WO2015046103A1 - Membrane de séparation de gaz, procédé de production de membrane de séparation de gaz, et module de membrane de séparation de gaz - Google Patents

Membrane de séparation de gaz, procédé de production de membrane de séparation de gaz, et module de membrane de séparation de gaz Download PDF

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Publication number
WO2015046103A1
WO2015046103A1 PCT/JP2014/075003 JP2014075003W WO2015046103A1 WO 2015046103 A1 WO2015046103 A1 WO 2015046103A1 JP 2014075003 W JP2014075003 W JP 2014075003W WO 2015046103 A1 WO2015046103 A1 WO 2015046103A1
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group
gas separation
separation membrane
polymer
general formula
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PCT/JP2014/075003
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English (en)
Japanese (ja)
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岳史 成田
賢志 狩野
福田　誠
上平　茂生
佐野　聡
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富士フイルム株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B01D2256/245—Methane
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0233—Other waste gases from cement factories
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/025—Other waste gases from metallurgy plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/34—Use of radiation
    • B01D2323/345—UV-treatment
    • 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

Definitions

  • the present invention relates to a gas separation membrane, a manufacturing method thereof, and a gas separation membrane module. More specifically, the present invention relates to a gas separation membrane having high separation selectivity and permeability under high pressure and high organic solvent resistance, a method for producing the same, and a gas separation membrane module having this gas separation membrane.
  • a material composed of a polymer compound has gas permeability specific to each material. Based on the property, a desired gas component can be selectively permeated and separated by a membrane composed of a specific polymer compound.
  • this gas separation membrane As an industrial application of this gas separation membrane, it is related to the problem of global warming, and it is considered to separate and recover it from large-scale carbon dioxide generation sources in thermal power plants, cement plants, steelworks blast furnaces, etc. Has been. And this membrane separation technique attracts attention as a means for solving environmental problems that can be achieved with relatively small energy. Natural gas and biogas (gas generated by fermentation and anaerobic digestion of biological waste, organic fertilizers, biodegradable substances, sewage, garbage, energy crops, etc.) are mainly mixed gases containing methane and carbon dioxide. Membrane separation methods have been studied as means for removing the carbon dioxide and the like.
  • an asymmetric membrane As a membrane separation method for ensuring gas permeability and separability by thinning a portion that contributes to gas separation in order to make a practical gas separation membrane, an asymmetric membrane (Asymmetric Membrane)
  • a thin layer composite film Thin film composite
  • Thin film composite a thin layer called a skin layer or a support as a material having mechanical strength and a thin film layer (Selective Layer) contributing to gas separation are provided thereon.
  • a method using a hollow fiber (Hollow fiber) including a high-density layer that contributes to gas separation is known.
  • a layer contributing to gas separation is called a separation layer.
  • Patent Document 1 discloses a thin-layer composite membrane in which a separation layer is provided on a support provided with a porous layer on a nonwoven fabric.
  • Non-Patent Document 1 discloses that a gas separation membrane having a separation layer using polyimide or the like is plasticized under a high pressure condition and a high carbon dioxide concentration condition in a plant, which causes a reduction in separation selectivity.
  • it is effective to introduce a cross-linked structure into the polymer compound constituting the membrane, but since there is a trade-off relationship between gas separation selectivity and permeability, the introduction of the cross-linked structure is required. It is described that the permeability is lowered by the above.
  • Non-Patent Document 2 discloses that mixed gases such as natural gas and biogas include trace amounts of water, hydrocarbons such as tetrahydrofuran (THF), hydrogen sulfide, and long-chain hydrocarbons (HC), benzene, toluene, and xylene (BTX).
  • THF tetrahydrofuran
  • HC long-chain hydrocarbons
  • BTX xylene
  • the impurities such as aromatic compounds are contained, and as the gas separation by the membrane continues, these impurities stay in the separation membrane module, resulting in damage such as plasticization or hydrolysis of the membrane. It is described that the separation selectivity is lowered.
  • Patent Document 1 discloses a gas separation composite membrane having a gas separation layer containing a crosslinked polyimide resin on the upper side of a gas permeable support layer, and has a structure in which a polyimide compound is crosslinked via a specific crosslinking chain. It is described that the gas separation composite membrane has high gas separation selectivity while having excellent gas permeability.
  • Patent Document 2 discloses a gas separation membrane having high plasticization resistance by using cross-linking. By using a cross-linked polyimide having ester cross-linking, high permeability and high separation selectivity are realized. A method is described for obtaining hollow fibers that can be produced.
  • JP 2013-46902 A US Patent US2009 / 0249950
  • the problem to be solved by the present invention is to provide a gas separation membrane having high separation selectivity and permeability under high pressure and high resistance to organic solvents.
  • cross-linking that suppresses plasticization is achieved by using a polymer having a cross-linked structure that is cross-linked by using a ketene imine compound as a cross-linking agent as a material for the separation layer. Because it can be introduced, it can achieve both high separation selectivity and high permeability under high pressure, and can form a strong crosslink between covalent bonds between polymers, making it difficult to dissolve in organic solvents and high resistance to organic solvents. It came to discover that the gas separation membrane which has can be provided.
  • the present invention which is a specific means for solving the above problems, is as follows. [1] having a separation layer containing a polymer having a crosslinked structure; A gas separation membrane in which a polymer having a crosslinked structure contains a structure crosslinked through a linking group derived from a ketene imine crosslinking agent having at least two groups represented by the following general formula (1).
  • General formula (1) (In general formula (1), R 22 and R 23 each independently represent a substituent, and * represents a binding site.)
  • the linking group derived from the ketene imine crosslinking agent is preferably —NH—R 21 —NH— (wherein R 21 represents a divalent linking group).
  • the crosslinked structure having a reactive group has a structure of —C ( ⁇ O) —NH—R 21 —NH—C ( ⁇ O) — (R 21 is a divalent group). Represents a linking group).
  • R 21 is preferably an alkylene group, an arylene group, or a divalent linking group in which two or more alkylene groups or an arylene group are bonded. .
  • R 21 is preferably a divalent linking group having 1 to 15 carbon atoms.
  • R 21 is preferably a divalent linking group containing at least one arylene group.
  • the ketene imine crosslinking agent is preferably a compound represented by the following general formula (2).
  • R 11 represents an alkylene group, an arylene group, or a divalent linking group in which two or more alkylene groups or an arylene group are bonded directly or via R 31 , and R 12 to R 15 Each independently represents an alkyl group or an aryl group, and R 31 represents any one of the linking groups represented by the following group.
  • the polymer having a crosslinked structure is preferably a crosslinked polyimide.
  • the polymer having a reactive group preferably includes a polyimide unit and a repeating unit having a carboxyl group, an amino group or a hydroxyl group in the side chain.
  • a separation layer containing a polymer having a crosslinked structure is obtained by crosslinking a composition containing a polymer having a reactive group and a ketene imine crosslinking agent having at least two groups represented by the following general formula (1).
  • a manufacturing method of a gas separation membrane including the process of forming.
  • General formula (1) (In general formula (1), R 22 and R 23 each independently represent a substituent, and * represents a binding site.)
  • the polymer having a reactive group preferably includes a polyimide unit and a repeating unit having a carboxyl group, an amino group or a hydroxyl group in a side chain.
  • a gas separation membrane module having the gas separation membrane according to any one of [1] to [10].
  • FIG. 1 is a schematic view showing a cross section of an example of the gas separation membrane of the present invention.
  • FIG. 2 is a schematic view showing a cross section of another example of the gas separation membrane of the present invention.
  • FIG. 3 is a schematic view showing a cross section of another example of the gas separation membrane of the present invention.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • substituents when there are a plurality of substituents, linking groups, and the like (hereinafter referred to as substituents) indicated by specific symbols, or when a plurality of substituents are specified simultaneously or alternatively, It means that a substituent etc. may mutually be same or different. Further, even if not specifically stated, it means that when a plurality of substituents and the like are close to each other, they may be connected to each other or condensed to form a ring.
  • the gas separation membrane of the present invention has a separation layer containing a polymer having a crosslinked structure, and the polymer having a crosslinked structure is derived from a ketene imine crosslinking agent having at least two groups represented by the following general formula (1). Contains a structure crosslinked through a linking group.
  • General formula (1) In general formula (1), R 22 and R 23 each independently represent a substituent, and * represents a binding site.
  • the gas separation membrane of the present invention has high separation selectivity and permeability under high pressure and high resistance to organic solvents.
  • preferred embodiments of the gas separation membrane of the present invention will be described.
  • the gas separation membrane of the present invention is preferably a thin layer composite membrane, an asymmetric membrane or a hollow fiber.
  • the gas separation membrane is preferably a thin layer composite membrane.
  • the case where the gas separation membrane is a thin layer composite membrane may be described as a representative example, but the gas separation membrane of the present invention is not limited to the thin layer composite membrane.
  • the gas separation membrane of the present invention is produced, when the membrane is formed using a so-called phase separation method of passing through a poor solvent after applying the solution, the gas separation membrane has a void portion having a void and a void. Not divided into separate layers.
  • the thickness of the separation layer can be obtained by observing the cross section of the gas separation membrane by SEM and measuring the thickness of the portion where no void exists.
  • FIG. 1 is a longitudinal sectional view schematically showing a gas separation membrane 10 of a thin layer composite membrane which is a preferred embodiment of the present invention.
  • 1 is a separation layer
  • 12 is a support 4 made of a porous layer.
  • FIG. 2 is a cross-sectional view schematically showing a gas separation membrane 10 which is a preferred embodiment of the present invention.
  • a nonwoven fabric 13 is added as a part of the support 4, and the support 4 has the porous layer 12 and the nonwoven fabric 13.
  • upper support means that another layer may be interposed between the support and the separation layer.
  • the direction in which the gas to be separated is supplied is “upper”, and the direction in which the separated gas is emitted is “lower”.
  • the gas separation membrane 10 is a thin layer composite membrane, and the gas separation membrane 10 is formed on the separation layer 1 and the separation layer 1. And a protective layer 2 (Protective Layer).
  • the separation layer 1 is preferably formed on the support 4.
  • the gas separation membrane 10 of the present invention preferably has a smooth layer (Gutter Layer) 3 between the separation layer 1 and the support 4.
  • the gas separation membrane of the present invention includes a separation layer containing a polymer having a crosslinked structure, and the polymer having a crosslinked structure is derived from a ketene imine crosslinking agent having at least two groups represented by the following general formula (1). Contains a structure crosslinked through a group.
  • General formula (1) (In general formula (1), R 22 and R 23 each independently represent a substituent, and * represents a binding site.)
  • the separation layer may have an unreacted ketene imine crosslinking agent after the crosslinking reaction. It can be confirmed by IR spectrum that the separation layer has an unreacted ketene imine crosslinking agent.
  • the polymer having a crosslinked structure contains a structure crosslinked via a linking group derived from a ketene imine crosslinking agent having at least two groups represented by the general formula (1).
  • crosslinked polyimide also referred to as polyimide having a crosslinked structure
  • polyamide having a crosslinked structure cellulose having a crosslinked structure
  • polyethylene glycol having a crosslinked structure a crosslinked structure
  • polybenzoxazole having a crosslinked structure it is more preferable that it is at least one selected from polyimide having a crosslinked structure, polybenzoxazole having a crosslinked structure, and cellulose acetate having a crosslinked structure, and particularly preferably a polyimide having a crosslinked structure.
  • the polymer having a crosslinked structure is a polyimide having a crosslinked structure
  • the present invention is limited to the case where the polymer having a crosslinked structure is a polyimide having a crosslinked structure. is not.
  • the linking group derived from the ketene imine crosslinking agent is preferably —NH—R 21 —NH— (wherein R 21 represents a divalent linking group).
  • R 21 represents a divalent linking group.
  • R 21 is preferably an alkylene group, an arylene group, or a divalent linking group in which two or more alkylene groups and an arylene group are bonded directly or via R 24 , and is an alkylene group, an arylene group, or 2 A divalent linking group in which the above alkylene group and arylene group are directly bonded is more preferable.
  • the alkylene group represented by R 21 is preferably an alkylene group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and particularly preferably an alkylene group having 1 carbon atom. is there.
  • the arylene group represented by R 21 is preferably an arylene group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 10 carbon atoms, and more preferably an arylene group having 6 carbon atoms. is there.
  • the divalent linking group in which two or more alkylene groups and arylene groups represented by R 21 are bonded directly or via R 24 is not particularly limited, but is a divalent linking group having 1 to 15 carbon atoms. And more preferably a divalent linking group having 1 to 15 carbon atoms containing at least one arylene group, and particularly a divalent linking group having 1 to 15 carbon atoms containing two arylene groups.
  • a divalent linking group having 1 to 15 carbon atoms having two arylene groups on both sides of the alkylene group is more preferable.
  • R 21 is a divalent linking group in which two or more alkylene groups and an arylene group are bonded directly or via a linking group
  • R 24 between the two or more alkylene groups and the arylene group is represented by the following group: And is preferably —SO 2 —.
  • R 21 is preferably an alkylene group or a divalent linking group in which two or more alkylene groups and an arylene group are bonded.
  • R 21 is preferably a divalent linking group having 1 to 15 carbon atoms from the viewpoint of gas separation.
  • R 21 is preferably a divalent linking group containing at least one arylene group from the viewpoint of affinity with the polyimide in the examples.
  • the linking group represented by R 21 may be further substituted with a substituent, and examples of the substituent include the substituents listed in the substituent group Z described later.
  • a crosslinked chain having a linking group derived from a ketene imine crosslinking agent as described above has an advantageous effect on improving the stability and separation selectivity of a polymer having a crosslinked structure.
  • amide [—NHC ( ⁇ O) —] is generally a stable bond, which is considered to contribute to the stabilization of the film.
  • Such an amide bond is generally considered to be much more stable than an ester bond with respect to acids and alkalis.
  • Crosslinking can be performed between the above reactive polymer chains or inside the reactive polymer chain.
  • a crosslinked chain having a linking group derived from a ketene imine crosslinking agent is excellent in production suitability.
  • the preferred range of the aryl group represented by R 22 and R 23 is the same as the preferred range of the aryl group described in Substituent group Z described later. More preferably, R 22 and R 23 are each independently an aryl group. However, in the present specification, the aryl group includes a heteroaryl group.
  • the heteroaryl group refers to a group in which at least one of the ring-constituting atoms of a 5-membered, 6-membered or 7-membered ring exhibiting aromaticity or a condensed ring thereof is substituted with a heteroatom.
  • heteroaryl groups include imidazolyl, pyridyl, quinolyl, furyl, thienyl, benzoxazolyl, indolyl, benzimidazolyl, benzthiazolyl, carbazolyl, and azepinyl groups.
  • the hetero atom contained in the heteroaryl group is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, and particularly preferably an oxygen atom or a nitrogen atom.
  • the substituent represented by R 22 and R 23 may be further substituted by a further substituent, and examples of the further substituent include the substituents listed in the substituent group Z described later.
  • the ketene imine crosslinking agent is preferably a compound represented by the following general formula (2).
  • General formula (2) (In the general formula (2), R 11 represents an alkylene group, an arylene group, or a divalent linking group in which two or more alkylene groups or an arylene group are bonded directly or via R 31 , and R 12 to R 15 Each independently represents an alkyl group or an aryl group, and R 31 represents any one of the linking groups represented by the following group.)
  • the preferred range of R 11 is the same as the preferred range of R 21 described above.
  • the preferred ranges of R 12 to R 15 are the same as the preferred ranges of R 22 and R 23 described above.
  • a preferred range for R 31 is the same as the preferred range for R 24 described above.
  • ketene imine crosslinking agent Specific examples of the ketene imine crosslinking agent are shown below, but the present invention is not limited thereto.
  • the ketene imine cross-linking agent is a compound having at least two ketene imine groups.
  • the ketene imine cross-linking agent is preferably added in an amount of 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, based on the polymer having a reactive group, More preferably, it is added so as to be 0.2 to 2% by mass.
  • the ketene imine cross-linking agent is preferably reacted in an amount of 5 to 99%, preferably 10 to 90%, more preferably 20 to 80%.
  • reaction rate is too low, the plastic resistance and the resistance to organic solvents deteriorate, and if the reactivity is too high, the viscosity may increase and film formation may be difficult.
  • the reaction rate of the ketene imine crosslinking agent can be obtained from the IR spectrum of the polyester film, and can be calculated from the peak at 2000 cm ⁇ 1 .
  • the crosslinking of the polymer having a reactive group is preferably performed together with the formation of the separation layer. Details will be described in [Method for producing gas separation membrane] below.
  • the polymer having a crosslinked structure used in the present invention has a structure in which a polymer having a reactive group is crosslinked via a crosslinking chain which is a linking group derived from the ketene imine crosslinking agent.
  • a crosslinking method via a crosslinking chain is typically a method using a crosslinking reaction including the following reaction schemes (1) and (2).
  • the sequential two-stage crosslinking reaction represented by the following schemes (1) and (2) is shown, but the crosslinking reaction in the present invention is a sequential two-stage crosslinking reaction. It is not limited to.
  • R A1 represents a divalent linking group
  • R A2 , R A3 , R B2 and R B3 each independently represent a substituent
  • Poly 1 and Poly 2 each independently represent an arbitrary reactive polymer skeleton.
  • the preferred range for R A1 is the same as the preferred range for R 21 described above.
  • the preferred ranges of R A2 , R A3 , R B2 and R B3 are the same as the preferred ranges of R 22 and R 23 described above.
  • Poly 1 and Poly 2 are preferably structures other than reactive groups of the reactive polymer described later.
  • the separation layer containing a polymer having a crosslinked structure is formed by crosslinking a composition containing a polymer having a reactive group and a ketene imine crosslinking agent having at least two groups represented by the general formula (1). It is preferable to become.
  • Polymers having reactive groups include polyimides having reactive groups, polyamides having reactive groups, celluloses having reactive groups, polyethylene glycols having reactive groups, polybenzoxazoles having reactive groups It is preferable that it is at least one selected from polyimide having a reactive group, polybenzoxazole having a reactive group, and cellulose acetate having a reactive group, and a polyimide having a reactive group. It is particularly preferred.
  • the polymer having a reactive group is a polyimide having a reactive group
  • the present invention may be used when the polymer having a reactive group is a polyimide having a reactive group. It is not limited.
  • the polyimide compound having a reactive group is a polymer having a reactive group, a polyimide unit and a reactive group (preferably a nucleophilic reactive group in the side chain, more preferably a carboxyl group, And a repeating unit having an amino group or a hydroxyl group. More specifically, the polymer having a reactive group is represented by at least one repeating unit represented by the following formula (I) and the following formula (III-a) or (III-b): It is preferable to include at least one repeating unit.
  • the polymer having a reactive group includes at least one repeating unit represented by the following formula (I) and at least one repeating unit represented by the following formula (II-a) or (II-b): And at least one repeating unit represented by the following formula (III-a) or (III-b).
  • the polyimide having a reactive group used in the present invention may contain a repeating unit other than the above repeating units, and the number of moles thereof is 100 as the sum of the number of moles of each repeating unit represented by the above formulas. Is preferably 20 or less, more preferably 0 to 10. It is particularly preferable that the polyimide having a reactive group used in the present invention consists only of each repeating unit represented by the following formulas.
  • R represents a group having a structure represented by any of the following formulas (Ia) to (Ih).
  • * represents a bonding site with the carbonyl group of the formula (I).
  • R in the formula (I) may be referred to as a mother nucleus, and the mother nucleus R is preferably a group represented by the formula (Ia), (Ib) or (Id), A group represented by (Ia) or (Id) is more preferred, and a group represented by (Ia) is particularly preferred.
  • ⁇ X 1 , X 2 , X 3 X 1 , X 2 and X 3 represent a single bond or a divalent linking group.
  • the divalent linking group —C (R x ) 2 — (R x represents a hydrogen atom or a substituent. When R x is a substituent, they may be linked to each other to form a ring), —O—, —SO 2 —, —C ( ⁇ O) —, —S—, —NR Y — (R Y represents a hydrogen atom, an alkyl group (preferably a methyl group or an ethyl group) or an aryl group (preferably a phenyl group).
  • R x represents a substituent
  • R x represents a substituent
  • specific examples thereof include the substituent group Z described below.
  • an alkyl group preferably the same as the substituent group Z described later
  • a halogen atom is substituted with a substituent.
  • trifluoromethyl is particularly preferable.
  • ⁇ L L represents —CH 2 ⁇ CH 2 — or —CH 2 —, preferably —CH 2 ⁇ CH 2 —.
  • R 1 , R 2 R 1 and R 2 represent a hydrogen atom or a substituent.
  • substituent any one selected from the substituent group Z shown below can be used.
  • R 1 and R 2 may be bonded to each other to form a ring.
  • R 1 and R 2 are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom.
  • R 3 represents an alkyl group or a halogen atom. Preferable examples of these alkyl groups and halogen atoms are the same as the preferable ranges of the alkyl groups and halogen atoms defined in Substituent group Z described later.
  • L1 representing the number of R 3 is an integer of 0 to 4, preferably 1 to 4, and more preferably 3 to 4.
  • R 3 is preferably an alkyl group, and more preferably a methyl group or an ethyl group.
  • R 4 , R 5 R 4 and R 5 each represents an alkyl group or a halogen atom, or a group that forms a ring together with X 2 by being linked to each other.
  • Preferable examples of these alkyl groups and halogen atoms are the same as the preferable ranges of the alkyl groups and halogen atoms defined in Substituent group Z described later.
  • the structure in which R 4 and R 5 are linked is not particularly limited, but a single bond, —O— or —S— is preferable.
  • M1 and n1 representing the number of R 4 and R 5 are integers of 0 to 4, preferably 1 to 4, and more preferably 3 to 4.
  • R 4 and R 5 are alkyl groups, they are preferably methyl groups or ethyl groups, and trifluoromethyl is also preferable.
  • R 6 , R 7 , R 8 R 6 , R 7 and R 8 represent a substituent.
  • R 7 and R 8 may be bonded to each other to form a ring.
  • L2, m2, and n2 representing the number of substituents are integers of 0 to 4, preferably 0 to 2, and more preferably 0 to 1.
  • J 1 J 1 represents a single bond or a divalent linking group.
  • As the linking group * —COO — N + R b R c R d — ** (R b to R d are a hydrogen atom, an alkyl group, and an aryl group, and preferred ranges thereof are those described in Substituent Group Z below. synonymous), * -. SO 3 - N + R e R f R g - ** (R e ⁇ R g is a hydrogen atom, an alkyl group, an aryl group, its preferred range is below substituent group Z And an alkylene group or an arylene group.
  • J 1 is preferably a single bond, a methylene group or a phenylene group, and particularly preferably a single bond.
  • a 1 is not particularly limited as long as it is a group capable of undergoing a crosslinking reaction with a ketene imine crosslinking agent, but is preferably a nucleophilic reactive group, and is —COOH, amino group, —OH, and —S ( ⁇ O More preferably, it represents a group selected from 2 OH.
  • the preferable range of this amino group is synonymous with the preferable range of the amino group demonstrated by the substituent group Z mentioned later.
  • a 1 is particularly preferably a carboxyl group, an amino group or a hydroxyl group, more particularly preferably —COOH or —OH, and particularly preferably a carboxyl group.
  • Substituent group Z An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl) , N-decyl, n-hexadecyl), a cycloalkyl group (preferably a cycloalkyl group having 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, particularly preferably 3 to 10 carbon atoms, such as cyclopropyl, Cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyl, allyl, -Butenyl, 3-pentenyl, etc.), alky
  • an aryl group having 6 to 12 carbon atoms such as phenyl, p-methylphenyl, naphthyl, anthranyl, etc.
  • amino group amino group, alkylamino group, arylamino group, hetero
  • a cyclic amino group preferably an amino group having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzyl Amino, diphenylamino, ditolylamino, etc.
  • alkoxy groups preferably having 1 carbon atom
  • alkoxy groups preferably having 1 carbon atom
  • an alkoxy group having 1 to 20 carbon atoms particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.
  • an aryloxy group preferably An aryloxy group having
  • Heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy and the like. ),
  • An acyl group (preferably an acyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.), alkoxy A carbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), aryloxy A carbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl), an acyloxy group ( Preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, especially Preferably, it is an acyloxy group having 2 to 10 carbon atoms, such as acet
  • alkoxycarbonylamino group preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino
  • aryl Oxycarbonylamino group preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino group
  • a sulfonylamino group preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino, benzenesulfonylamino, etc.
  • a sulfamoyl group Preferably 0-30 carbon atoms, more preferred 0 to 20 carbon atoms, particularly preferably a sulfam
  • a carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like.
  • An alkylthio group preferably an alkylthio group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio
  • an arylthio group Preferably, it is an arylthio group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.
  • a heterocyclic thio group preferably having 1 carbon atom
  • a heterocyclic thio group e.g. pyridylthio, 2-benzoxazolyl thio, and 2-benzthiazolylthio the like.
  • a sulfonyl group (preferably a sulfonyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl, etc.), a sulfinyl group (preferably A sulfinyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably having 1 carbon atom) -30, more preferably a ureido group having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), a phosphoramide group (preferably having a carbon number) A phosphoric acid amide group having 1 to 30, more preferably 1 to 20 carbon
  • the hetero atom may be a non-aromatic hetero ring, and examples of the hetero atom constituting the hetero ring include a nitrogen atom, an oxygen atom and a sulfur atom, preferably 0 to 30 carbon atoms, more preferably 1 to 12 carbon atoms.
  • silyl group examples thereof include imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl, azepinyl and the like, and a silyl group (preferably).
  • Groups such as trimethylsilyl and triphenylsilyl), silyloxy groups (preferably silyloxy groups having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms).
  • substituents may be further substituted with any one or more substituents selected from the above substituent group Z.
  • substituents when one structural site has a plurality of substituents, these substituents are connected to each other to form a ring, or condensed with a part or all of the above structural sites to form an aromatic group.
  • a ring or an unsaturated heterocyclic ring may be formed.
  • the ratio of each repeating unit represented by the formula (I), (II-a), (II-b), (III-a), (III-b) is particularly limited.
  • the gas permeability and separation selectivity are appropriately adjusted according to the purpose of gas separation (recovery rate, purity, etc.).
  • the formulas (III-a) and (III-b) with respect to the total number of moles (E II ) of each repeating unit of the formulas (II-a) and (II-b) The ratio (E II / E III ) of the total number of moles (E III ) of each repeating unit is preferably 5/95 to 95/5, more preferably 10/90 to 80/20, More preferably, it is 20/80 to 60/40.
  • the molecular weight of the polyimide having a reactive group used in the present invention is preferably 10,000 to 1,000,000 as a weight average molecular weight, more preferably 15,000 to 500,000, and still more preferably 20,000. ⁇ 200,000.
  • the molecular weight and the degree of dispersion are values measured using a GPC (gel filtration chromatography) method, and the molecular weight is a weight average molecular weight in terms of polystyrene.
  • the gel packed in the column used in the GPC method is preferably a gel having an aromatic compound as a repeating unit, and examples thereof include a gel made of a styrene-divinylbenzene copolymer. Two to six columns are preferably connected and used.
  • the solvent used include ether solvents such as tetrahydrofuran and amide solvents such as N-methylpyrrolidinone.
  • the measurement is preferably performed at a solvent flow rate in the range of 0.1 to 2 mL / min, and most preferably in the range of 0.5 to 1.5 mL / min. By performing the measurement within this range, the apparatus is not loaded and the measurement can be performed more efficiently.
  • the measurement temperature is preferably 10 to 50 ° C, most preferably 20 to 40 ° C. Note that the column and carrier to be used can be appropriately selected according to the physical properties of the polymer compound that is symmetrical to the measurement.
  • the polyimide having a reactive group that can be used in the present invention can be synthesized by condensation polymerization of a specific bifunctional acid anhydride (tetracarboxylic dianhydride) and a specific diamine.
  • a specific bifunctional acid anhydride tetracarboxylic dianhydride
  • a specific diamine tetracarboxylic dianhydride
  • the method described in a general book for example, published by NTS, edited by Ikuo Imai, Rikio Yokota, latest polyimide-basics and applications-pages 3-49, etc.
  • At least one tetracarboxylic dianhydride used as a raw material is represented by the following formula (VI). All of the tetracarboxylic dianhydrides used as raw materials are preferably represented by the following formula (VI).
  • R has the same meaning as R in formula (I) above.
  • tetracarboxylic dianhydrides that can be used in the present invention include the following.
  • At least one diamine compound used as a raw material is represented by the following formula (VII-a) or (VII-b), and at least one kind is represented by the following formula: It is represented by (VIII-a) or (VIII-b). All of the diamine compounds used as raw materials are preferably represented by any one of the following formulas (VII-a), (VII-b), (VIII-a) and (VIII-b).
  • polyimides having a reactive group that can be used in the present invention are listed below, but the present invention is not limited thereto.
  • “100”, “x”, and “y” represent copolymerization ratios (molar ratios). Examples of “x”, “y” and weight average molecular weight are shown in Table 1 below. In the polyimide compound that can be used in the present invention, y does not become 0.
  • oligomers or prepolymers may be used.
  • the polymer for obtaining the polymer compound may be a block copolymer, a copolymer having any form such as a random copolymer, a graft copolymer, etc., but in particular, a block copolymer or a graft copolymer.
  • a polymer it is preferable from a viewpoint of a viscosity and compatibility.
  • the polyimide having a reactive group that can be used in the present invention can be obtained by mixing each of the above raw materials in a solvent and performing condensation polymerization by a conventional method.
  • the solvent is not particularly limited, but ester organic solvents such as methyl acetate, ethyl acetate, and butyl acetate, and aliphatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, cyclopentanone, and cyclohexanone.
  • Ether organic solvents such as ethylene glycol dimethyl ether, dibutyl butyl ether, tetrahydrofuran, methylcyclopentyl ether, dioxane, amide organic solvents such as N-methylpyrrolidone, 2-pyrrolidone, dimethylformamide, dimethylimidazolidinone, dimethylacetamide, dimethyl sulfoxide And sulfur-containing organic solvents such as sulfolane.
  • These organic solvents are appropriately selected as long as it is possible to dissolve tetracarboxylic dianhydride as a reaction substrate, diamine compound, polyamic acid as a reaction intermediate, and polyimide compound as a final product.
  • ester type preferably butyl acetate
  • aliphatic ketone preferably methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, cyclopentanone, cyclohexanone
  • ether type diethylene glycol monomethyl ether, methyl cyclopentyl) Ether
  • amide-based amide-based
  • sulfur-containing dimethyl sulfoxide, sulfolane
  • the polymerization reaction temperature is not particularly limited, and a temperature that can be generally employed in the synthesis of a polyimide having a reactive group can be employed. Specifically, it is preferably ⁇ 40 to 60 ° C., more preferably ⁇ 30 to 50 ° C.
  • a polyimide having a reactive group can be obtained by imidizing the polyamic acid produced by the above polymerization reaction by a dehydration ring-closing reaction in the molecule.
  • a method of dehydrating and ring-closing the method described in a general book (for example, published by NTS, edited by Ikuo Imai, edited by Rikio Yokota, latest polyimide-basics and applications, pages 3-49, etc.) It can be used as a reference.
  • acetic anhydride or dicyclohexyl is heated in the presence of a basic catalyst such as pyridine, triethylamine or DBU by heating to 120 ° C to 200 ° C for reaction while removing by-product water out of the system.
  • a technique such as so-called chemical imidization using a dehydration condensing agent such as carbodiimide and triphenyl phosphite is preferably used.
  • the total concentration of tetracarboxylic dianhydride and diamine compound in the polymerization reaction liquid of polyimide having a reactive group is not particularly limited, but is preferably 5 to 70% by mass, more preferably 5%. Is preferably 50 to 50% by mass, more preferably 5 to 30% by mass.
  • the thickness of the separation layer is preferably a thin film as much as possible under the condition of imparting high gas permeability while maintaining mechanical strength and separation selectivity.
  • the separation layer of the gas separation membrane of the present invention is preferably a thin layer.
  • the thickness of the separation layer is usually 10 ⁇ m or less, preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, further preferably 2 ⁇ m or less, further preferably 1 ⁇ m or less, 0 More preferably, it is 5 ⁇ m or less.
  • the thickness of the separation layer is usually 0.01 ⁇ m or more, and preferably 0.03 ⁇ m or more from a practical viewpoint.
  • the variation coefficient of the thickness of the separation layer is preferably 1 or less, more preferably 0.5 or less, and further preferably 0.3 or less.
  • the coefficient of variation is a value calculated by randomly selecting 10 film thickness measurement sites separated from each other by 1 cm or more in the separation layer constituting the gas separation membrane and measuring the film thickness at these sites.
  • the gas separation membrane of the present invention preferably comprises a protective layer formed on the separation layer.
  • the protective layer is preferably at least one selected from polydimethylsiloxane (hereinafter also referred to as PDMS), poly (1-trimethylsilyl-1-propyne) (hereinafter also referred to as PTMSP), and polyethylene oxide. More preferred is siloxane or poly (1-trimethylsilyl-1-propyne), and particularly preferred is polydimethylsiloxane.
  • the thickness of the protective layer is preferably 20 nm to 3 ⁇ m, more preferably 50 nm to 2 ⁇ m, and particularly preferably 100 nm to 1 ⁇ m.
  • the gas separation membrane of the present invention preferably has a support, and preferably has two or more separation layers on at least one surface side of the support.
  • the support is preferably a porous substrate that is a thin and porous material because sufficient gas permeability can be secured.
  • a separation layer may be formed and disposed on the surface or inner surface of a porous support, and at least on the surface, it can be easily formed into a thin layer composite membrane.
  • the gas separation membrane of the present invention is a thin-layer composite membrane
  • the thin-layer composite membrane is coated with a coating liquid (dope) that forms the above-mentioned separation layer on at least the surface of the porous support (coated in this specification). It is a meaning including the aspect attached to the surface by immersion.) It is preferable to form by carrying out.
  • the support is preferably formed of a non-woven fabric (Non-Woven) and a porous layer (Porous Layer) provided on at least one side of the non-woven fabric. Specifically, the support separates the porous layer. It is more preferable to have it on the layer side, and it is particularly preferable that it is a laminate of a porous layer and a nonwoven fabric arranged on the separation layer side.
  • the porous layer preferably applied to the support is not particularly limited as long as it has the purpose of satisfying the provision of mechanical strength and high gas permeability, and may be either organic or inorganic material. However, it is preferably a porous film of an organic polymer, and its thickness is 1 to 3000 ⁇ m, preferably 5 to 500 ⁇ m, more preferably 5 to 150 ⁇ m.
  • the porous structure of this porous layer usually has an average pore diameter of 10 ⁇ m or less, preferably 0.5 ⁇ m or less, more preferably 0.2 ⁇ m or less, and a porosity of preferably 20 to 90%. Preferably, it is 30 to 80%.
  • the molecular weight cut-off of the porous layer is preferably 100,000 or less, and the gas permeability is 3 ⁇ 10 ⁇ 5 cm 3 (STP) / cm 2 ⁇ cm ⁇ sec. It is preferable that it is cmHg (30 GPU) or more.
  • the material for the porous layer include conventionally known polymers such as polyolefin resins such as polyethylene and polypropylene, fluorine-containing resins such as polytetrafluoroethylene, polyvinyl fluoride, and polyvinylidene fluoride, polystyrene, cellulose acetate, and polyurethane.
  • the shape of the porous layer may be any shape such as a flat plate shape, a spiral shape, a tubular shape, and a hollow fiber shape.
  • a woven fabric, a nonwoven fabric, a net, etc. are provided in the lower part of the porous layer that is preferably arranged on the separation layer side, in order to impart mechanical strength.
  • non-woven fabrics are preferably used.
  • the nonwoven fabric fibers made of polyester, polypropylene, polyacrylonitrile, polyethylene, polyamide or the like may be used alone or in combination.
  • the nonwoven fabric can be produced, for example, by making a main fiber and a binder fiber uniformly dispersed in water using a circular net or a long net, and drying with a dryer.
  • it is also preferable to apply a heat treatment by sandwiching a non-woven fabric between two rolls for the purpose of removing fluff and improving mechanical properties.
  • the gas separation membrane of the present invention is a thin layer composite membrane, it is preferable to have a smooth layer between the separation layer and the support.
  • the smooth layer preferably has a functional group in order to improve adhesion with the separation layer.
  • functional groups include epoxy groups, oxetane groups, carboxyl groups, amino groups, hydroxyl groups, and thiol groups.
  • the smooth layer includes an epoxy group, an oxetane group, a carboxyl group, and a resin having two or more of these groups.
  • a resin is preferably formed on a support by curing the radiation curable composition by irradiation with radiation.
  • the polymerizable dialkylsiloxane is a monomer having a dialkylsiloxane group, a polymerizable oligomer having a dialkylsiloxane group, or a polymer having a dialkylsiloxane group.
  • the smooth layer may be formed from a partially crosslinked radiation curable composition having dialkylsiloxane groups.
  • the dialkylsiloxane group include a group represented by — ⁇ O—Si (CH 3 ) 2 ⁇ n — (n is 1 to 100, for example).
  • a poly (dialkylsiloxane) compound having a vinyl group at the terminal can also be preferably used.
  • the material of the smooth layer is preferably at least one selected from polydimethylsiloxane (hereinafter also referred to as PDMS), poly (1-trimethylsilyl-1-propyne) (hereinafter also referred to as PTMSP), and polyethylene oxide. More preferred is polydimethylsiloxane or poly (1-trimethylsilyl-1-propyne), and particularly preferred is polydimethylsiloxane.
  • PDMS polydimethylsiloxane
  • PTMSP poly (1-trimethylsilyl-1-propyne
  • polyethylene oxide More preferred is polydimethylsiloxane or poly (1-trimethylsilyl-1-propyne), and particularly preferred is polydimethylsiloxane.
  • UV9300 polydimethylsiloxane (PDMS) manufactured by Momentive
  • PDMS polydimethylsiloxane
  • UV9300 polydimethylsiloxane (PDMS) manufactured by Momentive
  • the material of the smooth layer can be prepared as a composition containing an organic solvent when the smooth layer is formed, and is preferably a curable composition.
  • the film thickness of the smooth layer is not particularly limited, but the film thickness of the smooth layer is preferably 25 to 1200 nm, more preferably 30 to 800 nm, and particularly preferably 50 to 650 nm.
  • the thickness may be 70 to 120 nm, 130 to 170 nm, 180 to 220 nm, 230 to 270 nm, 300 to 360 nm, 380 to 450 nm, 470 to 540 nm, or 560 to 630 nm.
  • the film thickness of the smooth layer can be determined by SEM.
  • the film thickness of the smooth layer can be controlled by adjusting the coating amount of the curable composition.
  • the separation membrane of the present invention can be suitably used as a gas separation recovery method and a gas separation purification method.
  • a gas separation purification method for example, hydrogen, helium, carbon monoxide, carbon dioxide, hydrogen sulfide, oxygen, nitrogen, ammonia, sulfur oxides, nitrogen oxides, hydrocarbons such as methane and ethane, unsaturated hydrocarbons such as propylene, tetrafluoroethane, etc.
  • a gas separation membrane capable of efficiently separating a specific gas from a gas mixture containing a gas such as a perfluoro compound.
  • the gas separation membrane of the present invention is preferably a gas separation membrane for separating at least one acidic gas from a gas mixture of acidic gas and non-acidic gas.
  • the acid gas examples include carbon dioxide, hydrogen sulfide, carbonyl sulfide, sulfur oxide (SOx), and nitrogen oxide (NOx), and carbon dioxide, hydrogen sulfide, carbonyl sulfide, sulfur oxide (SOx), and nitrogen. It is preferably at least one selected from oxides (NOx), more preferably carbon dioxide, hydrogen sulfide or sulfur oxide (SOx), and particularly preferably carbon dioxide.
  • the non-acid gas is preferably at least one selected from hydrogen, methane, nitrogen, and carbon monoxide, more preferably methane and hydrogen, and particularly preferably methane.
  • the gas separation membrane of the present invention is preferably a gas separation membrane that selectively separates carbon dioxide from a gas mixture containing carbon dioxide / hydrocarbon (methane).
  • the permeability of carbon dioxide at 40 ° C. and 5 MPa is preferably more than 30 GPU, more preferably 30 to 300 GPU.
  • 40 to 300 GPU is particularly preferable, and 50 to 300 GPU is more preferable.
  • 1 GPU is 1 ⁇ 10 ⁇ 6 cm 3 (STP) / cm 2 ⁇ sec ⁇ cmHg.
  • the gas to be separated is a mixed gas of carbon dioxide and methane
  • the ratio P CO2 / P CH4 of the carbon dioxide permeation flux to the methane permeation flux at 40 ° C. and 5 MPa is used.
  • the separation selectivity is preferably 15 or more, and more preferably 20 or more.
  • the method for producing a gas separation membrane of the present invention comprises a crosslinking structure comprising a composition comprising a polymer having a reactive group and a ketene imine crosslinking agent having at least two groups represented by the following general formula (1) to form a crosslinked structure.
  • a separation layer containing a polymer having General formula (1) In general formula (1), R 22 and R 23 each independently represent a substituent, and * represents a binding site.
  • the method for producing a gas separation membrane of the present invention is excellent in production suitability. Specifically, a catalyst, an initiator, and an acid generator are not required at the time of film formation, and no special treatment such as UV treatment is necessary.
  • the gas separation membrane manufacturing method may include other steps in addition to the step of forming the separation layer. For example, a step of forming a separation layer, a step of arranging two or more separation layers without being adjacent to each other, a step of surface-treating one surface of the outermost separation layer, and a surface treatment of the separation layer were performed. It is preferable to include a step of forming a protective layer on the surface.
  • the method for forming a separation layer includes a polymer having a crosslinked structure by crosslinking a composition including a polymer having a reactive group and a ketene imine crosslinking agent having at least two groups represented by the general formula (1).
  • Forming a separation layer a gas separation membrane containing a polymer having a crosslinked structure is prepared by preparing a coating solution by mixing at least one or more polymers having a reactive group and a ketene imine crosslinking agent in a solvent.
  • the coating solution is preferably applied on the lower layer (for example, a support or a smooth layer) for the gas separation membrane in a thin state so that the crosslinking and separation layers are simultaneously formed.
  • a coating method is not particularly limited and a known method can be used. For example, a spin coating method can be used. At that time, in the coating solution containing the polymer having a reactive group and the ketene imine crosslinking agent, the crosslinking reaction does not proceed, or the traveling speed is sufficiently suppressed to the extent that gelation does not occur before coating. It is preferable. By keeping the concentration of the reactive group-containing polymer and ketene imine crosslinking agent in the coating solution below a certain level, the progress of the crosslinking reaction in the coating solution can be suppressed to a predetermined level, enabling thin-layer coating. Can maintain a low viscosity state.
  • the concentration of the polymer having a reactive group in the coating solution at the time of coating is preferably 0.1 to 20.0% by mass, more preferably 0.2 to 10.0% by mass.
  • the content is 0.5 to 5.0% by mass.
  • the concentration of the ketene imine crosslinking agent in the coating solution at the time of coating is preferably 0.2 to 30% by mass, more preferably 0.5 to 20% by mass, and 1 to 10% by mass. Further preferred.
  • the cross-linking reaction proceeds rapidly with rapid solvent evaporation, and the ketene imine cross-linking agent Forms a cross-linked structure of origin.
  • the separated layer comprised from the polymer which has a crosslinked structure can be formed on a support body.
  • the coating solution When the coating solution is applied in a thin layer, the specific interface area increases and the evaporation rate of the solvent increases remarkably. Along with the rapid evaporation of the solvent, the concentration of the polymer having a reactive group and the ketene imine cross-linking agent increases at a stretch, and as a result, the cross-linking reaction proceeds rapidly and a polymer structure having a cross-linked structure is rapidly formed. Since the formation of the polymer having a crosslinked structure proceeds rapidly after application of the coating liquid, the coating liquid hardly penetrates into the porous support (gelates before penetration). As a result, a more uniform separation layer with fewer defects can be formed.
  • the organic solvent used as a medium for the coating solution is not particularly limited, but is a hydrocarbon organic solvent such as n-hexane or n-heptane, an ester organic solvent such as methyl acetate, ethyl acetate or butyl acetate, Lower alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol, aliphatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, cyclopentanone and cyclohexanone, ethylene glycol , Diethylene glycol, triethylene glycol, glycerin, propylene glycol, ethylene glycol monomethyl or monoethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, triplicate Ether-based organics
  • organic solvents are appropriately selected as long as they do not adversely affect the substrate, such as ester-based (preferably butyl acetate), alcohol-based (preferably methanol, ethanol, isopropanol).
  • ester-based preferably butyl acetate
  • alcohol-based preferably methanol, ethanol, isopropanol
  • Isobutanol aliphatic ketones (preferably methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, cyclopentanone, cyclohexanone)
  • ether type ethylene glycol, diethylene glycol monomethyl ether, methyl cyclopentyl ether
  • these can be used 1 type or in combination of 2 or more types.
  • the conditions for forming the separation layer of the gas separation membrane of the present invention are not particularly limited, but the crosslinking reaction is preferably performed at 80 ° C. or lower.
  • the temperature of the crosslinking reaction is more preferably from ⁇ 30 ° C. to less than 80 ° C., particularly preferably from ⁇ 10 ° C. to less than 80 ° C., and particularly preferably from 5 to 50 ° C.
  • the manufacturing method of a gas separation membrane includes the process of forming a protective layer on the surface of a separation layer, or the surface which performed the surface treatment of the separation layer.
  • a protective layer on the surface which performed the surface treatment of the separated layer.
  • an organic solvent the organic solvent used for formation of a separated layer can be mentioned.
  • a coating method is not particularly limited and a known method can be used. For example, a spin coating method can be used.
  • the irradiation time is preferably 1 to 30 seconds.
  • the radiant energy is preferably 10 to 500 mW / cm 2 .
  • the method for producing a gas separation membrane of the present invention may include a step of forming a smooth layer on a support.
  • a coating method is not particularly limited and a known method can be used. For example, a spin coating method can be used.
  • the irradiation time is preferably 1 to 30 seconds.
  • the radiant energy is preferably 10 to 500 mW / cm 2 .
  • the gas mixture can be separated.
  • the components of the raw material gas mixture are affected by the raw material production area, application, or use environment, and are not particularly defined.
  • the main components are preferably carbon dioxide and methane, carbon dioxide and nitrogen or carbon dioxide and hydrogen. That is, the proportion of carbon dioxide and methane or carbon dioxide and hydrogen in the gas mixture is preferably 5 to 50%, more preferably 10 to 40% as the proportion of carbon dioxide.
  • the separation method of the gas mixture using the gas separation membrane of the present invention exhibits particularly excellent performance, preferably carbonization such as carbon dioxide and methane. Excellent performance in separation of hydrogen, carbon dioxide and nitrogen, and carbon dioxide and hydrogen.
  • the method for separating the gas mixture is preferably a method including selectively permeating carbon dioxide from a mixed gas containing carbon dioxide and methane. Since the gas separation membrane of the present invention has high separation selectivity and permeability under high pressure and high resistance to organic solvents, gas separation can be performed under higher pressure than before.
  • the pressure at the time of gas separation is preferably 3 to 10 MPa, more preferably 5 to 6 MPa.
  • the gas separation temperature is preferably ⁇ 30 to 90 ° C., more preferably 15 to 70 ° C.
  • the gas separation membrane module of the present invention has the gas separation membrane of the present invention.
  • the gas separation membrane of the present invention is preferably a thin layer composite membrane combined with a porous support, and more preferably a gas separation membrane module using this.
  • it can be set as the gas separation apparatus which has a means for carrying out separation recovery of the gas using the gas separation membrane of this invention, a thin layer composite membrane, or a gas separation membrane module.
  • the gas separation membrane of the present invention can be suitably used in a modular form. Examples of modules include spiral type, hollow fiber type, pleated type, tubular type, plate & frame type and the like.
  • the 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, for example, JP-A-2007-297605.
  • the radiation curable polymer solution was cooled to 20 ° C. and diluted by adding n-heptane to 5 mass%.
  • the resulting solution was filtered using a filter paper having a filtration accuracy of 2.7 ⁇ m to prepare a radiation curable composition.
  • Ti (OiPr) 4 Dolf Chemical Chemicals isopropoxide titanium (IV)
  • PAN polyacrylonitrile porous film
  • UV intensity UV treatment Fusion UV System, Light Hammer 10, D-bulb
  • the obtained polymer crystals were suction filtered and blown dry at 60 ° C. to obtain 50.5 g of polymer (P-101).
  • Plasma treatment was performed on the smooth layer for 5 seconds under plasma treatment conditions of an oxygen flow rate of 50 cm 3 (STP) / min, an argon flow rate of 100 cm 3 (STP) / min, and a discharge output of 10 W.
  • STP oxygen flow rate
  • STP argon flow rate
  • 10 W discharge output
  • 0.038 g of ketene imine crosslinking agent the above ketene imine (1)
  • 8.6 g of methyl ethyl ketone were mixed and stirred at 25 ° C. for 30 minutes. did. Thereafter, the stirred solution was spin-coated on the smooth layer to form a separation layer having a thickness of 100 nm.
  • the polymerizable radiation-curable composition used for forming the smooth layer is spin-coated on the separation layer, and then subjected to UV treatment under the same UV treatment conditions as for the formation of the smooth layer.
  • a protective layer having a thickness of 600 nm was formed on the substrate, and dried for 8 hours with a blower dryer at 50 ° C. to prepare a gas separation membrane. The obtained separation membrane was used as the gas separation membrane of Example 1.
  • Example 2 In Example 1, instead of ketene imine (1) as a ketene imine cross-linking agent when forming the separation layer, ketene imine (2) synthesized by the same method except that ketene imine (1) and the material used were changed were used. A gas separation membrane of Example 2 was obtained in the same manner as Example 1 except that the same amount was used. Ketenimine (2)
  • Example 1 a gas separation membrane of Comparative Example 1 was obtained in the same manner as in Example 1 except that ketene imine 1 was not added when forming the separation layer.
  • Example 2 a gas separation membrane of Comparative Example 2 was obtained in the same manner as in Example 1 except that the separation layer was formed on the smooth layer by the following method.
  • polymer (P-1) having a reactive group polymer (P-1) having a reactive group, crosslinker Denacol EX861 (manufactured by Nagase ChemteX Corp., polyethylene glycol diglycidyl ether, both having 22 ethylene glycol repeating units) Terminal epoxy group-containing compound) 0.038 g and methyl ethyl ketone 8.6 g were mixed and stirred for 30 minutes.
  • P-1 polymer having a reactive group
  • crosslinker Denacol EX861 manufactured by Nagase ChemteX Corp., polyethylene glycol diglycidyl ether, both having 22 ethylene glycol repeating units
  • Terminal epoxy group-containing compound 0.038 g
  • methyl ethyl ketone 8.6 g were mixed and stirred for 30 minutes.
  • the gas separation properties (that is, separation selectivity) of the gas separation membranes of the Examples and Comparative Examples are the ratio of the CO 2 permeability coefficient P CO2 to the CH 4 permeability coefficient P CH4 of this membrane (P CO2 / P CH4 ). As calculated.
  • the CO 2 permeability of the gas separation membrane of each Example and Comparative Example was defined as the CO 2 permeability Q CO2 (unit: GPU) of this membrane.
  • barrer 1 ⁇ 10 ⁇ 10 cm 3 (STP) ⁇ cm / cm 2 ⁇ sec ⁇ cmHg) representing a transmission coefficient.
  • the unit of GPU is represented by the symbol Q
  • the unit of barrer is represented by the symbol P.
  • This THF solution was filtered through a 0.45 ⁇ m filter, and the amount of the lysate was quantified by GPC (gel permeation chromatography) measurement.
  • the amount of the separation layer single membrane before dissolution in THF was taken as 100%, and the value obtained by subtracting the amount of dissolved material obtained by GPC measurement was taken as the dissolution test residual rate.
  • the results are shown in Table 2 below.
  • the result of the residual rate correlates with the plasticization phenomenon when the gas separation membrane is exposed to a gas containing THF (estimated that solvent molecules enter between polymer chains and the polymer molecular chains become slippery), and the residual rate is high. It shows that the resistance to plasticization is high. It can be considered that this result also represents plasticization resistance against other aromatic compounds such as benzene, toluene, xylene and the like.
  • the gas separation membrane of the present invention has high separation selectivity and permeability under high pressure and high resistance to organic solvents.
  • the separation layer of the gas separation membrane of this invention contained the structure bridge
  • the separation layer of the gas separation membrane of the present invention contains an unreacted ketene imine crosslinking agent.
  • the gas separation membrane of Comparative Example 1 having a separation layer containing a polymer that does not contain a structure cross-linked through a linking group derived from a ketene imine cross-linking agent has very low resistance to organic solvents. I understood it.
  • the gas separation membrane of Comparative Example 2 having a separation layer containing a polymer that does not contain a structure crosslinked through a linking group derived from a ketene imine crosslinking agent has low permeability. It was also found that the resistance to organic solvents was low.
  • the resistance to organic solvents could be improved without lowering the CO 2 permeability by the ketene imine crosslinking agent. It is estimated that the fact that it is difficult to dissolve in an organic solvent suppresses the plasticization phenomenon that the solvent molecules do not easily enter the polymer film and the polymer molecular chains slip.
  • Examples 101 and 102 -modularization- Using the gas separation membranes produced in Examples 1 and 2, a spiral module was produced with reference to JP-A-5-168869. The obtained gas separation membrane module was used as the gas separation membrane module of Examples 101 and 102. It was confirmed that the produced gas separation membrane modules of Examples 101 and 102 were good according to the performance of the built-in gas separation membrane.

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  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention concerne une membrane de séparation de gaz ayant une couche de séparation qui contient un polymère ayant une structure réticulée, dans laquelle le polymère ayant une structure réticulée contient une structure qui est réticulée par l'intermédiaire d'un groupe de liaison dérivé d'un agent de réticulation de kéténimine ayant au moins deux groupes représentés par la formule générale (1) (dans laquelle chacun de R22 et R23 représente indépendamment un substituant et * représente un site de liaison). Cette membrane de séparation de gaz a une sélectivité de séparation élevée et une perméabilité à haute pression, tout en présentant une résistance élevée aux solvants organiques. L'invention concerne en outre un procédé de production d'une membrane de séparation de gaz et un module de membrane de séparation de gaz. FIG.: AA%%%Formule générale (1)
PCT/JP2014/075003 2013-09-24 2014-09-22 Membrane de séparation de gaz, procédé de production de membrane de séparation de gaz, et module de membrane de séparation de gaz WO2015046103A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3692745A (en) * 1970-01-24 1972-09-19 Akzona Inc Method for chemically modifying thread-forming polyesters
JPS63243323A (ja) * 1987-03-16 1988-10-11 アクゾ・エヌ・ヴエー ポリエチレンテレフタレートを溶融紡糸することによる糸の製造方法
US20090249950A1 (en) * 2001-12-20 2009-10-08 Chevron U.S.A. Inc. Crosslinked membrane and polymer for making same and method of using membrane
JP2013046902A (ja) * 2011-07-28 2013-03-07 Fujifilm Corp ガス分離複合膜、それを用いたガス分離モジュール、ガス分離装置およびガス分離方法
JP2013509317A (ja) * 2009-10-30 2013-03-14 フジフィルム・イメイジング・カラランツ・リミテッド 印刷方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3692745A (en) * 1970-01-24 1972-09-19 Akzona Inc Method for chemically modifying thread-forming polyesters
JPS63243323A (ja) * 1987-03-16 1988-10-11 アクゾ・エヌ・ヴエー ポリエチレンテレフタレートを溶融紡糸することによる糸の製造方法
US20090249950A1 (en) * 2001-12-20 2009-10-08 Chevron U.S.A. Inc. Crosslinked membrane and polymer for making same and method of using membrane
JP2013509317A (ja) * 2009-10-30 2013-03-14 フジフィルム・イメイジング・カラランツ・リミテッド 印刷方法
JP2013046902A (ja) * 2011-07-28 2013-03-07 Fujifilm Corp ガス分離複合膜、それを用いたガス分離モジュール、ガス分離装置およびガス分離方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A-LIM, D.S.T. ET AL.: "Crosslinking of carboxyl functional (meth) acrylate copolymers with bisketeneimine", POLYMER BULLETIN, vol. 32, no. 4, April 1994 (1994-04-01), pages 455 - 461 *

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