CA2481435C - Use of hydrophobically modified copolymers based on n-vinyl monomers for the production of membranes - Google Patents
Use of hydrophobically modified copolymers based on n-vinyl monomers for the production of membranes Download PDFInfo
- Publication number
- CA2481435C CA2481435C CA2481435A CA2481435A CA2481435C CA 2481435 C CA2481435 C CA 2481435C CA 2481435 A CA2481435 A CA 2481435A CA 2481435 A CA2481435 A CA 2481435A CA 2481435 C CA2481435 C CA 2481435C
- Authority
- CA
- Canada
- Prior art keywords
- carboxylic acids
- weight
- monoethylenically unsaturated
- alkyl
- polymers
- 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.)
- Expired - Fee Related
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 63
- 229920001577 copolymer Polymers 0.000 title claims abstract description 32
- 239000000178 monomer Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 title abstract description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 48
- 150000001408 amides Chemical class 0.000 claims abstract description 18
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 17
- -1 alkyl vinyl ether Chemical compound 0.000 claims abstract description 17
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 11
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 10
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims abstract description 6
- PBGPBHYPCGDFEZ-UHFFFAOYSA-N 1-ethenylpiperidin-2-one Chemical compound C=CN1CCCCC1=O PBGPBHYPCGDFEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920002492 poly(sulfone) Polymers 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- 229940068965 polysorbates Drugs 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 229920001220 nitrocellulos Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims description 2
- 239000010695 polyglycol Substances 0.000 claims description 2
- 229920001600 hydrophobic polymer Polymers 0.000 claims 3
- 239000002202 Polyethylene glycol Substances 0.000 claims 2
- 229920000058 polyacrylate Polymers 0.000 claims 2
- 125000005907 alkyl ester group Chemical group 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 3
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 3
- 229940018557 citraconic acid Drugs 0.000 description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 239000012510 hollow fiber Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 3
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 150000007513 acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- SGKNPYKCCQCHAE-UHFFFAOYSA-N (1-hydroxy-2-methylpropyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)OC(=O)C(C)=C SGKNPYKCCQCHAE-UHFFFAOYSA-N 0.000 description 1
- RKVMKJUCXYJHEH-UHFFFAOYSA-N (1-hydroxy-2-methylpropyl) prop-2-enoate Chemical compound CC(C)C(O)OC(=O)C=C RKVMKJUCXYJHEH-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- REWARORKCPYWIH-UHFFFAOYSA-N 1-(prop-2-enoylamino)butan-2-ylphosphonic acid Chemical compound CCC(P(O)(O)=O)CNC(=O)C=C REWARORKCPYWIH-UHFFFAOYSA-N 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 1
- MMFCEMSIUPCRLD-UHFFFAOYSA-N 1-ethenyl-4-methylimidazole Chemical compound CC1=CN(C=C)C=N1 MMFCEMSIUPCRLD-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- NEYTXADIGVEHQD-UHFFFAOYSA-N 2-hydroxy-2-(prop-2-enoylamino)acetic acid Chemical compound OC(=O)C(O)NC(=O)C=C NEYTXADIGVEHQD-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NSEZBHCLFOJDKC-QXMHVHEDSA-N 2-methyl-n-[(z)-octadec-9-enyl]prop-2-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCCNC(=O)C(C)=C NSEZBHCLFOJDKC-QXMHVHEDSA-N 0.000 description 1
- CFOHEGHZKCXHQT-UHFFFAOYSA-N 2-methyl-n-nonylprop-2-enamide Chemical compound CCCCCCCCCNC(=O)C(C)=C CFOHEGHZKCXHQT-UHFFFAOYSA-N 0.000 description 1
- PABGQABTFFNYFH-UHFFFAOYSA-N 2-methyl-n-octadecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)C(C)=C PABGQABTFFNYFH-UHFFFAOYSA-N 0.000 description 1
- IMCBLSMMFWHLSN-UHFFFAOYSA-N 2-methyl-n-octylprop-2-enamide Chemical compound CCCCCCCCNC(=O)C(C)=C IMCBLSMMFWHLSN-UHFFFAOYSA-N 0.000 description 1
- BPEZHABUVGDGNE-UHFFFAOYSA-N 2-methyl-n-tetradecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCNC(=O)C(C)=C BPEZHABUVGDGNE-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- CMVNWVONJDMTSH-UHFFFAOYSA-N 7-bromo-2-methyl-1h-quinazolin-4-one Chemical compound C1=CC(Br)=CC2=NC(C)=NC(O)=C21 CMVNWVONJDMTSH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021353 Lignoceric acid Nutrition 0.000 description 1
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229920003291 Ultrason® E Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- BXOBFMUWVVHLFK-QXMHVHEDSA-N [(z)-octadec-9-enyl] 2-methylprop-2-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)C(C)=C BXOBFMUWVVHLFK-QXMHVHEDSA-N 0.000 description 1
- ASAPXSLRMDUMFX-QXMHVHEDSA-N [(z)-octadec-9-enyl] prop-2-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)C=C ASAPXSLRMDUMFX-QXMHVHEDSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- KHAYCTOSKLIHEP-UHFFFAOYSA-N docosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C=C KHAYCTOSKLIHEP-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 230000000322 hemodialysis Effects 0.000 description 1
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 1
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 description 1
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Chemical class 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- VLNBKZOBXNLNGX-UHFFFAOYSA-N n-(2-ethylhexyl)-2-methylprop-2-enamide Chemical compound CCCCC(CC)CNC(=O)C(C)=C VLNBKZOBXNLNGX-UHFFFAOYSA-N 0.000 description 1
- WEWMLPXWLVIVNW-UHFFFAOYSA-N n-(2-ethylhexyl)prop-2-enamide Chemical compound CCCCC(CC)CNC(=O)C=C WEWMLPXWLVIVNW-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- JROSKIFCGJOXDY-QXMHVHEDSA-N n-[(z)-octadec-9-enyl]prop-2-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCCNC(=O)C=C JROSKIFCGJOXDY-QXMHVHEDSA-N 0.000 description 1
- SNPAMTGUOWHTMN-UHFFFAOYSA-N n-decyl-2-methylprop-2-enamide Chemical compound CCCCCCCCCCNC(=O)C(C)=C SNPAMTGUOWHTMN-UHFFFAOYSA-N 0.000 description 1
- AWDYCSUWSUENQK-UHFFFAOYSA-N n-decylprop-2-enamide Chemical compound CCCCCCCCCCNC(=O)C=C AWDYCSUWSUENQK-UHFFFAOYSA-N 0.000 description 1
- GSGIFYPFGUIMQA-UHFFFAOYSA-N n-docosyl-2-methylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCNC(=O)C(C)=C GSGIFYPFGUIMQA-UHFFFAOYSA-N 0.000 description 1
- JLCNIMCQBVMUIN-UHFFFAOYSA-N n-docosylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCNC(=O)C=C JLCNIMCQBVMUIN-UHFFFAOYSA-N 0.000 description 1
- HOZLHJIPBBRFGM-UHFFFAOYSA-N n-dodecyl-2-methylprop-2-enamide Chemical compound CCCCCCCCCCCCNC(=O)C(C)=C HOZLHJIPBBRFGM-UHFFFAOYSA-N 0.000 description 1
- XQPVIMDDIXCFFS-UHFFFAOYSA-N n-dodecylprop-2-enamide Chemical compound CCCCCCCCCCCCNC(=O)C=C XQPVIMDDIXCFFS-UHFFFAOYSA-N 0.000 description 1
- YRGCLADHMAKURN-UHFFFAOYSA-N n-hexadecyl-2-methylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCNC(=O)C(C)=C YRGCLADHMAKURN-UHFFFAOYSA-N 0.000 description 1
- BKWMQCLROIZNLX-UHFFFAOYSA-N n-hexadecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCNC(=O)C=C BKWMQCLROIZNLX-UHFFFAOYSA-N 0.000 description 1
- VDHDIPGCUFYGIL-UHFFFAOYSA-N n-nonylprop-2-enamide Chemical compound CCCCCCCCCNC(=O)C=C VDHDIPGCUFYGIL-UHFFFAOYSA-N 0.000 description 1
- CNWVYEGPPMQTKA-UHFFFAOYSA-N n-octadecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)C=C CNWVYEGPPMQTKA-UHFFFAOYSA-N 0.000 description 1
- AWGZKFQMWZYCHF-UHFFFAOYSA-N n-octylprop-2-enamide Chemical compound CCCCCCCCNC(=O)C=C AWGZKFQMWZYCHF-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- DBLNSVZHOZOZQX-UHFFFAOYSA-N n-tetradecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCNC(=O)C=C DBLNSVZHOZOZQX-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- RZKYDQNMAUSEDZ-UHFFFAOYSA-N prop-2-enylphosphonic acid Chemical compound OP(O)(=O)CC=C RZKYDQNMAUSEDZ-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical class C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/402—Polymers based on the polymerisation of fumaric acid or derivatives thereof
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/403—Polymers based on the polymerisation of maleic acid or derivatives thereof
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/404—Polymers based on the polymerisation of crotonic acid
-
- 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
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
- B01D71/441—Polyvinylpyrrolidone
-
- 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
- B01D2323/00—Details relating to membrane preparation
- B01D2323/04—Hydrophobization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
-
- 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
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
Abstract
The invention relates to the use of A copolymers containing a) 50 to 99 percent by weight of at least one N-vinyl lactam or N-vinyl amine, selected among the group comprising N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, N-vinyl imidazole, methylized N-vinyl imidazole, and N-vinyl formamide, and b) 1 to 50 percent by weight of at least one monomer, selected among one of the groups comprising b1) C8-C30 alkyl ester of monoethylenically unsaturated C3-C8 carboxylic acids; b2) N-C8-C30 alkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids; b3) N,N-C8-C30 dialkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids; b4) vinyl ester of aliphatic C8-C30 carboxylic acids; b5) C8-C30 alkyl vinyl ether, for the production of membranes.
Description
USE OF HYDROPHOBICALLY MODIFIED COPOLYMERS BASED ON
N VINYL MONOMERS FOR THE PRODUCTION OF MEMBRANES
The present invention relates to the use of copolymers A
containing a) from 50 to 99% by weight of at least one N-vinyllactam or N-vinylamine selected from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylimidazole, methylated N-vinylimidazole, and N-vinylformamide, and b) from 1 to 50% by weight of at least one monomer selected from the group consisting of bl) Ce-C3o-alkyl esters of monoethylenically unsaturated C3-Ce carboxylic acids;
b2) N-C8-C3o-alkyl-substituted amides of monoethylenically unsaturated C~-CS carboxylic acids;
b3) N,N-C$-C3o-dialkyl-substituted~amides of monoethylenically unsaturated C3-Cg carboxylic acids;
b4) vinyl esters of aliphatic CB-C3o carboxylic acids; and b5) Ce-C3o-alkyl vinyl ethers to produce membranes.
The present invention further provides a semipermeable membrane comprising, as well as the copolymers described above, one or more hyrophobic polymers and also one or more hydrophilic polymers.
For a multiplicity of industrial applications use is nowadays made of membranes. For instance, membranes can be used to convert salt water into drinking water by reverse osmosis. Membranes are additionally suitable for cleaning industrial wastewaters or for recovering substances of value: for example, for recovering coating materials by ultrafiltration from electrocoating baths.
In the sectors of food technology, medicine and pharmacy, as well, membranes are increasingly finding application. For example, solutions of different macromolecules can be fractionated using membranes, or urea and toxins can be removed from the bloodstream in hemodialysis. For skin-controlled delivery of drugs, too, membranes can be used.
1a It is known that the morphology of a membrane is a critical determinant of its field of use. Selectivity and permeability are defined by the surface structure and surface coverage of a porous membrane, while the internal structure influences the mechanical properties of a membrane. In the manufacture of a membrane, therefore, attempts are made to tailor both the surface and the internal structure by an appropriate combination of the parameters which are set during the production process. Important influencing variables, such as the nature and composition of the polymers and solvents used to form the membranes, have been described in detail in EP-A 0 168 783.
EP-A 0 168 783 describes asymmetric microporous hollow fiber membranes for blood treatment which are composed of more than 90%
by weight of a hydrophobic polysulfone matrix polymer and also from 1 to 10% by weight of hydrophilic polyvinylpyrrolidone, which are readily wettable by water, and which exhibit excellent biocompatibility; that is, the substances of the body's own defence system which are present in the blood do not respond to the surface of the membranes. The incompatible hydrophilic polymers serve as pore formers and are washed out of the membrane following its solidification, although a certain fraction is to remain in order to render the otherwise hydrophobic membrane hydrophilic.
Causing part of the hydrophilic PVP to remain in the polysulfone matrix is achieved in accordance with EP-A 0 168 783 by extruding the solution of the two polymers within a narrowly confined viscosity range, thereby ensuring that the structure of the extruded hollow-fibrous formation is maintained until the fiber-forming polymer is precipitated and that, although the majority of the PVP used is washed from the spinning composition during precipitation, a fraction nevertheless remains in the membrane.
DE-A 19817364 describes producing membranes with predetermined hydrophilicity and porosity. To this end a hydrophilic polymer with bimodal molecular weight distribution is used. The low molecular weight fraction which can be washed out more readily following precipitation serves here to tailor the porosity. The high molecular weight fraction on the other hand, which is less readily washed out, determines the hydrophilicity of the membrane.
From EP-A 0 550 798 it is known that in membranes, like those obtained, for example, in accordance with EP-A 0 168 783, water-soluble PVP is still present. Accordingly, it is impossible to avoid minimal amounts being given off from these membranes to the medium under filtration when these membranes are used repeatedly a large number of times. As a result there is a change in (among other things) the retention properties of such membranes to more indistinct cutoff limits. Possibilities for making the PVP present in polysulfone membranes insoluble in water are described, for example, in EP-A 0 OB2 433 and EP-A 0 550 798. They describe formation of a three-dimensional network by means of chemical crosslinking and, respectively, crosslinking by means of ionizing radiation.
EP-A 0 876 819 and EP-A 0 953 358 disclose the use of copolymers of N-vinyllactams or N-vinylamine compounds and hydrophobically modified monomers as matrix components for producing solid pharmaceutical administration forms or cosmetic presentation forms.
It is an object of the present invention to reduce or suppress entirely the propensity of the hydrophilicizing component to be washed out of the membrane while retaining the membrane porosity.
We have found that this object is achieved by the use of the above-defined copolymers A in the production of semipermeable membranes and by the corresponding membranes.
Components a) of the copolymers A include the following polymerizable hydrophilic comonomers:
N-vinyllactams and N-vinylamines, especially N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, and N-vinylformamide.
Preferred hydrophilic components are N-vinylpyrrolidone, N-vinylimidazole and N-vinylcaprolactam, with particular preference N-vinylpyrrolidone.
The fraction of the hydrophilic monomer units a) in the copolymer is in the range from 50 to 99% by weight, preferably from 60 to 99% by weight, with particular preference from 65 to 98% by weight.
Components b) include the following polymerizable hydrophobic comonomers:
bl) esters of monoethylenically unsaturated C3-Ce carboxylic acids with a C8-C3o alcohol, preferably a C12-C22 alcohol.
N VINYL MONOMERS FOR THE PRODUCTION OF MEMBRANES
The present invention relates to the use of copolymers A
containing a) from 50 to 99% by weight of at least one N-vinyllactam or N-vinylamine selected from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylimidazole, methylated N-vinylimidazole, and N-vinylformamide, and b) from 1 to 50% by weight of at least one monomer selected from the group consisting of bl) Ce-C3o-alkyl esters of monoethylenically unsaturated C3-Ce carboxylic acids;
b2) N-C8-C3o-alkyl-substituted amides of monoethylenically unsaturated C~-CS carboxylic acids;
b3) N,N-C$-C3o-dialkyl-substituted~amides of monoethylenically unsaturated C3-Cg carboxylic acids;
b4) vinyl esters of aliphatic CB-C3o carboxylic acids; and b5) Ce-C3o-alkyl vinyl ethers to produce membranes.
The present invention further provides a semipermeable membrane comprising, as well as the copolymers described above, one or more hyrophobic polymers and also one or more hydrophilic polymers.
For a multiplicity of industrial applications use is nowadays made of membranes. For instance, membranes can be used to convert salt water into drinking water by reverse osmosis. Membranes are additionally suitable for cleaning industrial wastewaters or for recovering substances of value: for example, for recovering coating materials by ultrafiltration from electrocoating baths.
In the sectors of food technology, medicine and pharmacy, as well, membranes are increasingly finding application. For example, solutions of different macromolecules can be fractionated using membranes, or urea and toxins can be removed from the bloodstream in hemodialysis. For skin-controlled delivery of drugs, too, membranes can be used.
1a It is known that the morphology of a membrane is a critical determinant of its field of use. Selectivity and permeability are defined by the surface structure and surface coverage of a porous membrane, while the internal structure influences the mechanical properties of a membrane. In the manufacture of a membrane, therefore, attempts are made to tailor both the surface and the internal structure by an appropriate combination of the parameters which are set during the production process. Important influencing variables, such as the nature and composition of the polymers and solvents used to form the membranes, have been described in detail in EP-A 0 168 783.
EP-A 0 168 783 describes asymmetric microporous hollow fiber membranes for blood treatment which are composed of more than 90%
by weight of a hydrophobic polysulfone matrix polymer and also from 1 to 10% by weight of hydrophilic polyvinylpyrrolidone, which are readily wettable by water, and which exhibit excellent biocompatibility; that is, the substances of the body's own defence system which are present in the blood do not respond to the surface of the membranes. The incompatible hydrophilic polymers serve as pore formers and are washed out of the membrane following its solidification, although a certain fraction is to remain in order to render the otherwise hydrophobic membrane hydrophilic.
Causing part of the hydrophilic PVP to remain in the polysulfone matrix is achieved in accordance with EP-A 0 168 783 by extruding the solution of the two polymers within a narrowly confined viscosity range, thereby ensuring that the structure of the extruded hollow-fibrous formation is maintained until the fiber-forming polymer is precipitated and that, although the majority of the PVP used is washed from the spinning composition during precipitation, a fraction nevertheless remains in the membrane.
DE-A 19817364 describes producing membranes with predetermined hydrophilicity and porosity. To this end a hydrophilic polymer with bimodal molecular weight distribution is used. The low molecular weight fraction which can be washed out more readily following precipitation serves here to tailor the porosity. The high molecular weight fraction on the other hand, which is less readily washed out, determines the hydrophilicity of the membrane.
From EP-A 0 550 798 it is known that in membranes, like those obtained, for example, in accordance with EP-A 0 168 783, water-soluble PVP is still present. Accordingly, it is impossible to avoid minimal amounts being given off from these membranes to the medium under filtration when these membranes are used repeatedly a large number of times. As a result there is a change in (among other things) the retention properties of such membranes to more indistinct cutoff limits. Possibilities for making the PVP present in polysulfone membranes insoluble in water are described, for example, in EP-A 0 OB2 433 and EP-A 0 550 798. They describe formation of a three-dimensional network by means of chemical crosslinking and, respectively, crosslinking by means of ionizing radiation.
EP-A 0 876 819 and EP-A 0 953 358 disclose the use of copolymers of N-vinyllactams or N-vinylamine compounds and hydrophobically modified monomers as matrix components for producing solid pharmaceutical administration forms or cosmetic presentation forms.
It is an object of the present invention to reduce or suppress entirely the propensity of the hydrophilicizing component to be washed out of the membrane while retaining the membrane porosity.
We have found that this object is achieved by the use of the above-defined copolymers A in the production of semipermeable membranes and by the corresponding membranes.
Components a) of the copolymers A include the following polymerizable hydrophilic comonomers:
N-vinyllactams and N-vinylamines, especially N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, and N-vinylformamide.
Preferred hydrophilic components are N-vinylpyrrolidone, N-vinylimidazole and N-vinylcaprolactam, with particular preference N-vinylpyrrolidone.
The fraction of the hydrophilic monomer units a) in the copolymer is in the range from 50 to 99% by weight, preferably from 60 to 99% by weight, with particular preference from 65 to 98% by weight.
Components b) include the following polymerizable hydrophobic comonomers:
bl) esters of monoethylenically unsaturated C3-Ce carboxylic acids with a C8-C3o alcohol, preferably a C12-C22 alcohol.
By monoethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms are meant, for example, acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, malefic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid, crotonic acid, fumaric acid, mesaconic acid, and itaconic acid.
From this group of carboxylic acids use is made preferably of acrylic acid, methacrylic acid, malefic acid or mixtures of said carboxylic acids, with particular preference methacrylic acid.
Particular importance here is attached to the esters of acrylic and/or methacrylic acid with fatty alcohols having a chain length of from 12 to 22 carbon atoms.
Mention may be made here preferably of the following: myristyl acrylate, cetyl acrylate, stearyl acrylate, oleyl acrylate, behenyl acrylate, myristyl methacrylate, cetyl methacrylate, stearyl methacrylate, oleyl methacrylate, and behenyl methacrylate, particular preference being given, from this group, to the C12-C22-alkyl esters of methacrylic acid.
As further hydrophobic comonomers it is possible to use b2) N-Cg-C3o-alkyl-substituted or b3) N,N-Ce-C3o-dialkyl-substituted amides of monoethylenically unsaturated C3-CB carboxylic acids, the alkyl radicals being aliphatic or cycloaliphatic alkyl radicals having from 8 to 30, preferably from 8 to 22, with particular preference from 12 to 18 carbon atoms.
The amidated monoethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms may, as already mentioned above, stand, for example, for acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, malefic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid, crotonic acid, fumaric acid, mesaconic acid, and itaconic acid.
From this group of carboxylic acids preference is likewise given to using acrylic acid, methacrylic acid, malefic acid or mixtures of said carboxylic acids.
Examples of preferred amidated comonomers are N-octylacrylamide, N-(2-ethylhexyl)acrylamide, N-nonylacrylamide, N-decylacrylamide, N-laurylacrylamide, N-myristylacrylamide, N-cetylacrylamide, N-stearylacrylamide, N-oleylacrylamide, N-behenylacrylamide, N-octylmethacrylamide, N-(2-ethylhexyl)methacrylamide, N-nonylmethacrylamide, N-decylmethacrylamide, N-laurylmethacrylamide, N-myristylmethacrylamide, N-cetylmethacrylamide, N-stearylmethacrylamide, N-oleylmethacrylamide, and N-behenylmethacrylamide, particular emphasis being placed, from this group, on the Clz-Cls-alkylamides.
From this group of carboxylic acids use is made preferably of acrylic acid, methacrylic acid, malefic acid or mixtures of said carboxylic acids, with particular preference methacrylic acid.
Particular importance here is attached to the esters of acrylic and/or methacrylic acid with fatty alcohols having a chain length of from 12 to 22 carbon atoms.
Mention may be made here preferably of the following: myristyl acrylate, cetyl acrylate, stearyl acrylate, oleyl acrylate, behenyl acrylate, myristyl methacrylate, cetyl methacrylate, stearyl methacrylate, oleyl methacrylate, and behenyl methacrylate, particular preference being given, from this group, to the C12-C22-alkyl esters of methacrylic acid.
As further hydrophobic comonomers it is possible to use b2) N-Cg-C3o-alkyl-substituted or b3) N,N-Ce-C3o-dialkyl-substituted amides of monoethylenically unsaturated C3-CB carboxylic acids, the alkyl radicals being aliphatic or cycloaliphatic alkyl radicals having from 8 to 30, preferably from 8 to 22, with particular preference from 12 to 18 carbon atoms.
The amidated monoethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms may, as already mentioned above, stand, for example, for acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, malefic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid, crotonic acid, fumaric acid, mesaconic acid, and itaconic acid.
From this group of carboxylic acids preference is likewise given to using acrylic acid, methacrylic acid, malefic acid or mixtures of said carboxylic acids.
Examples of preferred amidated comonomers are N-octylacrylamide, N-(2-ethylhexyl)acrylamide, N-nonylacrylamide, N-decylacrylamide, N-laurylacrylamide, N-myristylacrylamide, N-cetylacrylamide, N-stearylacrylamide, N-oleylacrylamide, N-behenylacrylamide, N-octylmethacrylamide, N-(2-ethylhexyl)methacrylamide, N-nonylmethacrylamide, N-decylmethacrylamide, N-laurylmethacrylamide, N-myristylmethacrylamide, N-cetylmethacrylamide, N-stearylmethacrylamide, N-oleylmethacrylamide, and N-behenylmethacrylamide, particular emphasis being placed, from this group, on the Clz-Cls-alkylamides.
As a further, additional component b) it is possible to use vinyl esters of long-chain aliphatic, saturated or unsaturated C8-C3o carboxylic acids, such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, lignoceric acid, cerotinic acid, and melissic acid.
Vinyl esters of the abovementioned C8-C1$ carboxylic acids find preferred use.
Furthermore, C8-C3o-alkyl vinyl ethers, preferably C8-Czz-alkyl vinyl ethers, can be copolymerized as comonomers b5).
Preferred C8-Czz-alkyl radicals of the vinyl ethers include unbranched alkyl chains such as n-octyl, 2-ethylhexyl, n-nonyl, n-~iecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, and n-octadecyl.
The fraction of the hydrophobic monomer units b) in the copolymer A is in the range from 1 to 50% by weight, preferably from 1 to 40% by weight, with particular preference from 2 to 35% by weight.
It will be appreciated that mixtures of two or more carboxylic acids, carboxamides, alkyl vinyl ethers or vinyl esters can be used as long as the sum of the fractions of these comonomers does not exceed 50% by weight.
Where appropriate it may be sensible to use, for the polymerization, not only the abovementioned monomers units a) and b) but also the comonomers c) listed below:
monoethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms such as acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, malefic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid, crotonic acid, fumaric acid, mesaconic acid, and itaconic acid.
From this group of monomers it is preferred to use acrylic acid, methacrylic acid, malefic acid or mixtures of said carboxylic acids.
The monoethylenically unsaturated carboxylic acids can be used in the form of the free acids and - where available - the anhydrides or in partly or fully neutralized form for the copolymerization.
Vinyl esters of the abovementioned C8-C1$ carboxylic acids find preferred use.
Furthermore, C8-C3o-alkyl vinyl ethers, preferably C8-Czz-alkyl vinyl ethers, can be copolymerized as comonomers b5).
Preferred C8-Czz-alkyl radicals of the vinyl ethers include unbranched alkyl chains such as n-octyl, 2-ethylhexyl, n-nonyl, n-~iecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, and n-octadecyl.
The fraction of the hydrophobic monomer units b) in the copolymer A is in the range from 1 to 50% by weight, preferably from 1 to 40% by weight, with particular preference from 2 to 35% by weight.
It will be appreciated that mixtures of two or more carboxylic acids, carboxamides, alkyl vinyl ethers or vinyl esters can be used as long as the sum of the fractions of these comonomers does not exceed 50% by weight.
Where appropriate it may be sensible to use, for the polymerization, not only the abovementioned monomers units a) and b) but also the comonomers c) listed below:
monoethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms such as acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, malefic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid, crotonic acid, fumaric acid, mesaconic acid, and itaconic acid.
From this group of monomers it is preferred to use acrylic acid, methacrylic acid, malefic acid or mixtures of said carboxylic acids.
The monoethylenically unsaturated carboxylic acids can be used in the form of the free acids and - where available - the anhydrides or in partly or fully neutralized form for the copolymerization.
For neutralization it is preferred to use alkali metal or alkaline earth metal bases, ammonia or amines, e.g., sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, potash, sodium hydrogen carbonate, magnesium oxide, calcium hydroxide, calcium oxide, gaseous or aqueous ammonia, triethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine.
Examples of further suitable comonomers c) are the C1-C4-alkyl or hydroxyalkyl esters, amides, and nitriles of the abovementioned carboxylic acids, e.g., methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyisobutyl acrylate, hydroxyisobutyl methacrylate, monomethyl maleate, dimethyl maleate, monoethyl maleate, diethyl maleate, acrylamide, methacrylamide, N,N-dimethylacrylamide, N-tert-butylacrylamide, acrylonitrile, methacrylonitrile, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the salts of the last-mentioned monomers with carboxylic acids or mineral acids, and also the quaternized products.
Also suitable as other, copolymerizable monomers are acrylamidoglycolic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, and acrylamidomethylpropanesulfonic acid, and also monomers containing phosphonic acid groups, such as vinylphosphonic acid, allylphosphonic acid, and acrylamidomethylpropanephosphonic acid.
30' The fraction of the monomer units-c) in the copolymer can be in the range from 0 to 30% by weight, preferably from 0 to 20% by weight, with particular preference from 0 to 10% by weight, the percentages by weight for components a) to c) adding up to 100%.
Used preferably are water-insoluble copolymers A containing a) from 60 to 99% by weight of N-vinylpyrrolidone and b) from 1 to 40% by weight of at least one monomer selected from the group consisting of bl) CB-C3p-alkyl esters of monoethylenically unsaturated C3-C8 carboxylic acids;
b2) N-C8-C3o-alkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b3) N,N-CB-C3o-dialkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
Examples of further suitable comonomers c) are the C1-C4-alkyl or hydroxyalkyl esters, amides, and nitriles of the abovementioned carboxylic acids, e.g., methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyisobutyl acrylate, hydroxyisobutyl methacrylate, monomethyl maleate, dimethyl maleate, monoethyl maleate, diethyl maleate, acrylamide, methacrylamide, N,N-dimethylacrylamide, N-tert-butylacrylamide, acrylonitrile, methacrylonitrile, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the salts of the last-mentioned monomers with carboxylic acids or mineral acids, and also the quaternized products.
Also suitable as other, copolymerizable monomers are acrylamidoglycolic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, and acrylamidomethylpropanesulfonic acid, and also monomers containing phosphonic acid groups, such as vinylphosphonic acid, allylphosphonic acid, and acrylamidomethylpropanephosphonic acid.
30' The fraction of the monomer units-c) in the copolymer can be in the range from 0 to 30% by weight, preferably from 0 to 20% by weight, with particular preference from 0 to 10% by weight, the percentages by weight for components a) to c) adding up to 100%.
Used preferably are water-insoluble copolymers A containing a) from 60 to 99% by weight of N-vinylpyrrolidone and b) from 1 to 40% by weight of at least one monomer selected from the group consisting of bl) CB-C3p-alkyl esters of monoethylenically unsaturated C3-C8 carboxylic acids;
b2) N-C8-C3o-alkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b3) N,N-CB-C3o-dialkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b4) vinyl esters of aliphatic C8-C3o carboxylic acids; and bs) Ca-C3o-alkyl vinyl ethers.
L3se is made with particular preference of water-insoluble copolymers A containing a) from 60 to 99% by weight of N-vinylpyrrolidone and b) from 1 to 40% by weight of at least one monomer selected from the group consisting of bl) Ci2-C22-alkyl esters of monoethylenically unsaturated C3-Ca carboxylic acids;
b2) N-C12-Cis-alkyl-substituted amides of monoethylenically unsaturated C3-Ca carboxylic acids;
b3) N,N-C12-C1$-dialkyl-substituted amides of monoethylenically unsaturated C3-Ca carboxylic acids;
b4) vinyl esters of aliphatic Ca-C1a carboxylic acids; and b5) CB-C2z-alkyl vinyl ethers.
Particularly suitable are copolymers A including as monomer units b) the monomers bl) with an alkyl radical of chain length C14 to Cis.
The copolymers are prepared by known processes, e.g., solution, precipitation, emulsion or inverted suspension polymerization, using compounds which form free radicals under the polymerization conditions.
The temperatures of polymerization are usually in the range from 30 to 200~C, preferably from 40 to 110~C.
Examples of suitable initiators are azo compounds and peroxy compounds and also the customary redox initiator systems, such as combinations of hydrogen peroxide and compounds having a reducing action, e.g., sodium sulfite, sodium bisulfate, sodium formaldehyde-sulfoxylate, and hydrazine.
The copolymers A possess K values of at least 20, preferably from 25 to 100, with particular preference from 30 to 80. The K values are determined by the method of H. Fikentscher, Cellulose-Chemie, Volume 13, 58 to 64 and 71 to 74 (1932) in aqueous or alcoholic solution at 25~C, at concentrations of between 0.1% and 5%
depending on the K value range.
L3se is made with particular preference of water-insoluble copolymers A containing a) from 60 to 99% by weight of N-vinylpyrrolidone and b) from 1 to 40% by weight of at least one monomer selected from the group consisting of bl) Ci2-C22-alkyl esters of monoethylenically unsaturated C3-Ca carboxylic acids;
b2) N-C12-Cis-alkyl-substituted amides of monoethylenically unsaturated C3-Ca carboxylic acids;
b3) N,N-C12-C1$-dialkyl-substituted amides of monoethylenically unsaturated C3-Ca carboxylic acids;
b4) vinyl esters of aliphatic Ca-C1a carboxylic acids; and b5) CB-C2z-alkyl vinyl ethers.
Particularly suitable are copolymers A including as monomer units b) the monomers bl) with an alkyl radical of chain length C14 to Cis.
The copolymers are prepared by known processes, e.g., solution, precipitation, emulsion or inverted suspension polymerization, using compounds which form free radicals under the polymerization conditions.
The temperatures of polymerization are usually in the range from 30 to 200~C, preferably from 40 to 110~C.
Examples of suitable initiators are azo compounds and peroxy compounds and also the customary redox initiator systems, such as combinations of hydrogen peroxide and compounds having a reducing action, e.g., sodium sulfite, sodium bisulfate, sodium formaldehyde-sulfoxylate, and hydrazine.
The copolymers A possess K values of at least 20, preferably from 25 to 100, with particular preference from 30 to 80. The K values are determined by the method of H. Fikentscher, Cellulose-Chemie, Volume 13, 58 to 64 and 71 to 74 (1932) in aqueous or alcoholic solution at 25~C, at concentrations of between 0.1% and 5%
depending on the K value range.
The average molecular weight of the polymers A used in accordance with the invention is in the range from 30 000 to 10 000 000, preferably from 35 000 to 2 000 000, with particular preference from 40 000 to 1 500 000.
The polymer dispersions or solutions obtained can be converted into powder form by various drying processes such as, for example, spray drying, fluidized spray drying, roller drying or freeze drying, and an aqueous dispersion can be produced from this powder form by redispersing it in water.
Besides the copolymers A for use in accordance with the invention the membranes comprise, as a further component, component B, one or more polymers selected from the group consisting of polysulfones such as polyaryl ether sulfones, polycarbonates, polyamides, polyvinyl chloride, hydrophobically modified acrylic acid polymers, polyethers, polyurethanes, polyurethane copolymers, water-insoluble cellulose derivatives such as cellulose acetates, cellulose nitrates, and mixtures thereof. The preparation of these polymers is common knowledge. In production of the membranes they can be used in amounts of from 50 to 90.9%
by weight, preferably from 60 to 90% by weight. It is preferred to use polysulfones, polyamides or blends of polysulfones and polyamides.
The membranes may further comprise one or more hydrophilic polymers C selected from the group consisting of polyvinylpyrrolidones, polyethylene glycols, polyglycol monoesters, polyethylene glycol-propylene glycol copolymers, water-soluble cellulose derivates, and polysorbates. These hydrophilic polymers C may be used in amounts of from 0 to 50% by weight, preferably from 10 to 40% by weight, in the production of the membranes. As polymers C it is preferred to use polyvinylpyrrolidones, with particular preference in combination with polysulfones, polyamides or blends of polysulfones and polyamides.
In principle the copolymers A used in accordance with the invention are suitable for producing any of a very wide variety of wettable membrane types such as microporous membranes, examples being microporous hollow fiber membranes, homogeneous membranes, symmetrical membranes, and asymmetrical membranes.
With preference, microporous or asymmetrical membranes can be produced. The production of the various types of membrane is known to the skilled worker from the prior art.
The polymer dispersions or solutions obtained can be converted into powder form by various drying processes such as, for example, spray drying, fluidized spray drying, roller drying or freeze drying, and an aqueous dispersion can be produced from this powder form by redispersing it in water.
Besides the copolymers A for use in accordance with the invention the membranes comprise, as a further component, component B, one or more polymers selected from the group consisting of polysulfones such as polyaryl ether sulfones, polycarbonates, polyamides, polyvinyl chloride, hydrophobically modified acrylic acid polymers, polyethers, polyurethanes, polyurethane copolymers, water-insoluble cellulose derivatives such as cellulose acetates, cellulose nitrates, and mixtures thereof. The preparation of these polymers is common knowledge. In production of the membranes they can be used in amounts of from 50 to 90.9%
by weight, preferably from 60 to 90% by weight. It is preferred to use polysulfones, polyamides or blends of polysulfones and polyamides.
The membranes may further comprise one or more hydrophilic polymers C selected from the group consisting of polyvinylpyrrolidones, polyethylene glycols, polyglycol monoesters, polyethylene glycol-propylene glycol copolymers, water-soluble cellulose derivates, and polysorbates. These hydrophilic polymers C may be used in amounts of from 0 to 50% by weight, preferably from 10 to 40% by weight, in the production of the membranes. As polymers C it is preferred to use polyvinylpyrrolidones, with particular preference in combination with polysulfones, polyamides or blends of polysulfones and polyamides.
In principle the copolymers A used in accordance with the invention are suitable for producing any of a very wide variety of wettable membrane types such as microporous membranes, examples being microporous hollow fiber membranes, homogeneous membranes, symmetrical membranes, and asymmetrical membranes.
With preference, microporous or asymmetrical membranes can be produced. The production of the various types of membrane is known to the skilled worker from the prior art.
Generally, the various components are converted into a solution which is then shaped appropriately, by casting or spinning for example.
The membranes are produced conventionally, for example, by a phase inversion process, such as is described in EP-A 082 433, hereby incorporated by reference.
Furthermore, it is also possible to obtain hollow fiber membranes by extrusion and precipitation of a polymer-containing spinning solution. A process of this kind is described, for example, in EP-A 168 783, likewise incorporated by reference.
Surprisingly it has been found that when the copolymers A of the invention are used the fraction of water-soluble polymer component which can be washed out of a membrane is reduced. With no change in the hydrophilicity of the membrane surface and with partial or complete replacement of the water-soluble polymers by the copolymers, the surface of the membrane was found to be permanent in respect of pore size and pore distribution.
The following examples are intended to illustrate but not restrict the process of the invention.
Examples Example 1 A polymer solution composed of 16% by weight of polysulfone (Ultrason E 6020P, BASF), 1% by weight of polyvinylpyrrolidone having a K value of 90, 7% by weight of polyvinylpyrrolidone having a K value of 30 and 1% by weight of a vinylpyrrolidone-stearyl methacrylate copolymer (VP:StMA=70:30) in N-methylpyrrolidone was applied in a 200 Eun film using a casting apparatus to a PVC carrier web and was coagulated in water for 10 minutes at 20°C. The membrane was dried at 40°C for 24 hours.
The dry membrane was weighed, after which water was passed through it for 30 minutes. The weight loss was determined after the membrane had been dried again at 40°C fvr 24 hours. In order to assess the washout of the hydrophilic polymer components, this procedure was repeated twice after 20 hours and 36 hours of water passage.
Examples 2 to 6 The membranes were obtained from polymer solutions differing in composition in analogy to the production instructions from Example 1. The weight loss of membranes in the following examples was determined in analogy to example 1.
Ex-B C C Copolymer A Weight loss am-_ PVP PVP [wt. %] [%]
poly K30 K90 ple~~ ~ [wt. [wt. Composition VP/5MA 0.5 ~ %J %] 70:30 h h h 1 64 28 4 4 14.7 22.624.5 2 64 28 0 8 11.8 21.423.1 3 64 28 8 0 11.4 26.128.3 4 53.3 33.3 6.6 6.6 21.2 35.235.9 5 53.3 33.3 0 13.3 17.9 34.435.3 6 53.3 33.3 13.3 0 27.2 43.444.4 The percentages by weight indicated in~the table refer to the theoretical content which is to be expected in the membrane in its dry state.
Examples 7 to 12 The membranes obtained in accordance with examples 1 to 6 were subjected to contact angle measurements using a contact angle measuring instrument of the type OCAH200 from Data Physics.
Example Membrane from exampleContact [degrees) angle (dist.
water) O.ls is lOs
The membranes are produced conventionally, for example, by a phase inversion process, such as is described in EP-A 082 433, hereby incorporated by reference.
Furthermore, it is also possible to obtain hollow fiber membranes by extrusion and precipitation of a polymer-containing spinning solution. A process of this kind is described, for example, in EP-A 168 783, likewise incorporated by reference.
Surprisingly it has been found that when the copolymers A of the invention are used the fraction of water-soluble polymer component which can be washed out of a membrane is reduced. With no change in the hydrophilicity of the membrane surface and with partial or complete replacement of the water-soluble polymers by the copolymers, the surface of the membrane was found to be permanent in respect of pore size and pore distribution.
The following examples are intended to illustrate but not restrict the process of the invention.
Examples Example 1 A polymer solution composed of 16% by weight of polysulfone (Ultrason E 6020P, BASF), 1% by weight of polyvinylpyrrolidone having a K value of 90, 7% by weight of polyvinylpyrrolidone having a K value of 30 and 1% by weight of a vinylpyrrolidone-stearyl methacrylate copolymer (VP:StMA=70:30) in N-methylpyrrolidone was applied in a 200 Eun film using a casting apparatus to a PVC carrier web and was coagulated in water for 10 minutes at 20°C. The membrane was dried at 40°C for 24 hours.
The dry membrane was weighed, after which water was passed through it for 30 minutes. The weight loss was determined after the membrane had been dried again at 40°C fvr 24 hours. In order to assess the washout of the hydrophilic polymer components, this procedure was repeated twice after 20 hours and 36 hours of water passage.
Examples 2 to 6 The membranes were obtained from polymer solutions differing in composition in analogy to the production instructions from Example 1. The weight loss of membranes in the following examples was determined in analogy to example 1.
Ex-B C C Copolymer A Weight loss am-_ PVP PVP [wt. %] [%]
poly K30 K90 ple~~ ~ [wt. [wt. Composition VP/5MA 0.5 ~ %J %] 70:30 h h h 1 64 28 4 4 14.7 22.624.5 2 64 28 0 8 11.8 21.423.1 3 64 28 8 0 11.4 26.128.3 4 53.3 33.3 6.6 6.6 21.2 35.235.9 5 53.3 33.3 0 13.3 17.9 34.435.3 6 53.3 33.3 13.3 0 27.2 43.444.4 The percentages by weight indicated in~the table refer to the theoretical content which is to be expected in the membrane in its dry state.
Examples 7 to 12 The membranes obtained in accordance with examples 1 to 6 were subjected to contact angle measurements using a contact angle measuring instrument of the type OCAH200 from Data Physics.
Example Membrane from exampleContact [degrees) angle (dist.
water) O.ls is lOs
Claims (11)
1. The use of a copolymer A containing a) from 50 to 99% by weight of at least one N-vinyllactam or N-vinylamine selected from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylimidazole, methylated N-vinylimidazole, and N-vinylformamide, and b) from 1 to 50% by weight of at least one monomer selected from the group consisting of b1) C8-C30-alkyl esters of monoethylenically unsaturated C3-C8 carboxylic acids;
b2) N-C8-C30-alkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b3) N,N-C8-C30-dialkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b4) vinyl esters of aliphatic C8-C30 carboxylic acids;
and b5) C8-C30-alkyl vinyl ethers to produce a membrane, the membrane comprising, as further component, hydrophobic polymers B selected from the group consisting of polysulfones, polycarbonates, polyamides, polyvinyl chloride, hydrophobically modified acrylic polymers, polyethers, polyurethanes, polyurethane copolymers, water-insoluble cellulose derivatives, and mixtures of such polymers.
b2) N-C8-C30-alkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b3) N,N-C8-C30-dialkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b4) vinyl esters of aliphatic C8-C30 carboxylic acids;
and b5) C8-C30-alkyl vinyl ethers to produce a membrane, the membrane comprising, as further component, hydrophobic polymers B selected from the group consisting of polysulfones, polycarbonates, polyamides, polyvinyl chloride, hydrophobically modified acrylic polymers, polyethers, polyurethanes, polyurethane copolymers, water-insoluble cellulose derivatives, and mixtures of such polymers.
2. The use as claimed in claim 1 of a copolymer A containing a) from 60 to 99% by weight of N-vinylpyrrolidone and b) from 1 to 40% by weight of at least one monomer selected from the group consisting of b1) C8-C30-alkyl esters of monoethylenically unsaturated C3-C8 carboxylic acids;
b2) N-C8-C30-alkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b3) N,N-C8-C30-dialkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b4) vinyl esters of aliphatic C8-C30 carboxylic acids;
and b5) C8-C30-alkyl vinyl ethers.
b2) N-C8-C30-alkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b3) N,N-C8-C30-dialkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b4) vinyl esters of aliphatic C8-C30 carboxylic acids;
and b5) C8-C30-alkyl vinyl ethers.
3. The use as claimed in claim 1 or 2 of copolymer A containing a) from 60 to 99% by weight of N-vinylpyrrolidone and b) from 1 to 40% by weight of at least one monomer selected from the group consisting of b1) C12-C22-alkyl esters of monoethylenically unsaturated C3-C8 carboxylic acids;
b2) N-C12-C18-alkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b3) N,N-C12-C18-dialkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b4) vinyl esters of aliphatic C8-C18 carboxylic acids;
and b5) C8-C22-alkyl vinyl ethers.
b2) N-C12-C18-alkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b3) N,N-C12-C18-dialkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b4) vinyl esters of aliphatic C8-C18 carboxylic acids;
and b5) C8-C22-alkyl vinyl ethers.
4. The use as claimed in any of claims 1 to 4, wherein the copolymer A is used in amounts of from 0.1 to 25% by weight, based on the total amount of polymers used.
5. The use as claimed in any of claims 1 to 4, wherein the copolymer A is used in combination with one or more further polymers.
6. The use as claimed in any of claims 1 to 5, wherein the hydrophobic polymers B are used in amounts of from 50 to 99.9 by weight, based on the total amount of polymers used.
7. The use as claimed in any of claims 1 to 6, wherein the membrane further comprises, as polymers C, hydrophilic polymers selected from the group consisting of polyvinylpyrrolidones, polyethylene glycols, polyethylene glycol monoesters, polyethylene glycol-propylene glycol copolymers, water-soluble cellulose derivatives, polysorbates, and mixtures of such polymers.
8. The use as claimed in claim 7, wherein the hydrophilic polymers C are used in amounts of from 10 to 40% by weight, based on the total amount of polymers used.
9. A semipermeable, water-wettable membrane comprising at least one copolymer A formed from a) from 50 to 99% by weight of at least one N-vinyllactam or N-vinylamine selected from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylimidazole, methylated N-vinylimidazole, and N-vinylformamide, and b) from 1 to 50% by weight of at least one monomer selected from the group consisting of b1) C8-C30-alkyl esters of monoethylenically unsaturated C3-C8 carboxylic acids;
b2) N-C8-C30-alkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b3) N,N-C8-C30-dialkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b4) vinyl esters of aliphatic C8-C30 carboxylic acids;
and b5) C8-C30-alkyl vinyl ethers, and, as hydrophobic polymer component B, a polymer selected from the group consisting of polysulfones, polycarbonates, polyamides, polyvinyl chloride, hydrophobically modified acrylic polymers, polyethers, polyurethanes, polyurethane copolymers, cellulose acetates, cellulose nitrates, and mixtures thereof.
b2) N-C8-C30-alkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b3) N,N-C8-C30-dialkyl-substituted amides of monoethylenically unsaturated C3-C8 carboxylic acids;
b4) vinyl esters of aliphatic C8-C30 carboxylic acids;
and b5) C8-C30-alkyl vinyl ethers, and, as hydrophobic polymer component B, a polymer selected from the group consisting of polysulfones, polycarbonates, polyamides, polyvinyl chloride, hydrophobically modified acrylic polymers, polyethers, polyurethanes, polyurethane copolymers, cellulose acetates, cellulose nitrates, and mixtures thereof.
10. A membrane as claimed in claim 9, obtainable using a copolymer A in amounts of from 0.1 to 25% by weight.
11. A membrane as claimed in claim 9 or 10 comprising in addition a hydrophilic polymer C selected from the group consisting of polyvinylpyrrolidones, polyethylene glycols, polyglycol monoesters, copolymers of polyethylene glycol with propylene glycol, water-soluble derivatives of cellulose, polysorbates, and mixtures thereof.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10217440A DE10217440A1 (en) | 2002-04-18 | 2002-04-18 | Use of hydrophobically modified copolymers based on N-vinyl monomers for the production of membranes |
DE10217440.7 | 2002-04-18 | ||
PCT/EP2003/003764 WO2003086594A1 (en) | 2002-04-18 | 2003-04-11 | Use of hydrophobically modified copolymers based on n-vinyl monomers for the production of membranes |
Publications (2)
Publication Number | Publication Date |
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CA2481435A1 CA2481435A1 (en) | 2003-10-23 |
CA2481435C true CA2481435C (en) | 2011-02-01 |
Family
ID=28798565
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA2481435A Expired - Fee Related CA2481435C (en) | 2002-04-18 | 2003-04-11 | Use of hydrophobically modified copolymers based on n-vinyl monomers for the production of membranes |
Country Status (8)
Country | Link |
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US (1) | US7347938B2 (en) |
EP (1) | EP1499426B1 (en) |
JP (1) | JP4443231B2 (en) |
AT (1) | ATE321602T1 (en) |
AU (1) | AU2003229642A1 (en) |
CA (1) | CA2481435C (en) |
DE (2) | DE10217440A1 (en) |
WO (1) | WO2003086594A1 (en) |
Families Citing this family (9)
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DE10343901A1 (en) * | 2003-09-19 | 2005-04-14 | Basf Ag | Amide group-containing ethylene terpolymers and their use |
DE102004058952A1 (en) * | 2004-12-07 | 2006-06-14 | Basf Ag | Process for preparing aqueous secondary dispersions of water-insoluble polymers |
DE102009006586B4 (en) * | 2009-01-29 | 2013-02-28 | Neenah Gessner Gmbh | Filter medium and filter element for the liquid filtration |
JP5791592B2 (en) * | 2010-03-04 | 2015-10-07 | 積水化学工業株式会社 | Polymer water treatment membrane and production method thereof |
EP3134250B1 (en) | 2014-04-25 | 2023-11-15 | Carbon, Inc. | Continuous three dimensional fabrication from immiscible liquids |
JP6939547B2 (en) * | 2016-02-29 | 2021-09-22 | 東レ株式会社 | Laminated semipermeable membrane |
EP3616778B1 (en) * | 2017-04-28 | 2022-10-26 | Toray Industries, Inc. | Semipermeable composite membrane and method for producing same |
CN110860211B (en) * | 2019-11-29 | 2021-10-19 | 绿邦膜分离技术(江苏)有限公司 | Preparation method of homogeneous phase PVC-based anion exchange membrane |
CN112870980B (en) * | 2021-01-11 | 2022-10-21 | 宁波方太厨具有限公司 | Preparation method of nanofiltration membrane with adjustable desalination rate |
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EP0082355B1 (en) * | 1981-12-21 | 1986-06-11 | Aligena Ag | Semipermeable membranes of modified polystyrene, process for their manufacture and their use |
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DE3426331A1 (en) | 1984-07-17 | 1986-01-30 | 6380 Bad Homburg Fresenius AG | ASYMMETRIC MICROPOROUS HOLLOW FIBER FOR HAEMODIALYSIS AND METHOD FOR THE PRODUCTION THEREOF |
DE3434822A1 (en) * | 1984-09-22 | 1986-04-03 | Bayer Ag, 5090 Leverkusen | MEMBRANE FOR REAGENT CARRIER LAYERS, METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE IN ANALYTICAL AGENTS AND ANALYZING METHOD |
US4976897A (en) * | 1987-12-16 | 1990-12-11 | Hoechst Celanese Corporation | Composite porous membranes and methods of making the same |
DE4123602A1 (en) * | 1991-07-17 | 1993-01-21 | Bayer Ag | MEMBRANES OF AROMATIC HETEROCYCLIC POLYAMIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
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DE59405007D1 (en) * | 1993-07-30 | 1998-02-19 | Bayer Ag | Membranes made from acrylonitrile copolymers, process for their preparation and their use |
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DE19627204A1 (en) * | 1996-07-05 | 1998-01-08 | Basf Ag | Cosmetic or pharmaceutical compositions for use on the skin |
DE19719187A1 (en) | 1997-05-07 | 1998-11-12 | Basf Ag | Use of copolymers of N-vinyl-pyrrolidone in preparations of water-insoluble substances |
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DE19814730A1 (en) * | 1998-04-02 | 1999-10-07 | Basf Ag | Pharmaceutical and cosmetic compositions with matrix containing N-vinyllactam or N-vinylamine based copolymer |
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-
2002
- 2002-04-18 DE DE10217440A patent/DE10217440A1/en not_active Withdrawn
-
2003
- 2003-04-11 WO PCT/EP2003/003764 patent/WO2003086594A1/en active IP Right Grant
- 2003-04-11 EP EP03722446A patent/EP1499426B1/en not_active Expired - Lifetime
- 2003-04-11 DE DE50302817T patent/DE50302817D1/en not_active Expired - Lifetime
- 2003-04-11 JP JP2003583598A patent/JP4443231B2/en not_active Expired - Fee Related
- 2003-04-11 US US10/507,362 patent/US7347938B2/en not_active Expired - Fee Related
- 2003-04-11 AU AU2003229642A patent/AU2003229642A1/en not_active Abandoned
- 2003-04-11 AT AT03722446T patent/ATE321602T1/en not_active IP Right Cessation
- 2003-04-11 CA CA2481435A patent/CA2481435C/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP1499426B1 (en) | 2006-03-29 |
WO2003086594A1 (en) | 2003-10-23 |
AU2003229642A1 (en) | 2003-10-27 |
ATE321602T1 (en) | 2006-04-15 |
JP4443231B2 (en) | 2010-03-31 |
JP2005527351A (en) | 2005-09-15 |
DE10217440A1 (en) | 2003-11-06 |
US20050126987A1 (en) | 2005-06-16 |
CA2481435A1 (en) | 2003-10-23 |
US7347938B2 (en) | 2008-03-25 |
EP1499426A1 (en) | 2005-01-26 |
DE50302817D1 (en) | 2006-05-18 |
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