WO2017096126A1 - Zwitterionic sulfone polymer flat sheet membrane - Google Patents
Zwitterionic sulfone polymer flat sheet membrane Download PDFInfo
- Publication number
- WO2017096126A1 WO2017096126A1 PCT/US2016/064557 US2016064557W WO2017096126A1 WO 2017096126 A1 WO2017096126 A1 WO 2017096126A1 US 2016064557 W US2016064557 W US 2016064557W WO 2017096126 A1 WO2017096126 A1 WO 2017096126A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- flat sheet
- formula
- structural units
- sulfone
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 232
- 239000012528 membrane Substances 0.000 title claims abstract description 172
- 150000003457 sulfones Chemical class 0.000 title claims abstract description 104
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims description 46
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 28
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 20
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 14
- 229920006393 polyether sulfone Polymers 0.000 claims description 7
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 3
- 229920002959 polymer blend Polymers 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 42
- 238000005266 casting Methods 0.000 description 41
- 238000000034 method Methods 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 230000008569 process Effects 0.000 description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- -1 2- methylcyclopentyl Chemical group 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 108090000623 proteins and genes Proteins 0.000 description 10
- 102000004169 proteins and genes Human genes 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000012360 testing method Methods 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- 125000000524 functional group Chemical group 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 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 5
- 238000001035 drying Methods 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 229920001223 polyethylene glycol Chemical group 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 4
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Chemical group 0.000 description 4
- 230000000996 additive effect 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
- 239000010408 film Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000007306 functionalization reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 150000003462 sulfoxides Chemical class 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-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
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000000151 deposition 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
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002145 thermally induced phase separation 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
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-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
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-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
- 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
- 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
- 108091003079 Bovine Serum Albumin Proteins 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- 229940098773 bovine serum albumin Drugs 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 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
- 230000006870 function Effects 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
- 150000002576 ketones Chemical class 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
- 238000001471 micro-filtration Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 239000013557 residual solvent Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 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
- 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
- 238000000108 ultra-filtration Methods 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
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-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
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-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
- 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
- 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
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 1
- WFNXYMSIAASORV-UHFFFAOYSA-N 2-[1-(2-hydroxyphenyl)cyclohexyl]phenol Chemical compound OC1=CC=CC=C1C1(C=2C(=CC=CC=2)O)CCCCC1 WFNXYMSIAASORV-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
- DRYYJQYUHPRVBN-UHFFFAOYSA-N 3-ethyl-1-methylpiperidin-2-one Chemical compound CCC1CCCN(C)C1=O DRYYJQYUHPRVBN-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HSTXWFCGRUJCET-UHFFFAOYSA-N 4,4-bis(4-hydroxyphenyl)-2-phenyl-3ah-isoindole-1,3-dione Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C(C(=O)N(C2=O)C=3C=CC=CC=3)C2=CC=C1 HSTXWFCGRUJCET-UHFFFAOYSA-N 0.000 description 1
- JPSMTGONABILTP-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)sulfanyl-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(SC=2C=C(C)C(O)=C(C)C=2)=C1 JPSMTGONABILTP-UHFFFAOYSA-N 0.000 description 1
- YNWRQXYZKFAPSH-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)sulfinyl-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(S(=O)C=2C=C(C)C(O)=C(C)C=2)=C1 YNWRQXYZKFAPSH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- IKQWMLALTXOOGU-UHFFFAOYSA-N 4-[(4-hydroxy-2,6-dimethylphenyl)methyl]-3,5-dimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1CC1=C(C)C=C(O)C=C1C IKQWMLALTXOOGU-UHFFFAOYSA-N 0.000 description 1
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 description 1
- BUGLKPUHRTVBDI-UHFFFAOYSA-N 4-[1-(4-hydroxy-3,5-dimethylphenyl)-1-phenylethyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C=2C=CC=CC=2)C=2C=C(C)C(O)=C(C)C=2)=C1 BUGLKPUHRTVBDI-UHFFFAOYSA-N 0.000 description 1
- SVOBELCYOCEECO-UHFFFAOYSA-N 4-[1-(4-hydroxy-3-methylphenyl)cyclohexyl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(CCCCC2)C=2C=C(C)C(O)=CC=2)=C1 SVOBELCYOCEECO-UHFFFAOYSA-N 0.000 description 1
- BHWMWBACMSEDTE-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)cyclododecyl]phenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCCCCCCCC1 BHWMWBACMSEDTE-UHFFFAOYSA-N 0.000 description 1
- OVVCSFQRAXVPGT-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)cyclopentyl]phenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCC1 OVVCSFQRAXVPGT-UHFFFAOYSA-N 0.000 description 1
- PCAOSZNSMXPEQE-UHFFFAOYSA-N 4-[2-(4-hydroxy-2-phenylphenyl)propan-2-yl]-3-phenylphenol Chemical compound C=1C=C(O)C=C(C=2C=CC=CC=2)C=1C(C)(C)C1=CC=C(O)C=C1C1=CC=CC=C1 PCAOSZNSMXPEQE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BKTRENAPTCBBFA-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-phenylphenyl)propan-2-yl]-2-phenylphenol Chemical compound C=1C=C(O)C(C=2C=CC=CC=2)=CC=1C(C)(C)C(C=1)=CC=C(O)C=1C1=CC=CC=C1 BKTRENAPTCBBFA-UHFFFAOYSA-N 0.000 description 1
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 1
- ADHQFDNEARRZPH-UHFFFAOYSA-N 4-[4-(4-hydroxyphenyl)-3-bicyclo[2.2.1]heptanyl]phenol Chemical compound C1=CC(O)=CC=C1C1C(C=2C=CC(O)=CC=2)(C2)CCC2C1 ADHQFDNEARRZPH-UHFFFAOYSA-N 0.000 description 1
- GAIZUCZZMVHBQO-UHFFFAOYSA-N 4-[4-[4-(4-hydroxyphenoxy)phenyl]phenoxy]phenol Chemical group C1=CC(O)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(O)=CC=3)=CC=2)C=C1 GAIZUCZZMVHBQO-UHFFFAOYSA-N 0.000 description 1
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 1
- BPMBNLJJRKCCRT-UHFFFAOYSA-N 4-phenylbenzonitrile Chemical compound C1=CC(C#N)=CC=C1C1=CC=CC=C1 BPMBNLJJRKCCRT-UHFFFAOYSA-N 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
- 101100192215 Arabidopsis thaliana PTAC7 gene Proteins 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- 241001285221 Breviceps Species 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 108060003951 Immunoglobulin Proteins 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 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
- LLJNTLUXOZPFQB-UHFFFAOYSA-N [4-(4-fluorobenzoyl)phenyl]-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(C(=O)C=2C=CC(F)=CC=2)C=C1 LLJNTLUXOZPFQB-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 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
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- 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
- 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
- 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003750 conditioning effect Effects 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
- 238000004821 distillation Methods 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
- 238000011067 equilibration 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
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 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
- 239000012510 hollow fiber Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 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
- 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
- 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
- 229910000032 lithium hydrogen 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
- 125000002950 monocyclic group Chemical group 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- IFTIBNDWGNYRLS-UHFFFAOYSA-N n,n-dipropylacetamide Chemical compound CCCN(C(C)=O)CCC IFTIBNDWGNYRLS-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
- 238000000655 nuclear magnetic resonance spectrum Methods 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 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
- 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
- 229920006254 polymer film Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 229920000136 polysorbate Polymers 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
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- 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
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000000638 solvent extraction Methods 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
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
-
- 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
- B01D69/06—Flat membranes
-
- 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
- B01D2325/28—Degradation or stability over time
-
- 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
Definitions
- This disclosure relates generally to polymers and polymer blends used for making flat sheet membranes.
- the polymers and polymer blends comprise at least one polymer comprising zwitterionic groups.
- Porous flat sheet polymeric membranes are employed in many applications such as ultrafiltration, nanofiltration, reverse osmosis, gas separation, microfiltration, and pervaporation. For many of these applications, membranes with optimal selectivity as well as chemical, thermal and mechanical stability are desirable. In many applications (for example, water filtration) it may also be desirable to have membranes with one or more of improved hydrophilicity, or low fouling.
- Polyarylene ethers in particular, polyethersulfones and polysulfones are often used as membrane materials because of their mechanical, thermal, and chemical stability.
- these polymers are hydrophobic and lack the hydrophilicity required for aqueous applications. Improvements in membrane hydrophilicity have been achieved by polymer blending, for example, fabricating the porous membrane in the presence of small amounts of hydrophilic polymers such as polyvinylpyrollidone (PVP).
- PVP polyvinylpyrollidone
- hydrophilicity has been achieved via functionalization of the polymer backbone and introduction of carboxyl, nitrile or polyethylene glycol functionality.
- polymers and polymer blends which alleviate certain limitations of previously known methods for the manufacture of flat sheet membranes.
- the present polymers and polymer blends increase processability of functionalized polymers and also reduce the need for post-casting functionalization of membranes.
- flat sheet membranes comprising a polymer comprising structural units of formula IB attached to structural units of formula II, wherein formula IB and formula II are described in the detailed description section below.
- flat sheet membranes comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer:
- flat sheet membranes 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 structural units of formula IA or formula IB attached to structural units of formula II and wherein the second polymer comprising a sulfone polymer comprises structural units having the structure 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.
- FIG. 1 shows water permeability of membranes of Example 1 measured in liters per square meter per hour per pounds square inch (LMH/PSI).
- FIG. 2 shows a comparison of polyethersulfone membranes and zwitterionic sulfone polymer membranes comprising structural units of formula (VII).
- FIG. 3 shows the 10 mil membrane of Example 1 at higher magnification showing the asymmetric pore structure.
- FIG. 4 shows protein binding for membranes of Example 2 compared to commercially available membranes.
- FIG. 5 shows permeability of the membrane of Example 2.
- FIG. 6 shows a scanning electron micrograph (SEM) of the membrane of Example 2.
- zwitterionic sulfone polymers and blends of polymers comprising sulfone polymers and zwitterionic sulfone polymers which alleviate the need for post-fabrication functionalization of membranes.
- the zwitterionic sulfone polymers and blends thereof described herein can improve polymer network structure and result in better mechanical performance.
- the zwitterionic sulfone polymers and blends thereof described herein also confer improved processability allowing for easier manufacture of membranes, including flat sheet membranes.
- the zwitterionic sulfone polymers and blends thereof described herein confer the desired hydrophilicity and/or anti-fouling properties to the membranes.
- a zwitterionic sulfone polymer which can be processed into flat sheet membranes.
- the processability of zwitterionic sulfone polymers into membranes is improved.
- the mechanical properties of membranes comprising said polymeric blends are significantly improved while maintaining membrane morphology and low binding characteristics of the membranes.
- the present membranes alleviate problems associated with leaching of water soluble polymers such as PVP from the matrix, thereby reducing product variability.
- the zwitterionic sulfone polymers and blends thereof described herein provide easy adjustment and significant improvement of membrane processibility (e.g. low dope viscosity) and mechanical property (e.g. high tensile elongation), and also provide some cost reduction by replacing expensive zwitterionic sulfone polymers with less expensive sulfone polymers in the blends.
- membrane processibility e.g. low dope viscosity
- mechanical property e.g. high tensile elongation
- Approximating language 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” is not to be limited to the precise value specified. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value.
- 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.
- sulfone polymer is any polymer comprising one or more subunits of structure aryl-SC -aryl. Typically sulfone polymers are prepared via a reaction between a diphenol and a bis(4-chlorophenyl)sulfone by elimination of sodium chloride: Sulfone polymers include and are not limited to polysulfones, polyarylsulfones (alternatively referred to as polyphenylsulfones or polypheny lenesulf ones), poly ethersulf ones, and the like.
- sulfone polymer having zwitterionic functionality or a “zwitterionic sulfone polymer” is any polymer comprising one or more subunits of structure aryl-SC -aryl and having one or more subunits comprising zwitterionic functionality.
- flat sheet membrane refers to flat membrane structures including separating layers present at the surface.
- the flat sheet membrane may function using "inside-outside” or “outside-inside” mechanism.
- flat sheet membrane and membrane are used herein interchangeably, unless the context clearly indicates otherwise.
- alkyl refers to a straight- or branched-chain alkyl group having from 1 to 12 carbon atoms in the chain.
- 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 monocyclic or polycyclic non-aromatic hydrocarbon groups having from 3 to 12 carbon atoms.
- Non-limiting of cycloalkyl groups include, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-methylcyclopropyl, 2- methylcyclopentyl, octahydro-lH-indene, decahydronaphthalene, and the like.
- aryl represents a mono- or bi-cyclic aromatic, hydrocarbon ring structure.
- Aryl rings can have 6 or 10 carbon atoms in the ring.
- flat sheet membranes comprising a polymer comprising structural units of formula IB attached to structural units of
- R 1 and R 2 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; k is from 0 to 10; Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an aryl ring; R 4 is a bond, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring;
- R 5 and R 6 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring;
- n are each, independently, 0 or 1.
- flat sheet membrane modules comprising a plurality of flat sheet membranes comprising a polymer comprising structural units of formula IB attached to structural units of formula II, where the structures of formula IB and formula II are as shown above.
- flat sheet membrane modules comprising a plurality of flat sheet membranes comprising the polymer of structure (VII) noted above.
- a process for forming flat sheet membranes described herein comprising:
- the casting solution may have a total polymer content in the casting solution which is less than about 50% by weight of the casting solution. In additional embodiments, the casting solution may have a total polymer content in the casting solution which is between about 10% and about 30% by weight of the casting solution.
- flat sheet membranes comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer.
- flat sheet membranes 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 structural units of formula IA or formula
- R 1 and R 2 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; k is from 0 to 10;
- Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an aryl ring;
- R 4 is a bond, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring;
- R 5 and R 6 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring;
- n are each, independently, 0 or 1.
- flat sheet membranes comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer, wherein the second polymer comprising a sulfone polymer comprises structural units having the structure of formula II, III IV,
- R 5 and R 6 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring;
- the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IA or formula IB attached to structural units of formula II:
- R 1 and R 2 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; k is from 0 to 10;
- Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an aryl ring;
- R 4 is a bond, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring;
- R 5 and R 6 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring;
- Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an 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
- the second polymer comprising a sulfone polymer comprises structural units having the structure of formula II, IV, or V
- the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula VI: wherein w is 0, 1, 2, or 3.
- the first polymer comprising a sulfone polymer having zwitterionic functionality comprises
- the mole fraction of the zwitterion-functionalized structural units of formula IB in the first polymer is less than about 50 mole percent of the total moles of the units of formula IB and formula II in the first polymer. In some embodiments of the flat sheet membranes described above, the mole fraction of the zwitterion-functionalized structural units of formula IB in the first polymer is in a range from about 30 mole percent to about 50 mole percent of the total moles of the units of formula IB and formula II in the first polymer.
- the molecular weight of the first polymer comprising a sulfone polymer having zwitterionic functionality is in a range from about 10000 g/mol to about 80000 g/mol.
- the second polymer comprising a sulfone polymer comprises a polysulfone comprising structural units of formula II.
- the second polymer comprising a sulfone polymer comprises a polyphenyl sulfone comprising structural units of formula IV.
- the second polymer comprising a sulfone polymer comprises a polyethersulfone comprising structural units of formula V.
- the second polymer comprising a sulfone polymer is in an amount from about 0.5 weight % to about 5 weight % of the total weight of polymer in the membrane.
- the molecular weight of the second polymer comprising a sulfone polymer is in a range from about 50000 g/mol to about 80000 g/mol.
- the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB attached to structural units of formula II
- the second polymer comprising a sulfone polymer comprises structural units of formula II
- the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB attached to structural units of formula II, and the second
- the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB attached to structural units of formula II, and the second
- flat sheet membrane modules comprising a plurality of flat sheet membranes wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB attached to structural units of formula II, and the second polymer comprising a sulfone polymer comprises structural units of formula II.
- flat sheet membrane modules comprising a plurality of flat sheet membranes wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB attached to structural units of formula II, and the second polymer comprising a sulfone polymer comprises structural units of formula IV.
- flat sheet membrane modules comprising a plurality of flat sheet membranes wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB attached to structural units of formula II, and the second polymer comprising a sulfone polymer comprises structural units of formula V.
- the casting solution may have a total polymer content in the casting solution which is less than about 50% by weight of the casting solution. In additional embodiments, the casting solution may have a total polymer content in the casting solution which is between about 10% and about 30% by weight of the casting solution. It will be understood that the actual content of polymers in the membrane may not always be identical to the amount of polymers in the casting solution (dope). By way of illustration only, a 2.5 weight% sulfone polymer (second polymer) content in the membrane may arise from 0.4 weight% sulfone polymer in the casting solution along with 15.6 weight% of the sulfone polymer comprising zwitterionic functionality in the casting solution.
- the flat sheet membrane which is formed from step (B) above comprises the second polymer in an amount from about 0.5 weight % to about 5 weight % of the total weight of polymer in the membrane. In certain embodiments, the flat sheet membrane which is formed from step (B) above comprises the second polymer in an amount from about 0.5 weight % to about 3 weight % of the total weight of polymer in the membrane.
- the sulfone polymers and/or the sulfone polymers having zwitterionic functionality described herein are synthesized using any suitable techniques known in the art.
- the sulfone polymer are 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 (for example, piperazine amide group) capable of being converted to the zwitterion functional group.
- the aromatic dihydroxy compound may be functionalized with a suitable functional group.
- at least one of the aromatic dihydroxy compound and the aromatic dihalide compound may include a sulfone moiety.
- the aromatic dihalide compound may include the sulfone moiety.
- Exemplary aromatic dihalide compounds that may be used include 4,4'- bis(chlorophenyl)sulfone, 2,4'-bis(chlorophenyl)sulfone, 2,4- bis(chlorophenyl)sulfone, 4,4'-bis(fluorophenyl)sulfone, 2,4'- bis(fluorophenyl)sulfone, 2,4-bis(fluorophenyl)sulfone, 4,4'- bis(chlorophenyl)sulfoxide, 2,4'-bis(chlorophenyl)sulfoxide, 4,4'-bis(fluorophenyl)sulfoxide, 2,4'- bis(fluorophenyl)sulfoxide, 2,4-bis(fluorophenyl)sulfoxide, 4,4'- bis(fluorophenyl)ketone, 2,4'-bis(fluoropheny
- Non-limiting examples of suitable aromatic dihydroxy compounds include 4,4'-dihydroxyphenyl sulfone, 2,4'-dihydroxyphenyl sulfone, 4,4'- dihydroxyphenyl sulfoxide, 2,4'-dihydroxyphenyl sulfoxide, bis(3,5-dimethyl-4- hydroxyphenyl) sulfoxide, bis(3,5-dimethyl-4-hydroxyphenyl) sulfone, 4,4- (phenylphosphinyl)diphenol, 4,4'-oxydiphenol,4,4'-thiodiphenol, 4,4'- dihydroxybenzophenone, 4,4'dihydroxyphenylmethane, hydroquinone, resorcinol, 5- cyano- 1 ,3-dihydroxybenzene, 4-cyano- 1 ,3,-dihydroxybenzene, 2-cyano- 1 ,4- dihydroxybenzene, 2-methoxyhydroquinone,
- the reaction may be effected in a polar aprotic solvent in the presence of an alkali metal compound, and optionally, in the presence of catalysts.
- a basic salt of an alkali metal compound may be used to effect the reaction between the dihalo and dihydroxy aromatic 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 hydrogen carbonates, such as but not limited to lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate. Combinations of these compounds may also be used to effect the reaction.
- 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
- alkali metal hydrogen carbonates such as but not limited to lithium hydrogen carbonate, sodium hydrogen carbonate
- aprotic polar solvents include and are not limited to N,N- dimethylformamide, N,N-diethylformamide, ⁇ , ⁇ -dimethylacetamide, N,N- diethylacetamide, N,N-dipropylacetamide, ⁇ , ⁇ -dimethylbenzamide, N-methyl-2- pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2- pyrrolidone, N-n-propyl-2-pyrrolidone, N-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-pyrrol
- the reaction may be conducted at a temperature in a range from about 100°C to about 300°C in some embodiments, from about 120°C to about 200°C in some embodiments, and from about 150°C to about 200°C in particular embodiments.
- the reaction mixture may be further dried by addition to the initial reaction mixture of, along with the polar aprotic solvent, a solvent that forms an azeotrope with water. 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 elevated temperatures described above.
- the reaction is typically conducted for a time period ranging from about 1 hour to about 72 hours in some embodiments, and from about 1 hour to about 10 hours in particular embodiments.
- the polymer may be separated from the inorganic salts, precipitated into a non-solvent and collected by filtration and drying.
- non-solvents include water, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, and combinations thereof.
- the glass transition temperature, T g , of the polymers described herein may be in a range from about 120°C to about 280°C in one embodiment, and may be in a range from about 140°C to about 200°C in another embodiment.
- the polymers may be further characterized by the weight average molecular weight (M w ) obtained from gel permeation chromatography based on polystyrene standards.
- M w weight average molecular weight
- the Mw of the polymer may be in the range from about 10000 grams per mole (g/mol) to about 100000 g/mol.
- the M w may be in a range from about 10000 g/mol to about 75000 g/mol.
- the M w may be in a range from about 40000 g/mol to about 55000 g/mol. In a further embodiment, the M w may be in a range from about 50000 g/mol to about 80000 g/mol.
- the polymers and the membranes including the blended polymers described herein may be further characterized by their respective hydrophilicities.
- the sulfone polymer having zwitterionic functionality has a contact angle with water less than about 80 degrees measured on a surface of the polymer cast as a film on a glass substrate.
- the sulfone polymer having zwitterionic functionality has a contact angle with water less than about 50 degrees measured on a surface of the polymer cast as a film on a glass substrate.
- the sulfone polymer having zwitterionic functionality has a contact angle with water less than about 30 degrees measured on a surface of the polymer cast as a film on a glass substrate.
- the membranes in accordance with embodiments described herein are made by processes known in the art. Suitable techniques include, but are not limited to: dry- phase separation membrane formation process; wet-phase separation membrane formation process; dry-wet phase separation membrane formation process; thermally- induced phase-separation membrane formation process. Further, post membrane- formation, the membrane may be subjected to a membrane conditioning process or a treatment process prior to its use in a separation application. Representative processes may include thermal annealing to relieve stresses or pre-equilibration in a solution similar to the feed stream the membrane will contact.
- the membranes may be prepared by phase inversion.
- the phase inversion process includes 1) vapor-induced phase separation (VIPS), also called “dry casting” or “air casting”; 2) liquid-induced phase separation (LIPS), mostly referred to as “immersion casting” or “wet casting”; and 3) thermally induced phase separation (TIPS), frequently called “melt casting”.
- VIPS vapor-induced phase separation
- LIPS liquid-induced phase separation
- TIPS thermally induced phase separation
- the phase inversion process can produce integrally skinned asymmetric membranes.
- the membranes may be cross-linked to provide additional support.
- the membrane may be designed and fabricated to have specific pore sizes so that solutes having sizes greater than the pore sizes may not be able to pass through.
- the pore size may be in a range from about 0.5 nanometers to about 100 nanometers.
- the pore size may be in a range from about 1 nanometer to about 25 nm.
- a method of forming a flat sheet membrane described herein includes providing a casting solution comprising a polymer or a polymer blend as described earlier and a solvent. The method further includes depositing the casting solution on a suitable substrate to form the flat sheet membrane.
- suitable solvents include N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, tetrahydrofuran, methyl ethyl ketone, formylpiperidine, or combinations thereof.
- 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; alkali metal halides; and combinations thereof.
- 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.
- the additive may be present in the casting solution in an amount (total amount) in a range from about 0.1 weight percent to about 30 weight percent, in some embodiments. Further, the sulfone polymer and the sulfone polymer comprising zwitterionic functionality are present in the casting solution in an amount in a range from about 10 weight percent to about 30 weight percent of the weight of the casting solution.
- any flat sheet membrane described above further comprise at least one additional polymer.
- the additional polymer may be blended with the polymer or polymer blend described above to impart different properties such as better heat resistance, biocompatibility, and the like.
- the additional polymer may be added to the casting solution during the membrane formation to modify the morphology of the phase inverted membrane structure produced upon phase inversion, such as asymmetric membrane structures.
- the additional polymer may be a sulfone polymer which persists in the final membrane and/or an additive (e.g., PVP, PEG and the like) which is lost in the fabrication process but is not completely removed.
- an additive e.g., PVP, PEG and the like
- the additional polymer blended is a hydrophilic polymer.
- suitable hydrophilic polymers include polyvinylpyrrolidone (PVP), polyoxazoline, polyethyleneglycol, polypropylene glycol, polyglycolmonoester, polymer of polyethyleneglycol with polypropylene glycol, water-soluble cellulose derivative, polysorbate, polyethylene-polypropylene oxide polymer, polyethyleneimine, and combinations thereof.
- the casting solution blend may comprise additional polymers, such as, poly ether urethane, polyamide, polyether-amide, poly aery lonitrile, and combinations thereof.
- membranes described herein have use in various applications, such as, water purification, ultrafiltration, nanofiltration, gas separation, microfiltration, reverse osmosis, and pervaporation.
- the polymers and polymer blends described herein confer the desired mechanical properties so as to support the porous flat sheet membrane structure during manufacture and use.
- the polymers and polymer blends described above confer adequate thermal properties so as to reduce or prevent degradation during high temperature steam sterilization processes.
- the polymers and/or polymer blends and membranes thereof have optimal hydrophilicity and fouling is minimized for improved performance.
- the mixture was heated and samples taken every two hours until the desired molecular weight was achieved (8-10 hrs).
- the reaction viscosity increased over the course of the run with the reaction showing an opaque greyish color.
- the reaction was diluted with 0.8 liters of NMP and cooled to 50°C 1,3-Propane sultone was then added (149.7g, 1.227 moles) and the reaction mixture gradually heated to 80°C.
- the reaction was complete in ⁇ 4hrs. Gradually after the addition is complete the reaction color lightens to an off- white slurry. Based on solution viscosity the reaction mixture may be diluted further.
- the mixture was then precipitated into 12.0 L of water using a high speed blender, producing a white precipitate.
- the precipitate was collected by filtration then re-slurried in 5.0 liters of warm water (40-50°C) for 6 hours. The solid was collected by filtration. The resulting polymer was dried under vacuum initially at 50°C under a purge of nitrogen for 24 hrs then an additional 24 hrs at 80- 100°C under full vacuum to provide approximately 950 grams of polymer after drying ( ⁇ 95% recovery).
- Zwitterionic poly sulf one of formula (VII) that had a molecular weight of 42kg/mol and 41mol% of the zwitterionic polymer repeat was used in preparation of two solutions (dopes), dope 1 and dope 2.
- the dopes were then cast on to a non-woven porous polymer support (Freudenberg) by blade coating with 5 and 10 mil thicknesses.
- the coated supports were then placed in a water bath to initiate the non-solvent phase inversion process.
- the membranes were allowed to extract residual solvent for >24 hours before drying. Water permeability of the membranes was measured as shown in FIG. 1.
- Example 1 The procedure in Example 1 was repeated in a commercial toll producer. A polymer having a molecular weight of 49.2 kg/mol and 39 mol% of the zwitterion polymer repeat was used. The dope was cast onto the membrane support using a blade casting thickness of 6 mil. The casted material was placed into water baths of 10, 21, and 32°C to allow for the phase inversion process. The membranes were extracted for -72 hours and transferred to a 20wt% glycerol solution for >12h hours before drying. Protein binding of the membranes was consistent with the previous results: -40% (or less) of the protein binding observed in the commercial PES membranes, and lower than other commercial membrane materials as shown in FIG. 4. Water permeability is shown in FIG. 5, consistent with a commercial lOkD membrane.
- polymer blends were prepared by dissolving the polymers in a suitable solvent.
- Dope solutions for casting membranes were prepared by dissolving the polymer blends and any optional additives in a suitable solvent.
- the membranes comprising blends were tested as described herein. Test for protein binding
- a modified ELISA test was performed to determine the degree of protein binding on the membrane surface (an indicator of fouling performance).
- Nonspecific protein binding was measured using an immunoglobulin protein labeled with a horseradish peroxidase (HRP) functional group.
- HRP horseradish peroxidase
- the PBS was replaced with 2 ml of a 10 ⁇ g/ml solution of HRP-protein. After 2 hours of soaking, the antibody solution was removed and the membranes were washed thoroughly with PBS.
- CPB citrate -phosphate buffer
- the CPB was replaced with 0.5 ml of a CPB-based solution containing 0.5 mg/ml o-phenylenediamine (OPD) and 0.015% hydrogen peroxide.
- OPD o-phenylenediamine
- the HRP tag on the protein converts the OPD to a yellow colored dissolved compound.
- the solution was transferred to small-volume disposable cuvette.
- the absorbance was measured at 450 nm to quantify the amount of converted OPD, which is directly proportional to the amount of protein nonspecifically adsorbed onto the surface of the membrane. This quantity was normalized by membrane surface area (including inner and outer lumen, as well as the exposed cross-sectional faces. Protein binding was determined to be -40% (or less) of the protein binding observed in the commercial polyethersulfone (PES) membranes.
- PES polyethersulfone
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Abstract
Provided herein are certain sulfone polymers having zwitterionic functionality and blends thereof which are suitable for preparation of flat sheet membranes. The polymer blends comprise a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer.
Description
ZWITTERIONIC SULFONE POLYMER FLAT
SHEET MEMBRANE
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation in part of US Patent Application No. 14/547,306 titled "Zwitterion-Functionalized Polymer Hollow-Fiber Membranes And Associated Method" filed November 19, 2014, which is incorporated herein by reference in its entirety.
BACKGROUND
[0002] This disclosure relates generally to polymers and polymer blends used for making flat sheet membranes. The polymers and polymer blends comprise at least one polymer comprising zwitterionic groups.
[0003] Porous flat sheet polymeric membranes are employed in many applications such as ultrafiltration, nanofiltration, reverse osmosis, gas separation, microfiltration, and pervaporation. For many of these applications, membranes with optimal selectivity as well as chemical, thermal and mechanical stability are desirable. In many applications (for example, water filtration) it may also be desirable to have membranes with one or more of improved hydrophilicity, or low fouling.
[0004] Polyarylene ethers, in particular, polyethersulfones and polysulfones are often used as membrane materials because of their mechanical, thermal, and chemical stability. However, these polymers are hydrophobic and lack the hydrophilicity required for aqueous applications. Improvements in membrane hydrophilicity have been achieved by polymer blending, for example, fabricating the porous membrane in the presence of small amounts of hydrophilic polymers such as polyvinylpyrollidone (PVP). However, since PVP is water-soluble it is slowly leached 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 functionality. However, these chemical modifications
may be complicated, expensive and inefficient. Further, addition of the functional groups may make it difficult to fabricate flat sheet membranes from the functionalized polymers. One approach to solving the problems due to functional groups has been to functionalize the membranes post-fabrication; but such an approach increases the cost of manufacture of the membranes.
[0005] There is a need in the field for materials which are easy to process and/or fabricate into membranes, including flat sheet membranes, but which also reduce fouling and provide good mechanical properties suited for aqueous applications.
BRIEF DESCRIPTION
[0006] Provided herein are polymers and polymer blends which alleviate certain limitations of previously known methods for the manufacture of flat sheet membranes. The present polymers and polymer blends increase processability of functionalized polymers and also reduce the need for post-casting functionalization of membranes.
[0007] In a first aspect, provided herein are flat sheet membranes comprising a polymer comprising structural units of formula IB attached to structural units of formula II, wherein formula IB and formula II are described in the detailed description section below.
[0008] In a further aspect, provided herein are flat sheet membranes, comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer:
[0009] In a further aspect, provided herein are flat sheet membranes, 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 structural units of formula IA or formula IB attached to structural units of formula II and wherein the second polymer comprising a sulfone polymer comprises structural units having the structure 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
[0010] 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:
[0011] FIG. 1 shows water permeability of membranes of Example 1 measured in liters per square meter per hour per pounds square inch (LMH/PSI).
[0012] FIG. 2 shows a comparison of polyethersulfone membranes and zwitterionic sulfone polymer membranes comprising structural units of formula (VII).
[0013] FIG. 3 shows the 10 mil membrane of Example 1 at higher magnification showing the asymmetric pore structure.
[0014] FIG. 4 shows protein binding for membranes of Example 2 compared to commercially available membranes.
[0015] FIG. 5 shows permeability of the membrane of Example 2.
[0016] FIG. 6 shows a scanning electron micrograph (SEM) of the membrane of Example 2.
DETAILED DESCRIPTION
[0017] Flat sheet membranes are typically employed in aqueous applications where a hydrophilic barrier is required. Zwitterionic sulfone polymers are hydrophilic and cause low fouling, including low biofouling. However, zwitterionic sulfone polymers tend to be difficult to process into membranes, and the resulting membranes often have poor mechanical properties. Previous attempts at improving hydrophilicity of sulfone polymer-containing membranes have focused on post-fabrication functionalization of polymers and/or membranes.
[0018] By contrast, provided herein are certain polymers comprising zwitterionic sulfone polymers and blends of polymers comprising sulfone polymers and zwitterionic sulfone polymers which alleviate the need for post-fabrication functionalization of membranes. Further, the zwitterionic sulfone polymers and blends thereof described herein can improve polymer network structure and result in better mechanical performance. The zwitterionic sulfone polymers and blends thereof described herein also confer improved processability allowing for easier manufacture of membranes, including flat sheet membranes. In addition, the zwitterionic sulfone polymers and blends thereof described herein confer the desired hydrophilicity and/or anti-fouling properties to the membranes. In one embodiment is a zwitterionic sulfone polymer which can be processed into flat sheet membranes. In another embodiment, by blending a low amount of sulfone polymers with zwitterionic sulfone polymers, the processability of zwitterionic sulfone polymers into membranes is improved. Further, the mechanical properties of membranes comprising said polymeric blends are significantly improved while maintaining membrane morphology and low binding characteristics of the membranes. Advantageously, the present membranes alleviate problems associated with leaching of water soluble polymers such as PVP from the matrix, thereby reducing product variability.
[0019] The zwitterionic sulfone polymers and blends thereof described herein provide easy adjustment and significant improvement of membrane processibility (e.g. low dope viscosity) and mechanical property (e.g. high tensile elongation), and also provide some cost reduction by replacing expensive zwitterionic sulfone polymers with less expensive sulfone polymers in the blends.
Certain terms
[0020] 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" is not to be limited to the precise value specified. In some instances, 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.
[0021] In the following specification and the 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 at least one of the referenced components being present and includes instances in which a combination of the referenced components may be present, unless the context clearly dictates otherwise.
[0022] As used herein a "sulfone polymer" is any polymer comprising one or more subunits of structure aryl-SC -aryl. Typically sulfone polymers are prepared via a reaction between a diphenol and a bis(4-chlorophenyl)sulfone by elimination of sodium chloride: Sulfone polymers include and are not limited to polysulfones, polyarylsulfones (alternatively referred to as polyphenylsulfones or polypheny lenesulf ones), poly ethersulf ones, and the like.
[0023] As used herein a "sulfone polymer having zwitterionic functionality" or a "zwitterionic sulfone polymer" is any polymer comprising one or more subunits of structure aryl-SC -aryl and having one or more subunits comprising zwitterionic functionality.
[0024] The term "flat sheet membrane" as used herein refers to flat membrane structures including separating layers present at the surface. The flat sheet membrane may function using "inside-outside" or "outside-inside" mechanism. The terms "flat sheet membrane" and "membrane" are used herein interchangeably, unless the context clearly indicates otherwise.
[0025] The term "alkyl" refers to a straight- or branched-chain alkyl group having from 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.
[0026] "Cycloalkyl" refers to monocyclic or polycyclic non-aromatic hydrocarbon groups having from 3 to 12 carbon atoms. Non-limiting of cycloalkyl groups include, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-methylcyclopropyl, 2- methylcyclopentyl, octahydro-lH-indene, decahydronaphthalene, and the like.
[0027] The term "aryl" represents a mono- or bi-cyclic aromatic, hydrocarbon ring structure. Aryl rings can have 6 or 10 carbon atoms in the ring.
Flat sheet membranes comprising zwitterionic sulfone polymers
[0028] In a first aspect, described herein are flat sheet membranes comprising a polymer comprising structural units of formula IB attached to structural units of
wherein
R1 and R2 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; k is from 0 to 10;
Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an aryl ring; R4 is a bond, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring;
R5 and R6 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; and
Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an 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.
[0029] In one group of embodiments, provided herein are flat sheet membranes
(VII) wherein P+Q = 1, P = 0.30-0.50, Q = 0.50-0.70.
[0030] Also provided herein are flat sheet membrane modules comprising a plurality of flat sheet membranes comprising a polymer comprising structural units of formula IB attached to structural units of formula II, where the structures of formula IB and formula II are as shown above. Further provided herein are flat sheet membrane modules comprising a plurality of flat sheet membranes comprising the polymer of structure (VII) noted above.
[0031] Also provided herein is a process for forming flat sheet membranes described herein comprising:
(A) providing a casting solution comprising a polymer of formula VII wherein the total polymer content in the casting solution is less than about 20% by weight of the casting solution; and
(B) depositing the casting solution on a substrate to form the flat sheet membrane.
[0032] In alternate embodiments, the casting solution may have a total polymer content in the casting solution which is less than about 50% by weight of the casting solution. In additional embodiments, the casting solution may have a total polymer content in the casting solution which is between about 10% and about 30% by weight of the casting solution.
Flat sheet membranes comprising blends
[0033] Also provided herein are flat sheet membranes, comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer.
[0034] In one aspect are flat sheet membranes, 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 structural units of formula IA or formula
wherein
R1 and R2 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; k is from 0 to 10;
Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an aryl ring; R4 is a bond, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring;
R5 and R6 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; and
Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an 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.
[0035] In another aspect are flat sheet membranes, comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer, wherein the second polymer comprising a
sulfone polymer comprises structural units having the structure of formula II, III IV,
R5 and R6 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; and
Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an 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.
[0036] In some embodiments of the flat sheet membranes described above, the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IA or formula IB attached to structural units of formula II:
wherein
R1 and R2 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; k is from 0 to 10;
Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an aryl ring; R4 is a bond, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring;
R5 and R6 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; and
Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an 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
[0037] In some embodiments of the flat sheet membranes described above, the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula VI:
wherein w is 0, 1, 2, or 3.
[0038] In some embodiments of the flat sheet membranes described above, the first polymer comprising a sulfone polymer having zwitterionic functionality comprises
(VII) wherein P+Q = 1, P = 0.30-0.50, Q = 0.50-0.70.
[0039] In some embodiments of the flat sheet membranes described above, the mole fraction of the zwitterion-functionalized structural units of formula IB in the first polymer is less than about 50 mole percent of the total moles of the units of formula IB and formula II in the first polymer. In some embodiments of the flat sheet membranes described above, the mole fraction of the zwitterion-functionalized structural units of formula IB in the first polymer is in a range from about 30 mole percent to about 50 mole percent of the total moles of the units of formula IB and formula II in the first polymer.
[0040] In some embodiments of the flat sheet membranes described above, the molecular weight of the first polymer comprising a sulfone polymer having zwitterionic functionality is in a range from about 10000 g/mol to about 80000 g/mol.
[0041] In some embodiments of the flat sheet membranes described above, the second polymer comprising a sulfone polymer comprises a polysulfone comprising structural units of formula II.
[0042] In some embodiments of the flat sheet membranes described above, the second polymer comprising a sulfone polymer comprises a polyphenyl sulfone comprising structural units of formula IV.
[0043] In some embodiments of the flat sheet membranes described above, the second polymer comprising a sulfone polymer comprises a polyethersulfone comprising structural units of formula V.
[0044] In some embodiments of the flat sheet membranes described above, the second polymer comprising a sulfone polymer is in an amount from about 0.5 weight % to about 5 weight % of the total weight of polymer in the membrane.
[0045] In some embodiments of the flat sheet membranes described above, the molecular weight of the second polymer comprising a sulfone polymer is in a range from about 50000 g/mol to about 80000 g/mol.
[0046] In some embodiments of the flat sheet membranes described above, the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB attached to structural units of formula II, and the second polymer comprising a sulfone polymer comprises structural units of formula II
[0047] In some embodiments of the flat sheet membranes described above, the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB attached to structural units of formula II, and the second
[0048] In some embodiments of the flat sheet membranes described above, the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB attached to structural units of formula II, and the second
[0049] Provided herein are flat sheet membrane modules comprising a plurality of flat sheet membranes wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB attached to structural units of formula II, and the second polymer comprising a sulfone polymer comprises structural units of formula II.
[0050] Provided herein are flat sheet membrane modules comprising a plurality of flat sheet membranes wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB attached to structural units of formula II, and the second polymer comprising a sulfone polymer comprises structural units of formula IV.
[0051] Provided herein are flat sheet membrane modules comprising a plurality of flat sheet membranes wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB attached to structural units of formula II, and the second polymer comprising a sulfone polymer comprises structural units of formula V.
[0052] Also provided herein is a process for forming flat sheet membranes described herein comprising:
(A) providing a casting solution comprising a blend of the first polymer and the second polymer, wherein the total polymer content in the casting solution is less than about 20% by weight of the casting solution; and
(B) depositing the casting solution on a substrate to form the flat sheet membrane.
[0053] In alternate embodiments, the casting solution may have a total polymer content in the casting solution which is less than about 50% by weight of the casting solution. In additional embodiments, the casting solution may have a total polymer content in the casting solution which is between about 10% and about 30% by weight of the casting solution. It will be understood that the actual content of polymers in the membrane may not always be identical to the amount of polymers in the casting solution (dope). By way of illustration only, a 2.5 weight% sulfone polymer (second
polymer) content in the membrane may arise from 0.4 weight% sulfone polymer in the casting solution along with 15.6 weight% of the sulfone polymer comprising zwitterionic functionality in the casting solution.
[0054] In certain embodiments, the flat sheet membrane which is formed from step (B) above comprises the second polymer in an amount from about 0.5 weight % to about 5 weight % of the total weight of polymer in the membrane. In certain embodiments, the flat sheet membrane which is formed from step (B) above comprises the second polymer in an amount from about 0.5 weight % to about 3 weight % of the total weight of polymer in the membrane.
[0055] The sulfone polymers and/or the sulfone polymers having zwitterionic functionality described herein are synthesized using any suitable techniques known in the art. In certain embodiments, the sulfone polymer are 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 (for example, piperazine amide group) capable of being converted to the zwitterion functional group. In some embodiments, the aromatic dihydroxy compound may be functionalized with a suitable functional group. Further, at least one of the aromatic dihydroxy compound and the aromatic dihalide compound may include a sulfone moiety. In some embodiments, the aromatic dihalide compound may include the sulfone moiety.
[0056] Exemplary aromatic dihalide compounds that may be used include 4,4'- bis(chlorophenyl)sulfone, 2,4'-bis(chlorophenyl)sulfone, 2,4- bis(chlorophenyl)sulfone, 4,4'-bis(fluorophenyl)sulfone, 2,4'- bis(fluorophenyl)sulfone, 2,4-bis(fluorophenyl)sulfone, 4,4'- bis(chlorophenyl)sulfoxide, 2,4'-bis(chlorophenyl)sulfoxide, 2,4- bis(chlorophenyl)sulfoxide, 4,4'-bis(fluorophenyl)sulfoxide, 2,4'- bis(fluorophenyl)sulfoxide, 2,4-bis(fluorophenyl)sulfoxide, 4,4'- bis(fluorophenyl)ketone, 2,4'-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)-l,l'-biphenyl, 4,4'-bis(4-chlorophenylsulfonyl)-l,l'- biphenyl, 4,4'-bis(4-fluorophenylsulfoxide)-l,l'-biphenyl, 4,4'-bis(4- chlorophenylsulfoxide)-l,l'-biplienyl, and combinations thereof.
[0057] Non-limiting examples of suitable aromatic dihydroxy compounds that may be used include 4,4'-dihydroxyphenyl sulfone, 2,4'-dihydroxyphenyl sulfone, 4,4'- dihydroxyphenyl sulfoxide, 2,4'-dihydroxyphenyl sulfoxide, bis(3,5-dimethyl-4- hydroxyphenyl) sulfoxide, bis(3,5-dimethyl-4-hydroxyphenyl) sulfone, 4,4- (phenylphosphinyl)diphenol, 4,4'-oxydiphenol,4,4'-thiodiphenol, 4,4'- dihydroxybenzophenone, 4,4'dihydroxyphenylmethane, hydroquinone, resorcinol, 5- cyano- 1 ,3-dihydroxybenzene, 4-cyano- 1 ,3,-dihydroxybenzene, 2-cyano- 1 ,4- dihydroxybenzene, 2-methoxyhydroquinone, 2,2'-biphenol, 4,4'-biphenol, 2,2'- dimethylbiphenol 2,2',6,6'-tetramethylbiphenol, 2,2',3,3',6,6'-hexamethylbiphenol, 3,3',5,5'-tetrabromo-2,2'6,6'-tetramethylbiphenol, 4,4'-isopropylidenediphenol (bisphenol A), 4,4'-isopropylidenebis(2,6-dimethylphenol) (teramethylbisphenol 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'-isopropylidenebis(3- phenylphenol), 4,4'-isopropylidene-bis(2-phenylphenol), 4,4'-(l,4- phenylenediisoproylidene)bisphenol (bisphenol P), 4,4'-ethylidenediphenol (bisphenol E), 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-thiobis(2,6-dimethylphenol), 4,4'- sufonyldiphenol, 4,4'-sufonylbis(2,6-dimethylphenol) 4,4'-sulfinyldiphenol, 4,4'- hexafluoroisoproylidene)bisphenol (Bisphenol AF), 4,4'-hexafluoroisoproylidene) bis(2,6-dimethylphenol), 4,4'-(l-phenylethylidene)bisphenol (Bisphenol AP), 4,4'-(l- 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)diphenol, 4,4'-
(cyclohexylidene)diphenol (Bisphenol Z), 4,4'-(cyclohexylidene)bis(2-methylphenol), 4,4'-(cyclododecylidene)diphenol, 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H- fluorene-9,9-diyl)diphenol, 3,3'-bis(4-hydroxyphenyl)isobenzofuran-l(3H)-one, l-(4-
hydroxyphenyl)-3,3'-dimethyl-2,3-dihydro-lH-inden-5-ol, l-(4-hydroxy-3,5- dimethylphenyl)-l,3,3',4,6-pentamethyl-2,3-dihydro-lH-in- den-5-ol, 3, 3, 3', 3'- tetramethyl-2,2',3,3'-tetrahydro-l, -spirobi[indene]— 5,6'-diol (Spirobiindane), dihydroxybenzophenone (bisphenol K), thiodiphenol (Bisphenol S), bis(4- hydroxyphenyl) diphenyl methane, 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.
[0058] The reaction may be effected in a polar aprotic solvent in the presence of an alkali metal compound, and optionally, in the presence of catalysts. A basic salt of an alkali metal compound may be used to effect the reaction between the dihalo and dihydroxy aromatic 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 hydrogen carbonates, such as but not limited to lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate. Combinations of these compounds may also be used to effect the reaction.
[0059] Some examples of aprotic polar solvents include and are not limited to N,N- dimethylformamide, N,N-diethylformamide, Ν,Ν-dimethylacetamide, N,N- diethylacetamide, N,N-dipropylacetamide, Ν,Ν-dimethylbenzamide, N-methyl-2- pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2- pyrrolidone, N-n-propyl-2-pyrrolidone, N-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- ethylpiperidone, dimethylsulfoxide (DMSO), diethylsulfoxide, sulfolane, 1-methyl-l- oxosulfolane, 1 -ethyl- 1-oxosulfolane, 1 -phenyl- 1-oxosulfolane, Ν,Ν'- dimethylimidazolidinone (DMI), diphenylsulfone, and combinations thereof. The
amount of solvent to be used is typically an amount that is sufficient to dissolve the dihalo and dihydroxy aromatic compounds.
[0060] The reaction may be conducted at a temperature in a range from about 100°C to about 300°C in some embodiments, from about 120°C to about 200°C in some embodiments, and from about 150°C to about 200°C in particular embodiments. The reaction mixture may be further dried by addition to the initial reaction mixture of, along with the polar aprotic solvent, a solvent that forms an azeotrope with water. 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 elevated temperatures described above. The reaction is typically conducted for a time period ranging from about 1 hour to about 72 hours in some embodiments, and from about 1 hour to about 10 hours in particular embodiments.
[0061] After completion of the reaction, the polymer may be separated from the inorganic salts, 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.
[0062] The glass transition temperature, Tg, of the polymers described herein may be in a range from about 120°C to about 280°C in one embodiment, and may be in a range from about 140°C to about 200°C in another embodiment. The polymers may be further characterized by the weight average molecular weight (Mw) obtained from gel permeation chromatography based on polystyrene standards. In one embodiment, the Mw of the polymer may be in the range from about 10000 grams per mole (g/mol) to about 100000 g/mol. In another embodiment, the Mw may be in a range from about 10000 g/mol to about 75000 g/mol. In another embodiment, the Mw may be in a range from about 40000 g/mol to about 55000 g/mol. In a further embodiment, the Mw may be in a range from about 50000 g/mol to about 80000 g/mol.
[0063] Mechanical testing is conducted by using an Instron (Model 4202). In a typical test, a segment of membrane with a length of about 2-in is loaded in a pair of
pneumatic clamps leaving a gauge length of exactly 1-in. The test sample is stretched at a rate of 0.5-in/min, and the test is stopped when the sample is broken. Data recorded from the test include sample modulus, maximum load and maximum elongation, load and elongation at break.
[0064] The polymers and the membranes including the blended polymers described herein may be further characterized by their respective hydrophilicities. In some embodiments, the sulfone polymer having zwitterionic functionality has a contact angle with water less than about 80 degrees measured on a surface of the polymer cast as a film on a glass substrate. In some embodiments, the sulfone polymer having zwitterionic functionality has a contact angle with water less than about 50 degrees measured on a surface of the polymer cast as a film on a glass substrate. In particular embodiments, the sulfone polymer having zwitterionic functionality has a contact angle with water less than about 30 degrees measured on a surface of the polymer cast as a film on a glass substrate.
[0065] The membranes in accordance with embodiments described herein are made by processes known in the art. Suitable techniques include, but are not limited to: dry- phase separation membrane formation process; wet-phase separation membrane formation process; dry-wet phase separation membrane formation process; thermally- induced phase-separation membrane formation process. Further, post membrane- formation, the membrane may be subjected to a membrane conditioning process or a treatment process prior to its use in a separation application. Representative processes may include thermal annealing to relieve stresses or pre-equilibration in a solution similar to the feed stream the membrane will contact.
[0066] In one embodiment, the membranes may be prepared by phase inversion. The phase inversion process includes 1) vapor-induced phase separation (VIPS), also called "dry casting" or "air casting"; 2) liquid-induced phase separation (LIPS), mostly referred to as "immersion casting" or "wet casting"; and 3) thermally induced phase separation (TIPS), frequently called "melt casting". The phase inversion process can produce integrally skinned asymmetric membranes. In some embodiments, the membranes may be cross-linked to provide additional support.
[0067] The membrane may be designed and fabricated to have specific pore sizes so that solutes having sizes greater than the pore sizes may not be able to 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 a range from about 1 nanometer to about 25 nm.
[0068] Also provided herein is a method of forming a flat sheet membrane described herein. The method includes providing a casting solution comprising a polymer or a polymer blend as described earlier and a solvent. The method further includes depositing the casting solution on a suitable substrate to form the flat sheet membrane. Non-limiting examples of suitable solvents include N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, tetrahydrofuran, methyl ethyl ketone, formylpiperidine, or combinations thereof.
[0069] In some embodiments, for any flat sheet membranes described above, 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; alkali metal halides; 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.
[0070] The additive may be present in the casting solution in an amount (total amount) in a range from about 0.1 weight percent to about 30 weight percent, in some embodiments. Further, the sulfone polymer and the sulfone polymer comprising zwitterionic functionality are present in the casting solution in an amount in a range from about 10 weight percent to about 30 weight percent of the weight of the casting solution.
[0071] In some embodiments, any flat sheet membrane described above further comprise at least one additional polymer. The additional polymer may be blended with the polymer or polymer blend described above to impart different properties such as better heat resistance, biocompatibility, and the like. Furthermore, the additional
polymer may be added to the casting solution during the membrane formation to modify the morphology of the phase inverted membrane structure produced upon phase inversion, such as asymmetric membrane structures. In some instances, the additional polymer may be a sulfone polymer which persists in the final membrane and/or an additive (e.g., PVP, PEG and the like) which is lost in the fabrication process but is not completely removed. Such membranes are also contemplated within the scope of embodiments presented herein.
[0072] In some embodiments, the additional polymer blended is a hydrophilic polymer. Non-limiting examples of suitable hydrophilic polymers include polyvinylpyrrolidone (PVP), polyoxazoline, polyethyleneglycol, polypropylene glycol, polyglycolmonoester, polymer of polyethyleneglycol with polypropylene glycol, water-soluble cellulose derivative, polysorbate, polyethylene-polypropylene oxide polymer, polyethyleneimine, and combinations thereof. In some embodiments, the casting solution blend may comprise additional polymers, such as, poly ether urethane, polyamide, polyether-amide, poly aery lonitrile, and combinations thereof.
[0073] The membranes described herein have use in various applications, such as, water purification, ultrafiltration, nanofiltration, gas separation, microfiltration, reverse osmosis, and pervaporation.
[0074] The polymers and polymer blends described herein confer the desired mechanical properties so as to support the porous flat sheet membrane structure during manufacture and use. In addition, the polymers and polymer blends described above confer adequate thermal properties so as to reduce or prevent degradation during high temperature steam sterilization processes. Further, the polymers and/or polymer blends and membranes thereof have optimal hydrophilicity and fouling is minimized for improved performance.
EXAMPLES
[0075] Chemicals were purchased from Aldrich and Sloss Industries and used as received, unless otherwise noted. NMR spectra were recorded on a Bruker Avance 400 (¾ 400 MHz) spectrometer and referenced versus residual solvent shifts.
Molecular weights are reported as number average (Mn) or weight average (Mw) molecular weight and were determined by gel permeation chromatography (GPC) analysis on a Perkin Elmer Series 200 instrument equipped with UV detector. Polymer thermal analysis was performed on a Perkin Elmer DSC7 equipped with a TAC7/DX thermal analyzer and processed using Pyris Software.
[0076] Glass transition temperatures were recorded on the second heating scan. Contact angle measurements were taken on a VCA 2000 (Advanced Surface Technology, Inc.) instrument using VCA optima Software for evaluation. Polymer films were obtained from casting a thin film from an appropriate solution, such as, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), and dimethylacetamide (DMAC) onto a clean glass slide and evaporation of the solvent. Advancing contact angles with water (73 Dynes/cm) were determined on both sides of the film (facing air and facing glass slide). Consistently lower values were obtained on the side facing the glass slide presumably due to the smoother surface.
Example A - Synthesis of sulfone polymer having zwitterionic functionality
[0077] The preparation of a polymer of formula (VII) and final derivatization to 45 mole% Zwitterion (one pot synthesis, 3.25 mole% chain stopper) was carried out as follows: To a 5.0L three neck flask equipped with an overhead mechanical stirrer, shorthead distillation apparatus, and a nitrogen inlet was charged bis phenol A (BPA) (228.1g,1.000 moles), N-methyl piperazine diphenolamide (301.17g, 0.8182 moles), p-cumyl phenol (12.468g, 0.0591 moles), and 1.60 L N-methyl pyrrolidinone (NMP) immersed in an oil bath. This mixture was stirred at room temperature then potassium carbonate (401.5g, 2.909 moles) was added in portions followed by 0.800L of toluene. This mixture was heated under a slow stream of nitrogen to remove toluene followed by azeotropic removal of residual water to dry the reaction mixture. The oil bath temperature was gradually raised from 125-150°C 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 raised to 165°C. During the heat up a mild exotherm was observed at about 100°C. The mixture was heated and samples taken every two hours until the
desired molecular weight was achieved (8-10 hrs). The reaction viscosity increased over the course of the run with the reaction showing an opaque greyish color. When the desired molecular weight was achieved the reaction was diluted with 0.8 liters of NMP and cooled to 50°C 1,3-Propane sultone was then added (149.7g, 1.227 moles) and the reaction mixture gradually heated to 80°C. The reaction was complete in ~ 4hrs. Gradually after the addition is complete the reaction color lightens to an off- white slurry. Based on solution viscosity the reaction mixture may be diluted further. The mixture was then precipitated into 12.0 L of water using a high speed blender, producing a white precipitate. The precipitate was collected by filtration then re-slurried in 5.0 liters of warm water (40-50°C) for 6 hours. The solid was collected by filtration. The resulting polymer was dried under vacuum initially at 50°C under a purge of nitrogen for 24 hrs then an additional 24 hrs at 80- 100°C under full vacuum to provide approximately 950 grams of polymer after drying ( ~ 95% recovery).
Example 1
[0078] Zwitterionic poly sulf one of formula (VII) that had a molecular weight of 42kg/mol and 41mol% of the zwitterionic polymer repeat was used in preparation of two solutions (dopes), dope 1 and dope 2.
[0079] The dopes were then cast on to a non-woven porous polymer support (Freudenberg) by blade coating with 5 and 10 mil thicknesses. The coated supports were then placed in a water bath to initiate the non-solvent phase inversion process. The membranes were allowed to extract residual solvent for >24 hours before drying. Water permeability of the membranes was measured as shown in FIG. 1.
[0080] Scanning electron micrographs were taken of the membranes. A comparison of the polyethersulfone membranes and zwitterionic sulfone polymer membranes demonstrate similar morphologies (lOmil casting shown) in FIG. 2.
Example 2
[0081] The procedure in Example 1 was repeated in a commercial toll producer. A polymer having a molecular weight of 49.2 kg/mol and 39 mol% of the zwitterion
polymer repeat was used. The dope was cast onto the membrane support using a blade casting thickness of 6 mil. The casted material was placed into water baths of 10, 21, and 32°C to allow for the phase inversion process. The membranes were extracted for -72 hours and transferred to a 20wt% glycerol solution for >12h hours before drying. Protein binding of the membranes was consistent with the previous results: -40% (or less) of the protein binding observed in the commercial PES membranes, and lower than other commercial membrane materials as shown in FIG. 4. Water permeability is shown in FIG. 5, consistent with a commercial lOkD membrane.
[0082] Several polymer solutions were cast at a rate of -14 fpm to produce membranes with a thickness of 3 mil (75μιη) on a 7 mil (175μιη) non-woven support, for a total of 10 mil (250μιη) and immersed into a water bath. After exiting the bath, the membranes were transferred for solvent extraction. Finally, the membranes were passed through a dryer. A summary of the membrane performance for passage of bovine serum albumin (BSA) and C15 grade polyvinylpyrrolidone (PVP) in aqueous solutions for various flat sheets (FS) is shown in the table below.
[0083] In addition to the examples noted above, polymer blends were prepared by dissolving the polymers in a suitable solvent. Dope solutions for casting membranes were prepared by dissolving the polymer blends and any optional additives in a suitable solvent. The membranes comprising blends were tested as described herein.
Test for protein binding
[0084] A modified ELISA test was performed to determine the degree of protein binding on the membrane surface (an indicator of fouling performance). Nonspecific protein binding was measured using an immunoglobulin protein labeled with a horseradish peroxidase (HRP) functional group. One-inch long pieces of each membrane were placed in 35x10 mm petri dishes and washed thoroughly in phosphate buffered saline (pH=7.4) to remove residual glycerol, salts, or porogens from the membranes. The PBS was replaced with 2 ml of a 10 μg/ml solution of HRP-protein. After 2 hours of soaking, the antibody solution was removed and the membranes were washed thoroughly with PBS. The membranes were then cut into quarters, and the 4 quarters were transferred collectively to the wells of a 24-well plate containing 0.5 ml 50 mM citrate -phosphate buffer (CPB) (pH=5). The samples were soaked for 30 minutes.
[0085] The CPB was replaced with 0.5 ml of a CPB-based solution containing 0.5 mg/ml o-phenylenediamine (OPD) and 0.015% hydrogen peroxide. The HRP tag on the protein converts the OPD to a yellow colored dissolved compound. After 3 minutes, the solution was transferred to small-volume disposable cuvette. The absorbance was measured at 450 nm to quantify the amount of converted OPD, which is directly proportional to the amount of protein nonspecifically adsorbed onto the surface of the membrane. This quantity was normalized by membrane surface area (including inner and outer lumen, as well as the exposed cross-sectional faces. Protein binding was determined to be -40% (or less) of the protein binding observed in the commercial polyethersulfone (PES) membranes.
[0086] 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
1. A flat sheet membrane comprising a polymer comprising structural units of formula IB attached to structural units of formula II
R1 and R2 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; k is from 0 to 10;
Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an aryl ring; R4 is a bond, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring;
R5 and R6 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; and
Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an 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 flat sheet membrane of claim 1, wherein the polymer
structural units of formula VII:
(VII) wherein P+Q = 1, P = 0.30-0.50, Q = 0.50-0.70.
3. The flat sheet membrane of claim 2, wherein the mole fraction of the zwitterion-functionalized structural units of formula IB in the polymer is in a range from about 30 mole percent to about 50 mole percent of the total moles of the units of formula IB and formula II.
4. The flat sheet membrane of claim 1, wherein the molecular weight of the polymer is in a range from about 10000 g/mol to about 80000 g/mol.
5. A flat sheet membrane module comprising a plurality of flat sheet membranes of claim 1.
6. A flat sheet membrane module comprising a plurality of flat sheet membranes of claim 2.
7. A flat sheet membrane, comprising a blend of a first polymer comprising a sulfone polymer having zwitterionic functionality and a second polymer comprising a sulfone polymer.
8. The flat sheet membrane of claim 7, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IA or formula IB attached to structural units of formula II:
wherein
R1 and R2 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; k is from 0 to 10;
Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an aryl ring; R4 is a bond, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring;
R5 and R6 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; and
Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an 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.
9. The flat sheet membrane of claim 7, wherein the second polymer comprising a sulfone polymer comprises structural units having the structure of formula II, III IV, or V
wherein
R5 and R6 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; and
Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an 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.
10. The flat sheet membrane of claim 7, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IA or formula IB attached to structural units of formula II:
R1 and R2 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; k is from 0 to 10;
Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an aryl ring; R4 is a bond, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring;
R5 and R6 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 alkyl, a C3-C12 cycloalkyl, or an aryl ring; and
Y' and R' are each, independently, hydrogen, C1-C20 alkyl, or an 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
11. The flat sheet membrane of claim 10, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula VI:
12. The flat sheet membrane of claim 10, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula VII:
(VII) wherein P+Q = 1, P = 0.30-0.50, Q = 0.50-0.70.
13. The flat sheet membrane of claim 12, wherein the mole fraction of the zwitterion-functionalized structural units of formula IB in the first polymer is in a range from about 30 mole percent to about 50 mole percent of the total moles of the units of formula IB and formula II.
14. The flat sheet membrane of claim 7, wherein the molecular weight of the first polymer comprising a sulfone polymer having zwitterionic functionality is in a range from about 10000 g/mol to about 80000 g/mol.
15. The flat sheet membrane of claim 10, wherein the second polymer comprising a sulfone polymer comprises a polysulfone comprising structural units of formula II.
16. The flat sheet membrane of claim 10, wherein the second polymer comprising a sulfone polymer comprises a polyphenyl sulfone comprising structural units of formula IV.
17. The flat sheet membrane of claim 10, wherein the second polymer comprising a sulfone polymer comprises a polyethersulfone comprising structural units of formula V.
18. The flat sheet membrane of claim 7, wherein the second polymer comprising a sulfone polymer is in an amount from about 0.5 weight % to about 5 weight % of the total weight of polymer in the membrane.
19. The flat sheet membrane of claim 7, wherein the molecular weight of the second polymer comprising a sulfone polymer is in a range from about 50000 g/mol to about 80000 g/mol.
20. The flat sheet membrane of claim 10, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB attached to structural units of formula II, and the second polymer comprising a sulfone polymer comprises structural units of formula II
(IB)
21. The flat sheet membrane of claim 10, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB attached to structural units of formula II, and the second polymer comprising a sulfone polymer comprises structural units of formula IV
22. The flat sheet membrane of claim 10, wherein the first polymer comprising a sulfone polymer having zwitterionic functionality comprises structural units of formula IB attached to structural units of formula II, and the second polymer comprising a sulfone polymer comprises structural units of formula V
23. A flat sheet membrane module comprising a plurality of flat sheet membranes of claim 20.
24. A flat sheet membrane module comprising a plurality of flat sheet membranes of claim 21.
25. A flat sheet membrane module comprising a plurality of flat sheet membranes of claim 22.
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Cited By (2)
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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 |
US10851241B2 (en) | 2014-11-19 | 2020-12-01 | Cytiva Sweden Ab | Zwitterion-functionalized multicomponent copolymers and associated polymer blends and membranes |
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US5071448A (en) * | 1990-12-05 | 1991-12-10 | Union Carbide Industrial Gases Technology Corporation | Semipermeable membranes based on certain sulfonated substituted polysulfone polymers |
US20100044314A1 (en) * | 2008-08-25 | 2010-02-25 | General Electric Company | Polyarylether compositions bearing zwitterion functionalities |
US20150328597A1 (en) * | 2014-05-16 | 2015-11-19 | General Electric Company | Zwitterion-functionalized block copolymer membranes and associated block copolymer composition |
Family Cites Families (1)
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US5043398A (en) * | 1989-05-12 | 1991-08-27 | Hoechst Celanese Corporation | Grafting of functional compounds onto functional oxymethylene polymer backbones, with diisocyanate coupling agents, and the graft polymers thereof |
-
2016
- 2016-12-02 WO PCT/US2016/064557 patent/WO2017096126A1/en active Application Filing
- 2016-12-02 EP EP16871556.3A patent/EP3383523A4/en not_active Ceased
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5071448A (en) * | 1990-12-05 | 1991-12-10 | Union Carbide Industrial Gases Technology Corporation | Semipermeable membranes based on certain sulfonated substituted polysulfone polymers |
US20100044314A1 (en) * | 2008-08-25 | 2010-02-25 | General Electric Company | Polyarylether compositions bearing zwitterion functionalities |
US20150328597A1 (en) * | 2014-05-16 | 2015-11-19 | General Electric Company | Zwitterion-functionalized block copolymer membranes and associated block copolymer composition |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10851241B2 (en) | 2014-11-19 | 2020-12-01 | Cytiva Sweden Ab | Zwitterion-functionalized multicomponent copolymers and associated polymer blends and membranes |
US11407897B2 (en) | 2014-11-19 | 2022-08-09 | 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 |
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EP3383523A4 (en) | 2019-07-24 |
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