WO2011122560A1 - 複合半透膜 - Google Patents
複合半透膜 Download PDFInfo
- Publication number
- WO2011122560A1 WO2011122560A1 PCT/JP2011/057637 JP2011057637W WO2011122560A1 WO 2011122560 A1 WO2011122560 A1 WO 2011122560A1 JP 2011057637 W JP2011057637 W JP 2011057637W WO 2011122560 A1 WO2011122560 A1 WO 2011122560A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composite semipermeable
- semipermeable membrane
- group
- membrane
- acid
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 119
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000000926 separation method Methods 0.000 claims abstract description 42
- 230000002378 acidificating effect Effects 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000002346 layers by function Substances 0.000 claims description 16
- 125000000524 functional group Chemical group 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- 150000002500 ions Chemical class 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000007859 condensation product Substances 0.000 abstract description 6
- 239000012466 permeate Substances 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 238000010612 desalination reaction Methods 0.000 abstract description 2
- 239000003651 drinking water Substances 0.000 abstract description 2
- 235000020188 drinking water Nutrition 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000013535 sea water Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 18
- 239000007788 liquid Substances 0.000 description 16
- 239000010408 film Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- -1 acryloyloxy group Chemical group 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229920002492 poly(sulfone) Polymers 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- YENKRZXDJWBUIY-UHFFFAOYSA-N 1-phosphonooxypropan-2-yl 2-methylprop-2-enoate Chemical compound OP(=O)(O)OCC(C)OC(=O)C(C)=C YENKRZXDJWBUIY-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-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
- 229960002130 benzoin Drugs 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- IREVRWRNACELSM-UHFFFAOYSA-J ruthenium(4+);tetrachloride Chemical compound Cl[Ru](Cl)(Cl)Cl IREVRWRNACELSM-UHFFFAOYSA-J 0.000 description 2
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 2
- ZZCNGCMJBJERQI-UHFFFAOYSA-N (1-prop-2-enoylpiperidin-4-yl) dihydrogen phosphate Chemical compound OP(O)(=O)OC1CCN(C(=O)C=C)CC1 ZZCNGCMJBJERQI-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- IJAOUFAMBRPHSJ-UHFFFAOYSA-N (4-ethenylphenyl)methylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=C(C=C)C=C1 IJAOUFAMBRPHSJ-UHFFFAOYSA-N 0.000 description 1
- CJBYXOUKKQTXPF-UHFFFAOYSA-N (4-ethenylphenyl)phosphonic acid Chemical compound OP(O)(=O)C1=CC=C(C=C)C=C1 CJBYXOUKKQTXPF-UHFFFAOYSA-N 0.000 description 1
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- MLKIVXXYTZKNMI-UHFFFAOYSA-N 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one Chemical compound CCCCCCCCCCCCC1=CC=C(C(=O)C(C)(C)O)C=C1 MLKIVXXYTZKNMI-UHFFFAOYSA-N 0.000 description 1
- CFKBCVIYTWDYRP-UHFFFAOYSA-N 10-phosphonooxydecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCOP(O)(O)=O CFKBCVIYTWDYRP-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- UHWLJHBFRWUMNP-UHFFFAOYSA-N 2-(2-methylprop-2-enoylamino)ethylphosphonic acid Chemical compound CC(=C)C(=O)NCCP(O)(O)=O UHWLJHBFRWUMNP-UHFFFAOYSA-N 0.000 description 1
- OKKJMXCNNZVCPO-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethylphosphonic acid Chemical compound CC(=C)C(=O)OCCP(O)(O)=O OKKJMXCNNZVCPO-UHFFFAOYSA-N 0.000 description 1
- XXEYEDZRUQKMLI-UHFFFAOYSA-N 2-(2-phosphonoethoxymethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)COCCP(O)(O)=O XXEYEDZRUQKMLI-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 1
- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=C(C)C=C1 PUBNJSZGANKUGX-UHFFFAOYSA-N 0.000 description 1
- AAMTXHVZOHPPQR-UHFFFAOYSA-N 2-(hydroxymethyl)prop-2-enoic acid Chemical compound OCC(=C)C(O)=O AAMTXHVZOHPPQR-UHFFFAOYSA-N 0.000 description 1
- GPLACOONWGSIIP-UHFFFAOYSA-N 2-(n-[2-hydroxy-3-(2-methylprop-2-enoyloxy)propyl]anilino)acetic acid Chemical compound CC(=C)C(=O)OCC(O)CN(CC(O)=O)C1=CC=CC=C1 GPLACOONWGSIIP-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- AZCYBBHXCQYWTO-UHFFFAOYSA-N 2-[(2-chloro-6-fluorophenyl)methoxy]benzaldehyde Chemical compound FC1=CC=CC(Cl)=C1COC1=CC=CC=C1C=O AZCYBBHXCQYWTO-UHFFFAOYSA-N 0.000 description 1
- JDKSTARXLKKYPS-UHFFFAOYSA-N 2-[10-(2-methylprop-2-enoyloxy)decyl]propanedioic acid Chemical compound CC(=C)C(=O)OCCCCCCCCCCC(C(O)=O)C(O)=O JDKSTARXLKKYPS-UHFFFAOYSA-N 0.000 description 1
- LBNDGEZENJUBCO-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethyl]butanedioic acid Chemical compound CC(=C)C(=O)OCCC(C(O)=O)CC(O)=O LBNDGEZENJUBCO-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 description 1
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- FJXHGUOSFCDKJT-UHFFFAOYSA-N 2-ethyl-4-methoxypentanoic acid Chemical compound C(C)C(C(=O)O)CC(C)OC FJXHGUOSFCDKJT-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- MCIIDRLDHRQKPH-UHFFFAOYSA-N 2-methyl-3-phenylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=CC=C1 MCIIDRLDHRQKPH-UHFFFAOYSA-N 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-UHFFFAOYSA-N 0.000 description 1
- XDXCRCUBZYXJFW-UHFFFAOYSA-M 3-(3-ethenylimidazol-1-ium-1-yl)propyl-trimethoxysilane;chloride Chemical group [Cl-].CO[Si](OC)(OC)CCC[N+]=1C=CN(C=C)C=1 XDXCRCUBZYXJFW-UHFFFAOYSA-M 0.000 description 1
- RUEMJMLXCZVLPB-UHFFFAOYSA-M 3-[3-[(4-ethenylphenyl)methyl]imidazol-3-ium-1-yl]propyl-trimethoxysilane;chloride Chemical group [Cl-].CO[Si](OC)(OC)CCCN1C=C[N+](CC=2C=CC(C=C)=CC=2)=C1 RUEMJMLXCZVLPB-UHFFFAOYSA-M 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- ATBDZSAENDYQDW-UHFFFAOYSA-N 3-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(C=C)=C1 ATBDZSAENDYQDW-UHFFFAOYSA-N 0.000 description 1
- VWXZFDWVWMQRQR-UHFFFAOYSA-N 3-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C=C)=C1 VWXZFDWVWMQRQR-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- OXEZLYIDQPBCBB-UHFFFAOYSA-N 4-(3-piperidin-4-ylpropyl)piperidine Chemical compound C1CNCCC1CCCC1CCNCC1 OXEZLYIDQPBCBB-UHFFFAOYSA-N 0.000 description 1
- LUOHHCFFFGGPPJ-UHFFFAOYSA-M 5-[3-(3-trimethoxysilylpropyl)imidazol-3-ium-1-yl]pent-1-en-3-one;chloride Chemical group [Cl-].CO[Si](OC)(OC)CCC[N+]=1C=CN(CCC(=O)C=C)C=1 LUOHHCFFFGGPPJ-UHFFFAOYSA-M 0.000 description 1
- PIEJYLBGEXCEPO-UHFFFAOYSA-N 7-cyanooctanoic acid Chemical compound N#CC(C)CCCCCC(O)=O PIEJYLBGEXCEPO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- MEWCWKPCZOAQHT-UHFFFAOYSA-N CC1(CC=CC=2C(C3=CC=CC=C3SC12)=O)C Chemical compound CC1(CC=CC=2C(C3=CC=CC=C3SC12)=O)C MEWCWKPCZOAQHT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 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 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- DKKXSNXGIOPYGQ-UHFFFAOYSA-N diphenylphosphanyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(C=1C=CC=CC=1)C1=CC=CC=C1 DKKXSNXGIOPYGQ-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000004693 imidazolium salts Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- RZKYDQNMAUSEDZ-UHFFFAOYSA-N prop-2-enylphosphonic acid Chemical compound OP(O)(=O)CC=C RZKYDQNMAUSEDZ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000000626 sulfinic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- VBCHPEHFLCAQHA-UHFFFAOYSA-M trimethoxy-[3-(3-methylimidazol-3-ium-1-yl)propyl]silane;chloride Chemical group [Cl-].CO[Si](OC)(OC)CCCN1C=C[N+](C)=C1 VBCHPEHFLCAQHA-UHFFFAOYSA-M 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
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
- B01D65/022—Membrane sterilisation
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/34—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling by radiation
- B01D2321/343—By UV radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/14—Membrane materials having negatively charged functional groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
- B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Definitions
- the present invention relates to a composite semipermeable membrane for selectively separating components of a liquid mixture and a method for producing the same. Specifically, the present invention relates to a composite semipermeable membrane comprising a separation functional layer and a microporous support for supporting the separation functional layer and having excellent selective separation.
- membrane separation methods have been actively used in the water treatment field as a low-cost process for saving energy and resources.
- Typical membranes used in membrane separation methods include microfiltration membranes, ultrafiltration membranes, nanofiltration membranes (NF membranes), and reverse osmosis membranes (RO membranes).
- RO membranes and NF membranes are composite semipermeable membranes, most of which have a thin layer (separation functional layer) obtained by crosslinking a gel layer and a polymer on a microporous support membrane, and a microporous
- a thin layer obtained by crosslinking a gel layer and a polymer on a microporous support membrane
- a microporous One of those having a thin film layer (separation function layer) obtained by polycondensing monomers on a support membrane, and a crosslinked polyamide is frequently used as a material for these thin film layers.
- Semipermeable membranes are widely used by being applied to reverse osmosis membranes and NF membranes because the water permeability and the salt removal rate are likely to be high.
- Patent Document 3 an organic / inorganic compound in which a hydrophilic organic polymer and a condensation product of a silicon compound are combined using intermolecular interaction as in Patent Document 3, Patent Document 4, and Non-Patent Document 1.
- Hybrid materials are known, but no examples of practical use in industrial applications have been reported so far.
- an object of the present invention is to provide a composite semipermeable membrane excellent in selective separation of divalent ions with respect to monovalent ions and further excellent in long-term resistance, and a method for producing the same. .
- the present invention for achieving the above object has the following configuration.
- a composite semipermeable membrane having a separation functional layer on a microporous support membrane, wherein the separation functional layer is a polymer having an acidic group and a functional group represented by the general formula (1) in the side chain A composite semipermeable membrane comprising a condensation product.
- n is an integer of 1 to 4, and R 1 and R 2 are each selected from a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, or are mutually shared.
- R 3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- the polymer is obtained by polymerizing at least one of a compound represented by the general formula (2) and a compound having an acidic group and a polymerizable double bond (I) or (II) ) Composite semipermeable membrane.
- n is an integer of 1 to 4.
- R 1 and R 2 are each selected from a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, or are mutually shared.
- R 3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
- R 4 represents a functional group having a polymerizable double bond, and
- Y ⁇ represents any anion. .
- a composite semipermeable membrane excellent in selective separation of divalent ions relative to monovalent ions can be obtained.
- the composite semipermeable membrane of the present invention has superior selective separation, so it is economically superior to conventional composite semipermeable membranes, and the chlorine-containing raw water is permeated continuously or intermittently to sterilize the membrane. Even if it goes, it does not deteriorate as the conventional composite semipermeable membrane.
- a separation functional layer having substantially separation performance is coated on a microporous support membrane having substantially no separation performance.
- the microporous support membrane is intended to give strength to the separation functional layer that has substantially no separation performance such as ions and substantially has separation performance.
- the size and distribution of the pores are not particularly limited.
- the pores have uniform and fine pores or fine pores that gradually change greatly from the surface on the side where the separation functional layer is formed to the other surface, and have a separation function.
- a microporous support membrane having a micropore size of 0.1 nm to 100 nm on the surface on which the layer is formed is preferred.
- the material used for the microporous support membrane and its shape are not particularly limited, but it is usually composed of a porous support formed on a base material, for example, at least one selected from polyester or aromatic polyamide as a main component Polysulfone, cellulose acetate, polyvinyl chloride, or a mixture thereof (porous support) reinforced with a fabric (base material) is preferably used.
- a material used as the porous support it is particularly preferable to use polysulfone having high chemical, mechanical and thermal stability.
- polysulfone composed of repeating units represented by the following chemical formula because the pore diameter is easy to control and the dimensional stability is high.
- N, N-dimethylformamide (DMF) solution of the above polysulfone is cast on a densely woven polyester cloth or non-woven fabric to a certain thickness and wet coagulated in water, thereby increasing the surface mass.
- a microporous support membrane having fine pores with a diameter of several tens of nm or less can be obtained.
- the thickness of the above-mentioned microporous support membrane affects the strength of the composite semipermeable membrane and the packing density when it is used as an element. In order to obtain sufficient mechanical strength and packing density, it is preferably in the range of 50 ⁇ m or more and 300 ⁇ m or less, more preferably in the range of 100 ⁇ m or more and 250 ⁇ m or less.
- the thickness of the porous support in the microporous support membrane is preferably in the range of 10 ⁇ m to 200 ⁇ m, more preferably in the range of 30 ⁇ m to 100 ⁇ m.
- the form of the porous support can be observed with a scanning electron microscope, a transmission electron microscope, or an atomic microscope.
- a scanning electron microscope the porous support is peeled off from the base material, and then cut by a freeze cleaving method to obtain a sample for cross-sectional observation.
- the sample is thinly coated with platinum, platinum-palladium, or ruthenium tetrachloride, preferably ruthenium tetrachloride, and observed with a high-resolution field emission scanning electron microscope (UHR-FE-SEM) at an acceleration voltage of 3 to 6 kV.
- UHR-FE-SEM high-resolution field emission scanning electron microscope
- Hitachi S-900 electron microscope can be used as the high-resolution field emission scanning electron microscope.
- the film thickness and surface pore diameter of the porous support are determined from the obtained electron micrograph.
- the thickness and the hole diameter in the present invention mean an average value when measured five times.
- the separation functional layer is a layer substantially having separation performance, and is characterized by comprising a condensation product of a polymer having an acidic group and a functional group represented by the general formula (1). is there.
- this separation functional layer it is considered that a desired effect can be obtained by the present invention because the acidic group and the functional group represented by the general formula (1) are ionically bonded.
- Examples of the method for forming the separation functional layer include a coating containing at least one compound having an acidic group and at least one polymerizable double bond, and the compound represented by the general formula (2).
- Examples of the method include a step of applying a liquid, a step of removing a solvent, a step of polymerizing a polymerizable double bond, and a step of condensing a hydrolyzable group. In the step of polymerizing the polymerizable double bond, the hydrolyzable group may be condensed at the same time.
- a method for obtaining a coating liquid for example, at least one compound having an acidic group and at least one polymerizable double bond and a compound represented by the general formula (2) are used as a solvent.
- distributes is mentioned inside, the method will not be limited if the said coating liquid contains 2 types of compounds.
- a part of the compound having an acidic group and at least one polymerizable double bond or the compound represented by the general formula (2) is ionized in water according to its dissociation equilibrium constant.
- the method for applying the coating liquid on the microporous support film is not particularly limited, and it can be applied by various known methods such as dip coating, spin coating, spray coating, and brush coating.
- the film is allowed to stand by being covered with a film such as a polyester film whose degree of polymerization does not change by contact with a solvent. preferable. This is because the necessary amount of coating liquid is reduced and the operation is simple.
- the standing time is preferably 30 seconds or more and 2 minutes or less. Further, after peeling off the film, it is desirable to sufficiently drain the liquid so that no droplets remain on the film.
- a method for draining a method of forcibly draining by blowing air such as nitrogen from an air nozzle can be used.
- the composite semipermeable membrane of the present invention is obtained by applying the coating liquid onto the microporous support membrane, irradiating with energy rays, and then drying by heating.
- polymerization of at least one compound having an acidic group and at least one polymerizable double bond with the compound represented by the general formula (2) by irradiation with energy rays, and an acidic group and at least one compound It is considered that polymerization between compounds having a polymerizable double bond and polymerization between compounds represented by the general formula (2) occur.
- the irradiation time of the energy beam is preferably 5 seconds or more and 30 minutes or less.
- the functional group represented by the general formula (1) is condensed by heating and a condensation product is obtained.
- the heating temperature at this time is the performance as a separation membrane because the microporous support membrane is melted. Is required to be lower than the temperature at which the temperature decreases.
- the reaction temperature is preferably 150 ° C. or lower. If the reaction temperature is 0 ° C. or higher, the hydrolysis and condensation reaction proceed rapidly, and if it is 150 ° C. or lower, the hydrolysis and condensation reaction are easily controlled. Further, by adding a catalyst that promotes hydrolysis or condensation, the reaction can proceed even at a lower temperature.
- the heating condition and the humidity condition are selected so that the separation functional layer has pores, and the condensation reaction is appropriately performed.
- the composite semipermeable membrane obtained by the above production method is preferably hydrophilized by immersing it in an alcohol aqueous solution for 1 to 20 minutes. This is because alcohol is soluble in water and easily compatible with the hydrophobic membrane surface, so that the membrane surface can be hydrophilized and the amount of membrane water can be increased.
- an aqueous alcohol solution used for hydrophilization a 10 wt% isopropyl alcohol aqueous solution is generally used.
- Examples of the acidic group in the present invention include, but are not limited to, a sulfonic acid group, a sulfinic acid group, a carboxyl group, a phosphonic acid group, a phosphinic acid group, a hydroxyl group, and a thiol group.
- a sulfonic acid group a sulfinic acid group
- a carboxyl group a phosphonic acid group
- a phosphinic acid group a hydroxyl group
- a thiol group examples of the acidic group in the present invention.
- at least one selected from a carboxyl group, a sulfonic acid group, and a phosphonic acid group is preferable from the viewpoint of acidity and availability of the reagent.
- the polymer having an acidic group and a functional group represented by the general formula (1) includes at least one compound having at least one polymerizable double bond and the general formula. It is preferable to polymerize the compound represented by (2).
- Examples of the polymerizable double bond in the present invention include (meth) acryloyl group, (meth) acryloyloxy group, (meth) acrylamide group, allyl group, vinyl group, and styryl group, but are not limited thereto. is not.
- examples of the compound having a carboxylic acid group include the following. Maleic acid, maleic anhydride, acrylic acid, methacrylic acid, 2- (hydroxymethyl) acrylic acid, 4- (meth) acryloyloxyethyl trimellitic acid and the corresponding anhydride, 10-methacryloyloxydecylmalonic acid, N- ( 2-hydroxy-3-methacryloyloxypropyl) -N-phenylglycine and 4-vinylbenzoic acid.
- the compounds having a phosphonic acid group include vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinylbenzylphosphonic acid, 2-methacryloyloxyethylphosphonic acid, 2-methacrylamidoethylphosphonic acid, 4-methacrylamideamido-4-methyl-phenyl-phosphonic acid, 2- [4- (dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid and Illustrative is 2- [2-dihydroxyphosphoryl) -ethoxymethyl] -acrylic acid-2,4,6-trimethyl-phenyl ester.
- the phosphoric acid ester compounds include 2-methacryloyloxypropyl monohydrogen phosphate and 2-methacryloyloxypropyl dihydrogen phosphate.
- the compound having a sulfonic acid group may be vinyl sulfonic acid, 4-vinylphenyl sulfonic acid, or 3- (methacrylamide) propyl.
- a sulfonic acid is mentioned.
- vinyl sulfonic acid and its salt For example, vinyl sulfonic acid and its salt, allyl sulfonic acid, o-styrene sulfonic acid and its salt, p-styrene sulfonic acid and its salt, m-styrene sulfonic acid and its salt, 2-vinyl benzoic acid and its salt, 3 -Vinylbenzoic acid and its salt, 4-vinylbenzoic acid and its salt, acrylic acid and its salt, methacrylic acid and its salt, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 3,5 -Diacrylamide benzoic acid, vinyl phosphonic acid, allyl phosphonic acid, o-styrene phosphonic acid and its salt, p-styrene phosphonic acid and its salt, m-styrene phosphonic acid and its salt, and the like.
- the compounds represented by the general formula (2) are R 1 and R 2 are hydrogen atoms, R 4 is an allyl group, and n is 3.
- R 1 and R 2 are hydrogen atoms
- R 4 is an allyl group
- n is 3.
- the acidic group of the polymer present in the thin film is preferably at least one selected from a carboxylic acid group, a sulfonic acid group, and a phosphonic acid group.
- the content of the compound represented by the general formula (2) in the coating liquid is preferably about 10% by weight to 90% by weight in the reactive tissue. More preferably, it is about 50% by weight or more.
- the acidic group present in the condensation product as the separation functional layer of the composite semipermeable membrane and the imidazolium group in the functional group represented by the general formula (1) form an ionic bond. It is characterized by that.
- the solvent used in the coating solution any solvent that does not dissolve the microporous support membrane and is miscible with water can be used without particular limitation.
- the coating solution preferably contains equimolar or more water with respect to the number of condensable functional groups of the functional group represented by the general formula (1). .
- a polymerization initiator In addition, a polymerization initiator, a polymerization aid, and other additives may be included as long as the effects of the present invention are not impaired.
- a polymerization initiator In the production method of the present invention, it is preferable to add a polymerization initiator, a polymerization accelerator or the like in order to increase the polymerization reactivity.
- the polymerization initiator and the polymerization accelerator are not particularly limited, and are appropriately selected according to the structure of the compound containing one or more polymerizable double bonds, the polymerization technique, and the like.
- any known one can be used without particular limitation as long as it is soluble in the solvent used.
- ultraviolet rays As the energy rays, ultraviolet rays, plasma, gamma rays, electron beams, and the like can be used. Among them, ultraviolet rays are preferably used and a wavelength of 172 nm is more preferably used because of ease of apparatus and handling.
- the concentration of the polymerization initiator to be added is 5% by weight in the reactive composition. The following is preferable.
- the composite semipermeable membrane of the present invention formed in this way has a large number of pores together with a raw water channel material such as a plastic net, a permeate channel material such as tricot, and a film for increasing pressure resistance if necessary. Is wound around a cylindrical water collecting pipe and is suitably used as a spiral composite semipermeable membrane element. Furthermore, a composite semipermeable membrane module in which these elements are connected in series or in parallel and accommodated in a pressure vessel can be obtained.
- the above-described composite semipermeable membrane, its elements, and modules can be combined with a pump for supplying raw water to them, a device for pretreating the raw water, and the like to constitute a fluid separation device.
- a separation device By using this separation device, permeated water such as drinking water and concentrated water that has not permeated through the membrane can be separated from raw water to obtain water suitable for the purpose, and can be expected to be used in industrial applications. .
- the rejection rate (Rej) of the composite semipermeable membrane is calculated by the following equation (3)
- the permeation rate (Flux) of the composite semipermeable membrane is calculated by the following equation (4).
- an excimer lamp UER20-172 manufactured by USHIO INC. which can irradiate ultraviolet rays of 172 nm, is used, and the distance between the lamp and the microporous support film is set to 1 cm. It was set and irradiated with ultraviolet rays for 10 minutes, and then dried with a hot air dryer at 120 ° C. for 2 hours to obtain a composite semipermeable membrane.
- the composite semipermeable membrane thus obtained was immersed in a 10% isopropyl alcohol aqueous solution for 10 minutes, and then 500 ppm saline adjusted to pH 6.5 was used as a feed solution, and the conditions were reversed under conditions of 0.75 MPa and 25 ° C.
- Table 1 shows the results of a reverse osmosis test conducted under the conditions of 0.75 MPa and 25 ° C. using a 1500 ppm MgSO 4 aqueous solution as a supply liquid.
- Example 2 Coating liquid A was prepared by adding 1.5 parts by weight of sodium p-styrenesulfonate, 3.5 parts by weight of 1-allyl-3- (3-trimethoxysilylpropyl) imidazolium chloride and 2,2-dimethoxy-1,2-diphenyl.
- coating solution B consisting of 0.15 parts by weight of ethane-1-one and 94.76 parts by weight of 65% isopropyl alcohol aqueous solution
- an excimer lamp UER20-172 manufactured by Ushio Electric Co., Ltd. which can irradiate 172 nm ultraviolet rays
- the distance of the microporous support membrane was set to 1 cm, and the process of irradiating ultraviolet rays for 10 minutes was performed using a UV irradiation device TOSCURE752 manufactured by Harrison Toshiba Lighting Co., which can irradiate 365 nm ultraviolet rays, and the irradiation intensity was set to 20 mW / cm 2.
- a composite semipermeable membrane was prepared in the same manner as in Example 1 except that the step of irradiating with 30 minutes was used. The composite semipermeable membrane thus obtained was evaluated in the same manner as in Example 1, and the performance shown in Table 1 was obtained.
- Example 3 Except that 1-allyl-3- (3-trimethoxysilylpropyl) imidazolium chloride used in Example 1 was replaced with 1- (2-acryloylethyl) -3- (3-trimethoxysilylpropyl) imidazolium chloride A composite semipermeable membrane was produced in the same manner as in Example 1. The composite semipermeable membrane thus obtained was evaluated in the same manner as in Example 1, and the performance shown in Table 1 was obtained.
- Example 4 1-Allyl-3- (3-trimethoxysilylpropyl) imidazolium chloride used in Example 1 was replaced with 1- (4-vinylbenzyl) -3- (3-trimethoxysilylpropyl) imidazolium chloride.
- a composite semipermeable membrane was produced in the same manner as in Example 1. The composite semipermeable membrane thus obtained was evaluated in the same manner as in Example 1, and the performance shown in Table 1 was obtained.
- Example 5 Same as Example 1 except that 1-allyl-3- (3-trimethoxysilylpropyl) imidazolium chloride used in Example 1 is replaced with 1-vinyl-3- (3-trimethoxysilylpropyl) imidazolium chloride. Thus, a composite semipermeable membrane was produced. The composite semipermeable membrane thus obtained was evaluated in the same manner as in Example 1, and the performance shown in Table 1 was obtained.
- Example 6 The coating solution A used in Example 1 was 0.8 parts by weight of acrylic acid, 3.0 parts by weight of 1-allyl-3- (3-trimethoxysilylpropyl) imidazolium chloride, and 2,2-dimethoxy-1,2 A composite semipermeable membrane was prepared in the same manner as in Example 1 except that the coating liquid C was composed of 0.14 parts by weight of -diphenylethane-1-one and 96.06 parts by weight of 65% isopropyl alcohol aqueous solution. The composite semipermeable membrane thus obtained was evaluated in the same manner as in Example 1, and the performance shown in Table 1 was obtained.
- Example 7 Coating solution A used in Example 1 was prepared by adding 1.0 part by weight of p-vinylbenzoic acid, 3.0 parts by weight of 1-allyl-3- (3-trimethoxysilylpropyl) imidazolium chloride and 2,2-dimethoxy- A composite semipermeable membrane was prepared in the same manner as in Example 1 except that the coating solution C was changed to 0.14 parts by weight of 1,2-diphenylethane-1-one and 95.86 parts by weight of 65% isopropyl alcohol aqueous solution. The composite semipermeable membrane thus obtained was evaluated in the same manner as in Example 1, and the performance shown in Table 1 was obtained.
- Comparative Example 1 On the microporous support membrane produced by the same method as in Example 1, 0.8% by weight of piperazine, 0.2% by weight of 1,3-bis (4-piperidyl) propane, a surfactant (Japanese emulsifier ( New Coal 271A) 0.5% by weight and an aqueous solution containing 1.0% by weight of trisodium phosphate were applied, drained with an air knife, and then air-dried with warm air at 120 ° C. for 40 seconds. Thereafter, a 0.3 wt% decane solution of trimesic acid chloride was applied, and then heat treated with hot air at 100 ° C.
- a surfactant Japanese emulsifier ( New Coal 271A) 0.5% by weight
- an aqueous solution containing 1.0% by weight of trisodium phosphate were applied, drained with an air knife, and then air-dried with warm air at 120 ° C. for 40 seconds. Thereafter, a 0.3 wt% de
- the composite semipermeable membrane obtained in Comparative Example 1 is inferior in the selective separation of divalent ions with respect to monovalent ions as compared with the composite semipermeable membranes obtained in Examples 1 to 7. It was shown that.
- Comparative Example 2 A composite semipermeable membrane in the same manner as in Example 1 except that 1-allyl-3- (3-trimethoxysilylpropyl) imidazolium chloride is replaced with 3-methyl-1- (3-trimethoxysilylpropyl) imidazolium chloride. was made. The composite semipermeable membrane thus obtained was evaluated in the same manner as in Example 1, and the performance shown in Table 1 was obtained.
- Comparative Example 3 A composite semipermeable membrane was prepared in the same manner as in Example 1 except that 1-allyl-3- (3-trimethoxysilylpropyl) imidazolium chloride was replaced with 3-chloropropyltrimethoxysilane. The composite semipermeable membrane thus obtained was evaluated in the same manner as in Example 1, and the performance shown in Table 1 was obtained.
- Example 4 The reaction solution in Example 1 was the same as Example 1 except that 1-allyl-3- (3-trimethoxysilylpropyl) imidazolium chloride was not contained and 5% by weight of sodium p-styrenesulfonate was used. Thus, a composite semipermeable membrane was produced. The obtained composite semipermeable membrane was evaluated in the same manner as in Example 1, and the results shown in Table 1 were obtained.
- Example 5 The reaction solution in Example 1 did not contain sodium p-styrenesulfonate, and was the same as Example 1 except that 1-allyl-3- (3-trimethoxysilylpropyl) imidazolium chloride was 5% by weight. Thus, a composite semipermeable membrane was produced. The obtained composite semipermeable membrane was evaluated in the same manner as in Example 1, and the results shown in Table 1 were obtained.
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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- Separation Using Semi-Permeable Membranes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
(II)酸性基がカルボキシル基、スルホン酸基、およびホスホン酸基のうちから選ばれる、少なくとも1種であることを特徴とする、(I)に記載の複合半透膜。
Flux(m/d)=(一日の透過液量)/(膜面積) ・・・式(4)
実施例1
21cm×15cmのポリエステル不織布(通気度0.5~1cc/cm2/sec)上にポリスルホンの15.3重量%ジメチルホルムアミド(DMF)溶液を200μmの厚みで室温(25℃)でキャストし、ただちに純水中に浸漬して5分間放置することによって微多孔性支持膜を作製した。
塗液Aをp-スチレンスルホン酸ナトリウム1.5重量部、1-アリル-3-(3-トリメトキシシリルプロピル)イミダゾリウムクロリド3.5重量部、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン0.15重量部、65%イソプロピルアルコール水溶液94.76重量部からなる塗液Bに代え、172nmの紫外線が照射できるウシオ電機社製エキシマランプUER20-172を用い、照射窓と微多孔性支持膜の距離を1cmに設定し紫外線を10分間照射する工程を365nmの紫外線が照射できるハリソン東芝ライティング社製UV照射装置TOSCURE752を用い、照射強度を20mW/cm2に設定し、紫外線を30分間照射する工程に代える以外は実施例1と同様にして複合半透膜を作製した。また、このようにして得られた複合半透膜を実施例1と同様にして評価を行い、表1に示す性能が得られた。
実施例1で使用した1-アリル-3-(3-トリメトキシシリルプロピル)イミダゾリウムクロリドを1-(2-アクリロイルエチル)-3-(3-トリメトキシシリルプロピル)イミダゾリウムクロリドに代える以外は実施例1と同様にして複合半透膜を作製した。また、このようにして得られた複合半透膜を実施例1と同様にして評価を行い、表1に示す性能が得られた。
実施例1で使用した1-アリル-3-(3-トリメトキシシリルプロピル)イミダゾリウムクロリドを1-(4-ビニルベンジル)-3-(3-トリメトキシシリルプロピル)イミダゾリウムクロリドに代える以外は実施例1と同様にして複合半透膜を作製した。また、このようにして得られた複合半透膜を実施例1と同様にして評価を行い、表1に示す性能が得られた。
実施例1で使用した1-アリル-3-(3-トリメトキシシリルプロピル)イミダゾリウムクロリドを1-ビニル-3-(3-トリメトキシシリルプロピル)イミダゾリウムクロリドに代える以外は実施例1と同様にして複合半透膜を作製した。また、このようにして得られた複合半透膜を実施例1と同様にして評価を行い、表1に示す性能が得られた。
実施例1で使用した塗液Aをアクリル酸0.8重量部、1-アリル-3-(3-トリメトキシシリルプロピル)イミダゾリウムクロリド3.0重量部、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン0.14重量部、65%イソプロピルアルコール水溶液96.06重量部からなる塗液Cに代える以外は実施例1と同様にして複合半透膜を作製した。また、このようにして得られた複合半透膜を実施例1と同様にして評価を行い、表1に示す性能が得られた。
実施例1で使用した塗液Aをp-ビニル安息香酸1.0重量部、1-アリル-3-(3-トリメトキシシリルプロピル)イミダゾリウムクロリド3.0重量部、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン0.14重量部、65%イソプロピルアルコール水溶液95.86重量部からなる塗液Cに代える以外は実施例1と同様にして複合半透膜を作製した。また、このようにして得られた複合半透膜を実施例1と同様にして評価を行い、表1に示す性能が得られた。
実施例1と同様の方法にて作製した微多孔性支持膜上に、ピペラジン0.8重量%、1,3-ビス(4-ピペリジル)プロパン0.2重量%、界面活性剤(日本乳化剤(株)製、ニューコール271A)0.5重量%、リン酸三ナトリウム1.0重量%を含有した水溶液を塗布し、エアーナイフで液切りした後、120℃の温風で40秒間風乾した。その後、トリメシン酸クロライドの0.3重量%デカン溶液を塗布し、その後、100℃の熱風で5分間熱処理し、反応を進行させてから、炭酸ナトリウム5.0重量%とドデシル硫酸ナトリウム0.1重量%からなるアルカリ水溶液を塗布して反応を停止させ、複合半透膜を得た。また、このようにして得られた複合半透膜を実施例1と同様にして評価を行い、表1に示す性能が得られた。
1-アリル-3-(3-トリメトキシシリルプロピル)イミダゾリウムクロリドを3-メチル-1-(3-トリメトキシシリルプロピル)イミダゾリウムクロリドに代える以外は実施例1と同様にして複合半透膜を作製した。また、このようにして得られた複合半透膜を実施例1と同様にして評価を行い、表1に示す性能が得られた。
1-アリル-3-(3-トリメトキシシリルプロピル)イミダゾリウムクロリドを3-クロロプロピルトリメトキシシランに代える以外は実施例1と同様にして複合半透膜を作製した。また、このようにして得られた複合半透膜を実施例1と同様にして評価を行い、表1に示す性能が得られた。
実施例1における反応液中に、1-アリル-3-(3-トリメトキシシリルプロピル)イミダゾリウムクロリドを含まず、p-スチレンスルホン酸ナトリウムを5重量%とする以外は実施例1と同様にして複合半透膜を作製した。得られた複合半透膜を実施例1と同様にして評価を行い、表1に示す結果が得られた。
実施例1における反応液中に、p-スチレンスルホン酸ナトリウムを含まず、1-アリル-3-(3-トリメトキシシリルプロピル)イミダゾリウムクロリドを5重量%とする以外は実施例1と同様にして複合半透膜を作製した。得られた複合半透膜を実施例1と同様にして評価を行い、表1に示す結果が得られた。
Claims (3)
- 酸性基がカルボキシル基、スルホン酸基、およびホスホン酸基のうちから選ばれる、少なくとも1種であることを特徴とする、請求項1に記載の複合半透膜。
Priority Applications (7)
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US13/579,138 US8672143B2 (en) | 2010-03-30 | 2011-03-28 | Composite semipermeable membrane |
AU2011235748A AU2011235748A1 (en) | 2010-03-30 | 2011-03-28 | Composite semipermeable membrane |
KR1020127023589A KR101744207B1 (ko) | 2010-03-30 | 2011-03-28 | 복합 반투막 |
EP11762784.4A EP2554249B1 (en) | 2010-03-30 | 2011-03-28 | Composite semipermeable membrane |
SG2012062022A SG183809A1 (en) | 2010-03-30 | 2011-03-28 | Composite semipermeable membrane |
CN201180017098.6A CN102834167B (zh) | 2010-03-30 | 2011-03-28 | 复合半透膜 |
JP2011526730A JP5776550B2 (ja) | 2010-03-30 | 2011-03-28 | 複合半透膜 |
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EP (1) | EP2554249B1 (ja) |
JP (1) | JP5776550B2 (ja) |
KR (1) | KR101744207B1 (ja) |
CN (1) | CN102834167B (ja) |
AU (1) | AU2011235748A1 (ja) |
SG (1) | SG183809A1 (ja) |
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US20140371340A1 (en) * | 2011-10-31 | 2014-12-18 | The Board Of Trustees Of The University Of Arkansas | Catalytic Membranes And Applications Thereof |
JP2015066494A (ja) * | 2013-09-30 | 2015-04-13 | 東レ株式会社 | 複合半透膜およびその製造方法 |
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WO2010113656A1 (ja) * | 2009-03-31 | 2010-10-07 | 東レ株式会社 | 複合半透膜およびその製造方法 |
US8757396B2 (en) * | 2010-05-24 | 2014-06-24 | Dow Global Technologies Llc | Composite membrane with coating comprising polyalkylene oxide and oxy-substituted phenyl compounds |
CN104927079B (zh) * | 2015-07-10 | 2018-03-02 | 常州大学 | 一种碱性阴离子交换膜的制备方法 |
CN115448943A (zh) * | 2021-06-09 | 2022-12-09 | 华为技术有限公司 | 离子液体及其制备方法、表面修饰的二氧化硅及其应用 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US20140371340A1 (en) * | 2011-10-31 | 2014-12-18 | The Board Of Trustees Of The University Of Arkansas | Catalytic Membranes And Applications Thereof |
US9339803B2 (en) * | 2011-10-31 | 2016-05-17 | Board Of Trustees Of The University Of Arkansas | Catalytic membranes and applications thereof |
US20160256861A1 (en) * | 2011-10-31 | 2016-09-08 | The Board Of Trustees Of The University Of Arkansas | Catalytic membranes and applications thereof |
US10118168B2 (en) * | 2011-10-31 | 2018-11-06 | Board Of Trustees Of The University Of Arkansas | Catalytic membranes and applications thereof |
JP2015066494A (ja) * | 2013-09-30 | 2015-04-13 | 東レ株式会社 | 複合半透膜およびその製造方法 |
Also Published As
Publication number | Publication date |
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EP2554249A1 (en) | 2013-02-06 |
AU2011235748A1 (en) | 2012-09-27 |
CN102834167A (zh) | 2012-12-19 |
KR20130038195A (ko) | 2013-04-17 |
US20130032530A1 (en) | 2013-02-07 |
EP2554249B1 (en) | 2016-02-10 |
KR101744207B1 (ko) | 2017-06-07 |
CN102834167B (zh) | 2014-11-05 |
JPWO2011122560A1 (ja) | 2013-07-08 |
SG183809A1 (en) | 2012-10-30 |
JP5776550B2 (ja) | 2015-09-09 |
EP2554249A4 (en) | 2013-12-04 |
US8672143B2 (en) | 2014-03-18 |
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