JP2010155206A - Vinyl alcohol polymer composite-membrane comprising silyl group excellent in water resistance for use in gas separation membrane - Google Patents
Vinyl alcohol polymer composite-membrane comprising silyl group excellent in water resistance for use in gas separation membrane Download PDFInfo
- Publication number
- JP2010155206A JP2010155206A JP2008334852A JP2008334852A JP2010155206A JP 2010155206 A JP2010155206 A JP 2010155206A JP 2008334852 A JP2008334852 A JP 2008334852A JP 2008334852 A JP2008334852 A JP 2008334852A JP 2010155206 A JP2010155206 A JP 2010155206A
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- JP
- Japan
- Prior art keywords
- vinyl alcohol
- crosslinking agent
- alcohol polymer
- composite membrane
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000012528 membrane Substances 0.000 title claims abstract description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 66
- 238000000926 separation method Methods 0.000 title claims abstract description 43
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 title claims abstract description 37
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 60
- 239000002131 composite material Substances 0.000 claims abstract description 58
- -1 amine compound Chemical class 0.000 claims abstract description 29
- 230000014759 maintenance of location Effects 0.000 claims abstract description 19
- 238000010521 absorption reaction Methods 0.000 claims abstract description 16
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 125000003172 aldehyde group Chemical group 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 8
- 238000007127 saponification reaction Methods 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008119 colloidal silica Substances 0.000 claims description 7
- 239000000412 dendrimer Substances 0.000 claims description 6
- 229920000736 dendritic polymer Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 15
- 239000000178 monomer Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000001569 carbon dioxide Substances 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229920001661 Chitosan Polymers 0.000 description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 229920002689 polyvinyl acetate Polymers 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- SENLDUJVTGGYIH-UHFFFAOYSA-N n-(2-aminoethyl)-3-[[3-(2-aminoethylamino)-3-oxopropyl]-[2-[bis[3-(2-aminoethylamino)-3-oxopropyl]amino]ethyl]amino]propanamide Chemical compound NCCNC(=O)CCN(CCC(=O)NCCN)CCN(CCC(=O)NCCN)CCC(=O)NCCN SENLDUJVTGGYIH-UHFFFAOYSA-N 0.000 description 6
- 229920001567 vinyl ester resin Polymers 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- UALUSSOHQPEICU-UHFFFAOYSA-N prop-2-enamide;trimethoxy(propyl)silane Chemical compound NC(=O)C=C.CCC[Si](OC)(OC)OC UALUSSOHQPEICU-UHFFFAOYSA-N 0.000 description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- ZQYKGADTDCTWSZ-UHFFFAOYSA-N trimethyl-[(prop-2-enoylamino)methyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CNC(=O)C=C ZQYKGADTDCTWSZ-UHFFFAOYSA-N 0.000 description 2
- CCVMLEHYQVSFOM-UHFFFAOYSA-N trimethyl-[2-(prop-2-enoylamino)ethyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCNC(=O)C=C CCVMLEHYQVSFOM-UHFFFAOYSA-N 0.000 description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 2
- IDXCKOANSQIPGX-UHFFFAOYSA-N (acetyloxy-ethenyl-methylsilyl) acetate Chemical compound CC(=O)O[Si](C)(C=C)OC(C)=O IDXCKOANSQIPGX-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- 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 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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- JWCDUUFOAZFFMX-UHFFFAOYSA-N 2-ethenoxy-n,n-dimethylethanamine Chemical compound CN(C)CCOC=C JWCDUUFOAZFFMX-UHFFFAOYSA-N 0.000 description 1
- OPVZITRSTBLYCG-UHFFFAOYSA-M 2-ethenoxyethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC=C OPVZITRSTBLYCG-UHFFFAOYSA-M 0.000 description 1
- KQCSQWMHCAFBDD-UHFFFAOYSA-N 2-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C#N)CC(C)C KQCSQWMHCAFBDD-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- SJIBSEBLLOLBMW-UHFFFAOYSA-N 8,8-dimethoxyoctoxy(ethenyl)silane Chemical compound COC(OC)CCCCCCCO[SiH2]C=C SJIBSEBLLOLBMW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 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
- VNROOHCSOCDWOD-UHFFFAOYSA-N C(C)[Si](OC)(OC)OC.C(C=C)(=O)N Chemical compound C(C)[Si](OC)(OC)OC.C(C=C)(=O)N VNROOHCSOCDWOD-UHFFFAOYSA-N 0.000 description 1
- OFHUUAQNTFGSRB-UHFFFAOYSA-N C(CC)[Si](OC(C)=O)(OC(C)=O)OC(C)=O.C(C=C)(=O)N Chemical compound C(CC)[Si](OC(C)=O)(OC(C)=O)OC(C)=O.C(C=C)(=O)N OFHUUAQNTFGSRB-UHFFFAOYSA-N 0.000 description 1
- ILRGKSAHCJNIRU-UHFFFAOYSA-N C(CC)[Si](OC)(C)C.C(C=C)(=O)N Chemical compound C(CC)[Si](OC)(C)C.C(C=C)(=O)N ILRGKSAHCJNIRU-UHFFFAOYSA-N 0.000 description 1
- ZBHGUYAWZGHVDP-UHFFFAOYSA-N C(CCCCCCCCCCC)(=O)OC=C.C(CCCCCCCCCCC)(=O)OOC Chemical compound C(CCCCCCCCCCC)(=O)OC=C.C(CCCCCCCCCCC)(=O)OOC ZBHGUYAWZGHVDP-UHFFFAOYSA-N 0.000 description 1
- RADIZGQSFSEOQU-UHFFFAOYSA-N CC(C[Si](OC)(OC)OC)C.C(C=C)(=O)N Chemical compound CC(C[Si](OC)(OC)OC)C.C(C=C)(=O)N RADIZGQSFSEOQU-UHFFFAOYSA-N 0.000 description 1
- LECFJERLKGYDEV-UHFFFAOYSA-N C[Si](OC)(OC)OC.C(C=C)(=O)N Chemical compound C[Si](OC)(OC)OC.C(C=C)(=O)N LECFJERLKGYDEV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical class N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 239000004593 Epoxy Substances 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
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- OXPXVTOVLOKXNI-UHFFFAOYSA-N N.[Zr+4].[Zr+4] Chemical compound N.[Zr+4].[Zr+4] OXPXVTOVLOKXNI-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- KQZYTXDFRDHOJL-UHFFFAOYSA-N [Cl-].C(CC)[NH2+]CCC[Si](OC)(OC)OC.C(C=C)(=O)N Chemical compound [Cl-].C(CC)[NH2+]CCC[Si](OC)(OC)OC.C(C=C)(=O)N KQZYTXDFRDHOJL-UHFFFAOYSA-N 0.000 description 1
- FYULEVLWWAHIIO-UHFFFAOYSA-N [Cl-].CC(C[NH2+]CCC[Si](OC)(OC)OC)C.C(C=C)(=O)N Chemical compound [Cl-].CC(C[NH2+]CCC[Si](OC)(OC)OC)C.C(C=C)(=O)N FYULEVLWWAHIIO-UHFFFAOYSA-N 0.000 description 1
- OAJHWYJGCSAOTQ-UHFFFAOYSA-N [Zr].CCCCCCCCO.CCCCCCCCO.CCCCCCCCO.CCCCCCCCO Chemical compound [Zr].CCCCCCCCO.CCCCCCCCO.CCCCCCCCO.CCCCCCCCO OAJHWYJGCSAOTQ-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- XRLWQTOZMISADO-UHFFFAOYSA-N [diacetyloxy(prop-2-enyl)silyl] acetate Chemical compound CC(=O)O[Si](CC=C)(OC(C)=O)OC(C)=O XRLWQTOZMISADO-UHFFFAOYSA-N 0.000 description 1
- KTVHXOHGRUQTPX-UHFFFAOYSA-N [ethenyl(dimethyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(C)C=C KTVHXOHGRUQTPX-UHFFFAOYSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- IQCDTWQIGNEYMY-UHFFFAOYSA-N n',n'-dimethylprop-2-enehydrazide Chemical compound CN(C)NC(=O)C=C IQCDTWQIGNEYMY-UHFFFAOYSA-N 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
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 1
- QWWGTCDRRYWYBC-UHFFFAOYSA-N n-(ethenoxymethyl)-n-ethylethanamine Chemical compound CCN(CC)COC=C QWWGTCDRRYWYBC-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
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- 239000003345 natural gas Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- VRQWWCJWSIOWHG-UHFFFAOYSA-J octadecanoate;zirconium(4+) Chemical compound [Zr+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O VRQWWCJWSIOWHG-UHFFFAOYSA-J 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- ADGFKRMKSIAMAI-UHFFFAOYSA-L oxygen(2-);zirconium(4+);chloride;hydroxide Chemical compound [OH-].[O-2].[Cl-].[Zr+4] ADGFKRMKSIAMAI-UHFFFAOYSA-L 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
- 150000002978 peroxides Chemical class 0.000 description 1
- MOTIOMSENWHXDQ-UHFFFAOYSA-N phenylsilyl acetate Chemical compound CC(=O)O[SiH2]c1ccccc1 MOTIOMSENWHXDQ-UHFFFAOYSA-N 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
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- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- FHAHRSFZQANXFS-UHFFFAOYSA-N prop-2-enamide tris(2-methoxyethoxy)-propylsilane Chemical compound NC(=O)C=C.CCC[Si](OCCOC)(OCCOC)OCCOC FHAHRSFZQANXFS-UHFFFAOYSA-N 0.000 description 1
- NOVHGUXJIQPGOV-UHFFFAOYSA-N prop-2-enamide;triethoxy(propyl)silane Chemical compound NC(=O)C=C.CCC[Si](OCC)(OCC)OCC NOVHGUXJIQPGOV-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical group [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、水蒸気の含まれる混合ガスから特定のガス種を分離するガス分離膜用複合膜に関する。 The present invention relates to a composite membrane for a gas separation membrane that separates a specific gas species from a mixed gas containing water vapor.
近年、分離膜を用いた分離技術がめざましく進展している。このような分離技術には、例えば飲料水を得るために不純物を分離するといった液体と固体の分離から、選択透過性を有する分離膜を用いて二酸化炭素と水素、あるいは二酸化炭素とメタンの分離といった気体の分離まで、種々のものが含まれる。特に、気体の分離技術は、油田のオフガスや火力発電の排ガス、天然ガスからの二酸化炭素分離などに広く応用されるので、二酸化炭素を選択的に分離する技術が精力的に検討されている。 In recent years, a separation technique using a separation membrane has been remarkably advanced. Such separation techniques include, for example, separation of liquid and solid such as separation of impurities to obtain drinking water, separation of carbon dioxide and hydrogen, or separation of carbon dioxide and methane using a selectively permeable separation membrane. Various things are included up to gas separation. In particular, gas separation technology is widely applied to off-gas in oil fields, exhaust gas from thermal power generation, carbon dioxide separation from natural gas, and the like, and technology for selectively separating carbon dioxide has been energetically studied.
しかしながら、従来の高分子膜では二酸化炭素の選択性（二酸化炭素の膜透過速度／分離対象ガスの膜透過速度）が不十分で、目的とする濃度で二酸化炭素を回収することが出来なかった。そのため、二酸化炭素選択性に優れた分離膜の開発が望まれていた。このような膜を得るために、二酸化炭素に対して選択的に親和性が高い素材を用いることが提案されている。たとえば、室温で液状物質であるポリアミドアミンデンドリマーを、微多孔質の支持体に含浸させた分離膜が提案されている（非特許文献１および２）。この含浸膜の分離性能は、膜に圧力差を設けない状況では１０００を超える優れた二酸化炭素選択性を示すものの、この膜に圧力を掛けると、含浸させたポリアミドアミンデンドリマーが時間と共に支持体から抜け出して、性能を維持できないため、実用に供することが困難であった。 However, the conventional polymer membrane has insufficient carbon dioxide selectivity (the membrane permeation rate of carbon dioxide / the membrane permeation rate of the separation target gas), and carbon dioxide could not be recovered at the target concentration. Therefore, development of a separation membrane having excellent carbon dioxide selectivity has been desired. In order to obtain such a membrane, it has been proposed to use a material having a high selective affinity for carbon dioxide. For example, a separation membrane in which a microporous support is impregnated with a polyamidoamine dendrimer that is a liquid substance at room temperature has been proposed (Non-Patent Documents 1 and 2). Although the separation performance of the impregnated membrane shows excellent carbon dioxide selectivity exceeding 1000 in a situation where no pressure difference is provided in the membrane, when the pressure is applied to the membrane, the impregnated polyamidoamine dendrimer is separated from the support over time. It has been difficult to put it to practical use because it cannot escape and maintain its performance.
この問題を解決する方法として、架橋剤で架橋された吸水性高分子材料のマトリックス中に特定のアミン化合物を包含させた気体分離層を多孔質性の支持膜の表面部分に形成させた複合膜が提案されている（特許文献１）。この複合膜の分離性能は、高い選択性を有すると共に、圧力差に耐え実用に供することが可能な分離膜である。しかしながら、気体分離膜ではその分離対象となる混合ガスに水蒸気が含まれる場合が多いため、混合ガスと膜表面との親和性を発現するための適度な親水性と、一方で水蒸気に対して経時的に分離性能が低下することのない耐水性という相反する性能を持ち合わせることが要求される。前記の複合膜の分離性能は、水蒸気を含む混合ガスを用いると、包含させたアミン化合物が時間と共に複合膜から抜け出して、性能を維持できないため、実用に供することが困難であり、水蒸気が含まれる混合ガスでも使用可能な耐水性に優れる分離膜の開発が切望されていた。 As a method for solving this problem, a composite membrane in which a gas separation layer containing a specific amine compound in a matrix of a water-absorbing polymer material crosslinked with a crosslinking agent is formed on the surface of a porous support membrane. Has been proposed (Patent Document 1). The separation performance of this composite membrane is a separation membrane that has high selectivity and can withstand pressure differences and can be put to practical use. However, in a gas separation membrane, water vapor is often contained in the mixed gas to be separated, so that it has an appropriate hydrophilicity for expressing the affinity between the mixed gas and the membrane surface, while the water vapor over time. In particular, it is required to have the contradictory performance of water resistance without degrading the separation performance. As for the separation performance of the composite membrane, when a mixed gas containing water vapor is used, the included amine compound escapes from the composite membrane with time, and the performance cannot be maintained. The development of a separation membrane with excellent water resistance that can be used even with mixed gas is desired.
本発明は上記課題を解決するためになされたものであり、水蒸気が含まれる混合ガスであっても特定のガス種を分離することが可能な耐水性に優れるガス分離膜用複合膜を提供することを目的とするものである。 The present invention has been made to solve the above problems, and provides a composite membrane for gas separation membranes that is excellent in water resistance and that can separate a specific gas species even in a mixed gas containing water vapor. It is for the purpose.
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、シリル基を特定量含有するビニルアルコール系重合体と特定の水溶性アミン化合物が特定の架橋剤で架橋された複合膜であって、該複合膜を一定温度の蒸留水に一定時間浸漬させた時の該複合膜の重量保持率が特定の範囲にあり、かつ該複合膜の吸水量を特定のものにすることによって、高い選択性を有すると共に、水蒸気の含まれる混合ガスに耐え実用に供することが可能な耐水性に優れるガス分離膜用複合膜を得ることを見出し、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a composite film in which a vinyl alcohol polymer containing a specific amount of a silyl group and a specific water-soluble amine compound are cross-linked with a specific cross-linking agent. The weight retention of the composite membrane when the composite membrane is immersed in distilled water at a constant temperature for a predetermined time is in a specific range, and the water absorption of the composite membrane is made specific. The present inventors have found that a composite membrane for gas separation membranes having high selectivity and having excellent water resistance that can withstand a mixed gas containing water vapor and can be used practically has been achieved.
すなわち上記課題は、シリル基を０．０１〜５モル％含有するビニルアルコール系重合体（Ａ）および水溶性アミン化合物（Ｂ）が多官能性の架橋剤（Ｃ）で架橋されてなる複合膜であって、該複合膜を６０℃の蒸留水に３時間浸漬させた時の該複合膜の重量保持率が５０〜１００重量％で、かつ該複合膜１００重量部に対する吸水量が３０〜１０００重量部であることを特徴とする耐水性に優れるガス分離膜用シリル基含有ビニルアルコール系重合体複合膜を提供することによって解決される。 That is, the above-mentioned problem is a composite film in which a vinyl alcohol polymer (A) containing 0.01 to 5 mol% of a silyl group and a water-soluble amine compound (B) are crosslinked with a polyfunctional crosslinking agent (C). The composite membrane has a weight retention of 50 to 100% by weight when immersed in distilled water at 60 ° C. for 3 hours, and has a water absorption of 30 to 1000 with respect to 100 parts by weight of the composite membrane. It is solved by providing a silyl group-containing vinyl alcohol polymer composite membrane for gas separation membranes, which is excellent in water resistance, characterized by being part by weight.
このとき、ビニルアルコール系重合体（Ａ）の重合度が３００〜２５００であり、けん化度が９５〜９９．９モル％であることが好適であり、水溶性アミン化合物（Ｂ）が、ポリアミドアミン系デンドリマーであることが好適である。また、ビニルアルコール系重合体（Ａ）のエチレン単位の含有量が１〜２０モル％であることが好適であり、ビニルアルコール系重合体（Ａ）と多官能性の架橋剤（Ｃ）の重量配合比率（Ａ）／（Ｃ）が９９．９／０．１〜５０／５０であることが好適である。また、多官能性の架橋剤（Ｃ）が、チタン系架橋剤、ジルコニウム系架橋剤、コロイダルシリカ、および官能基としてエポキシ基またはアルデヒド基を有する架橋剤からなる群から選択される少なくとも１種であることが好適であり、多官能性の架橋剤（Ｃ）が、チタン系架橋剤、ジルコニウム系架橋剤、コロイダルシリカ、および官能基としてエポキシ基またはアルデヒド基を有する架橋剤からなる群から選択される少なくとも２種以上であることも好適である。 At this time, it is preferable that the degree of polymerization of the vinyl alcohol polymer (A) is 300 to 2500, and the degree of saponification is 95 to 99.9 mol%, and the water-soluble amine compound (B) is polyamidoamine. A dendrimer is preferred. Moreover, it is suitable that content of the ethylene unit of a vinyl alcohol-type polymer (A) is 1-20 mol%, and the weight of a vinyl alcohol-type polymer (A) and a polyfunctional crosslinking agent (C). The blending ratio (A) / (C) is preferably 99.9 / 0.1 to 50/50. The multifunctional crosslinking agent (C) is at least one selected from the group consisting of a titanium-based crosslinking agent, a zirconium-based crosslinking agent, colloidal silica, and a crosslinking agent having an epoxy group or an aldehyde group as a functional group. Preferably, the polyfunctional crosslinking agent (C) is selected from the group consisting of a titanium-based crosslinking agent, a zirconium-based crosslinking agent, colloidal silica, and a crosslinking agent having an epoxy group or an aldehyde group as a functional group. It is also suitable that there are at least two or more.
本発明により、水蒸気が含まれる混合ガスであっても高い選択性をもって実用に供することが可能な耐水性に優れるガス分離膜用複合膜が提供される。 The present invention provides a composite membrane for gas separation membranes that is excellent in water resistance and can be practically used with high selectivity even if it is a mixed gas containing water vapor.
本発明の耐水性に優れるガス分離膜用シリル基含有ビニルアルコール系重合体複合膜は、シリル基を０．０１〜５モル％含有するビニルアルコール系重合体（Ａ）および水溶性アミン化合物（Ｂ）が多官能性の架橋剤（Ｃ）で架橋されてなる複合膜であって、該複合膜を６０℃の蒸留水に３時間浸漬させた時の該複合膜の重量保持率が５０〜１００重量％であり、かつ該複合膜１００重量部に対する吸水量が３０〜１０００重量部であることを特徴とする。 The silyl group-containing vinyl alcohol polymer composite membrane for gas separation membranes having excellent water resistance according to the present invention comprises a vinyl alcohol polymer (A) containing 0.01 to 5 mol% of silyl groups and a water-soluble amine compound (B ) Is a composite membrane formed by crosslinking with a polyfunctional crosslinking agent (C), and the composite membrane has a weight retention of 50 to 100 when immersed in distilled water at 60 ° C. for 3 hours. The water absorption is 30 to 1000 parts by weight with respect to 100 parts by weight of the composite membrane.
本発明に用いられるビニルアルコール系重合体（Ａ）のシリル単位の含有量は０．０１〜５モル％である。シリル単位の含有量が０．０１モル％未満の場合には、本発明の複合膜の効果が発現されず耐水性が低下するおそれがあり、０．０５モル％以上であることが好ましく、０．１モル％以上であることがより好ましい。一方、シリル単位の含有量が５モル％を超える場合には、ビニルアルコール系重合体（Ａ）溶液の安定性が低下したり、均質な複合膜が得られにくく、目的とする耐水性に優れる複合膜が得られないおそれがあり、３．５モル％以下であることが好ましく、２．５モル％以下であることがより好ましい。 The content of the silyl unit in the vinyl alcohol polymer (A) used in the present invention is 0.01 to 5 mol%. When the content of the silyl unit is less than 0.01 mol%, the effect of the composite film of the present invention may not be exhibited and the water resistance may be lowered, and the content is preferably 0.05 mol% or more. More preferably, it is 1 mol% or more. On the other hand, when the content of the silyl unit exceeds 5 mol%, the stability of the vinyl alcohol polymer (A) solution is reduced, a homogeneous composite film is difficult to obtain, and the target water resistance is excellent. There is a possibility that a composite membrane may not be obtained, and it is preferably 3.5 mol% or less, more preferably 2.5 mol% or less.
シリル基含有のビニルアルコール系重合体（Ａ）の粘度平均重合度（以下、重合度と略記することがある）は３００〜２５００が好ましく、３３０〜２２００がより好ましく、３６０〜２０００が特に好ましい。重合度（Ｐ）は、ＪＩＳ−Ｋ６７２６に準じて測定される。すなわち、ビニルアルコール系重合体（Ａ）を再けん化し、精製した後、３０℃の水中で測定した極限粘度［η］から次式により求められる。
Ｐ＝（［η］×１０３／８．２９）（１／０．６２）
重合度が３００未満の場合には、複合膜のマトリックスを構成する機能が低下して複合膜の耐水性が低下するおそれがある。重合度が２５００を超える場合には、複合膜を作成する際のビニルアルコール系重合体（Ａ）と水溶性アミン化合物（Ｂ）からなる溶液の粘度が高くなりすぎる場合があり、作業性が低下するのみならず均質な複合膜が得られないおそれがある。
The viscosity average polymerization degree of the silyl group-containing vinyl alcohol polymer (A) (hereinafter sometimes abbreviated as polymerization degree) is preferably 300 to 2500, more preferably 330 to 2200, and particularly preferably 360 to 2000. The degree of polymerization (P) is measured according to JIS-K6726. That is, after re-saponifying and purifying the vinyl alcohol polymer (A), it is obtained from the intrinsic viscosity [η] measured in water at 30 ° C. by the following equation.
P = ([η] × 10 3 /8.29) (1 / 0.62)
When the degree of polymerization is less than 300, the function constituting the matrix of the composite membrane may be reduced, and the water resistance of the composite membrane may be reduced. When the degree of polymerization exceeds 2500, the viscosity of the solution composed of the vinyl alcohol polymer (A) and the water-soluble amine compound (B) when forming the composite film may become too high, and the workability is lowered. In addition, there is a possibility that a homogeneous composite film cannot be obtained.
本発明で用いられるビニルアルコール系重合体（Ａ）のけん化度は９５〜９９．９モル％であることが好ましい。けん化度が９５モル％未満の場合には、複合膜の耐水性が低下するおそれがあり、９６モル％以上であることがより好ましい。一方、けん化度が９９．９モル％を超える場合には、製膜時の作業性が低下したり、複合膜を作成する際のビニルアルコール系重合体（Ａ）と水溶性アミン化合物（Ｂ）からなる溶液の粘度安定性が低下するおそれがある。 The saponification degree of the vinyl alcohol polymer (A) used in the present invention is preferably 95 to 99.9 mol%. When the degree of saponification is less than 95 mol%, the water resistance of the composite membrane may be lowered, and it is more preferably 96 mol% or more. On the other hand, when the degree of saponification exceeds 99.9 mol%, the workability during film formation is reduced, or the vinyl alcohol polymer (A) and the water-soluble amine compound (B) when forming a composite film There is a possibility that the viscosity stability of the solution consisting of may be reduced.
本発明で用いられるビニルアルコール系重合体（Ａ）の中でも、下記の化１または化２の構造単位を有するビニルアルコール系重合体（Ａ）が好ましい。 Among the vinyl alcohol polymers (A) used in the present invention, a vinyl alcohol polymer (A) having a structural unit of the following chemical formula 1 or chemical formula 2 is preferable.
上記の化１および化２において、Ｒ１、Ｒ２、Ｒ３およびＲ５は水素原子または炭素数８以下の炭化水素基を表し、Ｒ４は炭素数１〜４０のアルコキシル基またはアシロキシル基（ここで、アルコキシル基、アシロキシル基は酸素を含有する置換基を有していてもよい。）を表し、Ｒ６は炭素数５以下のアルキレン基または連鎖炭素原子が酸素もしくは窒素で中断された２価の有機残基を表し、ｎは０〜４の整数を表し、ｋは０〜２の整数およびｍは０〜３の整数であってｋ＋ｍは３以下であることを表し、Ｘは１価の金属または水素原子を表す。 In the above Chemical Formula 1 and Chemical Formula 2, R 1 , R 2 , R 3 and R 5 represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms, and R 4 represents an alkoxyl group or acyloxyl group having 1 to 40 carbon atoms ( Here, the alkoxyl group and the acyloxyl group may have an oxygen-containing substituent.), And R 6 represents an alkylene group having 5 or less carbon atoms or a chain carbon atom interrupted with oxygen or nitrogen. N represents an integer of 0 to 4, k represents an integer of 0 to 2, and m represents an integer of 0 to 3, and k + m represents 3 or less, and X represents a monovalent group. Represents a metal or hydrogen atom.
本発明で用いられるビニルアルコール系重合体（Ａ）は、好適には上記の化１または化２の構造単位に変換しうるオレフィン性不飽和単量体とビニルエステルとの共重合体をけん化することにより得られる。また、本発明で用いられるビニルアルコール系重合体（Ａ）は、その原料である変性ビニルエステル系重合体中のアルコキシシラン基がけん化反応時に加水分解されてシラノール基またはその塩基に変換されていても差し支えない。また、本発明で用いられるビニルアルコール系重合体（Ａ）は、シリル基を含有する構造単位が重合体の分子中にランダムに、導入されているもののほかに、重合体の分子末端に導入されているものでもよい。 The vinyl alcohol polymer (A) used in the present invention preferably saponifies a copolymer of an olefinically unsaturated monomer and a vinyl ester that can be converted into the structural unit of Chemical Formula 1 or Chemical Formula 2 above. Can be obtained. In the vinyl alcohol polymer (A) used in the present invention, the alkoxysilane group in the modified vinyl ester polymer that is the raw material is hydrolyzed during the saponification reaction to be converted into a silanol group or a base thereof. There is no problem. In addition, the vinyl alcohol polymer (A) used in the present invention is introduced at the molecular end of the polymer in addition to the structural unit containing a silyl group being randomly introduced into the polymer molecule. It may be what you have.
本発明で用いられるビニルアルコール系重合体（Ａ）としては、分子中にシリル基を含有すると共にさらにエチレン単位を含有するＰＶＡが好ましい。エチレン単位の含有量としては、１〜２０モル％が好ましい。エチレン単位の含有量が１モル％未満の場合には耐水性が不充分となるおそれがあり、１．５モル％以上であることがより好ましく、２モル％以上であることがさらに好ましい。一方、エチレン単位の含有量が２０モル％を超える場合には水溶性が低下して作業効率が低下するおそれがあり、１８モル％以下であることがより好ましく、１５モル％以下であることがさらに好ましい。 The vinyl alcohol polymer (A) used in the present invention is preferably PVA containing a silyl group in the molecule and further containing an ethylene unit. As content of an ethylene unit, 1-20 mol% is preferable. When the content of the ethylene unit is less than 1 mol%, the water resistance may be insufficient, more preferably 1.5 mol% or more, and further preferably 2 mol% or more. On the other hand, when the content of the ethylene unit exceeds 20 mol%, the water solubility may decrease and the working efficiency may decrease, and it is more preferably 18 mol% or less, and 15 mol% or less. Further preferred.
前記の化１に変換しうるオレフィン性不飽和単量体の具体例としては、ビニルトリメトキシシラン、ビニルトリス−（β−メトキシエトキシ）シラン、アリルトリメトキシシラン、ビニルトリアセトキシシラン、アリルトリアセトキシシラン、ビニルメチルジメトキシシラン、ビニルジメチルメトキシシラン、ビニルメチルジエトキシシラン、ビニルジメチルエトキシシラン、ビニルメチルジアセトキシシラン、ビニルジメチルアセトキシシラン、ビニルイソブチルジメトキシシラン、ビニルトリイソプロポキシシラン、ビニルトリブトキシシラン、ビニルトリヘキシロキシシラン、ビニルメトキシジヘキシロキシシラン、ビニルジメトキシオクチロキシシラン、ビニルメトキシジオクチロキシシラン、ビニルトリオクチロキシシラン、ビニルメトキシジラウリロキシシラン、ビニルジメトキシラウリロキシシラン、ビニルメトキシジオレイロキシシラン、ビニルジメトキシオレイロキシシランなどが挙げられる。 Specific examples of the olefinically unsaturated monomer that can be converted into Chemical Formula 1 include vinyltrimethoxysilane, vinyltris- (β-methoxyethoxy) silane, allyltrimethoxysilane, vinyltriacetoxysilane, and allyltriacetoxysilane. , Vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinylmethyldiacetoxysilane, vinyldimethylacetoxysilane, vinylisobutyldimethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyl Trihexyloxysilane, vinylmethoxydihexyloxysilane, vinyldimethoxyoctyloxysilane, vinylmethoxydioctyloxysilane, vinyltrioctyloxysilane, vinyl Methoxy dilaurate Lilo silane, vinyl dimethoxy Lau Lilo silane, vinyl methoxy geo Ray B silanes, and vinyl dimethoxy I acetoxyphenyl silane.
前記の化２に変換しうるオレフィン性不飽和単量体の具体例としては、３−（メタ）アクリルアミド−プロピルトリメトキシシラン、３−（メタ）アクリルアミド−プロピルトリエトキシシラン、３−（メタ）アクリルアミド−プロピルトリ（β−メトキシエトキシ）シラン、２−（メタ）アクリルアミド−２−メチルプロピルトリメトキシシラン、２−（メタ）アクリルアミド−２−メチルエチルトリメトキシシラン、Ｎ−（２−（メタ）アクリルアミド−エチル）−アミノプロピルトリメトキシシラン、３−（メタ）アクリルアミド−プロピルトリアセトキシシラン、２−（メタ）アクリルアミド−エチルトリメトキシシラン、１−（メタ）アクリルアミド−メチルトリメトキシシラン、３−（メタ）アクリルアミド−プロピルメチルジメトキシシラン、３−（メタ）アクリルアミド−プロピルジメチルメトキシシラン、３−（Ｎ−メチル−（メタ）アクリルアミド）−プロピルトリメトキシシラン、３−（（メタ）アクリルアミド−メトキシ）−３−ハイドロキシプロピルトリメトキシシラン、３−（（メタ）アクリルアミド−メトキシ）−プロピルトリメトキシシラン、ジメチル−３−（メタ）アクリルアミド−プロピル−３−（トリメトキシシリル）−プロピルアンモニウムクロライド、ジメチル−２−（メタ）アクリルアミド−２−メチルプロピル−３−（トリメトキシシリル）−プロピルアンモニウムクロライドなどが挙げられる。 Specific examples of the olefinically unsaturated monomer that can be converted into the chemical formula 2 include 3- (meth) acrylamide-propyltrimethoxysilane, 3- (meth) acrylamide-propyltriethoxysilane, and 3- (meth). Acrylamide-propyltri (β-methoxyethoxy) silane, 2- (meth) acrylamide-2-methylpropyltrimethoxysilane, 2- (meth) acrylamide-2-methylethyltrimethoxysilane, N- (2- (meth) Acrylamide-ethyl) -aminopropyltrimethoxysilane, 3- (meth) acrylamide-propyltriacetoxysilane, 2- (meth) acrylamide-ethyltrimethoxysilane, 1- (meth) acrylamide-methyltrimethoxysilane, 3- ( (Meth) acrylamide-propylmethyldi Toxisilane, 3- (meth) acrylamide-propyldimethylmethoxysilane, 3- (N-methyl- (meth) acrylamide) -propyltrimethoxysilane, 3-((meth) acrylamide-methoxy) -3-hydroxypropyltrimethoxysilane 3-((meth) acrylamide-methoxy) -propyltrimethoxysilane, dimethyl-3- (meth) acrylamide-propyl-3- (trimethoxysilyl) -propylammonium chloride, dimethyl-2- (meth) acrylamide-2 -Methylpropyl-3- (trimethoxysilyl) -propylammonium chloride and the like.
また、本発明において使用される前記の化１または化２の構造単位を有するビニルアルコール系重合体（Ａ）は、好適には前記の化１または化２に変換しうるオレフィン性不飽和単量体とビニルエステルとの共重合体をけん化することにより得られる。共重合の方法としては、塊状重合法、溶液重合法、懸濁重合法、乳化重合法などの公知の方法を採用することができる。その中でも、無溶媒あるいはアルコールなどの溶媒中で重合する塊状重合法や溶液重合法が通常採用される。また、高重合度のものを得る場合には、乳化重合法が採用される。溶液重合時に溶媒として使用されるアルコールとしては、メチルアルコール、エチルアルコール、プロピルアルコールなどの低級アルコールが挙げられる。共重合に使用される開始剤としては、例えば、α，α'−アゾビスイソブチロニトリル、２，２'−アゾビス（２,４−ジメチルバレロニトリル）、２，２'−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、過酸化ベンゾイル、ｎ−プロピルパーオキシカーボネートなどのアゾ系開始剤または過酸化物系開始剤などの公知の開始剤が挙げられる。重合温度については特に制限はないが、−３０〜１５０℃の範囲が適当である。 Further, the vinyl alcohol polymer (A) having the structural unit of Chemical Formula 1 or Chemical Formula 2 used in the present invention is preferably an olefinically unsaturated monomer capable of being converted into Chemical Formula 1 or Chemical Formula 2 above. It is obtained by saponifying a copolymer of a vinyl ester with a vinyl ester. As a copolymerization method, known methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be employed. Among them, a bulk polymerization method or a solution polymerization method in which polymerization is performed without solvent or in a solvent such as alcohol is usually employed. Moreover, when obtaining a thing with a high degree of polymerization, an emulsion polymerization method is employ | adopted. Examples of alcohol used as a solvent during solution polymerization include lower alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol. Examples of the initiator used in the copolymerization include α, α′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4- Known initiators such as azo initiators or peroxide initiators such as methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, and n-propyl peroxycarbonate. Although there is no restriction | limiting in particular about superposition | polymerization temperature, The range of -30-150 degreeC is suitable.
上述の方法で用いるビニルエステルとしては、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、バレリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、ピバリン酸ビニルおよびバーサティック酸ビニル等が挙げられる。これらの中でも酢酸ビニルが好ましい。 Vinyl esters used in the above method include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate and vinyl versatate. Can be mentioned. Among these, vinyl acetate is preferable.
本発明で用いられるビニルアルコール系重合体（Ａ）は、さらに、アニオン基もしくはカチオン基を含有していてもよい。これらアニオン基もしくはカチオン基を有する単量体としては、フマール酸、マレイン酸、イタコン酸、無水マレイン酸、無水フタル酸、無水トリメリット酸または無水イタコン酸等に由来するカルボキシル基を有する単量体；エチレンスルホン酸、アリルスルホン酸、メタアリルスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸等に由来するスルホン酸基を有する単量体；ビニロキシエチルトリメチルアンモニウムクロライド、ビニロキシブチルトリメチルアンモニウムクロライド、ビニロキシエチルジメチルアミン、ビニロキシメチルジエチルアミン、Ｎ−アクリルアミドメチルトリメチルアンモニウムクロライド、Ｎ−アクリルアミドエチルトリメチルアンモニウムクロライド、Ｎ−アクリルアミドジメチルアミン、アリルトリメチルアンモニウムクロライド、メタアリルトリメチルアンモニウムクロライド、ジメチルアリルアミン、アリルエチルアミン等に由来するカチオン基を有する単量体が挙げられる。これらの単量体の中でも、入手のし易さおよび共重合性の観点から、無水マレイン酸、無水マレイン酸のハーフエステル、イタコン酸、アリルスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸、Ｎ−アクリルアミドメチルトリメチルアンモニウムクロライド、Ｎ−アクリルアミドエチルトリメチルアンモニウムクロライドに由来する単量体が好ましい。これらの単量体単位の含有量は、通常１０モル％以下であり、０．１〜８モル％がより好ましい。 The vinyl alcohol polymer (A) used in the present invention may further contain an anionic group or a cationic group. Monomers having a carboxyl group derived from fumaric acid, maleic acid, itaconic acid, maleic anhydride, phthalic anhydride, trimellitic anhydride, itaconic anhydride, etc. Monomers having sulfonic acid groups derived from ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, etc .; vinyloxyethyl trimethyl ammonium chloride, vinyloxy butyl trimethyl ammonium chloride , Vinyloxyethyldimethylamine, vinyloxymethyldiethylamine, N-acrylamidomethyltrimethylammonium chloride, N-acrylamidoethyltrimethylammonium chloride, N-acrylamidodimethylamine, Lil trimethylammonium chloride, methallyl trimethylammonium chloride, dimethyl allyl amine include monomers having a cationic group derived from the allyl ethyl amine. Among these monomers, maleic anhydride, maleic anhydride half ester, itaconic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, from the viewpoint of availability and copolymerizability, Monomers derived from N-acrylamidomethyltrimethylammonium chloride and N-acrylamidoethyltrimethylammonium chloride are preferred. The content of these monomer units is usually 10 mol% or less, more preferably 0.1 to 8 mol%.
本発明で用いられるビニルアルコール系重合体（Ａ）は、本発明の効果を損なわない範囲であれば、ビニルアルコール単位およびビニルエステル単位以外の単量体単位を含有していても良い。このような単量体単位としては、アクリル酸およびその塩；アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸ｉ−プロピル等のアクリル酸エステル；メタクリル酸およびその塩；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロピル、メタクリル酸ｉ−プロピル等のメタクリル酸エステル；アクリルアミド；Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド等のアクリルアミド誘導体；メタクリルアミド；Ｎ−メチルメタクリルアミド、Ｎ−エチルメタクリルアミド等のメタクリルアミド誘導体；メチルビニルエーテル、エチルビニルエーテル、ｎ−プロピルビニルエーテル、ｉ−プロピルビニルエーテル等のビニルエーテル；アクリロニトリル、メタクリロニトリル等のニトリル；塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン等のハロゲン化ビニル；酢酸アリル、塩化アリル等のアリル化合物；マレイン酸、その塩またはそのエステル；イタコン酸、その塩またはそのエステル；ビニルトリメトキシシラン等のビニルシリル化合物；酢酸イソプロペニル等の単量体由来の単位が挙げられる。これらの単量体単位の含有量としては、１０モル％以下が好ましく、５モル％以下がより好ましく、３モル％以下がさらに好ましい。 The vinyl alcohol polymer (A) used in the present invention may contain monomer units other than vinyl alcohol units and vinyl ester units as long as the effects of the present invention are not impaired. Examples of such monomer units include acrylic acid and its salts; acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate and i-propyl acrylate; methacrylic acid and its salts; methyl methacrylate , Methacrylates such as ethyl methacrylate, n-propyl methacrylate and i-propyl methacrylate; acrylamides; acrylamide derivatives such as N-methylacrylamide and N-ethylacrylamide; methacrylamide; N-methylmethacrylamide and N-ethyl Methacrylamide derivatives such as methacrylamide; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether and i-propyl vinyl ether; Nitriles such as acrylonitrile and methacrylonitrile; Vinyl halides such as nyl, vinylidene chloride, vinyl fluoride, vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; maleic acid, salts thereof or esters thereof; itaconic acid, salts thereof or esters thereof; vinyltrimethoxysilane Units derived from monomers such as isopropenyl acetate; The content of these monomer units is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 3 mol% or less.
本発明において使用されるビニルアルコール系重合体（Ａ）を水に溶解するには、通常ビニルアルコール系重合体（Ａ）を水に分散後、場合によっては水酸化ナトリウムなどのアルカリを添加し、撹拌しながら加温することによって均一な水溶液を得ることができる。 In order to dissolve the vinyl alcohol polymer (A) used in the present invention in water, after dispersing the vinyl alcohol polymer (A) in water, an alkali such as sodium hydroxide is added in some cases, A uniform aqueous solution can be obtained by heating with stirring.
次に、水溶性アミン化合物（Ｂ）について説明する。水溶性アミン化合物（Ｂ）は、分離対象のガスによって自由に選択することができる。ただし、本発明においては、シリル基含有のビニルアルコール系重合体（Ａ）と親和性を有すことが必要であるために、水溶性であることが必須である。本発明で用いられる水溶性アミン化合物（Ｂ）としては、注目度の高い二酸化炭素の分離を念頭において例示すれば、ポリアミドアミン系デンドリマー、その他の化合物としてモノエタノールアミン、ジエタノールアミン、２，３−ジアミノプロピオン酸、ポリアリルアミン、ポリエチレンイミンなど、１級のアミノ基を有する化合物が挙げられるが、アミノ基の数が多く二酸化炭素の吸着能力の点でポリアミドアミン系デンドリマーが好ましく用いられる。 Next, the water-soluble amine compound (B) will be described. The water-soluble amine compound (B) can be freely selected depending on the gas to be separated. However, in the present invention, since it is necessary to have an affinity for the silyl group-containing vinyl alcohol polymer (A), it is essential to be water-soluble. Examples of the water-soluble amine compound (B) used in the present invention include polyamidoamine-based dendrimers and other compounds such as monoethanolamine, diethanolamine, and 2,3-diamino. A compound having a primary amino group, such as propionic acid, polyallylamine, and polyethyleneimine, can be mentioned, but a polyamidoamine-based dendrimer is preferably used in terms of the number of amino groups and the ability to adsorb carbon dioxide.
シリル基含有のビニルアルコール系重合体（Ａ）と水溶性アミン化合物（Ｂ）の質量比率（Ａ／Ｂ）には特に制限はないが、通常は２０／８０〜８０／２０の質量比で、より好ましくは３０／７０〜６０／４０の質量比で用いられる。 The mass ratio (A / B) of the silyl group-containing vinyl alcohol polymer (A) and the water-soluble amine compound (B) is not particularly limited, but is usually a mass ratio of 20/80 to 80/20. More preferably, it is used at a mass ratio of 30/70 to 60/40.
次に、多官能性の架橋剤（Ｃ）について説明する。本発明に用いられる架橋剤（Ｃ）は、シリル基含有のビニルアルコール系重合体（Ａ）同士や、あるいはシリル基含有のビニルアルコール系重合体（Ａ）と水溶性アミン化合物（Ｂ）を架橋するのに用いられる架橋剤であって、特に限定されるものでなく、チタン系架橋剤、ジルコニウム系架橋剤、コロイダルシリカ、および官能基としてエポキシ基、アルデヒド基、ハロゲン原子などの官能基を２個以上有する化合物が挙げられる。中でも、チタン系架橋剤、ジルコニウム系架橋剤、コロイダルシリカ、および官能基としてエポキシ基またはアルデヒド基を有する架橋剤からなる群から選択される少なくとも１種であることが好ましい。 Next, the polyfunctional crosslinking agent (C) will be described. The crosslinking agent (C) used in the present invention crosslinks silyl group-containing vinyl alcohol polymers (A) with each other or a silyl group-containing vinyl alcohol polymer (A) and a water-soluble amine compound (B). There are no particular limitations on the cross-linking agent used, and titanium-based cross-linking agent, zirconium-based cross-linking agent, colloidal silica, and functional groups such as epoxy groups, aldehyde groups, and halogen atoms as functional groups. The compound which has more than one is mentioned. Among these, at least one selected from the group consisting of a titanium-based crosslinking agent, a zirconium-based crosslinking agent, colloidal silica, and a crosslinking agent having an epoxy group or an aldehyde group as a functional group is preferable.
チタン系架橋剤としては、チタンジイソプロポキシビス(トリエタノールアミネート)、チタンラクテートアンモニウム塩など、チタンのアルコシキド系架橋剤が好ましい。また、ジルコニウム系架橋剤としては、酸塩化ジルコニウム、硫酸ジルコニウム、硝酸ジルコニウム、酢酸ジルコニウム、炭酸ジルコニウム、炭酸ジルコニウムアンモニウム、ステアリン酸ジルコニウム、オクチル酸ジルコニウム、珪酸ジルコニウムなどが挙げられる。これらのジルコニウム化合物のなかでも水溶性のものが好ましく、塩素を持たないものがさらに好ましい。具体的には硫酸ジルコニウム、硝酸ジルコニウム、酢酸ジルコニウム、炭酸ジルコニウムアンモニウムが挙げられる。エポキシ基を有する架橋剤としては、たとえば、エポキシクロロヒドリン、ジエポキシアルカン、ジエポキシアルケン、（ポリ）エチレングリコールジグリシジルエーテル、（ポリ）プロピレングリコールジグリシジルエーテル、（ポリ）グリセリンジグリシジルエーテルなどのジグリシジルエーテル化合物が挙げられ、とくにエチレングリコールジグリシジルエーテルが好ましい。また、アルデヒド基を有する架橋剤としては、グルタルアルデヒド、スクシンアルデヒド、マロンジアルデヒド、テレフタルアルデヒド、イソフタルアルデヒドなどのジアルデヒド化合物が挙げられ、とくにグルタルアルデヒドが好ましい。 As the titanium-based crosslinking agent, titanium alkoxide-based crosslinking agents such as titanium diisopropoxybis (triethanolaminate) and titanium lactate ammonium salt are preferable. Examples of the zirconium-based crosslinking agent include zirconium oxychloride, zirconium sulfate, zirconium nitrate, zirconium acetate, zirconium carbonate, zirconium zirconium ammonium, zirconium stearate, zirconium octylate, and zirconium silicate. Of these zirconium compounds, water-soluble ones are preferred, and those having no chlorine are more preferred. Specific examples include zirconium sulfate, zirconium nitrate, zirconium acetate, and ammonium ammonium carbonate. Examples of the crosslinking agent having an epoxy group include epoxy chlorohydrin, diepoxy alkane, diepoxy alkene, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, and (poly) glycerin diglycidyl ether. The diglycidyl ether compound is particularly preferable ethylene glycol diglycidyl ether. Examples of the crosslinking agent having an aldehyde group include dialdehyde compounds such as glutaraldehyde, succinaldehyde, malondialdehyde, terephthalaldehyde, and isophthalaldehyde, and glutaraldehyde is particularly preferable.
上記の多官能性の架橋剤（Ｃ）は単独で使用しても性能は発現するが、異なる系の多官能性の架橋剤（Ｃ）を２種以上混合して用いる方が効果は高い。すなわち、多官能性の架橋剤（Ｃ）が、チタン系架橋剤、ジルコニウム系架橋剤、コロイダルシリカ、および官能基としてエポキシ基またはアルデヒド基を有する架橋剤からなる群から選択される少なくとも２種以上であることが好適な実施態様である。 Although the above-mentioned polyfunctional crosslinking agent (C) exhibits performance even when used alone, it is more effective to use a mixture of two or more different types of multifunctional crosslinking agents (C). That is, the polyfunctional crosslinking agent (C) is at least two or more selected from the group consisting of a titanium-based crosslinking agent, a zirconium-based crosslinking agent, colloidal silica, and a crosslinking agent having an epoxy group or an aldehyde group as a functional group. Is a preferred embodiment.
本発明の複合膜において、該複合膜１００重量部（乾燥重量）当りの吸水量は、３０〜１０００重量部の範囲である。吸水量がこの範囲にあることにより、混合ガスに水蒸気が含まれた場合であっても適度な親和性を有することとなる。吸水量が３０重量部未満であると、水蒸気の含まれる混合ガスにおいてガス分離の選択性が低下するおそれがあり、５０重量部以上であることが好ましく、７０重量部以上であることがより好ましい。一方、吸水量が１０００重量部を超えると耐水性が発現しないため、水溶性アミン化合物（Ｂ）に固有の高い分離性能を発揮させることができなくなるおそれがあり、８００重量部以下であることが好ましく、５００重量部以下であることがより好ましい。 In the composite membrane of the present invention, the water absorption per 100 parts by weight (dry weight) of the composite membrane is in the range of 30 to 1000 parts by weight. When the amount of water absorption is within this range, even if water vapor is contained in the mixed gas, it has an appropriate affinity. If the water absorption is less than 30 parts by weight, the gas separation selectivity may be reduced in a mixed gas containing water vapor, preferably 50 parts by weight or more, and more preferably 70 parts by weight or more. . On the other hand, if the amount of water absorption exceeds 1000 parts by weight, water resistance will not be exhibited, so that the water-soluble amine compound (B) may not be able to exhibit the high separation performance inherent, and may be 800 parts by weight or less. Preferably, it is 500 parts by weight or less.
また、本発明において、該複合膜を６０℃の蒸留水に３時間浸漬させた時の該複合膜の重量保持率は、５０〜１００重量％の範囲である。重量保持率がこの範囲にあることにより、耐水性を有し分離性能が低下することのない本発明の複合膜が得られることとなる。重量保持率が５０重量％未満であると、シリル基含有のビニルアルコール系重合体（Ａ）マトリックスに水溶性アミン化合物（Ｂ）を固定化する目的が達成されず耐水性が低下するおそれがあり、６０重量％以上であることが好ましく、７０重量％以上であることがより好ましい。 In the present invention, when the composite membrane is immersed in distilled water at 60 ° C. for 3 hours, the weight retention of the composite membrane is in the range of 50 to 100% by weight. When the weight retention is in this range, the composite membrane of the present invention that has water resistance and does not deteriorate separation performance can be obtained. If the weight retention is less than 50% by weight, the purpose of immobilizing the water-soluble amine compound (B) on the silyl group-containing vinyl alcohol polymer (A) matrix may not be achieved and the water resistance may be reduced. 60% by weight or more, more preferably 70% by weight or more.
本発明の複合膜における吸水量と重量保持率を上記の範囲になるようにするには、シリル基含有のビニルアルコール系重合体（Ａ）と水溶性アミン化合物（Ｂ）と多官能性の架橋剤（Ｃ）との種類および使用比率を適宜選択することにより行うことができる。 In order to make the water absorption and weight retention in the composite membrane of the present invention within the above ranges, a silyl group-containing vinyl alcohol polymer (A), a water-soluble amine compound (B), and a multifunctional crosslink It can be carried out by appropriately selecting the type and the use ratio with the agent (C).
本発明の複合膜において、ビニルアルコール系重合体（Ａ）と多官能性の架橋剤（Ｃ）との重量配合比率（Ａ）／（Ｃ）は、９９．９／０．１〜５０／５０であることが好ましく、９９．５／０．５〜６０／４０であることがより好ましく、９９／１〜７０／３０であることがさらに好ましい。重量配合比率（Ａ）／（Ｃ）が９９．９／０．１を超える場合には得られる複合膜の耐水性が充分でないおそれがある。一方、重量配合比率（Ａ）／（Ｃ）が５０／５０未満の場合には製膜時の作業性が低下したり、複合膜を作成する際のビニルアルコール系重合体（Ａ）と水溶性アミン化合物（Ｂ）および多官能性の架橋剤（Ｃ）からなる溶液の粘度安定性が低下するおそれがある。 In the composite membrane of the present invention, the weight blending ratio (A) / (C) of the vinyl alcohol polymer (A) and the polyfunctional crosslinking agent (C) is 99.9 / 0.1-50 / 50. It is preferable that it is 99.5 / 0.5-60 / 40, and it is further more preferable that it is 99 / 1-70 / 30. If the weight ratio (A) / (C) exceeds 99.9 / 0.1, the resulting composite membrane may not have sufficient water resistance. On the other hand, when the weight blending ratio (A) / (C) is less than 50/50, workability during film formation is reduced, or the vinyl alcohol polymer (A) and water-solubility when forming a composite film There is a possibility that the viscosity stability of the solution comprising the amine compound (B) and the polyfunctional crosslinking agent (C) may be lowered.
本発明の耐水性に優れるガス分離膜用ビニルアルコール系重合体複合膜を得る点から、該複合膜の熱処理は重要である。多官能性の架橋剤（Ｃ）によるマトリックスの架橋のみならず、熱処理によるビニルアルコール系重合体（Ａ）の結晶化を促進することで耐水性を更に向上させることができる。熱処理の温度としては、６０〜２００℃が好ましく、９０〜１８０℃が更に好ましい。６０℃未満である場合、熱処理の効果が不十分となるおそれがある。２００℃を超えるとビニルアルコール系重合体（Ａ）や水溶性アミン化合物（Ｂ）が分解する場合があり好ましくない。熱処理の時間としては条件や設備によって異なるために特に制限はないが、１秒から１時間の範囲にあることが好ましい。１秒未満である場合、熱処理の効果が不十分となるおそれがある。１時間を超えると工業的な実施に難があるのみならず、ビニルアルコール系重合体（Ａ）や水溶性アミン化合物（Ｂ）が分解する場合があり好ましくない。 The heat treatment of the composite membrane is important from the viewpoint of obtaining the vinyl alcohol polymer composite membrane for gas separation membrane having excellent water resistance of the present invention. Water resistance can be further improved by promoting not only the matrix crosslinking by the polyfunctional crosslinking agent (C) but also the crystallization of the vinyl alcohol polymer (A) by heat treatment. As temperature of heat processing, 60-200 degreeC is preferable and 90-180 degreeC is still more preferable. If it is lower than 60 ° C., the effect of heat treatment may be insufficient. If it exceeds 200 ° C., the vinyl alcohol polymer (A) and the water-soluble amine compound (B) may be decomposed, which is not preferable. The heat treatment time varies depending on conditions and equipment and is not particularly limited, but is preferably in the range of 1 second to 1 hour. If it is less than 1 second, the effect of heat treatment may be insufficient. Exceeding 1 hour is not preferable because not only industrial implementation is difficult, but also the vinyl alcohol polymer (A) and the water-soluble amine compound (B) may be decomposed.
本発明の耐水性に優れるビニルアルコール系重合体複合膜は、水蒸気の含まれる混合ガスに耐え実用に供することが可能なガス分離膜に好適に使用される。ガス分離膜は支持膜と本発明の複合膜から構成され、公知の支持膜の表面に本発明の複合膜が形成される。支持膜を構成する疎水性高分子としては従来公知の膜形成用の樹脂が使用できる。かかる疎水性樹脂としては、例えばポリスルホン、ポリエーテルスルホン、ポリアミド、ポリイミド、ポリアクリロニトリル、ポリスチレン、ポリフッ化ビニリデン、ポリ塩化ビニル、ポリアミド、ポリメタクリル酸メチル等が例示できる。 The vinyl alcohol polymer composite membrane excellent in water resistance of the present invention is suitably used for a gas separation membrane that can withstand mixed gas containing water vapor and can be used practically. The gas separation membrane is composed of a support membrane and the composite membrane of the present invention, and the composite membrane of the present invention is formed on the surface of a known support membrane. As the hydrophobic polymer constituting the support membrane, a conventionally known resin for film formation can be used. Examples of the hydrophobic resin include polysulfone, polyethersulfone, polyamide, polyimide, polyacrylonitrile, polystyrene, polyvinylidene fluoride, polyvinyl chloride, polyamide, polymethyl methacrylate, and the like.
以下、実施例を挙げて本発明を更に詳しく説明するが、本発明はこれらの実施例によりなんら限定されるものではない。なお、実施例中で特に断りのない限り、「％」および「部」はそれぞれ「重量％」および「重量部」を意味する。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited at all by these Examples. Unless otherwise specified in the examples, “%” and “part” mean “% by weight” and “part by weight”, respectively.
［複合膜の耐水性評価］
シート状物の吸水量、重量保持率はそれぞれ次式で求めた。
吸水量（部）＝［（Ｗ１／Ｗ２）−１］×１００
重量保持率（％）＝｛１−［（Ｗ３−Ｗ２）／Ｗ３］｝×１００
上記の式において、記号は下記の意味を有する。
Ｗ１：膨潤後の試料の重量
Ｗ２：膨潤後さらに乾燥した後の試料重量
Ｗ３：膨潤前の試料重量
[Water resistance evaluation of composite membrane]
The amount of water absorption and the weight retention of the sheet-like material were determined by the following formulas.
Water absorption (parts) = [(W1 / W2) -1] × 100
Weight retention (%) = {1-[(W3-W2) / W3]} × 100
In the above formula, the symbols have the following meanings.
W1: Weight of sample after swelling W2: Sample weight after swelling and further drying W3: Sample weight before swelling
合成例１
［シリル基とエチレン単位を有するビニルアルコール系重合体（Ａ）の合成例］
撹拌機、窒素導入口、エチレン導入口および開始剤添加口を備えた１００Ｌ加圧反応槽に酢酸ビニル５６ｋｇ、メタノール５．８ｋｇおよびビニルトリメトキシシラン１２１ｇを仕込み、６０℃に昇温した後、３０分間窒素バブリングにより系中を窒素置換した。次いで反応槽圧力が７．０ｋｇ／ｃｍ２になるようにエチレンを導入仕込みした。開始剤として２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）をメタノールに溶解した濃度２.８ｇ／Ｌ溶液を調製し、窒素ガスによるバブリングを行って窒素置換した。上記の反応槽内温を６０℃に調整した後、上記の開始剤溶液５０ｍＬを注入し、重合を開始した。重合中はエチレンを導入して反応槽圧力を７．０ｋｇ／ｃｍ２に、重合温度を６０℃に維持し、上記の開始剤溶液を１７０ｍＬ/ｈｒで連続添加した。６時間後に重合率が４０％に達したところで冷却して重合を停止した。反応槽を解放して脱エチレンしたあと窒素ガスをバブリングして脱エチレンを完全に行った。次いで減圧下に未反応酢酸ビニルモノマーを除去し、ポリ酢酸ビニル（以下、ＰＶＡｃと略記する。）のメタノール溶液とした。２０％に調整した該溶液にモル比（ＮａＯＨのモル数／ポリ酢酸ビニル中の酢酸ビニル単位のモル数）０．０５のＮａＯＨメタノール溶液（１０％濃度）を添加してけん化した。得られたＰＶＡ（ＰＶＡ−１）のけん化度は９９.４モル％であった。
Synthesis example 1
[Synthesis Example of Vinyl Alcohol Polymer (A) Having Silyl Group and Ethylene Unit]
A 100 L pressurized reaction vessel equipped with a stirrer, nitrogen inlet, ethylene inlet and initiator addition port was charged with 56 kg of vinyl acetate, 5.8 kg of methanol and 121 g of vinyltrimethoxysilane, heated to 60 ° C., The system was purged with nitrogen by nitrogen bubbling for 1 minute. Next, ethylene was introduced and charged so that the reactor pressure was 7.0 kg / cm 2 . A 2.8 g / L solution in which 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) was dissolved in methanol as an initiator was prepared, and nitrogen substitution was performed by bubbling with nitrogen gas. After adjusting the temperature inside the reaction vessel to 60 ° C., 50 mL of the initiator solution was injected to initiate polymerization. During the polymerization, ethylene was introduced to maintain the reactor pressure at 7.0 kg / cm 2 , the polymerization temperature at 60 ° C., and the above initiator solution was continuously added at 170 mL / hr. After 6 hours, when the polymerization rate reached 40%, the polymerization was stopped by cooling. The reaction vessel was opened and deethylene removed, and then nitrogen gas was bubbled to completely remove ethylene. Subsequently, the unreacted vinyl acetate monomer was removed under reduced pressure to obtain a methanol solution of polyvinyl acetate (hereinafter abbreviated as PVAc). The solution adjusted to 20% was saponified by adding a NaOH methanol solution (concentration of 10%) having a molar ratio (number of moles of NaOH / number of moles of vinyl acetate units in polyvinyl acetate) of 0.05. The degree of saponification of the obtained PVA (PVA-1) was 99.4 mol%.
重合後、未反応酢酸ビニルモノマーを除去して得られたＰＶＡｃのメタノール溶液をｎ−ヘキサンに沈殿、アセトンで溶解する再沈精製を３回行った後、６０℃で減圧乾燥して精製ＰＶＡｃを得た。該ＰＶＡｃのアルカリ消費量を測定して求めたエチレン変性量は６.５モル％であった。上記のＰＶＡｃのメタノール溶液をアルカリモル比０．２でけん化した後、メタノールソックスレーを３日間実施し、次いで乾燥して精製ＰＶＡを得た。常法のＪＩＳ Ｋ６７２６に準じて、該ＰＶＡの平均重合度を測定したところ１４８０であった。また該ＰＶＡについて１Ｈ−ＮＭＲからビニルトリメトキシシランの含有量を測定したところ０．２６モル％であった。 After polymerization, the methanol solution of PVAc obtained by removing the unreacted vinyl acetate monomer was precipitated in n-hexane and reprecipitation purification was performed three times by dissolving with acetone, and then dried at 60 ° C. under reduced pressure to obtain purified PVAc. Obtained. The ethylene modification amount determined by measuring the alkali consumption of PVAc was 6.5 mol%. After saponifying the above methanol solution of PVAc at an alkali molar ratio of 0.2, methanol soxhlet was carried out for 3 days and then dried to obtain purified PVA. It was 1480 when the average degree of polymerization of this PVA was measured according to JIS K6726 of the usual method. Moreover, when content of vinyltrimethoxysilane was measured from 1 H-NMR for the PVA, it was 0.26 mol%.
実施例１
ビニルトリメトキシシランと酢酸ビニルとの共重合体をけん化してシリル基をビニルシラン単位として０．２５モル％含有し、酢酸ビニル単位のけん化度９８．６モル％、重合度１６５０の分子内にシリル基を含むＰＶＡを得た。このＰＶＡを水に溶解し、ＰＶＡの３％水溶液を作成した。その水溶液１００重量部に対し、水溶性アミン化合物（Ｂ）としてＰＡＭＡＭデンドリマー（表面基：−ＣＯＮＨＣＨ２ＣＨ２ＮＨ２、表面基の数：４個）の２０％メタノール溶液（アルドリッチ社製）を１５重量部と、ジルコゾールＺＣ−２（第一稀元素化学工業（株）製）を酸化ジルコニウム換算で濃度０．２％の水溶液４５部を攪拌しながら徐々に加えて調整した。この溶液を流延し、２０℃で乾燥して厚さ１００μｍのシート状物を得た。得られたシート状物を枠に固定して熱風乾燥機で１５０℃、１０分間熱処理をした。この熱処理したシート状物を温水（６０℃）に３時間浸漬した後、吸水量および重量保持率を測定した。シート状物の吸水量は６５０重量部、重量保持率は７６％であり、しっかりとした皮膜状態を維持していた。結果を表１に示す。
Example 1
A copolymer of vinyltrimethoxysilane and vinyl acetate was saponified to contain 0.25 mol% of silyl groups as vinyl silane units. The saponification degree of vinyl acetate units was 98.6 mol% and the polymerization degree was 1650 in the molecule. A PVA containing group was obtained. This PVA was dissolved in water to prepare a 3% aqueous solution of PVA. 15% of a 20% methanol solution (manufactured by Aldrich) of PAMAM dendrimer (surface group: —CONHCH 2 CH 2 NH 2 , number of surface groups: 4) as a water-soluble amine compound (B) with respect to 100 parts by weight of the aqueous solution. Part by weight and 45 parts of an aqueous solution having a concentration of 0.2% in terms of zirconium oxide were gradually added and adjusted with Zircosol ZC-2 (manufactured by Daiichi Rare Element Chemical Co., Ltd.). This solution was cast and dried at 20 ° C. to obtain a sheet-like material having a thickness of 100 μm. The obtained sheet was fixed to a frame and heat-treated at 150 ° C. for 10 minutes with a hot air dryer. The heat-treated sheet was immersed in warm water (60 ° C.) for 3 hours, and the water absorption and weight retention were measured. The sheet had a water absorption of 650 parts by weight and a weight retention of 76%, maintaining a firm film state. The results are shown in Table 1.
比較例１
分子量５０万のキトサン（商品名：キトサンＨ、キミカ株式会社製）／分子量５万のキトサン（商品名：キトサンＬＬ、キミカ株式会社製）＝１００／１０の混合キトサンを酢酸２重量％水溶液に徐々に加え、６０分攪拌して０．５重量％のキトサン溶液を調製した。その後、１．０μｍのろ紙でろ過したキトサンの酢酸水溶液１００重量部に対し、架橋剤（Ｃ）としてエチレングリコールジグリシジルエーテル（ＥＧＤＧＥ）（東京化成工業株式会社製）を２０重量部攪拌しながら徐々に加えて調整した。この溶液を流延し、２０℃で乾燥して厚さ１００μｍのシート状物を得た。得られたシート状物を枠に固定して大過剰の０．１Ｍの水酸化ナトリウム水溶液に１０分間浸漬した。引き続き、蒸留水とエタノール１：１の混合溶媒に６０分間浸漬した後に、６０℃で８時間乾燥した。
Comparative Example 1
Chitosan having a molecular weight of 500,000 (trade name: Chitosan H, manufactured by Kimika Co., Ltd.) / Chitosan having a molecular weight of 50,000 (trade name: Chitosan LL, manufactured by Kimika Co., Ltd.) = 100/10 mixed chitosan was gradually added to a 2% by weight aqueous solution of acetic acid. In addition, the mixture was stirred for 60 minutes to prepare a 0.5 wt% chitosan solution. Then, ethylene glycol diglycidyl ether (EGDGE) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a crosslinking agent (C) was gradually stirred with respect to 100 parts by weight of an aqueous acetic acid solution of chitosan filtered through a 1.0 μm filter paper. In addition to the adjustment. This solution was cast and dried at 20 ° C. to obtain a sheet-like material having a thickness of 100 μm. The obtained sheet was fixed to a frame and immersed in a large excess of 0.1 M aqueous sodium hydroxide solution for 10 minutes. Subsequently, it was immersed in a mixed solvent of distilled water and ethanol 1: 1 for 60 minutes, and then dried at 60 ° C. for 8 hours.
さらに、得た枠に固定された乾燥シート状物を、水溶性アミン化合物（Ｂ）として実施例１で使用されたものと同じＰＡＭＡＭデンドリマーの２０％メタノール溶液（アルドリッチ社製）を水で２倍希釈した大過剰の溶液中に３０分間浸漬した。その後６０℃で８時間乾燥した。重量測定から該シート状物には、キトサン１００重量部に対してＰＡＭＡＭデンドリマーは１００重量部包含されていた。さらに、１２０℃、１０分間熱処理をした。この熱処理したシート状物を温水（６０℃）に３時間浸漬した後、吸水量および重量保持率を測定した。シート状物の吸水量は１７０重量部、重量保持率は３６％であり、皮膜状態はしっかりとしていたが、重量保持率は低いものであった。結果を表１に示す。 Furthermore, the dry sheet-like material fixed to the obtained frame was doubled with a 20% methanol solution (manufactured by Aldrich) of the same PAMAM dendrimer used in Example 1 as the water-soluble amine compound (B). It was immersed in the diluted large excess solution for 30 minutes. Thereafter, it was dried at 60 ° C. for 8 hours. From the weight measurement, the sheet-like material contained 100 parts by weight of PAMAM dendrimer with respect to 100 parts by weight of chitosan. Further, heat treatment was performed at 120 ° C. for 10 minutes. The heat-treated sheet was immersed in warm water (60 ° C.) for 3 hours, and the water absorption and weight retention were measured. The sheet had a water absorption of 170 parts by weight and a weight retention of 36%, and the film state was firm, but the weight retention was low. The results are shown in Table 1.
比較例２
比較例１で用いた架橋剤（Ｃ）であるＥＧＤＧＥに代えて、グルタルアルデヒド（ＧＡ；和光純薬製）を３重量部用いた以外は、比較例１と同様にして熱処理したシート状物を得た。重量保持率は低いものであった。結果を表１に示す。
Comparative Example 2
Instead of EGDGE, which is the crosslinking agent (C) used in Comparative Example 1, a sheet-like material that was heat-treated in the same manner as in Comparative Example 1 except that 3 parts by weight of glutaraldehyde (GA; manufactured by Wako Pure Chemical Industries, Ltd.) was used. Obtained. The weight retention was low. The results are shown in Table 1.
実施例２〜４
実施例１で用いた変性ＰＶＡの種類およびＰＡＭＡＭデンドリマーの量、架橋剤（Ｃ）の種類および量、熱処理温度を表１に示すものに代えた以外は、実施例１と同様に行った。結果を表１に示す。
Examples 2-4
The procedure was the same as in Example 1 except that the type of modified PVA and the amount of PAMAM dendrimer used in Example 1 and the type and amount of the crosslinking agent (C) and the heat treatment temperature were changed to those shown in Table 1. The results are shown in Table 1.
比較例３
シリル基を含有しないＰＶＡ−１２０（株式会社クラレ製）を使用する以外は、実施例１と同様にして熱処理したシート状物を得た。得られたシート状物を枠に固定してグルタルアルデヒドと等量の硫酸水溶液に６０℃で１０分間浸漬した。引き続き、蒸留水とエタノール１：１の混合溶媒に６０分間浸漬した後に、６０℃で８時間乾燥した。シリル基を含有しないシート状物は、６０℃の温水に浸漬したところ溶解した。
Comparative Example 3
A heat-treated sheet was obtained in the same manner as in Example 1 except that PVA-120 (manufactured by Kuraray Co., Ltd.) containing no silyl group was used. The obtained sheet was fixed to a frame and immersed in an aqueous sulfuric acid solution in an amount equal to glutaraldehyde at 60 ° C. for 10 minutes. Subsequently, it was immersed in a mixed solvent of distilled water and ethanol 1: 1 for 60 minutes, and then dried at 60 ° C. for 8 hours. The sheet-like material containing no silyl group dissolved when immersed in warm water at 60 ° C.
実施例５〜７
実施例１で用いたシリル基含有ＰＶＡを用いて架橋剤（Ｃ）の種類および量、熱処理温度を表１に示すものに代えた以外は、実施例１と同様に行った。結果を表１に示す。
Examples 5-7
The same procedure as in Example 1 was performed except that the type and amount of the crosslinking agent (C) and the heat treatment temperature were changed to those shown in Table 1 using the silyl group-containing PVA used in Example 1. The results are shown in Table 1.
実施例８
合成例１で示したシリル基とエチレン単位を有するＰＶＡを用いて、架橋剤（Ｃ）の種類および量を表１に示すものに代えた以外は、実施例１と同様に行った。得られたシート状物は重量保持率が高く耐水性が向上していた。結果を表１に示す。
Example 8
The same procedure as in Example 1 was carried out except that PVA having a silyl group and an ethylene unit shown in Synthesis Example 1 was used and the type and amount of the crosslinking agent (C) were changed to those shown in Table 1. The obtained sheet was high in weight retention and improved in water resistance. The results are shown in Table 1.
実施例９〜１３
実施例８で用いたシリル基とエチレン単位を有するＰＶＡの種類およびＰＡＭＡＭデンドリマーの量、架橋剤（Ｃ）の種類および量、熱処理温度を表１に示すものに代えた以外は、実施例８と同様に行った。結果を表１に示す。
Examples 9-13
Except that the type of PVA having a silyl group and an ethylene unit used in Example 8 and the amount of PAMAM dendrimer, the type and amount of the crosslinking agent (C), and the heat treatment temperature were changed to those shown in Table 1, Example 8 and The same was done. The results are shown in Table 1.
比較例４〜５
実施例１および８において、架橋剤（Ｃ）を用いず熱処理温度を１２０℃で行った以外は実施例１および８と同様に行った。架橋剤（Ｃ）を用いないシート状物は、水に浸漬したところ溶解した。結果を表１に示す。
Comparative Examples 4-5
In Example 1 and 8, it carried out like Example 1 and 8 except having performed heat processing temperature at 120 degreeC, without using a crosslinking agent (C). The sheet-like material not using the crosslinking agent (C) dissolved when immersed in water. The results are shown in Table 1.
実施例１４
実施例１で用いたシリル基含有ＰＶＡのコモノマー種、ＰＡＭＡＭデンドリマーの量、架橋剤（Ｃ）の量を表１に示すものに代えた以外は、実施例１と同様に行った。結果を表１に示す。
Example 14
The same procedure as in Example 1 was conducted except that the comonomer species of the silyl group-containing PVA used in Example 1, the amount of PAMAM dendrimer, and the amount of the crosslinking agent (C) were changed to those shown in Table 1. The results are shown in Table 1.
実施例１５〜１６
実施例１で用いたＰＶＡを用いて、架橋剤（Ｃ）を２種類使用することに加えて、架橋剤（Ｃ）の量を表１に示すものに代えた以外は、実施例１と同様に行って熱処理シートを得た。さらに、比較例３と同様にして酸処理および洗浄、乾燥を行った。結果を表１に示す。
Examples 15-16
Using PVA used in Example 1, in addition to using two types of crosslinking agents (C), the same as Example 1 except that the amount of crosslinking agent (C) was changed to that shown in Table 1 To obtain a heat-treated sheet. Further, acid treatment, washing and drying were performed in the same manner as in Comparative Example 3. The results are shown in Table 1.
実施例１７〜１９
実施例８において、架橋剤（Ｃ）を２種類使用することに加えて、架橋剤（Ｃ）の量を表１に示すものに代えた以外は、実施例８と同様に行った。架橋剤（Ｃ）を２種類使用することによって重量保持率は高く耐水性に優れるものであった。結果を表１に示す。
Examples 17-19
In Example 8, in addition to using two types of crosslinking agents (C), the procedure was the same as in Example 8 except that the amount of the crosslinking agent (C) was changed to that shown in Table 1. By using two types of crosslinking agents (C), the weight retention was high and the water resistance was excellent. The results are shown in Table 1.
比較例６
実施例１で用いた変性ＰＶＡに代えてシリル含量が７．２ｍｏｌ％のシリル基含有ＰＶＡを用いて、実施例１と同様にシート作成用の溶液を調整したが、ジルコゾールＺＣ−２を添加すると溶液がゲル化してシートが得られなかった。
Comparative Example 6
In place of the modified PVA used in Example 1, a silyl group-containing PVA having a silyl content of 7.2 mol% was used to prepare a sheet-forming solution in the same manner as in Example 1. However, when zircozole ZC-2 was added, The solution gelled and no sheet was obtained.
比較例７
比較例３で用いたＰＶＡに代えて実施例１で用いた変性ＰＶＡを用い、得られたシートの熱処理を行わなかった以外は、比較例３と同様に行った。結果を表１に示す。
Comparative Example 7
The same procedure as in Comparative Example 3 was performed except that the modified PVA used in Example 1 was used instead of the PVA used in Comparative Example 3 and the obtained sheet was not heat-treated. The results are shown in Table 1.
Claims (7)
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Cited By (7)
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| JP2011167591A (en) * | 2010-02-16 | 2011-09-01 | Research Institute Of Innovative Technology For The Earth | Composite membrane for separating gas |
| EP2405308A1 (en) | 2010-07-07 | 2012-01-11 | Konica Minolta Business Technologies, Inc. | Image forming apparatus and method of stopping cleaning its image carrier |
| JP2012192316A (en) * | 2011-03-15 | 2012-10-11 | Research Institute Of Innovative Technology For The Earth | Gas separation composite membrane |
| WO2013031621A1 (en) * | 2011-08-26 | 2013-03-07 | Tdk株式会社 | Gas separation membrane |
| WO2014192838A1 (en) * | 2013-05-29 | 2014-12-04 | 株式会社クラレ | Ethylene-vinyl alcohol copolymer-containing resin composition, film, laminate, packaging material, vacuum heat-insulating body, film production method, and laminate production method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011167591A (en) * | 2010-02-16 | 2011-09-01 | Research Institute Of Innovative Technology For The Earth | Composite membrane for separating gas |
| EP2405308A1 (en) | 2010-07-07 | 2012-01-11 | Konica Minolta Business Technologies, Inc. | Image forming apparatus and method of stopping cleaning its image carrier |
| JP2012192316A (en) * | 2011-03-15 | 2012-10-11 | Research Institute Of Innovative Technology For The Earth | Gas separation composite membrane |
| WO2013031621A1 (en) * | 2011-08-26 | 2013-03-07 | Tdk株式会社 | Gas separation membrane |
| JPWO2013031621A1 (en) * | 2011-08-26 | 2015-03-23 | Tdk株式会社 | Gas separation membrane |
| WO2014192838A1 (en) * | 2013-05-29 | 2014-12-04 | 株式会社クラレ | Ethylene-vinyl alcohol copolymer-containing resin composition, film, laminate, packaging material, vacuum heat-insulating body, film production method, and laminate production method |
| US10047204B2 (en) | 2013-05-29 | 2018-08-14 | Kuraray Co., Ltd. | Ethylene-vinyl alcohol copolymer-containing resin composition, film, laminate, packaging material, vacuum thermal insulator, film production method, and laminate production method |
| JP2015024373A (en) * | 2013-07-26 | 2015-02-05 | ニッポン高度紙工業株式会社 | Separation membrane comprising inorganic/organic hybrid compound and its manufacturing method |
| JP2015059216A (en) * | 2013-09-20 | 2015-03-30 | 株式会社クラレ | Resin composition containing ethylene-vinyl alcohol copolymer, film, laminate, packaging material and film production method |
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