JP2017012987A - Composite semipermeable membrane and production method of the same - Google Patents
Composite semipermeable membrane and production method of the same Download PDFInfo
- Publication number
- JP2017012987A JP2017012987A JP2015131324A JP2015131324A JP2017012987A JP 2017012987 A JP2017012987 A JP 2017012987A JP 2015131324 A JP2015131324 A JP 2015131324A JP 2015131324 A JP2015131324 A JP 2015131324A JP 2017012987 A JP2017012987 A JP 2017012987A
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- JP
- Japan
- Prior art keywords
- semipermeable membrane
- composite semipermeable
- skin layer
- polyamide
- carbodiimide 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.)
- Pending
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- 239000012528 membrane Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- -1 carbodiimide compound Chemical class 0.000 claims abstract description 39
- 229920002647 polyamide Polymers 0.000 claims abstract description 23
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 21
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 46
- 150000001412 amines Chemical class 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 150000004820 halides Chemical class 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 17
- 229920006122 polyamide resin Polymers 0.000 claims description 11
- 239000002152 aqueous-organic solution Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 238000011282 treatment Methods 0.000 abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 8
- 230000035699 permeability Effects 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 38
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000011247 coating layer Substances 0.000 description 10
- 229920002492 poly(sulfone) Polymers 0.000 description 10
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 9
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 9
- 239000012670 alkaline solution Substances 0.000 description 8
- 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
- 150000003839 salts Chemical class 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- OCIDXARMXNJACB-UHFFFAOYSA-N n'-phenylethane-1,2-diamine Chemical compound NCCNC1=CC=CC=C1 OCIDXARMXNJACB-UHFFFAOYSA-N 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- BMTZEAOGFDXDAD-UHFFFAOYSA-M 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholin-4-ium;chloride Chemical compound [Cl-].COC1=NC(OC)=NC([N+]2(C)CCOCC2)=N1 BMTZEAOGFDXDAD-UHFFFAOYSA-M 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009292 forward osmosis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- UQBNGMRDYGPUOO-UHFFFAOYSA-N 1-n,3-n-dimethylbenzene-1,3-diamine Chemical compound CNC1=CC=CC(NC)=C1 UQBNGMRDYGPUOO-UHFFFAOYSA-N 0.000 description 1
- BAHPQISAXRFLCL-UHFFFAOYSA-N 2,4-Diaminoanisole Chemical compound COC1=CC=C(N)C=C1N BAHPQISAXRFLCL-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- ITTFEPALADGOBD-UHFFFAOYSA-N 2-butylpropanedioyl dichloride Chemical compound CCCCC(C(Cl)=O)C(Cl)=O ITTFEPALADGOBD-UHFFFAOYSA-N 0.000 description 1
- IPOVOSHRRIJKBR-UHFFFAOYSA-N 2-ethylpropanedioyl dichloride Chemical compound CCC(C(Cl)=O)C(Cl)=O IPOVOSHRRIJKBR-UHFFFAOYSA-N 0.000 description 1
- FEUFNKALUGDEMQ-UHFFFAOYSA-N 2-isocyanato-1,3-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N=C=O FEUFNKALUGDEMQ-UHFFFAOYSA-N 0.000 description 1
- MLNSYGKGQFHSNI-UHFFFAOYSA-N 2-propylpropanedioyl dichloride Chemical compound CCCC(C(Cl)=O)C(Cl)=O MLNSYGKGQFHSNI-UHFFFAOYSA-N 0.000 description 1
- CNSVHYQBYNMMHW-UHFFFAOYSA-N 3-chlorosulfonylphthalic acid Chemical compound OC(=O)C1=CC=CC(S(Cl)(=O)=O)=C1C(O)=O CNSVHYQBYNMMHW-UHFFFAOYSA-N 0.000 description 1
- GNIZQCLFRCBEGE-UHFFFAOYSA-N 3-phenylbenzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(Cl)=O GNIZQCLFRCBEGE-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- JHDONXSUZJAJEY-UHFFFAOYSA-N C=CC(C)(C)N=C=N Chemical compound C=CC(C)(C)N=C=N JHDONXSUZJAJEY-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- YARQLHBOIGUVQM-UHFFFAOYSA-N benzene-1,2,3-trisulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC(S(Cl)(=O)=O)=C1S(Cl)(=O)=O YARQLHBOIGUVQM-UHFFFAOYSA-N 0.000 description 1
- YBGQXNZTVFEKEN-UHFFFAOYSA-N benzene-1,2-disulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1S(Cl)(=O)=O YBGQXNZTVFEKEN-UHFFFAOYSA-N 0.000 description 1
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 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
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- BZFATHSFIGBGOT-UHFFFAOYSA-N butane-1,1,1-tricarbonyl chloride Chemical compound CCCC(C(Cl)=O)(C(Cl)=O)C(Cl)=O BZFATHSFIGBGOT-UHFFFAOYSA-N 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- XWALRFDLDRDCJG-UHFFFAOYSA-N cyclobutane-1,1,2,2-tetracarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCC1(C(Cl)=O)C(Cl)=O XWALRFDLDRDCJG-UHFFFAOYSA-N 0.000 description 1
- LXLCHRQXLFIZNP-UHFFFAOYSA-N cyclobutane-1,1-dicarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCC1 LXLCHRQXLFIZNP-UHFFFAOYSA-N 0.000 description 1
- PBWUKDMYLKXAIP-UHFFFAOYSA-N cyclohexane-1,1,2-tricarbonyl chloride Chemical compound ClC(=O)C1CCCCC1(C(Cl)=O)C(Cl)=O PBWUKDMYLKXAIP-UHFFFAOYSA-N 0.000 description 1
- MLCGVCXKDYTMRG-UHFFFAOYSA-N cyclohexane-1,1-dicarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCCCC1 MLCGVCXKDYTMRG-UHFFFAOYSA-N 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-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
- DCXMNNZFVFSGJX-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCCC1(C(Cl)=O)C(Cl)=O DCXMNNZFVFSGJX-UHFFFAOYSA-N 0.000 description 1
- JREFGECMMPJUHM-UHFFFAOYSA-N cyclopentane-1,1,2-tricarbonyl chloride Chemical compound ClC(=O)C1CCCC1(C(Cl)=O)C(Cl)=O JREFGECMMPJUHM-UHFFFAOYSA-N 0.000 description 1
- YYLFLXVROAGUFH-UHFFFAOYSA-N cyclopentane-1,1-dicarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCCC1 YYLFLXVROAGUFH-UHFFFAOYSA-N 0.000 description 1
- CRMQURWQJQPUMY-UHFFFAOYSA-N cyclopropane-1,1,2-tricarbonyl chloride Chemical compound ClC(=O)C1CC1(C(Cl)=O)C(Cl)=O CRMQURWQJQPUMY-UHFFFAOYSA-N 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RTXRIXRVOABMAI-UHFFFAOYSA-N n'-(2,4,6-trimethylphenyl)methanediimine Chemical compound CC1=CC(C)=C(N=C=N)C(C)=C1 RTXRIXRVOABMAI-UHFFFAOYSA-N 0.000 description 1
- AMAWVOFJIULRGK-UHFFFAOYSA-N n'-(2,6-dimethylphenyl)-n-[4-[(2,6-dimethylphenyl)iminomethylideneamino]phenyl]methanediimine Chemical compound CC1=CC=CC(C)=C1N=C=NC1=CC=C(N=C=NC=2C(=CC=CC=2C)C)C=C1 AMAWVOFJIULRGK-UHFFFAOYSA-N 0.000 description 1
- MOQZJHKYQDFURQ-UHFFFAOYSA-N n'-tert-butyl-n-[4-(tert-butyliminomethylideneamino)butyl]methanediimine Chemical compound CC(C)(C)N=C=NCCCCN=C=NC(C)(C)C MOQZJHKYQDFURQ-UHFFFAOYSA-N 0.000 description 1
- PCIACFZGYVEWNX-UHFFFAOYSA-N n'-tert-butyl-n-[4-(tert-butyliminomethylideneamino)phenyl]methanediimine Chemical compound CC(C)(C)N=C=NC1=CC=C(N=C=NC(C)(C)C)C=C1 PCIACFZGYVEWNX-UHFFFAOYSA-N 0.000 description 1
- JCNCSCMYYGONLU-UHFFFAOYSA-N n,n'-bis(2-methylphenyl)methanediimine Chemical compound CC1=CC=CC=C1N=C=NC1=CC=CC=C1C JCNCSCMYYGONLU-UHFFFAOYSA-N 0.000 description 1
- XLDBGFGREOMWSL-UHFFFAOYSA-N n,n'-bis[2,6-di(propan-2-yl)phenyl]methanediimine Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N=C=NC1=C(C(C)C)C=CC=C1C(C)C XLDBGFGREOMWSL-UHFFFAOYSA-N 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- WUQGUKHJXFDUQF-UHFFFAOYSA-N naphthalene-1,2-dicarbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(C(=O)Cl)=CC=C21 WUQGUKHJXFDUQF-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- LSHSZIMRIAJWRM-UHFFFAOYSA-N oxolane-2,3-dicarbonyl chloride Chemical compound ClC(=O)C1CCOC1C(Cl)=O LSHSZIMRIAJWRM-UHFFFAOYSA-N 0.000 description 1
- MTAAPVANJNSBGV-UHFFFAOYSA-N pentane-1,1,1-tricarbonyl chloride Chemical compound CCCCC(C(Cl)=O)(C(Cl)=O)C(Cl)=O MTAAPVANJNSBGV-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- VLRIRAGKJXODNO-UHFFFAOYSA-N propane-1,1,1-tricarbonyl chloride Chemical compound CCC(C(Cl)=O)(C(Cl)=O)C(Cl)=O VLRIRAGKJXODNO-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-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
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
本発明は、スキン層とこれを支持する多孔性支持体とを含む複合半透膜及びその製造方法に関する。かかる複合半透膜は、超純水の製造、かん水または海水の脱塩などに好適であり、また染色排水や電着塗料排水などの公害発生原因である汚れなどから、その中に含まれる汚染源あるいは有効物質を除去・回収し、排水のクローズ化に寄与することができる。また、食品用途などで有効成分の濃縮、浄水や下水用途等での有害成分の除去などの高度処理に用いることができる。また、油田やシェールガス田などにおける排水処理に用いることができる。 The present invention relates to a composite semipermeable membrane comprising a skin layer and a porous support for supporting the skin layer, and a method for producing the same. Such a composite semipermeable membrane is suitable for production of ultrapure water, desalination of brine or seawater, etc., and it is also a source of contamination contained in it due to contamination that causes pollution such as dye wastewater and electrodeposition paint wastewater. Alternatively, effective substances can be removed and recovered, contributing to the closure of wastewater. Moreover, it can be used for advanced treatments such as concentration of active ingredients in food applications and removal of harmful components in water purification and sewage applications. It can also be used for wastewater treatment in oil fields, shale gas fields, and the like.
複合半透膜はその濾過性能や処理方法に応じてＲＯ（逆浸透）膜、ＮＦ（ナノ濾過）膜、ＦＯ（正浸透）膜と呼ばれ、超純水製造、海水淡水化、かん水の脱塩処理、排水の再利用処理などに用いることができる。 Composite semipermeable membranes are called RO (reverse osmosis) membranes, NF (nanofiltration) membranes, and FO (forward osmosis) membranes depending on their filtration performance and treatment methods. Ultrapure water production, seawater desalination, dewatering of brine It can be used for salt treatment, wastewater reuse treatment, and the like.
工業的に利用される複合半透膜としては、例えば、多官能アミン成分と多官能酸ハライド成分とを反応させてなるポリアミド系樹脂を含むスキン層が多孔性支持体の表面に形成されている複合半透膜が挙げられる。 As a composite semipermeable membrane utilized industrially, for example, a skin layer containing a polyamide-based resin obtained by reacting a polyfunctional amine component and a polyfunctional acid halide component is formed on the surface of the porous support. A composite semipermeable membrane is mentioned.
前記複合半透膜には、安定した水分離性能を有することが求められる。汚染物質を含む水（例えば、下水）を複合半透膜で処理すると、汚染物質がスキン層表面に吸着し、次第に透水量が低下する傾向にある。そのため、定期的に複合半透膜を洗浄処理することが必要である。特に近年では、廃水処理などにおいて原水の水質が多岐にわたっており、洗浄回数が増加する傾向にある。 The composite semipermeable membrane is required to have stable water separation performance. When water containing contaminants (for example, sewage) is treated with a composite semipermeable membrane, the contaminants are adsorbed on the surface of the skin layer, and the water permeability tends to decrease gradually. Therefore, it is necessary to periodically clean the composite semipermeable membrane. In particular, in recent years, the quality of raw water has been diversified in wastewater treatment and the like, and the number of washings tends to increase.
複合半透膜の洗浄処理には強アルカリ溶液がよく用いられるが、強アルカリ溶液で複合半透膜を洗浄処理すると複合半透膜の性質が変化し、透水量が大きく変動するという問題があった。 A strong alkaline solution is often used for cleaning the composite semipermeable membrane. However, when the composite semipermeable membrane is washed with a strong alkaline solution, the properties of the composite semipermeable membrane change and the amount of water permeation varies greatly. It was.
一方、特許文献１には、高い塩除去性とともにホウ素のような中性領域では非解離の物質にも高い阻止性能を持つ複合半透膜を得ることを目的として、微多孔性支持膜上に多官能アミンと多官能酸ハロゲン化物との重縮合反応によってポリアミド分離機能層を形成し、続いて、前記ポリアミド分離機能層にカルボン酸と縮合剤とを含む水溶液を接触させることを特徴とする複合半透膜の製造方法が開示されている。 On the other hand, Patent Document 1 discloses a composite semipermeable membrane on a microporous support membrane for the purpose of obtaining a high degree of salt removal and a high blocking performance for non-dissociated substances in a neutral region such as boron. A polyamide separation functional layer is formed by a polycondensation reaction between a polyfunctional amine and a polyfunctional acid halide, and then the polyamide separation functional layer is contacted with an aqueous solution containing a carboxylic acid and a condensing agent. A method of manufacturing a semipermeable membrane is disclosed.
本発明の目的は、強アルカリ溶液で洗浄処理しても透水性能が変化しにくい複合半透膜及びその製造方法を提供することにある。 An object of the present invention is to provide a composite semipermeable membrane in which the water permeation performance hardly changes even after washing with a strong alkaline solution, and a method for producing the same.
本発明者は、前記課題を解決すべく鋭意検討を重ねた結果、以下に示す複合半透膜により上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventor has found that the above object can be achieved by a composite semipermeable membrane shown below, and has completed the present invention.
すなわち、本発明は、ポリアミド系樹脂を含むスキン層が多孔性支持体の表面に形成されている複合半透膜において、前記ポリアミド系樹脂は、原料成分としてカルボジイミド化合物を含むことを特徴とする複合半透膜、に関する。 That is, the present invention provides a composite semipermeable membrane in which a skin layer containing a polyamide resin is formed on the surface of a porous support, wherein the polyamide resin contains a carbodiimide compound as a raw material component. Semipermeable membrane.
強アルカリ溶液で複合半透膜を洗浄処理すると、複合半透膜の透水量が大きく変動する理由は明らかではないが、強アルカリ溶液によってスキン層が構造変化（膨潤）していると考えられる。そして、本発明者は、スキン層の形成材料であるポリアミド系樹脂中に存在するカルボキシル基とカルボジイミド化合物とを反応させて、カルボキシル基を消失させ、ポリアミド系樹脂中に架橋構造を新たに形成することにより、強アルカリ溶液によるスキン層の構造変化を抑制でき、強アルカリ溶液で洗浄処理しても透水性能が変化しにくい複合半透膜が得られることを見出した。 When the composite semipermeable membrane is washed with a strong alkaline solution, the reason why the water permeability of the composite semipermeable membrane varies greatly is not clear, but it is considered that the structure of the skin layer is changed (swelled) by the strong alkaline solution. And this inventor makes the carboxyl group which exists in the polyamide-type resin which is a formation material of a skin layer react, and a carbodiimide compound, lose | disappears a carboxyl group, and forms a crosslinked structure newly in a polyamide-type resin. As a result, it was found that the structural change of the skin layer due to the strong alkaline solution can be suppressed, and a composite semipermeable membrane in which the water permeation performance does not easily change even when washing with the strong alkaline solution is obtained.
前記カルボジイミド化合物は、非水溶性であることが好ましく、Ｎ，Ｎ’−ジシクロヘキシルカルボジイミド及びＮ，Ｎ’−ジイソプロピルカルボジイミドからなる群より選択される少なくとも１種であることが好ましい。非水溶性のカルボジイミド化合物は、スキン層を形成するための多官能酸ハライド成分を含む有機溶液に直接添加することができ、それにより複合半透膜の製造工程を簡素化できるため好適である。 The carbodiimide compound is preferably water-insoluble, and is preferably at least one selected from the group consisting of N, N′-dicyclohexylcarbodiimide and N, N′-diisopropylcarbodiimide. A water-insoluble carbodiimide compound can be directly added to an organic solution containing a polyfunctional acid halide component for forming a skin layer, which is preferable because the manufacturing process of the composite semipermeable membrane can be simplified.
また、本発明は、多官能アミン成分を含む水溶液と多官能酸ハライド成分を含む有機溶液とを多孔性支持体上で接触させて、ポリアミド系樹脂を含むスキン層を多孔性支持体の表面に形成する工程を含む複合半透膜の製造方法において、前記水溶液又は有機溶液は、カルボジイミド化合物を含むことを特徴とする複合半透膜の製造方法、に関する。 In addition, the present invention provides an aqueous solution containing a polyfunctional amine component and an organic solution containing a polyfunctional acid halide component in contact with each other on the porous support so that a skin layer containing a polyamide resin is formed on the surface of the porous support. The manufacturing method of the composite semipermeable membrane including the process of forming WHEREIN: The said aqueous solution or organic solution is related with the manufacturing method of the composite semipermeable membrane characterized by including a carbodiimide compound.
さらに、本発明は、多官能アミン成分を含む水溶液と多官能酸ハライド成分を含む有機溶液とを多孔性支持体上で接触させて、ポリアミド系樹脂を含むスキン層を多孔性支持体の表面に形成する工程を含む複合半透膜の製造方法において、ポリアミド系樹脂を含むスキン層を多孔性支持体の表面に形成した後、カルボジイミド化合物を含む溶液を前記スキン層に接触させることを特徴とする複合半透膜の製造方法、に関する。 Furthermore, the present invention is such that an aqueous solution containing a polyfunctional amine component and an organic solution containing a polyfunctional acid halide component are brought into contact with each other on a porous support, and a skin layer containing a polyamide-based resin is formed on the surface of the porous support. In the method for producing a composite semipermeable membrane including a forming step, a skin layer containing a polyamide-based resin is formed on the surface of a porous support, and then a solution containing a carbodiimide compound is brought into contact with the skin layer. The present invention relates to a method for producing a composite semipermeable membrane.
前記複合半透膜の製造方法において、カルボジイミド化合物は、非水溶性であることが好ましく、Ｎ，Ｎ’−ジシクロヘキシルカルボジイミド及びＮ，Ｎ’−ジイソプロピルカルボジイミドからなる群より選択される少なくとも１種であることが好ましい。 In the method for producing a composite semipermeable membrane, the carbodiimide compound is preferably water-insoluble, and is at least one selected from the group consisting of N, N′-dicyclohexylcarbodiimide and N, N′-diisopropylcarbodiimide. It is preferable.
本発明の複合半透膜のスキン層は、ポリアミド系樹脂中のカルボキシル基とカルボジイミド化合物との反応によって形成された架橋構造を有しているため、耐アルカリ性に優れており、強アルカリ溶液で洗浄処理しても透水性能が変化しにくい。本発明の複合半透膜を用いると、強アルカリ溶液で洗浄を繰り返しても透水量が変動しにくいため、水処理の運転操作が容易になる。 The skin layer of the composite semipermeable membrane of the present invention has a cross-linked structure formed by a reaction between a carboxyl group in a polyamide-based resin and a carbodiimide compound, and thus has excellent alkali resistance and is washed with a strong alkali solution. Even if it is treated, the water permeability is unlikely to change. When the composite semipermeable membrane of the present invention is used, the water permeation amount hardly changes even when washing with a strong alkaline solution is repeated, so that the water treatment operation is facilitated.
以下、本発明の実施の形態について説明する。本発明の複合半透膜は、ポリアミド系樹脂を含むスキン層が多孔性支持体の表面に形成されているものである。 Embodiments of the present invention will be described below. In the composite semipermeable membrane of the present invention, a skin layer containing a polyamide-based resin is formed on the surface of a porous support.
前記ポリアミド系樹脂は、多官能アミン成分と多官能酸ハロゲン成分とを重合して得られる。 The polyamide resin is obtained by polymerizing a polyfunctional amine component and a polyfunctional acid halogen component.
多官能アミン成分とは、２以上の反応性アミノ基を有する多官能アミンであり、芳香族、脂肪族及び脂環式の多官能アミンが挙げられる。 The polyfunctional amine component is a polyfunctional amine having two or more reactive amino groups, and examples thereof include aromatic, aliphatic and alicyclic polyfunctional amines.
芳香族多官能アミンとしては、例えば、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、ｏ−フェニレンジアミン、１，３，５−トリアミノベンゼン、１，２，４−トリアミノベンゼン、３，５−ジアミノ安息香酸、２，４−ジアミノトルエン、２，６−ジアミノトルエン、Ｎ，Ｎ’−ジメチル−ｍ−フェニレンジアミン、２，４−ジアミノアニソール、アミドール、キシリレンジアミン等が挙げられる。 Examples of the aromatic polyfunctional amine include m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, and 3,5-diamino. Examples include benzoic acid, 2,4-diaminotoluene, 2,6-diaminotoluene, N, N′-dimethyl-m-phenylenediamine, 2,4-diaminoanisole, amidole, xylylenediamine and the like.
脂肪族多官能アミンとしては、例えば、エチレンジアミン、プロピレンジアミン、トリス（２−アミノエチル）アミン、ｎ−フェニル−エチレンジアミン等が挙げられる。 Examples of the aliphatic polyfunctional amine include ethylenediamine, propylenediamine, tris (2-aminoethyl) amine, and n-phenyl-ethylenediamine.
脂環式多官能アミンとしては、例えば、１，３−ジアミノシクロヘキサン、１，２−ジアミノシクロヘキサン、１，４−ジアミノシクロヘキサン、ピペラジン、２，５−ジメチルピペラジン、４−アミノメチルピペラジン等が挙げられる。 Examples of the alicyclic polyfunctional amine include 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylpiperazine, 4-aminomethylpiperazine, and the like. .
これらの多官能アミンは１種で用いてもよく、２種以上を併用してもよい。高塩阻止性能のスキン層を得るためには、芳香族多官能アミンを用いることが好ましい。 These polyfunctional amines may be used alone or in combination of two or more. In order to obtain a skin layer having a high salt inhibition performance, it is preferable to use an aromatic polyfunctional amine.
多官能酸ハライド成分とは、反応性カルボニル基を２個以上有する多官能酸ハライドである。 The polyfunctional acid halide component is a polyfunctional acid halide having two or more reactive carbonyl groups.
多官能酸ハライドとしては、芳香族、脂肪族及び脂環式の多官能酸ハライドが挙げられる。 Examples of the polyfunctional acid halide include aromatic, aliphatic and alicyclic polyfunctional acid halides.
芳香族多官能酸ハライドとしては、例えば、トリメシン酸トリクロライド、テレフタル酸ジクロライド、イソフタル酸ジクロライド、ビフェニルジカルボン酸ジクロライド、ナフタレンジカルボン酸ジクロライド、ベンゼントリスルホン酸トリクロライド、ベンゼンジスルホン酸ジクロライド、クロロスルホニルベンゼンジカルボン酸ジクロライド等が挙げられる。 Examples of aromatic polyfunctional acid halides include trimesic acid trichloride, terephthalic acid dichloride, isophthalic acid dichloride, biphenyldicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, benzenetrisulfonic acid trichloride, benzenedisulfonic acid dichloride, chlorosulfonylbenzene dicarboxylic acid. An acid dichloride etc. are mentioned.
脂肪族多官能酸ハライドとしては、例えば、プロパンジカルボン酸ジクロライド、ブタンジカルボン酸ジクロライド、ペンタンジカルボン酸ジクロライド、プロパントリカルボン酸トリクロライド、ブタントリカルボン酸トリクロライド、ペンタントリカルボン酸トリクロライド、グルタリルハライド、アジポイルハライド等が挙げられる。 Examples of the aliphatic polyfunctional acid halide include propanedicarboxylic acid dichloride, butanedicarboxylic acid dichloride, pentanedicarboxylic acid dichloride, propanetricarboxylic acid trichloride, butanetricarboxylic acid trichloride, pentanetricarboxylic acid trichloride, glutaryl halide, adipoid Examples include luhalides.
脂環式多官能酸ハライドとしては、例えば、シクロプロパントリカルボン酸トリクロライド、シクロブタンテトラカルボン酸テトラクロライド、シクロペンタントリカルボン酸トリクロライド、シクロペンタンテトラカルボン酸テトラクロライド、シクロヘキサントリカルボン酸トリクロライド、テトラハイドロフランテトラカルボン酸テトラクロライド、シクロペンタンジカルボン酸ジクロライド、シクロブタンジカルボン酸ジクロライド、シクロヘキサンジカルボン酸ジクロライド、テトラハイドロフランジカルボン酸ジクロライド等が挙げられる。 Examples of the alicyclic polyfunctional acid halide include cyclopropane tricarboxylic acid trichloride, cyclobutane tetracarboxylic acid tetrachloride, cyclopentane tricarboxylic acid trichloride, cyclopentane tetracarboxylic acid tetrachloride, cyclohexane tricarboxylic acid trichloride, and tetrahydrofuran. Examples thereof include tetracarboxylic acid tetrachloride, cyclopentane dicarboxylic acid dichloride, cyclobutane dicarboxylic acid dichloride, cyclohexane dicarboxylic acid dichloride, and tetrahydrofurandicarboxylic acid dichloride.
これら多官能酸ハライドは１種で用いてもよく、２種以上を併用してもよい。高塩阻止性能のスキン層を得るためには、芳香族多官能酸ハライドを用いることが好ましい。また、多官能酸ハライド成分の少なくとも一部に３価以上の多官能酸ハライドを用いて、架橋構造を形成するのが好ましい。 These polyfunctional acid halides may be used alone or in combination of two or more. In order to obtain a skin layer having a high salt inhibition performance, it is preferable to use an aromatic polyfunctional acid halide. Moreover, it is preferable to form a crosslinked structure by using a trifunctional or higher polyfunctional acid halide as at least a part of the polyfunctional acid halide component.
また、ポリアミド系樹脂を含むスキン層の性能を向上させるために、ポリビニルアルコール、ポリビニルピロリドン、ポリアクリル酸などのポリマー、ソルビトール、グリセリンなどの多価アルコールなどを共重合させてもよい。 In order to improve the performance of the skin layer containing a polyamide-based resin, a polymer such as polyvinyl alcohol, polyvinyl pyrrolidone, or polyacrylic acid, a polyhydric alcohol such as sorbitol, glycerin, or the like may be copolymerized.
スキン層を支持する多孔性支持体は、スキン層を支持しうるものであれば特に限定されず、通常平均孔径１０〜５００Å程度の微孔を有する限外濾過膜が好ましく用いられる。多孔性支持体の形成材料としては、例えば、ポリスルホン、ポリエーテルスルホンのようなポリアリールエーテルスルホン、ポリイミド、ボリフッ化ビニリデンなど種々のものをあげることができるが、特に化学的、機械的、熱的に安定である点からポリスルホン、ポリアリールエーテルスルホンが好ましく用いられる。かかる多孔性支持体の厚さは、通常約２５〜１２５μｍ、好ましくは約４０〜７５μｍであるが、必ずしもこれらに限定されるものではない。なお、多孔性支持体は織布、不織布等の基材による裏打ちにて補強されていている。 The porous support that supports the skin layer is not particularly limited as long as it can support the skin layer, and usually an ultrafiltration membrane having micropores with an average pore diameter of about 10 to 500 mm is preferably used. Examples of the material for forming the porous support include polysulfone, polyarylethersulfone such as polyethersulfone, polyimide, polyvinylidene fluoride, and the like. Polysulfone and polyarylethersulfone are preferably used from the viewpoint of stability. The thickness of such a porous support is usually about 25 to 125 μm, preferably about 40 to 75 μm, but is not necessarily limited thereto. The porous support is reinforced by backing with a base material such as a woven fabric or a non-woven fabric.
ポリアミド系樹脂を含むスキン層を多孔性支持体の表面に形成する方法は特に制限されず、あらゆる公知の手法を用いることができる。例えば、界面縮合法、相分離法、薄膜塗布法などが挙げられる。界面縮合法とは、具体的に、多官能アミン成分を含有するアミン水溶液と、多官能酸ハライド成分を含有する有機溶液とを接触させて界面重合させることによりスキン層を形成し、該スキン層を多孔性支持体上に載置する方法や、多孔性支持体上での前記界面重合によりポリアミド系樹脂のスキン層を多孔性支持体上に直接形成する方法である。かかる界面縮合法の条件等の詳細は、特開昭５８−２４３０３号公報、特開平１−１８０２０８号公報等に記載されており、それらの公知技術を適宜採用することができる。 The method for forming the skin layer containing the polyamide resin on the surface of the porous support is not particularly limited, and any known technique can be used. For example, an interfacial condensation method, a phase separation method, a thin film coating method, and the like can be given. Specifically, the interfacial condensation method is a method in which a skin layer is formed by bringing an aqueous amine solution containing a polyfunctional amine component into contact with an organic solution containing a polyfunctional acid halide component to cause interfacial polymerization. Is a method in which a polyamide resin skin layer is directly formed on a porous support by interfacial polymerization on the porous support. Details of the conditions of the interfacial condensation method are described in JP-A-58-24303, JP-A-1-180208 and the like, and those known techniques can be appropriately employed.
本発明においては、多官能アミン成分を含むアミン水溶液からなる水溶液被覆層を多孔性支持体上に形成し、次いで多官能酸ハライド成分を含有する有機溶液と水溶液被覆層とを接触させて界面重合させることによりスキン層を形成する方法が好ましい。 In the present invention, an aqueous solution coating layer comprising an aqueous amine solution containing a polyfunctional amine component is formed on a porous support, and then an organic solution containing the polyfunctional acid halide component is contacted with the aqueous solution coating layer to perform interfacial polymerization. The method of forming a skin layer by making it preferable is preferable.
また、本発明においては、ポリアミド系樹脂中に存在するカルボキシル基とカルボジイミド化合物とを反応させて、ポリアミド系樹脂中に架橋構造を形成するために、前記アミン水溶液又は有機溶液にカルボジイミド化合物を添加することが好ましく、特に有機溶液にカルボジイミド化合物を添加することが好ましい。 Further, in the present invention, a carbodiimide compound is added to the aqueous amine solution or organic solution in order to react a carboxyl group present in the polyamide-based resin with a carbodiimide compound to form a crosslinked structure in the polyamide-based resin. It is particularly preferable to add a carbodiimide compound to the organic solution.
カルボジイミド化合物は、分子内に１個以上のカルボジイミド基を有する化合物であり、例えば、Ｎ，Ｎ’−ジイソプロピルカルボジイミド、Ｎ，Ｎ’−ジ（ｏ−トルイル）カルボジイミド、Ｎ，Ｎ’−ジシクロヘキシルカルボジイミド、及びＮ，Ｎ’−ビス（２，６−ジイソプロピルフェニル）カルボジイミドなどの一官能性カルボジイミド化合物；ｐ−フェニレン−ビス（２，６−キシリルカルボジイミド）、ｐ−フェニレン−ビス（ｔ−ブチルカルボジイミド）、ｐ−フェニレン−ビス（メシチルカルボジイミド）、テトラメチレン−ビス（ｔ−ブチルカルボジイミド）、及びシクロヘキサン−１，４−ビス（メチレン−ｔ−ブチルカルボジイミド）などの二官能性カルボジイミド化合物；１，５−ナフタレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、４，４’−ジフェニルジメチルメタンジイソシアネート、１，３−フェニレンジイソシアネート、１，４−フェニレンジイソシアネート、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、２，４−トリレンジイソシアネートと２，６−トリレンジイソシアネートの混合物、ヘキサメチレンジイソシアネート、シクロヘキサン−１，４−ジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン−４，４’−ジイソシアネート、メチルシクロヘキサンジイソシアネート、テトラメチルキシリレンジイソシアネート、２，６−ジイソプロピルフェニルイソシアネート、１，３，５−トリイソプロピルベンゼン−２，４−ジイソシアネート、及びポリフェニルポリイソシアネートなどのイソシアネートの縮合物である多官能性カルボジイミド化合物；これらの塩などが挙げられる。 The carbodiimide compound is a compound having one or more carbodiimide groups in the molecule, such as N, N′-diisopropylcarbodiimide, N, N′-di (o-toluyl) carbodiimide, N, N′-dicyclohexylcarbodiimide, And monofunctional carbodiimide compounds such as N, N′-bis (2,6-diisopropylphenyl) carbodiimide; p-phenylene-bis (2,6-xylylcarbodiimide), p-phenylene-bis (t-butylcarbodiimide) , P-phenylene-bis (mesitylcarbodiimide), tetramethylene-bis (t-butylcarbodiimide), and cyclohexane-1,4-bis (methylene-t-butylcarbodiimide); 1,5 -Naphthalene diisocyanate, 4, '-Diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tril Mixture of diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diene Isocyanate, 2,6-diisopropylphenyl isocyanate, 1,3,5-triisopropylbenzene-2,4-diiso Aneto, and condensation products of isocyanates such as polyphenyl polyisocyanate polyfunctional carbodiimide compound; and salts thereof and the like.
前記カルボジイミド化合物のうち、非水溶性カルボジイミド化合物を用いることが好ましく、特にＮ，Ｎ’−ジシクロヘキシルカルボジイミド及びＮ，Ｎ’−ジイソプロピルカルボジイミドからなる群より選択される少なくとも１種を用いることが好ましい。 Of the carbodiimide compounds, water-insoluble carbodiimide compounds are preferably used, and at least one selected from the group consisting of N, N′-dicyclohexylcarbodiimide and N, N′-diisopropylcarbodiimide is particularly preferable.
前記アミン水溶液又は有機溶液中のカルボジイミド化合物の濃度は特に制限されないが、０．０１〜５重量％であることが好ましく、より好ましくは０．１〜３重量％である。カルボジイミド化合物の濃度が０．０１重量％未満の場合には、ポリアミド系樹脂中に架橋構造が十分に形成されないため、強アルカリ溶液によるスキン層の構造変化を抑制し難くなる傾向にある。一方、カルボジイミド化合物の濃度が５重量％を超える場合には、ポリアミド形成反応が阻害されるため、ポリアミド構造が十分に形成されない傾向にある。 The concentration of the carbodiimide compound in the aqueous amine solution or organic solution is not particularly limited, but is preferably 0.01 to 5% by weight, more preferably 0.1 to 3% by weight. When the concentration of the carbodiimide compound is less than 0.01% by weight, a sufficient cross-linked structure is not formed in the polyamide-based resin, so that the structural change of the skin layer due to the strong alkali solution tends to be difficult to suppress. On the other hand, when the concentration of the carbodiimide compound exceeds 5% by weight, the polyamide formation reaction is inhibited, so that the polyamide structure tends not to be sufficiently formed.
前記界面重合法において、アミン水溶液中の多官能アミン成分の濃度は特に制限されないが、０．１〜５重量％であることが好ましく、さらに好ましくは０．５〜２重量％である。多官能アミン成分の濃度が０．１重量％未満の場合にはスキン層にピンホール等の欠陥が生じやすくなり、また塩阻止性能が低下する傾向にある。一方、多官能アミン成分の濃度が５重量％を超える場合には、多官能アミン成分が多孔性支持体中に浸透しやすくなったり、膜厚が厚くなりすぎて透過抵抗が大きくなって透過流束が低下する傾向にある。 In the interfacial polymerization method, the concentration of the polyfunctional amine component in the aqueous amine solution is not particularly limited, but is preferably 0.1 to 5% by weight, more preferably 0.5 to 2% by weight. When the concentration of the polyfunctional amine component is less than 0.1% by weight, defects such as pinholes are likely to occur in the skin layer, and the salt blocking performance tends to decrease. On the other hand, when the concentration of the polyfunctional amine component exceeds 5% by weight, the polyfunctional amine component is likely to penetrate into the porous support, or the film thickness becomes too thick to increase the permeation resistance and increase the permeation flow. The bundle tends to decrease.
前記有機溶液中の多官能酸ハライド成分の濃度は特に制限されないが、０．０１〜５重量％であることが好ましく、さらに好ましくは０．０５〜３重量％である。多官能酸ハライド成分の濃度が０．０１重量％未満の場合には、未反応多官能アミン成分が残留しやすくなったり、スキン層にピンホール等の欠陥が生じやすくなって塩阻止性能が低下する傾向にある。一方、多官能酸ハライド成分の濃度が５重量％を超える場合には、未反応多官能酸ハライド成分が残留しやすくなったり、膜厚が厚くなりすぎて透過抵抗が大きくなり、透過流束が低下する傾向にある。 The concentration of the polyfunctional acid halide component in the organic solution is not particularly limited, but is preferably 0.01 to 5% by weight, and more preferably 0.05 to 3% by weight. If the concentration of the polyfunctional acid halide component is less than 0.01% by weight, the unreacted polyfunctional amine component tends to remain, or defects such as pinholes are likely to occur in the skin layer, resulting in a decrease in salt blocking performance. Tend to. On the other hand, when the concentration of the polyfunctional acid halide component exceeds 5% by weight, the unreacted polyfunctional acid halide component tends to remain, or the film thickness becomes too thick to increase the permeation resistance, thereby increasing the permeation flux. It tends to decrease.
前記有機溶液に用いられる有機溶媒としては、水に対する溶解度が低く、多孔性支持体を劣化させず、多官能酸ハライド成分を溶解するものであれば特に限定されず、例えば、シクロヘキサン、ヘプタン、オクタン、及びノナン等の飽和炭化水素、１，１，２−トリクロロトリフルオロエタン等のハロゲン置換炭化水素などを挙げることができる。好ましくは沸点が３００℃以下、さらに好ましくは沸点が２００℃以下の飽和炭化水素またはナフテン系溶媒である。有機溶媒は１種単独で用いてもよく、２種以上の混合溶媒として用いてもよい。 The organic solvent used in the organic solution is not particularly limited as long as it has low solubility in water, does not deteriorate the porous support, and dissolves the polyfunctional acid halide component. For example, cyclohexane, heptane, octane And saturated hydrocarbons such as nonane, and halogen-substituted hydrocarbons such as 1,1,2-trichlorotrifluoroethane. A saturated hydrocarbon or naphthenic solvent having a boiling point of 300 ° C. or lower, more preferably 200 ° C. or lower is preferable. The organic solvent may be used alone or as a mixed solvent of two or more.
前記アミン水溶液又は有機溶液には、製膜を容易にしたり、得られる複合半透膜の性能を向上させるための目的で各種の添加剤を加えることができる。前記添加剤としては、例えば、ドデシルベンゼンスルホン酸ナトリウム、ドデシル硫酸ナトリウム、及びラウリル硫酸ナトリウム等の界面活性剤、重合により生成するハロゲン化水素を除去する水酸化ナトリウム、リン酸三ナトリウム、及びトリエチルアミン等の塩基性化合物、アシル化触媒、特開平８−２２４４５２号公報記載の溶解度パラメータが８〜１４（ｃａｌ／ｃｍ３）１／２の化合物などが挙げられる。 Various additives can be added to the aqueous amine solution or the organic solution for the purpose of facilitating film formation or improving the performance of the resulting composite semipermeable membrane. Examples of the additive include surfactants such as sodium dodecylbenzenesulfonate, sodium dodecylsulfate, and sodium laurylsulfate, sodium hydroxide that removes hydrogen halide generated by polymerization, trisodium phosphate, and triethylamine. And basic compounds, acylation catalysts, compounds having a solubility parameter of 8 to 14 (cal / cm 3 ) 1/2 described in JP-A-8-224452, and the like.
本発明においては、ポリアミド系樹脂中に存在するカルボキシル基とカルボジイミド化合物とを反応させて、ポリアミド系樹脂中に架橋構造を形成するために、前記アミン水溶液又は有機溶液にカルボジイミド化合物を添加する代わりに、多孔性支持体の表面にスキン層を形成（ある程度形成した状態を含む）した後に、スキン層にカルボジイミド化合物を含む溶液を接触させてもよい。スキン層にカルボジイミド化合物を含む溶液を接触させた後、スキン層を加熱してポリアミド系樹脂中に存在するカルボキシル基とカルボジイミド化合物との反応を促進させてもよい。 In the present invention, instead of adding a carbodiimide compound to the amine aqueous solution or the organic solution in order to react a carboxyl group present in the polyamide resin with a carbodiimide compound to form a crosslinked structure in the polyamide resin. After the skin layer is formed on the surface of the porous support (including a state where the skin layer is formed to some extent), the skin layer may be contacted with a solution containing a carbodiimide compound. After contacting the skin layer with a solution containing a carbodiimide compound, the skin layer may be heated to promote the reaction between the carboxyl group present in the polyamide resin and the carbodiimide compound.
前記溶液は、水溶液であってもよく、有機溶液であってもよいが、有機溶液であることが好ましい。また、溶液中のカルボジイミド化合物の濃度は特に制限されないが、前記と同程度である。 The solution may be an aqueous solution or an organic solution, but is preferably an organic solution. Further, the concentration of the carbodiimide compound in the solution is not particularly limited, but is about the same as described above.
多孔性支持体上に形成したスキン層の厚みは特に制限されないが、通常０．０５〜２μｍ程度であり、好ましくは、０．１〜１μｍである。 The thickness of the skin layer formed on the porous support is not particularly limited, but is usually about 0.05 to 2 μm, preferably 0.1 to 1 μm.
本発明の複合半透膜は、その形状になんら制限を受けるものではない。すなわち平膜状、あるいはスパイラルエレメント状など、考えられるあらゆる膜形状が可能である。また、複合半透膜の塩阻止性、透水性、及び耐酸化剤性等を向上させるために、従来公知の各種処理を施してもよい。 The composite semipermeable membrane of the present invention is not limited in its shape. That is, any conceivable membrane shape such as a flat membrane shape or a spiral element shape is possible. Moreover, in order to improve the salt-blocking property, water permeability, oxidation resistance, etc. of the composite semipermeable membrane, various conventionally known treatments may be performed.
以下に実施例をあげて本発明を説明するが、本発明はこれら実施例によりなんら限定されるものではない。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
〔評価及び測定方法〕
（透過流束の測定）
作製した平膜状の複合半透膜を所定の形状、サイズに切断し、平膜評価用のセルにセットした。２０００ｍｇ／ＬのＮａＣｌを含みかつｐＨ７に調整した水溶液を２５℃で膜の供給側と透過側に１．５５ＭＰａの差圧を与えて膜に接触させた。この操作によって得られた透過水の透過速度を測定し、透過流束（ｍ３／ｍ２・ｄ）を算出した。また、作製した平膜状の複合半透膜に、水酸化ナトリウムによりｐＨ１２．５に調整したアルカリ水溶液を１．５ＭＰａの圧力で３０分間通水した。その後、前記と同様の方法で透過流束を測定した。
[Evaluation and measurement method]
(Measurement of permeation flux)
The produced flat membrane-like composite semipermeable membrane was cut into a predetermined shape and size and set in a cell for flat membrane evaluation. An aqueous solution containing 2000 mg / L NaCl and adjusted to pH 7 was brought into contact with the membrane at 25 ° C. by applying a differential pressure of 1.55 MPa to the supply side and the permeation side of the membrane. The permeation rate of the permeated water obtained by this operation was measured, and the permeation flux (m 3 / m 2 · d) was calculated. Further, an alkaline aqueous solution adjusted to pH 12.5 with sodium hydroxide was passed through the produced flat membrane-shaped composite semipermeable membrane at a pressure of 1.5 MPa for 30 minutes. Thereafter, the permeation flux was measured by the same method as described above.
実施例１
Ｎ−フェニルエチレンジアミン３重量％、ラウリル硫酸ナトリウム０．１５重量％、トリエチルアミン３重量％、カンファースルホン酸６重量％、及びイソプロピルアルコール４重量％を含有するアミン水溶液を多孔性ポリスルホン支持膜（薄膜形成側平均孔径２０ｎｍ、非対称膜）上に塗布し、その後、余分なアミン水溶液を除去することにより水溶液被覆層を形成した。次に、前記水溶液被覆層の表面にトリメシン酸クロライド０．２重量％を含有するイソオクタン溶液を塗布し、余分な溶液を除去し、そして４０秒間風乾して乾燥膜を形成した。その後、乾燥膜の表面にＮ，Ｎ’−ジシクロヘキシルカルボジイミド（ＤＣＣ）１重量％を含むイソオクタン溶液を塗布して１０秒間保持し、そして３０秒間風乾し、その後、１３０℃の熱風乾燥機中で３分間保持して、多孔性ポリスルホン支持膜上にポリアミド系樹脂を含むスキン層（厚み１μｍ）を形成して複合半透膜を作製した。
Example 1
An aqueous amine solution containing 3% by weight of N-phenylethylenediamine, 0.15% by weight of sodium lauryl sulfate, 3% by weight of triethylamine, 6% by weight of camphorsulfonic acid, and 4% by weight of isopropyl alcohol was treated with a porous polysulfone support membrane (thin film forming side). An aqueous solution coating layer was formed by removing the excess amine aqueous solution. Next, an isooctane solution containing 0.2% by weight of trimesic acid chloride was applied to the surface of the aqueous solution coating layer, the excess solution was removed, and air-dried for 40 seconds to form a dry film. Thereafter, an isooctane solution containing 1% by weight of N, N′-dicyclohexylcarbodiimide (DCC) was applied to the surface of the dried film, held for 10 seconds, and then air-dried for 30 seconds. The composite semipermeable membrane was prepared by holding for a minute and forming a skin layer (thickness 1 μm) containing a polyamide-based resin on the porous polysulfone support membrane.
実施例２
Ｎ，Ｎ’−ジシクロヘキシルカルボジイミド（ＤＣＣ）１重量％を含むイソオクタン溶液の代わりに、Ｎ，Ｎ’−ジイソプロピルカルボジイミド（ＤＩＣ）１重量％を含むイソオクタン溶液を用いた以外は実施例１と同様の方法で複合半透膜を作製した。
Example 2
The same method as in Example 1 except that an isooctane solution containing 1% by weight of N, N′-diisopropylcarbodiimide (DIC) was used instead of the isooctane solution containing 1% by weight of N, N′-dicyclohexylcarbodiimide (DCC). A composite semipermeable membrane was prepared.
実施例３
Ｎ−フェニルエチレンジアミン３重量％、ラウリル硫酸ナトリウム０．１５重量％、トリエチルアミン３重量％、カンファースルホン酸６重量％、及びイソプロピルアルコール４重量％を含有するアミン水溶液を多孔性ポリスルホン支持膜（薄膜形成側平均孔径２０ｎｍ、非対称膜）上に塗布し、その後、余分なアミン水溶液を除去することにより水溶液被覆層を形成した。次に、前記水溶液被覆層の表面にトリメシン酸クロライド０．２重量％及びＮ，Ｎ’−ジイソプロピルカルボジイミド０．１重量％を含有するイソオクタン溶液を塗布した。その後、余分な溶液を除去し、さらに１３０℃の熱風乾燥機中で３分間保持して、多孔性ポリスルホン支持膜上にポリアミド系樹脂を含むスキン層（厚み１μｍ）を形成して複合半透膜を作製した。
Example 3
An aqueous amine solution containing 3% by weight of N-phenylethylenediamine, 0.15% by weight of sodium lauryl sulfate, 3% by weight of triethylamine, 6% by weight of camphorsulfonic acid, and 4% by weight of isopropyl alcohol was treated with a porous polysulfone support membrane (thin film forming side). An aqueous solution coating layer was formed by removing the excess amine aqueous solution. Next, an isooctane solution containing 0.2% by weight of trimesic acid chloride and 0.1% by weight of N, N′-diisopropylcarbodiimide was applied to the surface of the aqueous solution coating layer. Thereafter, the excess solution is removed, and further kept in a hot air dryer at 130 ° C. for 3 minutes to form a skin layer (thickness: 1 μm) containing a polyamide-based resin on the porous polysulfone support membrane to form a composite semipermeable membrane. Was made.
比較例１
トリメシン酸クロライド０．２重量％及びＮ，Ｎ’−ジイソプロピルカルボジイミド０．１重量％を含有するイソオクタン溶液の代わりに、トリメシン酸クロライド０．２重量％を含有するイソオクタン溶液を用いた以外は実施例３と同様の方法で複合半透膜を作製した。
Comparative Example 1
Example except that an isooctane solution containing 0.2% by weight of trimesic acid chloride was used instead of an isooctane solution containing 0.2% by weight of trimesic acid chloride and 0.1% by weight of N, N′-diisopropylcarbodiimide A composite semipermeable membrane was prepared in the same manner as in No. 3.
比較例２
Ｎ−フェニルエチレンジアミン３重量％、ラウリル硫酸ナトリウム０．１５重量％、トリエチルアミン３重量％、カンファースルホン酸６重量％、及びイソプロピルアルコール４重量％を含有するアミン水溶液を多孔性ポリスルホン支持膜（薄膜形成側平均孔径２０ｎｍ、非対称膜）上に塗布し、その後、余分なアミン水溶液を除去することにより水溶液被覆層を形成した。次に、前記水溶液被覆層の表面にトリメシン酸クロライド０．２重量％を含有するイソオクタン溶液を塗布し、余分な溶液を除去し、そして４０秒間風乾し、さらに１３０℃の熱風乾燥機中で３分間保持して、多孔性ポリスルホン支持膜上にポリアミド系樹脂を含むスキン層（厚み１μｍ）を形成して複合半透膜を作製した。その後、４−（４，６−ジメトキシ−１，３，５−トリアジン−２−イル）−４−メチルモルホリニウムクロリド（ＤＭＴ）１重量％を含む水溶液中に複合半透膜を１時間浸漬してスキン層を処理した。
Comparative Example 2
An aqueous amine solution containing 3% by weight of N-phenylethylenediamine, 0.15% by weight of sodium lauryl sulfate, 3% by weight of triethylamine, 6% by weight of camphorsulfonic acid, and 4% by weight of isopropyl alcohol was treated with a porous polysulfone support membrane (thin film forming side). An aqueous solution coating layer was formed by removing the excess amine aqueous solution. Next, an isooctane solution containing 0.2% by weight of trimesic acid chloride is applied to the surface of the aqueous solution coating layer, the excess solution is removed, air-dried for 40 seconds, and further heated in a hot air dryer at 130 ° C. The composite semipermeable membrane was prepared by holding for a minute and forming a skin layer (thickness 1 μm) containing a polyamide-based resin on the porous polysulfone support membrane. Thereafter, the composite semipermeable membrane was immersed in an aqueous solution containing 1% by weight of 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (DMT) for 1 hour. And treated the skin layer.
比較例３
Ｎ−フェニルエチレンジアミン３重量％、ラウリル硫酸ナトリウム０．１５重量％、トリエチルアミン３重量％、カンファースルホン酸６重量％、イソプロピルアルコール４重量％、及び４−（４，６−ジメトキシ−１，３，５−トリアジン−２−イル）−４−メチルモルホリニウムクロリド１重量％を含有するアミン水溶液を多孔性ポリスルホン支持膜（薄膜形成側平均孔径２０ｎｍ、非対称膜）上に塗布し、その後、余分なアミン水溶液を除去することにより水溶液被覆層を形成した。次に、前記水溶液被覆層の表面にトリメシン酸クロライド０．２重量％を含有するイソオクタン溶液を塗布した。その後、余分な溶液を除去し、さらに１３０℃の熱風乾燥機中で３分間保持して、多孔性ポリスルホン支持膜上にポリアミド系樹脂を含むスキン層（厚み１μｍ）を形成して複合半透膜を作製した。
Comparative Example 3
N-phenylethylenediamine 3% by weight, sodium lauryl sulfate 0.15% by weight, triethylamine 3% by weight, camphorsulfonic acid 6% by weight, isopropyl alcohol 4% by weight, and 4- (4,6-dimethoxy-1,3,5 -Triazin-2-yl) -4-Methylmorpholinium chloride containing 1% by weight of an amine aqueous solution was coated on a porous polysulfone support membrane (thin film forming side average pore size 20 nm, asymmetric membrane), and then excess amine An aqueous solution coating layer was formed by removing the aqueous solution. Next, an isooctane solution containing 0.2% by weight of trimesic acid chloride was applied to the surface of the aqueous solution coating layer. Thereafter, the excess solution is removed, and further kept in a hot air dryer at 130 ° C. for 3 minutes to form a skin layer (thickness: 1 μm) containing a polyamide-based resin on the porous polysulfone support membrane to form a composite semipermeable membrane. Was made.
本発明の複合半透膜は、超純水の製造、かん水または海水の脱塩などに好適であり、また染色排水や電着塗料排水などの公害発生原因である汚れなどから、その中に含まれる汚染源あるいは有効物質を除去・回収し、排水のクローズ化に寄与することができる。また、食品用途などで有効成分の濃縮、浄水や下水用途等での有害成分の除去などの高度処理に用いることができる。また、油田やシェールガス田などにおける排水処理に用いることができる。 The composite semipermeable membrane of the present invention is suitable for the production of ultrapure water, brine or desalination of seawater, etc., and it is included in dirt, which is a cause of pollution such as dye wastewater and electrodeposition paint wastewater, etc. It can contribute to the closure of wastewater by removing and recovering contaminated sources or effective substances. Moreover, it can be used for advanced treatments such as concentration of active ingredients in food applications and removal of harmful components in water purification and sewage applications. It can also be used for wastewater treatment in oil fields, shale gas fields, and the like.
Claims (7)
The method for producing a composite semipermeable membrane according to any one of claims 4 to 6, wherein the carbodiimide compound is at least one selected from the group consisting of N, N'-dicyclohexylcarbodiimide and N, N'-diisopropylcarbodiimide.
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| WO2012090862A1 (en) * | 2010-12-28 | 2012-07-05 | 東レ株式会社 | Composite semipermeable membrane |
| JP2014523340A (en) * | 2012-05-31 | 2014-09-11 | エルジー・ケム・リミテッド | Highly permeable reverse osmosis membrane containing carbodiimide compound and method for producing the same |
| WO2015046582A1 (en) * | 2013-09-30 | 2015-04-02 | 東レ株式会社 | Composite semipermeable membrane and method for manufacturing same |
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| WO2012090862A1 (en) * | 2010-12-28 | 2012-07-05 | 東レ株式会社 | Composite semipermeable membrane |
| JP2014523340A (en) * | 2012-05-31 | 2014-09-11 | エルジー・ケム・リミテッド | Highly permeable reverse osmosis membrane containing carbodiimide compound and method for producing the same |
| WO2015046582A1 (en) * | 2013-09-30 | 2015-04-02 | 東レ株式会社 | Composite semipermeable membrane and method for manufacturing same |
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