JP2007268321A - Gas separation membrane and its manufacturing method - Google Patents
Gas separation membrane and its manufacturing method Download PDFInfo
- Publication number
- JP2007268321A JP2007268321A JP2006093417A JP2006093417A JP2007268321A JP 2007268321 A JP2007268321 A JP 2007268321A JP 2006093417 A JP2006093417 A JP 2006093417A JP 2006093417 A JP2006093417 A JP 2006093417A JP 2007268321 A JP2007268321 A JP 2007268321A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- modified polysiloxane
- gas separation
- separation membrane
- membrane
- 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.)
- Granted
Links
- 238000000926 separation method Methods 0.000 title claims abstract description 73
- 239000012528 membrane Substances 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- -1 polysiloxane copolymer Polymers 0.000 claims abstract description 108
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 60
- 239000004814 polyurethane Substances 0.000 claims abstract description 23
- 229920002635 polyurethane Polymers 0.000 claims abstract description 22
- 229920000162 poly(ureaurethane) Polymers 0.000 claims abstract description 20
- 239000012948 isocyanate Substances 0.000 claims abstract description 18
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 28
- 239000002904 solvent Substances 0.000 abstract description 18
- 239000010409 thin film Substances 0.000 abstract description 16
- 230000035699 permeability Effects 0.000 abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 50
- 239000001301 oxygen Substances 0.000 description 42
- 229910052760 oxygen Inorganic materials 0.000 description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 41
- 239000007789 gas Substances 0.000 description 40
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 25
- 229920000642 polymer Polymers 0.000 description 24
- 239000010408 film Substances 0.000 description 22
- 239000010410 layer Substances 0.000 description 22
- 239000002131 composite material Substances 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 8
- 125000005442 diisocyanate group Chemical group 0.000 description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229920004482 WACKER® Polymers 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229920002396 Polyurea Polymers 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 238000006124 Pilkington process Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 229920003242 poly[1-(trimethylsilyl)-1-propyne] Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- FNFSKEAFJOOCCQ-UHFFFAOYSA-N 2,2,3,3-tetrachlorocyclopropan-1-one Chemical compound ClC1(Cl)C(=O)C1(Cl)Cl FNFSKEAFJOOCCQ-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
本発明は気体分離膜に関するものであり、特に大気中からの酸素ないし窒素の分離に適しており、溶液塗工法により簡便かつ高い生産性で製造できる気体分離膜に関するものである。 The present invention relates to a gas separation membrane, and more particularly to a gas separation membrane that is suitable for separation of oxygen or nitrogen from the atmosphere and can be produced simply and with high productivity by a solution coating method.
気体分離膜による気体の分離・濃縮は、蒸留法や高圧吸着法などと比べエネルギー効率に優れた省エネルギーで安全性の高い方法であり、近年再び注目を集めている。大気中の酸素を濃縮する酸素富化膜は、燃焼機器、空調機器、医療機器、健康機器等に利用される他、逆に濃縮酸素を排除して得られる窒素富化空気を利用してディーゼルエンジンの窒素酸化物の低減や消火システムへの活用が検討されている。また合成ガスや天然ガスなどから温室効果ガスである二酸化炭素を気体分離膜を用いて除去回収する方法についても近年盛んに検討が行われている。 Gas separation / concentration by gas separation membranes is an energy-saving and highly safe method that is superior in energy efficiency compared to distillation methods and high-pressure adsorption methods, and has recently attracted attention again. Oxygen-enriched membranes that concentrate oxygen in the atmosphere are used in combustion equipment, air-conditioning equipment, medical equipment, health equipment, etc., and conversely diesel using nitrogen-enriched air obtained by eliminating concentrated oxygen Reduction of engine nitrogen oxides and use in fire extinguishing systems are being studied. In recent years, a method for removing and recovering carbon dioxide, which is a greenhouse gas, from synthetic gas and natural gas using a gas separation membrane has been actively studied.
一般に、気体分離膜の性能は、透過速度と分離係数を指標として表される。透過速度は（分離層の透過係数）／（分離層の厚み）で表される。分離層の透過係数は、分離層の素材に固有の単位厚みあたりの気体透過性能である。上記式から明らかなように、気体透過速度の大きな膜を得るためには、分離層を透過係数の大きな素材とし、分離層の厚みを可能な限り薄くすることが必要である。また、分離係数は分離しようとする２種の気体の気体透過速度の比で表され、原則的には分離層の素材に依存する値であるが、分離層にピンホールが存在する場合には分離係数は大きく低下する。以上のことから、気体分離膜として実用的な膜を得るためには透過係数の大きな素材を用い、ピンホールを生じさせることなくその厚みを可能な限り薄くすることが必要となる。 In general, the performance of a gas separation membrane is expressed using a permeation rate and a separation coefficient as indices. The permeation speed is expressed by (separation coefficient of separation layer) / (thickness of separation layer). The permeability coefficient of the separation layer is a gas permeation performance per unit thickness inherent to the material of the separation layer. As is apparent from the above formula, in order to obtain a membrane having a high gas permeation rate, it is necessary to use a material having a high permeation coefficient and to make the thickness of the separation layer as thin as possible. The separation factor is expressed as the ratio of the gas permeation speeds of the two gases to be separated, and is in principle dependent on the material of the separation layer, but when there are pinholes in the separation layer The separation factor is greatly reduced. From the above, in order to obtain a practical membrane as a gas separation membrane, it is necessary to use a material having a large permeability coefficient and to reduce the thickness as much as possible without causing pinholes.
酸素透過性能の高い素材としては、ポリ［１−（トリメチルシリル）−１−プロピン］が知られている。ポリ［１−（トリメチルシリル）−１−プロピン］は、初期における酸素の透過係数が約６０×１０−８ｃｍ３（ＳＴＰ）・ｃｍ／ｃｍ２・ｓｅｃ・ｃｍＨｇであり、高分子材料の中で最も高い酸素透過性能を示す。しかしながら、この酸素富化膜は酸素の透過係数に著しい経時変化があるため実用段階にはない（例えば特許文献１および非特許文献１参照）。 Poly [1- (trimethylsilyl) -1-propyne] is known as a material having high oxygen permeability. Poly [1- (trimethylsilyl) -1-propyne] has an initial oxygen permeability coefficient of about 60 × 10 −8 cm 3 (STP) · cm / cm 2 · sec · cmHg. Shows the highest oxygen permeation performance. However, this oxygen-enriched film is not in a practical stage because there is a significant change with time in the oxygen permeability coefficient (see, for example, Patent Document 1 and Non-Patent Document 1).
ポリ［１−（トリメチルシリル）−１−プロピン］に次ぐ酸素透過係数を示す高分子素材として、ポリジメチルシロキサンが知られている。ポリジメチルシロキサンは、酸素透過係数が約３×１０−８ｃｍ３（ＳＴＰ）・ｃｍ／ｃｍ２・ｓｅｃ・ｃｍＨｇであり、酸素透過性の長期信頼性にも優れている（例えば特許文献２参照）。しかしながら機械的強度が低いことから、多孔質支持体上に分離層を積層する複合膜においてもピンホールを生じることなく薄膜化することが困難であった。そこで、この問題を解決すべくポリジメチルシロキサン骨格を有する種々の共重合体が検討されてきた。中でもポリウレタンやポリ尿素骨格を導入したポリジメチルシロキサン／ポリウレタン共重合体、ポリジメチルシロキサン／ポリ尿素共重合体は、分子間に形成される水素結合により強度の高い膜を形成し、気体分離膜として期待が持たれる（例えば特許文献３〜７参照）。 Polydimethylsiloxane is known as a polymer material having an oxygen permeability coefficient next to poly [1- (trimethylsilyl) -1-propyne]. Polydimethylsiloxane has an oxygen permeability coefficient of about 3 × 10 −8 cm 3 (STP) · cm / cm 2 · sec · cmHg, and is excellent in long-term reliability of oxygen permeability (see, for example, Patent Document 2). ). However, since the mechanical strength is low, it has been difficult to reduce the thickness of a composite membrane in which a separation layer is laminated on a porous support without causing pinholes. Therefore, various copolymers having a polydimethylsiloxane skeleton have been studied to solve this problem. Among them, polydimethylsiloxane / polyurethane copolymer and polydimethylsiloxane / polyurea copolymer with polyurethane or polyurea skeleton introduced form a high strength membrane by hydrogen bonds formed between molecules, and serve as gas separation membranes. Expectation is held (for example, see Patent Documents 3 to 7).
一方、多孔質支持体上に薄膜を形成する方法としては、分離層として用いる高分子の溶液を水面上に展開して薄膜を形成させ、次いでこの薄膜を支持体と接触させることにより支持体上に積層する水面展開法が一般に採用されている（例えば特許文献８参照）。この方法は１μｍ以下、特に１００ｎｍ以下の薄膜を形成するのに有利な方法であるが、水面上に形成された強度の弱い薄膜を取り扱うため作業性が非常に悪く、さらに膜に欠陥を生じやすい傾向があることから大量生産性に適さないという問題点を有する。 On the other hand, as a method of forming a thin film on a porous support, a polymer solution used as a separation layer is spread on a water surface to form a thin film, and then the thin film is brought into contact with the support. In general, a water surface expansion method of laminating is used (see, for example, Patent Document 8). This method is advantageous for forming a thin film having a thickness of 1 μm or less, particularly 100 nm or less. However, since a thin film with low strength formed on the water surface is handled, the workability is very poor and the film is likely to be defective. There is a problem that it is not suitable for mass productivity because of its tendency.
これに対し、高分子溶液を支持体に直接塗布し溶剤を乾燥させて複合膜とする溶液塗工法では生産性は大幅に向上するが、高分子溶液が支持体の孔に浸透してしまい薄膜を支持体の表面にのみ形成することが困難であるという問題点があった。
本発明は上記事情に鑑みてなされたものであり、溶液塗工法を用いて多孔質支持体上に薄膜を形成することができ、かつ膜強度および気体透過性能に優れた分離層として機能するポリシロキサン共重合体を用いた気体分離膜を提供することを課題とする。 The present invention has been made in view of the above circumstances, and can be used to form a thin film on a porous support using a solution coating method and to function as a separation layer excellent in membrane strength and gas permeation performance. It is an object of the present invention to provide a gas separation membrane using a siloxane copolymer.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、ポリシロキサン／ポリ尿素／ポリウレタン共重合体を多官能イソシアネート化合物で変性することにより得られる変性ポリシロキサン共重合体が、ポリ尿素やポリウレタンの優れた成膜性と膜強度を保ちつつ多孔質支持体上での薄膜形成性に極めて優れることを見いだし、この知見に基づいて本発明を完成させるに至った。 As a result of intensive studies to solve the above problems, the present inventors have obtained a modified polysiloxane copolymer obtained by modifying a polysiloxane / polyurea / polyurethane copolymer with a polyfunctional isocyanate compound, It has been found that the film-forming property and film strength of polyurea and polyurethane are excellent and the film-forming property on the porous support is extremely excellent, and the present invention has been completed based on this finding.
すなわち、本発明は、
（１）下記一般式（Ｉ）で表される繰り返し単位を有するポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）１００重量部に対し、イソシアネート基を少なくとも２個有する多官能イソシアネート化合物（Ｂ）を０．１〜５重量部反応させて得られる溶媒に可溶性の変性ポリシロキサン共重合体（Ｃ）を分離層として用いることを特徴とする気体分離膜、
That is, the present invention
(1) Polyfunctional isocyanate compound (B) having at least two isocyanate groups with respect to 100 parts by weight of polysiloxane / polyurea / polyurethane copolymer (A) having a repeating unit represented by the following general formula (I) A gas separation membrane characterized by using a modified polysiloxane copolymer (C) soluble in a solvent obtained by reacting 0.1 to 5 parts by weight as a separation layer,
（式中、Ｒ１〜Ｒ８は各々独立にフッ素で置換されていてもよい炭素数１〜２０の１価の炭化水素基を表し、Ｘ１およびＸ２は各々独立に炭素数２〜２０の２価の炭化水素基を表し、ａおよびｃは各々独立に２〜１０の整数を表し、ｂおよびｄは各々独立に１〜４０００の整数を表し、ｍおよびｎは各々独立に０または正の整数を表し、ｍとｎが同時に０であることはない。）
（２）変性ポリシロキサン共重合体（Ｃ）のポリスチレン換算数平均分子量が１０万〜１００万であることを特徴とする前記（１）の変性ポリシロキサン共重合体（Ｃ）、
（３）前記（１）または（２）に記載の変性ポリシロキサン共重合体（Ｃ）を分離層として用いることを特徴とする気体分離膜、
（４）前記（１）または（２）に記載の変性ポリシロキサン共重合体（Ｃ）を多孔質支持体上に積層してなる前記（１）または（２）の気体分離膜、
（５）前記（１）または（２）記載の変性ポリシロキサン共重合体（Ｃ）の溶液を多孔質支持体に塗工することを特徴とする気体分離膜の製造法
を提供するものである。
(In the formula, R 1 to R 8 each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with fluorine, and X 1 and X 2 each independently represent 2 to 20 carbon atoms. A and c each independently represents an integer of 2 to 10, b and d each independently represents an integer of 1 to 4000, and m and n each independently represents 0 or positive And m and n are not 0 at the same time.)
(2) The modified polysiloxane copolymer (C) of (1) above, wherein the modified polysiloxane copolymer (C) has a polystyrene-equivalent number average molecular weight of 100,000 to 1,000,000.
(3) A gas separation membrane using the modified polysiloxane copolymer (C) according to (1) or (2) as a separation layer,
(4) The gas separation membrane according to (1) or (2), wherein the modified polysiloxane copolymer (C) according to (1) or (2) is laminated on a porous support,
(5) Provided is a method for producing a gas separation membrane, characterized in that a solution of the modified polysiloxane copolymer (C) described in (1) or (2) is applied to a porous support. .
本発明によれば、特に大気中からの酸素ないし窒素の分離に好適であり、膜強度および気体透過性能に優れ、溶液塗工法により簡便かつ高い生産性で製造できる気体分離膜が提供される。 According to the present invention, there is provided a gas separation membrane that is particularly suitable for separation of oxygen or nitrogen from the atmosphere, has excellent membrane strength and gas permeation performance, and can be produced simply and with high productivity by a solution coating method.
以下、本発明について具体的に説明する。 Hereinafter, the present invention will be specifically described.
本発明に用いられるポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）は下記一般式（Ｉ）で表される繰り返し単位を有する。 The polysiloxane / polyurea / polyurethane copolymer (A) used in the present invention has a repeating unit represented by the following general formula (I).
式中、Ｒ１〜Ｒ８は各々独立にフッ素で置換されていてもよい炭素数１〜２０の１価の炭化水素基を表し、Ｘ１およびＸ２は各々独立に炭素数２〜２０の２価の炭化水素基を表し、ａおよびｃは各々独立に２〜１０の整数を表し、ｂおよびｄは各々独立に１〜４０００の整数を表し、ｍおよびｎは各々独立に０または正の整数を表し、ｍとｎが同時に０であることはない。
Ｒ１〜Ｒ８の具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、イソオクチル基、ビニル基、フェニル基、１−フェニルエチル基、２−フェニルエチル基、シクロペンチル基、シクロヘキシル基、ノルボルニル基、３，３，３−トリフルオロプロピル基等が挙げられ、特にメチル基が好ましい。
Ｘ１およびＸ２の具体例としては、以下の構造式で表される直鎖アルキレン基、環式アルキレン基、アラルキレン基が挙げられる。
In the formula, R 1 to R 8 each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with fluorine, and X 1 and X 2 each independently represent 2 to 20 carbon atoms. A divalent hydrocarbon group, a and c each independently represents an integer of 2 to 10, b and d each independently represents an integer of 1 to 4000, and m and n are each independently 0 or positive Represents an integer, and m and n are not 0 at the same time.
Specific examples of R 1 to R 8 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Examples include octyl group, isooctyl group, vinyl group, phenyl group, 1-phenylethyl group, 2-phenylethyl group, cyclopentyl group, cyclohexyl group, norbornyl group, 3,3,3-trifluoropropyl group, etc. Groups are preferred.
Specific examples of X 1 and X 2 include linear alkylene groups, cyclic alkylene groups, and aralkylene groups represented by the following structural formulas.
ｂおよびｄは好ましくは２５〜２５０の整数であり、ａおよびｃは好ましくは３である。
ポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）は、下記一般式（ＩＩ）、（ＩＩＩ）でそれぞれ表される両末端アミノ変性ポリシロキサン（Ｄ）および／または両末端ＯＨ変性ポリシロキサン（Ｅ）とジイソシアネートの反応により製造される。具体的な製造方法としては、例えば特開平１０−３１０６２８号公報、特表２００４−５３６９５４公報、特開２００５−２３４０公報等に記載された方法を利用することができる。
b and d are preferably integers of 25 to 250, and a and c are preferably 3.
The polysiloxane / polyurea / polyurethane copolymer (A) is a double-terminal amino-modified polysiloxane (D) and / or a double-terminal OH-modified polysiloxane (E) represented by the following general formulas (II) and (III), respectively. ) And diisocyanate. As specific manufacturing methods, for example, methods described in JP-A-10-310628, JP-T 2004-53694, JP-A-2005-2340, and the like can be used.
（式中、Ｒ１〜Ｒ８およびａ、ｂ、ｃ、ｄは各々上記で定義した通りである。）
ポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）の製造に用いられるジイソシアネートの具体例としては、ヘキサメチレン−１，６−ジイソシアネート、テトラメチレン−１，４−ジイソシアネート、ジシクロヘキシルメタン−４，４’−ジイソシアネート、イソホロンジイソシアネート、ジフェニルメタン−４，４’−ジイソシアネート、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、ｍ−フェニレンジイソシアネート、ｐ−フェニレンジイソシアネート、ｍ−キシリレンジイソシアネート、テトラメチル−ｍ−キシリレンジイソシアネート、１，５−ナフタレンジイソシアネート、ｏ−トリジンジイソシアネート等が挙げられる。これらのジイソシアネートは１種のみを使用するだけでなく、複数種を組み合わせて使用することができる。
ポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）の製造に当たっては、（Ａ）の機械的特性を改善する目的で、上記両末端アミノ変性ポリシロキサン（Ｄ）および／または両末端ＯＨ変性ポリシロキサン（Ｅ）に加えてジアミンやジヒドロキシ化合物を連鎖延長剤として併用することができる。ジアミンおよびジヒドロキシ化合物の具体例としては、エチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、デカメチレンジアミン、シクロヘキサンジアミン、４，４’−ジアミノシクロヘキシルメタン、ピペラジン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエーテル、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、１，４−シクロヘキサンジメタノール、水等を挙げることができる。これらの連鎖延長剤は１種のみを使用するだけでなく、複数種を組み合わせて使用することができる。
ポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）中には、尿素基とウレタン基の合計量に対し５０モル％以上、より好適には７５モル％以上の尿素基が含有されていることが膜の機械的強度の観点から好ましい。また（Ａ）中のポリシロキサン鎖の含有量は、本発明の気体分離膜の気体透過性能を大きく左右するものであり、（Ａ）の重量を基準としてポリシロキサン鎖が６０重量％以上、より好ましくは７０重量％以上、更に好ましくは８０重量％以上含まれることが好ましい。ここで言うポリシロキサン鎖の含有量とは、ポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）中に占める下記連鎖の合計の重量割合を指す。
(Wherein R 1 to R 8 and a, b, c and d are as defined above.)
Specific examples of the diisocyanate used in the production of the polysiloxane / polyurea / polyurethane copolymer (A) include hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, dicyclohexylmethane-4,4 ′. -Diisocyanate, isophorone diisocyanate, diphenylmethane-4,4'-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, m-xylylene diisocyanate, tetramethyl- Examples include m-xylylene diisocyanate, 1,5-naphthalene diisocyanate, o-tolidine diisocyanate, and the like. These diisocyanates can be used not only alone but also in combination of two or more.
In the production of the polysiloxane / polyurea / polyurethane copolymer (A), for the purpose of improving the mechanical properties of (A), the above-mentioned both-terminal amino-modified polysiloxane (D) and / or both-terminal OH-modified polysiloxane In addition to (E), a diamine or a dihydroxy compound can be used in combination as a chain extender. Specific examples of the diamine and dihydroxy compound include ethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine, cyclohexanediamine, 4,4′-diaminocyclohexylmethane, piperazine, m-phenylenediamine, p-phenylenediamine, 4, List 4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-cyclohexanedimethanol, water, etc. Can do. These chain extenders can be used not only alone but also in combination of two or more.
The polysiloxane / polyurea / polyurethane copolymer (A) contains 50 mol% or more, more preferably 75 mol% or more of urea groups based on the total amount of urea groups and urethane groups. It is preferable from the viewpoint of the mechanical strength of the film. Further, the content of the polysiloxane chain in (A) greatly affects the gas permeation performance of the gas separation membrane of the present invention, and the polysiloxane chain is 60% by weight or more based on the weight of (A). It is preferably contained at 70% by weight or more, more preferably 80% by weight or more. The content of the polysiloxane chain referred to herein refers to the total weight ratio of the following chains in the polysiloxane / polyurea / polyurethane copolymer (A).
（式中、Ｒ１〜Ｒ８およびｂ、ｄは上記で定義した通りである。）
ポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）の好ましい分子量は、多官能イソシアネート化合物（Ｂ）との反応性や、反応後に得られる変性ポリシロキサン共重合体（Ｃ）の好適分子量を考慮してポリスチレン換算数平均分子量で１０００〜１０万の範囲である。
本発明に用いられるイソシアネート基を少なくとも２個有する多官能イソシアネート化合物（Ｂ）としては、下記の一般式で表される化合物が使用される。
(Wherein R 1 to R 8 and b and d are as defined above.)
The preferred molecular weight of the polysiloxane / polyurea / polyurethane copolymer (A) is based on the reactivity with the polyfunctional isocyanate compound (B) and the preferred molecular weight of the modified polysiloxane copolymer (C) obtained after the reaction. The number average molecular weight in terms of polystyrene is in the range of 1,000 to 100,000.
As the polyfunctional isocyanate compound (B) having at least two isocyanate groups used in the present invention, a compound represented by the following general formula is used.
（式中、Ｙ１、Ｙ３、およびＹ５は各々独立に炭素数２〜２０の２価の炭化水素基を表し、Ｙ２は酸素、窒素を含んでいてもよい炭素数２〜２０の３価の有機基を表し、Ｙ４は炭素数２〜２０の３価の炭化水素基を表し、ｐは１〜１０の整数を表す。）
式（ＩＶ）で表されるジイソシアネートの具体例としては、ヘキサメチレン−１，６−ジイソシアネート、テトラメチレン−１，４−ジイソシアネート、ジシクロヘキシルメタン−４，４’−ジイソシアネート、イソホロンジイソシアネート、ジフェニルメタン−４，４’−ジイソシアネート、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、ｍ−フェニレンジイソシアネート、ｐ−フェニレンジイソシアネート、ｍ−キシリレンジイソシアネート、テトラメチル−ｍ−キシリレンジイソシアネート、１，５−ナフタレンジイソシアネート、ｏ−トリジンジイソシアネート等が挙げられる。
式（Ｖ）で表されるトリイソシアネートの具体例としては、トリフェニルメタン−４，４’，４’’−トリイソシアネートや、ヘキサメチレン−１，６−ジイソシアネートから誘導される下記式のような変性イソシアネートが挙げられる。
(In the formula, Y 1 , Y 3 and Y 5 each independently represent a divalent hydrocarbon group having 2 to 20 carbon atoms, and Y 2 has 2 to 20 carbon atoms which may contain oxygen and nitrogen. Represents a trivalent organic group, Y 4 represents a trivalent hydrocarbon group having 2 to 20 carbon atoms, and p represents an integer of 1 to 10.)
Specific examples of the diisocyanate represented by the formula (IV) include hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, diphenylmethane-4, 4'-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, m-xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate, 1,5- Examples include naphthalene diisocyanate and o-tolidine diisocyanate.
Specific examples of the triisocyanate represented by the formula (V) include triphenylmethane-4,4 ′, 4 ″ -triisocyanate and the following formula derived from hexamethylene-1,6-diisocyanate. Modified isocyanate is mentioned.
式（ＶＩ）で表される多官能イソシアネートの具体例としては、下記式で表されるポリメチレンポリフェニルポリイソシアネートが挙げられる。
Specific examples of the polyfunctional isocyanate represented by the formula (VI) include polymethylene polyphenyl polyisocyanate represented by the following formula.
（式中、ｑは１〜１０の整数を表す。）
これらの多官能イソシアネート化合物はそれぞれ単独で用いられるだけでなく、複数種を組み合わせて用いることができる。
本発明のポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）としては、一般式（I）で表される繰り返し単位を有するものであれば市販品を使用してもよい。例えば、Ｗａｃｋｅｒ社からＧｅｎｉｏｍｅｒの商品名で市販されているポリシロキサン／ポリウレタン共重合体などが好適に使用できる。
(In the formula, q represents an integer of 1 to 10.)
These polyfunctional isocyanate compounds can be used not only independently but also in combination of two or more.
As the polysiloxane / polyurea / polyurethane copolymer (A) of the present invention, a commercially available product may be used as long as it has a repeating unit represented by the general formula (I). For example, a polysiloxane / polyurethane copolymer commercially available under the trade name of Geniomer from Wacker can be suitably used.
本発明の気体分離膜の分離層として用いられる変性ポリシロキサン共重合体（Ｃ）は、上記ポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）と多官能イソシアネート化合物（Ｂ）を反応させることにより得られるものである。変性ポリシロキサン共重合体（Ｃ）を用いて後述する多孔質支持体上に溶液塗工法により安定な薄膜を形成するためには、ポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）と多官能イソシアネート化合物（Ｂ）の反応を制御して適度な分子量と適度なネットワーク構造を有する変性ポリシロキサン共重合体（Ｃ）を得る必要があり、ポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）１００重量部に対する多官能イソシアネート（Ｂ）の使用量は０．１〜５重量部、より好ましくは０．５〜４重量部の範囲で選ぶ必要がある。さらには溶液塗工を行う必要から変性ポリシロキサン共重合体（Ｃ）は溶媒に可溶な状態で得る必要がある。多官能イソシアネート化合物（Ｂ）の使用量が０．１重量部未満では分子量の上昇やネットワーク構造の形成は不充分であり、多孔質支持体上に溶液を塗工した場合支持体の孔中にポリマー分子が浸入、浸透してしまい塗膜を形成しなくなるか、また塗膜を支持体表面に形成したとしても成膜性が悪くピンホール等の欠陥ができやすくなる。一方、多官能イソシアネート化合物（Ｂ）の使用量が５重量部を超えると変性ポリシロキサン重合体（Ｃ）の分子量が高くなりすぎ溶媒への溶解性が低下したり、著しい場合には架橋により溶媒に不溶となるため溶液塗工には適さなくなる。そのような観点から反応後の変性ポリシロキサン共重合体（Ｃ）分子量は、ポリスチレン換算数平均分子量で１０万〜１００万の範囲とすることが好ましい。
また、変性ポリシロキサン共重合体（Ｃ）の分子量とネットワーク構造を制御するという観点から、多官能性イソシアネート化合物（Ｂ）としては上記式（ＩＶ）で表されるジイソシアネートが特に好適である。
The modified polysiloxane copolymer (C) used as the separation layer of the gas separation membrane of the present invention is obtained by reacting the polysiloxane / polyurea / polyurethane copolymer (A) with the polyfunctional isocyanate compound (B). It is obtained. In order to form a stable thin film by the solution coating method on the porous support described later using the modified polysiloxane copolymer (C), polysiloxane / polyurea / polyurethane copolymer (A) and polyfunctional It is necessary to control the reaction of the isocyanate compound (B) to obtain a modified polysiloxane copolymer (C) having an appropriate molecular weight and an appropriate network structure. The polysiloxane / polyurea / polyurethane copolymer (A) 100 The amount of polyfunctional isocyanate (B) used relative to parts by weight should be selected in the range of 0.1 to 5 parts by weight, more preferably 0.5 to 4 parts by weight. Furthermore, since it is necessary to perform solution coating, the modified polysiloxane copolymer (C) needs to be obtained in a solvent-soluble state. When the amount of the polyfunctional isocyanate compound (B) used is less than 0.1 parts by weight, the molecular weight is not increased and the network structure is not sufficiently formed. When the solution is applied on the porous support, Polymer molecules permeate and permeate and no coating film is formed, or even if a coating film is formed on the surface of the support, the film forming property is poor and defects such as pinholes are likely to occur. On the other hand, when the amount of the polyfunctional isocyanate compound (B) used exceeds 5 parts by weight, the molecular weight of the modified polysiloxane polymer (C) becomes too high, so that the solubility in the solvent is lowered, or in the case of remarkably, the solvent is caused by crosslinking. It becomes insoluble in solution, so it is not suitable for solution coating. From such a viewpoint, the molecular weight of the modified polysiloxane copolymer (C) after the reaction is preferably in the range of 100,000 to 1,000,000 in terms of polystyrene-equivalent number average molecular weight.
Further, from the viewpoint of controlling the molecular weight and network structure of the modified polysiloxane copolymer (C), the diisocyanate represented by the above formula (IV) is particularly suitable as the polyfunctional isocyanate compound (B).
変性ポリシロキサン共重合体（Ｃ）の構造は今のところ詳らかではないが、ポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）の末端のアミノ基や水酸基が多官能イソシアネート化合物（Ｂ）と反応する他、ポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）中の尿素基やウレタン基と多官能イソシアネート化合物が反応して、それぞれビウレット結合やアロファネート結合が形成され、変性ポリシロキサン共重合体（Ｃ）が適度なネットワーク構造を取ることにより、溶媒への溶解性を残したまま多孔質支持体上での塗膜の形成能が飛躍的に向上し、気体分離に適した薄膜の形成に有利になるものと推察される。
ポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）と多官能性イソシアネート化合物（Ｂ）を反応させる方法は特に制限されず、溶媒を使用して溶液中で反応させる方法、溶媒を用いずに押出機や、バンバリーミキサー、ブラベンダー中で反応させる方法が挙げられる。溶液中で反応する場合に用いられる溶媒としては、テトラヒドロフラン、１，４−ジオキサン、ビス（２−エトキシエチル）エーテルなどのエーテル系溶剤、クロロホルム、塩化メチレン、テトラクロロエチレンなどのハロゲン系溶剤、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶剤、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミドなどの非プロトン性極性溶剤などを挙げることができ、特にテトラヒドロフランが好適である。
Although the structure of the modified polysiloxane copolymer (C) is not yet known in detail, the terminal amino group or hydroxyl group of the polysiloxane / polyurea / polyurethane copolymer (A) reacts with the polyfunctional isocyanate compound (B). In addition, the polyfunctional isocyanate compound reacts with the urea group or urethane group in the polysiloxane / polyurea / polyurethane copolymer (A) to form biuret bonds and allophanate bonds, respectively, and the modified polysiloxane copolymer ( C) has an appropriate network structure, which dramatically improves the ability to form a coating on a porous support while remaining soluble in a solvent, and is advantageous for forming a thin film suitable for gas separation. It is inferred that
The method for reacting the polysiloxane / polyurea / polyurethane copolymer (A) with the polyfunctional isocyanate compound (B) is not particularly limited, and the method of reacting in a solution using a solvent, extrusion without using a solvent. And reacting in a machine, Banbury mixer, Brabender. Solvents used in the reaction in solution include ether solvents such as tetrahydrofuran, 1,4-dioxane, bis (2-ethoxyethyl) ether, halogen solvents such as chloroform, methylene chloride, tetrachloroethylene, methyl ethyl ketone, methyl Examples thereof include ketone solvents such as isobutyl ketone, and aprotic polar solvents such as N-methyl-2-pyrrolidone and N, N-dimethylacetamide. Tetrahydrofuran is particularly preferable.
また、本反応には触媒を使用することができる。適当な触媒としてはジブチル錫ジラウレート、ジブチル錫ジアセテートなどのジアルキル錫化合物、Ｎ，Ｎ−ジメチルシクロヘキシルアミン、２−ジメチルアミノエタノール、４−ジメチルアミノピリジンなどの３級アミンが挙げられ、多官能イソシアネート化合物（Ｂ）に対し０．０５〜５重量％の割合で使用される。
反応温度および反応時間については特に制限はなく、５０℃〜２００℃、１分〜１０時間の範囲で反応の速度に応じて適宜選択される。
Moreover, a catalyst can be used for this reaction. Suitable catalysts include dialkyltin compounds such as dibutyltin dilaurate and dibutyltin diacetate, and tertiary amines such as N, N-dimethylcyclohexylamine, 2-dimethylaminoethanol and 4-dimethylaminopyridine. It is used in a proportion of 0.05 to 5% by weight based on the compound (B).
There is no restriction | limiting in particular about reaction temperature and reaction time, According to the speed | rate of reaction in the range of 50 to 200 degreeC and 1 minute-10 hours, it selects suitably.
本発明の変性ポリシロキサン共重合体（Ｃ）は成膜性および機械的強度に優れるため、単独で製膜して気体分離膜として使用することができる。しかし、気体分離膜として充分な気体透過流量を得るためには薄膜とする必要があり、薄膜化した際の強度や取り扱い性の点から多孔質支持体上に薄膜を形成・積層させ複合膜として用いるのが通常である。
本発明に用いられる多孔質支持体としては、多孔質フォーム、不織布、織布などが挙げられ、孔の大きさ、孔径の均一性、支持体の厚みなどの点から多孔質フォームを用いることが好ましい。多孔質フォームは抽出法、延伸法、物理的な開口法など様々な方法によって製造されるが、製法に限定されることなく使用できる。多孔質支持体の形状としては、平膜状、中空糸状、チューブ状などが挙げられ、特に平膜状のものが好適である。また、多孔質支持体は対称構造でも非対称構造でも使用できる。
Since the modified polysiloxane copolymer (C) of the present invention is excellent in film formability and mechanical strength, it can be formed alone and used as a gas separation membrane. However, in order to obtain a sufficient gas permeation flow rate as a gas separation membrane, it is necessary to form a thin film. From the viewpoint of strength and handleability when thinned, a thin film is formed and laminated on a porous support to form a composite membrane. Usually used.
Examples of the porous support used in the present invention include porous foam, non-woven fabric, woven fabric, etc., and it is preferable to use a porous foam from the viewpoints of pore size, uniformity of pore diameter, thickness of the support, and the like. preferable. The porous foam is produced by various methods such as an extraction method, a stretching method, and a physical opening method, but can be used without being limited to the production method. Examples of the shape of the porous support include a flat membrane shape, a hollow fiber shape, and a tube shape, and a flat membrane shape is particularly preferable. The porous support can be used in either a symmetric structure or an asymmetric structure.
多孔質支持体の材質としては特に制約はないが、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール、ポリスチレン、ポリメチルメタクリレート、ポリアクリロニトリル、ポリカーボネート、ポリフェニレンオキシド、ポリアミド、ポリエステル、ポリスルホン、ポリエーテルスルホン、ポリスルホンアミド、ポリイミド、酢酸セルロース、ポリテトラフルオロエチレン、ポリフッ化ビニリデン等の高分子材料、ガラス、金属、セラミック等の無機材料を用いることができる。特に賦形性、柔軟性、機械的強度などの点から高分子材料を用いることが好ましく、特に耐溶剤性に優れたポリエチレン、ポリプロピレン等のポリオレフィンが好適に用いられる。 The material of the porous support is not particularly limited, but polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polyacrylonitrile, polycarbonate, polyphenylene oxide, polyamide, polyester, polysulfone, poly Polymer materials such as ether sulfone, polysulfonamide, polyimide, cellulose acetate, polytetrafluoroethylene, and polyvinylidene fluoride, and inorganic materials such as glass, metal, and ceramic can be used. In particular, it is preferable to use a polymer material from the viewpoints of formability, flexibility, mechanical strength, and the like, and particularly polyolefins such as polyethylene and polypropylene having excellent solvent resistance are preferably used.
多孔質支持体の孔の大きさは０．００１μｍ〜１μｍが好適であり、より好ましくは０．０１μｍ〜０．１μｍである。孔の大きさが０．００１μｍよりも小さい場合、得られる複合膜の気体透過速度が不充分となる場合がある。逆に孔の大きさが１μｍより大きくなると、分離層を塗工した際、分離層が孔中に浸透したり孔中に落ち込んだりして孔中に充填されてしまうため、やはり気体透過速度の低下を引き起こしやすくなり問題である。また、多孔質支持体の空隙率を表す透気度は、ＪＩＳ Ｐ ８１１７に従って測定した値が２０秒〜３０００秒、より好ましくは５０秒〜１０００秒の範囲が適する。透気度が２０秒未満のものは機械的強度が不足する場合があり、逆に透気度が３０００秒を超えると充分な気体透過速度が得られず問題となる場合がある。
多孔質支持体の膜厚は５μｍ〜５ｍｍのものが使用でき、より好ましくは１０μｍ〜５００μｍであり、さらに好ましくは１０μｍ〜１００μｍである。膜厚が５μｍより薄くなると支持体としての強度が充分でない場合が多く、５ｍｍより大きいと膜の柔軟性が損なわれ取り扱いが難しくなったり、気体透過の抵抗が大きくなることがあるため好ましくない。
The pore size of the porous support is preferably 0.001 μm to 1 μm, more preferably 0.01 μm to 0.1 μm. When the pore size is smaller than 0.001 μm, the gas permeation rate of the resulting composite membrane may be insufficient. On the contrary, if the pore size is larger than 1 μm, when the separation layer is applied, the separation layer penetrates into the pores or falls into the pores and is filled in the pores. It is a problem that tends to cause a drop. Further, the air permeability representing the porosity of the porous support has a value measured according to JIS P 8117 of 20 seconds to 3000 seconds, more preferably 50 seconds to 1000 seconds. If the air permeability is less than 20 seconds, the mechanical strength may be insufficient. Conversely, if the air permeability exceeds 3000 seconds, a sufficient gas permeation rate may not be obtained, which may be a problem.
The film thickness of the porous support can be 5 μm to 5 mm, more preferably 10 μm to 500 μm, still more preferably 10 μm to 100 μm. When the film thickness is thinner than 5 μm, the strength as a support is often insufficient, and when it is larger than 5 mm, the flexibility of the film is impaired, handling becomes difficult, and gas permeation resistance increases, which is not preferable.
多孔質支持体上に分離層を積層する方法としては、変性ポリシロキサン共重合体（Ｃ）を溶剤に溶解後、水面上に展開して薄膜を形成させ、次いでこの薄膜を支持体と接触させることにより支持体上に積層する水面展開法、変性ポリシロキサン共重合体（Ｃ）を溶剤に溶解し多孔質支持体上に塗工した後、溶媒を乾燥させ複合膜とする溶液塗工法等が挙げられるが、品質の安定した膜を簡便に大量生産できる点から溶液塗工法が最も好ましい。以下、溶液塗工法について説明する。 As a method of laminating the separation layer on the porous support, after dissolving the modified polysiloxane copolymer (C) in a solvent, it is spread on the water surface to form a thin film, and then the thin film is brought into contact with the support. The water surface development method of laminating on a support, the modified polysiloxane copolymer (C) dissolved in a solvent and coated on a porous support, and then the solvent is dried to form a composite film. Among them, the solution coating method is most preferable from the viewpoint that a film with stable quality can be easily mass-produced. Hereinafter, the solution coating method will be described.
溶液塗工法を行うにあたり用いられる溶剤は変性ポリシロキサン共重合体（Ｃ）を溶解するものであれば特に限定されず、テトラヒドロフラン、１，４−ジオキサン、ビス（２−エトキシエチル）エーテルなどのエーテル系溶剤、クロロホルム、塩化メチレン、テトラクロロエチレンなどのハロゲン系溶剤、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶剤、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミドなどの非プロトン性極性溶剤などが挙げられる。これらは１種単独でも２種以上を組み合わせても使用することができる。 The solvent used for performing the solution coating method is not particularly limited as long as it dissolves the modified polysiloxane copolymer (C), and ethers such as tetrahydrofuran, 1,4-dioxane, bis (2-ethoxyethyl) ether, etc. Solvent, halogen solvents such as chloroform, methylene chloride and tetrachloroethylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, aprotic polar solvents such as N-methyl-2-pyrrolidone and N, N-dimethylacetamide It is done. These can be used singly or in combination of two or more.
溶液塗工に用いられる溶液中における変性ポリシロキサン共重合体（Ｃ）の濃度は０．０１重量％〜５０重量％が好ましく、０．１重量％〜１０重量％がより好ましい。変性ポリシロキサン共重合体（Ｃ）の濃度が０．０１重量％よりも小さい場合は薄膜を形成しにくかったり、ピンホールなどの欠陥が生じる傾向が強まり好ましくない。逆に５０重量％よりも大きい場合は多孔質支持体上に形成される分離層の厚みが大きくなりやすく充分な気体透過量が達成されなくなるため好ましくない。 The concentration of the modified polysiloxane copolymer (C) in the solution used for solution coating is preferably 0.01% by weight to 50% by weight, and more preferably 0.1% by weight to 10% by weight. When the concentration of the modified polysiloxane copolymer (C) is less than 0.01% by weight, it is difficult to form a thin film or a tendency to cause defects such as pinholes is not preferable. On the other hand, when it is larger than 50% by weight, the thickness of the separation layer formed on the porous support tends to be large, and a sufficient gas permeation amount cannot be achieved.
変性ポリシロキサン共重合体（Ｃ）の溶液を多孔質支持体に塗布する方法としては種々の方法を用いることができ、バーコーター、ロールコーター、リバースコーター、グラビアコーター、エアナイフコーター、オフセットコーター、多段ロールコーター、スプレーコーター、スピンコーター等を用いる公知の塗工方法が利用できる。また、変性ポリシロキサン共重合体（Ｃ）の溶液に多孔質支持体を浸漬するディップコート法や、溶液表面に多孔質支持体の片面のみを接触させるフロートコート法も利用できる。 Various methods can be used as a method of applying the solution of the modified polysiloxane copolymer (C) to the porous support, such as bar coater, roll coater, reverse coater, gravure coater, air knife coater, offset coater, multistage. A known coating method using a roll coater, spray coater, spin coater or the like can be used. Moreover, the dip coating method which immerses a porous support body in the solution of a modified polysiloxane copolymer (C), and the float coating method which makes only one side of a porous support body contact the solution surface can also be utilized.
塗工は大気中で行うことができるが、溶剤が揮発する際大気中の水蒸気が結露して分離層の形成に影響を及ぼすことを防ぐため、相対湿度２０％以下の乾燥空気下で塗工を行うか、実質的に水蒸気を含まない窒素、ヘリウム、アルゴンなどの不活性ガス雰囲気下で塗工を行うことが望ましい。 Coating can be performed in the air, but it is applied under dry air with a relative humidity of 20% or less in order to prevent moisture in the atmosphere from condensing and affecting the formation of the separation layer when the solvent volatilizes. It is desirable to carry out the coating under an inert gas atmosphere such as nitrogen, helium, or argon that does not substantially contain water vapor.
塗工が終了した多孔質支持体は続いて乾燥工程を経るが、乾燥は大気中で行われても、窒素、ヘリウム、アルゴンなどの不活性ガス雰囲気下で行われても、減圧下にて行われてもよい。また乾燥に際し多孔質支持体に損傷を与えない程度に加熱を行うことが望ましい。 The porous support after the coating is subsequently subjected to a drying process, but drying may be performed in the air, or in an inert gas atmosphere such as nitrogen, helium, argon, or under reduced pressure. It may be done. Further, it is desirable to perform heating to such an extent that the porous support is not damaged during drying.
本発明による気体分離膜は、混合気体からある特定の気体の濃度を変化させるために用いられる限りにおいては特にその使用方法に限定はない。対象とする気体は、特に限定されないが、例えば酸素、窒素、水素、二酸化炭素、メタン、一酸化炭素、アンモニア、二酸化硫黄、酸化窒素類、ハロゲン含有ガスが挙げられるが、最も好適に用いられるのは、大気中からの酸素ないし窒素の濃縮用途である。 The gas separation membrane according to the present invention is not particularly limited in its usage as long as it is used for changing the concentration of a specific gas from a mixed gas. The target gas is not particularly limited, and examples thereof include oxygen, nitrogen, hydrogen, carbon dioxide, methane, carbon monoxide, ammonia, sulfur dioxide, nitric oxides, and halogen-containing gases, but are most preferably used. Is for the concentration of oxygen or nitrogen from the atmosphere.
以下、本発明を実施例に基づき具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
物性の測定は以下に述べる方法により行った。
（１）ポリマーの分子量
ＨＬＣ−８１２０ＧＰＣ（東ソー社製）にＴＳＫｇｕａｒｄｃｏｌｕｍｎＨＸＬ−Ｌ、ＴＳＫｇｅｌＧ５０００ＨＸＬおよびＴＳＫｇｅｌＧ４０００ＨｘＬ（いずれも東ソー社製）を取り付けた装置を用い、テトラヒドロフランを溶離液とし示差屈折計により測定を行った。標準試料として単分散ポリスチレンを使用し数平均分子量（Ｍｎ）を求めた。
（２）複合膜の分離層厚み
膜を液体窒素冷却下で割断し白金蒸着した後、走査型電子顕微鏡ＦＥ−ＳＥＭ Ｓ−８００（日立製作所製）により断面写真を撮影し分離層の厚みを求めた。
（３）酸素透過速度および分離係数
作製した複合膜より直径４７ｍｍの円形試料を切り出し、タンク付きステンレスホルダーＫＳＴ−４７（アドバンテック東洋社製）に取り付けた。次いで２５℃の恒温下でゲージ圧０．１ＭＰaの酸素および窒素を透過させ、１５ｍｌの気体が透過するのに要する時間を計測することにより酸素透過速度および窒素透過速度を求めた。分離係数は酸素透過速度と窒素透過速度の比より求めた。
The physical properties were measured by the methods described below.
(1) Molecular weight of polymer Using an apparatus equipped with HSK-8120GPC (manufactured by Tosoh Corporation) with TSK guard column H XL- L, TSK gel G5000H XL and TSKgel G4000H xL (all manufactured by Tosoh Corporation), tetrahydrofuran was used as the eluent, and measurement was performed with a differential refractometer. went. The number average molecular weight (Mn) was determined using monodisperse polystyrene as a standard sample.
(2) Separation Layer Thickness of Composite Membrane After the membrane was cleaved under liquid nitrogen cooling and platinum was deposited, a sectional photograph was taken with a scanning electron microscope FE-SEM S-800 (manufactured by Hitachi, Ltd.) to determine the thickness of the separation layer It was.
(3) Oxygen transmission rate and separation factor A circular sample having a diameter of 47 mm was cut out from the prepared composite membrane and attached to a stainless steel holder KST-47 with tank (manufactured by Advantech Toyo Co., Ltd.). Next, oxygen permeation rate and nitrogen permeation rate were determined by allowing oxygen and nitrogen at a gauge pressure of 0.1 MPa to permeate at a constant temperature of 25 ° C. and measuring the time required for permeation of 15 ml of gas. The separation factor was determined from the ratio of oxygen transmission rate and nitrogen transmission rate.
［実施例１］
ポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）として、両末端アミノプロピルポリジメチルシロキサン（ジメチルシロキサンの繰り返し単位数約４０）とジシクロヘキシルメタン−４，４’−ジイソシアネートの共重合体であるＷａｃｋｅｒ社のＧｅｎｉｏｍｅｒ（登録商標）１４０（Ｍｎ＝３６，０００）を使用した。このポリマーは一般式（Ｉ）においてＲ１〜Ｒ４がメチル基、Ｘ１が４，４’−ジシクロヘキシルメチル基であり、ａ＝３、ｂ＝約３９、ｎ＝０である場合に相当する。このポリマー１００ｇ、ジシクロヘキシルメタン−４，４’−ジイソシアネート４．０ｇ、およびジブチル錫ジラウレート０．０２ｇを混合し、東洋精機製作所製ラボプラストミルを用いて１９０℃で１０分間混練することにより変性ポリシロキサン共重合体を得た。得られたポリマーはテトラヒドロフランに可溶であり、Ｍｎ＝３２０，０００であった。
[Example 1]
Wacker, a copolymer of polypropylene / polyurea copolymer (A) having aminopropylpolydimethylsiloxane at both ends (approximately 40 repeating units of dimethylsiloxane) and dicyclohexylmethane-4,4′-diisocyanate. Geniomer® 140 (Mn = 36,000) was used. This polymer corresponds to the case where R 1 to R 4 in formula (I) are methyl groups, X 1 is 4,4′-dicyclohexylmethyl group, a = 3, b = about 39, and n = 0. . 100 g of this polymer, 4.0 g of dicyclohexylmethane-4,4′-diisocyanate, and 0.02 g of dibutyltin dilaurate are mixed and kneaded at 190 ° C. for 10 minutes using a lab plast mill manufactured by Toyo Seiki Seisakusho. A copolymer was obtained. The obtained polymer was soluble in tetrahydrofuran, and Mn = 320,000.
このポリマーのテトラヒドロフラン溶液（濃度０．５重量％）を調製し、旭化成ケミカルズ製ポリエチレン多孔質膜ハイポア（登録商標）ＮＢ６３０（膜厚３０μｍ）用いて、窒素雰囲気下にて膜の片面のみを溶液表面に浮遊・接触させ、連続的に引き上げる方法（フロート法）で塗工を行った。得られた複合膜の塗工層の厚みは３００ｎｍであった。
この複合膜を用いて酸素および窒素の透過速度を測定したところ、酸素の透過速度は１，４００×１０−６ｃｍ３（ＳＴＰ）／ｃｍ２・ｓｅｃ・ｃｍＨｇ、酸素／窒素の分離係数は２．０であった。
A tetrahydrofuran solution (concentration of 0.5% by weight) of this polymer was prepared, and the surface of the solution was coated on only one side of the membrane in a nitrogen atmosphere using a polyethylene porous membrane Hypore (registered trademark) NB630 (thickness 30 μm) manufactured by Asahi Kasei Chemicals. The coating was carried out by floating (contacting) and continuously pulling up (floating method). The thickness of the coating layer of the obtained composite film was 300 nm.
When the permeation rate of oxygen and nitrogen was measured using this composite membrane, the permeation rate of oxygen was 1,400 × 10 −6 cm 3 (STP) / cm 2 · sec · cmHg, and the separation factor of oxygen / nitrogen was 2 0.0.
［実施例２］
実施例１と同じく両末端アミノプロピルポリジメチルシロキサン（ジメチルシロキサンの繰り返し単位数約４０）とジシクロヘキシルメタン−４，４’−ジイソシアネートの共重合体であるＷａｃｋｅｒ社のＧｅｎｉｏｍｅｒ（登録商標）１４０（Ｍｎ＝３６，０００）を用いた。このポリマー１００ｇ、ジシクロヘキシルメタン−４，４’−ジイソシアネート４．０ｇ、およびジブチル錫ジラウレート０．０２ｇをテトラヒドロフラン５００ｍｌに溶解し、ステンレス製オートクレーブを用いて１５０℃で３０分間反応を行うことにより変性ポリシロキサン共重合体を得た。反応後の溶液は均一透明であり、溶解しているポリマーの分子量を測定したところＭｎ＝２４０，０００であった。
[Example 2]
Wacker Geniomer (registered trademark) 140 (Mn = a copolymer of both ends aminopropylpolydimethylsiloxane (about 40 repeating units of dimethylsiloxane) and dicyclohexylmethane-4,4′-diisocyanate as in Example 1. 36,000). 100 g of this polymer, 4.0 g of dicyclohexylmethane-4,4′-diisocyanate, and 0.02 g of dibutyltin dilaurate are dissolved in 500 ml of tetrahydrofuran, and the reaction is performed at 150 ° C. for 30 minutes using a stainless steel autoclave, thereby modifying the modified polysiloxane. A copolymer was obtained. The solution after the reaction was uniform and transparent, and the molecular weight of the dissolved polymer was measured to be Mn = 240,000.
この反応溶液をポリマー濃度０．５重量％まで希釈し、旭化成ケミカルズ製ポリエチレン多孔質膜ハイポア（登録商標）ＮＢ６３０（膜厚３０μｍ）用いて、窒素雰囲気下にて膜の片面のみを溶液表面に浮遊・接触させ、連続的に引き上げる方法（フロート法）で塗工を行った。得られた複合膜の塗工層の厚みは２８０ｎｍであった。
この複合膜を用いて酸素および窒素の透過速度を測定したところ、酸素の透過速度は１，５００×１０−６ｃｍ３（ＳＴＰ）／ｃｍ２・ｓｅｃ・ｃｍＨｇ、酸素／窒素の分離係数は２．０であった。
This reaction solution was diluted to a polymer concentration of 0.5% by weight, and only one side of the membrane was floated on the solution surface in a nitrogen atmosphere using a polyethylene porous membrane Hypore (registered trademark) NB630 (thickness 30 μm) manufactured by Asahi Kasei Chemicals. -Coating was carried out by a method of contacting and continuously pulling up (float method). The thickness of the coating layer of the obtained composite film was 280 nm.
When the permeation rate of oxygen and nitrogen was measured using this composite membrane, the permeation rate of oxygen was 1,500 × 10 −6 cm 3 (STP) / cm 2 · sec · cmHg, and the separation factor of oxygen / nitrogen was 2 0.0.
［実施例３］
ポリシロキサン／ポリ尿素／ポリウレタン共重合体（Ａ）として、両末端アミノプロピルポリジメチルシロキサン（ジメチルシロキサンの繰り返し単位数約４０）とヘキサメチレン−１，６−ジイソシアネートの共重合体であるＷａｃｋｅｒ社のＧｅｎｉｏｍｅｒ（登録商標）６０（Ｍｎ＝８３，０００）を使用した。このポリマーは一般式（Ｉ）においてＲ１〜Ｒ４がメチル基、Ｘ１が１，６−ヘキサメチレン基であり、ａ＝３、ｂ＝約３９、ｎ＝０である場合に相当する。このポリマー１００ｇ、ヘキサメチレン−１，６−ジイソシアネート３．０ｇ、およびジブチル錫ジラウレート０．０２ｇを混合し、東洋精機製作所製ラボプラストミルを用いて１７０℃で１０分間混練することにより変性ポリシロキサン共重合体を得た。得られたポリマーはテトラヒドロフランに可溶であり、Ｍｎ＝４３０，０００であった。
[Example 3]
As a polysiloxane / polyurea / polyurethane copolymer (A), Wacker's copolymer, which is a copolymer of aminopropylpolydimethylsiloxane at both ends (approximately 40 repeating units of dimethylsiloxane) and hexamethylene-1,6-diisocyanate, is used. Geniomer® 60 (Mn = 83,000) was used. This polymer corresponds to the case where R 1 to R 4 are methyl groups, X 1 is 1,6-hexamethylene group, a = 3, b = about 39, and n = 0 in the general formula (I). 100 g of this polymer, 3.0 g of hexamethylene-1,6-diisocyanate, and 0.02 g of dibutyltin dilaurate are mixed and kneaded at 170 ° C. for 10 minutes using a lab plast mill manufactured by Toyo Seiki Seisakusho. A polymer was obtained. The obtained polymer was soluble in tetrahydrofuran, and Mn = 430,000.
このポリマーのテトラヒドロフラン溶液（濃度０．５重量％）を調製し、旭化成ケミカルズ製ポリエチレン多孔質膜ハイポア（登録商標）ＮＢ６３０（膜厚３０μｍ）用いて、窒素雰囲気下にて膜の片面のみを溶液表面に浮遊・接触させ、連続的に引き上げる方法（フロート法）で塗工を行った。得られた複合膜の塗工層の厚みは２５０ｎｍであった。
この複合膜を用いて酸素および窒素の透過速度を測定したところ、酸素の透過速度は１，６００×１０−６ｃｍ３（ＳＴＰ）／ｃｍ２・ｓｅｃ・ｃｍＨｇ、酸素／窒素の分離係数は１．９であった。
A tetrahydrofuran solution (concentration of 0.5% by weight) of this polymer was prepared, and the surface of the solution was coated on only one side of the membrane in a nitrogen atmosphere using a polyethylene porous membrane Hypore (registered trademark) NB630 (thickness 30 μm) manufactured by Asahi Kasei Chemicals. The coating was carried out by floating (contacting) and continuously pulling up (floating method). The thickness of the coating layer of the obtained composite film was 250 nm.
When the permeation rate of oxygen and nitrogen was measured using this composite membrane, the permeation rate of oxygen was 1,600 × 10 −6 cm 3 (STP) / cm 2 · sec · cmHg, and the separation factor of oxygen / nitrogen was 1. .9.
［実施例４］
実施例３と同じく両末端アミノプロピルポリジメチルシロキサン（ジメチルシロキサンの繰り返し単位数約４０）とヘキサメチレン−１，６−ジイソシアネートの共重合体であるＷａｃｋｅｒ社のＧｅｎｉｏｍｅｒ（登録商標）６０（Ｍｎ＝８３，０００）を用いた。このポリマー１００重量部、イソホロンジイソシアネート２重量部、およびジブチル錫ジラウレート０．０１重量部を均一に混合し、テクノベル社製押出機（ＫＺＷ１５−４５ＭＧ）を用いて１８０℃にて溶融混練することにより変性ポリシロキサン共重合体を得た。得られたポリマーはテトラヒドロフランに可溶であり、Ｍｎ＝５７０，０００であった。
[Example 4]
As in Example 3, Wacker Geniomer (registered trademark) 60 (Mn = 83), which is a copolymer of aminopropylpolydimethylsiloxane at both ends (about 40 repeating units of dimethylsiloxane) and hexamethylene-1,6-diisocyanate. , 000) was used. 100 parts by weight of this polymer, 2 parts by weight of isophorone diisocyanate, and 0.01 parts by weight of dibutyltin dilaurate were uniformly mixed, and modified by melt kneading at 180 ° C. using an extruder (KZW15-45MG) manufactured by Technobel. A polysiloxane copolymer was obtained. The obtained polymer was soluble in tetrahydrofuran, and Mn = 570,000.
このポリマーのテトラヒドロフラン溶液（濃度０．５重量％）を調製し、旭化成ケミカルズ製ポリエチレン多孔質膜ハイポア（登録商標）Ｎ９４２０Ｇ（膜厚２０μｍ）用いて、窒素雰囲気下にて膜の片面のみを溶液表面に浮遊・接触させ、連続的に引き上げる方法（フロート法）で塗工を行った。得られた複合膜の塗工層の厚みは３４０ｎｍであった。
この複合膜を用いて酸素および窒素の透過速度を測定したところ、酸素の透過速度は１，２００×１０−６ｃｍ３（ＳＴＰ）／ｃｍ２・ｓｅｃ・ｃｍＨｇ、酸素／窒素の分離係数は２．０であった。
A tetrahydrofuran solution (concentration of 0.5% by weight) of this polymer was prepared, and the surface of the solution was coated on only one side of the membrane in a nitrogen atmosphere using a polyethylene porous membrane Hypore (registered trademark) N9420G (thickness 20 μm) manufactured by Asahi Kasei Chemicals. The coating was carried out by floating (contacting) and continuously pulling up (floating method). The thickness of the coating layer of the obtained composite film was 340 nm.
When the permeation rate of oxygen and nitrogen was measured using this composite membrane, the permeation rate of oxygen was 1,200 × 10 −6 cm 3 (STP) / cm 2 · sec · cmHg, and the separation factor of oxygen / nitrogen was 2 0.0.
［実施例５］
実施例１において、反応に使用するジシクロヘキシルメタン−４，４’−ジイソシアネートの使用量を１．０ｇ、ジブチル錫ジラウレートの使用量を０．０１ｇとする以外はまったく同じ条件・方法で混練を行った。得られたポリマーはテトラヒドロフランに可溶であり、Ｍｎ＝８６，０００であった。
[Example 5]
In Example 1, kneading was performed under exactly the same conditions and method except that the amount of dicyclohexylmethane-4,4′-diisocyanate used in the reaction was 1.0 g and the amount of dibutyltin dilaurate was 0.01 g. . The obtained polymer was soluble in tetrahydrofuran, and Mn = 86,000.
このポリマーのテトラヒドロフラン溶液（濃度０．５重量％）を調製し、旭化成ケミカルズ製ポリエチレン多孔質膜ハイポア（登録商標）ＮＢ６３０（膜厚３０μｍ）用いて、窒素雰囲気下にて膜の片面のみを溶液表面に浮遊・接触させ、連続的に引き上げる方法（フロート法）で塗工を行った。得られた複合膜の塗工層の厚みは３００ｎｍであった。 A tetrahydrofuran solution (concentration of 0.5% by weight) of this polymer was prepared, and only one side of the membrane was used as a solution surface under a nitrogen atmosphere using a polyethylene porous membrane Hypore (registered trademark) NB630 (thickness 30 μm) manufactured by Asahi Kasei Chemicals. The coating was carried out by a method (float method) in which the material was floated and brought into contact with the substrate and continuously pulled up. The thickness of the coating layer of the obtained composite film was 300 nm.
この複合膜を用いて酸素および窒素の透過速度を測定したところ、酸素の透過速度は１，９００×１０−６ｃｍ３（ＳＴＰ）／ｃｍ２・ｓｅｃ・ｃｍＨｇ、酸素／窒素の分離係数は１．４であった。実施例１の結果と比較すると、酸素透過速度は向上しているが、分離係数が低下しており、分子量が好ましい範囲（１０万〜１００万）よりもやや低いことが原因であると推察された。 When the permeation rate of oxygen and nitrogen was measured using this composite membrane, the permeation rate of oxygen was 1,900 × 10 −6 cm 3 (STP) / cm 2 · sec · cmHg, and the separation factor of oxygen / nitrogen was 1. .4. Compared with the results of Example 1, the oxygen permeation rate is improved, but the separation factor is decreased, and it is assumed that the cause is that the molecular weight is slightly lower than the preferred range (100,000 to 1,000,000). It was.
［比較例１］
実施例１および２で使用した両末端アミノプロピルポリジメチルシロキサン（ジメチルシロキサンの繰り返し単位数約４０）とジシクロヘキシルメタン−４，４’−ジイソシアネートの共重合体であるＷａｃｋｅｒ社のＧｅｎｉｏｍｅｒ（登録商標）１４０（Ｍｎ＝３６，０００）をジイソシアネート変性反応を行うことなく、未反応のままテトラヒドロフランに溶解し、２．５重量％の溶液とした。この溶液を使用し、旭化成ケミカルズ製ポリエチレン多孔質膜ハイポア（登録商標）ＮＢ６３０（膜厚３０μｍ）用いて、窒素雰囲気下にて膜の片面のみを溶液表面に浮遊・接触させ、連続的に引き上げる方法（フロート法）で塗工を行った。得られた複合膜の塗工層の厚みは９５０ｎｍであった。
[Comparative Example 1]
Wacker Geniomer® 140, which is a copolymer of both-end aminopropyl polydimethylsiloxane (approximately 40 repeating units of dimethylsiloxane) and dicyclohexylmethane-4,4′-diisocyanate used in Examples 1 and 2. (Mn = 36,000) was dissolved in tetrahydrofuran unreacted without performing a diisocyanate modification reaction to give a 2.5 wt% solution. Using this solution, using Asahi Kasei Chemicals polyethylene porous membrane Hypore (registered trademark) NB630 (thickness 30 μm), only one side of the membrane is floated and brought into contact with the solution surface in a nitrogen atmosphere and continuously pulled up. Coating was performed by (float method). The thickness of the coating layer of the obtained composite film was 950 nm.
この複合膜を用いて酸素および窒素の透過速度を測定したところ、酸素の透過速度は６，０００×１０−６ｃｍ３（ＳＴＰ）／ｃｍ２・ｓｅｃ・ｃｍＨｇ、酸素／窒素の分離係数は１．０であった。実施例１および実施例２よりも分離層の厚みを厚くしたにも拘わらず、酸素透過速度は極めて大きくなり、しかも分離係数が１．０であることから分離層にはピンホール等の欠陥が生じており、気体分離膜として機能していないと判断された。 When the permeation rate of oxygen and nitrogen was measured using this composite membrane, the permeation rate of oxygen was 6,000 × 10 −6 cm 3 (STP) / cm 2 · sec · cmHg, and the separation factor of oxygen / nitrogen was 1. 0.0. Despite the thickness of the separation layer being thicker than in Example 1 and Example 2, the oxygen permeation rate is extremely high and the separation factor is 1.0, so that the separation layer has defects such as pinholes. It has occurred and was judged not to function as a gas separation membrane.
［比較例２］
実施例１において、反応に使用するジシクロヘキシルメタン−４，４’−ジイソシアネートの使用量を１０．０ｇ、ジブチル錫ジラウレートの使用量を０．１ｇとする以外はまったく同じ条件・方法で混練を行った。得られたポリマーはテトラヒドロフランには完全に溶解せず多くのゲル分が認められた。このゲル分は濾過等の方法では除去するのが困難であり、溶液塗工に使用するのは不適当と判断された。
[Comparative Example 2]
In Example 1, kneading was carried out under exactly the same conditions and method except that the amount of dicyclohexylmethane-4,4′-diisocyanate used in the reaction was 10.0 g and the amount of dibutyltin dilaurate was 0.1 g. . The obtained polymer was not completely dissolved in tetrahydrofuran and a large amount of gel was observed. This gel content was difficult to remove by a method such as filtration, and was judged to be inappropriate for use in solution coating.
以上の実施例および比較例から明らかなように、本発明に基づきジイソシアネートで変性を施したポリシロキサン／ポリ尿素共重合体は、ポリエチレン製多孔質膜に欠陥を生じることなく薄膜塗工でき、実用性のある酸素分離機能を示した。一方、ジイソシアネート変性を施さないか（比較例１）、本発明の範囲からはずれた条件で変性を施した場合（比較例２）には、塗工膜に欠陥が生じるか、塗工を行うことができず、分離膜として使用できるものではなかった。 As is clear from the above Examples and Comparative Examples, the polysiloxane / polyurea copolymer modified with diisocyanate based on the present invention can be applied in a thin film without causing defects in the polyethylene porous film. The oxygen separation function was demonstrated. On the other hand, if the diisocyanate modification is not performed (Comparative Example 1), or if the modification is performed under conditions deviating from the scope of the present invention (Comparative Example 2), the coating film may be defective or coated. It was not possible to use as a separation membrane.
本発明の気体分離膜は、燃焼機器、空調機器、医療機器、健康機器等の分野における空気からの酸素富化ないし窒素富化用途として好適である。 The gas separation membrane of the present invention is suitable for oxygen enrichment or nitrogen enrichment from air in the fields of combustion equipment, air conditioning equipment, medical equipment, health equipment, and the like.
Claims (5)
（式中、Ｒ１〜Ｒ８は各々独立にフッ素で置換されていてもよい炭素数１〜２０の１価の炭化水素基を表し、Ｘ１およびＸ２は各々独立に炭素数２〜２０の２価の炭化水素基を表し、ａおよびｃは各々独立に２〜１０の整数を表し、ｂおよびｄは各々独立に１〜４０００の整数を表し、ｍおよびｎは各々独立に０または正の整数を表し、ｍとｎが同時に０であることはない。） The polyfunctional isocyanate compound (B) having at least two isocyanate groups is added to 0.1 part by weight of 100 parts by weight of the polysiloxane / polyurea / polyurethane copolymer (A) having a repeating unit represented by the following general formula (I). Modified polysiloxane copolymer (C) for gas separation membrane obtained by reacting 1 to 5 parts by weight.
(In the formula, R 1 to R 8 each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with fluorine, and X 1 and X 2 each independently represent 2 to 20 carbon atoms. A and c each independently represents an integer of 2 to 10, b and d each independently represents an integer of 1 to 4000, and m and n each independently represents 0 or positive And m and n are not 0 at the same time.)
A method for producing a gas separation membrane, wherein the solution of the modified polysiloxane copolymer (C) according to claim 1 or 2 is applied to a porous support.
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