WO2015072692A1 - 가교구조를 갖는 열전환 폴리(벤즈옥사졸-이미드) 공중합체, 이를 포함하는 기체분리막 및 그 제조방법 - Google Patents
가교구조를 갖는 열전환 폴리(벤즈옥사졸-이미드) 공중합체, 이를 포함하는 기체분리막 및 그 제조방법 Download PDFInfo
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- WO2015072692A1 WO2015072692A1 PCT/KR2014/010513 KR2014010513W WO2015072692A1 WO 2015072692 A1 WO2015072692 A1 WO 2015072692A1 KR 2014010513 W KR2014010513 W KR 2014010513W WO 2015072692 A1 WO2015072692 A1 WO 2015072692A1
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- WIPO (PCT)
- Prior art keywords
- copolymer
- formula
- benzoxazole
- imide
- gas separation
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- 239000012528 membrane Substances 0.000 title claims abstract description 192
- 229920001577 copolymer Polymers 0.000 title claims abstract description 135
- 238000000926 separation method Methods 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000004642 Polyimide Substances 0.000 claims abstract description 142
- 229920001721 polyimide Polymers 0.000 claims abstract description 142
- 239000007789 gas Substances 0.000 claims abstract description 95
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 57
- 238000004132 cross linking Methods 0.000 claims abstract description 42
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003546 flue gas Substances 0.000 claims abstract description 36
- 150000002009 diols Chemical class 0.000 claims abstract description 11
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 71
- 125000003118 aryl group Chemical group 0.000 claims description 48
- 239000002253 acid Substances 0.000 claims description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 36
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 35
- 229910052717 sulfur Inorganic materials 0.000 claims description 35
- 238000004519 manufacturing process Methods 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 32
- 229920005575 poly(amic acid) Polymers 0.000 claims description 30
- 150000004984 aromatic diamines Chemical class 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 21
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 230000002194 synthesizing effect Effects 0.000 claims description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 14
- 239000008096 xylene Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 8
- 230000000630 rising effect Effects 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004581 coalescence Methods 0.000 claims description 2
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 230000008707 rearrangement Effects 0.000 abstract 2
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 45
- 238000003786 synthesis reaction Methods 0.000 description 42
- 229920000642 polymer Polymers 0.000 description 35
- 229920002577 polybenzoxazole Polymers 0.000 description 31
- 230000035699 permeability Effects 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 27
- 230000008569 process Effects 0.000 description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 125000005462 imide group Chemical group 0.000 description 10
- 230000004580 weight loss Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000003949 imides Chemical class 0.000 description 8
- -1 diol compound Chemical class 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 6
- 150000004985 diamines Chemical class 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 6
- AIIPIXSXYANFAP-UHFFFAOYSA-N 1,3,5-trimethylcyclohexa-3,5-diene-1,2-diamine Chemical compound CC1=CC(C)(N)C(N)C(C)=C1 AIIPIXSXYANFAP-UHFFFAOYSA-N 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000006114 decarboxylation reaction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 3
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- 239000000178 monomer Substances 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
- 239000012071 phase Substances 0.000 description 3
- 238000001485 positron annihilation lifetime spectroscopy Methods 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- VKPJOERCBNIOLN-UHFFFAOYSA-N 1,3-benzoxazole-2-carboxylic acid Chemical group C1=CC=C2OC(C(=O)O)=NC2=C1 VKPJOERCBNIOLN-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
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- 238000001035 drying Methods 0.000 description 2
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- 229920001519 homopolymer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 238000012856 packing Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000807 solvent casting Methods 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- HDGLPTVARHLGMV-UHFFFAOYSA-N 2-amino-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound NC1=CC(C(C(F)(F)F)C(F)(F)F)=CC=C1O HDGLPTVARHLGMV-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 0 Nc(ccc(C*Cc(cc1)cc(O)c1N)c1)c1O Chemical compound Nc(ccc(C*Cc(cc1)cc(O)c1N)c1)c1O 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—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
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
Definitions
- the present invention relates to a thermally converting poly (benzoxazole-imide) copolymer having a crosslinked structure, a gas separation membrane including the same, and a method for manufacturing the same (except for the flue gas separation membrane), and more specifically, A heat-converted poly (benzoxazole-imide) copolymer membrane having a crosslinked structure by direct thermal crosslinking and thermal conversion at the same time by only heat treating a film prepared from an ortho-hydroxy polyimide copolymer having an acid, or Or a crosslinked structure having a content of benzoxazole group in the copolymer polymer chain of less than 80% by transesterification crosslinking reaction between ortho-hydroxy polyimide copolymer having carboxylic acid and diol compound and subsequent thermal conversion.
- the present invention relates to a gas separation membrane comprising a thermally converting poly (benzoxazole-imide) copolymer, and a method for preparing the same. Be).
- microporous organic polymers polymers with high levels of free volume, known as microporous organic polymers, have emerged as one of the strongest candidates in the separation process because of their ability to adsorb on small gas molecules as well as their enhanced diffusion capacity. Therefore, organic polymers that can be applied as gas separation membranes, noting that inherent microporous polymers based on rigid ladder-type structures with twisted regions that prevent efficient packing of polymer chain spaces exhibit relatively high gas permeability and selectivity. Various studies are underway to develop the system.
- Non-Patent Document 1 It has been reported that the transmittance of 10 to 100 times higher, the selectivity of carbon dioxide / methane (CO 2 / CH 4 ) is still equivalent to the conventional commercialized cellulose acetate membrane, there is room for improvement (Non-Patent Document 1 ).
- the present inventors reported a result of increasing the stiffness of the polymer chain by thermally converting the hydroxy polyimide copolymer membrane to introduce benzoxazole groups, thereby improving gas separation performance by the contribution of free volume elements. If more than 80% of the benzoxazole groups are introduced into the polymer chain, they are too hard to break easily, and mechanical shrinkage or shrinkage of the membrane area occurs due to the release of large amounts of CO 2 during the thermal conversion process. In the area
- a polybenzoxazole membrane was prepared by thermally converting a blend membrane of polyimide having a hydroxy group at the ortho position with poly (styrene sulfonic acid) at 300 to 650 ° C. to prepare a polybenzoxazole membrane. It has been reported that the selectivity of carbon dioxide / methane (CO 2 / CH 4 ) is improved by up to 95% compared to polybenzoxazole membrane prepared by thermal conversion from hydroxypolyimide containing no sulfonic acid. However, the method for synthesizing polyimide, which is ultimately a precursor for preparing polybenzoxazole membranes, has not been disclosed in detail.
- the properties of the thermally converted polybenzoxazole are increased by various methods such as solution phase thermal imidization, solid phase thermal imidization, and chemical imidization based on the fact that the properties of the aromatic polybenzoxazole are affected by the synthesis method of the aromatic polyimide.
- solution phase thermal imidization solid phase thermal imidization
- chemical imidization based on the fact that the properties of the aromatic polybenzoxazole are affected by the synthesis method of the aromatic polyimide.
- a polyimide having a hydroxy group at the ortho position is synthesized by chemical imidization method, and thermally converted to obtain a polybenzoxazole film, and finally irradiated with ultraviolet (UV) light to form a polybenzoxazole having a crosslinked structure.
- UV ultraviolet
- the polyimide membrane is thermally imidized because the polyimide is manufactured by chemical imidization, and thus the polybenzoxazole membrane thermally converted from the polybenzoxazole membrane has a crosslinked structure.
- Patent Document 3 there is a disadvantage in the process of using an ultraviolet irradiation device in order to form a crosslinked structure.
- thermally-converted polybenzoxazole membranes can be regarded as precursors of polyimide, the content of benzoxazole groups in polymer chains, and crosslinking of polymer chains.
- a polyimide membrane having a hydroxyl group and a carboxylic acid in a polyimide repeating unit is synthesized by a solution-phase thermal imidization method, and then only heat treated to have a cross-linked structure and a polybenzoxazole by thermal conversion. It was found that a membrane was obtained.
- a solution phase thermal imidization method synthesizes a copolymer having a hydroxyl group and a carboxylic acid in a polyimide repeat unit and having a hydroxy polyimide content of less than 80% in the copolymer polymer chain, and then chemically crosslinking and subsequent thermal conversion.
- the polybenzoxazole membrane having a crosslinked structure having a benzoxazole group content of less than 80% in the copolymer polymer chain is formed by thermal conversion at the same time as thermal crosslinking or direct thermal crosslinking, the mechanical properties and thermal properties are excellent and the separation performance as a gas separation membrane Knowing this remarkable improvement, it came to complete this invention.
- Patent Document 1 Korean Laid-Open Patent Publication No. 10-2012-0100920
- Patent Document 2 United States Patent Application Publication US 2012/0305484
- Patent Document 3 Japanese Patent Application Publication No. 2012-521871
- Non-Patent Document 1 Y.M. Lee et al., Science 318, 254-258 (2007)
- Non Patent Literature 2 Y.M. Lee et al., J. Membr. Science 350, 301-309 (2010)
- the present invention has been made in view of the above problems, and an object of the present invention is a method for producing a thermally converting poly (benzoxazole-imide) copolymer membrane having a cross-linking structure for gas separation excellent in gas permeability and selectivity at the same time. And it is to provide a gas separation membrane prepared thereby (except for the flue gas separation membrane).
- Still another object of the present invention is to provide a thermally converting poly (benzoxazole-imide) copolymer having a novel crosslinked structure having a content of benzoxazole group in the copolymer polymer chain of less than 80%, and mechanical properties thereof. It is to provide a gas separation membrane having excellent thermal characteristics, a shrinkage ratio of the membrane area, and high gas permeability and selectivity at the same time, and a method of manufacturing the same (except for the flue gas separation membrane).
- the present invention for achieving the object as described above, i) by reacting 3, 5-diaminobenzoic acid as an acid dianhydride, ortho-hydroxy diamine and a comonomer to obtain a polyamic acid solution, the azeotropic thermal imidization method Synthesizing an ortho-hydroxy polyimide copolymer having a carboxylic acid;
- step ii) dissolving the ortho-hydroxy polyimide copolymer having the carboxylic acid synthesized in step i) in an organic solvent and casting the film;
- step iii heat-treating the membrane obtained in step ii); and a method for preparing a thermally converting poly (benzoxazole-imide) membrane having a gas separation crosslinking structure (except for the flue gas separation membrane). to provide.
- the acid dianhydride of step i) is characterized in that represented by the following formula (1).
- Ar is an aromatic ring group selected from a substituted or unsubstituted tetravalent C6-C24 arylene group and a substituted or unsubstituted tetravalent C4-C24 heterocyclic group, the aromatic ring group Present alone or two or more form a condensed ring with each other; two or more single bonds, O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10 ), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 or CO-NH)
- Ortho-hydroxy diamine of step i) is characterized in that represented by the following formula (2).
- Q is a single bond; O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 , CO-NH, C (CH 3 ) (CF 3 ), or a substituted or unsubstituted phenylene group)
- the azeotropic thermal imidization method of step i) is characterized in that toluene or xylene is added to the polyamic acid solution and stirred to perform an imidization reaction at 180 to 200 ° C. for 6 to 12 hours.
- Heat treatment of step iii) is carried out by increasing the temperature to 350 ⁇ 450 °C at a temperature rising rate of 1 ⁇ 20 °C / min in a high purity inert gas atmosphere and is maintained by isothermal for 0.1 to 3 hours.
- the present invention provides a heat conversion poly (benzoxazole-imide) membrane (except for the flue gas separation membrane) having a cross-linked structure for gas separation prepared by the above production method.
- the membrane is characterized by having a repeating unit represented by the following formula (1).
- Ar is an aromatic ring group selected from a substituted or unsubstituted tetravalent C6-C24 arylene group and a substituted or unsubstituted tetravalent C4-C24 heterocyclic group, the aromatic ring group alone Two or more form a condensed ring with each other; two or more single bonds, O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10) , (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 or CO-NH,
- Q is a single bond; O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 , CO-NH, C (CH 3 ) (CF 3 ), or a substituted or unsubstituted phenylene group,
- the film is characterized in that the interplanar distance ( d- spacing) is 0.62 ⁇ 0.67 nm.
- the membrane is characterized in that the density is 1.38 ⁇ 1.43 g / cm 3 .
- the membrane is characterized in that the d 3 average pore diameter is 4.0 mm 3 , and the d 4 average pore diameter is 8.6 mm 3.
- the present invention also provides a crosslinked heat conversion poly (benzoxazole-imide) copolymer having a repeating unit represented by the following formula (2).
- Ar 1 is an aromatic ring group selected from a substituted or unsubstituted tetravalent C6-C24 arylene group and a substituted or unsubstituted tetravalent C4-C24 heterocyclic group, the aromatic ring group Present alone or two or more form a condensed ring with each other; two or more single bonds, O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10 ), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 or CO-NH,
- Q is a single bond; O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 , CO-NH, C (CH 3 ) (CF 3 ), or a substituted or unsubstituted phenylene group,
- Ar 2 is an aromatic ring group selected from a substituted or unsubstituted divalent C6-C24 arylene group and a substituted or unsubstituted divalent C4-C24 heterocyclic group, said aromatic ring group being present alone; Two or more of each other form a condensed ring; At least two single bonds, O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 or CO-NH,
- the cross-linked heat conversion poly (benzoxazole-imide) copolymer is characterized in that the inter-planar distance ( d- spacing) is 6.67 ⁇ 6.69 kPa.
- the crosslinked thermally converting poly (benzoxazole-imide) copolymer has a density of 1.38 to 1.43 g / cm 3 .
- the present invention provides a polyamic acid solution by reacting an aromatic diamine, 3, 5-diaminobenzoic acid as I) an acid dianhydride, an ortho-hydroxy diamine and a comonomer, followed by carboxyl by azeotropic thermal imidization. Synthesizing an ortho-hydroxy polyimide copolymer having an acid;
- step II reacting the polyimide copolymer of step I) with a diol to synthesize a monoesterified ortho-hydroxy polyimide copolymer;
- Acid dianhydride of step I) is characterized in that represented by the general formula (3).
- Ar 1 is an aromatic ring group selected from a substituted or unsubstituted tetravalent C6-C24 arylene group and a substituted or unsubstituted tetravalent C4-C24 heterocyclic group, and the aromatic ring
- the groups are present alone; at least two form a condensed ring with each other; at least two are single bonds, O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 or CO-NH)
- Ortho-hydroxy diamine of step I) is characterized in that represented by the general formula (2).
- the aromatic diamine of step I) is characterized in that represented by the general formula (4).
- Ar 2 is an aromatic ring group selected from a substituted or unsubstituted divalent C6-C24 arylene group and a substituted or unsubstituted divalent C4-C24 heterocyclic group, the aromatic ring
- the groups are present alone; at least two form a condensed ring with each other; at least two are single bonds, O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 or CO-NH)
- the azeotropic thermal imidization method of step I) is characterized in that toluene or xylene is added to the polyamic acid solution and stirred to perform an imidization reaction at 180 to 200 ° C. for 6 to 12 hours.
- the diol of step II) is any one selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and benzenedimethanol It is characterized by one.
- step III) The monoesterification of step III) is carried out for 18-24 hours at 140-160 ° C. with an excess of diol corresponding to at least 50 times the carboxylic acid equivalent contained in the copolymer of step I) under a para-toluenesulfonic acid catalyst. It is characterized by.
- Transesterification crosslinking reaction of step III) is characterized in that carried out by heat treatment under vacuum at 200 ⁇ 250 °C, 18 ⁇ 24 hours.
- step IV The thermal conversion of step IV) is performed by increasing the temperature to 350-450 ° C. at a temperature rising rate of 1-20 ° C./min in a high purity inert gas atmosphere, and then maintaining the isothermal state for 0.1-3 hours.
- the present invention provides a gas separation membrane (except for the flue gas separation membrane) comprising a cross-linked heat conversion poly (benzoxazole-imide) copolymer having a repeating unit represented by the formula (2). do.
- the present invention is a) acid dianhydride, ortho-hydroxy diamine and a comonomer to react with aromatic diamine, 3, 5-diaminobenzoic acid to obtain a polyamic acid solution, and then azeotropic thermal imidization Synthesizing an ortho-hydroxy polyimide copolymer having a;
- step b) forming an ortho-hydroxy polyimide copolymer having a carboxylic acid synthesized in step a) in an organic solvent and casting the film;
- a gas separation membrane comprising a cross-linked thermally converting poly (benzoxazole-imide) copolymer having a repeating unit represented by Chemical Formula 2, including the step of heat-treating the membrane obtained in step b). , Except for flue gas separation membranes).
- the acid dianhydride of step a) is characterized in that represented by the general formula (3).
- the ortho-hydroxy diamine of step a) is characterized in that represented by the general formula (2).
- the aromatic diamine of step a) is characterized in that represented by the general formula (4).
- step a toluene or xylene is added to the polyamic acid solution, followed by stirring to perform an imidization reaction at 180 to 200 ° C. for 6 to 12 hours.
- step c) The heat treatment of step c) is carried out by increasing the temperature to 350 ⁇ 450 °C at an elevated temperature rate of 1 ⁇ 20 °C / min in a high purity inert gas atmosphere, characterized in that it is carried out by maintaining an isothermal state for 0.1 to 3 hours.
- Gas separation membrane comprising a cross-linked heat conversion poly (benzoxazole-imide) copolymer having a repeating unit represented by the formula (2) prepared by the steps a) to c) (however, flue gas separation Membrane is excluded) is characterized in that the d- spacing distance is 6.39 ⁇ 6.57 ⁇ .
- Gas separation membrane comprising a cross-linked heat conversion poly (benzoxazole-imide) copolymer having a repeating unit represented by the formula (2) prepared by the steps a) to c) (however, flue gas separation Except for the membrane) is characterized in that the density is 1.38 ⁇ 1.41 g / cm 3 .
- a heat-converting poly (benzoxazole-imide) copolymer membrane having a crosslinking structure for gas separation using only heat treatment without undergoing a chemical process for forming a crosslinked structure and UV irradiation, etc. Except for flue gas separation membranes, and the gas separation membranes (except for flue gas separation membranes) manufactured therefrom are not only excellent in permeability and selectivity but also simple in the manufacturing process. Commercialization is possible.
- thermally converting poly (benzoxazole-imide) copolymers having a novel crosslinking structure having a content of benzoxazole groups in the copolymer polymer chains of the present invention less than 80% are less packed with polymer chains, and more Having a structure with space, there is enough room for small molecules to permeate and diffuse.
- the gas separation membrane containing the copolymer (except for the flue gas separation membrane) has excellent mechanical and thermal properties, a shrinkage of the membrane area, and high gas permeability and selectivity at the same time. outstanding.
- FIG. 3 is an ATR-FTIR spectrum of a thermally converting poly (benzoxazole-imide) copolymer membrane having a crosslinked structure prepared according to Examples 2 to 6.
- FIG. 3 is an ATR-FTIR spectrum of a thermally converting poly (benzoxazole-imide) copolymer membrane having a crosslinked structure prepared according to Examples 2 to 6.
- thermogravimetric-mass spectrometry (TG-MS) graph showing the thermogravimetric reduction characteristics of the HPIDABA-25 membrane obtained in Preparation Example 6.
- HPIDABA-5 and HPIDABA-25 obtained according to Film Production Examples 2 and 6, HPI formed according to Reference Example 1, and HPIMPD-5 formed according to Reference Example 2, respectively.
- FIG. 7 is a graph showing the permeability and selectivity of CO 2 from a CO 2 / CH 4 mixed gas using poly (benzoxazole-imide) copolymer membrane prepared according to Examples 7 to 11 and Comparative Examples 2 and 3 .
- FIG 9 is a graph showing the permeability and selectivity of CO 2 from a CO 2 / CH 4 mixed gas using poly (benzoxazole-imide) copolymer membrane prepared according to Examples 12 to 16 and Comparative Examples 2 and 3 .
- FIG 10 is a graph showing the permeability and selectivity of CO 2 from a CO 2 / N 2 mixed gas using poly (benzoxazole-imide) copolymer membrane prepared according to Examples 12 to 16 and Comparative Examples 2 and 3 .
- Flue gas refers to gases emitted from partial or complete combustion of hydrocarbon fuels, which mainly include carbon dioxide, water vapor and nitrogen, and in some cases, affect one or more hydrogen, oxygen and carbon monoxide changes in the global environment. It is defined as a trace amount of contaminants containing nitrogen oxides, sulfur oxides, and fine particle materials, and in the present invention, a method for preparing a gas separation membrane except for the flue gas separation membrane and a gas excluding the flue gas separation membrane produced thereby. It is to provide a separator.
- the heat conversion poly (benzoxazole-imide) gas separation membrane having a crosslinked structure prepared according to the present invention is based on the synthesis of polyimide prepared by imidizing a polyamic acid obtained by reacting an acid dianhydride with a diamine. Furthermore, in order to have a crosslinked structure between polymer chains only by heat treatment, a repeating unit must have a functional group such as carboxylic acid. In addition, the structure is converted from polyimide to polybenzoxazole during the heat treatment process, so that a functional group such as a hydroxy group in the ortho-position of the aromatic imide linkage attacks the carbonyl group of the imide ring to form a carboxy-benzoxazole structure.
- a copolymer membrane is prepared.
- an acid dianhydride, an ortho-hydroxy diamine, and a comonomer are reacted with 3, 5-diaminobenzoic acid to obtain a polyamic acid solution, followed by azeotropic thermal imidization, Synthesizing a so-hydroxy polyimide copolymer;
- step ii) dissolving the ortho-hydroxy polyimide copolymer having the carboxylic acid synthesized in step i) in an organic solvent and casting the film;
- step iii) heat-treating the membrane obtained in step ii); preparing a thermally converting poly (benzoxazole-imide) copolymer membrane having a gas separation crosslinking structure, except for the flue gas separation membrane.
- an acid dianhydride in order to synthesize polyimide, first, an acid dianhydride must be reacted with a diamine to obtain a polyamic acid.
- a compound represented by the following general formula (1) is used as the acid dianhydride.
- Ar is an aromatic ring group selected from a substituted or unsubstituted tetravalent C6-C24 arylene group and a substituted or unsubstituted tetravalent C4-C24 heterocyclic group, the aromatic ring group Present alone or two or more form a condensed ring with each other; two or more single bonds, O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10 ), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 or CO-NH)
- any acid dianhydride may be used without limitation as long as it is defined in Formula 1, but considering the fact that the thermal and chemical properties of the synthesized polyimide can be further improved. It is preferable to use 4,4'-hexafluoroisopropylidene phthalic anhydride (6FDA) which has.
- 6FDA 4,4'-hexafluoroisopropylidene phthalic anhydride
- the ortho-hydroxy polyimide in order to have a poly (benzoxazole-imide) copolymer structure, can be introduced by thermal conversion of ortho-hydroxy polyimide.
- the compound represented by following General formula (2) is used as an ortho-hydroxy diamine.
- Q is a single bond; O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 , CO-NH, C (CH 3 ) (CF 3 ), or a substituted or unsubstituted phenylene group)
- any one as defined in the general formula (2) can be used without limitation, but in view of being able to further improve the thermal and chemical properties of the polyimide to be synthesized 2, More preferably, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPAF) is used.
- bisAPAF 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
- ortho-hydroxy polyimide copolymers having carboxylic acids can be synthesized by reacting 5-acid aminoanhydride of Formula 1 with ortho-hydroxy diamine of Formula 2 using 5-diaminobenzoic acid. .
- step i) the acid dianhydride of Formula 1, ortho-hydroxy diamine of Formula 2 and 3, 5-diaminobenzoic acid are dissolved in an organic solvent such as N-methylpyrrolidone (NMP) and After stirring to obtain a polyamic acid solution, an ortho-hydroxy polyimide copolymer having a carboxylic acid represented by the following structural formula 1 is synthesized by azeotropic thermal imidization.
- NMP N-methylpyrrolidone
- the azeotropic thermal imidization method adds toluene or xylene to the polyamic acid solution and stirs it to perform an imidization reaction at 180 to 200 ° C. for 6 to 12 hours, during which the water released while the imide ring is generated. Is separated as an azeotrope of toluene or xylene.
- step ii) a polymer solution obtained by dissolving an ortho-hydroxy polyimide copolymer having the carboxylic acid of step i) represented by Formula 1 in an organic solvent such as N-methylpyrrolidone (NMP) By casting on a glass plate to form a film, an ortho-hydroxy polyimide copolymer film having a carboxylic acid is obtained.
- NMP N-methylpyrrolidone
- a heat conversion poly (benzoxazole-imide) copolymer membrane of a gas separation crosslinked structure having a repeating unit represented by the following formula (1), which is a final target, is prepared by only heat treating the membrane obtained in step ii).
- Ar is an aromatic ring group selected from a substituted or unsubstituted tetravalent C6-C24 arylene group and a substituted or unsubstituted tetravalent C4-C24 heterocyclic group, the aromatic ring group alone Two or more form a condensed ring with each other; two or more single bonds, O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10) , (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 or CO-NH,
- Q is a single bond; O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 , CO-NH, C (CH 3 ) (CF 3 ), or a substituted or unsubstituted phenylene group,
- the heat treatment is completed by increasing the temperature up to 350 ⁇ 450 °C at a temperature rising rate of 1 ⁇ 20 °C / min in a high-purity inert gas atmosphere, and then isothermally maintained for 0.1 to 3 hours.
- the present invention provides a cross-linked heat conversion poly (benzoxazole-imide) copolymer having a repeating unit represented by the following formula (2).
- Ar 1 is an aromatic ring group selected from a substituted or unsubstituted tetravalent C6-C24 arylene group and a substituted or unsubstituted tetravalent C4-C24 heterocyclic group, the aromatic ring group Present alone or two or more form a condensed ring with each other; two or more single bonds, O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10 ), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 or CO-NH,
- Q is a single bond; O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 , CO-NH, C (CH 3 ) (CF 3 ), or a substituted or unsubstituted phenylene group,
- Ar 2 is an aromatic ring group selected from a substituted or unsubstituted divalent C6-C24 arylene group and a substituted or unsubstituted divalent C4-C24 heterocyclic group, said aromatic ring group being present alone; Two or more of each other form a condensed ring; At least two single bonds, O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 or CO-NH,
- the structure of the poly (benzoxazole-imide) copolymer represented by the formula (2) is based on the synthesis of a polyimide prepared by imidizing a polyamic acid obtained by reacting an acid dianhydride with a diamine. Furthermore, in order to have a crosslinked structure in a chemically covalently bonded state, as shown in the z-side structural unit of Chemical Formula 2, it must have a structure of a polyimide copolymer derived from a diamine compound having a functional group such as carboxylic acid.
- the thermally converting polybenzoxazole has a functional group such as a hydroxyl group at the ortho-position of the aromatic imide linkage attacking the carbonyl group of the imide ring to form an intermediate of the carboxy-benzoxazole structure. It is synthesize
- the heat conversion poly (benzoxazole-imide) copolymer synthesized in this way is too hard to be broken when manufactured into a membrane when the content of the benzoxazole group in the copolymer polymer chain is 80% or more, and mechanical properties The amount of CO 2 is released during the heat conversion process, or the shrinkage of the membrane area may occur, and thus the gas permeability and selectivity of the large-area membrane may be reduced. Therefore, the present invention provides benzoxazole in the copolymer polymer chain. Another technical feature is to lower the content of groups to less than 80%, more preferably to less than 50%.
- cross-linked heat conversion poly (benzox) having a repeating unit represented by the formula (2) having a content of the benzoxazole group in the copolymer polymer chain is less than 80% through a multi-step synthetic route as follows Sol-imide) copolymer is prepared.
- step II reacting the polyimide copolymer of step I) with a diol to synthesize a monoesterified ortho-hydroxy polyimide copolymer;
- Ar 1 is an aromatic ring group selected from a substituted or unsubstituted tetravalent C6-C24 arylene group and a substituted or unsubstituted tetravalent C4-C24 heterocyclic group, and the aromatic ring
- the groups are present alone; at least two form a condensed ring with each other; at least two are single bonds, O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 or CO-NH)
- any acid dianhydride may be used without limitation as long as it is defined in Formula 3, but considering the fact that the thermal and chemical properties of the synthesized polyimide can be further improved. It is preferable to use 4,4'-hexafluoroisopropylidene phthalic anhydride (6FDA) which has.
- 6FDA 4,4'-hexafluoroisopropylidene phthalic anhydride
- the ortho-hydroxy polyimide in order to have a poly (benzoxazole-imide) copolymer structure, can be introduced by thermal conversion of ortho-hydroxy polyimide.
- the compound represented by General formula (2) is used as an ortho-hydroxy diamine.
- Q is a single bond; O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 , CO-NH, C (CH 3 ) (CF 3 ), or a substituted or unsubstituted phenylene group)
- any one can be used without limitation as long as it is defined in Formula 2, but it is more preferable to use 3,3-dihydroxybenzidine (HAB) which is easy to react.
- HAB 3,3-dihydroxybenzidine
- a polyimide structural unit is introduced into the copolymer by reacting with the acid dianhydride of the general formula (3).
- Ar 2 is an aromatic ring group selected from a substituted or unsubstituted divalent C6-C24 arylene group and a substituted or unsubstituted divalent C4-C24 heterocyclic group, the aromatic ring
- the groups are present alone; at least two form a condensed ring with each other; at least two are single bonds, O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 or CO-NH)
- aromatic diamine any one as defined in the general formula (4) can be used without limitation, but the lower the cost, the lower the cost of the entire process during mass production is preferred, 2,4,6-trimethyl-phenylenediamine (DAM ) Can be used more preferably.
- DAM 2,4,6-trimethyl-phenylenediamine
- step I) the acid dianhydride of Formula 3, ortho-hydroxy diamine of Formula 2, and the aromatic diamine of Formula 4 and 3, 5-diaminobenzoic acid (DABA) react together together as a comonomer
- Terpolymers having repeating units consisting of -hydroxy polyimide structural units-polyimide structural units-carboxylic acid-containing polyimide structural units can be synthesized and thus thermally converted to polybenzoxazoles by a later heat treatment process
- the content of ortho-hydroxy polyimide structural units can be controlled to less than 80%.
- step I) the acid dianhydride of Formula 3, ortho-hydroxy diamine of Formula 2, aromatic diamine of Formula 4, and 3, 5-diaminobenzoic acid (DABA) are N-methylpyrrolidone
- organic solvent such as (NMP)
- ortho-hydroxy polyimide aerial having a carboxylic acid represented by the following structural formula 2 by azeotropic thermal imidization Synthesize the coalesce.
- the azeotropic thermal imidization method adds toluene or xylene to the polyamic acid solution and stirs it to perform an imidization reaction at 180 to 200 ° C. for 6 to 12 hours, during which the water released while the imide ring is generated. Is separated as an azeotrope of toluene or xylene.
- step I) the polyimide copolymer of step I) and the diol are reacted to synthesize a monoesterified ortho-hydroxy polyimide copolymer represented by Structural Formula 3 below.
- the diol is any one selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and benzenedimethanol 1,4-butylene glycol is more preferred, but is not limited thereto.
- step II is carried out at a temperature of 18 to 140-160 °C an excess of diol corresponding to at least 50 times the carboxylic acid equivalent contained in the polyimide copolymer represented by the formula (2) under a para-toluenesulfonic acid catalyst Reaction for ⁇ 24 hours.
- the monoesterified ortho-hydroxy polyimide copolymer of step II) represented by Structural Formula 3 above has an crosslinked structure represented by the following Structural Formula 4 by transesterification crosslinking reaction. Synthesize the coalesce.
- heat treatment is performed under vacuum at 200 to 250 ° C. for 18 to 24 hours.
- the heat-converting poly (benzoxazole) having a crosslinked structure represented by Chemical Formula 2, which is a final target, by thermally converting the ortho-hydroxy polyimide copolymer having the crosslinked structure of step III) represented by Structural Formula 4 above -Imide) copolymer is prepared.
- the thermal conversion is completed by raising the temperature up to 350 ⁇ 450 °C at a temperature rising rate of 1 ⁇ 20 °C / min in a high-purity inert gas atmosphere and then maintained isothermal for 0.1 to 3 hours.
- a copolymer in the form of a film is obtained during the manufacturing process including the steps I) to IV), thereby having a repeating unit represented by the formula (2), a thermally converting poly (benzoxa) having a crosslinked structure.
- a gas separation membrane (except for the flue gas separation membrane) including a sol-imide copolymer is provided.
- the present invention includes a cross-linked thermally converting poly (benzoxazole-imide) copolymer having a repeating unit represented by Chemical Formula 2 by only heat treatment without undergoing a chemical process or a complicated process such as UV irradiation.
- Another technical feature is a method for producing a gas separation membrane (except the flue gas separation membrane).
- an acid dianhydride, an ortho-hydroxy diamine and a comonomer are reacted with an aromatic diamine, 3, 5-diaminobenzoic acid to obtain a polyamic acid solution, followed by azeotropic thermal imidization.
- step b) forming an ortho-hydroxy polyimide copolymer having a carboxylic acid synthesized in step a) in an organic solvent and casting the film;
- a gas separation membrane comprising a cross-linked thermally converting poly (benzoxazole-imide) copolymer having a repeating unit represented by Chemical Formula 2, including the step of heat-treating the membrane obtained in step b). , Except for flue gas separation membranes).
- Ar 1 is an aromatic ring group selected from a substituted or unsubstituted tetravalent C6-C24 arylene group and a substituted or unsubstituted tetravalent C4-C24 heterocyclic group, and the aromatic ring
- the groups are present alone; at least two form a condensed ring with each other; at least two are single bonds, O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 or CO-NH)
- any acid dianhydride may be used without limitation as long as it is defined in Formula 3, but considering the fact that the thermal and chemical properties of the synthesized polyimide can be further improved. It is preferable to use 4,4'-hexafluoroisopropylidene phthalic anhydride (6FDA) which has.
- 6FDA 4,4'-hexafluoroisopropylidene phthalic anhydride
- the ortho-hydroxy polyimide in order to have a poly (benzoxazole-imide) copolymer structure, can be introduced by thermal conversion of ortho-hydroxy polyimide.
- the compound represented by following General formula (2) is used as an ortho-hydroxy diamine.
- Q is a single bond; O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 , CO-NH, C (CH 3 ) (CF 3 ), or a substituted or unsubstituted phenylene group)
- any one can be used without limitation as long as it is defined in Formula 2, but it is more preferable to use 3,3-dihydroxybenzidine (HAB) which is easy to react.
- HAB 3,3-dihydroxybenzidine
- a polyimide structural unit is introduced into the copolymer by reacting with the acid dianhydride of the general formula (3).
- Ar 2 is an aromatic ring group selected from a substituted or unsubstituted divalent C6-C24 arylene group and a substituted or unsubstituted divalent C4-C24 heterocyclic group, the aromatic ring
- the groups are present alone; at least two form a condensed ring with each other; at least two are single bonds, O, S, CO, SO 2 , Si (CH 3 ) 2 , (CH 2 ) p (1 ⁇ P ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C (CH 3 ) 2 , C (CF 3 ) 2 or CO-NH)
- aromatic diamine any one as defined in the general formula (4) can be used without limitation, but the lower the cost, the lower the cost of the entire process during mass production is preferred, 2,4,6-trimethyl-phenylenediamine (DAM ) Can be used more preferably.
- DAM 2,4,6-trimethyl-phenylenediamine
- a functional group such as carboxylic acid in the repeating unit in order to have a crosslinked structure between the polymer chains by only a simple heat treatment step without undergoing a complicated process such as chemical crosslinking or UV irradiation, and as another comonomer
- DABA 3, 5-diaminobenzoic acid
- another polyimide structural unit having a carboxylic acid in the copolymer is introduced by reacting with the acid dianhydride of the general formula (3).
- step a) the acid dianhydride of formula 3, ortho-hydroxy diamine of formula 2, and the aromatic diamine of formula 4 and 3, 5-diaminobenzoic acid (DABA) react together together as a comonomer
- DABA 5-diaminobenzoic acid
- Terpolymers having repeating units consisting of -hydroxy polyimide structural units-polyimide structural units-carboxylic acid-containing polyimide structural units can be synthesized and thus thermally converted to polybenzoxazoles by a later heat treatment process
- the content of ortho-hydroxy polyimide structural units can be controlled to less than 80%.
- step a) the acid dianhydride of Formula 3, ortho-hydroxy diamine of Formula 2, aromatic diamine of Formula 4, and 3, 5-diaminobenzoic acid (DABA) are N-methylpyrrolidone
- an organic solvent such as (NMP)
- ortho-hydroxy polyimide aerial having a carboxylic acid represented by the following structural formula 2 by azeotropic thermal imidization Synthesize the coalesce.
- the azeotropic thermal imidization method adds toluene or xylene to the polyamic acid solution and stirs it to perform an imidization reaction at 180 to 200 ° C. for 6 to 12 hours, during which the water released while the imide ring is generated. Is separated as an azeotrope of toluene or xylene.
- step b) the polymer solution obtained by dissolving the ortho-hydroxy polyimide copolymer having the carboxylic acid of step a) represented by Formula 2 in an organic solvent such as N-methylpyrrolidone (NMP)
- NMP N-methylpyrrolidone
- the gas separation membrane comprising a cross-linked heat-converting poly (benzoxazole-imide) copolymer having a repeating unit represented by the formula (2) as a final target by only heat-treating the membrane obtained in step b) , Except for flue gas separation membranes).
- the heat treatment is completed by increasing the temperature up to 350 ⁇ 450 °C at a temperature rising rate of 1 ⁇ 20 °C / min in a high-purity inert gas atmosphere, and then isothermally maintained for 0.1 to 3 hours.
- the heat-converting poly (benzoxazole-imide) copolymer membrane having a crosslinking structure for gas separation according to the present invention (except for the flue gas separation membrane), and the content of the benzoxazole group in the copolymer polymer chain
- the defect-free films obtained from the film forming examples 1 to 6 were cut into 3 cm x 3 cm sizes and placed between quartz plates to prevent deformation of the film due to temperature rise in muffle.
- the sample was heated up to 450 ° C. at an elevated temperature rate of 5 ° C./min in a high purity argon gas atmosphere, and then kept isothermal for 1 hour.
- HPIMPD-5 obtained from Reference Example 2 was heat-treated in the same manner as in Example 1 to prepare a thermally converting poly (benzoxazole-imide) copolymer membrane having no crosslinked structure, which was named PBOMPD-5.
- the obtained copolymer solution was cooled to room temperature, immersed in a distillation shoe, washed several times to remove unreacted 1,4-butylene glycol, and dried in a vacuum oven at 70 ° C. for 24 hours.
- mono-esterified ortho-hydroxy polyimide copolymer represented by the formula (6) was synthesized.
- the monoesterified ortho-hydroxy polyimide copolymer obtained from Synthesis Examples 12 to 16 was dissolved in NMP to prepare a 15 wt% solution and then cast on a glass plate. It was placed in a vacuum oven and slowly heated up to 250 ° C. while maintaining at 100 ° C., 150 ° C., 200 ° C. and 250 ° C. for one hour to evaporate NMP. Subsequently, a transesterification crosslinking reaction was performed by heat-treating the copolymer film at 250 ° C. for 24 hours in a vacuum atmosphere to synthesize an ortho-hydroxy polyimide copolymer having a crosslinked structure represented by the following Formula 7.
- the defect-free films obtained from Synthesis Examples 17 to 21 were cut into 3 cm x 3 cm size and placed between quartz plates to prevent deformation of the film due to temperature rise in muffle.
- the sample was heated up to 450 ° C. at an elevated temperature rate of 5 ° C./min in a high purity argon gas atmosphere, and then kept isothermal for 1 hour. After the heat treatment, the muffle was slowly cooled to room temperature at a cooling rate of less than 10 ° C / min to prepare a heat-converting poly (benzoxazole-imide) copolymer having a crosslinked structure represented by the formula (8).
- An ortho-hydroxy polyimide copolymer having a carboxylic acid synthesized from Synthesis Examples 7 to 11 was dissolved in NMP to prepare a 15 wt% solution and then cast on a glass plate. It was placed in a vacuum oven and kept at 100 ° C., 150 ° C. and 200 ° C. for 1 hour, respectively, while evaporating and drying the residual NMP to obtain an ortho-hydroxy polyimide copolymer membrane having carboxylic acid, which was then used in Examples 7 to 7.
- the heat conversion poly (benzoxazole-imide) copolymer (membrane) which has a crosslinked structure was manufactured by heat processing by the method similar to 11.
- FIG. 1 shows 1 H- of an ortho-hydroxy polyimide copolymer having a carboxylic acid synthesized from Synthesis Example 4 among the synthesis examples of the ortho-hydroxy polyimide copolymer having a carboxylic acid according to the present invention. NMR spectrum is shown. It can be seen from the characteristic peaks of hydrogen in the repeating unit that can be confirmed from the 1 H-NMR spectrum of FIG. 1 that an ortho-hydroxy polyimide copolymer having a carboxylic acid was synthesized.
- FIG. 2 shows ATR-FTIR spectra of HPIDABA-15, HPIDABA-20 and HPIDABA-25 obtained according to Film Formation Examples 4 to 6 among the film forming examples of the ortho-hydroxy polyimide copolymer film having a carboxylic acid according to the present invention. Indicated. As shown in FIG.
- FIG. 3 shows a crosslinked structure by only heat treatment according to the preparation method of Examples 2 to 6 of the present invention, and a heat-converted poly (benzoxazole-imide) copolymer membrane and a conventional polybenzoxazole membrane ( PBO) shows the ATR-FTIR spectrum.
- the absorption band inherent in the imide group was also found, and the thermal stability of the aromatic imide linkage was confirmed even at the heat treatment temperature of 450 ° C.
- Table 2 shows the density and the interplanar spacing ( d- spacing) of the samples prepared according to Example 1 to 6, Examples 1 to 6, Reference Example 2 and Comparative Example 1, Examples 1 to 6
- the interplanar distance of the thermally converted poly (benzoxazole-imide) copolymer film having a crosslinking structure according to the present invention is 0.62 to 0.67 nm, and the interplanar distance of the hydroxy polyimide copolymer film before thermal conversion according to film forming examples 1 to 6 0.54 to 0.57 nm), the interplanar distance (0.53 nm) of the hydroxy polyimide copolymer membrane before thermal conversion without DABA according to Reference Example 2, and the heat-converted poly (benz) having no crosslinking structure according to Comparative Example 1 Longer than the interplanar distance (0.59 nm) of the oxazole-imide) copolymer membrane, it can be easily seen that the average interchain distance was significantly increased, which is a function of the heat-converted poly (benzoxazo
- the crosslinked heat conversion poly (benzoxazole-imide) copolymer membrane prepared according to the present invention has a structure in which the polymer chain is less packed and has more space, so that small molecules can permeate and diffuse. There is enough room to be used as a gas separation membrane.
- PBODABA-5, PBODABA-10, PBODABA-15, PBODABA- in a thermally converting poly (benzoxazole-imide) copolymer membrane PBODABA-Y having a crosslinked structure prepared according to Examples 1 to 6 of the present invention.
- the analyzer (PALS: positron annihilation lifetime spectroscopy) was used and the results are shown in Table 4.
- the thermally converting poly (benzoxazole-imide) copolymer membrane PBODABA-Y having a crosslinked structure prepared according to an embodiment of the present invention has two o-Ps components, ⁇ 3 and ⁇ 4 , which means that there are two kinds of pores in the membrane.
- Permeability and selectivity of the thermally converting poly (benzoxazole-imide) copolymer membrane PBODABA-Y having a crosslinked structure prepared according to Examples 1 to 6 of the present invention from Tables 5 and 6 were prepared according to Comparative Example 1. It can be seen that the overall permeability and selectivity of the thermally converting poly (benzoxazole-imide) copolymer membrane PBOMPD-5 having no crosslinked structure. It is generally known that the gas permeation properties of glassy polymers depend on the distribution and size of the free volume element, which demonstrates that the permeability coefficients of the PBODABA-Y membranes are greater than the permeability coefficients of the PBOMPD-5 membranes. This is consistent with the result with pores of size.
- the PBODABA-Y membrane of the present invention was excellent in permeability and selectivity at the same time to overcome the trade-off relationship of general permeability-selectivity.
- the CO 2 / CH 4 mixed gas maintains a high selectivity even though the permeability of CO 2 reaches 615 barrer.
- a gas separation crosslinking structure is obtained by merely heat treating a hydroxy polyimide copolymer membrane having a carboxylic acid without undergoing a chemical process for forming a crosslinking structure and a complicated process such as UV irradiation. It is possible to prepare a heat conversion poly (benzoxazole-imide) membrane having, and the gas separation membrane thus prepared is not only excellent in permeability and selectivity, but also a simple manufacturing process is commercialized by mass production.
- FIG. 6 shows the ATR-FTIR spectrum of the poly (benzoxazole-imide) membrane obtained by thermally converting the copolymer obtained from Synthesis Example 17 according to various heat treatment temperatures. As shown in FIG. 6, as the heat treatment temperature is increased from 375 ° C. to 450 ° C., a wide range of stretching vibration peaks due to OH of hydroxypolyimide gradually disappears from 3580 cm ⁇ 1 to polybenzoxazole. It can be seen that the heat conversion process proceeds.
- the heat treatment process for the heat conversion from hydroxy polyimide to polybenzoxazole according to the present invention is preferably carried out at 350 ⁇ 450 °C, preferably at 375 ⁇ 450 °C.
- Table 7 shows the interplanar distance ( d- spacing) and the density of the samples prepared according to Examples 7 to 16 and Comparative Examples 2 and 3.
- Example 7 6.67 1.38
- Example 8 6.74 1.40
- Example 9 6.79 1.40
- Example 10 6.70 1.42
- Example 11 6.72 1.43
- Example 12 6.52 1.40
- Example 13 6.57 1.41
- Example 14 6.39 1.39
- Example 15 6.53 1.38
- Example 16 6.55 1.40 Comparative Example 2 6.37 1.41 Comparative Example 3 6.20 1.43
- the interplanar distances of the heat-converted poly (benzoxazole-imide) copolymers having a crosslinked structure according to Examples 7 to 11 and Examples 12 to 16 were 6.67-6.67 kPa and 6.39-6.67 mm, respectively.
- the crosslinked heat conversion poly (benzoxazole-imide) copolymer prepared according to the present invention has a structure in which the polymer chain is less packed and has more space, so that small molecules can permeate and diffuse. There is enough room to be used as a gas separation membrane.
- Table 8 shows the mechanical properties and thermal properties of the samples prepared according to Examples 7 to 16 and Comparative Examples 2 and 3 and the shrinkage of the film area in the heat conversion process.
- the samples prepared according to Examples 7 to 16 of the present invention are more than four times higher in tensile strength and four times higher in mechanical properties than the samples prepared according to Comparative Examples 2 and 3. It can be seen that excellent.
- the shrinkage ratio of the film area involved in the heat conversion step is also expected to reduce the Examples 7 to 16 compared to Comparative Examples 2 and 3, it is expected that the large-area film can be produced.
- the heat conversion poly (benzoxazole-imide) copolymer having a crosslinked structure prepared according to the present invention is an ortho-hydroxy polyimide structural unit-polyimide structural unit-carboxylic acid-containing polyimide structural unit.
- the content of the benzoxazole group in the polymer chain of the thermally-converting poly (benzoxazole-imide) copolymer having a crosslinked structure, which is derived from a terpolymer having a repeating unit, is lower than 80%, ortho- Aromatic diamine-derived polyimides having a crosslinked structure and a heat-converting poly (benzoxazole-imide) copolymer having no crosslinking structure derived from a binary copolymer having a repeating unit consisting of a hydroxy polyimide structural unit-polyimide structural unit No amide structural unit, and the content of benzoxazole groups in the polymer chain of the thermally converting poly (benzoxazole-imide) copolymer Compared with a high copolymer, it is excellent in mechanical physical property and shrinkage rate of a film area falls.
- Table 9 shows the results of measuring the permeability of various gases in order to confirm the gas separation performance of the samples prepared according to Examples 7 to 16 of the present invention and the samples prepared according to Comparative Examples 2 and 3.
- the gas permeability of the heat-converting poly (benzoxazole-imide) copolymer membrane having a crosslinked structure prepared according to Examples 7 to 11 of the present invention from Table 9 is shown in the heat-converting poly (benz) prepared according to Comparative Examples 2 and 3. Compared to the gas permeability of the oxazole-imide) copolymer membrane, it can be seen that the value is high in almost all gases.
- the gas separation performance from the CO 2 / CH 4, CO 2 / N 2 mixed gas using the gas separation membrane according to Examples 7 to 11 in Figures 7 and 8 , Examples 12 to 16 in Figures 9 and 10 are compared with the commercial gas separation membrane, the CO 2 permeability significantly nopeumyeonseo also, the selection of the CO 2 to CH 4 also does not fall even in comparison to the membrane selectivity of CO 2, some commercialized for and N 2, a cross-linked structure prepared according to examples 7 to 16 of the present invention It can be seen that the thermally-converted poly (benzoxazole-imide) copolymer membrane having a high permeability and selectivity at the same time has excellent gas separation performance.
- a gas separation membrane comprising a heat-converting poly (benzoxazole-imide) copolymer having a novel crosslinking structure having a content of benzoxazole group in the copolymer polymer chain of less than 80% (but flue gas) Separation membrane is excluded) is excellent in mechanical properties and thermal properties, the shrinkage of the membrane area is reduced, the gas permeability and selectivity at the same time has excellent gas separation performance.
- thermal conversion poly (benzoxazole) having a novel crosslinked structure having a content of benzoxazole groups in the copolymer polymer chain of less than 80% by only heat treatment without undergoing complicated processes such as chemical methods and UV irradiation to form a crosslinked structure. Since the gas separation membrane including -imide) copolymer can be prepared, the manufacturing process is simple and economical, and commercialization by mass production is possible.
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Abstract
Description
합성예 | HAB | DAM | DABA | x | y | z |
합성예 8 | 5.0 | 4.0 | 1.0 | 0.5 | 0.4 | 0.1 |
합성예 9 | 5.0 | 3.0 | 2.0 | 0.5 | 0.3 | 0.2 |
합성예 10 | 4.5 | 5.0 | 0.5 | 0.45 | 0.5 | 0.05 |
합성예 11 | 4.0 | 5.5 | 0.5 | 0.4 | 0.55 | 0.05 |
샘플 | 밀도(g/cm3) | d-spacing(nm) |
HPIDABA-2.5 | 1.51 | 0.54 |
HPIDABA-5 | 1.52 | 0.55 |
HPIDABA-10 | 1.51 | 0.55 |
HPIDABA-15 | 1.51 | 0.54 |
HPIDABA-20 | 1.52 | 0.57 |
HPIDABA-25 | 1.50 | 0.55 |
PBODABA-2.5 | 1.41 | 0.62 |
PBODABA-5 | 1.42 | 0.62 |
PBODABA-10 | 1.40 | 0.66 |
PBODABA-15 | 1.38 | 0.67 |
PBODABA-20 | 1.38 | 0.66 |
PBODABA-25 | 1.43 | 0.65 |
HPIMPD-5 | 1.50 | 0.53 |
PBOMPD-5 | 1.45 | 0.59 |
샘플 | Tga(℃) | TTR b(℃) | DABA CO2 중량감소c(%) | 열전환 공정 CO2 중량감소d(%) | 전체 CO2 중량감소d(%) | 전체 CO2 중량감소e(%) |
HPI | 300 | 407 | - | 11.36 | 11.36 | 11.25 |
HPIDABA-2.5 | 308 | 410 | 0.20 | 11.08 | 11.28 | 11.04 |
HPIDABA-5 | 305 | 417 | 0.39 | 10.79 | 11.18 | 11.04 |
HPIDABA-10 | 313 | 426 | 0.78 | 10.22 | 11.00 | 8.98 |
HPIDABA-15 | 314 | 430 | 1.18 | 9.66 | 10.84 | 8.87 |
HPIDABA-20 | 314 | 423 | 1.57 | 9.09 | 10.66 | 9.98 |
HPIDABA-25 | 300 | 429 | 1.96 | 8.52 | 10.48 | 8.80 |
HPIMPD-5 | 280 | 400 | - | 10.79 | 10.79 | 10.78 |
샘플 | τ3 (ns) | I3 (%) | τ4 (ns) | I4 (%) | 기공직경d3(Å) | 기공직경d4(Å) |
PBOMPD-5 | 1.118±0.144 | 7.223±0.936 | 3.750±0.046 | 12.987±0.369 | 3.69±0.86 | 8.20±0.11 |
PBODABA-5 | 1.097±0.112 | 7.040±0.813 | 4.034±0.041 | 12.316±0.746 | 3.63±0.68 | 8.52±0.09 |
PBODABA-10 | 1.073±0.054 | 6.165±0.416 | 4.146±0.030 | 10.342±0.097 | 3.55±0.33 | 8.64±0.06 |
PBODABA-15 | 1.194±0.053 | 6.655±0.733 | 4.332±0.011 | 11.942±0.387 | 3.91±0.30 | 8.84±0.02 |
PBODABA-20 | 1.155±0.107 | 6.689±0.770 | 4.198±0.056 | 10.919±0.332 | 3.80±0.62 | 8.69±0.12 |
PBODABA-25 | 1.205±0.121 | 6.257±0.875 | 3.987±0.037 | 11.887±0.375 | 3.94±0.67 | 8.47±0.08 |
샘플 | d-spacing(Å) | 밀도(g/cm3) |
실시예 7 | 6.67 | 1.38 |
실시예 8 | 6.74 | 1.40 |
실시예 9 | 6.79 | 1.40 |
실시예 10 | 6.70 | 1.42 |
실시예 11 | 6.72 | 1.43 |
실시예 12 | 6.52 | 1.40 |
실시예 13 | 6.57 | 1.41 |
실시예 14 | 6.39 | 1.39 |
실시예 15 | 6.53 | 1.38 |
실시예 16 | 6.55 | 1.40 |
비교예 2 | 6.37 | 1.41 |
비교예 3 | 6.20 | 1.43 |
샘플 | 인장강도(Mpa) | 연신율(%) | 수축률(%) | TTR a(℃) | Tgb(℃) |
실시예 7 | 98 | 20 | 13 | 407 | 398 |
실시예 8 | 106 | 22 | 12 | 426 | 402 |
실시예 9 | 107 | 22 | 11 | 430 | 405 |
실시예 10 | 79 | 16 | 12 | 412 | 402 |
실시예 11 | 98 | 20 | 12 | 415 | 410 |
실시예 12 | 99 | 24 | 15 | 413 | 398 |
실시예 13 | 96 | 21 | 12 | 430 | 405 |
실시예 14 | 90 | 19 | 11 | 435 | 410 |
실시예 15 | 94 | 20 | 12 | 420 | 390 |
실시예 16 | 100 | 18 | 12 | 423 | 388 |
비교예 2 | 38 | 6 | 16 | 445 | 385 |
비교예 3 | 45 | 5 | 20 | 412 | 305 |
Claims (31)
- i) 산이무수물, 오르쏘-히드록시 디아민 및 공단량체로서 3, 5-디아미노벤조산을 반응시켜 폴리아믹산 용액을 얻은 후, 공비 열 이미드화법에 의하여 카르복실산을 갖는 오르쏘-히드록시 폴리이미드 공중합체를 합성하는 단계;ii) 상기 i) 단계에서 합성한 카르복실산을 갖는 오르쏘-히드록시 폴리이미드공중합체를 유기용매에 녹이고 캐스팅하여 제막하는 단계; 및iii) 상기 ii) 단계에서 얻어진 막을 열처리하는 단계;를 포함하는 기체분리용가교구조를 갖는 열전환 폴리(벤즈옥사졸-이미드) 공중합체 막(단, 배연가스 분리용 막은 제외한다)의 제조방법.
- 제1항에 있어서, 상기 i) 단계의 산이무수물은 하기 일반식 1로 표시되는 것을 특징으로 하는 기체분리용 가교구조를 갖는 열전환 폴리(벤즈옥사졸-이미드) 공중합체 막의 제조방법.<일반식 1>(상기 일반식 1에서, Ar은 치환 또는 비치환된 4가의 탄소수 6 내지 24의 아릴렌기 및 치환 또는 비치환된 4가의 탄소수 4 내지 24의 복소환기에서 선택되는 방향족 고리기이고, 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 축합 고리를 형성하거나; 2개 이상이 단일결합, O, S, CO, SO2, Si(CH3)2, (CH2)p (1≤P≤10), (CF2)q (1≤q≤10), C(CH3)2, C(CF3)2 또는 CO-NH로 연결되어 있다)
- 제1항에 있어서, 상기 i) 단계의 공비 열 이미드화법은 폴리아믹산 용액에 톨루엔 또는 자일렌을 첨가하고 교반하여 180~200℃에서 6~12시간 동안 이미드화 반응을 수행하는 것을 특징으로 하는 기체분리용 가교구조를 갖는 열전환 폴리(벤즈옥사졸-이미드) 공중합체 막의 제조방법.
- 제1항에 있어서, 상기 iii) 단계의 열처리는 고순도의 불활성 가스 분위기에서 1~20℃/min의 승온 속도로 350~450℃까지 승온한 후 0.1~3시간 동안 등온 상태를 유지함으로써 수행되는 것을 특징으로 하는 기체분리용 가교구조를 갖는 열전환 폴리(벤즈옥사졸-이미드) 공중합체 막의 제조방법.
- 제1항 내지 제5항 중 어느 한 항의 제조방법에 의하여 제조된 기체분리용 가교구조를 갖는 열전환 폴리(벤즈옥사졸-이미드) 공중합체 막(단, 배연가스 분리용 막은 제외한다).
- 제6항에 있어서, 상기 막은 하기 화학식 1로 표시되는 반복단위를 갖는 것을 특징으로 하는 기체분리용 가교구조를 갖는 열전환 폴리(벤즈옥사졸-이미드) 공중합체 막.<화학식 1>(상기 화학식 1에서, Ar은 치환 또는 비치환된 4가의 탄소수 6 내지 24의 아릴렌기 및 치환 또는 비치환된 4가의 탄소수 4 내지 24의 복소환기에서 선택되는 방향족 고리기이고, 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 축합 고리를 형성하거나; 2개 이상이 단일결합, O, S, CO, SO2, Si(CH3)2, (CH2)p (1≤P≤10), (CF2)q (1≤q≤10), C(CH3)2, C(CF3)2 또는 CO-NH로 연결되어 있고,Q는 단일결합이거나; O, S, CO, SO2, Si(CH3)2, (CH2)p (1≤P≤10), (CF2)q (1≤q≤10), C(CH3)2, C(CF3)2, CO-NH, C(CH3)(CF3), 또는 치환 또는 비치환된 페닐렌기이며,x, y는 각각 반복단위 내 몰분율로서 0.75≤x≤0.975, 0.025≤y≤0.25 이고, x+y=1 이다)
- 제7항에 있어서, 상기 막은 면간 거리(d-spacing)가 0.62~0.67 nm인 것을 특징으로 하는 기체분리용 가교구조를 갖는 열전환 폴리(벤즈옥사졸-이미드) 공중합체막.
- 제7항에 있어서, 상기 막은 밀도가 1.38~1.43 g/cm3인 것을 특징으로 하는 기체분리용 가교구조를 갖는 열전환 폴리(벤즈옥사졸-이미드) 공중합체 막.
- 제7항에 있어서, 상기 막은 d3 평균 기공 직경이 4.0 Å이고, d4 평균 기공 직경이 8.6 Å인 것을 특징으로 하는 기체분리용 가교구조를 갖는 열전환 폴리(벤즈옥사졸-이미드) 공중합체 막.
- 하기 화학식 2로 표시되는 반복단위를 갖는, 가교구조의 열전환 폴리(벤즈옥사졸-이미드) 공중합체.<화학식 2>(상기 화학식 2에서, Ar1은 치환 또는 비치환된 4가의 탄소수 6 내지 24의 아릴렌기 및 치환 또는 비치환된 4가의 탄소수 4 내지 24의 복소환기에서 선택되는 방향족 고리기이고, 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 축합 고리를 형성하거나; 2개 이상이 단일결합, O, S, CO, SO2, Si(CH3)2, (CH2)p (1≤P≤10), (CF2)q (1≤q≤10), C(CH3)2, C(CF3)2 또는 CO-NH로 연결되어 있고,Q는 단일결합이거나; O, S, CO, SO2, Si(CH3)2, (CH2)p (1≤P≤10), (CF2)q (1≤q≤10), C(CH3)2, C(CF3)2, CO-NH, C(CH3)(CF3), 또는 치환 또는 비치환된 페닐렌기이며,Ar2는 치환 또는 비치환된 2가의 탄소수 6 내지 24의 아릴렌기 및 치환 또는 비치환된 2가의 탄소수 4 내지 24의 복소환기에서 선택되는 방향족 고리기이고, 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 축합 고리를 형성하거나; 2개 이상이 단일결합, O, S, CO, SO2, Si(CH3)2, (CH2)p (1≤P≤10), (CF2)q (1≤q≤10), C(CH3)2, C(CF3)2 또는 CO-NH로 연결되어 있고,x, y, z는 각각 반복단위 내 몰분율로서 x<0.8 이고, x+y+z=1 이며, x, y 또는 z=0 인 경우는 없다)
- 제11항에 있어서, 상기 공중합체는 면간 거리(d-spacing)가 6.67~6.79 Å인 것을 특징으로 하는 가교구조의 열전환 폴리(벤즈옥사졸-이미드) 공중합체.
- 제11항에 있어서, 상기 공중합체는 밀도가 1.38~1.43 g/cm3인 것을 특징으로 하는 가교구조의 열전환 폴리(벤즈옥사졸-이미드) 공중합체.
- I) 산이무수물, 오르쏘-히드록시 디아민 및 공단량체로서 방향족 디아민, 3, 5-디아미노벤조산을 반응시켜 폴리아믹산 용액을 얻은 후, 공비 열 이미드화법에 의하여 카르복실산을 갖는 오르쏘-히드록시 폴리이미드 공중합체를 합성하는 단계;II) 상기 I) 단계의 폴리이미드 공중합체와 디올을 반응시켜 모노에스테르화 오르쏘-히드록시 폴리이미드 공중합체를 합성하는 단계;III) 상기 II) 단계의 모노에스테르화 오르쏘-히드록시 폴리이미드 공중합체를 트랜스에스테르화 가교반응에 의하여 가교구조를 갖는 오르쏘-히드록시 폴리이미드 공중합체를 합성하는 단계; 및IV) 상기 III) 단계의 가교구조를 갖는 오르쏘-히드록시 폴리이미드 공중합체를 열전환 하는 단계;를 포함하는 제11항의 화학식 2로 표시되는 가교구조의 열전환 폴리(벤즈옥사졸-이미드) 공중합체의 제조방법.
- 제14항에 있어서, 상기 I) 단계의 산이무수물은 하기 일반식 3으로 표시되는 것을 특징으로 하는 제11항의 화학식 2로 표시되는 가교구조의 열전환 폴리(벤즈옥사졸-이미드) 공중합체의 제조방법.<일반식 3>(상기 일반식 3에서, Ar1은 치환 또는 비치환된 4가의 탄소수 6 내지 24의 아릴렌기 및 치환 또는 비치환된 4가의 탄소수 4 내지 24의 복소환기에서 선택되는 방향족 고리기이고, 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 축합 고리를 형성하거나; 2개 이상이 단일결합, O, S, CO, SO2, Si(CH3)2, (CH2)p (1≤P≤10), (CF2)q (1≤q≤10), C(CH3)2, C(CF3)2 또는 CO-NH로 연결되어 있다)
- 제14항에 있어서, 상기 I) 단계의 방향족 디아민은 하기 일반식 4로 표시되는 것을 특징으로 하는 제11항의 화학식 2로 표시되는 가교구조의 열전환 폴리(벤즈옥사졸-이미드) 공중합체의 제조방법.<일반식 4>(상기 일반식 4에서, Ar2는 치환 또는 비치환된 2가의 탄소수 6 내지 24의 아릴렌기 및 치환 또는 비치환된 2가의 탄소수 4 내지 24의 복소환기에서 선택되는 방향족 고리기이고, 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 축합 고리를 형성하거나; 2개 이상이 단일결합, O, S, CO, SO2, Si(CH3)2, (CH2)p (1≤P≤10), (CF2)q (1≤q≤10), C(CH3)2, C(CF3)2 또는 CO-NH로 연결되어 있다)
- 제14항에 있어서, 상기 I) 단계의 공비 열 이미드화법은 폴리아믹산 용액에 톨루엔 또는 자일렌을 첨가하고 교반하여 180~200℃에서 6~12시간 동안 이미드화 반응을 수행하는 것을 특징으로 하는 제11항의 화학식 2로 표시되는 가교구조의 열전환 폴리(벤즈옥사졸-이미드) 공중합체의 제조방법.
- 제14항에 있어서, 상기 II) 단계의 디올은 에틸렌글리콜, 프로필렌글리콜, 1,4-부틸렌글리콜, 1,3-프로판디올, 1,2-부탄디올, 1,3-부탄디올, 및 벤젠디메탄올로 이루어진 군으로부터 선택된 어느 하나의 것을 특징으로 하는 제11항의 화학식 2로 표시되는 가교구조의 열전환 폴리(벤즈옥사졸-이미드) 공중합체의 제조방법.
- 제14항에 있어서, 상기 II) 단계의 모노에스테르화는 파라-톨루엔술폰산 촉매하에서 I) 단계의 공중합체에 함유된 카르복실산 당량의 50배 이상에 해당하는 과량의 디올을 140~160℃에서 18~24시간 동안 반응시키는 것을 특징으로 하는 제11항의 화학식 2로 표시되는 가교구조의 열전환 폴리(벤즈옥사졸-이미드) 공중합체의 제조방법.
- 제14항에 있어서, 상기 III) 단계의 트랜스에스테르화 가교반응은 진공하에서 200~250℃, 18~24 시간 열처리함으로써 수행되는 것을 특징으로 하는 제11항의 화학식 2로 표시되는 가교구조의 열전환 폴리(벤즈옥사졸-이미드) 공중합체의 제조방법.
- 제14항에 있어서, 상기 IV) 단계의 열전환은 고순도의 불활성 가스 분위기에서 1~20℃/min의 승온 속도로 350~450℃까지 승온한 후 0.1~3시간 동안 등온 상태를 유지함으로써 수행되는 것을 특징으로 하는 제11항의 화학식 2로 표시되는 가교구조의 열전환 폴리(벤즈옥사졸-이미드) 공중합체의 제조방법.
- 제11항의 화학식 2로 표시되는 가교구조의 열전환 폴리(벤즈옥사졸-이미드) 공중합체를 포함하는 기체분리막(단, 배연가스 분리용 막은 제외한다).
- a) 산이무수물, 오르쏘-히드록시 디아민 및 공단량체로서 방향족 디아민, 3, 5-디아미노벤조산을 반응시켜 폴리아믹산 용액을 얻은 후, 공비 열 이미드화법에 의하여 카르복실산을 갖는 오르쏘-히드록시 폴리이미드 공중합체를 합성하는 단계;b) 상기 a) 단계에서 합성한 카르복실산을 갖는 오르쏘-히드록시 폴리이미드공중합체를 유기용매에 녹이고 캐스팅하여 제막하는 단계; 및c) 상기 b) 단계에서 얻어진 막을 열처리하는 단계;를 포함하는 제23항의 기체분리막(단, 배연가스 분리용 막은 제외한다)의 제조방법.
- 제24항에 있어서, 상기 a) 단계의 산이무수물은 하기 일반식 3으로 표시되는 것을 특징으로 하는 제23항의 기체분리막(단, 배연가스 분리용 막은 제외한다)의 제조방법.<일반식 3>(상기 일반식 3에서, Ar1은 치환 또는 비치환된 4가의 탄소수 6 내지 24의 아릴렌기 및 치환 또는 비치환된 4가의 탄소수 4 내지 24의 복소환기에서 선택되는 방향족 고리기이고, 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 축합 고리를 형성하거나; 2개 이상이 단일결합, O, S, CO, SO2, Si(CH3)2, (CH2)p (1≤P≤10), (CF2)q (1≤q≤10), C(CH3)2, C(CF3)2 또는 CO-NH로 연결되어 있다)
- 제24항에 있어서, 상기 a) 단계의 방향족 디아민은 하기 일반식 4로 표시되는 것을 특징으로 하는 제23항의 기체분리막(단, 배연가스 분리용 막은 제외한다)의 제조방법.<일반식 4>(상기 일반식 4에서, Ar2는 치환 또는 비치환된 2가의 탄소수 6 내지 24의 아릴렌기 및 치환 또는 비치환된 2가의 탄소수 4 내지 24의 복소환기에서 선택되는 방향족 고리기이고, 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 축합 고리를 형성하거나; 2개 이상이 단일결합, O, S, CO, SO2, Si(CH3)2, (CH2)p (1≤P≤10), (CF2)q (1≤q≤10), C(CH3)2, C(CF3)2 또는 CO-NH로 연결되어 있다)
- 제24항에 있어서, 상기 a) 단계의 공비 열 이미드화법은 폴리아믹산 용액에 톨루엔 또는 자일렌을 첨가하고 교반하여 180~200℃에서 6~12시간 동안 이미드화 반응을 수행하는 것을 특징으로 하는 제23항의 기체분리막(단, 배연가스 분리용 막은 제외한다)의 제조방법.
- 제24항에 있어서, 상기 c) 단계의 열처리는 고순도의 불활성 가스 분위기에서 1~20℃/min의 승온 속도로 350~450℃까지 승온한 후 0.1~3시간 동안 등온 상태를 유지함으로써 수행되는 것을 특징으로 하는 제23항의 기체분리막(단, 배연가스 분리용 막은 제외한다)의 제조방법.
- 제24항에 있어서, 상기 기체분리막(단, 배연가스 분리용 막은 제외한다)은 면간 거리(d-spacing)가 6.39~6.57 Å인 것을 특징으로 하는 제23항의 기체분리막(단, 배연가스 분리용 막은 제외한다)의 제조방법.
- 제24항에 있어서, 상기 기체분리막(단, 배연가스 분리용 막은 제외한다)은 밀도가 1.38~1.41 g/cm3인 것을 특징으로 하는 제23항의 기체분리막(단, 배연가스 분리용 막은 제외한다)의 제조방법.
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CA2930843A CA2930843C (en) | 2013-11-15 | 2014-11-05 | Crosslinked, thermally rearranged poly(benzoxazole-co-imide), gas separation membranes comprising the same and preparation method thereof |
CN201480062704.XA CN105899580B (zh) | 2013-11-15 | 2014-11-05 | 经交联、热重排的聚(苯并*唑-共-酰亚胺),包含其的气体分离膜以及其制备方法 |
US15/036,620 US10035109B2 (en) | 2013-11-15 | 2014-11-05 | Crosslinked, thermally rearranged poly(benzoxazole-co-imide), gas separation membranes comprising the same and preparation method thereof |
EP14861608.9A EP3070113A4 (en) | 2013-11-15 | 2014-11-05 | Thermally rearranged poly(benzoxazole-imide) copolymer having cross-linked structure, gas separation membrane comprising same and preparation method therefor |
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KR1020130139213A KR101599898B1 (ko) | 2013-11-15 | 2013-11-15 | 기체분리용 가교구조를 갖는 열전환 폴리(벤즈옥사졸-이미드) 막의 제조방법 및 그에 의하여 제조된 기체분리막 |
KR10-2013-0139215 | 2013-11-15 | ||
KR1020130139215A KR101772647B1 (ko) | 2013-11-15 | 2013-11-15 | 가교구조를 갖는 열전환 폴리(벤즈옥사졸-이미드) 공중합체, 이를 포함하는 기체분리막 및 그 제조방법 |
KR10-2013-0139213 | 2013-11-15 |
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US (1) | US10035109B2 (ko) |
EP (1) | EP3070113A4 (ko) |
CN (1) | CN105899580B (ko) |
CA (1) | CA2930843C (ko) |
WO (1) | WO2015072692A1 (ko) |
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CN105848768B (zh) * | 2013-11-15 | 2019-02-15 | 汉阳大学校产学协力团 | 包含经交联、热重排的聚(苯并*唑-共-酰亚胺)的用于烟道气分离的膜以及其制备方法 |
CN110591094B (zh) * | 2018-06-13 | 2020-11-20 | 北京大学 | 基于2,5-二烯丙氧基对苯二胺单体的聚苯并噁唑高分子材料及其制备方法 |
CN111764001B (zh) * | 2020-06-24 | 2021-06-29 | 东华大学 | 一种高强高模聚酰亚胺纤维的制备方法 |
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Also Published As
Publication number | Publication date |
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CN105899580A (zh) | 2016-08-24 |
CN105899580B (zh) | 2019-01-01 |
CA2930843C (en) | 2018-12-11 |
EP3070113A4 (en) | 2017-07-26 |
CA2930843A1 (en) | 2015-05-21 |
US20160271570A1 (en) | 2016-09-22 |
US10035109B2 (en) | 2018-07-31 |
EP3070113A1 (en) | 2016-09-21 |
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