CN105315447A - 亲水性嵌段共聚物和由其制备的膜 - Google Patents
亲水性嵌段共聚物和由其制备的膜 Download PDFInfo
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- CN105315447A CN105315447A CN201510521120.0A CN201510521120A CN105315447A CN 105315447 A CN105315447 A CN 105315447A CN 201510521120 A CN201510521120 A CN 201510521120A CN 105315447 A CN105315447 A CN 105315447A
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- Prior art keywords
- segmented copolymer
- film
- hydrophobic polymer
- reaction mixture
- polymer chains
- Prior art date
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Links
- 229920001400 block copolymer Polymers 0.000 title abstract description 11
- 239000012528 membrane Substances 0.000 title abstract description 11
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 58
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 58
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 47
- 238000002360 preparation method Methods 0.000 claims abstract description 34
- 229920001577 copolymer Polymers 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 44
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 24
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 23
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 22
- 235000015320 potassium carbonate Nutrition 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- -1 poly (aryl ether sulfone ketone Chemical class 0.000 claims description 14
- 239000004697 Polyetherimide Substances 0.000 claims description 11
- 229920001601 polyetherimide Polymers 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 8
- 229920002530 polyetherether ketone Polymers 0.000 claims description 8
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000007766 curtain coating Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 229920002492 poly(sulfone) Polymers 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000004417 polycarbonate Substances 0.000 claims description 6
- 229920000515 polycarbonate Polymers 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229920001721 polyimide Polymers 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
- 239000004962 Polyamide-imide Substances 0.000 claims description 3
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 3
- 229920001652 poly(etherketoneketone) Polymers 0.000 claims description 3
- 229920002312 polyamide-imide Polymers 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
- 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
- 239000002585 base Substances 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
- 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
- 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
- 230000002209 hydrophobic effect Effects 0.000 abstract description 9
- 239000000080 wetting agent Substances 0.000 abstract description 9
- 125000003118 aryl group Chemical group 0.000 abstract 2
- 229920000223 polyglycerol Polymers 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 description 80
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 47
- 239000000047 product Substances 0.000 description 40
- 239000007787 solid Substances 0.000 description 21
- 238000013019 agitation Methods 0.000 description 19
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 19
- 238000005245 sintering Methods 0.000 description 19
- 238000005266 casting Methods 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- 239000012530 fluid Substances 0.000 description 18
- 238000001556 precipitation Methods 0.000 description 17
- 239000000126 substance Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 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 5
- 238000009434 installation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect 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
- 125000000524 functional group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012038 nucleophile Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 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
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 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
- 150000001412 amines Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration 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
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 238000001728 nano-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
- 230000000704 physical effect Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003457 sulfones Chemical class 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
- 238000005406 washing Methods 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
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-UHFFFAOYSA-N 0.000 description 1
- RSFFTZBPSXWHRR-UHFFFAOYSA-N 4-(4-propylphenoxy)phthalic acid Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 RSFFTZBPSXWHRR-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-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
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-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
- 229920003082 Povidone K 90 Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 230000010100 anticoagulation Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009292 forward osmosis Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
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- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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Abstract
公开了式A-B-A(I)或A-B(II)的嵌段共聚物,其包含嵌段A和B,其中嵌段A为包含聚甘油的亲水性聚合物链段,嵌段B为芳族疏水性聚合物链段。该嵌段共聚物作为润湿剂用于由芳族疏水性聚合物如聚醚砜制备多孔膜。
Description
发明背景
由于芳族疏水性聚合物如聚砜、聚醚砜、二氮杂萘酮联苯聚芳醚砜酮(poly(phthalazinoneethersulfoneketone))、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)和聚醚醚酮的化学稳定性、加工性能、机械强度、柔韧性和热稳定性,它们可用于制备多孔膜。因为这些聚合物通常是疏水性的,所以由这些聚合物制备的膜也是疏水性的,并且因此缺乏所需的表面性质如润湿性、低蛋白吸附、抗凝血性能和受控的表面化学反应性。
已尝试改进由芳族疏水性聚合物制成的膜的一种或多种表面性能。例如,已用高能辐射或等离子体处理膜,以赋予亲水性。在其它实例中,将亲水性的单体接枝到疏水性膜表面上。还已尝试用水溶性聚合物如聚乙二醇或聚乙烯基吡咯烷酮涂覆疏水性膜。然而,上述改进性能,特别是亲水性的尝试具有一种或更多种缺点,如缺乏可再现性,缺乏改进的稳定性,和/或孔堵塞。
以上表明对于由芳族疏水性聚合物形成的亲水性膜,以及对于将亲水性赋予由芳族疏水性聚合物形成的膜的方法存在未满足的需求。
发明简述
本发明提供了一种包含亲水性链段的嵌段共聚物,其可用于由芳族疏水性聚合物制备亲水性膜。因此,本发明提供了式A-B-A(I)或A-B(II)的嵌段共聚物,其包含嵌段A和B,其中嵌段A是包含聚甘油的亲水性聚合物链段,和嵌段B是芳族疏水性聚合物链段。
本发明还提供了一种制备嵌段共聚物的方法,包括:(i)提供具有一个或多个端基官能团的芳族疏水性聚合物链段;和(ii)在碱存在下对芳族疏水性聚合物链段进行缩水甘油的开环聚合。
本发明还提供了包含芳族疏水性聚合物和如上所述的嵌段共聚物的亲水性多孔膜,以及制备这样的多孔膜的方法。
本发明具有一个或多个以下优点。其提供了一种在多孔膜中调节所需亲水性程度的简易方法。由芳族疏水性聚合物产生了多种亲水性程度的嵌段共聚物。所述嵌段共聚物的组成容易由公知技术表征。使用所述嵌段共聚物制备的多孔膜可萃取性低。所述嵌段共聚物具有对芳族疏水性聚合物的强粘合性。所述多孔膜对加工条件如高压法、蒸煮和异丙醇(IPA)萃取是稳定的。
附图简述
图1A描述了由根据本发明的实施方式的嵌段共聚物制备的多孔膜的横截面的SEM。
图1B描述了图1A的更高放大倍数的SEM。
图2描述了阐释亲水性多孔膜微观结构的图。1表示芳族疏水性聚合物,2表示根据本发明的实施方式的嵌段共聚物的芳族疏水性聚合物链段,和3表示所述嵌段共聚物的亲水性链段。
图3A描述了根据本发明的实施方式的膜横截面的SEM图像。图3B描述了图3A中所描述的图像的更高放大倍数的SEM图像。
发明详述
根据一个实施方式,本发明提供了包含嵌段A和B的式A-B-A(I)或A-B(II)的嵌段共聚物,其中嵌段A是包含聚甘油(也称为聚缩水甘油)的亲水性聚合物链段,和嵌段B是芳族疏水性聚合物链段。包含本发明的嵌段共聚物和芳族疏水性聚合物的多孔膜是亲水性的。
根据一个实施方式,所述聚甘油具有一个或多个以下重复单元:
在一个实施方式中,嵌段A包含一个或多个以下结构:
根据一个实施方式,所述嵌段共聚物的芳族疏水性聚合物链段选自聚砜、聚醚砜、聚氧化亚苯基、聚苯醚、聚碳酸酯、二氮杂萘酮联苯聚芳醚砜酮、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。
所述芳族疏水性聚合物链段的实施方式包括聚砜(PS)、聚醚砜(PES)、聚碳酸酯(PC)、聚醚醚酮(PEEK)、二氮杂萘酮联苯聚芳醚砜酮(PPESK)、聚苯硫醚(PPS)、聚苯醚(PPE)、聚氧化亚苯基(PPO)和聚醚酰亚胺(PEI),其具有以下结构:
每个上述芳族疏水性链段内的重复单元数n可以是约10至约1000,优选为约30至约300,更优选为约50至约250。
根据一个实施方式,其中聚醚砜是芳族疏水性链段的本发明的嵌段共聚物具有以下结构:
其中n为约10至约1000,优选为约50至175,更优选为约60至约100。
如果聚砜为芳族疏水性聚合物链段,则n为约10至约1000,优选为约30至约225,更优选为约45至约130。
根据一个实施方式,嵌段A在共聚物中以约20%至约60mol%的量存在,和嵌段B以约30%至约80mol%的量存在。优选地,嵌段A约40%至约55mol%的量存在,和嵌段B以约40%至约60mol%的量存在。
根据一个实施方式,本发明还提供了制备上述嵌段共聚物的方法,所述方法包括:
(i)提供具有一个或多个端基官能团的芳族疏水性聚合物链段,所述端基官能团选自羟基、巯基和氨基;和
(ii)对所述芳族疏水性聚合物链段进行缩水甘油的开环聚合。
根据一个实施方式,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、二氮杂萘酮联苯聚芳醚砜酮、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。所述芳族疏水性聚合物链段包括一个或多个,优选一个或两个端基官能团,所述端基官能团选自羟基、巯基或氨基。
可以通过本领域技术人员已知方法在所述芳族疏水性链段上提供所述官能团。例如,美国专利4,611,048和7,230,066中描述了羟基封端的聚醚酰亚胺合成。因此,例如可以通过双醚酸酐与二胺反应,随后与氨基醇反应,制备羟基封端的聚醚酰亚胺。解释性地,可以通过双(4-(3,4-二羧基苯氧基)苯基)丙烷二酸酐与间苯二胺反应,随后与对氨基苯酚反应,制备羟基封端的聚醚酰亚胺。
可以通过双醚酸酐与二胺的反应制备胺封端的聚醚酰亚胺。因此,例如可以使双(4-(3,4-二羧基-苯氧基)苯基)丙烷二酸酐与间苯二胺反应而产生胺封端的聚醚酰亚胺。例如参见美国专利3,847,867。
JournalofPolymerSciencePartB2006,44,541和JournalofAppliedScience2007,106,2936中公开了羟基封端的PEEK。因此,例如可以通过采用碳酸钾作为催化剂的4,4’-二氟二苯甲酮与叔丁基对苯二酚的亲核取代反应制备具有悬垂叔丁基的羟基封端的PEEK。
JournalofPolymerScience:PolymerChemistryEdition1982,20,2289中描述了羟基封端的聚碳酸酯。因此,例如可以通过双酚A和光气的反应,在光气化之前或期间原位封端一些苯酚基,制备羟基封端的聚碳酸酯。可以将三甲基氯硅烷、三氟乙酸酐或三氟乙酸用于封端。可以在聚合结束时除去封端基团。
可以如美国专利3,318,959中所述制备羟基封端的PPO。因此,例如可以使聚2,6-二甲基苯醚与氢氧化钠反应,以获得每分子具有2.3至3个羟基的羟基含量的PPO。
在一个实施方式中,所述具有一个或多个羟基的芳族疏水性聚合物链段具有下式:
其中n为约10至约1000,优选为约50至175,且更优选为约60至约100。
例如,聚醚砜可以从Solvay以VIRANTAGETMVW-10700商购获得,其具有式其具有GPC分子量21000g/mol和210μeq/gOH端基;可以从Solvay以VIRANTAGEVW-10200商购获得,其具有通式并具有GPC分子量44,200g/mol和80μeq/g的OH端基;和可以从Sumitomo以SUMIKAEXCELTM5003PS商购获得,其具有通式并具有0.50[溶于DMF中的1%PES]的降低的粘度和每分子0.6-1.4范围的OH端基。
缩水甘油或2,3-环氧-1-丙醇包含一个环氧环和一个羟基作为官能端基。两种官能端基能够彼此反应以形成作为甘油衍生物的大分子。所产生的大分子继续反应以形成聚甘油。通过亲核物质,即以端基官能团(氨基)存在的或通过芳族疏水性聚合物链段上的末端基团(OH或SH)与反应中使用的碱反应产生的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,引发缩水甘油的环氧开环。在一个实施方式中,当SH起亲核物质的作用时,任选使用碱。当氨基是亲核物质时,则不需要碱。
可以使用任意合适的碱,例如选自碳酸钾、碳酸钠、碳酸铯、叔丁醇钠、叔丁醇钾、四甲基氢氧化铵、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、氨基钠和氨基锂及其组合物的碱。
根据一个实施方式,可以在合适的溶剂,特别是极性非质子溶剂中进行所述开环聚合。合适的溶剂的实例包括N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲亚砜和N-甲基吡咯烷酮及其混合物。
芳族疏水性聚合物或缩水甘油可以以任意合适的浓度存在于聚合介质中,例如浓度约5重量%至约60重量%或更大,优选为约10重量%至约50重量%,更优选为约20重量%至约40重量%。在一个实施方式中,所述浓度为约30重量%。
进行所述开环聚合使得反应混合物中所述疏水性聚合物链段与缩水甘油的比例优选为约1∶0.1至约1∶1.1,更优选为约1∶0.7至约1∶0.9,甚至更优选为约1∶0.8。
所述开环聚合在合适的温度,例如25℃至约120℃,优选约50℃至约110℃,更优选约90℃至100℃进行。
所述聚合可以进行任意合适长度的时间,例如约1小时至约100小时或更久,优选约2小时至约20小时,更优选约3小时至约10小时。所述聚合时间可以尤其根据所需聚合度和反应混合物的温度而改变。
可以通过用酸猝灭反应混合物终止所述聚合。可以通过用非溶剂例如异丙醇或水沉淀从所述反应混合物分离所述嵌段共聚物。干燥得到的聚合物,以除去任意剩余溶剂或非溶剂。
可以通过任意合适的分析技术表征所述嵌段共聚物。例如,可以通过质子NMR谱测定疏水性聚合物链段的量和缩水甘油嵌段(聚甘油)的量。
本发明进一步提供了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。本发明进一步提供了制备包含芳族疏水性聚合物和嵌段共聚物的多孔膜的方法,所述方法包括:
(i)提供包含溶剂、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)将所述聚合物溶液流延为薄膜;
(iii)使所述薄膜经历相转变,以获得多孔膜;和任选地
(iv)洗涤所述多孔膜。
用于制备膜的聚合物溶液包含聚合物和嵌段共聚物作为润湿剂。典型的聚合物溶液包含至少一种溶剂,并可以进一步包含至少一种非溶剂。合适的溶剂包括例如N,N-二甲基甲酰胺(DMF);N,N-二甲基乙酰胺(DMAC);N-甲基吡咯烷酮(NMP);二甲亚砜(DMSO)、甲基亚砜、四甲基脲;二噁烷;琥珀酸二乙酯;氯仿;和四氯乙烷及其混合物。合适的非溶剂包括例如水;多种聚乙二醇(PEGs;例如PEG-200、PEG-300、PEG-400、PEG-1000);多种聚丙二醇;多种醇,如甲醇、乙醇、异丙醇(IPA)、戊醇、己醇、庚醇和辛醇;烷烃,例如己烷、丙烷、硝基丙烷、庚烷和辛烷;和酮、醚和酯,如丙酮、丁基醚、乙酸乙酯和乙酸戊酯;酸,如乙酸、柠檬酸和乳酸;和多种盐,如氯化钙、氯化镁和氯化锂;及其混合物。
典型的流延溶液包含约10重量%至约35重量%的树脂的聚合物,约0.1至约10重量%、优选约0.2%至约2%、更优选约0.3%至约1%的亲水性嵌段共聚物,约0至约90重量%的NMP,约0至约90重量%的DMF,和约0至约90重量%的DMAC。
流延溶液的合适组分是本领域已知的,可以按照需求使用。包含聚合物的说明性溶液、说明性溶剂和非溶剂包括例如美国专利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中公开的那些。
例如,可以通过包括非溶剂诱导的聚合物沉淀的溶液加工制备膜样品,或通过水蒸气扩散或直接在水中骤冷制备膜样品。典型地,首先用溶剂DMAC或DMAC/NMP、造孔剂PEG400和其它添加剂制备聚合物如PES或PPESK的溶液。使用具有10-15密耳间隙的刮刀将所述溶液施加至玻璃板,从而均匀地形成聚合物涂液膜.然后,将所述膜放置在具有受控的温度、气流速度和湿度的室中,或直接浸入具有预定温度的水浴中,保持一定时间,使得所述涂液转变为固体膜。在50-70%乙醇/水,50℃至80℃温度的热水中过滤得到的固体膜样品,然后在50-70℃温度的烘箱中干燥,提供多孔聚合物膜的片。
作为一个实例,典型的制剂由以下组成:约15-25重量%的PPESK聚合物树脂,约200-300phr的溶剂(NMP/DMAC),5-25phr典型范围,最高至50phr的润湿聚合物试剂。以50phr至100phr范围的浓度引入造孔剂PEG400。可以如每个单独的制剂所需使用低百分比0.5-3.0%的其它添加剂。
在玻璃板上或在移动基材如移动带上将所述流延溶液流延为平坦片材。或者,将所述流延溶液流延为中空纤维。
可以通过任意已知方法进行相转变。相转变可以包括蒸发所述溶剂和非溶剂(干燥过程);暴露至非溶剂蒸气,如水蒸气,其吸附在暴露的表面上(蒸气相-诱导的沉淀过程);在非溶剂液体、通常为水中骤冷(湿法工艺);或热骤冷热膜,使得突然极大地降低所述聚合物的溶解度(热工艺)。
在一个实施方式中,通过将所述流延溶液暴露至非溶剂蒸气,例如受控湿度的气氛,随后将所述流延溶液浸入非溶剂浴如水浴中,进行相转变。
或者,可以用亲水性嵌段共聚物涂覆疏水性膜。因此,例如在由芳族疏水性聚合物形成的多孔膜上涂覆所述嵌段共聚物的溶液,或将多孔膜浸入所述嵌段共聚物的溶液中,并任选加热,以获得亲水性改性多孔膜。
如图2所示,根据本发明的实施方式的多孔膜的微观结构包括膜孔表面上的亲水性链段3,从而改进所述膜的亲水性。嵌段共聚物的疏水性聚合物链段2自身取向芳族疏水性聚合物1。
根据本发明的实施方式的多孔膜用于微滤、超滤、纳滤、反渗透、气体分离、全蒸发或蒸气浸透、透析、膜蒸馏、层析膜和/或正向渗透和压力延迟渗透。
根据本发明的实施方式的多孔膜具有约0.05μm至约10μm的孔径,并用作微滤膜。根据本发明的某些实施方式的多孔膜具有约1nm至约0.5μm的孔径,并用作纳滤膜。
根据本发明的实施方式的多孔膜具有约70至约90达因/厘米或更大的临界湿润表面张力(CWST),例如72,74,76,78,80,82,84或86达因/厘米。
根据本发明的一个实施方式可以用于多种应用,包括例如诊断应用(包括,例如样品制备和/或诊断侧向流装置),喷墨应用,过滤用于制药工业的流体,过滤用于医学应用的流体(包括家用的和/或患者使用的,例如静脉应用,还包括例如过滤生物流体如血液(例如除去白细胞)),过滤用于电子工业的流体(例如,过滤微电子工业中的光致刻蚀剂流体),过滤用于食品和饮料工业的流体,净化、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),细胞收获和/或过滤细胞培养液。可选或额外地,根据本发明的实施方式的膜可用于过滤空气和/或气体,和/或可以用于通气应用(例如使空气和/或气体通过,但不使流体通过)。根据本发明的实施方式的膜可以用于多种装置,包括外科装置和产品,例如眼科手术产品。
根据本发明的实施方式,所述多孔膜可以具有多种构造,包括平面、平坦片材、褶皱、管状、螺旋形和中空纤维。
根据本发明的实施方式的多孔膜典型地布置在包括至少一个入口和至少一个出口的壳体中,并在所述入口和所述出口之间限定至少一个流体流动路径,其中至少一个本发明的膜或包括至少一个本发明的膜的过滤器横跨所述液体流动路径,以提供过滤器装置或过滤器模块。在一个实施方式中,提供了一种过滤器装置,其包括含入口和第一出口的壳体,并在所述入口和所述第一出口之间限定第一流体流动路径,以及至少一个本发明的膜或包括至少一个本发明的膜的过滤器,所述本发明的膜或包括至少一个本发明的膜的过滤器布置在壳体中横跨第一流体流动路径。
优选地,为了横向流应用,将至少一个本发明的膜或包含至少一个本发明的膜的过滤器布置在包括至少一个入口和至少两个出口的壳体中,所述壳体在所述入口和所述第一出口之间至少限定第一流体流动路径,并在所述入口和所述第二出口之间限定第二流体流动路径,其中本发明的膜或包括至少一个本发明的膜的过滤器横跨所述第一流体流动路径,以提供过滤器装置或过滤器模块。在一个示例性实施方式中,所述过滤器装置包括横向流过滤器模块,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的壳体,并在所述入口和所述第一出口之间限定第一流体流动路径,并在所述入口和所述第二出口之间限定第二流体流动路径,其中布置至少一个本发明的膜或包括至少一个本发明的膜的过滤器横跨所述第一流体流动路径。
所述过滤器装置或模块可以是可消毒的。可以使用合适形状的任意壳体,并提供入口和一个或多个出口。
可以由任意合适的刚性不可渗透性材料,包括与被处理的流体相容的任意不可渗透性热塑性材料生产所述壳体。例如,可以由金属如不锈钢,或由聚合物,例如透明或半透明聚合物如丙烯酸系、聚丙烯、聚苯乙烯或聚碳酸酯树脂生产所述壳体。
以下实施例进一步阐释了本发明,但是当然不应该被认为是以任意方式限制本发明的范围。
实施例1
本实施例阐释了一种制备根据本发明的实施方式的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g的BASFE6020级聚醚砜溶于DMAc(250ml)。在剧烈搅拌下,在2小时内实现完全溶解。添加碳酸钾(2g)至混合物中,并将反应混合物混合30分钟,随后添加缩水甘油(70mL)。将反应混合物保持在100℃,持续搅拌8小时。通过添加乙酸(20mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5L的IPA∶水(90∶10v/v)来沉淀产物。将获得的沉淀物经由烧结的布氏漏斗过滤,用水(500mL)和IPA(250mL)洗涤。然后将产生的白色固体粉末干燥,以生成140g的期望的产物,通过质子NMR谱测定具有40mol%的PES和60mol%的缩水甘油基。
实施例2
本实施例阐释了制备另一种根据本发明的实施方式的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g的Sumitomo5003PS级聚醚砜溶于DMAc(250mL)中。在剧烈搅拌下,在2小时内实现完全溶解。添加碳酸钾(2g)至混合物中,并将反应混合物混合30分钟,随后添加缩水甘油(100mL)。将反应混合物保持在100℃,持续搅拌5小时。通过添加乙酸(20mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5L的IPA∶水(90∶10v/v)来沉淀产物。将获得的沉淀物经由烧结布氏漏斗过滤,用水(500mL)和IPA(250mL)洗涤。然后将产生的白色固体干燥,以生成130g所需产物,通过质子NMR谱测定具有40mol%的PES和60mol%的缩水甘油基。
实施例3
本实施例阐释了制备又一种根据本发明的实施方式的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g分子量为45KD的SolvayVIRANTAGEVW-10200RP级聚醚砜溶于DMAc(230mL)中。添加碳酸钾(1.5g),并将反应混合物混合30分钟,随后添加缩水甘油(20mL)。将反应混合物保持在100℃,持续搅拌8小时。通过添加乙酸(4mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5升DI水,沉淀所述产物。将获得的沉淀物经由烧结布氏漏斗过滤并用水(500mL)和IPA(250mL)洗涤。将产生的固体干燥,以生成105g期望的产物,通过质子NMR谱测定具有90mol%PES和10mol%缩水甘油基。
实施例4
本实施例阐释了制备又一种根据本发明的实施方式的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g分子量为22KD的SolvayVIRANTAGEVW-10700RP级聚醚砜溶于DMAc(230mL)中。添加碳酸钾(2g),并将反应混合物混合30分钟,随后添加缩水甘油(15mL)。将反应混合物保持在100℃,持续搅拌8小时。通过添加乙酸(4mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5升DI水,沉淀所述产物。将获得的沉淀物经由烧结布氏漏斗过滤并用IPA(500mL)洗涤。将产生的固体干燥,以生成107g期望的产物,通过质子NMR谱测定具有90mol%PES和10mol%缩水甘油基。
实施例5
本实施例阐释了制备又一种根据本发明的实施方式的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g分子量为22KD的SolvayVIRANTAGEVW-10700RP级聚醚砜溶于DMAc(230mL)中。添加碳酸钾(2g),并将反应混合物混合30分钟,随后添加缩水甘油(25mL)。将反应混合物保持在100℃,持续搅拌8小时。通过添加乙酸(5mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5升DI水,沉淀所述产物。将获得的沉淀物经由烧结布氏漏斗过滤并用IPA(500mL)洗涤。将产生的固体干燥,以生成107g期望的产物,通过质子NMR谱测定具有85mol%PES和15mol%缩水甘油基。
实施例6
本实施例阐释了制备又一种根据本发明的实施方式的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g分子量为22KD的SolvayVIRANTAGEVW-10700RP级聚醚砜溶于DMAc(230mL)中。添加碳酸钾(2g),并将反应混合物混合30分钟,随后添加缩水甘油(35mL)。将反应混合物保持在100℃,持续搅拌5小时。通过添加乙酸(5mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5升DI水,沉淀获得的产物。将获得的沉淀物经由烧结布氏漏斗过滤并用IPA(500mL)洗涤。将产生的固体干燥,以生成110g期望的产物,通过质子NMR谱测定具有80mol%PES和20mol%缩水甘油基。
实施例7
本实施例阐释了制备又一种根据本发明的实施方式的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g分子量为22KD的SolvayVIRANTAGEVW-10700RP级聚醚砜溶于DMAc(230mL)中。添加碳酸钾(2g),并将反应混合物混合30分钟,随后添加缩水甘油(50mL)。将反应混合物保持在100℃,持续搅拌8小时。通过添加乙酸(8mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5升DI水,沉淀获得的产物。将获得的沉淀物经由烧结布氏漏斗过滤并用IPA(500mL)洗涤。将产生的固体干燥,以生成110g期望的产物,通过质子NMR谱测定具有67mol%PES和33mol%缩水甘油基。
实施例8
本实施例阐释了制备又一种根据本发明的实施方式的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g分子量为22KD的SolvayVIRANTAGEVW-10700RP级聚醚砜溶于DMAc(230mL)中。添加碳酸钾(2g),并将反应混合物混合30分钟,随后添加缩水甘油(60mL)。将反应混合物保持在100℃,持续搅拌8小时。通过添加乙酸(10mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5L的DI水∶IPA(80∶20v/v),沉淀获得的产物。将获得的沉淀物经由烧结布氏漏斗过滤并用DI水(250mL)和IPA(500mL)洗涤。将产生的固体干燥,以获得110g期望的产物,通过质子NMR谱测定具有53mol%PES和47mol%缩水甘油基。
实施例9
本实施例阐释了制备又一种根据本发明的实施方式的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g分子量为22KD的SolvayVIRANTAGEVW-10700RP级聚醚砜溶于DMAc(230mL)中。添加碳酸钾(2g),并将反应混合物混合30分钟,随后添加缩水甘油(80mL)。将反应混合物保持在100℃,持续搅拌8小时。通过添加乙酸(10mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5L的DI水∶IPA(80∶20v/v),沉淀获得的产物。将获得的沉淀物经由烧结布氏漏斗过滤并用DI水(500mL)和IPA(500mL)洗涤。将产生的固体干燥,以获得120g期望的产物,通过质子NMR谱测定具有35mol%PES和65mol%缩水甘油基。
实施例10
本实施例阐释了一种制备部分可溶于水的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g分子量为22KD的SolvayVIRANTAGEVW-10700RP级聚醚砜溶于DMAc(230mL)中。添加碳酸钾(2g),并将反应混合物混合30分钟,随后添加缩水甘油(100mL)。将反应混合物保持在100℃,持续搅拌8小时。通过添加乙酸(20mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5升IPA,沉淀获得的产物。然后将获得的沉淀物经由烧结布氏漏斗过滤并用DI水(500mL)和IPA(500mL)洗涤。将产生的固体干燥,以获得110g期望的产物,通过质子NMR谱测定具有25mol%PES和75mol%缩水甘油基。
实施例11
本实施例阐释了一种制备可溶于水的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g分子量为22KD的SolvayVIRANTAGEVW-10700RP级聚醚砜溶于DMAc(230mL)中。添加碳酸钾(2g),并将反应混合物混合30分钟,随后添加缩水甘油(150mL)。将反应混合物保持在100℃,持续搅拌8小时。通过添加乙酸(20mL)猝灭反应混合物,使之冷却至室温。通过将反应混合物缓慢添加至1.5升IPA,沉淀获得的产物。然后将获得的沉淀物经由烧结布氏漏斗过滤并用DI水(500mL)和IPA(500mL)洗涤。将产生的固体干燥,以获得130g期望的产物,通过质子NMR谱测定具有10mol%PES和90mol%缩水甘油基。
实施例12
本实施例阐释了制备又一种根据本发明的实施方式的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g分子量为45KD的SolvayVIRANTAGEVW-10200RP级的聚醚砜溶于DMAc(230mL)中。添加碳酸钾(1.5g),并将反应混合物混合30分钟,随后添加缩水甘油(40mL)。将反应混合物保持在100℃,持续搅拌8小时。通过添加乙酸(4mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5升DI水,沉淀获得的产物。将获得的沉淀物经由烧结布氏漏斗过滤并用水(500mL)和IPA(250mL)洗涤。将产生的固体干燥,以生成105g期望的产物,通过质子NMR谱测定具有85mol%PES和15mol%缩水甘油基。
实施例13
本实施例阐释了制备又一种根据本发明的实施方式的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g分子量为45KD的SolvayVIRANTAGEVW-10200RP级的聚醚砜溶于DMAc(230mL)中。添加碳酸钾(1.5g),并将反应混合物混合30分钟,随后添加缩水甘油(50mL)。将反应混合物保持在100℃,持续搅拌8小时。通过添加乙酸(6mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5升DI水,沉淀获得的产物。将获得的沉淀物经由烧结布氏漏斗过滤并用水(500mL)和IPA(250mL)洗涤。将产生的固体干燥,以获得105g期望的产物,通过质子NMR谱测定具有80mol%PES和20mol%缩水甘油基。
实施例14
本实施例阐释了制备又一种根据本发明的实施方式的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g分子量为45KD的SolvayVIRANTAGEVW-10200RP级的聚醚砜溶于DMAc(230mL)中。添加碳酸钾(1.5g),并将反应混合物混合30分钟,随后添加缩水甘油(60mL)。将反应混合物保持在100℃,持续搅拌8小时。然后通过添加乙酸(8mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5升DI水,沉淀获得的产物。将获得的沉淀物经由烧结布氏漏斗过滤并用水(500mL)和IPA(250mL)洗涤。将产生的固体干燥,以获得110g期望的产物,通过质子NMR谱测定具有70mol%PES和30mol%缩水甘油基。
实施例15
本实施例阐释了制备又一种根据本发明的实施方式的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g分子量为45KD的SolvayVIRANTAGEVW-10200RP级的聚醚砜溶于DMAc(230mL)中。添加碳酸钾(1.5g),并将反应混合物混合30分钟,随后添加缩水甘油(70mL)。将反应混合物保持在100℃,持续搅拌8小时。然后通过添加乙酸(10mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5L的DI水∶IPA(80∶20v/v),沉淀获得的产物。将产生的沉淀物经由烧结布氏漏斗过滤并用水(500mL)和IPA(250mL)洗涤。将产生的固体干燥,以获得115g期望的产物,通过质子NMR谱测定具有55mol%PES和45mol%缩水甘油基。
实施例16
本实施例阐释了制备又一种根据本发明的实施方式的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100g分子量为45KD的SolvayVIRANTAGEVW-10200RP级的聚醚砜溶于DMAc(230mL)中。添加碳酸钾(1.5g),并将反应混合物混合30分钟,随后添加缩水甘油(120mL)。将反应混合物保持在100℃,持续搅拌8小时。通过添加乙酸(10mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5L的DI水∶IPA(80∶20v/v),沉淀产生的产物。将获得的沉淀物经由烧结布氏漏斗过滤并用水(500mL)和IPA(250mL)洗涤。将产生的固体干燥,以获得140g期望的产物,通过质子NMR谱测定具有30mol%PES和70mol%缩水甘油基。
实施例17
本实施例阐释了一种制备部分可溶于水的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100gBASFE6020级的聚醚砜溶于DMAc(230mL)中。在剧烈搅拌下,在2小时内实现完全溶解。将碳酸钾(2g)添加至混合物中,并将反应混合物混合30分钟,随后添加缩水甘油(110mL)。将反应混合物保持在100℃,持续搅拌8小时.通过添加乙酸(20mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5L的IPA∶水(90∶10v/v),沉淀获得的产物。将获得的沉淀物经由烧结布氏漏斗过滤并用水(500mL)和IPA(250mL)洗涤。将产生的白色固体粉末干燥,以获得150g期望的产物,通过质子NMR谱测定具有20mol%PES和80mol%缩水甘油基。
实施例18
本实施例阐释了制备另一种部分可溶于水的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100gBASFE7020级的聚醚砜溶于DMAc(300mL)中。将碳酸钾(2g)添加至混合物中,并将反应混合物混合30分钟,随后添加缩水甘油(100mL)。将反应混合物保持在100℃,持续搅拌12小时。通过添加乙酸(20mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5L的IPA∶水(80∶20v/v),沉淀获得的产物。将获得的沉淀物经由烧结布氏漏斗过滤并用水(500mL)和IPA(250mL)洗涤。将产生的白色固体粉末干燥,以获得150g期望的产物,通过质子NMR谱测定具有30mol%PES和70mol%缩水甘油基。
实施例19
本实施例阐释了制备又一种根据本发明的实施方式的嵌段共聚物的方法。
在100℃于500mL烧瓶中,将100gSumitomo5400P级的聚醚砜溶于DMAc(230mL)中。将碳酸钾(1.5g)添加至混合物中,并将反应混合物混合30分钟,随后添加缩水甘油(100mL)。将反应混合物保持在100℃,持续搅拌12小时。通过添加乙酸(20mL)猝灭反应混合物,并使之冷却至室温。通过将反应混合物缓慢添加至1.5L的IPA∶水(80∶20v/v),沉淀获得的产物。将获得的沉淀物经由烧结布氏漏斗过滤并用水(500mL)和IPA(250mL)洗涤。将产生的白色固体粉末干燥,以获得140g期望的产物,通过质子NMR谱测定具有35mol%PES和65mol%缩水甘油基。
实施例20
本实施例阐释了根据本发明的实施方式的嵌段共聚物的一些性质。
表1.嵌段共聚物性质
实施例21
本实施例阐释了制备根据本发明的实施方式的多孔膜。
将实施例1和2中制备的嵌段共聚物(PES-Pg)作为润湿剂用于制备多孔PES膜。所述润湿剂以所述PES的6.9phr使用。膜流延溶液的组成连同对照膜的组成列于下表2中,其中PVPK-90用作润湿剂。所述流延溶液如注释所述是透明的。
表2.使用来自实施例1和2的PES-Pg制备的PES膜制剂
对照 | PES-Pg | PES-Pg | PES-Pg | PES-Pg | |
% | % | % | % | % | |
PEG | 64.5 | 64.5 | 63.6 | 64.9 | 64.5 |
H2O | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 |
DMF | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 |
NMP | 7.6 | 7.6 | 7.6 | 7.6 | 7.6 |
PES | 13.0 | 13.0 | 13.0 | 13.0 | 13.0 |
甘油 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
润湿剂 | 0.9 | 0.9 | 1.80 | 0.45 | 0.9 |
PVP K90 | 实施例1 | 实施例1 | 实施例1 | 实施例2 | |
注释 | 透明混合物 | 透明混合物 | 透明混合物 | 透明混合物 | 透明混合物 |
使用蒸气诱导的相分离方法流延所述膜流延溶液,流延温度为43℃,相对湿度75%,干球温度25℃。没有观察到制剂缺陷。使用SumitomoPES。
测量经干燥的膜的物理性质和CWST,并列于表3中。还测试所述膜的样品的IPA可萃取性。将6个47mm直径的盘在80℃干燥1小时,并用IPA索氏(Soxhlet)萃取3小时,随后在80℃最终干燥循环1小时。计算可萃取%。在IPA萃取后再次测量CWST,并列于表3中。
表3.多孔膜的物理性质和CWST
实施例22
本实施例阐释了制备根据本发明的实施方式的另外的多孔膜。
将实施例2和7中制备的嵌段共聚物(PES-Pg)作为润湿剂用于制备多孔PES膜。所述润湿剂以PES的6.9phr使用。膜流延溶液的组成列于表4中,膜流延条件列于表5中。
表4.膜流延溶液的组成
组分 | 对照 | 实施例7 | 实施例7 | 实施例2 | 实施例2 |
% | % | % | % | % | |
PEG-400 | 66.40 | 66.40 | 64.40 | 66.40 | 64.40 |
PES(Sumitomo) | 14.0 | 13.0 | 13.0 | 13.0 | 11.0 |
实施例7 | -- | 1.0 | 3.0 | -- | -- |
实施例2 | -- | -- | -- | 1.0 | 3.0 |
RO水 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
DMF | 11.0 | 11.0 | 11.0 | 11.0 | 11.0 |
NMP | 6.6 | 6.6 | 6.6 | 6.6 | 6.6 |
表5:膜流延条件
条件 | 设定 |
混合温度(℃) | 38 |
流延厚度(密耳) | 12 |
流延板温度(℃) | 43 |
室板温度(℃) | 38 |
干球(℃) | 25 |
RH(%) | 75 |
气流速度(fps) | 5.0 |
过滤 | 环境水/乙醇-水(1∶1)/热水(40℃) |
干燥(℃) | 60 |
生产0.2μm直径多孔膜,并且它们不含任何膜缺陷,表明共聚物与基体PES的相容性。所述膜的一些性质列于表6中。与对照膜相比,所述嵌段共聚物添加剂增加了本发明的膜的CWST。来自实施例2的嵌段共聚物具有高于来自实施例7的嵌段共聚物的分子量,并且导致CWST的明显增加。采用实施例2的嵌段共聚物制备的膜具有明显高的水流速率。
所述膜的SEM图像表明PES-Pg膜具有膜流动、强度和过滤寿命性能所需的典型的PES膜多孔结构。图1A描述了由实施例7嵌段共聚物制备的膜的横截面的SEM,和图1B描述了图1A的更高放大倍数SEM,显示所述膜具有对称和高度互通的孔结构。
实施例23
本实施例阐释了多孔膜的孔径与制备根据本发明的实施方式的多孔膜中所使用的亲水性嵌段共聚物量的函数关系。
制备流延溶液,所述流延溶液包含12.1%聚醚砜树脂,在NMP溶液中的22.5%叔戊醇,和以下之一:0.3%,0.6%,1%或2%的亲水性嵌段共聚物。将所述溶液以薄膜形式沉积到聚酯薄膜片材或织构基材载体上。基于气隙开始相转变。通过控制风扇速率,控制缝隙上的空气速率。通过将其浸入非溶剂浴,随后在RO水中冲洗和烘箱干燥来完成相转变。获得的结果列于下表7中,表明亲水性嵌段共聚物的非常小的浓度,例如在0.3%时,获得高的CWST。在0.3%和0.6%的亲水性嵌段共聚物浓度时,获得的孔径为10nm。
实施例24
本实施例阐释了包含PPESK和PES-聚甘油(PES-Pg)共混物作为润湿剂的多孔膜的制备。
制备包含15重量%的PPESK树脂,300phr溶剂NMP/DMAc(v/v),10phr的实施例2的PES-Pg的流延溶液,并在28℃,空气温度32℃,相对湿度72%下流延为15密耳厚的膜。水浴温度设定为80℃。将涂液放置在环境室中15秒,并在室温下浸没于水中。所述膜具有76达因/厘米的CWST。通过SEM表征膜的形态。图3A描述了根据本发明的实施方式的膜的横截面的SEM图像。图3B描述了图3A中描述的图像的更高放大倍数的SEM图像。所述膜具有从一侧到另一侧的非对称的孔结构分布。所述孔呈具有低互通性的蜂窝形式。
本文引用的所有参考文献,包括出版物、专利申请和专利,在此通过参考以如下相同的程度并入本文中:如同各参考文献单独且明确地表明通过参考且以其整体并入本文中或以其整体列举。
在描述本发明的上下文中(特别是在随后权利要求书的上下文中)的术语“一,,和“一个,,和“所述(该),,和“至少一个”和相似的术语的使用,除非本文另有说明或通过上下文明显矛盾,将被解释为涵盖单数和复数。跟随一系列一个或多个项目(例如,“A和B中的至少一个”)的术语“至少一个,,的使用,除非本文另有说明或通过上下文明显矛盾,将被解释为本意是选自所列出的项目中的一项(A或B)或两个或更多个所列出的项目的任意组合(A和B)。除非另有说明,术语“包含”、“具有”、“包括”和“含有,,将被解释为开放式术语(即,意为“包括,但不限于”)。除非本文另有说明,本文数值范围的记载仅意为简记法,其独立地涉及落在该范围内的每个单独的值,且将每个单独的值如同其独立地被记载在本文而并入说明书中。除非本文另有说明或通过上下文明显矛盾,本文描述的所有方法可以以任何合适的顺序实施。除非另有要求,任何和所有实例的使用或本文提供的示例性语言(例如,“例如(如)”)仅旨在更好地说明本发明而不对本发明的范围施加限制。在说明书中没有语言应该被解释为指示任何未要求保护的要素对本发明的实施是必要的。
在本文中描述了本发明优选的实施方案,包括本发明人已知的用于实施本发明的最佳模式。通过阅读上面的描述,这些优选的实施方案的变体对于本领域的普通技术人员可变得显而易见。本发明人预期本领域技术人员视情况而定会使用这些变体,且本发明人意在除了按照本文的具体描述不同地实践本发明。因此,本发明包括所附的权利要求中记载的主题的所有被适用的法律允许的变型和等价物。此外,除非本文另有说明或通过上下文明显矛盾,本发明涵盖了以其所有可能的变体形式的上述要素的任意组合。
Claims (18)
1.式A-B-A(I)或A-B(II)的嵌段共聚物,其包含嵌段A和B,其中嵌段A是包含聚甘油的亲水性聚合物链段,且嵌段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,所述聚甘油具有一个或多个以下重复单元:
3.根据权利要求1或2所述的嵌段共聚物,其中,嵌段A包含一个或多个以下结构:
4.根据权利要求1-3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、二氮杂萘酮联苯聚芳醚砜酮、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。
5.根据权利要求4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。
6.根据权利要求5所述的嵌段共聚物,其具有以下结构:
其中n为约10至约1000。
7.根据权利要求1-6中任一项所述的嵌段共聚物,其中,嵌段A以约20mol%至约60mol%的量存在,嵌段B以约30mol%至约80mol%的量存在。
8.根据权利要求7所述的嵌段共聚物,其中,嵌段A以约40mol%至约55mol%的量存在,嵌段B以约40mol%至约60mol%的量存在。
9.制备根据权利要求1-8中任一项所述的嵌段共聚物的方法,包括:
(i)提供具有一个或多个端基官能团的芳族疏水性聚合物链段,所述端基官能团选自羟基、巯基和氨基;和
(ii)对所述芳族疏水性聚合物链段进行缩水甘油的开环聚合。
10.根据权利要求9所述的方法,其中,所述芳族疏水性聚合物链段具有一个或多个端羟基。
11.根据权利要求9或10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至约1000。
12.根据权利要求9-11中任一项所述的方法,其中,在碱存在下进行所述开环聚合。
13.根据权利要求12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、四甲基氢氧化铵、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、氨基钠和氨基锂及其组合。
14.根据权利要求9-13中任一项所述的方法,其中,在选自N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲亚砜和N-甲基吡咯烷酮及其混合物的溶剂中进行所述缩水甘油的开环聚合。
15.根据权利要求9-14中任一项所述的方法,其中,所述芳族疏水性聚合物链段与缩水甘油的摩尔比为约1∶0.1至约1∶1.1。
16.根据权利要求9-15中任一项所述的方法,其中,所述芳族疏水性聚合物链段与缩水甘油的摩尔比为约1∶0.7至约1∶0.9。
17.多孔膜,其包含芳族疏水性聚合物和根据权利要求1-8中任一项所述的嵌段共聚物。
18.制备包含芳族疏水性聚合物和根据权利要求1-8中任一项所述的嵌段共聚物的多孔膜的方法,所述方法包括:
(i)提供包含溶剂、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)将所述聚合物溶液流延为薄膜;
(iii)使所述薄膜经历相转变,以获得多孔膜;和任选地
(iv)洗涤所述多孔膜。
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EP2963077A1 (en) | 2016-01-06 |
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