WO2015129554A1 - Gas separation membrane, gas separation module, gas separation device, and gas separation method - Google Patents
Gas separation membrane, gas separation module, gas separation device, and gas separation method Download PDFInfo
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- WO2015129554A1 WO2015129554A1 PCT/JP2015/054682 JP2015054682W WO2015129554A1 WO 2015129554 A1 WO2015129554 A1 WO 2015129554A1 JP 2015054682 W JP2015054682 W JP 2015054682W WO 2015129554 A1 WO2015129554 A1 WO 2015129554A1
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- gas separation
- gas
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- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
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- 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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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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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 gas separation membrane, a gas separation module, a gas separation device, and a gas separation method.
- 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. As an industrial utilization mode of this gas separation membrane, it is considered to separate and recover it from a large-scale carbon dioxide generation source in a thermal power plant, a cement plant, a steelworks blast furnace, etc. in connection with the problem of global warming. Has been. And this membrane separation technique attracts attention as a means for solving environmental problems that can be achieved with relatively small energy.
- Non-Patent Document 1 describes that the separation selectivity of the gas separation membrane is improved by using a polyimide compound into which a polar group such as a carboxy group or a hydroxyl group is introduced.
- the membrane is plasticized due to the influence of high-pressure conditions and impurities (for example, benzene, toluene, xylene) present in natural gas, resulting in a problem of lowering separation selectivity.
- impurities for example, benzene, toluene, xylene
- a polymer compound such as a polyimide compound is formed into an asymmetric membrane by a phase separation method so that a portion contributing to the separation is made into a thin layer called a dense layer or a skin layer.
- the dense layer serves as a gas separation layer
- the portion other than the dense layer functions as a support layer that bears the mechanical strength of the membrane.
- a composite membrane is also known in which a material responsible for gas separation and a material responsible for mechanical strength are separated.
- This composite membrane has a structure in which a thin gas separation layer made of a polymer compound such as polyimide is formed on a gas permeable support having mechanical strength.
- Gas permeability or gas separation selectivity can be adjusted by adjusting the copolymer component of the polymer compound that constitutes the gas separation layer, but both are in a trade-off relationship, and both are compatible at a higher level. For this purpose, it is necessary to further improve the material of the gas separation layer itself.
- the present invention is a gas separation membrane having both good gas permeability and gas separation selectivity, and the gas separation performance hardly deteriorates even when used under high-pressure conditions. Moreover, such as toluene present in natural gas. It is an object of the present invention to provide a gas separation membrane that is hardly affected by impurity components. Another object of the present invention is to provide a gas separation module, a gas separation device, and a gas separation method using the gas separation membrane.
- the present inventors made extensive studies in view of the above problems. As a result, by forming a gas separation layer using a polyimide compound containing a specific amount of carbamoyl groups, both gas permeability and gas separation selectivity are excellent, and gas separation is possible even when used under high pressure conditions. It has been found that a gas separation membrane is obtained that is less likely to deteriorate in performance and that is highly resistant to impurity components such as toluene. The present invention has been completed based on these findings.
- a gas separation membrane having a gas separation layer containing a polyimide compound A gas separation membrane, wherein the polyimide compound has a carbamoyl group, and the content of the carbamoyl group in the polyimide compound is 0.1 to 3.0 mmol / g.
- R represents a group having a structure represented by any of the following formulas (I-1) to (I-28).
- X 1 to X 3 represent a single bond or a divalent linking group
- L represents —CH ⁇ CH— or —CH 2 —
- R 1 and R 2 represent a hydrogen atom or a substituent
- * represents a formula ( A binding site with the carbonyl group in A) is shown.
- R 4 represents a substituent
- l1 represents an integer of 1 to 4. When l1 is 1, R 4 is a group having a carbamoyl group. When l1 is 2 to 4, at least one of R 4 is a group having a carbamoyl group.
- R has the same meaning as R in formula (A).
- R 5 and R 6 represent a substituent.
- m1 and n1 are integers of 0 to 4, but neither m1 nor n1 is 0.
- m1 is 0, at least one of R 6 is a group having a carbamoyl group, and when n1 is 0, at least one of R 5 is a group having a carbamoyl group.
- n1 are both 1 or more, at least one of R 5 and R 6 is a group having a carbamoyl group.
- X 4 represents a single bond or a divalent linking group.
- R has the same meaning as R in formula (A).
- R 4a is a hydrogen atom or a substituent having no carbamoyl group.
- the support layer includes a porous layer on the gas separation layer side and a nonwoven fabric layer on the opposite side.
- the gas to be separated is a mixed gas of carbon dioxide and methane, the permeation rate of carbon dioxide at 40 ° C.
- 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. The same applies to the definition of the number of substituents and the like. Further, when there are repetitions of a plurality of partial structures represented by the same indication in the formula, each partial structure or repeating unit may be the same or different. Further, even if not specifically stated, when a plurality of substituents and the like are close (particularly adjacent), they may be connected to each other or condensed to form a ring.
- a substituent that does not specify substitution / non-substitution means that the group may have an arbitrary substituent as long as a desired effect is achieved. . This is also synonymous for compounds that do not specify substitution / non-substitution.
- the substituent group Z is a preferred range unless otherwise specified.
- the gas separation membrane, gas separation module, and gas separation device of the present invention have excellent gas permeability and high gas separation performance. Further, even when used under high pressure conditions or for separation of a gas containing an impurity component such as toluene, the gas separation performance is hardly lowered.
- gas can be separated with higher permeability and higher selectivity. Furthermore, even if the gas is separated under high pressure conditions or impurities are present in the gas, high gas separation performance is maintained.
- FIG. 1 is a cross-sectional view schematically showing an embodiment of the gas separation composite membrane of the present invention.
- FIG. 2 is a cross-sectional view schematically showing another embodiment of the gas separation composite membrane of the present invention.
- the gas separation membrane of the present invention includes a gas separation layer containing a specific amount of a polyimide compound having a carbamoyl group.
- the polyimide compound used in the present invention contains a carbamoyl group (—C ( ⁇ O) NH 2 ) in its structure.
- the content of the carbamoyl group in the polyimide compound used in the present invention is 0.1 to 3.0 mmol / g. If the content of the carbamoyl group in the polyimide compound is less than 0.1 mmol / g, the polyimide compound cannot be imparted with sufficient polarity, and as a result, the interaction between the polyimide molecular chains is weak, and the polyimide film is sufficient.
- the content of the carbamoyl group in the polyimide compound used in the present invention is preferably 0.2 to 2.5 mmol / g, more preferably 0.3 to 2.0 mmol / g, and 0.4 to More preferably, it is 1.5 mmol / g.
- the structure having a carbamoyl group in the polyimide compound used in the present invention is not particularly limited. Specifically, when the polyimide compound is synthesized by a polycondensation reaction between a tetracarboxylic dianhydride and a diamine compound as described later, the tetracarboxylic dianhydride component may have a carbamoyl group.
- the diamine component may have a carbamoyl group, or both the tetracarboxylic dianhydride component and the diamine component may have a carbamoyl group.
- the polyimide compound used in the present invention preferably contains at least a repeating unit represented by the following formula (A) or (B).
- R represents a group having a structure represented by any of the following formulas (I-1) to (I-28).
- * represents a binding site with the carbonyl group of the formula (A).
- R in the formula (A) may be referred to as a mother nucleus, and the mother nucleus R is preferably a group represented by the formula (I-1), (I-2) or (I-4), The group represented by (I-1) or (I-4) is more preferred, and the group represented by (I-1) is particularly preferred.
- X 1 to 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
- specific examples thereof include the substituent group Z described below, and an alkyl group (preferably the same as the alkyl group shown in the substituent group Z described below) is preferable.
- An alkyl group having a halogen atom as a substituent is more preferable, and trifluoromethyl is particularly preferable.
- X 3 is connected to one of the two carbon atoms described on the left side and one of the two carbon atoms described on the right side thereof.
- L represents —CH ⁇ CH— or —CH 2.
- R 1 and R 2 represent a hydrogen atom or a substituent.
- substituents include groups listed in the substituent group Z described later.
- 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.
- the carbon atoms shown in the formulas (I-1) to (I-28) may further have a substituent.
- this substituent include the substituent group Z described later, and among them, an alkyl group or an aryl group is preferable.
- R 4 represents a substituent, and l1 represents an integer of 1 to 4.
- R 4 is a group having a carbamoyl group (—C ( ⁇ O) NH 2 ).
- l1 is 2 to 4, it is preferable that at least one of R 4 is a group having a carbamoyl group, and one or two of R 4 is a group having a carbamoyl group.
- R 4 is a substituent that does not have a carbamoyl group
- substituent group Z include the substituent group Z described later, and among them, an alkyl group (more preferably having 1 to 10 carbon atoms, more preferably An alkyl group having 1 to 5 carbon atoms, more preferably ethyl or methyl), a halogen atom, an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms), or an aromatic group (preferably Is an aromatic group having 3 to 20 carbon atoms, more preferably an aromatic heterocyclic group having 3 to 20 carbon atoms (preferably containing a nitrogen atom as a ring constituent atom), and further preferably an aromatic hetero group having 4 to 15 carbon atoms.
- a ring group (preferably containing a nitrogen atom as a ring constituent atom) is preferred.
- the “group having a carbamoyl group” is not particularly limited as long as it has a carbamoyl group.
- the carbamoyl group or carbamoylalkyl group (preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms) is preferable.
- the repeating unit represented by the above formula (A) is preferably a repeating unit represented by the following formula (a).
- R has the same meaning as R in formula (A), and the preferred form is also the same.
- R 4a is a hydrogen atom or a substituent having no carbamoyl group.
- substituent having no carbamoyl group include the substituent group Z described below, and among them, an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, More preferably ethyl or methyl), a halogen atom, an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms), or an aromatic group (preferably an aromatic group having 3 to 20 carbon atoms).
- an aromatic heterocyclic group having 3 to 20 carbon atoms preferably including a nitrogen atom as a ring constituent atom
- further preferably an aromatic heterocyclic group having 4 to 15 carbon atoms preferably including a ring constituent atom.
- Nitrogen atoms are preferred).
- a form in which all of R 4a are hydrogen atoms, a form in which all of R 4a are halogen atoms, and two R 4a located in the ortho position relative to the carbamoyl group are hydrogen atoms and are located in the para position.
- R 4a is an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, more preferably ethyl or methyl), an alkoxy group (preferably 1 to 10 carbon atoms, more preferably a carbon atom).
- An alkoxy group having 1 to 5 carbon atoms, or an aromatic group preferably an aromatic group having 3 to 20 carbon atoms, more preferably an aromatic heterocyclic group having 3 to 20 carbon atoms (preferably a nitrogen atom as a ring constituent atom).
- R one of a are hydrogen atom, the remaining two R 4a is an alkoxy group (preferably having a carbon number of 1 to 10, more preferably an alkoxy group having 1 to 5 carbon atoms), or an aromatic group (preferably 3 carbon atoms
- R has the same meaning as R in formula (A).
- R 5 and R 6 represent a substituent.
- m1 and n1 are both integers from 0 to 4, but neither m1 nor n1 is 0.
- R 6 When m1 is 0, at least one of R 6 is a group having a carbamoyl group. That is, when m1 is 0, when n1 is 1, R 6 is a group having a carbamoyl group, and when n1 is 2, one or two of R 6 is a group having a carbamoyl group, When n1 is 3, one, two or three of R 6 are groups having a carbamoyl group, and when n1 is 4, one, two, three or four of R 6 are carbamoyl. A group having a group. When m1 is 0, n1 is preferably 1.
- R 5 When n1 is 0, at least one of R 5 is a group having a carbamoyl group. That is, when n1 is 0, when m1 is 1, R 5 is a group having a carbamoyl group, and when m1 is 2, one or two of R 5 is a group having a carbamoyl group, When m1 is 3, one, two or three of R 5 are groups having a carbamoyl group, and when m1 is 4, one, two, three or four of R 5 are carbamoyl. A group having a group. When n1 is 0, m1 is preferably 1. When m1 and n1 are both 1 or more, at least one of R 5 and R 6 is a group having a carbamoyl group.
- “at least one of R 5 and R 6 is a group having a carbamoyl group” means that at least one of R 5 is a group having a carbamoyl group and not all of R 6 have a carbamoyl group , And at least one of R 6 is a group having a carbamoyl group, and all of R 5 are used to include an embodiment having no carbamoyl group.
- m1 and n1 are both 1 or more, it is preferable that at least one of R 5 is a group having a carbamoyl group and at least one of R 6 is a group having a carbamoyl group.
- m1 and n1 are both 1, and R 5 and R 6 are both groups having a carbamoyl group.
- R 5 and R 6 are not a group having a carbamoyl group
- substituent group Z an alkyl group (more preferably a carbon number).
- An alkyl group having 1 to 10, more preferably 1 to 5 carbon atoms, more preferably ethyl or methyl) or a halogen atom is preferable.
- X 4 has the same meaning as X 1 in the above formula (I-1), and the preferred form is also the same.
- the polyimide compound used in the present invention may contain a repeating unit represented by the following formula (C) or (D).
- R 7 to R 9 represent a substituent.
- the substituent include a substituent group Z described later.
- R 7 is preferably an alkyl group, a halogen atom, a carboxy group or a hydroxy group.
- P2 representing the number of R 7 is an integer of 0 to 4, preferably 1 to 4, more preferably 2 to 4, more preferably 3 or 4.
- R 7 is alkyl, the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, still more preferably 1 to 3, and still more preferably methyl, ethyl Or trifluoromethyl.
- the two linking sites for incorporation into the polyimide compound of the diamine component are located at the meta position or the para position.
- the structure represented by the formula (C) does not include the structure represented by the formula (A) (that is, the structure represented by the formula (C) is a carbamoyl group. Do not have).
- R 8 and R 9 preferably represent an alkyl group or a halogen atom, or are groups that are linked together to form a ring together with X 4 . Further, a form in which two R 8 are connected to form a ring and a form in which two R 9 are connected to form a ring are also preferred.
- the structure in which R 8 and R 9 are linked is not particularly limited, but a single bond, —O— or —S— is preferable.
- Q2 and r2 representing the numbers of R 8 and R 9 are integers of 0 to 4, preferably 0 to 3, and more preferably 0 to 2.
- the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and still more preferably Is methyl, ethyl or trifluoromethyl.
- X 4 has the same meaning as X 1 in the above formula (I-1), and the preferred form is also the same.
- the structure represented by the formula (D) does not include the structure represented by the formula (B) (that is, the structure represented by the formula (D) is a carbamoyl 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
- 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 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, and a heterocyclic thio group (preferably having 1 to 30 carbon atoms).
- heterocyclic thio group having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and 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.
- a silyl group (preferably). Is a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms.
- trimethylsilyl, triphenylsilyl, etc. a silyloxy group (preferably a silyloxy group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, Examples thereof include trimethylsilyloxy and triphenylsilyloxy).
- These 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.
- a compound or a substituent when a compound or a substituent includes an alkyl group, an alkenyl group, etc., these may be linear or branched, and may be substituted or unsubstituted. When an aryl group, a heterocyclic group, or the like is included, they may be monocyclic or condensed, and may be substituted or unsubstituted.
- substituent group Z when the name of each group is only described ( For example, when only “alkyl group” is described), preferred ranges and specific examples of the corresponding group in the substituent group Z are applied.
- the content of the repeating unit represented by the above formula (A) or (B) in the polyimide compound there is no particular limitation, and it is appropriately adjusted according to the purpose of gas separation (recovery rate, purity, etc.) in consideration of gas permeability and gas separation selectivity.
- the polyimide compound used in the present invention has the formula (A) or (R) with respect to the sum (100 mol%) of the repeating units represented by the formulas (A), (B), (C) and (D).
- the total amount of the repeating units represented by B) is preferably 5 mol% or more, more preferably 10 to 90 mol%, further preferably 20 to 80 mol%, more preferably 30 to 70 mol%. More preferably. If the repeating unit of formula (A) or (B) has a large number of carbamoyl groups, even if the amount of the repeating unit represented by formula (A) or (B) is reduced to some extent, the carbamoyl group in the polyimide compound The amount can be within the range defined by the present invention, and a desired effect can be obtained.
- the polyimide compound used in the present invention preferably has a structure in which all of the repeating units are represented by the formula (A), (B), (C) or (D).
- the molecular weight of the polyimide compound 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 to 300. , 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.
- 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 terminal group of the polyimide compound having a repeating unit represented by the formula (A) or (B) used in the present invention is determined by the synthesis method and reaction raw material described later, and is obvious.
- the terminal group is, for example, a hydrogen atom, a carboxy group, or an amino group. Further, the end group may be substituted by capping. In this case, examples of the terminal group include an aryl group and a heteroaryl group.
- the polyimide compound used in the present invention can be synthesized by condensation polymerization of a specific bifunctional acid anhydride (tetracarboxylic dianhydride) and a specific diamine.
- tetracarboxylic dianhydride a specific bifunctional acid anhydride
- diamine a specific diamine
- a general book for example, edited by Ikuo Imai and Rikio Yokota, “Latest Polyimide: Fundamentals and Applications”, NTS Corporation, August 25, 2010, p. 3 to 49, Etc.
- one or both of a tetracarboxylic dianhydride and a diamine compound used as a raw material have a carbamoyl group.
- At least one tetracarboxylic dianhydride used as a raw material is preferably represented by the following formula (IV). It is preferable that all tetracarboxylic dianhydrides used as raw materials are represented by the following formula (IV).
- R has the same meaning as R in the above formula (A).
- tetracarboxylic dianhydrides that can be used in the present invention include the following.
- At least one diamine compound used as a raw material is preferably represented by the following formula (A-1) or (B-1).
- R 4 and 11 are the same as R 4 and 11 in formula (A), respectively, and the preferred forms are also the same.
- the diamine compound represented by the above formula (A-1) is preferably a compound represented by the following formula (a-1).
- R 4a has the same meaning as R 4a in formula (a), and the preferred form is also the same.
- R 5 , R 6, X 4, m1 and n1 are respectively synonymous with R 5, R 6, X 4 , m1 and n1 in the formula (B), preferred forms are also the same It is.
- diamine represented by the formula (A-1) or (B-1) include those shown below.
- R 7 and p2 have the same meanings as R 7 and p2 in formula (C), respectively, and have the same preferred forms.
- the diamine represented by the formula (C-1) does not include the diamine represented by the formula (A-1).
- R 8 , R 9, X 4, q2 and r2 are respectively synonymous with R 8, R 9, X 4 , q2 and r2 in formula (D), preferred embodiments are also the same It is.
- the diamine represented by the formula (D-1) does not include the diamine represented by the formula (B-1).
- diamine represented by the formula (C-1) or (D-1) for example, the following can be used.
- the polyimide compound used in the present invention may be any of a block copolymer, a random copolymer and a graft copolymer.
- the polyimide compound used in the present invention can be obtained by mixing each of the above raw materials in a solvent and subjecting it to condensation polymerization by an ordinary method.
- the solvent is not particularly limited, but ester organic solvents such as methyl acetate, ethyl acetate, and butyl acetate; aliphatics such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, cyclopentanone, and cyclohexanone.
- Ether organic solvents such as ketone, ethylene glycol dimethyl ether, dibutyl butyl ether, tetrahydrofuran, methylcyclopentyl ether, dioxane, amide organic solvents such as N-methylpyrrolidone, 2-pyrrolidone, dimethylformamide, dimethylimidazolidinone, dimethylacetamide, dimethyl And sulfur-containing organic solvents such as sulfoxide and 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 preferably N-methylpyrrolidone
- sulfur-containing dimethyl sulfoxide, sulfolane
- the polymerization reaction temperature is not particularly limited, and a temperature that can be usually employed in the synthesis of a polyimide compound can be employed. Specifically, it is preferably ⁇ 40 to 60 ° C., more preferably ⁇ 30 to 50 ° C.
- a polyimide compound is obtained by imidizing the polyamic acid produced by the above polymerization reaction by a dehydration ring-closing reaction in the molecule.
- a method for dehydrating and closing a ring a general book (for example, Ikuo Imai, edited by Rikio Yokota, “Latest Polyimide: Fundamentals and Applications”, NTS Inc., August 25, 2010, p. 3) To 49, etc.) can be referred to.
- 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 solution of the polyimide compound is not particularly limited, but is preferably 5 to 70% by mass, more preferably 5 to 50% by mass. And more preferably 5 to 30% by mass.
- polyimide compound used in the present invention examples include P-01 to P-17 and P-01 to P-17 described in the examples described later, in which the molar ratio of each structural unit is appropriately changed.
- the present invention is not limited to these, and a wide range of polyimide compounds satisfying the provisions of the present invention can be used.
- FIG. 1 is a longitudinal sectional view schematically showing a gas separation composite membrane 10 which is one preferred embodiment of the present invention.
- FIG. 2 is a cross-sectional view schematically showing a gas separation composite membrane 20 which is another preferred embodiment of the present invention.
- a nonwoven fabric layer 3 is added as a support layer in addition to the gas separation layer 1 and the porous layer 2.
- upper support layer means that another layer may be interposed between the support layer and the gas 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”.
- a gas separation layer may be formed and disposed on the surface or inner surface of a porous support (support layer). be able to.
- a gas separation layer By forming a gas separation layer on at least the surface of the porous support, a composite membrane having the advantages of having both high separation selectivity, high gas permeability, and mechanical strength can be obtained.
- 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 thickness of the gas separation layer is not particularly limited, but is preferably 0.01 to 5.0 ⁇ m, more preferably 0.05 to 2.0 ⁇ m.
- the porous support (porous layer) preferably applied to the gas permeable support layer is not particularly limited as long as it has the purpose of meeting the provision of mechanical strength and high gas permeability.
- Either an inorganic material or an inorganic material may be used, but an organic polymer porous film is preferable, and the thickness thereof is 1 to 3,000 ⁇ m, preferably 5 to 500 ⁇ m, and more preferably 5 to 150 ⁇ m.
- the pore structure of this porous membrane usually has an average pore diameter of 10 ⁇ m or less, preferably 0.5 ⁇ m or less, more preferably 0.2 ⁇ m or less.
- the porosity is preferably 20 to 90%, more preferably 30 to 80%.
- the molecular weight cut-off of the porous layer is preferably 100,000 or less.
- the gas permeability is preferably 3 ⁇ 10 ⁇ 5 cm 3 (STP) / cm 2 ⁇ sec ⁇ cmHg (30 GPU) or more at 40 ° C. and 4 MPa, preferably 100 GPU or more. Is more preferable, and 200 GPU or more is more preferable.
- any polymer for example, a polyolefin resin such as polyethylene and polypropylene, a fluorine-containing resin such as polytetrafluoroethylene, polyvinyl fluoride, and polyvinylidene fluoride, polystyrene, cellulose acetate, polyurethane, Various resins such as polyacrylonitrile, polyphenylene oxide, polysulfone, polyethersulfone, polyimide, and polyaramide can be exemplified.
- the shape of the porous membrane may be any shape such as a flat plate shape, a spiral shape, a tubular shape, and a hollow fiber shape.
- a support is formed to further impart mechanical strength to the lower part of the support layer forming the gas separation layer.
- a support include woven fabric, non-woven fabric, and net, but a non-woven fabric is preferably used from the viewpoint of film forming property and cost.
- 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.
- the production method of the composite membrane of the present invention is preferably a production method including forming a gas separation layer by applying a coating solution containing the polyimide compound on a support.
- the content of the polyimide compound in the coating solution is not particularly limited, but is preferably 0.1 to 30% by mass, and more preferably 0.5 to 10% by mass. If the content of the polyimide compound is too low, when the film is formed on the porous support, it easily penetrates into the lower layer, so that there is a high possibility that defects will occur in the surface layer that contributes to separation.
- the gas separation membrane of the present invention can be appropriately produced by adjusting the molecular weight, structure, composition, and solution viscosity of the polymer in the separation layer.
- 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 organic solvent such as n-
- 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.
- another layer may exist between the support layer and the gas separation layer.
- a preferred example of the other layer is a siloxane compound layer.
- the siloxane compound layer By providing the siloxane compound layer, the unevenness on the outermost surface of the support can be smoothed, and the separation layer can be easily thinned.
- the siloxane compound forming the siloxane compound layer include those having a main chain made of polysiloxane and compounds having a siloxane structure and a non-siloxane structure in the main chain.
- siloxane compounds whose main chain consists of polysiloxane-
- the siloxane compound having a main chain made of polysiloxane that can be used in the siloxane compound layer include one or more polyorganosiloxanes represented by the following formula (1) or (2). Moreover, these polyorganosiloxanes may form a crosslinking reaction product.
- a cross-linked reaction product for example, a compound represented by the following formula (1) is cross-linked by a polysiloxane compound having groups at both ends that react with the reactive group X of the following formula (1) and connect. In the form of compounds.
- R is a non-reactive group, and is an alkyl group (preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 15 carbon atoms). More preferably an aryl group having 6 to 12 carbon atoms, still more preferably phenyl).
- X is a reactive group, and is a group selected from a hydrogen atom, a halogen atom, a vinyl group, a hydroxyl group, and a substituted alkyl group (preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms).
- Y and Z are the above R or X.
- the viscosity of the siloxane compound used in the present invention is not particularly limited, but the viscosity at 25 ° C. is preferably 10 to 100,000 mPa ⁇ s, more preferably 20 to 50,000 mPa ⁇ s. . m is a number of 1 or more, preferably 1 to 100,000. n is a number of 0 or more, preferably 0 to 100,000.
- X, Y, Z, R, m and n have the same meanings as X, Y, Z, R, m and n in the formula (1), respectively.
- non-reactive group R when the non-reactive group R is an alkyl group, examples of the alkyl group include methyl, ethyl, hexyl, octyl, decyl, and octadecyl.
- examples of the fluoroalkyl group include —CH 2 CH 2 CF 3 and —CH 2 CH 2 C 6 F 13 .
- examples of the alkyl group include hydroxyalkyl groups having 1 to 18 carbon atoms and aminoalkyl groups having 1 to 18 carbon atoms.
- the number of carbon atoms of the alkyl group constituting the hydroxyalkyl group is preferably an integer of 1 to 10, for example, —CH 2 CH 2 CH 2 OH.
- the number of carbon atoms of the alkyl group constituting the aminoalkyl group is preferably an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 NH 2 .
- the number of carbon atoms of the alkyl group constituting the carboxyalkyl group is preferably an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 COOH.
- the number of carbon atoms of the alkyl group constituting the chloroalkyl group is preferably an integer of 1 to 10, and a preferred example is —CH 2 Cl.
- a preferable carbon number of the alkyl group constituting the glycidoxyalkyl group is an integer of 1 to 10, and a preferred example is 3-glycidyloxypropyl.
- the preferable number of carbon atoms of the epoxy cyclohexyl alkyl group having 7 to 16 carbon atoms is an integer of 8 to 12.
- a preferable carbon number of the (1-oxacyclobutan-3-yl) alkyl group having 4 to 18 carbon atoms is an integer of 4 to 10.
- a preferable carbon number of the alkyl group constituting the methacryloxyalkyl group is an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 —OOC—C (CH 3 ) ⁇ CH 2 .
- a preferable carbon number of the alkyl group constituting the mercaptoalkyl group is an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 SH.
- m and n are preferably numbers that give a molecular weight of 5,000 to 1,000,000 of the compound.
- a reactive group-containing siloxane unit (wherein the number is a structural unit represented by n) and a siloxane unit having no reactive group (wherein the number is m)
- the distribution of the structural unit represented by That is, in the formulas (1) and (2), the (Si (R) (R) —O) units and the (Si (R) (X) —O) units may be randomly distributed.
- R, m and n have the same meanings as R, m and n in formula (1), respectively.
- R ′ is —O— or —CH 2 —
- R ′′ is a hydrogen atom or methyl. Both ends of the formula (3) are preferably an amino group, a hydroxyl group, a carboxy group, a trimethylsilyl group, an epoxy group, a vinyl group, a hydrogen atom, or a substituted alkyl group.
- n and n are synonymous with m and n in Formula (1), respectively.
- m and n have the same meanings as m and n in formula (1), respectively.
- m and n are synonymous with m and n in Formula (1), respectively. It is preferable that the both ends of Formula (6) have an amino group, a hydroxyl group, a carboxy group, a trimethylsilyl group, an epoxy group, a vinyl group, a hydrogen atom, or a substituted alkyl group bonded thereto.
- m and n are synonymous with m and n in formula (1), respectively. It is preferable that an amino group, a hydroxyl group, a carboxy group, a trimethylsilyl group, an epoxy, a vinyl group, a hydrogen atom, or a substituted alkyl group is bonded to both ends of the formula (7).
- the siloxane structural unit and the non-siloxane structural unit may be randomly distributed.
- the compound having a siloxane structure and a non-siloxane structure in the main chain preferably contains 50 mol% or more of siloxane structural units, more preferably 70 mol% or more, based on the total number of moles of all repeating structural units. .
- the weight average molecular weight of the siloxane compound used in the siloxane compound layer is preferably 5,000 to 1,000,000 from the viewpoint of achieving both a thin film and durability.
- the method for measuring the weight average molecular weight is as described above.
- siloxane compound which comprises a siloxane compound layer is enumerated below.
- the thickness of the siloxane compound layer is preferably from 0.01 to 5 ⁇ m, more preferably from 0.05 to 1 ⁇ m, from the viewpoint of smoothness and gas permeability.
- the gas permeability at 40 ° C. and 4 MPa of the siloxane compound layer is preferably 100 GPU or more, more preferably 300 GPU or more, and further preferably 1,000 GPU or more in terms of carbon dioxide transmission rate.
- the gas separation membrane of the present invention may be an asymmetric membrane.
- the asymmetric membrane can be formed by a phase change method using a solution containing a polyimide compound.
- the phase inversion method is a known method for forming a film while bringing a polymer solution into contact with a coagulation liquid to cause phase conversion.
- a so-called dry / wet method is suitably used.
- a thin polymer layer gas separation layer
- coagulating liquid solvent is compatible with the solvent of the polymer solution and the polymer is an insoluble solvent.
- forming a porous layer by utilizing the phase separation phenomenon that occurs at that time, and a proposal by Rob Thrillerjan et al. (For example, US Pat. No. 3,133,132) Description).
- the thickness of a surface layer (gas separation layer) that contributes to gas separation called a dense layer or a skin layer is not particularly limited.
- the thickness is preferably from 01 to 5.0 ⁇ m, more preferably from 0.05 to 1.0 ⁇ m.
- the porous layer below the dense layer lowers the gas permeability resistance and at the same time plays a role of imparting mechanical strength, and its thickness is particularly limited as long as it is self-supporting as an asymmetric membrane.
- it is preferably 5 to 500 ⁇ m, more preferably 5 to 200 ⁇ m, and still more preferably 5 to 100 ⁇ m.
- the gas separation asymmetric membrane of the present invention may be a flat membrane or a hollow fiber membrane.
- the asymmetric hollow fiber membrane can be produced by a dry and wet spinning method.
- the dry-wet spinning method is a method for producing an asymmetric hollow fiber membrane by applying a dry-wet method to a polymer solution that is discharged from a spinning nozzle to have a hollow fiber-shaped target shape. More specifically, the polymer solution is discharged from a nozzle into a hollow fiber-shaped target shape, and after passing through an air or nitrogen gas atmosphere immediately after discharge, the polymer is not substantially dissolved and is compatible with the solvent of the polymer solution.
- an asymmetric structure is formed by immersing in a coagulating liquid containing, then dried, and further heat-treated as necessary to produce a separation membrane.
- the solution viscosity of the solution containing the polyimide compound discharged from the nozzle is 2 to 17,000 Pa ⁇ s, preferably 10 to 1,500 Pa ⁇ s, particularly 20 to 1,000 Pa ⁇ s at the discharge temperature (for example, 10 ° C.). It is preferable because a shape after discharge such as a hollow fiber shape can be stably obtained.
- the film is immersed in the primary coagulation liquid and solidified to such an extent that the shape of the hollow fiber or the like can be maintained. It is preferable to solidify. It is efficient to dry the coagulated film after replacing the coagulating liquid with a solvent such as hydrocarbon.
- the heat treatment for drying is preferably performed at a temperature lower than the softening point or secondary transition point of the used polyimide compound.
- the tensile strength of the gas separation asymmetric membrane of the present invention is preferably 10 N / mm 2 or more, and more preferably 12 N / mm 2 or more in order to further increase the mechanical strength.
- the upper limit of the tensile strength usually is at 25 N / mm 2 or less, may be 20 N / mm 2 or less.
- the compressive strength of the gas separation asymmetric membrane of the present invention is preferably 10 MPa or more, and more preferably 15 MPa or more.
- limiting in particular in the upper limit of this compressive strength Usually, it is 50 MPa or less, and 40 MPa or less may be sufficient.
- the elongation at break of the gas separation asymmetric membrane of the present invention is preferably 12% or more, and more preferably 16% or more.
- the upper limit of the elongation at break is not particularly limited, but is usually 25% or less and may be 20% or less.
- the tensile elastic modulus of the gas separation asymmetric membrane of the present invention is preferably 100 MPa or less, more preferably 90 MPa or less, and further preferably 80 MPa or less.
- the lower limit of the tensile elastic modulus is usually 10 MPa or more, 20 MPa or more, 30 MPa or more, or 40 MPa or more in order to achieve compatibility with mechanical strength. .
- the content of the polyimide compound in the gas separation layer is not particularly limited as long as desired gas separation performance can be obtained.
- the content of the polyimide compound in the gas separation layer is preferably 20% by mass or more, more preferably 40% by mass or more, and 60% by mass or more. Is preferable, and it is more preferable that it is 70 mass% or more.
- the content of the polyimide compound in the gas separation layer may be 100% by mass, but is usually 99% by mass or less.
- the gas separation membrane (composite membrane and asymmetric membrane) of the present invention can be suitably used for gas separation recovery and gas separation purification.
- gas separation membrane capable of efficiently separating a specific gas from a gas mixture containing a gas such as a perfluoro compound.
- a gas separation membrane that selectively separates carbon dioxide from a gas mixture containing carbon dioxide / hydrocarbon (methane) is preferable.
- the permeation rate of carbon dioxide at 40 ° C. and 5 MPa is preferably more than 20 GPU, more preferably more than 30 GPU, More preferably, it is 50 to 500 GPU.
- the permeation rate ratio of carbon dioxide to methane (R CO2 / R CH4 ) is preferably 15 or more, more preferably 20 or more, further preferably 23 or more, and preferably 25 to 50. Particularly preferred.
- R CO2 represents the permeation rate of carbon dioxide
- R CH4 represents the permeation rate of methane.
- 1 GPU is 1 ⁇ 10 ⁇ 6 cm 3 (STP) / cm 2 ⁇ sec ⁇ cmHg.
- Various polymer compounds can be added to the gas separation layer of the gas separation membrane of the present invention in order to adjust the membrane properties.
- High molecular compounds include acrylic polymers, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellac, vinyl resins, acrylic resins, rubber resins. Waxes and other natural resins can be used. Two or more of these may be used in combination.
- nonionic surfactants, cationic surfactants, organic fluoro compounds, and the like can be added to adjust liquid properties.
- the surfactant include alkylbenzene sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfonate of higher fatty acid ester, sulfate ester of higher alcohol ether, sulfonate of higher alcohol ether, higher alkyl
- Anionic surfactants such as alkyl carboxylates of sulfonamides, alkyl phosphates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, ethylene oxide adducts of acetylene glycol,
- Nonionic surfactants such as ethylene oxide adducts of glycerin and polyoxyethylene sorbitan fatty acid esters, and other amphoteric boundaries such as alkyl betaines and amide betaines
- a polymer dispersant may be included, and specific examples of the polymer dispersant include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, and polyacrylamide. Of these, polyvinylpyrrolidone is preferably used.
- the conditions for forming the gas separation membrane of the present invention are not particularly limited, but the temperature is preferably ⁇ 30 to 100 ° C., more preferably ⁇ 10 to 80 ° C., and particularly preferably 5 to 50 ° C.
- a gas such as air or oxygen may coexist at the time of forming the film, but it is preferably in an inert gas atmosphere.
- the gas separation method of the present invention is a method including selectively permeating carbon dioxide from a mixed gas containing carbon dioxide and methane using the gas separation membrane of the present invention.
- the pressure during gas separation is preferably 0.5 to 10 MPa, more preferably 1 to 10 MPa, and further preferably 2 to 7 MPa.
- the gas separation temperature is preferably ⁇ 30 to 90 ° C., more preferably 15 to 70 ° C.
- a gas separation module can be prepared using the gas separation membrane of the present invention.
- modules include spiral type, hollow fiber type, pleated type, tubular type, plate & frame type and the like.
- a gas separation apparatus having means for separating and recovering or purifying gas can be obtained using the gas separation membrane or gas separation membrane module of the present invention.
- the gas separation membrane of the present invention may be applied, for example, 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.
- the hydrogen pressure and the temperature of the heater were adjusted, and stirring was continued for 7 hours while maintaining the temperature of the reaction solution at 35 to 45 ° C.
- the reaction solution was transferred from the pressure vessel to a 2 L flask with an aspirator and cooled rapidly through Celite to remove palladium carbon, so that the product or the like was not precipitated. Methanol was removed under reduced pressure from the reddish brown solution obtained by filtration. The obtained solid was purified by recrystallization using methanol and water to obtain 3.4 g of the desired 3,5-diaminobenzamide.
- the white powder obtained by suction filtration was repeatedly washed four times with 250 mL of methanol to remove N-methylpyrrolidone to 0.1% or less, and then blown at 40 ° C. for 12 hours with an air dryer. It was dried to obtain 9.23 g (yield 90%) of polyimide (P-01).
- the content of carbamoyl group in polyimide (P-01) was 0.71 mmol / g.
- ⁇ Comparative polymer> As a cellulose acetate comprising the following structural units (repeating units), a commercially available product (trade name: L-70, manufactured by Daicel Corporation, acetylation degree 0.55) was used. The degree of acetylation means the weight percentage of bound acetic acid per unit weight.
- Example 18 Production of Asymmetric Membrane 2.5 g of methyl ethyl ketone, 2.5 g of N, N-dimethylformamide, and 0.6 g of n-butanol were added to 0.5 g of polyimide (P-01) prepared in the same manner as described above. After adding and dissolving a mixed solution, it filtered with the microfiltration membrane made from PTFE with a hole diameter of 5.0 micrometers, and this was made into dope solution. A non-woven fabric made of polyester (made by Awa Paper Co., Ltd., film thickness: 95 ⁇ m) is laid on a clean glass plate, and the dope solution is developed in an environment at room temperature (20 ° C.) and allowed to stand for 30 seconds.
- P-01 polyimide
- an asymmetric membrane After immersing in (0 ° C., 75 wt% methanol aqueous solution) for 1 hour, and further dipping in a secondary coagulation liquid (0 ° C., 75 wt% methanol aqueous solution) for 1 hour, an asymmetric membrane was produced. After washing the obtained asymmetric membrane with methanol, the methanol is replaced with isooctane, and further heating is carried out at 50 ° C. for 8 hours and at 110 ° C. for 6 hours to evaporate and dry isooctane, so that the dense skin layer is 0.1 ⁇ m or less. An asymmetric membrane (Example 18) having a total polyimide layer thickness of 40 ⁇ m was obtained.
- Example 19 Production of asymmetric membrane An asymmetric membrane of Example 19 was produced in the same manner as in Example 18 except that polyimide (P-01) was changed to polyimide (P-02) in Example 18 above. .
- Comparative Example 6 Production of Asymmetric Membrane An asymmetric membrane of Comparative Example 6 was produced in the same manner as in Example 18 except that polyimide (P-01) was changed to comparative polyimide 01 in Example 18.
- Comparative Example 7 Production of Asymmetric Membrane Asymmetric membrane of Comparative Example 7 was produced in the same manner as in Example 18 except that polyimide (P-01) was changed to cellulose acetate (comparative polymer) in Example 18. .
- a gas permeability measuring device manufactured by GTR Tech Co., Ltd.
- a mixed gas of carbon dioxide (CO 2 ) and methane (CH 4 ) of 40:60 (volume ratio) is used, and the total pressure on the gas supply side is 4 MPa (minus CO 2 The pressure was adjusted to 1.6 MPa), the flow rate was 500 mL / min, and 40 ° C. was supplied.
- the permeated gas was analyzed by gas chromatography.
- the gas permeability of the membrane was compared by calculating the gas permeation rate as gas permeability (Permeance).
- the gas separation selectivity was calculated as the ratio of the CO 2 permeation rate R CO2 to the CH 4 permeation rate R CH4 of this membrane (R CO2 / R CH4 ).
- the gas separation membrane produced using the polyimide compound having no carbamoyl group resulted in inferior in both CO 2 permeation rate and gas separation selectivity under high pressure (comparison). Examples 1 and 2).
- the gas separation membrane manufactured using the polyimide compound whose content of carbamoyl groups is less than that defined in the present invention was inferior in CO 2 permeation rate and gas separation selectivity (Comparative Example 3).
- the content of the carbamoyl group was larger than specified in the present invention, the polarity was so high that it was not dissolved in the solvent and could not be formed (Comparative Example 4).
- the gas separation membrane of the present invention can provide an excellent gas separation method, a gas separation module, and a gas separation apparatus equipped with this gas separation module.
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Abstract
Provided are the following: a gas separation membrane having a gas separation layer containing a polyimide compound, wherein the polyimide compound has a carbamoyl group, and the amount of the carbamoyl group contained in the polyimide compound is 0.1 to 3.0 mmol/g; and a gas separation module, a gas separation device, and a gas separation method using the gas separation membrane.
Description
本発明は、ガス分離膜、ガス分離モジュール、ガス分離装置、及びガス分離方法に関する。
The present invention relates to a gas separation membrane, a gas separation module, a gas separation device, and a gas separation method.
高分子化合物からなる素材には、その素材ごとに特有の気体透過性がある。その性質に基づき、特定の高分子化合物から構成された膜によって、所望の気体成分を選択的に透過させて分離することができる。この気体分離膜の産業上の利用態様として、地球温暖化の問題と関連し、火力発電所やセメントプラント、製鉄所高炉等において、大規模な二酸化炭素発生源からこれを分離回収することが検討されている。そして、この膜分離技術は、比較的小さなエネルギーで達成できる環境問題の解決手段として着目されている。一方、天然ガスやバイオガス(生物の排泄物、有機質肥料、生分解性物質、汚水、ゴミ、エネルギー作物などの発酵、嫌気性消化により発生するガス)は主としてメタンと二酸化炭素を含む混合ガスであり、その二酸化炭素等の不純物を除去する手段として膜分離方法が検討されている(特許文献1)。
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. As an industrial utilization mode of this gas separation membrane, it is considered to separate and recover it from a large-scale carbon dioxide generation source in a thermal power plant, a cement plant, a steelworks blast furnace, etc. in connection with the problem of global warming. Has been. And this membrane separation technique attracts attention as a means for solving environmental problems that can be achieved with relatively small energy. On the other hand, natural gas and biogas (gas generated by fermentation and anaerobic digestion of biological waste, organic fertilizer, biodegradable substances, sewage, garbage, energy crops, etc.) are mainly mixed gases containing methane and carbon dioxide. A membrane separation method has been studied as a means for removing impurities such as carbon dioxide (Patent Document 1).
膜分離方法を用いた天然ガスの精製では、より効率的にガスを分離するために、優れたガス透過性と分離選択性が求められる。これを実現するために種々の膜素材が検討されており、具体例として、ポリイミド化合物を用いたガス分離膜の検討が行われてきた。例えば非特許文献1には、カルボキシ基や水酸基等の極性基を導入したポリイミド化合物を用いることで、ガス分離膜の分離選択性を高めたことが記載されている。
また、実際のプラントにおいては、高圧条件や天然ガス中に存在する不純物(例えば、ベンゼン、トルエン、キシレン)の影響等によって膜が可塑化し、これによる分離選択性の低下が問題となる。この膜の可塑化を抑制するために、膜を構成するポリイミド化合物に架橋構造や分岐構造を導入することが有効であることが知られている(例えば、特許文献2~7)。 In the purification of natural gas using a membrane separation method, excellent gas permeability and separation selectivity are required in order to separate gases more efficiently. In order to realize this, various membrane materials have been studied. As a specific example, a gas separation membrane using a polyimide compound has been studied. For example, Non-PatentDocument 1 describes that the separation selectivity of the gas separation membrane is improved by using a polyimide compound into which a polar group such as a carboxy group or a hydroxyl group is introduced.
In an actual plant, the membrane is plasticized due to the influence of high-pressure conditions and impurities (for example, benzene, toluene, xylene) present in natural gas, resulting in a problem of lowering separation selectivity. In order to suppress plasticization of the film, it is known that it is effective to introduce a crosslinked structure or a branched structure into the polyimide compound constituting the film (for example,Patent Documents 2 to 7).
また、実際のプラントにおいては、高圧条件や天然ガス中に存在する不純物(例えば、ベンゼン、トルエン、キシレン)の影響等によって膜が可塑化し、これによる分離選択性の低下が問題となる。この膜の可塑化を抑制するために、膜を構成するポリイミド化合物に架橋構造や分岐構造を導入することが有効であることが知られている(例えば、特許文献2~7)。 In the purification of natural gas using a membrane separation method, excellent gas permeability and separation selectivity are required in order to separate gases more efficiently. In order to realize this, various membrane materials have been studied. As a specific example, a gas separation membrane using a polyimide compound has been studied. For example, Non-Patent
In an actual plant, the membrane is plasticized due to the influence of high-pressure conditions and impurities (for example, benzene, toluene, xylene) present in natural gas, resulting in a problem of lowering separation selectivity. In order to suppress plasticization of the film, it is known that it is effective to introduce a crosslinked structure or a branched structure into the polyimide compound constituting the film (for example,
実用的なガス分離膜とするためには、ガス分離選択性を確保するだけでなく、ガス分離層を薄層にして十分なガス透過性も確保しなければならない。そのための手法として、ポリイミド化合物等の高分子化合物を相分離法により非対称膜とすることで、分離に寄与する部分を緻密層あるいはスキン層と呼ばれる薄層にする方法がある。この非対称膜では、緻密層をガス分離層とし、緻密層以外の部分を膜の機械的強度を担う支持層として機能させる。
また、上記非対称膜の他に、ガス分離機能を担う素材と機械強度を担う素材とを別素材とする複合膜の形態も知られている。この複合膜は、機械強度の担うガス透過性支持体上に、ポリイミド等の高分子化合物からなる薄層のガス分離層が形成された構造を持つ。 In order to obtain a practical gas separation membrane, not only gas separation selectivity but also a sufficient gas permeability must be ensured by making the gas separation layer thin. As a technique for this, there is a method in which a polymer compound such as a polyimide compound is formed into an asymmetric membrane by a phase separation method so that a portion contributing to the separation is made into a thin layer called a dense layer or a skin layer. In this asymmetric membrane, the dense layer serves as a gas separation layer, and the portion other than the dense layer functions as a support layer that bears the mechanical strength of the membrane.
In addition to the asymmetric membrane, a composite membrane is also known in which a material responsible for gas separation and a material responsible for mechanical strength are separated. This composite membrane has a structure in which a thin gas separation layer made of a polymer compound such as polyimide is formed on a gas permeable support having mechanical strength.
また、上記非対称膜の他に、ガス分離機能を担う素材と機械強度を担う素材とを別素材とする複合膜の形態も知られている。この複合膜は、機械強度の担うガス透過性支持体上に、ポリイミド等の高分子化合物からなる薄層のガス分離層が形成された構造を持つ。 In order to obtain a practical gas separation membrane, not only gas separation selectivity but also a sufficient gas permeability must be ensured by making the gas separation layer thin. As a technique for this, there is a method in which a polymer compound such as a polyimide compound is formed into an asymmetric membrane by a phase separation method so that a portion contributing to the separation is made into a thin layer called a dense layer or a skin layer. In this asymmetric membrane, the dense layer serves as a gas separation layer, and the portion other than the dense layer functions as a support layer that bears the mechanical strength of the membrane.
In addition to the asymmetric membrane, a composite membrane is also known in which a material responsible for gas separation and a material responsible for mechanical strength are separated. This composite membrane has a structure in which a thin gas separation layer made of a polymer compound such as polyimide is formed on a gas permeable support having mechanical strength.
上記のように、ガス透過性を向上させるためにガス分離層を薄層化した場合でも、ガス透過性とガス分離選択性を高いレベルで両立するのは容易ではない。ガス分離層を構成する高分子化合物の共重合成分を調整することで、ガス透過性又はガス分離選択性を調整することができるが、両者はトレードオフ関係にあり、両者をより高いレベルで両立するにはガス分離層の素材自体のさらなる改良が必要である。
As described above, even when the gas separation layer is thinned to improve gas permeability, it is not easy to achieve both gas permeability and gas separation selectivity at a high level. Gas permeability or gas separation selectivity can be adjusted by adjusting the copolymer component of the polymer compound that constitutes the gas separation layer, but both are in a trade-off relationship, and both are compatible at a higher level. For this purpose, it is necessary to further improve the material of the gas separation layer itself.
本発明は、ガス透過性とガス分離選択性のいずれも良好なガス分離膜であって、高圧条件下で使用してもガス分離性能が低下しにくく、しかも天然ガス中に存在するトルエン等の不純物成分の影響も受けにくいガス分離膜を提供することを課題とする。また、本発明は、上記ガス分離膜を用いたガス分離モジュール、ガス分離装置、及びガス分離方法を提供することを課題とする。
The present invention is a gas separation membrane having both good gas permeability and gas separation selectivity, and the gas separation performance hardly deteriorates even when used under high-pressure conditions. Moreover, such as toluene present in natural gas. It is an object of the present invention to provide a gas separation membrane that is hardly affected by impurity components. Another object of the present invention is to provide a gas separation module, a gas separation device, and a gas separation method using the gas separation membrane.
本発明者らは上記課題に鑑み鋭意検討を重ねた。その結果、カルバモイル基を特定量含有するポリイミド化合物を用いてガス分離層を形成することで、ガス透過性とガス分離選択性のいずれにも優れ、且つ、高圧条件下で使用してもガス分離性能が低下しにくく、しかもトルエン等の不純物成分に対して高い耐性を示すガス分離膜が得られることを見い出した。本発明は、これらの知見に基づき完成させるに至ったものである。
The present inventors made extensive studies in view of the above problems. As a result, by forming a gas separation layer using a polyimide compound containing a specific amount of carbamoyl groups, both gas permeability and gas separation selectivity are excellent, and gas separation is possible even when used under high pressure conditions. It has been found that a gas separation membrane is obtained that is less likely to deteriorate in performance and that is highly resistant to impurity components such as toluene. The present invention has been completed based on these findings.
本発明によれば、以下の手段が提供される。
〔1〕
ポリイミド化合物を含有してなるガス分離層を有するガス分離膜であって、
上記ポリイミド化合物がカルバモイル基を有し、上記ポリイミド化合物中の上記カルバモイル基の含有量が0.1~3.0mmol/gである、ガス分離膜。
〔2〕
上記ポリイミド化合物が、下記式(A)又は(B)で表される繰り返し単位を含む、〔1〕に記載のガス分離膜。 According to the present invention, the following means are provided.
[1]
A gas separation membrane having a gas separation layer containing a polyimide compound,
A gas separation membrane, wherein the polyimide compound has a carbamoyl group, and the content of the carbamoyl group in the polyimide compound is 0.1 to 3.0 mmol / g.
[2]
The gas separation membrane according to [1], wherein the polyimide compound includes a repeating unit represented by the following formula (A) or (B).
〔1〕
ポリイミド化合物を含有してなるガス分離層を有するガス分離膜であって、
上記ポリイミド化合物がカルバモイル基を有し、上記ポリイミド化合物中の上記カルバモイル基の含有量が0.1~3.0mmol/gである、ガス分離膜。
〔2〕
上記ポリイミド化合物が、下記式(A)又は(B)で表される繰り返し単位を含む、〔1〕に記載のガス分離膜。 According to the present invention, the following means are provided.
[1]
A gas separation membrane having a gas separation layer containing a polyimide compound,
A gas separation membrane, wherein the polyimide compound has a carbamoyl group, and the content of the carbamoyl group in the polyimide compound is 0.1 to 3.0 mmol / g.
[2]
The gas separation membrane according to [1], wherein the polyimide compound includes a repeating unit represented by the following formula (A) or (B).
式(A)中、Rは下記式(I-1)~(I-28)のいずれかで表される構造の基を示す。ここでX1~X3は単結合又は2価の連結基を、Lは-CH=CH-又は-CH2-を、R1及びR2は水素原子又は置換基を示し、*は式(A)中のカルボニル基との結合部位を示す。R4は置換基を示し、l1は1~4の整数を示す。l1が1の場合、R4はカルバモイル基を有する基である。l1が2~4の場合、R4の少なくとも1つはカルバモイル基を有する基である。
In the formula (A), R represents a group having a structure represented by any of the following formulas (I-1) to (I-28). Here, X 1 to X 3 represent a single bond or a divalent linking group, L represents —CH═CH— or —CH 2 —, R 1 and R 2 represent a hydrogen atom or a substituent, and * represents a formula ( A binding site with the carbonyl group in A) is shown. R 4 represents a substituent, and l1 represents an integer of 1 to 4. When l1 is 1, R 4 is a group having a carbamoyl group. When l1 is 2 to 4, at least one of R 4 is a group having a carbamoyl group.
式(B)中、Rは上記式(A)におけるRと同義である。R5及びR6は置換基を示す。m1及びn1は0~4の整数であるが、m1とn1が共に0であることはない。m1が0の場合、R6の少なくとも1つはカルバモイル基を有する基であり、n1が0の場合、R5の少なくとも1つはカルバモイル基を有する基である。m1とn1が共に1以上である場合、R5及びR6の少なくとも1つはカルバモイル基を有する基である。X4は単結合又は2価の連結基を示す。
In formula (B), R has the same meaning as R in formula (A). R 5 and R 6 represent a substituent. m1 and n1 are integers of 0 to 4, but neither m1 nor n1 is 0. When m1 is 0, at least one of R 6 is a group having a carbamoyl group, and when n1 is 0, at least one of R 5 is a group having a carbamoyl group. When m1 and n1 are both 1 or more, at least one of R 5 and R 6 is a group having a carbamoyl group. X 4 represents a single bond or a divalent linking group.
〔3〕
上記式(A)で表される繰り返し単位が、下記式(a)で表される繰り返し単位である、〔2〕に記載のガス分離膜: [3]
The gas separation membrane according to [2], wherein the repeating unit represented by the formula (A) is a repeating unit represented by the following formula (a):
上記式(A)で表される繰り返し単位が、下記式(a)で表される繰り返し単位である、〔2〕に記載のガス分離膜: [3]
The gas separation membrane according to [2], wherein the repeating unit represented by the formula (A) is a repeating unit represented by the following formula (a):
式(a)中、Rは上記式(A)のRと同義である。R4aは、水素原子であるか、又はカルバモイル基を有さない置換基を示す。
〔4〕
上記ガス分離膜が、上記ガス分離層をガス透過性の支持層上側に有するガス分離複合膜である、〔1〕~〔3〕のいずれかに記載のガス分離膜。
〔5〕
上記支持層が、ガス分離層側の多孔質層と、その逆側の不織布層とからなる、〔4〕に記載のガス分離膜。
〔6〕
分離処理されるガスが二酸化炭素とメタンの混合ガスである場合において、40℃、5MPaにおける二酸化炭素の透過速度が20GPU超であり、二酸化炭素とメタンとの透過速度比(RCO2/RCH4)が15以上である、〔1〕~〔5〕のいずれかに記載のガス分離膜。
〔7〕
二酸化炭素及びメタンを含むガスから二酸化炭素を選択的に透過させるために用いられる、〔1〕~〔6〕のいずれかに記載のガス分離膜。
〔8〕
〔1〕~〔7〕のいずれかに記載のガス分離膜を具備するガス分離モジュール。
〔9〕
〔8〕に記載のガス分離モジュールを備えたガス分離装置。
〔10〕
〔1〕~〔7〕のいずれかに記載のガス分離膜を用いて、二酸化炭素及びメタンを含むガスから二酸化炭素を選択的に透過させるガス分離方法。 In formula (a), R has the same meaning as R in formula (A). R 4a is a hydrogen atom or a substituent having no carbamoyl group.
[4]
The gas separation membrane according to any one of [1] to [3], wherein the gas separation membrane is a gas separation composite membrane having the gas separation layer above the gas-permeable support layer.
[5]
The gas separation membrane according to [4], wherein the support layer includes a porous layer on the gas separation layer side and a nonwoven fabric layer on the opposite side.
[6]
In the case where the gas to be separated is a mixed gas of carbon dioxide and methane, the permeation rate of carbon dioxide at 40 ° C. and 5 MPa exceeds 20 GPU, and the permeation rate ratio of carbon dioxide and methane (R CO2 / R CH4 ) The gas separation membrane according to any one of [1] to [5], wherein is 15 or more.
[7]
The gas separation membrane according to any one of [1] to [6], which is used for selectively permeating carbon dioxide from a gas containing carbon dioxide and methane.
[8]
[1] A gas separation module comprising the gas separation membrane according to any one of [7].
[9]
[8] A gas separation device comprising the gas separation module according to [8].
[10]
A gas separation method for selectively permeating carbon dioxide from a gas containing carbon dioxide and methane, using the gas separation membrane according to any one of [1] to [7].
〔4〕
上記ガス分離膜が、上記ガス分離層をガス透過性の支持層上側に有するガス分離複合膜である、〔1〕~〔3〕のいずれかに記載のガス分離膜。
〔5〕
上記支持層が、ガス分離層側の多孔質層と、その逆側の不織布層とからなる、〔4〕に記載のガス分離膜。
〔6〕
分離処理されるガスが二酸化炭素とメタンの混合ガスである場合において、40℃、5MPaにおける二酸化炭素の透過速度が20GPU超であり、二酸化炭素とメタンとの透過速度比(RCO2/RCH4)が15以上である、〔1〕~〔5〕のいずれかに記載のガス分離膜。
〔7〕
二酸化炭素及びメタンを含むガスから二酸化炭素を選択的に透過させるために用いられる、〔1〕~〔6〕のいずれかに記載のガス分離膜。
〔8〕
〔1〕~〔7〕のいずれかに記載のガス分離膜を具備するガス分離モジュール。
〔9〕
〔8〕に記載のガス分離モジュールを備えたガス分離装置。
〔10〕
〔1〕~〔7〕のいずれかに記載のガス分離膜を用いて、二酸化炭素及びメタンを含むガスから二酸化炭素を選択的に透過させるガス分離方法。 In formula (a), R has the same meaning as R in formula (A). R 4a is a hydrogen atom or a substituent having no carbamoyl group.
[4]
The gas separation membrane according to any one of [1] to [3], wherein the gas separation membrane is a gas separation composite membrane having the gas separation layer above the gas-permeable support layer.
[5]
The gas separation membrane according to [4], wherein the support layer includes a porous layer on the gas separation layer side and a nonwoven fabric layer on the opposite side.
[6]
In the case where the gas to be separated is a mixed gas of carbon dioxide and methane, the permeation rate of carbon dioxide at 40 ° C. and 5 MPa exceeds 20 GPU, and the permeation rate ratio of carbon dioxide and methane (R CO2 / R CH4 ) The gas separation membrane according to any one of [1] to [5], wherein is 15 or more.
[7]
The gas separation membrane according to any one of [1] to [6], which is used for selectively permeating carbon dioxide from a gas containing carbon dioxide and methane.
[8]
[1] A gas separation module comprising the gas separation membrane according to any one of [7].
[9]
[8] A gas separation device comprising the gas separation module according to [8].
[10]
A gas separation method for selectively permeating carbon dioxide from a gas containing carbon dioxide and methane, using the gas separation membrane according to any one of [1] to [7].
本明細書において、特定の符号で表示された置換基や連結基等(以下、置換基等という)が複数あるとき、あるいは複数の置換基等を同時もしくは択一的に規定するときには、それぞれの置換基等は互いに同一でも異なっていてもよいことを意味する。このことは、置換基等の数の規定についても同様である。また、式中に同一の表示で表された複数の部分構造の繰り返しがある場合は、各部分構造ないし繰り返し単位は同一でも異なっていてもよい。また、特に断らない場合であっても、複数の置換基等が近接(特に隣接)するときにはそれらが互いに連結したり縮環したりして環を形成していてもよい意味である。
In the present specification, 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. The same applies to the definition of the number of substituents and the like. Further, when there are repetitions of a plurality of partial structures represented by the same indication in the formula, each partial structure or repeating unit may be the same or different. Further, even if not specifically stated, when a plurality of substituents and the like are close (particularly adjacent), they may be connected to each other or condensed to form a ring.
本明細書において化合物の表示については、化合物そのもののほか、その塩、そのイオンを含む意味に用いる。また、目的の効果を奏する範囲で、構造の一部を変化させた誘導体を含む意味である。
本明細書において置換・無置換を明記していない置換基(連結基についても同様)については、所望の効果を奏する範囲で、その基に任意の置換基を有していてもよい意味である。これは置換・無置換を明記していない化合物についても同義である。
本明細書において置換基というときには、特に断らない限り、後記置換基群Zをその好ましい範囲とする。 In this specification, about the display of a compound, it uses in the meaning containing its salt and its ion besides the compound itself. In addition, it is meant to include derivatives in which a part of the structure is changed within the range where the desired effect is achieved.
In the present specification, a substituent that does not specify substitution / non-substitution (the same applies to a linking group) means that the group may have an arbitrary substituent as long as a desired effect is achieved. . This is also synonymous for compounds that do not specify substitution / non-substitution.
In the present specification, the substituent group Z is a preferred range unless otherwise specified.
本明細書において置換・無置換を明記していない置換基(連結基についても同様)については、所望の効果を奏する範囲で、その基に任意の置換基を有していてもよい意味である。これは置換・無置換を明記していない化合物についても同義である。
本明細書において置換基というときには、特に断らない限り、後記置換基群Zをその好ましい範囲とする。 In this specification, about the display of a compound, it uses in the meaning containing its salt and its ion besides the compound itself. In addition, it is meant to include derivatives in which a part of the structure is changed within the range where the desired effect is achieved.
In the present specification, a substituent that does not specify substitution / non-substitution (the same applies to a linking group) means that the group may have an arbitrary substituent as long as a desired effect is achieved. . This is also synonymous for compounds that do not specify substitution / non-substitution.
In the present specification, the substituent group Z is a preferred range unless otherwise specified.
本発明のガス分離膜、ガス分離モジュール、及びガス分離装置は、ガス透過性に優れ、且つ、ガス分離性能も高い。また、高圧条件下における使用や、トルエン等の不純物成分を含むガスの分離に用いても、ガス分離性能の低下が生じにくい。
The gas separation membrane, gas separation module, and gas separation device of the present invention have excellent gas permeability and high gas separation performance. Further, even when used under high pressure conditions or for separation of a gas containing an impurity component such as toluene, the gas separation performance is hardly lowered.
本発明のガス分離方法によれば、より高い透過性で、且つ、より高い選択性でガスを分離することができる。さらに、高圧条件下でガスを分離しても、また、ガス中に不純物が存在しても、高いガス分離性能が持続する。
本発明の上記及び他の特徴及び利点は、適宜添付の図面を参照して、下記の記載からより明らかになるであろう。 According to the gas separation method of the present invention, gas can be separated with higher permeability and higher selectivity. Furthermore, even if the gas is separated under high pressure conditions or impurities are present in the gas, high gas separation performance is maintained.
The above and other features and advantages of the present invention will become more apparent from the following description, with reference where appropriate to the accompanying drawings.
本発明の上記及び他の特徴及び利点は、適宜添付の図面を参照して、下記の記載からより明らかになるであろう。 According to the gas separation method of the present invention, gas can be separated with higher permeability and higher selectivity. Furthermore, even if the gas is separated under high pressure conditions or impurities are present in the gas, high gas separation performance is maintained.
The above and other features and advantages of the present invention will become more apparent from the following description, with reference where appropriate to the accompanying drawings.
以下、本発明について詳細に説明する。
本発明のガス分離膜は、特定量のカルバモイル基を有するポリイミド化合物を含んでなるガス分離層を備えている。 Hereinafter, the present invention will be described in detail.
The gas separation membrane of the present invention includes a gas separation layer containing a specific amount of a polyimide compound having a carbamoyl group.
本発明のガス分離膜は、特定量のカルバモイル基を有するポリイミド化合物を含んでなるガス分離層を備えている。 Hereinafter, the present invention will be described in detail.
The gas separation membrane of the present invention includes a gas separation layer containing a specific amount of a polyimide compound having a carbamoyl group.
[ポリイミド化合物]
本発明に用いるポリイミド化合物は、その構造中にカルバモイル基(-C(=O)NH2)を含有する。本発明に用いるポリイミド化合物中のカルバモイル基の含有量は、0.1~3.0mmol/gである。ポリイミド化合物中のカルバモイル基の含有量が0.1mmol/gより少ないと、ポリイミド化合物に十分な極性を付与することができず、その結果、ポリイミド分子鎖間の相互作用が弱く、ポリイミド膜を十分に緻密化できない(ポリイミド分子鎖間の相互作用によるポリイミド分子の集合が十分に密にならない)ため、所望のガス分離性能が得られにくくなる。また、ポリイミド化合物中のカルバモイル基の含有量が3.0mmol/gよりも多いと、ポリイミド化合物間の相互作用が強くなりすぎて溶媒に対する溶解性が低下し、成膜しにくくなる。また、成膜できた場合でも、十分なガス透過性を示さないことがある。本発明に用いるポリイミド化合物中のカルバモイル基の含有量は、0.2~2.5mmol/gであることが好ましく、0.3~2.0mmol/gであることがより好ましく、0.4~1.5mmol/gであることがさらに好ましい。 [Polyimide compound]
The polyimide compound used in the present invention contains a carbamoyl group (—C (═O) NH 2 ) in its structure. The content of the carbamoyl group in the polyimide compound used in the present invention is 0.1 to 3.0 mmol / g. If the content of the carbamoyl group in the polyimide compound is less than 0.1 mmol / g, the polyimide compound cannot be imparted with sufficient polarity, and as a result, the interaction between the polyimide molecular chains is weak, and the polyimide film is sufficient. Therefore, it is difficult to obtain a desired gas separation performance because the aggregation of polyimide molecules due to the interaction between polyimide molecular chains is not sufficiently dense. Moreover, when there is more content of carbamoyl group in a polyimide compound than 3.0 mmol / g, the interaction between polyimide compounds will become strong too much, the solubility with respect to a solvent will fall, and it will become difficult to form into a film. Even when the film can be formed, sufficient gas permeability may not be exhibited. The content of the carbamoyl group in the polyimide compound used in the present invention is preferably 0.2 to 2.5 mmol / g, more preferably 0.3 to 2.0 mmol / g, and 0.4 to More preferably, it is 1.5 mmol / g.
本発明に用いるポリイミド化合物は、その構造中にカルバモイル基(-C(=O)NH2)を含有する。本発明に用いるポリイミド化合物中のカルバモイル基の含有量は、0.1~3.0mmol/gである。ポリイミド化合物中のカルバモイル基の含有量が0.1mmol/gより少ないと、ポリイミド化合物に十分な極性を付与することができず、その結果、ポリイミド分子鎖間の相互作用が弱く、ポリイミド膜を十分に緻密化できない(ポリイミド分子鎖間の相互作用によるポリイミド分子の集合が十分に密にならない)ため、所望のガス分離性能が得られにくくなる。また、ポリイミド化合物中のカルバモイル基の含有量が3.0mmol/gよりも多いと、ポリイミド化合物間の相互作用が強くなりすぎて溶媒に対する溶解性が低下し、成膜しにくくなる。また、成膜できた場合でも、十分なガス透過性を示さないことがある。本発明に用いるポリイミド化合物中のカルバモイル基の含有量は、0.2~2.5mmol/gであることが好ましく、0.3~2.0mmol/gであることがより好ましく、0.4~1.5mmol/gであることがさらに好ましい。 [Polyimide compound]
The polyimide compound used in the present invention contains a carbamoyl group (—C (═O) NH 2 ) in its structure. The content of the carbamoyl group in the polyimide compound used in the present invention is 0.1 to 3.0 mmol / g. If the content of the carbamoyl group in the polyimide compound is less than 0.1 mmol / g, the polyimide compound cannot be imparted with sufficient polarity, and as a result, the interaction between the polyimide molecular chains is weak, and the polyimide film is sufficient. Therefore, it is difficult to obtain a desired gas separation performance because the aggregation of polyimide molecules due to the interaction between polyimide molecular chains is not sufficiently dense. Moreover, when there is more content of carbamoyl group in a polyimide compound than 3.0 mmol / g, the interaction between polyimide compounds will become strong too much, the solubility with respect to a solvent will fall, and it will become difficult to form into a film. Even when the film can be formed, sufficient gas permeability may not be exhibited. The content of the carbamoyl group in the polyimide compound used in the present invention is preferably 0.2 to 2.5 mmol / g, more preferably 0.3 to 2.0 mmol / g, and 0.4 to More preferably, it is 1.5 mmol / g.
本発明に用いるポリイミド化合物中、カルバモイル基を有する構造に特に制限はない。具体的には、後述するようにポリイミド化合物がテトラカルボン酸二無水物とジアミン化合物との縮重合反応により合成される場合、テトラカルボン酸二無水物成分がカルバモイル基を有していても良いし、ジアミン成分がカルバモイル基を有していても良いし、テトラカルボン酸二無水物成分とジアミン成分の双方がカルバモイル基を有していてもよい。
The structure having a carbamoyl group in the polyimide compound used in the present invention is not particularly limited. Specifically, when the polyimide compound is synthesized by a polycondensation reaction between a tetracarboxylic dianhydride and a diamine compound as described later, the tetracarboxylic dianhydride component may have a carbamoyl group. The diamine component may have a carbamoyl group, or both the tetracarboxylic dianhydride component and the diamine component may have a carbamoyl group.
本発明に用いるポリイミド化合物は、下記式(A)又は(B)で表される繰り返し単位を少なくとも含むことが好ましい。
The polyimide compound used in the present invention preferably contains at least a repeating unit represented by the following formula (A) or (B).
式(A)において、Rは、下記式(I-1)~(I-28)のいずれかで表される構造の基を示す。下記式(I-1)~(I-28)において、*は式(A)のカルボニル基との結合部位を示す。式(A)におけるRを母核と呼ぶことがあるが、この母核Rは式(I-1)、(I-2)または(I-4)で表される基であることが好ましく、(I-1)または(I-4)で表される基であることがより好ましく、(I-1)で表される基であることが特に好ましい。
In the formula (A), R represents a group having a structure represented by any of the following formulas (I-1) to (I-28). In the following formulas (I-1) to (I-28), * represents a binding site with the carbonyl group of the formula (A). R in the formula (A) may be referred to as a mother nucleus, and the mother nucleus R is preferably a group represented by the formula (I-1), (I-2) or (I-4), The group represented by (I-1) or (I-4) is more preferred, and the group represented by (I-1) is particularly preferred.
上記式(I-1)、(I-9)及び(I-18)中、X1~X3は、単結合又は2価の連結基を示す。この2価の連結基としては、-C(Rx)2-(Rxは水素原子又は置換基を示す。Rxが置換基の場合、互いに連結して環を形成してもよい)、-O-、-SO2-、-C(=O)-、-S-、-NRY-(RYは水素原子、アルキル基(好ましくはメチル基又はエチル基)又はアリール基(好ましくはフェニル基))、-C6H4-(フェニレン基)、又はこれらの組み合わせが好ましく、単結合又は-C(Rx)2-がより好ましい。Rxが置換基を示すとき、その具体例としては、後記置換基群Zが挙げられ、なかでもアルキル基(好ましい範囲は後記置換基群Zに示されたアルキル基と同義である)が好ましく、ハロゲン原子を置換基として有するアルキル基がより好ましく、トリフルオロメチルが特に好ましい。なお、本明細書において「互いに連結して環を形成してもよい」というときには、単結合、二重結合等により結合して環状構造を形成するものであってもよく、また、縮合して縮環構造を形成するものであってもよい。なお、式(I-18)は、X3が、その左側に記載された2つの炭素原子のいずれか一方、及び、その右側に記載された2つの炭素原子のうちいずれか一方と連結していることを意味する。
In the above formulas (I-1), (I-9) and (I-18), X 1 to X 3 represent a single bond or a divalent linking group. As 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). group)), - C 6 H 4 - ( phenylene group), or a combination thereof, more preferably a single bond or -C (R x) 2 - are more preferable. When R x represents a substituent, specific examples thereof include the substituent group Z described below, and an alkyl group (preferably the same as the alkyl group shown in the substituent group Z described below) is preferable. An alkyl group having a halogen atom as a substituent is more preferable, and trifluoromethyl is particularly preferable. In the present specification, when “may be linked to each other to form a ring”, it may be bonded by a single bond, a double bond or the like to form a cyclic structure, It may form a condensed ring structure. Note that in the formula (I-18), X 3 is connected to one of the two carbon atoms described on the left side and one of the two carbon atoms described on the right side thereof. Means that
上記式(I-4)、(I-15)、(I-17)、(I-20)、(I-21)及び(I-23)中、Lは-CH=CH-又は-CH2-を示す。
In the above formulas (I-4), (I-15), (I-17), (I-20), (I-21) and (I-23), L represents —CH═CH— or —CH 2. -Is shown.
上記式(I-7)中、R1、R2は水素原子又は置換基を示す。その置換基としては、後述する置換基群Zに列挙された基が挙げられる。R1およびR2は互いに結合して環を形成していてもよい。
In the above formula (I-7), R 1 and R 2 represent a hydrogen atom or a substituent. Examples of the substituent include groups listed in the substituent group Z described later. R 1 and R 2 may be bonded to each other to form a ring.
R1、R2は水素原子又はアルキル基であることが好ましく、水素原子、メチル基又はエチル基であることがより好ましく、水素原子であることが更に好ましい。
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.
式(I-1)~(I-28)中に示された炭素原子はさらに置換基を有していてもよい。この置換基の具体例としては、後記置換基群Zが挙げられ、なかでもアルキル基又はアリール基が好ましい。
The carbon atoms shown in the formulas (I-1) to (I-28) may further have a substituent. Specific examples of this substituent include the substituent group Z described later, and among them, an alkyl group or an aryl group is preferable.
上記式(A)中、R4は置換基を示し、l1は1~4の整数を示す。l1が1の場合、R4はカルバモイル基(-C(=O)NH2)を有する基である。l1が2~4の場合、R4の少なくとも1つはカルバモイル基を有する基であり、R4の1つ又は2つがカルバモイル基を有する基であることが好ましい。R4がカルバモイル基を有さない置換基である場合、この置換基の具体例としては、後記置換基群Zが挙げられ、なかでもアルキル基(より好ましくは炭素数1~10、さらに好ましくは炭素数1~5のアルキル基、さらに好ましくはエチル又はメチル)、ハロゲン原子、アルコキシ基(好ましくは炭素数1~10、より好ましくは炭素数1~5のアルコキシ基)、又は芳香族基(好ましくは炭素数3~20の芳香族基、より好ましくは炭素数3~20の芳香族複素環基(好ましくは環構成原子に窒素原子を含む)、さらに好ましくは炭素数4~15の芳香族複素環基(好ましくは環構成原子に窒素原子を含む))が好ましい。
本明細書において、「カルバモイル基を有する基」はカルバモイル基を有していれば特に制限はないが、カルバモイル基又はカルバモイルアルキル基(好ましくは炭素数2~10、より好ましくは炭素数2~5のカルバモイルアルキル基、さらに好ましくはカルバモイルエチル又はカルバモイルメチル、さらに好ましくはカルバモイルメチル)が好ましく、なかでもカルバモイル基又はカルバモイルメチルが好ましい。 In the above formula (A), R 4 represents a substituent, and l1 represents an integer of 1 to 4. When l1 is 1, R 4 is a group having a carbamoyl group (—C (═O) NH 2 ). When l1 is 2 to 4, it is preferable that at least one of R 4 is a group having a carbamoyl group, and one or two of R 4 is a group having a carbamoyl group. When R 4 is a substituent that does not have a carbamoyl group, specific examples of this substituent include the substituent group Z described later, and among them, an alkyl group (more preferably having 1 to 10 carbon atoms, more preferably An alkyl group having 1 to 5 carbon atoms, more preferably ethyl or methyl), a halogen atom, an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms), or an aromatic group (preferably Is an aromatic group having 3 to 20 carbon atoms, more preferably an aromatic heterocyclic group having 3 to 20 carbon atoms (preferably containing a nitrogen atom as a ring constituent atom), and further preferably an aromatic hetero group having 4 to 15 carbon atoms. A ring group (preferably containing a nitrogen atom as a ring constituent atom) is preferred.
In the present specification, the “group having a carbamoyl group” is not particularly limited as long as it has a carbamoyl group. However, the carbamoyl group or carbamoylalkyl group (preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms) is preferable. Carbamoylalkyl group, more preferably carbamoylethyl or carbamoylmethyl, more preferably carbamoylmethyl), among which carbamoyl group or carbamoylmethyl is preferable.
本明細書において、「カルバモイル基を有する基」はカルバモイル基を有していれば特に制限はないが、カルバモイル基又はカルバモイルアルキル基(好ましくは炭素数2~10、より好ましくは炭素数2~5のカルバモイルアルキル基、さらに好ましくはカルバモイルエチル又はカルバモイルメチル、さらに好ましくはカルバモイルメチル)が好ましく、なかでもカルバモイル基又はカルバモイルメチルが好ましい。 In the above formula (A), R 4 represents a substituent, and l1 represents an integer of 1 to 4. When l1 is 1, R 4 is a group having a carbamoyl group (—C (═O) NH 2 ). When l1 is 2 to 4, it is preferable that at least one of R 4 is a group having a carbamoyl group, and one or two of R 4 is a group having a carbamoyl group. When R 4 is a substituent that does not have a carbamoyl group, specific examples of this substituent include the substituent group Z described later, and among them, an alkyl group (more preferably having 1 to 10 carbon atoms, more preferably An alkyl group having 1 to 5 carbon atoms, more preferably ethyl or methyl), a halogen atom, an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms), or an aromatic group (preferably Is an aromatic group having 3 to 20 carbon atoms, more preferably an aromatic heterocyclic group having 3 to 20 carbon atoms (preferably containing a nitrogen atom as a ring constituent atom), and further preferably an aromatic hetero group having 4 to 15 carbon atoms. A ring group (preferably containing a nitrogen atom as a ring constituent atom) is preferred.
In the present specification, the “group having a carbamoyl group” is not particularly limited as long as it has a carbamoyl group. However, the carbamoyl group or carbamoylalkyl group (preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms) is preferable. Carbamoylalkyl group, more preferably carbamoylethyl or carbamoylmethyl, more preferably carbamoylmethyl), among which carbamoyl group or carbamoylmethyl is preferable.
上記式(A)で表される繰り返し単位は、下記式(a)で表される繰り返し単位であることが好ましい。
The repeating unit represented by the above formula (A) is preferably a repeating unit represented by the following formula (a).
式(a)中、Rは上記式(A)におけるRと同義であり、好ましい形態も同じである。R4aは水素原子であるか、又はカルバモイル基を有さない置換基を示す。このカルバモイル基を有さない置換基の具体例としては、後記置換基群Zが挙げられ、なかでもアルキル基(より好ましくは炭素数1~10、さらに好ましくは炭素数1~5のアルキル基、さらに好ましくはエチル又はメチル)、ハロゲン原子、アルコキシ基(好ましくは炭素数1~10、より好ましくは炭素数1~5のアルコキシ基)、又は芳香族基(好ましくは炭素数3~20の芳香族基、より好ましくは炭素数3~20の芳香族複素環基(好ましくは環構成原子に窒素原子を含む)、さらに好ましくは炭素数4~15の芳香族複素環基(好ましくは環構成原子に窒素原子を含む))が好ましい。なかでも、R4aのすべてが水素原子である形態、R4aのすべてがハロゲン原子である形態、カルバモイル基に対してオルト位に位置する2つのR4aが水素原子であり、パラ位に位置するR4aがアルキル基(より好ましくは炭素数1~10、さらに好ましくは炭素数1~5のアルキル基、さらに好ましくはエチル又はメチル)、アルコキシ基(好ましくは炭素数1~10、より好ましくは炭素数1~5のアルコキシ基)、又は芳香族基(好ましくは炭素数3~20の芳香族基、より好ましくは炭素数3~20の芳香族複素環基(好ましくは環構成原子に窒素原子を含む)、さらに好ましくは炭素数4~15の芳香族複素環基(好ましくは環構成原子に窒素原子を含む))である形態、カルバモイル基に対してオルト位に位置するR4aのうち1つが水素原子であり、残る2つのR4aがアルコキシ基(好ましくは炭素数1~10、より好ましくは炭素数1~5のアルコキシ基)、又は芳香族基(好ましくは炭素数3~20の芳香族基、より好ましくは炭素数3~20の芳香族複素環基(好ましくは環構成原子に窒素原子を含む)、さらに好ましくは炭素数4~15の芳香族複素環基(好ましくは環構成原子に窒素原子を含む))である形態が好ましい。
In formula (a), R has the same meaning as R in formula (A), and the preferred form is also the same. R 4a is a hydrogen atom or a substituent having no carbamoyl group. Specific examples of the substituent having no carbamoyl group include the substituent group Z described below, and among them, an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, More preferably ethyl or methyl), a halogen atom, an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms), or an aromatic group (preferably an aromatic group having 3 to 20 carbon atoms). Group, more preferably an aromatic heterocyclic group having 3 to 20 carbon atoms (preferably including a nitrogen atom as a ring constituent atom), further preferably an aromatic heterocyclic group having 4 to 15 carbon atoms (preferably including a ring constituent atom). Nitrogen atoms are preferred)). Among them, a form in which all of R 4a are hydrogen atoms, a form in which all of R 4a are halogen atoms, and two R 4a located in the ortho position relative to the carbamoyl group are hydrogen atoms and are located in the para position. R 4a is an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, more preferably ethyl or methyl), an alkoxy group (preferably 1 to 10 carbon atoms, more preferably a carbon atom). An alkoxy group having 1 to 5 carbon atoms, or an aromatic group (preferably an aromatic group having 3 to 20 carbon atoms, more preferably an aromatic heterocyclic group having 3 to 20 carbon atoms (preferably a nitrogen atom as a ring constituent atom). including), still preferably located ortho to it form, a carbamoyl group which aromatic Hajime Tamaki having 4 to 15 carbon atoms (preferably containing a nitrogen atom in the ring constituting atom)) R one of a are hydrogen atom, the remaining two R 4a is an alkoxy group (preferably having a carbon number of 1 to 10, more preferably an alkoxy group having 1 to 5 carbon atoms), or an aromatic group (preferably 3 carbon atoms An aromatic heterocyclic group having 20 to 20 carbon atoms, more preferably an aromatic heterocyclic group having 3 to 20 carbon atoms (preferably containing a nitrogen atom in the ring constituent atoms), more preferably an aromatic heterocyclic group having 4 to 15 carbon atoms (preferably Is preferably a form in which a ring atom contains a nitrogen atom))).
式(B)中、Rは上記式(A)におけるRと同義である。R5及びR6は置換基を示す。m1及びn1はいずれも0~4の整数であるが、m1とn1が共に0であることはない。
In formula (B), R has the same meaning as R in formula (A). R 5 and R 6 represent a substituent. m1 and n1 are both integers from 0 to 4, but neither m1 nor n1 is 0.
m1が0の場合、R6の少なくとも1つはカルバモイル基を有する基である。すなわち、m1が0の場合において、n1が1の場合にはR6はカルバモイル基を有する基であり、n1が2の場合にはR6の1つ又は2つがカルバモイル基を有する基であり、n1が3の場合には、R6の1つ、2つ又は3つがカルバモイル基を有する基であり、n1が4の場合には、R6の1つ、2つ、3つ又は4つがカルバモイル基を有する基である。m1が0の場合、n1が1であることが好ましい。
When m1 is 0, at least one of R 6 is a group having a carbamoyl group. That is, when m1 is 0, when n1 is 1, R 6 is a group having a carbamoyl group, and when n1 is 2, one or two of R 6 is a group having a carbamoyl group, When n1 is 3, one, two or three of R 6 are groups having a carbamoyl group, and when n1 is 4, one, two, three or four of R 6 are carbamoyl. A group having a group. When m1 is 0, n1 is preferably 1.
n1が0の場合、R5の少なくとも1つはカルバモイル基を有する基である。すなわち、n1が0の場合において、m1が1の場合にはR5はカルバモイル基を有する基であり、m1が2の場合にはR5の1つ又は2つがカルバモイル基を有する基であり、m1が3の場合には、R5の1つ、2つ又は3つがカルバモイル基を有する基であり、m1が4の場合には、R5の1つ、2つ、3つ又は4つがカルバモイル基を有する基である。n1が0の場合、m1が1であることが好ましい。
m1とn1が共に1以上である場合、R5及びR6の少なくとも1つがカルバモイル基を有する基である。ここで、「R5及びR6の少なくとも1つがカルバモイル基を有する基である」とは、R5の少なくとも1つがカルバモイル基を有する基であってR6のすべてがカルバモイル基を有さない態様、及びR6の少なくとも1つがカルバモイル基を有する基であってR5のすべてがカルバモイル基を有さない態様を含む意味に用いる。m1とn1が共に1以上である場合、R5の少なくとも1つがカルバモイル基を有する基であり、且つ、R6の少なくとも1つがカルバモイル基を有する基であることが好ましい。なかでも、m1とn1が共に1であり、且つ、R5とR6が共にカルバモイル基を有する基であることが好ましい。 When n1 is 0, at least one of R 5 is a group having a carbamoyl group. That is, when n1 is 0, when m1 is 1, R 5 is a group having a carbamoyl group, and when m1 is 2, one or two of R 5 is a group having a carbamoyl group, When m1 is 3, one, two or three of R 5 are groups having a carbamoyl group, and when m1 is 4, one, two, three or four of R 5 are carbamoyl. A group having a group. When n1 is 0, m1 is preferably 1.
When m1 and n1 are both 1 or more, at least one of R 5 and R 6 is a group having a carbamoyl group. Here, “at least one of R 5 and R 6 is a group having a carbamoyl group” means that at least one of R 5 is a group having a carbamoyl group and not all of R 6 have a carbamoyl group , And at least one of R 6 is a group having a carbamoyl group, and all of R 5 are used to include an embodiment having no carbamoyl group. When m1 and n1 are both 1 or more, it is preferable that at least one of R 5 is a group having a carbamoyl group and at least one of R 6 is a group having a carbamoyl group. Among these, it is preferable that m1 and n1 are both 1, and R 5 and R 6 are both groups having a carbamoyl group.
m1とn1が共に1以上である場合、R5及びR6の少なくとも1つがカルバモイル基を有する基である。ここで、「R5及びR6の少なくとも1つがカルバモイル基を有する基である」とは、R5の少なくとも1つがカルバモイル基を有する基であってR6のすべてがカルバモイル基を有さない態様、及びR6の少なくとも1つがカルバモイル基を有する基であってR5のすべてがカルバモイル基を有さない態様を含む意味に用いる。m1とn1が共に1以上である場合、R5の少なくとも1つがカルバモイル基を有する基であり、且つ、R6の少なくとも1つがカルバモイル基を有する基であることが好ましい。なかでも、m1とn1が共に1であり、且つ、R5とR6が共にカルバモイル基を有する基であることが好ましい。 When n1 is 0, at least one of R 5 is a group having a carbamoyl group. That is, when n1 is 0, when m1 is 1, R 5 is a group having a carbamoyl group, and when m1 is 2, one or two of R 5 is a group having a carbamoyl group, When m1 is 3, one, two or three of R 5 are groups having a carbamoyl group, and when m1 is 4, one, two, three or four of R 5 are carbamoyl. A group having a group. When n1 is 0, m1 is preferably 1.
When m1 and n1 are both 1 or more, at least one of R 5 and R 6 is a group having a carbamoyl group. Here, “at least one of R 5 and R 6 is a group having a carbamoyl group” means that at least one of R 5 is a group having a carbamoyl group and not all of R 6 have a carbamoyl group , And at least one of R 6 is a group having a carbamoyl group, and all of R 5 are used to include an embodiment having no carbamoyl group. When m1 and n1 are both 1 or more, it is preferable that at least one of R 5 is a group having a carbamoyl group and at least one of R 6 is a group having a carbamoyl group. Among these, it is preferable that m1 and n1 are both 1, and R 5 and R 6 are both groups having a carbamoyl group.
R5及びR6がカルバモイル基を有する基でない場合、R5及びR6が採用しうる置換基の具体例としては、後記置換基群Zが挙げられ、なかでもアルキル基(より好ましくは炭素数1~10、さらに好ましくは炭素数1~5のアルキル基、さらに好ましくはエチル又はメチル)又はハロゲン原子が好ましい。
When R 5 and R 6 are not a group having a carbamoyl group, specific examples of the substituent that can be adopted by R 5 and R 6 include the substituent group Z described later, and among them, an alkyl group (more preferably a carbon number). An alkyl group having 1 to 10, more preferably 1 to 5 carbon atoms, more preferably ethyl or methyl) or a halogen atom is preferable.
上記式(B)中、X4は上記式(I-1)におけるX1と同義であり、好ましい形態も同じである。
本発明に用いるポリイミド化合物は、下記式(C)又は(D)で表される繰り返し単位を含んでもよい。 In the above formula (B), X 4 has the same meaning as X 1 in the above formula (I-1), and the preferred form is also the same.
The polyimide compound used in the present invention may contain a repeating unit represented by the following formula (C) or (D).
本発明に用いるポリイミド化合物は、下記式(C)又は(D)で表される繰り返し単位を含んでもよい。 In the above formula (B), X 4 has the same meaning as X 1 in the above formula (I-1), and the preferred form is also the same.
The polyimide compound used in the present invention may contain a repeating unit represented by the following formula (C) or (D).
上記式(C)及び(D)中、Rは式(A)中のRと同義であり、好ましい形態も同じである。R7~R9は置換基を示す。置換基としては、後述する置換基群Zが挙げられる。
上記式(C)において、R7はアルキル基、ハロゲン原子、カルボキシ基又はヒドロキシ基であることが好ましい。R7の数を示すp2は0~4の整数であるが、1~4であることが好ましく、2~4であることがより好ましく、より好ましくは3又は4である。R7がアルキルである場合、このアルキル基の炭素数は1~10であることが好ましく、1~5であることがより好ましく、1~3であることがさらに好ましく、さらに好ましくはメチル、エチル又はトリフルオロメチルである。
式(C)において、ジアミン成分(すなわちR7を有しうるフェニレン基)のポリイミド化合物に組み込まれるための2つの連結部位は、互いにメタ位又はパラ位に位置することが好ましい。
本発明において、上記式(C)で表される構造には、上記式(A)で表される構造は含まれないものとする(すなわち、上記式(C)で表される構造はカルバモイル基を有さない)。 In said formula (C) and (D), R is synonymous with R in formula (A), and its preferable form is also the same. R 7 to R 9 represent a substituent. Examples of the substituent include a substituent group Z described later.
In the above formula (C), R 7 is preferably an alkyl group, a halogen atom, a carboxy group or a hydroxy group. P2 representing the number of R 7 is an integer of 0 to 4, preferably 1 to 4, more preferably 2 to 4, more preferably 3 or 4. When R 7 is alkyl, the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, still more preferably 1 to 3, and still more preferably methyl, ethyl Or trifluoromethyl.
In the formula (C), it is preferable that the two linking sites for incorporation into the polyimide compound of the diamine component (that is, the phenylene group that may have R 7 ) are located at the meta position or the para position.
In the present invention, the structure represented by the formula (C) does not include the structure represented by the formula (A) (that is, the structure represented by the formula (C) is a carbamoyl group. Do not have).
上記式(C)において、R7はアルキル基、ハロゲン原子、カルボキシ基又はヒドロキシ基であることが好ましい。R7の数を示すp2は0~4の整数であるが、1~4であることが好ましく、2~4であることがより好ましく、より好ましくは3又は4である。R7がアルキルである場合、このアルキル基の炭素数は1~10であることが好ましく、1~5であることがより好ましく、1~3であることがさらに好ましく、さらに好ましくはメチル、エチル又はトリフルオロメチルである。
式(C)において、ジアミン成分(すなわちR7を有しうるフェニレン基)のポリイミド化合物に組み込まれるための2つの連結部位は、互いにメタ位又はパラ位に位置することが好ましい。
本発明において、上記式(C)で表される構造には、上記式(A)で表される構造は含まれないものとする(すなわち、上記式(C)で表される構造はカルバモイル基を有さない)。 In said formula (C) and (D), R is synonymous with R in formula (A), and its preferable form is also the same. R 7 to R 9 represent a substituent. Examples of the substituent include a substituent group Z described later.
In the above formula (C), R 7 is preferably an alkyl group, a halogen atom, a carboxy group or a hydroxy group. P2 representing the number of R 7 is an integer of 0 to 4, preferably 1 to 4, more preferably 2 to 4, more preferably 3 or 4. When R 7 is alkyl, the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, still more preferably 1 to 3, and still more preferably methyl, ethyl Or trifluoromethyl.
In the formula (C), it is preferable that the two linking sites for incorporation into the polyimide compound of the diamine component (that is, the phenylene group that may have R 7 ) are located at the meta position or the para position.
In the present invention, the structure represented by the formula (C) does not include the structure represented by the formula (A) (that is, the structure represented by the formula (C) is a carbamoyl group. Do not have).
上記式(D)において、R8及びR9はアルキル基もしくはハロゲン原子を示すか、又は互いに連結してX4と共に環を形成する基であることが好ましい。また、2つのR8が連結して環を形成している形態や、2つのR9が連結して環を形成している形態も好ましい。R8とR9が連結した構造に特に制限はないが、単結合、-O-又は-S-が好ましい。R8及びR9の数を示すq2及びr2は0~4の整数であり、0~3であることが好ましく、0~2であることがより好ましい。R8及びR9がアルキル基である場合、このアルキル基の炭素数は1~10であることが好ましく、1~5であることがより好ましく、1~3であることがさらに好ましく、さらに好ましくはメチル、エチル又はトリフルオロメチルである。
In the above formula (D), R 8 and R 9 preferably represent an alkyl group or a halogen atom, or are groups that are linked together to form a ring together with X 4 . Further, a form in which two R 8 are connected to form a ring and a form in which two R 9 are connected to form a ring are also preferred. The structure in which R 8 and R 9 are linked is not particularly limited, but a single bond, —O— or —S— is preferable. Q2 and r2 representing the numbers of R 8 and R 9 are integers of 0 to 4, preferably 0 to 3, and more preferably 0 to 2. When R 8 and R 9 are alkyl groups, the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and still more preferably Is methyl, ethyl or trifluoromethyl.
上記式(D)中、X4は上記式(I-1)におけるX1と同義であり、好ましい形態も同じである。
In the above formula (D), X 4 has the same meaning as X 1 in the above formula (I-1), and the preferred form is also the same.
本発明において、上記式(D)で表される構造には、上記式(B)で表される構造は含まれないものとする(すなわち、上記式(D)で表される構造はカルバモイル基を有さな)。
In the present invention, the structure represented by the formula (D) does not include the structure represented by the formula (B) (that is, the structure represented by the formula (D) is a carbamoyl group. )
置換基群Z:
アルキル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~10のアルキル基であり、例えばメチル、エチル、iso-プロピル、tert-ブチル、n-オクチル、n-デシル、n-ヘキサデシル)、シクロアルキル基(好ましくは炭素数3~30、より好ましくは炭素数3~20、特に好ましくは炭素数3~10のシクロアルキル基であり、例えばシクロプロピル、シクロペンチル、シクロヘキシルなどが挙げられる。)、アルケニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10のアルケニル基であり、例えばビニル、アリル、2-ブテニル、3-ペンテニルなどが挙げられる。)、アルキニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10のアルキニル基であり、例えばプロパルギル、3-ペンチニルなどが挙げられる。)、アリール基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12のアリール基であり、例えばフェニル、p-メチルフェニル、ナフチル、アントラニルなどが挙げられる。)、アミノ基(アミノ基、アルキルアミノ基、アリールアミノ基、ヘテロ環アミノ基を含み、好ましくは炭素数0~30、より好ましくは炭素数0~20、特に好ましくは炭素数0~10のアミノ基であり、例えばアミノ、メチルアミノ、ジメチルアミノ、ジエチルアミノ、ジベンジルアミノ、ジフェニルアミノ、ジトリルアミノなどが挙げられる。)、アルコキシ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~10のアルコキシ基であり、例えばメトキシ、エトキシ、ブトキシ、2-エチルヘキシロキシなどが挙げられる。)、アリールオキシ基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12のアリールオキシ基であり、例えばフェニルオキシ、1-ナフチルオキシ、2-ナフチルオキシなどが挙げられる。)、ヘテロ環オキシ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12のヘテロ環オキシ基であり、例えばピリジルオキシ、ピラジルオキシ、ピリミジルオキシ、キノリルオキシなどが挙げられる。)、 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.), alkynyl group (preferably having 2 to 30 carbon atoms, more preferably An alkynyl group having 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as propargyl and 3-pentynyl, and an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 carbon atoms). To 20 and particularly preferably 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) 30, more preferably 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 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyloxy, 1-naphthyloxy, 2-naphthyloxy, and the like. 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. ),
アルキル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~10のアルキル基であり、例えばメチル、エチル、iso-プロピル、tert-ブチル、n-オクチル、n-デシル、n-ヘキサデシル)、シクロアルキル基(好ましくは炭素数3~30、より好ましくは炭素数3~20、特に好ましくは炭素数3~10のシクロアルキル基であり、例えばシクロプロピル、シクロペンチル、シクロヘキシルなどが挙げられる。)、アルケニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10のアルケニル基であり、例えばビニル、アリル、2-ブテニル、3-ペンテニルなどが挙げられる。)、アルキニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10のアルキニル基であり、例えばプロパルギル、3-ペンチニルなどが挙げられる。)、アリール基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12のアリール基であり、例えばフェニル、p-メチルフェニル、ナフチル、アントラニルなどが挙げられる。)、アミノ基(アミノ基、アルキルアミノ基、アリールアミノ基、ヘテロ環アミノ基を含み、好ましくは炭素数0~30、より好ましくは炭素数0~20、特に好ましくは炭素数0~10のアミノ基であり、例えばアミノ、メチルアミノ、ジメチルアミノ、ジエチルアミノ、ジベンジルアミノ、ジフェニルアミノ、ジトリルアミノなどが挙げられる。)、アルコキシ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~10のアルコキシ基であり、例えばメトキシ、エトキシ、ブトキシ、2-エチルヘキシロキシなどが挙げられる。)、アリールオキシ基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12のアリールオキシ基であり、例えばフェニルオキシ、1-ナフチルオキシ、2-ナフチルオキシなどが挙げられる。)、ヘテロ環オキシ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12のヘテロ環オキシ基であり、例えばピリジルオキシ、ピラジルオキシ、ピリミジルオキシ、キノリルオキシなどが挙げられる。)、 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.), alkynyl group (preferably having 2 to 30 carbon atoms, more preferably An alkynyl group having 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as propargyl and 3-pentynyl, and an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 carbon atoms). To 20 and particularly preferably 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) 30, more preferably 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 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyloxy, 1-naphthyloxy, 2-naphthyloxy, and the like. 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. ),
アシル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12のアシル基であり、例えばアセチル、ベンゾイル、ホルミル、ピバロイルなどが挙げられる。)、アルコキシカルボニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~12のアルコキシカルボニル基であり、例えばメトキシカルボニル、エトキシカルボニルなどが挙げられる。)、アリールオキシカルボニル基(好ましくは炭素数7~30、より好ましくは炭素数7~20、特に好ましくは炭素数7~12のアリールオキシカルボニル基であり、例えばフェニルオキシカルボニルなどが挙げられる。)、アシルオキシ基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10のアシルオキシ基であり、例えばアセトキシ、ベンゾイルオキシなどが挙げられる。)、アシルアミノ基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10のアシルアミノ基であり、例えばアセチルアミノ、ベンゾイルアミノなどが挙げられる。)、
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 acetoxy, benzoyloxy, etc.), an acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably carbon atoms). An acylamino group of 2 to 10, for example, acetylamino, benzoylamino and the like),
アルコキシカルボニルアミノ基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~12のアルコキシカルボニルアミノ基であり、例えばメトキシカルボニルアミノなどが挙げられる。)、アリールオキシカルボニルアミノ基(好ましくは炭素数7~30、より好ましくは炭素数7~20、特に好ましくは炭素数7~12のアリールオキシカルボニルアミノ基であり、例えばフェニルオキシカルボニルアミノなどが挙げられる。)、スルホニルアミノ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばメタンスルホニルアミノ、ベンゼンスルホニルアミノなどが挙げられる。)、スルファモイル基(好ましくは炭素数0~30、より好ましくは炭素数0~20、特に好ましくは炭素数0~12のスルファモイル基であり、例えばスルファモイル、メチルスルファモイル、ジメチルスルファモイル、フェニルスルファモイルなどが挙げられる。)、
An 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 sulfamoyl group having 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and the like phenylsulfamoyl.),
アルキルチオ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12のアルキルチオ基であり、例えばメチルチオ、エチルチオなどが挙げられる。)、アリールチオ基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12のアリールチオ基であり、例えばフェニルチオなどが挙げられる。)、ヘテロ環チオ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12のヘテロ環チオ基であり、例えばピリジルチオ、2-ベンズイミゾリルチオ、2-ベンズオキサゾリルチオ、2-ベンズチアゾリルチオなどが挙げられる。)、
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 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, and a heterocyclic thio group (preferably having 1 to 30 carbon atoms). More preferably a heterocyclic thio group having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like. ),
スルホニル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12のスルホニル基であり、例えばメシル、トシルなどが挙げられる。)、スルフィニル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12のスルフィニル基であり、例えばメタンスルフィニル、ベンゼンスルフィニルなどが挙げられる。)、ウレイド基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12のウレイド基であり、例えばウレイド、メチルウレイド、フェニルウレイドなどが挙げられる。)、リン酸アミド基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12のリン酸アミド基であり、例えばジエチルリン酸アミド、フェニルリン酸アミドなどが挙げられる。)、ヒドロキシ基、メルカプト基、ハロゲン原子(例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子であり、より好ましくはフッ素原子が挙げられる)、
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 atoms, particularly preferably 1 to 12 carbon atoms, For example, diethyl phosphoric acid amide, phenylphosphoric acid amide, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, more preferably fluorine atom) ,
シアノ基、スルホ基、カルボキシ基、オキソ基、ニトロ基、ヒドロキサム酸基、スルフィノ基、ヒドラジノ基、イミノ基、ヘテロ環基(好ましくは3~7員環のヘテロ環基で、芳香族ヘテロ環でも芳香族でないヘテロ環であってもよく、ヘテロ環を構成するヘテロ原子としては、窒素原子、酸素原子、硫黄原子が挙げられる。炭素数は0~30が好ましく、より好ましくは炭素数1~12のヘテロ環基であり、具体的には例えばイミダゾリル、ピリジル、キノリル、フリル、チエニル、ピペリジル、モルホリノ、ベンズオキサゾリル、ベンズイミダゾリル、ベンズチアゾリル、カルバゾリル、アゼピニルなどが挙げられる。)、シリル基(好ましくは炭素数3~40、より好ましくは炭素数3~30、特に好ましくは炭素数3~24のシリル基であり、例えばトリメチルシリル、トリフェニルシリルなどが挙げられる。)、シリルオキシ基(好ましくは炭素数3~40、より好ましくは炭素数3~30、特に好ましくは炭素数3~24のシリルオキシ基であり、例えばトリメチルシリルオキシ、トリフェニルシリルオキシなどが挙げられる。)などが挙げられる。これらの置換基は、更に上記置換基群Zより選択されるいずれか1つ以上の置換基により置換されてもよい。
なお、本発明において、1つの構造部位に複数の置換基があるときには、それらの置換基は互いに連結して環を形成していたり、上記構造部位の一部又は全部と縮環して芳香族環もしくは不飽和複素環を形成していたりしてもよい。 A cyano group, a sulfo group, a carboxy group, an oxo group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, a heterocyclic group (preferably a 3- to 7-membered heterocyclic group, even an aromatic heterocyclic ring 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. Specific examples thereof include imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl, azepinyl and the like, and a silyl group (preferably). Is a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms. For example, trimethylsilyl, triphenylsilyl, etc.), a silyloxy group (preferably a silyloxy group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, Examples thereof include trimethylsilyloxy and triphenylsilyloxy). These substituents may be further substituted with any one or more substituents selected from the above substituent group Z.
In the present invention, 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.
なお、本発明において、1つの構造部位に複数の置換基があるときには、それらの置換基は互いに連結して環を形成していたり、上記構造部位の一部又は全部と縮環して芳香族環もしくは不飽和複素環を形成していたりしてもよい。 A cyano group, a sulfo group, a carboxy group, an oxo group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, a heterocyclic group (preferably a 3- to 7-membered heterocyclic group, even an aromatic heterocyclic ring 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. Specific examples thereof include imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl, azepinyl and the like, and a silyl group (preferably). Is a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms. For example, trimethylsilyl, triphenylsilyl, etc.), a silyloxy group (preferably a silyloxy group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, Examples thereof include trimethylsilyloxy and triphenylsilyloxy). These substituents may be further substituted with any one or more substituents selected from the above substituent group Z.
In the present invention, 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.
化合物ないし置換基等がアルキル基、アルケニル基等を含むとき、これらは直鎖状でも分岐状でもよく、置換されていても無置換でもよい。またアリール基、ヘテロ環基等を含むとき、それらは単環でも縮環でもよく、置換されていても無置換でもよい。
本明細書において、単に置換基としてしか記載されていないものは、特に断わりのない限りこの置換基群Zを参照するものであり、また、各々の基の名称が記載されているだけのとき(例えば、「アルキル基」と記載されているだけのとき)は、この置換基群Zの対応する基における好ましい範囲、具体例が適用される。 When a compound or a substituent includes an alkyl group, an alkenyl group, etc., these may be linear or branched, and may be substituted or unsubstituted. When an aryl group, a heterocyclic group, or the like is included, they may be monocyclic or condensed, and may be substituted or unsubstituted.
In the present specification, what is merely described as a substituent refers to this substituent group Z unless otherwise specified, and when the name of each group is only described ( For example, when only “alkyl group” is described), preferred ranges and specific examples of the corresponding group in the substituent group Z are applied.
本明細書において、単に置換基としてしか記載されていないものは、特に断わりのない限りこの置換基群Zを参照するものであり、また、各々の基の名称が記載されているだけのとき(例えば、「アルキル基」と記載されているだけのとき)は、この置換基群Zの対応する基における好ましい範囲、具体例が適用される。 When a compound or a substituent includes an alkyl group, an alkenyl group, etc., these may be linear or branched, and may be substituted or unsubstituted. When an aryl group, a heterocyclic group, or the like is included, they may be monocyclic or condensed, and may be substituted or unsubstituted.
In the present specification, what is merely described as a substituent refers to this substituent group Z unless otherwise specified, and when the name of each group is only described ( For example, when only “alkyl group” is described), preferred ranges and specific examples of the corresponding group in the substituent group Z are applied.
本発明に用いるポリイミド化合物が上記式(A)又は(B)で表される繰り返し単位を含む場合において、ポリイミド化合物中の上記式(A)又は(B)で表される繰り返し単位の含有量に特に制限はなく、ガス分離の目的(回収率、純度など)に応じガス透過性とガス分離選択性を考慮して適宜に調整される。
本発明に用いるポリイミド化合物は、式(A)、(B)、(C)及び(D)の各式で表される繰り返し単位の総和(100モル%)に対して、式(A)又は(B)で表される繰り返し単位の総量が5モル%以上であることが好ましく、10~90モル%であることがより好ましく、20~80モル%であることがさらに好ましく、30~70モル%であることがさらに好ましい。式(A)又は(B)の繰り返し単位が有するカルバモイル基の数が多ければ、式(A)又は(B)で表される繰り返し単位の量をある程度減らしても、ポリイミド化合物中のカルバモイル基の量を本発明で規定する範囲内とすることができ、所望の効果を得ることができる。本発明に用いるポリイミド化合物は、繰り返し単位のすべてが式(A)、(B)、(C)又は(D)で表される構造であることが好ましい。 In the case where the polyimide compound used in the present invention contains a repeating unit represented by the above formula (A) or (B), the content of the repeating unit represented by the above formula (A) or (B) in the polyimide compound There is no particular limitation, and it is appropriately adjusted according to the purpose of gas separation (recovery rate, purity, etc.) in consideration of gas permeability and gas separation selectivity.
The polyimide compound used in the present invention has the formula (A) or (R) with respect to the sum (100 mol%) of the repeating units represented by the formulas (A), (B), (C) and (D). The total amount of the repeating units represented by B) is preferably 5 mol% or more, more preferably 10 to 90 mol%, further preferably 20 to 80 mol%, more preferably 30 to 70 mol%. More preferably. If the repeating unit of formula (A) or (B) has a large number of carbamoyl groups, even if the amount of the repeating unit represented by formula (A) or (B) is reduced to some extent, the carbamoyl group in the polyimide compound The amount can be within the range defined by the present invention, and a desired effect can be obtained. The polyimide compound used in the present invention preferably has a structure in which all of the repeating units are represented by the formula (A), (B), (C) or (D).
本発明に用いるポリイミド化合物は、式(A)、(B)、(C)及び(D)の各式で表される繰り返し単位の総和(100モル%)に対して、式(A)又は(B)で表される繰り返し単位の総量が5モル%以上であることが好ましく、10~90モル%であることがより好ましく、20~80モル%であることがさらに好ましく、30~70モル%であることがさらに好ましい。式(A)又は(B)の繰り返し単位が有するカルバモイル基の数が多ければ、式(A)又は(B)で表される繰り返し単位の量をある程度減らしても、ポリイミド化合物中のカルバモイル基の量を本発明で規定する範囲内とすることができ、所望の効果を得ることができる。本発明に用いるポリイミド化合物は、繰り返し単位のすべてが式(A)、(B)、(C)又は(D)で表される構造であることが好ましい。 In the case where the polyimide compound used in the present invention contains a repeating unit represented by the above formula (A) or (B), the content of the repeating unit represented by the above formula (A) or (B) in the polyimide compound There is no particular limitation, and it is appropriately adjusted according to the purpose of gas separation (recovery rate, purity, etc.) in consideration of gas permeability and gas separation selectivity.
The polyimide compound used in the present invention has the formula (A) or (R) with respect to the sum (100 mol%) of the repeating units represented by the formulas (A), (B), (C) and (D). The total amount of the repeating units represented by B) is preferably 5 mol% or more, more preferably 10 to 90 mol%, further preferably 20 to 80 mol%, more preferably 30 to 70 mol%. More preferably. If the repeating unit of formula (A) or (B) has a large number of carbamoyl groups, even if the amount of the repeating unit represented by formula (A) or (B) is reduced to some extent, the carbamoyl group in the polyimide compound The amount can be within the range defined by the present invention, and a desired effect can be obtained. The polyimide compound used in the present invention preferably has a structure in which all of the repeating units are represented by the formula (A), (B), (C) or (D).
本発明に用いるポリイミド化合物の分子量は、重量平均分子量として10,000~1,000,000であることが好ましく、より好ましくは15,000~500,000であり、さらに好ましくは20,000~300,000である。
The molecular weight of the polyimide compound 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 to 300. , 000.
本明細書において分子量及び分散度は特に断らない限りGPC(ゲルろ過クロマトグラフィー)法を用いて測定した値とし、分子量はポリスチレン換算の重量平均分子量とする。GPC法に用いるカラムに充填されているゲルは芳香族化合物を繰り返し単位に持つゲルが好ましく、例えばスチレン-ジビニルベンゼン共重合体からなるゲルが挙げられる。カラムは2~6本連結させて用いることが好ましい。用いる溶媒は、テトラヒドロフラン等のエーテル系溶媒、N-メチルピロリジノン等のアミド系溶媒が挙げられる。測定は、溶媒の流速が0.1~2mL/minの範囲で行うことが好ましく、0.5~1.5mL/minの範囲で行うことが最も好ましい。この範囲内で測定を行うことで、装置に負荷がかからず、さらに効率的に測定ができる。測定温度は10~50℃で行うことが好ましく、20~40℃で行うことが最も好ましい。なお、使用するカラム及びキャリアは測定対称となる高分子化合物の物性に応じて適宜選定することができる。
本発明に用いる、例えば式(A)または(B)で表される繰り返し単位を有するポリイミド化合物の末端基は、後述の合成方法、反応原料により定まり自明である。末端基は例えば、水素原子、カルボキシ基、アミノ基である。さらにキャッピングを行って末端基を置換してもよい。この場合、末端基としては、アリール基、ヘテロアリール基が挙げられる。 In the present specification, unless otherwise specified, 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. Examples of 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.
For example, the terminal group of the polyimide compound having a repeating unit represented by the formula (A) or (B) used in the present invention is determined by the synthesis method and reaction raw material described later, and is obvious. The terminal group is, for example, a hydrogen atom, a carboxy group, or an amino group. Further, the end group may be substituted by capping. In this case, examples of the terminal group include an aryl group and a heteroaryl group.
本発明に用いる、例えば式(A)または(B)で表される繰り返し単位を有するポリイミド化合物の末端基は、後述の合成方法、反応原料により定まり自明である。末端基は例えば、水素原子、カルボキシ基、アミノ基である。さらにキャッピングを行って末端基を置換してもよい。この場合、末端基としては、アリール基、ヘテロアリール基が挙げられる。 In the present specification, unless otherwise specified, 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. Examples of 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.
For example, the terminal group of the polyimide compound having a repeating unit represented by the formula (A) or (B) used in the present invention is determined by the synthesis method and reaction raw material described later, and is obvious. The terminal group is, for example, a hydrogen atom, a carboxy group, or an amino group. Further, the end group may be substituted by capping. In this case, examples of the terminal group include an aryl group and a heteroaryl group.
(ポリイミド化合物の合成)
本発明に用いるポリイミド化合物は、特定の2官能酸無水物(テトラカルボン酸二無水物)と特定のジアミンとを縮合重合させることで合成することができる。その方法としては一般的な書籍(例えば、今井淑夫、横田力男編著、「最新ポリイミド~基礎と応用~」、株式会社エヌ・ティー・エス、2010年8月25日、p.3~49、など)に記載の手法を適宜選択することができる。
本発明に用いるポリイミド化合物の合成において、原料として用いるテトラカルボン酸二無水物及びジアミン化合物のいずれか一方又は双方がカルバモイル基を有している。 (Synthesis of polyimide compounds)
The polyimide compound used in the present invention can be synthesized by condensation polymerization of a specific bifunctional acid anhydride (tetracarboxylic dianhydride) and a specific diamine. As a method for this, a general book (for example, edited by Ikuo Imai and Rikio Yokota, “Latest Polyimide: Fundamentals and Applications”, NTS Corporation, August 25, 2010, p. 3 to 49, Etc.) can be appropriately selected.
In the synthesis of the polyimide compound used in the present invention, one or both of a tetracarboxylic dianhydride and a diamine compound used as a raw material have a carbamoyl group.
本発明に用いるポリイミド化合物は、特定の2官能酸無水物(テトラカルボン酸二無水物)と特定のジアミンとを縮合重合させることで合成することができる。その方法としては一般的な書籍(例えば、今井淑夫、横田力男編著、「最新ポリイミド~基礎と応用~」、株式会社エヌ・ティー・エス、2010年8月25日、p.3~49、など)に記載の手法を適宜選択することができる。
本発明に用いるポリイミド化合物の合成において、原料として用いるテトラカルボン酸二無水物及びジアミン化合物のいずれか一方又は双方がカルバモイル基を有している。 (Synthesis of polyimide compounds)
The polyimide compound used in the present invention can be synthesized by condensation polymerization of a specific bifunctional acid anhydride (tetracarboxylic dianhydride) and a specific diamine. As a method for this, a general book (for example, edited by Ikuo Imai and Rikio Yokota, “Latest Polyimide: Fundamentals and Applications”, NTS Corporation, August 25, 2010, p. 3 to 49, Etc.) can be appropriately selected.
In the synthesis of the polyimide compound used in the present invention, one or both of a tetracarboxylic dianhydride and a diamine compound used as a raw material have a carbamoyl group.
本発明に用いうるポリイミド化合物の合成において、原料とするテトラカルボン酸二無水物の少なくとも1種は、下記式(IV)で表されることが好ましい。原料とするテトラカルボン酸二無水物のすべてが下記式(IV)で表されることが好ましい。
In the synthesis of the polyimide compound that can be used in the present invention, at least one tetracarboxylic dianhydride used as a raw material is preferably represented by the following formula (IV). It is preferable that all tetracarboxylic dianhydrides used as raw materials are represented by the following formula (IV).
式(IV)中、Rは上記式(A)におけるRと同義である。
In the formula (IV), R has the same meaning as R in the above formula (A).
本発明に用いうるテトラカルボン酸二無水物の具体例としては、例えば以下に示すものが挙げられる。
Specific examples of tetracarboxylic dianhydrides that can be used in the present invention include the following.
本発明に用いるポリイミド化合物の合成において、原料とするジアミン化合物の少なくとも1種は、下記式(A-1)又は(B-1)で表されることが好ましい。
In the synthesis of the polyimide compound used in the present invention, at least one diamine compound used as a raw material is preferably represented by the following formula (A-1) or (B-1).
式(A-1)中、R4及びl1は、それぞれ上記式(A)におけるR4及びl1と同義であり、好ましい形態も同じである。
In formula (A-1), R 4 and 11 are the same as R 4 and 11 in formula (A), respectively, and the preferred forms are also the same.
上記式(A-1)で表されるジアミン化合物は、下記式(a-1)で表される化合物が好ましい。
The diamine compound represented by the above formula (A-1) is preferably a compound represented by the following formula (a-1).
式(a-1)中、R4aは、上記式(a)におけるR4aと同義であり、好ましい形態も同じである。
In formula (a-1), R 4a has the same meaning as R 4a in formula (a), and the preferred form is also the same.
式(B-1)中、R5、R6、X4、m1及びn1は、それぞれ上記式(B)におけるR5、R6、X4、m1及びn1と同義であり、好ましい形態も同じである。
Wherein (B-1), R 5 , R 6, X 4, m1 and n1 are respectively synonymous with R 5, R 6, X 4 , m1 and n1 in the formula (B), preferred forms are also the same It is.
式(A-1)又は(B-1)で表されるジアミンの具体例としては、例えば、下記に示すものを挙げることができる。
Specific examples of the diamine represented by the formula (A-1) or (B-1) include those shown below.
また、本発明に用いうるポリイミド化合物の合成において、原料とするジアミン化合物として、上記式(A-1)又は(B-1)で表されるジアミンに加えて、下記式(C-1)又は(D-1)で表されるジアミンを用いてもよい。
In the synthesis of the polyimide compound that can be used in the present invention, as a diamine compound as a raw material, in addition to the diamine represented by the above formula (A-1) or (B-1), the following formula (C-1) or A diamine represented by (D-1) may be used.
式(C-1)中、R7及びp2は、それぞれ上記式(C)におけるR7及びp2と同義であり、好ましい形態の同じである。式(C-1)で表されるジアミンには、式(A-1)で表されるジアミンは含まれない。
In formula (C-1), R 7 and p2 have the same meanings as R 7 and p2 in formula (C), respectively, and have the same preferred forms. The diamine represented by the formula (C-1) does not include the diamine represented by the formula (A-1).
式(D-1)中、R8、R9、X4、q2及びr2は、それぞれ上記式(D)におけるR8、R9、X4、q2及びr2と同義であり、好ましい形態も同じである。式(D-1)で表されるジアミンには、式(B-1)で表されるジアミンは含まれない。
Wherein (D-1), R 8 , R 9, X 4, q2 and r2 are respectively synonymous with R 8, R 9, X 4 , q2 and r2 in formula (D), preferred embodiments are also the same It is. The diamine represented by the formula (D-1) does not include the diamine represented by the formula (B-1).
式(C-1)又は(D-1)で表されるジアミンとして、例えば下記に示すものを用いることができる。
As the diamine represented by the formula (C-1) or (D-1), for example, the following can be used.
本発明に用いるポリイミド化合物は、ブロック共重合体、ランダム共重合体、グラフト共重合体のいずれでもよい。
The polyimide compound used in the present invention may be any of a block copolymer, a random copolymer and a graft copolymer.
本発明に用いるポリイミド化合物は、上記各原料を溶媒中に混合して、通常の方法で縮合重合させて得ることができる。
上記溶媒としては、特に限定されるものではないが、酢酸メチル、酢酸エチル、酢酸ブチル等のエステル系有機溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジアセトンアルコール、シクロペンタノン、シクロヘキサノン等の脂肪族ケトン、エチレングリコールジメチルエーテル、ジブチルブチルエーテル、テトラヒドロフラン、メチルシクロペンチルエーテル、ジオキサン等のエーテル系有機溶剤、N-メチルピロリドン、2-ピロリドン、ジメチルホルムアミド、ジメチルイミダゾリジノン、ジメチルアセトアミド等のアミド系有機溶剤、ジメチルスルホキシド、スルホラン等の含硫黄系有機溶剤などが挙げられる。これらの有機溶剤は反応基質であるテトラカルボン酸二無水物、ジアミン化合物、反応中間体であるポリアミック酸、さらに最終生成物であるポリイミド化合物を溶解させることを可能とする範囲で適切に選択されるものであるが、好ましくは、エステル系(好ましくは酢酸ブチル)、脂肪族ケトン(好ましくは、メチルエチルケトン、メチルイソブチルケトン、ジアセトンアルコール、シクロペンタノン、シクロヘキサノン)、エーテル系(ジエチレングリコールモノメチルエーテル、メチルシクロペンチルエーテル)、アミド系(好ましくはN-メチルピロリドン)、含硫黄系(ジメチルスルホキシド、スルホラン)が好ましい。また、これらは、1種又は2種以上を組み合わせて用いることができる。 The polyimide compound used in the present invention can be obtained by mixing each of the above raw materials in a solvent and subjecting it to condensation polymerization by an ordinary method.
The solvent is not particularly limited, but ester organic solvents such as methyl acetate, ethyl acetate, and butyl acetate; aliphatics such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, cyclopentanone, and cyclohexanone. Ether organic solvents such as ketone, ethylene glycol dimethyl ether, dibutyl butyl ether, tetrahydrofuran, methylcyclopentyl ether, dioxane, amide organic solvents such as N-methylpyrrolidone, 2-pyrrolidone, dimethylformamide, dimethylimidazolidinone, dimethylacetamide, dimethyl And sulfur-containing organic solvents such as sulfoxide and 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. Preferably, 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 (preferably N-methylpyrrolidone), and sulfur-containing (dimethyl sulfoxide, sulfolane) are preferable. Moreover, these can be used 1 type or in combination of 2 or more types.
上記溶媒としては、特に限定されるものではないが、酢酸メチル、酢酸エチル、酢酸ブチル等のエステル系有機溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジアセトンアルコール、シクロペンタノン、シクロヘキサノン等の脂肪族ケトン、エチレングリコールジメチルエーテル、ジブチルブチルエーテル、テトラヒドロフラン、メチルシクロペンチルエーテル、ジオキサン等のエーテル系有機溶剤、N-メチルピロリドン、2-ピロリドン、ジメチルホルムアミド、ジメチルイミダゾリジノン、ジメチルアセトアミド等のアミド系有機溶剤、ジメチルスルホキシド、スルホラン等の含硫黄系有機溶剤などが挙げられる。これらの有機溶剤は反応基質であるテトラカルボン酸二無水物、ジアミン化合物、反応中間体であるポリアミック酸、さらに最終生成物であるポリイミド化合物を溶解させることを可能とする範囲で適切に選択されるものであるが、好ましくは、エステル系(好ましくは酢酸ブチル)、脂肪族ケトン(好ましくは、メチルエチルケトン、メチルイソブチルケトン、ジアセトンアルコール、シクロペンタノン、シクロヘキサノン)、エーテル系(ジエチレングリコールモノメチルエーテル、メチルシクロペンチルエーテル)、アミド系(好ましくはN-メチルピロリドン)、含硫黄系(ジメチルスルホキシド、スルホラン)が好ましい。また、これらは、1種又は2種以上を組み合わせて用いることができる。 The polyimide compound used in the present invention can be obtained by mixing each of the above raw materials in a solvent and subjecting it to condensation polymerization by an ordinary method.
The solvent is not particularly limited, but ester organic solvents such as methyl acetate, ethyl acetate, and butyl acetate; aliphatics such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, cyclopentanone, and cyclohexanone. Ether organic solvents such as ketone, ethylene glycol dimethyl ether, dibutyl butyl ether, tetrahydrofuran, methylcyclopentyl ether, dioxane, amide organic solvents such as N-methylpyrrolidone, 2-pyrrolidone, dimethylformamide, dimethylimidazolidinone, dimethylacetamide, dimethyl And sulfur-containing organic solvents such as sulfoxide and 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. Preferably, 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 (preferably N-methylpyrrolidone), and sulfur-containing (dimethyl sulfoxide, sulfolane) are preferable. Moreover, these can be used 1 type or in combination of 2 or more types.
重合反応温度に特に制限はなくポリイミド化合物の合成において通常採用されうる温度を採用することができる。具体的には-40~60℃であることが好ましく、より好ましくは-30~50℃である。
The polymerization reaction temperature is not particularly limited, and a temperature that can be usually employed in the synthesis of a polyimide compound can be employed. Specifically, it is preferably −40 to 60 ° C., more preferably −30 to 50 ° C.
上記の重合反応により生成したポリアミック酸を分子内で脱水閉環反応させることによりイミド化することで、ポリイミド化合物が得られる。脱水閉環させる方法としては、一般的な書籍(例えば、今井淑夫、横田力男編著、「最新ポリイミド~基礎と応用~」、株式会社エヌ・ティー・エス、2010年8月25日、p.3~49、など)に記載の方法を参考とすることができる。例えば、120℃~200℃に加熱して、副生する水を系外に除去しながら反応させる熱イミド化法や、ピリジンやトリエチルアミン、DBUのような塩基性触媒共存下で、無水酢酸やジシクロヘキシルカルボジイミド、亜リン酸トリフェニルのような脱水縮合剤を用いるいわゆる化学イミド化等の手法が好適に用いられる。
A polyimide compound is obtained by imidizing the polyamic acid produced by the above polymerization reaction by a dehydration ring-closing reaction in the molecule. As a method for dehydrating and closing a ring, a general book (for example, Ikuo Imai, edited by Rikio Yokota, “Latest Polyimide: Fundamentals and Applications”, NTS Inc., August 25, 2010, p. 3) To 49, etc.) can be referred to. For example, 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.
本発明において、ポリイミド化合物の重合反応液中のテトラカルボン酸二無水物及びジアミン化合物の総濃度は特に限定されるものではないが、5~70質量%が好ましく、より好ましくは5~50質量%が好ましく、さらに好ましくは5~30質量%である。
In the present invention, the total concentration of tetracarboxylic dianhydride and diamine compound in the polymerization reaction solution of the polyimide compound is not particularly limited, but is preferably 5 to 70% by mass, more preferably 5 to 50% by mass. And more preferably 5 to 30% by mass.
本発明に用いるポリイミド化合物の具体例としては、後述する実施例に記載のP-01~P-17や、P-01~P-17において、各構造単位のモル比を適宜に変更したものが挙げられるが、本発明はこれらに限定されるものではなく、本発明の規定を満たすポリイミド化合物を広く用いることができる。
Specific examples of the polyimide compound used in the present invention include P-01 to P-17 and P-01 to P-17 described in the examples described later, in which the molar ratio of each structural unit is appropriately changed. However, the present invention is not limited to these, and a wide range of polyimide compounds satisfying the provisions of the present invention can be used.
[ガス分離膜]
(ガス分離複合膜)
本発明のガス分離膜の好ましい態様であるガス分離複合膜は、ガス透過性の支持層の上側に、特定のポリイミド化合物を含有してなるガス分離層が形成されている。この複合膜は、多孔質の支持体の少なくとも表面に、上記のガス分離層をなす塗布液(ドープ)を塗布(本明細書において塗布とは浸漬により表面に付着される態様を含む意味である。)することにより形成することが好ましい。
図1は、本発明の一つの好ましい実施形態であるガス分離複合膜10を模式的に示す縦断面図である。1はガス分離層、2は多孔質層からなる支持層(ガス透過性支持層)である。図2は、本発明の別の好ましい実施形態であるガス分離複合膜20を模式的に示す断面図である。この実施形態では、ガス分離層1及び多孔質層2に加え、支持層として不織布層3が追加されている。 [Gas separation membrane]
(Gas separation composite membrane)
In the gas separation composite membrane which is a preferred embodiment of the gas separation membrane of the present invention, a gas separation layer containing a specific polyimide compound is formed on the upper side of the gas permeable support layer. This composite membrane is applied to the above-mentioned coating solution (dope) forming the gas separation layer on at least the surface of the porous support (in this specification, coating is meant to include an aspect in which it is attached to the surface by dipping) )) Is preferable.
FIG. 1 is a longitudinal sectional view schematically showing a gasseparation composite membrane 10 which is one preferred embodiment of the present invention. Reference numeral 1 denotes a gas separation layer, and reference numeral 2 denotes a support layer (gas permeable support layer) made of a porous layer. FIG. 2 is a cross-sectional view schematically showing a gas separation composite membrane 20 which is another preferred embodiment of the present invention. In this embodiment, a nonwoven fabric layer 3 is added as a support layer in addition to the gas separation layer 1 and the porous layer 2.
(ガス分離複合膜)
本発明のガス分離膜の好ましい態様であるガス分離複合膜は、ガス透過性の支持層の上側に、特定のポリイミド化合物を含有してなるガス分離層が形成されている。この複合膜は、多孔質の支持体の少なくとも表面に、上記のガス分離層をなす塗布液(ドープ)を塗布(本明細書において塗布とは浸漬により表面に付着される態様を含む意味である。)することにより形成することが好ましい。
図1は、本発明の一つの好ましい実施形態であるガス分離複合膜10を模式的に示す縦断面図である。1はガス分離層、2は多孔質層からなる支持層(ガス透過性支持層)である。図2は、本発明の別の好ましい実施形態であるガス分離複合膜20を模式的に示す断面図である。この実施形態では、ガス分離層1及び多孔質層2に加え、支持層として不織布層3が追加されている。 [Gas separation membrane]
(Gas separation composite membrane)
In the gas separation composite membrane which is a preferred embodiment of the gas separation membrane of the present invention, a gas separation layer containing a specific polyimide compound is formed on the upper side of the gas permeable support layer. This composite membrane is applied to the above-mentioned coating solution (dope) forming the gas separation layer on at least the surface of the porous support (in this specification, coating is meant to include an aspect in which it is attached to the surface by dipping) )) Is preferable.
FIG. 1 is a longitudinal sectional view schematically showing a gas
本明細書において「支持層上側」とは、支持層とガス分離層との間に他の層が介在してもよい意味である。また、上下の表現については、特に断らない限り、分離対象となるガスが供給される方向を「上」とし、分離されたガスが出される方向を「下」とする。
In the present specification, “upper support layer” means that another layer may be interposed between the support layer and the gas separation layer. As for the upper and lower expressions, unless otherwise specified, 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”.
本発明のガス分離複合膜は、多孔質性の支持体(支持層)の表面ないし内面にガス分離層を形成・配置するようにしてもよく、少なくとも表面に形成して簡便に複合膜とすることができる。多孔質性の支持体の少なくとも表面にガス分離層を形成することで、高分離選択性と高ガス透過性、更には機械的強度を兼ね備えるという利点を有する複合膜とすることができる。分離層の膜厚としては機械的強度、分離選択性を維持しつつ高ガス透過性を付与する条件において可能な限り薄膜であることが好ましい。
In the gas separation composite membrane of the present invention, a gas separation layer may be formed and disposed on the surface or inner surface of a porous support (support layer). be able to. By forming a gas separation layer on at least the surface of the porous support, a composite membrane having the advantages of having both high separation selectivity, high gas permeability, and mechanical strength can be obtained. 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.
本発明のガス分離複合膜において、ガス分離層の厚さは特に限定されないが、0.01~5.0μmであることが好ましく、0.05~2.0μmであることがより好ましい。
In the gas separation composite membrane of the present invention, the thickness of the gas separation layer is not particularly limited, but is preferably 0.01 to 5.0 μm, more preferably 0.05 to 2.0 μm.
ガス透過性支持層に好ましく適用される多孔質支持体(多孔質層)は、機械的強度及び高気体透過性の付与に合致する目的のものであれば、特に限定されるものではなく有機、無機どちらの素材であっても構わないが、好ましくは有機高分子の多孔質膜であり、その厚さは1~3,000μm、好ましくは5~500μmであり、より好ましくは5~150μmである。この多孔質膜の細孔構造は、通常平均細孔直径が10μm以下、好ましくは0.5μm以下、より好ましくは0.2μm以下である。空孔率は好ましくは20~90%であり、より好ましくは30~80%である。また、多孔質層の分画分子量が100,000以下であることが好ましい。さらに、その気体透過率は40℃、4MPaにおいて、二酸化炭素透過速度で3×10-5cm3(STP)/cm2・sec・cmHg(30GPU)以上であることが好ましく、100GPU以上であることがより好ましく、200GPU以上であることがさらに好ましい。多孔質膜の素材としては、任意の高分子、例えばポリエチレン、ポリプロピレン等のポリオレフィン系樹脂等、ポリテトラフルオロエチレン、ポリフッ化ビニル、ポリフッ化ビニリデン等の含フッ素樹脂等、ポリスチレン、酢酸セルロース、ポリウレタン、ポリアクリロニトリル、ポリフェニレンオキシド、ポリスルホン、ポリエーテルスルホン、ポリイミド、ポリアラミド等の各種樹脂を挙げることができる。多孔質膜の形状としては、平板状、スパイラル状、管状、中空糸状などいずれの形状をとることもできる。
The porous support (porous layer) preferably applied to the gas permeable support layer is not particularly limited as long as it has the purpose of meeting the provision of mechanical strength and high gas permeability. Either an inorganic material or an inorganic material may be used, but an organic polymer porous film is preferable, and the thickness thereof is 1 to 3,000 μm, preferably 5 to 500 μm, and more preferably 5 to 150 μm. . The pore structure of this porous membrane usually has an average pore diameter of 10 μm or less, preferably 0.5 μm or less, more preferably 0.2 μm or less. The porosity is preferably 20 to 90%, more preferably 30 to 80%. Further, the molecular weight cut-off of the porous layer is preferably 100,000 or less. Further, the gas permeability is preferably 3 × 10 −5 cm 3 (STP) / cm 2 · sec · cmHg (30 GPU) or more at 40 ° C. and 4 MPa, preferably 100 GPU or more. Is more preferable, and 200 GPU or more is more preferable. As a material of the porous membrane, any polymer, for example, a polyolefin resin such as polyethylene and polypropylene, a fluorine-containing resin such as polytetrafluoroethylene, polyvinyl fluoride, and polyvinylidene fluoride, polystyrene, cellulose acetate, polyurethane, Various resins such as polyacrylonitrile, polyphenylene oxide, polysulfone, polyethersulfone, polyimide, and polyaramide can be exemplified. The shape of the porous membrane may be any shape such as a flat plate shape, a spiral shape, a tubular shape, and a hollow fiber shape.
本発明のガス分離複合膜においては、ガス分離層を形成する支持層の下部にさらに機械的強度を付与するために支持体が形成されていることが好ましい。このような支持体としては、織布、不織布、ネット等が挙げられるが、製膜性およびコスト面から不織布が好適に用いられる。不織布としてはポリエステル、ポリプロピレン、ポリアクリロニトリル、ポリエチレン、ポリアミド等からなる繊維を単独あるいは複数を組み合わせて用いてもよい。不織布は、例えば、水に均一に分散した主体繊維とバインダー繊維を円網や長網等で抄造し、ドライヤーで乾燥することにより製造できる。また、毛羽を除去したり機械的性質を向上させたり等の目的で、不織布を2本のロールで挟んで圧熱加工を施すことも好ましい。
In the gas separation composite membrane of the present invention, it is preferable that a support is formed to further impart mechanical strength to the lower part of the support layer forming the gas separation layer. Examples of such a support include woven fabric, non-woven fabric, and net, but a non-woven fabric is preferably used from the viewpoint of film forming property and cost. As 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. In addition, for the purpose of removing fluff or improving mechanical properties, it is also preferable to apply a heat treatment by sandwiching the nonwoven fabric between two rolls.
<ガス分離複合膜の製造方法>
本発明の複合膜の製造方法は、好ましくは、上記ポリイミド化合物を含有する塗布液を支持体上に塗布してガス分離層を形成することを含む製造方法が好ましい。塗布液中のポリイミド化合物の含有量は特に限定されないが、0.1~30質量%であることが好ましく、0.5~10質量%であることがより好ましい。ポリイミド化合物の含有量が低すぎると、多孔質支持体上に製膜した際に、容易に下層に浸透してしまうがために分離に寄与する表層に欠陥が生じる可能性が高くなる。また、ポリイミド化合物の含有量が高すぎると、多孔質支持体上に製膜した際に孔内に高濃度に充填されてしまい、透過性が低くなる可能性がある。本発明のガス分離膜は、分離層のポリマーの分子量、構造、組成さらには溶液粘度を調整することで適切に製造することができる。 <Method for producing gas separation composite membrane>
The production method of the composite membrane of the present invention is preferably a production method including forming a gas separation layer by applying a coating solution containing the polyimide compound on a support. The content of the polyimide compound in the coating solution is not particularly limited, but is preferably 0.1 to 30% by mass, and more preferably 0.5 to 10% by mass. If the content of the polyimide compound is too low, when the film is formed on the porous support, it easily penetrates into the lower layer, so that there is a high possibility that defects will occur in the surface layer that contributes to separation. On the other hand, if the content of the polyimide compound is too high, the pores are filled at a high concentration when the film is formed on the porous support, and the permeability may be lowered. The gas separation membrane of the present invention can be appropriately produced by adjusting the molecular weight, structure, composition, and solution viscosity of the polymer in the separation layer.
本発明の複合膜の製造方法は、好ましくは、上記ポリイミド化合物を含有する塗布液を支持体上に塗布してガス分離層を形成することを含む製造方法が好ましい。塗布液中のポリイミド化合物の含有量は特に限定されないが、0.1~30質量%であることが好ましく、0.5~10質量%であることがより好ましい。ポリイミド化合物の含有量が低すぎると、多孔質支持体上に製膜した際に、容易に下層に浸透してしまうがために分離に寄与する表層に欠陥が生じる可能性が高くなる。また、ポリイミド化合物の含有量が高すぎると、多孔質支持体上に製膜した際に孔内に高濃度に充填されてしまい、透過性が低くなる可能性がある。本発明のガス分離膜は、分離層のポリマーの分子量、構造、組成さらには溶液粘度を調整することで適切に製造することができる。 <Method for producing gas separation composite membrane>
The production method of the composite membrane of the present invention is preferably a production method including forming a gas separation layer by applying a coating solution containing the polyimide compound on a support. The content of the polyimide compound in the coating solution is not particularly limited, but is preferably 0.1 to 30% by mass, and more preferably 0.5 to 10% by mass. If the content of the polyimide compound is too low, when the film is formed on the porous support, it easily penetrates into the lower layer, so that there is a high possibility that defects will occur in the surface layer that contributes to separation. On the other hand, if the content of the polyimide compound is too high, the pores are filled at a high concentration when the film is formed on the porous support, and the permeability may be lowered. The gas separation membrane of the present invention can be appropriately produced by adjusting the molecular weight, structure, composition, and solution viscosity of the polymer in the separation layer.
-有機溶剤-
塗布液の媒体とする有機溶剤としては、特に限定されるものではないが、n-ヘキサン、n-ヘプタン等の炭化水素系有機溶剤、酢酸メチル、酢酸エチル、酢酸ブチル等のエステル系有機溶剤、メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノール、tert-ブタノール等の低級アルコール、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジアセトンアルコール、シクロペンタノン、シクロヘキサノン等の脂肪族ケトン、エチレングリコール、ジエチレングリコール、トリエチレングリコール、グリセリン、プロピレングリコール、エチレングリコールモノメチル又はモノエチルエーテル、プロピレングリコールメチルエーテル、ジプロピレングリコールメチルエーテル、トリプロピレングリコールメチルエーテル、エチレングリコールフェニルエーテル、プロピレングリコールフェニルエーテル、ジエチレングリコールモノメチル又はモノエチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノメチル又はモノエチルエーテル、ジブチルブチルエーテル、テトラヒドロフラン、メチルシクロペンチルエーテル、ジオキサン等のエーテル系有機溶剤、N-メチルピロリドン、2-ピロリドン、ジメチルホルムアミド、ジメチルイミダゾリジノン、ジメチルスルホキシド、ジメチルアセトアミドなどが挙げられる。これらの有機溶剤は支持体を浸蝕するなどの悪影響を及ぼさない範囲で適切に選択されるものであるが、好ましくは、エステル系(好ましくは酢酸ブチル)、アルコール系(好ましくはメタノール、エタノール、イソプロパノール、イソブタノール)、脂肪族ケトン(好ましくは、メチルエチルケトン、メチルイソブチルケトン、ジアセトンアルコール、シクロペンタノン、シクロヘキサノン)、エーテル系(エチレングリコール、ジエチレングリコールモノメチルエーテル、メチルシクロペンチルエーテル)が好ましく、さらに好ましくは脂肪族ケトン系、アルコール系、エーテル系である。またこれらは、1種又は2種以上を組み合わせて用いることができる。 -Organic solvent-
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 such as pyrene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol phenyl ether, diethylene glycol monomethyl or monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl or monoethyl ether, dibutylbutyl ether, tetrahydrofuran, methylcyclopentyl ether, dioxane Examples thereof include solvents, N-methylpyrrolidone, 2-pyrrolidone, dimethylformamide, dimethylimidazolidinone, dimethyl sulfoxide, dimethylacetamide and the like. These 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). , 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) are preferred, and more preferred are fats Group-based ketones, alcohols, and ethers. Moreover, these can be used 1 type or in combination of 2 or more types.
塗布液の媒体とする有機溶剤としては、特に限定されるものではないが、n-ヘキサン、n-ヘプタン等の炭化水素系有機溶剤、酢酸メチル、酢酸エチル、酢酸ブチル等のエステル系有機溶剤、メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノール、tert-ブタノール等の低級アルコール、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジアセトンアルコール、シクロペンタノン、シクロヘキサノン等の脂肪族ケトン、エチレングリコール、ジエチレングリコール、トリエチレングリコール、グリセリン、プロピレングリコール、エチレングリコールモノメチル又はモノエチルエーテル、プロピレングリコールメチルエーテル、ジプロピレングリコールメチルエーテル、トリプロピレングリコールメチルエーテル、エチレングリコールフェニルエーテル、プロピレングリコールフェニルエーテル、ジエチレングリコールモノメチル又はモノエチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノメチル又はモノエチルエーテル、ジブチルブチルエーテル、テトラヒドロフラン、メチルシクロペンチルエーテル、ジオキサン等のエーテル系有機溶剤、N-メチルピロリドン、2-ピロリドン、ジメチルホルムアミド、ジメチルイミダゾリジノン、ジメチルスルホキシド、ジメチルアセトアミドなどが挙げられる。これらの有機溶剤は支持体を浸蝕するなどの悪影響を及ぼさない範囲で適切に選択されるものであるが、好ましくは、エステル系(好ましくは酢酸ブチル)、アルコール系(好ましくはメタノール、エタノール、イソプロパノール、イソブタノール)、脂肪族ケトン(好ましくは、メチルエチルケトン、メチルイソブチルケトン、ジアセトンアルコール、シクロペンタノン、シクロヘキサノン)、エーテル系(エチレングリコール、ジエチレングリコールモノメチルエーテル、メチルシクロペンチルエーテル)が好ましく、さらに好ましくは脂肪族ケトン系、アルコール系、エーテル系である。またこれらは、1種又は2種以上を組み合わせて用いることができる。 -Organic solvent-
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 such as pyrene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol phenyl ether, diethylene glycol monomethyl or monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl or monoethyl ether, dibutylbutyl ether, tetrahydrofuran, methylcyclopentyl ether, dioxane Examples thereof include solvents, N-methylpyrrolidone, 2-pyrrolidone, dimethylformamide, dimethylimidazolidinone, dimethyl sulfoxide, dimethylacetamide and the like. These 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). , 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) are preferred, and more preferred are fats Group-based ketones, alcohols, and ethers. Moreover, these can be used 1 type or in combination of 2 or more types.
<支持層とガス分離層の間の他の層>
本発明のガス分離複合膜において、支持層とガス分離層との間には他の層が存在していてもよい。他の層の好ましい例として、シロキサン化合物層が挙げられる。シロキサン化合物層を設けることで、支持体最表面の凹凸を平滑化することができ、分離層の薄層化が容易になる。シロキサン化合物層を形成するシロキサン化合物としては、主鎖がポリシロキサンからなるものと、主鎖にシロキサン構造と非シロキサン構造を有する化合物とが挙げられる。 <Other layers between the support layer and the gas separation layer>
In the gas separation composite membrane of the present invention, another layer may exist between the support layer and the gas separation layer. A preferred example of the other layer is a siloxane compound layer. By providing the siloxane compound layer, the unevenness on the outermost surface of the support can be smoothed, and the separation layer can be easily thinned. Examples of the siloxane compound forming the siloxane compound layer include those having a main chain made of polysiloxane and compounds having a siloxane structure and a non-siloxane structure in the main chain.
本発明のガス分離複合膜において、支持層とガス分離層との間には他の層が存在していてもよい。他の層の好ましい例として、シロキサン化合物層が挙げられる。シロキサン化合物層を設けることで、支持体最表面の凹凸を平滑化することができ、分離層の薄層化が容易になる。シロキサン化合物層を形成するシロキサン化合物としては、主鎖がポリシロキサンからなるものと、主鎖にシロキサン構造と非シロキサン構造を有する化合物とが挙げられる。 <Other layers between the support layer and the gas separation layer>
In the gas separation composite membrane of the present invention, another layer may exist between the support layer and the gas separation layer. A preferred example of the other layer is a siloxane compound layer. By providing the siloxane compound layer, the unevenness on the outermost surface of the support can be smoothed, and the separation layer can be easily thinned. Examples of the siloxane compound forming the siloxane compound layer include those having a main chain made of polysiloxane and compounds having a siloxane structure and a non-siloxane structure in the main chain.
-主鎖がポリシロキサンからなるシロキサン化合物-
シロキサン化合物層に用いうる、主鎖がポリシロキサンからなるシロキサン化合物としては、下記式(1)もしくは(2)で表されるポリオルガノシロキサンの1種又は2種以上が挙げられる。また、これらのポリオルガノシロキサンは架橋反応物を形成していてもよい。この架橋反応物としては、例えば、下記式(1)で表される化合物が、下記式(1)の反応性基Xと反応して連結する基を両末端に有するポリシロキサン化合物により架橋された形態の化合物が挙げられる。 -Siloxane compounds whose main chain consists of polysiloxane-
Examples of the siloxane compound having a main chain made of polysiloxane that can be used in the siloxane compound layer include one or more polyorganosiloxanes represented by the following formula (1) or (2). Moreover, these polyorganosiloxanes may form a crosslinking reaction product. As the cross-linked reaction product, for example, a compound represented by the following formula (1) is cross-linked by a polysiloxane compound having groups at both ends that react with the reactive group X of the following formula (1) and connect. In the form of compounds.
シロキサン化合物層に用いうる、主鎖がポリシロキサンからなるシロキサン化合物としては、下記式(1)もしくは(2)で表されるポリオルガノシロキサンの1種又は2種以上が挙げられる。また、これらのポリオルガノシロキサンは架橋反応物を形成していてもよい。この架橋反応物としては、例えば、下記式(1)で表される化合物が、下記式(1)の反応性基Xと反応して連結する基を両末端に有するポリシロキサン化合物により架橋された形態の化合物が挙げられる。 -Siloxane compounds whose main chain consists of polysiloxane-
Examples of the siloxane compound having a main chain made of polysiloxane that can be used in the siloxane compound layer include one or more polyorganosiloxanes represented by the following formula (1) or (2). Moreover, these polyorganosiloxanes may form a crosslinking reaction product. As the cross-linked reaction product, for example, a compound represented by the following formula (1) is cross-linked by a polysiloxane compound having groups at both ends that react with the reactive group X of the following formula (1) and connect. In the form of compounds.
式(1)中、Rは非反応性基であって、アルキル基(好ましくは炭素数1~18、より好ましくは炭素数1~12のアルキル基)又はアリール基(好ましくは炭素数6~15、より好ましくは炭素数6~12のアリール基、さらに好ましくはフェニル)であることが好ましい。
Xは反応性基であって、水素原子、ハロゲン原子、ビニル基、ヒドロキシル基、及び置換アルキル基(好ましくは炭素数1~18、より好ましくは炭素数1~12のアルキル基)から選ばれる基であることが好ましい。
Y及びZは上記R又はXである。
本発明に用いるシロキサン化合物の粘度は、特に規定されるものではないが、25℃における粘度が10~100,000mPa・sであることが好ましく、20~50,000mPa・sであることがより好ましい。
mは1以上の数であり、好ましくは1~100,000である。
nは0以上の数であり、好ましくは0~100,000である。 In the formula (1), R is a non-reactive group, and is an alkyl group (preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 15 carbon atoms). More preferably an aryl group having 6 to 12 carbon atoms, still more preferably phenyl).
X is a reactive group, and is a group selected from a hydrogen atom, a halogen atom, a vinyl group, a hydroxyl group, and a substituted alkyl group (preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms). It is preferable that
Y and Z are the above R or X.
The viscosity of the siloxane compound used in the present invention is not particularly limited, but the viscosity at 25 ° C. is preferably 10 to 100,000 mPa · s, more preferably 20 to 50,000 mPa · s. .
m is a number of 1 or more, preferably 1 to 100,000.
n is a number of 0 or more, preferably 0 to 100,000.
Xは反応性基であって、水素原子、ハロゲン原子、ビニル基、ヒドロキシル基、及び置換アルキル基(好ましくは炭素数1~18、より好ましくは炭素数1~12のアルキル基)から選ばれる基であることが好ましい。
Y及びZは上記R又はXである。
本発明に用いるシロキサン化合物の粘度は、特に規定されるものではないが、25℃における粘度が10~100,000mPa・sであることが好ましく、20~50,000mPa・sであることがより好ましい。
mは1以上の数であり、好ましくは1~100,000である。
nは0以上の数であり、好ましくは0~100,000である。 In the formula (1), R is a non-reactive group, and is an alkyl group (preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 15 carbon atoms). More preferably an aryl group having 6 to 12 carbon atoms, still more preferably phenyl).
X is a reactive group, and is a group selected from a hydrogen atom, a halogen atom, a vinyl group, a hydroxyl group, and a substituted alkyl group (preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms). It is preferable that
Y and Z are the above R or X.
The viscosity of the siloxane compound used in the present invention is not particularly limited, but the viscosity at 25 ° C. is preferably 10 to 100,000 mPa · s, more preferably 20 to 50,000 mPa · s. .
m is a number of 1 or more, preferably 1 to 100,000.
n is a number of 0 or more, preferably 0 to 100,000.
式(2)中、X、Y、Z、R、m及びnは、それぞれ式(1)のX、Y、Z、R、m及びnと同義である。
In the formula (2), X, Y, Z, R, m and n have the same meanings as X, Y, Z, R, m and n in the formula (1), respectively.
上記式(1)及び(2)において、非反応性基Rがアルキル基である場合、このアルキル基の例としては、メチル、エチル、へキシル、オクチル、デシル、及びオクタデシルを挙げることができる。また、非反応性基Rがフルオロアルキル基である場合、このフルオロアルキル基としては、例えば、-CH2CH2CF3、-CH2CH2C6F13が挙げられる。
In the above formulas (1) and (2), when the non-reactive group R is an alkyl group, examples of the alkyl group include methyl, ethyl, hexyl, octyl, decyl, and octadecyl. When the non-reactive group R is a fluoroalkyl group, examples of the fluoroalkyl group include —CH 2 CH 2 CF 3 and —CH 2 CH 2 C 6 F 13 .
上記式(1)及び(2)において、反応性基Xが置換アルキル基である場合、このアルキル基の例としては、炭素数1~18のヒドロキシアルキル基、炭素数1~18のアミノアルキル基、炭素数1~18のカルボキシアルキル基、炭素数1~18のクロロアルキル基、炭素数1~18のグリシドキシアルキル基、グリシジル基、炭素数7~16のエポキシシクロへキシルアルキル基、炭素数4~18の(1-オキサシクロブタン-3-イル)アルキル基、メタクリロキシアルキル基、及びメルカプトアルキル基が挙げられる。
上記ヒドロキシアルキル基を構成するアルキル基の炭素数は1~10の整数であることが好ましく、例えば、-CH2CH2CH2OHが挙げられる。
上記アミノアルキル基を構成するアルキル基の好ましい炭素数は1~10の整数であることが好ましく、例えば、-CH2CH2CH2NH2が挙げられる。
上記カルボキシアルキル基を構成するアルキル基の好ましい炭素数は1~10の整数であることが好ましく、例えば、-CH2CH2CH2COOHが挙げられる。
上記クロロアルキル基を構成するアルキル基の好ましい炭素数は1~10の整数であることが好ましく、好ましい例としては-CH2Clが挙げられる。
上記グリシドキシアルキル基を構成するアルキル基の好ましい炭素数は1~10の整数であり、好ましい例としては、3-グリシジルオキシプロピルが挙げられる。
上記炭素数7~16のエポキシシクロへキシルアルキル基の好ましい炭素数は8~12の整数である。
炭素数4~18の(1-オキサシクロブタン-3-イル)アルキル基の好ましい炭素数は4~10の整数である。
上記メタクリロキシアルキル基を構成するアルキル基の好ましい炭素数は1~10の整数であり、例えば、-CH2CH2CH2-OOC-C(CH3)=CH2が挙げられる。
上記メルカプトアルキル基を構成するアルキル基の好ましい炭素数は1~10の整数であり、例えば、-CH2CH2CH2SHが挙げられる。
m及びnは、化合物の分子量が5,000~1,000,000になる数であることが好ましい。 In the above formulas (1) and (2), when the reactive group X is a substituted alkyl group, examples of the alkyl group include hydroxyalkyl groups having 1 to 18 carbon atoms and aminoalkyl groups having 1 to 18 carbon atoms. A carboxyalkyl group having 1 to 18 carbon atoms, a chloroalkyl group having 1 to 18 carbon atoms, a glycidoxyalkyl group having 1 to 18 carbon atoms, a glycidyl group, an epoxycyclohexylalkyl group having 7 to 16 carbon atoms, carbon Examples thereof include a (1-oxacyclobutan-3-yl) alkyl group, a methacryloxyalkyl group, and a mercaptoalkyl group having 4 to 18.
The number of carbon atoms of the alkyl group constituting the hydroxyalkyl group is preferably an integer of 1 to 10, for example, —CH 2 CH 2 CH 2 OH.
The number of carbon atoms of the alkyl group constituting the aminoalkyl group is preferably an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 NH 2 .
The number of carbon atoms of the alkyl group constituting the carboxyalkyl group is preferably an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 COOH.
The number of carbon atoms of the alkyl group constituting the chloroalkyl group is preferably an integer of 1 to 10, and a preferred example is —CH 2 Cl.
A preferable carbon number of the alkyl group constituting the glycidoxyalkyl group is an integer of 1 to 10, and a preferred example is 3-glycidyloxypropyl.
The preferable number of carbon atoms of the epoxy cyclohexyl alkyl group having 7 to 16 carbon atoms is an integer of 8 to 12.
A preferable carbon number of the (1-oxacyclobutan-3-yl) alkyl group having 4 to 18 carbon atoms is an integer of 4 to 10.
A preferable carbon number of the alkyl group constituting the methacryloxyalkyl group is an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 —OOC—C (CH 3 ) ═CH 2 .
A preferable carbon number of the alkyl group constituting the mercaptoalkyl group is an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 SH.
m and n are preferably numbers that give a molecular weight of 5,000 to 1,000,000 of the compound.
上記ヒドロキシアルキル基を構成するアルキル基の炭素数は1~10の整数であることが好ましく、例えば、-CH2CH2CH2OHが挙げられる。
上記アミノアルキル基を構成するアルキル基の好ましい炭素数は1~10の整数であることが好ましく、例えば、-CH2CH2CH2NH2が挙げられる。
上記カルボキシアルキル基を構成するアルキル基の好ましい炭素数は1~10の整数であることが好ましく、例えば、-CH2CH2CH2COOHが挙げられる。
上記クロロアルキル基を構成するアルキル基の好ましい炭素数は1~10の整数であることが好ましく、好ましい例としては-CH2Clが挙げられる。
上記グリシドキシアルキル基を構成するアルキル基の好ましい炭素数は1~10の整数であり、好ましい例としては、3-グリシジルオキシプロピルが挙げられる。
上記炭素数7~16のエポキシシクロへキシルアルキル基の好ましい炭素数は8~12の整数である。
炭素数4~18の(1-オキサシクロブタン-3-イル)アルキル基の好ましい炭素数は4~10の整数である。
上記メタクリロキシアルキル基を構成するアルキル基の好ましい炭素数は1~10の整数であり、例えば、-CH2CH2CH2-OOC-C(CH3)=CH2が挙げられる。
上記メルカプトアルキル基を構成するアルキル基の好ましい炭素数は1~10の整数であり、例えば、-CH2CH2CH2SHが挙げられる。
m及びnは、化合物の分子量が5,000~1,000,000になる数であることが好ましい。 In the above formulas (1) and (2), when the reactive group X is a substituted alkyl group, examples of the alkyl group include hydroxyalkyl groups having 1 to 18 carbon atoms and aminoalkyl groups having 1 to 18 carbon atoms. A carboxyalkyl group having 1 to 18 carbon atoms, a chloroalkyl group having 1 to 18 carbon atoms, a glycidoxyalkyl group having 1 to 18 carbon atoms, a glycidyl group, an epoxycyclohexylalkyl group having 7 to 16 carbon atoms, carbon Examples thereof include a (1-oxacyclobutan-3-yl) alkyl group, a methacryloxyalkyl group, and a mercaptoalkyl group having 4 to 18.
The number of carbon atoms of the alkyl group constituting the hydroxyalkyl group is preferably an integer of 1 to 10, for example, —CH 2 CH 2 CH 2 OH.
The number of carbon atoms of the alkyl group constituting the aminoalkyl group is preferably an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 NH 2 .
The number of carbon atoms of the alkyl group constituting the carboxyalkyl group is preferably an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 COOH.
The number of carbon atoms of the alkyl group constituting the chloroalkyl group is preferably an integer of 1 to 10, and a preferred example is —CH 2 Cl.
A preferable carbon number of the alkyl group constituting the glycidoxyalkyl group is an integer of 1 to 10, and a preferred example is 3-glycidyloxypropyl.
The preferable number of carbon atoms of the epoxy cyclohexyl alkyl group having 7 to 16 carbon atoms is an integer of 8 to 12.
A preferable carbon number of the (1-oxacyclobutan-3-yl) alkyl group having 4 to 18 carbon atoms is an integer of 4 to 10.
A preferable carbon number of the alkyl group constituting the methacryloxyalkyl group is an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 —OOC—C (CH 3 ) ═CH 2 .
A preferable carbon number of the alkyl group constituting the mercaptoalkyl group is an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 SH.
m and n are preferably numbers that give a molecular weight of 5,000 to 1,000,000 of the compound.
上記式(1)及び(2)において、反応性基含有シロキサン単位(式中、その数がnで表される構成単位)と反応性基を有さないシロキサン単位(式中、その数がmで表される構成単位)の分布に特に制限はない。すなわち、式(1)及び(2)中、(Si(R)(R)-O)単位と(Si(R)(X)-O)単位はランダムに分布していてもよい。
In the above formulas (1) and (2), a reactive group-containing siloxane unit (wherein the number is a structural unit represented by n) and a siloxane unit having no reactive group (wherein the number is m The distribution of the structural unit represented by That is, in the formulas (1) and (2), the (Si (R) (R) —O) units and the (Si (R) (X) —O) units may be randomly distributed.
-主鎖にシロキサン構造と非シロキサン構造を有する化合物-
シロキサン化合物層に用いうる、主鎖にシロキサン構造と非シロキサン構造を有する化合物としては、例えば、下記式(3)~(7)で表される化合物が挙げられる。 -Compounds with siloxane and non-siloxane structures in the main chain-
Examples of the compound having a siloxane structure and a non-siloxane structure in the main chain that can be used in the siloxane compound layer include compounds represented by the following formulas (3) to (7).
シロキサン化合物層に用いうる、主鎖にシロキサン構造と非シロキサン構造を有する化合物としては、例えば、下記式(3)~(7)で表される化合物が挙げられる。 -Compounds with siloxane and non-siloxane structures in the main chain-
Examples of the compound having a siloxane structure and a non-siloxane structure in the main chain that can be used in the siloxane compound layer include compounds represented by the following formulas (3) to (7).
式(3)中、R、m及びnは、それぞれ式(1)のR、m及びnと同義である。R’は-O-又は-CH2-であり、R’’は水素原子又はメチルである。式(3)の両末端はアミノ基、水酸基、カルボキシ基、トリメチルシリル基、エポキシ基、ビニル基、水素原子、置換アルキル基であることが好ましい。
In formula (3), R, m and n have the same meanings as R, m and n in formula (1), respectively. R ′ is —O— or —CH 2 —, and R ″ is a hydrogen atom or methyl. Both ends of the formula (3) are preferably an amino group, a hydroxyl group, a carboxy group, a trimethylsilyl group, an epoxy group, a vinyl group, a hydrogen atom, or a substituted alkyl group.
式(4)中、m及びnは、それぞれ式(1)におけるm及びnと同義である。
In Formula (4), m and n are synonymous with m and n in Formula (1), respectively.
式(5)中、m及びnは、それぞれ式(1)におけるm及びnと同義である。
In formula (5), m and n have the same meanings as m and n in formula (1), respectively.
式(6)中、m及びnは、それぞれ式(1)におけるm及びnと同義である。式(6)の両末端はアミノ基、水酸基、カルボキシ基、トリメチルシリル基、エポキシ基、ビニル基、水素原子、又は置換アルキル基が結合していることが好ましい。
In Formula (6), m and n are synonymous with m and n in Formula (1), respectively. It is preferable that the both ends of Formula (6) have an amino group, a hydroxyl group, a carboxy group, a trimethylsilyl group, an epoxy group, a vinyl group, a hydrogen atom, or a substituted alkyl group bonded thereto.
式(7)中、m及びnは、それぞれ式(1)におけるm及びnと同義である。式(7)の両末端はアミノ基、水酸基、カルボキシ基、トリメチルシリル基、エポキシ、ビニル基、水素原子、又は置換アルキル基が結合していることが好ましい。
In formula (7), m and n are synonymous with m and n in formula (1), respectively. It is preferable that an amino group, a hydroxyl group, a carboxy group, a trimethylsilyl group, an epoxy, a vinyl group, a hydrogen atom, or a substituted alkyl group is bonded to both ends of the formula (7).
上記式(3)~(7)において、シロキサン構造単位と非シロキサン構造単位とは、ランダムに分布していてもよい。
In the above formulas (3) to (7), the siloxane structural unit and the non-siloxane structural unit may be randomly distributed.
主鎖にシロキサン構造と非シロキサン構造を有する化合物は、全繰り返し構造単位の合計モル数に対して、シロキサン構造単位を50モル%以上含有することが好ましく、70モル%以上含有することがさらに好ましい。
The compound having a siloxane structure and a non-siloxane structure in the main chain preferably contains 50 mol% or more of siloxane structural units, more preferably 70 mol% or more, based on the total number of moles of all repeating structural units. .
シロキサン化合物層に用いるシロキサン化合物の重量平均分子量は、薄膜化と耐久性の両立の観点から、5,000~1,000,000であることが好ましい。重量平均分子量の測定方法は上述したとおりである。
The weight average molecular weight of the siloxane compound used in the siloxane compound layer is preferably 5,000 to 1,000,000 from the viewpoint of achieving both a thin film and durability. The method for measuring the weight average molecular weight is as described above.
さらに、シロキサン化合物層を構成するシロキサン化合物の好ましい例を以下に列挙する。
ポリジメチルシロキサン、ポリメチルフェニルシロキサン、ポリジフェニルシロキサン、ポリスルホン-ポリヒドロキシスチレン-ポリジメチルシロキサン共重合体、ジメチルシロキサン-メチルビニルシロキサン共重合体、ジメチルシロキサン-ジフェニルシロキサン-メチルビニルシロキサン共重合体、メチル-3,3,3-トリフルオロプロピルシロキサン-メチルビニルシロキサン共重合体、ジメチルシロキサン-メチルフェニルシロキサン-メチルビニルシロキサン共重合体、ジフェニルシロキサン-ジメチルシロキサン共重合体末端ビニル、ポリジメチルシロキサン末端ビニル、ポリジメチルシロキサン末端H、及びジメチルシロキサン-メチルハイドロシロキサン共重合体から選ばれる1種又は2種以上。なお、これらは架橋反応物を形成している形態も含まれる。 Furthermore, the preferable example of the siloxane compound which comprises a siloxane compound layer is enumerated below.
Polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, polysulfone-polyhydroxystyrene-polydimethylsiloxane copolymer, dimethylsiloxane-methylvinylsiloxane copolymer, dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer, methyl -3,3,3-trifluoropropylsiloxane-methylvinylsiloxane copolymer, dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymer, diphenylsiloxane-dimethylsiloxane copolymer terminal vinyl, polydimethylsiloxane terminal vinyl, One or more selected from polydimethylsiloxane terminal H and dimethylsiloxane-methylhydrosiloxane copolymer. In addition, these include the form which forms the cross-linking reaction product.
ポリジメチルシロキサン、ポリメチルフェニルシロキサン、ポリジフェニルシロキサン、ポリスルホン-ポリヒドロキシスチレン-ポリジメチルシロキサン共重合体、ジメチルシロキサン-メチルビニルシロキサン共重合体、ジメチルシロキサン-ジフェニルシロキサン-メチルビニルシロキサン共重合体、メチル-3,3,3-トリフルオロプロピルシロキサン-メチルビニルシロキサン共重合体、ジメチルシロキサン-メチルフェニルシロキサン-メチルビニルシロキサン共重合体、ジフェニルシロキサン-ジメチルシロキサン共重合体末端ビニル、ポリジメチルシロキサン末端ビニル、ポリジメチルシロキサン末端H、及びジメチルシロキサン-メチルハイドロシロキサン共重合体から選ばれる1種又は2種以上。なお、これらは架橋反応物を形成している形態も含まれる。 Furthermore, the preferable example of the siloxane compound which comprises a siloxane compound layer is enumerated below.
Polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, polysulfone-polyhydroxystyrene-polydimethylsiloxane copolymer, dimethylsiloxane-methylvinylsiloxane copolymer, dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer, methyl -3,3,3-trifluoropropylsiloxane-methylvinylsiloxane copolymer, dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymer, diphenylsiloxane-dimethylsiloxane copolymer terminal vinyl, polydimethylsiloxane terminal vinyl, One or more selected from polydimethylsiloxane terminal H and dimethylsiloxane-methylhydrosiloxane copolymer. In addition, these include the form which forms the cross-linking reaction product.
本発明の複合膜において、シロキサン化合物層の厚さは、平滑性およびガス透過性の観点から、0.01~5μmであることが好ましく、0.05~1μmであることがより好ましい。
また、シロキサン化合物層の40℃、4MPaにおける気体透過率は二酸化炭素透過速度で100GPU以上であることが好ましく、300GPU以上であることがより好ましく、1,000GPU以上であることがさらに好ましい。 In the composite film of the present invention, the thickness of the siloxane compound layer is preferably from 0.01 to 5 μm, more preferably from 0.05 to 1 μm, from the viewpoint of smoothness and gas permeability.
Further, the gas permeability at 40 ° C. and 4 MPa of the siloxane compound layer is preferably 100 GPU or more, more preferably 300 GPU or more, and further preferably 1,000 GPU or more in terms of carbon dioxide transmission rate.
また、シロキサン化合物層の40℃、4MPaにおける気体透過率は二酸化炭素透過速度で100GPU以上であることが好ましく、300GPU以上であることがより好ましく、1,000GPU以上であることがさらに好ましい。 In the composite film of the present invention, the thickness of the siloxane compound layer is preferably from 0.01 to 5 μm, more preferably from 0.05 to 1 μm, from the viewpoint of smoothness and gas permeability.
Further, the gas permeability at 40 ° C. and 4 MPa of the siloxane compound layer is preferably 100 GPU or more, more preferably 300 GPU or more, and further preferably 1,000 GPU or more in terms of carbon dioxide transmission rate.
(ガス分離非対称膜)
本発明のガス分離膜は、非対称膜であってもよい。非対称膜は、ポリイミド化合物を含む溶液を用いて相転換法によって形成することができる。相転換法は、ポリマー溶液を凝固液と接触させて相転換させながら膜を形成する公知の方法であり、本発明ではいわゆる乾湿式法が好適に用いられる。乾湿式法は、膜形状にしたポリマー溶液の表面の溶液を蒸発させて薄い緻密層(ガス分離層)を形成し、ついで凝固液(ポリマー溶液の溶媒とは相溶し、ポリマーは不溶な溶剤)に浸漬し、その際生じる相分離現象を利用して微細孔を形成して多孔質層を形成させる方法であり、ロブ・スリラージャンらの提案(例えば、米国特許第3,133,132号明細書)したものである。 (Gas separation asymmetric membrane)
The gas separation membrane of the present invention may be an asymmetric membrane. The asymmetric membrane can be formed by a phase change method using a solution containing a polyimide compound. The phase inversion method is a known method for forming a film while bringing a polymer solution into contact with a coagulation liquid to cause phase conversion. In the present invention, a so-called dry / wet method is suitably used. In the dry-wet method, a thin polymer layer (gas separation layer) is formed by evaporating the solution on the surface of the polymer solution in the form of a film, and then coagulating liquid (solvent is compatible with the solvent of the polymer solution and the polymer is an insoluble solvent. ) And forming a porous layer by utilizing the phase separation phenomenon that occurs at that time, and a proposal by Rob Thrillerjan et al. (For example, US Pat. No. 3,133,132) Description).
本発明のガス分離膜は、非対称膜であってもよい。非対称膜は、ポリイミド化合物を含む溶液を用いて相転換法によって形成することができる。相転換法は、ポリマー溶液を凝固液と接触させて相転換させながら膜を形成する公知の方法であり、本発明ではいわゆる乾湿式法が好適に用いられる。乾湿式法は、膜形状にしたポリマー溶液の表面の溶液を蒸発させて薄い緻密層(ガス分離層)を形成し、ついで凝固液(ポリマー溶液の溶媒とは相溶し、ポリマーは不溶な溶剤)に浸漬し、その際生じる相分離現象を利用して微細孔を形成して多孔質層を形成させる方法であり、ロブ・スリラージャンらの提案(例えば、米国特許第3,133,132号明細書)したものである。 (Gas separation asymmetric membrane)
The gas separation membrane of the present invention may be an asymmetric membrane. The asymmetric membrane can be formed by a phase change method using a solution containing a polyimide compound. The phase inversion method is a known method for forming a film while bringing a polymer solution into contact with a coagulation liquid to cause phase conversion. In the present invention, a so-called dry / wet method is suitably used. In the dry-wet method, a thin polymer layer (gas separation layer) is formed by evaporating the solution on the surface of the polymer solution in the form of a film, and then coagulating liquid (solvent is compatible with the solvent of the polymer solution and the polymer is an insoluble solvent. ) And forming a porous layer by utilizing the phase separation phenomenon that occurs at that time, and a proposal by Rob Thrillerjan et al. (For example, US Pat. No. 3,133,132) Description).
本発明のガス分離非対称膜において、緻密層あるいはスキン層と呼ばれるガス分離に寄与する表層(ガス分離層)の厚さは特に限定されないが、実用的なガス透過性を付与する観点から、0.01~5.0μmであることが好ましく、0.05~1.0μmであることがより好ましい。一方、緻密層より下部の多孔質層はガス透過性の抵抗を下げると同時に機械強度の付与の役割を担うものであり、その厚さは非対称膜としての自立性が付与される限りにおいては特に限定されるものではないが5~500μmであることが好ましく、5~200μmであることがより好ましく、5~100μmであることがさらに好ましい。
In the gas separation asymmetric membrane of the present invention, the thickness of a surface layer (gas separation layer) that contributes to gas separation called a dense layer or a skin layer is not particularly limited. The thickness is preferably from 01 to 5.0 μm, more preferably from 0.05 to 1.0 μm. On the other hand, the porous layer below the dense layer lowers the gas permeability resistance and at the same time plays a role of imparting mechanical strength, and its thickness is particularly limited as long as it is self-supporting as an asymmetric membrane. Although not limited, it is preferably 5 to 500 μm, more preferably 5 to 200 μm, and still more preferably 5 to 100 μm.
本発明のガス分離非対称膜は、平膜であってもあるいは中空糸膜であってもよい。非対称中空糸膜は乾湿式紡糸法により製造することができる。乾湿式紡糸法は、乾湿式法を紡糸ノズルから吐出して中空糸状の目的形状としたポリマー溶液に適用して非対称中空糸膜を製造する方法である。より詳しくは、ポリマー溶液をノズルから中空糸状の目的形状に吐出させ、吐出直後に空気又は窒素ガス雰囲気中を通した後、ポリマーを実質的には溶解せず且つポリマー溶液の溶媒とは相溶性を有する凝固液に浸漬して非対称構造を形成し、その後乾燥し、さらに必要に応じて加熱処理して分離膜を製造する方法である。
The gas separation asymmetric membrane of the present invention may be a flat membrane or a hollow fiber membrane. The asymmetric hollow fiber membrane can be produced by a dry and wet spinning method. The dry-wet spinning method is a method for producing an asymmetric hollow fiber membrane by applying a dry-wet method to a polymer solution that is discharged from a spinning nozzle to have a hollow fiber-shaped target shape. More specifically, the polymer solution is discharged from a nozzle into a hollow fiber-shaped target shape, and after passing through an air or nitrogen gas atmosphere immediately after discharge, the polymer is not substantially dissolved and is compatible with the solvent of the polymer solution. In this method, an asymmetric structure is formed by immersing in a coagulating liquid containing, then dried, and further heat-treated as necessary to produce a separation membrane.
ノズルから吐出させるポリイミド化合物を含む溶液の溶液粘度は、吐出温度(例えば10℃)で2~17,000Pa・s、好ましくは10~1,500Pa・s、特に20~1,000Pa・sであることが、中空糸状などの吐出後の形状を安定に得ることができるので好ましい。凝固液への浸漬は、一次凝固液に浸漬して中空糸状等の膜の形状が保持出来る程度に凝固させた後、案内ロールに巻き取り、ついで二次凝固液に浸漬して膜全体を十分に凝固させることが好ましい。凝固した膜の乾燥は、凝固液を炭化水素などの溶媒に置換してから行うのが効率的である。乾燥のための加熱処理は、用いたポリイミド化合物の軟化点又は二次転移点よりも低い温度で実施することが好ましい。
The solution viscosity of the solution containing the polyimide compound discharged from the nozzle is 2 to 17,000 Pa · s, preferably 10 to 1,500 Pa · s, particularly 20 to 1,000 Pa · s at the discharge temperature (for example, 10 ° C.). It is preferable because a shape after discharge such as a hollow fiber shape can be stably obtained. For immersion in the coagulation liquid, the film is immersed in the primary coagulation liquid and solidified to such an extent that the shape of the hollow fiber or the like can be maintained. It is preferable to solidify. It is efficient to dry the coagulated film after replacing the coagulating liquid with a solvent such as hydrocarbon. The heat treatment for drying is preferably performed at a temperature lower than the softening point or secondary transition point of the used polyimide compound.
本発明のガス分離非対称膜は、機械的強度をより高めるために、その引張強度は10N/mm2以上が好ましく、12N/mm2以上がより好ましい。この引張強度の上限に特に制限はないが、通常には25N/mm2以下であり、20N/mm2以下であってもよい。また、本発明のガス分離非対称膜の圧縮強さは、10MPa以上が好ましく、15MPa以上がより好ましい。この圧縮強さの上限に特に制限はないが、通常には50MPa以下であり、40MPa以下であってもよい。
The tensile strength of the gas separation asymmetric membrane of the present invention is preferably 10 N / mm 2 or more, and more preferably 12 N / mm 2 or more in order to further increase the mechanical strength. There is no particular limitation on the upper limit of the tensile strength, usually is at 25 N / mm 2 or less, may be 20 N / mm 2 or less. Further, the compressive strength of the gas separation asymmetric membrane of the present invention is preferably 10 MPa or more, and more preferably 15 MPa or more. Although there is no restriction | limiting in particular in the upper limit of this compressive strength, Usually, it is 50 MPa or less, and 40 MPa or less may be sufficient.
本発明のガス分離非対称膜に、上記機械的強度と共に適度な柔軟性も付与するために、本発明のガス分離非対称膜の破断伸度は、12%以上が好ましく、16%以上がより好ましい。この破断伸度の上限に特に制限はないが、通常には25%以下であり、20%以下であってもよい。また、同様の観点から、本発明のガス分離非対称膜の引張弾性率は、100MPa以下であることが好ましく、90MPa以下であることがより好ましく、80MPa以下であることがさらに好ましい。引張弾性率の下限値は、機械的強度との両立を図るために、通常には10MPa以上であり、20MPa以上であってもよく、30MPa以上であってもよく、40MPa以上とすることもできる。
In order to give the gas separation asymmetric membrane of the present invention moderate flexibility as well as the above mechanical strength, the elongation at break of the gas separation asymmetric membrane of the present invention is preferably 12% or more, and more preferably 16% or more. The upper limit of the elongation at break is not particularly limited, but is usually 25% or less and may be 20% or less. From the same viewpoint, the tensile elastic modulus of the gas separation asymmetric membrane of the present invention is preferably 100 MPa or less, more preferably 90 MPa or less, and further preferably 80 MPa or less. The lower limit of the tensile elastic modulus is usually 10 MPa or more, 20 MPa or more, 30 MPa or more, or 40 MPa or more in order to achieve compatibility with mechanical strength. .
本発明のガス分離膜において、ガス分離層中のポリイミド化合物の含有量は、所望のガス分離性能が得られれば特に制限はない。ガス分離性能をより向上させる観点から、ガス分離層中のポリイミド化合物の含有量は、20質量%以上であることが好ましく、40質量%以上であることがより好ましく、60質量%以上であることが好ましく、70質量%以上であることがさらに好ましい。また、ガス分離層中のポリイミド化合物の含有量は、100質量%であってもよいが、通常は99質量%以下である。
In the gas separation membrane of the present invention, the content of the polyimide compound in the gas separation layer is not particularly limited as long as desired gas separation performance can be obtained. From the viewpoint of further improving the gas separation performance, the content of the polyimide compound in the gas separation layer is preferably 20% by mass or more, more preferably 40% by mass or more, and 60% by mass or more. Is preferable, and it is more preferable that it is 70 mass% or more. The content of the polyimide compound in the gas separation layer may be 100% by mass, but is usually 99% by mass or less.
(ガス分離膜の用途と特性)
本発明のガス分離膜(複合膜及び非対称膜)は、ガス分離回収、ガス分離精製に好適に用いることができる。例えば、水素、ヘリウム、一酸化炭素、二酸化炭素、硫化水素、酸素、窒素、アンモニア、硫黄酸化物、窒素酸化物、メタン、エタンなどの炭化水素、プロピレンなどの不飽和炭化水素、テトラフルオロエタンなどのパーフルオロ化合物などのガスを含有する気体混合物から特定の気体を効率よく分離し得るガス分離膜とすることができる。特に二酸化炭素/炭化水素(メタン)を含む気体混合物から二酸化炭素を選択分離するガス分離膜とすることが好ましい。 (Use and characteristics of gas separation membrane)
The gas separation membrane (composite membrane and asymmetric membrane) of the present invention can be suitably used for gas separation recovery and gas separation purification. 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. In particular, a gas separation membrane that selectively separates carbon dioxide from a gas mixture containing carbon dioxide / hydrocarbon (methane) is preferable.
本発明のガス分離膜(複合膜及び非対称膜)は、ガス分離回収、ガス分離精製に好適に用いることができる。例えば、水素、ヘリウム、一酸化炭素、二酸化炭素、硫化水素、酸素、窒素、アンモニア、硫黄酸化物、窒素酸化物、メタン、エタンなどの炭化水素、プロピレンなどの不飽和炭化水素、テトラフルオロエタンなどのパーフルオロ化合物などのガスを含有する気体混合物から特定の気体を効率よく分離し得るガス分離膜とすることができる。特に二酸化炭素/炭化水素(メタン)を含む気体混合物から二酸化炭素を選択分離するガス分離膜とすることが好ましい。 (Use and characteristics of gas separation membrane)
The gas separation membrane (composite membrane and asymmetric membrane) of the present invention can be suitably used for gas separation recovery and gas separation purification. 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. In particular, a gas separation membrane that selectively separates carbon dioxide from a gas mixture containing carbon dioxide / hydrocarbon (methane) is preferable.
とりわけ、分離処理されるガスが二酸化炭素とメタンとの混合ガスである場合においては、40℃、5MPaにおける二酸化炭素の透過速度が20GPU超であることが好ましく、30GPU超であることがより好ましく、50~500GPUであることがより好ましい。二酸化炭素とメタンとの透過速度比(RCO2/RCH4)は15以上であることが好ましく、20以上であることがより好ましく、23以上であることがさらに好ましく、25~50であることが特に好ましい。RCO2は二酸化炭素の透過速度、RCH4はメタンの透過速度を示す。
なお、1GPUは1×10-6cm3(STP)/cm2・sec・cmHgである。 In particular, when the gas to be separated is a mixed gas of carbon dioxide and methane, the permeation rate of carbon dioxide at 40 ° C. and 5 MPa is preferably more than 20 GPU, more preferably more than 30 GPU, More preferably, it is 50 to 500 GPU. The permeation rate ratio of carbon dioxide to methane (R CO2 / R CH4 ) is preferably 15 or more, more preferably 20 or more, further preferably 23 or more, and preferably 25 to 50. Particularly preferred. R CO2 represents the permeation rate of carbon dioxide, and R CH4 represents the permeation rate of methane.
1 GPU is 1 × 10 −6 cm 3 (STP) / cm 2 · sec · cmHg.
なお、1GPUは1×10-6cm3(STP)/cm2・sec・cmHgである。 In particular, when the gas to be separated is a mixed gas of carbon dioxide and methane, the permeation rate of carbon dioxide at 40 ° C. and 5 MPa is preferably more than 20 GPU, more preferably more than 30 GPU, More preferably, it is 50 to 500 GPU. The permeation rate ratio of carbon dioxide to methane (R CO2 / R CH4 ) is preferably 15 or more, more preferably 20 or more, further preferably 23 or more, and preferably 25 to 50. Particularly preferred. R CO2 represents the permeation rate of carbon dioxide, and R CH4 represents the permeation rate of methane.
1 GPU is 1 × 10 −6 cm 3 (STP) / cm 2 · sec · cmHg.
(その他の成分等)
本発明のガス分離膜のガス分離層には、膜物性を調整するため、各種高分子化合物を添加することもできる。高分子化合物としては、アクリル系重合体、ポリウレタン樹脂、ポリアミド樹脂、ポリエステル樹脂、エポキシ樹脂、フェノール樹脂、ポリカーボネート樹脂、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、シェラック、ビニル系樹脂、アクリル系樹脂、ゴム系樹脂、ワックス類、その他の天然樹脂等が使用できる。また、これらは2種以上併用してもかまわない。
また、液物性調整のためにノニオン性界面活性剤、カチオン性界面活性剤や、有機フルオロ化合物などを添加することもできる。 (Other ingredients)
Various polymer compounds can be added to the gas separation layer of the gas separation membrane of the present invention in order to adjust the membrane properties. High molecular compounds include acrylic polymers, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellac, vinyl resins, acrylic resins, rubber resins. Waxes and other natural resins can be used. Two or more of these may be used in combination.
Further, nonionic surfactants, cationic surfactants, organic fluoro compounds, and the like can be added to adjust liquid properties.
本発明のガス分離膜のガス分離層には、膜物性を調整するため、各種高分子化合物を添加することもできる。高分子化合物としては、アクリル系重合体、ポリウレタン樹脂、ポリアミド樹脂、ポリエステル樹脂、エポキシ樹脂、フェノール樹脂、ポリカーボネート樹脂、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、シェラック、ビニル系樹脂、アクリル系樹脂、ゴム系樹脂、ワックス類、その他の天然樹脂等が使用できる。また、これらは2種以上併用してもかまわない。
また、液物性調整のためにノニオン性界面活性剤、カチオン性界面活性剤や、有機フルオロ化合物などを添加することもできる。 (Other ingredients)
Various polymer compounds can be added to the gas separation layer of the gas separation membrane of the present invention in order to adjust the membrane properties. High molecular compounds include acrylic polymers, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellac, vinyl resins, acrylic resins, rubber resins. Waxes and other natural resins can be used. Two or more of these may be used in combination.
Further, nonionic surfactants, cationic surfactants, organic fluoro compounds, and the like can be added to adjust liquid properties.
界面活性剤の具体例としては、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、高級脂肪酸塩、高級脂肪酸エステルのスルホン酸塩、高級アルコールエーテルの硫酸エステル塩、高級アルコールエーテルのスルホン酸塩、高級アルキルスルホンアミドのアルキルカルボン酸塩、アルキルリン酸塩などのアニオン界面活性剤、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、アセチレングリコールのエチレンオキサイド付加物、グリセリンのエチレンオキサイド付加物、ポリオキシエチレンソルビタン脂肪酸エステルなどの非イオン性界面活性剤、また、この他にもアルキルベタインやアミドベタインなどの両性界面活性剤、シリコン系界面活性剤、フッソ系界面活性剤などを含めて、任意の界面活性剤及びその誘導体から適宜選ぶことができる。
Specific examples of the surfactant include alkylbenzene sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfonate of higher fatty acid ester, sulfate ester of higher alcohol ether, sulfonate of higher alcohol ether, higher alkyl Anionic surfactants such as alkyl carboxylates of sulfonamides, alkyl phosphates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, ethylene oxide adducts of acetylene glycol, Nonionic surfactants such as ethylene oxide adducts of glycerin and polyoxyethylene sorbitan fatty acid esters, and other amphoteric boundaries such as alkyl betaines and amide betaines Active agents, silicone surface active agents, including such fluorine-based surfactant, can be appropriately selected from any surfactant and derivatives thereof.
また、高分子分散剤を含んでいてもよく、この高分子分散剤として、具体的にはポリビニルピロリドン、ポリビニルアルコール、ポリビニルメチルエーテル、ポリエチレンオキシド、ポリエチレングリコール、ポリプロピレングリコール、ポリアクリルアミド等が挙げられ、中でもポリビニルピロリドンを用いることが好ましい。
In addition, a polymer dispersant may be included, and specific examples of the polymer dispersant include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, and polyacrylamide. Of these, polyvinylpyrrolidone is preferably used.
本発明のガス分離膜を形成する条件に特に制限はないが、温度は-30~100℃が好ましく、-10~80℃がより好ましく、5~50℃が特に好ましい。
The conditions for forming the gas separation membrane of the present invention are not particularly limited, but the temperature is preferably −30 to 100 ° C., more preferably −10 to 80 ° C., and particularly preferably 5 to 50 ° C.
本発明においては、膜を形成時に空気や酸素などの気体を共存させてもよいが、不活性ガス雰囲気下であることが望ましい。
In the present invention, a gas such as air or oxygen may coexist at the time of forming the film, but it is preferably in an inert gas atmosphere.
[ガス混合物の分離方法]
本発明のガス分離方法は、本発明のガス分離膜を用いて二酸化炭素及びメタンを含む混合ガスから二酸化炭素を選択的に透過させることを含む方法である。ガス分離の際の圧力は0.5~10MPaであることが好ましく、1~10MPaであることがより好ましく、2~7MPaであることがさらに好ましい。また、ガス分離温度は、-30~90℃であることが好ましく、15~70℃であることがさらに好ましい。二酸化炭素とメタンガスとを含む混合ガスにおいて、二酸化炭素とメタンガスの混合比に特に制限はないが、二酸化炭素:メタンガス=1:99~99:1(体積比)であることが好ましく、二酸化炭素:メタンガス=5:95~90:10であることがより好ましい。 [Separation method of gas mixture]
The gas separation method of the present invention is a method including selectively permeating carbon dioxide from a mixed gas containing carbon dioxide and methane using the gas separation membrane of the present invention. The pressure during gas separation is preferably 0.5 to 10 MPa, more preferably 1 to 10 MPa, and further preferably 2 to 7 MPa. The gas separation temperature is preferably −30 to 90 ° C., more preferably 15 to 70 ° C. In the mixed gas containing carbon dioxide and methane gas, the mixing ratio of carbon dioxide and methane gas is not particularly limited, but is preferably carbon dioxide: methane gas = 1: 99 to 99: 1 (volume ratio). More preferably, methane gas = 5: 95 to 90:10.
本発明のガス分離方法は、本発明のガス分離膜を用いて二酸化炭素及びメタンを含む混合ガスから二酸化炭素を選択的に透過させることを含む方法である。ガス分離の際の圧力は0.5~10MPaであることが好ましく、1~10MPaであることがより好ましく、2~7MPaであることがさらに好ましい。また、ガス分離温度は、-30~90℃であることが好ましく、15~70℃であることがさらに好ましい。二酸化炭素とメタンガスとを含む混合ガスにおいて、二酸化炭素とメタンガスの混合比に特に制限はないが、二酸化炭素:メタンガス=1:99~99:1(体積比)であることが好ましく、二酸化炭素:メタンガス=5:95~90:10であることがより好ましい。 [Separation method of gas mixture]
The gas separation method of the present invention is a method including selectively permeating carbon dioxide from a mixed gas containing carbon dioxide and methane using the gas separation membrane of the present invention. The pressure during gas separation is preferably 0.5 to 10 MPa, more preferably 1 to 10 MPa, and further preferably 2 to 7 MPa. The gas separation temperature is preferably −30 to 90 ° C., more preferably 15 to 70 ° C. In the mixed gas containing carbon dioxide and methane gas, the mixing ratio of carbon dioxide and methane gas is not particularly limited, but is preferably carbon dioxide: methane gas = 1: 99 to 99: 1 (volume ratio). More preferably, methane gas = 5: 95 to 90:10.
[ガス分離モジュール・ガス分離装置]
本発明のガス分離膜を用いてガス分離モジュールを調製することができる。モジュールの例としては、スパイラル型、中空糸型、プリーツ型、管状型、プレート&フレーム型などが挙げられる。
また、本発明のガス分離膜又はガス分離膜モジュールを用いて、ガスを分離回収又は分離精製させるための手段を有するガス分離装置を得ることができる。本発明のガス分離膜は、例えば、特開2007-297605号公報に記載のような吸収液と併用した膜・吸収ハイブリッド法としての気体分離回収装置に適用してもよい。 [Gas separation module / gas separator]
A gas separation module can be prepared using the gas separation membrane of the present invention. Examples of modules include spiral type, hollow fiber type, pleated type, tubular type, plate & frame type and the like.
In addition, a gas separation apparatus having means for separating and recovering or purifying gas can be obtained using the gas separation membrane or gas separation membrane module of the present invention. The gas separation membrane of the present invention may be applied, for example, 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.
本発明のガス分離膜を用いてガス分離モジュールを調製することができる。モジュールの例としては、スパイラル型、中空糸型、プリーツ型、管状型、プレート&フレーム型などが挙げられる。
また、本発明のガス分離膜又はガス分離膜モジュールを用いて、ガスを分離回収又は分離精製させるための手段を有するガス分離装置を得ることができる。本発明のガス分離膜は、例えば、特開2007-297605号公報に記載のような吸収液と併用した膜・吸収ハイブリッド法としての気体分離回収装置に適用してもよい。 [Gas separation module / gas separator]
A gas separation module can be prepared using the gas separation membrane of the present invention. Examples of modules include spiral type, hollow fiber type, pleated type, tubular type, plate & frame type and the like.
In addition, a gas separation apparatus having means for separating and recovering or purifying gas can be obtained using the gas separation membrane or gas separation membrane module of the present invention. The gas separation membrane of the present invention may be applied, for example, 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.
以下に実施例に基づき本発明を更に詳細に説明するが、本発明はこれらの実施例により限定されるものではない。
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
[合成例]
<ポリイミド(P-01)の合成>
2Lフラスコに、3,5-ジニトロベンズアミド(Sigma-Aldrich社製)14.0g(66mmol)を入れた後、メタノール600mLを加えて完溶させた。この3,5-ジニトロベンズアミドの溶液をSUS製耐圧容器(容量1.0L、日東高圧社製)に移した後、パラジウム炭素(パラジウム含率5%、約50%水湿潤品、川研ファインケミカル社製)2.8gを添加し、攪拌しながら1.0~8.0MPaの水素圧をかけ、接触水素化を行った。接触水素化中は、水素圧とヒーターの温度を調整し、反応溶液の温度を35~45℃に保ったまま、7時間撹拌し続けた。生成物等が析出しないように、反応溶液は約40℃のまま冷却せずに、耐圧容器からアスピレーターで2Lフラスコに移し、速やかにセライトろ過してパラジウム炭素を除いた。ろ過で得られた赤褐色溶液から、メタノールを減圧除去した。得られた固体をメタノールと水を用いた再結晶により精製し、目的の3,5-ジアミノベンズアミド3.4gを得た。
上記合成により得られた3,5-ジアミノベンズアミド1.09g(7.24mmol)、2,3,5,6-テトラメチル-1,4-フェニレンジアミン1.78g(10.86mmol)、N-メチルピロリドン50mLを300mLフラスコに入れて、窒素雰囲気下、攪拌して完溶させた。氷冷メタノールにより溶液を-10℃まで冷却した後、6FDA(4,4’-(ヘキサフルオロイソプロピリデン)ジフタル酸無水物)(東京化成工業社製)8.04g(18.1mmol)を添加し、N-メチルピロリドン6mLで洗い込んだ。オイルバスにより反応溶液を40℃まで昇温させた後、5時間攪拌した。ピリジン(和光純薬工業社製)0.43g(5.4mmol)、無水酢酸(和光純薬工業社製)6.10g(59.7mmol)を加え、反応溶液を80℃まで昇温させた後、3時間攪拌した。反応溶液を室温まで冷却し、アセトン80mLを加え、30分攪拌した。メタノール250mLを10分間かけて加え、P-01を白色粉体として析出させた。吸引ろ過して得られた白色粉体に対し、メタノール250mLを用いたリスラリー洗浄を4回繰り返し行い、N-メチルピロリドンを0.1%以下まで除去した後、送風乾燥機で40℃、12時間乾燥し、ポリイミド(P-01)9.23g(収率90%)を得た。ポリイミド(P-01)中のカルバモイル基の含有量は0.71mmol/gであった。 [Synthesis example]
<Synthesis of polyimide (P-01)>
After putting 14.0 g (66 mmol) of 3,5-dinitrobenzamide (manufactured by Sigma-Aldrich) into a 2 L flask, 600 mL of methanol was added to complete dissolution. This 3,5-dinitrobenzamide solution was transferred to a SUS pressure vessel (capacity 1.0 L, manufactured by Nitto High Pressure Co., Ltd.), and then palladium carbon (palladium content 5%, approximately 50% water wet product, Kawaken Fine Chemical Co., Ltd.) 2.8 g) was added, and a hydrogen pressure of 1.0 to 8.0 MPa was applied with stirring to perform catalytic hydrogenation. During the catalytic hydrogenation, the hydrogen pressure and the temperature of the heater were adjusted, and stirring was continued for 7 hours while maintaining the temperature of the reaction solution at 35 to 45 ° C. The reaction solution was transferred from the pressure vessel to a 2 L flask with an aspirator and cooled rapidly through Celite to remove palladium carbon, so that the product or the like was not precipitated. Methanol was removed under reduced pressure from the reddish brown solution obtained by filtration. The obtained solid was purified by recrystallization using methanol and water to obtain 3.4 g of the desired 3,5-diaminobenzamide.
1.09 g (7.24 mmol) of 3,5-diaminobenzamide obtained by the above synthesis, 1.78 g (10.86 mmol) of 2,3,5,6-tetramethyl-1,4-phenylenediamine, N-methyl Pyrrolidone (50 mL) was placed in a 300 mL flask and stirred to dissolve completely in a nitrogen atmosphere. After cooling the solution to −10 ° C. with ice-cold methanol, 8.04 g (18.1 mmol) of 6FDA (4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. Washed with 6 mL of N-methylpyrrolidone. The reaction solution was heated to 40 ° C. with an oil bath and stirred for 5 hours. After adding 0.43 g (5.4 mmol) of pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) and 6.10 g (59.7 mmol) of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), the reaction solution was heated to 80 ° C. Stir for 3 hours. The reaction solution was cooled to room temperature, 80 mL of acetone was added, and the mixture was stirred for 30 minutes. Methanol (250 mL) was added over 10 minutes to precipitate P-01 as a white powder. The white powder obtained by suction filtration was repeatedly washed four times with 250 mL of methanol to remove N-methylpyrrolidone to 0.1% or less, and then blown at 40 ° C. for 12 hours with an air dryer. It was dried to obtain 9.23 g (yield 90%) of polyimide (P-01). The content of carbamoyl group in polyimide (P-01) was 0.71 mmol / g.
<ポリイミド(P-01)の合成>
2Lフラスコに、3,5-ジニトロベンズアミド(Sigma-Aldrich社製)14.0g(66mmol)を入れた後、メタノール600mLを加えて完溶させた。この3,5-ジニトロベンズアミドの溶液をSUS製耐圧容器(容量1.0L、日東高圧社製)に移した後、パラジウム炭素(パラジウム含率5%、約50%水湿潤品、川研ファインケミカル社製)2.8gを添加し、攪拌しながら1.0~8.0MPaの水素圧をかけ、接触水素化を行った。接触水素化中は、水素圧とヒーターの温度を調整し、反応溶液の温度を35~45℃に保ったまま、7時間撹拌し続けた。生成物等が析出しないように、反応溶液は約40℃のまま冷却せずに、耐圧容器からアスピレーターで2Lフラスコに移し、速やかにセライトろ過してパラジウム炭素を除いた。ろ過で得られた赤褐色溶液から、メタノールを減圧除去した。得られた固体をメタノールと水を用いた再結晶により精製し、目的の3,5-ジアミノベンズアミド3.4gを得た。
上記合成により得られた3,5-ジアミノベンズアミド1.09g(7.24mmol)、2,3,5,6-テトラメチル-1,4-フェニレンジアミン1.78g(10.86mmol)、N-メチルピロリドン50mLを300mLフラスコに入れて、窒素雰囲気下、攪拌して完溶させた。氷冷メタノールにより溶液を-10℃まで冷却した後、6FDA(4,4’-(ヘキサフルオロイソプロピリデン)ジフタル酸無水物)(東京化成工業社製)8.04g(18.1mmol)を添加し、N-メチルピロリドン6mLで洗い込んだ。オイルバスにより反応溶液を40℃まで昇温させた後、5時間攪拌した。ピリジン(和光純薬工業社製)0.43g(5.4mmol)、無水酢酸(和光純薬工業社製)6.10g(59.7mmol)を加え、反応溶液を80℃まで昇温させた後、3時間攪拌した。反応溶液を室温まで冷却し、アセトン80mLを加え、30分攪拌した。メタノール250mLを10分間かけて加え、P-01を白色粉体として析出させた。吸引ろ過して得られた白色粉体に対し、メタノール250mLを用いたリスラリー洗浄を4回繰り返し行い、N-メチルピロリドンを0.1%以下まで除去した後、送風乾燥機で40℃、12時間乾燥し、ポリイミド(P-01)9.23g(収率90%)を得た。ポリイミド(P-01)中のカルバモイル基の含有量は0.71mmol/gであった。 [Synthesis example]
<Synthesis of polyimide (P-01)>
After putting 14.0 g (66 mmol) of 3,5-dinitrobenzamide (manufactured by Sigma-Aldrich) into a 2 L flask, 600 mL of methanol was added to complete dissolution. This 3,5-dinitrobenzamide solution was transferred to a SUS pressure vessel (capacity 1.0 L, manufactured by Nitto High Pressure Co., Ltd.), and then palladium carbon (palladium content 5%, approximately 50% water wet product, Kawaken Fine Chemical Co., Ltd.) 2.8 g) was added, and a hydrogen pressure of 1.0 to 8.0 MPa was applied with stirring to perform catalytic hydrogenation. During the catalytic hydrogenation, the hydrogen pressure and the temperature of the heater were adjusted, and stirring was continued for 7 hours while maintaining the temperature of the reaction solution at 35 to 45 ° C. The reaction solution was transferred from the pressure vessel to a 2 L flask with an aspirator and cooled rapidly through Celite to remove palladium carbon, so that the product or the like was not precipitated. Methanol was removed under reduced pressure from the reddish brown solution obtained by filtration. The obtained solid was purified by recrystallization using methanol and water to obtain 3.4 g of the desired 3,5-diaminobenzamide.
1.09 g (7.24 mmol) of 3,5-diaminobenzamide obtained by the above synthesis, 1.78 g (10.86 mmol) of 2,3,5,6-tetramethyl-1,4-phenylenediamine, N-methyl Pyrrolidone (50 mL) was placed in a 300 mL flask and stirred to dissolve completely in a nitrogen atmosphere. After cooling the solution to −10 ° C. with ice-cold methanol, 8.04 g (18.1 mmol) of 6FDA (4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. Washed with 6 mL of N-methylpyrrolidone. The reaction solution was heated to 40 ° C. with an oil bath and stirred for 5 hours. After adding 0.43 g (5.4 mmol) of pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) and 6.10 g (59.7 mmol) of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), the reaction solution was heated to 80 ° C. Stir for 3 hours. The reaction solution was cooled to room temperature, 80 mL of acetone was added, and the mixture was stirred for 30 minutes. Methanol (250 mL) was added over 10 minutes to precipitate P-01 as a white powder. The white powder obtained by suction filtration was repeatedly washed four times with 250 mL of methanol to remove N-methylpyrrolidone to 0.1% or less, and then blown at 40 ° C. for 12 hours with an air dryer. It was dried to obtain 9.23 g (yield 90%) of polyimide (P-01). The content of carbamoyl group in polyimide (P-01) was 0.71 mmol / g.
<ポリイミド(P-02~17)、比較ポリイミド01~04の合成>
上記合成例に準じて、下記構造単位(繰り返し単位)からなるポリイミド(P-02~17、比較ポリイミド01~04)を合成した。 <Synthesis of Polyimide (P-02 to 17) and Comparative Polyimide 01 to 04>
According to the above synthesis example, polyimides (P-02 to 17, comparative polyimides 01 to 04) composed of the following structural units (repeating units) were synthesized.
上記合成例に準じて、下記構造単位(繰り返し単位)からなるポリイミド(P-02~17、比較ポリイミド01~04)を合成した。 <Synthesis of Polyimide (P-02 to 17) and Comparative Polyimide 01 to 04>
According to the above synthesis example, polyimides (P-02 to 17, comparative polyimides 01 to 04) composed of the following structural units (repeating units) were synthesized.
<比較ポリマー>
下記構造単位(繰り返し単位)からなるセルロースアセテートとして市販品(商品名:L-70、ダイセル社製、酢化度0.55)を用いた。酢化度は、単位重量当たりの結合酢酸の重量百分率を意味する。 <Comparative polymer>
As a cellulose acetate comprising the following structural units (repeating units), a commercially available product (trade name: L-70, manufactured by Daicel Corporation, acetylation degree 0.55) was used. The degree of acetylation means the weight percentage of bound acetic acid per unit weight.
下記構造単位(繰り返し単位)からなるセルロースアセテートとして市販品(商品名:L-70、ダイセル社製、酢化度0.55)を用いた。酢化度は、単位重量当たりの結合酢酸の重量百分率を意味する。 <Comparative polymer>
As a cellulose acetate comprising the following structural units (repeating units), a commercially available product (trade name: L-70, manufactured by Daicel Corporation, acetylation degree 0.55) was used. The degree of acetylation means the weight percentage of bound acetic acid per unit weight.
[実施例1] 複合膜の作製
<平滑層付PAN多孔質膜の作製>
(ジアルキルシロキサン基を有する放射線硬化性ポリマーの調製)
150mLの3口フラスコにUV9300(Momentive社製)39g、X-22-162C(信越化学工業社製)10g、DBU(1,8-ジアザビシクロ[5.4.0]ウンデカ-7-エン)0.007gを加え、n-ヘプタン50gに溶解させた。これを95℃で168時間維持させて、ポリ(シロキサン)基を有する放射線硬化性ポリマー溶液(25℃で粘度22.8mPa・s)を得た。 [Example 1] Production of composite membrane <Production of PAN porous membrane with smooth layer>
(Preparation of radiation curable polymer having dialkylsiloxane group)
In a 150 mL three-necked flask, 39 g of UV9300 (manufactured by Momentive), 10 g of X-22-162C (manufactured by Shin-Etsu Chemical), DBU (1,8-diazabicyclo [5.4.0] undec-7-ene). 007 g was added and dissolved in 50 g of n-heptane. This was maintained at 95 ° C. for 168 hours to obtain a radiation curable polymer solution having a poly (siloxane) group (viscosity of 22.8 mPa · s at 25 ° C.).
<平滑層付PAN多孔質膜の作製>
(ジアルキルシロキサン基を有する放射線硬化性ポリマーの調製)
150mLの3口フラスコにUV9300(Momentive社製)39g、X-22-162C(信越化学工業社製)10g、DBU(1,8-ジアザビシクロ[5.4.0]ウンデカ-7-エン)0.007gを加え、n-ヘプタン50gに溶解させた。これを95℃で168時間維持させて、ポリ(シロキサン)基を有する放射線硬化性ポリマー溶液(25℃で粘度22.8mPa・s)を得た。 [Example 1] Production of composite membrane <Production of PAN porous membrane with smooth layer>
(Preparation of radiation curable polymer having dialkylsiloxane group)
In a 150 mL three-necked flask, 39 g of UV9300 (manufactured by Momentive), 10 g of X-22-162C (manufactured by Shin-Etsu Chemical), DBU (1,8-diazabicyclo [5.4.0] undec-7-ene). 007 g was added and dissolved in 50 g of n-heptane. This was maintained at 95 ° C. for 168 hours to obtain a radiation curable polymer solution having a poly (siloxane) group (viscosity of 22.8 mPa · s at 25 ° C.).
(重合性の放射線硬化性組成物の調製)
上記放射線硬化性ポリマー溶液5gを20℃まで冷却し、n-ヘプタン95gで希釈した。得られた溶液に対し、光重合開始剤であるUV9380C(Momentive社製)0.5gおよびオルガチックスTA-10(マツモトファインケミカル社製)0.1gを添加し、重合性の放射線硬化性組成物を調製した。 (Preparation of polymerizable radiation curable composition)
5 g of the radiation curable polymer solution was cooled to 20 ° C. and diluted with 95 g of n-heptane. To the obtained solution, 0.5 g of UV9380C (manufactured by Momentive) as a photopolymerization initiator and 0.1 g of organics TA-10 (manufactured by Matsumoto Fine Chemical) are added, and a polymerizable radiation curable composition is prepared. Prepared.
上記放射線硬化性ポリマー溶液5gを20℃まで冷却し、n-ヘプタン95gで希釈した。得られた溶液に対し、光重合開始剤であるUV9380C(Momentive社製)0.5gおよびオルガチックスTA-10(マツモトファインケミカル社製)0.1gを添加し、重合性の放射線硬化性組成物を調製した。 (Preparation of polymerizable radiation curable composition)
5 g of the radiation curable polymer solution was cooled to 20 ° C. and diluted with 95 g of n-heptane. To the obtained solution, 0.5 g of UV9380C (manufactured by Momentive) as a photopolymerization initiator and 0.1 g of organics TA-10 (manufactured by Matsumoto Fine Chemical) are added, and a polymerizable radiation curable composition is prepared. Prepared.
(重合性の放射線硬化性組成物の多孔質支持体への塗布、平滑層の形成)
PAN(ポリアクリロニトリル)多孔質膜(不織布上にポリアクリロニトリル多孔質膜が存在、不織布を含め、膜厚は約180μm)を支持体として上記の重合性の放射線硬化性組成物をスピンコートした後、UV強度24kW/m、処理時間10秒のUV処理条件でUV処理(Fusion UV System社製、Light Hammer 10、D-バルブ)を行った後、乾燥させた。このようにして、多孔質支持体上にジアルキルシロキサン基を有する厚み1μmの平滑層を形成した。 (Application of polymerizable radiation curable composition to porous support, formation of smooth layer)
PAN (polyacrylonitrile) porous membrane (polyacrylonitrile porous membrane is present on the nonwoven fabric, including the nonwoven fabric, the film thickness is about 180 μm) After spin coating the above polymerizable radiation curable composition as a support, After UV treatment (Fusion UV System,Light Hammer 10, D-bulb) under UV treatment conditions with a UV intensity of 24 kW / m and a treatment time of 10 seconds, it was dried. In this way, a smooth layer having a thickness of 1 μm and having a dialkylsiloxane group was formed on the porous support.
PAN(ポリアクリロニトリル)多孔質膜(不織布上にポリアクリロニトリル多孔質膜が存在、不織布を含め、膜厚は約180μm)を支持体として上記の重合性の放射線硬化性組成物をスピンコートした後、UV強度24kW/m、処理時間10秒のUV処理条件でUV処理(Fusion UV System社製、Light Hammer 10、D-バルブ)を行った後、乾燥させた。このようにして、多孔質支持体上にジアルキルシロキサン基を有する厚み1μmの平滑層を形成した。 (Application of polymerizable radiation curable composition to porous support, formation of smooth layer)
PAN (polyacrylonitrile) porous membrane (polyacrylonitrile porous membrane is present on the nonwoven fabric, including the nonwoven fabric, the film thickness is about 180 μm) After spin coating the above polymerizable radiation curable composition as a support, After UV treatment (Fusion UV System,
<複合膜の作製>
30ml褐色バイアル瓶に、ポリイミド(P-01)を1.4g、テトラヒドロフラン8.6gを混合して30分攪拌した後、上記平滑層を付与したPAN多孔質膜上にスピンコートし、複合膜(実施例1)を得た。ポリイミド(P-01)層の厚さは約150nmであり、ポリアクリロニトリル多孔質膜の厚さは不織布を含めて約180μmであった。
なお、これらのポリアクリロニトリル多孔質膜の分画分子量は100,000以下のものを使用した。また、この多孔質膜の40℃、5MPaにおける二酸化炭素の透過性は、25,000GPUであった。 <Production of composite membrane>
In a 30 ml brown vial, 1.4 g of polyimide (P-01) and 8.6 g of tetrahydrofuran were mixed and stirred for 30 minutes, and then spin-coated on the PAN porous membrane provided with the above smooth layer to form a composite membrane ( Example 1) was obtained. The thickness of the polyimide (P-01) layer was about 150 nm, and the thickness of the polyacrylonitrile porous membrane including the nonwoven fabric was about 180 μm.
These polyacrylonitrile porous membranes had a molecular weight cut-off of 100,000 or less. Further, the permeability of carbon dioxide at 40 ° C. and 5 MPa of this porous membrane was 25,000 GPU.
30ml褐色バイアル瓶に、ポリイミド(P-01)を1.4g、テトラヒドロフラン8.6gを混合して30分攪拌した後、上記平滑層を付与したPAN多孔質膜上にスピンコートし、複合膜(実施例1)を得た。ポリイミド(P-01)層の厚さは約150nmであり、ポリアクリロニトリル多孔質膜の厚さは不織布を含めて約180μmであった。
なお、これらのポリアクリロニトリル多孔質膜の分画分子量は100,000以下のものを使用した。また、この多孔質膜の40℃、5MPaにおける二酸化炭素の透過性は、25,000GPUであった。 <Production of composite membrane>
In a 30 ml brown vial, 1.4 g of polyimide (P-01) and 8.6 g of tetrahydrofuran were mixed and stirred for 30 minutes, and then spin-coated on the PAN porous membrane provided with the above smooth layer to form a composite membrane ( Example 1) was obtained. The thickness of the polyimide (P-01) layer was about 150 nm, and the thickness of the polyacrylonitrile porous membrane including the nonwoven fabric was about 180 μm.
These polyacrylonitrile porous membranes had a molecular weight cut-off of 100,000 or less. Further, the permeability of carbon dioxide at 40 ° C. and 5 MPa of this porous membrane was 25,000 GPU.
[実施例2~17] 複合膜の作製
上記実施例1において、ポリイミド(P-01)を表1に記載のとおりに変更したこと以外は実施例1と同様にして、表1に示す実施例2~17の複合膜を作製した。 [Examples 2 to 17] Preparation of composite membrane Examples 1 and 2 shown in Table 1 were the same as Example 1 except that polyimide (P-01) was changed as shown in Table 1. 2 to 17 composite membranes were prepared.
上記実施例1において、ポリイミド(P-01)を表1に記載のとおりに変更したこと以外は実施例1と同様にして、表1に示す実施例2~17の複合膜を作製した。 [Examples 2 to 17] Preparation of composite membrane Examples 1 and 2 shown in Table 1 were the same as Example 1 except that polyimide (P-01) was changed as shown in Table 1. 2 to 17 composite membranes were prepared.
[比較例1~5] 複合膜の作製
上記実施例1において、ポリイミド(P-01)を比較ポリイミド01~04又はセルロースアセテート(比較ポリマー)に変更したこと以外は実施例1と同様にして、比較例1~5の複合膜を作製した。 [Comparative Examples 1 to 5] Preparation of Composite Film In the above Example 1, except that the polyimide (P-01) was changed to comparative polyimides 01 to 04 or cellulose acetate (comparative polymer), the same as in Example 1, Composite films of Comparative Examples 1 to 5 were produced.
上記実施例1において、ポリイミド(P-01)を比較ポリイミド01~04又はセルロースアセテート(比較ポリマー)に変更したこと以外は実施例1と同様にして、比較例1~5の複合膜を作製した。 [Comparative Examples 1 to 5] Preparation of Composite Film In the above Example 1, except that the polyimide (P-01) was changed to comparative polyimides 01 to 04 or cellulose acetate (comparative polymer), the same as in Example 1, Composite films of Comparative Examples 1 to 5 were produced.
[実施例18] 非対称膜の作製
上記と同様に調製したポリイミド(P-01)の0.5gに対してメチルエチルケトン2.5g、N,N-ジメチルホルムアミド2.5g、n-ブタノール0.6gの混合溶液を加えて溶解させたのち、孔径5.0μmのPTFE製精密濾過膜でろ過し、これをドープ液とした。清浄なガラス板の上にポリエステル製不織布(阿波製紙社製、膜厚:95μm)を敷き、さらに上記ドープ液を室温(20℃)の環境で展開し、30秒静置したのち、一次凝固液(0℃、75重量%メタノール水溶液)に1時間浸漬したのち、さらに二次凝固液(0℃、75重量%メタノール水溶液)に1時間浸漬することで非対称膜を作製した。得られた非対称膜をメタノールで洗浄した後、イソオクタンでメタノールを置換し、更に50℃で8時間、110℃で6時間加熱してイソオクタンを蒸発乾燥させることで緻密なスキン層が0.1μm以下、ポリイミド層総膜厚が40μmの非対称膜(実施例18)を得た。 Example 18 Production of Asymmetric Membrane 2.5 g of methyl ethyl ketone, 2.5 g of N, N-dimethylformamide, and 0.6 g of n-butanol were added to 0.5 g of polyimide (P-01) prepared in the same manner as described above. After adding and dissolving a mixed solution, it filtered with the microfiltration membrane made from PTFE with a hole diameter of 5.0 micrometers, and this was made into dope solution. A non-woven fabric made of polyester (made by Awa Paper Co., Ltd., film thickness: 95 μm) is laid on a clean glass plate, and the dope solution is developed in an environment at room temperature (20 ° C.) and allowed to stand for 30 seconds. After immersing in (0 ° C., 75 wt% methanol aqueous solution) for 1 hour, and further dipping in a secondary coagulation liquid (0 ° C., 75 wt% methanol aqueous solution) for 1 hour, an asymmetric membrane was produced. After washing the obtained asymmetric membrane with methanol, the methanol is replaced with isooctane, and further heating is carried out at 50 ° C. for 8 hours and at 110 ° C. for 6 hours to evaporate and dry isooctane, so that the dense skin layer is 0.1 μm or less. An asymmetric membrane (Example 18) having a total polyimide layer thickness of 40 μm was obtained.
上記と同様に調製したポリイミド(P-01)の0.5gに対してメチルエチルケトン2.5g、N,N-ジメチルホルムアミド2.5g、n-ブタノール0.6gの混合溶液を加えて溶解させたのち、孔径5.0μmのPTFE製精密濾過膜でろ過し、これをドープ液とした。清浄なガラス板の上にポリエステル製不織布(阿波製紙社製、膜厚:95μm)を敷き、さらに上記ドープ液を室温(20℃)の環境で展開し、30秒静置したのち、一次凝固液(0℃、75重量%メタノール水溶液)に1時間浸漬したのち、さらに二次凝固液(0℃、75重量%メタノール水溶液)に1時間浸漬することで非対称膜を作製した。得られた非対称膜をメタノールで洗浄した後、イソオクタンでメタノールを置換し、更に50℃で8時間、110℃で6時間加熱してイソオクタンを蒸発乾燥させることで緻密なスキン層が0.1μm以下、ポリイミド層総膜厚が40μmの非対称膜(実施例18)を得た。 Example 18 Production of Asymmetric Membrane 2.5 g of methyl ethyl ketone, 2.5 g of N, N-dimethylformamide, and 0.6 g of n-butanol were added to 0.5 g of polyimide (P-01) prepared in the same manner as described above. After adding and dissolving a mixed solution, it filtered with the microfiltration membrane made from PTFE with a hole diameter of 5.0 micrometers, and this was made into dope solution. A non-woven fabric made of polyester (made by Awa Paper Co., Ltd., film thickness: 95 μm) is laid on a clean glass plate, and the dope solution is developed in an environment at room temperature (20 ° C.) and allowed to stand for 30 seconds. After immersing in (0 ° C., 75 wt% methanol aqueous solution) for 1 hour, and further dipping in a secondary coagulation liquid (0 ° C., 75 wt% methanol aqueous solution) for 1 hour, an asymmetric membrane was produced. After washing the obtained asymmetric membrane with methanol, the methanol is replaced with isooctane, and further heating is carried out at 50 ° C. for 8 hours and at 110 ° C. for 6 hours to evaporate and dry isooctane, so that the dense skin layer is 0.1 μm or less. An asymmetric membrane (Example 18) having a total polyimide layer thickness of 40 μm was obtained.
[実施例19] 非対称膜の作製
上記実施例18において、ポリイミド(P-01)をポリイミド(P-02)に変更したこと以外は実施例18と同様にして実施例19の非対称膜を作製した。 [Example 19] Production of asymmetric membrane An asymmetric membrane of Example 19 was produced in the same manner as in Example 18 except that polyimide (P-01) was changed to polyimide (P-02) in Example 18 above. .
上記実施例18において、ポリイミド(P-01)をポリイミド(P-02)に変更したこと以外は実施例18と同様にして実施例19の非対称膜を作製した。 [Example 19] Production of asymmetric membrane An asymmetric membrane of Example 19 was produced in the same manner as in Example 18 except that polyimide (P-01) was changed to polyimide (P-02) in Example 18 above. .
[比較例6] 非対称膜の作製
上記実施例18において、ポリイミド(P-01)を比較ポリイミド01に変更したこと以外は実施例18と同様にして比較例6の非対称膜を作製した。 Comparative Example 6 Production of Asymmetric Membrane An asymmetric membrane of Comparative Example 6 was produced in the same manner as in Example 18 except that polyimide (P-01) was changed to comparative polyimide 01 in Example 18.
上記実施例18において、ポリイミド(P-01)を比較ポリイミド01に変更したこと以外は実施例18と同様にして比較例6の非対称膜を作製した。 Comparative Example 6 Production of Asymmetric Membrane An asymmetric membrane of Comparative Example 6 was produced in the same manner as in Example 18 except that polyimide (P-01) was changed to comparative polyimide 01 in Example 18.
[比較例7] 非対称膜の作製
上記実施例18において、ポリイミド(P-01)をセルロースアセテート(比較ポリマー)に変更したこと以外は実施例18と同様にして比較例7の非対称膜を作製した。 Comparative Example 7 Production of Asymmetric Membrane Asymmetric membrane of Comparative Example 7 was produced in the same manner as in Example 18 except that polyimide (P-01) was changed to cellulose acetate (comparative polymer) in Example 18. .
上記実施例18において、ポリイミド(P-01)をセルロースアセテート(比較ポリマー)に変更したこと以外は実施例18と同様にして比較例7の非対称膜を作製した。 Comparative Example 7 Production of Asymmetric Membrane Asymmetric membrane of Comparative Example 7 was produced in the same manner as in Example 18 except that polyimide (P-01) was changed to cellulose acetate (comparative polymer) in Example 18. .
[試験例1] ガス分離膜のCO2透過速度及びガス分離選択性の評価-1
上記各実施例および比較例のガス分離膜(複合膜及び非対称膜)を用いて、ガス分離性能を以下のように評価した。
ガス分離膜を多孔質支持体(支持層)ごと直径47mmに切り取り、透過試験サンプルを作製した。GTRテック株式会社製ガス透過率測定装置を用い、二酸化炭素(CO2)、メタン(CH4)が40:60(体積比)の混合ガスをガス供給側の全圧力が4MPa(CO2の分圧:1.6MPa)、流量500mL/min、40℃となるように調整し供給した。透過してきたガスをガスクロマトグラフィーにより分析した。膜のガス透過性は、ガス透過率(Permeance)としてガス透過速度を算出することにより比較した。ガス透過率(ガス透過速度)の単位はGPU(ジーピーユー)単位〔1GPU=1×10-6cm3(STP)/cm2・sec・cmHg〕で表した。ガス分離選択性は、この膜のCH4の透過速度RCH4に対するCO2の透過速度RCO2の比率(RCO2/RCH4)として計算した。 [Test Example 1] Evaluation of gas separation membrane CO 2 permeation rate and gas separation selectivity-1
Using the gas separation membranes (composite membranes and asymmetric membranes) of the above Examples and Comparative Examples, the gas separation performance was evaluated as follows.
The gas separation membrane was cut to a diameter of 47 mm together with the porous support (support layer) to prepare a permeation test sample. Using a gas permeability measuring device manufactured by GTR Tech Co., Ltd., a mixed gas of carbon dioxide (CO 2 ) and methane (CH 4 ) of 40:60 (volume ratio) is used, and the total pressure on the gas supply side is 4 MPa (minus CO 2 The pressure was adjusted to 1.6 MPa), the flow rate was 500 mL / min, and 40 ° C. was supplied. The permeated gas was analyzed by gas chromatography. The gas permeability of the membrane was compared by calculating the gas permeation rate as gas permeability (Permeance). The unit of gas permeability (gas permeation rate) was expressed in GPU (GPI) unit [1 GPU = 1 × 10 −6 cm 3 (STP) / cm 2 · sec · cmHg]. The gas separation selectivity was calculated as the ratio of the CO 2 permeation rate R CO2 to the CH 4 permeation rate R CH4 of this membrane (R CO2 / R CH4 ).
上記各実施例および比較例のガス分離膜(複合膜及び非対称膜)を用いて、ガス分離性能を以下のように評価した。
ガス分離膜を多孔質支持体(支持層)ごと直径47mmに切り取り、透過試験サンプルを作製した。GTRテック株式会社製ガス透過率測定装置を用い、二酸化炭素(CO2)、メタン(CH4)が40:60(体積比)の混合ガスをガス供給側の全圧力が4MPa(CO2の分圧:1.6MPa)、流量500mL/min、40℃となるように調整し供給した。透過してきたガスをガスクロマトグラフィーにより分析した。膜のガス透過性は、ガス透過率(Permeance)としてガス透過速度を算出することにより比較した。ガス透過率(ガス透過速度)の単位はGPU(ジーピーユー)単位〔1GPU=1×10-6cm3(STP)/cm2・sec・cmHg〕で表した。ガス分離選択性は、この膜のCH4の透過速度RCH4に対するCO2の透過速度RCO2の比率(RCO2/RCH4)として計算した。 [Test Example 1] Evaluation of gas separation membrane CO 2 permeation rate and gas separation selectivity-1
Using the gas separation membranes (composite membranes and asymmetric membranes) of the above Examples and Comparative Examples, the gas separation performance was evaluated as follows.
The gas separation membrane was cut to a diameter of 47 mm together with the porous support (support layer) to prepare a permeation test sample. Using a gas permeability measuring device manufactured by GTR Tech Co., Ltd., a mixed gas of carbon dioxide (CO 2 ) and methane (CH 4 ) of 40:60 (volume ratio) is used, and the total pressure on the gas supply side is 4 MPa (minus CO 2 The pressure was adjusted to 1.6 MPa), the flow rate was 500 mL / min, and 40 ° C. was supplied. The permeated gas was analyzed by gas chromatography. The gas permeability of the membrane was compared by calculating the gas permeation rate as gas permeability (Permeance). The unit of gas permeability (gas permeation rate) was expressed in GPU (GPI) unit [1 GPU = 1 × 10 −6 cm 3 (STP) / cm 2 · sec · cmHg]. The gas separation selectivity was calculated as the ratio of the CO 2 permeation rate R CO2 to the CH 4 permeation rate R CH4 of this membrane (R CO2 / R CH4 ).
[試験例2] トルエン暴露試験
トルエン溶媒を張った蓋のできるガラス製容器内に、100mlの空のビーカーを静置し、さらに実施例および比較例において作製したガス分離膜の切片をビーカーの中に入れ、ガラス製容器にガラス製の蓋を施し、密閉系とした。その後、40℃条件下で5時間保存した後、上記[試験例1]と同様にガス分離性能を評価した。トルエン暴露によって、ベンゼン、トルエン、キシレン等の不純物成分に対するガス分離膜の可塑化耐性を評価できる。 [Test Example 2] Toluene exposure test A 100 ml empty beaker was allowed to stand in a glass container with a lid covered with a toluene solvent, and the gas separation membrane sections prepared in Examples and Comparative Examples were placed in the beaker. And a glass lid was applied to the glass container to make a closed system. Then, after storing for 5 hours at 40 ° C., gas separation performance was evaluated in the same manner as in [Test Example 1]. By exposure to toluene, it is possible to evaluate the plasticization resistance of the gas separation membrane against impurity components such as benzene, toluene and xylene.
トルエン溶媒を張った蓋のできるガラス製容器内に、100mlの空のビーカーを静置し、さらに実施例および比較例において作製したガス分離膜の切片をビーカーの中に入れ、ガラス製容器にガラス製の蓋を施し、密閉系とした。その後、40℃条件下で5時間保存した後、上記[試験例1]と同様にガス分離性能を評価した。トルエン暴露によって、ベンゼン、トルエン、キシレン等の不純物成分に対するガス分離膜の可塑化耐性を評価できる。 [Test Example 2] Toluene exposure test A 100 ml empty beaker was allowed to stand in a glass container with a lid covered with a toluene solvent, and the gas separation membrane sections prepared in Examples and Comparative Examples were placed in the beaker. And a glass lid was applied to the glass container to make a closed system. Then, after storing for 5 hours at 40 ° C., gas separation performance was evaluated in the same manner as in [Test Example 1]. By exposure to toluene, it is possible to evaluate the plasticization resistance of the gas separation membrane against impurity components such as benzene, toluene and xylene.
[試験例3] ガス分離膜のCO2透過速度及びガス分離選択性の評価-2
上記実施例1、5、8、18及び19並びに比較例2、5、6及び7のガス分離膜(複合膜及び非対称膜)を用いて、ガス分離性能を以下のように評価した。
ガス分離膜を多孔質支持体(支持層)ごと直径47mmに切り取り、透過試験サンプルを作成した。GTRテック株式会社製ガス透過率測定装置を用い、二酸化炭素(CO2)、メタン(CH4)が10:90(体積比)の混合ガスをガス供給側の全圧力が4MPa(CO2の分圧:0.4MPa)、流量500mL/min、30℃となるように調整し供給した。透過してきたガスをガスクロマトグラフィーにより分析した。CO2透過速度とガス分離選択性は試験例1と同様にして評価した。 [Test Example 3] Evaluation of CO 2 permeation rate and gas separation selectivity of gas separation membrane-2
Using the gas separation membranes (composite membranes and asymmetric membranes) of Examples 1, 5, 8, 18, and 19 and Comparative Examples 2, 5, 6, and 7, the gas separation performance was evaluated as follows.
The gas separation membrane was cut to a diameter of 47 mm together with the porous support (support layer) to prepare a permeation test sample. Using a gas permeability measuring device manufactured by GTR Tech Co., Ltd., a mixed gas of 10:90 (volume ratio) of carbon dioxide (CO 2 ) and methane (CH 4 ) is 4 MPa (a fraction of CO 2 ) The pressure was adjusted to 0.4 MPa), the flow rate was 500 mL / min, and 30 ° C. was supplied. The permeated gas was analyzed by gas chromatography. The CO 2 permeation rate and gas separation selectivity were evaluated in the same manner as in Test Example 1.
上記実施例1、5、8、18及び19並びに比較例2、5、6及び7のガス分離膜(複合膜及び非対称膜)を用いて、ガス分離性能を以下のように評価した。
ガス分離膜を多孔質支持体(支持層)ごと直径47mmに切り取り、透過試験サンプルを作成した。GTRテック株式会社製ガス透過率測定装置を用い、二酸化炭素(CO2)、メタン(CH4)が10:90(体積比)の混合ガスをガス供給側の全圧力が4MPa(CO2の分圧:0.4MPa)、流量500mL/min、30℃となるように調整し供給した。透過してきたガスをガスクロマトグラフィーにより分析した。CO2透過速度とガス分離選択性は試験例1と同様にして評価した。 [Test Example 3] Evaluation of CO 2 permeation rate and gas separation selectivity of gas separation membrane-2
Using the gas separation membranes (composite membranes and asymmetric membranes) of Examples 1, 5, 8, 18, and 19 and Comparative Examples 2, 5, 6, and 7, the gas separation performance was evaluated as follows.
The gas separation membrane was cut to a diameter of 47 mm together with the porous support (support layer) to prepare a permeation test sample. Using a gas permeability measuring device manufactured by GTR Tech Co., Ltd., a mixed gas of 10:90 (volume ratio) of carbon dioxide (CO 2 ) and methane (CH 4 ) is 4 MPa (a fraction of CO 2 ) The pressure was adjusted to 0.4 MPa), the flow rate was 500 mL / min, and 30 ° C. was supplied. The permeated gas was analyzed by gas chromatography. The CO 2 permeation rate and gas separation selectivity were evaluated in the same manner as in Test Example 1.
上記の各試験例の結果を下記表1に示す。
The results of the above test examples are shown in Table 1 below.
上記表1に示されるように、カルバモイル基を有さないポリイミド化合物を用いて製造したガス分離膜は、高圧下でのCO2透過速度、ガス分離選択性の双方において劣る結果となった(比較例1及び2)。また、カルバモイル基の含有量が本発明で規定するよりも少ないポリイミド化合物を用いて製造したガス分離膜は、CO2透過速度、ガス分離選択性に劣っていた(比較例3)。逆に、カルバモイル基の含有量が本発明で規定するよりも多い場合には、極性が高く成り過ぎて溶媒に溶解せず、成膜することができなかった(比較例4)。さらに、ガス分離層に、ポリイミドに代えてセルロースアセテートを用いた場合には、CO2透過速度とガス分離選択性の双方に劣る結果となった(比較例5)。
これに対し、カルバモイル基を本発明で規定する量含有するポリイミド化合物を用いて形成したガス分離層を有するガス分離膜は、試験例1において80GPU以上のCO2透過速度を示し、CO2透過性に優れていた。さらに、ガス分離選択性については試験例1においていずれも25以上の高い性能を有し、このガス分離選択性はトルエン暴露によっても大きく低下することはなかった。さらに、分離対象となるガスの温度並びにCO2とCH4の混合比を変えた試験例3においても、優れたCO2透過速度、ガス分離選択性を示し、安定したガス分離膜性能を示すこともわかった。 As shown in Table 1 above, the gas separation membrane produced using the polyimide compound having no carbamoyl group resulted in inferior in both CO 2 permeation rate and gas separation selectivity under high pressure (comparison). Examples 1 and 2). Moreover, the gas separation membrane manufactured using the polyimide compound whose content of carbamoyl groups is less than that defined in the present invention was inferior in CO 2 permeation rate and gas separation selectivity (Comparative Example 3). On the other hand, when the content of the carbamoyl group was larger than specified in the present invention, the polarity was so high that it was not dissolved in the solvent and could not be formed (Comparative Example 4). Further, when cellulose acetate was used instead of polyimide for the gas separation layer, both the CO 2 permeation rate and the gas separation selectivity were inferior (Comparative Example 5).
On the other hand, a gas separation membrane having a gas separation layer formed using a polyimide compound containing a carbamoyl group in an amount specified in the present invention shows a CO 2 permeation rate of 80 GPU or more in Test Example 1, and CO 2 permeability. It was excellent. Furthermore, as for gas separation selectivity, all of Test Examples 1 had a high performance of 25 or more, and this gas separation selectivity was not greatly reduced by exposure to toluene. Furthermore, even in Test Example 3 in which the temperature of the gas to be separated and the mixing ratio of CO 2 and CH 4 were changed, excellent CO 2 permeation rate and gas separation selectivity were exhibited, and stable gas separation membrane performance was exhibited. I understand.
これに対し、カルバモイル基を本発明で規定する量含有するポリイミド化合物を用いて形成したガス分離層を有するガス分離膜は、試験例1において80GPU以上のCO2透過速度を示し、CO2透過性に優れていた。さらに、ガス分離選択性については試験例1においていずれも25以上の高い性能を有し、このガス分離選択性はトルエン暴露によっても大きく低下することはなかった。さらに、分離対象となるガスの温度並びにCO2とCH4の混合比を変えた試験例3においても、優れたCO2透過速度、ガス分離選択性を示し、安定したガス分離膜性能を示すこともわかった。 As shown in Table 1 above, the gas separation membrane produced using the polyimide compound having no carbamoyl group resulted in inferior in both CO 2 permeation rate and gas separation selectivity under high pressure (comparison). Examples 1 and 2). Moreover, the gas separation membrane manufactured using the polyimide compound whose content of carbamoyl groups is less than that defined in the present invention was inferior in CO 2 permeation rate and gas separation selectivity (Comparative Example 3). On the other hand, when the content of the carbamoyl group was larger than specified in the present invention, the polarity was so high that it was not dissolved in the solvent and could not be formed (Comparative Example 4). Further, when cellulose acetate was used instead of polyimide for the gas separation layer, both the CO 2 permeation rate and the gas separation selectivity were inferior (Comparative Example 5).
On the other hand, a gas separation membrane having a gas separation layer formed using a polyimide compound containing a carbamoyl group in an amount specified in the present invention shows a CO 2 permeation rate of 80 GPU or more in Test Example 1, and CO 2 permeability. It was excellent. Furthermore, as for gas separation selectivity, all of Test Examples 1 had a high performance of 25 or more, and this gas separation selectivity was not greatly reduced by exposure to toluene. Furthermore, even in Test Example 3 in which the temperature of the gas to be separated and the mixing ratio of CO 2 and CH 4 were changed, excellent CO 2 permeation rate and gas separation selectivity were exhibited, and stable gas separation membrane performance was exhibited. I understand.
以上の結果から、本発明のガス分離膜により、優れたガス分離方法、ガス分離モジュール、このガス分離モジュールを備えたガス分離装置を提供することができることが分かった。
From the above results, it was found that the gas separation membrane of the present invention can provide an excellent gas separation method, a gas separation module, and a gas separation apparatus equipped with this gas separation module.
本発明をその実施態様とともに説明したが、我々は特に指定しない限り我々の発明を説明のどの細部においても限定しようとするものではなく、添付の請求の範囲に示した発明の精神と範囲に反することなく幅広く解釈されるべきであると考える。
While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.
本願は、2014年2月26日に日本国で特許出願された特願2014-036036に基づく優先権を主張するものであり、これはここに参照してその内容を本明細書の記載の一部として取り込む。
This application claims priority based on Japanese Patent Application No. 2014-036036 filed in Japan on February 26, 2014, which is hereby incorporated herein by reference. Capture as part.
1 ガス分離層
2 多孔質層
3 不織布層
10、20 ガス分離複合膜 DESCRIPTION OFSYMBOLS 1 Gas separation layer 2 Porous layer 3 Nonwoven fabric layer 10, 20 Gas separation composite membrane
2 多孔質層
3 不織布層
10、20 ガス分離複合膜 DESCRIPTION OF
Claims (10)
- ポリイミド化合物を含有してなるガス分離層を有するガス分離膜であって、
前記ポリイミド化合物がカルバモイル基を有し、前記ポリイミド化合物中の前記カルバモイル基の含有量が0.1~3.0mmol/gである、ガス分離膜。 A gas separation membrane having a gas separation layer containing a polyimide compound,
A gas separation membrane, wherein the polyimide compound has a carbamoyl group, and the content of the carbamoyl group in the polyimide compound is 0.1 to 3.0 mmol / g. - 前記ポリイミド化合物が、下記式(A)又は(B)で表される繰り返し単位を含む、請求項1に記載のガス分離膜。
- 前記式(A)で表される繰り返し単位が、下記式(a)で表される繰り返し単位である、請求項2に記載のガス分離膜:
- 前記ガス分離膜が、前記ガス分離層をガス透過性の支持層上側に有するガス分離複合膜である、請求項1~3のいずれか1項に記載のガス分離膜。 The gas separation membrane according to any one of claims 1 to 3, wherein the gas separation membrane is a gas separation composite membrane having the gas separation layer on a gas permeable support layer.
- 前記支持層が、ガス分離層側の多孔質層と、その逆側の不織布層とからなる、請求項4に記載のガス分離膜。 The gas separation membrane according to claim 4, wherein the support layer comprises a porous layer on the gas separation layer side and a nonwoven fabric layer on the opposite side.
- 分離処理されるガスが二酸化炭素とメタンの混合ガスである場合において、40℃、5MPaにおける二酸化炭素の透過速度が20GPU超であり、二酸化炭素とメタンとの透過速度比(RCO2/RCH4)が15以上である、請求項1~5のいずれか1項に記載のガス分離膜。 When the gas to be separated is a mixed gas of carbon dioxide and methane, the permeation rate of carbon dioxide at 40 ° C. and 5 MPa exceeds 20 GPU, and the permeation rate ratio between carbon dioxide and methane (R CO2 / R CH4 ) The gas separation membrane according to any one of Claims 1 to 5, wherein is 15 or more.
- 二酸化炭素及びメタンを含むガスから二酸化炭素を選択的に透過させるために用いられる、請求項1~6のいずれか1項に記載のガス分離膜。 The gas separation membrane according to any one of claims 1 to 6, which is used for selectively permeating carbon dioxide from a gas containing carbon dioxide and methane.
- 請求項1~7のいずれか1項に記載のガス分離膜を具備するガス分離モジュール。 A gas separation module comprising the gas separation membrane according to any one of claims 1 to 7.
- 請求項8に記載のガス分離モジュールを備えたガス分離装置。 A gas separation apparatus comprising the gas separation module according to claim 8.
- 請求項1~7のいずれか1項に記載のガス分離膜を用いて、二酸化炭素及びメタンを含むガスから二酸化炭素を選択的に透過させるガス分離方法。 A gas separation method for selectively permeating carbon dioxide from a gas containing carbon dioxide and methane, using the gas separation membrane according to any one of claims 1 to 7.
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JP2014036037A JP6038058B2 (en) | 2014-02-26 | 2014-02-26 | Gas separation membrane, gas separation module, gas separation device, and gas separation method |
JP2014-036037 | 2014-02-26 |
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WO2018042894A1 (en) * | 2016-08-31 | 2018-03-08 | 富士フイルム株式会社 | Novel m-phenylenediamine compound and method for producing polymer compound using same |
JPWO2018180793A1 (en) * | 2017-03-28 | 2019-11-07 | 富士フイルム株式会社 | Gas detection element and manufacturing method thereof |
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CN113490543A (en) * | 2019-02-28 | 2021-10-08 | 富士胶片株式会社 | Polymer and method for producing same, gas separation membrane, gas separation module, and gas separation device using same, and m-phenylenediamine compound |
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