵌段共聚物制备的多孔膜的可萃取物低。嵌段共聚物对于芳族疏水性聚合物具有强的附着力。多孔膜对于处理条件如高压处理、蒸汽处理和异丙醇(IPA)萃取是稳定的。
附图的几个视图的简要说明
图1A描述了根据本发明一个实施方案由PES和PES-PolyAGE的共混物制备的多孔膜截面的SEM图像。图1B描述了图1A中描述的截面的更高倍放大SEM图像。
图2A描述了根据本发明一个实施方案由PES和PES-MPS的共混物制备的多孔膜截面的SEM图像。图2B描述了图2A中描述的截面的更高倍放大SEM图像。
图3示出亲水性多孔膜的微结构。1表示芳族疏水性聚合物,2表示根据本发明一个实施方案的嵌段共聚物的芳族疏水性聚合物链段,3表示嵌段共聚物的亲水性聚合物链段。
图4A描述了根据本发明一个实施方案的膜截面的SEM图像。图4B描述了图4A中描述的图像的更高倍放大SEM图像。
发明详述
根据一个实施方案,本发明提供一种式A-B-A(I)或者A-B(II)的嵌段共聚物,包含嵌段A和B,
其中嵌段A是:
(i)烯丙基缩水甘油醚的聚合物,所述聚合物具有烯丙基;或者
(ii)烯丙基缩水甘油醚的聚合物,其中所述烯丙基中的一个或多个被1,2-二羟基丙基或式-(CH2)a-S-(CH2)b-X的基团代替,其中a为3且b为1至3,并且X选自酸性基团、碱性基团、阳离子、阴离子、两性离子、卤素、羟基、酰基、酰氧基、烷基硫基、烷氧基、醛基、酰氨基、氨基甲酰基、脲基、氰基、硝基、环氧基、式-C(H)(COOH)(NH2)的基团和式-C(H)(COOH)(NMAc)的基团或其盐;和
嵌段B是芳族疏水性聚合物链段。
根据一个实施方案,烯丙基缩水甘油醚的聚合物具有下式的重复单元:
其中R是烯丙基。
根据另一实施方案,嵌段A是烯丙基缩水甘油醚的聚合物,其中所述烯丙基中的一个或多个被1,2-二羟基丙基或式-(CH2)a-S-(CH2)b-X的基团代替,其中a和b独立地为1至3,并且X为选自以下的基团:酸性基团、碱性基团、阳离子、阴离子、两性离子、卤素、羟基、酰基、酰氧基、烷基硫基、烷氧基、醛基、酰氨基、氨基甲酰基、脲基、氰基、硝基、环氧基、式-C(H)(COOH)(NH2)的基团和式-C(H)(COOH)(NHAc)的基团或其盐。
根据一个实施方案,两性离子是式-N+(R1R2)(CH2)cSO3 -的季铵烷基磺酸根基,其中R1和R2是烷基,且c为1至3。
根据一个实施方案,嵌段共聚物的芳族疏水性聚合物链段选自聚砜、聚醚砜、聚苯醚、聚氧化亚苯基、聚碳酸酯、聚(酞嗪酮醚砜酮)、聚醚酮、聚醚醚酮、聚醚酮酮、聚酰亚胺、聚醚酰亚胺和聚酰胺-酰亚胺,优选聚醚砜。
疏水性聚合物链段的具体实例包括聚砜(PS)、聚醚砜(PES)、聚碳酸酯(PC)、聚醚醚酮(PEEK)、聚(酞嗪酮醚砜酮)(PPESK)、聚苯硫醚(PPS)、聚苯醚(PPE)、聚苯醚(PPO)和聚醚-酰亚胺(PEI),其具有以下结构:
在每个上述芳族疏水性链段中重复单元的数目n,可以是约10至约1000,优选约30至约300,更优选约50至约250。
根据一个实施方案,本发明的嵌段共聚物,其中聚醚砜是芳族疏水性链段,具有以下结构中的任一种:
其中n、m1和m2独立地为约10至约1000,优选约30至约300,更优选约50至约250。
在实施方案中的任一个中,嵌段A以约20%至约60mol%的量存在,嵌段B以约40%至约80mol%的量存在,并且优选嵌段A以约40%至约55mol%的量存在,嵌段B以约45%至约60mol%的量存在。
本发明进一步提供制备式A-B-A(I)或者A-B(II)的嵌段共聚物的方法,其中嵌段A是烯丙基缩水甘油醚的聚合物,所述聚合物具有烯丙基;和嵌段B是芳族疏水性聚合物链段;该方法包括:(i)提供具有一种或多种选自羟基、巯基和氨基的末端官能团的芳族疏水性聚合物链段;和(ii)在芳族疏水性聚合物链段上,进行烯丙基缩水甘油醚的开环聚合。
根据一个实施方案,芳族疏水性聚合物链段选自聚砜、聚醚砜、聚苯醚、聚氧化亚苯基、聚碳酸酯、聚(酞嗪酮醚砜酮)、聚醚酮、聚醚醚酮、聚醚酮酮、聚酰亚胺、聚醚酰亚胺和聚酰胺-酰亚胺,优选聚醚砜。芳族疏水性聚合物链段包含一种或多种、优选一种或两种选自羟基、巯基或氨基的末端官能团。
可以通过本领域技术人员公知的方法将官能团提供在芳族疏水性链段上。例如,羟基封端的聚醚酰亚胺的合成描述在美国专利4,611,048和7,230,066中。因此,例如,羟基封端的聚醚酰亚胺可以通过双醚酐和二胺的反应,然后与氨基醇反应来制备。示例性地,羟基封端的聚醚酰亚胺可以通过双(4-(3,4-二羰基-苯氧基)苯基)丙烷二酐与间苯二胺的反应,然后与对氨基苯酚反应来制备。
胺封端的聚醚酰亚胺可以通过双醚酐和二胺的反应来制备。因此,例如,双(4-(3,4-二羧基-苯氧基)苯基)丙烷二酐与间苯二胺可以反应生成胺封端的聚醚酰亚胺。参见例如美国专利3,847,867。
羟基封端的PEEK描述在JournalofPolymerSciencePartB2006,44,541和JournalofAppliedScience2007,106,2936中。因此,例如,具有侧叔丁基的羟基封端的PEEK,可通过4,4’-二氟二苯甲酮与叔丁基氢醌用碳酸钾作为催化剂的亲核取代反应制备。
羟基封端的聚碳酸酯描述在JournalofPolymerScience:PolymerChemistryEdition1982,20,2289中。因此,例如,羟基封端的聚碳酸酯可以通过双酚A与光气的反应制备,在光气化之前或过程中,原位封闭一些酚基团。三甲基氯硅烷、三氟乙酸酐或三氟乙酸可以用于封闭。封闭基团可以在聚合结束时被移除。
羟基封端的PPO可以按照美国专利3,318,959中所述来制备。因此,例如,聚-2,6-二甲基亚苯基醚可与氢氧化钠反应,以得到每分子具有2.3至3个羟基的羟基含量的PPO。
在一个实施方案中,具有一个或多个羟基的芳族疏水性聚合物链段是下式:
其中n是约10至约1000,优选约50至175,更优选为约60至约100。
聚醚砜是市售的,例如,作为来自Solvay的VIRANTAGETMVW-10700,具有式其具有21000g/mol的GPC分子量和210μeq/g的OH端基;作为来自Solvay的VIRANTAGEVW-10200,具有式其具有44,200g/mol的GPC分子量和80μeq/g的OH端基;和作为来自Sumitomo的SMIKAEXCELTM5003PS,具有式其具有0.50的比浓粘度[1%的PES溶于DMF中]和每分子0.6-1.4的OH端基。
缩水甘油的环氧环的打开,由亲核试剂(即芳族疏水性聚合物链段的氧化物阴离子、氨基或硫化物阴离子,其作为末端官能团(氨基)存在)引发,或者由芳族疏水性聚合物链段上的末端基团(OH或SH)与反应中使用的碱的反应来产生。在碱的存在下,开环的环氧化物不断打开下一个烯丙基缩水甘油醚的环氧基,并且烯丙基缩水甘油醚以这种方式进行聚合。当SH作为亲核试剂时,碱的使用是任选的。当氨基是亲核试剂时,则不需要碱。
开环聚合可以用任何合适的碱进行。例如,碱选自碳酸钾、碳酸钠、碳酸铯、叔丁醇钠、叔丁醇钾、氢氧化四甲铵、氢氧化铵、四丁基氢氧化铵、氢氧化钠、氢氧化钾、氢氧化锂、碳酸钡、氢氧化钡、氢氧化铯、碳酸锂、碳酸镁、氢氧化镁、氨基钠和氨基锂,以及它们的组合。
开环聚合可在任何合适的溶剂中进行。例如,溶剂选自N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲基亚砜和N-甲基吡咯烷酮,以及它们的组合。
疏水性聚合物和烯丙基缩水甘油醚的量可以按任何合适的浓度存在于聚合介质中,例如,以重量计约5%至约60%或更高的浓度,优选约10%至约50%,更优选约20%至约40%。在一个实施方案中,浓度为约30重量%。
进行开环聚合反应,使得反应混合物中疏水性聚合物链段与烯丙基缩水甘油醚的比例优选为约1∶0.1至约1∶2,更优选约1∶0.7至约1∶1.2,甚至更优选约1∶0.8。
开环聚合反应在合适的温度下进行,例如25℃至约130℃,优选约50℃至约120℃,更优选约90℃至110℃。
聚合反应可以进行任何合适的时间长度,例如约1小时至约100小时,优选约2小时至约40小时,更优选约3至约20小时。聚合时间尤其可根据所需的聚合度和反应混合物的温度而变化。
嵌段共聚物可以通过用非溶剂沉淀从反应混合物中分离,所述非溶剂例如甲醇、乙醇或丙醇。将所得聚合物干燥以除去任何残留溶剂或非溶剂。
嵌段共聚物可以通过任何合适的分析技术来表征。例如,疏水性聚合物链段的量和烯丙基缩水甘油醚嵌段的量,可以通过质子NMR光谱测定。
在一个实施方案中,嵌段B的芳族疏水性聚合物链段具有下式:
其中n是约10至约1000,优选约50至175,更优选为约60至约100。
本发明进一步提供了一种制备式A-B-A(I)或者A-B(II)的嵌段共聚物的方法,其中嵌段A是烯丙基缩水甘油醚的聚合物,其中所述烯丙基中的一个或多个被1,2-二羟基丙基或式-(CH2)a-S-(CH2)b-X的基团代替,其中a为3且b为1至3,并且X为选自以下的基团:酸性基团、碱性基团、阳离子、阴离子、两性离子、卤素、羟基、酰基、酰氧基、烷氧基、烷基硫基、醛基、酰氨基、氨基甲酰基、脲基、氰基、硝基、环氧基、式-C(H)(COOH)(NH2)的基团和式-C(H)(COOH)(NHAc)的基团或其盐;并且嵌段B是芳族疏水性聚合物链段;
该方法包括:
(i)提供式A-B-A(Ia)或者A-B(IIa)的嵌段共聚物,其中嵌段A是烯丙基缩水甘油醚的聚合物,所述聚合物具有烯丙基;并且嵌段B是芳族疏水性聚合物链段;和
(ii)使(i)中所述嵌段共聚物的烯丙基中的一个或多个与选自以下的试剂反应:氧化剂,带酸基团的烷硫醇,带碱性基团的烷硫醇,带两性离子的烷硫醇,卤代烷硫醇,羟基烷硫醇,酰基烷硫醇,烷氧基烷硫醇,烷硫基烷硫醇,醛基烷硫醇,酰氨基烷硫醇,氨基甲酰基烷硫醇,脲基烷硫醇,氰基烷硫醇,硝基烷硫醇,环氧基烷硫醇,半胱氨酸,或酰基半胱氨酸。
嵌段共聚物Ia和Ib上的烯丙基中的一个或多个可与合适的试剂反应,以实现所希望的变化。例如,烯丙基可以通过与氧化剂如四氧化锇、碱性高锰酸盐或过氧化氢反应,转化为1,2-二羟丙基。
烯丙基可以转化为式-(CH2)a-S-(CH2)b-X的基团,其中a为3且b为1至3,并且X为通过使烯丙基与带酸基团的硫醇如HS-(CH2)b-X反应而成的酸性基团,其中X是COOH、PO4H、PO3H或SO3H,其中b是1至3。
烯丙基可以转化为式-(CH2)a-S-(CH2)b-X的基团,其中a为3且b为1至3,并且X是通过使烯丙基与带碱性基团的硫醇如HS-(CH2)b-X反应而成的碱性基团,其中X为NH2、NHR或NRR,其中R为C1-C6烷基,并且b为1至3。
烯丙基可以转化为式-(CH2)a-S-(CH2)b-X的基团,其中a为3且b为1至3,并且X是通过使烯丙基与带阳离子基团的硫醇如HS-(CH2)b-X反应而成的阳离子基团,其中X为NH3 +、NHRR+或NRRR+,其中R是C1-C6烷基,且b为1至3。
烯丙基可以转化为式-(CH2)a-S-(CH2)b-X的基团,其中a为3且b为1至3,和X是通过使烯丙基与带两性离子基团的硫醇如HS-(CH2)b-X反应而成的两性离子基团,其中X是带两性离子的基团,例如-N+(R)2-(CH2)c-SO3 -,其中R是C1-C6烷基,b和c独立地为1至3。
烯丙基中的一个或多个可通过与卤代烷硫醇反应而被代替,例如与氟代烷硫醇、氯代烷硫醇、溴代烷硫醇或碘代烷硫醇反应。酰基烷硫醇的酰基可以是甲酰基、乙酰基、丙酰基或丁基。烷氧基烷硫醇的烷氧基部分可以是C1-C6烷氧基。烷硫基烷硫醇的烷硫基部分可以是C1-C6烷基。
在一个实施方案中,烯丙基中的一个或多个可以与以下物质反应:羧酸烷硫醇或其盐,磷酸烷硫醇或其盐,膦酸烷硫醇或其盐,磺酸烷硫醇或其盐,(二烷基氨基)烷硫醇或其盐,氨基烷硫醇或其盐,烷基氨基烷硫醇,二烷基氨基烷硫醇,和磺酸烷基铵烷硫醇或其盐。
根据一个实施方案,嵌段共聚物的芳族疏水性聚合物链段选自聚砜、聚醚砜、聚苯醚、聚氧化亚苯基、聚碳酸酯、聚(酞嗪酮醚砜酮)、聚醚酮、聚醚醚酮、聚醚酮酮、聚酰亚胺、聚醚酰亚胺和聚酰胺-酰亚胺,优选聚醚砜。
本发明进一步提供一种包含如上所述的芳族疏水性聚合物和嵌段共聚物的多孔膜。
本发明还提供一种制备包含如上所述的芳族疏水性聚合物和嵌段共聚物的多孔膜的方法,包括:(i)制备包含溶剂和所述芳族疏水性聚合物和所述嵌段共聚物的聚合物溶液;
(ii)使所述聚合物溶液流延为薄膜;
(iii)使所述薄膜经历相转化,得到多孔膜;和任选地
(iv)洗涤所述多孔膜。
聚合物溶液含有聚合物和作为润湿剂的嵌段共聚物。典型的聚合物溶液包含至少一种溶剂,并且可以进一步包含至少一种非溶剂。合适的溶剂包括,例如,二甲基甲酰胺(DMF);N,N-二甲基乙酰胺(DMAc);N-甲基吡咯烷酮(NMP);二甲基亚砜(DMSO)、甲基亚砜、四甲基脲;二噁烷;丁二酸二乙酯;氯仿;和四氯乙烷;和它们的混合物。根据一个实施方案,聚合物溶液含有N,N-二甲基甲酰氨基、N-甲基吡咯烷酮或者它们的混合物作为溶剂。
合适的非溶剂包括,例如,水;各种聚乙二醇(PEG,例如PEG-200、PEG-300、PEG-400、PEG-1000);各种聚丙二醇;各种醇,例如甲醇、乙醇、异丙醇(IPA)、戊醇、己醇、庚醇和辛醇;烷烃,如己烷、丙烷、硝基丙烷、庚烷和辛烷;和酮、醚和酯,如丙酮、丁醚、乙酸乙酯、乙酸戊酯;酸,如乙酸,柠檬酸和乳酸;和各种盐,如氯化钙、氯化镁和氯化锂;和它们的混合物。
典型的流延溶液含有以下范围的聚合物作为成孔剂:约10wt%至约35wt%的树脂,约0.1%至约10wt%,优选约0.2%至约2%,和更优选约0.3%至约1%范围内的本发明的嵌段共聚物,约0至约90wt%范围内的NMP,约0至约90wt%范围内的DMF,和在约0至约90wt%范围内的DMAc。
合适的溶液组分是现有技术中公知的。示例性的包含聚合物的溶液以及示例性的溶剂和非溶剂,包括公开在例如美国专利4,629,563;4,900,449;4,964,990;5,444,097;5,846,422;5,906,742;5,928,774;6,045,899和7,208,200中的那些。
例如,膜样品可以通过涉及非溶剂诱导的聚合物沉淀的溶液工艺制备,或者通过水蒸气扩散或直接在水中急冷而制备。通常,聚合物例如PES或PPESK的溶液通过首先用溶剂DMAC或DMAC/NMP、成孔剂PEG400和其他添加剂制备。使用刮刀将该溶液以10-15密耳的空间间隙施加到玻璃板,均匀地形成聚合物原液(dope)的膜。然后将该膜放置于温度、空气速度和湿度受控的腔室中,或直接浸入具有预设温度的水浴中,允许一段时间使原液转换成固体膜。将得到的固体膜样品在50-70%乙醇/水、温度范围从50℃至80℃的热水中浸滤(leach),然后在温度范围为50-70℃的烘箱中干燥,得到多孔聚合物膜的片材。
作为一个实例,典型的配制物由约15-25wt%的PPESK聚合物树脂、约200-300phr的溶剂(NMP/DMAC)、5-25phr至多50phr的典型范围的润湿聚合物试剂组成。将成孔剂PEG400以50phr至100phr的浓度范围引入。对于每个单独的配制物,根据需要可以0.5-3.0%的低浓度使用其他添加剂。
根据一个实施方案,聚合物溶液以约20%比约80%至约80%比约20%的质量比,含有芳族疏水性聚合物或嵌段共聚物。
将流延溶液作为平片流延在玻璃板上或在移动基板如移动带上。可选地,将流延溶液流延成中空纤维。
相转化可以通过任何已知的方法来实现。相转化可以包括溶剂和非溶剂的蒸发(干法);暴露于非溶剂蒸气,如水蒸气,其吸收在暴露的表面上(气相诱导析出过程);在非溶剂性液体(通常为水)中急冷(湿法);或者使热的膜热急冷,使得聚合物的溶解度突然大幅度降低(热过程)。
在一个实施方案中,相转化通过以下来实现:将流延溶液暴露于非溶剂蒸气,例如湿度受控的气氛,然后将流延溶液浸渍在非溶剂浴如水浴中。
如图3中所示,根据本发明一个实施方案的多孔膜的微结构包括在膜的孔表面上的亲水性链段3,从而改进膜的亲水性。嵌段共聚物的疏水性聚合物链段B2,使自身依照芳族疏水性聚合物1取向。
根据本发明实施方案的多孔膜具有作为微滤膜或超滤膜的用途,或者在制备钠滤膜、反渗透膜、气体分离膜、全蒸发膜或蒸气渗透膜、渗析膜、膜蒸馏、层析膜和/或正向渗透膜和压力延迟渗透膜中的用途。
根据本发明的实施方案的多孔膜具有约0.05μm至约10μm或更多的孔尺寸,并具有作为微滤膜的用途。根据本发明的某些实施方案的多孔膜具有约1nm至约0.5μm的孔径,并具有作为纳滤膜的用途。
根据本发明的多孔膜具有约70至约90达因/cm或更高的临界润湿表面张力(CWST),例如72、74、76、78、80、82、84或86达因/cm。
根据本发明一个实施方案的多孔膜可以用于多种应用中,包括,例如诊断应用(包括,例如样品制备和/或诊断横向流动装置),喷墨应用,过滤制药工业用流体,过滤医疗应用用流体(包括用于家用和/或用于患者使用,例如静脉内应用,也包括例如过滤生物流体如血液(例如除去白细胞)),过滤电子工业用流体(例如,在微电子工业中过滤光致抗蚀剂流体),过滤食品和饮料工业用流体,澄清,过滤含抗体和/或蛋白质的流体,过滤含核酸的流体,细胞检测(包括原位),细胞收集,和/或过滤细胞培养液。可选地,或另外地,根据本发明实施方案的膜可用于过滤空气和/或气体,和/或可用于通风应用(例如,允许空气和/或气体,但不是液体,从中通过)。根据本发明实施方案的多孔膜可以用于各种装置中,包括外科装置和产品,例如眼外科产品。
根据本发明的实施方案,多孔膜可具有多种构型,包括平面的、平片、褶状、管状、螺旋和中空纤维。
根据本发明实施方案的多孔膜通常位于壳体中,所述壳体包括至少一个入口和至少一个出口,并在入口和出口之间限定至少一个流体流动通道,其中至少一个本发明的膜或者包括至少一个本发明的膜的过滤器横跨所述流体流动通道,以提供过滤器装置或过滤器模块。在一个实施方案中,提供一种过滤器装置,其包括壳体,所述壳体包括入口和第一出口,并在入口和第一出口之间限定第一流体流动通道;和至少一个本发明的膜或者包括至少一个本发明的膜的过滤器置于横跨第一流体流动通道的壳体中。
优选地,对于交叉流动应用,至少一个本发明的膜或者包括至少一个本发明的膜的过滤器置于壳体中,所述壳体包括至少一个入口和至少两个出口,并且在入口和第一出口之间限定至少第一流体流动通道,在入口和第二出口之间限定第二流体流动通道,其中本发明的膜或者包括至少一个本发明的膜的过滤器横跨第一流体流动通道,以提供过滤器装置或过滤器模块。在示例性实施方案中,过滤器装置包括交叉流动过滤器模块,该壳体包括入口、包括浓缩物出口的第一出口和包括渗透物出口的第二出口,并且在入口和第一出口之间限定第一流体流动通道,在入口与第二出口之间限定第二流体流动通道,其中至少一个本发明的膜或者包括至少一个本发明的膜的过滤器横跨置于第一流体流动通道。
过滤装置或模块可以是可灭菌的。可以采用形状合适并提供入口和一个或多个出口的任何壳体。
壳体可由任何合适的刚性不透过的材料制成,包括任何不透过的热塑性材料,其与被处理的流体相容。例如,壳体可以由金属如不锈钢制成;或者由聚合物制成,聚合物例如透明的或半透明的聚合物,如丙烯酸类、聚丙烯、聚苯乙烯或聚碳酸酯树脂。
以下实施例进一步说明本发明,但是当然,不应该被解释为以任何方式限制本发明的范围。
实施例1
本实施例说明根据本发明实施方案的聚醚砜和烯丙基缩水甘油醚的嵌段共聚物的制备。
在110℃下将BASFULTRASONE6020聚醚砜(100g)缓慢添加到具有顶部搅拌器的1L反应器中的DMAc(250g)中。聚合物完全溶解后,添加K2CO3(2.5g)。在110℃下另外搅拌2.5小时之后,添加烯丙基缩水甘油醚(100mL),并将反应混合物在110℃下搅拌19小时。将热的反应混合物添加到剧烈搅拌的IPA(3L),并继续再搅拌三小时。过滤该混合物,并将所得产物再悬浮于IPA(1.5L)中。另外搅拌3小时之后,将产物过滤,并在水中的30%IPA中以及在IPA(200mL)中洗涤。将所得产物在50℃的真空烘箱中干燥一整夜,得到105gPES和烯丙基缩水甘油醚的A-B-A型共聚物,PES-PolyAGE。共聚物的质子NMR表征显示,存在10mol%的烯丙基缩水甘油醚和90mol%的PES。
实施例2
本实施例说明根据本发明实施方案的聚醚砜和烯丙基缩水甘油醚的另一嵌段共聚物的制备。
在110℃下将BASFULTRASONE7020(200g)聚醚砜缓慢添加到1L反应烧瓶中的DMAc(600mL)中。聚合物完全溶解后,添加K2CO3(10g)。在110℃下另外搅拌1小时之后,用氮气吹扫反应混合物10分钟,添加烯丙基缩水甘油醚(200g)。将反应混合物在110℃下搅拌72小时,在甲醇(2L)中沉淀,过滤,并将得到的固体再悬浮在甲醇(750mL)中。在另外搅拌5小时之后,过滤得到的产物,并在水中的30%甲醇中和在甲醇(100mL)中洗涤。将所得的产物在50℃的真空烘箱中干燥一整夜,得到260g所需产物,PES和烯丙基缩水甘油醚的A-B-A型共聚物。质子NMR表征显示,嵌段共聚物具有62mol%的PES和38mol%的烯丙基缩水甘油醚。
实施例3
本实施例说明根据本发明实施方案的亲水性嵌段共聚物PES-MAA的制备。
将15g来自实施例2的共聚物PES-PolyAGE在80℃下溶解在DMAc(30mL)中。聚合物完全溶解后,将溶液用氮气吹扫5分钟,并添加氢硫基乙酸(或巯基乙酸)(15mL)和2,2’-偶氮双(2-甲基丙脒)二氢氯化物(750mg)。将反应混合物在80℃下搅拌一整夜。将该热溶液逐滴添加至乙醇(250mL),并将所得的沉淀物在乙醇中再搅拌2小时。过滤沉淀物,用0.1MNaOH(150mL)、水(300mL)和乙醇(100mL)清洗,在50℃的真空烘箱中干燥一整夜,得到17g所需产物PES-MAA。质子NMR表征显示,存在62mol%的PES、30mol%的巯基乙酸和8mol%的烯丙基缩水甘油醚残留在产物(PES-MAA)中,其对应于在硫醇烯与巯基乙酸(MAA)反应期间,PES-PolyAGE的烯丙基的74%转化率。
实施例4
本实施例说明根据本发明实施方案的亲水性嵌段共聚物PES-MPS的制备。
将30g来自实施例2的PES-PolyAGE在60℃下溶解在DMAc(80mL)中。聚合物完全溶解后,将溶液用氮气吹扫5分钟。添加巯基丙烷磺酸钠盐(15g)和2,2’-偶氮双(2-甲基丙脒)二氢氯化物(200mg),并将反应混合物在60℃下搅拌一整夜。将该热溶液通过逐滴添加至异丙醇(IPA)(750mL)来沉淀。将沉淀物在IPA中再搅拌5小时,过滤,并在50℃的真空烘箱中干燥一整夜,得到36gPES-MPS。质子NMR表征证实,硫醇烯反应中烯丙基完全消失。PES-MPS共聚物具有62mol%的PES和38mol%的巯基丙烷磺酸基。
实施例5
本实施例说明根据本发明实施方案的亲水性嵌段共聚物PES-MEDMA的制备。
将16.1g来自实施例2的PolyAGE在80℃下溶解在DMAc(60mL)中。聚合物完全溶解后,将溶液用氮气吹扫5分钟。添加2-(二甲基氨基)乙烷硫醇氢氯化物(16.1g)和2,2’-偶氮双(2-甲基丙脒)二氢氯化物(80.5mg),并将反应混合物在80℃下搅拌一整夜。将该热反应混合物通过逐滴添加至IPA(250mL)来沉淀。将得到的沉淀物在IPA(100mL)中再搅拌2小时。将沉淀物过滤,并用去离子水(1000mL)洗涤,然后用IPA(500mL)洗涤。将得到的产物在50℃的真空烘箱中干燥一整夜,得到PES-MEDMA,通过质子NMR测定,其具有62mol%的PES、32mol%的二甲氨基乙硫醇基和6mol%剩余的烯丙基。
实施例6
本实施例说明根据本发明实施方案的亲水性嵌段共聚物PES-ACys的制备。
将3g来自实施例2的PES-PolyAGE在100℃下溶解在DMAc(10mL)中。聚合物完全溶解后,将溶液用氮气吹扫5分钟。向反应混合物中添加乙酰基-L-半胱氨酸(3g)和2,2’-偶氮双(2-甲基丙脒)二氢氯化物(50mg),并将混合物在100℃下搅拌一整夜。将形成的产物在IPA(100mL)中沉淀。在IPA(50mL)中再搅拌3小时之后,将沉淀物过滤,并用在水中的50%IPA(200mL)洗涤,并在50℃的真空烘箱中干燥一整夜,得到3.4gPES-ACys。质子NMR表征显示,存在62mol%的PES和30mol%的乙酰基-L-半胱氨酸,与8mol%剩余的烯丙基缩水甘油基。
实施例7
本实施例说明根据本发明实施方案的亲水性嵌段共聚物PES-MES的制备。
将15g来自实施例2的PES-PolyAGE在80℃下溶解在DMAc(40mL)中。聚合物完全溶解后,将溶液用氮气吹扫5分钟。添加钠-2-巯基乙烷磺酸盐(11.7g)和2,2’-偶氮双(2-甲基丙脒)二氢氯化物(250mg),并将反应混合物在80℃下搅拌一整夜。然后将热溶液通过逐滴添加至IPA(250mL)来沉淀,将沉淀物在IPA中再搅拌2小时,然后过滤,并在50℃的真空烘箱中干燥一整夜。得到16gPES-MES,通过质子NMR测定,其具有62mol%的PES、25mol%的巯基乙烷磺酸和13mol%的烯丙基。
实施例8
本实施例说明根据本发明实施方案的亲水性嵌段共聚物PES-MEA的制备。
将3g来自实施例2的PES-PolyAGE在80℃下溶解在DMAc(10mL)中。聚合物完全溶解后,将溶液用氮气吹扫5分钟。添加氨基乙硫醇氢氯化物(3g)和2,2’-偶氮双(2-甲基丙脒)二氢氯化物(50mg),并将反应混合物在80℃下搅拌21小时。然后将热溶液通过逐滴添加至乙醇(250mL)来沉淀。将得到的沉淀物在乙醇(50mL)中复原,并再搅拌2小时。将得到的沉淀物过滤,并在50℃的真空烘箱中干燥一整夜,得到3.3gPES-MEA,如通过质子NMR测定的,其具有62mol%的PES、34mol%的氨基乙硫醇基和4mol%的烯丙基。
实施例9
本实施例说明多孔膜的制备,所述多孔膜包含PES和实施例1的聚合物(PES-PolyAGE)的共混物,或者PES和实施例4的嵌段共聚物(PES-MPS)的共混物。
通过将聚合物、溶剂、非溶剂和成孔剂混合来制备膜流延溶液,如下表1所列。
表1膜流延溶液的组成
实施例1的PES-PolyAGE | 实施例4的PES-MPS | |
% | % | |
PEG 400 | 64.50 | 64.52 |
H2O | 3.00 | 3.00 |
DMF | 10.00 | 10.00 |
NMP | 7.60 | 7.60 |
PES | 6.95 | 10.40 |
甘油 | 1.00 | 1.00 |
PES-P | 6.95 | 3.48 |
总量 | 100.00 | 100.00 |
使用气相诱导相分离过程将流延溶液流延成10密耳原液厚度的薄膜,流延温度30℃,相对湿度70%,和干球温度25℃。将原液置于水蒸气室15秒,并在浸入13℃温度的水浴中。
在干燥膜上测量CWST。膜的样品还测试IPA可萃取物。将47mm直径的6个盘在80℃下干燥1小时,然后用IPA索氏萃取3小时,然后在80℃下最终干燥循环1小时。计算%可萃取物。在IPA萃取之后在几个盘上再次测量CWST。所得到的结果列于表2中。使用聚乙烯基吡咯烷酮作为润湿剂制备的聚醚砜膜用作对照样。
表2IPA可萃取物
**相对于PES基质的量。
如所示的,用实施例1的PES-PolyAGE制备的多孔膜具有59达因/cm的CWST和1.19%的低可萃取物水平;它立即被水浸湿。用实施例4的PES-MPS制备的多孔膜具有77达因/cm的CWST和1.19%的低可萃取物水平;它也立即被水浸湿。相比之下,使用聚乙烯吡咯烷酮制备的聚醚砜膜具有87达因/cm的CWST;然而,IPA可萃取物高达2.44%。
使用具有用铂/金预溅射的样品的Hitachi-3400IISEM表征膜的形态。由PES和PES-PolyAGE的共混物制备的膜的截面的SEM图像示于图1A和1B中。由PES和PES-MPS共混物制备的膜截面的SEM图像示于图2A和2B中。
实施例10
本实施例说明包含PPESK和PES-PolyAGE的共混物作为润湿剂的多孔膜的制备。
制备含有25wt%的PPESK树脂、300phr的溶剂NMP/DMAC(v/v)、15wt%的实施例2的PES-PolyAGE的流延溶液,并在28℃、空气温度32℃、相对湿度72%下流延为15密尔厚的膜。将原液置于环境室中15秒,并在室温下浸入水中。通过SEM表征膜的形态。图4A描述根据本发明实施方案的膜的截面的SEM图像。图4B描述了图4A中描述的图像的更高放大倍数SEM图像。该膜具有从一侧到另一侧的对称孔结构分布。孔是具有低互连性的胞状形态。
本文引用的所有文献,包括出版物、专利申请和专利,在此通过参考引入,其程度如同各文献被单独并具体地通过参考引入并在本文中阐述其全部。
在描述本发明的上下文中(特别是在所附权利要求书的上下文中),术语“一个”和“一种”和“该”和“至少一个”和类似指代的使用被解释为覆盖单数和复数两者,除非本文另有说明或者与上下文明显矛盾。后面跟随一个或多个项目的列表的术语“至少一个”的使用(例如,“A和B中的至少一个”),应被解释为是指从列出的项目中选择一项(A或B),或者两个或更多个所列项目的任意组合(A和B),除非本文另有说明或者与上下文明显矛盾。术语“包含”、“具有”、“包括”和“含有”将被理解为开放式术语(即意思是“包括但不限于”),除非另有说明。本文数值的范围限定仅旨在用作单独提及每个单独落在该范围内的值的速记方法,除非本文另有说明,并且各单独的值被并入说明书中,如同其在本文中单独列举一样。本文所述的所有方法可以以任何合适的顺序进行,除非本文另有说明或者以其他方式与上下文明显矛盾。本文所提供的任何和所有实例,或示例性语言(例如,“如”)的使用,仅是为了更好地阐明本发明,而不会构成对本发明范围的限制,除非另有要求。说明书中的任何语言不应被解释为表示任何未要求保护的元素对于本发明的实施是必需的。
本文描述了本发明的优选实施方案,包括发明人已知的用于实施本发明的最佳模式。在阅读了前面的描述之后,那些优选实施方案的变型对于本领域技术人员变得明显。发明人期望本领域技术人员适当地采用这些变型,并且发明人希望可以与按照本文的具体描述不同地来实施本发明。因此,本发明包括在本文中所附权利要求书中所限定的主题的所有修改和等同物,如可适用的法律所允许的。此外,在它所有可能的变化中,上述元素的任何组合由本发明所包括,除非本文另外指出或者以其他方式与上下文明显矛盾。
Claims (19)
1.式A-B-A(I)或者A-B(II)的嵌段共聚物,
其中嵌段A是:
(i)烯丙基缩水甘油醚的聚合物,所述聚合物具有烯丙基;或者
(ii)烯丙基缩水甘油醚的聚合物,其中所述烯丙基中的一个或多个被1,2-二羟基丙基或式-(CH2)a-S-(CH2)b-X的基团代替,其中a为3且b为1至3,并且X选自酸性基团、碱性基团、阳离子、阴离子、两性离子、卤素、羟基、酰基、酰氧基、烷基硫基、烷氧基、醛基、酰氨基、氨基甲酰基、脲基、氰基、硝基、环氧基、式-C(H)(COOH)(NH2)的基团和式-C(H)(COOH)(NHAc)的基团或其盐;和
嵌段B是芳族疏水性聚合物链段。
2.根据权利要求1所述的嵌段共聚物,其中所述烯丙基缩水甘油醚的聚合物具有下式的重复单元:
其中R是烯丙基。
3.根据权利要求1所述的嵌段共聚物,其中嵌段A是烯丙基缩水甘油醚的聚合物,其中所述烯丙基中的一个或多个被1,2-二羟基丙基或式-(CH2)a-S-(CH2)b-X的基团代替,其中a和b独立地为1至3,且X为选自以下的基团:酸性基团、碱性基团、阳离子、阴离子、两性离子、卤素、羟基、酰基、酰氧基、烷基硫基、烷氧基、醛基、酰氨基、氨基甲酰基、脲基、氰基、硝基、环氧基、式-C(H)(COOH)(NH2)的基团和式-C(H)(COOH)(NHAc)的基团或其盐。
4.根据权利要求1或3所述的嵌段共聚物,其中所述两性离子是式-N+(R1R2)(CH2)cSO3 -的季铵烷基磺酸根基,其中R1和R2是烷基,且c为1至3。
5.根据权利要求1-4中任一项所述的嵌段共聚物,其中所述芳族疏水性聚合物链段选自聚砜、聚醚砜、聚苯醚、聚氧化亚苯基、聚碳酸酯、聚(酞嗪酮醚砜酮)、聚醚酮、聚醚醚酮、聚醚酮酮、聚酰亚胺、聚醚酰亚胺和聚酰胺-酰亚胺。
6.根据叔利要求5所述的嵌段共聚物,其中所述芳族疏水性聚合物链段是聚醚砜。
7.根据权利要求1-6中任一项所述的嵌段共聚物,其具有以下结构之一:
其中n、m1和m2独立地为约10至约1000。
8.根据权利要求1-7中任一项所述的嵌段共聚物,其中嵌段A以约20%至约60mol%的量存在,嵌段B以约40%至约80mol%的量存在。
9.根据权利要求8所述的嵌段共聚物,其中嵌段A以约40%至约55mol%的量存在,嵌段B以约45%至约60mol%的量存在。
10.式A-B-A(I)或者A-B(II)的嵌段共聚物的制备方法,其中嵌段A是烯丙基缩水甘油醚的聚合物,所述聚合物具有烯丙基;和嵌段B是芳族疏水性聚合物链段;
所述方法包括:
(i)提供具有一种或多种选自羟基、巯基和氨基的末端官能团的芳族疏水性聚合物链段;和
(ii)在所述芳族疏水性聚合物链段上进行烯丙基缩水甘油醚的开环聚合。
11.根据权利要求10所述的方法,其中所述开环聚合在碱的存在下进行。
12.根据权利要求11所述的方法,其中所述碱选自碳酸钾、碳酸钠、碳酸铯、叔丁醇钠、叔丁醇钾、氢氧化四甲铵、氢氧化铵、四丁基氢氧化铵、氢氧化钠、氢氧化钾、氢氧化锂、碳酸钡、氢氧化钡、氢氧化铯、碳酸锂、碳酸镁、氢氧化镁、氨基钠和氨基锂,以及它们的组合。
13.根据权利要求10-12中任一项所述的方法,其中所述开环聚合在溶剂中进行,所述溶剂选自N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲基亚砜和N-甲基吡咯烷酮,以及它们的组合。
14.根据权利要求10-13中任一项所述的方法,其中所述芳族疏水性聚合物链段具有下式:
其中n为约10到约1000。
15.式A-B-A(I)或者A-B(II)的嵌段共聚物的制备方法,其中嵌段A是烯丙基缩水甘油醚的聚合物,其中所述烯丙基中的一个或多个被1,2-二羟基丙基或式-(CH2)a-S-(CH2)b-X的基团代替,其中a为3且b为1至3,并且X为选自以下的基团:酸性基团、碱性基团、阳离子、阴离子、两性离子、卤素、羟基、酰基、酰氧基、烷基硫基、烷氧基、醛基、酰氨基、氨基甲酰基、脲基、氰基、硝基、环氧基、式-C(H)(COOH)(NH2)的基团和式-C(H)(COOH)(NHAc)的基团或其盐;和
嵌段B是芳族疏水性聚合物链段;
所述方法包括:
(i)提供式A-B-A(Ia)或者A-B(IIa)的嵌段共聚物,其中嵌段A是烯丙基缩水甘油醚的聚合物,所述聚合物具有烯丙基;和嵌段B是芳族疏水性聚合物链段;和
(ii)使(i)中所述嵌段共聚物的烯丙基中的一个或多个与选自以下的试剂反应:氧化剂,羧基烷硫醇或其盐,磺酸烷硫醇或其盐,(二烷基氨基)烷硫醇或其盐,卤代烷硫醇,羟基烷硫醇,酰基烷硫醇,烷氧基烷硫醇,烷硫基烷硫醇,醛基烷硫醇,酰氨基烷硫醇,氨基甲酰基烷硫醇,脲基烷硫醇,氰基烷硫醇,硝基烷硫醇,环氧基烷硫醇,半胱氨酸,酰基半胱氨酸,氨基烷硫醇或其盐,烷基氨基烷硫醇,二烷基氨基烷硫醇,和磺酸烷基铵烷硫醇或其盐。
16.根据权利要求15所述的方法,其中所述芳族疏水性聚合物链段选自聚砜、聚醚砜、聚苯醚、聚氧化亚苯基、聚碳酸酯、聚(酞嗪酮醚砜酮)、聚醚酮、聚醚醚酮、聚醚酮酮、聚酰亚胺、聚醚酰亚胺和聚酰胺-酰亚胺。
17.根据权利要求16所述的方法,其中所述芳族疏水性聚合物链段是聚醚砜。
18.多孔膜,其包含芳族疏水性聚合物和根据权利要求1-9中任一项所述的嵌段共聚物。
19.包含芳族疏水性聚合物和根据权利要求1-9中任一项所述的嵌段共聚物的多孔膜的制备方法,所述方法包括:
(i)制备包含溶剂和所述芳族疏水性聚合物和所述嵌段共聚物的聚合物溶液;
(ii)使所述聚合物溶液流延为薄膜;
(iii)使所述薄膜经历相转化,得到多孔膜;和任选地
(iv)洗涤所述多孔膜。
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CN113578076A (zh) * | 2020-12-31 | 2021-11-02 | 太原科技大学 | 一种化学交联带羧基的聚酰亚胺氢气分离膜及其制备方法 |
CN113578076B (zh) * | 2020-12-31 | 2024-03-29 | 太原科技大学 | 一种化学交联带羧基的聚酰亚胺氢气分离膜及其制备方法 |
CN115260504A (zh) * | 2022-07-15 | 2022-11-01 | 中国科学院长春应用化学研究所 | 含有两性离子的聚芳醚砜嵌段共聚物、抗污染超滤膜及制备方法、应用 |
CN115260504B (zh) * | 2022-07-15 | 2023-08-29 | 中国科学院长春应用化学研究所 | 含有两性离子的聚芳醚砜嵌段共聚物、抗污染超滤膜及制备方法、应用 |
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JP2016020493A (ja) | 2016-02-04 |
KR20160008101A (ko) | 2016-01-21 |
EP2963076B1 (en) | 2023-09-13 |
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DK2963076T3 (da) | 2023-11-13 |
SG10201504770TA (en) | 2016-01-28 |
JP6080136B2 (ja) | 2017-02-15 |
US9718924B2 (en) | 2017-08-01 |
EP2963076A1 (en) | 2016-01-06 |
KR101726796B1 (ko) | 2017-04-13 |
FI2963076T3 (fi) | 2023-11-08 |
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US20150376341A1 (en) | 2015-12-31 |
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