JPS6261322B2 - - Google Patents
Info
- Publication number
- JPS6261322B2 JPS6261322B2 JP58230527A JP23052783A JPS6261322B2 JP S6261322 B2 JPS6261322 B2 JP S6261322B2 JP 58230527 A JP58230527 A JP 58230527A JP 23052783 A JP23052783 A JP 23052783A JP S6261322 B2 JPS6261322 B2 JP S6261322B2
- Authority
- JP
- Japan
- Prior art keywords
- polyimide
- thin film
- formula
- composition
- liquid
- 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.)
- Expired
Links
- 229920001721 polyimide Polymers 0.000 claims description 67
- 239000004642 Polyimide Substances 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 38
- 239000010409 thin film Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 28
- 239000012528 membrane Substances 0.000 claims description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- -1 aromatic carboxylic acid compound Chemical class 0.000 claims description 12
- 230000001112 coagulating effect Effects 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 4
- 150000004984 aromatic diamines Chemical class 0.000 claims description 4
- 239000008240 homogeneous mixture Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 description 25
- 239000010408 film Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229940090668 parachlorophenol Drugs 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 2
- ASDLSKCKYGVMAI-UHFFFAOYSA-N 9,10-dioxoanthracene-2-carboxylic acid Chemical compound C1=CC=C2C(=O)C3=CC(C(=O)O)=CC=C3C(=O)C2=C1 ASDLSKCKYGVMAI-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CCFAKBRKTKVJPO-UHFFFAOYSA-N 1-anthroic acid Chemical compound C1=CC=C2C=C3C(C(=O)O)=CC=CC3=CC2=C1 CCFAKBRKTKVJPO-UHFFFAOYSA-N 0.000 description 1
- WGSDYFKWNLUWHH-UHFFFAOYSA-N 2-(2-carboxyphenyl)-5-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=C([N+]([O-])=O)C=C1C(O)=O WGSDYFKWNLUWHH-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- CXOWHCCVISNMIX-UHFFFAOYSA-N 2-aminonaphthalene-1-carboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(N)=CC=C21 CXOWHCCVISNMIX-UHFFFAOYSA-N 0.000 description 1
- RZRJYURCNBXIST-UHFFFAOYSA-N 2-anthroic acid Chemical compound C1=CC=CC2=CC3=CC(C(=O)O)=CC=C3C=C21 RZRJYURCNBXIST-UHFFFAOYSA-N 0.000 description 1
- HUNGHFUNVZTRKO-UHFFFAOYSA-N 2-chloronaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(Cl)C=CC2=C1 HUNGHFUNVZTRKO-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- XFXOLBNQYFRSLQ-UHFFFAOYSA-N 3-amino-2-naphthoic acid Chemical compound C1=CC=C2C=C(C(O)=O)C(N)=CC2=C1 XFXOLBNQYFRSLQ-UHFFFAOYSA-N 0.000 description 1
- GMZKNRDHSHYMHG-UHFFFAOYSA-N 3-bromo-4-methylphenol Chemical compound CC1=CC=C(O)C=C1Br GMZKNRDHSHYMHG-UHFFFAOYSA-N 0.000 description 1
- OTUYBYTUBWJBLO-UHFFFAOYSA-N 3-bromo-5-methylphenol Chemical compound CC1=CC(O)=CC(Br)=C1 OTUYBYTUBWJBLO-UHFFFAOYSA-N 0.000 description 1
- MNOJRWOWILAHAV-UHFFFAOYSA-N 3-bromophenol Chemical compound OC1=CC=CC(Br)=C1 MNOJRWOWILAHAV-UHFFFAOYSA-N 0.000 description 1
- VQZRLBWPEHFGCD-UHFFFAOYSA-N 3-chloro-4-methylphenol Chemical compound CC1=CC=C(O)C=C1Cl VQZRLBWPEHFGCD-UHFFFAOYSA-N 0.000 description 1
- XNLWJFYYOIRPIO-UHFFFAOYSA-N 3-phenylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1 XNLWJFYYOIRPIO-UHFFFAOYSA-N 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
- IWJGMJHAIUBWKT-UHFFFAOYSA-N 4-bromo-2-methylphenol Chemical compound CC1=CC(Br)=CC=C1O IWJGMJHAIUBWKT-UHFFFAOYSA-N 0.000 description 1
- GPOQODYGMUTOQL-UHFFFAOYSA-N 4-bromo-3-methylphenol Chemical compound CC1=CC(O)=CC=C1Br GPOQODYGMUTOQL-UHFFFAOYSA-N 0.000 description 1
- FIJIPZQZVLCOMB-UHFFFAOYSA-N 4-bromonaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(Br)C2=C1 FIJIPZQZVLCOMB-UHFFFAOYSA-N 0.000 description 1
- XRWGZDGUXYNIOS-UHFFFAOYSA-N 4-chloro-1-hydroxynaphthalene-2-carboxylic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC(Cl)=C21 XRWGZDGUXYNIOS-UHFFFAOYSA-N 0.000 description 1
- RHPUJHQBPORFGV-UHFFFAOYSA-N 4-chloro-2-methylphenol Chemical compound CC1=CC(Cl)=CC=C1O RHPUJHQBPORFGV-UHFFFAOYSA-N 0.000 description 1
- CFKMVGJGLGKFKI-UHFFFAOYSA-N 4-chloro-m-cresol Chemical compound CC1=CC(O)=CC=C1Cl CFKMVGJGLGKFKI-UHFFFAOYSA-N 0.000 description 1
- NNJMFJSKMRYHSR-UHFFFAOYSA-N 4-phenylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=CC=C1 NNJMFJSKMRYHSR-UHFFFAOYSA-N 0.000 description 1
- OONJCAWRVJDVBB-UHFFFAOYSA-N 5-bromo-2-methylphenol Chemical compound CC1=CC=C(Br)C=C1O OONJCAWRVJDVBB-UHFFFAOYSA-N 0.000 description 1
- KKFPXGXMSBBNJI-UHFFFAOYSA-N 5-chloro-2-methylphenol Chemical compound CC1=CC=C(Cl)C=C1O KKFPXGXMSBBNJI-UHFFFAOYSA-N 0.000 description 1
- KSDKUTSQPZBFLM-UHFFFAOYSA-N 5-nitro-9,10-dioxoanthracene-2-carboxylic acid Chemical compound [N+](=O)([O-])C1=CC=CC=2C(C3=CC(=CC=C3C(C12)=O)C(=O)O)=O KSDKUTSQPZBFLM-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- JJUJLQXTYRRNJE-UHFFFAOYSA-N 5-phenylbenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C=2C=CC=CC=2)=C1 JJUJLQXTYRRNJE-UHFFFAOYSA-N 0.000 description 1
- LNRMRAOUVYWVAG-UHFFFAOYSA-N 6-(2-carboxyphenyl)-2,3-dimethylbenzoic acid Chemical compound OC(=O)C1=C(C)C(C)=CC=C1C1=CC=CC=C1C(O)=O LNRMRAOUVYWVAG-UHFFFAOYSA-N 0.000 description 1
- XGWFJBFNAQHLEF-UHFFFAOYSA-N 9-anthroic acid Chemical compound C1=CC=C2C(C(=O)O)=C(C=CC=C3)C3=CC2=C1 XGWFJBFNAQHLEF-UHFFFAOYSA-N 0.000 description 1
- HTPXFGUCAUTOEL-UHFFFAOYSA-N 9h-fluorene-1-carboxylic acid Chemical compound C1C2=CC=CC=C2C2=C1C(C(=O)O)=CC=C2 HTPXFGUCAUTOEL-UHFFFAOYSA-N 0.000 description 1
- DNVJGJUGFFYUPT-UHFFFAOYSA-N 9h-fluorene-9-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)C3=CC=CC=C3C2=C1 DNVJGJUGFFYUPT-UHFFFAOYSA-N 0.000 description 1
- LRXTWTOKIXUWJL-UHFFFAOYSA-N C(C)(=O)C1=C(C(=CC2=CC=CC=C12)C(=O)O)O Chemical compound C(C)(=O)C1=C(C(=CC2=CC=CC=C12)C(=O)O)O LRXTWTOKIXUWJL-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- HEULMVKOOVHXME-UHFFFAOYSA-N Parietinic acid Chemical compound C1=C(C(O)=O)C=C2C(=O)C3=CC(OC)=CC(O)=C3C(=O)C2=C1O HEULMVKOOVHXME-UHFFFAOYSA-N 0.000 description 1
- FCDLCPWAQCPTKC-UHFFFAOYSA-N Rhein Chemical compound C1=CC=C2C(=O)C3=CC(C(=O)O)=CC(O)=C3C(=O)C2=C1O FCDLCPWAQCPTKC-UHFFFAOYSA-N 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- RECUKUPTGUEGMW-UHFFFAOYSA-N carvacrol Chemical compound CC(C)C1=CC=C(C)C(O)=C1 RECUKUPTGUEGMW-UHFFFAOYSA-N 0.000 description 1
- HHTWOMMSBMNRKP-UHFFFAOYSA-N carvacrol Natural products CC(=C)C1=CC=C(C)C(O)=C1 HHTWOMMSBMNRKP-UHFFFAOYSA-N 0.000 description 1
- 235000007746 carvacrol Nutrition 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- WYXXLXHHWYNKJF-UHFFFAOYSA-N isocarvacrol Natural products CC(C)C1=CC=C(O)C(C)=C1 WYXXLXHHWYNKJF-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- KHARCSTZAGNHOT-UHFFFAOYSA-N naphthalene-2,3-dicarboxylic acid Chemical compound C1=CC=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 KHARCSTZAGNHOT-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- WYQIVZKSGGKUAX-UHFFFAOYSA-N phenanthrene-3-carboxylic acid Chemical compound C1=CC=C2C3=CC(C(=O)O)=CC=C3C=CC2=C1 WYQIVZKSGGKUAX-UHFFFAOYSA-N 0.000 description 1
- LMFJKKGDLAICPF-UHFFFAOYSA-N phenanthrene-9-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC3=CC=CC=C3C2=C1 LMFJKKGDLAICPF-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
- B01D67/00113—Pretreatment of the casting solutions, e.g. thermal treatment or ageing
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Description
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The present invention relates to a method for manufacturing a polyimide semipermeable membrane. In particular, aromatic polyimide semipermeable membranes are highly anticipated as heat-resistant gas separation membranes that have excellent chemical resistance, mechanical properties, and the like. The manufacturing method of polyimide semi-permeable membrane is disclosed in Japanese Patent Application Laid-Open No. 1986-
No. 21602 states as follows: That is, the general formula (However, R is a divalent residue of aromatic diamine excluding the amino group.) 90
% or more of polyimides dissolved in a melt of a phenolic compound, a liquid thin film of the polyimide composition is formed, and then the thin film is This is a method for producing a polyimide semipermeable membrane, characterized by coagulating it by immersing it in a coagulating liquid. As a result of various studies in order to further improve the above invention, the present inventor added a certain amount of a specific aromatic carboxylic acid compound to a polyimide composition consisting of polyimide and a phenolic compound, that is, a dope solution. When a semipermeable membrane is manufactured by film forming, the semipermeable membrane has significantly superior gas permeation performance compared to the semipermeable membrane manufactured by the method of the above invention, in particular, without reducing the permeation rate. The present invention was completed based on the discovery that the degree of separation can be improved. That is, the present invention provides: (a) one or more of the polyimides described above; (b) a phenolic solvent; and (c) a homogeneous mixture of the polyimide and the phenolic solvent having the general formula Ar-(COOH)n Ar and n
is as described in the claims) using a polyimide composition containing 5 to 40% by weight of the polyimide weight of the specific aromatic carboxylic acid compound shown in the claims. This method consists of a method for producing a polyimide semipermeable membrane, which is characterized by forming a thin film, and then immersing the thin film in a coagulating liquid to coagulate it. The polyimide used in the present invention has the general formula (However, R is a divalent residue excluding the amino group of an aromatic diamine represented by the general formula H 2 N-R-NH 2. ) 90% of the total structural units are The aromatic polyimide preferably has a proportion of 95% or more in the polymer main chain and is soluble in the melt of the phenolic compound. The above aromatic polyimide is 3, 3', 4, 4'-
Biphenyltracarboxylic acid component, 2, 3, 3',
A biphenyltetracarboxylic acid component such as a 4'-biphenyltetracarboxylic acid component and a general formula H 2 N-R
It is obtained from an aromatic diamine component represented by -NH 2 through a polycondensation reaction and an imidization reaction (imide cyclization reaction). The manufacturing method, manufacturing conditions, etc. are described in JP-A-56-21602, so they will not be described in detail here. The phenolic solvent used in the method of the present invention is a phenolic compound having a melting point of about 100°C or less, preferably 80°C or less, and a boiling point of about 300°C or less, preferably 280°C or less at normal pressure. For example, monovalent phenols such as phenol, o-, m-, or p-cresol, 3,5-xylenol, carvacrol, thymol, or halogenated phenols in which the hydrogen of the monovalent phenol is replaced with a halogen. can be preferably mentioned. In particular, as a halogenated phenol, the general formula
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ããããã®ééç¹æ§ã¯ç¬¬ïŒè¡šã«ç€ºãã[Formula] (However, in the above general formula, R 2 is hydrogen or an alkyl group having 1 to 3 carbon atoms, and X is a halogen atom), and its melting point is about 100
A halogenated phenol compound having a boiling point of about 300°C or less, preferably 280°C or less at normal pressure is optimal because it has excellent solubility in polyimide. In the method of the present invention, examples of halogenated phenols include 3-chlorophenol (metachlorophenol), 4-chlorophenol (parachlorophenol), 3-bromophenol, 4-chlorophenol, and 4-chlorophenol.
-bromophenol, 2-chloro-4-hydroxytoluene, 2-chloro-5-hydroxytoluene, 3-chloro-6-hydroxytoluene, 4-
Chloro-2-hydroxytoluene, 2-bromo-
4-hydroxytoluene, 2-bromo-5-hydroxytoluene, 3-bromo-5-hydroxytoluene, 3-bromo-6-hydroxytoluene,
Examples include 4-bromo-2-hydroxytoluene. In the method of the present invention, the polyimide composition further contains a specific aromatic carboxylic acid compound in a homogeneous mixture of the polyimide and a phenolic solvent in an amount of 5 to 40% by weight based on the weight of the polyimide. That is, in the polyimide composition used in the present invention, 5 to 40% by weight of a specific aromatic carboxylic acid compound based on the polyimide is contained in the polyimide composition, that is, the dove solution. If the above conditions are not met, it is not suitable because sufficient separation cannot be obtained or the permeation rate is low. Specific aromatic compounds of the general formula Ar-(COOH)n (Ar and n are as described above) suitable for addition to the polyimide composition in the present invention include, for example, ()Ar In the case of a naphthalene ring Monocarboxylic acids such as 1- or 2-naphthoic acid, dicarboxylic acids such as 1,2- or 2,3-naphthalene dicarboxylic acid, 1,2,5- or 1,4,5-naphthalene dicarboxylic acid, etc. - tricarboxylic acids such as carboxylic acid, amino-substituted derivatives such as 2-amino-1-naphthoic acid or 3-amino-2-naphthoic acid, 4-bromo-1-naphthoic acid or 2-
Halogen-substituted derivatives such as chloro-1-naphthoic acid, polysubstituted derivatives such as 4-acetyl-3-hydroxy-2-naphthoic acid, 1-hydroxy-4-chloro-2-naphthoic acid, etc., where ()Ar is a biphenyl ring Monocarboxylic acids such as 2- or 3- or 4-biphenylcarboxylic acid, dicarboxylic acids such as 2,2'- or 3,3'- or 3,5-biphenyldicarboxylic acid, 3,3'- Substituted derivatives such as dimethyl-2,2'-biphenyl dicarboxylic acid and 4-nitro-2,2'-biphenyl dicarboxylic acid, when ()Ar is another ring 1-, 2-, or 9-anthracenecarboxylic acid , 9,10-anthraquinone-2-carboxylic acid,
1,3- or 1,4- or 4,5-dihydroxy-9,10-anthraquinone-2-carboxylic acid, 4,5-dihydroxy-7-methoxy-9,10
-anthraquinone-2-carboxylic acid, 1- or 5-nitro-9,10-anthraquinone-2-carboxylic acid, 1- or 2-, or 3- or 9-phenanthrenecarboxylic acid, 1- or 9-fluorene Carboxylic acid 9-fluorenone-1 or 2- or 3- or 4
-carboxylic acids and the like. The liquid polyimide composition, i.e., dope, used in the method of the present invention contains (a) at least 5% by weight of the polyimide, based on the total composition, and (c) a specific aromatic carboxylic acid compound containing the polyimide. It is necessary to contain at least 5 to 40% by weight of the component, and if the composition has a component ratio outside of this range, it is difficult to obtain a semipermeable membrane with the excellent permeation performance that is the objective of the present invention. Undesirable. As described above, the present invention manufactures a semipermeable membrane using a polyimide composition in which a specific amount of a specific aromatic carboxylic acid compound is added to polyimide and a phenolic solvent as a dope solution. The semipermeable membrane obtained by the production method of the present invention has excellent heat resistance, which is possessed by a semipermeable membrane produced using a polyimide composition composed of polyimide and a phenolic solvent as a dope liquid. In addition to having the same chemical resistance and mechanical properties, there is a marked improvement in gas permeation performance in particular. Therefore, the semipermeable membrane obtained by the production method of the present invention is suitable for use in selectively separating a desired gas from a mixture of various gases. Combinations of gases constituting such gas mixtures include, for example, combinations of hydrogen and carbon monoxide, oxygen and nitrogen, hydrogen and nitrogen, carbon dioxide and methane, helium and methane, helium and nitrogen, etc. . When carrying out the method of the present invention, if a phenolic solvent is used as a reaction solvent in the polyimide synthesis reaction, the phenolic solvent may be further added to the reaction mixture as necessary to adjust the concentration, composition, viscosity, etc. After adjustment, the aromatic carboxylic acid compound as described above is added and mixed uniformly, and used as a polyimide composition for film formation. In the method of the present invention, a composition containing two or more kinds of polyimides represented by the above general formula can be used as the polyimide composition, and furthermore, a composition containing two or more kinds of polyimides represented by the above general formula and other aromatic polyimides can be used. It is also possible to use compositions containing polyimide. The above aromatic polyimide was heated at 30°C and at a concentration of 0.5.
g/100mlml solvent (mixed solvent of 4 volumes of parachlorophenol and 1 volume of orthochlorophenol)
Logarithmic viscosity measured at 0.3-7.0, especially 0.4-5.0,
More preferably, a wide range of about 0.5 to 4.0 can be used. In the method of the present invention, the concentration of the total polyimide contained in the polyimide composition is preferably in the range of 6 to 30% by weight, more preferably 8 to 25% by weight, based on the total composition. In addition, the polyimide composition has a film forming temperature of 0 to 120°C, especially 5°C.
It is preferable that a uniform liquid composition with a rotational viscosity of at least 100 centipoise, particularly about 500 to 10,000 poise, be formed within the range of ~100° C., and can be used as a dope solution for film formation. In the method of the present invention, the above-mentioned polyimide composition is heated if necessary and used as a dope solution for film formation, and the dope solution of the polyimide composition is used to form a liquid thin film (for example, a flat film shape, a hollow fiber shape). A semipermeable polyimide membrane is produced by forming a tubular thin film) and then immersing the thin film in a coagulating liquid to coagulate it. In the method of the present invention, it is preferable to use a suitable known filter to remove solid matter from the liquid polyimide composition or to sufficiently degas it to obtain a dope solution for film formation. A method for forming a liquid thin film from a dope solution of a polyimide composition can be carried out by a method similar to a conventionally known casting film forming method. A dope solution of the polyimide composition is cast onto the surface of the polyimide composition, and then a liquid thin film with a uniform thickness is formed using a doctor blade. A thin film is formed by supplying a liquid and casting it to a uniform thickness using a doctor knife placed close to the roll surface, or by extruding the polyimide composition into a thin film from a T-die and wrapping it around the roll surface. A continuous film forming method such as forming a thin film can be adopted. In the method of the present invention, the temperature of the dope solution of the polyimide composition during film formation should be set to a temperature that provides a rotational viscosity suitable for film formation, depending on the relationship between the rotational viscosity of the polyimide composition and temperature. However, preferably 0 to 120
The temperature range is preferably about 5 to 100 degrees Celsius, most preferably about 10 to 60 degrees Celsius.
Further, the thickness of the liquid thin film formed as described above is preferably about 10 to 500 microns, particularly about 20 to 200 microns. The liquid thin film formed as described above can be obtained by partially evaporating the phenolic solvent from one side of the liquid thin film while forming the liquid thin film or after forming the liquid thin film. This is preferred because an asymmetric thin film is effectively formed by solidification. A method for partially evaporating the phenolic solvent from one side of a liquid thin film is to apply a gas at 0 to 100°C, especially 5 to 90°C, to the liquid thin film on the peripheral surface of a flat plate or roll for at least 1 second, especially 5 to 90°C. It is preferable to spray the film for 10 seconds to 20 minutes, or for 10 seconds to 20 minutes.
It may also be a method of leaving it for 30 seconds to 30 minutes, or for 30 seconds to 20 minutes. In the method of the present invention, the coagulating liquid used to coagulate the polyimide liquid thin film formed as described above may be any liquid that is freely mixed and compatible with the phenolic solvent, for example, Lower alcohols such as methanol, ethanol, and propanol, ketones such as acetone, methyl ethyl ketone, diethyl ketone, and methyl propyl ketone, tetrahydrofuran, dioxane,
Examples include ethers such as ethylene glycol monomethyl ether, amides such as dimethyl acetamide and dimethyl formamide, dimethyl sulfoxide, and mixtures of water and the above-mentioned alcohols, ketones, ethers, and amides. . In particular, as a coagulating liquid, the mixing ratio (relative to the unit amount of water used) is 0.1 to 10, especially 0.2.
A mixed solution of water and alcohols, water and ethers, water and ketones, or water and amides having a molecular weight of about 5 to 5 is preferable. The method of coagulating a liquid thin film with the above-mentioned coagulating liquid is as follows:
Any known method may be used, but it is preferable to immerse the thin film together with the base material on which the thin film is formed (cast) in the coagulation solution,
Also, the temperature of the coagulating liquid is below 50â, especially -10 to 30â.
â, more preferably about -5 to 20â. The time for which the thin film is immersed in the coagulation solution as described above varies depending on the type of polyimide composition, the type of coagulation solution, and other conditions, but is generally 0.1 to 20 hours, 0.5 to 10 hours. It only takes about an hour. The membrane solidified from the liquid thin film as described above already has a porous layer with sufficient properties as a semipermeable membrane, but it is also coated with methyl alcohol, ethyl alcohol, propyl alcohol, etc. Approximately 0 to 50â in lower alcohols
After immersing for 0.5 to 10 hours, post-treatment is performed to wash and remove residual phenolic solvents in the coagulated membrane.The membrane is immersed in an aliphatic hydrocarbon such as heptane or hexane, and then dried to obtain a dry semipermeable membrane. Heat treatment may be performed if necessary. Next, reference examples (polyimide synthesis examples), examples, and comparative examples are shown. In Examples and Comparative Examples, the gas permeation performance of porous membranes was tested using the following method. A porous membrane was set in a stainless steel cell with a membrane area of 14.65 cm 2 , hydrogen gas was introduced under pressure at 1 kg/cm 2 into one side of the cell, and the rate at which hydrogen gas permeated through the membrane was measured using a flowmeter. . Carbon monoxide was also measured in the same way. Note that the measurement temperature was maintained constant at 30°C using a constant temperature bath. From the obtained measured values, the transmittance and resolution were calculated according to the following equations. Permeability (P') = permeated gas amount/membrane area (cm 2 ), permeation time (seconds), pressure difference (cmHg) Separation rate = hydrogen permeability (P H2 )/carbon monoxide permeability (P' CO ) Reference Example 40 mmol of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 40 mmol of 4,4'-diaminodiphenyl ether, and 165 g of parachlorophenol (PCP) were mixed with a stirrer and The reaction solution was placed in a separable flask equipped with a nitrogen gas inlet tube, and while flowing nitrogen gas and stirring, the reaction solution was heated from room temperature to 180â in about 50 minutes, and then the reaction solution was heated to 180â. Holding for 8 hours, polymerization and imidization were carried out in one step to produce aromatic polyimide and produce a viscous homogeneous solution of polyimide. The homogeneous solution of polyimide has a polymer concentration of approximately 10% by weight and a polymer logarithmic viscosity (50
â, 0.5g/100ml PCP) is 2.2, and the imidization rate of the polymer is measured by infrared absorption spectrum.
It was over 95%. Comparative Example 1 The homogeneous polyimide solution produced in Reference Example was cast onto a glass plate at 60° to form a thin film with a thickness of 0.2 mm, and after being left at 60°C for 3 minutes (drying time), the thin film was soaked in ethanol. The thin film was immersed in a coagulating solution (0° C.) of a mixture of 1 volume of water and 1 volume of water, and left to stand for about 20 hours to solidify the thin film. The coagulated film was immersed in ethanol at 20° for an additional 20 hours, and then in n-hexane for 25 hours.
After being immersed for 20 hours at 20°C, it was air-dried at 25°C for 5 hours under air circulation, and then at 100°C for 1 hour to obtain a polyimide film. Table 1 shows the film forming conditions and the permeation characteristic values of the film. Comparative Example 2 The same procedure as Comparative Example 1 was carried out except that the film was formed at 80° and the drying time was 2 minutes. Film forming conditions and results are shown in Table 1. Examples 1 to 11 and Comparative Examples 3 to 8 A predetermined amount of the additive shown in Table 1 was added to the polymer to a homogeneous solution of polyimide produced in the same manner as in the reference example, and after making a homogeneous solution, the additives shown in Table 1 were added. The same procedure as in Comparative Example 1 was conducted except that the film was formed under the film forming conditions shown.
The transmission characteristics of each are shown in Table 1.
Claims (1)
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ã90ïŒ ä»¥äžæããããªã€ããã®ïŒçš®ãŸãã¯ïŒçš®
以äžïŒ (b) ããšããŒã«ç³»æº¶å€ïŒãã㊠(c) äžèšããªã€ãããšããšããŒã«ç³»æº¶å€ã®åäžæ··
åç©ã«äžè¬åŒ ArâïŒCOOHïŒïœ ArïŒãåŒã ãåŒããåŒã ãåŒã ãåŒããåŒã ãåŒãã ãŸãã¯ãããã®èªå°äœã ïœïŒïŒãïŒã®æŽæ° ã§ç€ºãããè³éŠæã«ã«ãã³é žååç©ãããªã€ãã
ééã®ïŒã40ïŒ å«æããããªã€ããçµæç©ã䜿çš
ããŠããã®ããªã€ããçµæç©ã®æ¶²ç¶ã®èèã圢æ
ãããã€ãã§ããã®èèãååºæ¶²äžã«æµžæŒ¬ããŠå
åºãããããšãç¹åŸŽãšããããªã€ããåéèã®è£œ
é æ³ã[Claims] 1 (a) General formula (However, R is a divalent residue of an aromatic diamine excluding an amino group.) One or more polyimides having 90% or more of repeating units: (b) a phenolic solvent: and (c) A homogeneous mixture of the above polyimide and a phenolic solvent has the general formula Ar-(COOH)n Ar: [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula], or derivatives thereof; Using a polyimide composition containing an aromatic carboxylic acid compound represented by n: an integer of 1 to 3 in an amount of 5 to 40% by weight of the polyimide, a liquid thin film of the polyimide composition is formed, and then the thin film is A method for producing a polyimide semipermeable membrane, which is characterized by immersing it in a coagulating solution and coagulating it.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58230527A JPS60125209A (en) | 1983-12-08 | 1983-12-08 | Improvement in preparation of polyimide separation membrane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58230527A JPS60125209A (en) | 1983-12-08 | 1983-12-08 | Improvement in preparation of polyimide separation membrane |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60125209A JPS60125209A (en) | 1985-07-04 |
JPS6261322B2 true JPS6261322B2 (en) | 1987-12-21 |
Family
ID=16909140
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58230527A Granted JPS60125209A (en) | 1983-12-08 | 1983-12-08 | Improvement in preparation of polyimide separation membrane |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60125209A (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4880442A (en) * | 1987-12-22 | 1989-11-14 | E. I. Du Pont De Nemours And Company | Polyimide gas separation membranes |
US5026823A (en) * | 1989-09-12 | 1991-06-25 | The Dow Chemical Company | Novel alicyclic polyimides and a process for making the same |
US4988371A (en) * | 1989-09-12 | 1991-01-29 | The Dow Chemical Company | Novel alicyclic polyimide gas separation membranes |
DE19957499A1 (en) * | 1999-11-29 | 2001-06-07 | Karosseriewerk Heinrich Meyer | Loadable articulated train, especially for the transport of food |
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1983
- 1983-12-08 JP JP58230527A patent/JPS60125209A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS60125209A (en) | 1985-07-04 |
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