CN108430613B - Zwitterionic sulfone polymer blend and hollow fiber membranes - Google Patents
Zwitterionic sulfone polymer blend and hollow fiber membranes Download PDFInfo
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- CN108430613B CN108430613B CN201680070265.6A CN201680070265A CN108430613B CN 108430613 B CN108430613 B CN 108430613B CN 201680070265 A CN201680070265 A CN 201680070265A CN 108430613 B CN108430613 B CN 108430613B
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- hollow fiber
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- sulfone
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- 239000012528 membrane Substances 0.000 title claims abstract description 136
- 150000003457 sulfones Chemical class 0.000 title claims abstract description 118
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 92
- 229920002959 polymer blend Polymers 0.000 title abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 259
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 125000003118 aryl group Chemical group 0.000 claims description 60
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 40
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 36
- 238000005266 casting Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 26
- 125000005843 halogen group Chemical group 0.000 claims description 22
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 238000001631 haemodialysis Methods 0.000 claims description 11
- 230000000322 hemodialysis Effects 0.000 claims description 11
- 229920002492 poly(sulfone) Polymers 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000002615 hemofiltration Methods 0.000 claims description 7
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 28
- 239000010408 film Substances 0.000 description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- -1 2-methylcyclopentyl Chemical group 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 11
- 108090000623 proteins and genes Proteins 0.000 description 11
- 102000004169 proteins and genes Human genes 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 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 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process 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
- 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
- 238000001471 micro-filtration Methods 0.000 description 6
- 229920001223 polyethylene glycol Chemical group 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 5
- 239000002202 Polyethylene glycol Chemical group 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
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- 239000011521 glass Substances 0.000 description 4
- 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
- QXWJCZBPMSOYIM-UHFFFAOYSA-N 1-fluoro-2-(2-fluorophenyl)sulfinylbenzene Chemical compound FC1=CC=CC=C1S(=O)C1=CC=CC=C1F QXWJCZBPMSOYIM-UHFFFAOYSA-N 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
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- 230000000996 additive effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229920001477 hydrophilic polymer Polymers 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002953 phosphate buffered saline Substances 0.000 description 3
- 229920005597 polymer membrane Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000002145 thermally induced phase separation Methods 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical group C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 2
- NYKRSGJRIJJRRK-UHFFFAOYSA-N 1-chloro-2-(2-chlorophenyl)sulfonylbenzene Chemical compound ClC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1Cl NYKRSGJRIJJRRK-UHFFFAOYSA-N 0.000 description 2
- DQFSSJGXWZMREB-UHFFFAOYSA-N 1-fluoro-2-(2-fluorophenyl)sulfonylbenzene Chemical compound FC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1F DQFSSJGXWZMREB-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-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
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- SUCTVKDVODFXFX-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)sulfonyl-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(S(=O)(=O)C=2C=C(C)C(O)=C(C)C=2)=C1 SUCTVKDVODFXFX-UHFFFAOYSA-N 0.000 description 2
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 2
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 2
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 2
- GIXXQTYGFOHYPT-UHFFFAOYSA-N Bisphenol P Chemical compound C=1C=C(C(C)(C)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 GIXXQTYGFOHYPT-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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- GNDHXHLGYBJDRD-UHFFFAOYSA-N bis(2-fluorophenyl)methanone Chemical compound FC1=CC=CC=C1C(=O)C1=CC=CC=C1F GNDHXHLGYBJDRD-UHFFFAOYSA-N 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
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 125000002950 monocyclic group Chemical group 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 238000005373 pervaporation Methods 0.000 description 2
- 239000003880 polar aprotic solvent Substances 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
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 description 1
- SICLLPHPVFCNTJ-UHFFFAOYSA-N 1,1,1',1'-tetramethyl-3,3'-spirobi[2h-indene]-5,5'-diol Chemical compound C12=CC(O)=CC=C2C(C)(C)CC11C2=CC(O)=CC=C2C(C)(C)C1 SICLLPHPVFCNTJ-UHFFFAOYSA-N 0.000 description 1
- BSJWDQYZFBYNIM-UHFFFAOYSA-N 1,3,4,5-tetramethylpyrrolidin-2-one Chemical compound CC1C(C)N(C)C(=O)C1C BSJWDQYZFBYNIM-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
- BCNBMSZKALBQEF-UHFFFAOYSA-N 1,3-dimethylpyrrolidin-2-one Chemical compound CC1CCN(C)C1=O BCNBMSZKALBQEF-UHFFFAOYSA-N 0.000 description 1
- NCNWTBAWLAFYDR-UHFFFAOYSA-N 1,6-dimethylpiperidin-2-one Chemical compound CC1CCCC(=O)N1C NCNWTBAWLAFYDR-UHFFFAOYSA-N 0.000 description 1
- IVUYGANTXQVDDG-UHFFFAOYSA-N 1-(2-methylpropyl)pyrrolidin-2-one Chemical compound CC(C)CN1CCCC1=O IVUYGANTXQVDDG-UHFFFAOYSA-N 0.000 description 1
- OZUNPRDEUXITBO-UHFFFAOYSA-N 1-(4-chlorophenyl)sulfonyl-4-[4-(4-chlorophenyl)sulfonylphenyl]benzene Chemical group C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(C=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(Cl)=CC=2)C=C1 OZUNPRDEUXITBO-UHFFFAOYSA-N 0.000 description 1
- NDTOCQNXMGILGR-UHFFFAOYSA-N 1-(4-fluorophenyl)sulfonyl-4-[4-(4-fluorophenyl)sulfonylphenyl]benzene Chemical group C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(C=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(F)=CC=2)C=C1 NDTOCQNXMGILGR-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical group CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- FEWLNYSYJNLUOO-UHFFFAOYSA-N 1-Piperidinecarboxaldehyde Chemical compound O=CN1CCCCC1 FEWLNYSYJNLUOO-UHFFFAOYSA-N 0.000 description 1
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 description 1
- JQIZBZDGJCYYLA-UHFFFAOYSA-N 1-chloro-2-(2-chlorophenyl)sulfinylbenzene Chemical compound ClC1=CC=CC=C1S(=O)C1=CC=CC=C1Cl JQIZBZDGJCYYLA-UHFFFAOYSA-N 0.000 description 1
- IVVVGBHWWAJRAY-UHFFFAOYSA-N 1-ethyl-3-methylpyrrolidin-2-one Chemical compound CCN1CCC(C)C1=O IVVVGBHWWAJRAY-UHFFFAOYSA-N 0.000 description 1
- VUQMOERHEHTWPE-UHFFFAOYSA-N 1-ethylpiperidin-2-one Chemical compound CCN1CCCCC1=O VUQMOERHEHTWPE-UHFFFAOYSA-N 0.000 description 1
- GVYKABJIEOOUOX-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfinylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)C1=CC=C(F)C=C1 GVYKABJIEOOUOX-UHFFFAOYSA-N 0.000 description 1
- 125000006432 1-methyl cyclopropyl group Chemical group [H]C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical compound CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 description 1
- GVDQKJQFVPXADH-UHFFFAOYSA-N 1-propan-2-ylpiperidin-2-one Chemical compound CC(C)N1CCCCC1=O GVDQKJQFVPXADH-UHFFFAOYSA-N 0.000 description 1
- GHELJWBGTIKZQW-UHFFFAOYSA-N 1-propan-2-ylpyrrolidin-2-one Chemical compound CC(C)N1CCCC1=O GHELJWBGTIKZQW-UHFFFAOYSA-N 0.000 description 1
- DCALJVULAGICIX-UHFFFAOYSA-N 1-propylpyrrolidin-2-one Chemical compound CCCN1CCCC1=O DCALJVULAGICIX-UHFFFAOYSA-N 0.000 description 1
- JFZAJWBGISKERI-UHFFFAOYSA-N 2,4-dihydroxybenzonitrile Chemical compound OC1=CC=C(C#N)C(O)=C1 JFZAJWBGISKERI-UHFFFAOYSA-N 0.000 description 1
- APGLXTXFTYAQKC-UHFFFAOYSA-N 2,5-dihydroxybenzonitrile Chemical compound OC1=CC=C(O)C(C#N)=C1 APGLXTXFTYAQKC-UHFFFAOYSA-N 0.000 description 1
- AYKMXKNVEUMLFQ-UHFFFAOYSA-N 2-(1,8-naphthyridin-2-yl)phenol Chemical compound OC1=CC=CC=C1C1=CC=C(C=CC=N2)C2=N1 AYKMXKNVEUMLFQ-UHFFFAOYSA-N 0.000 description 1
- WREVCRYZAWNLRZ-UHFFFAOYSA-N 2-allyl-6-methyl-phenol Chemical compound CC1=CC=CC(CC=C)=C1O WREVCRYZAWNLRZ-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- GHCZTIFQWKKGSB-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O GHCZTIFQWKKGSB-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- RKSBPFMNOJWYSB-UHFFFAOYSA-N 3,3-Bis(4-hydroxyphenyl)pentane Chemical compound C=1C=C(O)C=CC=1C(CC)(CC)C1=CC=C(O)C=C1 RKSBPFMNOJWYSB-UHFFFAOYSA-N 0.000 description 1
- ABHOEQJNEOMTEK-UHFFFAOYSA-N 3,5-dihydroxybenzonitrile Chemical compound OC1=CC(O)=CC(C#N)=C1 ABHOEQJNEOMTEK-UHFFFAOYSA-N 0.000 description 1
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- 239000004698 Polyethylene Substances 0.000 description 1
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- PISLKPDKKIDMQT-UHFFFAOYSA-N [3-(4-fluorobenzoyl)phenyl]-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC(C(=O)C=2C=CC(F)=CC=2)=C1 PISLKPDKKIDMQT-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- 238000000137 annealing Methods 0.000 description 1
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- 238000003556 assay Methods 0.000 description 1
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- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
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- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 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
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- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229940109239 creatinine Drugs 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229940016681 dipropylacetamide Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229940037395 electrolytes Drugs 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000024924 glomerular filtration Effects 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 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
- BNRNAKTVFSZAFA-UHFFFAOYSA-N hydrindane Chemical compound C1CCCC2CCCC21 BNRNAKTVFSZAFA-UHFFFAOYSA-N 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 102000018358 immunoglobulin Human genes 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 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
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 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
- 239000002207 metabolite Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- IMNDHOCGZLYMRO-UHFFFAOYSA-N n,n-dimethylbenzamide Chemical compound CN(C)C(=O)C1=CC=CC=C1 IMNDHOCGZLYMRO-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 group 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000008363 phosphate buffer Substances 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
- 229920000412 polyarylene 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
- 229920000136 polysorbate Polymers 0.000 description 1
- 229940068965 polysorbates Drugs 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000012460 protein solution Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 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
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229940045136 urea Drugs 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
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 are blends of polymers suitable for use in making hollow fiber membranes. The polymer blend comprises a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer.
Description
Cross Reference to Related Applications
This application is a continuation-in-part application of U.S. patent application No. 14/547,306 entitled zwitterionic-Functionalized Polymer Hollow-Fiber Membranes And Associated Method, filed 11/19/2014, the entire contents of which are incorporated herein by reference.
Background
The present disclosure generally relates to polymer blends for making hollow fiber membranes. The polymer blend comprises at least one polymer comprising zwitterionic groups.
Porous hollow fiber polymer membranes are used in many applications, such as hemodialysis, ultrafiltration, nanofiltration, reverse osmosis, gas separation, microfiltration, and pervaporation. For many of these applications, membranes with optimal selectivity and chemical, thermal and mechanical stability are desirable. In many applications (e.g., bio-separation or water filtration), membranes having one or more of improved hydrophilicity, improved biocompatibility, or low fouling may also be desirable.
Polyarylene ethers, in particular polyether sulfones and polysulfones, are frequently used as membrane materials because of their mechanical, thermal and chemical stability. However, these polymers are hydrophobic and lack biocompatibility and hydrophilicity as required for aqueous applications. Improvements in membrane hydrophilicity have been achieved by polymer blending, for example making porous membranes in the presence of small amounts of hydrophilic polymers such as polyvinylpyrrolidone (PVP). However, since PVP is water soluble, it leaches slowly from the porous polymer matrix, creating product variability. Alternatively, hydrophilicity has been achieved via functionalization of the polymer backbone and introduction of carboxyl, nitrile, or polyethylene glycol functional groups. However, these chemical modifications can be complex, expensive and inefficient. Furthermore, the addition of functional groups may make it difficult to manufacture hollow fiber membranes from functionalized polymers. One approach to solving the problems due to functional groups is to functionalize the membrane after fabrication; but this approach increases the manufacturing cost of the membrane.
There is a need in the art for materials that are easily processed and/or manufactured into membranes (including hollow fiber membranes), but that also reduce protein binding and/or fouling and provide good mechanical properties suitable for aqueous applications.
SUMMARY
Provided herein are polymer blends that mitigate certain limitations of previously known methods for making hollow fiber membranes. The blends of the present invention improve the processability of the functionalized polymers and also reduce the need for post-casting functionalization of the film.
Provided herein are hollow fiber membranes comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functional groups and a second polymer comprising a sulfone polymer:
in one aspect, provided herein is a hollow fiber membrane comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IA or formula IB attached to a structural unit of formula II, and wherein the second polymer comprising a sulfone polymer comprises a structural unit of formula II, III, IV or V, wherein the structures of formula IA, IB, II, III, IV and V are as described in the detailed description section below.
Drawings
These and other features, aspects, and advantages of the present invention will become better understood when the following detailed description is read with reference to the accompanying drawings in which like characters represent like parts throughout the drawings, wherein:
figure 1 shows a comparison between the cross-sections of a hollow fiber membrane comprising a high molecular weight polymer and a hollow fiber membrane comprising the claimed polymer blend of the present invention.
Fig. 2 shows a comparison between the protein binding properties (fouling) of hollow fiber membranes: (1) high molecular weight Polysulfone (PSU) (MW 54kg/mol) ultrafiltration hollow fiber membranes, (2) high molecular weight Polysulfone (PSU) (MW 54kg/mol) microfiltration hollow fiber membranes, (3) PSU (zwpsu) microfiltration hollow fiber membranes comprising zwitterionic groups, (4) microfiltration hollow fiber membranes comprising the polymer blend of the present invention (MW-49.3 kg/mol), and (5) PSU (zwpsu) microfiltration hollow fiber membranes comprising zwitterionic groups. No or minimal effect on morphology and IgG binding (ELISA) was observed from high molecular weight polymers to polymer blends.
Detailed description of the invention
Hollow fiber membranes are commonly used in applications where a hydrophilic and/or biocompatible barrier is required. Zwitterionic sulfone polymers are hydrophilic and result in low protein binding and biofouling. However, zwitterionic sulfone polymers tend to be difficult to process into films, and the resulting films often have poor mechanical properties. Previous attempts to improve the hydrophilicity of sulfone-containing polymer membranes have focused on post-fabrication functionalization of the polymer and/or membrane.
In contrast, provided herein are novel blends of polymers comprising sulfone polymers and zwitterionic sulfone polymers that alleviate the need for post-fabrication functionalization of membranes. In addition, the polymer blends described herein can improve the polymer network structure and lead to better mechanical properties. The polymer blends described herein also impart improved processability, allowing easier manufacture of membranes, including hollow fiber membranes. In addition, the polymer blends described herein provide desirable hydrophilicity and/or biocompatibility to the membrane. Thus, by blending low amounts of sulfone polymer with zwitterionic sulfone polymer, the film forming processability of the zwitterionic sulfone polymer is improved. Furthermore, the mechanical properties of the films comprising the polymer blends are significantly improved while maintaining the film morphology and low bonding characteristics of the films. Advantageously, the films of the present invention alleviate the problems associated with leaching water soluble polymers such as PVP from the matrix, thereby reducing product variability.
The polymer blends described herein provide simple adjustment and significant improvement in film processability (e.g., low coating viscosity) and mechanical properties (e.g., high tensile elongation), and also provide some cost reduction by replacing the expensive zwitterionic sulfone polymers with the less expensive sulfone polymers in the blend.
Certain terms
Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as "about" and "substantially", are not to be limited to the precise value specified. In some cases, the approximating language may correspond to the precision of an instrument for measuring the value. Here and throughout the specification and claims, range limitations may be combined and/or interchanged, such ranges are identified and include all the sub-ranges contained therein unless context or language indicates otherwise.
In the following specification and claims, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. As used herein, the term "or" is not meant to be exclusive and refers to the presence of at least one of the referenced components and includes instances where combinations of the referenced components may be present, unless the context clearly dictates otherwise.
As used herein, a "sulfone polymer" is a polymer comprising the structure aryl-SO2Any polymer of one or more subunits of aryl groups. Typically, sulfone polymers are prepared via the reaction between a bisphenol and bis (4-chlorophenyl) sulfone by elimination of sodium chloride: sulfone polymers include, but are not limited to, polysulfone, polyarylsulfone (otherwise known as polyphenylsulfone or polyphenylsulfone), polyethersulfone, and the like.
As used herein, a "sulfone polymer with zwitterionic functionality" or "zwitterionic sulfone polymer" is a polymer comprising the structure aryl-SO2Any polymer of one or more subunits of an aryl group and having one or more subunits comprising a zwitterionic functional group.
The term "hollow fiber membrane" as used herein refers to a fiber-based membrane structure comprising a separation layer present at the surface. Hollow fiber membranes can function using "inside-outside" or "outside-inside" mechanisms. The terms "hollow fiber membrane" and "membrane" are used interchangeably herein unless the context clearly indicates otherwise.
The term "alkyl" refers to straight or branched chain alkyl groups having 1 to 12 carbon atoms in the chain. Examples of alkyl groups include methyl (Me) ethyl (Et), n-propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl (tBu), pentyl, isopentyl, tert-pentyl, hexyl, isohexyl, and the like.
"cycloalkyl" refers to a monocyclic or polycyclic non-aromatic hydrocarbon group having 3 to 12 carbon atoms. Non-limiting examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-methylcyclopropyl, 2-methylcyclopentyl, octahydro-1H-indene, decahydronaphthalene, and the like.
The term "aryl" denotes a monocyclic or bicyclic aromatic hydrocarbon ring structure. The aryl ring may have 6 or 10 carbon atoms in the ring.
Described herein are hollow fiber membranes comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer.
In one aspect, the hollow fiber membrane comprises a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IA or formula IB linked to a structural unit of formula II:
wherein
R1And R2Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
k is 0 to 10;
y 'and R' are each independently hydrogen, C1-C20An alkyl or aryl ring;
R4is a bond, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R5and R6Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring; and
y 'and R' are each independently hydrogen, C1-C20An alkyl or aryl ring;
a. a' and b are independently at each occurrence 0, 1, 2,3, or 4; and
m and n are each independently 0 or 1.
In another aspect, a hollow fiber membrane comprises a blend of a first polymer comprising a sulfone polymer having zwitterionic functional groups and a second polymer comprising a sulfone polymer, wherein the second polymer comprising a sulfone polymer comprises structural units having a structure of formula II, III, IV, or V,
wherein
R5And R6Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring; and
y 'and R' are each independently hydrogen, C1-C20An alkyl or aryl ring;
a and b are independently at each occurrence 0, 1, 2,3, or 4; and
m and n are each independently 0 or 1.
In some embodiments of the above hollow fiber membranes, the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IA or formula IB attached to a structural unit of formula II:
wherein
R1And R2Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
k is 0 to 10;
y 'and R' are each independently hydrogen, C1-C20An alkyl or aryl ring;
R4is a bond, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R5and R6Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring; and
y 'and R' are each independently hydrogen, C1-C20An alkyl or aryl ring;
a. a' and b are independently at each occurrence 0, 1, 2,3, or 4;
m and n are each independently 0 or 1; and
wherein the second polymer comprising a sulfone polymer comprises structural units having the structure of formula II, IV or V
In some embodiments of the above hollow fiber membranes, the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula VI:
wherein w is 0, 1, 2 or 3.
In some embodiments of the above hollow fiber membranes, the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula VII:
wherein P + Q = 1, P = 0.30-0.50, Q = 0.50-0.70.
In some embodiments of the above hollow fiber membranes, the mole fraction of zwitterionic functionalized structural units of formula IB in the first polymer is less than about 50 mole% of the total moles of units of formula IB and formula II in the first polymer. In some embodiments of the above hollow fiber membranes, the mole fraction of zwitterionic functionalized structural units of formula IB in the first polymer is in the range of about 30 mole% to about 50 mole% of the total moles of units of formula IB and formula II in the first polymer.
In some embodiments of the above hollow fiber membranes, the first polymer comprising a sulfone polymer having zwitterionic functionality has a molecular weight in a range of about 10000g/mol to about 80000 g/mol.
In some embodiments of the above hollow fiber membranes, the second polymer comprising a sulfone polymer comprises a polysulfone comprising structural units of formula II.
In some embodiments of the above hollow fiber membranes, the second polymer comprising a sulfone polymer comprises a polyphenylsulfone comprising structural units of formula IV.
In some embodiments of the above hollow fiber membranes, the second polymer comprising a sulfone polymer comprises a polyethersulfone comprising structural units of formula V.
In some embodiments of the above hollow fiber membranes, the amount of the second polymer comprising sulfone polymer is from about 0.5 wt% to about 5 wt% of the total weight of the polymers in the membrane.
In some embodiments of the above hollow fiber membranes, the molecular weight of the second polymer comprising a sulfone polymer is in a range of about 50000g/mol to about 80000 g/mol.
In some embodiments of the above hollow fiber membranes, the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and the second polymer comprising a sulfone polymer comprises a structural unit of formula II
In some embodiments of the above hollow fiber membranes, the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB linked to structural units of formula II, and the second polymer comprising a sulfone polymer comprises structural units of formula IV
In some embodiments of the above hollow fiber membranes, the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and the second polymer comprising a sulfone polymer comprises a structural unit of formula V
Provided herein is a hollow fiber membrane module comprising a plurality of hollow fiber membranes, wherein a first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and a second polymer comprising a sulfone polymer comprises a structural unit of formula II. Also provided herein are hemodialysis or hemofiltration devices comprising a hollow fiber membrane module, wherein a first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and a second polymer comprising a sulfone polymer comprises a structural unit of formula II.
Provided herein is a hollow fiber membrane module comprising a plurality of hollow fiber membranes, wherein a first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and a second polymer comprising a sulfone polymer comprises a structural unit of formula IV. Also provided herein are hemodialysis or hemofiltration devices comprising a hollow fiber membrane module, wherein a first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and a second polymer comprising a sulfone polymer comprises a structural unit of formula IV.
Provided herein is a hollow fiber membrane module comprising a plurality of hollow fiber membranes, wherein a first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and a second polymer comprising a sulfone polymer comprises a structural unit of formula V. Also provided herein are hemodialysis or hemofiltration devices comprising a hollow fiber membrane module, wherein a first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and a second polymer comprising a sulfone polymer comprises a structural unit of formula V.
In yet another aspect, provided herein are compositions comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer.
In some embodiments, provided herein is a composition comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and the second polymer comprising a sulfone polymer comprises a structural unit of formula II
Wherein
R1And R2Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
k is 0 to 10;
R3and Y is independently a hydrogen atom, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R4is a bond, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R5and R6Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
a. a' and b are independently at each occurrence 0, 1, 2,3, or 4; and
m and n are each independently 0 or 1.
In some embodiments, provided herein is a composition comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and the second polymer comprising a sulfone polymer comprises a structural unit of formula IV
Wherein
R1And R2Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
k is 0 to 10;
R3and Y is independently a hydrogen atom, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R4is a bond, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R5and R6Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
a. a' and b are independently at each occurrence 0, 1, 2,3, or 4; and
m and n are each independently 0 or 1.
In some embodiments, provided herein is a composition comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and the second polymer comprising a sulfone polymer comprises a structural unit of formula V
Wherein
R1And R2Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
k is 0 to 10;
R3and Y is independently a hydrogen atom, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R4is a bond, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R5and R6Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
a. a' and b are independently at each occurrence 0, 1, 2,3, or 4; and
m and n are each independently 0 or 1.
Also provided herein is a method for forming a hollow fiber membrane described herein, comprising:
(A) providing a casting solution comprising a blend of a first polymer and a second polymer, wherein the total polymer content in the casting solution is less than about 20% by weight of the casting solution; and
(B) extruding the casting solution through an annular channel to form the hollow fiber membrane.
In an alternative embodiment, the casting solution may have a total polymer content in the casting solution of less than about 50 weight percent of the casting solution. In further embodiments, the casting solution may have a total polymer content in the casting solution that is from about 10 wt% to about 30 wt% of the casting solution. It should be understood that the actual content of polymer in the film may not always be the same as the amount of polymer in the casting solution (dope). By way of illustration only, a 2.5 wt% sulfone polymer (second polymer) content in the membrane may result from 0.4 wt% sulfone polymer in the casting solution along with 15.6 wt% sulfone polymer containing zwitterionic functionality in the casting solution.
In certain embodiments, the hollow fiber membrane formed by step (B) above comprises the second polymer in an amount from about 0.5 wt% to about 5 wt% of the total weight of the polymers in the membrane. In other embodiments, the hollow fiber membrane formed by step (B) above comprises the second polymer in an amount from about 0.5 wt% to about 3 wt% of the total weight of the polymers in the membrane.
The sulfone polymers described herein and/or sulfone polymers having zwitterionic functionality are synthesized using any suitable technique known in the art. In certain embodiments, the sulfone polymer is synthesized by reacting at least one aromatic dihydroxy compound with at least one aromatic dihalide compound. At least one of the aromatic dihydroxy compound and the aromatic dihalide compound may be functionalized with a suitable functional group capable of being converted to a zwitterionic functional group (e.g., a piperazine amide group). In some embodiments, the aromatic dihydroxy compound may be functionalized with suitable functional groups. Further, at least one of the aromatic dihydroxy compound and the aromatic dihalide compound may contain a sulfone moiety. In some embodiments, the aromatic dihalide compound may contain a sulfone moiety.
Exemplary aromatic dihalide compounds that may be used include 4,4' -bis (chlorophenyl) sulfone, 2, 4-bis (chlorophenyl) sulfone, 4,4' -bis (fluorophenyl) sulfone, 2, 4-bis (fluorophenyl) sulfone, 4,4' -bis (chlorophenyl) sulfoxide, 2, 4-bis (fluorophenyl) sulfoxide, 4,4' -bis (fluorophenyl) sulfoxide, 2, 4-bis (fluorophenyl) sulfoxide, 4,4' -bis (fluorophenyl) ketone, 2, 4-bis (fluorophenyl) ketone, 1, 3-bis (4-fluorobenzoyl) benzene, 1, 4-bis (4-fluorobenzoyl) benzene, 4,4 '-bis (4-chlorophenyl) phenylphosphine oxide, 4,4' -bis (4-fluorophenyl) phenylphosphine oxide, 4,4 '-bis (4-fluorophenylsulfonyl) -1,1' -biphenyl, 4,4 '-bis (4-chlorophenylsulfonyl) -1,1' -biphenyl, 4,4 '-bis (4-fluorophenylsulfoxide) -1,1' -biphenyl, 4,4 '-bis (4-chlorophenylsulfoxide) -1,1' -biphenyl, and combinations thereof.
Non-limiting examples of suitable aromatic dihydroxy compounds that may be used include 4,4 '-dihydroxyphenylsulfone, 2,4' -dihydroxyphenylsulfone, 4,4 '-dihydroxyphenylsulfoxide, 2,4' -dihydroxyphenylsulfoxide, bis (3, 5-dimethyl-4-hydroxyphenyl) sulfoxide, bis (3, 5-dimethyl-4-hydroxyphenyl) sulfone, 4,4- (phenylphosphino) bisphenol, 4,4 '-oxybisphenol, 4,4' -thiobisphenol, 4,4 '-dihydroxybenzophenone, 4,4' -dihydroxyphenylmethane, hydroquinone, m-phenylbisphenol, 5-cyano-1, 3-dihydroxybenzene, 4-cyano-1, 3-dihydroxybenzene, 2-cyano-1, 4-dihydroxybenzene, 2-methoxyhydroquinone, 2,2' -bisphenol, 4,4' -bisphenol, 2,2' -dimethylbisphenol, 2,2',6,6' -tetramethylbisphenol, 2,2',3,3', 6,6' -hexamethylbisphenol, 3,3',5,5' -tetrabromo-2, 2',6,6' -tetramethylbisphenol, 4,4' -isopropylidenebisphenol (bisphenol A), 4,4' -isopropylidenebis (2, 6-dimethylphenol) (tetramethylbisphenol A), 4,4' -isopropylidenebis (2-methylphenol), 4,4' -isopropylidenebis (2-allylphenol), 4,4' -isopropylidenebis (2-allyl-6-methylphenol), 4,4' (1, 3-phenylenediisopropylidene) bisphenol (bisphenol M), 4,4' -isopropylidene bis (3-phenylphenol), 4,4' -isopropylidene-bis (2-phenylphenol), 4,4' - (1, 4-phenylenediisopropylidene) bisphenol (bisphenol P), 4,4' -ethylidene bisphenol (bisphenol E), 4,4' -oxybisphenol, 4,4' -thiobisphenol, 4,4' -thiobis (2, 6-dimethylphenol), 4,4' -sulfonylbisphenol, 4,4' -sulfonylbis (2, 6-dimethylphenol), 4,4' -sulfinylbisphenol, 4,4' -hexafluoroisopropylidene) bisphenol (bisphenol AF), 4,4' -hexafluoroisopropylidene) bis (2, 6-dimethylphenol), 4,4'- (1-phenylethylidene) bisphenol (bisphenol AP), 4,4' - (1-phenylethylidene) bis (2, 6-dimethylphenol), bis (4-hydroxyphenyl) -2, 2-dichloroethylene (bisphenol C), bis (4-hydroxyphenyl) methane (bisphenol F), bis (2, 6-dimethyl-4-hydroxyphenyl) methane, 2, 2-bis (4-hydroxyphenyl) butane, 3, 3-bis (4-hydroxyphenyl) pentane, 4,4'- (cyclopentylidene) bisphenol, 4,4' - (cyclohexylidene) bisphenol (bisphenol Z), 4,4'- (cyclohexylidene) bis (2-methylphenol), 4,4' - (cyclododecylidene) bisphenol, 4,4'- (bicyclo [2.2.1] heptylene) bisphenol, 4,4' - (9H-fluorene-9, 9-diyl) bisphenol, 3,3 '-bis (4-hydroxyphenyl) isobenzofuran-1 (3H) -one, 1- (4-hydroxyphenyl) -3,3' -dimethyl-2, 3-dihydro-1H-inden-5-ol, 1- (4-hydroxy-3, 5-dimethylphenyl) -1,3,3',4, 6-pentamethyl-2, 3-dihydro-1H-inden-5-ol, 3,3,3',3 '-tetramethyl-2, 2',3,3 '-tetrahydro-1, 1' -spiro [ indene ] -5,6' -diol (spirobiindane), dihydroxybenzophenone (bisphenol K), thiobisphenol (bisphenol S), bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenoxy) -4,4' -biphenyl, 4,4' -bis (4-hydroxyphenyl) diphenyl ether, 9, 9-bis (3-methyl-4-hydroxyphenyl) fluorene, N-phenyl-3, 3-bis- (4-hydroxyphenyl) phthalimide and combinations thereof.
The reaction may be carried out in a polar aprotic solvent in the presence of an alkali metal compound, and optionally in the presence of a catalyst. Basic salts of alkali metal compounds are useful in effecting the reaction between dihalogenated and dihydroxyaromatic compounds. Exemplary compounds include alkali metal hydroxides such as, but not limited to, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; alkali metal carbonates such as, but not limited to, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate; and alkali metal bicarbonate salts such as, but not limited to, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, and cesium bicarbonate. Combinations of these compounds may also be used to effect the reaction.
Some examples of aprotic polar solvents include, but are not limited to, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, N-diethylacetamide, N-dipropylacetamide, N-dimethylbenzamide, N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, n-ethyl-3-methyl-pyrrolidone, N-methyl-3, 4, 5-trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, N-isopropyl-2-piperidone, N-methyl-6-methyl-2-piperidone, N-methyl-3-ethyl-piperidone, dimethyl sulfoxide (DMSO), diethyl sulfoxide, sulfolane, 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, N' -Dimethylimidazolidinone (DMI), diphenylsulfone, and combinations thereof. The amount of solvent to be used is generally an amount sufficient to dissolve the dihalo-and dihydroxy aromatic compounds.
The reaction may be carried out at a temperature in the range of from about 100 ℃ to about 300 ℃ in some embodiments, from about 120 ℃ to about 200 ℃ in some embodiments, and from about 150 ℃ to about 200 ℃ in particular embodiments. The reaction mixture may be further dried by adding a solvent that forms an azeotrope with water to the initial reaction mixture along with the polar aprotic solvent. Examples of such solvents include toluene, benzene, xylene, ethylbenzene and chlorobenzene. After removal of residual water by azeotropic drying, the reaction may be carried out at the above-mentioned elevated temperature. The reaction is generally carried out for a period of time in some embodiments from about 1 hour to about 72 hours, and in specific embodiments from about 1 hour to about 10 hours.
After the reaction is complete, the polymer may be separated from the inorganic salt, precipitated into a non-solvent and collected by filtration and drying. Examples of non-solvents include water, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, and combinations thereof.
Glass transition temperature T of the polymers described hereingIn one embodiment may be in the range of from about 120 ℃ to about 280 ℃, and in another embodiment may be in the range of from about 140 ℃ to about 200 ℃. The polymer may further have a weight average molecular weight (M) obtained by gel permeation chromatography based on polystyrene standardsw) To characterize. In one embodiment, M of the polymerwMay be in a range of about 10000 grams per mole (g/mol) to about 100000 g/mol. In another embodiment, MwMay be in the range of about 10000g/mol to about 75000 g/mol. In another embodiment, MwCan be in the range of from about 40000g/mol to about 55000 g/mol. In another embodiment, MwCan be in the range of about 50000g/mol to about 80000 g/mol.
Mechanical testing was performed by using an Instron (model 4202). In a typical test, a length of hollow fiber membrane of about 2 inches in length is loaded into a pair of pneumatic clamps with a gauge length of exactly 1 inch. The test specimen was pulled at a rate of 0.5 inch/min and the test was stopped when the specimen broke. The data recorded from the tests included sample modulus, maximum load and maximum elongation, load and elongation at break.
Polymers and membranes comprising the polymer blends described herein can be further characterized by their respective hydrophilicity. In some embodiments, the sulfone polymer with zwitterionic functionality has a contact angle with water of less than about 80 degrees, as measured on the surface of the polymer cast as a film on a glass substrate. In some embodiments, the sulfone polymer with zwitterionic functionality has a contact angle with water of less than about 50 degrees, as measured on the surface of the polymer cast as a film on a glass substrate. In particular embodiments, the sulfone polymer having zwitterionic functional groups has a contact angle with water of less than about 30 degrees, as measured on the surface of the polymer cast as a film on a glass substrate.
Membranes according to embodiments described herein are prepared by methods known in the art. Suitable techniques include, but are not limited to: a dry phase separation membrane forming process; a wet phase separation membrane forming process; a dry-wet phase separation membrane forming process; thermally induced phase separation membrane formation process. Further, after membrane formation, the membrane may be subjected to a membrane conditioning process or treatment process prior to its use in separation applications. Representative methods may include thermal annealing to relieve stress or pre-equilibrium in a solution similar to the feed stream with which the film will be contacted.
In one embodiment, the film may be prepared by phase inversion. The phase inversion process involves 1) Vapor Induced Phase Separation (VIPS), also known as "dry casting" or "air casting"; 2) liquid Induced Phase Separation (LIPS), primarily referred to as "immersion casting" or "wet casting"; and 3) Thermally Induced Phase Separation (TIPS), commonly referred to as "melt casting". The phase inversion process can produce an integrally skinned asymmetric membrane. In some embodiments, the membrane may be crosslinked to provide additional support.
Membranes can be designed and manufactured with specific pore sizes such that solutes of a size larger than the pore size may not pass through. In one embodiment, the pore size may be in a range from about 0.5 nanometers to about 100 nanometers. In another embodiment, the pore size may be in the range of about 1 nanometer to about 25 nm.
Also provided herein are methods of forming the hollow fiber membranes described herein. The method includes providing a casting solution comprising the polymer blend and a solvent as previously described. The method also includes extruding the casting solution through the annular channel to form a hollow fiber membrane. Non-limiting examples of suitable solvents include N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, tetrahydrofuran, methyl ethyl ketone, formylpiperidine, or combinations thereof.
In some embodiments, the casting solution may further include an additive selected from the group consisting of polymers such as polyvinylpyrrolidone and polyethylene glycol; anti-solvents, such as water, alcohols, glycols, glycol ethers and salts; an alkali metal halide; and combinations thereof. In some embodiments, the additive may include an alkali metal bromide, such as, but not limited to, lithium bromide, sodium bromide, potassium bromide, cesium bromide, or combinations thereof.
In some embodiments, the additives may be present in the casting solution in an amount (total) in the range of about 0.1 wt% to about 30 wt%. Further, the sulfone polymer and the sulfone polymer comprising a zwitterionic functional group are present in the casting solution in an amount from about 10 wt% to about 30 wt% of the weight of the casting solution.
In some embodiments, any of the hollow fiber membrane blends described above comprises at least one additional polymer. Additional polymers may be blended with the polymer blends described above to impart different properties, such as better heat resistance, biocompatibility, and the like. In addition, additional polymers may be added to the casting solution during film formation to alter the morphology of the phase inversion film structure produced upon phase inversion, such as an asymmetric film structure. In some cases, the additional polymer may be a sulfone polymer that remains in the final membrane and/or an additive that is lost during the manufacturing process but not completely removed (e.g., PVP, PEG, etc.). Such films are also considered to be within the scope of the embodiments presented herein.
In some embodiments, the blended additional polymer is a hydrophilic polymer. Non-limiting examples of suitable hydrophilic polymers include polyvinylpyrrolidone (PVP), polyoxazoline, polyethylene glycol, polypropylene glycol, polyethylene glycol monoesters, polymers of polyethylene glycol and polypropylene glycol, water-soluble cellulose derivatives, polysorbates, polyethylene oxide-polypropylene oxide polymers, polyethyleneimines, and combinations thereof. In some embodiments, the casting solution blend may comprise additional polymers, such as polyether urethanes, polyamides, polyether-amides, polyacrylonitriles, and combinations thereof.
The membranes described herein may be used in a variety of applications, such as bioseparations, water purifications, hemofiltrations, hemodialysis, ultrafiltration, nanofiltration, gas separations, microfiltration, reverse osmosis, and pervaporation. In particular embodiments, the membranes may have applications in the biopharmaceutical and biomedical fields where improved hydrophilicity and biocompatibility are desired.
In some embodiments, provided herein are hollow fiber membranes for bioseparation. Hollow fiber membrane fractions suitable for bioseparations are characterized by protein binding. In some embodiments, the hollow fiber membranes provided herein have less than about 30ng/cm2The protein of (3) is bound. The film is composed of a polymer blend as described herein. In another aspect, provided herein is a bioseparation device comprising a plurality of porous hollow fibers comprised of a porous membrane provided herein.
In some embodiments, the membranes described herein are used for hemodialysis. Dialysis refers to a process effected by one or more membranes, wherein transport is driven primarily by a pressure differential across the thickness of the one or more membranes. Hemodialysis refers to a dialysis process in which biologically undesirable and/or toxic solutes, such as metabolites and by-products, are removed from the blood. Hemodialysis membranes are porous membranes that allow the passage of low molecular weight solutes (typically less than 5,000 daltons), such as urea, creatinine, uric acid, electrolytes, and water, but prevent the passage of higher molecular weight proteins and blood cellular components. Blood filtration, which more closely represents kidney glomerular filtration, requires an even higher permeability membrane to allow complete passage of solutes with molecular weights less than 50,000 daltons and in some cases less than 20,000 daltons.
The polymer blends described herein impart desirable mechanical properties to support the porous hollow fiber membrane structure during manufacture and use. In addition, the polymer blend imparts suitable thermal properties, thereby reducing or preventing degradation during high temperature steam sterilization processes. In addition, the polymer blends and membranes have optimal biocompatibility such that protein fouling is minimized and thrombosis of the treated blood does not occur.
Examples
Unless otherwise indicated, chemicals were purchased from Aldrich and Sloss Industries and used as received. In Bruker Avance 400(1H, 400 MHz) spectrometer and reference to residual solvent shift. Molecular weight is the number average molecular weight (Mn) Or weight average molecular weight (M)w) Reported, and determined by Gel Permeation Chromatography (GPC) analysis on a Perkin Elmer Series 200 instrument equipped with a UV detector. Thermal analysis of the polymer was performed on a Perkin Elmer DSC7 equipped with a TAC7/DX thermal analyzer and processed using Pyris software.
The glass transition temperature was recorded in the second heating scan. Contact angle measurements were performed on a VCA 2000(Advanced Surface Technology, Inc.) instrument evaluated using VCA optima software. Polymeric membranes are obtained by casting thin films from suitable solutions such as dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP) and Dimethylacetamide (DMAC) onto clean glass slides and evaporating the solvent. The advancing contact angle with water (73 dynes/cm) was determined on both sides of the membrane (facing air and facing the slide). It is assumed that, due to the smoother surface, consistently lower values are obtained on the side facing the slide.
Synthesis of sulfone polymers with zwitterionic functionality
The preparation and final derivatization of the polymer of the formula (VII) to 45 mol% zwitterion (one-pot synthesis, 3.25 mol% chain terminator) was carried out as follows: A5.0L three-necked flask equipped with an overhead mechanical stirrer, short head distillation apparatus, and nitrogen inlet was charged with bisphenol A (BPA) (228.1g, 1.000 moles), N-methylpiperazine bisphenol amide (301.17g, 0.8182 moles), p-cumylphenol (12.468g, 0.0591 moles), and 1.60L N-methylpyrrolidone (NMP) and immersed in an oil bath. The mixture was stirred at room temperature, then potassium carbonate (401.5g, 2.909 moles) was added in portions, followed by 0.800L of toluene. The mixture was heated under a slow stream of nitrogen to remove toluene and then the residual water was azeotropically removed to dry the reaction mixture. The oil bath temperature was gradually increased from 125-150 ℃ to remove most of the toluene (> 90%). The slurry was then cooled to room temperature, then difluorodiphenyl sulfone (469.63g, 1.8482 moles) was added as a solid and the reaction temperature was gradually increased to 165 ℃. During heating, a mild exotherm was observed at about 100 ℃. The mixture was heated and sampled every two hours until the desired molecular weight was reached (8-10 hours). The reaction viscosity increased during the reaction run, showing an opaque light gray color. When the desired molecular weight was reached, the reaction was diluted with 0.8 l of NMP and cooled to 50 ℃.1, 3-propane sultone (149.7g, 1.227 mole) was then added and the reaction mixture was gradually heated to 80 ℃. The reaction is completed within-4 hours. After the addition was complete, the reaction color gradually lightened to an off-white slurry. The reaction mixture may be further diluted based on the solution viscosity. The mixture was then precipitated into 12.0L of water using a high speed blender, resulting in a white precipitate. The precipitate was collected by filtration and then reslurried in 5.0 warm water (40-50 ℃) for 6 hours. The solid was collected by filtration. The resulting polymer was dried under vacuum initially at 50 ℃ under a nitrogen purge for 24 hours and then at 80-100 ℃ under full vacuum for a further 24 hours to provide about 950 grams of polymer after drying (-95% recovery).
Casting of hollow fiber membranes was performed using methods known in the art and using the methods described herein. The polymer blend is prepared by dissolving the polymer in a suitable solvent. The coating solution for casting the hollow fiber membrane is prepared by dissolving the polymer blend and any optional additives in a suitable solvent.
Assay for protein binding
Nonspecific protein binding was measured using immunoglobulin proteins labeled with horseradish peroxidase (HRP) functional groups. A 1 inch strip of each hollow fiber was placed in a 35 x 10mm petri dish and washed thoroughly in phosphate buffered saline (pH = 7.4) to remove residual glycerol, salts, or porogens from the fibers. PBS was replaced by 2ml of 10. mu.g/ml HRP-protein solution. After soaking for 2 hours, the antibody solution was removed and the fibers were washed thoroughly with PBS. The fibers were then cut into four equal parts and the four equal parts were co-transferred to wells of a 24-well plate containing 0.5ml of 50mM citrate-phosphate buffer (CPB) (pH = 5). The samples were soaked for 30 minutes.
CPB was replaced by 0.5ml of a CPB-based solution containing 0.5mg/ml o-phenylenediamine (OPD) and 0.015% hydrogen peroxide. HRP labels on the proteins convert OPD to yellow dissolved compounds. After 3 minutes, the solution was transferred to a small capacity disposable cuvette. Absorbance was measured at 450nm to quantify the amount of converted OPD, which is proportional to the amount of protein that is not specifically adsorbed onto the membrane surface. This amount is normalized by the membrane surface area (including the inner and outer lumens and the exposed cross-section). The results are shown in fig. 2.
While only certain features of the invention have been illustrated and described herein, many modifications and changes will occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.
Claims (26)
1. A hollow fiber membrane comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IA or formula IB linked to a structural unit of formula II:
wherein
R1And R2Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
k is 0 to 10;
R4is a bond, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R5and R6Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring; and
y 'and R' are each independently hydrogen, C1-C20An alkyl or aryl ring;
a. a' and b are independently at each occurrence 0, 1, 2,3, or 4; and
m and n are each independently 0 or 1.
2. The hollow fiber membrane of claim 1, wherein the second polymer comprising a sulfone polymer comprises structural units having the structure of formula II, III, IV, or V:
wherein
R5And R6Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring; and
y 'and R' are each independently hydrogen, C1-C20An alkyl or aryl ring;
a and b are independently at each occurrence 0, 1, 2,3, or 4; and
m and n are each independently 0 or 1.
3. The hollow fiber membrane of claim 1, wherein the first polymer comprising a sulfone polymer with zwitterionic functionality comprises structural units of formula VI:
wherein w is 0, 1, 2 or 3.
4. The hollow fiber membrane of claim 1, wherein the first polymer comprising a sulfone polymer with zwitterionic functionality comprises structural units of formula VII:
wherein P + Q = 1, P = 0.30-0.50, Q = 0.50-0.70.
5. The hollow fiber membrane of claim 4, wherein the mole fraction of zwitterionic functionalized structural units of formula IB in the first polymer is in the range of 30 mole% to 50 mole% of the total moles of units of formula IB and formula II in the first polymer.
6. The hollow fiber membrane of claim 1, wherein the first polymer comprising a sulfone polymer with zwitterionic functionality has a molecular weight in the range of 10000g/mol to 80000 g/mol.
7. The hollow fiber membrane of claim 2, wherein the second polymer comprising a sulfone polymer comprises a polysulfone comprising structural units of formula II.
8. The hollow fiber membrane of claim 2, wherein the second polymer comprising a sulfone polymer comprises a polyphenylsulfone comprising structural units of formula IV.
9. The hollow fiber membrane of claim 2, wherein the second polymer comprising a sulfone polymer comprises a polyethersulfone comprising structural units of formula V.
10. The hollow fiber membrane of claim 1, wherein the amount of the second polymer comprising a sulfone polymer is from 0.5 wt% to 5 wt% of the total weight of polymers in the membrane.
11. The hollow fiber membrane of claim 1, wherein the second polymer comprising a sulfone polymer has a molecular weight in a range of 50000g/mol to 80000 g/mol.
12. The hollow fiber membrane of claim 1, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and the second polymer comprising a sulfone polymer comprises a structural unit of formula II
13. The hollow fiber membrane of claim 1, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and the second polymer comprising a sulfone polymer comprises a structural unit of formula IV
14. The hollow fiber membrane of claim 1, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and the second polymer comprising a sulfone polymer comprises a structural unit of formula V
15. A hollow fiber membrane module comprising a plurality of hollow fiber membranes of claim 12.
16. A hemodialysis or hemofiltration device comprising the hollow fiber membrane module according to claim 15.
17. A hollow fiber membrane module comprising a plurality of hollow fiber membranes of claim 13.
18. A hemodialysis or hemofiltration device comprising the hollow fiber membrane module of claim 17.
19. A hollow fiber membrane module comprising a plurality of hollow fiber membranes of claim 14.
20. A hemodialysis or hemofiltration device comprising the hollow fiber membrane module of claim 19.
21. A composition comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IA or formula IB linked to a structural unit of formula II:
wherein
R1And R2Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
k is 0 to 10;
R4is a bond, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R5and R6Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring; and
y 'and R' are each independently hydrogen, C1-C20An alkyl or aryl ring;
a. a' and b are independently at each occurrence 0, 1, 2,3, or 4; and
m and n are each independently 0 or 1.
22. The composition of claim 21, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and the second polymer comprising a sulfone polymer comprises a structural unit of formula II:
wherein
R1And R2Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
k is 0 to 10;
R3and Y is independently a hydrogen atom, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R4is a bond, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R5and R6Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
a. a' and b are independently at each occurrence 0, 1, 2,3, or 4; and
m and n are each independently 0 or 1.
23. The composition of claim 21, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and the second polymer comprising a sulfone polymer comprises a structural unit of formula IV:
wherein
R1And R2Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
k is 0 to 10;
R3and Y is independently a hydrogen atom, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R4is a bond, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R5and R6Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
a. a' and b are independently at each occurrence 0, 1, 2,3, or 4; and
m and n are each independently 0 or 1.
24. The composition of claim 21, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises a structural unit of formula IB linked to a structural unit of formula II, and the second polymer comprising a sulfone polymer comprises a structural unit of formula V:
wherein
R1And R2At each time of dischargeIndependently at present is hydrogen atom, halogen atom, nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl, or aryl ring;
k is 0 to 10;
R3and Y is independently a hydrogen atom, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R4is a bond, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
R5and R6Independently at each occurrence is a hydrogen atom, a halogen atom, a nitro group, C1-C12Alkyl radical, C3-C12A cycloalkyl or aryl ring;
a. a' and b are independently at each occurrence 0, 1, 2,3, or 4; and
m and n are each independently 0 or 1.
25. A method of forming the hollow fiber membrane of claim 1, comprising:
(A) providing a casting solution comprising a blend of a first polymer and a second polymer, wherein the total polymer content in the casting solution is less than 20% by weight of the casting solution; and
(B) extruding the casting solution through an annular channel to form the hollow fiber membrane.
26. The method of claim 25, wherein the hollow fiber membrane comprises a second polymer in an amount of 0.5 wt% to 5 wt% of the total weight of polymers in the membrane.
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| 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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| WO2019219486A1 (en) * | 2018-05-15 | 2019-11-21 | General Electric Company | Zwitterion-functionalized multicomponent copolymers and associated polymer blends and membranes |
| KR20220104813A (en) * | 2019-12-05 | 2022-07-26 | 솔베이 스페셜티 폴리머즈 유에스에이, 엘.엘.씨. | Process for making poly(aryl ether sulfone) (PAES) polymers |
| 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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