JPS59179103A - Composite semipermeable membrane and its manufacture - Google Patents
Composite semipermeable membrane and its manufactureInfo
- Publication number
- JPS59179103A JPS59179103A JP58052515A JP5251583A JPS59179103A JP S59179103 A JPS59179103 A JP S59179103A JP 58052515 A JP58052515 A JP 58052515A JP 5251583 A JP5251583 A JP 5251583A JP S59179103 A JPS59179103 A JP S59179103A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- diamine
- crosslinking
- composite
- composite semipermeable
- 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.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000012982 microporous membrane Substances 0.000 claims abstract description 17
- 150000004985 diamines Chemical class 0.000 claims abstract description 16
- 239000010409 thin film Substances 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims 1
- -1 aliphatic secondary amine Chemical class 0.000 abstract description 20
- 238000004132 cross linking Methods 0.000 abstract description 15
- 125000001931 aliphatic group Chemical group 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 125000003118 aryl group Chemical group 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 238000011033 desalting Methods 0.000 abstract description 3
- 150000004820 halides Chemical class 0.000 abstract description 3
- 229920000620 organic polymer Polymers 0.000 abstract description 3
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 150000003141 primary amines Chemical class 0.000 abstract description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract 1
- 125000004427 diamine group Chemical group 0.000 abstract 1
- 125000002128 sulfonyl halide group Chemical group 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 21
- 239000010408 film Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 13
- 238000001223 reverse osmosis Methods 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 229920002492 poly(sulfone) Polymers 0.000 description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000004953 Aliphatic polyamide Substances 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 229920003231 aliphatic polyamide Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920006037 cross link polymer Polymers 0.000 description 7
- 239000000645 desinfectant Substances 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 229920013730 reactive polymer Polymers 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000008101 lactose Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SWRRWODUBVHJBC-UHFFFAOYSA-N 1-(2-piperidin-1-ylpropan-2-yl)piperidine Chemical compound N1(CCCCC1)C(C)(C)N1CCCCC1 SWRRWODUBVHJBC-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920004934 Dacron® Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 239000003513 alkali Substances 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
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
Abstract
Description
【発明の詳細な説明】
技術分野
本発明は複合半透膜に関するものであり、更に詳しくは
優れた手透膜性能を具備し、且つ耐酸化性にも優れた複
合半透膜に関するものでちる。[Detailed Description of the Invention] Technical Field The present invention relates to a composite semipermeable membrane, and more particularly to a composite semipermeable membrane that has excellent hand permeability and oxidation resistance. .
背景技術
当初、ロウブ（Ｌｏｅｂ）およびスリラージャン（Ｓｏ
ｕｒｉｒａｊａｎ）らによ郵開発された酢酸セルロース
系逆浸透膜が、そのすぐれた基本性能と製造の容易さの
故に広く用いられてきた。Background technology Initially, Loeb and Thriller Jean (So
A cellulose acetate-based reverse osmosis membrane developed by J. Urirajan et al. has been widely used because of its excellent basic performance and ease of manufacture.
一方、その欠点を複うために合成高分子による新しい逆
浸透膜例えば全芳香族ポリアミドによる逆浸透膜も提案
された。On the other hand, in order to overcome these drawbacks, new reverse osmosis membranes made of synthetic polymers, such as reverse osmosis membranes made of wholly aromatic polyamides, have been proposed.
これらの膜はいずれも相分離法といわれる方法でｖＩ４
整される不均質膜と呼ばれるものであり、分離に関与す
る均質層と膜の強度保持等に関係する多孔質層とが同一
素材からなっていた。All of these membranes are made with vI4 using a method called phase separation method.
The homogeneous layer involved in separation and the porous layer involved in maintaining membrane strength were made of the same material.
ところが、予め多孔質層を別素材で調整しておき、その
上で親水性反応性ポリマーと架橋剤とを反応せしめ架橋
化した薄膜状の分離層をその上に形成せしめる方法が提
案され、基本性能の向上に加えて、加水分解性、微生物
分解性、圧密性および乾燥保存性等に大幅な改善を行い
得ることが示唆された。ノース・スター研究所では、か
かる親水性、反応性ポリマーとしてポリエチレンイミン
を、又架橋剤としてイソフタル酸クロライドやトルイレ
ンジインシアネートの如きポリ酸クロライド又はポリイ
ンシアネートを用いて上記改善が可能なことを実証した
が、かくして得られた膜は原料のポリエチレンイミンの
アミン含量が大きすぎ仝ために１形成される架橋層が非
常に弱くなり、スパイラルモジュールの形態にするには
大きな問題が存在することが判明した。一方、ユニバー
サル・オイル・プロダクツ社では、上記の如き欠点を改
善するためにアミン変性ポリエピクロルヒドリンを親水
性反応性ポリマーとして用いることにより、上記の欠点
を改善することに成功したが、原料のエビアミンの製造
が難しいために透水量の犬なる膜が作りにくいこと、及
び長期耐久性に問題のあることが最近明らかとなってき
た。However, a method has been proposed in which a porous layer is prepared in advance using a different material, and then a hydrophilic reactive polymer is reacted with a crosslinking agent to form a crosslinked thin film-like separation layer on top of the porous layer. In addition to improved performance, it was suggested that significant improvements could be made in hydrolyzability, microbial degradability, compactability, dry storage stability, etc. North Star Laboratories has demonstrated that the above improvements are possible using polyethyleneimine as the hydrophilic, reactive polymer and polyacid chloride or polyincyanate such as isophthalic acid chloride or toluylene diincyanate as the crosslinking agent. However, in the membrane thus obtained, the amine content of the raw material polyethyleneimine was too high, resulting in a very weak crosslinked layer, and it was found that there was a major problem in making it into a spiral module form. did. On the other hand, Universal Oil Products Co., Ltd. succeeded in improving the above drawbacks by using amine-modified polyepichlorohydrin as a hydrophilic reactive polymer. It has recently become clear that it is difficult to produce membranes with high water permeability due to manufacturing difficulties, and that there are problems with long-term durability.
また最近、フィルムチック社（発明者、ジョン・イー・
カドツテ）によシ、メタフェニレンシアミン、パラフエ
ニレンンアミン等の低分子芳香族アミンを微多孔膜上に
て、トリメシン酸クロライドの如き芳香族ポリ酸ノ・２
イドで架橋せしめてなる複合膜が提案され（特開昭５５
−１４７１０６号公報参照）、極めて良好々脱塩性能と
耐酸化性を有するものであるとの開示力Ｉなされた。Also recently, Filmtic Co., Ltd. (inventor, John E.
Aromatic polyacids such as trimesic acid chloride, etc.
A composite membrane cross-linked with hydrogen was proposed (Japanese Unexamined Patent Application Publication No. 1983-1999).
(Refer to Japanese Patent Publication No. 147106), it has been disclosed that it has extremely good desalination performance and oxidation resistance.
しかしながら本発明者による検討の結果、この膜の耐酸
化性も短期的なものにすぎず、本発明の比較例に示すよ
うに４〜ｓ ｐｐｍの活性塩素共存下での連続逆浸透テ
ストに於てはわず力・１５０時間経過した時点から脱塩
率の低下及び透水量の増加という典聾的な膜劣化現象を
呈し始めることが明確にｌν九。However, as a result of studies by the present inventors, the oxidation resistance of this membrane is only short-term, and as shown in the comparative example of the present invention, continuous reverse osmosis tests in the coexistence of 4 to s ppm active chlorine It is clear that after 150 hours, typical membrane deterioration phenomena such as a decrease in salt removal rate and an increase in water permeation rate begin to occur.
また先に、二級アミノ基のみを有するポリアミンを芳香
族ポリ酸ノ・ライドで架橋して得られる耐酸化性のすぐ
れた複合膜が提案されている（特開昭５５−１３９８０
２号公報参照）がこの膜は一般に脱塩率が上りに＜＜、
塩化マグネシウムなどの大きな溶質の分離においてさえ
その塩排除率は高々９０〜９５％程度のものしか得られ
ず、しかも、ショ糖の分離においてもその排除率は９５
％を越えがたいという難点を有していた。Furthermore, a composite membrane with excellent oxidation resistance obtained by crosslinking a polyamine having only secondary amino groups with an aromatic polyacid has been proposed (Japanese Patent Laid-Open No. 55-13980).
(Refer to Publication No. 2) However, this membrane generally has a high salt removal rate.
Even in the separation of large solutes such as magnesium chloride, the salt rejection rate is only about 90-95%, and even in the separation of sucrose, the rejection rate is 95%.
The problem was that it was difficult to exceed %.
発明の開示
本発明者は、従来提案されてきたこれらの膜の欠点に鑑
みこれらを解決すべく鋭意検討した結果、驚くべきこと
に従来耐酸化性が悪いとされてきた脂肪族第１級アミド
結合を有するポリアミドからも酸成分を適切に選択する
ことにより、従来公知の半透膜特に前記カドツテらの発
明したｗＸＫ比べても格段にすぐれた耐酸化性を有しか
つ高い脱塩性能をも有する高性能半透膜が得られること
を見い出し提案した（特開昭５８−２４３０３号）。し
かるにその後の検討により、上記複合膜を作成するに際
してジアミン成分として脂肪族１級ジアミンと脂肪族２
級ジアミンとを特定のモル比で混合して用い架橋反応を
行うことにより、脱塩性能を維持しつつ透水量を飛躍的
に向上させうろことが判明し、本発明を完成するに至っ
た。DISCLOSURE OF THE INVENTION In view of the drawbacks of these previously proposed membranes, the inventors of the present invention have conducted intensive studies to solve these problems, and have surprisingly found that aliphatic primary amides, which have been conventionally considered to have poor oxidation resistance, have been developed. By appropriately selecting an acid component from a polyamide having bonds, it is possible to obtain a membrane that has far superior oxidation resistance and high desalting performance compared to conventionally known semipermeable membranes, especially the wXK invented by Kadotsute et al. It was discovered and proposed that a high-performance semipermeable membrane having the following properties can be obtained (Japanese Patent Application Laid-Open No. 58-24303). However, subsequent studies revealed that aliphatic primary diamine and aliphatic secondary diamine were used as diamine components when creating the above composite membrane.
It has been found that water permeation can be dramatically improved while maintaining desalting performance by mixing the same with a specific molar ratio of chlorine-based diamine and carrying out a crosslinking reaction, leading to the completion of the present invention.
すなわち、本発明は
（１） 多孔膜、及びその上に形成された下記式ＣＩ
）で表わされる構成単位〔Ａ〕、及び上記式［１）中の
Ｒ１及びＲ２を共に水素原子とした場合の構成単位〔Ｂ
）を有し、構成単位ＣＢ）を上記〔Ａ〕とＣＢ）全体の
２０モルチ以上５０モルチ未満含有して成る架橋薄膜と
からなる複合半透膜、及び
ミノ中に占める割合が２０モルチ以上５ｏモで表わされ
る架橋剤と接触させい必要に応じて加熱処理することを
特徴とする複合半透膜の製造方法
である。That is, the present invention provides (1) a porous film, and a film of the following formula CI formed thereon.
), and the structural unit [B] when both R1 and R2 in the above formula [1] are hydrogen atoms.
), and a composite semipermeable membrane consisting of the above [A] and a crosslinked thin film containing the structural unit CB) from 20 to less than 50 mole of the total CB), and a composite semipermeable membrane having a proportion of 20 to less than 50 mole in the total amount of CB). This is a method for producing a composite semipermeable membrane, which is characterized by contacting with a crosslinking agent represented by (a) and heat-treating as necessary.
本発明の複合半透膜は後述する微多孔膜上に構成単位（
Ａ）及び構成単位〔Ｂ〕を、〔Ｂ〕が上記式全体の２０
モルチ以上５０モルチ未満になる割合で有する架橋高分
子薄膜を設けたものであるが、式ＣＤ中、ＲＩＩＲ９は
ヒドロキシル基を有してもよい炭素原子数１〜３のアル
キル基でありうるが、好ましくは−ＣＨ，、−Ｃ，Ｈ，
、−Ｃ２Ｈ４ｏＨ，−ｃ、Ｈ７であり特に−０２穐 で
ある。The composite semipermeable membrane of the present invention has a structural unit (
A) and the structural unit [B], [B] is 20 of the entire above formula.
A crosslinked polymer thin film having a ratio of molti to less than 50 molti is provided, but in the formula CD, RIIR9 can be an alkyl group having 1 to 3 carbon atoms which may have a hydroxyl group, Preferably -CH, -C,H,
, -C2H4oH, -c, H7, especially -02 Aki.
また、Ｒ１とＲ３は互いに結合し、それらが結合してい
る２個の窒素原子及びＲ２と共にメチル基で置換されて
いてもよいピペラジル基を形成し得、好ましくは非置換
のピペラジル基を形成するものである。Further, R1 and R3 may be bonded to each other to form a piperazyl group which may be substituted with a methyl group together with the two nitrogen atoms to which they are bonded and R2, and preferably form an unsubstituted piperazyl group. It is something.
また、鳥は酸素原子を有していてもよい炭素原子数２〜
１５好ましくは２〜１４の脂肪族炭化水素残基であるが
、ここで脂肪族とは直鎖及び分岐状脂肪族でもよく、ま
ｆｃ環状脂肪族でもよい。In addition, birds have 2 to 2 carbon atoms, which may have an oxygen atom.
15, preferably 2 to 14 aliphatic hydrocarbon residues, but aliphatic herein may be straight-chain or branched aliphatic, or may be cycloaliphatic.
しかして、Ｒ２としては、−（Ｊ１２ＣＨ２−、−ＣＨ
，・ＣＩ、・Ｃ馴、 −（Ｅ）−、−ＣＨ，舎Ｃ−ぐＸ
）０１Ｈ，−、舎Ｃ）Ｔ、Ｘ工ｘ’ｔ’ ４７）。Therefore, as R2, -(J12CH2-, -CH
,・CI,・C familiar, -(E)-, -CH,shaC-guX
) 01H, -, building C) T, X engineering x't' 47).
Ａｒとしては縮合型又は非縮合型の芳香族炭化Ｘはカル
ボニル結合又はスルボニル結合であるが、カルボニル結
合が好ましい。As for Ar, the condensed or non-condensed aromatic carbide X is a carbonyl bond or a sulfonyl bond, and a carbonyl bond is preferable.
Ｙはその少なくとも一部が直接結合であって架橋点とな
ることが必要であり、その他のものできる。ここでＭけ
水素原子、アルカリ金属、アルカリ土類金属又はアンモ
ニウム基であるが、中でも水素原子又はアルカリ金属が
好ましい。At least a portion of Y must be a direct bond and serve as a crosslinking point, and other types can be used. Here, M is a hydrogen atom, an alkali metal, an alkaline earth metal, or an ammonium group, and a hydrogen atom or an alkali metal is particularly preferred.
Ｙけ好ｆＬ（はその３０〜９０％、特に好ましくは５０
〜７０％が直接結合であって架橋に関与していることが
好ましく、出来ればすべて架橋に関与していることが好
ましい。Y value fL (is 30 to 90% of that, particularly preferably 50
Preferably, ~70% of the bond is a direct bond and is involved in crosslinking, preferably all of it is involved in crosslinking.
前記架橋高分子薄膜は、上記の如き構成からなる式ＣＩ
）で表わされる構成単位〔Ａ〕を少なくとも５０モル係
含有し、がっ式〔［〕中のＲ１と鳥とが同時に水素原子
である様な構成単位〔Ｂ〕を２０モルチ以上５０モルチ
未満含有することが必要である。The crosslinked polymer thin film has a formula CI having the above structure.
) contains at least 50 moles of the structural unit [A], and contains 20 moles or more and less than 50 moles of the constituent unit [B] in which R1 and bird in the formula [[] are hydrogen atoms at the same time. It is necessary to.
かかる第一級アミン基のみを含肩する脂肪族ジアミンに
由来する構成単位を上記割合で含有する場合には、耐酸
化性及び高塩排除性という本発明の効果を損なわず、高
い透水性を発現できる点で従来技術に比べ格段に有利で
ある。When containing structural units derived from aliphatic diamines containing only such primary amine groups in the above ratio, high water permeability can be achieved without impairing the effects of the present invention, which are oxidation resistance and high salt exclusion properties. It is much more advantageous than the conventional technology in that it can be expressed.
本発明の架橋高分子薄膜は更に保護膜で覆ゎｈることか
でき、保護膜としてはポリビニルピロリドン、ポリビニ
ルメチルエーテルの如き水溶性ポリマーの膜又は水不溶
性のポリビニルアルコール膜又は多孔性脂肪族ポリアミ
ド膜を挙げることができる。中でも水不溶性ポリビニル
アルコール膜又は多孔性脂肪族ポリアミド膜が好ましく
、水不溶性ポリビニルアルコール膜としてはポリビニル
アルコールを熱ゲル化したもの又はグルタルアルデヒド
、ホルマリン、グリオキザール又はそれらの亜硫酸付加
物で架橋化したものが挙げられ、多孔性脂肪族ポリアミ
ド膜としてはポリ−６−カプロアミド、ポリヘキサメチ
ルアジボアミドの如き脂肪族ポリアミドの多孔質膜が挙
げられる。The crosslinked polymer thin film of the present invention can be further covered with a protective film, and the protective film may be a film of a water-soluble polymer such as polyvinylpyrrolidone or polyvinyl methyl ether, a water-insoluble polyvinyl alcohol film, or a porous aliphatic polyamide film. Membranes can be mentioned. Among these, water-insoluble polyvinyl alcohol membranes or porous aliphatic polyamide membranes are preferred, and the water-insoluble polyvinyl alcohol membranes include polyvinyl alcohol that has been thermally gelled or cross-linked with glutaraldehyde, formalin, glyoxal, or sulfite adducts thereof. Examples of porous aliphatic polyamide membranes include porous membranes of aliphatic polyamides such as poly-6-caproamide and polyhexamethylaziboamide.
本発明における支持体としての微多孔膜としては、ガラ
ス質多孔材、焼結金属、セラミックスとかセルロースエ
ステル、ポリスチレン、ビニルブチラール、ポリスルホ
ン、垣化ビニル等の有機ポリマーが挙げられる。Examples of the microporous membrane used as a support in the present invention include porous glass materials, sintered metals, ceramics, and organic polymers such as cellulose esters, polystyrene, vinyl butyral, polysulfone, and vinyl fences.
ポリスルホン膜は本発明の微多孔膜として特にすぐれた
性能を有するものであり、ポリビニルクロライドも又有
効である。ポリスルホン微多孔膜の製造法は、米国塩水
局レポート（ｏｓｗＲｅＰｏｒｔ ） ノに３５９にも
記載されている。Polysulfone membranes have particularly excellent performance as microporous membranes of the present invention, and polyvinyl chloride is also effective. A method for producing microporous polysulfone membranes is also described in US Salt Water Service Report (oswRePort) No. 359.
かかる膜は表面の孔の大きさが一般に約１００〜１００
０オングストロームの間にあるものが好ましいが、これ
に限′られるものではなく、最終の複合膜の用途などに
応じて、表面の孔の太きさは５０Ｘ〜５ｏｏｏＸの間で
変化しうる。これらの微多孔膜は対称構造でも非対称構
造でも使用できるが、望ましくは非対称構造のものがよ
い。しかしながら、これらの微多孔膜は膜定数が１ｏ’
ｆ／ｄｉ・式・ａｔｍ以下の場合は透水量が低くなりす
ぎ、また１ｒ／−・就・ａｔｍ以上の場合は脱塩率が極
めて低くなりやすく好ましくない。Such membranes generally have a surface pore size of about 100 to 100
The diameter of the surface pores is preferably between 0 angstroms, but is not limited to this, and depending on the final use of the composite membrane, etc., the diameter of the surface pores can vary between 50X and 500X. These microporous membranes can be used with either a symmetrical or asymmetrical structure, but preferably an asymmetrical structure. However, these microporous membranes have a membrane constant of 1o'
If it is less than f/di.atm, the water permeability will be too low, and if it is more than 1r/-.atm, the desalination rate will tend to be extremely low, which is not preferable.
従って好ましい膜定数としては１〜】０ タ／ｌ’ｒｌ
・ｗ・ａｔｍ、特に好ましくは１０’ 〜］０−３５＋
／−・冠・ａｔｍの範囲のものが最も好ましい結果を与
える。なお、ここでいう膜定数とけ、２ｈ ／ ａ／１
の圧力下での純水の透過４Ｂを表わす値で、単位はｆ
／ｃＴＡ −ｓｃ φａ ｔｍである。Therefore, the preferred film constant is 1~]0 ta/l'rl
・w・atm, particularly preferably 10'~]0-35+
The range of /-・cap・atm gives the most favorable results. In addition, the film constant here is 2h/a/1
The value represents the permeation of pure water under the pressure of 4B, and the unit is f
/cTA-sc φa tm.
このような微多孔膜は、裏側を織布又は不織布なとで補
強した形態で使用するのめ；好プしい。Such a microporous membrane is preferably used with the back side reinforced with a woven or nonwoven fabric.
かかる織布又は不織布としては、ポリエチレンテレフタ
シー１１ポリスチレン、ポリプロピレン、ナイロン又は
塩化ビニル等によるものが好適表側として挙げられる。Preferred examples of such woven or nonwoven fabrics include those made of polyethylene terephthalate 11 polystyrene, polypropylene, nylon, vinyl chloride, or the like.
かくして本発明の：顔合半透膜は厚さ４０μｍ〜５１１
１１１１位の微多孔膜、竹に有機ポリマー微多孔膜の場
合は厚さ４０μｍ〜７０μｊｎの微多孔膜の上Ｋ。Thus, the facial semipermeable membrane of the present invention has a thickness of 40 μm to 511 μm.
1111th place microporous membrane, in the case of bamboo and organic polymer microporous membrane, the upper K of the microporous membrane with a thickness of 40 μm to 70 μjn.
厚さ２００Ｘ〜１５００Ｘの前記架橋高分子薄膜を設け
、必要に応じ更にその上に厚さ０．１μｍ〜１μｍの保
護膜を設けたものである。The crosslinked polymer thin film with a thickness of 200X to 1500X is provided, and if necessary, a protective film with a thickness of 0.1 μm to 1 μm is further provided thereon.
本発明の複合膜は次式［ＴＩＴ）
ＲｌＮＨ−Ｒ２−ＮＨＲ３−−−−−−−−＝−ＣＩ旧
で表わされる脂肪族ジアミンを少なくとも５０モルφ及
び式： Ｈ２Ｎ−Ｒ，−ＮＨ２で表わされる脂肪族１級
ジアミノをＭ４ 記ジアミン〔■〕に対して２０モルチ
以上５０モル襲未満混合してなるジアミン混合物の水溶
液を微多孔膜上にて次式（ＩＶ）−Ｙ
で表わされる芳香族ポリ酸ハライドから主として成る架
橋剤と架橋反応せしめて得られるものである。The composite membrane of the present invention contains at least 50 moles φ of an aliphatic diamine represented by the following formula [TIT] An aqueous solution of a diamine mixture prepared by mixing 20 moles or more and less than 50 moles of aliphatic primary diamino with respect to the M4 diamine [■] was applied to an aromatic compound represented by the following formula (IV)-Y on a microporous membrane. It is obtained by a crosslinking reaction with a crosslinking agent mainly consisting of polyacid halide.
上記式（ＩＴ）で表わされる本発明に使用される脂肪族
ジアミンとしては溶媒、好捷しくけ水又は低級アルコー
ルに可溶性のものが用いられる。As the aliphatic diamine represented by the above formula (IT) used in the present invention, one that is soluble in a solvent, a hydrophobic solution, or a lower alcohol is used.
その様なジアミンを例示すると次の如くである。Examples of such diamines are as follows.
（１） 直鎖状脂肪族２級ジアミン
Ｃ馬ＮＨＣＨ２ＣＨ，ＮＨＣＨＪ
Ｃ，Ｉ（６ＮＨＣＨ２Ｃ１２ＮＨＣ２Ｈ５ＨＯＣＨ，Ｃ
Ｈ，ＮＨＣＨ２ＣＩ、ＮＨＣＨ２ＣＩ（，０Ｈ（２）
環状脂肪族二級ジアミン
ジピペリジルプロパン（ｎｗ３→ＣＨ２÷３ぺＺＮＨ）
これらのジアミンの内で特眞好ましいものはピペラジン
である。また、核２級アミンと組合せて用いられるーＲ
′）アミンとしては次の様な化合物を例示することがで
きる。(1) Linear aliphatic secondary diamine C NHCH2CH,NHCHJ C,I (6NHCH2C12NHC2H5HOCH,C
H, NHCH2CI, NHCH2CI(,0H(2)
Cycloaliphatic secondary diamine dipiperidylpropane (nw3→CH2÷3peZNH)
Particularly preferred among these diamines is piperazine. Also used in combination with nuclear secondary amines -R
') As the amine, the following compounds can be exemplified.
Ｈ２ＮＣＨ２ＣＨ２ＮＨ２，Ｈ２ＮＣＨ２ＣＨ２ＮＨ２
ＮＨ。H2NCH2CH2NH2, H2NCH2CH2NH2
N.H.
Ｈ２ＮモＣＨ２＋ＮＪ（２，Ｈ２Ｎ（−ＣＨ２−） Ｎ
Ｈ２Ｈ２Ｎ（−Ｃ）Ｔ２−）−ＮＨ２，Ｈ２Ｎ÷ＣＨ，
＋ＮＨ２Ｈ２Ｎ（−ＣＨ，−） ＮＨ２，Ｈ，Ｎ−１−
Ｃ２塊ＮＨＣジ
Ｈ２Ｎ＋ ＣＩ（、−） ＮＨ２、’ Ｈ２Ｎ（−Ｃ２
塊ＮＨＣ（ＣＭＪ−）−ＮＨＣＨ２ＣＭ２ＮＨ２，（Ｃ
２塊＋ＮＨＣＨ２ＣＨ２ＮＨ。H2Nmo CH2+NJ(2,H2N(-CH2-) N
H2H2N(-C)T2-)-NH2, H2N÷CH,
+NH2H2N(-CH,-) NH2,H,N-1-
C2 lump NHC diH2N+ CI(,-) NH2,' H2N(-C2
Mass NHC(CMJ-)-NHCH2CM2NH2, (C
2 lumps + NHCH2CH2NH.
ＨＯＣＨ２ＣＨ２ＮＨＣＨ２ＣＨ２ＮＨ，、喝？ＨＣＨ
，ＮＨＣＩｆ、ＣＩ（２Ｎ’ｆ（２Ｈ
馬Ｎ舎Ｏ舎隅１ ”２ＮＣＨ２不Ｙ←咀冊２これらの脂
肪族ジアミンのうちで特に好ましいものはエチレンジア
ミン及びシクロヘキサンジアミンである。上記の脂肪族
ジアミンは単独でも或いは２種類以上組合せて用いても
構わない。HOCH2CH2NHCH2CH2NH,, cheer? HCH
,NHCIf,CI(2N'f(2H) They may be used alone or in combination of two or more.
前記のジアミン化合物を用いて本発明の複合膜を得るた
めには、これらのアミン化合物の溶液を後述の微多孔膜
上に塗布（ａｐｐｌｙ） ｌ−なければならない。この
塗布方法としでは浸漬法、ロールコーティング法、ウィ
ックコーティング法、等如何なる方法でも良いが、塗布
されたアミン化合物層の厚みが０．０１〜２μ、好咬し
くけ０．０２〜１μ、更に好ましくは０．０５〜０．７
μとなるように塗布条件をコントロールすべきである。In order to obtain the composite membrane of the present invention using the diamine compounds described above, a solution of these amine compounds must be applied onto the microporous membrane described below. The coating method may be any method such as dipping, roll coating, wick coating, etc., but the thickness of the applied amine compound layer is preferably 0.01 to 2μ, more preferably 0.02 to 1μ. is 0.05-0.7
Coating conditions should be controlled so that μ.
該アミン化合物層の塗布層が上記下限値（すなわち０，
０１μ）よりも小さいと、最終的に得られる複１合膜の
活性層が薄くなりすぎ機絨的強度が低下する。ま尼該Ｍ
布厚が２μよりも厚いと活性層の膜厚が厚くなりすさ゛
、複合膜の透水性を損ねる傾向が大きくなる。かかるジ
アミンは可溶性でなければならないが、特に水、メタノ
ール、エタノール、イソプロパツール、メチルセロンル
ブ、ジオキザン或いはテトラヒドロフラン又はこれら２
ｆ１１１以上の混合溶媒に０．１ｆ／１０Ｇ−以上、好
畜゛シ＜はｏ、５ｆ／１０〇−以上可溶である仁とが好
ましい。特に水に対して０．１ ｆ／ｌ ｏ Ｏ−以上
、更には０．５ｆ７’ｘｏｏ−以上の溶解性を崩するも
のが好ましい。The coating layer of the amine compound layer has the above lower limit value (i.e. 0,
If it is smaller than 01 μ), the active layer of the composite film finally obtained will be too thin and the mechanical strength will be reduced. M
If the fabric thickness is thicker than 2 μm, the active layer becomes thicker and the water permeability of the composite membrane tends to be impaired. Such diamines must be soluble, especially in water, methanol, ethanol, isopropanol, methylceronelube, dioxane or tetrahydrofuran or the like.
It is preferable that it is soluble in a mixed solvent of f111 or more at 0.1 f/10 G- or more, animal-loving, or 5 f/100- or more. Particularly preferred are those that have a solubility in water of 0.1 f/l o O- or more, more preferably 0.5 f7'xoo- or more.
これらの溶媒群より選ばれた少なくとも１種の溶媒（特
に好ましくは水）に少なくとも０．１チ溶解せしめた本
発明のジアミン化合物溶液は、微多孔性を有する前記微
多孔膜に塗布又は含浸せしめられる。The diamine compound solution of the present invention, which is dissolved at least 0.1% in at least one solvent selected from these solvent groups (particularly preferably water), is applied or impregnated onto the microporous membrane having microporosity. It will be done.
前述のジアミンが塗布された微多孔膜は、該アミノ基と
反応してカンボンアミド結合又はスルホンアミド結合の
いずれかを形成しうる官能基を含有する前述の式（ＩＶ
）で表わされる芳香族酸ハライドを用いる架橋処理に付
され、微多孔Ｍ上にて前述のジアミンが架橋薄膜化され
る。The microporous membrane coated with the diamine described above contains a functional group capable of reacting with the amino group to form either a cambonamide bond or a sulfonamide bond.
) The diamine described above is crosslinked into a thin film on the microporous M.
本発明に用いうる架橋剤としての多官能性化合物が含有
する官能基はカルボニルノ・ライド基（Ｃ，ＯＺ） 、
スルホニル７＼ライド基（−ＳＯ，Ｚ）のいずれかであ
り、工分子中にこれら官能基を３個含ひものでるる。％
に好適な官能基は酸クロライド基及びスルホニルクロラ
イド基である。これら１分子中に存在する複数個の官能
基は同一種のものであってもよく或いは互に異なるもの
であってもかまわない。また、多官能性化合物としては
芳香族性多官能性化合物が有効でおる。The functional groups contained in the polyfunctional compound as a crosslinking agent that can be used in the present invention are carbonylno-ride groups (C, OZ),
It is either a sulfonyl 7\ride group (-SO, Z), and contains three of these functional groups in the engineering molecule. %
Suitable functional groups are acid chloride groups and sulfonyl chloride groups. The plurality of functional groups present in one molecule may be of the same type or may be different from each other. Moreover, aromatic polyfunctional compounds are effective as polyfunctional compounds.
これらの架橋剤の具体例としては次のものが挙げられる
。Specific examples of these crosslinking agents include the following.
上記した芳香族の多官能性化合物はそれぞれ単独で用い
るととができ或いは２種又はそれ以上混合して用いＣも
よい。The above-mentioned aromatic polyfunctional compounds can be used alone or in combination of two or more.
本発明の複合膜を得るためには前述のジアミンを微多孔
膜上にて上記した多官能性化合物の溶液と接触させるこ
とにより行うことができる。The composite membrane of the present invention can be obtained by bringing the diamine described above into contact with a solution of the polyfunctional compound described above on the microporous membrane.
多官能性化合物の溶解に使用する溶媒は、該ポリアミン
化合物及び基材物質を実質的に溶解しないものであり、
例えば、ｎ−ヘキサン、ｎ −ヘプタン、ｎ−オクタン
、シクロヘキサン、ｈ−ノナン、ｎ−デカン等の炭化水
素系溶媒及び四塩化炭素、シフ０ロチトラクロルエタン
、トリフ０ロトリクロロエタン、ヘキサクロルエタン、
等のハロケン系炭化水素などが挙げられる。The solvent used to dissolve the polyfunctional compound is one that does not substantially dissolve the polyamine compound and the base material,
For example, hydrocarbon solvents such as n-hexane, n-heptane, n-octane, cyclohexane, h-nonane, n-decane, carbon tetrachloride, trichlorotrichloroethane, hexachloroethane,
Examples include halokene hydrocarbons such as.
溶媒中の好適な多官能性化合物濃度は該化合物の種類、
溶媒、基材、その他の条件によって変化しうるが、実験
により最適値を決定することができる。The suitable concentration of the polyfunctional compound in the solvent depends on the type of the compound,
Although it may vary depending on the solvent, substrate, and other conditions, the optimum value can be determined through experiment.
１７かし、一般的に約０．１〜５．０、好ましくは０．
５〜３．Ｏ３量％で十分効果を発揮しうる。17, generally about 0.1 to 5.0, preferably 0.1 to 5.0.
5-3. The effect can be sufficiently exhibited with O3 amount %.
多官能性化合物によるポリアミン化合物の架橋は好適に
は該ポリアミン化合物を塗布した膜を多官能性化合物の
溶液ＩＣ浸漬することによシ、膜と溶液との界面におけ
る反応により達成される。その際、この界面架橋反応を
促進させるために前述のジアミン化合物中に或いは上記
多官能性化合物溶液中に界面反応促進剤を予め含ませる
ことも可能である。その様な促進剤としては、力性アル
カリ、リン酸ソーダ、ピリジン、３級アミン、界面活性
剤、酢酸ソーダなどが好適に用いられる。Crosslinking of the polyamine compound with a polyfunctional compound is preferably achieved by immersing a membrane coated with the polyamine compound in an IC solution of the polyfunctional compound, resulting in a reaction at the interface between the membrane and the solution. At this time, in order to promote this interfacial crosslinking reaction, it is also possible to previously include an interfacial reaction accelerator in the diamine compound described above or in the solution of the polyfunctional compound. As such a promoter, alkali, sodium phosphate, pyridine, tertiary amine, surfactant, sodium acetate, etc. are suitably used.
ジアミン化合物と多官能性化合物とのかかる界面架橋反
応は室温乃至約ｉｏｏ℃、好ましくは２０〜５０℃の温
度において２秒〜ｌＯ分、好ましく、はｌＯ秒〜５分間
行うことができる。Such interfacial crosslinking reaction between the diamine compound and the polyfunctional compound can be carried out at a temperature of room temperature to about 100°C, preferably 20 to 50°C, for 2 seconds to 10 minutes, preferably 10 seconds to 5 minutes.
この界面架橋反応は膜の表面に主として集中されるよう
に行うことができる。This interfacial crosslinking reaction can be carried out so that it is mainly concentrated on the surface of the membrane.
次いで、基材に支持された膜は必要に応じて余分の多官
能性化合物溶液をｌθ秒〜２分間ドレンした後、室温に
て或いは必要に応じて４０〜１３０℃、好ましくは５０
〜８０℃の温□度において、約１〜３０分間、好ましく
は約５〜２０分間の間加熱処理する。これにより、核界
面架橋反応を完結せしめることができ且つ前記ジアミノ
化合物の水不溶性化が達成される。The membrane supported on the substrate is then heated at room temperature or at 40 to 130°C, preferably at 50°C, after draining excess polyfunctional compound solution for lθ seconds to 2 minutes, if necessary.
Heat treatment is carried out at a temperature of ~80°C for about 1 to 30 minutes, preferably about 5 to 20 minutes. Thereby, the nuclear interfacial crosslinking reaction can be completed and the diamino compound can be rendered water-insoluble.
かくして微多孔膜面上に、選択透過性を有する架橋され
た重縮合体の薄い膜を有する複合膜が得られる。In this way, a composite membrane having a thin membrane of a crosslinked polycondensate having permselectivity on the microporous membrane surface is obtained.
以上はジアミノ化合物を微多孔膜上に先に塗布する例に
ついて述べたが、逆に架橋剤を先に微多孔膜上に塗布し
、しかるのちジアミン化合物と反応せしめることもでき
る。Although the above example has been described in which the diamino compound is first applied onto the microporous membrane, it is also possible to apply the crosslinking agent onto the microporous membrane first and then react with the diamine compound.
かぐの如くして得られる本発明の複合Ｍはその優れた基
本的逆浸透性能、耐圧密性、耐熱性、耐ｐＨ性などに加
えて、極めて驚異的な耐酸化性を備えておシ、従来公知
の膜とは全く異゛なった有利性、及び特徴を有するもの
と言える。In addition to its excellent basic reverse osmosis performance, compaction resistance, heat resistance, pH resistance, etc., the composite M of the present invention obtained by Kaguno-like has extremely amazing oxidation resistance. It can be said that it has advantages and characteristics completely different from conventionally known membranes.
本発明においては、上記の如くして得られた複合半透膜
の架橋高分子薄膜の上に１更に水溶性又は水不溶性の保
護膜を設けることができる。In the present invention, a water-soluble or water-insoluble protective film can be further provided on the crosslinked polymer thin film of the composite semipermeable membrane obtained as described above.
かかる保移膜としてはポリビニルピロリドン、ポリビニ
ルメチルエーテルの如き化合物の膜が水溶性保護膜とし
て挙げることが出来、また水溶性保護膜としては水不溶
化ポリビニルアルコール膜及び多孔性脂肪族ポリアミド
膜を挙げることができる。Examples of such a storage film include films of compounds such as polyvinylpyrrolidone and polyvinyl methyl ether as water-soluble protective films, and examples of water-soluble protective films include water-insolubilized polyvinyl alcohol films and porous aliphatic polyamide films. I can do it.
ポリビニルピロリドンやポリビニルメチルエーテルの保
護膜は、水、低級アルコール、又はこれらの混合溶媒の
如き溶剤に上記ポリマーを溶解し、架橋高分子薄膜上に
当該溶液を塗布し、乾燥することにょシ得られる。A protective film of polyvinyl pyrrolidone or polyvinyl methyl ether can be obtained by dissolving the above polymer in a solvent such as water, lower alcohol, or a mixed solvent thereof, applying the solution on a crosslinked polymer thin film, and drying it. .
水不溶化ポリビニルアルコール膜はポリビニルアルコー
ルをホルマリン、クリオキサール、グルタルアルデヒド
及びこれらの亜硫酸塩から選ばれる１種以上の化合物と
共に、或いは過硫酸アンモン及び／又は過硫酸カリと共
鈍水に溶解し、架橋高分子ｉ膜上に途布した後、５０〜
１２０℃好ましくは７０〜１００℃で５分〜３０分、熱
処理することＫより、アセタール架橋又は自己ゲル化さ
せることにょシ得られる。A water-insolubilized polyvinyl alcohol film is produced by dissolving polyvinyl alcohol together with one or more compounds selected from formalin, cryoxal, glutaraldehyde, and their sulfites, or with ammonium persulfate and/or potassium persulfate in water to achieve high crosslinking. After dispersion on the molecular i membrane, 50~
Heat treatment at 120°C, preferably 70 to 100°C, for 5 to 30 minutes can result in acetal crosslinking or self-gelation.
多孔性脂肪族ポリアミド膜は、脂肪族ポリアミドを例え
ば塩化カルシウムの如き開孔剤を含有するメタノール溶
液に溶解し、当該溶液を架橋高分子薄膜上に塗布して乾
燥しポリアミド膜を形成せしめた後、水で開孔剤を抽出
して多孔化することにより得ることができる。A porous aliphatic polyamide membrane is prepared by dissolving aliphatic polyamide in a methanol solution containing a pore opening agent such as calcium chloride, applying the solution onto a crosslinked polymer thin membrane and drying it to form a polyamide membrane. , can be obtained by extracting the pore-opening agent with water to make it porous.
かくして得られた複々半透膜は種々の膜分離繰作に応用
できる。通常の膜分離繰作においては一定時間処理した
後、殺菌剤を用いて膜を洗浄するが、その際塩素系殺菌
剤が多用される。The multilayer semipermeable membrane thus obtained can be applied to various membrane separation operations. In normal membrane separation operations, after a certain period of treatment, the membrane is cleaned with a disinfectant, and chlorine-based disinfectants are often used.
高濃度の塩素系殺菌剤で処理すると従来の膜は劣化して
いたが、本発明の複合膜は耐酸化性が高いので十分使用
に耐える。更に本発明においては塩素系殺菌剤で処理し
た後、還元剤溶液で膜を処理するとと拠よシ、膜に吸着
している塩素を除去して膜の性能を更に回復するととも
有効である。Conventional membranes deteriorate when treated with high-concentration chlorine-based disinfectants, but the composite membrane of the present invention has high oxidation resistance and can be used satisfactorily. Furthermore, in the present invention, it is effective to treat the membrane with a reducing agent solution after treatment with a chlorine-based disinfectant, thereby removing chlorine adsorbed on the membrane and further recovering the performance of the membrane.
かかる殺菌方法としては、次亜塩素酸ナトリウム、次亜
塩素酸、次皿臭素酸、過酸化水素、過ホウ素酸ナトリウ
ム、ヨードホール、ナトリウムジクジルインシアヌレー
トの如き殺菌剤を０．５ ｐｐｍ 〜５０００ ｐｐｍ
含有するｐＨ４〜ｐＨ７の水溶液を用いて、ｌθ℃〜５
０℃で１０分〜１００分、膜に接触させる方法があげら
れる。Such sterilization methods include using disinfectants such as sodium hypochlorite, hypochlorous acid, subbromic acid, hydrogen peroxide, sodium perborate, iodophor, and sodium dicyanurate at concentrations of 0.5 ppm to 5000 ppm
Using an aqueous solution containing pH 4 to pH 7, lθ℃ to 5
An example is a method of contacting the membrane at 0° C. for 10 minutes to 100 minutes.
上記殺菌剤の内、塩素系殺菌剤を用いた場合に引き続き
適用される還元剤処理方法としては、チオ硫酸ナトリウ
ム、ナトリウムハイドロサルファイド、亜硫酸ソーダ、
重亜硫酸ソーダの如き還元剤を１０ ｐｐｍ〜ｓ ｏ
ｏ ｏ ｐｐｍ含有する水溶液を用いて、１０℃〜５０
℃で１０分〜１００分膜に接触させる方法が挙げられる
。Among the above disinfectants, reducing agent treatment methods that can be applied after using chlorine disinfectants include sodium thiosulfate, sodium hydrosulfide, sodium sulfite,
10 ppm to 10 ppm of reducing agent such as sodium bisulfite
10°C to 50°C using an aqueous solution containing o ppm
A method of contacting with a membrane for 10 minutes to 100 minutes at °C is mentioned.
上記膜の再生方法は、微生物が繁殖しやすい溶液、例え
ば糖類、アミノ酸類、アルコール類又は有機カルボン酸
等を含有する水溶液を膜分離する分野において特に有効
である。The membrane regeneration method described above is particularly effective in the field of membrane separation of solutions in which microorganisms easily propagate, such as aqueous solutions containing sugars, amino acids, alcohols, or organic carboxylic acids.
以下、実施例により本発明をさらに詳しく説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
逆浸透試験法
通常の連続式ポンプ型逆浸透装置を用い、２５℃にてｓ
ｏ ｏ ｏ ｐｐｍのＮａＣＬ及び４〜５ ｐｐｍの
次亜塩素酸を常時含むｐＨ６，０〜６．５の水溶液を原
液とし、操作圧力は４２．５ ｈ／ｃｒ／ｌ Ｇ Ｋて
行なった。Reverse osmosis test method Using a regular continuous pump type reverse osmosis device, s at 25℃
The stock solution was an aqueous solution with a pH of 6.0 to 6.5 that always contained o o o ppm of NaCL and 4 to 5 ppm of hypochlorous acid, and the operation pressure was 42.5 h/cr/l GK.
促進耐塩素性評価方法
上記逆浸透試験法の他に、次亜塩素酸濃度を１０００
ＰＰｍに上げて、耐塩素性の促進試験を行なった。なお
、この場合の膜性能は、更に還元剤処理した後のデータ
を示した。Accelerated chlorine resistance evaluation method In addition to the above reverse osmosis test method, the hypochlorous acid concentration was
An accelerated test of chlorine resistance was carried out by raising the temperature to PPm. Note that the membrane performance in this case shows data after further treatment with a reducing agent.
塩排除率
実施例中の塩排除率とは次式にょシ求められる値である
。Salt rejection rate The salt rejection rate in the examples is a value obtained using the following formula.
参考例１
ポリスルホン多孔質支持膜の製造
密に織ったダクロン（Ｄａｃｒｏｎ）製不織布（目付蓋
１８０り／−）をガラス板上に固定した。次イテ、該不
織布上にポリスルホン１２．５ ｗｔ％、メグルセロソ
ルプ１２．５ ｗｔ％、および残部ジメチルホルムアミ
ドを含む溶液を厚さ約０．２１１＋Ｉ＋の層状にキャス
トし、直ちにポリスルホン層を室温の水浴中にてゲル化
させることにより、不織布補強多孔性ポリスルホン膜を
得た。Reference Example 1 Production of Polysulfone Porous Support Membrane A densely woven Dacron nonwoven fabric (fabric weight 180 mm/-) was fixed on a glass plate. Next, a solution containing 12.5 wt% polysulfone, 12.5 wt% meglucerosol, and the remainder dimethylformamide was cast onto the nonwoven fabric to form a layer with a thickness of about 0.211+I+, and the polysulfone layer was immediately placed in a water bath at room temperature. By gelling the mixture, a nonwoven reinforced porous polysulfone membrane was obtained.
この様にして得られた多孔性ポリスルホン層は厚みが約
４０〜７０μであり、非対称構造を有しており、かつ表
面には約２００〜７００Ｘの微孔が多数存在することが
電子顕微鏡写真により観察された。またこれらの多孔性
基材は２ｈ／ａｄ Ｇ Ｋおける純水の透過量（膜定数
）が約３．０〜？、ＯＸ １０ ｙ／〜・就・ａｔｍ
であった。Electron micrographs show that the porous polysulfone layer thus obtained has a thickness of about 40 to 70μ, has an asymmetric structure, and has many micropores of about 200 to 700× on the surface. observed. In addition, these porous substrates have a pure water permeation rate (membrane constant) of about 3.0 or more in 2 hours/ad GK. , OX 10 y/~・service・atm
Met.
実施例】
蒸留直後のエチレンジアミン０．１１Ｆ、ピペラジン０
．３１を蒸留水にとかした水溶液中に、参考例１によシ
得たポリスルホン多孔膜を１ｓ分間浸漬した。しかるの
ち、該多孔膜をドレインし膜表面に付着している過剰の
水溶液をロールプレスにより除去した後で、トリメシン
酸クロライド０．１ｗｔ％のｎ−ヘキサン溶液中に該膜
を５秒間浸漬した。Example: Ethylenediamine 0.11F, piperazine 0 immediately after distillation
．． The polysulfone porous membrane obtained in Reference Example 1 was immersed in an aqueous solution of No. 31 dissolved in distilled water for 1 s. Thereafter, the porous membrane was drained to remove excess aqueous solution adhering to the membrane surface by a roll press, and then the membrane was immersed for 5 seconds in an n-hexane solution containing 0.1 wt % trimesic acid chloride.
このようにして得られた複合膜を４２．５にり／−１２
５℃にて０．５ ｗｔ％ＮａＣｔ水を原液として逆浸透
テストを行なった処、透水量１．２０ｔβ七ｒ。The composite membrane thus obtained was 42.5/-12
A reverse osmosis test was conducted at 5°C using 0.5 wt% NaCt water as a stock solution, and the water permeability was 1.20 tβ7r.
脱塩率９１．９％という値かえられた。引き続き、原液
として１ ｗｔ％乳糖水溶液を用いて同様の条件で逆浸
透テストした処、透水量１１ｓ Ｌ／ｒｄ・ｈｒ、乳糖
排除率９９．２％と極めてすぐれた初期性能を示した。The desalination rate was increased to 91.9%. Subsequently, a reverse osmosis test was conducted under the same conditions using a 1 wt% lactose aqueous solution as the stock solution, and it showed extremely excellent initial performance with a water permeation rate of 11 s L/rd·hr and a lactose rejection rate of 99.2%.
一度該逆浸透テストラインを水洗したのち、該系に１０
０ ｐｐｍの次亜塩素酸を添加し、原液ｐＨを５．０に
調整しで３０分間塩素殺菌処理を４２．５Ｋｙ／（ρ、
２５℃にて行なったのち、同一条件下でひき続きａ ｏ
ｏ ｐｐｍのナトリウムハイドロサルファイド水溶液
を用いて膜の還元処理を３０分行なった。さらに水洗を
・３０分行なったのち再び塩素処理を行うという殺菌処
理全行うという殺菌処理サイクルを１０００回くり返し
た処、透水量ｘｏａｚ／−・ｈｒ 、脱塩＄９４．Ｂ％
という極めて安定なＮｉｌ塩素性を示した。After washing the reverse osmosis test line with water, add 10% to the system.
Add 0 ppm hypochlorous acid, adjust the pH of the stock solution to 5.0, and perform chlorine sterilization treatment for 30 minutes at 42.5 Ky/(ρ,
After the test was carried out at 25°C, ao
The membrane was subjected to reduction treatment for 30 minutes using 0 ppm sodium hydrosulfide aqueous solution. After repeating the sterilization cycle 1000 times by washing with water for 30 minutes and then chlorinating again, the water permeability rate was xoaz/-hr, desalination was $94. B%
It showed an extremely stable Nil chloride property.
比較例１及び２
実施例１に於て、アミン成分としてエチレンジアミンと
ピペラジンの混合物を用いる代シに、各々単独で用いた
処、下記表−１に記載の性能の複合膜しか得られなかっ
た。Comparative Examples 1 and 2 In Example 1, instead of using a mixture of ethylenediamine and piperazine as the amine component, each was used alone, and only composite membranes with the performance shown in Table 1 below were obtained.
表 −１
実施例２〜５
実施例１に於てアミンとしてエチレンジアミンとピペラ
ジンとの混合物を用いる代りに下表２に記載のアミン混
合物を用いて複合膜をえた。Table 1 Examples 2 to 5 Composite membranes were obtained by using the amine mixtures listed in Table 2 below instead of using the mixture of ethylenediamine and piperazine as the amine in Example 1.
それらの逆浸透性能を合せて表−２に示す。Table 2 shows their reverse osmosis performance.
Claims (1)
）で表わされる構成単位〔Ａ〕、及び上記式〔■〕Ｋお
けるＲ１及びＲ３が共に水素原子とした場合の構成単位
〔Ｂ〕を有し、構成単位〔Ｂ′３を上記（Ａ）と〔Ｂ〕
全全体２０モルチ以上５０モルチ未満含有して成る架橋
薄膜とからなる複合半透膜。 Ｈ２Ｎ−Ｒ２−ＮＨ，で表されるジアミンを後者のジア
ミンが全体中に占める割合が２０モルチ以上５０モルチ
未満となるように混合した水溶液を微多孔膜に含浸また
は塗布したのち １ 原子を表わし、Ｘは ＼Ｃ２０又はＳ０２を表わす。Ａｒは前記式（ｒ）にお
ける定義に同じ。）で表わされる架橋剤と接触させ、必
要に応じて加熱処理することを特徴とする複合半透膜の
製造方法。(1) Porous armpit and the following formula CI' formed thereon
), and the structural unit [B] when R1 and R3 in the above formula [■] K are both hydrogen atoms, and the structural unit [B'3 is the above (A)]. [B]
A composite semipermeable membrane comprising a crosslinked thin film having a total content of 20 moles or more and less than 50 moles. After impregnating or coating a microporous membrane with an aqueous solution of a diamine represented by H2N-R2-NH, mixed in such a manner that the proportion of the latter diamine in the whole is 20 molti or more and less than 50 molti, representing 1 atom, X represents \C20 or S02. Ar has the same definition as in formula (r) above. ) A method for producing a composite semipermeable membrane, which comprises bringing it into contact with a crosslinking agent represented by the following formula, and subjecting it to heat treatment if necessary.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58052515A JPS59179103A (en) | 1983-03-30 | 1983-03-30 | Composite semipermeable membrane and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58052515A JPS59179103A (en) | 1983-03-30 | 1983-03-30 | Composite semipermeable membrane and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59179103A true JPS59179103A (en) | 1984-10-11 |
| JPH0239299B2 JPH0239299B2 (en) | 1990-09-05 |
Family
ID=12916868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58052515A Granted JPS59179103A (en) | 1983-03-30 | 1983-03-30 | Composite semipermeable membrane and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59179103A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989006153A1 (en) * | 1988-01-11 | 1989-07-13 | Toray Industries, Inc. | Process for producing composite semipermeable membrane |
| WO1991011250A1 (en) * | 1990-01-26 | 1991-08-08 | Toray Industries, Inc. | Composite semipermeable membrane and production thereof |
| US5324538A (en) * | 1991-03-12 | 1994-06-28 | Toray Industries, Inc. | Process for producing composite semipermeable membrane employing a polyfunctional amine solution and high flash point - solvent |
| EP2014350A2 (en) | 2001-03-19 | 2009-01-14 | Nitto Denko Corporation | Water-treating method |
-
1983
- 1983-03-30 JP JP58052515A patent/JPS59179103A/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989006153A1 (en) * | 1988-01-11 | 1989-07-13 | Toray Industries, Inc. | Process for producing composite semipermeable membrane |
| JPH01180208A (en) * | 1988-01-11 | 1989-07-18 | Toray Ind Inc | Production of compound semipermeable membrane |
| JPH0568293B2 (en) * | 1988-01-11 | 1993-09-28 | Toray Industries | |
| WO1991011250A1 (en) * | 1990-01-26 | 1991-08-08 | Toray Industries, Inc. | Composite semipermeable membrane and production thereof |
| US5324538A (en) * | 1991-03-12 | 1994-06-28 | Toray Industries, Inc. | Process for producing composite semipermeable membrane employing a polyfunctional amine solution and high flash point - solvent |
| EP2014350A2 (en) | 2001-03-19 | 2009-01-14 | Nitto Denko Corporation | Water-treating method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0239299B2 (en) | 1990-09-05 |
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