WO2023022126A1 - Gas separation membrane - Google Patents
Gas separation membrane Download PDFInfo
- Publication number
- WO2023022126A1 WO2023022126A1 PCT/JP2022/030868 JP2022030868W WO2023022126A1 WO 2023022126 A1 WO2023022126 A1 WO 2023022126A1 JP 2022030868 W JP2022030868 W JP 2022030868W WO 2023022126 A1 WO2023022126 A1 WO 2023022126A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas separation
- separation membrane
- functional group
- silica nanoparticles
- chemical formula
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 171
- 238000000926 separation method Methods 0.000 title claims abstract description 135
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 142
- 239000002105 nanoparticle Substances 0.000 claims abstract description 117
- 239000002131 composite material Substances 0.000 claims abstract description 96
- 229920000642 polymer Polymers 0.000 claims abstract description 72
- 239000000126 substance Substances 0.000 claims abstract description 60
- 125000000524 functional group Chemical group 0.000 claims abstract description 43
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 42
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 125000000962 organic group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000001343 alkyl silanes Chemical group 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 206
- 230000035699 permeability Effects 0.000 description 88
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 238000005259 measurement Methods 0.000 description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 32
- 229910052760 oxygen Inorganic materials 0.000 description 32
- 239000001301 oxygen Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 27
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 21
- 239000010408 film Substances 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 239000011521 glass Substances 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- -1 polydimethylsiloxane Polymers 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000009210 therapy by ultrasound Methods 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 239000004642 Polyimide Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000004941 mixed matrix membrane Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 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 2
- OOSOZOSYULELHA-UHFFFAOYSA-N 1',1',2',2'-tetramethylspiro[1,2-dihydroindene-3,3'-indene] Chemical compound C1CC2=CC=CC=C2C21C1=CC=CC=C1C(C)(C)C2(C)C OOSOZOSYULELHA-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- PCRSJGWFEMHHEW-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-dicarbonitrile Chemical compound FC1=C(F)C(C#N)=C(F)C(F)=C1C#N PCRSJGWFEMHHEW-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- ZVDSMYGTJDFNHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3-diamine Chemical compound CC1=CC(C)=C(N)C(C)=C1N ZVDSMYGTJDFNHN-UHFFFAOYSA-N 0.000 description 1
- QKTWWGYCVXCKOJ-UHFFFAOYSA-N 2-methoxy-1-(2-methoxyphenyl)-2-phenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1OC QKTWWGYCVXCKOJ-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000877 multi-layer micromoulding Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 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
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
Definitions
- the present invention relates to gas separation membranes.
- This application claims priority based on Japanese Patent Application No. 2021-134151 filed in Japan on August 19, 2021, the content of which is incorporated herein.
- a method of separating gases using a gas separation membrane containing polymers and inorganic particles is known.
- the gas separation method using a gas separation membrane (hereinafter referred to as "polymer gas separation membrane method”) can separate and recover gas without phase change of gas, compared to other gas separation methods
- the operation is simple, the device can be made compact, and gas separation can be performed continuously, so it has the characteristic of having little environmental load.
- such a polymer gas separation membrane method has attracted attention as a technique for separating and recovering greenhouse gases, producing oxygen-enriched air, and purifying natural gas, and is expected to be put into practical use.
- further improvement is required in terms of gas separation performance and gas permeation characteristics such as gas permeation amount.
- MMM Mated-Matrix Membrane
- MMM is a polymer composite membrane in which nanoparticles having high gas separation performance and gas permeation function are contained in the polymer membrane.
- gas separation membrane for example, surface hyperbranched modified silica nanoparticles obtained by adding a hyperbranched polymer to the surface of silica nanoparticles having a nano-order particle size, or dendrimer polymers added to the surface of the silica nanoparticles. and a matrix resin are known (see, for example, Patent Document 1).
- Gas separation membranes are required to further improve their gas permeation properties.
- the gas separation membrane of Patent Document 1 has a problem that sufficient gas permeation characteristics are not obtained in practical use.
- the gas separation membrane is treated with methanol to temporarily improve the performance.
- the gas permeation property of the gas separation membrane is improved by about 5 to 10 times by the methanol treatment, there is a problem that the gas permeation property is dramatically reduced after several hours to several days.
- the present invention has been made in view of the above circumstances, and has excellent gas permeation characteristics, and even without methanol treatment, gas permeation characteristics comparable to or higher than those of conventional gas separation membranes subjected to methanol treatment.
- An object of the present invention is to provide a gas separation membrane that provides
- the present invention has the following aspects.
- a gas separation membrane composed of a composite material containing silica nanoparticles and a polymer, wherein the silica nanoparticles are surface functional group-modified silica nanoparticles surface-modified with a functional group-containing silane coupling agent. and the functional group-containing silane coupling agent is at least one selected from the group consisting of a compound represented by the following chemical formula (1), the following chemical formula (2), and the following chemical formula (3) , gas separation membrane.
- Y is a divalent organic group (where Y contains a single bond)
- Z is a monovalent It is an organic group.
- the functional group - containing silane coupling agent has the following chemical formula :
- Z is —CH ⁇ CH 2 , —CCH 3 ⁇ CH 2 , —C ⁇
- Z is a group represented by the following chemical formula (6)
- the gas separation membrane according to [1] which is a glycidyloxyalkylsilane group represented by the chemical formula (7) of
- the Z is —O—(C ⁇ O)—CH ⁇ CH 2
- a gas separation membrane which is excellent in gas permeation characteristics and which can obtain gas permeation characteristics equal to or higher than those of conventional gas separation membranes treated with methanol without methanol treatment. can be done.
- the gas separation membrane of this embodiment is composed of a composite material containing silica nanoparticles and a polymer.
- Silica nanoparticles are surface functional group-modified silica nanoparticles that are surface-modified with a functional group-containing silane coupling agent described below.
- the gas separation membrane of the present embodiment is formed by depositing a composite material containing silica nanoparticles and a polymer to an arbitrary thickness.
- the content of silica nanoparticles is 20% by mass or more, preferably 30% by mass or more, more preferably more than 50% by mass, and 60% by mass or more and 85% by mass. More preferably: If the content of silica nanoparticles is less than 20% by mass, the effect of improving the gas permeation characteristics of the gas separation membrane cannot be obtained.
- the gas separation membrane of the present embodiment has a silica nanoparticle content of 20% by mass or more, and therefore has a structure in which a polymer is contained in the silica nanoparticle matrix.
- the thickness of the gas separation membrane is adjusted as appropriate according to the location where the gas separation membrane is installed and the use of the gas separation membrane.
- Silica nanoparticles Silica nanoparticles have hydroxyl groups (—OH groups) on their surfaces.
- the number of hydroxyl groups present on the surface of the silica nanoparticles is preferably 1 nm ⁇ 2 or more and 4 nm ⁇ 2 or less. When the number of hydroxyl groups is within the above range, a gas separation membrane made of the above composite material can be formed even if the content of silica nanoparticles exceeds 50% by mass.
- the amount of methane generated by the reaction between the Grignard reagent (CH 3 MgI) and the hydroxyl groups present on the surface of the silica nanoparticles is quantified.
- the particle size of silica nanoparticles is preferably 1 nm or more.
- a gas separation membrane made of the composite material can be formed even if the content of the silica nanoparticles exceeds 50% by mass.
- Examples of methods for measuring the particle size of silica nanoparticles include a method using a transmission electron microscope (TEM), a dynamic light scattering method, a differential electrical mobility measurement method, and the like.
- TEM transmission electron microscope
- dynamic light scattering method dynamic light scattering method
- differential electrical mobility measurement method differential electrical mobility measurement method
- the functional group-containing silane coupling agent is at least one selected from the group consisting of the compound represented by the following chemical formula (1), the following chemical formula (2) and the following chemical formula (3). That is, these functional group-containing silane coupling agents may be used singly or in combination of two or more.
- Y is a divalent organic group (where Y contains a single bond)
- Z is a monovalent It is an organic group.
- Certain olefinylsilanes are preferred.
- Z is a group represented by the following chemical formula (6)
- Glycidyloxyalkylsilane which is the group represented by (7), is preferred.
- -O-( Acryloyloxyalkylsilanes where C ⁇ O)—CCH 3 ⁇ CH 2 — are preferred.
- R is an alkyl or aryl group having 0 to 4 carbon atoms.
- functional group-containing silane coupling agents include vinyltrimethoxysilane represented by the following chemical formula (9), 3-methacryloxypropyltrimethoxysilane represented by the following chemical formula (10), N-phenyl-3-aminopropyltrimethoxysilane represented by the following chemical formula (11), phenyltrimethoxysilane represented by the following chemical formula (12), 3-glycides represented by the following chemical formula (13) xypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane represented by the following chemical formula (14), N-2-(aminoethyl)-3-aminopropyltrimethoxysilane represented by the following chemical formula (15) , 3-mercaptopropyltrimethoxysilane represented by the following chemical formula (16), 3-isocyanatotrimethoxysilane represented by the following chemical formula (17), 3-isocyanatotrimethoxysilane represented by the following chemical formula (18) Methoxys
- the functional group-containing silane coupling agent modification ratio is expressed as a ratio to the hydroxyl groups present on the surface of the silica nanoparticles, and is preferably 0.5 or more and 8 or less.
- the functional group-containing silane coupling agent modification rate is within the above range, even if the content of the functional group-containing silane coupling agent exceeds 50% by mass, a gas separation membrane made of the composite material can be formed. can be done.
- silica nanoparticles examples include silica nanoparticles surface-modified with N-phenyl-3-aminopropyltrimethoxysilane represented by the following chemical formula (19) and represented by the above chemical formula (11), Silica nanoparticles surface-modified with vinyltrimethoxysilane represented by the following formula (20) and represented by the above chemical formula (9), represented by the following formula (21), and represented by the above chemical formula (10) Silica nanoparticles surface-modified with 3-methacryloxypropyltrimethoxysilane, silica nanoparticles surface-modified with phenyltrimethoxysilane represented by the following formula (22), the above chemical formula (12), etc. are mentioned.
- the polymer is not particularly limited as long as it contains surface functional group-modified silica nanoparticles and can be formed into a thin film, and as long as it contains surface functional group-modified silica nanoparticles and can be formed into a thin film. It is not particularly limited.
- Polymers include, for example, polyimide, polysulfone, polyether, polydimethylsiloxane, polysubstituted acetylene, poly-4-methylpentene, and natural rubber.
- a glassy polymer or a rubbery polymer which will be described later, is preferable.
- glassy polymers such as the compound (PIM-1) represented by the following chemical formula (23) and the compound (6FDA-3MPA) represented by the following chemical formula (24) are preferably used. be done.
- the compound (PIM-1) represented by formula (23) above is an intrinsic microporous polymer.
- An intrinsic microporous polymer is a polymer that has a rigid ladder-like structure and a bent skeleton and forms micropores inside the membrane.
- the weight average molecular weight (Mw) of PIM-1 is preferably 1.0 ⁇ 10 5 or more and 5.0 ⁇ 10 5 or less.
- the molecular weight distribution (Mw/Mn) of PIM-1 is preferably 1 or more and 20 or less.
- the molecular weight distribution (Mw/Mn) is represented by the weight average molecular weight (Mw) relative to the number average molecular weight (Mn) of PIM-1.
- the compound (6FDA-3MPA) represented by the above formula (24) is a fluorine-containing polyimide.
- the weight average molecular weight (Mw) of 6FDA-3MPA is preferably 1.0 ⁇ 10 5 or more and 5.0 ⁇ 10 5 or less. Further, the molecular weight distribution (Mw/Mn) of 6FDA-3MPA is preferably 1 or more and 5 or less.
- a rubber-like polymer represented by the following formula (25) is preferably used.
- the gas separation membrane of the present embodiment is composed of a composite material containing silica nanoparticles and a polymer, and the silica nanoparticles are surface functional group-modified silica nanoparticles that are surface-modified with a functional group-containing silane coupling agent.
- the functional group-containing silane coupling agent is at least one selected from the group consisting of the compound represented by the above chemical formula (1), the above chemical formula (2), and the above chemical formula (3).
- the method for producing a gas separation membrane of the present embodiment includes a step of adding surface functional group-modified silica nanoparticles to a solution prepared by dissolving a polymer in a solvent, stirring and mixing to form a uniform solution, and a casting method. and the like to form a coating film made of the solution, and a step of drying the coating film.
- the solvent for dissolving the polymer is not particularly limited as long as it can dissolve the polymer, and examples thereof include tetrahydrofuran (THF).
- Example 2 Purification of intrinsic microporous polymer (PIM-1)"
- PIM-1 intrinsic microporous polymer
- Example 3 "Gel Permeation Chromatography (GPC) Measurement of Inherent Microporous Polymer (PIM-1)"
- GPC GPC measurement of Inherent Microporous Polymer
- the purified product had a high molecular weight with a wide molecular weight distribution (weight average molecular weight: 4.7 ⁇ 10 5 , polydispersity index: 10.5) to a relatively low molecular weight distribution with a narrow molecular weight distribution (weight average molecular weight: 1 up to .1 ⁇ 10 5 , polydispersity index 1.6).
- Example 4 "Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 500,000) and surface functional group-modified silica nanoparticles (1)" After dissolving 0.15 g of an intrinsic microporous polymer, PIM-1 (see formula (23) below), in 6.7 mL of tetrahydrofuran (THF), the polymer solution has a content of 60% by weight relative to the polymer. As shown, the surface functional group-modified silica nanoparticles (1) were added and sonicated for 1 hour. As the surface functional group-modified silica nanoparticles (1), those represented by the above chemical formula (19) were used.
- the polymer solution was stirred overnight at a stirring speed of 1200 rpm, and after stirring was again subjected to ultrasonic treatment for 1 hour. After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm. After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 6 hours to prepare a composite membrane. The produced composite membrane was heat-treated at 70° C. for 18 hours. The film thickness of the obtained film was 79 ⁇ m.
- Example 5 "Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 500,000) and Surface Functional Group-Modified Silica Nanoparticles (1)"
- the gas permeability of the composite membrane obtained in Example 4 was measured.
- K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used for the gas permeability measurement. Oxygen and nitrogen were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 1 shows the results.
- the composite gas separation membrane of Example 4 had an oxygen permeability about four times that of the PIM-1 gas separation membrane of Comparative Example 1.
- Example 6 "Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 500,000) and surface functional group-modified silica nanoparticles (2)" After dissolving 0.15 g of the intrinsic microporous polymer, PIM-1 (see formula (23) above), in 6.7 mL of tetrahydrofuran (THF), the polymer solution has a content of 20% by weight relative to the polymer. As shown, the surface functional group-modified silica nanoparticles (2) were added and sonicated for 1 hour. As the surface functional group-modified silica nanoparticles (2), those represented by the above formula (20) were used.
- the polymer solution was stirred overnight at a stirring speed of 1200 rpm, and after stirring was again subjected to ultrasonic treatment for 1 hour. After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm. After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 6 hours to prepare a composite membrane. The produced composite membrane was heat-treated at 70° C. for 18 hours. The film thickness of the obtained film was 51 ⁇ m.
- Example 7 "Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 500,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
- the gas permeability of the composite membrane obtained in Example 6 was measured.
- K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used for the gas permeability measurement. Oxygen and nitrogen were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 2 shows the results.
- Example 8 "Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 500,000) and surface functional group-modified silica nanoparticles (2)"
- An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 6, except that the amount of the surface functional group-modified silica nanoparticles (2) added was 40% by mass.
- the gas permeability of the resulting composite membrane was measured in the same manner as in Example 7. Table 2 shows the results.
- Example 9 "Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 500,000) and surface functional group-modified silica nanoparticles (2)"
- An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 6, except that the amount of the surface functional group-modified silica nanoparticles (2) added was 60% by mass.
- the gas permeability of the resulting composite membrane was measured in the same manner as in Example 7. Table 2 shows the results.
- Example 10 "Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 500,000) and surface functional group-modified silica nanoparticles (2)"
- An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 6, except that the amount of the surface functional group-modified silica nanoparticles (2) added was 70% by mass.
- the gas permeability of the resulting composite membrane was measured in the same manner as in Example 7. Table 2 shows the results.
- Example 6 had an oxygen permeability about 2.7 times that of Comparative Example 2.
- Example 8 had an oxygen permeability about 5.3 times that of Comparative Example 2.
- Example 9 had an oxygen permeability of about 9.8 times that of Comparative Example 2.
- Example 10 had an oxygen permeability of about 10.8 times that of Comparative Example 2.
- Example 11 "Formation of Organic-Inorganic Composite Gas Separation Membrane Using PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (1)"
- PIM-1 Molecular Weight Average Molecular Weight 100,000
- SPF tetrahydrofuran
- the polymer solution has a content of 50% by weight relative to the polymer.
- the surface functional group-modified silica nanoparticles (1) were added and sonicated for 1 hour.
- the surface functional group-modified silica nanoparticles (1) those represented by the above formula (1) were used.
- the polymer solution was stirred overnight at a stirring speed of 1200 rpm, and after stirring was again subjected to ultrasonic treatment for 1 hour. After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm. After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 6 hours to prepare a composite membrane. The produced composite membrane was heat-treated at 70° C. for 18 hours. The film thickness of the obtained film was 67 ⁇ m.
- Example 12 "Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (1)"
- the gas permeability of the composite membrane obtained in Example 11 was measured.
- K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used for the gas permeability measurement. Carbon dioxide, oxygen, nitrogen, and methane were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 3 shows the results.
- Example 13 "Formation of Organic-Inorganic Composite Gas Separation Membrane Using PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (1)"
- An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 11, except that the amount of silica nanoparticles (1) added was 80% by mass.
- the gas permeability of the resulting composite membrane was measured in the same manner as in Example 12. Table 3 shows the results.
- Example 11 has an oxygen permeability of about 1.4 times, a carbon dioxide permeability of about 1.3 times, and a nitrogen permeability of about 1.5 times that of Comparative Example 3. , and the methane permeability was about 1.8 times.
- Example 13 had an oxygen permeability of about 6.4 times and a nitrogen permeability of about 8.9 times that of Comparative Example 3.
- Example 14 "Formation of Organic-Inorganic Composite Gas Separation Membrane Using PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (2)" After dissolving 0.15 g of the intrinsic microporous polymer, PIM-1 (see formula (23) above), in 6.7 mL of tetrahydrofuran (THF), the polymer solution has a content of 60% by weight relative to the polymer. As shown, the surface functional group-modified silica nanoparticles (2) were added and sonicated for 1 hour. As the surface functional group-modified silica nanoparticles (2), those represented by the above chemical formula (20) were used.
- the polymer solution was stirred overnight at a stirring speed of 1200 rpm, and after stirring was again subjected to ultrasonic treatment for 1 hour. After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm. After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 6 hours to prepare a composite membrane. The produced composite membrane was heat-treated at 70° C. for 18 hours. The film thickness of the obtained film was 94 ⁇ m.
- Example 15 "Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
- the gas permeability of the composite membrane obtained in Example 14 was measured.
- K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used for the gas permeability measurement. Carbon dioxide, oxygen, nitrogen, and methane were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 4 shows the results.
- Example 16 "Formation of Organic-Inorganic Composite Gas Separation Membrane Using PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
- An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 14, except that the amount of the surface functional group-modified silica nanoparticles (2) added was 85% by mass.
- the gas permeability of the resulting composite membrane was measured in the same manner as in Example 15. Table 4 shows the results.
- Example 14 had an oxygen permeability of about 5.5 times and a nitrogen permeability of about 7.9 times that of Comparative Example 4.
- Example 16 has an oxygen permeability of about 14.6 times, a carbon dioxide permeability of about 13.9 times, a nitrogen permeability of about 22.2 times, and a methane permeability of about 22.2 times that of Comparative Example 4. It was about 30.6 times.
- Example 17 Evaluation of Gas Permeation Stability of Organic-Inorganic Composite Gas Separation Membrane Using PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
- the composite gas separation membrane of Example 15 containing 60% by mass of the intrinsic microporous polymer synthesized in Example 1, PIM-1 (see chemical formula (23) above) and surface functional group-modified silica nanoparticles (2) at room temperature It was preserved in a desiccator containing silica gel for 14 days. After that, the gas permeability measurement of the composite membrane was performed.
- K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Oxygen and nitrogen were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 5 shows the results.
- Example 20 "Formation of Organic-Inorganic Composite Gas Separation Membrane Using 6FDA-3MPA and Surface Functional Group-Modified Silica Nanoparticles (1)" After dissolving 1.5 g of fluorine-containing polyimide, 6FDA-3MPA (see chemical formula (24) below) in 6.7 mL of tetrahydrofuran (THF), add The surface functional group-modified silica nanoparticles (1) were added to the solution and subjected to ultrasonic treatment for 1 hour. As the surface functional group-modified silica nanoparticles (1), those represented by the above chemical formula (19) were used.
- This polymer solution was stirred overnight with a magnetic stirrer, and after stirring, was again subjected to ultrasonic treatment for 1 hour. After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm. After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 4 hours to prepare a composite membrane. The produced composite membrane was heat-treated at 150° C. for 15 hours. The film thickness of the obtained film was 35 ⁇ m.
- Example 21 "Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (1)"
- the gas permeability of the composite membrane obtained in Example 20 was measured.
- K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used for the gas permeability measurement. Oxygen and nitrogen were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 6 shows the results.
- Example 22 "Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (1)"
- An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 20, except that the amount of surface functional group-modified silica nanoparticles (1) added was 40% by mass.
- the gas permeability of the obtained composite membrane was measured in the same manner as in Example 21. Table 6 shows the results.
- Example 23 "Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (1)"
- An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 20, except that the amount of surface functional group-modified silica nanoparticles (1) added was 60% by mass.
- the gas permeability of the obtained composite membrane was measured in the same manner as in Example 21. Table 6 shows the results.
- Example 24 "Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (1)"
- An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 20, except that the amount of surface functional group-modified silica nanoparticles (1) added was 70% by mass.
- the gas permeability of the obtained composite membrane was measured in the same manner as in Example 21. Table 6 shows the results.
- Example 20 had an oxygen permeability approximately three times that of Comparative Example 6.
- Example 24 had an oxygen permeability about 3.4 times that of Comparative Example 6.
- Example 25 "Formation of organic-inorganic composite gas separation membrane using 6FDA-3MPA and surface functional group-modified silica nanoparticles (3)" After dissolving 1.5 g of fluorine-containing polyimide, 6FDA-3MPA (see chemical formula (24) above) in 6.7 mL of tetrahydrofuran (THF), add The surface functional group-modified silica nanoparticles (3) were added to the solution and subjected to ultrasonic treatment for 1 hour. As the surface functional group-modified silica nanoparticles (3), those represented by the above chemical formula (21) were used. This polymer solution was stirred overnight with a magnetic stirrer, and after stirring, was again subjected to ultrasonic treatment for 1 hour.
- 6FDA-3MPA see chemical formula (24) above
- THF tetrahydrofuran
- this polymer solution was cast on a glass petri dish with a diameter of 6 cm. After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 4 hours to prepare a composite membrane. The produced composite membrane was heat-treated at 150° C. for 15 hours. The film thickness of the obtained film was 48 ⁇ m.
- Example 26 "Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (3)"
- the gas permeability of the composite membrane obtained in Example 25 was measured.
- K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used for the gas permeability measurement. Oxygen and nitrogen were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 7 shows the results.
- Example 27 "Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (3)"
- An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 25, except that the amount of the surface functional group-modified silica nanoparticles (3) added was 40% by mass.
- the gas permeability measurement of the resulting composite membrane was performed in the same manner as in Example 26. Table 7 shows the results.
- Example 28 "Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (3)"
- An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 25, except that the amount of the surface functional group-modified silica nanoparticles (3) added was 60% by mass.
- the gas permeability measurement of the resulting composite membrane was performed in the same manner as in Example 26. Table 7 shows the results.
- Example 29 "Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (3)"
- An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 25, except that the amount of the surface functional group-modified silica nanoparticles (3) added was 70% by mass.
- the gas permeability measurement of the resulting composite membrane was performed in the same manner as in Example 26. Table 7 shows the results.
- Example 25 had an oxygen permeability about 2.5 times that of Comparative Example 6.
- Example 27 had an oxygen permeability about 4.6 times that of Comparative Example 6.
- Example 30 "Formation of organic-inorganic composite gas separation membrane using 6FDA-3MPA and surface functional group-modified silica nanoparticles (4)" After dissolving 1.5 g of fluorine-containing polyimide, 6FDA-3MPA (see chemical formula (24) above) in 6.7 mL of tetrahydrofuran (THF), add The surface functional group-modified silica nanoparticles (4) were added to the solution and subjected to ultrasonic treatment for 1 hour. As the surface functional group-modified silica nanoparticles (4), those represented by the above chemical formula (22) were used.
- This polymer solution was stirred overnight with a magnetic stirrer, and after stirring, was again subjected to ultrasonic treatment for 1 hour. After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm. After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 4 hours to prepare a composite membrane. The produced composite membrane was heat-treated at 150° C. for 15 hours. The film thickness of the obtained film was 51 ⁇ m.
- Example 31 "Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (4)"
- the gas permeability of the composite membrane obtained in Example 25 was measured.
- K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used for the gas permeability measurement. Carbon dioxide, oxygen, nitrogen, and methane were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 7 shows the results.
- Example 30 has an oxygen permeability of about 5.4 times, a carbon dioxide permeability of about 4.7 times, and a nitrogen permeability of about 6.5 times that of Comparative Example 6. , the permeability of methane was 9 times higher.
- Example 32 "Formation of Organic-Inorganic Composite Gas Separation Membrane Using Silicone and Surface Functional Group-Modified Silica Nanoparticles (2)" 0.431 g of silicone (manufactured by Shin-Etsu Co., Ltd.: X-22-164A, functional group equivalent 860 gmol ⁇ 1 , density 0.98 gcm ⁇ 3 ) was weighed into a 10 mL vial.
- PEMP pentaerythritol tetrakis(3-mercaptopropionate)
- the resulting solution was cast on a Teflon (registered trademark) tray having a side of about 6 cm, and was irradiated with UV light (Chibi Light DX BOX-S1100, Chibi Light DX BOX-S1100, Peak wavelength: 380 nm) to prepare a composite membrane.
- the film thickness of the obtained film was 135 ⁇ m.
- Example 33 "Gas Permeability of Composite Gas Separation Membrane of Silicone and Surface Functional Group Modified Silica Nanoparticles (2)"
- the gas permeability of the composite membrane obtained in Example 32 was measured.
- K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used for the gas permeability measurement. Carbon dioxide, oxygen, nitrogen, and methane were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 9 shows the results.
- Example 32 had an oxygen permeability of about 2.1 times and a nitrogen permeability of about 2.1 times that of Comparative Example 7.
- Example 35 Purification of intrinsic microporous polymer (PIM-1)"
- PIM-1 intrinsic microporous polymer
- Example 36 "Gel Permeation Chromatography (GPC) Measurement of Inherent Microporous Polymer (PIM-1)"
- GPC GPC measurement of Inherent Microporous Polymer
- the purified product had a high molecular weight with a wide molecular weight distribution (weight average molecular weight: 5.4 ⁇ 10 5 , polydispersity index: 9.5) to a relatively low molecular weight distribution with a narrow molecular weight distribution (weight average molecular weight: 3 up to .7 ⁇ 10 5 with a polydispersity index of 4.3).
- Example 37 "Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 370,000) and surface functional group-modified silica nanoparticles (2)" After dissolving 0.15 g of the intrinsic microporous polymer, PIM-1 (see formula (23) above), in 6.7 mL of tetrahydrofuran (THF), the polymer solution has a content of 85% by weight relative to the polymer. As shown, the surface functional group-modified silica nanoparticles (2) were added and sonicated for 1 hour. As the surface functional group-modified silica nanoparticles (2), those represented by the above chemical formula (20) were used.
- the polymer solution was stirred overnight at a stirring speed of 1200 rpm, and after stirring was again subjected to ultrasonic treatment for 1 hour. After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm. After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 6 hours to prepare a composite membrane. The produced composite membrane was heat-treated at 70° C. for 18 hours. The film thickness of the obtained film was 115 ⁇ m.
- Example 38 "Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 370,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
- the gas permeability of the composite membrane obtained in Example 37 was measured.
- K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used for the gas permeability measurement. Carbon dioxide, oxygen, nitrogen, and methane were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 10 shows the results.
- the gas separation membrane of the present invention is composed of a composite material containing silica nanoparticles and a polymer, and the silica nanoparticles are surface functional group-modified silica nanoparticles that are surface-modified with a functional group-containing silane coupling agent, Since the functional group-containing silane coupling agent is at least one selected from the group consisting of the compound represented by the above chemical formula (1), the above chemical formula (2) and the above chemical formula (3), gas permeation It has excellent characteristics, and even without methanol treatment, gas permeation characteristics equivalent to or higher than those of conventional gas separation membranes treated with methanol can be obtained. Therefore, the gas separation membrane of the present invention can be preferably used as a filter.
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Abstract
This gas separation membrane is composed of a composite material containing silica nanoparticles and a polymer, wherein: the silica nanoparticles are surface functional group-modified silica nanoparticles which have been surface-treated with a functional group-containing silane coupling agent; and the functional group-containing silane coupling agent is at least one selected from the group consisting of a compound represented by chemical formula (1), chemical formula (2), and chemical formula (3).
Description
本発明は、気体分離膜に関する。
本願は、２０２１年８月１９日に日本に出願された特願２０２１－１３４１５１号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to gas separation membranes.
This application claims priority based on Japanese Patent Application No. 2021-134151 filed in Japan on August 19, 2021, the content of which is incorporated herein.
本願は、２０２１年８月１９日に日本に出願された特願２０２１－１３４１５１号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to gas separation membranes.
This application claims priority based on Japanese Patent Application No. 2021-134151 filed in Japan on August 19, 2021, the content of which is incorporated herein.
高分子と無機粒子を含む気体分離膜を用いて気体を分離する方法が知られている。気体分離膜を用いた気体分離法（以下、「高分子気体分離膜法」と言う。）は、気体の相変化を伴わずに気体の分離・回収ができ、他の気体分離法に比べて操作が簡便で装置の小型化が可能であり、連続的に気体分離を行うことができるため、環境負荷が少ないという特性を有している。このような高分子気体分離膜法は、近年、特に温室効果ガスの分離・回収や酸素富化空気の作製、天然ガスの精製技術として注目を集め、実用化が期待されている。また、高分子気体分離膜法では、気体分離性能および気体透過量等の気体透過特性の点でさらなる改善が求められている。
A method of separating gases using a gas separation membrane containing polymers and inorganic particles is known. The gas separation method using a gas separation membrane (hereinafter referred to as "polymer gas separation membrane method") can separate and recover gas without phase change of gas, compared to other gas separation methods The operation is simple, the device can be made compact, and gas separation can be performed continuously, so it has the characteristic of having little environmental load. In recent years, such a polymer gas separation membrane method has attracted attention as a technique for separating and recovering greenhouse gases, producing oxygen-enriched air, and purifying natural gas, and is expected to be put into practical use. Further, in the polymer gas separation membrane method, further improvement is required in terms of gas separation performance and gas permeation characteristics such as gas permeation amount.
近年、ＭＭＭ（Ｍｉｘｅｄ－Ｍａｔｒｉｘ Ｍｅｍｂｒａｎｅ）が盛んに研究されている。ＭＭＭとは、高い気体分離性能や気体透過機能を有するナノ粒子を高分子膜内に含有した高分子複合膜のことである。近年、様々なナノ粒子が合成されるようになった結果、ナノ粒子の新しい機能が見出されて、ＭＭＭの検討が非常に多く行われている。
気体分離膜としては、例えば、ナノオーダーの粒子径を有するシリカナノ粒子の表面にハイパーブランチ高分子が付加されてなる表面ハイパーブランチ修飾シリカナノ粒子、または前記シリカナノ粒子の表面にデンドリマー高分子が付加されてなる表面デンドリマー修飾シリカナノ粒子と、マトリクス樹脂とを含有するものが知られている（例えば、特許文献１参照）。 In recent years, MMM (Mixed-Matrix Membrane) has been actively studied. MMM is a polymer composite membrane in which nanoparticles having high gas separation performance and gas permeation function are contained in the polymer membrane. In recent years, as a result of the synthesis of various nanoparticles, new functions of nanoparticles have been discovered, and MMMs have been extensively studied.
As the gas separation membrane, for example, surface hyperbranched modified silica nanoparticles obtained by adding a hyperbranched polymer to the surface of silica nanoparticles having a nano-order particle size, or dendrimer polymers added to the surface of the silica nanoparticles. and a matrix resin are known (see, for example, Patent Document 1).
気体分離膜としては、例えば、ナノオーダーの粒子径を有するシリカナノ粒子の表面にハイパーブランチ高分子が付加されてなる表面ハイパーブランチ修飾シリカナノ粒子、または前記シリカナノ粒子の表面にデンドリマー高分子が付加されてなる表面デンドリマー修飾シリカナノ粒子と、マトリクス樹脂とを含有するものが知られている（例えば、特許文献１参照）。 In recent years, MMM (Mixed-Matrix Membrane) has been actively studied. MMM is a polymer composite membrane in which nanoparticles having high gas separation performance and gas permeation function are contained in the polymer membrane. In recent years, as a result of the synthesis of various nanoparticles, new functions of nanoparticles have been discovered, and MMMs have been extensively studied.
As the gas separation membrane, for example, surface hyperbranched modified silica nanoparticles obtained by adding a hyperbranched polymer to the surface of silica nanoparticles having a nano-order particle size, or dendrimer polymers added to the surface of the silica nanoparticles. and a matrix resin are known (see, for example, Patent Document 1).
気体分離膜では、さらなる気体透過特性の向上が求められている。しかしながら、特許文献１の気体分離膜では、実用する際に十分な気体透過特性が得られていないという課題があった。また、従来、気体分離膜の気体透過特性を評価する場合に、気体分離膜をメタノール処理して、一時的に性能を向上させていた。しかしながら、メタノール処理により気体分離膜の気体透過特性が５～１０倍程度向上するものの、数時間～数日で気体透過特性が劇的に減少するという課題があった。
Gas separation membranes are required to further improve their gas permeation properties. However, the gas separation membrane of Patent Document 1 has a problem that sufficient gas permeation characteristics are not obtained in practical use. Conventionally, when evaluating the gas permeation characteristics of a gas separation membrane, the gas separation membrane is treated with methanol to temporarily improve the performance. However, although the gas permeation property of the gas separation membrane is improved by about 5 to 10 times by the methanol treatment, there is a problem that the gas permeation property is dramatically reduced after several hours to several days.
本発明は、上記事情に鑑みてなされたものであって、気体透過特性に優れ、かつメタノール処理を行わなくとも、メタノール処理を行った従来の気体分離膜と同程度またはそれ以上の気体透過特性が得られる気体分離膜を提供することを目的とする。
The present invention has been made in view of the above circumstances, and has excellent gas permeation characteristics, and even without methanol treatment, gas permeation characteristics comparable to or higher than those of conventional gas separation membranes subjected to methanol treatment. An object of the present invention is to provide a gas separation membrane that provides
本発明は以下の態様を有する。
The present invention has the following aspects.
［１］シリカナノ粒子と、高分子と、を含む複合体材料から構成される気体分離膜であって、前記シリカナノ粒子は、官能基含有シランカップリング剤で表面修飾された表面官能基修飾シリカナノ粒子であり、前記官能基含有シランカップリング剤は、下記の化学式（１）で表される化合物、下記の化学式（２）および下記の化学式（３）からなる群から選択される少なくとも１種である、気体分離膜。
[1] A gas separation membrane composed of a composite material containing silica nanoparticles and a polymer, wherein the silica nanoparticles are surface functional group-modified silica nanoparticles surface-modified with a functional group-containing silane coupling agent. and the functional group-containing silane coupling agent is at least one selected from the group consisting of a compound represented by the following chemical formula (1), the following chemical formula (2), and the following chemical formula (3) , gas separation membrane.
［２］前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝０～１７）、前記Ｚが－ＣｎＨ２ｎ＋１（ｎ＝１～１８）、下記の化学式（４）で表される基、下記の化学式（５）で表される基であるアルキルシランである、［１］に記載の気体分離膜。
[2] The functional group - containing silane coupling agent has the following chemical formula : The gas separation membrane according to [1], wherein the group represented by (4) is an alkylsilane group represented by the following chemical formula (5).
［３］前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝０～６）、前記Ｚが－ＣＨ＝ＣＨ２、－ＣＣＨ３＝ＣＨ２、－Ｃ≡ＣＨであるオレフィニルシランである、［１］に記載の気体分離膜。
[3] In the functional group-containing silane coupling agent, Y is —(CH 2 ) n —(n=0 to 6), Z is —CH═CH 2 , —CCH 3 ═CH 2 , —C≡ The gas separation membrane according to [1], which is an olefinylsilane that is CH.
［４］前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝０～６）、前記Ｚが－Ａｒ、－ＯＡｒであるアリールシランである、［１］に記載の気体分離膜。
[4] The functional group-containing silane coupling agent is an arylsilane in which the Y is -(CH 2 ) n - (n = 0 to 6) and the Z is -Ar or -OAr, according to [1] A gas separation membrane as described.
［５］前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－ＯＣＨ２－（ｎ＝１～６）、前記Ｚが下記の化学式（６）で表される基、下記の化学式（７）で表される基であるであるグリシジルオキシアルキルシランである、［１］に記載の気体分離膜。
[5] In the functional group-containing silane coupling agent, Y is -(CH 2 ) n -OCH 2 - (n = 1 to 6), Z is a group represented by the following chemical formula (6), The gas separation membrane according to [1], which is a glycidyloxyalkylsilane group represented by the chemical formula (7) of
［６］前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝１～６）、前記Ｚが－Ｏ－（Ｃ＝Ｏ）－ＣＨ＝ＣＨ２、－Ｏ－（Ｃ＝Ｏ）－ＣＣＨ３＝ＣＨ２－であるアクロイルオキシアルキルシランである、［１］に記載の気体分離膜。
[6] In the functional group-containing silane coupling agent, the Y is —(CH 2 ) n —(n=1 to 6), the Z is —O—(C═O)—CH═CH 2 , —O The gas separation membrane according to [1], which is an acryloyloxyalkylsilane wherein -(C=O)-CCH 3 =CH 2 -.
［７］前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝１～６）、前記Ｚが－ＮＲ２（Ｒは炭素数０～４のアルキル基、アリール基）、－ＮＨ－（ＣＨ２）ｍ－ＮＲ２（ｍ＝２～６、Ｒは炭素数０～４のアルキル基、アリール基）であるアミノアルキルシランである、［１］に記載の気体分離膜。
[7] In the functional group-containing silane coupling agent, the Y is —(CH 2 ) n —(n=1 to 6), the Z is —NR 2 (R is an alkyl group having 0 to 4 carbon atoms, an aryl group), -NH-(CH 2 ) m -NR 2 (m = 2 to 6, R is an alkyl group having 0 to 4 carbon atoms, an aryl group). Separation membrane.
［８］前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝１～６）、前記Ｚが－ＣｎＦ２ｎ＋１－（ｎ＝１～８）であるフルオロアルキルシランである、［１］に記載の気体分離膜。
[8] In the functional group-containing silane coupling agent, the Y is -(CH 2 ) n - (n = 1 to 6) and the Z is -C n F 2n+1 - (n = 1 to 8). The gas separation membrane according to [1], which is an alkylsilane.
［９］前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝１～６）、－（ＣＨ２）ｎ－Ａｒ－（ＣＨ２）ｍ－（ｍ＝１～６、ｎ＝１～６）、下記の化学式（８）で表される基、前記Ｚが－Ｃｌ、－Ｂｒ、－Ｉ、－ＣＮ、－Ｎ３、－ＮＨ（Ｃ＝Ｏ）ＮＨ２－、－ＳＨ、－Ｎ＝Ｃ＝Ｏである化合物である、［１］に記載の気体分離膜。
[9] In the functional group-containing silane coupling agent, the Y is -(CH 2 ) n -(n=1 to 6), -(CH 2 ) n -Ar-(CH 2 ) m -(m=1 ~ 6, n = 1 to 6), a group represented by the following chemical formula (8), wherein Z is -Cl, -Br, -I, -CN, -N 3 , -NH(C=O)NH 2 The gas separation membrane according to [1], which is a compound of -, -SH, -N=C=O.
［１０］前記シリカナノ粒子の含有量が２０質量％以上である、［１］～［９］のいずれかに記載の気体分離膜。
[10] The gas separation membrane according to any one of [1] to [9], wherein the content of the silica nanoparticles is 20% by mass or more.
［１１］前記高分子は、ガラス状高分子またはゴム状高分子である、［１］～［１０］のいずれかに記載の気体分離膜。
[11] The gas separation membrane according to any one of [1] to [10], wherein the polymer is a glassy polymer or a rubbery polymer.
本発明によれば、気体透過特性に優れ、かつメタノール処理を行わなくとも、メタノール処理を行った従来の気体分離膜と同程度またはそれ以上の気体透過特性が得られる気体分離膜を提供することができる。
According to the present invention, there is provided a gas separation membrane which is excellent in gas permeation characteristics and which can obtain gas permeation characteristics equal to or higher than those of conventional gas separation membranes treated with methanol without methanol treatment. can be done.
本発明の一実施形態に係る気体分離膜の実施の形態について説明する。
なお、本実施の形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。 An embodiment of a gas separation membrane according to one embodiment of the present invention will be described.
It should be noted that the present embodiment is specifically described for better understanding of the gist of the invention, and does not limit the invention unless otherwise specified.
なお、本実施の形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。 An embodiment of a gas separation membrane according to one embodiment of the present invention will be described.
It should be noted that the present embodiment is specifically described for better understanding of the gist of the invention, and does not limit the invention unless otherwise specified.
［気体分離膜］
本実施形態の気体分離膜は、シリカナノ粒子と、高分子と、を含む複合体材料から構成される。シリカナノ粒子は、後述する官能基含有シランカップリング剤で表面修飾された表面官能基修飾シリカナノ粒子である。本実施形態の気体分離膜は、シリカナノ粒子と、高分子と、を含む複合体材料を、任意の厚さとなるように成膜したものである。 [Gas separation membrane]
The gas separation membrane of this embodiment is composed of a composite material containing silica nanoparticles and a polymer. Silica nanoparticles are surface functional group-modified silica nanoparticles that are surface-modified with a functional group-containing silane coupling agent described below. The gas separation membrane of the present embodiment is formed by depositing a composite material containing silica nanoparticles and a polymer to an arbitrary thickness.
本実施形態の気体分離膜は、シリカナノ粒子と、高分子と、を含む複合体材料から構成される。シリカナノ粒子は、後述する官能基含有シランカップリング剤で表面修飾された表面官能基修飾シリカナノ粒子である。本実施形態の気体分離膜は、シリカナノ粒子と、高分子と、を含む複合体材料を、任意の厚さとなるように成膜したものである。 [Gas separation membrane]
The gas separation membrane of this embodiment is composed of a composite material containing silica nanoparticles and a polymer. Silica nanoparticles are surface functional group-modified silica nanoparticles that are surface-modified with a functional group-containing silane coupling agent described below. The gas separation membrane of the present embodiment is formed by depositing a composite material containing silica nanoparticles and a polymer to an arbitrary thickness.
本実施形態の気体分離膜では、シリカナノ粒子の含有量が２０質量％以上であり、３０質量％以上であることが好ましく、５０質量％超であることがより好ましく、６０質量％以上８５質量％以下であることがさらに好ましい。シリカナノ粒子の含有量が２０質量％未満では、気体分離膜の気体透過特性の向上という効果が得られない。
In the gas separation membrane of the present embodiment, the content of silica nanoparticles is 20% by mass or more, preferably 30% by mass or more, more preferably more than 50% by mass, and 60% by mass or more and 85% by mass. More preferably: If the content of silica nanoparticles is less than 20% by mass, the effect of improving the gas permeation characteristics of the gas separation membrane cannot be obtained.
本実施形態の気体分離膜では、シリカナノ粒子の含有量が２０質量％以上であるから、シリカナノ粒子のマトリクスに高分子が含まれる構造をなしている。
The gas separation membrane of the present embodiment has a silica nanoparticle content of 20% by mass or more, and therefore has a structure in which a polymer is contained in the silica nanoparticle matrix.
気体分離膜の厚さは、気体分離膜を設置する場所や、気体分離膜の用途等に応じて適宜調整する。
The thickness of the gas separation membrane is adjusted as appropriate according to the location where the gas separation membrane is installed and the use of the gas separation membrane.
「シリカナノ粒子」
シリカナノ粒子は、表面に水酸基（－ＯＨ基）を有する。シリカナノ粒子の表面に存在する水酸基の数は、１個ｎｍ－２以上４個ｎｍ－２以下であることが好ましい。水酸基の数が前記範囲内であると、シリカナノ粒子の含有量を５０質量％超としても、前記の複合体材料からなる気体分離膜を成膜することができる。 "Silica nanoparticles"
Silica nanoparticles have hydroxyl groups (—OH groups) on their surfaces. The number of hydroxyl groups present on the surface of the silica nanoparticles is preferably 1 nm −2 or more and 4 nm −2 or less. When the number of hydroxyl groups is within the above range, a gas separation membrane made of the above composite material can be formed even if the content of silica nanoparticles exceeds 50% by mass.
シリカナノ粒子は、表面に水酸基（－ＯＨ基）を有する。シリカナノ粒子の表面に存在する水酸基の数は、１個ｎｍ－２以上４個ｎｍ－２以下であることが好ましい。水酸基の数が前記範囲内であると、シリカナノ粒子の含有量を５０質量％超としても、前記の複合体材料からなる気体分離膜を成膜することができる。 "Silica nanoparticles"
Silica nanoparticles have hydroxyl groups (—OH groups) on their surfaces. The number of hydroxyl groups present on the surface of the silica nanoparticles is preferably 1 nm −2 or more and 4 nm −2 or less. When the number of hydroxyl groups is within the above range, a gas separation membrane made of the above composite material can be formed even if the content of silica nanoparticles exceeds 50% by mass.
気体分離膜に含まれるシリカナノ粒子の表面に存在する水酸基の数の定量方法としては、例えば、Ｇｒｉｇｎａｒｄ試薬（ＣＨ３ＭｇＩ）とシリカナノ粒子の表面に存在する水酸基との反応により発生するメタン量を定量することにより算出する方法が挙げられる。
As a method for quantifying the number of hydroxyl groups present on the surface of the silica nanoparticles contained in the gas separation membrane, for example, the amount of methane generated by the reaction between the Grignard reagent (CH 3 MgI) and the hydroxyl groups present on the surface of the silica nanoparticles is quantified. A method of calculating by
シリカナノ粒子の粒径は、１ｎｍ以上であることが好ましい。シリカナノ粒子の粒径が前記範囲内であると、シリカナノ粒子の含有量を５０質量％超としても、前記の複合体材料からなる気体分離膜を成膜することができる。
The particle size of silica nanoparticles is preferably 1 nm or more. When the particle size of the silica nanoparticles is within the above range, a gas separation membrane made of the composite material can be formed even if the content of the silica nanoparticles exceeds 50% by mass.
シリカナノ粒子の粒径の測定方法としては、例えば、透過型電子顕微鏡（ＴＥＭ）を用いた方法、動的光散乱法、微分型電気移動度測定方法等が挙げられる。
Examples of methods for measuring the particle size of silica nanoparticles include a method using a transmission electron microscope (TEM), a dynamic light scattering method, a differential electrical mobility measurement method, and the like.
［官能基含有シランカップリング剤］
官能基含有シランカップリング剤は、下記の化学式（１）で表される化合物、下記の化学式（２）および下記の化学式（３）からなる群から選択される少なくとも１種である。すなわち、これらの官能基含有シランカップリング剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 [Functional Group-Containing Silane Coupling Agent]
The functional group-containing silane coupling agent is at least one selected from the group consisting of the compound represented by the following chemical formula (1), the following chemical formula (2) and the following chemical formula (3). That is, these functional group-containing silane coupling agents may be used singly or in combination of two or more.
官能基含有シランカップリング剤は、下記の化学式（１）で表される化合物、下記の化学式（２）および下記の化学式（３）からなる群から選択される少なくとも１種である。すなわち、これらの官能基含有シランカップリング剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 [Functional Group-Containing Silane Coupling Agent]
The functional group-containing silane coupling agent is at least one selected from the group consisting of the compound represented by the following chemical formula (1), the following chemical formula (2) and the following chemical formula (3). That is, these functional group-containing silane coupling agents may be used singly or in combination of two or more.
官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝０～１７）、前記Ｚが－ＣｎＨ２ｎ＋１（ｎ＝１～１８）、下記の化学式（４）で表される基、下記の化学式（５）で表される基であるアルキルシランが好ましい。
In the functional group-containing silane coupling agent, the Y is -(CH 2 ) n - (n = 0 to 17), the Z is -C n H 2n+1 (n = 1 to 18), and the following chemical formula (4) Alkylsilane, which is a group represented by the following chemical formula (5), is preferred.
また、官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝０～６）、前記Ｚが－ＣＨ＝ＣＨ２、－ＣＣＨ３＝ＣＨ２、－Ｃ≡ＣＨであるオレフィニルシランが好ましい。
In the functional group-containing silane coupling agent, the Y is -(CH 2 ) n - (n = 0 to 6), and the Z is -CH=CH 2 , -CCH 3 =CH 2 , -C≡CH. Certain olefinylsilanes are preferred.
また、官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝０～６）、前記Ｚが－Ａｒ、－ＯＡｒであるアリールシランが好ましい。
Further, the functional group-containing silane coupling agent is preferably an arylsilane in which Y is —(CH 2 ) n —(n=0 to 6) and Z is —Ar or —OAr.
また、官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－ＯＣＨ２－（ｎ＝１～６）、前記Ｚが下記の化学式（６）で表される基、下記の化学式（７）で表される基であるグリシジルオキシアルキルシランが好ましい。
In the functional group-containing silane coupling agent, Y is -(CH 2 ) n -OCH 2 - (n = 1 to 6), Z is a group represented by the following chemical formula (6), Glycidyloxyalkylsilane, which is the group represented by (7), is preferred.
また、官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝１～６）、前記Ｚが－Ｏ－（Ｃ＝Ｏ）－ＣＨ＝ＣＨ２、－Ｏ－（Ｃ＝Ｏ）－ＣＣＨ３＝ＣＨ２－であるアクロイルオキシアルキルシランが好ましい。
In the functional group-containing silane coupling agent, the Y is -(CH 2 ) n -(n=1 to 6), the Z is -O-(C=O)-CH=CH 2 , -O-( Acryloyloxyalkylsilanes where C═O)—CCH 3 ═CH 2 — are preferred.
また、官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝１～６）、前記Ｚが－ＮＲ２（Ｒは炭素数０～４のアルキル基、アリール基）、－ＮＨ－（ＣＨ２）ｍ－ＮＲ２（ｍ＝２～６、Ｒは炭素数０～４のアルキル基、アリール基）であるアミノアルキルシランが好ましい。
In the functional group-containing silane coupling agent, Y is —(CH 2 ) n — (n=1 to 6) and Z is —NR 2 (R is an alkyl group having 0 to 4 carbon atoms or an aryl group). , —NH—(CH 2 ) m —NR 2 (m=2 to 6, R is an alkyl or aryl group having 0 to 4 carbon atoms).
また、官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝１～６）、前記Ｚが－ＣｎＦ２ｎ＋１－（ｎ＝１～８）であるフルオロアルキルシランが好ましい。
In the functional group-containing silane coupling agent, the Y is -(CH 2 ) n -(n=1 to 6), and the Z is -C n F 2n+1 -(n=1 to 8). is preferred.
また、官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝１～６）、－（ＣＨ２）ｎ－Ａｒ－（ＣＨ２）ｍ－（ｍ＝１～６、ｎ＝１～６）、下記の式（８）で表される基、前記Ｚが－Ｃｌ、－Ｂｒ、－Ｉ、－ＣＮ、－Ｎ３、－ＮＨ（Ｃ＝Ｏ）ＮＨ２－、－ＳＨ、－Ｎ＝Ｃ＝Ｏである化合物が好ましい。
In the functional group-containing silane coupling agent, Y is -(CH 2 ) n -(n=1 to 6), -(CH 2 ) n -Ar-(CH 2 ) m -(m=1 to 6) , n = 1 to 6), a group represented by the following formula (8), the Z is -Cl, -Br, -I, -CN, -N 3 , -NH(C=O)NH 2 -, Compounds in which -SH, -N=C=O are preferred.
官能基含有シランカップリング剤の具体例としては、例えば、下記の化学式（９）で表されるビニルトリメトキシシラン、下記の化学式（１０）で表される３－メタクリロキシプロピルトリメトキシシラン、下記の化学式（１１）で表されるＮ－フェニル－３－アミノプロピルトリメトキシシラン、下記の化学式（１２）で表されるフェニルトリメトキシシラン、下記の化学式（１３）で表される３－グリシドキシプロピルトリメトキシシラン、下記の化学式（１４）で表される３－アミノプロピルトリメトキシシラン、下記の化学式（１５）で表されるＮ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、下記の化学式（１６）で表される３－メルカプトプロピルトリメトキシシラン、下記の化学式（１７）で表される３－イソシアネートトリメトキシシラン、下記の化学式（１８）で表される３－イソシアネートトリメトキシシラン等が挙げられる。
Specific examples of functional group-containing silane coupling agents include vinyltrimethoxysilane represented by the following chemical formula (9), 3-methacryloxypropyltrimethoxysilane represented by the following chemical formula (10), N-phenyl-3-aminopropyltrimethoxysilane represented by the following chemical formula (11), phenyltrimethoxysilane represented by the following chemical formula (12), 3-glycides represented by the following chemical formula (13) xypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane represented by the following chemical formula (14), N-2-(aminoethyl)-3-aminopropyltrimethoxysilane represented by the following chemical formula (15) , 3-mercaptopropyltrimethoxysilane represented by the following chemical formula (16), 3-isocyanatotrimethoxysilane represented by the following chemical formula (17), 3-isocyanatotrimethoxysilane represented by the following chemical formula (18) Methoxysilane and the like can be mentioned.
表面官能基修飾シリカナノ粒子において、官能基含有シランカップリング剤修飾率は、シリカナノ粒子の表面に存在する水酸基に対する割合で表され、０．５以上８以下であることが好ましい。官能基含有シランカップリング剤修飾率が前記範囲内であると、官能基含有シランカップリング剤の含有量を５０質量％超としても、前記の複合体材料からなる気体分離膜を成膜することができる。
In the surface functional group-modified silica nanoparticles, the functional group-containing silane coupling agent modification ratio is expressed as a ratio to the hydroxyl groups present on the surface of the silica nanoparticles, and is preferably 0.5 or more and 8 or less. When the functional group-containing silane coupling agent modification rate is within the above range, even if the content of the functional group-containing silane coupling agent exceeds 50% by mass, a gas separation membrane made of the composite material can be formed. can be done.
表面官能基修飾シリカナノ粒子としては、例えば、下記の化学式（１９）で表され、上記の化学式（１１）で表されるＮ－フェニル－３－アミノプロピルトリメトキシシランで表面修飾されたシリカナノ粒子、下記の式（２０）で表され、上記の化学式（９）で表されるビニルトリメトキシシランで表面修飾されたシリカナノ粒子、下記の式（２１）で表され、上記の化学式（１０）で表される３－メタクリロキシプロピルトリメトキシシランで表面修飾されたシリカナノ粒子、下記の式（２２）で表され、上記の化学式（１２）で表されるフェニルトリメトキシシランで表面修飾されたシリカナノ粒子等が挙げられる。
Examples of surface functional group-modified silica nanoparticles include silica nanoparticles surface-modified with N-phenyl-3-aminopropyltrimethoxysilane represented by the following chemical formula (19) and represented by the above chemical formula (11), Silica nanoparticles surface-modified with vinyltrimethoxysilane represented by the following formula (20) and represented by the above chemical formula (9), represented by the following formula (21), and represented by the above chemical formula (10) Silica nanoparticles surface-modified with 3-methacryloxypropyltrimethoxysilane, silica nanoparticles surface-modified with phenyltrimethoxysilane represented by the following formula (22), the above chemical formula (12), etc. are mentioned.
「高分子」
高分子としては、表面官能基修飾シリカナノ粒子を含有して、薄膜に成膜できるものであれば特に限定されず、表面官能基修飾シリカナノ粒子を含有して、薄膜に成膜できるものであれば特に限定されない。高分子としては、例えば、ポリイミド、ポリスルホン、ポリエーテル、ポリジメチルシロキサン、ポリ置換アセチレン、ポリ－４－メチルペンテン、天然ゴム等が挙げられる。高分子としては、後述するガラス状高分子またはゴム状高分子が好ましい。 "High molecular"
The polymer is not particularly limited as long as it contains surface functional group-modified silica nanoparticles and can be formed into a thin film, and as long as it contains surface functional group-modified silica nanoparticles and can be formed into a thin film. It is not particularly limited. Polymers include, for example, polyimide, polysulfone, polyether, polydimethylsiloxane, polysubstituted acetylene, poly-4-methylpentene, and natural rubber. As the polymer, a glassy polymer or a rubbery polymer, which will be described later, is preferable.
高分子としては、表面官能基修飾シリカナノ粒子を含有して、薄膜に成膜できるものであれば特に限定されず、表面官能基修飾シリカナノ粒子を含有して、薄膜に成膜できるものであれば特に限定されない。高分子としては、例えば、ポリイミド、ポリスルホン、ポリエーテル、ポリジメチルシロキサン、ポリ置換アセチレン、ポリ－４－メチルペンテン、天然ゴム等が挙げられる。高分子としては、後述するガラス状高分子またはゴム状高分子が好ましい。 "High molecular"
The polymer is not particularly limited as long as it contains surface functional group-modified silica nanoparticles and can be formed into a thin film, and as long as it contains surface functional group-modified silica nanoparticles and can be formed into a thin film. It is not particularly limited. Polymers include, for example, polyimide, polysulfone, polyether, polydimethylsiloxane, polysubstituted acetylene, poly-4-methylpentene, and natural rubber. As the polymer, a glassy polymer or a rubbery polymer, which will be described later, is preferable.
高分子としては、例えば、下記の化学式（２３）で表される化合物（ＰＩＭ－１）、下記の化学式（２４）で表される化合物（６ＦＤＡ－３ＭＰＡ）等のガラス状高分子が好適に用いられる。
As the polymer, for example, glassy polymers such as the compound (PIM-1) represented by the following chemical formula (23) and the compound (6FDA-3MPA) represented by the following chemical formula (24) are preferably used. be done.
上記の式（２３）で表される化合物（ＰＩＭ－１）は、固有微細孔性高分子である。固有微細孔性高分子とは、剛直な梯子型構造および折れ曲がり骨格を有し、膜内部に微細孔を形成する高分子のことである。
ＰＩＭ－１の重量平均分子量（Ｍｗ）は、１．０×１０５以上５．０×１０５以下であることが好ましい。
また、ＰＩＭ－１の分子量分布（Ｍｗ／Ｍｎ）は、１以上２０以下であることが好ましい。なお、分子量分布（Ｍｗ／Ｍｎ）は、ＰＩＭ－１の数平均分子量（Ｍｎ）に対する重量平均分子量（Ｍｗ）で表される。 The compound (PIM-1) represented by formula (23) above is an intrinsic microporous polymer. An intrinsic microporous polymer is a polymer that has a rigid ladder-like structure and a bent skeleton and forms micropores inside the membrane.
The weight average molecular weight (Mw) of PIM-1 is preferably 1.0×10 5 or more and 5.0×10 5 or less.
Also, the molecular weight distribution (Mw/Mn) of PIM-1 is preferably 1 or more and 20 or less. The molecular weight distribution (Mw/Mn) is represented by the weight average molecular weight (Mw) relative to the number average molecular weight (Mn) of PIM-1.
ＰＩＭ－１の重量平均分子量（Ｍｗ）は、１．０×１０５以上５．０×１０５以下であることが好ましい。
また、ＰＩＭ－１の分子量分布（Ｍｗ／Ｍｎ）は、１以上２０以下であることが好ましい。なお、分子量分布（Ｍｗ／Ｍｎ）は、ＰＩＭ－１の数平均分子量（Ｍｎ）に対する重量平均分子量（Ｍｗ）で表される。 The compound (PIM-1) represented by formula (23) above is an intrinsic microporous polymer. An intrinsic microporous polymer is a polymer that has a rigid ladder-like structure and a bent skeleton and forms micropores inside the membrane.
The weight average molecular weight (Mw) of PIM-1 is preferably 1.0×10 5 or more and 5.0×10 5 or less.
Also, the molecular weight distribution (Mw/Mn) of PIM-1 is preferably 1 or more and 20 or less. The molecular weight distribution (Mw/Mn) is represented by the weight average molecular weight (Mw) relative to the number average molecular weight (Mn) of PIM-1.
上記の式（２４）で表される化合物（６ＦＤＡ－３ＭＰＡ）は、含フッ素ポリイミドである。
６ＦＤＡ－３ＭＰＡの重量平均分子量（Ｍｗ）は、１．０×１０５以上５．０×１０５以下であることが好ましい。
また、６ＦＤＡ－３ＭＰＡの分子量分布（Ｍｗ／Ｍｎ）は、１以上５以下であることが好ましい。 The compound (6FDA-3MPA) represented by the above formula (24) is a fluorine-containing polyimide.
The weight average molecular weight (Mw) of 6FDA-3MPA is preferably 1.0×10 5 or more and 5.0×10 5 or less.
Further, the molecular weight distribution (Mw/Mn) of 6FDA-3MPA is preferably 1 or more and 5 or less.
６ＦＤＡ－３ＭＰＡの重量平均分子量（Ｍｗ）は、１．０×１０５以上５．０×１０５以下であることが好ましい。
また、６ＦＤＡ－３ＭＰＡの分子量分布（Ｍｗ／Ｍｎ）は、１以上５以下であることが好ましい。 The compound (6FDA-3MPA) represented by the above formula (24) is a fluorine-containing polyimide.
The weight average molecular weight (Mw) of 6FDA-3MPA is preferably 1.0×10 5 or more and 5.0×10 5 or less.
Further, the molecular weight distribution (Mw/Mn) of 6FDA-3MPA is preferably 1 or more and 5 or less.
高分子としては、例えば、下記の式（２５）で表されるゴム状高分子（シリコーン）が好適に用いられる。
As the polymer, for example, a rubber-like polymer (silicone) represented by the following formula (25) is preferably used.
本実施形態の気体分離膜によれば、シリカナノ粒子と、高分子と、を含む複合体材料から構成され、シリカナノ粒子は、官能基含有シランカップリング剤で表面修飾された表面官能基修飾シリカナノ粒子であり、官能基含有シランカップリング剤は、上記の化学式（１）で表される化合物、上記の化学式（２）および上記の化学式（３）からなる群から選択される少なくとも１種であるため、気体透過特性に優れ、かつメタノール処理を行わなくとも、メタノール処理を行った従来の気体分離膜と同程度またはそれ以上の気体透過特性が得られる気体分離膜を提供することができる。また、本実施形態の気体分離膜は、長期にわたって、気体透過特性が減少しにくい。
According to the gas separation membrane of the present embodiment, it is composed of a composite material containing silica nanoparticles and a polymer, and the silica nanoparticles are surface functional group-modified silica nanoparticles that are surface-modified with a functional group-containing silane coupling agent. and the functional group-containing silane coupling agent is at least one selected from the group consisting of the compound represented by the above chemical formula (1), the above chemical formula (2), and the above chemical formula (3). Thus, it is possible to provide a gas separation membrane which is excellent in gas permeation characteristics and which can obtain gas permeation characteristics comparable to or higher than those of conventional gas separation membranes treated with methanol without methanol treatment. In addition, the gas separation membrane of the present embodiment is less likely to decrease in gas permeation properties over a long period of time.
［気体分離膜の製造方法］
本実施形態の気体分離膜の製造方法は、高分子を溶媒に溶解して調製した溶液に、表面官能基修飾シリカナノ粒子を投入し、攪拌、混合して均一な溶液とする工程と、キャスティング法等により、その溶液からなる塗工膜を形成する工程と、塗工膜を乾燥する工程と、を有する。 [Method for producing gas separation membrane]
The method for producing a gas separation membrane of the present embodiment includes a step of adding surface functional group-modified silica nanoparticles to a solution prepared by dissolving a polymer in a solvent, stirring and mixing to form a uniform solution, and a casting method. and the like to form a coating film made of the solution, and a step of drying the coating film.
本実施形態の気体分離膜の製造方法は、高分子を溶媒に溶解して調製した溶液に、表面官能基修飾シリカナノ粒子を投入し、攪拌、混合して均一な溶液とする工程と、キャスティング法等により、その溶液からなる塗工膜を形成する工程と、塗工膜を乾燥する工程と、を有する。 [Method for producing gas separation membrane]
The method for producing a gas separation membrane of the present embodiment includes a step of adding surface functional group-modified silica nanoparticles to a solution prepared by dissolving a polymer in a solvent, stirring and mixing to form a uniform solution, and a casting method. and the like to form a coating film made of the solution, and a step of drying the coating film.
高分子を溶解する溶媒としては、上記高分子を溶解することができるものであれば特に限定されないが、例えば、テトラヒドロフラン（ＴＨＦ）等が挙げられる。
The solvent for dissolving the polymer is not particularly limited as long as it can dissolve the polymer, and examples thereof include tetrahydrofuran (THF).
以下、実施例および比較例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。
The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
［実施例１］
「固有微細孔性高分子（ＰＩＭ－１）の合成」
あらかじめ窒素フローを行っていた１Ｌ三つ口フラスコに強制撹拌機を装着し、その三つ口フラスコ内に、５，５’，６，６’－ｔｅｔｒａｈｙｄｒｏｘｙ－３，３，３’，３’－ｔｅｔｒａｍｅｔｈｙｌ－１，１’－ｓｐｉｒｏｂｉｉｎｄａｎを１６．３９５ｇ（４４．７７ｍｍｏｌ）と、２，３，５，６－ｔｅｔｒａｆｌｕｏｒｏｔｅｒｅｐｈｔｈａｌｏｎｉｔｒｉｌｅを８．９５８ｇ（４４．７７ｍｍｏｌ）を投入し、脱水Ｎ，Ｎジメチルホルムアミド（ＤＭＦ）を３００ｍＬ加え、室温、３００ｒｐｍで３０分間撹拌した。
モノマーが溶解した後、モノマーに対し６モル等量の炭酸カリウム（Ｋ２ＣＯ３）を３７．１３ｇ加えると溶液が黄色に変化した。
その後、６５℃、３００ｒｐｍで７２時間撹拌した。
７２時間による反応終了後、ＡＤＶＡＮＴＥＣ社製の直径９ｃｍの定量ろ紙Ｎｏ．３を用いて、粗生成物を吸引濾過により回収した。
この粗生成物を、２００ｍＬのＤＭＦ、１００ｍＬのアセトン、４００ｍＬの水で順次洗浄した。
炭酸カリウムを溶解除去するために、洗浄物を２Ｌビーカーに移し、２Ｌの水を注いで４０℃にて熱水攪拌し、これを再び吸引濾過した。
もう一度、熱水攪拌を行い、吸引濾過後の生成物を３００ｍＬの水、１００ｍＬのアセトンで洗浄した。加えて、３００ｍＬの１，４－ジオキサンを少しずつ加えながら洗浄し、その後５０ｍＬのアセトン、３００ｍＬの水でさらなる洗浄を行った。
吸引瓶の中にｐＨ試験紙を入れ、濾液が中性であることを確認し、濾過で得られた蛍光黄色の固体を回収して、真空オーブンで９５℃、１５時間の条件で乾燥を行い、黄色固体の生成物を得た。乾燥後のＰＩＭ－１の収量は１８．８９ｇであった。
ＰＩＭ－１の合成に関する反応式を、下記の化学反応式（２６）に示す。 [Example 1]
"Synthesis of intrinsic microporous polymer (PIM-1)"
A 1 L three-necked flask that had been flowed with nitrogen in advance was equipped with a forced stirrer, and 5,5′,6,6′-tetrahydroxy-3,3,3′,3′- 16.395 g (44.77 mmol) of tetramethyl-1,1′-spirobiindan and 8.958 g (44.77 mmol) of 2,3,5,6-tetrafluoroterephthalonitrile were added, and dehydrated N,N dimethylformamide (DMF) was added. was added, and stirred at room temperature and 300 rpm for 30 minutes.
After the monomer was dissolved, 37.13 g of potassium carbonate (K 2 CO 3 ), which was 6 molar equivalents to the monomer, was added and the solution turned yellow.
After that, the mixture was stirred at 65° C. and 300 rpm for 72 hours.
After completion of the reaction for 72 hours, quantitative filter paper No. 9 cm in diameter manufactured by ADVANTEC. Using 3, the crude product was collected by suction filtration.
The crude product was washed sequentially with 200 mL DMF, 100 mL acetone and 400 mL water.
In order to dissolve and remove potassium carbonate, the washed material was transferred to a 2 L beaker, 2 L of water was poured into the beaker, hot water was stirred at 40° C., and suction filtration was performed again.
Hot water stirring was performed once again, and the product after suction filtration was washed with 300 mL of water and 100 mL of acetone. In addition, 300 mL of 1,4-dioxane was added in portions for washing, followed by further washing with 50 mL of acetone and 300 mL of water.
Put pH test paper in the suction bottle, confirm that the filtrate is neutral, collect the fluorescent yellow solid obtained by filtration, and dry it in a vacuum oven at 95°C for 15 hours. , to give the product as a yellow solid. The yield of PIM-1 after drying was 18.89 g.
A reaction formula for the synthesis of PIM-1 is shown in chemical reaction formula (26) below.
「固有微細孔性高分子（ＰＩＭ－１）の合成」
あらかじめ窒素フローを行っていた１Ｌ三つ口フラスコに強制撹拌機を装着し、その三つ口フラスコ内に、５，５’，６，６’－ｔｅｔｒａｈｙｄｒｏｘｙ－３，３，３’，３’－ｔｅｔｒａｍｅｔｈｙｌ－１，１’－ｓｐｉｒｏｂｉｉｎｄａｎを１６．３９５ｇ（４４．７７ｍｍｏｌ）と、２，３，５，６－ｔｅｔｒａｆｌｕｏｒｏｔｅｒｅｐｈｔｈａｌｏｎｉｔｒｉｌｅを８．９５８ｇ（４４．７７ｍｍｏｌ）を投入し、脱水Ｎ，Ｎジメチルホルムアミド（ＤＭＦ）を３００ｍＬ加え、室温、３００ｒｐｍで３０分間撹拌した。
モノマーが溶解した後、モノマーに対し６モル等量の炭酸カリウム（Ｋ２ＣＯ３）を３７．１３ｇ加えると溶液が黄色に変化した。
その後、６５℃、３００ｒｐｍで７２時間撹拌した。
７２時間による反応終了後、ＡＤＶＡＮＴＥＣ社製の直径９ｃｍの定量ろ紙Ｎｏ．３を用いて、粗生成物を吸引濾過により回収した。
この粗生成物を、２００ｍＬのＤＭＦ、１００ｍＬのアセトン、４００ｍＬの水で順次洗浄した。
炭酸カリウムを溶解除去するために、洗浄物を２Ｌビーカーに移し、２Ｌの水を注いで４０℃にて熱水攪拌し、これを再び吸引濾過した。
もう一度、熱水攪拌を行い、吸引濾過後の生成物を３００ｍＬの水、１００ｍＬのアセトンで洗浄した。加えて、３００ｍＬの１，４－ジオキサンを少しずつ加えながら洗浄し、その後５０ｍＬのアセトン、３００ｍＬの水でさらなる洗浄を行った。
吸引瓶の中にｐＨ試験紙を入れ、濾液が中性であることを確認し、濾過で得られた蛍光黄色の固体を回収して、真空オーブンで９５℃、１５時間の条件で乾燥を行い、黄色固体の生成物を得た。乾燥後のＰＩＭ－１の収量は１８．８９ｇであった。
ＰＩＭ－１の合成に関する反応式を、下記の化学反応式（２６）に示す。 [Example 1]
"Synthesis of intrinsic microporous polymer (PIM-1)"
A 1 L three-necked flask that had been flowed with nitrogen in advance was equipped with a forced stirrer, and 5,5′,6,6′-tetrahydroxy-3,3,3′,3′- 16.395 g (44.77 mmol) of tetramethyl-1,1′-spirobiindan and 8.958 g (44.77 mmol) of 2,3,5,6-tetrafluoroterephthalonitrile were added, and dehydrated N,N dimethylformamide (DMF) was added. was added, and stirred at room temperature and 300 rpm for 30 minutes.
After the monomer was dissolved, 37.13 g of potassium carbonate (K 2 CO 3 ), which was 6 molar equivalents to the monomer, was added and the solution turned yellow.
After that, the mixture was stirred at 65° C. and 300 rpm for 72 hours.
After completion of the reaction for 72 hours, quantitative filter paper No. 9 cm in diameter manufactured by ADVANTEC. Using 3, the crude product was collected by suction filtration.
The crude product was washed sequentially with 200 mL DMF, 100 mL acetone and 400 mL water.
In order to dissolve and remove potassium carbonate, the washed material was transferred to a 2 L beaker, 2 L of water was poured into the beaker, hot water was stirred at 40° C., and suction filtration was performed again.
Hot water stirring was performed once again, and the product after suction filtration was washed with 300 mL of water and 100 mL of acetone. In addition, 300 mL of 1,4-dioxane was added in portions for washing, followed by further washing with 50 mL of acetone and 300 mL of water.
Put pH test paper in the suction bottle, confirm that the filtrate is neutral, collect the fluorescent yellow solid obtained by filtration, and dry it in a vacuum oven at 95°C for 15 hours. , to give the product as a yellow solid. The yield of PIM-1 after drying was 18.89 g.
A reaction formula for the synthesis of PIM-1 is shown in chemical reaction formula (26) below.
［実施例２］
「固有微細孔性高分子（ＰＩＭ－１）の精製」
実施例１にて合成した生成物を、クロロホルムに溶解させ、貧溶媒のメタノールを少しずつ加えることでＰＩＭ－１を沈殿させた。
任意の領域のポリマーを得るため、沈殿物は数回に分けて回収し、９５℃、１５時間真空乾燥した。 [Example 2]
"Purification of intrinsic microporous polymer (PIM-1)"
The product synthesized in Example 1 was dissolved in chloroform, and methanol as a poor solvent was added little by little to precipitate PIM-1.
In order to obtain a polymer in an arbitrary region, the precipitate was collected in several batches and vacuum-dried at 95° C. for 15 hours.
「固有微細孔性高分子（ＰＩＭ－１）の精製」
実施例１にて合成した生成物を、クロロホルムに溶解させ、貧溶媒のメタノールを少しずつ加えることでＰＩＭ－１を沈殿させた。
任意の領域のポリマーを得るため、沈殿物は数回に分けて回収し、９５℃、１５時間真空乾燥した。 [Example 2]
"Purification of intrinsic microporous polymer (PIM-1)"
The product synthesized in Example 1 was dissolved in chloroform, and methanol as a poor solvent was added little by little to precipitate PIM-1.
In order to obtain a polymer in an arbitrary region, the precipitate was collected in several batches and vacuum-dried at 95° C. for 15 hours.
［実施例３］
「固有微細孔性高分子（ＰＩＭ－１）のゲル透過クロマトグラフィー（ＧＰＣ）測定」
実施例２にて精製したＰＩＭ－１の分子量を測定するために、ＧＰＣ測定を行った。
ＰＩＭ－１約４．０ｍｇを量りとってサンプル管に入れ、テトラヒドロフラン（ＴＨＦ）を４．０ｍＬ加え、超音波洗浄機を用いて完全に溶解させた。
孔径０．４５μｍのポリテトラフルオロエチレン（ＰＴＦＥ）シリンジフィルターを装着したシリンジで溶液を濾過し、ＧＰＣ測定を行った。
測定の結果、精製により高分子量で分子量分布が広いもの（重量平均分子量４．７×１０５、多分散指数１０．５）から、比較的低分子量分布で分子量分布が狭いもの（重量平均分子量１．１×１０５、多分散指数１．６）まで得られた。 [Example 3]
"Gel Permeation Chromatography (GPC) Measurement of Inherent Microporous Polymer (PIM-1)"
In order to measure the molecular weight of PIM-1 purified in Example 2, GPC measurement was performed.
About 4.0 mg of PIM-1 was weighed and placed in a sample tube, 4.0 mL of tetrahydrofuran (THF) was added, and completely dissolved using an ultrasonic cleaner.
The solution was filtered with a syringe equipped with a polytetrafluoroethylene (PTFE) syringe filter with a pore size of 0.45 μm, and GPC measurement was performed.
As a result of the measurement, it was found that the purified product had a high molecular weight with a wide molecular weight distribution (weight average molecular weight: 4.7 × 10 5 , polydispersity index: 10.5) to a relatively low molecular weight distribution with a narrow molecular weight distribution (weight average molecular weight: 1 up to .1×10 5 , polydispersity index 1.6).
「固有微細孔性高分子（ＰＩＭ－１）のゲル透過クロマトグラフィー（ＧＰＣ）測定」
実施例２にて精製したＰＩＭ－１の分子量を測定するために、ＧＰＣ測定を行った。
ＰＩＭ－１約４．０ｍｇを量りとってサンプル管に入れ、テトラヒドロフラン（ＴＨＦ）を４．０ｍＬ加え、超音波洗浄機を用いて完全に溶解させた。
孔径０．４５μｍのポリテトラフルオロエチレン（ＰＴＦＥ）シリンジフィルターを装着したシリンジで溶液を濾過し、ＧＰＣ測定を行った。
測定の結果、精製により高分子量で分子量分布が広いもの（重量平均分子量４．７×１０５、多分散指数１０．５）から、比較的低分子量分布で分子量分布が狭いもの（重量平均分子量１．１×１０５、多分散指数１．６）まで得られた。 [Example 3]
"Gel Permeation Chromatography (GPC) Measurement of Inherent Microporous Polymer (PIM-1)"
In order to measure the molecular weight of PIM-1 purified in Example 2, GPC measurement was performed.
About 4.0 mg of PIM-1 was weighed and placed in a sample tube, 4.0 mL of tetrahydrofuran (THF) was added, and completely dissolved using an ultrasonic cleaner.
The solution was filtered with a syringe equipped with a polytetrafluoroethylene (PTFE) syringe filter with a pore size of 0.45 μm, and GPC measurement was performed.
As a result of the measurement, it was found that the purified product had a high molecular weight with a wide molecular weight distribution (weight average molecular weight: 4.7 × 10 5 , polydispersity index: 10.5) to a relatively low molecular weight distribution with a narrow molecular weight distribution (weight average molecular weight: 1 up to .1×10 5 , polydispersity index 1.6).
［実施例４］
「ＰＩＭ－１（分子量：重量平均分子量５０万）と表面官能基修飾シリカナノ粒子（１）を用いた有機－無機複合気体分離膜の製膜」
０．１５ｇの固有微細孔ポリマー、ＰＩＭ－１（下記の化学式（２３）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が６０質量％となるように、表面官能基修飾シリカナノ粒子（１）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（１）としては、上記の化学式（１９）で表されるものを用いた。
このポリマー溶液を攪拌速度１２００ｒｐｍで一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、６時間かけて真空にして複合膜を作製した。
作製した複合膜は、７０℃、１８時間の熱処理を行った。得られた膜の膜厚は７９μｍであった。 [Example 4]
"Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 500,000) and surface functional group-modified silica nanoparticles (1)"
After dissolving 0.15 g of an intrinsic microporous polymer, PIM-1 (see formula (23) below), in 6.7 mL of tetrahydrofuran (THF), the polymer solution has a content of 60% by weight relative to the polymer. As shown, the surface functional group-modified silica nanoparticles (1) were added and sonicated for 1 hour.
As the surface functional group-modified silica nanoparticles (1), those represented by the above chemical formula (19) were used.
The polymer solution was stirred overnight at a stirring speed of 1200 rpm, and after stirring was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 6 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 70° C. for 18 hours. The film thickness of the obtained film was 79 μm.
「ＰＩＭ－１（分子量：重量平均分子量５０万）と表面官能基修飾シリカナノ粒子（１）を用いた有機－無機複合気体分離膜の製膜」
０．１５ｇの固有微細孔ポリマー、ＰＩＭ－１（下記の化学式（２３）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が６０質量％となるように、表面官能基修飾シリカナノ粒子（１）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（１）としては、上記の化学式（１９）で表されるものを用いた。
このポリマー溶液を攪拌速度１２００ｒｐｍで一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、６時間かけて真空にして複合膜を作製した。
作製した複合膜は、７０℃、１８時間の熱処理を行った。得られた膜の膜厚は７９μｍであった。 [Example 4]
"Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 500,000) and surface functional group-modified silica nanoparticles (1)"
After dissolving 0.15 g of an intrinsic microporous polymer, PIM-1 (see formula (23) below), in 6.7 mL of tetrahydrofuran (THF), the polymer solution has a content of 60% by weight relative to the polymer. As shown, the surface functional group-modified silica nanoparticles (1) were added and sonicated for 1 hour.
As the surface functional group-modified silica nanoparticles (1), those represented by the above chemical formula (19) were used.
The polymer solution was stirred overnight at a stirring speed of 1200 rpm, and after stirring was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 6 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 70° C. for 18 hours. The film thickness of the obtained film was 79 μm.
［実施例５］
「ＰＩＭ－１（分子量：重量平均分子量５０万）と表面官能基修飾シリカナノ粒子（１）の複合気体分離膜の気体透過特性」
実施例４で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として酸素、窒素を用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表１に示す。 [Example 5]
"Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 500,000) and Surface Functional Group-Modified Silica Nanoparticles (1)"
The gas permeability of the composite membrane obtained in Example 4 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Oxygen and nitrogen were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 1 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量５０万）と表面官能基修飾シリカナノ粒子（１）の複合気体分離膜の気体透過特性」
実施例４で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として酸素、窒素を用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表１に示す。 [Example 5]
"Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 500,000) and Surface Functional Group-Modified Silica Nanoparticles (1)"
The gas permeability of the composite membrane obtained in Example 4 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Oxygen and nitrogen were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 1 shows the results.
［比較例１］
「ＰＩＭ－１（分子量：重量平均分子量５０万）気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（１）を添加しないこと以外は実施例４と同様にして、ＰＩＭ－１気体分離膜を作製した。
得られた膜の気体透過率測定を、実施例５と同様にして行った。結果を表１に示す。 [Comparative Example 1]
"PIM-1 (molecular weight: weight average molecular weight 500,000) gas separation membrane production"
A PIM-1 gas separation membrane was produced in the same manner as in Example 4, except that the surface functional group-modified silica nanoparticles (1) were not added.
The gas permeability of the resulting membrane was measured in the same manner as in Example 5. Table 1 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量５０万）気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（１）を添加しないこと以外は実施例４と同様にして、ＰＩＭ－１気体分離膜を作製した。
得られた膜の気体透過率測定を、実施例５と同様にして行った。結果を表１に示す。 [Comparative Example 1]
"PIM-1 (molecular weight: weight average molecular weight 500,000) gas separation membrane production"
A PIM-1 gas separation membrane was produced in the same manner as in Example 4, except that the surface functional group-modified silica nanoparticles (1) were not added.
The gas permeability of the resulting membrane was measured in the same manner as in Example 5. Table 1 shows the results.
表１に示す結果から、実施例４の複合気体分離膜は、比較例１のＰＩＭ－１気体分離膜よりも、酸素の透過率が約４倍であった。
From the results shown in Table 1, the composite gas separation membrane of Example 4 had an oxygen permeability about four times that of the PIM-1 gas separation membrane of Comparative Example 1.
［実施例６］
「ＰＩＭ－１（分子量：重量平均分子量５０万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
０．１５ｇの固有微細孔ポリマー、ＰＩＭ－１（上記の化学式（２３）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が２０質量％となるように、表面官能基修飾シリカナノ粒子（２）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（２）としては、上記の式（２０）で表されるものを用いた。
このポリマー溶液を攪拌速度１２００ｒｐｍで一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、６時間かけて真空にして複合膜を作製した。
作製した複合膜は、７０℃、１８時間の熱処理を行った。得られた膜の膜厚は５１μｍであった。 [Example 6]
"Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 500,000) and surface functional group-modified silica nanoparticles (2)"
After dissolving 0.15 g of the intrinsic microporous polymer, PIM-1 (see formula (23) above), in 6.7 mL of tetrahydrofuran (THF), the polymer solution has a content of 20% by weight relative to the polymer. As shown, the surface functional group-modified silica nanoparticles (2) were added and sonicated for 1 hour.
As the surface functional group-modified silica nanoparticles (2), those represented by the above formula (20) were used.
The polymer solution was stirred overnight at a stirring speed of 1200 rpm, and after stirring was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 6 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 70° C. for 18 hours. The film thickness of the obtained film was 51 μm.
「ＰＩＭ－１（分子量：重量平均分子量５０万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
０．１５ｇの固有微細孔ポリマー、ＰＩＭ－１（上記の化学式（２３）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が２０質量％となるように、表面官能基修飾シリカナノ粒子（２）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（２）としては、上記の式（２０）で表されるものを用いた。
このポリマー溶液を攪拌速度１２００ｒｐｍで一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、６時間かけて真空にして複合膜を作製した。
作製した複合膜は、７０℃、１８時間の熱処理を行った。得られた膜の膜厚は５１μｍであった。 [Example 6]
"Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 500,000) and surface functional group-modified silica nanoparticles (2)"
After dissolving 0.15 g of the intrinsic microporous polymer, PIM-1 (see formula (23) above), in 6.7 mL of tetrahydrofuran (THF), the polymer solution has a content of 20% by weight relative to the polymer. As shown, the surface functional group-modified silica nanoparticles (2) were added and sonicated for 1 hour.
As the surface functional group-modified silica nanoparticles (2), those represented by the above formula (20) were used.
The polymer solution was stirred overnight at a stirring speed of 1200 rpm, and after stirring was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 6 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 70° C. for 18 hours. The film thickness of the obtained film was 51 μm.
［実施例７］
「ＰＩＭ－１（分子量：重量平均分子量５０万）と表面官能基修飾シリカナノ粒子（２）の複合気体分離膜の気体透過特性」
実施例６で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として酸素、窒素を用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表２に示す。 [Example 7]
"Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 500,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
The gas permeability of the composite membrane obtained in Example 6 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Oxygen and nitrogen were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 2 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量５０万）と表面官能基修飾シリカナノ粒子（２）の複合気体分離膜の気体透過特性」
実施例６で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として酸素、窒素を用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表２に示す。 [Example 7]
"Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 500,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
The gas permeability of the composite membrane obtained in Example 6 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Oxygen and nitrogen were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 2 shows the results.
［実施例８］
「ＰＩＭ－１（分子量：重量平均分子量５０万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（２）の添加量を４０質量％としたこと以外は実施例６と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例７と同様にして行った。結果を表２に示す。 [Example 8]
"Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 500,000) and surface functional group-modified silica nanoparticles (2)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 6, except that the amount of the surface functional group-modified silica nanoparticles (2) added was 40% by mass.
The gas permeability of the resulting composite membrane was measured in the same manner as in Example 7. Table 2 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量５０万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（２）の添加量を４０質量％としたこと以外は実施例６と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例７と同様にして行った。結果を表２に示す。 [Example 8]
"Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 500,000) and surface functional group-modified silica nanoparticles (2)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 6, except that the amount of the surface functional group-modified silica nanoparticles (2) added was 40% by mass.
The gas permeability of the resulting composite membrane was measured in the same manner as in Example 7. Table 2 shows the results.
［実施例９］
「ＰＩＭ－１（分子量：重量平均分子量５０万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（２）の添加量を６０質量％としたこと以外は実施例６と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例７と同様にして行った。結果を表２に示す。 [Example 9]
"Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 500,000) and surface functional group-modified silica nanoparticles (2)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 6, except that the amount of the surface functional group-modified silica nanoparticles (2) added was 60% by mass.
The gas permeability of the resulting composite membrane was measured in the same manner as in Example 7. Table 2 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量５０万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（２）の添加量を６０質量％としたこと以外は実施例６と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例７と同様にして行った。結果を表２に示す。 [Example 9]
"Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 500,000) and surface functional group-modified silica nanoparticles (2)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 6, except that the amount of the surface functional group-modified silica nanoparticles (2) added was 60% by mass.
The gas permeability of the resulting composite membrane was measured in the same manner as in Example 7. Table 2 shows the results.
［実施例１０］
「ＰＩＭ－１（分子量：重量平均分子量５０万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（２）の添加量を７０質量％としたこと以外は実施例６と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例７と同様にして行った。結果を表２に示す。 [Example 10]
"Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 500,000) and surface functional group-modified silica nanoparticles (2)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 6, except that the amount of the surface functional group-modified silica nanoparticles (2) added was 70% by mass.
The gas permeability of the resulting composite membrane was measured in the same manner as in Example 7. Table 2 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量５０万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（２）の添加量を７０質量％としたこと以外は実施例６と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例７と同様にして行った。結果を表２に示す。 [Example 10]
"Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 500,000) and surface functional group-modified silica nanoparticles (2)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 6, except that the amount of the surface functional group-modified silica nanoparticles (2) added was 70% by mass.
The gas permeability of the resulting composite membrane was measured in the same manner as in Example 7. Table 2 shows the results.
［比較例２］
「ＰＩＭ－１（分子量：重量平均分子量５０万）気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（２）を添加しないこと以外は実施例６と同様にして、ＰＩＭ－１気体分離膜を作製した。
得られた気体分離膜の気体透過率測定を、実施例７と同様にして行った。結果を表２に示す。 [Comparative Example 2]
"PIM-1 (molecular weight: weight average molecular weight 500,000) gas separation membrane production"
A PIM-1 gas separation membrane was produced in the same manner as in Example 6, except that the surface functional group-modified silica nanoparticles (2) were not added.
The gas permeability of the obtained gas separation membrane was measured in the same manner as in Example 7. Table 2 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量５０万）気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（２）を添加しないこと以外は実施例６と同様にして、ＰＩＭ－１気体分離膜を作製した。
得られた気体分離膜の気体透過率測定を、実施例７と同様にして行った。結果を表２に示す。 [Comparative Example 2]
"PIM-1 (molecular weight: weight average molecular weight 500,000) gas separation membrane production"
A PIM-1 gas separation membrane was produced in the same manner as in Example 6, except that the surface functional group-modified silica nanoparticles (2) were not added.
The gas permeability of the obtained gas separation membrane was measured in the same manner as in Example 7. Table 2 shows the results.
表２に示す結果から、実施例６は、比較例２よりも、酸素の透過率が約２．７倍であった。実施例８は、比較例２よりも、酸素の透過率が約５．３倍であった。実施例９は、比較例２よりも、酸素の透過率が約９．８倍であった。実施例１０は、比較例２よりも、酸素の透過率が約１０．８倍であった。
From the results shown in Table 2, Example 6 had an oxygen permeability about 2.7 times that of Comparative Example 2. Example 8 had an oxygen permeability about 5.3 times that of Comparative Example 2. Example 9 had an oxygen permeability of about 9.8 times that of Comparative Example 2. Example 10 had an oxygen permeability of about 10.8 times that of Comparative Example 2.
［実施例１１］
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（１）を用いた有機－無機複合気体分離膜の製膜」
０．１５ｇの固有微細孔ポリマー、ＰＩＭ－１（上記の化学式（２３）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が５０質量％となるように、表面官能基修飾シリカナノ粒子（１）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（１）としては、上記の式（１）で表されるものを用いた。
このポリマー溶液を攪拌速度１２００ｒｐｍで一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、６時間かけて真空にして複合膜を作製した。
作製した複合膜は、７０℃、１８時間の熱処理を行った。得られた膜の膜厚は６７μｍであった。 [Example 11]
"Formation of Organic-Inorganic Composite Gas Separation Membrane Using PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (1)"
After dissolving 0.15 g of the intrinsic microporous polymer, PIM-1 (see formula (23) above), in 6.7 mL of tetrahydrofuran (THF), the polymer solution has a content of 50% by weight relative to the polymer. As shown, the surface functional group-modified silica nanoparticles (1) were added and sonicated for 1 hour.
As the surface functional group-modified silica nanoparticles (1), those represented by the above formula (1) were used.
The polymer solution was stirred overnight at a stirring speed of 1200 rpm, and after stirring was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 6 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 70° C. for 18 hours. The film thickness of the obtained film was 67 μm.
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（１）を用いた有機－無機複合気体分離膜の製膜」
０．１５ｇの固有微細孔ポリマー、ＰＩＭ－１（上記の化学式（２３）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が５０質量％となるように、表面官能基修飾シリカナノ粒子（１）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（１）としては、上記の式（１）で表されるものを用いた。
このポリマー溶液を攪拌速度１２００ｒｐｍで一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、６時間かけて真空にして複合膜を作製した。
作製した複合膜は、７０℃、１８時間の熱処理を行った。得られた膜の膜厚は６７μｍであった。 [Example 11]
"Formation of Organic-Inorganic Composite Gas Separation Membrane Using PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (1)"
After dissolving 0.15 g of the intrinsic microporous polymer, PIM-1 (see formula (23) above), in 6.7 mL of tetrahydrofuran (THF), the polymer solution has a content of 50% by weight relative to the polymer. As shown, the surface functional group-modified silica nanoparticles (1) were added and sonicated for 1 hour.
As the surface functional group-modified silica nanoparticles (1), those represented by the above formula (1) were used.
The polymer solution was stirred overnight at a stirring speed of 1200 rpm, and after stirring was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 6 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 70° C. for 18 hours. The film thickness of the obtained film was 67 μm.
［実施例１２］
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（１）の複合気体分離膜の気体透過特性」
実施例１１で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として二酸化炭素、酸素、窒素、メタンを用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表３に示す。 [Example 12]
"Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (1)"
The gas permeability of the composite membrane obtained in Example 11 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Carbon dioxide, oxygen, nitrogen, and methane were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 3 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（１）の複合気体分離膜の気体透過特性」
実施例１１で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として二酸化炭素、酸素、窒素、メタンを用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表３に示す。 [Example 12]
"Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (1)"
The gas permeability of the composite membrane obtained in Example 11 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Carbon dioxide, oxygen, nitrogen, and methane were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 3 shows the results.
［実施例１３］
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（１）を用いた有機－無機複合気体分離膜の製膜」
シリカナノ粒子（１）の添加量を８０質量％としたこと以外は実施例１１と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例１２と同様にして行った。結果を表３に示す。 [Example 13]
"Formation of Organic-Inorganic Composite Gas Separation Membrane Using PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (1)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 11, except that the amount of silica nanoparticles (1) added was 80% by mass.
The gas permeability of the resulting composite membrane was measured in the same manner as in Example 12. Table 3 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（１）を用いた有機－無機複合気体分離膜の製膜」
シリカナノ粒子（１）の添加量を８０質量％としたこと以外は実施例１１と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例１２と同様にして行った。結果を表３に示す。 [Example 13]
"Formation of Organic-Inorganic Composite Gas Separation Membrane Using PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (1)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 11, except that the amount of silica nanoparticles (1) added was 80% by mass.
The gas permeability of the resulting composite membrane was measured in the same manner as in Example 12. Table 3 shows the results.
［比較例３］
「ＰＩＭ－１（分子量：重量平均分子量１０万）気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（１）を添加しないこと以外は実施例１１と同様にして、ＰＩＭ－１気体分離膜を作製した。
得られた気体分離膜の気体透過率測定を、実施例１２と同様にして行った。結果を表３に示す。 [Comparative Example 3]
"Preparation of PIM-1 (molecular weight: weight average molecular weight 100,000) gas separation membrane"
A PIM-1 gas separation membrane was produced in the same manner as in Example 11, except that the surface functional group-modified silica nanoparticles (1) were not added.
The gas permeability of the obtained gas separation membrane was measured in the same manner as in Example 12. Table 3 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量１０万）気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（１）を添加しないこと以外は実施例１１と同様にして、ＰＩＭ－１気体分離膜を作製した。
得られた気体分離膜の気体透過率測定を、実施例１２と同様にして行った。結果を表３に示す。 [Comparative Example 3]
"Preparation of PIM-1 (molecular weight: weight average molecular weight 100,000) gas separation membrane"
A PIM-1 gas separation membrane was produced in the same manner as in Example 11, except that the surface functional group-modified silica nanoparticles (1) were not added.
The gas permeability of the obtained gas separation membrane was measured in the same manner as in Example 12. Table 3 shows the results.
表３に示す結果から、実施例１１は、比較例３よりも、酸素の透過率が約１．４倍、二酸化炭素の透過率が約１．３倍、窒素の透過率が約１．５倍、メタンの透過率が約１．８倍であった。実施例１３は、比較例３よりも、酸素の透過率が約６．４倍、窒素の透過率が約８．９倍であった。
From the results shown in Table 3, Example 11 has an oxygen permeability of about 1.4 times, a carbon dioxide permeability of about 1.3 times, and a nitrogen permeability of about 1.5 times that of Comparative Example 3. , and the methane permeability was about 1.8 times. Example 13 had an oxygen permeability of about 6.4 times and a nitrogen permeability of about 8.9 times that of Comparative Example 3.
［実施例１４］
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
０．１５ｇの固有微細孔ポリマー、ＰＩＭ－１（上記の化学式（２３）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が６０質量％となるように、表面官能基修飾シリカナノ粒子（２）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（２）としては、上記の化学式（２０）で表されるものを用いた。
このポリマー溶液を攪拌速度１２００ｒｐｍで一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、６時間かけて真空にして複合膜を作製した。
作製した複合膜は、７０℃、１８時間の熱処理を行った。得られた膜の膜厚は９４μｍであった。 [Example 14]
"Formation of Organic-Inorganic Composite Gas Separation Membrane Using PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
After dissolving 0.15 g of the intrinsic microporous polymer, PIM-1 (see formula (23) above), in 6.7 mL of tetrahydrofuran (THF), the polymer solution has a content of 60% by weight relative to the polymer. As shown, the surface functional group-modified silica nanoparticles (2) were added and sonicated for 1 hour.
As the surface functional group-modified silica nanoparticles (2), those represented by the above chemical formula (20) were used.
The polymer solution was stirred overnight at a stirring speed of 1200 rpm, and after stirring was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 6 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 70° C. for 18 hours. The film thickness of the obtained film was 94 μm.
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
０．１５ｇの固有微細孔ポリマー、ＰＩＭ－１（上記の化学式（２３）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が６０質量％となるように、表面官能基修飾シリカナノ粒子（２）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（２）としては、上記の化学式（２０）で表されるものを用いた。
このポリマー溶液を攪拌速度１２００ｒｐｍで一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、６時間かけて真空にして複合膜を作製した。
作製した複合膜は、７０℃、１８時間の熱処理を行った。得られた膜の膜厚は９４μｍであった。 [Example 14]
"Formation of Organic-Inorganic Composite Gas Separation Membrane Using PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
After dissolving 0.15 g of the intrinsic microporous polymer, PIM-1 (see formula (23) above), in 6.7 mL of tetrahydrofuran (THF), the polymer solution has a content of 60% by weight relative to the polymer. As shown, the surface functional group-modified silica nanoparticles (2) were added and sonicated for 1 hour.
As the surface functional group-modified silica nanoparticles (2), those represented by the above chemical formula (20) were used.
The polymer solution was stirred overnight at a stirring speed of 1200 rpm, and after stirring was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 6 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 70° C. for 18 hours. The film thickness of the obtained film was 94 μm.
［実施例１５］
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（２）の複合気体分離膜の気体透過特性」
実施例１４で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として二酸化炭素、酸素、窒素、メタンを用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表４に示す。 [Example 15]
"Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
The gas permeability of the composite membrane obtained in Example 14 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Carbon dioxide, oxygen, nitrogen, and methane were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 4 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（２）の複合気体分離膜の気体透過特性」
実施例１４で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として二酸化炭素、酸素、窒素、メタンを用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表４に示す。 [Example 15]
"Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
The gas permeability of the composite membrane obtained in Example 14 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Carbon dioxide, oxygen, nitrogen, and methane were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 4 shows the results.
［実施例１６］
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（２）の添加量を８５質量％としたこと以外は実施例１４と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例１５と同様にして行った。結果を表４に示す。 [Example 16]
"Formation of Organic-Inorganic Composite Gas Separation Membrane Using PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 14, except that the amount of the surface functional group-modified silica nanoparticles (2) added was 85% by mass.
The gas permeability of the resulting composite membrane was measured in the same manner as in Example 15. Table 4 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（２）の添加量を８５質量％としたこと以外は実施例１４と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例１５と同様にして行った。結果を表４に示す。 [Example 16]
"Formation of Organic-Inorganic Composite Gas Separation Membrane Using PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 14, except that the amount of the surface functional group-modified silica nanoparticles (2) added was 85% by mass.
The gas permeability of the resulting composite membrane was measured in the same manner as in Example 15. Table 4 shows the results.
［比較例４］
「ＰＩＭ－１（分子量：重量平均分子量１０万）気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（２）を添加しないこと以外は実施例１４と同様にして、ＰＩＭ－１気体分離膜を作製した。
得られた気体分離膜の気体透過率測定を、実施例１５と同様にして行った。結果を表４に示す。 [Comparative Example 4]
"Preparation of PIM-1 (molecular weight: weight average molecular weight 100,000) gas separation membrane"
A PIM-1 gas separation membrane was produced in the same manner as in Example 14, except that the surface functional group-modified silica nanoparticles (2) were not added.
The gas permeability of the obtained gas separation membrane was measured in the same manner as in Example 15. Table 4 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量１０万）気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（２）を添加しないこと以外は実施例１４と同様にして、ＰＩＭ－１気体分離膜を作製した。
得られた気体分離膜の気体透過率測定を、実施例１５と同様にして行った。結果を表４に示す。 [Comparative Example 4]
"Preparation of PIM-1 (molecular weight: weight average molecular weight 100,000) gas separation membrane"
A PIM-1 gas separation membrane was produced in the same manner as in Example 14, except that the surface functional group-modified silica nanoparticles (2) were not added.
The gas permeability of the obtained gas separation membrane was measured in the same manner as in Example 15. Table 4 shows the results.
表４に示す結果から、実施例１４は、比較例４よりも、酸素の透過率が約５．５倍、窒素の透過率が約７．９倍であった。実施例１６は、比較例４よりも、酸素の透過率が約１４．６倍、二酸化炭素の透過率が約１３．９倍、窒素の透過率が約２２．２倍、メタンの透過率が約３０．６倍であった。
From the results shown in Table 4, Example 14 had an oxygen permeability of about 5.5 times and a nitrogen permeability of about 7.9 times that of Comparative Example 4. Example 16 has an oxygen permeability of about 14.6 times, a carbon dioxide permeability of about 13.9 times, a nitrogen permeability of about 22.2 times, and a methane permeability of about 22.2 times that of Comparative Example 4. It was about 30.6 times.
［実施例１７］
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の気体透過安定性の評価」
実施例１で合成した固有微細孔ポリマー、ＰＩＭ－１（上記の化学式（２３）参照）と表面官能基修飾シリカナノ粒子（２）を６０質量％含有した実施例１５の複合気体分離膜を室温で１４日間、シリカゲル入りのデシケーター内で保存した。
その後、複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として酸素、窒素を用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表５に示す。 [Example 17]
"Evaluation of Gas Permeation Stability of Organic-Inorganic Composite Gas Separation Membrane Using PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
The composite gas separation membrane of Example 15 containing 60% by mass of the intrinsic microporous polymer synthesized in Example 1, PIM-1 (see chemical formula (23) above) and surface functional group-modified silica nanoparticles (2) at room temperature It was preserved in a desiccator containing silica gel for 14 days.
After that, the gas permeability measurement of the composite membrane was performed.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Oxygen and nitrogen were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 5 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の気体透過安定性の評価」
実施例１で合成した固有微細孔ポリマー、ＰＩＭ－１（上記の化学式（２３）参照）と表面官能基修飾シリカナノ粒子（２）を６０質量％含有した実施例１５の複合気体分離膜を室温で１４日間、シリカゲル入りのデシケーター内で保存した。
その後、複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として酸素、窒素を用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表５に示す。 [Example 17]
"Evaluation of Gas Permeation Stability of Organic-Inorganic Composite Gas Separation Membrane Using PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
The composite gas separation membrane of Example 15 containing 60% by mass of the intrinsic microporous polymer synthesized in Example 1, PIM-1 (see chemical formula (23) above) and surface functional group-modified silica nanoparticles (2) at room temperature It was preserved in a desiccator containing silica gel for 14 days.
After that, the gas permeability measurement of the composite membrane was performed.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Oxygen and nitrogen were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 5 shows the results.
［比較例５］
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（２）の複合気体分離膜の気体透過特性」
実施例１７と同様にして作製した複合気体分離膜について、作製後すぐに、気体透過率測定を行った。
気体透過率測定は、実施例１７と同様とした。結果を表５に示す。 [Comparative Example 5]
"Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
A composite gas separation membrane produced in the same manner as in Example 17 was measured for gas permeability immediately after production.
The gas permeability measurement was the same as in Example 17. Table 5 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量１０万）と表面官能基修飾シリカナノ粒子（２）の複合気体分離膜の気体透過特性」
実施例１７と同様にして作製した複合気体分離膜について、作製後すぐに、気体透過率測定を行った。
気体透過率測定は、実施例１７と同様とした。結果を表５に示す。 [Comparative Example 5]
"Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 100,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
A composite gas separation membrane produced in the same manner as in Example 17 was measured for gas permeability immediately after production.
The gas permeability measurement was the same as in Example 17. Table 5 shows the results.
表５に示す結果から、実施例１７の複合膜は、エタノール処理を行っていないが、保存により酸素の透過率が減少しなかった。
From the results shown in Table 5, although the composite membrane of Example 17 was not treated with ethanol, the oxygen permeability did not decrease during storage.
［実施例１８］
「含フッ素ポリイミド（６ＦＤＡ－３ＭＰＡ）の合成」
昇華精製した２，２’－ビス（３，４’－ジヒドロジカルボキシフェニル）ヘキサフルオロプロペン（６ＦＤＡ）および再結晶精製した２，４，６－トリメチル－１，３－フェニレンジアミン（３ＭＰＡ）を有機溶媒中で縮重合し、ポリイミドを得た。反応は穏和な条件下で進行し、架橋反応等の副反応が生じにくい化学イミド化法を採用した。
５００ｍＬ三口フラスコに３ＭＰＡを６．９８ｇ（４６．４６ｍｍｏｌ）、ジメチルアセトアミド（ＤＭＡｃ）を１１８ｍＬ加えて溶解させ、６ＦＤＡを２０．６４ｇ（４６．４６ｍｍｏｌ）、ＤＭＡｃを６３ｍＬ加えた。
窒素雰囲気下、６００ｒｐｍで１日間撹拌した後、無水酢酸を２２．０ｍＬ（１滴／１秒）、トリエチルアミン（ＴＥＡ）を３２．４ｍＬ（１滴／２秒）滴下した。
さらに、３日間撹拌した後、反応溶液を３Ｌのメタノール中へ滴下し、粒状の６ＦＤＡ－３ＭＰＡを得た。
メタノールを３回入れ替えてスラリーを洗浄し、未反応物を十分に取り除いた後、真空乾燥（１５０℃、１５時間）した。
６ＦＤＡ－３ＭＰＡの合成に関する反応式を、下記の式（２７）に示す。 [Example 18]
"Synthesis of fluorine-containing polyimide (6FDA-3MPA)"
Sublimation purified 2,2′-bis(3,4′-dihydrodicarboxyphenyl)hexafluoropropene (6FDA) and recrystallized purified 2,4,6-trimethyl-1,3-phenylenediamine (3MPA) were organically Polyimide was obtained by condensation polymerization in a solvent. A chemical imidization method was adopted in which the reaction proceeds under mild conditions and side reactions such as cross-linking are unlikely to occur.
6.98 g (46.46 mmol) of 3MPA and 118 mL of dimethylacetamide (DMAc) were added and dissolved in a 500 mL three-necked flask, and 20.64 g (46.46 mmol) of 6FDA and 63 mL of DMAc were added.
After stirring at 600 rpm for one day in a nitrogen atmosphere, 22.0 mL (1 drop/1 second) of acetic anhydride and 32.4 mL (1 drop/2 seconds) of triethylamine (TEA) were added dropwise.
Further, after stirring for 3 days, the reaction solution was dropped into 3 L of methanol to obtain granular 6FDA-3MPA.
The slurry was washed by changing the methanol three times to sufficiently remove unreacted substances, and then vacuum-dried (150° C., 15 hours).
A reaction formula for the synthesis of 6FDA-3MPA is shown in formula (27) below.
「含フッ素ポリイミド（６ＦＤＡ－３ＭＰＡ）の合成」
昇華精製した２，２’－ビス（３，４’－ジヒドロジカルボキシフェニル）ヘキサフルオロプロペン（６ＦＤＡ）および再結晶精製した２，４，６－トリメチル－１，３－フェニレンジアミン（３ＭＰＡ）を有機溶媒中で縮重合し、ポリイミドを得た。反応は穏和な条件下で進行し、架橋反応等の副反応が生じにくい化学イミド化法を採用した。
５００ｍＬ三口フラスコに３ＭＰＡを６．９８ｇ（４６．４６ｍｍｏｌ）、ジメチルアセトアミド（ＤＭＡｃ）を１１８ｍＬ加えて溶解させ、６ＦＤＡを２０．６４ｇ（４６．４６ｍｍｏｌ）、ＤＭＡｃを６３ｍＬ加えた。
窒素雰囲気下、６００ｒｐｍで１日間撹拌した後、無水酢酸を２２．０ｍＬ（１滴／１秒）、トリエチルアミン（ＴＥＡ）を３２．４ｍＬ（１滴／２秒）滴下した。
さらに、３日間撹拌した後、反応溶液を３Ｌのメタノール中へ滴下し、粒状の６ＦＤＡ－３ＭＰＡを得た。
メタノールを３回入れ替えてスラリーを洗浄し、未反応物を十分に取り除いた後、真空乾燥（１５０℃、１５時間）した。
６ＦＤＡ－３ＭＰＡの合成に関する反応式を、下記の式（２７）に示す。 [Example 18]
"Synthesis of fluorine-containing polyimide (6FDA-3MPA)"
Sublimation purified 2,2′-bis(3,4′-dihydrodicarboxyphenyl)hexafluoropropene (6FDA) and recrystallized purified 2,4,6-trimethyl-1,3-phenylenediamine (3MPA) were organically Polyimide was obtained by condensation polymerization in a solvent. A chemical imidization method was adopted in which the reaction proceeds under mild conditions and side reactions such as cross-linking are unlikely to occur.
6.98 g (46.46 mmol) of 3MPA and 118 mL of dimethylacetamide (DMAc) were added and dissolved in a 500 mL three-necked flask, and 20.64 g (46.46 mmol) of 6FDA and 63 mL of DMAc were added.
After stirring at 600 rpm for one day in a nitrogen atmosphere, 22.0 mL (1 drop/1 second) of acetic anhydride and 32.4 mL (1 drop/2 seconds) of triethylamine (TEA) were added dropwise.
Further, after stirring for 3 days, the reaction solution was dropped into 3 L of methanol to obtain granular 6FDA-3MPA.
The slurry was washed by changing the methanol three times to sufficiently remove unreacted substances, and then vacuum-dried (150° C., 15 hours).
A reaction formula for the synthesis of 6FDA-3MPA is shown in formula (27) below.
［実施例１９］
「含フッ素ポリイミド（６ＦＤＡ－３ＭＰＡ）のゲル透過クロマトグラフィー（ＧＰＣ）測定」
実施例１８にて合成した６ＦＤＡ－３ＭＰＡの分子量を測定するために、ＧＰＣ測定を行った。
６ＦＤＡ－３ＭＰＡ約４．０ｍｇを量りとってサンプル管にいれ、テトラヒドロフラン（ＴＨＦ）を４．０ｍＬ加え、超音波洗浄機を用いて完全に溶解させた。
孔径０．４５μｍのポリテトラフルオロエチレン（ＰＴＦＥ）シリンジフィルターを装着したシリンジで溶液を濾過し、ＧＰＣ測定を行った。
測定の結果、重量平均分子量は１．３×１０５、多分散指数は４．０であった。 [Example 19]
"Gel permeation chromatography (GPC) measurement of fluorine-containing polyimide (6FDA-3MPA)"
In order to measure the molecular weight of 6FDA-3MPA synthesized in Example 18, GPC measurement was performed.
About 4.0 mg of 6FDA-3MPA was weighed out and placed in a sample tube, 4.0 mL of tetrahydrofuran (THF) was added, and completely dissolved using an ultrasonic cleaner.
The solution was filtered with a syringe equipped with a polytetrafluoroethylene (PTFE) syringe filter with a pore size of 0.45 μm, and GPC measurement was performed.
As a result of measurement, the weight average molecular weight was 1.3×10 5 and the polydispersity index was 4.0.
「含フッ素ポリイミド（６ＦＤＡ－３ＭＰＡ）のゲル透過クロマトグラフィー（ＧＰＣ）測定」
実施例１８にて合成した６ＦＤＡ－３ＭＰＡの分子量を測定するために、ＧＰＣ測定を行った。
６ＦＤＡ－３ＭＰＡ約４．０ｍｇを量りとってサンプル管にいれ、テトラヒドロフラン（ＴＨＦ）を４．０ｍＬ加え、超音波洗浄機を用いて完全に溶解させた。
孔径０．４５μｍのポリテトラフルオロエチレン（ＰＴＦＥ）シリンジフィルターを装着したシリンジで溶液を濾過し、ＧＰＣ測定を行った。
測定の結果、重量平均分子量は１．３×１０５、多分散指数は４．０であった。 [Example 19]
"Gel permeation chromatography (GPC) measurement of fluorine-containing polyimide (6FDA-3MPA)"
In order to measure the molecular weight of 6FDA-3MPA synthesized in Example 18, GPC measurement was performed.
About 4.0 mg of 6FDA-3MPA was weighed out and placed in a sample tube, 4.0 mL of tetrahydrofuran (THF) was added, and completely dissolved using an ultrasonic cleaner.
The solution was filtered with a syringe equipped with a polytetrafluoroethylene (PTFE) syringe filter with a pore size of 0.45 μm, and GPC measurement was performed.
As a result of measurement, the weight average molecular weight was 1.3×10 5 and the polydispersity index was 4.0.
［実施例２０］
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（１）を用いた有機－無機複合気体分離膜の製膜」
１．５ｇの含フッ素ポリイミド、６ＦＤＡ－３ＭＰＡ（下記の化学式（２４）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が３０質量％となるように、表面官能基修飾シリカナノ粒子（１）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（１）としては、上記の化学式（１９）で表されるものを用いた。
このポリマー溶液をマグネチックスターラーにて一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、４時間かけて真空にして複合膜を作製した。
作製した複合膜は、１５０℃、１５時間の熱処理を行った。得られた膜の膜厚は３５μｍであった。 [Example 20]
"Formation of Organic-Inorganic Composite Gas Separation Membrane Using 6FDA-3MPA and Surface Functional Group-Modified Silica Nanoparticles (1)"
After dissolving 1.5 g of fluorine-containing polyimide, 6FDA-3MPA (see chemical formula (24) below) in 6.7 mL of tetrahydrofuran (THF), add The surface functional group-modified silica nanoparticles (1) were added to the solution and subjected to ultrasonic treatment for 1 hour.
As the surface functional group-modified silica nanoparticles (1), those represented by the above chemical formula (19) were used.
This polymer solution was stirred overnight with a magnetic stirrer, and after stirring, was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 4 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 150° C. for 15 hours. The film thickness of the obtained film was 35 μm.
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（１）を用いた有機－無機複合気体分離膜の製膜」
１．５ｇの含フッ素ポリイミド、６ＦＤＡ－３ＭＰＡ（下記の化学式（２４）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が３０質量％となるように、表面官能基修飾シリカナノ粒子（１）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（１）としては、上記の化学式（１９）で表されるものを用いた。
このポリマー溶液をマグネチックスターラーにて一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、４時間かけて真空にして複合膜を作製した。
作製した複合膜は、１５０℃、１５時間の熱処理を行った。得られた膜の膜厚は３５μｍであった。 [Example 20]
"Formation of Organic-Inorganic Composite Gas Separation Membrane Using 6FDA-3MPA and Surface Functional Group-Modified Silica Nanoparticles (1)"
After dissolving 1.5 g of fluorine-containing polyimide, 6FDA-3MPA (see chemical formula (24) below) in 6.7 mL of tetrahydrofuran (THF), add The surface functional group-modified silica nanoparticles (1) were added to the solution and subjected to ultrasonic treatment for 1 hour.
As the surface functional group-modified silica nanoparticles (1), those represented by the above chemical formula (19) were used.
This polymer solution was stirred overnight with a magnetic stirrer, and after stirring, was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 4 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 150° C. for 15 hours. The film thickness of the obtained film was 35 μm.
［実施例２１］
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（１）の複合気体分離膜の気体透過特性」
実施例２０で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として酸素、窒素を用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表６に示す。 [Example 21]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (1)"
The gas permeability of the composite membrane obtained in Example 20 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Oxygen and nitrogen were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 6 shows the results.
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（１）の複合気体分離膜の気体透過特性」
実施例２０で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として酸素、窒素を用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表６に示す。 [Example 21]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (1)"
The gas permeability of the composite membrane obtained in Example 20 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Oxygen and nitrogen were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 6 shows the results.
［実施例２２］
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（１）の複合気体分離膜の気体透過特性」
表面官能基修飾シリカナノ粒子（１）の添加量を４０質量％としたこと以外は実施例２０と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例２１と同様にして行った。結果を表６に示す。 [Example 22]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (1)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 20, except that the amount of surface functional group-modified silica nanoparticles (1) added was 40% by mass.
The gas permeability of the obtained composite membrane was measured in the same manner as in Example 21. Table 6 shows the results.
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（１）の複合気体分離膜の気体透過特性」
表面官能基修飾シリカナノ粒子（１）の添加量を４０質量％としたこと以外は実施例２０と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例２１と同様にして行った。結果を表６に示す。 [Example 22]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (1)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 20, except that the amount of surface functional group-modified silica nanoparticles (1) added was 40% by mass.
The gas permeability of the obtained composite membrane was measured in the same manner as in Example 21. Table 6 shows the results.
［実施例２３］
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（１）の複合気体分離膜の気体透過特性」
表面官能基修飾シリカナノ粒子（１）の添加量を６０質量％としたこと以外は実施例２０と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例２１と同様にして行った。結果を表６に示す。 [Example 23]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (1)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 20, except that the amount of surface functional group-modified silica nanoparticles (1) added was 60% by mass.
The gas permeability of the obtained composite membrane was measured in the same manner as in Example 21. Table 6 shows the results.
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（１）の複合気体分離膜の気体透過特性」
表面官能基修飾シリカナノ粒子（１）の添加量を６０質量％としたこと以外は実施例２０と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例２１と同様にして行った。結果を表６に示す。 [Example 23]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (1)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 20, except that the amount of surface functional group-modified silica nanoparticles (1) added was 60% by mass.
The gas permeability of the obtained composite membrane was measured in the same manner as in Example 21. Table 6 shows the results.
［実施例２４］
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（１）の複合気体分離膜の気体透過特性」
表面官能基修飾シリカナノ粒子（１）の添加量を７０質量％としたこと以外は実施例２０と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例２１と同様にして行った。結果を表６に示す。 [Example 24]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (1)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 20, except that the amount of surface functional group-modified silica nanoparticles (1) added was 70% by mass.
The gas permeability of the obtained composite membrane was measured in the same manner as in Example 21. Table 6 shows the results.
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（１）の複合気体分離膜の気体透過特性」
表面官能基修飾シリカナノ粒子（１）の添加量を７０質量％としたこと以外は実施例２０と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例２１と同様にして行った。結果を表６に示す。 [Example 24]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (1)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 20, except that the amount of surface functional group-modified silica nanoparticles (1) added was 70% by mass.
The gas permeability of the obtained composite membrane was measured in the same manner as in Example 21. Table 6 shows the results.
［比較例６］
「６ＦＤＡ－３ＭＰＡ気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（１）を添加しないこと以外は実施例２０と同様にして、６ＦＤＡ－３ＭＰＡ気体分離膜を作製した。
得られた気体分離膜の気体透過率測定を、実施例２１と同様にして行った。結果を表６に示す。 [Comparative Example 6]
"Preparation of 6FDA-3MPA Gas Separation Membrane"
A 6FDA-3MPA gas separation membrane was produced in the same manner as in Example 20, except that the surface functional group-modified silica nanoparticles (1) were not added.
The gas permeability of the obtained gas separation membrane was measured in the same manner as in Example 21. Table 6 shows the results.
「６ＦＤＡ－３ＭＰＡ気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（１）を添加しないこと以外は実施例２０と同様にして、６ＦＤＡ－３ＭＰＡ気体分離膜を作製した。
得られた気体分離膜の気体透過率測定を、実施例２１と同様にして行った。結果を表６に示す。 [Comparative Example 6]
"Preparation of 6FDA-3MPA Gas Separation Membrane"
A 6FDA-3MPA gas separation membrane was produced in the same manner as in Example 20, except that the surface functional group-modified silica nanoparticles (1) were not added.
The gas permeability of the obtained gas separation membrane was measured in the same manner as in Example 21. Table 6 shows the results.
表６に示す結果から、実施例２０は、比較例６よりも、酸素の透過率が約２．５倍であった。実施例２２は、比較例６よりも、酸素の透過率が約３倍であった。実施例２３は、比較例６よりも、酸素の透過率が約２１．７倍（Ｎ＝１）、約８．９倍（Ｎ＝２）であった。実施例２４は、比較例６よりも、酸素の透過率が約３．４倍であった。
From the results shown in Table 6, the oxygen permeability of Example 20 was about 2.5 times that of Comparative Example 6. Example 22 had an oxygen permeability approximately three times that of Comparative Example 6. In Example 23, the oxygen permeability was about 21.7 times (N=1) and about 8.9 times (N=2) as compared with Comparative Example 6. Example 24 had an oxygen permeability about 3.4 times that of Comparative Example 6.
［実施例２５］
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（３）を用いた有機－無機複合気体分離膜の製膜」
１．５ｇの含フッ素ポリイミド、６ＦＤＡ－３ＭＰＡ（上記の化学式（２４）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が３０質量％となるように、表面官能基修飾シリカナノ粒子（３）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（３）としては、上記の化学式（２１）で表されるものを用いた。
このポリマー溶液をマグネチックスターラーにて一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、４時間かけて真空にして複合膜を作製した。
作製した複合膜は、１５０℃、１５時間の熱処理を行った。得られた膜の膜厚は４８μｍであった。 [Example 25]
"Formation of organic-inorganic composite gas separation membrane using 6FDA-3MPA and surface functional group-modified silica nanoparticles (3)"
After dissolving 1.5 g of fluorine-containing polyimide, 6FDA-3MPA (see chemical formula (24) above) in 6.7 mL of tetrahydrofuran (THF), add The surface functional group-modified silica nanoparticles (3) were added to the solution and subjected to ultrasonic treatment for 1 hour.
As the surface functional group-modified silica nanoparticles (3), those represented by the above chemical formula (21) were used.
This polymer solution was stirred overnight with a magnetic stirrer, and after stirring, was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 4 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 150° C. for 15 hours. The film thickness of the obtained film was 48 μm.
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（３）を用いた有機－無機複合気体分離膜の製膜」
１．５ｇの含フッ素ポリイミド、６ＦＤＡ－３ＭＰＡ（上記の化学式（２４）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が３０質量％となるように、表面官能基修飾シリカナノ粒子（３）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（３）としては、上記の化学式（２１）で表されるものを用いた。
このポリマー溶液をマグネチックスターラーにて一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、４時間かけて真空にして複合膜を作製した。
作製した複合膜は、１５０℃、１５時間の熱処理を行った。得られた膜の膜厚は４８μｍであった。 [Example 25]
"Formation of organic-inorganic composite gas separation membrane using 6FDA-3MPA and surface functional group-modified silica nanoparticles (3)"
After dissolving 1.5 g of fluorine-containing polyimide, 6FDA-3MPA (see chemical formula (24) above) in 6.7 mL of tetrahydrofuran (THF), add The surface functional group-modified silica nanoparticles (3) were added to the solution and subjected to ultrasonic treatment for 1 hour.
As the surface functional group-modified silica nanoparticles (3), those represented by the above chemical formula (21) were used.
This polymer solution was stirred overnight with a magnetic stirrer, and after stirring, was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 4 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 150° C. for 15 hours. The film thickness of the obtained film was 48 μm.
［実施例２６］
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（３）の複合気体分離膜の気体透過特性」
実施例２５で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として酸素、窒素を用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表７に示す。 [Example 26]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (3)"
The gas permeability of the composite membrane obtained in Example 25 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Oxygen and nitrogen were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 7 shows the results.
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（３）の複合気体分離膜の気体透過特性」
実施例２５で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として酸素、窒素を用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表７に示す。 [Example 26]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (3)"
The gas permeability of the composite membrane obtained in Example 25 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Oxygen and nitrogen were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 7 shows the results.
［実施例２７］
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（３）の複合気体分離膜の気体透過特性」
表面官能基修飾シリカナノ粒子（３）の添加量を４０質量％としたこと以外は実施例２５と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例２６と同様にして行った。結果を表７に示す。 [Example 27]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (3)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 25, except that the amount of the surface functional group-modified silica nanoparticles (3) added was 40% by mass.
The gas permeability measurement of the resulting composite membrane was performed in the same manner as in Example 26. Table 7 shows the results.
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（３）の複合気体分離膜の気体透過特性」
表面官能基修飾シリカナノ粒子（３）の添加量を４０質量％としたこと以外は実施例２５と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例２６と同様にして行った。結果を表７に示す。 [Example 27]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (3)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 25, except that the amount of the surface functional group-modified silica nanoparticles (3) added was 40% by mass.
The gas permeability measurement of the resulting composite membrane was performed in the same manner as in Example 26. Table 7 shows the results.
［実施例２８］
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（３）の複合気体分離膜の気体透過特性」
表面官能基修飾シリカナノ粒子（３）の添加量を６０質量％としたこと以外は実施例２５と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例２６と同様にして行った。結果を表７に示す。 [Example 28]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (3)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 25, except that the amount of the surface functional group-modified silica nanoparticles (3) added was 60% by mass.
The gas permeability measurement of the resulting composite membrane was performed in the same manner as in Example 26. Table 7 shows the results.
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（３）の複合気体分離膜の気体透過特性」
表面官能基修飾シリカナノ粒子（３）の添加量を６０質量％としたこと以外は実施例２５と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例２６と同様にして行った。結果を表７に示す。 [Example 28]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (3)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 25, except that the amount of the surface functional group-modified silica nanoparticles (3) added was 60% by mass.
The gas permeability measurement of the resulting composite membrane was performed in the same manner as in Example 26. Table 7 shows the results.
［実施例２９］
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（３）の複合気体分離膜の気体透過特性」
表面官能基修飾シリカナノ粒子（３）の添加量を７０質量％としたこと以外は実施例２５と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例２６と同様にして行った。結果を表７に示す。 [Example 29]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (3)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 25, except that the amount of the surface functional group-modified silica nanoparticles (3) added was 70% by mass.
The gas permeability measurement of the resulting composite membrane was performed in the same manner as in Example 26. Table 7 shows the results.
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（３）の複合気体分離膜の気体透過特性」
表面官能基修飾シリカナノ粒子（３）の添加量を７０質量％としたこと以外は実施例２５と同様にして、有機－無機複合気体分離膜を作製した。
得られた複合膜の気体透過率測定を、実施例２６と同様にして行った。結果を表７に示す。 [Example 29]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (3)"
An organic-inorganic composite gas separation membrane was produced in the same manner as in Example 25, except that the amount of the surface functional group-modified silica nanoparticles (3) added was 70% by mass.
The gas permeability measurement of the resulting composite membrane was performed in the same manner as in Example 26. Table 7 shows the results.
表７に示す結果から、実施例２５は、比較例６よりも、酸素の透過率が約２．５倍であった。実施例２７は、比較例６よりも、酸素の透過率が約４．６倍であった。実施例２８は、比較例６よりも、酸素の透過率が約１４．９倍（Ｎ＝１）、約１２．８倍（Ｎ＝２）であった。実施例２９は、比較例６よりも、酸素の透過率が約８倍（Ｎ＝１）、約４倍（Ｎ＝２）であった。
From the results shown in Table 7, Example 25 had an oxygen permeability about 2.5 times that of Comparative Example 6. Example 27 had an oxygen permeability about 4.6 times that of Comparative Example 6. In Example 28, the oxygen permeability was about 14.9 times (N=1) and about 12.8 times (N=2) as compared with Comparative Example 6. In Example 29, the oxygen permeability was about 8 times (N=1) and about 4 times (N=2) as compared with Comparative Example 6.
［実施例３０］
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（４）を用いた有機－無機複合気体分離膜の製膜」
１．５ｇの含フッ素ポリイミド、６ＦＤＡ－３ＭＰＡ（上記の化学式（２４）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が６０質量％となるように、表面官能基修飾シリカナノ粒子（４）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（４）としては、上記の化学式（２２）で表されるものを用いた。
このポリマー溶液をマグネチックスターラーにて一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、４時間かけて真空にして複合膜を作製した。
作製した複合膜は、１５０℃、１５時間の熱処理を行った。得られた膜の膜厚は５１μｍであった。 [Example 30]
"Formation of organic-inorganic composite gas separation membrane using 6FDA-3MPA and surface functional group-modified silica nanoparticles (4)"
After dissolving 1.5 g of fluorine-containing polyimide, 6FDA-3MPA (see chemical formula (24) above) in 6.7 mL of tetrahydrofuran (THF), add The surface functional group-modified silica nanoparticles (4) were added to the solution and subjected to ultrasonic treatment for 1 hour.
As the surface functional group-modified silica nanoparticles (4), those represented by the above chemical formula (22) were used.
This polymer solution was stirred overnight with a magnetic stirrer, and after stirring, was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 4 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 150° C. for 15 hours. The film thickness of the obtained film was 51 μm.
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（４）を用いた有機－無機複合気体分離膜の製膜」
１．５ｇの含フッ素ポリイミド、６ＦＤＡ－３ＭＰＡ（上記の化学式（２４）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が６０質量％となるように、表面官能基修飾シリカナノ粒子（４）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（４）としては、上記の化学式（２２）で表されるものを用いた。
このポリマー溶液をマグネチックスターラーにて一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、４時間かけて真空にして複合膜を作製した。
作製した複合膜は、１５０℃、１５時間の熱処理を行った。得られた膜の膜厚は５１μｍであった。 [Example 30]
"Formation of organic-inorganic composite gas separation membrane using 6FDA-3MPA and surface functional group-modified silica nanoparticles (4)"
After dissolving 1.5 g of fluorine-containing polyimide, 6FDA-3MPA (see chemical formula (24) above) in 6.7 mL of tetrahydrofuran (THF), add The surface functional group-modified silica nanoparticles (4) were added to the solution and subjected to ultrasonic treatment for 1 hour.
As the surface functional group-modified silica nanoparticles (4), those represented by the above chemical formula (22) were used.
This polymer solution was stirred overnight with a magnetic stirrer, and after stirring, was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 4 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 150° C. for 15 hours. The film thickness of the obtained film was 51 μm.
［実施例３１］
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（４）の複合気体分離膜の気体透過特性」
実施例２５で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として二酸化炭素、酸素、窒素、メタンを用い、測定条件は、温度３５°Ｃ、圧力差７６ｃｍＨｇとした。結果を表７に示す。 [Example 31]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (4)"
The gas permeability of the composite membrane obtained in Example 25 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Carbon dioxide, oxygen, nitrogen, and methane were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 7 shows the results.
「６ＦＤＡ－３ＭＰＡと表面官能基修飾シリカナノ粒子（４）の複合気体分離膜の気体透過特性」
実施例２５で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として二酸化炭素、酸素、窒素、メタンを用い、測定条件は、温度３５°Ｃ、圧力差７６ｃｍＨｇとした。結果を表７に示す。 [Example 31]
"Gas Permeability of Composite Gas Separation Membrane of 6FDA-3MPA and Surface Functional Group Modified Silica Nanoparticles (4)"
The gas permeability of the composite membrane obtained in Example 25 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Carbon dioxide, oxygen, nitrogen, and methane were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 7 shows the results.
表８に示す結果から、実施例３０は、比較例６よりも、酸素の透過率が約５．４倍、二酸化炭素の透過率が約４．７倍、窒素の透過率が約６．５倍、メタンの透過率が９倍であった。
From the results shown in Table 8, Example 30 has an oxygen permeability of about 5.4 times, a carbon dioxide permeability of about 4.7 times, and a nitrogen permeability of about 6.5 times that of Comparative Example 6. , the permeability of methane was 9 times higher.
［実施例３２］
「シリコーンと表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
０．４３１ｇのシリコーン（信越工業株式会社製：Ｘ－２２－１６４Ａ、官能基当量８６０ｇｍｏｌ－１、密度０．９８ｇｃｍ－３）を１０ｍＬのバイアル瓶に測りとった。測りとったシリコーンの反応官能基数（０．５ｍｍｏｌ）に合わせて、架橋剤であるペンタエリトリトールテトラキス（３－メルカプトプロピオナート）（ＰＥＭＰ）（密度１．２８ｇｍＬ－１）０．２５ｍｍｏｌを加えた。このシリコーンとＰＥＭＰの混合物に対する含有量が４０質量％となるように、表面官能基修飾シリカナノ粒子（２）を添加した。
その後、光重合開始剤である２，２’－ジメトキシ－２－フェニルアセトフェノン（ＤＭＰＡ）（０．０１５ｍｍｏｌ）およびテトラヒドロフラン（ＴＨＦ）を加え、液全体が透明となるまで加え、その後、数分間の超音波処理を行った。
得られた溶液を１辺がおよそ６ｃｍのテフロン（登録商標）トレー上にキャストし、周囲を暗室に設定した環境下にて、１．５時間～２時間ＵＶ照射（ちびライトＤＸ ＢＯＸ－Ｓ１１００，ピーク波長：３８０ｎｍ）することによって複合膜を作製した。
得られた膜の膜厚は１３５μｍであった。 [Example 32]
"Formation of Organic-Inorganic Composite Gas Separation Membrane Using Silicone and Surface Functional Group-Modified Silica Nanoparticles (2)"
0.431 g of silicone (manufactured by Shin-Etsu Co., Ltd.: X-22-164A, functional group equivalent 860 gmol −1 , density 0.98 gcm −3 ) was weighed into a 10 mL vial. 0.25 mmol of pentaerythritol tetrakis(3-mercaptopropionate) (PEMP) (density 1.28 g mL −1 ), which is a cross-linking agent, was added according to the measured number of reactive functional groups of the silicone (0.5 mmol). The surface functional group-modified silica nanoparticles (2) were added so that the content of the mixture of silicone and PEMP was 40% by mass.
After that, 2,2′-dimethoxy-2-phenylacetophenone (DMPA) (0.015 mmol) and tetrahydrofuran (THF), which are photoinitiators, are added until the whole liquid becomes clear, and then heated for several minutes. Sonication was performed.
The resulting solution was cast on a Teflon (registered trademark) tray having a side of about 6 cm, and was irradiated with UV light (Chibi Light DX BOX-S1100, Chibi Light DX BOX-S1100, Peak wavelength: 380 nm) to prepare a composite membrane.
The film thickness of the obtained film was 135 μm.
「シリコーンと表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
０．４３１ｇのシリコーン（信越工業株式会社製：Ｘ－２２－１６４Ａ、官能基当量８６０ｇｍｏｌ－１、密度０．９８ｇｃｍ－３）を１０ｍＬのバイアル瓶に測りとった。測りとったシリコーンの反応官能基数（０．５ｍｍｏｌ）に合わせて、架橋剤であるペンタエリトリトールテトラキス（３－メルカプトプロピオナート）（ＰＥＭＰ）（密度１．２８ｇｍＬ－１）０．２５ｍｍｏｌを加えた。このシリコーンとＰＥＭＰの混合物に対する含有量が４０質量％となるように、表面官能基修飾シリカナノ粒子（２）を添加した。
その後、光重合開始剤である２，２’－ジメトキシ－２－フェニルアセトフェノン（ＤＭＰＡ）（０．０１５ｍｍｏｌ）およびテトラヒドロフラン（ＴＨＦ）を加え、液全体が透明となるまで加え、その後、数分間の超音波処理を行った。
得られた溶液を１辺がおよそ６ｃｍのテフロン（登録商標）トレー上にキャストし、周囲を暗室に設定した環境下にて、１．５時間～２時間ＵＶ照射（ちびライトＤＸ ＢＯＸ－Ｓ１１００，ピーク波長：３８０ｎｍ）することによって複合膜を作製した。
得られた膜の膜厚は１３５μｍであった。 [Example 32]
"Formation of Organic-Inorganic Composite Gas Separation Membrane Using Silicone and Surface Functional Group-Modified Silica Nanoparticles (2)"
0.431 g of silicone (manufactured by Shin-Etsu Co., Ltd.: X-22-164A, functional group equivalent 860 gmol −1 , density 0.98 gcm −3 ) was weighed into a 10 mL vial. 0.25 mmol of pentaerythritol tetrakis(3-mercaptopropionate) (PEMP) (density 1.28 g mL −1 ), which is a cross-linking agent, was added according to the measured number of reactive functional groups of the silicone (0.5 mmol). The surface functional group-modified silica nanoparticles (2) were added so that the content of the mixture of silicone and PEMP was 40% by mass.
After that, 2,2′-dimethoxy-2-phenylacetophenone (DMPA) (0.015 mmol) and tetrahydrofuran (THF), which are photoinitiators, are added until the whole liquid becomes clear, and then heated for several minutes. Sonication was performed.
The resulting solution was cast on a Teflon (registered trademark) tray having a side of about 6 cm, and was irradiated with UV light (Chibi Light DX BOX-S1100, Chibi Light DX BOX-S1100, Peak wavelength: 380 nm) to prepare a composite membrane.
The film thickness of the obtained film was 135 μm.
［実施例３３］
「シリコーンと表面官能基修飾シリカナノ粒子（２）の複合気体分離膜の気体透過特性」
実施例３２で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として二酸化炭素、酸素、窒素、メタンを用い、測定条件は、温度３５°Ｃ、圧力差７６ｃｍＨｇとした。結果を表９に示す。 [Example 33]
"Gas Permeability of Composite Gas Separation Membrane of Silicone and Surface Functional Group Modified Silica Nanoparticles (2)"
The gas permeability of the composite membrane obtained in Example 32 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Carbon dioxide, oxygen, nitrogen, and methane were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 9 shows the results.
「シリコーンと表面官能基修飾シリカナノ粒子（２）の複合気体分離膜の気体透過特性」
実施例３２で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として二酸化炭素、酸素、窒素、メタンを用い、測定条件は、温度３５°Ｃ、圧力差７６ｃｍＨｇとした。結果を表９に示す。 [Example 33]
"Gas Permeability of Composite Gas Separation Membrane of Silicone and Surface Functional Group Modified Silica Nanoparticles (2)"
The gas permeability of the composite membrane obtained in Example 32 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Carbon dioxide, oxygen, nitrogen, and methane were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 9 shows the results.
［比較例７］
「シリコーン気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（２）を添加しないこと以外は実施例３２と同様にして、シリコーン気体分離膜を作製した。
得られた気体分離膜の気体透過率測定を、実施例３３と同様にして行った。結果を表９に示す。 [Comparative Example 7]
"Formation of Silicone Gas Separation Membrane"
A silicone gas separation membrane was produced in the same manner as in Example 32, except that the surface functional group-modified silica nanoparticles (2) were not added.
The gas permeability of the obtained gas separation membrane was measured in the same manner as in Example 33. Table 9 shows the results.
「シリコーン気体分離膜の製膜」
表面官能基修飾シリカナノ粒子（２）を添加しないこと以外は実施例３２と同様にして、シリコーン気体分離膜を作製した。
得られた気体分離膜の気体透過率測定を、実施例３３と同様にして行った。結果を表９に示す。 [Comparative Example 7]
"Formation of Silicone Gas Separation Membrane"
A silicone gas separation membrane was produced in the same manner as in Example 32, except that the surface functional group-modified silica nanoparticles (2) were not added.
The gas permeability of the obtained gas separation membrane was measured in the same manner as in Example 33. Table 9 shows the results.
表９に示す結果から、実施例３２は、比較例７よりも、酸素の透過率が約２．１、窒素の透過率が約２．１倍であった。
From the results shown in Table 9, Example 32 had an oxygen permeability of about 2.1 times and a nitrogen permeability of about 2.1 times that of Comparative Example 7.
［実施例３４］
「固有微細孔性高分子（ＰＩＭ－１）の合成」
あらかじめ窒素フローを行っていた１Ｌ三つ口フラスコに強制撹拌機を装着し、その三つ口フラスコ内に、５，５’，６，６’－ｔｅｔｒａｈｙｄｒｏｘｙ－３，３，３’，３’－ｔｅｔｒａｍｅｔｈｙｌ－１，１’－ｓｐｉｒｏｂｉｉｎｄａｎを１４．８０１ｇ（４３．４８ｍｍｏｌ）と、２，３，５，６－ｔｅｔｒａｆｌｕｏｒｏｔｅｒｅｐｈｔｈａｌｏｎｉｔｒｉｌｅを８．７００ｇ（４３．４８ｍｍｏｌ）を投入し、脱水Ｎ，Ｎジメチルホルムアミド（ＤＭＦ）を３００ｍＬ加え、室温、３００ｒｐｍで３０分間撹拌した。
モノマーが溶解した後、モノマーに対し６モル等量の炭酸カリウム（Ｋ２ＣＯ３）を３６．１５ｇ加えると溶液が黄色に変化した。
その後、６５℃、３００ｒｐｍで７２時間撹拌した。
７２時間による反応終了後、ＡＤＶＡＮＴＥＣ社製の直径９ｃｍの定量ろ紙Ｎｏ．３を用いて、粗生成物を吸引濾過により回収した。
この粗生成物を、２００ｍＬのＤＭＦ、１００ｍＬのアセトン、４００ｍＬの水で順次洗浄した。
炭酸カリウムを溶解除去するために、洗浄物を２Ｌビーカーに移し、２Ｌの水を注いで４０℃にて熱水攪拌し、これを再び吸引濾過した。
もう一度、熱水攪拌を行い、吸引濾過後の生成物を３００ｍＬの水、１００ｍＬのアセトンで洗浄した。加えて、３００ｍＬの１，４－ジオキサンを少しずつ加えながら洗浄し、その後５０ｍＬのアセトン、３００ｍＬの水でさらなる洗浄を行った。
吸引瓶の中にｐＨ試験紙を入れ、濾液が中性であることを確認し、濾過で得られた蛍光黄色の固体を回収して、真空オーブンで９５℃、１５時間の条件で乾燥を行い、黄色固体の生成物を得た。乾燥後のＰＩＭ－１の収量は１７．８０ｇであった。 [Example 34]
"Synthesis of intrinsic microporous polymer (PIM-1)"
A 1 L three-necked flask that had been flowed with nitrogen in advance was equipped with a forced stirrer, and 5,5′,6,6′-tetrahydroxy-3,3,3′,3′- 14.801 g (43.48 mmol) of tetramethyl-1,1′-spirobiindan and 8.700 g (43.48 mmol) of 2,3,5,6-tetrafluoroterephthalonitrile were added, and dehydrated N,N dimethylformamide (DMF) was added. was added, and stirred at room temperature and 300 rpm for 30 minutes.
After the monomers dissolved, 36.15 g of potassium carbonate (K 2 CO 3 ), which was 6 molar equivalents to the monomers, was added and the solution turned yellow.
After that, the mixture was stirred at 65° C. and 300 rpm for 72 hours.
After completion of the reaction for 72 hours, quantitative filter paper No. 9 cm in diameter manufactured by ADVANTEC. Using 3, the crude product was collected by suction filtration.
The crude product was washed sequentially with 200 mL DMF, 100 mL acetone and 400 mL water.
In order to dissolve and remove the potassium carbonate, the washed material was transferred to a 2 L beaker, 2 L of water was added, hot water was stirred at 40° C., and suction filtration was performed again.
Hot water stirring was performed once again, and the product after suction filtration was washed with 300 mL of water and 100 mL of acetone. In addition, 300 mL of 1,4-dioxane was added in portions for washing, followed by further washing with 50 mL of acetone and 300 mL of water.
Place pH test paper in the suction bottle, confirm that the filtrate is neutral, collect the fluorescent yellow solid obtained by filtration, and dry it in a vacuum oven at 95°C for 15 hours. , to give the product as a yellow solid. The yield of PIM-1 after drying was 17.80 g.
「固有微細孔性高分子（ＰＩＭ－１）の合成」
あらかじめ窒素フローを行っていた１Ｌ三つ口フラスコに強制撹拌機を装着し、その三つ口フラスコ内に、５，５’，６，６’－ｔｅｔｒａｈｙｄｒｏｘｙ－３，３，３’，３’－ｔｅｔｒａｍｅｔｈｙｌ－１，１’－ｓｐｉｒｏｂｉｉｎｄａｎを１４．８０１ｇ（４３．４８ｍｍｏｌ）と、２，３，５，６－ｔｅｔｒａｆｌｕｏｒｏｔｅｒｅｐｈｔｈａｌｏｎｉｔｒｉｌｅを８．７００ｇ（４３．４８ｍｍｏｌ）を投入し、脱水Ｎ，Ｎジメチルホルムアミド（ＤＭＦ）を３００ｍＬ加え、室温、３００ｒｐｍで３０分間撹拌した。
モノマーが溶解した後、モノマーに対し６モル等量の炭酸カリウム（Ｋ２ＣＯ３）を３６．１５ｇ加えると溶液が黄色に変化した。
その後、６５℃、３００ｒｐｍで７２時間撹拌した。
７２時間による反応終了後、ＡＤＶＡＮＴＥＣ社製の直径９ｃｍの定量ろ紙Ｎｏ．３を用いて、粗生成物を吸引濾過により回収した。
この粗生成物を、２００ｍＬのＤＭＦ、１００ｍＬのアセトン、４００ｍＬの水で順次洗浄した。
炭酸カリウムを溶解除去するために、洗浄物を２Ｌビーカーに移し、２Ｌの水を注いで４０℃にて熱水攪拌し、これを再び吸引濾過した。
もう一度、熱水攪拌を行い、吸引濾過後の生成物を３００ｍＬの水、１００ｍＬのアセトンで洗浄した。加えて、３００ｍＬの１，４－ジオキサンを少しずつ加えながら洗浄し、その後５０ｍＬのアセトン、３００ｍＬの水でさらなる洗浄を行った。
吸引瓶の中にｐＨ試験紙を入れ、濾液が中性であることを確認し、濾過で得られた蛍光黄色の固体を回収して、真空オーブンで９５℃、１５時間の条件で乾燥を行い、黄色固体の生成物を得た。乾燥後のＰＩＭ－１の収量は１７．８０ｇであった。 [Example 34]
"Synthesis of intrinsic microporous polymer (PIM-1)"
A 1 L three-necked flask that had been flowed with nitrogen in advance was equipped with a forced stirrer, and 5,5′,6,6′-tetrahydroxy-3,3,3′,3′- 14.801 g (43.48 mmol) of tetramethyl-1,1′-spirobiindan and 8.700 g (43.48 mmol) of 2,3,5,6-tetrafluoroterephthalonitrile were added, and dehydrated N,N dimethylformamide (DMF) was added. was added, and stirred at room temperature and 300 rpm for 30 minutes.
After the monomers dissolved, 36.15 g of potassium carbonate (K 2 CO 3 ), which was 6 molar equivalents to the monomers, was added and the solution turned yellow.
After that, the mixture was stirred at 65° C. and 300 rpm for 72 hours.
After completion of the reaction for 72 hours, quantitative filter paper No. 9 cm in diameter manufactured by ADVANTEC. Using 3, the crude product was collected by suction filtration.
The crude product was washed sequentially with 200 mL DMF, 100 mL acetone and 400 mL water.
In order to dissolve and remove the potassium carbonate, the washed material was transferred to a 2 L beaker, 2 L of water was added, hot water was stirred at 40° C., and suction filtration was performed again.
Hot water stirring was performed once again, and the product after suction filtration was washed with 300 mL of water and 100 mL of acetone. In addition, 300 mL of 1,4-dioxane was added in portions for washing, followed by further washing with 50 mL of acetone and 300 mL of water.
Place pH test paper in the suction bottle, confirm that the filtrate is neutral, collect the fluorescent yellow solid obtained by filtration, and dry it in a vacuum oven at 95°C for 15 hours. , to give the product as a yellow solid. The yield of PIM-1 after drying was 17.80 g.
［実施例３５］
「固有微細孔性高分子（ＰＩＭ－１）の精製」
実施例３４にて合成した生成物を、クロロホルムに溶解させ、貧溶媒のメタノールを少しずつ加えることでＰＩＭ－１を沈殿させた。
任意の領域のポリマーを得るため、沈殿物は数回に分けて回収し、９５℃、１５時間真空乾燥した。 [Example 35]
"Purification of intrinsic microporous polymer (PIM-1)"
The product synthesized in Example 34 was dissolved in chloroform, and methanol as a poor solvent was added little by little to precipitate PIM-1.
In order to obtain a polymer in an arbitrary region, the precipitate was collected in several batches and vacuum-dried at 95° C. for 15 hours.
「固有微細孔性高分子（ＰＩＭ－１）の精製」
実施例３４にて合成した生成物を、クロロホルムに溶解させ、貧溶媒のメタノールを少しずつ加えることでＰＩＭ－１を沈殿させた。
任意の領域のポリマーを得るため、沈殿物は数回に分けて回収し、９５℃、１５時間真空乾燥した。 [Example 35]
"Purification of intrinsic microporous polymer (PIM-1)"
The product synthesized in Example 34 was dissolved in chloroform, and methanol as a poor solvent was added little by little to precipitate PIM-1.
In order to obtain a polymer in an arbitrary region, the precipitate was collected in several batches and vacuum-dried at 95° C. for 15 hours.
［実施例３６］
「固有微細孔性高分子（ＰＩＭ－１）のゲル透過クロマトグラフィー（ＧＰＣ）測定」
実施例３５にて精製したＰＩＭ－１の分子量を測定するために、ＧＰＣ測定を行った。
ＰＩＭ－１約４．０ｍｇを量りとってサンプル管に入れ、テトラヒドロフラン（ＴＨＦ）を４．０ｍＬ加え、超音波洗浄機を用いて完全に溶解させた。
孔径０．４５μｍのポリテトラフルオロエチレン（ＰＴＦＥ）シリンジフィルターを装着したシリンジで溶液を濾過し、ＧＰＣ測定を行った。
測定の結果、精製により高分子量で分子量分布が広いもの（重量平均分子量５．４×１０５、多分散指数９．５）から、比較的低分子量分布で分子量分布が狭いもの（重量平均分子量３．７×１０５、多分散指数４．３）まで得られた。 [Example 36]
"Gel Permeation Chromatography (GPC) Measurement of Inherent Microporous Polymer (PIM-1)"
In order to measure the molecular weight of PIM-1 purified in Example 35, GPC measurement was performed.
About 4.0 mg of PIM-1 was weighed and placed in a sample tube, 4.0 mL of tetrahydrofuran (THF) was added, and completely dissolved using an ultrasonic cleaner.
The solution was filtered with a syringe equipped with a polytetrafluoroethylene (PTFE) syringe filter with a pore size of 0.45 μm, and GPC measurement was performed.
As a result of the measurement, it was found that the purified product had a high molecular weight with a wide molecular weight distribution (weight average molecular weight: 5.4 × 10 5 , polydispersity index: 9.5) to a relatively low molecular weight distribution with a narrow molecular weight distribution (weight average molecular weight: 3 up to .7×10 5 with a polydispersity index of 4.3).
「固有微細孔性高分子（ＰＩＭ－１）のゲル透過クロマトグラフィー（ＧＰＣ）測定」
実施例３５にて精製したＰＩＭ－１の分子量を測定するために、ＧＰＣ測定を行った。
ＰＩＭ－１約４．０ｍｇを量りとってサンプル管に入れ、テトラヒドロフラン（ＴＨＦ）を４．０ｍＬ加え、超音波洗浄機を用いて完全に溶解させた。
孔径０．４５μｍのポリテトラフルオロエチレン（ＰＴＦＥ）シリンジフィルターを装着したシリンジで溶液を濾過し、ＧＰＣ測定を行った。
測定の結果、精製により高分子量で分子量分布が広いもの（重量平均分子量５．４×１０５、多分散指数９．５）から、比較的低分子量分布で分子量分布が狭いもの（重量平均分子量３．７×１０５、多分散指数４．３）まで得られた。 [Example 36]
"Gel Permeation Chromatography (GPC) Measurement of Inherent Microporous Polymer (PIM-1)"
In order to measure the molecular weight of PIM-1 purified in Example 35, GPC measurement was performed.
About 4.0 mg of PIM-1 was weighed and placed in a sample tube, 4.0 mL of tetrahydrofuran (THF) was added, and completely dissolved using an ultrasonic cleaner.
The solution was filtered with a syringe equipped with a polytetrafluoroethylene (PTFE) syringe filter with a pore size of 0.45 μm, and GPC measurement was performed.
As a result of the measurement, it was found that the purified product had a high molecular weight with a wide molecular weight distribution (weight average molecular weight: 5.4 × 10 5 , polydispersity index: 9.5) to a relatively low molecular weight distribution with a narrow molecular weight distribution (weight average molecular weight: 3 up to .7×10 5 with a polydispersity index of 4.3).
［実施例３７］
「ＰＩＭ－１（分子量：重量平均分子量３７万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
０．１５ｇの固有微細孔ポリマー、ＰＩＭ－１（上記の化学式（２３）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が８５質量％となるように、表面官能基修飾シリカナノ粒子（２）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（２）としては、上記の化学式（２０）で表されるものを用いた。
このポリマー溶液を攪拌速度１２００ｒｐｍで一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、６時間かけて真空にして複合膜を作製した。
作製した複合膜は、７０℃、１８時間の熱処理を行った。得られた膜の膜厚は１１５μｍであった。 [Example 37]
"Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 370,000) and surface functional group-modified silica nanoparticles (2)"
After dissolving 0.15 g of the intrinsic microporous polymer, PIM-1 (see formula (23) above), in 6.7 mL of tetrahydrofuran (THF), the polymer solution has a content of 85% by weight relative to the polymer. As shown, the surface functional group-modified silica nanoparticles (2) were added and sonicated for 1 hour.
As the surface functional group-modified silica nanoparticles (2), those represented by the above chemical formula (20) were used.
The polymer solution was stirred overnight at a stirring speed of 1200 rpm, and after stirring was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 6 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 70° C. for 18 hours. The film thickness of the obtained film was 115 μm.
「ＰＩＭ－１（分子量：重量平均分子量３７万）と表面官能基修飾シリカナノ粒子（２）を用いた有機－無機複合気体分離膜の製膜」
０．１５ｇの固有微細孔ポリマー、ＰＩＭ－１（上記の化学式（２３）参照）を６．７ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解した後、このポリマー溶液に、ポリマーに対する含有量が８５質量％となるように、表面官能基修飾シリカナノ粒子（２）を添加し、１時間の超音波処理を行った。
表面官能基修飾シリカナノ粒子（２）としては、上記の化学式（２０）で表されるものを用いた。
このポリマー溶液を攪拌速度１２００ｒｐｍで一晩攪拌し、攪拌後、再び１時間の超音波処理を行った。
その後、このポリマー溶液を直径６ｃｍのガラスシャーレ上にキャストした。
その後、３０℃に設定したオーブン内にこのガラスシャーレを入れ、６時間かけて真空にして複合膜を作製した。
作製した複合膜は、７０℃、１８時間の熱処理を行った。得られた膜の膜厚は１１５μｍであった。 [Example 37]
"Formation of organic-inorganic composite gas separation membrane using PIM-1 (molecular weight: weight average molecular weight 370,000) and surface functional group-modified silica nanoparticles (2)"
After dissolving 0.15 g of the intrinsic microporous polymer, PIM-1 (see formula (23) above), in 6.7 mL of tetrahydrofuran (THF), the polymer solution has a content of 85% by weight relative to the polymer. As shown, the surface functional group-modified silica nanoparticles (2) were added and sonicated for 1 hour.
As the surface functional group-modified silica nanoparticles (2), those represented by the above chemical formula (20) were used.
The polymer solution was stirred overnight at a stirring speed of 1200 rpm, and after stirring was again subjected to ultrasonic treatment for 1 hour.
After that, this polymer solution was cast on a glass petri dish with a diameter of 6 cm.
After that, the glass petri dish was placed in an oven set at 30° C., and the oven was evacuated for 6 hours to prepare a composite membrane.
The produced composite membrane was heat-treated at 70° C. for 18 hours. The film thickness of the obtained film was 115 μm.
［実施例３８］
「ＰＩＭ－１（分子量：重量平均分子量３７万）と表面官能基修飾シリカナノ粒子（２）の複合気体分離膜の気体透過特性」
実施例３７で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として二酸化炭素、酸素、窒素、メタンを用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表１０に示す。 [Example 38]
"Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 370,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
The gas permeability of the composite membrane obtained in Example 37 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Carbon dioxide, oxygen, nitrogen, and methane were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 10 shows the results.
「ＰＩＭ－１（分子量：重量平均分子量３７万）と表面官能基修飾シリカナノ粒子（２）の複合気体分離膜の気体透過特性」
実施例３７で得られた複合膜の気体透過率測定を行った。
気体透過率測定には、理科精機工業株式会社製：Ｋ－３１５Ｎ－０１Ｃを使用した。供給気体として二酸化炭素、酸素、窒素、メタンを用い、測定条件は、温度３５℃、圧力差７６ｃｍＨｇとした。結果を表１０に示す。 [Example 38]
"Gas Permeability of Composite Gas Separation Membrane of PIM-1 (Molecular Weight: Weight Average Molecular Weight 370,000) and Surface Functional Group-Modified Silica Nanoparticles (2)"
The gas permeability of the composite membrane obtained in Example 37 was measured.
For the gas permeability measurement, K-315N-01C manufactured by Rika Seiki Kogyo Co., Ltd. was used. Carbon dioxide, oxygen, nitrogen, and methane were used as supply gases, and the measurement conditions were a temperature of 35° C. and a pressure difference of 76 cmHg. Table 10 shows the results.
表１０に示す結果から、実施例３７の複合気体分離膜は、二酸化炭素、酸素、窒素、メタンの透過率が高いことが分かった。
From the results shown in Table 10, it was found that the composite gas separation membrane of Example 37 had high permeabilities of carbon dioxide, oxygen, nitrogen, and methane.
本発明の気体分離膜は、シリカナノ粒子と、高分子と、を含む複合体材料から構成され、シリカナノ粒子は、官能基含有シランカップリング剤で表面修飾された表面官能基修飾シリカナノ粒子であり、官能基含有シランカップリング剤は、上記の化学式（１）で表される化合物、上記の化学式（２）および上記の化学式（３）からなる群から選択される少なくとも１種であるため、気体透過特性に優れ、かつメタノール処理を行わなくとも、メタノール処理を行った従来の気体分離膜と同程度またはそれ以上の気体透過特性が得られる。従って、本発明の気体分離膜は、フィルタとして好ましく使用することができる。
The gas separation membrane of the present invention is composed of a composite material containing silica nanoparticles and a polymer, and the silica nanoparticles are surface functional group-modified silica nanoparticles that are surface-modified with a functional group-containing silane coupling agent, Since the functional group-containing silane coupling agent is at least one selected from the group consisting of the compound represented by the above chemical formula (1), the above chemical formula (2) and the above chemical formula (3), gas permeation It has excellent characteristics, and even without methanol treatment, gas permeation characteristics equivalent to or higher than those of conventional gas separation membranes treated with methanol can be obtained. Therefore, the gas separation membrane of the present invention can be preferably used as a filter.
Claims (11)
- シリカナノ粒子と、高分子と、を含む複合体材料から構成される気体分離膜であって、
前記シリカナノ粒子は、官能基含有シランカップリング剤で表面修飾された表面官能基修飾シリカナノ粒子であり、
前記官能基含有シランカップリング剤は、下記の化学式（１）で表される化合物、下記の化学式（２）および下記の化学式（３）からなる群から選択される少なくとも１種である、気体分離膜。
The silica nanoparticles are surface functional group-modified silica nanoparticles surface-modified with a functional group-containing silane coupling agent,
The functional group-containing silane coupling agent is at least one selected from the group consisting of a compound represented by the following chemical formula (1), the following chemical formula (2), and the following chemical formula (3), gas separation film.
- 前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝０～１７）、前記Ｚが－ＣｎＨ２ｎ＋１（ｎ＝１～１８）、下記の化学式（４）で表される基、下記の化学式（５）で表される基であるアルキルシランである、請求項１に記載の気体分離膜。
- 前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝０～６）、前記Ｚが－ＣＨ＝ＣＨ２、－ＣＣＨ３＝ＣＨ２、－Ｃ≡ＣＨであるオレフィニルシランである、請求項１に記載の気体分離膜。 In the functional group-containing silane coupling agent, Y is —(CH 2 ) n —(n=0 to 6), and Z is —CH═CH 2 , —CCH 3 ═CH 2 , —C≡CH. 2. The gas separation membrane of claim 1, which is an olefinylsilane.
- 前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝０～６）、前記Ｚが－Ａｒ、－ＯＡｒであるアリールシランである、請求項１に記載の気体分離膜。 The gas according to claim 1, wherein the functional group-containing silane coupling agent is an arylsilane in which the Y is -(CH 2 ) n - (n = 0 to 6) and the Z is -Ar, -OAr. Separation membrane.
- 前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－ＯＣＨ２－（ｎ＝１～６）、前記Ｚが下記の化学式（６）で表される基、下記の化学式（７）で表される基であるであるグリシジルオキシアルキルシランである、請求項１に記載の気体分離膜。
- 前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝１～６）、前記Ｚが－Ｏ－（Ｃ＝Ｏ）－ＣＨ＝ＣＨ２、－Ｏ－（Ｃ＝Ｏ）－ＣＣＨ３＝ＣＨ２－であるアクロイルオキシアルキルシランである、請求項１に記載の気体分離膜。 In the functional group-containing silane coupling agent, the Y is —(CH 2 ) n —(n=1 to 6), the Z is —O—(C═O)—CH═CH 2 , —O—(C The gas separation membrane of claim 1, wherein the acryloyloxyalkylsilane is ═O)—CCH 3 ═CH 2 —.
- 前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝１～６）、前記Ｚが－ＮＲ２（Ｒは炭素数０～４のアルキル基、アリール基）、－ＮＨ－（ＣＨ２）ｍ－ＮＲ２（ｍ＝２～６、Ｒは炭素数０～４のアルキル基、アリール基）であるアミノアルキルシランである、請求項１に記載の気体分離膜。 In the functional group-containing silane coupling agent, the Y is -(CH 2 ) n - (n = 1 to 6), the Z is -NR 2 (R is an alkyl group having 0 to 4 carbon atoms, an aryl group), 2. The gas separation membrane according to claim 1, wherein the aminoalkylsilane is -NH-(CH 2 ) m -NR 2 (m=2 to 6, R is an alkyl group or an aryl group having 0 to 4 carbon atoms).
- 前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝１～６）、前記Ｚが－ＣｎＦ２ｎ＋１－（ｎ＝１～８）であるフルオロアルキルシランである、請求項１に記載の気体分離膜。 The functional group-containing silane coupling agent is a fluoroalkylsilane in which Y is —(CH 2 ) n — (n=1 to 6) and Z is —C n F 2n+1 — (n=1 to 8). The gas separation membrane of claim 1, wherein the gas separation membrane is
- 前記官能基含有シランカップリング剤は、前記Ｙが－（ＣＨ２）ｎ－（ｎ＝１～６）、－（ＣＨ２）ｎ－Ａｒ－（ＣＨ２）ｍ－（ｍ＝１～６、ｎ＝１～６）、下記の化学式（８）で表される基、前記Ｚが－Ｃｌ、－Ｂｒ、－Ｉ、－ＣＮ、－Ｎ３、－ＮＨ（Ｃ＝Ｏ）ＮＨ２－、－ＳＨ、－Ｎ＝Ｃ＝Ｏである化合物である、請求項１に記載の気体分離膜。
- 前記シリカナノ粒子の含有量が２０質量％以上である、請求項１に記載の気体分離膜。 The gas separation membrane according to claim 1, wherein the content of the silica nanoparticles is 20% by mass or more.
- 前記高分子は、ガラス状高分子またはゴム状高分子である、請求項１～１０のいずれか１項に記載の気体分離膜。 The gas separation membrane according to any one of claims 1 to 10, wherein the polymer is a glassy polymer or a rubbery polymer.
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| CN117861466A (en) * | 2024-03-12 | 2024-04-12 | 安徽先材科技有限公司 | Functional composite membrane based on trimesic acid chloride and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013072065A (en) * | 2011-09-29 | 2013-04-22 | Toray Ind Inc | Polymer-modified inorganic particles, coating composition containing polymer-modified inorganic particles, and method for manufacturing polymer-modified inorganic particles |
| JP2015222364A (en) * | 2014-05-23 | 2015-12-10 | 大日本印刷株式会社 | Hard coat film and manufacturing method thereof |
| WO2018038027A1 (en) * | 2016-08-23 | 2018-03-01 | 日産化学工業株式会社 | Gas separation membrane containing irregularly shaped silica nanoparticles |
| JP2020163375A (en) * | 2019-03-26 | 2020-10-08 | 日東電工株式会社 | Separation membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013072065A (en) * | 2011-09-29 | 2013-04-22 | Toray Ind Inc | Polymer-modified inorganic particles, coating composition containing polymer-modified inorganic particles, and method for manufacturing polymer-modified inorganic particles |
| JP2015222364A (en) * | 2014-05-23 | 2015-12-10 | 大日本印刷株式会社 | Hard coat film and manufacturing method thereof |
| WO2018038027A1 (en) * | 2016-08-23 | 2018-03-01 | 日産化学工業株式会社 | Gas separation membrane containing irregularly shaped silica nanoparticles |
| JP2020163375A (en) * | 2019-03-26 | 2020-10-08 | 日東電工株式会社 | Separation membrane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117861466A (en) * | 2024-03-12 | 2024-04-12 | 安徽先材科技有限公司 | Functional composite membrane based on trimesic acid chloride and preparation method thereof |
| CN117861466B (en) * | 2024-03-12 | 2024-05-17 | 安徽先材科技有限公司 | Functional composite membrane based on trimesic acid chloride and preparation method thereof |
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