WO1985001222A1 - Treatment of porous membranes - Google Patents
Treatment of porous membranes Download PDFInfo
- Publication number
- WO1985001222A1 WO1985001222A1 PCT/AU1984/000179 AU8400179W WO8501222A1 WO 1985001222 A1 WO1985001222 A1 WO 1985001222A1 AU 8400179 W AU8400179 W AU 8400179W WO 8501222 A1 WO8501222 A1 WO 8501222A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- membrane
- component
- pores
- walls
- hydrophilic
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 97
- 238000011282 treatment Methods 0.000 title description 15
- 239000011148 porous material Substances 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- 239000004952 Polyamide Substances 0.000 claims abstract description 26
- 229920002647 polyamide Polymers 0.000 claims abstract description 26
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004814 polyurethane Substances 0.000 claims abstract description 12
- 229920002635 polyurethane Polymers 0.000 claims abstract description 12
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003822 epoxy resin Substances 0.000 claims abstract description 10
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 229920000728 polyester Polymers 0.000 claims abstract description 9
- 239000004642 Polyimide Substances 0.000 claims abstract description 8
- 229920001721 polyimide Polymers 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 10
- 238000000034 method Methods 0.000 claims description 39
- -1 heterocyclic amines Chemical class 0.000 claims description 32
- 238000009472 formulation Methods 0.000 claims description 19
- 239000000839 emulsion Substances 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 230000000903 blocking effect Effects 0.000 claims description 9
- 235000013877 carbamide Nutrition 0.000 claims description 7
- 230000003019 stabilising effect Effects 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 230000007717 exclusion Effects 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 4
- 230000006641 stabilisation Effects 0.000 claims description 4
- 150000003573 thiols Chemical class 0.000 claims description 4
- 150000003672 ureas Chemical class 0.000 claims description 4
- 150000003673 urethanes Chemical class 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical class ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 238000011105 stabilization Methods 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 24
- 150000001299 aldehydes Chemical class 0.000 description 19
- 239000004743 Polypropylene Substances 0.000 description 16
- 229920001155 polypropylene Polymers 0.000 description 16
- 239000000126 substance Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000000151 deposition Methods 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 10
- WTFAGPBUAGFMQX-UHFFFAOYSA-N 1-[2-[2-(2-aminopropoxy)propoxy]propoxy]propan-2-amine Chemical compound CC(N)COCC(C)OCC(C)OCC(C)N WTFAGPBUAGFMQX-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- KKEBXNMGHUCPEZ-UHFFFAOYSA-N 4-phenyl-1-(2-sulfanylethyl)imidazolidin-2-one Chemical compound N1C(=O)N(CCS)CC1C1=CC=CC=C1 KKEBXNMGHUCPEZ-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 230000036512 infertility Effects 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- OTBHHUPVCYLGQO-UHFFFAOYSA-N bis(3-aminopropyl)amine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 0.000 description 4
- 239000010730 cutting oil Substances 0.000 description 4
- PGYPOBZJRVSMDS-UHFFFAOYSA-N loperamide hydrochloride Chemical compound Cl.C=1C=CC=CC=1C(C=1C=CC=CC=1)(C(=O)N(C)C)CCN(CC1)CCC1(O)C1=CC=C(Cl)C=C1 PGYPOBZJRVSMDS-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 3
- 108010058846 Ovalbumin Proteins 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 3
- 229940106681 chloroacetic acid Drugs 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 239000003906 humectant Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229940092253 ovalbumin Drugs 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 3
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- 229920003319 Araldite® Polymers 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- RXFCIXRFAJRBSG-UHFFFAOYSA-N 3,2,3-tetramine Chemical compound NCCCNCCNCCCN RXFCIXRFAJRBSG-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000720950 Gluta Species 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000001042 affinity chromatography Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000010796 biological waste Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004621 scanning probe microscopy Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- 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
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
Definitions
- OMPI but which had 5 leaky tubes at 300 kPa.
- the treatment required a high level of hydrophilicity so that 100% rejection of solubilised cutting oil B.P. FEDARO M would occur.
- the membrane must have all the pores below 100 nanometres so as to reject over 50% of protein of molecular weight 43,000 (ovalbumin).
- the treated membrane must be able to cope with a wide range of food industry wastes and must be able to produce optically clear permeates. It must also be able to withstand a hypochlorite sterilisation and a hot 20% hydrochloric acid clean.
Abstract
Hydrophobic fine pored membranes are rendered hydrophilic by coating the walls of the pores of the membrane with a hydrophilic material that is deposited on the pore walls by the reaction of first and second components of the hydrophilic material within the membrane. The hydrophilic materials include polyamides and polyimides, polyesters, polyurethanes, phenol/aldehyde resins, polyamide/aldehyde resins and epoxy resins as well as interpolymers and mixtures of those materials.
Description
TREATMENT OF POROUS MEMBRANES
FIELD OF INVENTION
This invention relates to porous membranes, particularly those having pores in the range of about 0.01 to 1 micron which are hereinafter called "fine pored filtration membranes".
BACKGROUND ART
Various types of fine pored filtration membranes have been developed, however, the cheaper and more useful types such as those made of polyolefines, polysulphones, • poly(vinylidenefluoride) , poly(dimethylphenyleneoxide) and poly(acrylonitrile) are normally hydrophobic and completely resist initial water permeation up to high pressures such as those above 10. Pa due to surface tension effects. The water permeation of the above-mentioned membranes can be substantially improved leading to hydraulic flow at low pressures, once the voids or pores have been wetted.
Although the voids or pores may be wetted by the addition of "surfactants" followed by continuous wet storage in water or humectant solutions, these procedures are not stable to washing, heating and drying as is required for heat sterilisation at 122°C. Such temporary wetting procedures fail with polypropylene.
There is a need for mechanically strong, highly stable membranes of controllable pore size and hydrophilicity and this need has been highlighted in recent symposia - see, for example, the chapter "Practical Aspects in the Development of a Polymer Matrix for Ultrafiltration" by Israel Cabasso in "Ultrafiltration Membranes and Application", editor A. R. Cooper (1979) ISBN 0-306-40548-2.
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The most recent approaches to the solution of this problem have involved preparing expensive hydrophilic special polymers. The cheaper hydrophilic polymers such as cellulose, hydrophilic nylons and cellulose esters do not resist hot, strong acids nor do they resist small concentrations of chlorine or hydrogen peroxide sterilants. Furthermore, some of these cheaper polymers do not even tolerate repeated wetting and drying. Many of them swell greatly in water and shrink on drying. Thus, the prior art is characterised by expensive experimental procedures to create a particular hydrophilicity for each new polymer and no stable post-formation control has been possible.
It is an object of this invention to provide hydrophilicity treatment systems for fine pored filtration membranes which are initially hydrophobic. It is a further object of the invention to provide treatment systems which permit continuous variations in hydrophilicity and in which pore size control extends beyond the surface to include selective spatial modification of the'pores such as more hydrophilic small pores rather than larger pores or vice versa.
DISCLOSURE OF INVENTION
According to the invention there is provided a process of treating a hydrophobic porous membrane so as to render it hydrophilic in which a hydrophilic material is deposited on the walls of the pores of the membrane.
The invention also provides a method of treating a hydrophobic porous membrane so as to render it hydrophilic by coating the walls of the pores of the membrane with a hydrophilic material in which the hydrophilic material is deposited on the walls of the pores by the reaction of first and second components of the material within the membrane.
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Preferably, the method of the invention includes the steps of:
(a) preparing a deposition formulation of the first component, (b) passing the deposition formulation through the membrane under conditions of humidity and temperature that will ensure that the selected material is deposited from the formulation on the walls of the pores of the membrane at the desired concentrations and form,
(c) passing the second component through the membrane so that it will react with the first component to form the selected material, and, if necessary,
(d) stabilising the so treated membrane.
The invention also provides a method of treating a' hydrophobic porous membrane so as to render it hydrophilic which comprises the steps of:
(a) selecting a material from the group:
(1) Polyamides and polyimides (2) Polyesters
(3) Polyurethanes
(4) Phenol/aldehyde resins
(5) Polyamide/aldehyde resins
(6) Epoxy resins (7) Interpolymers of materials 1 to 6
(8) Mixtures of materials 1 to 6
which can be formed on or in the membrane by the reaction of first and second components whereby the material is deposited on the walls of the pores of the membrane to provide the required hydrophilicity.
(b) preparing a deposition formulation of the first component,
(c) passing the deposition formulation through the membrane under conditions of humidity and temperature that will ensure that the selected material is deposited from the formulation on the walls of the pores of the membrane at the desired concentrations and form,
(d) passing the second component through the membrane so that it will react with the first component to form the selected material, and, if necessary, Ce) stabilising the so treated membrane.
Preferably, the deposition material is selected from:
(a) Polyamides and polyimides formed from a first component such as primary or secondary amines and a second component such as acid halides and in which at least one of the first and second components is aromatic or substituted aromatic. The acid halide is normally used in excess to give chemical resistance and the average functionality is above two so that there is considerable cross- linking.
(b) Polyesters formed from a first component such as an hydroxyaromatic and a second component such as aromatic or hetero-aromatic acid chlorides
(including sulphonylchlorides) reacted such that the average functionality is above or equal to t o.
(c) Polyurethanes formed from a first component having - a reactive hydrogen group such as alcohols, amines, acids, ureas, urethanes, phenols and thiols and a second component such as an isocyanate.
(d) Phenol/aldehyde resins which react very rapidly in aqueous media to precipitate fine, porous solids. Gaseous acidic catalysts may be used to ensure reaction in a mixture of polyhydroxyaromatics and low volatile aldehydes or pre-polymers of these two components. The water solvent can be easily evaporated from the hydrophobic porous base. Dry hydrochloric acid, sulphur trioxide, boron trifluoride or sulphury1 chloride may be admitted to speed up the reaction.
(e) Polyamine/aldehyde resins which are the reaction products of aromatic and heterocyclic amines (such as melamine) with aldehydes.
(f) Epoxy resins include all epoxides and their reaction products with reactive hydrogen groups such as alcohols, amines, acids, ureas, urethanes, phenols and thiols.
Preferably, the stabilisation step includes dissolving any unco bined material and hydrolysing excess terminal groups or reacting them further as desired to secure specific surface effects as given below. In some instances, the two components may be passed through the membrane together provided that there is sufficient delay in the commencement of the reaction between the components to enable them to be properly disposed.
The invention also provides a method of treating a membrane of non-uniform pore size so as to provide a membrane having a predetermined porosity in which a blocking material is deposited within selected pores and on the walls of the other pores of the membrane by the reaction of first and second components of the material within the membrane.
Preferably, the first component is an emulsion in which the size of the dispersed phase and its interfacial tension with the continuous phase are such as to cause exclusion of the dispersed phase from pores which are smaller than the predetermined pore size. The emulsion may be formed from a primary or secondary amine, which is converted into a polyamide by an acid halide as previously described.
The blocking material may also be formed from:
Ca) an alcohol such as polyvinylalcohol and an isocyanate,
(b) a phenol such as resorcinol and an aldehyde such _ as formaldehyde,
(c) an epoxy resin and an amine.
According to a further aspect of the invention there is provided a method of treating a membrane of non-uniform pore size so as to provide a membrane having a predetermined porosity comprising the steps of:
(a) selecting a material from the group defined above which can be formed on or in the membrane by the reaction of first and second components whereby the material is deposited within selected pores and on the walls of the other pores of the membrane,
(b) preparing an emulsion of the first component of predetermined size and of such interfacial tension with the continuous phase so as to cause exclusion from pores below the predetermined size but to allow entry into the pores above the predetermined size, (c) passing the emulsion through the membrane under conditions of humidity and temperature that will ensure that the emulsion is held in the pores above the predetermined size, and. <gTT_R£
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(d) passing the second component through the membrane so that it will react with the first component to form the selected material, and, if necessary,
(e) stabilising the so treated membrane.
The above aspects of the invention may be combined if so required and they may be complemented, either singularly or together, by further steps in which desired chemical groups such as carboxylic acid, sulphonic acid, quaternary bases, reducing groups, aldehydes or isothiocyanates as may be required in particular electrical, biological and affinity chromatographic applications of the fine pored filtration membranes.
The methods of the invention permit the preparation of fine pored filtration membranes of desired physical and/or chemical characteristics without the need of expensive experimental procedures.
The coatings or materials deposited by the methods of the invention will sometimes be in themselves novel and the particular method of application of the material may itself be novel. For example, it may be necessary to introduce new techniques such as supplying gaseous catalysts to affect spatially selected areas. When selecting the particular material with which to treat the otherwise unsuitable fine pored filtration membrane certain considerations must be borne in mind.
In general terms the choice of the material will be in the decreasing order of polyamide or polyimide, polyesters, polyurethanes, phenol/aldehyde resins, polyamine/aldehyde resins, epoxy resins, interpolymers of the foregoing and mixtures of the foregoing. The reasons for this preferred order include the availability of a wide range of cheap.
co mercial intermediates, chemical stability, controllability of deposition place, controllability of pore size, controllability of hydrophilicity, low cost due to minimum handling and safety of chemical handling.
The order of preference is one of average circumstance choice and those skilled in applied polymer chemistry and fine pored filtration will at once perceive whether some cheap chemical raw material will confer the required chemical or mechanical property on the membrane to be treated. For example, in the case of cation exchange necessitating -SO3H groups in a matrix resistant to 30% NaOH at 80°C the choice of material would not be polyamide or polyimide but rather a phenol/aldehyde resin.
When the treatment is for hydrophilicity, acid and chlorine resistance, polyamides would be the best choice.. Cross-linked polyamides (or polyimides if suitable acid chlorides are used) are particularly useful as they are resistant to hot hydrochloric acid and chlorine and pH 13 for at least a year. Many functional groups may be incorporated in their structure, for example, a -SO^H group may be incorporated by using sulfanilic acid. However, when incorporating such functional groups allowance must be made for the mono-functional nature of the single - H2 group.
The cheapest available aromatic acid chloride of functionality two is terephthaloylchloride and thus it would be the preferred material. Such a material will give resistant products with any diamine or polyamine but high hydrophilicity demands that there will be a limit to the ratio of hydrophobic carbon groups to the hydrophilic nitrogen group. Ethylene diamine or triethylene tetramine may be used. Also any polyamine containing up to 20 carbon atoms per nitrogen atom may be used to give a continuous spectrum of reliable hydrophilicity.
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The polyester treatment materials have advantages where phenolic functional groups or sulphonic functional groups are required. The phenolic hydroxyl groups are useful when reactions with epoxides are required. Such epoxides may be gaseous such as ethylene epichlorhydrin dilute vapour which produces highly hydroxylated surfaces. Ethyleneimine can also be used in such circumstances.
When the polyurethane materials are used the reaction is usually anhydrous and is most useful where very rapid homogeneous reactions precipitate fine polymeric substances. The products are stable and swell well in water so that the membranes are often useful f.or electrodialysis.
The phenol/aldehyde resins are useful for chelating metals and they also form good electrodialysis membranes. The polyamine/aldehyde resins tend to be most useful where excess aldehyde groups allow easy conversion to a wide range of other chemical groups or compounds. . For example, aldehydes are excellent for binding antibodies which are used in affinity chromatography to isolate useful or harmful biological products.
One of the main uses of the epoxy resins is to overcoat the phenol/aldehyde resins since the latter tend to be rather coarse. In some cases interpolymers and mixtures of the materials may be used.
The deposition formulation may bia prepared using a hydrophobic solvent such as hexane which is allowed to evaporate. In some cases, more uniform films are obtained if a small amount of surfactant is included in the formulation. Chemical considerations may suggest addition of a hydrochloric acid absorbing substance such as a tertiary amine to ensure complete reaction of the substitutable amines.
Alternatively, the treatment material may be dissolved in water, ethanol or a hydrophilic solvent. The hydrophilic solvent may contain a small amount of surfactant and a small amount of non-volatile hydrophilic humectant substance such as glycerol. Such hydrophilic solvent mixtures usually need considerable pressure to ensure displacement of all air from the membrane. Complete displacement of the air is vital if all the surface of the membrane is to be made hydrophilic. Lesser pressures leave the smaller pores hydrophobic which may, in some instances, be desired.
Irrespective of the nature of the formulation, control of the water content of the residual material film is essential for uniform results. For example, the water controls the rate of diffusion of terephthaloylchloride from a hydrophobic solvent in which it is applied. Water content control may be obtained by the relative humidity and temperature of the drying atmosphere and the hydrophilicity of the deposited film depends greatly on the composition and amount of any surfactant or humectant used.
DESCRIPTION OF PREFERRED EMBODIMENTS
In order that the invention may be more readily understood reference will now be made to the following examples:
Example 1
A bundle of hydrophobic polypropylene hollow fibre porous membranes are to be treated so as to be easily wettable with aqueous biological media after being heat sterilised and dried at 100°C. The treated bundle of membranes must be clearable by back-blowing with water containing 10 ppm chlorine and soaking at 50°C in 20% hydrochloric acid to dissolve any protein clots therein. The pore sizes of the polypropylene fibres to be treated are
from 0.05 to 0.5 microns but the use to which the bundle will be put indicates that some selective plugging of a small proportion of 1 to 5 micron large holes which undesirably allow the permeate to appear optically hazy.
The needs of hydrophilicity, acid and chlorine resistance can be readily met by a po'lyamide as defined above. Terephthaloylchloride was chosen as the acid chloride (i.e. the second component of the polyamide) and bis (3-aminopropyl) amine was selected as the first component of the polyamide because of its solubility in hexane to provide the deposition formulation. With such components, polyamide deposition should be complete within an hour.
In order to ensure that the material deposited into the pores of 1 to 5 microns in size, a fine dilute emulsion was formed in which the dispersed phase was of a size about 1 micron and its interfacial tension with the continuous phase was such so as to cause exclusion of the dispersed phase from the smaller pores but to allow entry into the coarser pores. The emulsion was formed as a mixture of:
Bis (3-aminopropyl) amine 3.93 grams P-tertiaryoctylphenoxy- polyethyleneglycolether 0.1 grams
Petroleum spirit (b.p. 60-80°C) 950 millilitres Absolute ethanol - 50 millilitres
Water was added drop-by-drop until a distinct opalescent turbidity indicated that droplets above the wave length of visible light were present. These would, of course, be above 1 micron in size. Care was taken to apply the second component namely a 1% weight per volume terephthaloylchloride solution in petroleum spirit as soon as the amine solution had evaporated to the desired film with droplets in the larger pores. When the treated
membrane was allowed to stand for 24 hours before fixing with the acid chloride (the second component) diffusion into the smaller pore occurred as is required for thermodynamic stability but that is to be avoided in order to produce the treated membrane required.
The treated membrane was washed in a 20% weight per volume aqueous hydrochloric acid to dissolve any uncro'ss- linked material and to hydrolyse the excess terminal acid chloride to carboxylic acid groups. A thorough water wash and drying at 60°C completed the treatment.
The properties of the treated membrane were excellent. Although the initial polypropylene had shown nil permeation rate of water at 125 kPa, the permeation rate of the treated membrane was 1800 litres per square metre per hour. Microfiltration was excellent since at 125 kPa suspension of extra-fine (i.e. under 1 micron) titanium oxide filtered at 1800 litres per square metre per hour gave a permeate which was optically clear at 650 nanometres. A 0.1% suspension of the cutting oil B.P. FEDARO M which is partly solubilised by wetting agent (i.e. the oil phase is not highly hydrophobic and has about zero interfacial surface tension between the suspended and continuous phases) at 125 kPa gave a permeate at 1080 litres per square metre per hour with 85% rejection of the turbidity at 650 nanometres. It should be noted that the oil is not a solid and that separation was determined by hydrophilicity. A coated polypropylene was so hydrophilic that it selectively passed the wetter solution rather than the hydrophilic micelles.
Example 2
In this example it was desired to treat an existing hydrophobic bundle of low-grade polypropylene hollow fibre porous membrane which was impermeable to water at 100 kPa
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but which had 5 leaky tubes at 300 kPa. The treatment required a high level of hydrophilicity so that 100% rejection of solubilised cutting oil B.P. FEDARO M would occur. The membrane must have all the pores below 100 nanometres so as to reject over 50% of protein of molecular weight 43,000 (ovalbumin). Furthermore the treated membrane must be able to cope with a wide range of food industry wastes and must be able to produce optically clear permeates. It must also be able to withstand a hypochlorite sterilisation and a hot 20% hydrochloric acid clean.
Again, a polyamide system as described in Example 1 will meet the cleaning and chemical criteria. An initial effort was made to deposit a formulated (H^NtCE^^)2NH film (the first component of the polyamide) using a solution of terephthaloylchloride (the second component of the polyamide). In order to obtain the required treated membrane all the pores will have to contain considerable fine pored filtration polyamide filling of the highest hydrophilicity. As polyamide fine pored filters absorb proteins to form a dynamic interactive pseudo-membrane, the pores may be larger than the radius of gyration of the ovalbumin. This requirement ensures that polyamides, polyesters and phenol/aldehyde resins are the main choices for the treatment material since they best absorb protein. A higher concentration of deposit than was the case with
Example 1 is necessary in order to give the finer porosity.
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A deposition formulation was made from:
H (-CH2-CH2-CH2-NH2 )2 10 gra s
Ethoxylated octylphenol 2 grams
Glycerol 20 grams NaOH 8 grams
Methylene blue 100 millilitres of 250 ppm solution
Sufficient water was added to make up 1000 millilitres of the solution which was forced through the fibres at 700 kPa to fill all the voids completely and to allow easy hydraulic flow. After draining, the fibres were dried at 22°C in a flow of 50 kPa air which was saturated with water at 15°C and 800 kPa before expansion to 50 kPa. The amine- coated ultrafilter was soaked in a 2% weight per volume terephthaloylchloride in hexane at 22°C -for 30 minutes. It was then freed of hexane by an air stream and electron scanning microscopy showed that the deposit was suitable.
The treated membrane was stabilised by washing with water at 400 kPa at a high rate of flow and it was then immersed in 7N hydrochloric acid overnight. It was then washed until neutral and its permeability tested with tap water. At 125 kPa the permeation rate was 864 litres per square metre per hour which confirmed a finer pore than that of Example 1. The 0.1% B.P. FEDARO M oil showed over 99.95% rejection which was the limit of instrumental detection. A faint haze in 40 cm thickness could just be detected and this was possibly due to wetter micelles. The ovalbumin showed 50% rejection. Biological wastes from a variety of food processes showed optical clarity.
In a modification of this example another membrane was produced using a reaction time of one hour instead of 30 minutes. The resultant membrane was excellent in every way.
Example 3
A defective polypropylene hollow fibre porous membrane cartridge leaked in many tubes when water was applied at only 40 kPa. As such a cartridge should not leak at 300 kPa it was apparent that there were many over-sized pores present in the membranes. Thus the object of the example was to seal the defective larger pores by position. As there were over 30% leaks, heat sealing and blocking off each end of a tube was uneconomical. Other requirements of the finished cartridge were that it must withstand concentrated hydrochloric acid, it must wet readily and it must possess no pore over 0.5 micron in diameter. The emulsion process of the previous examples was used except that the emulsion was made coarser by using:
HN(CH2-CH2-CH2-NH2)2 3.93 grams
Absolute ethanol 50 millilitres Cyclohexane 950 millilitres
Water was added drop-by-drop at 22°C until a distinct emulsion was formed. The emulsion was poured down the inside of the fibres so that the fast flow through the large pores caused suitable sized droplets to fill them, finally blocking them with over-sized droplets. The cyclohexane was rapidly evaporated by 50 kPa air passing down the inside of the fibres at 22°C. A 1% weight per volume solution of terephthaloylchloride (the second component of the polyamide) in cyclohexane was then poured down the inside of the tubes and left for 45 minutes. The cyclohexane swelled the polypropylene about 10% in all dimensions. The cyclohexane was then removed by blowing in air at 50 kPa.
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Hydrolysis overnight with ION hydrochloric acid followed by water washing showed that the relatively large holes were filled with the material but so much of the amine had been in the dispersed phase that insufficient had been left to confer the required hydrophilicity of the membranes. However after the drying step it was noted that there was no water leakage at 600 kPa.
In order to satisfy the other requirements of the membrane further treatment was necessary. Normally, treatment analogous to that set forth in Example 1 but without the emulsion formulation would have been used to secure overall hydrophilicity. With the view in mind of producing a fibre membrane that would reject over 90% commercial gelatin (preferably 95 - 98% rejection of high quality gelatin) it was decided to confer hydrophilicity by depositing an interstitial deposit of zirconyl or zirconium phosphate.
Before the phosphate treatment, the cartridge at 125 kPa gave an 80% rejection of 0.1% B.P. FEDARO M soluble cutting oil at 254 litres per square metre per hour. The cartridge was saturated with a 2% weight per volume aqueous solution sodium phosphate (Na3P04.12H20) and 0.2% ethoxylated octylphenol and dried with air at 60°C. A 2% weight per volume aqueous solution of zirconium chloride (Zr02Cl2.6H20) was then poured down the fibres under gravity and left for 30 minutes. The fibres were then washed with water and testing at 125 kPa with 0.1% FEDARO M cutting oil gave a permeation rate of 87 litres per square metre per hour but 100% rejection of visible oil.
Testing on 0.5% commercial gelatin at 22°C and pH 6.5 at 125 kPa gave a permeation rate of 12 litres per square metre per hour with an 80% rejection of all protein. Optimisation of the pH allowed 90% rejection of the protein. The zirconium phosphate was held on the
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hydrophilic base. The phosphate was washed out from untreated polypropylene. The zirconium phosphates resist ION hydrochloric acid, chlorine and most chelating agents. They may be washed out with hydrofluoric solution and redeposited.
All the fibres used in the following examples 4 to 9 were from the same batch of polypropylene. Their internal diameter was 200 microns and their external diameter was 600 microns. The porous walls had an average pore size of 0.2 microns. Bubble points varied- between 220 and 320 kPa, when using air and water.
These fibres, when treated, were subjected to a sterility test in which they were boiled in a large amount - of water for 1 hour, rinsed, and then heated to 122°C for 4 minutes. The fibres were then rewetted, redried tested and classified as follows:
(a) excellent immediate wetting,
(b) good wetting at 100 to 200 kPa transmembrane pressure, or, (c) no wetting.
During these tests it is possible to- measure pore size and ascertain whether the larger pores have been selectively blocked.
Example 4 (Polyurethane)
The polypropylene fibres were soaked in a solution of 5% l,2-bis(3-aminopropylamino)ethane and 1% p- tertiaryoctylphenoxypolyethyleneglycolether (I.C.I. TERIC X10) in ether for 15 minutes. After drying in air for 3 minutes the fibre was soaked in a solution of 5% I.C.I. SUPRASEC 5005 (the first component of the polyurethane) in acetone for 1 hour. It was then dried for 15 minutes at r ONTI
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65°C and then soaked in a solution of 2% Texas Chemicals JEFFAMINE M2005 (the second component of the polyurethane) in acetone for 15 hours. The hydrophilicity was excellent. Since SUPRASEC 5005 is a commercial diphenylmethanediisocyanate and JEFFAMINE M2005 is a polyglycolether of monoethanolamine, the coating represents a polyurethane resin. In contrast a fibre treated with JEFFAMINE M2005 only (although a known wetting agent) was apparently removed by the sterility test cycle and failed to wet. Also no trace of JEFFAMINE was detected by a test sensitive to 1 part per million as a possible contaminant of the invention coated fibre proving that hydrophilicity was due to the polyurethane coating only.
Example 5 (Urea/aldehyde Resins)
5g of Urea (the first component of the resin) and 0.5g of diethylenegycol were dissolved in 5ml of a 40% formaldehyde solution (the second component of the resin) at 20°C. The polypropylene fibres were impregnated by forcing the solution through the pores, followed by 400 kPa air for 2 minutes via the fibre lumen. The fibres were then immersed at once in 7N hydrochloric acid for 15 minutes. They were dried at 65°C for 1 hour, soaked in a solution of 5% SUPRASEC 5005 in acetone and again dried. Finally they were soaked in a 2% solution of JEFFAMINE M2005 in acetone for 1 hour. The fibres showed excellent wetting after the standard sterility test cycle given above.
Excellent amine/aldehyde coatings were similarly obtained from urea/glutaraldehyde resin, treated with sodium hypochlorite as well as from melamine/formaldehyde/polyethyleneglycol (Molecular Weight 600).
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Example 6 (Epoxy Resins)
The polypropylene porous, hollow fibres were soaked in 5% CIBA-GEIGY ARALDITE LCI91 (the first component of the resin) in acetone, dried in air for 3 minutes and then soaked for 2 hours in a solution of 5% l,2-bis(3- aminopropylamino) ethane and 1% TERIC X10 in ether. After the standard wet/dry sterility test hydrophilicity was good but a greater bubble-point test showed selective blocking of the larger pores. Selective blocking is against thermodynamic prediction and is economically more important when obtained simultaneously with hydrophilicity than either selective blocking or hydrophilicity.
A similar good coating was made from ARALDITE LCI91 and bis(3-aminopropyl)amine.
Example 7 (Phenol/aldehyde Resins)
Polypropylene fibres were soaked in a solution of 5g of resorcinol (the first component of the resin) and 2.5 ml of diethyleneglycol in 20 ml. of ethanol. They were dried at 65°C for 30 minutes and soaked for 1 hour in a 1:1 mixture of ION hydrochloric acid and 40% formaldehyde, (the second component of the resin) , redried as before, rinsed with 10% aqueous sodium hydroxide then water and then soaked for 2 hours in a solution of 5% chloroacetic acid in ethanol. The treated fibres were given the standard test and showed good hydrophilicity as well as the highly desirable increase in bubble-point without loss of much permeation rate.
Similar coatings were obtained from:-
(a) Resorcinol/formaldehyde/sodium hydroxide/chloroacetic acid sequences
(b) Resorcinol/formaldehyde/hydrochloric acid/hexamethylenediisocyanate/JEFFAMINE M2005 sequences
(c) Resorcinol/gluta aldehyde/hydrochloric acid/sodium hypochlorite sequences
(d) Phenol/formaldehyde/hydrochloric acid/chloroacetic acid sequences
Example 8 (Polyamide Resins)
Polypropylene hollow fibres were soaked for 10 minutes in a solution of 5% l,2-bis(3-aminopropylamino)ethane (the first component of the polyamide) in ether and dried in air for 3 minutes. They were then soaked for 10 minutes in 5% terephthaloylchloride (the second component of the polyamide) in ether, again dried and soaked in a solution of 2% JEFFAMINE M2005 in acetone for 15 hours. After the standard test hydrophilicity was excellent.
Similar excellent results were obtained from the sequential series of reactions:-
(a) 1,2-bis(3-aminopropylamino)- ethane/sebacoylchloride/JEFFAMINE M2005
(b) l,2-bis(3-aminopropylamino)ethane/terephthaloylch- loride/JEFFAMINE M2005
(c) Bis(3-aminopropyl)amine/terephthaloylchloride/- JEFF MINE M2005
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Example 9 (Polyvinylalcohol/Crosslinked Resin)
Polypropylene hollow fibres (prewetted with ethanol then water) were impregnated with a solution of 1.5% polyvinylalcohol (Molecular Weight 15,000) (the first component of the resin) in water by forcing the solution through the pores. They were dried at 65°C for 2 hours and soaked for 3 hours in a solution of 1% SUPRASEC 5005 (the second component of the resin) and 0.16% triethylenediamine in N-methyl-2-pyrrolidone. The chemical structure is a form of polyurethane. After the standard sterility cycle the hydrophilicity was good and the bubble-point was raised desirably, showing blocking of the larger pores.
In general terms the methods of the invention provide good control of pore size and distribution, good control of hydrophilic distribution and supply of functional groups can be obtained on cheap hydrophobic porous supports. Physical faults in such cheap porous supports can be corrected without recourse to monomolecular layers or surface chemical changes of the hydrophobic base.
The methods of the invention form adherent coatings, networks and interstitial porous precipitates and in so doing form novel membrane products.
Various modifications may be made in details of the deposition formulations, the method of treatment and the stabilisation treatments without departing from the scope and ambit of the invention.
Claims
1. A method of treating a hydrophobic porous membrane so as to render it hydrophilic in which a hydrophilic material is deposited on the walls of the pores of the membrane.
2. A method of treating a hydrophobic porous membrane so as to render it hydrophilic by coating the walls of the pores of the membrane with a hydrophilic material in which the hydrophilic material is deposited on the walls of the pores by the reaction of first and second components of the material within the membrane.
3. A method according to claim 2 including the steps of:
(a) preparing a deposition formulation of the first component,
(b) passing the deposition formulation through the - membrane under conditions of humidity and temperature that will ensure that the selected material is deposited from the formulation in the on the walls of the pores of the membrane at the desired concentrations and form,
(c) passing the second component through the membrane so that it will react with the first component to form the selected material, and, if necessary,
(d) stabilising the so treated membrane.
4. A method of treating a hydrophobic porous membrane so as to render it hydrophilic comprising the steps of:
(a) selecting a material from the group consisting of:
(1) Polyamides and polyimides
(2) Polyesters
(3) Polyurethanes
(4) Phenol/aldehyde resins
OMFI (5) Polyamide/aldehyde resins
(6) Epoxy resins
(7) Interpolymers of materials 1 to 6
(8) Mixtures of materials 1 to 6
which can be formed on or in the membrane by the reaction of first and second components whereby the material is deposited on the walls of the pores of the membrane to provide the required hydrophilicity,
(b) preparing a deposition formulation of the first component,
(c) passing the deposition formulation through the membrane under conditions of humidity and temperature that will ensure that the selected material is deposited from the formulation on the walls of the pores of the membrane at the desired concentrations and form,
(d) passing the second component through the membrane so that it will react with the first component to form the selected material, and, if necessary,
(e) stabilising the so treated membrane.
5. A method according to claim 4, wherein
(i) the polyamides and polyimides are those formed from a first component which is a primary or secondary amine and a second component which is an acid halide and in which at least one of the first and second components is aromatic or substituted aromatic; —
(ii) the polyesters are those formed from a first component which is an hydroxyaromatic and a second component which is an aromatic or hetero- aromatic acid chloride reacted such that the average functionality is above or equal to two; (iii) the polyurethanes are those formed from a first component having a reactive hydrogen group, and a second component which is an isocyanate; (iv) the phenol/aldehyde resins are those which react very rapidly in aqueous media to precipitate fine, porous solids; Cv) the polyamide/aldehyde resins which are the reaction products of aromatic and heterocyclic amines with aldehydes; (vi) the epoxy resins include all epoxides and their reaction products with reactive hydrogen groups.
6. A method according to claim 4, wherein the hydrophobic porous membrane is made from the group consisting of polyolefines, polysulphones, poly(vinylidenefluoride) , poly(dimethylphenyleneoxide) or poly(acrylonitrile) .
7. A method according to claim 5, wherein the second component of the polyester includes sulphonyl chlorides.
8. A method according to claim 5, wherein the first component of the polyurethanes is chosen from the group comprising alcohols, amines, acids, ureas, urethanes, phenols, and thiols.
9. A method according to claim 5, wherein the aromatic and heterocyclic amines of the polyamide/aldehyde resins include melamine.
10. A method according to claim 5, wherein the reactive hydrogen group is chosen from the group consisting of alcohols, amines, acids, ureas, urethanes, phenols and thiols.
11. A method according to claim 3 or claim 4 where the stabilisation step includes dissolving any uncombined material and hydrolysing excess terminal groups.
12. A method according to claim 11 modified in that the excess terminal groups are further reacted to provide a specific surface effect.
13. A method of treating a membrane having non-uniform pore size so as to provide a membrane having a predetermined porosity in which a blocking material is deposited within selected pores and on the walls of the other pores of the membrane by the reaction of first and second components of the material within the membrane.
14. A method according to claim 13 wherein the first component is an emulsion in which the size of the dispersed phase and its interfacial tension with the continuous phase are such as to cause exclusion of the dispersed phase from pores which are smaller than the predetermined pore size.
15. A method according to claim 14 wherein the emulsion is formed from a primary or secondary amine which can be converted into a polyamide by an acid halide.
16. A method according to claim 13 wherein the first component is an alcohol and the second component is an isocyanate.
17. A method according to claim 13 wherein the first component is a phenol and the second component is an aldehyde.
18. A method according to claim 16 wherein the alcohol is a polyvinylalcohol.
19. A method according to claim 16 wherein the phenol is resorcinol and the aldehyde is formaldehyde.
20. A method according to claim 13 wherein the first component is an epoxy resin and the second component is an amine.
21. A method of treating a membrane of noή-uniform pore size so as to provide a membrane having a predetermined porosity comprising the steps of:
(a) selecting a material from the group defined in claim 4 which can be formed on or in the membrane by the reaction of first and second components whereby the material is deposited within selected pores and on the walls of the pores of the membrane,
(b) preparing an emulsion of the first component in which the size of the dispersed phase and its interfacial tension with the continuous phase are such as to cause exclusion of the dispersed phase from pores which are smaller than the predetermined size,
(c) passing the emulsion through the membrane under conditions of humidity and temperature that will ensure that the emulsion is held in the pores above the predetermined size,
(d) passing the second component through the membrane so that it will react with the first component to form the selected material, and, if necessary,
(e) stabilising the so treated membrane.
22. A method according to claim 21 where the stabilization step includes dissolving any uncombined material and hydrolysing excess terminal groups.
23. A method according to claim 21 modified in that the excess terminal groups are further reacted to provide specific surface effects.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AUPG1368 | 1983-09-12 | ||
AUPG136883 | 1983-09-12 | ||
AUPG175983 | 1983-10-10 | ||
AUPG1759 | 1983-10-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1985001222A1 true WO1985001222A1 (en) | 1985-03-28 |
Family
ID=25642704
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AU1984/000179 WO1985001222A1 (en) | 1983-09-12 | 1984-09-12 | Treatment of porous membranes |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0156840A4 (en) |
WO (1) | WO1985001222A1 (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0204337A2 (en) * | 1985-06-05 | 1986-12-10 | Ube Industries, Ltd. | Porous hollow fiber |
US4774132A (en) * | 1986-05-01 | 1988-09-27 | Pall Corporation | Polyvinylidene difluoride structure |
WO1990011120A1 (en) * | 1989-03-18 | 1990-10-04 | International Applied Sciences, Inc. | Ultrafiltration membrane |
EP0399568A2 (en) * | 1985-01-10 | 1990-11-28 | TERUMO KABUSHIKI KAISHA trading as TERUMO CORPORATION | Hydrophilic porous membrane |
US5019261A (en) * | 1986-08-27 | 1991-05-28 | Dow Danmark A/S | Permeable, porous polymeric membrane with hydrophilic character methods for preparing said membranes and their use |
EP0440858A1 (en) * | 1988-08-11 | 1991-08-14 | Mitsubishi Gas Chemical Company, Inc. | Humidity sensor |
US5136274A (en) * | 1990-02-01 | 1992-08-04 | Mitsubishi Gas Chemical Company, Inc. | Humidity sensor |
WO1994009063A1 (en) * | 1992-10-21 | 1994-04-28 | Cornell Research Foundation, Inc. | Pore-size selective modification of porous materials |
WO1995001219A1 (en) * | 1993-06-29 | 1995-01-12 | Minnesota Mining And Manufacturing Company | Interfacial polymerization in a porous substrate and substrates functionalized with photochemical groups |
US5627217A (en) * | 1993-06-29 | 1997-05-06 | Minnesota Mining And Manufacturing Company | Interfacial polymerization in a porous substrate and substrates functionalized with photochemical groups |
NL1020950C2 (en) * | 2002-06-24 | 2003-12-30 | Saehan Ind Inc | Composite polyamide reverse osmosis membrane for desalination of seawater, comprises polyamide layer and hydrophilic coating of polyfunctional epoxy compound, formed sequentially on microporous support |
CN117654288A (en) * | 2024-02-01 | 2024-03-08 | 蓝星(杭州)膜工业有限公司 | Composite membrane and preparation method and application thereof |
CN117654288B (en) * | 2024-02-01 | 2024-04-19 | 蓝星(杭州)膜工业有限公司 | Composite membrane and preparation method and application thereof |
Citations (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU1736876A (en) * | 1975-09-22 | 1978-03-09 | Uop Inc. | Composite semipermeable membrane |
GB2011804A (en) * | 1977-11-25 | 1979-07-18 | Uop Inc | Gas Separation Membranes and Process for the Preparation Thereof |
GB2035133A (en) * | 1978-09-28 | 1980-06-18 | Wafilin Bv | A modified membrane for membrane filtration |
JPS55144036A (en) * | 1979-04-27 | 1980-11-10 | Nitto Electric Ind Co Ltd | Production of hydrophilic plastic molded article |
US4242208A (en) * | 1978-05-22 | 1980-12-30 | Teijin Limited | Semipermeable composite membrane and process for preparation thereof |
US4250029A (en) * | 1977-04-25 | 1981-02-10 | Rohm And Haas Company | Coated membranes |
US4256782A (en) * | 1976-06-04 | 1981-03-17 | Kansai Paint Co., Ltd. | Treating method for giving hydrophilic property to the surface of hydrophobic polymer substrate |
GB2058802A (en) * | 1979-09-04 | 1981-04-15 | Celanese Corp | Hydrophilic monomer treated microporous films |
GB2058798A (en) * | 1979-09-19 | 1981-04-15 | Aligena Ag | Porous polyacrylonitrile-containing membranes siutable for use in ultrafiltration and their preparation |
GB2075416A (en) * | 1980-05-02 | 1981-11-18 | Bend Res Inc | Reverse osmosis composite hollow fiber membrane |
US4302336A (en) * | 1978-09-06 | 1981-11-24 | Teijin Limited | Semipermeable composite membrane |
GB2076392A (en) * | 1980-04-28 | 1981-12-02 | Secr Defence | Porous glass membrane |
US4340479A (en) * | 1978-05-15 | 1982-07-20 | Pall Corporation | Process for preparing hydrophilic polyamide membrane filter media and product |
EP0061782A2 (en) * | 1981-03-31 | 1982-10-06 | Nitto Electric Industrial Co., Ltd. | Composite semipermeable membrane and process for preparation thereof |
US4359510A (en) * | 1980-07-31 | 1982-11-16 | Celanese Corporation | Hydrophilic polymer coated microporous membranes capable of use as a battery separator |
GB2103536A (en) * | 1981-06-24 | 1983-02-23 | Asahi Chemical Ind | Composite hydrophilic semipermeable membrane |
US4383923A (en) * | 1980-07-02 | 1983-05-17 | Bayer Aktiengesellschaft | Semipermeable membranes |
EP0094050A2 (en) * | 1982-05-06 | 1983-11-16 | Teijin Limited | Ultrathin film, process for production thereof, and use thereof for concentrating a specified gas in a gaseous mixture |
EP0100552A2 (en) * | 1982-08-02 | 1984-02-15 | Mitsubishi Rayon Co., Ltd. | Hydrophilized membrane of porous hydrophobic material and process of producing same |
EP0107336A1 (en) * | 1982-09-30 | 1984-05-02 | Uniroyal, Inc. | Preparation of P-nitrosodiphenylamine |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3744642A (en) * | 1970-12-30 | 1973-07-10 | Westinghouse Electric Corp | Interface condensation desalination membranes |
DE2537389A1 (en) * | 1975-08-22 | 1977-02-24 | 4 P Verpackungen Gmbh | Filter for aqueous solutions or dispersions - made by rendering hydrophobic thermoplastic film hydrophilic with surface active agent |
GB1538810A (en) * | 1976-08-10 | 1979-01-24 | Sumitomo Electric Industries | Hydrophilic porous fluorocarbon structures and process for their production |
US4239714A (en) * | 1978-11-15 | 1980-12-16 | Washington University | Method for modifying the pore size distribution of a microporous separation medium |
JPS59115704A (en) * | 1982-12-24 | 1984-07-04 | Toray Ind Inc | Treatment of semipermeable membrane |
-
1984
- 1984-09-12 EP EP19840903426 patent/EP0156840A4/en not_active Withdrawn
- 1984-09-12 WO PCT/AU1984/000179 patent/WO1985001222A1/en not_active Application Discontinuation
Patent Citations (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU1736876A (en) * | 1975-09-22 | 1978-03-09 | Uop Inc. | Composite semipermeable membrane |
US4256782A (en) * | 1976-06-04 | 1981-03-17 | Kansai Paint Co., Ltd. | Treating method for giving hydrophilic property to the surface of hydrophobic polymer substrate |
US4250029A (en) * | 1977-04-25 | 1981-02-10 | Rohm And Haas Company | Coated membranes |
GB2011804A (en) * | 1977-11-25 | 1979-07-18 | Uop Inc | Gas Separation Membranes and Process for the Preparation Thereof |
US4340479B1 (en) * | 1978-05-15 | 1996-08-27 | Pall Corp | Process for preparing hydrophilic polyamide membrane filter media and product |
US4340479A (en) * | 1978-05-15 | 1982-07-20 | Pall Corporation | Process for preparing hydrophilic polyamide membrane filter media and product |
US4242208A (en) * | 1978-05-22 | 1980-12-30 | Teijin Limited | Semipermeable composite membrane and process for preparation thereof |
US4302336A (en) * | 1978-09-06 | 1981-11-24 | Teijin Limited | Semipermeable composite membrane |
GB2035133A (en) * | 1978-09-28 | 1980-06-18 | Wafilin Bv | A modified membrane for membrane filtration |
JPS55144036A (en) * | 1979-04-27 | 1980-11-10 | Nitto Electric Ind Co Ltd | Production of hydrophilic plastic molded article |
GB2058802A (en) * | 1979-09-04 | 1981-04-15 | Celanese Corp | Hydrophilic monomer treated microporous films |
GB2058798A (en) * | 1979-09-19 | 1981-04-15 | Aligena Ag | Porous polyacrylonitrile-containing membranes siutable for use in ultrafiltration and their preparation |
GB2076392A (en) * | 1980-04-28 | 1981-12-02 | Secr Defence | Porous glass membrane |
GB2075416A (en) * | 1980-05-02 | 1981-11-18 | Bend Res Inc | Reverse osmosis composite hollow fiber membrane |
US4383923A (en) * | 1980-07-02 | 1983-05-17 | Bayer Aktiengesellschaft | Semipermeable membranes |
US4359510A (en) * | 1980-07-31 | 1982-11-16 | Celanese Corporation | Hydrophilic polymer coated microporous membranes capable of use as a battery separator |
EP0061782A2 (en) * | 1981-03-31 | 1982-10-06 | Nitto Electric Industrial Co., Ltd. | Composite semipermeable membrane and process for preparation thereof |
GB2103536A (en) * | 1981-06-24 | 1983-02-23 | Asahi Chemical Ind | Composite hydrophilic semipermeable membrane |
EP0094050A2 (en) * | 1982-05-06 | 1983-11-16 | Teijin Limited | Ultrathin film, process for production thereof, and use thereof for concentrating a specified gas in a gaseous mixture |
EP0100552A2 (en) * | 1982-08-02 | 1984-02-15 | Mitsubishi Rayon Co., Ltd. | Hydrophilized membrane of porous hydrophobic material and process of producing same |
EP0107336A1 (en) * | 1982-09-30 | 1984-05-02 | Uniroyal, Inc. | Preparation of P-nitrosodiphenylamine |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0399568A2 (en) * | 1985-01-10 | 1990-11-28 | TERUMO KABUSHIKI KAISHA trading as TERUMO CORPORATION | Hydrophilic porous membrane |
EP0399568A3 (en) * | 1985-01-10 | 1992-04-15 | TERUMO KABUSHIKI KAISHA trading as TERUMO CORPORATION | Hydrophilic porous membrane |
EP0204337A2 (en) * | 1985-06-05 | 1986-12-10 | Ube Industries, Ltd. | Porous hollow fiber |
EP0204337A3 (en) * | 1985-06-05 | 1987-01-28 | Ube Industries, Ltd. | Porous hollow fiber |
US4774132A (en) * | 1986-05-01 | 1988-09-27 | Pall Corporation | Polyvinylidene difluoride structure |
US4855163A (en) * | 1986-05-01 | 1989-08-08 | Pall Corporation | Method of making polyvinylidene difluoride structure |
US5019261A (en) * | 1986-08-27 | 1991-05-28 | Dow Danmark A/S | Permeable, porous polymeric membrane with hydrophilic character methods for preparing said membranes and their use |
US5091086A (en) * | 1986-08-27 | 1992-02-25 | Danisco A/S | Permeable, porous polymeric membrane with hydrophilic character, methods for preparing said membranes and their use |
EP0440858A1 (en) * | 1988-08-11 | 1991-08-14 | Mitsubishi Gas Chemical Company, Inc. | Humidity sensor |
WO1990011120A1 (en) * | 1989-03-18 | 1990-10-04 | International Applied Sciences, Inc. | Ultrafiltration membrane |
US5136274A (en) * | 1990-02-01 | 1992-08-04 | Mitsubishi Gas Chemical Company, Inc. | Humidity sensor |
WO1994009063A1 (en) * | 1992-10-21 | 1994-04-28 | Cornell Research Foundation, Inc. | Pore-size selective modification of porous materials |
WO1995001219A1 (en) * | 1993-06-29 | 1995-01-12 | Minnesota Mining And Manufacturing Company | Interfacial polymerization in a porous substrate and substrates functionalized with photochemical groups |
US5627217A (en) * | 1993-06-29 | 1997-05-06 | Minnesota Mining And Manufacturing Company | Interfacial polymerization in a porous substrate and substrates functionalized with photochemical groups |
AU687842B2 (en) * | 1993-06-29 | 1998-03-05 | Mcmaster University | Interfacial polymerization in a porous substrate and substrates functionalized with photochemical groups |
NL1020950C2 (en) * | 2002-06-24 | 2003-12-30 | Saehan Ind Inc | Composite polyamide reverse osmosis membrane for desalination of seawater, comprises polyamide layer and hydrophilic coating of polyfunctional epoxy compound, formed sequentially on microporous support |
GB2390042A (en) * | 2002-06-24 | 2003-12-31 | Saehan Ind Inc | Membrane comprising cross-linked polyfunctional epoxy compound |
FR2843045A1 (en) * | 2002-06-24 | 2004-02-06 | Saehan Ind Inc | Composite polyamide reverse osmosis membrane for desalination of seawater, comprises polyamide layer and hydrophilic coating of polyfunctional epoxy compound, formed sequentially on microporous support |
GB2390042B (en) * | 2002-06-24 | 2006-11-15 | Saehan Ind Inc | Selective membrane having a high fouling resistance |
CN117654288A (en) * | 2024-02-01 | 2024-03-08 | 蓝星(杭州)膜工业有限公司 | Composite membrane and preparation method and application thereof |
CN117654288B (en) * | 2024-02-01 | 2024-04-19 | 蓝星(杭州)膜工业有限公司 | Composite membrane and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
EP0156840A4 (en) | 1987-07-08 |
EP0156840A1 (en) | 1985-10-09 |
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