CN108430613A - Amphoteric ion sulfone polymer blend and hollow-fibre membrane - Google Patents
Amphoteric ion sulfone polymer blend and hollow-fibre membrane Download PDFInfo
- Publication number
- CN108430613A CN108430613A CN201680070265.6A CN201680070265A CN108430613A CN 108430613 A CN108430613 A CN 108430613A CN 201680070265 A CN201680070265 A CN 201680070265A CN 108430613 A CN108430613 A CN 108430613A
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- Prior art keywords
- polymer
- independently
- hollow
- structural unit
- alkyl
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 95
- 239000000835 fiber Substances 0.000 title claims abstract description 79
- -1 ion sulfone Chemical class 0.000 title description 25
- 229920002959 polymer blend Polymers 0.000 title description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 252
- 150000003457 sulfones Chemical class 0.000 claims abstract description 112
- 239000000203 mixture Substances 0.000 claims abstract description 50
- 125000003118 aryl group Chemical group 0.000 claims description 51
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 28
- 125000005843 halogen group Chemical group 0.000 claims description 22
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 22
- 239000012510 hollow fiber Substances 0.000 claims description 17
- 238000001631 haemodialysis Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 210000004369 blood Anatomy 0.000 claims description 10
- 239000008280 blood Substances 0.000 claims description 10
- 229920002492 poly(sulfone) Polymers 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 description 42
- 239000000243 solution Substances 0.000 description 29
- 229930185605 Bisphenol Natural products 0.000 description 26
- 239000002585 base Substances 0.000 description 26
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 238000005266 casting Methods 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 108090000623 proteins and genes Proteins 0.000 description 9
- 102000004169 proteins and genes Human genes 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 8
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 7
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
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- 238000000926 separation method Methods 0.000 description 6
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- 230000010148 water-pollination Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- 150000004987 o-phenylenediamines Chemical class 0.000 description 4
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- 239000011148 porous material Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 150000000345 2,6-xylenols Chemical class 0.000 description 3
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 108010001336 Horseradish Peroxidase Proteins 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
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- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
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- 229920006254 polymer film Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229940106691 bisphenol a Drugs 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
- 230000008859 change Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical group C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001207 fluorophenyl group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 229920001451 polypropylene glycol Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical class C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
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- BCNBMSZKALBQEF-UHFFFAOYSA-N 1,3-dimethylpyrrolidin-2-one Chemical class CC1CCN(C)C1=O BCNBMSZKALBQEF-UHFFFAOYSA-N 0.000 description 1
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- 239000012141 concentrate Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 125000006840 diphenylmethane group Chemical class 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical class C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 102000018358 immunoglobulin Human genes 0.000 description 1
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical class CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- IMNDHOCGZLYMRO-UHFFFAOYSA-N n,n-dimethylbenzamide Chemical class CN(C)C(=O)C1=CC=CC=C1 IMNDHOCGZLYMRO-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical class O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- IVXQBCUBSIPQGU-UHFFFAOYSA-N piperazine-1-carboxamide Chemical group NC(=O)N1CCNCC1 IVXQBCUBSIPQGU-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000765 poly(2-oxazolines) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012460 protein solution Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
- A61M1/16—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/36—Introduction of specific chemical groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/18—Membrane materials having mixed charged functional groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/34—Molecular weight or degree of polymerisation
Abstract
Provided herein is the blends of the polymer suitable for preparing hollow-fibre membrane.Blend polymer includes the blend of the first polymer containing the sulfone polymer with amphoteric ion functional group and the second polymer containing sulfone polymer.
Description
Cross reference to related applications
The application is entitled " the Zwitterion-Functionalized Polymer submitted on November 19th, 2014
Hollow-Fiber Membranes And Associated Method (the functionalized polymeric hollow fibres of amphoteric ion
Film and correlation technique) " U.S. Patent Application No. 14/547,306 part continuation application, entire contents are incorporated by reference into
Herein.
Background
The disclosure generally relates to prepare the blend polymer of hollow-fibre membrane.Blend polymer includes at least one wraps
The polymer of the group containing amphoteric ion.
Porous hollow fiber polymer film is used for many applications, such as haemodialysis, ultrafiltration, nanofiltration, reverse osmosis, gas point
From, micro-filtration and pervaporation.For many in these applications, there is best selective and chemistry, heat and mechanical stability
Film be ideal.In many applications (such as bio-separation or water filtering), there is improved hydrophily, improved biofacies
Capacitive or it is low be stained in one or more films be also likely to be desirable.
Poly (arylene ether), especially polyether sulfone and polysulfones, due to its machinery, thermally and chemically stability and be commonly used as membrane material
Material.However, these polymer are hydrophobic, and lack biocompatibility and aqueous using required hydrophily.Pass through polymerization
Object blending has been carried out the hydrophilic improvement of film, such as depositing at a small amount of hydrophilic polymer such as polyvinylpyrrolidone (PVP)
In lower manufacture perforated membrane.However, since PVP is water-soluble, it can slowly be leached from porous polymer matrix, generate product
Changeability.Alternatively, hydrophily via the functionalization of main polymer chain and carboxyl, nitrile or polyethylene glycol functional group introducing and
It realizes.However, these chemical modifications may be complicated, expensive and inefficient.In addition, addition functional group may make it difficult to
Hollow-fibre membrane is manufactured by functionalized polymeric.Solve the problems, such as that a kind of method caused due to functional group is after fabrication by film
Functionalization；But this method increases the manufacturing cost of film.
This field needs easy to process and/or manufacture film forming (including hollow-fibre membrane) but can also reduce protein combination
And/or it is stained and provides the material of the good mechanical properties suitable for aqueous application.
It summarizes
Provided herein is the blend polymers for the certain limitations for mitigating the previously known method for manufacturing hollow-fibre membrane.This hair
Bright blend improves the machinability of functionalized polymeric, and also reduces functionalized demand after the casting to film.
Provided herein is hollow-fibre membranes, and it includes the first polymers containing the sulfone polymer with amphoteric ion functional group
With the blend of the second polymer containing sulfone polymer：
On the one hand, provided herein is hollow-fibre membranes, poly- it includes first containing the sulfone polymer with amphoteric ion functional group
The blend of object and the second polymer containing sulfone polymer is closed, wherein including the sulfone polymer with amphoteric ion functional group
First polymer includes the structural unit of the Formulas I A or Formulas I B that are connect with the structural unit of Formula II, and wherein includes sulfone polymer
Second polymer includes the structural unit with Formula II, the structure of III, IV or V, the wherein knot of Formulas I A, IB, II, III, IV and V
Structure is as described in following detailed description part.
Attached drawing
When refer to the attached drawing reading is described in detail below, these and other features, aspects and advantages of the invention will become more preferable
Understand, wherein identical character represents identical part in all the appended drawings, wherein：
Fig. 1 shows the hollow-fibre membrane comprising heavy polymer and comprising claimed blend polymer
Comparison between the cross section of hollow-fibre membrane.
Fig. 2 shows the comparison between the protein-binding matter (being stained) of hollow-fibre membrane：(1) high molecular weight polysulfones
(PSU) (MW 54kg/mol) ultra filtration hollow fiber membrane, the hollow fibre of (2) high molecular weight polysulfones (PSU) (MW 54kg/mol) micro-filtration
Film is tieed up, (3) include PSU (ZwPSU) micro-filtration hollow-fibre membrane of amphoteric ion group, and (4) include that the polymer of the present invention is blended
The micro-filtration hollow-fibre membrane of object (MW 49.3kg/mol), and PSU (ZwPSU) micro-filtration of (5) comprising amphoteric ion group are hollow
Tunica fibrosa.From heavy polymer to blend polymer, observe combine (ELISA) without influencing form and IgG or
It influences minimum.
It is described in detail
Hollow-fibre membrane is commonly used in wherein needing the application of hydrophily and/or biocompatibility barrier.Amphoteric ion sulfone polymerize
Object is hydrophilic and leads to low-protein combination and biodeterioration.However, amphoteric ion sulfone polymer tends to be difficult to
Film forming, and gained film usually has the engineering properties of difference.The hydrophilic previous trial of improvement film containing sulfone polymer, which concentrates on, to gather
It is functionalized after closing the manufacture of object and/or film.
In contrast, provided herein is the novel blend of the polymer comprising sulfone polymer and amphoteric ion sulfone polymer,
It mitigates to functionalized needs after the manufacture of film.In addition, blend polymer as described herein can improve polymer network knot
Structure simultaneously leads to better mechanical performance.Blend polymer as described herein also assigns improved machinability, to allow more
Film, including hollow-fibre membrane is easily manufactured.In addition, blend polymer as described herein provides the desired hydrophily to film
And/or biocompatibility.Therefore, by the way that the sulfone polymer of low amounts to be blended with amphoteric ion sulfone polymer, improve amphoteric ion
The machinability of sulfone polymer film forming.In addition, the engineering properties of the film comprising the blend polymer significantly improves, protect simultaneously
Hold film form and the low combination feature of film.Advantageously, film of the invention mitigates has with from matrix leaching water-soluble polymer such as PVP
The problem of pass, to reduce product changeability.
Blend polymer as described herein provides film machinability (such as prepared paint viscosity (dope viscosity))
With the simple adjustment of engineering properties (such as high tensile elongation) and significantly improve, and also by with sulfone relatively inexpensive in blend
Polymer replaces expensive amphoteric ion sulfone polymer to provide some cost reductions.
Certain terms
Approximating language as used herein, which can be applied to modification, in entire disclosure and claims may allow to change
Any quantificational expression without leading to relative basic function variation.Therefore, for example " about " by one or more terms
" substantially " value modified is not limited to specified exact value.In some cases, approximating language can correspond to for surveying
The precision of the instrument of magnitude.In here and throughout the specification and claims book, scope limitation can be combined and/or mutually
It changes, such range is identified and includes all subranges wherein included, unless context or language are indicated otherwise.
In following specification and claims, unless the context clearly indicates otherwise, otherwise singulative " one ",
"one" and "the" include plural reference.As used herein, term "or" being not intended to be exhaustive property, and refer to it is existing at least
Component mentioned by one, and include wherein may exist the case where combination of mentioned component, unless context is in addition bright
Really instruction.
As used herein, " sulfone polymer " is comprising structure aryl-SO2One or more subelements of aryl it is any
Polymer.In general, sulfone polymer is prepared via the reaction between bis-phenol and bis- (4- chlorphenyls) sulfones by eliminating sodium chloride：Sulfone is poly-
It includes but not limited to polysulfones, polyarylsufone (or referred to as polyphenylsulphine or polyphenylsulfone), polyether sulfone etc. to close object.
As used herein, " sulfone polymer with amphoteric ion functional group " or " amphoteric ion sulfone polymer " are comprising knot
Structure aryl-SO2One or more subelements of aryl simultaneously have one or more subelements comprising amphoteric ion functional group
Any polymer.
Terms used herein " hollow-fibre membrane " refer to the film knot based on fiber for including the separating layer for being present in surface
Structure.Hollow-fibre membrane can use " inside and outside " or " in outer " mechanism to work.Term " hollow-fibre membrane " and " film " are herein
It is used interchangeably, unless the context clearly indicates otherwise.
Term " alkyl " refers to the linear or branched alkyl group with 1 to 12 carbon atom in chain.The example of alkyl includes
Methyl (Me) ethyl (Et), n-propyl, isopropyl, butyl, isobutyl group, sec-butyl, tertiary butyl (tBu), amyl, isopentyl, uncle
Amyl, hexyl, isohesyl etc..
" naphthenic base " refers to monocycle or polycyclic non-aromatic hydrocarbon group with 3 to 12 carbon atoms.Naphthenic base it is non-limiting
Example includes cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, 1- methylcyclopropyl groups, 2- methylcyclopentyls, octahydro -1H- indenes, decahydro
Naphthalene etc..
Term " aryl " indicates monocycle or bicyclic aromatic hydrocarbon ring structure.Aryl rings can have 6 or 10 carbon originals in ring
Son.
Described herein is hollow-fibre membrane, poly- it includes first containing the sulfone polymer with amphoteric ion functional group
Close the blend of object and the second polymer containing sulfone polymer.
On the one hand, hollow-fibre membrane includes the first polymer containing the sulfone polymer with amphoteric ion functional group and contains
There is the blend of the second polymer of sulfone polymer, wherein the comprising the sulfone polymer with amphoteric ion functional group first polymerization
Object includes the structural unit of the Formulas I A or Formulas I B that are connect with the structural unit of Formula II：
Wherein
R1And R2It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or virtue
Basic ring；
K is 0 to 10；
Y' and R' is each independently hydrogen, C1-C20Alkyl or aryl ring；
R4It is key, C1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R5And R6It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or virtue
Basic ring；With
Y' and R' is each independently hydrogen, C1-C20Alkyl or aryl ring；
A, a' and b independently is 0,1,2,3 or 4 at each occurrence；With
M and n is each independently 0 or 1.
On the other hand, hollow-fibre membrane include containing with amphoteric ion functional group sulfone polymer first polymer and
The blend of second polymer containing sulfone polymer, wherein comprising sulfone polymer second polymer include with Formula II,
The structural unit of the structure of III, IV or V,
Wherein
R5And R6It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or virtue
Basic ring；With
Y' and R' is each independently hydrogen, C1-C20Alkyl or aryl ring；
A and b independently is 0,1,2,3 or 4 at each occurrence；With
M and n is each independently 0 or 1.
In some embodiments of above-mentioned hollow-fibre membrane, include the of the sulfone polymer with amphoteric ion functional group
One polymer includes the structural unit of the Formulas I A or Formulas I B that are connect with the structural unit of Formula II：
Wherein
R1And R2It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or virtue
Basic ring；
K is 0 to 10；
Y' and R' is each independently hydrogen, C1-C20Alkyl or aryl ring；
R4It is key, C1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R5And R6It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or virtue
Basic ring；With
Y' and R' is each independently hydrogen, C1-C20Alkyl or aryl ring；
A, a' and b independently is 0,1,2,3 or 4 at each occurrence；
M and n is each independently 0 or 1；With
The second polymer for wherein including sulfone polymer includes the structural unit with Formula II, IV or V structure
In some embodiments of above-mentioned hollow-fibre membrane, including first of the sulfone polymer with amphoteric ion functional group is poly-
Close the structural unit that object includes Formula IV：
Wherein w is 0,1,2 or 3.
In some embodiments of above-mentioned hollow-fibre membrane, include the of the sulfone polymer with amphoteric ion functional group
One polymer includes the structural unit of Formula VII：
Wherein P+Q=1, P=0.30-0.50, Q=0.50-0.70.
In some embodiments of above-mentioned hollow-fibre membrane, the amphoteric ion functionalization knot of the Formulas I B in first polymer
The molar fraction of structure unit is less than about 50 moles of % of the total mole number of the unit of Formulas I B and Formula II in first polymer.Upper
In some embodiments for stating hollow-fibre membrane, mole of the amphoteric ion functionalized structure unit of the Formulas I B in first polymer
Within the scope of about 30 moles of % to about 50 moles of % of the total mole number of the unit of Formulas I B and Formula II of the score in first polymer.
In some embodiments of above-mentioned hollow-fibre membrane, include the of the sulfone polymer with amphoteric ion functional group
The molecular weight of one polymer is in the range of about 10000g/mol to about 80000g/mol.
In some embodiments of above-mentioned hollow-fibre membrane, including the second polymer of sulfone polymer contains Formula II
Structural unit polysulfones.
In some embodiments of above-mentioned hollow-fibre membrane, including the second polymer of sulfone polymer contains formula IV
Structural unit polyphenylsulphine.
In some embodiments of above-mentioned hollow-fibre membrane, including the second polymer of sulfone polymer contains Formula V
Structural unit polyether sulfone.
In some embodiments of above-mentioned hollow-fibre membrane, including the amount of the second polymer of sulfone polymer is in film
The about 0.5 weight % to about 5 weight % of the total weight of polymer.
In some embodiments of above-mentioned hollow-fibre membrane, including the molecular weight of the second polymer of sulfone polymer is about
In the range of 50000g/mol to about 80000g/mol.
In some embodiments of above-mentioned hollow-fibre membrane, include the of the sulfone polymer with amphoteric ion functional group
One polymer includes the structural unit for the Formulas I B being connect with the structural unit of Formula II, and includes the second polymer packet of sulfone polymer
Structural unit containing Formula II
In some embodiments of above-mentioned hollow-fibre membrane, including first of the sulfone polymer with amphoteric ion functional group is poly-
It includes the structural unit of Formulas I B connect with the structural unit of Formula II to close object, and include the second polymer of sulfone polymer includes formula
The structural unit of IV
In some embodiments of above-mentioned hollow-fibre membrane, including first of the sulfone polymer with amphoteric ion functional group is poly-
It includes the structural unit of Formulas I B connect with the structural unit of Formula II to close object, and include the second polymer of sulfone polymer includes formula
The structural unit of V
Provided herein is the hollow fiber membrane modules for including multiple hollow-fibre membranes, wherein including the sulfone with amphoteric ion functional group
The first polymer of polymer includes the structural unit of Formulas I B being connect with the structural unit of Formula II, and includes the of sulfone polymer
Dimerization object includes the structural unit of Formula II.The haemodialysis comprising hollow fiber membrane module or blood filtration dress is also provided herein
It sets, wherein the first polymer comprising the sulfone polymer with amphoteric ion functional group includes to be connect with the structural unit of Formula II
The structural unit of Formulas I B, and include that the second polymer of sulfone polymer includes the structural unit of Formula II.
Provided herein is the hollow fiber membrane modules for including multiple hollow-fibre membranes, wherein comprising having amphoteric ion functional group
The first polymer of sulfone polymer include the structural unit of Formulas I B being connect with the structural unit of Formula II, and include sulfone polymer
Second polymer include the structural unit of formula IV.The haemodialysis comprising hollow fiber membrane module or blood mistake is also provided herein
Device is filtered, wherein the first polymer comprising the sulfone polymer with amphoteric ion functional group includes to connect with the structural unit of Formula II
The structural unit of the Formulas I B connect, and include that the second polymer of sulfone polymer includes the structural unit of formula IV.
Provided herein is the hollow fiber membrane modules for including multiple hollow-fibre membranes, wherein comprising having amphoteric ion functional group
The first polymer of sulfone polymer include the structural unit of Formulas I B being connect with the structural unit of Formula II, and include sulfone polymer
Second polymer include the structural unit of Formula V.The haemodialysis comprising hollow fiber membrane module or blood mistake is also provided herein
Device is filtered, wherein the first polymer comprising the sulfone polymer with amphoteric ion functional group includes to connect with the structural unit of Formula II
The structural unit of the Formulas I B connect, and include that the second polymer of sulfone polymer includes the structural unit of Formula V.
Another aspect, provided herein is comprising the first polymer containing the sulfone polymer with amphoteric ion functional group and contain
There is the composition of the blend of the second polymer of sulfone polymer.
In some embodiments, provided herein is a kind of compositions, and it includes contain the sulfone with amphoteric ion functional group
The blend of the first polymer of polymer and second polymer containing sulfone polymer, wherein comprising having amphoteric ion function
The first polymer of the sulfone polymer of group includes the structural unit for the Formulas I B being connect with the structural unit of Formula II, and includes sulfone polymerization
The second polymer of object includes the structural unit of Formula II
Wherein
R1And R2It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or virtue
Basic ring；
K is 0 to 10；
R3It independently is hydrogen atom, C with Y1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R4It is key, C1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R5And R6It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or virtue
Basic ring；
A, a' and b independently is 0,1,2,3 or 4 at each occurrence；With
M and n is each independently 0 or 1.
In some embodiments, provided herein is a kind of compositions, and it includes contain the sulfone with amphoteric ion functional group
The blend of the first polymer of polymer and second polymer containing sulfone polymer, wherein comprising having amphoteric ion function
The first polymer of the sulfone polymer of group includes the structural unit for the Formulas I B being connect with the structural unit of Formula II, and includes sulfone polymerization
The second polymer of object includes the structural unit of formula IV
Wherein
R1And R2It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or virtue
Basic ring；
K is 0 to 10；
R3It independently is hydrogen atom, C with Y1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R4It is key, C1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R5And R6It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or virtue
Basic ring；
A, a' and b independently is 0,1,2,3 or 4 at each occurrence；With
M and n is each independently 0 or 1.
In some embodiments, provided herein is a kind of compositions, and it includes contain the sulfone with amphoteric ion functional group
The blend of the first polymer of polymer and second polymer containing sulfone polymer, wherein comprising having amphoteric ion function
The first polymer of the sulfone polymer of group includes the structural unit for the Formulas I B being connect with the structural unit of Formula II, and includes sulfone polymerization
The second polymer of object includes the structural unit of Formula V
Wherein
R1And R2It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or virtue
Basic ring；
K is 0 to 10；
R3It independently is hydrogen atom, C with Y1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R4It is key, C1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R5And R6It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or virtue
Basic ring；
A, a' and b independently is 0,1,2,3 or 4 at each occurrence；With
M and n is each independently 0 or 1.
The method for being used to form hollow-fibre membrane as described herein is also provided herein comprising：
(A) cast-solution that the blend comprising first polymer and second polymer is provided, wherein in the cast-solution
Total polymer content is less than about 20 weight % of the cast-solution；With
(B) cast-solution is squeezed out to form the hollow-fibre membrane by circular passage.
In alternative embodiment, cast-solution can have in the cast-solution less than about 50 weight % of cast-solution
Total polymer content.In a further embodiment, cast-solution can have the about 10 weight % to about 30 weights for cast-solution
Measure the total polymer content in the cast-solution of %.It should be understood that the actual content of polymer in film may not always with pour
The amount for casting the polymer in solution (coating) is identical.Only it is used as explanation, 2.5 weight % sulfone polymers (second polymer) in film
Content can include amphoteric ion official by 0.4 weight % sulfone polymers in cast-solution together with 15.6 weight % in cast-solution
The sulfone polymer that can be rolled into a ball generates.
In certain embodiments, include the total polymer weight in film by the hollow-fibre membrane that above-mentioned steps (B) are formed
About 0.5 weight % to about 5 weight % amount second polymer.In other embodiments, in being formed by above-mentioned steps (B)
Empty fiber membrane includes the second polymer of the amount of the about 0.5 weight % to about 3 weight % of the total polymer weight in film.
Sulfone polymer as described herein is synthesized using any suitable technology known in the art and/or there is amphoteric ion
The sulfone polymer of functional group.In certain embodiments, sulfone polymer by make at least one aromatic dihydroxy compound with extremely
A kind of few aromatic dihalide compound compound is reacted to synthesize.In aromatic dihydroxy compound and aromatic dihalide compound compound extremely
It is a kind of less that the appropriate functional group (such as piperazine amide group) that can be converted into amphoteric ion functional group can be used to be functionalized.One
In a little embodiments, aromatic dihydroxy compound can be functionalized with suitable functional group.In addition, aromatic dihydroxy compound and
At least one of aromatic dihalide compound compound can include sulfone part.In some embodiments, aromatic dihalide compound
It can includes sulfone part to close object.
The Exemplary aromatic dihalide compounds that can be used include bis- (chlorphenyl) sulfones of 4,4'-, 2,4'- bis- (chlorobenzenes
Base) sulfone, 2,4- bis- (chlorphenyl) sulfones, 4,4'- bis- (fluorophenyl) sulfones, 2,4'- bis- (fluorophenyl) sulfones, 2,4- bis- (fluorophenyl) sulfones,
4,4'- bis- (chlorphenyl) sulfoxides, 2,4'- bis- (chlorphenyl) sulfoxides, 2,4- bis- (fluorophenyl) sulfoxides, 4,4'- bis- (fluorophenyls) are sub-
Sulfone, 2,4'- bis- (fluorophenyl) sulfoxides, 2,4- bis- (fluorophenyl) sulfoxides, 4,4'- bis- (fluorophenyl) ketone, 2,4'- bis- (fluorophenyls)
Ketone, 2,4- bis- (fluorophenyl) ketone, 1,3- bis- (4- fluoro benzoyls) benzene, bis- (4- fluoro benzoyls) benzene of Isosorbide-5-Nitrae-, 4,4'- bis- (4-
Chlorphenyl) phenyl phosphine oxide, 4,4'- bis- (4- fluorophenyls) phenyl phosphine oxides, 4,4'- bis- (4- fluorophenylSulphonyls) -1,1'- connection
Benzene, 4,4'- bis- (4- Chlorophenylsulfonyls) -1,1'- biphenyl, 4,4'- bis- (4- fluorophenyls sulfoxide) -1,1'- biphenyl, 4,4'- is bis-
(4- chlorophenyls) -1,1'- biphenyl and combinations thereof.
The non-limiting examples for the suitable aromatic dihydroxy compounds that can be used include 4,4'- dihydroxy phenyl sulfones, 2,
4'- dihydroxy phenyl sulfones, 4,4'- dihydroxy phenyl sulfoxides, 2,4'- dihydroxy phenyl sulfoxides, bis- (3,5- dimethyl -4- hydroxyls
Phenyl) sulfoxide, bis- (3,5- dimethyl -4- hydroxy phenyls) sulfones, 4,4- (phenyl phosphino-) bis-phenols, 4,4'- oxygroup bis-phenols, 4,4'-
Thiobisphenol, 4,4'- dihydroxy benaophenonels, 4,4'- dihydroxy benzenes methylmethanes, quinhydrones, isophthalic bis-phenol, 5- cyano -1,3- bis-
Hydroxy benzenes, 4- cyano -1,3- dihydroxy benzenes, 2- cyano-Isosorbide-5-Nitrae-dihydroxy benzenes, 2- methoxyhydroquinons, 2,2'- bis-phenols, 4,4'- is bis-
Phenol, 2,2'- dimethyl bisphenols, 2,2', 6,6'- tetramethyl bis-phenols, 2,2', 3,3', 6,6'- hexamethyl bis-phenols, 3,3', 5,5'-
Tetrabromobisphenol, 2', 6,6'- tetramethyl bis-phenols, 4,4'- isopropylidene bisphenols (bisphenol-A), bis- (2, the 6- dimethyl of 4,4'- isopropylidenes
Phenol) (bisphenol-A), 4,4'- isopropylidenes are bis- (2- methylphenols), and 4,4'- isopropylidenes are bis- (2- chavicols),
4,4'- isopropylidenes are bis- (2- allyl -6- methylphenols), 4,4'(1,3- phenylenediisopropylidenes) bis-phenol (bis-phenol M), 4,
4'- isopropylidenes are bis- (3- phenylphenols), 4,4'- isopropylidenes-bis- (2- phenylphenols), and 4,4'- (Isosorbide-5-Nitrae-phenylene two is sub- different
Propyl) bis-phenol (bis-phenol P), 4,4'- ethylidene bis-phenols (bis-phenol E), 4,4'- oxygroup bis-phenols, 4,4'- thiobisphenols, 4,4'- is thio
Bis- (2,6- xylenols), 4,4'- sulfonyldiphenols, 4,4'- sulfonyls bis- (2,6- xylenols), 4,4'- sulfenyls
Base bis-phenol, 4,4'- hexafluoroisopropyli,enes) bis-phenol (bisphenol AF), 4,4'- hexafluoroisopropyli,enes) bis- (2,6- xylenols), 4,
4'- (1- phenyl-ethylenes) bis-phenol (bisphenol-ap), 4,4'- (1- phenyl-ethylenes) are bis- (2,6- xylenol), bis- (4- hydroxyls
Phenyl) -2,2- dichloroethylene (bisphenol-c), bis- (4- hydroxy phenyls) methane (Bisphenol F) are bis- (2,6- dimethyl -4- hydroxy phenyls)
Methane, 2,2- bis- (4- hydroxy phenyls) butane, 3,3- bis- (4- hydroxy phenyls) pentanes, 4,4'- (cyclopentylene) bis-phenols, 4,4'-
(cyclohexylidene) bis-phenol (bisphenol Z), 4,4'- (cyclohexylidenes) are bis- (2- methylphenols), 4,4'- (sub- cyclo-dodecyl) bis-phenols,
4,4'- (two rings [2.2.1] heptamethylene) bis-phenols, 4,4'- (9H- fluorenes -9,9- diyl) bis-phenols, 3,3'- bis- (4- hydroxy phenyls) are different
Benzofuran -1 (3H) -one, 1- (4- hydroxy phenyls) -3,3'- dimethyl -2,3- dihydro -1H- indenes -5- alcohol, 1- (hydroxyl -3 4-,
5- 3,5-dimethylphenyls) -1,3,3', 4,6- pentamethyl -2,3- dihydro -1H- indenes -5- alcohol, 3,3,3', 3'- tetramethyls -2,2', 3,
3'- tetrahydrochysenes -1,1'- spiral shell [indenes] -5,6'- glycol (spirobindene is full), dihydroxy benaophenonel (bis-phenol K), thiobisphenol (bis-phenol
S), bis- (4- hydroxy phenyls) diphenyl methanes, bis- (4- hydroxyphenoxies) -4,4'- biphenyl, 4,4'- bis- (4- hydroxy phenyls) two
Phenyl ether, 9,9- bis- (3- methyl -4- hydroxy phenyls) fluorenes, N- phenyl -3,3- is bis--(4- hydroxy phenyls) phthalimide and
A combination thereof.
The reaction can carry out in the presence of alkali metal compound in polar non-solute, and optionally in catalyst
In the presence of carry out.The basic salt of alkali metal compound can be used for realizing the reaction between dihalo and dihydroxy aromatic compounds.
Exemplary compounds include alkali metal hydroxide, such as, but not limited to lithium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide
Rubidium and cesium hydroxide；Alkali carbonate, such as, but not limited to lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate；With
Alkali metal hydrogencarbonate, such as, but not limited to lithium bicarbonate, sodium bicarbonate, saleratus, rubidium bicarbonate and caesium bicarbonate.These
The combination of compound can also be used for realizing reaction.
Some examples of aprotic polar solvent include but not limited to n,N-Dimethylformamide, N, N- diethyl formyls
Amine, n,N-dimethylacetamide, N, N- diethyl acetamides, N, N- Valpromides, N, N- dimethyl benzamides, N- first
Base -2-Pyrrolidone (NMP), N- ethyl-2-pyrrolidones, N- isopropyls -2-Pyrrolidone, N- isobutyl groups -2-Pyrrolidone,
N- n-propyls -2-Pyrrolidone, N- normal-butyls -2-Pyrrolidone, n-cyclohexyl-2-pyrrolidone, N- methyl -3- methyl -2-
Pyrrolidones, N- ethyl -3- methyl-pyrrolidons, N- methyl -3,4,5- trimethyls -2-Pyrrolidone, N- methyl -2- piperidines
Ketone, N- ethyl -2- piperidones, N- isopropyl -2- piperidones, N- methyl -6- methyl -2- piperidones, N- methyl -3- ethyl piperidines
Ketone, dimethyl sulfoxide (DMSO) (DMSO), diethyl sulfoxide, sulfolane, 1- methyl-1s-oxo sulfolane, 1- ethyl -1- oxo ring fourths
Sulfone, 1- phenyl -1- oxo sulfolane, N, N'- dimethyl-imidazolinones (DMI), diphenyl sulphone (DPS) and combinations thereof.Solvent ready for use
Amount is typically the amount for being enough to dissolve dihalo and dihydroxy aromatic compounds.
The reaction can be about 100 DEG C to about 300 DEG C in some embodiments, be about 120 in some embodiments
DEG C to about 200 DEG C, and it is to carry out at a temperature of about 150 DEG C to about 200 DEG C ranges in specific embodiments.Reaction mixture
It is further starting reaction mixture can be added to by the way that the solvent of azeotropic mixture will be formed with water together with polar non-solute
It is dry.The example of this solvent includes toluene, benzene, dimethylbenzene, ethylbenzene and chlorobenzene.By azeotropic drying remove remaining water it
Afterwards, reaction can carry out at above-mentioned raised temperature.The reaction usually carries out about 1 hour to about 72 in some embodiments
The period of hour, and about 1 hour to about 10 hours period is carried out in specific embodiments.
After completion of the reaction, polymer can be detached with inorganic salts, be deposited in non-solvent and by filtering and drying receipts
Collection.The example of non-solvent includes water, methanol, ethyl alcohol, propyl alcohol, butanol, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and its group
It closes.
The glass transition temperature T of polymer as described hereingIt in one embodiment can be at about 120 DEG C to about
In the range of 280 DEG C, and in another embodiment can be in the range of about 140 DEG C to about 200 DEG C.Polymer can be into
One step passes through the weight average molecular weight (M that is obtained from gel permeation chromatography based on polystyrene standardsw) characterize.Implement at one
In scheme, the M of polymerwIt can be in the range of about 10000 grams/mol (g/mol) be to about 100000g/mol.At another
In embodiment, MwIt can be in the range of about 10000g/mol to about 75000g/mol.In another embodiment, MwIt can
With in the range of about 40000g/mol to about 55000g/mol.In another embodiment, MwIt can be in about 50000g/
In the range of mol to about 80000g/mol.
Mechanical test is carried out by using Instron (model 4202).In typical test, the one of about 2 inches of length
Section hollow-fibre membrane is fitted into a pair of of air-actuated jaw, and gauge length is made to be exactly 1 inch.Test sample is with the rate of 0.5 inch/min
It stretches, and stops test when sample burst.Include sample modulus, peak load and maximum elongation from the data of test record
Rate, load and elongation at break.
Polymer and film including polymer blend as described herein can further pass through its respective Hydrophilic Characterization of Hydrophilic.
In some embodiments, the contact angle of the sulfone polymer with amphoteric ion functional group and water is less than about 80 degree, in glass base
It is measured on surface on material as the polymer of film casting.In some embodiments, the sulfone with amphoteric ion functional group is poly-
The contact angle for closing object and water is less than about 50 degree, is measured on the surface as the polymer of film casting on the glass substrate.Specific
Embodiment in, with amphoteric ion functional group sulfone polymer and water contact angle be less than about 30 degree, on the glass substrate
It is measured on the surface of polymer as film casting.
It is prepared by methods known in the art according to the film of the embodiments described herein.Suitable technology includes but not
It is limited to：Dry phase separation membrane forming process；Wetting phase seperation film forming process；Dry-wetting phase seperation film forming process；Thermal inactive film
Forming process.In addition, after film formation, film can be subjected to film adjustment process or processing procedure before it is used to detach application.
Exemplary process may include thermal annealing to mitigate the stress or pre-equilibration in the similar solution of the feeding flow of contact with film.
In one embodiment, film can be prepared by mutually converting.Phase transfer process includes 1) steam induction phase point
From (VIPS), also referred to as " dry method casting " or " air casting "；2) liquid induction phase separation (LIPS), main referred to as " immersion is poured
Casting " or " wet caste "；With 3) heating consumers (TIPS), commonly referred to as " melt casting ".Phase transfer process can generate
Asymmetric membrane integral into cortex.In some embodiments, film can be crosslinked to provide additional support.
Film can be designed and manufactured as having specific pore size so that the solute that size is more than pore size may not be able to lead to
It crosses.In one embodiment, pore size can be in the range of about 0.5 nanometer to about 100 nanometers.In another embodiment
In, pore size can be in the range of about 1 nanometer to about 25nm.
The method to form hollow-fibre membrane as described herein is also provided herein.This method includes providing comprising foregoing
The cast-solution of blend polymer and solvent.This method further includes squeezing out cast-solution by circular passage to form hollow fibre
Tie up film.The non-limiting examples of suitable solvent include n-methyl-2-pyrrolidone, dimethylacetylamide, dimethylformamide, and four
Hydrogen furans, methyl ethyl ketone, formyl piperidine or combinations thereof.
In some embodiments, cast-solution may further include selected from polymer such as polyvinylpyrrolidone and gather
The additive of ethylene glycol；Anti-solvent, such as water, alcohol, glycol, glycol ethers and salt；Alkali halide；And combinations thereof.In some realities
Apply in scheme, additive may include alkali metal bromide, such as, but not limited to lithium bromide, sodium bromide, potassium bromide, cesium bromide or
A combination thereof.
In some embodiments, additive can be deposited with the amount (total amount) within the scope of about 0.1 weight % to about 30 weight %
It is in cast-solution.In addition, the sulfone polymer and sulfone polymer comprising amphoteric ion functional group are with the cast-solution
The amount of about 10 weight % to about 30 weight % of weight be present in the cast-solution.
In some embodiments, above-mentioned any hollow-fibre membrane blend includes at least one other polymer.
Other polymer can be blended with above-mentioned blend polymer to assign heterogeneity, such as better heat resistance, biofacies
Capacitive etc..It is generated when mutually conversion furthermore, it is possible to which other polymer is added in cast-solution during film is formed with changing
Phase inversion membrane structure form, such as asymmetric membrane structure.In some cases, polymer in addition can be kept in
Sulfone polymer in most telolemma and/or the additive (such as PVP, PEG etc.) for losing but not being completely removed in the fabrication process.
Such film is recognized as in the range of embodiment presented herein.
In some embodiments, the other polymer of blending is hydrophilic polymer.Suitable hydrophilic polymer
Non-limiting examples include polyvinylpyrrolidone (PVP), polyoxazolines, polyethylene glycol, polypropylene glycol, polyglycols monoesters,
The polymer of polyethylene glycol and polypropylene glycol, water-soluble cellulose derivative, polysorbate, polyethylene oxide-polycyclic oxygen third
Alkane polymer, polyethyleneimine and combinations thereof.In some embodiments, cast-solution blend can include other polymerization
Object, such as polyether urethane, polyamide, polyether-amide, polyacrylonitrile and combinations thereof.
Film as described herein can be used for various applications, such as bio-separation, Water warfare, blood filtration, haemodialysis, super
Filter, nanofiltration, gas separation, micro-filtration, reverse osmosis and pervaporation.In specific embodiments, film can have and wherein need to change
Application in the bio-pharmaceuticals and biomedical sector of kind hydrophily and biocompatibility.
In some embodiments, provided herein is the hollow-fibre membranes for bio-separation.Suitable for bio-separation
Empty fiber membrane part is combined by protein and is characterized.In some embodiments, hollow-fibre membrane provided herein has and is less than
About 30ng/cm2Protein combine.The film is made of blend polymer as described herein.On the other hand, provided herein is one
Kind bio-separation device comprising multiple porous hollow fibers that perforated membrane provided herein is constituted.
In some embodiments, film as described herein is used for haemodialysis.Dialysis refers to being realized by one or more films
Process, wherein mainly driving conveying by the pressure difference of the thickness across one or more films.Haemodialysis refers to dialysis
Process, wherein not needing biologically and/or toxic solute is removed such as metabolin and by-product from blood.Haemodialysis
Film is that low molecular weight solutes (usually less than 5,000 dalton) such as urea, kreatinin, uric acid, electrolyte and water is allowed to pass through,
But prevent higher molecular weight protein and blood cell component by perforated membrane.Closer to the blood for representing renal glomerulus filtering
Liquid filtering needs even higher infiltrative film so that and molecular weight is less than 50,000 dalton and in some cases less than 20,
The solute of 000 dalton passes through completely.
Blend polymer as described herein assigns required engineering properties to manufacture and to support during use porous
Hollow fiber film structure.In addition, blend polymer assigns thermal property appropriate, to reduce or prevent high-temp steam sterilizing mistake
Degradation during journey.In addition, blend polymer and film have best biocompatibility so that protein be stained minimum and
The thrombosis of processed blood will not occur.
Embodiment
Unless otherwise stated, chemicals is purchased from Aldrich and Sloss Industries and uses as former state.
Bruker Avance 400(1H, 400 MHz) H NMR spectroscopy is recorded on spectrometer, and shifted with reference to residual solvent.Molecular weight is with number
Average molecular weight (Mn) or weight average molecular weight (Mw) report, and analyzed equipped with UV detectors by gel permeation chromatography (GPC)
It is measured on 200 instruments of Perkin Elmer Series.Polymer heat analysis is in the Perkin equipped with TAC7/DX thermal analyzers
It carries out on Elmer DSC7 and is handled using Pyris softwares.
Glass transition temperature is recorded in second of heat scan.What is assessed using VCA optima softwares
Contact-angle measurement is carried out on VCA 2000 (Advanced Surface Technology, Inc.) instrument.Polymer film is by the future
From appropriate solution such as dimethyl sulfoxide (DMSO) (DMSO), the film of n-methyl-2-pyrrolidone (NMP) and dimethylacetylamide (DMAC)
It is cast on clean glass slide and evaporates solvent and obtain.On the both sides (towards air and towards glass slide) of film determine with
The advancing contact angle (73 dynes/cm) of water.It is assumed that since surface is more smooth, the side towards glass slide obtain always compared with
Low value.
The synthesis of sulfone polymer with amphoteric ion functional group
The preparation of the polymer of formula (VII) and amphoteric ion (one-pot synthesis, the 3.25 moles of % chains ends for being finally derived as 45 moles of %
Only agent) it carries out as follows：It feeds to the 5.0L three-neck flasks equipped with overhead mechanical stirrer, brachycephaly distilling apparatus and nitrogen entrance double
Phenol A (BPA) (228.1g, 1.000 moles), N methyl piperazine bis-phenol amide (301.17g, 0.8182 mole), to cumyl benzene
Phenol (12.468g, 0.0591 mole) and 1.60L N-Methyl pyrrolidones (NMP), leaching is in oil bath.The mixture is at room temperature
Stirring, is then added portionwise potassium carbonate (401.5g, 2.909 moles), is subsequently added into 0.800L toluene.The mixture is slow
Under nitrogen stream then heating is azeotroped off remaining water with dry reaction mixture to remove toluene.Oil bath temperature is from 125-150
DEG C gradually rise with remove most of toluene (> 90%).Then slurry is cooled to room temperature, the difluoro as solid is then added
Reaction temperature is simultaneously gradually increased to 165 DEG C by diphenyl sulfone (469.63g, 1.8482 moles).During heating, at about 100 DEG C
Observe mild heat release.Heating mixture and every two hours sampling are until reach required molecular weight (8-10 hours).Anti-
Reaction viscosity increases during should running, and shows opaque light gray.When reaching required molecular weight, diluted with 0.8 liter of NMP
Reactant is simultaneously cooled to 50 DEG C.Then 1,3-propane sultone (149.7g, 1.227 moles) and reaction mixture is gradual is added
It is heated to 80 DEG C.Reaction is completed in ~ 4 hours.After the addition is complete, reaction color is shoaled gradually as greyish white mill base material.It is based on
Solution viscosity, can further diluted reaction mixture.Then use high speed blender by mixture precipitation to 12.0L water,
Generate white precipitate.Precipitation is collected by filtration, then repulped 6 hours in 5.0 heating water (40-50 DEG C).Pass through filtering
Collect solid.It is initially dried 24 hours in 50 DEG C of polymer being dried to obtain under nitrogen purge under vacuum, then in 80-
About 950 grams of polymer (~ 95% rate of recovery) after re-dry is dried for 24 hours with offer under full vacuum at 100 DEG C.
The casting of hollow-fibre membrane is carried out using methods known in the art and using method described herein.Polymer is total
Mixed object by preparing polymer dissolving in a suitable solvent.By the way that blend polymer and any optional additive is molten
Solution prepares the coating solution for hollow-fibre membrane of casting in a suitable solvent.
The test that protein combines
Nonspecific protein knot is measured using the immunoglobulin protein marked with horseradish peroxidase (HRP) functional group
It closes.1 inch strip of each doughnut is placed in 35 × 10mm culture dishes and in phosphate buffered saline (PBS) (pH=7.4)
Thoroughly washing from fiber to remove remaining glycerine, salt or pore-foaming agent.It is replaced with 10 μ g/ml HRP- protein solutions of 2ml
PBS.After impregnating 2 hours, antibody-solutions are removed, and fiber is fully washed with PBS.Then fiber is cut into quarter, and by this
Quarter is transferred to the hole of 24 orifice plates containing 0.5ml 50mM citrate-phosphate buffers (CPB) (pH=5) jointly
In.Sample impregnates 30 minutes.
It is replaced with the 0.5ml solution based on CPB for containing 0.5mg/ml o-phenylenediamines (OPD) and 0.015% hydrogen peroxide
CPB.HRP labels on protein convert OPD to the dissolved compound of yellow.After 3 minutes, low capacity one is transferred the solution into
In secondary property cuvette.Absorbance is measured at 450nm to quantify the amount of the OPD of conversion, with non-specific adsorption to film surface
On protein amount it is directly proportional.The amount passes through film surface product (including cross section of inner cavity and exocoel and exposure) normalization.
As a result it shows in fig. 2.
Although having only illustrated and described certain features of the present invention herein, those skilled in the art will expect many modifications
And variation.It is therefore understood that appended claims are intended to all such modifications that covering is fallen within the true spirit of the invention
And variation.
Claims (28)
1. a kind of hollow-fibre membrane it includes the first polymer containing the sulfone polymer with amphoteric ion functional group and contains
The blend of the second polymer of sulfone polymer.
2. the hollow-fibre membrane of claim 1, wherein described first comprising the sulfone polymer with amphoteric ion functional group is poly-
Close the structural unit that object includes the Formulas I A or Formulas I B that are connect with the structural unit of Formula II：
Wherein
R1And R2It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or aryl
Ring；
K is 0 to 10；
Y' and R' is each independently hydrogen, C1-C20Alkyl or aryl ring；
R4It is key, C1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R5And R6It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or aryl
Ring；With
Y' and R' is each independently hydrogen, C1-C20Alkyl or aryl ring；
A, a' and b independently is 0,1,2,3 or 4 at each occurrence；With
M and n is each independently 0 or 1.
3. the hollow-fibre membrane of claim 1, wherein the second polymer comprising sulfone polymer include with Formula II, III,
The structural unit of IV or IV structures：
Wherein
R5And R6It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or aryl
Ring；With
Y' and R' is each independently hydrogen, C1-C20Alkyl or aryl ring；
A and b independently is 0,1,2,3 or 4 at each occurrence；With
M and n is each independently 0 or 1.
4. the hollow-fibre membrane of claim 1, wherein described first comprising the sulfone polymer with amphoteric ion functional group is poly-
Close the structural unit that object includes the Formulas I A or Formulas I B that are connect with the structural unit of Formula II：
Wherein
R1And R2It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or aryl
Ring；
K is 0 to 10；
Y' and R' is each independently hydrogen, C1-C20Alkyl or aryl ring；
R4It is key, C1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R5And R6It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or aryl
Ring；With
Y' and R' is each independently hydrogen, C1-C20Alkyl or aryl ring；
A, a' and b independently is 0,1,2,3 or 4 at each occurrence；
M and n is each independently 0 or 1；With
The wherein described second polymer comprising sulfone polymer includes the structural unit with Formula II, the structure of IV or V：
。
5. the hollow-fibre membrane of claim 2, wherein described first comprising the sulfone polymer with amphoteric ion functional group is poly-
Close the structural unit that object includes Formula IV：
Wherein w is 0,1,2 or 3.
6. the hollow-fibre membrane of claim 2, wherein described first comprising the sulfone polymer with amphoteric ion functional group is poly-
Close the structural unit that object includes Formula VII：
Wherein P+Q=1, P=0.30-0.50, Q=0.50-0.70.
7. the hollow-fibre membrane of claim 6, wherein the amphoteric ion functionalized structure list of the Formulas I B in the first polymer
About 30 moles of % to about 50 of the total mole number of the unit of Formulas I B and Formula II of the molar fraction of member in the first polymer rub
Within the scope of your %.
8. the hollow-fibre membrane of claim 1, wherein described first comprising the sulfone polymer with amphoteric ion functional group is poly-
The molecular weight of object is closed in the range of about 10000g/mol to about 80000g/mol.
9. the hollow-fibre membrane of claim 3, wherein the second polymer comprising sulfone polymer includes the knot containing Formula II
The polysulfones of structure unit.
10. the hollow-fibre membrane of claim 3, wherein the second polymer comprising sulfone polymer includes the knot containing formula IV
The polyphenylsulphine of structure unit.
11. the hollow-fibre membrane of claim 3, wherein the second polymer comprising sulfone polymer includes the knot containing Formula V
The polyether sulfone of structure unit.
12. the hollow-fibre membrane of claim 1, wherein the amount of the second polymer comprising sulfone polymer is in the film
The about 0.5 weight % to about 5 weight % of total polymer weight.
13. the hollow-fibre membrane of claim 1, wherein the molecular weight of the second polymer comprising sulfone polymer is about
In the range of 50000g/mol to about 80000g/mol.
14. the hollow-fibre membrane of claim 4, wherein described first comprising the sulfone polymer with amphoteric ion functional group is poly-
Close the structural unit that object includes the Formulas I B being connect with the structural unit of Formula II, and the second polymer packet comprising sulfone polymer
Structural unit containing Formula II
。
15. the hollow-fibre membrane of claim 4, wherein described first comprising the sulfone polymer with amphoteric ion functional group is poly-
Close the structural unit that object includes the Formulas I B being connect with the structural unit of Formula II, and the second polymer packet comprising sulfone polymer
Structural unit containing formula IV
。
16. the hollow-fibre membrane of claim 4, wherein described first comprising the sulfone polymer with amphoteric ion functional group is poly-
Close the structural unit that object includes the Formulas I B being connect with the structural unit of Formula II, and the second polymer packet comprising sulfone polymer
Structural unit containing Formula V
。
17. a kind of hollow fiber membrane module, it includes the hollow-fibre membranes of multiple claims 14.
18. a kind of haemodialysis or blood filter device, it includes the hollow fiber membrane modules of claim 17.
19. a kind of hollow fiber membrane module, it includes the hollow-fibre membranes of multiple claims 15.
20. a kind of haemodialysis or blood filter device, it includes the hollow fiber membrane modules of claim 19.
21. a kind of hollow fiber membrane module, it includes the hollow-fibre membranes of multiple claims 16.
22. a kind of haemodialysis or blood filter device, it includes the hollow fiber membrane modules of claim 21.
23. a kind of composition it includes the first polymer containing the sulfone polymer with amphoteric ion functional group and contains sulfone
The blend of the second polymer of polymer.
24. the composition of claim 23, wherein first polymerization comprising the sulfone polymer with amphoteric ion functional group
Object includes the structural unit for the Formulas I B being connect with the structural unit of Formula II, and the second polymer comprising sulfone polymer includes
The structural unit of Formula II：
Wherein
R1And R2It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or aryl
Ring；
K is 0 to 10；
R3It independently is hydrogen atom, C with Y1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R4It is key, C1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R5And R6It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or aryl
Ring；
A, a' and b independently is 0,1,2,3 or 4 at each occurrence；With
M and n is each independently 0 or 1.
25. the composition of claim 23, wherein first polymerization comprising the sulfone polymer with amphoteric ion functional group
Object includes the structural unit for the Formulas I B being connect with the structural unit of Formula II, and the second polymer comprising sulfone polymer includes
The structural unit of formula IV：
Wherein
R1And R2It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or aryl
Ring；
K is 0 to 10；
R3It independently is hydrogen atom, C with Y1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R4It is key, C1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R5And R6It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or aryl
Ring；
A, a' and b independently is 0,1,2,3 or 4 at each occurrence；With
M and n is each independently 0 or 1.
26. the composition of claim 23, wherein first polymerization comprising the sulfone polymer with amphoteric ion functional group
Object includes the structural unit for the Formulas I B being connect with the structural unit of Formula II, and the second polymer comprising sulfone polymer includes
The structural unit of Formula V：
Wherein
R1And R2It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base, C3-C12
Naphthenic base or aryl rings；
K is 0 to 10；
R3It independently is hydrogen atom, C with Y1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R4It is key, C1-C12Alkyl, C3-C12Naphthenic base or aryl rings；
R5And R6It independently is hydrogen atom, halogen atom, nitro, C at each occurrence1-C12Alkyl, C3-C12Naphthenic base or aryl
Ring；
A, a' and b independently is 0,1,2,3 or 4 at each occurrence；With
M and n is each independently 0 or 1.
27. a kind of method for the hollow-fibre membrane forming claim 1, including：
(A) cast-solution that the blend comprising first polymer and second polymer is provided, wherein in the cast-solution
Total polymer content is less than about 20% weight of the cast-solution；With
(B) cast-solution is squeezed out to form the hollow-fibre membrane by circular passage.
28. the method for claim 27, wherein the hollow-fibre membrane includes about 0.5 weight of the total polymer weight in the film
% is measured to the second polymer of the amount of about 5 weight %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/958,937 US20160136588A1 (en) | 2014-11-19 | 2015-12-04 | Zwitterionic sulfone polymer blend and hollow-fiber membrane |
| US14/958937 | 2015-12-04 | ||
| PCT/US2016/064576 WO2017096140A1 (en) | 2015-12-04 | 2016-12-02 | Zwitterionic sulfone polymer blend and hollow-fiber membrane |
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| CN108430613A true CN108430613A (en) | 2018-08-21 |
| CN108430613B CN108430613B (en) | 2022-02-11 |
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| EP (1) | EP3383524A4 (en) |
| JP (1) | JP6983159B2 (en) |
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| CN114786795A (en) * | 2019-12-05 | 2022-07-22 | 索尔维特殊聚合物美国有限责任公司 | Process for preparing poly (aryl ether sulfone) (PAES) polymers |
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| US10851241B2 (en) | 2014-11-19 | 2020-12-01 | Cytiva Sweden Ab | Zwitterion-functionalized multicomponent copolymers and associated polymer blends and membranes |
| WO2019219486A1 (en) * | 2018-05-15 | 2019-11-21 | General Electric Company | Zwitterion-functionalized multicomponent copolymers and associated polymer blends and membranes |
| CN114941184A (en) * | 2022-06-29 | 2022-08-26 | 山东海科创新研究院有限公司 | Preparation method of spinning solution, spinning solution and filtering membrane |
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| Publication number | Publication date |
|---|---|
| JP6983159B2 (en) | 2021-12-17 |
| EP3383524A1 (en) | 2018-10-10 |
| EP3383524A4 (en) | 2019-07-24 |
| WO2017096140A1 (en) | 2017-06-08 |
| JP2019501013A (en) | 2019-01-17 |
| CN108430613B (en) | 2022-02-11 |
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