EP3794056A1 - Zwitterion-functionalized multicomponent copolymers and associated polymer blends and membranes - Google Patents
Zwitterion-functionalized multicomponent copolymers and associated polymer blends and membranesInfo
- Publication number
- EP3794056A1 EP3794056A1 EP19724389.2A EP19724389A EP3794056A1 EP 3794056 A1 EP3794056 A1 EP 3794056A1 EP 19724389 A EP19724389 A EP 19724389A EP 3794056 A1 EP3794056 A1 EP 3794056A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copolymer
- radical
- independently
- repeat unit
- ranges
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 159
- 239000012528 membrane Substances 0.000 title claims abstract description 73
- 229920002959 polymer blend Polymers 0.000 title claims abstract description 11
- 229920005597 polymer membrane Polymers 0.000 title description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- 229920001400 block copolymer Polymers 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- -1 sultone compound Chemical class 0.000 claims description 123
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 63
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 30
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 24
- 239000012510 hollow fiber Substances 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 125000005843 halogen group Chemical group 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000005266 casting Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 150000003457 sulfones Chemical class 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 239000003880 polar aprotic solvent Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000004193 piperazinyl group Chemical group 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 150000001350 alkyl halides Chemical group 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 5
- 229920005604 random copolymer Polymers 0.000 claims description 5
- 229920006037 cross link polymer Polymers 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 108090000623 proteins and genes Proteins 0.000 abstract description 26
- 102000004169 proteins and genes Human genes 0.000 abstract description 26
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 41
- 150000003254 radicals Chemical class 0.000 description 35
- 229920001897 terpolymer Polymers 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000010408 film Substances 0.000 description 28
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 14
- 229920002492 poly(sulfone) Polymers 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 125000000524 functional group Chemical group 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical group BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 7
- 229940106691 bisphenol a Drugs 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001631 haemodialysis Methods 0.000 description 5
- 230000000322 hemodialysis Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 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
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Chemical group 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
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001188 haloalkyl group Chemical group 0.000 description 4
- 229920001477 hydrophilic polymer Polymers 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 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 4
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 4
- 229920006393 polyether sulfone Polymers 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 150000003462 sulfoxides Chemical class 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 230000002730 additional effect Effects 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000008280 blood Substances 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000007922 dissolution test Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 229910052760 oxygen Chemical group 0.000 description 3
- 239000001301 oxygen Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Chemical group 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Chemical group 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000011593 sulfur Chemical group 0.000 description 3
- 150000008053 sultones Chemical class 0.000 description 3
- 238000002145 thermally induced phase separation Methods 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- 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
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 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
- 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 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-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
- 239000004695 Polyether sulfone Substances 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 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
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000003116 impacting effect Effects 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005373 pervaporation Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product 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
- 150000003839 salts Chemical class 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 238000011282 treatment Methods 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
- STEGFDZXEOTZDZ-UHFFFAOYSA-N 1,1,2,2-tetraiodoethane Chemical compound IC(I)C(I)I STEGFDZXEOTZDZ-UHFFFAOYSA-N 0.000 description 1
- LSZGWUKFJAIAEM-UHFFFAOYSA-N 1,1,2-triiodoethane Chemical compound ICC(I)I LSZGWUKFJAIAEM-UHFFFAOYSA-N 0.000 description 1
- AHAFJAUUVOYKFU-UHFFFAOYSA-N 1,1,3,3-tetrachloropropane Chemical compound ClC(Cl)CC(Cl)Cl AHAFJAUUVOYKFU-UHFFFAOYSA-N 0.000 description 1
- URWHLZCXYCQNSY-UHFFFAOYSA-N 1,1,3-trichloropropane Chemical compound ClCCC(Cl)Cl URWHLZCXYCQNSY-UHFFFAOYSA-N 0.000 description 1
- FTARUCALCVZUFE-UHFFFAOYSA-N 1,1,4,4-tetrabromobutane Chemical compound BrC(Br)CCC(Br)Br FTARUCALCVZUFE-UHFFFAOYSA-N 0.000 description 1
- UKNXJIYDMJNPRY-UHFFFAOYSA-N 1,1,4-tribromobutane Chemical compound BrCCCC(Br)Br UKNXJIYDMJNPRY-UHFFFAOYSA-N 0.000 description 1
- RDCXWDUHESIPFX-UHFFFAOYSA-N 1,1,4-trichlorobutane Chemical compound ClCCCC(Cl)Cl RDCXWDUHESIPFX-UHFFFAOYSA-N 0.000 description 1
- LIDQDHSTYNCIAC-UHFFFAOYSA-N 1,1,4-triiodobutane Chemical compound ICCCC(I)I LIDQDHSTYNCIAC-UHFFFAOYSA-N 0.000 description 1
- OFLHCCKIKXLKSM-UHFFFAOYSA-N 1,1,5,5-tetraiodopentane Chemical compound IC(I)CCCC(I)I OFLHCCKIKXLKSM-UHFFFAOYSA-N 0.000 description 1
- LUAPHMQYHZXMTO-UHFFFAOYSA-N 1,1,5-tribromopentane Chemical compound BrCCCCC(Br)Br LUAPHMQYHZXMTO-UHFFFAOYSA-N 0.000 description 1
- ACSNWXUMKJZXIB-UHFFFAOYSA-N 1,1,6,6-tetrachlorohexane Chemical compound ClC(Cl)CCCCC(Cl)Cl ACSNWXUMKJZXIB-UHFFFAOYSA-N 0.000 description 1
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- 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
- 238000011088 calibration curve Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000004775 chlorodifluoromethyl group Chemical group FC(F)(Cl)* 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229940109239 creatinine Drugs 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
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- GZYYOTJXMDCAJN-UHFFFAOYSA-N cyclohexyloxymethoxycyclohexane Chemical compound C1CCCCC1OCOC1CCCCC1 GZYYOTJXMDCAJN-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229940037395 electrolytes Drugs 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 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
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002615 hemofiltration Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000012633 leachable Substances 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
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- IMNDHOCGZLYMRO-UHFFFAOYSA-N n,n-dimethylbenzamide Chemical compound CN(C)C(=O)C1=CC=CC=C1 IMNDHOCGZLYMRO-UHFFFAOYSA-N 0.000 description 1
- IFTIBNDWGNYRLS-UHFFFAOYSA-N n,n-dipropylacetamide Chemical compound CCCN(C(C)=O)CCC IFTIBNDWGNYRLS-UHFFFAOYSA-N 0.000 description 1
- AJAZMOFONMJGNP-WMZOPIPTSA-N n-[(2s)-4-methyl-1-oxo-1-[[(2s)-3-oxo-4-(pyridin-2-ylsulfonylamino)butan-2-yl]amino]pentan-2-yl]-1-benzofuran-2-carboxamide Chemical compound O=C([C@H](C)NC(=O)[C@@H](NC(=O)C=1OC2=CC=CC=C2C=1)CC(C)C)CNS(=O)(=O)C1=CC=CC=N1 AJAZMOFONMJGNP-WMZOPIPTSA-N 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical group 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007339 nucleophilic aromatic substitution reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000765 poly(2-oxazolines) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 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
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000010069 protein adhesion Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 229920006296 quaterpolymer Polymers 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 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
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 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
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940045136 urea Drugs 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- 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
-
- 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
- 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
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2182—Organic additives
- B01D2323/21821—Alkanes
-
- 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
- B01D2325/30—Chemical resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
-
- 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
- Porous polymeric membranes may be employed in many applications, such as, hemodialysis, ultrafiltration, nanofiltration, reverse osmosis, gas separation, micro filtration, and pervaporation.
- membranes with optimal selectivity as well as chemical, thermal and mechanical stability are desirable.
- Polyarylene ethers in particular, polyethersulfones and polysulfones are often used as membrane materials because of their mechanical, thermal, and chemical stability.
- these polymers may not have optimal biocompatibility and hydrophilicity for many applications.
- Multiple approaches have been reported to lead to improvements in membrane hydrophilicity.
- improvements have also been shown to be accompanied by other undesired properties.
- improvements in membrane hydrophilicity have been reported by using polymer blending, for example, fabricating porous polymeric membranes in the presence of small amounts of hydrophilic polymers such as polyvinylpyrrolidone (PVP).
- PVP polyvinylpyrrolidone
- PVP polyvinylpyrrolidone
- a multicomponent copolymer includes at least one repeat unit AC having a structure (I), at least one repeat unit DC having a structure (II), and at least one repeat unit BC having a structure (III):
- R 1 , R 2 and R 5 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 - C 12 aromatic radical;
- R 3 , Y, Y and R 6 are each, independently, a hydrogen atom, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;
- a membrane that includes the multicomponent copolymer above is provided.
- FIG. 1 shows effects of zwitterion content on protein fouling, according to embodiments of the present disclosure
- FIG. 2 illustrates that protein fouling properties are mainly controlled by the zwitterion content, according to embodiments of the present disclosure
- FIG. 3 shows the conversion of the piperazine content to piperazine-zwitterion functionality over the reaction time, according to embodiments of the present disclosure
- FIG. 4 shows the effects of total piperazine content and fixed zwitterion content on protein fouling, according to embodiments of the present disclosure
- FIG. 5 shows a molecular weight build versus time plot of a multicomponent copolymer at 155 °C, according to embodiments of the present disclosure
- FIG. 6 shows the mechanical testing data of multicomponent copolymers, according to embodiments of the present disclosure
- FIG. 7 shows schemes for crosslinking chemistry, according to embodiments of the present disclosure.
- FIG. 8 shows dissolution test results of films formed from various copolymers, according to embodiments of the present disclosure.
- certain embodiments of the present disclosure include copolymers and its associated polymer blends and membranes. More particularly, certain embodiments of the present disclosure relate to multicomponent copolymers comprising zwitterion functional groups, and their associated polymer blends and membranes. In addition, certain embodiments of the present disclosure include conversion, functionalization and cross-linking of the multicomponent copolymers.
- 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.
- the term“zwitterion functional group” or“zwitterion” as used herein refers to a moiety including both positively and negatively charged groups in the same molecule.
- Non-limiting examples of the negative-charged component,“Z”, of the zwitterion functional group include, but are not limited to, SO3 and C0 2 .
- the term“aromatic radical” refers to an array of atoms having a valence of at least one comprising at least one aromatic group.
- the array of atoms having a valence of at least one comprising at least one aromatic group may include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be composed exclusively of carbon and hydrogen.
- the term“aromatic radical” includes but is not limited to phenyl, pyridyl, furanyl, thienyl, naphthyl, phenylene, and biphenyl radicals.
- the aromatic radical contains at least one aromatic group.
- the aromatic radical may also include nonaromatic components.
- a benzyl group is an aromatic radical, which comprises a phenyl ring (the aromatic group) and a methylene group (the nonaromatic component).
- a tetrahydronaphthyl radical is an aromatic radical comprising an aromatic group (CeFb) fused to a nonaromatic component -(CH 2 ) 4 -.
- aromatic radical is defined herein to encompass a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, haloaromatic groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, and the like.
- the 4-methylphenyl radical is a C 7 aromatic radical comprising a methyl group, the methyl group being a functional group which is an alkyl group.
- the 2-nitrophenyl group is a C 6 aromatic radical comprising a nitro group, the nitro group being a functional group.
- Aromatic radicals include halogenated aromatic radicals such as 4-trifluoromethylphenyl, hexafluoroisopropylidenebis(4-phen-l-yloxy) (i.e., -OPhC(CF3) 2 PhO-), 4- chloromethylphen-l-yl, 3-trifluorovinyl-2-thienyl, 3-trichloromethylphen-l-yl (i.e., 3- CChPh-), 4-(3-bromoprop-l-yl)phen-l-yl (i.e., 4-BrCH 2 CH 2 CH 2 Ph-), and the like.
- halogenated aromatic radicals such as 4-trifluoromethylphenyl, hexafluoroisopropylidenebis(4-phen-l-yloxy) (i.e., -OPhC(CF3) 2 PhO-), 4- chloromethylphen-l-yl, 3-trifluorovinyl-2-thienyl, 3-t
- aromatic radicals include 4-allyloxyphen-l-oxy, 4-aminophen-l- yl (i.e., 4-H 2 NR1I-), 3-aminocarbonylphen-l-yl (i.e., NH 2 COPI1-), 4-benzoylphen-l-yl, dicyanomethylidenebis(4-phen-l-yloxy) (i.e., -OPhC(CN) 2 PhO-), 3-methylphen-l-yl, methylenebis(4-phen-l-yloxy) (i.e., -OPhCH 2 PhO-), 2-ethylphen-l-yl, phenylethenyl, 3-formyl-2-thienyl, 2-hexyl-5-furanyl, hexamethylene-l,6-bis(4-phen- l-yloxy) (i.e., -OPh(CH 2 ) 6 PhO-), 4-hydroxymethylphen-l-yl (i.
- a C 3 - C 10 aromatic radical includes aromatic radicals containing at least three but no more than 10 carbon atoms.
- the aromatic radical l-imidazolyl (C 3 H 2 N 2 - ) represents a C 3 aromatic radical.
- the benzyl radical (C 7 H 7 -) represents a C 7 aromatic radical.
- cycloaliphatic radical refers to a radical having a valence of at least one, and comprising an array of atoms which is cyclic but which is not aromatic. As defined herein a“cycloaliphatic radical” does not contain an aromatic group.
- A“cycloaliphatic radical” may comprise one or more noncyclic components.
- a cyclohexylmethyl group (C6H1 1CH2-) is a cycloaliphatic radical which comprises a cyclohexyl ring (the array of atoms which is cyclic but which is not aromatic) and a methylene group (the noncyclic component).
- the cycloaliphatic radical may include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be composed exclusively of carbon and hydrogen.
- the term“cycloaliphatic radical” is defined herein to encompass a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, and the like.
- the 4-methylcyclopent-l-yl radical is a C 6 cycloaliphatic radical comprising a methyl group, the methyl group being a functional group which is an alkyl group.
- the 2-nitrocyclobut-l-yl radical is a C 4 cycloaliphatic radical comprising a nitro group, the nitro group being a functional group.
- a cycloaliphatic radical may comprise one or more halogen atoms, which may be the same or different. Halogen atoms include, for example; fluorine, chlorine, bromine, and iodine.
- Cycloaliphatic radicals comprising one or more halogen atoms include 2-trifluoromethylcyclohex-l- yl, 4-bromodifluoromethylcyclooct- 1 -yl, 2-chlorodifluoromethylcyclohex- 1 -yl, hexafluoroisopropylidene-2,2-bis (cyclohex-4-yl) (i.e., -O,H Tf f O,H o-), 2- chloromethylcyclohex-l-yl, 3- difluoromethylenecyclohex-l-yl, 4- trichloromethylcyclohex- 1 -yloxy, 4-bromodichloromethylcyclohex- 1 -ylthio, 2- bromoethylcyclopent-l-yl, 2-bromopropylcyclohex-l -yloxy (c.g.,
- cycloaliphatic radicals include 4-allyloxycyclohex-l-yl, 4-aminocyclohex-l-yl (i.e., H2NC6H10-), 4- aminocarbonylcyclopent-l-yl (i.e., NH2COC5H8-), 4-acetyloxycyclohex-l-yl, 2,2- dicyanoisopropylidenebis(cyclohex-4-yloxy) (i.e., -OC6H IO C(CN)2C6H IO O-), 3- methylcyclohex-l-yl, methylenebis(cyclohex-4-yloxy) (i.e., -OC6H10CH2C6H10O-), 1 -ethylcyclobut- 1 -yl, cy clopropylethenyl, 3 -formyl-2-terahydr
- a C3 - C10 cycloaliphatic radical includes cycloaliphatic radicals containing at least three but no more than 10 carbon atoms.
- the cycloaliphatic radical 2-tetrahydrofuranyl (C4H7O-) represents a C 4 cycloaliphatic radical.
- the cyclohexylmethyl radical (C6H1 1CH2-) represents a C 7 cycloaliphatic radical.
- aliphatic radical refers to an organic radical having a valence of at least one consisting of a linear or branched array of atoms which is not cyclic. Aliphatic radicals are defined to comprise at least one carbon atom. The array of atoms comprising the aliphatic radical may include heteroatoms such as nitrogen, sulfur, silicon, selenium and oxygen or may be composed exclusively of carbon and hydrogen.
- aliphatic radical is defined herein to encompass, as part of the“linear or branched array of atoms which is not cyclic” a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, and the like.
- the 4-methylpent-l-yl radical is a C 6 aliphatic radical comprising a methyl group, the methyl group being a functional group which is an alkyl group.
- the 4-nitrobut-l-yl group is a C 4 aliphatic radical comprising a nitro group, the nitro group being a functional group.
- An aliphatic radical may be a haloalkyl group which comprises one or more halogen atoms which may be the same or different.
- Halogen atoms include, for example; fluorine, chlorine, bromine, and iodine.
- Aliphatic radicals comprising one or more halogen atoms include the alkyl halides trifluoromethyl, bromodifluoromethyl, chlorodifluoromethyl, hexafluoroisopropylidene, chloromethyl, difluorovinylidene, trichloromethyl, bromodichloromethyl, bromoethyl, 2-bromotrimethylene (e.g., -CH 2 CHBrCH2-), and the like.
- aliphatic radicals include allyl, aminocarbonyl (i.e., - CONH 2 ), carbonyl, 2,2-dicyanoisopropylidene (i.e., -CH2C(CN)2CH2-), methyl (i.e., - CH3), methylene (i.e., -CH2-), ethyl, ethylene, formyl (i.e.,-CHO), hexyl, hexamethylene, hydroxymethyl (i.e.,-CH 2 0H), mercaptomethyl (i.e., -CH2SH), methylthio (i.e., -SCH3), methylthiomethyl (i.e., -CH2SCH3), methoxy, methoxycarbonyl (i.e., CH3OCO-), nitromethyl (i.e., -CH2NO2), thiocarbonyl, trimethylsilyl (i.e., (CH3)3Si
- a Ci - C10 aliphatic radical contains at least one but no more than 10 carbon atoms.
- a methyl group i.e., CH3-
- a decyl group i.e., CH3(CH2)S>-
- CH3(CH2)S>- is an example of a C10 aliphatic radical.
- haloalkane refers to an alkane substituted with one or more halide atoms, typically selected from the group consisting of chlorine, bromine and iodine.
- the alkane can typically comprise 2-12 carbon atoms and can be straight or branched.
- certain embodiments of the present disclosure are directed to a multicomponent copolymer.
- the term“multicomponent copolymer” as used herein refers to a macro molecule comprising two or more types of repeat units in the polymer chain. In certain embodiments, repeat units may have a structural unit of a monomer or a dimer formed from a reaction between two monomers.
- multicomponent copolymers include, but are not limited to, a bipolymer that comprises two types of repeat units in the polymer chain, a terpolymer that comprises three types of repeat units in the polymer chain, and a quaterpolymer that comprises four types of repeat units in the polymer chain.
- the term “multicomponent copolymer” and “copolymer” may be used interchangeably throughout the present disclosure.
- the multicomponent copolymer may be a random copolymer or a block copolymer.
- the term“random copolymer” or“random multicomponent copolymer” as used herein refers to a macromolecule comprising two or more types of repeat units in the polymer chain with randomly distributed sequences of each of the two or more types of repeat units, for example, a random bipolymer, a random terpolymer, etc.
- a random bipolymer comprises at least one repeat unit AC having a structure (I) and at least one repeat unit BC having a structure (III) as described above, and the copolymer has randomly distributed sequences of each of the repeat units AC and BC.
- a random terpolymer comprises at least one repeat unit AC having a structure (I), at least one repeat unit BC having a structure (III), and at least one repeat unit DC having a structure (II), and the copolymer has randomly distributed sequences of each of the repeat units AC, BC and DC.
- a random terpolymer comprises at least one repeat unit AC having a structure (I), at least one repeat unit BC having a structure (V), and at least one repeat unit DC having a structure (II), and the copolymer has randomly distributed sequences of each of the repeat units AC, BC and DC.
- block copolymer or“block multicomponent copolymer” as used herein refers to a macromolecule comprising two or more types of repeat units in the polymer chain, in which blocks of repeat units of the same type are arranged substantially in sequences in the polymer chain.
- a block (DC)-(BC) copolymer includes a first block formed from a plurality of repeat units of the same type (for example, repeat units DC); and a second block formed from a plurality of repeat units of another same type (repeat units BC).
- the blocks DC and BC may have the same or different block length, that is, the number of repeat units in the two blocks may be the same or different.
- a (AC)-(DC)-(BC) block terpolymer includes a first block (AC) formed from a plurality of repeat units of the same type (repeat units AC); a second block DC formed from a plurality of repeat units of another same type (repeat units DC), and a third block BC formed from a plurality of repeat units of yet another same type (repeat units BC).
- block copolymer refers to the zwitterion- functionalized block copolymer, unless the context clearly indicates otherwise.
- a block bipolymer includes a first block (AC) q comprising two or more repeat units AC each having the same structure (I); and a second block (BC) r comprising two or more repeat units BC each having the same structure (III), where q and r are integers equal or greater than 2 and correspond to block lengths of the blocks (AC) q and (BC) r , respectively.
- the blocks (AC) q and (BC) r may have the same or different block lengths. Therefore, the number of repeat units in the two blocks, q and r, respectively, may be the same or different.
- the blocks (AC) q and (BC) r may be arranged substantially in sequences in the polymer chain.
- a block terpolymer includes a first block (AC) q comprising two or more repeat units AC, each repeat unit AC having the same structure (I); a second block (BC) r comprising two or more repeat units BC, each repeat unit BC having the same structure (III), and a third block (DC) t comprising two or more repeat units DC, each repeat unit DC having the same structure (II), wherein q, r and t are integers equal or greater than 2 and correspond to block lengths of blocks (AC) q , (BC) r and (DC)t, respectively.
- the blocks (AC) q , (BC) r and (DC) t may be arranged substantially in sequences in the polymer chain.
- the blocks (AC) q , (BC) r and (DC) t may have the same block length or block lengths different from each other.
- the number of repeat units in each of the three blocks, for example, q, r and t, respectively, may be the same or different from each other.
- a block terpolymer includes a first block (AC) q comprising two or more repeat units AC, each repeat unit AC having the same structure (I); a second block (BC) r comprising two or more repeat units BC, each repeat unit BC having the same structure (V), and a third block (DC) t comprising two or more repeat units DC, each repeat unit DC having the same structure (II), wherein q, r and t are integers equal or greater than 2 and correspond to block lengths of blocks (AC) q , (BC) r and (DC)t, respectively.
- the blocks (AC) q , (BC) r and (DC) t may be arranged substantially in sequences in the polymer chain.
- the blocks (AC) q , (BC) r and (DC) t may have the same block length or block lengths different from each other.
- the number of repeat units in each of the three blocks, for example, q, r and t, respectively, may be the same or different from each other.
- a block copolymer comprising four or more repeat units.
- the block copolymer comprises a first block comprising two or more repeat units AC, a second block comprising two or more repeat units BC, a third block comprising two or more repeat units DC, and a fourth block comprising two or more repeat units different from any of the repeat units AC, BC and DC.
- certain embodiments of the present disclosure are directed to multicomponent copolymers comprising at least one repeat unit AC, at least one repeat unit BC, and at least one repeat unit DC.
- the at least one repeat unit AC has a structure (I):
- ‘k” ranges from 0 to 10; m” and“n” are each, independently, 0 or 1;
- R 1 and R 2 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 - C 12 aromatic radical; and
- R 3 and Y are each, independently, a hydrogen atom, a C1-C12 aliphatic radical, a C3-C12 cycloaliphatic radical, or a C3-C12 aromatic radical.
- the at least one repeat unit AC has the structure (I) above, wherein“k” ranges from 1 to 4; both“m” and“n” are 0; and R 1 , R 2 , R 3 and Y are independently at each occurrence a hydrogen atom or a C 1 -C 4 aliphatic radical.
- the at least one repeat unit AC has a structure (lb):
- the at least one repeat unit BC has a structure (III):
- R 2 and R 5 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 - C 12 aromatic radical, and
- Y’ and R 6 are each, independently, a hydrogen atom, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical.
- the at least one repeat unit BC has the structure (III) above, wherein both“m” and“n” are 0; and R 2 , R 5 , R 6 and Y are independently at each occurrence a hydrogen atom or a C1-C4 aliphatic radical.
- the at least one repeat unit BC has a structure (V):
- R 2 and R 5 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 aliphatic radical, a C3-C12 cycloaliphatic radical, or a C3-C12 aromatic radical.
- the at least one repeat unit BC has the structure (V) wherein o is 1 , p is 0, m is 0 and n is 0.
- the at least one repeat unit BC has the structure (V) wherein o is 1 , p is 1 , m is 0 and n is 0. [0046] In certain embodiments, the at least one repeat unit BC has the structure
- the at least one repeat unit BC has a structure (Illb) wherein both“b” and“c” are 4, and both R 2 and R 5 are a hydrogen atom:
- suitable repeat units BC include thermoplastic polymers such as polysulfones, polyethersulfones, polyketones, polyetherketones, or polyetheretherketones, or any combinations thereof
- the repeat units BC include polysulfone, polyethersulfone, or both.
- the at least one repeat unit DC has a structure (II):
- “k” ranges from 0 to 10; “m” and“n” are each, independently, 0 or 1;
- R 1 and R 2 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 - C 12 aromatic radical;
- R 3 and Y are independently at each occurrence a hydrogen atom, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;
- R 4 is a bond, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 - C 12 aromatic radical.
- the at least one repeat unit DC has a structure (Ha):
- “k” ranges from 0 to 10;
- R 1 and R 2 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 - C 12 aromatic radical;
- R 3 and Y are independently at each occurrence a hydrogen atom, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical.
- the at least one repeat unit DC has a structure (Ila) above, wherein“k” ranges from 1 to 4,“w” ranges from 2 to 5, and R 3 and Y are each, independently, a hydrogen atom or a Ci-C 4 aliphatic radical.
- the at least one repeat unit DC has a structure (lib):
- the multicomponent AC-BC-DC copolymer may be characterized by the numbers of repeat units in the polymer chain, for example, (AC) q -(BC) r -(DC) t copolymer, wherein q, r and t are integers equal or greater than 1 and correspond to numbers of repeat units AC, BC and DC, respectively, as discussed above.
- the number of AC repeat units ranges from about 1 to about 50.
- the number of BC repeat units ranges from about 2 to about 25.
- the number of DC repeat units ranges from about 5 to about 15.
- the copolymers may be characterized by mole fractions of repeat units.
- the multicomponent may be characterized by mole fractions of repeat units.
- Both repeat units AC and DC include piperazine- containing groups, or piperazine content, with the repeat unit AC having a free piperazine content (P*S) and repeat unit DC having a zwitterion content (Z*S).
- a mole fraction of the total piperazine content (S) in the copolymer is a sum of a mole fraction of the piperazine content (P*S) of the repeat unit(s) AC and a mole fraction of the zwitterion content (Z*S) of the repeat unit(s) DC in the copolymer.
- S ranges from about 0.02 to about 0.98.
- Z*S ranges from about 0.02 to about 0.98; ranges from about 0.25 to about 0.75 in certain embodiments; and ranges from about 0.30 to about 0.50 in certain embodiments.
- R ranges from about 0.02 to about 0.98.
- a random AC-BC-DC multicomponent copolymer comprises at least one repeat unit AC having a structure (I), at least one repeat unit BC having a structure (III), and at least one repeat unit DC having a structure (II), with each of the at least one repeat unit AC, BC and DC arranged randomly in the polymer chain.
- a block AC-BC-DC multicomponent copolymer comprises a first block AC comprising two or more repeat units AC, each repeat unit AC having a structure (I); a second block BC comprising two or more repeat units BC, each repeat unit BC having a structure (III), and a third block DC comprising two or more repeat units DC, each repeat unit DC having a structure (II).
- the blocks AC, BC and DC are arranged substantially in sequences in the polymer chain.
- Non-limiting examples of a block multicomponent copolymer may include at least one block AC having a structure (I), at least one block BC having a structure (III), and at least one block DC having a structure (II).
- the block copolymer may include at least one block AC having a structure (lb), at least one block BC having a structure (Illb), and at least one block DC having a structure (Ila) or (lib).
- the at least one block unit AC has the structure (I), wherein“k” ranges from 1 to 4; both“m” and“n” are 0; and R 1 , R 2 , R 3 and Y are independently at each occurrence a hydrogen atom or a Ci-C 4 aliphatic radical.
- the at least one block AC has a structure (lb).
- the at least one block BC has the structure (III), wherein both“m” and“n” are 0; and R 2 , R 5 , R 6 and Y are independently at each occurrence a hydrogen atom or a Ci-C 4 aliphatic radical.
- the at least one block BC has a structure (Illb) wherein both“b” and“c” are 1, and R 2 and R 5 are a hydrogen atom.
- the at least one block DC has a structure (Ila), wherein “k” ranges from 1 to 4,“w” ranges from 2 to 5, and R 3 and Y are each, independently, a hydrogen atom or a Ci-C 4 aliphatic radical.
- the at least one block DC has a structure (lib).
- the block copolymer has a formula of [(AC)p * s- (DC)Z* S -(BC)R]N, as described above.
- the block copolymer has structural units of (AC) 0 -(BC) p -(DC) q , as described above.
- the blocks AC, BC and DC may have block lengths of from about 2 to about 50 repeat units and the blocks comprising structural units I, II and III may be arranged in any particular order including, but not limited to, I-II-III, III-I-II, II-III-I, I-II-I-III-II.
- the multicomponent copolymers may be a random or a block copolymer and may be synthesized using any suitable techniques.
- the copolymers may be synthesized by poly condensation reactions through nucleophilic aromatic substitution of aromatic dihalide compounds with aromatic dihydroxy compounds in a polar aprotic solvent in the presence of a base, and optionally, in the presence of catalysts.
- a method of making a multicomponent copolymer includes: mixing an aromatic dihalide compound, an aromatic dihydroxy compound and a chain stopper compound in a polar aprotic solvent to form a mixture; adding, to the mixture, a base and an azeotrope-forming solvent for forming an azeotrope with water; removing the polar aprotic solvent and the azeotrope under heat to obtain a slurry; adding a dihalodiphenyl sulfone to the slurry and allowing polymerization to proceed until a targeted molecular weight or a predefined time was achieved to form an intermediate copolymer; reacting a sultone compound with the intermediate copolymer in the polar aprotic solvent to produce the multicomponent copolymer.
- the method further includes separating the intermediate polymer before reacting with the sultone compound.
- the multicomponent copolymer includes at least one repeat unit AC having a structure (I), at least one repeat unit DC having a structure (II), and at least one repeat unit BC having a structure (III).
- the intermediate copolymer is a bipolymer including at least one repeat unit AC having a structure (I), and at least one repeat unit BC having a structure (III).
- Non-limiting examples of suitable aromatic dihalide compounds 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(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-methoxyhydroquinon
- 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'(l ,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'-sufonyldi
- Non- limiting examples of dihalo diphenyl sulfone include 4,4 - bis(fluorophenyl)sulfone (DFDPS), 4,4'-bis(chlorophenyl)sulfone, (DCDPS) 2,4'- bis(chlorophenyl)sulfone, 2,4-bis(chlorophenyl)sulfone, 2,4'- bis(fluorophenyl)sulfone, and 2,4-bis(fluorophenyl)sulfone.
- Any chain stopper compound known to one skilled in the art may be used.
- Non limiting examples of a chain stopper compound include p-cumyl phenol.
- Non-limiting examples of the azeotrope-forming solvent include toluene, benzene, xylene, ethylbenzene, chlorobenzene, or any combinations thereof.
- a base may be used to affect the reaction between the aromatic dihalo and aromatic dihydroxy compounds.
- a base include alkali metal hydroxides including, but not limited to, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; alkali metal carbonates including, but not limited to, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate; and alkali metal hydrogen carbonates including, 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 affect the reaction.
- Non-limiting examples of the aprotic polar solvent include N,N- dimethylformamide (DMF), N,N-diethylformamide, N,N-dimethylacetamide, N,N- diethylacetamide, N,N-dipropylacetamide, N,N-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
- the polymerization reaction is conducted at a temperature ranging from about 100 °C to about 250 °C in certain embodiments, from about 140 °C to about 200 °C in certain embodiments, from about 150 °C to about 175 °C, and from about 155 °C to about 165 °C in certain embodiments.
- the reaction mixture may be further dried by adding to the initial reaction mixture, along with the polar aprotic solvent, an azeotrope-forming solvent that forms an azeotrope with water. 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 period ranging from about 1 hour to about 48 hours in certain embodiments, and from about 1 hour to about 24 hours in certain embodiments.
- the copolymer for example, the terpolymer
- the terpolymer 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 iso butyl ketone, or any combinations thereof.
- the glass transition temperature, T g , of the copolymer, for example, the terpolymer may be in a range from about 140 °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 copolymer for example, the terpolymer, and the membrane fabricated from the terpolymer may be further characterized by its hydrophilicity.
- the terpolymer has a contact angle with water less than about 80 degrees measured on a surface of the terpolymer cast as a film on a glass substrate.
- the terpolymer has a contact angle with water less than about 50 degrees measured on a surface of the terpolymer cast as a film on a glass substrate.
- the terpolymer has a contact angle with water less than about 30 degrees measured on a surface of the terpolymer cast as a film on a glass substrate.
- the membrane may have a hollow fiber configuration or a flat sheet configuration.
- a hollow fiber membrane comprising a terpolymer according to embodiments of the present disclosure, is provided.
- a hollow- fiber membrane module including a plurality of hollow- fiber membranes is presented.
- an apparatus comprising a hollow fiber module comprising a plurality of membranes is provided, where each membrane is a hollow fiber membrane.
- the membranes according to embodiments of the present disclosure may be 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; or any combinations thereof. 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”; 3) thermally induced phase separation (TIPS), frequently called“melt casting”; or any combinations thereof.
- VIPS vapor-induced phase separation
- LIPS liquid- induced phase separation
- TIPS thermally induced phase separation
- a cross-linked copolymer may be prepared to provide additional mechanical, thermal and chemical resistance by reacting a copolymer with a crosslinking agent.
- Non- limiting examples of crosslinking agents include 1 ,2-dichloroethane; 1,3- dichloropropane; 1 ,4-dichlorobutane; l,5-dichloropentane; l,6-dichlorohexane; 1,7- dichloroheptane; l,8-dichlorooctane; 1,9 dichlorononane; 1 ,2-dibromoethane; 1,3- dibromopropane; 1 ,4-dibromobutane; l,5-dibromopentane; l,6-dibromohexane; 1,7- dibromoheptane; l,8-dibromooctane; 1,9 dibromononane; 1 ,2-diiodoethane; 1,3- diiodopropane; 1 ,4-dichlorobutane; l,
- the membranes comprising multicomponent copolymers may be cross-linked to provide additional mechanical, thermal and chemical resistance by reacting the copolymer with one of the crosslinking agents described above. Also other crosslinking agents capable of reacting with piperazine nitrogens may be used, e.g.
- epoxide crosslinkers including, but not limited to, epichlorohydrin, epibromohydrin, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, glycerol di- or tri- glycidyl ether, pentaerythritol di-, tri- or tetraglycidyl ether, bisphenol A diglycidyl ether etc, or PEG diglycidyl ether etc.
- a method of forming a cross-linked polymer includes: providing a multicomponent copolymer; and crosslinking a piperazine group of the at least one repeat unit AC with a cross-linking agent.
- the cross-linking agent comprises at least two reactive groups.
- the crosslinking agent is a haloalkane selected from a group consisting of a dihaloalkane, a trihaloalkane, a tetrahaloalkane, and any combinations thereof.
- the haloalkane includes chloro, bromo, iodo group, or any combinations thereof.
- a number of carbon atoms of the haloalkane ranges from 1 to 12.
- the crosslinking agent is 1,6- dibromohexane.
- the cross-linked copolymer may be blended with a second polymer to impart different properties such as better heat resistance, biocompatibility, and the like.
- the second polymer includes at least one repeat unit having a structure (III) or structure (V), or combinations thereof:
- R 2 and R 5 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C1-C12 aliphatic radical, a C3-C12 cycloaliphatic radical, or a C3- C12 aromatic radical, and
- R 6 and Y’ are each, independently, a hydrogen atom, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical.
- the second polymer used in forming a polymer blend with either a multicomponent copolymer or a cross-linked copolymer is in an amount from about 0.5 weight percent to about 5 weight percent of the total weight of the polymer blend.
- the membranes may be designed and fabricated to have specific pore sizes so that solutes or particles having sizes greater than the pore sizes may not be able to pass through.
- the pore size may range from about 0.5 nanometers (nm) to about 1000 nanometers. In certain embodiments, the pore size may range from about 0.5 nanometers to about 100 nanometers. In certain embodiments, the pore size may range from about 1 nanometer to about 25 nanometers.
- a method of forming a hollow- fiber membrane includes providing a casting solution comprising the copolymer as described earlier and a solvent. The method further includes extruding the casting solution through an annular channel to form the hollow-fiber membrane.
- an (aqueous) bore liquid may be added to the inside of the annular channel and the extruded hollow fiber may be fed into an (aqueous) coagulation bath, with or without an air gap between the annular channel and a surface of the bath.
- the casting solution may further include an additive.
- the additive may include a polymer including, but not limited to, polyvinylpyrrolidone and/or polyethylene glycol.
- the additive may include anti- solvents including, but not limited to, water, alcohols, glycols, glycol ethers, and salts; alkali metal halides; or any combinations thereof.
- the additive may include an alkali metal bromide including, but not limited to, lithium bromide, sodium bromide, potassium bromide, cesium bromide, or any combinations thereof.
- the copolymer may be present in the casting solution in an amount ranging from about 10 weight percent to about 30 weight percent, in some embodiments.
- the additive may be present in the casting solution in an amount (that is, total amount of all additives present) ranging from about 0.1 weight percent to about 30 weight percent.
- the hollow fiber membrane or flat sheet membrane may include a blend of copolymers, for example, a terpolymer as described earlier, and at least one additional polymer to impart different properties such as better heat resistance, biocompatibility, and the like.
- the additional polymer may be added to the terpolymer during the membrane formation to modify the morphology of the phase inverted membrane structure produced upon phase inversion, such as asymmetric membrane structures.
- the at least one polymer blended with the terpolymer may be hydrophilic or hydrophobic in nature.
- the terpolymer is blended with a hydrophilic polymer.
- a suitable hydrophilic polymer includes polyvinylpyrrolidone (PVP).
- PVP polyvinylpyrrolidone
- other suitable hydrophilic polymers include polyoxazoline, poly ethyleneglycol, polypropylene glycol, polyglycolmo noester, copolymer of poly ethyleneglycol with polypropylene glycol, water-soluble cellulose derivative, polysorbate, polyethylene-polypropylene oxide copolymer, polyethyleneimine, or any combinations thereof.
- the terpolymer may be further blended with polymers including, but not limited to, polysulfone, polyether sulfone, polyether urethane, polyamide, polyether-amide, polyacrylonitrile, or any combinations thereof.
- a second polymer comprises at least one repeat unit having a structure (V):
- R 2 and R 5 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 - C 12 aromatic radical.
- a second polymer comprises at least one repeat unit having a structure (V) wherein o is 1, p is 0, m is 0 and n is 0.
- a second polymer comprises at least one repeat unit having a structure (V) wherein o is 1, p is 1, m is 0 and n is 0. [0099] In certain embodiments, a second polymer comprises at least one repeat unit having a structure (V) wherein o is 0, p is 0, m is 0 and n is 0.
- a second polymer comprises at least one repeat unit having a structure (III):
- R 2 and R 5 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 - C 12 aromatic radical
- R 6 and Y’ are each, independently, a hydrogen atom, a C1-C12 aliphatic radical, a C3-C12 cycloaliphatic radical, or a C3-C12 aromatic radical.
- a second polymer comprises at least one repeat unit having a structure (Illb) wherein both“b” and“c” are 4; and R 2 and R 5 are both a hydrogen atom.
- the membranes according to certain embodiments of the present disclosure may be used in various applications including, but not limited to, microfiltration, ultrafiltration, nanofiltration and reverse osmosis for drinking water, food and beverage, microelectronics, and purification, treatment and reuse of industrial and municipal wastewater, gas separation, recovery of organic vapors such as petro- chemical vapor recovery using pervaporation, fluid management and bioseparation in the biopharmaceutical industry, hemodialysis, fuel cell, battery separators, or electrolysis for chlorine production, or any combinations thereof.
- a hollow- fiber membrane for bio-separation is provided.
- a hollow-fiber membrane suitable for bio-separation may be characterized in part by a protein binding property.
- the hollow-fiber membranes may have protein binding (e.g. monoclonal IgG antibody) less than about 20 ng/cm 2 .
- the membrane is fabricated from a terpolymer according to embodiments of the present disclosure.
- a bio-separation apparatus is provided; the apparatus includes a hollow fiber module including a plurality of membranes according to embodiments of the present disclosure.
- the membranes according to embodiments of the present disclosure may be used for hemodialysis.
- Dialysis refers to a process effected by two or more membranes in which transport is driven primarily by pressure differences across the thickness of the two or more membranes.
- Hemodialysis refers to a dialysis process in which biologically undesired and/or toxic solutes, such as metabolites and by-products are removed from blood.
- Hemodialysis membranes are porous membranes permitting the passage of low molecular weight solutes, typically less than 5,000 Daltons (Da), such as urea, creatinine, uric acid, electrolytes and water, yet preventing the passage of higher molecular weight proteins and blood cellular elements.
- Da Daltons
- Hemofiltration which more closely represents the filtration in the glomerulus of the kidney, requires even more permeable membranes allowing complete passage of solutes of molecular weight of less than 50,000 g/mol, and, in some cases, less than 20,000 g/mol.
- the multicomponent copolymers according to certain embodiments of the present disclosure have the desired mechanical properties to support the porous membrane structure during manufacture and use.
- the copolymers have adequate thermal properties so as not to degrade during high temperature steam sterilization processes.
- the copolymers and the corresponding membranes have optimal biocompatibility, such that protein fouling is minimized and thrombosis of the treated blood does not occur.
- Scheme 1 is a non- limiting example of the synthesis route for random copolymers having zwitterion content. Either a one-pot or a two-pot synthesis can be used.
- Example 1 Synthesis of a multicomponent copolymer having zwitterion content (one- pot synthesis)
- 4-'-isopropylidenediphenol bisphenol-A or BP A, 228.1 g, 1 mole
- N-methyl piperazine diphenolamide 301.17 g, 0.8182 moles
- p-cumyl phenol 1.60 L of N-methyl pyrrolidinone (NMP) were charged.
- the precipitate was collected by filtration, and re- slurried in 5.0 liters of warm water (about 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 hours, and an additional 24 hours at 80-100 °C under full vacuum. 950 grams of the copolymer was obtained after drying (95% recovery).
- Example 2 Synthesis of a multicomponent copolymer having zwitterion content via a two -pot synthesis
- Copolymer of Bisphenol-A and N-Methyl Piperazino Diphenolamide Polysulfone A 250 ml three neck round bottom flask equipped with an overhead mechanical stirrer and distillation head to remove water/toluene azeotrope mixture was charged with bisphenol-A (7.434 g, 0.0326 moles), N-methyl piperazino diphenolamide (12.000 g, 0.0326 moles), p-cumyl phenol (0.069 g, 0.000326 moles), anhydrous potassium carbonate (18.340 g, 0.133 moles), 75 mL of N-methyl pyrrolidinone (NMP), and 75 mL of toluene.
- NMP N-methyl pyrrolidinone
- This mixture was heated to remove water by azeotropic distillation of toluene starting at about 120 °C and increasing temperature to 150 °C as most of toluene is removed under a stream of nitrogen.
- the toluene distillation was complete in about 6 hours with > 75% recovery of toluene and no visible sign of water in collected distillate.
- the reaction mixture was cooled and cooled to room temperature. At room temperature, difluorodiphenyl sulfone (16.560 g, 0.0652 moles) was added as a solid. Then the reaction mixture was heated to 155 °C until the mixture became very viscous, building sufficient molecular weight.
- Scheme 2 shows an example of synthesis route for making block copolymers with a formula [(AC)P*S-(DC)Z*S-(BC)R]N, according to embodiments of the present disclosure.
- Example 3 Fabrication of hollow- fiber membranes [00114] A solution containing 23 weight percent (wt%) of a copolymer of the formula [(AC)P*S-(DC)Z*S-(BC)R]N (as described in Example 1), 24 wt% polyvinylpyrrolidone, 3 wt% lithium bromide, and 50 wt% N-methylpyrrolidone was extruded through an annular nozzle into a coagulation bath containing water.
- the annulus bore included an inner coagulating fluid (a mixture of solvents and non- solvents) and a second, outer coagulation fluid was applied outside the annulus, forming a sheath around the freshly extruded polymer dope.
- the fiber was extruded through the bath at a rate of about 3-60 meter/min, and was collected in a second bath for further extraction.
- FIG. 1 shows effects of zwitterion content on protein fouling, as shown by the normalized protein binding performance (normalized with respect to a commercial polysulfone (PSU)) of membranes fabricated from a zwitterion-containing multicomponent copolymer according to embodiments of the present disclosure.
- PSU polysulfone
- FIG.l shows effects of zwitterion content on protein fouling, as shown by the normalized protein binding performance (normalized with respect to a commercial polysulfone (PSU)) of membranes fabricated from a zwitterion-containing multicomponent copolymer according to embodiments of the present disclosure.
- Tunable protein fouling properties of copolymers and/or membranes can be achieved.
- increasing the mole fraction of the zwitterion content in the copolymer e.g. Z*S
- leads to decreased protein binding e.g. IgG binding relative to a comparative example of a commercial PSU.
- Table 1 illustrates comparison of solubility properties of zwitterion- containing copolymers with a formula [(AC)P*S-(DC)Z*S-(BC)R]N (Examples 1A-1G) and various zwitterion contents (Z*S) ranging from about 0.10 to about 0.58. As shown, the copolymer with a mole fraction of the zwitterion content (Z*S) of about 0.58 become a gel unsuitable in NMP solvent for further processing (e.g. sample 1C)).
- targeting a mole fraction of the zwitterion content of 1.0 may leads to an insoluble gel (e.g. sample 1D).
- insoluble gel e.g. sample 1D
- Table 1 illustrate that, while low properties such as protein fouling may be controlled by the zwitterion contents in the copolymers, challenges and unmet needs remain in developing multicomponent copolymers and associated membranes in which other desirable properties (e.g. solubility/processability) may be adjustably controlled including, but not limited to, solubility/ processability properties, molecular weight and mechanical properties.
- Samples 1A-1G were synthesized using the one-pot synthesis approach illustrated in Scheme 1 but other methods including the two-pot synthesis method has also been used to obtain the samples.
- the inventors have further discovered, surprisingly, while the protein fouling properties may be adjustably controlled or tuned by varying a mole fraction of the zwitterion content in the copolymer, the total content of piperazine and the free piperazine content in the copolymer(s) do not play a significant role in impacting the protein fouling properties.
- This discovery leads to current development of alternative polymers having two or more tunable properties.
- Non-limiting examples of the tunable properties include improved protein fouling, processability, mechanical properties, or any combinations thereof.
- FIG. 2 shown as a non- limiting example, a terpolymer (FIG.
- protein fouling properties are mainly controlled by a mole fraction of the zwitterion content in addition, the total content of piperazine and/or the free piperazine content does not play a significant role in impacting the protein fouling properties, as terpolymers samples A and B differ significantly in these values.
- the terpolymers designed to include functional handles for example, free piperazine groups, may be further functionalized to impart additional properties to the polymers.
- the free piperazine groups may be further cross-linked to provide additional properties such as improved mechanical stability and processability, as described in more detail later.
- the free piperazine content of the multicomponent copolymers are adjustably controlled.
- FIG. 3 illustrates conversion of free piperazine-containing repeat units (AC) to zwitterion-containing repeat units (DC) through a reaction with a sultone (e.g. l,3-propanesultone) over time.
- Factors that may be used to adjustably control free piperazine content of the formed copolymers include, but not limited to, stoichiometry of the monomers (e.g. bisphenol-A, difluoro diphenyl sulfone (DFDPS)), polymerization reaction time, molar equivalents of the sultone, base, temperature, among others.
- FIG. 4 shows the effects of total piperazine content and zwitterion content on protein fouling.
- the conversion of the free piperazine content may be controlled to be 50%, yielding a copolymer with a zwitterion content of 0.25 (Z*S, mole fraction).
- the conversion of the free piperazine content may be controlled to be 100%, yielding a copolymer with a zwitterion content of 0.5 (Z*S, mole fraction), which has improved protein fouling properties. Therefore, by adjustably controlling mole fraction contents of various building blocks (e.g. repeat units or blocks comprising repeat units) in the copolymer, properties such as protein fouling may be tuned.
- building blocks e.g. repeat units or blocks comprising repeat units
- Table 2 provides non-limiting examples in which weight average molecular weight (M w ) may be tuned/adjustably controlled for multicomponent copolymers with a formula of [(AC)P*S-(DC)Z*S-(BC)R]N (Samples 2A-2H).
- Samples 2A-2H were prepared using experimental protocol listed for Example 1 or 2.
- Copolymers with various weight average molecular weight (M w ) were obtained by adjustably controlling reaction parameters including, but not limited to, stoichiometry of monomers (e.g. bisphenol-A, difluorodiphenyl sulfone (DFDPS)), relative molar ratio of a chain stopper (e.g. p-cumyl phenol), base, temperature, polymerization reaction time, amount of sultone, among others.
- monomers e.g. bisphenol-A, difluorodiphenyl sulfone (DFDPS)
- a chain stopper e.g. p-cumyl phenol
- molecular weight may be controlled by polymerizing an intermediate copolymer (for example, a AC-BC bipolymer) to a target molecular weight and then forming the zwitterion-containing copolymer, either in situ, or in a separate second step, via the addition of a corresponding sultone compound (e.g. l,3-propanesultone) to the reaction mixture.
- FIG. 5 illustrates an example of a typical molecular weight build versus time plot of a multicomponent copolymer of the present disclosure at 155 °C (y-axis: weight average molecular weight versus polystyrene standards).
- FIG. 6 shows the mechanical testing data of multicomponent copolymers according to embodiments of the present disclosure.
- a benchtop Instron testing system is used for mechanical testing, and all tests are conducted at ambient temperature. Maximum stress (in MPa) and maximum strain (%) are obtained from recorded stress-strain curve(s) for each test sample. All test samples are solution cast films with a thickness of about 0.015 inch, which are prepared by dissolving the copolymer in NMP at a 20 weight% concentration, casting on a glass plate with a doctor blade at 40 °C, and drying overnight in a vacuum oven at l05°C and then at l40°C for additional 24 hours.
- copolymers with M w in various ranges may be selected for their intended applications. Depending on applications, in certain embodiments, it may be preferable to adjustably control the Mw of the multicomponent copolymers to be lower than that of the commercial polysulfone (PSU with Mw in a range of about 70, 000 g/mol to about 80,000 g/mol).
- PSU commercial polysulfone
- M w of the copolymers may be adjustably controlled to be in a range of about 20,000 g/mol to about 90,000 g/mol, in a range of about 40,000 g/mol to about 75,000 g/mol, in a range of about 40,000 g/mol to about 70,000 g/mol, in a range of about 45,000 g/mol to about 70,000 g/mol in certain embodiments, or in a range of about 50,000 g/mol to about 60,000 g/mol in certain preferred embodiments, to provide copolymers with both improved mechanical properties and processability.
- the Mw of the multicomponent copolymers may be in a range of about 10,000 g/mol to about 90,000 g/mol, in a range of about 20,000 g/mol to about 75,000 g/mol, in a range of about 30,000 g/mol to about 70,000 g/mol, in a range of about 40,000 g/mol to about 60,000 g/mol, or in a range of about 50,000 g/mol to about 60,000 g/mol in certain embodiments, to provide copolymers with both improved mechanical properties and processability.
- FIG. 7 provides non- limiting examples of crosslinking chemistry.
- FIG. 8 shows representative dissolution test results of films formed from copolymers as provided in FIG. 7 A.
Abstract
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US20160136587A1 (en) * | 2014-11-19 | 2016-05-19 | General Electric Company | Zwitterion-functionalized copolymer hollow-fiber membranes and associated method |
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