JPH0119922B2 - - Google Patents
Info
- Publication number
- JPH0119922B2 JPH0119922B2 JP56045388A JP4538881A JPH0119922B2 JP H0119922 B2 JPH0119922 B2 JP H0119922B2 JP 56045388 A JP56045388 A JP 56045388A JP 4538881 A JP4538881 A JP 4538881A JP H0119922 B2 JPH0119922 B2 JP H0119922B2
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- formula
- aromatic
- water
- polyamine compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000001875 compounds Chemical class 0.000 claims description 63
- 239000012528 membrane Substances 0.000 claims description 56
- 125000003118 aryl group Chemical group 0.000 claims description 42
- 229920000768 polyamine Polymers 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000002131 composite material Substances 0.000 claims description 25
- -1 amine salt Chemical class 0.000 claims description 14
- 239000012982 microporous membrane Substances 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000002128 sulfonyl halide group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- 230000035699 permeability Effects 0.000 description 10
- 238000001223 reverse osmosis Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 229920002492 poly(sulfone) Polymers 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000012696 Interfacial polycondensation Methods 0.000 description 7
- 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 7
- 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 6
- 238000000576 coating method Methods 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 229920013730 reactive polymer Polymers 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- WFNVGXBEWXBZPL-UHFFFAOYSA-N 3,5-diaminophenol Chemical compound NC1=CC(N)=CC(O)=C1 WFNVGXBEWXBZPL-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000010406 interfacial reaction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000926 separation method 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
- JIMRSFDTUBLGOO-UHFFFAOYSA-N 1-chlorosulfonylcyclohexa-3,5-diene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(S(Cl)(=O)=O)(C(Cl)=O)C1 JIMRSFDTUBLGOO-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- KQEIJFWAXDQUPR-UHFFFAOYSA-N 2,4-diaminophenol;hydron;dichloride Chemical compound Cl.Cl.NC1=CC=C(O)C(N)=C1 KQEIJFWAXDQUPR-UHFFFAOYSA-N 0.000 description 1
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-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
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- KECOIASOKMSRFT-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(O)C(N)=CC(S(=O)(=O)C=2C=C(N)C(O)=CC=2)=C1 KECOIASOKMSRFT-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
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910006080 SO2X Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005011 alkyl ether group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 125000005521 carbonamide group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 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
- 244000005700 microbiome Species 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 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
- 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
- 239000000376 reactant Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 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
- 238000010998 test method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 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
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polyamides (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
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The present invention relates to a novel composite semipermeable membrane and a method for manufacturing the same. More specifically, the present invention relates to a composite semipermeable membrane for reverse osmosis that has excellent basic performance (particularly water permeability) and excellent oxidation resistance, and a method for manufacturing the same. Initially, the cellulose acetate-based reverse osmosis membrane developed by Loeb and Sourirajan was widely used due to its excellent basic performance and ease of manufacture. Disadvantages such as degradability, deterioration by microorganisms, compactability, and inability to be stored dry have become problems, and various new reverse osmosis membranes using synthetic polymers have been proposed to compensate for these drawbacks. DuPont proposed a reverse osmosis membrane made of fully aromatic polyamide, and although this achieved significant improvements in terms of hydrolyzability and microbial deterioration resistance, it did not surpass cellulose acetate in terms of basic performance. However, the disadvantages of compactability and dry maintainability still remained. All of these membranes are called heterogeneous membranes that are prepared using a method called phase separation, and the homogeneous layer involved in separation and the porous layer that maintains the strength of the membrane are made of the same material. Ta. However, a method has been proposed in which a porous layer is prepared in advance from another material, and then a hydrophilic reactive polymer is reacted with a crosslinking agent to form a crosslinked thin film-like separation layer thereon. In addition to improved performance, it was suggested that significant improvements could be made in hydrolyzability, microbial isolation, compaction, dry storage, etc. North Star Laboratories has demonstrated that the above improvements are possible by using polyethyleneimine as the hydrophilic, reactive polymer and polyacid chlorides or polyisocyanates such as isophthalic acid chloride and toluylene diisocyanate as the crosslinking agent. However, because the amine content of the raw material polyethyleneimine in the membrane thus obtained was too high, the crosslinked layer formed was extremely weak, and it was found that there was a major problem in forming it into a spiral module form. . On the other hand, Universal Oil Products Co., Ltd. succeeded in improving the above-mentioned drawbacks by using amine-modified polyepichlorohydrin as a hydrophilic reactive polymer. Since polyepichlorohydrin is extremely difficult to produce, it has the disadvantage that it is difficult to create a membrane with a large amount of water permeation. Recently, Filmtech Co., Ltd. (JECaddotte)
proposed a composite membrane consisting of a low-molecular weight aromatic polyamine such as metaphenylene diamine or paraphenylene diamine crosslinked with an aromatic polyacid halide such as trimesic acid chloride on a microporous membrane (Japanese Patent Application Laid-Open No. 55-147106)) It was demonstrated that it has extremely good desalting performance and also has better oxidation resistance than conventional polyamine crosslinked composite membranes.
However, this membrane cannot be said to have sufficient water permeability, and some kind of improvement is desired in order to exhibit high water permeability under low operating pressures, especially when desalting water with low salt concentration. Therefore, the present inventors conducted extensive research to obtain a low operating pressure, high water permeability composite membrane that does not have the above drawbacks.
This has led to the present invention. That is, the present invention provides a primary formula [I] (X 1 ) -l Ar 1 (-NH 2 ) n ... [I] [wherein X 1 represents a hydroxyl group, and Ar 1
represents a benzene ring or a dinuclear non-fused aromatic ring, l is 1 or 2, and m is 2, 3 or 4. ] An aromatic polyamine compound represented by the following formula [] Ar 2 (-Z) o1 ... [] [However, in the formula, Z represents a carbonyl halide group or a sulfonyl halide group, and Ar 2 represents a benzene ring or a dinuclear non-containing group. Represents a fused aromatic ring, n 1 is 2,
3 or 4, and n 1 Z's may be the same or different. ] A composite semipermeable membrane obtained by reacting an aromatic polyfunctional compound represented by the following on a microporous membrane to form a water-insoluble membrane, and 2. Water and a boiling point of 120 that is freely miscible with water. The following formula [ ] (X 1 ) -l Ar 1 (-Y) n ...[ ] [However, in the formula, X 1 represents a hydroxyl group,
Ar 1 represents a benzene ring or a dinuclear non-fused aromatic ring, Y represents -NH 2 or -NH 3 Y 1 ,
Y1 is a halogen ion, SO4 -- , NO3- , PO43- ,
It represents CH 3 COO - or HCOO - , l is 1 or 2, and m is 2, 3 or 4. ] A step of applying an aromatic polyamine compound represented by the following to a microporous membrane in a solution state; When the aromatic polyamine compound is in the form of an amine salt, the aromatic polyamine compound applied to the microporous membrane is Step of heating at °C or treatment with a deoxidizing agent; After drying the microporous membrane coated with the solution of the aromatic polyamine compound as necessary, the following formula [] Ar 2 (-Z) o1 ...[] [However, in the formula, Z represents a carbonyl halide group or a sulfonyl halide group, Ar 2 represents a benzene ring or a dinuclear non-fused aromatic ring, n 1 is 2,
3 or 4, and n 1 Z's may be the same or different. ] This is a method for producing a composite semipermeable membrane, comprising the steps of: contacting with a solution of an aromatic polyfunctional compound represented by; and air-drying the contact-treated composite membrane, and further heat-treating as necessary. The soluble aromatic polyamine compound used in the present invention has a benzene ring or a dinuclear non-fused aromatic ring as a core, and has 2 to 4 amino groups and 1 to 2 amino groups in the core.
It has 2 hydroxyl groups as a substituent. The aromatic polyamine compound must be soluble at room temperature in an amount of at least 0.1% by weight, preferably 0.5% by weight, in water and an organic solvent which is freely miscible with water and has a boiling point below 120°C. In addition to the above-mentioned substituents, these aromatic polyamine compounds also contain substituents that do not participate in the reaction with the aromatic acid halide described below, such as lower alkyl groups, halogen atoms, cyano groups, nitro groups, and lower alkyl ether groups. can have a functional group of Further, the aromatic polyamine compound can be used in the present invention after being reacted with an organic or inorganic acid to form an amine salt in order to improve its solubility. As such organic acids, lower carboxylic acids such as acetic acid and formic acid are preferably used. As the inorganic acid, hydrogen halides such as hydrogen chloride, hydrogen bromide, and hydrogen iodide, and mineral acids such as nitric acid, sulfuric acid, and phosphoric acid are preferably used. Such aromatic polyamine compounds and salts thereof preferably used in the present invention include 3,5-diaminophenol.
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[Formula] 2,4-diaminophenol
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[Formula] Diamine salt of 3,5-diaminophenol 4,4'-diamino-3,3'-dihydroxydiphenylamine 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone Examples include. These amines can be used alone or in combination of two or more.
Furthermore, by using these amines in combination with other polyamino compounds, it is possible within the scope of the present invention to obtain composite membranes having desired salt exclusion properties. Examples of such polyamino compounds include the following. (1) Aromatic polyamine: metaphenylenediamine
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[Formula] Paraphenylenediamine
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[Formula] Among these polyamino compounds, aromatic polyamines and cyclic polyamines can be particularly preferably used in the present invention. When these polyamines are used in combination with the above-mentioned aromatic polyamine compounds,
The ratio of the former to 100 parts by weight of the latter is
It is generally advantageous to use from 5 to 200 parts by weight, preferably from 10 to 100 parts by weight. In order to obtain the composite membrane of the present invention using the polyamine 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, spray coating, etc., but the thickness of the applied polyamine layer is 0.01 to 2Ό, preferably 0.02 to 2Ό.
Coating conditions should be controlled so that the thickness is 1Ό, more preferably 0.05 to 0.7Ό. If the coating thickness of the polyamine layer is smaller than the above lower limit (ie, 0.01Ό), the active layer of the final composite membrane will be too thin and its mechanical strength will decrease. In addition, if the coating thickness is greater than 2 Όm, the active layer becomes too thick, which tends to impair the water permeability of the composite membrane. When the polyamine compound is applied to the microporous membrane in the form of an amine salt, the amine salt must be converted into a free amine prior to or simultaneously with the reaction with the acid halide described below. For this conversion, heat treatment at 100 to 150°C or treatment with a deoxidizer is effective. Such a polyamino compound must be soluble, especially in water, methanol, ethanol, isopropanol, methyl cellosolve, dioxane or tetrahydrofuran or a mixed solvent of two or more thereof at a concentration of 0.5 g/100 ml or more, preferably 1 g/100
It is preferable that it is soluble in ml or more. Particularly preferred are those having a solubility in water of 0.5 g/100 ml or more, and further 1 g/100 ml or more. At least one solvent selected from these solvent groups (especially preferably water)
A solution of the polyamine compound of the present invention dissolved in at least 0.1% of the polyamine compound is applied to or impregnated onto a microporous substrate. Examples of such substrates include porous glass materials, sintered metals, ceramics, and organic polymers such as cellulose esters, polystyrene, vinyl butyral, polysulfone, and vinyl chloride. Polysulfone membranes have particularly excellent performance as substrates in the present invention, and polyvinyl chloride is also effective. The manufacturing method for polysulfone porous substrates is published in the U.S. Office of Salt Water Report (OSW Report)
It is also listed in No.359. Such substrates generally have a surface pore size of about 100
The surface pore size is preferably between ~1000 angstroms, but is not limited to this, depending on the final membrane application etc.
It can vary between 5000 Ã
. These substrates can be used in either symmetrical or asymmetrical structures, but asymmetrical structures are preferable. However, when the membrane constant of these base materials is less than 10 -4 g/cm 2 sec atm, the water permeability becomes too low;
If it is higher than atm, the desalination rate tends to be extremely low, which is not preferable. Therefore, the preferred supporting membrane constant is 1 to 10 -4 g/cm 2 sec atm, particularly preferably
A range of 10 -1 to 10 -3 g/cm 2 ·sec·atm gives the most favorable results. It should be noted that the irritating membrane constant here is a value representing the permeation amount of pure water under a pressure of 2 Kg/cm 2 , and the unit is g/cm 2 ·sec·atm. It is preferable to use such a base material in a form in which the back side is reinforced with a woven fabric or non-woven fabric. Suitable examples of such woven or nonwoven fabrics include those made of polyethylene terephthalate, polystyrene, polypropylene, nylon, or vinyl chloride. The base material on which the thin layer of the polyamino compound described above is formed has a functional group that can react with an amino group in the polyamino compound containing an amino group to form either a carbonamide or a sulfonamide bond. subjected to an interfacial polycondensation reaction using a compound containing at least two groups, on a substrate,
A thin pseudo-film of the polyamine compound described above is rendered water insolubilized. This water insolubilization is usually carried out by an interfacial polycondensation reaction between the surface of the polyamine compound pseudo-film and a reactive polyfunctional compound, and as a result, a thin film with selective permselectivity is formed on the surface of the base material. is formed. The functional group possessed by the polyfunctional compound as a surface reactant that can be used in the present invention is an acid halide group (-
COX) or a sulfonyl halide group ( -SO2X ) is suitable, and one molecule can contain at least two, preferably two or three, of these functional groups. Particularly preferred 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. Additionally, polyfunctional compounds generally have a cyclic structure, i.e. they can be of either aromatic, heterocyclic or alicyclic structure, although for the purposes of the present invention aromatic It has been found that polyfunctional compounds with properties are particularly effective. Therefore, aromatic polyfunctional compounds that can be advantageously used in the present invention have at least 2, preferably 2 to 3 functional groups bonded to an aromatic nucleus,
As long as it contains 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, either mononuclear or dinuclear carbon atoms can be suitably used. Further, it is preferable that no substituents other than the above-mentioned functional groups exist on the aromatic nucleus, such as lower alkyl groups, lower alkoxy groups,
There is no problem even if one or two groups, such as halogen atoms, do not substantially affect the crosslinking reaction. A particularly desirable group of such aromatic polyfunctional compounds includes the following formula: [In the formula, Ar 1 is a benzene ring, a naphthalene ring, or a
ãåŒãã®ç°ãåŒäžïŒ±ã¯âCH2 âãThe ring of [formula] [wherein Q is -CH 2 -,
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ããåŠãè¡šâïŒã«ç€ºããããªçµæããããããParticularly preferred aromatic polyfunctional compounds are isophthalic acid chloride , terephthalic acid chloride, trimesic acid chloride and 3-chlorosulfonylisophthalic acid chloride. The aromatic polyfunctional compounds described above can be used alone or in combination of two or more. According to the invention, the polyfunctional compound is trifunctional rather than difunctional when used alone, and even more advantageously when two or more are used in combination. It has been found that by using a combination of difunctional and trifunctional materials, the salt rejection rate and/or water permeability of the final membrane can be further improved. Thus, particularly suitable polyfunctional compounds in the present invention are trifunctional aromatic compounds or mixtures of difunctional and trifunctional aromatic compounds. When using a mixture of a bifunctional compound and a trifunctional compound, the mixing ratio of the two is not critical, but
Generally, the weight ratio of 2-/3-functional compounds is 10:
It is advantageous to mix in the range 1 to 1:3, preferably 5:1 to 1:1. The interfacial polycondensation reaction of the polyamine compound of the present invention can usually be carried out by bringing a membrane coated with the polyamine compound into contact with a solution of the above-mentioned polyfunctional compound. The solvent used for dissolving the polyfunctional compound is one that does not substantially dissolve the polyamine compound and the base material, for example, n-
Examples include hydrocarbon solvents such as hexane, n-heptane, n-octane, cyclohexane, n-nonane, and n-decane. Although the suitable concentration of the polyfunctional compound in the solvent may vary depending on the type of the compound, the solvent, the substrate, and other conditions, the optimal value can be determined by experiment. However, generally about 0.5 to 5.0% by weight, preferably 1.0 to 3.0% by weight can exhibit sufficient effects. The interfacial polycondensation reaction of a polyamine compound with a polyfunctional compound is preferably achieved at the interface between the membrane and the solution by immersing a membrane coated with the polyamine compound in a solution of the polyfunctional compound. At this time, it is also possible to previously include an interfacial reaction accelerator in the polyamine compound or the polyfunctional compound solution in order to promote this interfacial polycondensation reaction. As such a promoter, caustic alkali, sodium phosphate, pyridine, surfactant, sodium acetate, etc. are suitably used. Such an interfacial polycondensation reaction between the membrane surface and the polyfunctional compound can be carried out at a temperature of room temperature to about 100°C, preferably 20 to 50°C, for 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes. This interfacial reaction can be carried out so that it is mainly concentrated on the surface of the membrane, and there is no need to reduce the anti-water activity inside the membrane. The membrane supported on the substrate is then heated at room temperature or at 40-130°C, preferably at 50-80°C, after draining excess polyfunctional compound solution for 10 seconds to 2 minutes, if necessary. The heat treatment is carried out at a temperature of 0.degree. C. for a period of about 1 to 30 minutes, preferably about 5 to 20 minutes.
This makes it possible to complete the interfacial polycondensation reaction and to make the polyamino compound water-insoluble. In this way, a composite membrane having a thin membrane of a water-insolubilized polycondensate having permselectivity on the surface of a microporous substrate is obtained. Examples of polyamides that can form the composite membrane active layer of the present invention obtained in this way are shown below. The composite membrane of the present invention obtained as described above has excellent salt exclusion properties, chemical resistance, PH resistance, heat resistance, etc., as well as extremely high water permeability and chlorine resistance even in low pressure operation. Especially in these two points, it can be said that it has advantages and features that are completely different from those of conventionally proposed composite membranes. Hereinafter, the present invention will be explained in more detail with reference to Examples. Reference example 1 Reverse osmosis test method Using a regular continuous pump type reverse osmosis device, PH
6.0 to 6.5 at 25°C using a 1500 ppm NaCl aqueous solution as a stock solution. Note that the salt rejection rate in the examples is a value determined by the following formula. Salt rejection rate (%) = (1 - NaCl concentration in permeated water / NaCl concentration in stock solution) x
100 Reference Example 2 Manufacture of polysulfone porous support membrane A densely woven Dacron nonwoven fabric (fabric weight 180 g/m 2 ) was fixed on a glass plate. Next, a solution containing 12.5 wt% polysulfone, 125 wt% methyl cellosolve, and the remainder dimethylformamide was cast on the nonwoven fabric in a layer having a thickness of about 0.2 ÎŒm, and the polysulfone layer was immediately gelled in a water bath at room temperature. , a nonwoven reinforced porous polysulfone membrane was obtained. Electron micrographs show that the porous polysulfone layer obtained in this way has a thickness of about 40 to 70ÎŒ, has an asymmetric structure, and has many micropores of about 50 to 600Ã
on the surface. observed. In addition, these porous substrates have a pure water permeation rate (membrane constant) of approximately 3.0 to 7.0Ã10 -2 g/cm 2 at 2 Kg/cm 3 G.
It was sec/atm. Example 1 2,4-diaminophenol dihydrochloride 2g,
0.5 g of caustic soda and 100 ml of distilled water were mixed to form a homogeneous aqueous solution. After immersing the polysulfone microporous membrane obtained in Reference Example 2 in this aqueous solution for 5 minutes, the membrane was taken out from the aqueous solution, stood vertically, and drained at room temperature for 7 minutes. The thus drained membrane was then treated with 0.5wt of a 1:3 (weight ratio) mixture of trimesoyl chloride and isophthaloyl chloride.
% n-hexane solution for 2 minutes, then taken out from the solution and dried at room temperature for about 30 minutes. The thus obtained composite membrane was subjected to a reverse osmosis test under the conditions of Reference Example 1 (0.2wt% NaCl water, 18Kg/cm 2 , 25°C), and the salt removal rate was 94.1%, and the water permeation rate was 32.7%.
m2 ïŒ It showed an initial performance of hr. In order to investigate the chlorine resistance of this membrane, hydrochloric acid and sodium hypochlorite were added to the stock solution at a pH of 6.0 to 6.5 and an active chlorine concentration of 3 to 5 ppm, and a reverse osmosis test was continued for 250 hours. desalination rate of 94.3% and water permeability of 29.8/ m2 . hr and showed stable performance. Examples 2 to 5 Instead of using a mixture of trimesic acid chloride and isophthalic acid chloride as the crosslinking agent in Example 1, as shown in Table 1, trimesic acid chloride alone (Example 2) and isophthalic acid chloride alone (Example 3) Composite membranes were obtained in exactly the same manner except that terephthalic acid chloride alone (Example 4) and a 1:1 (weight ratio) mixture of terephthalic acid chloride and trimesic acid chloride were used. When these composite membranes were subjected to a reverse osmosis test in the same manner as in Example 1, the results shown in Table 1 were obtained.
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ãããã®è€åèæ§èœãåããŠè¡šâïŒã«ç€ºããã[Table] Example 6 In Example 1, 2,4-diaminophenol 2
A composite membrane was obtained by using metaphenylene diamine and 2,4-diaminophenol in combination (1:1 weight ratio) instead of using hydrochloride alone. The reverse osmosis performance of this product is the initial water permeability of 35.7/
m2 ïŒ hr, desalination rate 98.1%, 30.9/ after 200 hours
m2 ïŒ hr, 99.3%. Examples 7 and 8 and Reference Examples 1 and 2 In Example 1, 2,4-diaminophenol
Example 1 was carried out in exactly the same manner as in Example 1, except that an amino compound as shown in Table 2 was used instead of the dihydrochloride, and isophthalic acid chloride or trimesic acid chloride was used as the water-insolubilizing reaction agent for the amino compound. A composite membrane was obtained. The performance of these composite membranes is also shown in Table 2.
Claims (1)
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 Ar2ïŒâïŒo1 âŠâŠïŒ»ïŒœ ãäœãåŒäžïŒºã¯ã«ã«ããã«ãã©ã€ãåºåã¯ã¹ã«ã
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 Ar2ïŒâïŒo1 âŠâŠïŒ»ïŒœ ãäœãåŒäžïŒºã¯ã«ã«ããã«ãã©ã€ãåºåã¯ã¹ã«ã
ãã«ãã©ã€ãåºãè¡šãããAr2ã¯ãã³ãŒã³ç°åã¯
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ããããã ã§è¡šããããè³éŠæå€å®èœååç©ã®æº¶æ¶²ãšæ¥è§Šã
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ããŠæŽã«å ç±åŠçããå·¥çšïŒ ãããªãè€ååéèã®è£œé æ¹æ³ã[Claims] Primary formula [I] (X 1 ) -l Ar 1 (-NH 2 ) n ...[I] [However, in the formula, X 1 represents a hydroxyl group, and Ar 1 represents a benzene ring or 2 represents a non-fused aromatic ring of the nucleus,
l is 1 or 2 and m is 2, 3 or 4. ] An aromatic polyamine compound represented by the following formula [] Ar 2 (-Z) o1 ... [] [However, in the formula, Z represents a carbonyl halide group or a sulfonyl halide group, and Ar 2 represents a benzene ring or a dinuclear non-containing group. It represents a fused aromatic ring, and n 1 is 2, 3 or 4. However, n 1 Z's may be the same or different. ] A composite semipermeable membrane obtained by reacting an aromatic polyfunctional compound represented by the following on a microporous membrane to form a water-insoluble membrane. 2 The following formula [ ] (X 1 ) soluble at room temperature at least 0.1% by weight in at least one solvent selected from the group consisting of water and solvents with a boiling point of 120°C or less that are freely miscible with water. - l Ar 1 (-Y) n ... [] [However, in the formula, X 1 represents a hydroxyl group, and Ar 1
represents a benzene ring or a dinuclear non-fused aromatic ring, Y represents -NH2 or -NH3Y1 , Y1 is a halogen ion, SO4- , NO3- , PO43- ,
CH 3 COO - or HCOO - , l is 1 or 2
and m is 2, 3 or 4. ] A step of applying an aromatic polyamine compound represented by the following to a microporous membrane in a solution state; When the aromatic polyamine compound is in the form of an amine salt, the aromatic polyamine compound applied to the microporous membrane is Step of heating or treating with a deoxidizing agent at °C; After drying the microporous membrane coated with the solution of the aromatic polyamine compound as necessary, the following formula [] Ar 2 (-Z) o1 ... [] [However, in the formula, Z represents a carbonyl halide group or a sulfonyl halide group, Ar 2 represents a benzene ring or a dinuclear non-fused aromatic ring, n 1 is 2, 3 or 4, and n 1 Z represents They may be the same or different. ] A method for producing a composite semipermeable membrane, comprising: contacting with a solution of an aromatic polyfunctional compound represented by; and air-drying the contact-treated composite membrane, and further heat-treating as necessary.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4538881A JPS57159503A (en) | 1981-03-30 | 1981-03-30 | Composite semi-permeable membrane and preparation thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4538881A JPS57159503A (en) | 1981-03-30 | 1981-03-30 | Composite semi-permeable membrane and preparation thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57159503A JPS57159503A (en) | 1982-10-01 |
JPH0119922B2 true JPH0119922B2 (en) | 1989-04-13 |
Family
ID=12717879
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP4538881A Granted JPS57159503A (en) | 1981-03-30 | 1981-03-30 | Composite semi-permeable membrane and preparation thereof |
Country Status (1)
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JP (1) | JPS57159503A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60150806A (en) * | 1984-01-20 | 1985-08-08 | Agency Of Ind Science & Technol | Preparation of polyimide hollow yarn membrane |
JPS62121603A (en) * | 1985-08-05 | 1987-06-02 | Toray Ind Inc | Composite semipermeable membrane and preparation thereof |
US5091216A (en) * | 1988-04-13 | 1992-02-25 | E. I. Du Pont De Nemours And Company | Reactive post treatment for gas separation membranes |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4942579A (en) * | 1972-08-30 | 1974-04-22 | ||
JPS55147106A (en) * | 1979-02-22 | 1980-11-15 | Filmtec Corp | Osmotic membrane synthesized on interface |
-
1981
- 1981-03-30 JP JP4538881A patent/JPS57159503A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4942579A (en) * | 1972-08-30 | 1974-04-22 | ||
JPS55147106A (en) * | 1979-02-22 | 1980-11-15 | Filmtec Corp | Osmotic membrane synthesized on interface |
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JPS57159503A (en) | 1982-10-01 |
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