JP5413689B2 - モザイク荷電膜 - Google Patents
モザイク荷電膜 Download PDFInfo
- Publication number
- JP5413689B2 JP5413689B2 JP2011508388A JP2011508388A JP5413689B2 JP 5413689 B2 JP5413689 B2 JP 5413689B2 JP 2011508388 A JP2011508388 A JP 2011508388A JP 2011508388 A JP2011508388 A JP 2011508388A JP 5413689 B2 JP5413689 B2 JP 5413689B2
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- group
- block copolymer
- mol
- film
- 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.)
- Active
Links
- 239000012528 membrane Substances 0.000 title claims description 109
- 229920001400 block copolymer Polymers 0.000 claims description 80
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 66
- 239000000178 monomer Substances 0.000 claims description 57
- 125000002091 cationic group Chemical group 0.000 claims description 53
- 125000000129 anionic group Chemical group 0.000 claims description 45
- 229920000642 polymer Polymers 0.000 claims description 45
- 150000001450 anions Chemical class 0.000 claims description 19
- 150000001768 cations Chemical class 0.000 claims description 16
- 239000000470 constituent Substances 0.000 claims description 8
- 230000032258 transport Effects 0.000 claims description 3
- 239000010408 film Substances 0.000 description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- 239000004372 Polyvinyl alcohol Substances 0.000 description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- -1 vinyl compound Chemical class 0.000 description 34
- 239000007864 aqueous solution Substances 0.000 description 30
- 230000004907 flux Effects 0.000 description 30
- 238000000034 method Methods 0.000 description 30
- 238000006116 polymerization reaction Methods 0.000 description 27
- 150000003839 salts Chemical class 0.000 description 27
- 238000005342 ion exchange Methods 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 238000000502 dialysis Methods 0.000 description 19
- 238000005259 measurement Methods 0.000 description 19
- 125000003396 thiol group Chemical group [H]S* 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 238000004132 cross linking Methods 0.000 description 16
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 14
- 239000003957 anion exchange resin Substances 0.000 description 14
- 239000003729 cation exchange resin Substances 0.000 description 14
- 229910052783 alkali metal Inorganic materials 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 11
- 150000003863 ammonium salts Chemical class 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000007127 saponification reaction Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000008961 swelling Effects 0.000 description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 238000010526 radical polymerization reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229920001567 vinyl ester resin Polymers 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000011033 desalting Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229920006317 cationic polymer Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000010220 ion permeability Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000003204 osmotic effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920002959 polymer blend Polymers 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- QGFSQVPRCWJZQK-UHFFFAOYSA-N 9-Decen-1-ol Chemical compound OCCCCCCCCC=C QGFSQVPRCWJZQK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical compound OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical group OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- DCFJTMOYYVXKID-UHFFFAOYSA-M (3-ethenylphenyl)methyl-triethylazanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC(C=C)=C1 DCFJTMOYYVXKID-UHFFFAOYSA-M 0.000 description 1
- SFUTVNGZOYYCHP-UHFFFAOYSA-N (3-ethenylphenyl)methyl-trimethylazanium Chemical compound C[N+](C)(C)CC1=CC=CC(C=C)=C1 SFUTVNGZOYYCHP-UHFFFAOYSA-N 0.000 description 1
- WTWXMHBMXQXEOX-UHFFFAOYSA-M (3-ethenylphenyl)methyl-trimethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)CC1=CC=CC(C=C)=C1 WTWXMHBMXQXEOX-UHFFFAOYSA-M 0.000 description 1
- ZDEQQWGIEVYLSQ-UHFFFAOYSA-M (3-ethenylphenyl)methyl-trimethylazanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC(C=C)=C1 ZDEQQWGIEVYLSQ-UHFFFAOYSA-M 0.000 description 1
- RSGSRVZMECOJNA-UHFFFAOYSA-M (4-ethenylphenyl)methyl-triethylazanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=C(C=C)C=C1 RSGSRVZMECOJNA-UHFFFAOYSA-M 0.000 description 1
- WIKAJTNLVCYEQJ-UHFFFAOYSA-N (4-ethenylphenyl)methyl-trimethylazanium Chemical compound C[N+](C)(C)CC1=CC=C(C=C)C=C1 WIKAJTNLVCYEQJ-UHFFFAOYSA-N 0.000 description 1
- HSVXASICUZXWQE-UHFFFAOYSA-M (4-ethenylphenyl)methyl-trimethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)CC1=CC=C(C=C)C=C1 HSVXASICUZXWQE-UHFFFAOYSA-M 0.000 description 1
- VYYHGIIMGCZIIS-UHFFFAOYSA-M (4-ethenylphenyl)methyl-trimethylazanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=C(C=C)C=C1 VYYHGIIMGCZIIS-UHFFFAOYSA-M 0.000 description 1
- TVXNKQRAZONMHJ-UHFFFAOYSA-M (4-ethenylphenyl)methyl-trimethylazanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=C(C=C)C=C1 TVXNKQRAZONMHJ-UHFFFAOYSA-M 0.000 description 1
- YWZFPUQFDQLPPG-UHFFFAOYSA-N (4-prop-1-en-2-ylphenyl)phosphonic acid Chemical compound CC(=C)C1=CC=C(P(O)(O)=O)C=C1 YWZFPUQFDQLPPG-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 1
- APQXWKHOGQFGTB-UHFFFAOYSA-N 1-ethenyl-9h-carbazole Chemical class C12=CC=CC=C2NC2=C1C=CC=C2C=C APQXWKHOGQFGTB-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- IBTLFDCPAJLATQ-UHFFFAOYSA-N 1-prop-2-enoxybutane Chemical compound CCCCOCC=C IBTLFDCPAJLATQ-UHFFFAOYSA-N 0.000 description 1
- LWJHSQQHGRQCKO-UHFFFAOYSA-N 1-prop-2-enoxypropane Chemical compound CCCOCC=C LWJHSQQHGRQCKO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- ICHLZWNYHPCCQT-UHFFFAOYSA-N 2-(4-ethenylphenyl)ethanamine;hydrochloride Chemical compound [Cl-].[NH3+]CCC1=CC=C(C=C)C=C1 ICHLZWNYHPCCQT-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- MLMGJTAJUDSUKA-UHFFFAOYSA-N 2-ethenyl-1h-imidazole Chemical class C=CC1=NC=CN1 MLMGJTAJUDSUKA-UHFFFAOYSA-N 0.000 description 1
- MISYYDHMQJZYMH-UHFFFAOYSA-N 2-ethenylnaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(C=C)C=CC2=C1 MISYYDHMQJZYMH-UHFFFAOYSA-N 0.000 description 1
- ONUXAGYOFJLIQM-UHFFFAOYSA-N 2-ethenylnaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=C(C=C)C=CC2=C1 ONUXAGYOFJLIQM-UHFFFAOYSA-N 0.000 description 1
- ZDHWTWWXCXEGIC-UHFFFAOYSA-N 2-ethenylpyrimidine Chemical class C=CC1=NC=CC=N1 ZDHWTWWXCXEGIC-UHFFFAOYSA-N 0.000 description 1
- XUGNJOCQALIQFG-UHFFFAOYSA-N 2-ethenylquinoline Chemical class C1=CC=CC2=NC(C=C)=CC=C21 XUGNJOCQALIQFG-UHFFFAOYSA-N 0.000 description 1
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 1
- SSONCJTVDRSLNK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;hydrochloride Chemical compound Cl.CC(=C)C(O)=O SSONCJTVDRSLNK-UHFFFAOYSA-N 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 description 1
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- OJXVWULQHYTXRF-UHFFFAOYSA-N 3-ethenoxypropan-1-ol Chemical compound OCCCOC=C OJXVWULQHYTXRF-UHFFFAOYSA-N 0.000 description 1
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- LNIRBSSUMJWSBZ-UHFFFAOYSA-N 4-prop-1-en-2-ylbenzenesulfonic acid Chemical compound CC(=C)C1=CC=C(S(O)(=O)=O)C=C1 LNIRBSSUMJWSBZ-UHFFFAOYSA-N 0.000 description 1
- YUCOVHFIYPJDDN-UHFFFAOYSA-N 4-prop-1-en-2-ylbenzoic acid Chemical compound CC(=C)C1=CC=C(C(O)=O)C=C1 YUCOVHFIYPJDDN-UHFFFAOYSA-N 0.000 description 1
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002518 Polyallylamine hydrochloride Polymers 0.000 description 1
- 239000004153 Potassium bromate Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- FTWDWEZLMXLCJX-UHFFFAOYSA-N S(=O)(=O)=CC(=O)O[SiH](OC(C)=O)OC(C)=O Chemical compound S(=O)(=O)=CC(=O)O[SiH](OC(C)=O)OC(C)=O FTWDWEZLMXLCJX-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- NDCAQOIUIIGHEU-UHFFFAOYSA-M diethyl-methyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CCOC(=O)C(C)=C NDCAQOIUIIGHEU-UHFFFAOYSA-M 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PNZDZRMOBIIQTC-UHFFFAOYSA-N ethanamine;hydron;bromide Chemical compound Br.CCN PNZDZRMOBIIQTC-UHFFFAOYSA-N 0.000 description 1
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical group NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- ZHAONEHNCCQNSC-UHFFFAOYSA-M ethyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC[N+](C)(C)CCOC(=O)C(C)=C ZHAONEHNCCQNSC-UHFFFAOYSA-M 0.000 description 1
- CBPRYBYRYMOWDF-UHFFFAOYSA-N ethyl-dimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC[N+](C)(C)CCCNC(=O)C=C CBPRYBYRYMOWDF-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 125000004970 halomethyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052740 iodine Chemical group 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- WXPWPYISTQCNDP-UHFFFAOYSA-N oct-7-en-1-ol Chemical compound OCCCCCCC=C WXPWPYISTQCNDP-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 235000019396 potassium bromate Nutrition 0.000 description 1
- 229940094037 potassium bromate Drugs 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical class CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- NCDYOSPPJZENCU-UHFFFAOYSA-M triethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CCOC(=O)C=C NCDYOSPPJZENCU-UHFFFAOYSA-M 0.000 description 1
- UFBSHLICJBTXGQ-UHFFFAOYSA-M triethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CCOC(=O)C(C)=C UFBSHLICJBTXGQ-UHFFFAOYSA-M 0.000 description 1
- RJNGNWBDDLDAAP-UHFFFAOYSA-N triethyl-[2-(prop-2-enoylamino)ethyl]azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CCNC(=O)C=C RJNGNWBDDLDAAP-UHFFFAOYSA-N 0.000 description 1
- IHCQGWLMZOSZFM-UHFFFAOYSA-N triethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CCCNC(=O)C(C)=C IHCQGWLMZOSZFM-UHFFFAOYSA-N 0.000 description 1
- PLEPDIIXZWQNEP-UHFFFAOYSA-M triethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CCCOC(=O)C(C)=C PLEPDIIXZWQNEP-UHFFFAOYSA-M 0.000 description 1
- IACHBBYPUKLZPO-UHFFFAOYSA-N triethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CCCNC(=O)C=C IACHBBYPUKLZPO-UHFFFAOYSA-N 0.000 description 1
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 1
- GXJFCAAVAPZBDY-UHFFFAOYSA-N trimethyl-[2-(2-methylprop-2-enoylamino)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCC[N+](C)(C)C GXJFCAAVAPZBDY-UHFFFAOYSA-N 0.000 description 1
- USFMMZYROHDWPJ-UHFFFAOYSA-N trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical compound CC(=C)C(=O)OCC[N+](C)(C)C USFMMZYROHDWPJ-UHFFFAOYSA-N 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 1
- NFUDTVOYLQNLPF-UHFFFAOYSA-M trimethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCCC[N+](C)(C)C NFUDTVOYLQNLPF-UHFFFAOYSA-M 0.000 description 1
- PJBPZVVDWYDAHL-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)CCCNC(=O)C=C PJBPZVVDWYDAHL-UHFFFAOYSA-N 0.000 description 1
- XYAHMUGLVOAFIU-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCNC(=O)C=C XYAHMUGLVOAFIU-UHFFFAOYSA-N 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N vinyl ethyl ether Natural products CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
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
- B01D71/76—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
-
- 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
- B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
- B01D65/109—Testing of membrane fouling or clogging, e.g. amount or affinity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/18—Membrane materials having mixed charged functional groups
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Graft Or Block Polymers (AREA)
Description
末端にメルカプト基を含有するビニルアルコール系重合体は、例えば、特許文献4などに記載されている方法により得ることができる。すなわち、チオール酸の存在下にビニルエステル単量体、例えば酢酸ビニルを主体とするビニル系単量体をラジカル重合して得られるビニルエステル系重合体をけん化する方法が挙げられる。
(分子末端にメルカプト基を有するポリビニルアルコール系重合体の合成)
特開昭59−187003号広報に記載された方法によって、表1に示す分子末端にメルカプト基を有するポリビニルアルコール(PVA−1)を合成した。
1)膜電位試験からの荷電密度の測定
膜電位試験は図1に示す測定セルを用いて、両セルの濃度比r=5に保持した状態で両セルのKCl(ナカライテスク(株))濃度を変化させて膜電位を測定した。このとき電位は高濃度側を基準とした。低濃度側のKCl水溶液と測定膜電位との関係は下記の式(I)に示すTeorell-Meyer and Sievers 理論式(TMS理論)を用いて解析することで膜荷電密度を算出した。25℃で測定を行った。
ΔΦ:膜電位[V]
Cx:膜荷電密度(荷電基の符号を含む)[mol・m−3]
C0:低濃度側セルの塩濃度[mol・m−3]
ωc:カチオンの移動度[mol・m2・J−1・s−1]
ωa:アニオンの移動度[mol・m2・J−1・s−1]
F:ファラデー定数[C・mol−1]
R:ガス定数[J・K−1・mol−1]
T:絶対温度[K]
浸透水試験は図2に示す浸透水測定セル及び目盛り付キャピラリからなる装置を用いて行った。測定膜サンプルを自作セル間にセットし、左側セルに5.0×10−2ないしは
5.0×10−1(mol/L)のKCl溶液を約20ml、右側セルに脱イオン水を約20mlを入れ、キャピラリをセットし測定を開始した。測定は25℃で行った。所定時間tにおけるキャピラリのメニスカスの位置の変化を計測し、これよりキャピラリ内の水の移動距離Lを計測することで、移動した水のモル数nを計算した。得られた時間tと移動した水のモル数nとの初期勾配の値をキャピラリの断面積で除することで、水の体積流量[m・s−1]を得た。この結果より、水の透過流束JW[mol・m−2・s−1]を以下に示す下記の式(II)より算出した。
JV:体積流量[m・s−1]
圧透析試験による塩透過流束を測定するため、実施例及び比較例で得られたモザイク荷電膜を複合膜にして評価した。ビニロン合成紙(坪量:50±5g/m2、厚さ:160±25μm)とモザイク荷電膜を重ね合わせ、熱プレス機で温度150℃、圧力10Kg/cm2の条件で10分間熱プレスを行うことで、複合膜を得た。続いて、圧透析試験は図3に示す圧透析測定セルを用いて行った。フォルダに挟んだ複合膜を2つのセルの間に挟み、右側セル(加圧側)に濃度35000ppmのNaCl水溶液50mLを、左側セル(開放側)に濃度35000ppmのNaCl水溶液50mLを入れ、両セルをスターラーで撹拌させながら、右側セルの圧力3Mpa、25℃の一定温度下で開放側のセルの伝導度を1分毎に100分間測定した。次に、予め作成したNaCl−伝導度検量線を用いて得られた伝導度から開放側のNaCl濃度を決定した。この結果から、単位時間、単位面積あたりの塩透過流束(mol/(m2・s))を算出した。
還流冷却管、攪拌翼を備え付けた5L四つ口セパラブルフラスコに、水1140g、末端にメルカプト基を有するビニルアルコール系重合体として表1に示すPVA−1を344g仕込み、攪拌下95℃まで加熱して該ビニルアルコール系重合体を溶解した後、室温まで冷却した。該水溶液に1/2規定の硫酸を添加してpHを3.0に調整した。別に、メタクリル酸アミドプロピルトリメチルアンモニウムクロライド183gを水220gに溶解し、これを先に調製した水溶液に攪拌下添加した後、70℃まで加温し、また、水溶液中に窒素をバブリングしながら30分間系内を窒素置換した。窒素置換後、上記水溶液に過硫酸カリウムの2.5%水溶液176mLを1.5時間かけて逐次的に添加してブロック共重合を開始、進行させた後、系内温度を75℃に1時間維持して重合をさらに進行させ、ついで冷却して、固形分濃度15%のPVA−(b)−p−メタクリル酸アミドプロピルトリメチルアンモニウムクロライドブロック共重合体水溶液を得た。得られた水溶液の一部を乾燥した後、重水に溶解し、400MHzでの1H−NMR測定に付した結果、−メタクリル酸アミドプロピルトリメチルアンモニウムクロライド単位の変性量は10モル%であった。
末端にメルカプト基を有するビニルアルコール系重合体の種類と量、カチオン性基含有単量体の種類と仕込み量、重合開始剤の使用量などの重合条件を表2,3に示すように変化させた以外はP−1と同様の方法によりP−2〜P−6、P―8、P−10、P―12〜P−16を得た。得られたポリマーの物性を、表2、3に示す。
P−6の濃度15%水溶液に水酸化ナトリウムを0.08mol%添加して、110度、1時間加熱することで加水分解させて、固形分濃度14%のPVA−(b)−ビニルアミンブロック共重合体水溶液を得た(得られた水溶液の一部を乾燥した後、重水に溶解し、400MHzでの1H−NMR測定に付した結果、ビニルアミン単位の変性量は10モル%であった)。また、B型粘度計で測定した4%水溶液粘度は16ミリPa・s(20℃)であった。
P−8の水溶液を、縦270mm×横210mmのアクリル製のキャスト板に流し込み、余分な液、気泡を除去した後、50℃のホットプレート上で24時間乾燥させることにより、皮膜を作製した。こうして得られた皮膜を、ヨウ化メチルの蒸気中、室温下で10時間処理を行いビニルピリジン部分を四級化することで、PVA−(b)−四級化ビニルピリジンブロック共重合体したフィルムを得た(得られたフィルムを重水に溶解し、400MHzでの1H−NMR測定に付した結果、四級化ビニルピリジン単位の変性量は10モル%であった)。また、濃度4%に調整した水溶液をB型粘度計で測定したところ、粘度は16ミリPa・s(20℃)であった。
攪拌機、温度センサー、滴下漏斗及び還流冷却管を備え付けた6Lセパラブルフラスコに、酢酸ビニル1960g、メタノール820g、及びメタクリル酸アミドプロピルトリメチルアンモニウムクロライドを30質量%含有するメタノール溶液23gを仕込み、攪拌下に系内を窒素置換した後、内温を60℃まで上げた。この系に2,2’−アゾビスイソブチロニトリルを0.4g含有するメタノール20gを添加し、重合反応を開始した。重合開始時点よりメタクリル酸アミドプロピルトリメチルアンモニウムクロライドを30質量%含有するメタノール溶液300gを系内に添加しながら、4時間重合反応を行った後、重合反応を停止した。重合反応を停止した時点における系内の固形分濃度、すなわち、重合反応スラリー全体に対する固形分の含有率は22.3質量%であった。ついで、系内にメタノール蒸気を導入することにより、未反応の酢酸ビニル単量体を追い出し、ビニルエステル共重合体を55質量%含有するメタノール溶液を得た。
酢酸ビニル(VAc)、メタノール(MeOH)、イオン基含有単量体の種類と仕込み量、重合開始剤の使用量、イオン基を有する単量体の逐次添加条件などの重合条件、けん化反応の条件を表4に示すように変化させた以外はP−11と同様の方法により、P−17〜P−18を得た。得られたポリマーの物性を表4に示す。
(モザイク荷電膜の作製)
アニオン交換樹脂層:P−1に脱イオン水を必要量加えて濃度10%に調整した。この溶液を、縦270mm×横210mmのアクリル製のキャスト板に流し込み、余分な液、気泡を除去した後、50℃のホットプレート上で24時間乾燥させることにより、厚み100μmの皮膜を作製した。
カチオン交換樹脂層:P−12に脱イオン水を必要量加えて濃度10%に調整した。この溶液を、縦270mm×横210mmのアクリル製のキャスト板に流し込み、余分な液、気泡を除去した後、50℃のホットプレート上で24時間乾燥させることにより、厚み100μmの皮膜を作製した。
このようにして作製したモザイク荷電膜を、所望の大きさに裁断し、測定試料を作製した。得られた測定試料を用い、上記方法に従って、荷電密度及び水の透過流束の測定を行った。また、得られたモザイク荷電膜を上述したように複合膜とした際の、圧透析試験による塩透過流束の測定を行った。得られた結果を表5に示す。
アニオン交換樹脂とカチオン交換樹脂の種類、アニオン交換樹脂(カチオン性ブロック共重合体(P))とカチオン交換樹脂(アニオン性ブロック共重合体(Q))の荷電密度の比(a)/(b)、及び熱処理温度を表5に示す内容に変更した以外は、実施例1と同様にしてモザイク荷電膜を作製し、その膜特性を測定した。得られた測定結果を表5に示す。
アニオン交換樹脂層:200mL三角フラスコに、90mLの脱イオン水を入れ、ポリビニルアルコールPVA117(重合度1700、けん化度98.5mol%:(株)クラレ製)を15g加えてから、95℃のウオーターバスの中で加熱撹拌し溶解させた。その後、ポリジアリルジメチルアンモニウムクロライド(アルドリッチ製:濃度20%、分子量40−50万)を19g混合した後、所望の脱イオン水を加えて固形分濃度10%の水溶液を調製した(PVA117/ポリジアリルジメチルアンモニウムクロライド=80/20固形分重量部比率)。このようにして調製した分散液を、縦270mm×横210mmのアクリル製のキャスト板に流し込み、余分な液、気泡を除去した後、50℃のホットプレート上で24時間乾燥させることにより、厚み100μmの皮膜を作製した。
アニオン交換樹脂とカチオン交換樹脂の種類を表5に示す内容に変更した以外は、実施例1と同様にしてモザイク荷電膜を作製し、その膜特性を測定した。得られた測定結果を表5に示す。
アニオン交換樹脂とカチオン交換樹脂の代わりに無変性のポリビニルアルコールPVA117((株)クラレ製)を用いた以外は、実施例1と同様にして膜を作製し、その膜特性を測定した。得られた測定結果を表5に示す。
2:Ag−AgCl電極
3:試料膜(膜面積:7cm2)
4:電位計
5:試料膜(膜面積:3cm2)
6:キャピラリ
7:KCl水溶液
8:脱イオン水
9:セル
10:N2ボンベ
11:圧力計
12:スターラー
13:試料膜(膜面積:5cm2)
14:伝導度計
Claims (3)
- アニオンを輸送する正荷電領域とカチオンを輸送する負荷電領域がモザイク状に並んでいて、各領域が膜の両面まで貫通したモザイク荷電膜であって;
ビニルアルコール系重合体ブロック(A)及びカチオン性基を有する重合体ブロック(B)を構成成分とするカチオン性ブロック共重合体(P)からなる正荷電領域と、
ビニルアルコール系重合体ブロック(C)及びアニオン性基を有する重合体ブロック(D)を構成成分とするアニオン性ブロック共重合体(Q)からなる負荷電領域と、
を含有することを特徴とするモザイク荷電膜。 - 前記カチオン性ブロック共重合体(P)中のカチオン性基を有する単量体の含有量が0.1モル%以上である請求項1記載のモザイク荷電膜。
- 前記アニオン性ブロック共重合体(Q)中のアニオン性基を有する単量体の含有量が0.1モル%以上である請求項1記載のモザイク荷電膜。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011508388A JP5413689B2 (ja) | 2009-04-09 | 2010-04-08 | モザイク荷電膜 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009095209 | 2009-04-09 | ||
JP2009095209 | 2009-04-09 | ||
PCT/JP2010/056364 WO2010117036A1 (ja) | 2009-04-09 | 2010-04-08 | モザイク荷電膜 |
JP2011508388A JP5413689B2 (ja) | 2009-04-09 | 2010-04-08 | モザイク荷電膜 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPWO2010117036A1 JPWO2010117036A1 (ja) | 2012-10-18 |
JP5413689B2 true JP5413689B2 (ja) | 2014-02-12 |
Family
ID=42936317
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2011508388A Active JP5413689B2 (ja) | 2009-04-09 | 2010-04-08 | モザイク荷電膜 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20120034481A1 (ja) |
EP (1) | EP2418013A4 (ja) |
JP (1) | JP5413689B2 (ja) |
CN (1) | CN102548646B (ja) |
TW (1) | TW201041915A (ja) |
WO (1) | WO2010117036A1 (ja) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8716358B2 (en) * | 2009-03-25 | 2014-05-06 | Kuraray Co., Ltd. | Anion exchange membrane and method for producing same |
JP5531267B2 (ja) * | 2009-04-13 | 2014-06-25 | 国立大学法人山口大学 | イオン交換膜およびその製造方法 |
KR101768434B1 (ko) | 2009-12-28 | 2017-08-16 | 주식회사 쿠라레 | 모자이크 하전 복층막 및 그 제조 방법 |
JP5413684B2 (ja) * | 2010-09-29 | 2014-02-12 | 株式会社クラレ | 軟水の製造方法、軟水製造装置およびモザイク荷電膜 |
JP5413682B2 (ja) * | 2010-09-29 | 2014-02-12 | 株式会社クラレ | ミネラル水の製造方法、ミネラル水製造装置、およびモザイク荷電膜 |
KR101890747B1 (ko) * | 2011-11-03 | 2018-10-01 | 삼성전자주식회사 | 이온 교환막 충전용 조성물, 이온 교환막의 제조방법, 이온 교환막 및 레독스 플로우 전지 |
US9266066B2 (en) * | 2011-12-13 | 2016-02-23 | Pall Corporation | Membrane with localized asymmetries |
US9315113B2 (en) | 2012-12-21 | 2016-04-19 | Ample Inc. | Electric vehicle battery systems with exchangeable parallel electric vehicle battery modules |
CN106582304B (zh) * | 2016-12-30 | 2019-09-03 | 浙江工业大学 | 一种荷电镶嵌膜的制备方法 |
JP7349492B2 (ja) * | 2019-03-20 | 2023-09-22 | 東ソー・ファインケム株式会社 | 上限臨界溶液温度を有する新規なポリスチレンベースのポリアンホライト及びその用途 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11239720A (ja) * | 1998-02-25 | 1999-09-07 | Dainichiseika Color & Chem Mfg Co Ltd | 荷電モザイク膜、荷電モザイク膜の製造方法、荷電モザイク膜の使用方法及び荷電モザイク膜を備えた装置 |
JP2008188518A (ja) * | 2007-02-02 | 2008-08-21 | Yamaguchi Univ | イオンバリヤー膜および該イオンバリヤー膜を使用した分離装置 |
JP2008264704A (ja) * | 2007-04-20 | 2008-11-06 | Takuma Co Ltd | 両性荷電膜及びその製造方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IL63638A0 (en) * | 1980-09-16 | 1981-11-30 | Aligena Ag | Semipermeable composite membranes,their manufacture and their use |
JPS59187003A (ja) | 1983-04-07 | 1984-10-24 | Kuraray Co Ltd | 末端にメルカプト基を有するポリビニルアルコ−ル系重合体およびその製法 |
JPH0674304B2 (ja) | 1983-04-08 | 1994-09-21 | 株式会社クラレ | ポリビニルアルコール系重合体を一成分とするブロツク共重合体の製法 |
JPH0644977B2 (ja) | 1983-04-30 | 1994-06-15 | 東ソー株式会社 | 両性イオン交換膜を用いた有機化合物の脱塩方法 |
JP3234426B2 (ja) | 1994-11-30 | 2001-12-04 | 大日精化工業株式会社 | モザイク荷電膜の製造方法及びモザイク荷電膜 |
JP3453067B2 (ja) * | 1998-02-25 | 2003-10-06 | 大日精化工業株式会社 | 荷電モザイク膜、荷電モザイク膜の使用方法及び荷電モザイク膜を備えた装置 |
US7094490B2 (en) * | 2002-05-13 | 2006-08-22 | Polyfuel, Inc. | Ion conductive block copolymers |
CN1326598C (zh) * | 2004-12-17 | 2007-07-18 | 清华大学 | 一种利用自组装技术制备双极性膜的方法 |
JP4730942B2 (ja) | 2005-04-25 | 2011-07-20 | 株式会社タクマ | モザイク荷電膜及びその製造方法 |
CN1305553C (zh) * | 2005-06-22 | 2007-03-21 | 南京工业大学 | 自组装技术制备有机无机复合膜的方法 |
KR101137277B1 (ko) * | 2007-01-23 | 2012-04-20 | 가부시키가이샤 구라레 | 고분자 전해질막, 이의 제조 방법, 막-전극 접합체 및 고체 고분자형 연료 전지 |
CN101590377B (zh) * | 2009-07-09 | 2011-09-07 | 济南大学 | 用于渗透汽化的聚乙烯醇两性聚电解质膜及其制备方法 |
-
2010
- 2010-04-08 US US13/263,260 patent/US20120034481A1/en not_active Abandoned
- 2010-04-08 EP EP10761735.9A patent/EP2418013A4/en not_active Withdrawn
- 2010-04-08 JP JP2011508388A patent/JP5413689B2/ja active Active
- 2010-04-08 CN CN201080025729.4A patent/CN102548646B/zh not_active Expired - Fee Related
- 2010-04-08 TW TW99110876A patent/TW201041915A/zh unknown
- 2010-04-08 WO PCT/JP2010/056364 patent/WO2010117036A1/ja active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11239720A (ja) * | 1998-02-25 | 1999-09-07 | Dainichiseika Color & Chem Mfg Co Ltd | 荷電モザイク膜、荷電モザイク膜の製造方法、荷電モザイク膜の使用方法及び荷電モザイク膜を備えた装置 |
JP2008188518A (ja) * | 2007-02-02 | 2008-08-21 | Yamaguchi Univ | イオンバリヤー膜および該イオンバリヤー膜を使用した分離装置 |
JP2008264704A (ja) * | 2007-04-20 | 2008-11-06 | Takuma Co Ltd | 両性荷電膜及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
TW201041915A (en) | 2010-12-01 |
EP2418013A1 (en) | 2012-02-15 |
CN102548646A (zh) | 2012-07-04 |
CN102548646B (zh) | 2015-12-02 |
WO2010117036A1 (ja) | 2010-10-14 |
US20120034481A1 (en) | 2012-02-09 |
EP2418013A4 (en) | 2013-10-23 |
JPWO2010117036A1 (ja) | 2012-10-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5413689B2 (ja) | モザイク荷電膜 | |
JP5531267B2 (ja) | イオン交換膜およびその製造方法 | |
JP5715558B2 (ja) | 陰イオン交換膜及びその製造方法 | |
CA2814699C (en) | Anion exchange membranes and process for making | |
JP6150232B2 (ja) | 通液型コンデンサ、その製造方法、及びそれを有する脱塩装置 | |
JP5413684B2 (ja) | 軟水の製造方法、軟水製造装置およびモザイク荷電膜 | |
JP6300374B2 (ja) | 陽イオン交換膜及びその製造方法 | |
JP5413682B2 (ja) | ミネラル水の製造方法、ミネラル水製造装置、およびモザイク荷電膜 | |
JP2014124560A (ja) | イオン交換膜、その製造方法および電気透析装置 | |
JP5413683B2 (ja) | モザイク荷電膜の製造方法 | |
JP2017164718A (ja) | イオン交換膜 | |
JP2014124561A (ja) | イオン交換膜、その製造方法および逆電気透析発電装置 | |
JP5458265B2 (ja) | 有機化合物水溶液の脱塩方法、有機化合物水溶液の脱塩装置およびモザイク荷電膜 | |
JP2014088514A (ja) | 陰イオン交換膜及びその製造方法 | |
JP5633847B2 (ja) | モザイク荷電膜およびその製造方法 | |
JP6018006B2 (ja) | 果汁含有アルコール溶液中の電解質の除去方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20130313 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20130314 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20131015 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131030 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5413689 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |