WO2015005495A1 - 樹脂組成物及び炭酸ガス分離膜 - Google Patents
樹脂組成物及び炭酸ガス分離膜 Download PDFInfo
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- WO2015005495A1 WO2015005495A1 PCT/JP2014/068845 JP2014068845W WO2015005495A1 WO 2015005495 A1 WO2015005495 A1 WO 2015005495A1 JP 2014068845 W JP2014068845 W JP 2014068845W WO 2015005495 A1 WO2015005495 A1 WO 2015005495A1
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- SPUWFVKLHHEKGV-UHFFFAOYSA-N Cc1cc2c(C)cccc2cc1 Chemical compound Cc1cc2c(C)cccc2cc1 SPUWFVKLHHEKGV-UHFFFAOYSA-N 0.000 description 1
- APQSQLNWAIULLK-UHFFFAOYSA-N Cc1ccc(C)c2c1cccc2 Chemical compound Cc1ccc(C)c2c1cccc2 APQSQLNWAIULLK-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/145—Side-chains containing sulfur
- C08G2261/1452—Side-chains containing sulfur containing sulfonyl or sulfonate-groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
- C08G2261/3444—Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/516—Charge transport ion-conductive
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/262—Alkali metal carbonates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Definitions
- the present invention relates to a resin composition useful for producing a separation membrane for separating carbon dioxide from a raw material gas containing carbon dioxide, a carbon dioxide separation membrane obtained from the resin composition, and a carbon dioxide separation membrane module having the separation membrane And a carbon dioxide separator comprising at least one of the modules.
- Patent Document 1 describes the use of a vinyl alcohol-sodium acrylate copolymer as a resin useful for producing a separation membrane for separating carbon dioxide from a raw material gas containing carbon dioxide.
- the carbon dioxide separation membrane obtained by using the copolymer is not always satisfactory in carbon dioxide permeation performance (permeance) and durability performance.
- the present invention includes the following inventions [1] to [9].
- a resin composition comprising a substance that reacts reversibly with carbon dioxide and a hydrocarbon polymer containing a structural unit represented by the following formula (I):
- Ar is an arylene group constituting the main chain, and the arylene group has at least one ion-exchange group bonded directly or indirectly, and has a fluorine atom and a substituent.
- It can have one or more groups selected from the group consisting of a sulfonyl group, an optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms and a cyano group, m represents an integer of 1 or more, n represents an integer of 2 or more, and a plurality of Ars are each They may be the same or different, Y represents a direct bond, SO 2 , CO or O, and a plurality of Y may be the same or different.
- the resin composition according to [1], wherein the substance that reversibly reacts with carbon dioxide is an alkali metal carbonate, an alkali metal hydrogen carbonate, or an alkali metal hydroxide.
- the resin composition according to [1], wherein the substance that reacts reversibly with carbon dioxide is an alkali metal carbonate or an alkali metal bicarbonate.
- the resin composition according to [1], wherein the substance that reversibly reacts with carbon dioxide is cesium carbonate, cesium hydrogen carbonate, rubidium carbonate, or rubidium hydrogen carbonate.
- the resin composition according to [1], wherein the substance that reversibly reacts with carbon dioxide is cesium carbonate.
- [6] The total weight of the substance that reversibly reacts with carbon dioxide and the hydrocarbon polymer containing the structural unit represented by the formula (I), wherein the substance reacts reversibly with carbon dioxide.
- a carbon dioxide gas separation membrane comprising the resin composition according to any one of [1] to [6] and a porous membrane.
- a carbon dioxide separation membrane module having the carbon dioxide separation membrane according to [7].
- a carbon dioxide separator comprising at least one carbon dioxide membrane module according to [8].
- the hydrocarbon polymer used in the present invention includes a structural unit represented by the following formula (I).
- Ar is an arylene group constituting the main chain, and the arylene group has at least one ion-exchange group bonded directly or indirectly, and has a fluorine atom and a substituent.
- It may have one or more groups selected from the group consisting of a sulfonyl group, an optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms and a cyano group.
- m represents an integer of 1 or more
- n represents an integer of 2 or more.
- a plurality of Ar may be the same or different.
- Y represents a direct bond, SO 2 , CO or O.
- a plurality of Y may be the same or different.
- the carbon dioxide separation membrane produced by the method described below maintains sufficient water retention for carbon dioxide permeation, while suppressing the degree of swelling and mechanical strength. Has the advantage of being good.
- Ar in the formula (I) is an arylene group constituting the main chain, and the arylene group has at least one ion-exchange group bonded directly or indirectly. That is, the ion exchange group may be directly bonded to the aromatic ring of the arylene group constituting the main chain, or may be indirectly bonded via a group of the arylene group constituting the main chain. Although it is good, it is preferable that it is directly bonded.
- arylene group examples include a monocyclic aromatic group such as a phenylene group, a condensed aromatic group such as a naphthalenediyl group, an aromatic heterocyclic group such as a pyridinediyl group, a quinoxalinediyl group, and a thiophenediyl group.
- divalent arylene groups represented by the following formulas (ca) to (cj) are preferable from the viewpoint that industrially easily available raw materials can be used and raw materials that are easy to produce can be used.
- (cb) is particularly preferable because it is excellent in dimensional stability and water resistance during water absorption swelling.
- Examples of the ion exchange group bonded directly or indirectly to the arylene group include those described above, and preferred examples thereof are the same as those described above.
- the arylene group includes, in addition to the ion exchange group, a fluorine atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, and an optionally substituted alkoxy group having 1 to 20 carbon atoms.
- a group selected from an acyl group having 20 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms which may have a substituent, an alkylsulfonyl group having 1 to 20 carbon atoms which may have a substituent, and a cyano group Can have.
- Preferable groups include an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, and an optionally substituted group.
- examples thereof include an acyl group having 2 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms which may have a substituent, and a cyano group.
- a polyarylene block copolymer having such a group is preferable because it has high hydrolysis resistance.
- Particularly preferred groups include an acyl group having 2 to 20 carbon atoms which may have a substituent.
- a polyarylene block copolymer having such a group is preferable because of excellent water resistance.
- the two structural units having the acyl group are adjacent to each other, and the acyl groups in the two structural units are bonded to each other, or after the acyl groups are bonded to each other, a rearrangement reaction occurs. Or you may. Even when such acyl groups are linked to each other, the group after bonding (after the rearrangement reaction) has an alkyl group having 1 to 20 carbon atoms and a substituent which may have a substituent.
- a case where it corresponds to any of the acyl groups having 2 to 20 carbon atoms which may have a group is included in the polymer of the present invention. Whether or not such a reaction that the acyl groups are bonded to each other or a rearrangement reaction occurs after the bonding can be confirmed, for example, by measuring a 13 C-nuclear magnetic resonance spectrum.
- alkyl group having 1 to 20 carbon atoms which may have a substituent, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group N-pentyl group, 2,2-dimethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, 2-methylpentyl group, 2-ethylhexyl group, nonyl group, dodecyl group, hexadecyl group, octadecyl group, icosyl group
- alkyl groups having 1 to 20 carbon atoms and these alkyl groups replace hydroxyl group, cyano group, amino group, methoxy group, ethoxy group, isopropyloxy group, phenyl group, naphthyl group, phenoxy group, naphthyloxy group, etc
- alkoxy group having 1 to 20 carbon atoms which may have a substituent include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, a sec-butyloxy group, and a tert-butyloxy group.
- An aryl group having 20 or less total carbon atoms having a substituent of more than one species can be used.
- Examples of the acyl group having 2 to 20 carbon atoms that may have a substituent include 2 carbon atoms such as an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, a 1-naphthoyl group, and a 2-naphthoyl group. And an acyl group having 20 or less total carbon atoms, each having ⁇ 20 acyl groups and one or more substituents selected from the following substituent groups.
- Examples of the optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, sec-butylsulfonyl group , Isobutylsulfonyl group, n-pentylsulfonyl group, 2,2-dimethylpropylsulfonyl group, cyclopentylsulfonyl group, n-hexylsulfonyl group, cyclohexylsulfonyl group, 2-methylpentylsulfonyl group, 2-ethylhexylsulfonyl group, nonylsulfonyl group
- [Substituent group] Hydroxyl group, cyano group, amino group, methoxy group, ethoxy group, isopropyloxy group, phenyl group, naphthyl, phenoxy group, naphthyloxy group, etc.
- M in the formula (I) is an integer of 1 or more. m is preferably 1000 or less, and more preferably 500 or less. If m is in such a range, the obtained carbon dioxide separation membrane is preferable because it has sufficient mechanical strength and is easy to produce.
- N in the formula (I) is an integer of 2 or more.
- n is preferably 1000 or less, and more preferably 500 or less.
- the obtained carbon dioxide separation membrane is preferable because it has sufficient mechanical strength and is easy to produce.
- Y in the formula (I) represents a direct bond, SO 2 , CO or O, and is preferably a direct bond from the viewpoint of heat resistance.
- the “hydrocarbon polymer” means a polymer in which the carbon atom and the hydrogen atom are combined in an amount of 50 mol% or more in terms of element mass content ratio constituting the polymer.
- the “hydrocarbon polymer” herein may contain other atoms in addition to carbon atoms and hydrogen atoms. Examples of other elements include nitrogen atoms, oxygen atoms, sulfur atoms, and halogen atoms. And heteroatoms such as silicon atoms.
- the hydrocarbon polymer used in the present invention has an ion exchange group from the viewpoint of obtaining water retention necessary for permeation of carbon dioxide gas when a carbon dioxide separation membrane is obtained.
- the ion exchange group is contained in the structural unit represented by the formula (I), but may be contained in other structural units.
- the ion exchange group examples include an acidic ion exchange group (that is, a cation exchange group) or a basic ion exchange group (that is, an anion exchange group). From the viewpoint of obtaining necessary water retention, the ion exchange group is preferably a cation exchange group.
- the cation exchange group examples include a sulfo group (—SO 3 H), a carboxyl group (—COOH), a phosphono group (—PO 3 H 2 ), a sulfonylimide group (—SO 2 NHSO 2 —), a phenolic hydroxyl group, and the like. Can be given.
- a sulfo group or a phosphono group is more preferable, and a sulfo group is particularly preferable.
- These ion exchange groups may be partially or entirely exchanged with a metal ion, a quaternary ammonium ion or the like to form a salt.
- these ion exchange groups may be introduced into either one or both of the main chain and side chain of the polymer, but are preferably introduced into the main chain.
- the main chain of the polymer means the longest chain in the hydrocarbon polymer of the present invention. This chain is composed of carbon atoms bonded to each other by a covalent bond. In this case, this chain may be interrupted by a nitrogen atom, an oxygen atom, a sulfur atom, or the like.
- the introduction amount of the ion exchange group can be represented by an ion exchange group capacity which is the number of ion exchange groups per unit mass of the hydrocarbon polymer.
- the “ion exchange group capacity” is a value defined by the number of equivalents of ion exchange groups contained in 1 g of the dry resin of the hydrocarbon polymer constituting the resin composition [milli equivalent / g dry resin. ] (Hereinafter sometimes referred to as meq / g).
- “Dry resin” refers to a resin in which a hydrocarbon polymer is maintained at a temperature equal to or higher than the boiling point of water, the mass decrease is almost eliminated, and the change in mass with time converges to a substantially constant value.
- the amount of ion exchange groups introduced is preferably 0.5 meq / g or more and 6.0 meq / g or less in terms of ion exchange capacity; 1.0 meq / g or more. 6.0 meq / g or less; more preferably 2.0 meq / g or more and 5.5 meq / g or less; and most preferably 2.7 meq / g or more and 5.0 meq / g or less. .
- the hydrocarbon polymer is a hydrocarbon polymer in which an ion exchange group is introduced into a polymer having a main chain having an aromatic ring from the viewpoint of obtaining necessary heat resistance when a carbon dioxide gas separation membrane is obtained. Preferably there is.
- hydrocarbon polymer in which the ion exchange group is a sulfo group is mainly exemplified, but a hydrocarbon polymer in which the sulfo group is replaced with another ion exchange group may be used.
- the hydrocarbon polymer in which an ion exchange group is introduced into a polymer having an aromatic ring in the main chain may be a hydrocarbon polymer containing a hetero atom such as an oxygen atom in the main chain.
- hydrocarbon polymers include polyether ketone, polyether ether ketone, polysulfone, polyether sulfone, polyether ether sulfone, poly (arylene ether), polyimide, poly ((4-phenoxybenzoyl)- 1,4-phenylene), polyphenylquinoxalen, and other homopolymers include hydrocarbon polymers having sulfo groups introduced therein.
- the hydrocarbon polymer in which an ion exchange group is introduced into a polymer having an aromatic ring in the main chain may be a compound in which the main chain is interrupted by a hetero atom such as an oxygen atom.
- the hydrocarbon polymer in which an ion exchange group is introduced into a polymer having an aromatic ring in the main chain includes polyether ether ketone, polysulfone, polyether sulfone, poly (arylene ether), polyimide, poly (( 4-phenoxybenzoyl) -1,4-phenylene), polyphenylene sulfide, polyphenylquinoxalen, sulfoarylated polybenzimidazole, sulfoalkylated polybenzimidazole, phosphoalkylated polybenzimidazole, phosphonated poly (phenylene ether) Can be given.
- Such hydrocarbon polymers are disclosed in JP-A-9-110882 and J.P. Appl. Polym. Sci. 18, 1969 (1974).
- the hydrocarbon polymer has an aromatic ring constituting a main chain and is directly or indirectly bonded to the aromatic ring.
- a hydrocarbon polymer having an ion exchange group is preferred.
- it may have aromatics constituting the main chain, and may further have side chains having aromatic rings, and directly bonded to either the aromatic ring constituting the main chain or the aromatic ring of the side chain.
- An aromatic polymer having an ion exchange group is preferred.
- an aromatic polymer having an aromatic group constituting the main chain and further having a side chain having an aromatic ring, and having an ion exchange group directly bonded to the aromatic ring constituting the main chain is preferable. .
- the hydrocarbon polymer used in the resin composition in one embodiment of the present invention is preferably a copolymer composed of a structural unit having an ion exchange group and a structural unit having no ion exchange group.
- the copolymerization mode of the two kinds of structural units may be any of random copolymerization, block copolymerization, graft copolymerization or alternating copolymerization, and these copolymerization modes are combined. Also good.
- aromatic polymer having an ion exchange group examples include a polymer having a structural unit having an ion exchange group and a structural unit having no ion exchange group in the molecular structure.
- Examples of the structural unit having an ion exchange group include structural units represented by the above formula (I), and more specifically, structural units represented by the following formulas (11a) to (14a). Can be illustrated.
- Ar 1 to Ar 9 are the same or different and are arylene groups constituting the main chain, and the arylene groups have at least one ion-exchange group bonded directly or indirectly, and are fluorine atoms
- It may have one or more groups selected from the group consisting of a preferable arylsulfonyl group having 6 to 20 carbon atoms, an optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms, and a cyano group.
- Z and Z ′ are the same or different and represent CO or SO 2
- X, X ′ and X ′′ are the same or different, each represents O or S
- Y is a direct bond or represented by the following formula (15)
- P represents 0, 1 or 2
- q and r are the same or different and each represents 1, 2 or 3.
- Examples of the structural unit having no ion exchange group described above include structural units represented by the following formulas (11b) to (14b).
- Ar 11 to Ar 19 are the same or different and are arylene groups constituting the main chain, and the arylene groups each have 1 to 20 carbon atoms which may have a fluorine atom or a substituent.
- the arylene group does not have an ion exchange group.
- Z and Z ′ are the same or different and represent CO or SO 2
- X, X ′ and X ′′ are the same or different, each represents O or S
- Y is a direct bond or represented by the following formula (15)
- P ′ represents 0, 1 or 2
- q ′ and r ′ are the same or different and each represents 1, 2 or 3.
- R 1 and R 2 are the same or different and each is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon group having 1 to An alkoxy group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and a substituent.
- R 1 and R 2 may be linked to form a ring, and the group of formula (15) having a ring formed by linking R 1 and R 2 may be a cyclohexylidene group or the like. Examples thereof include divalent cyclic hydrocarbon groups having 5 to 20 carbon atoms.
- Ar 1 to Ar 9 are an arylene group constituting a main chain, and the arylene group is at least one bonded directly or indirectly It has an ion exchange group.
- the explanation and specific examples thereof are the same as those described above, and preferred examples thereof are also the same as those described above.
- Examples of the ion exchange group bonded directly or indirectly to the arylene group include those described above, and preferred examples thereof are the same as those described above.
- the arylene group includes, in addition to the ion exchange group, a fluorine atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, and an optionally substituted alkoxy group having 1 to 20 carbon atoms.
- a group selected from an acyl group having 20 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms which may have a substituent, an alkylsulfonyl group having 1 to 20 carbon atoms which may have a substituent, and a cyano group Specific examples thereof are the same as those described above, and preferred examples thereof are also the same as those described above.
- Ar 11 to Ar 19 are arylene groups constituting the main chain.
- Examples of the arylene group are the same as those described above, and preferred examples thereof are also the same as those described above.
- the arylene group includes, in addition to the ion exchange group, a fluorine atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, and an optionally substituted alkoxy group having 1 to 20 carbon atoms.
- a group selected from an acyl group having 20 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms which may have a substituent, an alkylsulfonyl group having 1 to 20 carbon atoms which may have a substituent, and a cyano group Specific examples thereof are the same as those described above, and preferred examples thereof are also the same as those described above.
- R 1 and R 2 are the same or different and each is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon number.
- a cyano group is represented, and specific examples thereof are the same as those described above, and preferred examples thereof are also the same as those described above.
- preferred hydrocarbon-based polymers are structural units having an ion exchange group composed of structural units represented by the formulas (11a) to (14a), and formulas (11b) to (14b). It is a hydrocarbon polymer having a structural unit composed of the structural units represented and having no ion exchange group.
- Such a hydrocarbon polymer can be obtained as a copolymer starting from a monomer or an oligomer corresponding to each of a structural unit having an ion exchange group and a structural unit having no ion exchange group.
- examples of the combination of a structural unit having an ion exchange group and a structural unit not having an ion exchange group include the combinations shown in ⁇ A> to ⁇ M> in Table 1 below.
- the structure of the hydrocarbon polymer suitably used in the present invention is ⁇ B>, ⁇ C>, ⁇ D>, ⁇ G>, ⁇ H>, ⁇ I>, ⁇ J>, ⁇ L> or ⁇ M>; even more preferably ⁇ G>, ⁇ H>, ⁇ L> or ⁇ M>.
- suitable copolymers include one or more structural units selected from the group of structural units having ion exchange groups shown below, and a group of structural units having no ion exchange groups shown below.
- the copolymer which consists of 1 type, or 2 or more types of structural units which can be mentioned can be mention
- the ion exchange group in the repeating unit which has an ion exchange group is illustrated by the suitable sulfo group. Any of the above-described ion exchange groups may be employed in place of the sulfo group.
- These structural units may be directly bonded to each other or may be connected to each other with an appropriate atom or atomic group.
- Typical examples of the atoms or atomic groups for bonding the structural units here include an arylene group, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or a divalent group formed by combining these. .
- r000 represents 0 or an integer of 1 or more; r000 is preferably 100 or less, more preferably 1 or more and 80 or less.
- the formulas representing the structural unit having an ion exchange group include the formulas (4a-1), (4a-2), (4a-3), (4a-4), (4a-5), ( 4a-6), (4a-7), (4a-8), (4a-9), (4a-10), (4a-11) and one or more selected from the group consisting of (4a-12) Structural units are preferred.
- one or more structural units selected from the group consisting of formulas (4a-10), (4a-11) and (4a-12) are more preferred; formula (4a-11) or (4a-12) is Particularly preferred.
- a hydrocarbon polymer having a segment containing such a structural unit particularly a hydrocarbon polymer having a segment containing such a structural unit as a repeating unit (a segment having an ion exchange group) has a polymorphic structure. Due to the arylene structure, chemical stability tends to be relatively good.
- formula (4b-14) are preferred.
- one or more selected from the group consisting of formula (4b-0), formula (4b-2), (4b-3), (4b-10), (4b-13) and (4b-14) A structural unit is more preferable; one or more structural units selected from the group consisting of formula (4b-0), formula (4b-2), (4b-3) and (4b-14) are particularly preferable.
- the hydrocarbon polymer according to the present invention is preferably a hydrocarbon polymer having a structural unit having an ion exchange group and a structural unit having no ion exchange group.
- the copolymerization mode of the two structural units may be any of random copolymerization, alternating copolymerization, block copolymerization, or graft copolymerization, or a combination of these copolymerization modes. Random copolymerization, block copolymerization, and graft copolymerization are preferred; random copolymerization and block copolymerization are more preferred.
- a segment mainly composed of a structural unit having an ion exchange group (segment having an ion exchange group) and a segment mainly composed of a structural unit not having an ion exchange group (that is, substantially having an ion exchange group) And a copolymer having a segment not included).
- a combination of a structural unit constituting a segment having a suitable ion exchange group and a structural unit constituting a segment substantially having no ion exchange group the combinations of the segments shown in ⁇ A> to ⁇ M> in Table 2 below are used. You can give a combination.
- the formulas (4a-1), (4a-2), (4a-3), and (4a-4) represent the structural units used for the repeating units constituting the segment having an ion exchange group.
- (4a-5), (4a-6), (4a-7), (4a-8), (4a-9), (4a-10), (4a-11) and (4a-12) One or more structural units selected from the group are preferred; one or more structural units selected from the group consisting of formulas (4a-10), (4a-11) and (4a-12) are more preferred; -11) or (4a-12) is particularly preferred.
- the block copolymer according to the present invention is that the main chain of the segment having an ion exchange group has a polyarylene structure in which a plurality of aromatic rings are substantially directly connected.
- the structural unit of such a segment the above-mentioned formulas (4a-10), (4a-11), (4a-12), (4a-13), (4a-14), (4a-15), One or more structural units selected from the group consisting of (4a-16), (4a-17), (4a-18), (4a-19) and (4a-20) are preferred; formula (4a-10) More preferably, one or more structural units selected from the group consisting of (4a-11) and (4a-12); particularly preferred are formulas (4a-11) or (4a-12).
- a hydrocarbon polymer having a segment including a repeating unit composed of such a structural unit that is, a segment having an ion exchange group
- a hydrocarbon polymer having a segment composed of such a repeating unit is sufficient. Therefore, since this segment has a polyarylene structure, the chemical stability tends to be relatively good.
- the “polyarylene structure” is a form in which the aromatic rings constituting the main chain are substantially directly bonded to each other. Specifically, the total number of bonds between the aromatic rings is 100. %, The direct bond ratio is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more.
- bonded by the direct bond are forms in which aromatic rings are couple
- formula (4b-0), formula (4b-1), (4b-2), (4b-3), ( 4b-4), (4b-5), (4b-6), (4b-7), (4b-8), (4b-9), (4b-10), (4b-11), (4b- 12), one or more structural units selected from the group consisting of (4b-13) and (4b-14) are preferred; formula (4b-0), formula (4b-2), (4b-3), ( 4b-9), (4b-10), (4b-13) and one or more structural units selected from the group consisting of (4b-14) are more preferred; Formula (4b-0), Formula (4b-2) ), (4b-3), (4b-13) and (4b-14).
- formula (4b-0), (4b-2), (4b-3) and one or more structural units selected from the group consisting of (4b-14) is particularly preferred.
- the segment having an ion exchange group and the segment having substantially no ion exchange group may be directly bonded or may be connected by an appropriate atom or atomic group.
- Typical examples of the atom or atomic group for bonding the segments here include an arylene group, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or a divalent group formed by combining these.
- Examples of the arylene group include the same arylene groups as Ar 1 to Ar 9 in formulas (11a) to (14a).
- Suitable block copolymers include a segment containing one or more structural units selected from the group of structural units having an ion exchange group shown above (ie, a segment having an ion exchange group), and A block copolymer comprising a segment containing one or more structural units selected from the group of structural units having no ion-exchange groups shown above (that is, a segment having substantially no ion-exchange groups). I can give you.
- the “segment having an ion exchange group” means that the ion exchange group is a segment containing an average of 0.5 or more per structural unit constituting the segment. It is more preferable that one or more ion exchange groups are contained on an average per unit.
- the “segment substantially having no ion exchange group” means that the ion exchange group is a segment having an average of less than 0.5 per structural unit constituting the segment,
- the average number of ion exchange groups per unit is preferably 0.1 or less, and more preferably 0.05 or less on average.
- a block copolymer in a form in which a segment having an ion exchange group and a segment having substantially no ion exchange group are bonded by a direct bond or bonded by an appropriate atom or atomic group. is there.
- the polymerization degree of a segment composed of one or more structural units selected from the structural units represented by the formulas (11a) to (14a) is 2 or more, preferably 1000 or less, and more preferably 500 or less. If the degree of polymerization is 2 or more, sufficient water retention is expressed as a hydrocarbon polymer for carbon dioxide gas separation, and if the degree of polymerization is 1000 or less, there is an advantage that production is easier.
- the polymerization degree of the segment composed of one or more structural units selected from the structural units represented by formulas (11b) to (14b) is 1 or more, preferably 2 or more, and more preferably 3 or more.
- the degree of polymerization of such segments is preferably 100 or less, more preferably 90 or less, and still more preferably 80 or less. If the degree of polymerization is within such a range, it is preferable as a hydrocarbon polymer for carbon dioxide gas separation because it has sufficient mechanical strength and is easy to produce. That is, the polymerization degree of the segment is preferably 1 or more and 100 or less; more preferably 2 or more and 90 or less; and further preferably 3 or more and 80 or less.
- the molecular weight of the hydrocarbon polymer used in the present invention is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 800,000, and more preferably from 10,000 to 600,000, expressed as a number average molecular weight in terms of polystyrene. More preferably, it is particularly preferably 15000 to 400,000.
- a hydrocarbon polymer having a molecular weight in such a range a hydrocarbon polymer film prepared by a method described later tends to stably maintain the shape of the film.
- the number average molecular weight is measured by gel permeation chromatography (GPC).
- the resin composition of the present invention contains a substance that reacts reversibly with carbon dioxide and a hydrocarbon polymer containing the structural unit represented by the formula (I).
- Examples of the substance that reacts reversibly with carbon dioxide include alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides, alkanolamines and the like as described in JP-A-7-112122. be able to. Alkali metal carbonates, alkali metal hydrogen carbonates or alkali metal hydroxides are preferred, alkali metal carbonates or alkali metal hydrogen carbonates are more preferred, cesium carbonate, cesium bicarbonate, rubidium carbonate or rubidium bicarbonate are more preferred, Even more preferred is cesium carbonate.
- the content of the substance that reacts reversibly with carbon dioxide depends on the type of the substance that reacts reversibly with carbon dioxide, but in the case of cesium carbonate, the total weight of cesium carbonate and the hydrocarbon polymer is On the other hand, it is preferably in the range of 20% by weight to 90% by weight, more preferably in the range of 45% by weight to 85% by weight.
- the resin composition of this invention is obtained by the manufacturing method including the following process A, for example.
- the hydrocarbon polymer may be used in the process A as it is, or may be used in the process A after a post-treatment such as neutralization.
- step A it is preferable to further mix water.
- the amount used is preferably an amount that can be present as a homogeneous solution when the resulting resin composition is subjected to Step B described later.
- the order of mixing in step A is not particularly limited, and the mixing temperature is preferably in the range of 5 ° C to 90 ° C.
- the resin composition of the present invention is supported on a porous membrane.
- porous film examples include a fluororesin, a polyolefin, a polyamide resin, a polysulfone resin, a ceramic, and a metal, and a fluororesin is preferable.
- a fluororesin is preferable.
- a tetrafluoroethylene copolymer (PTFE) porous film is preferable.
- the porous film preferably has heat resistance of 100 ° C. or higher, mechanical strength, and adhesiveness with the resin composition of the present invention. Those having a porosity of 50% or more and a pore diameter in the range of 0.01 ⁇ m or more and 10 ⁇ m or less are preferable, and those having a porosity of 55% or more and a pore diameter in the range of 0.1 ⁇ m or more and 1 ⁇ m or less are more preferable. .
- the porous membrane is preferably hydrophilic.
- a laminate of a hydrophilic porous membrane and a hydrophobic porous membrane can also be used.
- the method for producing a carbon dioxide separation membrane of the present invention includes the following steps A and B.
- Process A is as described above.
- the coating in the step B is preferably performed so that a layer containing a substance that reacts reversibly with carbon dioxide and the hydrocarbon polymer of the present invention is formed on at least one surface of the porous film.
- the resin composition supplied to Step B preferably contains water, and more preferably an aqueous solution.
- Application in the step B can be performed by an industrially usual method such as application by a coater (also referred to as a doctor blade) or application by brush coating.
- the thickness of the composition layer is the thickness of the film formed by the composition after coating, the concentration of the hydrocarbon polymer and water in the resin composition, the substance that reacts reversibly with carbon dioxide and the hydrocarbon system. It can be controlled by adjusting the amount ratio with the polymer.
- the method for producing a carbon dioxide separation membrane of the present invention preferably further includes steps C and D.
- C The process of drying the composition after application
- D The process of heat-processing a composition layer
- Drying in the step C represents removing water mainly contained in the composition after application.
- Such drying is performed by evaporating water from the coating film by, for example, natural drying under normal temperature and normal pressure, heating means such as a thermostatic bath or hot plate, decompression means such as a decompression device, or a combination of these means. Done.
- the conditions for the heating means and the decompression means can be appropriately selected within a range that does not lower the air permeability of the porous membrane.
- the internal pressure of the depressurizer may be set to about 1 to 1.0 ⁇ 10 5 Pa.
- step C and step D can be performed continuously.
- the composition after application in step C can be dried, and the heat treatment in step D can be subsequently performed under the same conditions.
- the heat treatment in step D is usually performed by a heating means such as a thermostatic bath or a hot plate.
- the heat treatment temperature is preferably in the range of 80 ° C to 160 ° C.
- the heat treatment time is preferably in the range of 10 minutes to 4 hours depending on the heat treatment temperature.
- the carbon dioxide separation membrane of the present invention can be a carbon dioxide separation membrane module.
- the carbon dioxide separation device of the present invention includes a carbon dioxide separation membrane or a carbon dioxide separation membrane module, and has means for separating and collecting or separating and purifying carbon dioxide.
- the carbon dioxide separation membrane of the present invention can be suitably used in a modular form.
- module types include spiral type, hollow fiber type, pleated type, tubular type, plate & frame type and the like.
- the carbon dioxide gas separation membrane of the present invention may be applied to a gas separation / recovery device as a membrane / absorption hybrid method used in combination with an absorbing solution as described in JP-A-2007-297605, for example.
- the carbon dioxide permeability coefficient [mol / m 2 / sec / kPa] was measured by an isobaric method using a gas permeation measuring apparatus (GTR Tech Co., Ltd., model: GTR-30XAF3SC).
- the temperature of the cell sandwiching the acid gas separation membrane was set to a predetermined temperature depending on the conditions.
- Carbon dioxide gas was allowed to flow on the supply side, and argon gas was allowed to flow on the permeate side.
- Each gas on the supply / permeation side was humidified through a bubbler heated to a predetermined temperature depending on conditions.
- the flow rates of carbon dioxide gas and argon gas were each set to 20 cc / min.
- the back pressure was 0 kPaG on both the supply side and the permeation side.
- the helium permeability coefficient [mol / m 2 / sec / kPa] was measured by an isobaric method using a gas permeation measuring apparatus (GTR Tech Co., Ltd., model: GTR-30XAF3SC).
- the temperature of the cell sandwiching the carbon dioxide separation membrane was set to 80 ° C.
- Helium gas was allowed to flow on the supply side, and argon gas was allowed to flow on the permeate side.
- Each gas on the supply and permeate side was humidified through a bubbler heated to 70 ° C.
- the flow rates of helium gas and argon gas were each set to 20 cc / min.
- the back pressure was 0 kPaG on both the supply side and the permeation side.
- the obtained polymerization solution was added to 2400 g of a 6 mol / L hydrochloric acid aqueous solution at room temperature and stirred for 30 minutes.
- the precipitated crude polymer is filtered, washed with water until the pH of the filtrate exceeds 4, and then further washed with a large amount of methanol to obtain 19.5 g of polymer 3 precursor containing an ion exchange group. Obtained.
- Example 1 To 200 g of the aromatic emulsion obtained in Synthesis Example 1 (including 198.74 g of water), 3.45 g of cesium carbonate was added and stirred at room temperature for a whole day and night to obtain a resin composition 1 for a carbon dioxide separation membrane.
- Example 2 Cesium carbonate (4.425 g) and water (143.1 g) were added to 201 g of the aromatic emulsion obtained in Synthesis Example 2 (including 199.9 g of water), and the mixture was stirred overnight at room temperature to obtain a resin composition 2 for carbon dioxide separation membrane. It was.
- Example 3 8.06 g of cesium carbonate was added to 2032 g of the aromatic emulsion obtained in Synthesis Example 3 (of which 2028.6 g of water), and the mixture was stirred overnight at room temperature to obtain a resin composition 3 for a carbon dioxide separation membrane.
- Example 4 The resin composition for carbon dioxide separation membrane obtained in Example 1 was placed on the surface of a hydrophilic PTFE porous membrane (manufactured by Sumitomo Electric Fine Polymer, WPW-045-80, film thickness 80 ⁇ m, pore diameter 0.45 ⁇ m). Applied. Next, the hydrophilic PTFE porous membrane after application of the resin composition was dried at 90 ° C. for 1 hour, and then thermally crosslinked at 120 ° C. for about 2 hours to obtain a carbon dioxide separation membrane 1. After drying, the resin composition layer thickness was 45 ⁇ m.
- Example 5 The carbon dioxide gas separation membrane resin composition obtained in Example 2 was formed in the same manner as in Example 4 to obtain a carbon dioxide gas separation membrane 2. After drying, the resin composition layer thickness was 28 ⁇ m.
- Example 6 The carbon dioxide gas separation membrane resin composition obtained in Example 3 was formed into a film by the same method as in Example 4 to obtain a carbon dioxide gas separation membrane 3. After drying, the resin composition layer thickness was 28 ⁇ m.
- Table 3 shows the results of measuring the carbon dioxide permeability coefficient [mol / m 2 / sec / kPa] and the selectivity [ ⁇ ] of the carbon dioxide gas separation membranes 1 to 3.
- the cell temperature was set to 80 ° C. and the bubbler temperature was set to 70 ° C.
- condition 2 the cell temperature was set to 70 ° C. and the bubbler temperature was set to 60 ° C.
- the selectivity was measured under condition 1.
- Table 4 shows the results of measuring the water absorption rate of the carbon dioxide gas separation membranes 1 to 3. From the results, it is considered that the carbon dioxide gas separation membranes 1, 2 and 3 have a low water absorption even under high humidity, and therefore have good mechanical strength even under high humidity.
- Table 5 shows the results of measuring the amount of fluidized gel of the carbon dioxide separation membrane 1. From the results, it can be seen that the carbon dioxide gas separation membrane 1 has high heat resistance.
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Abstract
Description
〔1〕炭酸ガスと可逆的に反応する物質と、下記式(I)で表される構造単位を含む炭化水素系高分子とを含む樹脂組成物:
式(I)中、Arは、主鎖を構成するアリーレン基であり、該アリーレン基は、直接または間接に結合した少なくとも1つのイオン交換基を有し、フッ素原子、置換基を有していてもよい炭素数1~20のアルキル基、置換基を有していてもよい炭素数1~20のアルコキシ基、置換基を有していてもよい炭素数6~20のアリール基、置換基を有していてもよい炭素数6~20のアリールオキシ基、置換基を有していてもよい炭素数2~20のアシル基、置換基を有していてもよい炭素数6~20のアリールスルホニル基、置換基を有していてもよい炭素数1~20のアルキルスルホニル基およびシアノ基からなる群より選ばれる1種以上の基を有することができ、mは1以上の整数を表し、nは2以上の整数を表し、複数存在するArは、それぞれ同一でも異なってもよく、Yは、直接結合、SO2、COまたはOを表し、複数存在するYはそれぞれ同一でも異なってもよい。
〔2〕炭酸ガスと可逆的に反応する物質が、アルカリ金属炭酸塩、アルカリ金属炭酸水素塩またはアルカリ金属水酸化物である〔1〕記載の樹脂組成物。
〔3〕炭酸ガスと可逆的に反応する物質が、アルカリ金属炭酸塩またはアルカリ金属炭酸水素塩である〔1〕記載の樹脂組成物。
〔4〕炭酸ガスと可逆的に反応する物質が、炭酸セシウム、炭酸水素セシウム、炭酸ルビジウムまたは炭酸水素ルビジウムである〔1〕記載の樹脂組成物。
〔5〕炭酸ガスと可逆的に反応する物質が、炭酸セシウムである〔1〕記載の樹脂組成物。
〔6〕炭酸ガスと可逆的に反応する物質の含有量が、炭酸ガスと可逆的に反応する物質と、前記式(I)で表される構造単位を含む炭化水素系高分子との合計重量に対して、20重量%から90重量%の範囲である〔1〕から〔5〕のいずれか一項記載の樹脂組成物。
〔7〕〔1〕から〔6〕のいずれか一項に記載の樹脂組成物と、多孔膜とを用いてなる炭酸ガス分離膜。
〔8〕〔7〕記載の炭酸ガス分離膜を有する炭酸ガス分離膜モジュール。
〔9〕〔8〕記載の炭酸ガス分離膜モジュールを少なくとも一種含む炭酸ガス分離装置。
まず、本発明の一実施態様における樹脂組成物に用いることができる炭化水素系高分子について説明する。本発明に使用する炭化水素系高分子は、下記式(I)で表される構造単位を含む。
式(I)中、Arは、主鎖を構成するアリーレン基であり、該アリーレン基は、直接または間接に結合した少なくとも1つのイオン交換基を有し、フッ素原子、置換基を有していてもよい炭素数1~20のアルキル基、置換基を有していてもよい炭素数1~20のアルコキシ基、置換基を有していてもよい炭素数6~20のアリール基、置換基を有していてもよい炭素数6~20のアリールオキシ基、置換基を有していてもよい炭素数2~20のアシル基、置換基を有していてもよい炭素数6~20のアリールスルホニル基、置換基を有していてもよい炭素数1~20のアルキルスルホニル基およびシアノ基からなる群より選ばれる1種以上の基を有することができる。mは1以上の整数を表し、nは2以上の整数を表す。複数存在するArは、それぞれ同一でも異なってもよい。Yは、直接結合、SO2、COまたはOを表す。複数存在するYはそれぞれ同一でも異なってもよい。
アシル基を有する場合、該アシル基を有する2つの構造単位が隣接し、該2つの構造単位にあるアシル基同士が結合したり、このようにしてアシル基同士が結合した後、転位反応を生じたり、する場合がある。このようなアシル基同士が連結した場合であっても、結合後(転位反応後)の基が、置換基を有していてもよい炭素数1~20のアルキル基、置換基を有していてもよい炭素数1~20のアルコキシ基、置換基を有していてもよい炭素数6~20のアリール基、置換基を有していてもよい炭素数6~20のアリールオキシ基または置換基を有していてもよい炭素数2~20のアシル基のいずれかに相当する場合は、本発明のポリマーに包含される。このようにアシル基同士が結合したり、結合後に転位反応を生じたり、するような反応が生じたか否かは、例えば13C−核磁気共鳴スペクトルの測定により確認することができる。
[置換基群]メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、イソブチル基、n−ペンチル基、2,2−ジメチルプロピル基、シクロペンチル基、n−ヘキシル基、シクロヘキシル基、2−メチルペンチル基、2−エチルヘキシル基、ノニル基、ドデシル基等の炭素数1~19のアルキル基、これらのアルキル基がヒドロキシル基、シアノ基、アミノ基、フェニル基、ナフチル基等を置換基として有するその総炭素数が19以下であるアルキル基およびヒドロキシル基、シアノ基、アミノ基、メトキシ基、エトキシ基、イソプロピルオキシ基、フェニル基、ナフチル、フェノキシ基、ナフチルオキシ基等
[置換基群]メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、イソブチル基、n−ペンチル基、2,2−ジメチルプロピル基、シクロペンチル基、n−ヘキシル基、シクロヘキシル基、2−メチルペンチル基、2−エチルヘキシル基、ノニル基、ドデシル基等の炭素数1~14のアルキル基、これらのアルキル基がヒドロキシル基、シアノ基、アミノ基、フェニル基、ナフチル基等を置換基として有するその総炭素数が14以下であるアルキル基およびヒドロキシル基、シアノ基、アミノ基、メトキシ基、エトキシ基、イソプロピルオキシ基、フェニル基、ナフチル、フェノキシ基、ナフチルオキシ基等
[置換基群]メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、イソブチル基、n−ペンチル基、2,2−ジメチルプロピル基、シクロペンチル基、n−ヘキシル基、シクロヘキシル基、2−メチルペンチル基、2−エチルヘキシル基、ノニル基、ドデシル基等の炭素数1~14のアルキル基、これらのアルキル基がヒドロキシル基、シアノ基、アミノ基、フェニル基、ナフチル基等を置換基として有するその総炭素数が14以下であるアルキル基およびヒドロキシル基、シアノ基、アミノ基、メトキシ基、エトキシ基、イソプロピルオキシ基、フェニル基、ナフチル、フェノキシ基、ナフチルオキシ基等
[置換基群]メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、イソブチル基、n−ペンチル基、2,2−ジメチルプロピル基、シクロペンチル基、n−ヘキシル基、シクロヘキシル基、2−メチルペンチル基、2−エチルヘキシル基、ノニル基、ドデシル基等の炭素数1~18のアルキル基、これらのアルキル基がヒドロキシル基、シアノ基、アミノ基、フェニル基、ナフチル基等を置換基として有するその総炭素数が18以下であるアルキル基およびヒドロキシル基、シアノ基、アミノ基、メトキシ基、エトキシ基、イソプロピルオキシ基、フェニル基、ナフチル、フェノキシ基、ナフチルオキシ基等
[置換基群]メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、イソブチル基、n−ペンチル基、2,2−ジメチルプロピル基、シクロペンチル基、n−ヘキシル基、シクロヘキシル基、2−メチルペンチル基、2−エチルヘキシル基、ノニル基、ドデシル基等の炭素数1~14のアルキル基、これらのアルキル基がヒドロキシル基、シアノ基、アミノ基、フェニル基、ナフチル基等を置換基として有するその総炭素数が14以下であるアルキル基およびヒドロキシル基、シアノ基、アミノ基、メトキシ基、エトキシ基、イソプロピルオキシ基、フェニル基、ナフチル、フェノキシ基、ナフチルオキシ基等
[置換基群]ヒドロキシル基、シアノ基、アミノ基、メトキシ基、エトキシ基、イソプロピルオキシ基、フェニル基、ナフチル、フェノキシ基、ナフチルオキシ基等
なお、ここでいう「炭化水素系高分子」とは炭素原子と水素原子の他に、他の原子を含んでもよく、他の元素とは、例えば、窒素原子、酸素原子、硫黄原子、ハロゲン原子、ケイ素原子などの複素原子などがあげられる。
カチオン交換基としては、例えば、スルホ基(−SO3H)、カルボキシル基(−COOH)、ホスホノ基(−PO3H2)、スルホニルイミド基(−SO2NHSO2−)、フェノール性水酸基等があげられる。これらの中でも、カチオン交換基としては、スルホ基またはホスホノ基がより好ましく、スルホ基が特に好ましい。なお、これらのイオン交換基は、部分的に、あるいは全てが、金属イオンや4級アンモニウムイオン等で交換されて塩を形成していてもよい。
本発明の樹脂組成物は、炭酸ガスと可逆的に反応する物質と、前記式(I)で表される構造単位を含む炭化水素系高分子とを含む。
A:炭酸ガスと可逆的に反応する物質と、前記炭化水素系高分子とを混合する工程
本発明の炭酸ガス分離膜は、前記本発明の樹脂組成物が多孔膜に担持されている。
A:炭酸ガスと可逆的に反応する物質と、前記炭化水素系高分子とを混合する工程
B:樹脂組成物を多孔膜に塗布する工程
C:塗布後の組成物を乾燥させて組成物層を形成する工程
D:組成物層を熱処理する工程
本発明の炭酸ガス分離膜は炭酸ガス分離膜モジュールとすることができる。本発明の炭酸ガス分離装置は、炭酸ガス分離膜または炭酸ガス分離膜モジュールを含み、炭酸ガスを分離回収または分離精製させるための手段を有する。
ガス透過測定装置(GTRテック(株)製、型式:GTR−30XAF3SC)を用いて、等圧法にて二酸化炭素透過係数[mol/m2/sec/kPa]を測定した。酸ガス分離膜を挟むセルの温度は条件によって所定の温度に設定した。供給側には炭酸ガスを流し、透過側にはアルゴンガスを流した。供給・透過側のそれぞれのガスは、条件によって所定の温度に加熱したバブラーを通して加湿した。炭酸ガス、アルゴンガスの流量はそれぞれ20cc/minに設定した。背圧は供給側、透過側共に0kPaGとした。
ガス透過測定装置(GTRテック(株)製、型式:GTR−30XAF3SC)を用いて、等圧法にてヘリウム透過係数[mol/m2/sec/kPa]を測定した。炭酸ガス分離膜を挟むセルの温度は80℃に設定した。供給側にはヘリウムガスを流し、透過側にはアルゴンガスを流した。供給・透過側のそれぞれのガスは、70℃に過熱したバブラーを通して加湿した。ヘリウムガス、アルゴンガスの流量はそれぞれ20cc/minに設定した。背圧は供給側、透過側共に0kPaGとした。得られたヘリウム透過係数と二酸化炭素透過係数を用いて、下記式より選択率を得た。
(選択率[−])=(二酸化炭素透過係数[mol/m2/sec/kPa])/(ヘリウム透過係数[mol/m2/sec/kPa])
調湿TG(Seiko Instrument Inc.製 型式:EXSTAR6000)を用いて、80℃、相対湿度50%、80%における炭酸ガス分離膜の吸水量を測定した。加湿ガスには窒素を用いた。吸水率は下記式により求めた。
(吸水量)/(乾燥全重量−乾燥多孔質基材重量)
炭酸ガス分離膜をサンプル管に入れ、130℃、相対湿度90%に設定したプレッシャークッカー(HIRAYAMA製 型式:PC−304R8)の中に72h放置した。高温高湿下で溶解し、サンプル管中に流動したゲル層の量を測定し、膜面積で規格化することで耐熱性を確かめた。
特開2007−177197号公報に記載の方法に従い、下記式:
で表される構造単位と、下記式:
nは繰り返し単位数を表す;
で示される構造単位とを有するイオン交換基を含む高分子1を合成した。該イオン交換基を含む高分子1のイオン交換容量は2.70meq/gであった。
特開2011−102388号公報パンフレットに記載の方法に従い、下記式:
で表される構造単位と、下記式:
nは繰り返し単位数を表す;
で表される構造単位を有するイオン交換基を含む高分子2を合成した。該イオン交換基を含む高分子2のイオン交換容量は4.70meq/gであった。
窒素雰囲気下、フラスコに無水臭化ニッケル2.9g(13.3mmol)と1−メチル−2−ピロリドン140gとを混合し、内温70℃に昇温し1時間攪拌した。これを60℃に冷却し、2,2’−ビピリジル2.3g(14.6mmol)を加え、撹拌しながら40℃に冷却し、ニッケル含有溶液を調製した。
窒素雰囲気下、フラスコに、4,4’−ジクロロビフェニル−2,2’−ジスルホン酸ジ(2,2−ジメチルプロピル)20.0g(38.2mmol)、2’,5’−ジクロロアセトフェノン5.4g(28.3mmol)を加え、1−メチル−2−ピロリドン400gに溶解させて50℃に調整した。得られた溶液に、亜鉛粉末8.7g(133.1mmol)を加え、撹拌しながら40℃に冷却した。これに、前記ニッケル含有溶液を注ぎ込み、40℃のまま5時間重合反応を行い、黒色の重合溶液を得た。
得られた重合溶液を、室温下で6mol/L塩酸水溶液2400gに投入し、30分攪拌した。析出した粗ポリマーを濾過し、さらに濾液のpHが4を越えるまで水洗を行ない、その後、大量のメタノールを用いて、さらに洗浄することで、イオン交換基を含む高分子3前駆体19.5gを得た。
で示される構造単位と下記式:
で示される構造単位とを有するイオン交換基を含む高分子3を14.2gを得た。
合成例1で得られた芳香族系エマルジョン200g(うち水198.74g)に炭酸セシウム3.45gを加えて室温で一昼夜攪拌して炭酸ガス分離膜用樹脂組成物1を得た。
合成例2で得られた芳香族系エマルジョン201g(うち水199.9g)に炭酸セシウム4.425gと水143.1gを加えて室温で一昼夜攪拌して炭酸ガス分離膜用樹脂組成物2を得た。
合成例3で得られた芳香族系エマルジョン2032g(うち水2028.6g)に炭酸セシウム8.06gを加え、室温で一昼夜攪拌して炭酸ガス分離膜用樹脂組成物3を得た。
実施例1で得られた炭酸ガス分離膜用樹脂組成物を、親水性PTFE多孔膜(住友電工ファインポリマー製、WPW−045−80、膜厚80μm、細孔径0.45μm)の面上に、塗布した。次に、前記樹脂組成物塗布後の親水性PTFE多孔膜を90℃で1時間乾燥させた後、さらに120℃で2時間程度熱架橋させて炭酸ガス分離膜1を得た。乾燥後樹脂組成物層厚みは45μmであった。
実施例2で得られた炭酸ガス分離膜用樹脂組成物を、実施例4と同様の方法で製膜し、炭酸ガス分離膜2を得た。乾燥後樹脂組成物層厚みは28μmであった。
実施例3で得られた炭酸ガス分離膜用樹脂組成物を実施例4と同様の方法で製膜し、炭酸ガス分離膜3を得た。乾燥後樹脂組成物層厚みは28μmであった。
炭酸ガス分離膜1から3の二酸化炭素透過係数[mol/m2/sec/kPa]および選択率[−]を測定した結果を表3に示す。条件1ではセル温度80℃、バブラー温度70℃に設定し、条件2ではセル温度70℃、バブラー温度60℃に設定した。選択率は条件1で測定した。
炭酸ガス分離膜1から3の吸水率を測定した結果を表4に示す。結果から、炭酸ガス分離膜1、2および3は高湿度下でも吸水率が小さいため、高湿度下においても機械強度が良好であると考えられる。
Claims (9)
- 炭酸ガスと可逆的に反応する物質と、下記式(I)で表される構造単位を含む炭化水素系高分子とを含む樹脂組成物:
式(I)中、Arは、主鎖を構成するアリーレン基であり、該アリーレン基は、直接または間接に結合した少なくとも1つのイオン交換基を有し、フッ素原子、置換基を有していてもよい炭素数1~20のアルキル基、置換基を有していてもよい炭素数1~20のアルコキシ基、置換基を有していてもよい炭素数6~20のアリール基、置換基を有していてもよい炭素数6~20のアリールオキシ基、置換基を有していてもよい炭素数2~20のアシル基、置換基を有していてもよい炭素数6~20のアリールスルホニル基、置換基を有していてもよい炭素数1~20のアルキルスルホニル基及びシアノ基からなる群より選ばれる1種以上の基を有することができ、mは1以上の整数を表し、nは2以上の整数を表し、複数存在するArは、それぞれ同一でも異なってもよく、Yは、直接結合、SO2、COまたはOを表し、複数存在するYはそれぞれ同一でも異なってもよい。 - 炭酸ガスと可逆的に反応する物質が、アルカリ金属炭酸塩、アルカリ金属炭酸水素塩またはアルカリ金属水酸化物である請求項1記載の樹脂組成物。
- 炭酸ガスと可逆的に反応する物質が、アルカリ金属炭酸塩またはアルカリ金属炭酸水素塩である請求項1記載の樹脂組成物。
- 炭酸ガスと可逆的に反応する物質が、炭酸セシウム、炭酸水素セシウム、炭酸ルビジウムまたは炭酸水素ルビジウムである請求項1記載の樹脂組成物。
- 炭酸ガスと可逆的に反応する物質が、炭酸セシウムである請求項1記載の樹脂組成物。
- 炭酸ガスと可逆的に反応する物質の含有量が、炭酸ガスと可逆的に反応する物質と、前記式(I)で表される構造単位を含む炭化水素系高分子との合計重量に対して、20重量%から90重量%の範囲である請求項1から5のいずれか一項記載の樹脂組成物。
- 請求項1から6のいずれか一項に記載の樹脂組成物と、多孔膜とを用いてなる炭酸ガス分離膜。
- 請求項7記載の炭酸ガス分離膜を有する炭酸ガス分離膜モジュール。
- 請求項8記載の炭酸ガス分離膜モジュールを少なくとも一種含む炭酸ガス分離装置。
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