WO2019044215A1 - Membrane de séparation de gaz, module de séparation de gaz, dispositif de séparation de gaz, procédé de séparation de gaz, et composé de polyimide - Google Patents

Membrane de séparation de gaz, module de séparation de gaz, dispositif de séparation de gaz, procédé de séparation de gaz, et composé de polyimide Download PDF

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WO2019044215A1
WO2019044215A1 PCT/JP2018/026649 JP2018026649W WO2019044215A1 WO 2019044215 A1 WO2019044215 A1 WO 2019044215A1 JP 2018026649 W JP2018026649 W JP 2018026649W WO 2019044215 A1 WO2019044215 A1 WO 2019044215A1
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gas separation
group
separation membrane
active hydrogen
hydrogen atom
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PCT/JP2018/026649
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English (en)
Japanese (ja)
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北村　哲
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富士フイルム株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a gas separation membrane, a gas separation module, a gas separation apparatus, a gas separation method, and a polyimide compound.
  • Materials made of polymer compounds have gas permeability that is unique to each material. Based on this property, a desired gas component can be selectively permeated and separated by a membrane composed of a specific polymer compound.
  • a gas separation membrane as a means for removing impurities such as carbon dioxide from mixed gas (natural gas, biogas, etc.) mainly containing methane and carbon dioxide, for example, using this gas separation membrane has been studied.
  • Patent Document 1 describes a gas separation membrane having a fluorine-containing polyimide resin as a constituent material of the gas separation layer.
  • Gas separation membranes used in purification of natural gas and the like are required to have excellent gas permeability to a gas to be permeated in order to separate the gas more efficiently. Further, in an actual natural gas plant, there is a problem that the gas separation membrane is plasticized by the influence of impurities (for example, benzene, toluene, xylene, etc.) present in the natural gas, and the gas separation selectivity is lowered. Therefore, the gas separation membrane is also required to have plasticization resistance that can continuously express desired gas separation selectivity.
  • impurities for example, benzene, toluene, xylene, etc.
  • polyimide compounds generally tend to be inferior in plasticization resistance, and gas separation performance tends to be degraded in the coexistence of a plasticizing component such as toluene.
  • An object of the present invention is to provide a gas separation membrane having excellent gas permeability and capable of continuously expressing desired gas separation selectivity even when exposed to a plasticizing component such as toluene. I assume. Another object of the present invention is to provide a gas separation module, a gas separation apparatus and a gas separation method using the gas separation membrane. Moreover, this invention makes it a subject to provide a polyimide compound suitable as a constituent material of the gas separation layer which the said gas separation membrane has.
  • the inventor of the present invention has intensively studied, and when the polyimide compound having a pentafluorosulfanyl group introduced therein is used as a constituent material of the gas separation layer, the gas permeability of the obtained gas separation membrane is enhanced. It has also been found that the plasticization resistance is also improved. As a result, it has become possible to provide a gas separation membrane capable of continuously performing efficient gas separation even in the presence of a plasticizing component.
  • a gas separation membrane having a gas separation layer containing a polyimide compound having a pentafluorosulfanyl group as a constituent material [1] A gas separation membrane having a gas separation layer containing a polyimide compound having a pentafluorosulfanyl group as a constituent material. [2] The gas separation membrane according to [1], wherein the proportion of the structural unit having a pentafluorosulfanyl group in the total structural units constituting the polyimide compound is 50 mol% or more. [3] The gas separation membrane according to [2], wherein the proportion of structural units having a pentafluorosulfanyl group in the total structural units constituting the polyimide compound is 70 mol% or more.
  • the polyimide compound has a structural unit represented by the following formula (1), or a structural unit represented by the following formula (2-1) and a structural unit represented by the following formula (2-2)
  • the gas separation membrane according to any one of [1] to [7].
  • Z 1 represents a tetravalent group.
  • X 1 represents a divalent group having a pentafluorosulfanyl group and an active hydrogen atom.
  • Z 2 and Z 3 represent a tetravalent group.
  • X 2 represents a divalent group having a pentafluorosulfanyl group and not having an active hydrogen atom
  • X 3 represents a divalent group having an active hydrogen atom and not having a pentafluorosulfanyl group.
  • the gas separation membrane of the [8] description whose structural unit represented by said Formula (1) is a structural unit represented by following formula (3).
  • L 1 represents a single bond or a divalent group (linking group).
  • R represents a substituent, and p is an integer of 1 to 4. However, p pieces of R contain at least one pentafluorosulfanyl group and at least one active hydrogen atom.
  • L 1 and L 2 each represent a single bond or a divalent group (linking group).
  • R 1 and R 2 each represent a substituent, q is an integer of 0 to 3, and r is an integer of 0 to 5. However, among q R 1 s and r R 2 s and L 2 s , at least one pentafluorosulfanyl group and at least one active hydrogen atom are included.
  • the gas separation membrane according to any one of [1] to [13] which is used to selectively permeate carbon dioxide from a mixed gas containing carbon dioxide and methane.
  • a gas separation module comprising the gas separation membrane according to any one of [1] to [14].
  • a gas separation apparatus comprising the gas separation membrane according to any one of [1] to [14].
  • the polyimide compound which has a structural unit represented by following formula (3).
  • L 1 represents a single bond or a divalent group (linking group).
  • R represents a substituent, and p is an integer of 1 to 4. However, p pieces of R contain at least one pentafluorosulfanyl group and at least one active hydrogen atom.
  • the numerical range represented by “to” in the present specification is a meaning including the numerical values described before and after that as the lower limit value and the upper limit value.
  • substituents and the like when there are a plurality of substituents, linking groups and the like (hereinafter referred to as substituents and the like) represented by specific symbols, or when a plurality of substituents and the like are defined simultaneously or alternatively,
  • the substituents and the like mean that they may be the same or different. The same applies to the definition of the number of substituents and the like.
  • each partial structure may be same or different.
  • the term "compound” or "group” is used in the meaning including the compound or group itself as well as the salts thereof and the ions thereof. Moreover, it is a meaning including what changed a part of structure in the range which show
  • a substituent which does not specify substitution or non-substitution means that the group may have any substituent within a range that produces a desired effect. . This is the same as for compounds in which no substitution or substitution is specified.
  • the following substituent group Z is the preferable range.
  • the gas separation membrane, gas separation module, and gas separation apparatus of the present invention have excellent gas permeability, and continuously exhibit desired gas separation selectivity even when exposed to a plasticizing component such as toluene. can do. According to the gas separation method of the present invention, it is possible to separate a target gas with excellent gas permeability and desired gas separation selectivity even in the presence of a plasticizing component such as toluene.
  • the polyimide compound of this invention is suitable as a constituent material of the gas separation layer which the said gas separation membrane has.
  • the gas separation membrane of the present invention contains a polyimide compound of a specific structure as a constituent material of the gas separation layer.
  • the polyimide compound is described below.
  • polyimide compound used in the gas separation membrane of the present invention has a pentafluorosulfanyl group (—SF 5 ) as a substituent.
  • polyimide compound used in the present invention has a -SF 5
  • gas separation layer having a polyimide compound permeability is enhanced, also plasticization resistance is also enhanced. The reason for this is not clear, but the formation of microvoids in the film by electron repulsion between fluorine atoms, and the decrease in affinity with a plasticizing component such as toluene due to the presence of fluorine atoms, etc.
  • the improvement of permeability and resistance to plasticization by the introduction of -SF 5 is not one that can be explained by this alone.
  • the permeability and plasticization resistance improving action by the introduction of -SF 5 is enhanced more effectively than when a plurality of trifluoromethyl groups (-CF 3 ), which are the same perfluoro groups as -SF 5, are introduced, for example.
  • the total structural units, the proportion of structural units having -SF 5 is preferably at least 50 mol%, more preferably at least 70 mol%, more preferably at least 80 mol%, 90 mol % Or more is particularly preferred.
  • structural units having —SF 5 preferably have 1 to 4 —SF 5 in this structural unit, more preferably 1 to 3 and even more preferably 1 or 2.
  • one tetracarboxylic acid dianhydride component and one diamine component are formed by condensation polymerization of one molecule of tetracarboxylic acid dianhydride and one molecule of diamine compound.
  • X 1 is a diamine component derived from one molecule of diamine compound, and the other portion is a tetracarboxylic acid dianhydride component derived from one molecule of tetracarboxylic acid dianhydride Do.
  • the polyimide compound used in the present invention together with -SF 5, it is also preferable to have an active hydrogen atom.
  • the gas separation layer formed using this polyimide compound can form microvoids, but can be appropriately adjusted by the hydrogen bonding interaction. It is possible to densify, effectively improve both the permeability and the resistance to plasticization, and also to increase the separation selectivity.
  • the distance of -SF 5 and the active hydrogen atom is more somewhat closer, permeability, can be triangular position at a higher level of plasticization resistance and separation selectivity.
  • the polyimide compound used in the present invention more preferably has a structural unit represented by Formula (1) described later.
  • active hydrogen atom means a hydrogen atom bonded to a nitrogen atom, an oxygen atom or a sulfur atom.
  • the active hydrogen atom is preferably a hydrogen atom contained in —OH, —COOH, —NHCO—, or —SO 2 NH—.
  • the proportion of structural units having an active hydrogen atom in the total structural units of the polyimide compound is preferably 5 mol% or more, more preferably 10 mol% or more, 20 mol% or more is more preferable, 50 mol% or more is especially preferable, and 70 mol% or more is the most preferable.
  • the structural unit having an active hydrogen atom preferably has 1 to 4 active hydrogen atoms in this structural unit, more preferably 1 to 3 and still more preferably 1 or 2.
  • Polyimide compound used in the present invention has an acid anhydride component is configured to include a diamine component preferably has a -SF 5 to at least a diamine component, an -SF 5 in the diamine component, an acid anhydride and more preferably is in the object component has no -SF 5.
  • the ratio of the molar amount of the diamine component having -SF 5 to the molar amount of all diamine components constituting this polyimide compound is preferably 50% or more, more preferably 70% or more.
  • diamine component having -SF 5 may have -SF 5 one during the diamine component may comprise two or more.
  • the diamine component having —SF 5 preferably has 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2 of —SF 5 .
  • the polyimide compound used in the present invention has a structural unit represented by the following formula (1), or a structural unit represented by the following formula (2-1) and a structure represented by the following formula (2-2) It is preferable to have a unit.
  • “having the structural unit represented by the formula (1) or having the structural unit represented by the formula (2-1) and the structural unit represented by the formula (2-2)” means And a structural unit represented by the formula (1), and a form not having at least one of the structural unit represented by the formula (2-1) and the structural unit represented by the formula (2-2) Form “1”), the structural unit represented by the formula (2-1), the structural unit represented by the formula (1) and the structural unit represented by the formula (2-2)
  • the structural unit represented by the formula (1), the structural unit represented by the formula (2-1) and the table by the formula (2-2) It is a meaning including the form (it calls "form 3") which has all the structural units which are.
  • the polyimide compound to be used in the present invention is usually in
  • Z 1 , Z 2 and Z 3 each represent a tetravalent group.
  • Z 1 , Z 2 and Z 3 preferably represent a group containing a structure represented by any of the following formulas (I-1) to (I-28).
  • * indicates a bonding site to the carbonyl group in formulas (1), (2-1) and (2-2).
  • the phrase “a group containing a structure” means that “a structure” further includes a form having a substituent in addition to “a structure” itself.
  • X A to X C each represent a single bond or a divalent group.
  • R x represents a hydrogen atom or a substituent.
  • R x When R x is a substituent, they may be linked to each other to form a ring.
  • R Y represents a hydrogen atom, an alkyl group (preferably methyl or ethyl), or an aryl group (preferably phenyl).
  • R x represents a substituent, specific examples thereof include a group selected from Substituent Group Z described later, and among them, an alkyl group or —SF 5 is preferable, and an alkyl group having 1 to 30 carbon atoms is more preferable.
  • An alkyl group having a halogen atom bonded thereto is more preferable, and trifluoromethyl is particularly preferable.
  • Formula (I-18) means that X C is connected to any carbon atom that constitutes one of the two ethylene units and any carbon atom that constitutes the other.
  • the divalent group represented by X A to X C preferably has a molecular weight of 500 or less, more preferably 350 or less, still more preferably 10 to 200.
  • R a and R b represent a hydrogen atom or a substituent. Examples of this substituent include groups selected from the substituent group Z described later. R a and R b may combine with each other to form a ring. R a and R b are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, methyl or ethyl, and still more preferably a hydrogen atom.
  • Z 1 , Z 2 and Z 3 are preferably a group containing a structure represented by (I-1), (I-2) or (I-4), (I-1) or (I-1)
  • the group containing the structure represented by -4) is more preferable, and the group containing the structure represented by (I-1) is particularly preferable.
  • Z 1 , Z 2 and Z 3 do not have -SF 5 . Further, Z 1, Z 2, and Z 3 preferably has no active hydrogen atoms.
  • X 1 represents a divalent group having —SF 5 and an active hydrogen atom.
  • X 1 preferably has a one ⁇ 3 -SF 5, more preferably -SF 5 one or two have, more preferably has one -SF 5.
  • X 1 preferably has 1 to 3 active hydrogen atoms, and more preferably 1 or 2 active hydrogen atoms.
  • X 1 preferably has an active hydrogen atom as —OH, —COOH, —NHCO—, and / or —SO 2 NH— (ie, X 1 is preferably —OH, —COOH, —NHCO—, and — SO 2 NH— having at least one group selected from
  • X 2 represents a divalent group having —SF 5 and no active hydrogen atom.
  • X 3 represents a divalent group having an active hydrogen atom and not having —SF 5 .
  • X 1 to X 3 have a benzene ring in the structure from the viewpoint of the rigidity of the polymer chain.
  • the molecular weight of X 1 to X 3 is preferably 75 to 500, and more preferably 100 to 400.
  • X 2 is preferably represented by the following formula (2-1-1) or the following formula (2-1-2).
  • R d represents an alkyl group, a halogen atom, or —SF 5
  • k 1 is an integer of 1 to 4.
  • R d has -SF 5 .
  • R d are having this -SF 5 is -SF 5 (when R d with -SF 5 is not -SF 5 itself, the R d is an alkyl group having -SF 5 as a substituent) .
  • the alkyl group which can be taken as R d preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably methyl, ethyl or trifluoromethyl.
  • R e and R f each represent an alkyl group, a halogen atom or —SF 5
  • m1 and n1 are integers of 0 to 4.
  • m1 and n1 will not both be 0, and at least one of m1 R e and n1 R f has —SF 5 .
  • R e and / or R f is -SF 5 having this -SF 5.
  • the alkyl group which can be taken as R e and R f preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably methyl, ethyl or trifluoromethyl.
  • X n has the same meaning as X A in formula (I-1), and the preferred form is also the same.
  • X 3 is preferably represented by the following formula (2-2-1) or the following formula (2-2-2).
  • R g represents an alkyl group, a halogen atom, or an active hydrogen atom-containing group
  • k1 is an integer of 1 to 4.
  • at least one (preferably one or two) R g has an active hydrogen atom-containing group.
  • active hydrogen atom-containing group means a functional group having an active hydrogen atom.
  • the active hydrogen atom-containing group is preferably a hydroxy group, a carboxy group, a carbamoyl group, or a sulfamoyl group, and more preferably a hydroxy group or a carboxy group.
  • R g having an active hydrogen atom-containing group is preferably an active hydrogen atom-containing group (when R g having an active hydrogen atom-containing group is not an active hydrogen atom-containing group itself, R g is an active hydrogen atom as a substituent An alkyl group having a containing group).
  • Alkyl group which may take as R g is preferably 1 to 10 carbon atoms, more preferably 1-5, more preferably 1-3, particularly preferably methyl, ethyl, or trifluoromethyl.
  • R h and R i each represent an alkyl group, a halogen atom or an active hydrogen atom-containing group, and m1 and n1 are integers of 0 to 4. However, m1 and n1 will not both be 0, and at least one of m1 R h and n1 R i has an active hydrogen atom-containing group. It is preferable that R h and / or R i having the active hydrogen atom-containing group be an active hydrogen atom-containing group.
  • the alkyl group which can be taken as R h and R i preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably methyl, ethyl or trifluoromethyl.
  • X n has the same meaning as X A in formula (I-1), and the preferred form is also the same.
  • the polyimide compound used in the present invention has the structural unit represented by the formula (2-1) and the structural unit represented by the formula (2-2), the polyimide compound occupies the entire structural units of the polyimide compound.
  • 50 mol% or more is preferable, and, as for the sum total of the ratio of the structural unit represented by Formula (2-1), and the ratio of the structural unit represented by Formula (2-2), 70 mol% or more is more preferable, and 80 mol % Or more is more preferable, and 90 mol% or more is particularly preferable.
  • the ratio of the structural unit represented by Formula (1) to all the structural units of this polyimide compound is 50 mol% The above is preferable, 70 mol% or more is more preferable, 80 mol% or more is more preferable, and 90 mol% or more is particularly preferable.
  • the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (3).
  • L 1 represents a single bond or a divalent group (linking group).
  • L 1 has the same meaning as X A in formula (I-1), and the preferred form is also the same.
  • R represents a substituent, and p is an integer of 1 to 4. However, at least one -SF 5 is contained in p R and at least one active hydrogen atom is contained. That is, the diamine component in the formula (3) contains at least one —SF 5 and at least one active hydrogen atom.
  • the number of —SF 5 contained in p Rs is preferably 1 to 3, more preferably 1 or 2.
  • the number of active hydrogen atoms contained in p R is preferably 1 to 3, and more preferably 1 or 2.
  • the structural unit represented by Formula (3) is more preferably a structural unit represented by the following Formula (4).
  • L 1 has the same meaning as L 1 in formula (3), a preferred form also the same.
  • L 2 represents a single bond or a divalent group.
  • R 1 and R 2 each represent a substituent, q is an integer of 0 to 3, and r is an integer of 0 to 5.
  • q is an integer of 0 to 3
  • r is an integer of 0 to 5.
  • the number of —SF 5 contained in the q R 1 s and the r R 2 s and L 2 s is preferably 1 to 3, more preferably 1 or 2.
  • R 1 is an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), a halogen atom, an aryl group (preferably phenyl or naphthyl), or Active hydrogen atom-containing groups are preferred.
  • R 2 represents 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 1 to 3 carbon atoms), an aryl group (preferably phenyl or naphthyl), a cyano group, a nitro group, a halogen atom, active hydrogen atom-containing group, or -SF 5 preferred.
  • the alkyl group and aryl group that can be taken as R 2 preferably have —SF 5 and / or an active hydrogen atom-containing group as a substituent.
  • L 2 has an active hydrogen atom
  • at least one of R 2 has r 1 and at least one R 2 has -SF 5 .
  • L 2 having an active hydrogen atom L 2 is -NHCO-, NR L CO -, - SO 2 NH-, or -SO 2 NR L - preferably contains, -NHCO-, or -SO 2 NH It is more preferable that it is-.
  • R 1 is preferably an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably methyl or ethyl).
  • R L represents a substituent, and this R L has an active hydrogen atom-containing group.
  • R L is preferably an aryl group (preferably phenyl or naphthyl) having an active hydrogen atom-containing group in a substituent.
  • the polyimide compound used in the present invention may have a structural unit which does not have -SF 5 and does not have an active hydrogen atom, in addition to the structural units described above, as long as the effects of the present invention are not impaired. Good.
  • the polyimide compound used in the present invention may be any of a block copolymer, a random copolymer and a graft copolymer.
  • Substituent group Z An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, iso-propyl, tert-butyl and n-octyl , N-decyl, n-hexadecyl), a cycloalkyl group (preferably having a carbon number of 3 to 30, more preferably 3 to 20, particularly preferably 3 to 10, and is, for example, cyclopropyl, And alkenyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms), such as vinyl, allyl, 2 -Butenyl, 3-pentenyl and the like), an alkynyl group (preferably having a carbon number of 2 to 30, more preferably It is an alkynyl group having 2 to 20 carbon atom
  • -20 particularly preferably an aryl group having a carbon number of 6 to 12, and examples thereof include phenyl, p-methylphenyl, naphthyl and anthranyl), an amino group (amino group, alkylamino group, arylamino group, hetero)
  • An amino group preferably an amino group having a carbon number of 0 to 30, more preferably a carbon number of 0 to 20, still more preferably a carbon number of 0 to 10, particularly preferably a carbon number of 0 to 6; Amino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino etc.), a A Coxy group (preferably an alkoxy group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy and 2-ethylhexyloxy An aryloxy group (preferably having 6 to 30
  • An acyl group (preferably an acyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, (Pivaloyl etc.), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably an alkoxycarbonyl group having 2 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl
  • An aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms), and examples thereof include phenyloxycarbonyl and the like.
  • an acyloxy group (preferably having 2 to 30 carbon atoms).
  • it is an acyloxy group having 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy, benzoyloxy and the like), an acylamino group (preferably having 2 to 30 carbon atoms, more preferably carbon)
  • acylamino groups each having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 5 carbon atoms, and examples thereof include acetylamino and benzoylamino.
  • Alkoxycarbonylamino group preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, etc.
  • aryl An oxycarbonylamino group preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino and the like).
  • a sulfonylamino group (preferably having a carbon number of 1 to 30, more preferably a carbon number of 1 to 20, particularly preferably a carbon number of 1 to 12, and examples include methanesulfonylamino, benzenesulfonylamino and the like), sulfamoyl group (Preferably having a carbon number of 0 to 30, more preferably Is a sulfamoyl group having 0 to 20 carbon atoms, more preferably 0 to 12 carbon atoms, particularly preferably 0 to 6 carbon atoms, and examples thereof include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl and the like.
  • a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, particularly preferably 1 to 7 carbon atoms); Group, diethyl carbamoyl group, phenyl carbamoyl group and the like.
  • alkylthio group preferably an alkylthio group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples include methylthio and ethylthio
  • an arylthio group preferably It is an arylthio group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenylthio and the like.
  • Heterocyclic thio groups (preferably 1 to 30 carbon atoms) More preferably a heterocyclic thio group having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like. Can be mentioned),
  • a sulfonyl group (preferably a sulfonyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl), and sulfinyl groups (preferably)
  • the hetero ring may be a hetero ring, and examples of the hetero atom constituting the hetero ring include a nitrogen atom, an oxygen atom and a sulfur atom
  • the carbon number is 0 to 30, more preferably a hetero ring having 1 to 12 carbon atoms.
  • silyl group (preferably having carbon atoms) 3 to 40, more preferably a silyl group having 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, For example, trimethylsilyl, triphenylsilyl and the like), silyloxy groups (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, for example, trimethylsilyloxy , Triphenylsilyloxy and the like), pentafluorosulfanyl group and the like.
  • substituents may be further substituted by any one or more substituents selected from the above-mentioned Substituent Group Z.
  • substituents when there is a plurality of substituents in one structural site, those substituents are linked to each other to form a ring, or condensed with a part or all of the above structural sites to be aromatic. It may form a ring or an unsaturated heterocyclic ring.
  • the compound or the substituent or the like contains an alkyl group, an alkenyl group or the like, these may be linear or branched, and may be substituted or unsubstituted. Further, when the aryl group, the heterocyclic group and the like are contained, they may be monocyclic or fused ring, and may be substituted or unsubstituted.
  • the weight average molecular weight of the polyimide compound used in the present invention is preferably 10,000 to 1,000,000, more preferably 15,000 to 500,000, and still more preferably 20,000 to 200,000. It is.
  • the molecular weight and the degree of dispersion are values measured using a GPC (gel filtration chromatography) method, and the molecular weight is a polystyrene-equivalent weight average molecular weight.
  • 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 composed of a styrene-divinylbenzene copolymer. It is preferable to use 2 to 6 columns connected.
  • the solvent to be used include ether solvents such as tetrahydrofuran and amide solvents such as N-methyl pyrrolidinone.
  • 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 load on the device is not applied, and the measurement can be performed more efficiently.
  • the measurement temperature is preferably 10 to 50 ° C., and 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 to be measured.
  • the polyimide compound can be synthesized by condensation polymerization of a specific bifunctional acid anhydride (tetracarboxylic acid dianhydride) and a specific diamine.
  • a specific bifunctional acid anhydride tetracarboxylic acid dianhydride
  • a specific diamine for example, general textbooks (for example, Ikuo Imai and Takuo Yokota, "Latest Polyimide-Basics and Applications", NTS Co., Ltd., August 25, 2010, p. 3-49, etc. It can synthesize
  • a tetracarboxylic acid dianhydride having —SF 5 is used as a raw material of the polyimide compound used in the present invention, for example, the compounds shown below can be used.
  • a tetracarboxylic acid dianhydride not having —SF 5 is used as a raw material of the polyimide compound used in the present invention
  • the following compounds can be used.
  • Ph is phenyl.
  • a diamine compound having —SF 5 and having an active hydrogen atom is used as a raw material of the polyimide compound used in the present invention, for example, the following compounds can be used.
  • a diamine compound having —SF 5 and having no active hydrogen atom is used as a raw material of the polyimide compound used in the present invention, for example, the following compounds can be used.
  • polyimide compound used in the present invention as long as the polyimide compound defined in the present invention can be obtained, without a -SF 5, and can also be used without diamine compound active hydrogen atoms.
  • the polyimide compound used in the present invention can be obtained by appropriately combining the above-mentioned respective raw materials, mixing them in a solvent, and subjecting them to condensation polymerization by a usual method.
  • the above solvent is not particularly limited, but ester organic solvents such as methyl acetate, ethyl acetate and butyl acetate, aliphatic ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, cyclopentanone and cyclohexanone Ether organic solvents such as ethylene glycol dimethyl ether, dibutyl butyl ether, tetrahydrofuran, methyl cyclopentyl ether, dioxane, amide organic solvents such as N-methylpyrrolidone, 2-pyrrolidone, dimethylformamide, dimethylimidazolidinone, dimethylacetamide, dimethyl sulfoxide And sulfur-containing organic
  • organic solvents are appropriately selected as long as they can dissolve the reaction substrate tetracarboxylic acid dianhydride, diamine compound, polyamic acid as reaction intermediate, and polyimide compound as the final product, but preferably Ester organic solvents (preferably butyl acetate), aliphatic ketone organic solvents (preferably methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, cyclopentanone, cyclohexanone), ether organic solvents (diethylene glycol monomethyl ether, methyl cyclopentyl ether ), Amide type organic solvents (preferably N-methyl pyrrolidone), and sulfur-containing type organic solvents (dimethyl sulfoxide, sulfolane) are preferable. Moreover, these can be used combining 1 type or 2 types or more.
  • the reaction temperature in the condensation polymerization is not particularly limited, and a temperature which 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 imidating the polyamic acid produced
  • a method for dehydrating and closing a ring a general book (for example, Ikuo Imai and Takuo Yokota, “Latest Polyimide-Basics and Applications-”, NTS Co., Ltd., August 25, 2010, p. The methods described in 3 to 49, etc.) can be referred to.
  • a thermal imidization method in which the reaction is carried out by heating to 120 ° C. to 200 ° C.
  • acetic anhydride in the coexistence of a basic catalyst such as pyridine, triethylamine or DBU.
  • a basic catalyst such as pyridine, triethylamine or DBU.
  • Methods such as so-called chemical imidization using a dehydrating condensing agent such as dicyclohexyl carbodiimide or triphenyl phosphite are preferably used.
  • the total concentration of tetracarboxylic acid dianhydride and diamine compound in the polymerization reaction solution of the polyimide compound is not particularly limited, but 5 to 70% by mass is preferable, 5 to 50% by mass is more preferable, and 5 to 30 % By mass is more preferred.
  • composition of gas separation membrane [Composition of gas separation membrane] Then, although the basic composition of the gas separation membrane of this invention is demonstrated, this invention is not limited to these forms except prescribing by this invention.
  • the gas separation composite membrane which is a preferred embodiment of the gas separation membrane, has a gas separation layer containing the above-described polyimide compound on a gas permeable support layer.
  • the gas separation composite membrane is preferably provided with the above-mentioned gas separation layer by applying a coating solution (dope) containing the above-mentioned polyimide compound on at least the surface of a porous support.
  • a coating solution dope
  • the term "coating” includes a mode of immersion in a coating solution.
  • FIG. 1 is a longitudinal sectional view schematically showing a gas separation composite membrane 10 according to a preferred embodiment of the present invention. In this embodiment, the gas separation layer 1 is provided on the support layer consisting of the porous layer 2.
  • the support layer includes the non-woven fabric layer 3
  • the gas separation composite membrane 20 comprises the non-woven fabric layer 3, the porous layer 2 and the gas separation layer 1 , Provided in this order.
  • 1 and 2 show an embodiment in which the permeate gas is enriched in carbon dioxide by selectively permeating carbon dioxide from a mixed gas containing carbon dioxide and methane.
  • a support layer means that another layer may be interposed between the support layer and the gas separation layer.
  • the side of the gas separation membrane to which the gas to be separated is supplied is referred to as “upper”, and the side from which the separated gas is discharged is referred to as “lower”.
  • the gas separation composite membrane has a gas separation layer above the support layer.
  • a porous support can be used as the support layer. It can be conveniently obtained by forming a gas separation layer on at least the surface of a porous support. By forming the gas separation layer on at least the surface of the porous support, a gas separation composite membrane having high separation selectivity, high gas permeability, and mechanical strength can be obtained. From the viewpoint of gas permeability, the film thickness of the gas separation layer is preferably as thin as possible within the range in which the mechanical strength and the gas separation selectivity can be maintained at desired levels.
  • the thickness of the gas separation layer is not particularly limited, but is preferably 0.01 to 5.0 ⁇ m, and more preferably 0.05 to 2.0 ⁇ m.
  • the support layer is not particularly limited as long as the mechanical strength and gas permeability are at desired levels, and either an organic material or an inorganic material may be used.
  • the support layer is preferably a porous layer of an organic polymer, and the thickness thereof is preferably 1 to 3000 ⁇ m, more preferably 5 to 500 ⁇ m, and still more preferably 5 to 150 ⁇ m.
  • the pore structure of the porous layer generally has an average pore diameter of preferably 10 ⁇ m or less, more preferably 0.5 ⁇ m or less, and still more preferably 0.2 ⁇ m or less.
  • the porosity is preferably 20 to 90%, more preferably 30 to 80%.
  • the support layer is “gas permeable” means that carbon dioxide is supplied to the support layer (a film consisting of only the support layer) at a temperature of 30 ° C. with the total pressure on the gas supply side being 5 MPa. It means that the permeation rate of carbon dioxide is at least 1 ⁇ 10 ⁇ 5 cm 3 (STP) / cm 2 ⁇ sec ⁇ cmHg (10 GPU). Furthermore, the gas permeability of the support layer is such that the carbon dioxide permeation rate is 3 ⁇ 10 -5 cm 3 (STP) / when carbon dioxide is supplied at a total pressure of 5 MPa at the gas supply side at a temperature of 30 ° C.
  • the porous layer As materials for the porous layer, conventionally known polymers such as polyolefin resins such as polyethylene and polypropylene, fluorine-containing resins such as polytetrafluoroethylene, polyvinyl fluoride and polyvinylidene fluoride, polystyrene, cellulose acetate, Various resins such as polyurethane, polyacrylonitrile, polyphenylene oxide, polysulfone, polyethersulfone, polyimide, polyaramid and the like can be mentioned.
  • any shape of the said porous layer any shape, such as flat form, spiral shape, a tubular shape, and hollow fiber shape, can also be taken.
  • a support is preferably formed in order 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, net and the like, but non-woven fabric is suitably used in view of film forming property and cost.
  • the non-woven fabric fibers made of polyester, polypropylene, polyacrylonitrile, polyethylene, polyamide or the like may be used alone or in combination.
  • the non-woven fabric can be manufactured, for example, by forming a main fiber and a binder fiber uniformly dispersed in water with a circular net or a long net, and drying it with a dryer. Further, for the purpose of removing fluff and improving mechanical properties, it is also preferable to perform pressure heat processing by sandwiching the non-woven fabric with two rolls.
  • the method for producing a gas separation membrane composite membrane preferably includes applying a coating solution containing the above-mentioned polyimide compound on a porous support to form a gas separation layer.
  • 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.
  • the coating solution can be prevented from being filled at a high concentration in the pores, so that a gas separation composite membrane having excellent permeability can be obtained.
  • the gas separation membrane of the present invention can be manufactured by adjusting the molecular weight, the structure, the composition and the solution viscosity of the polyimide compound used for forming the gas separation layer according to the purpose.
  • the organic solvent used as the medium of the coating solution is not particularly limited, and hydrocarbon organic solvents such as n-hexane and n-heptane, ester organic solvents such as methyl acetate, ethyl acetate and butyl acetate, methanol, ethanol, Alcohol organic solvents such as n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, aliphatic ketones such as diacetone alcohol, cyclopentanone, cyclohexanone, ethylene glycol, diethylene glycol , Triethylene glycol, glycerin, propylene glycol, ethylene glycol monomethyl or monoethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene Ether solvents such as glycol methyl
  • organic solvents are suitably selected in the range which does not exert an adverse effect such as corrosion of the support, but preferably an ester organic solvent (preferably butyl acetate), an alcohol organic solvent (preferably methanol) Ethanol, isopropanol, isobutanol), aliphatic ketones (preferably methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, cyclopentanone, cyclohexanone), ether organic solvents (ethylene glycol, diethylene glycol monomethyl ether, methyl cyclopentyl ether) Of these, aliphatic ketones, alcohol-based organic solvents, and ether-based organic solvents are more preferable. Moreover, these can be used combining 1 type or 2 types or more.
  • another layer may be present between the support layer and the gas separation layer.
  • a siloxane compound layer is mentioned as a preferable example of another layer.
  • the irregularities on the outermost surface of the support layer can be smoothed, and the gas separation layer can be easily thinned.
  • a siloxane compound which forms a siloxane compound layer the thing in which a principal chain consists of polysiloxane, and the compound which has a siloxane structure and a non-siloxane structure in a principal chain are mentioned.
  • these siloxane compound layers for example, those described in paragraphs ⁇ 0103> to ⁇ 0127> of JP-A-2015-160167 can be suitably applied.
  • a siloxane compound layer may be provided as a protective layer on the separation layer.
  • the siloxane compound layer used as the protective layer for example, those described in paragraphs ⁇ 0125> to ⁇ 0175> of WO 2017/002407 can be suitably applied.
  • the gas separation membrane of the present invention may be an asymmetric membrane.
  • An asymmetric membrane can be formed by a phase conversion method using a solution containing the above-mentioned polyimide compound.
  • the phase conversion method is a known method in which a polymer solution is brought into contact with a coagulating solution to form a film while phase conversion is performed, and in the present invention, a so-called dry-wet method is suitably used.
  • the solution on the surface of the polymer solution in the form of a film is evaporated to form a thin dense layer, and then it is immersed in a coagulating solution to form micropores using the phase separation phenomenon occurring at that time.
  • the thickness of the surface layer contributing to the gas separation which is called a dense layer or a skin layer, is not particularly limited, but it is 0.01 to 5.0 ⁇ m from the viewpoint of imparting practical gas permeability. Is preferable, and 0.05 to 1.0 ⁇ m is more preferable.
  • the porous layer below the dense layer lowers the gas permeability resistance and at the same time imparts mechanical strength, and its thickness is particularly limited as long as self-supporting property as an asymmetric membrane is given. It is not a thing.
  • the thickness of the lower porous layer in the asymmetric membrane 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-wet spinning method.
  • the dry-wet spinning method is a method of producing an asymmetric hollow fiber membrane by applying the dry-wet method to a polymer solution which has been discharged from a spinning nozzle to form a hollow fiber target shape. More specifically, the polymer solution is discharged from the nozzle into a hollow fiber target shape, and immediately after the discharge, it passes through an air or nitrogen gas atmosphere. Thereafter, the polymer is immersed in a coagulation solution which does not substantially dissolve and is compatible with the solvent of the polymer solution to form an asymmetric structure. Then, it is dried, and if necessary, it is heat-treated to produce a separation membrane.
  • the solution viscosity of the solution containing the polyimide compound to be discharged from the nozzle is preferably 2 to 17000 Pa ⁇ s, more preferably 10 to 1500 Pa ⁇ s, particularly preferably 20 to 1000 Pa ⁇ s at the discharge temperature (eg 10 ° C.). It is possible to stabilize the shape of the hollow fiber or the like after the discharge. Immersion in a coagulating solution is performed by immersing in a primary coagulating solution to coagulate to the extent that the shape of a membrane such as hollow fiber can be maintained, then wound on a guide roll, and then immersed in a secondary coagulating solution to sufficiently immerse the entire membrane.
  • the heat treatment for drying is preferably carried out at a temperature lower than the softening point or secondary transition point of the polyimide compound used.
  • the asymmetric membrane may have a form in which a protective layer is provided to cover the dense layer.
  • a protective layer those described for the protective layer in the composite film can be applied.
  • the gas separation membrane (composite membrane and asymmetric membrane) of the present invention can be suitably used as a gas separation and recovery method and a gas separation and purification method.
  • a gas separation membrane capable of efficiently separating a specific gas from a gas mixture containing a gas such as a perfluoro compound such as fluoroethane.
  • a gas separation membrane which selectively permeates and separates carbon dioxide from a gas mixture containing carbon dioxide and hydrocarbons (methane).
  • Various polymer compounds can also be added to the gas separation layer of the gas separation membrane of the present invention in order to adjust the membrane physical properties.
  • the polymer compound acrylic polymer, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, vinyl resin, acrylic resin, rubber resin , Waxes and other natural resins can be used. Moreover, two or more of these may be used in combination.
  • nonionic surfactant, cationic surfactant, an organic fluoro compound etc. can also be added for liquid physical-property adjustment.
  • the surfactant examples include alkyl benzene sulfonate, alkyl naphthalene sulfonate, higher fatty acid salt, sulfonate of higher fatty acid ester, sulfate of higher alcohol ether, sulfonate of higher alcohol ether, higher alkyl Sulfonamide alkyl carboxylate, anionic surfactant such as alkyl phosphate, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, ethylene oxide adduct of acetylene glycol, Non-ionic surfactants such as ethylene oxide adduct of glycerin, polyoxyethylene sorbitan fatty acid ester, and other amphoteric surfaces such as alkyl betaine and amido betaine Active agents, silicone surface active agents, including such fluorine-based surfactant, can be appropriately selected from surfactants and derivatives thereof are
  • 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. Among them, polyvinyl pyrrolidone 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 be made to coexist at the time of film formation, but it is desirable to be under an inert gas atmosphere.
  • the content of the polyimide compound in the gas separation layer is not particularly limited as long as a desired gas separation performance can be obtained. From the viewpoint of further improving the gas separation performance, the content of the above-mentioned 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 more preferably 70% by mass or more.
  • content of the said polyimide compound in a gas separation layer is 99 mass% or less normally.
  • 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.
  • the pressure at the time of gas separation is preferably 0.5 to 10 MPa, more preferably 1 to 10 MPa, and still more preferably 2 to 7 MPa.
  • the gas separation temperature is preferably -30 to 90 ° C, and more preferably 15 to 70 ° C.
  • a gas separation module can be prepared using the gas separation membrane of the present invention.
  • module types include spiral type, hollow fiber type, pleat type, tubular type, plate & frame type and the like.
  • the gas separation composite membrane or the gas separation module of the present invention can be used to obtain a gas separation device having means for separating, recovering or separating and purifying gas.
  • the gas separation composite membrane of the present invention may be applied to, for example, a gas separation and recovery apparatus as a membrane / absorption hybrid method used in combination with an absorbent as described in JP-A-2007-297605.
  • Synthetic intermediate 1 (17.63 g, 40.0 mmol) synthesized by the method described in International Publication WO 2017/002407, 4-aminophenylsulfur pentafluoride (9.21 g, 42.0 mmol, made by Tokyo Kasei Co., Ltd.), And acetonitrile (160 mL) were mixed and heated to reflux under nitrogen atmosphere for 8 hours.
  • the reaction solution was returned to room temperature, 300 mL of ethyl acetate and 300 mL of pure water were added to separate the layers, and the organic layer was washed with pure water three times.
  • Synthetic intermediate 2 (23.50 g, 37.7 mmol), 50 mass% sodium hydroxide aqueous solution (47.0 g, manufactured by Wako Pure Chemical Industries, Ltd.), and ethanol (47.0 g) are mixed, and it is under nitrogen atmosphere for 3 hours Heated to reflux.
  • the reaction solution was cooled to room temperature, 150 mL of pure water was added thereto, and concentrated hydrochloric acid was further added to adjust pH to about 7.
  • the precipitated solid is filtered, dispersed in 300 mL of pure water and filtered three times, and then dispersed in 300 mL of hexane and filtered once, and vacuum dried at 100 ° C. to give diamine 1 of 15 Obtained .30 g (yield 94%).
  • Compound 3 is the same as Compound 1 except that 2-amino-5- (pentafluorosulfanyl) phenol (manufactured by Aldrich) is used in place of 4-aminophenylsulfur pentafluoride in the synthesis of diamine 1. Synthesized.
  • Compound 5 is Helvetica Chim. Acta, 1939, 22nd p. 1278-1285.
  • the diamine 2 is synthesized according to the following scheme using 4-methyl-3,5-dinitrobenzoic acid chloride synthesized by the method described in 4. Further, in the synthesis of the compound 1, diamine 2 is used instead of diamine 1
  • the compound was synthesized in the same manner as the compound 1 except that 4,4′-biphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 6FDA.
  • the diamine is synthesized in the same manner as the synthesis of diamine 2 except that the 3 '-(pentafluorosulfanyl) biphenyl-4-amine synthesized by the method described in 4 is used, and in the synthesis of compound 5, 4,4'-
  • the compound was synthesized in the same manner as the compound 5 except that 4,4′-sulfonyldiphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of biphthalic anhydride.
  • Compound 8 is a compound 9 of 1,3-diamino-5-pentafluorosulfanylbenzene and diaminobenzoic acid synthesized by the method described in US Pat. No. 5,302,692 in place of diamine 1 in the synthesis of compound 1.
  • the compound was synthesized in the same manner as the compound 1 except that (molar ratio) was used.
  • the number average molecular weight Mn and the weight average molecular weight Mw of the compounds 1 to 9 are as shown in the table.
  • Comparative compound 1 is a compound described in US Pat. No. 5,302,692 (Mn: 44000, Mw 77000), comparative compound 2 is a compound described in JP-A-5-146650 (Mn: 71000, Mw 155000), and comparative compound 3 is It is a compound (Mn: 12000, Mw 22000) described in JP 2010-222279 A.
  • Example 1 Preparation of Composite Membrane ⁇ Preparation of PAN Porous Membrane with Smooth Layer> (Preparation of radiation curable polymer having dialkyl siloxane group)
  • 39 g of UV 9300 manufactured by Momentive
  • 10 g of X-22-162C manufactured by Shin-Etsu Chemical
  • 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 22.8 mPa ⁇ s at 25 ° C.).
  • the gas separation composite membrane shown in FIG. 2 was produced (the smooth layer is not shown in FIG. 2).
  • Compound 1 (0.08 g) and tetrahydrofuran (7.92 g) were mixed in a 30 ml brown vial, and stirred for 30 minutes, and then spin coated on the PAN porous membrane provided with the above smooth layer to obtain a gas separation layer To form a composite membrane.
  • the thickness of the polyimide (compound 1) layer was about 80 nm, and the thickness of the PAN porous film was about 180 ⁇ m including the non-woven fabric.
  • Comparative Examples 1 to 3 Preparation of Composite Membrane In the same manner as in Example 1 except that Comparative Compounds 1 to 3 were used instead of Compound 1 in Example 1 described above, the composite membranes of Comparative Examples 1 to 3 were used. Made.
  • Test Example 1 Evaluation of CO 2 Permeation Rate and Gas Separation Selectivity of Gas Separation Membrane-1
  • the gas separation performance was evaluated as follows using the gas separation membranes (composite membranes) of the respective Examples and Comparative Examples.
  • the gas separation membrane was cut into a diameter of 5 cm together with the porous support (support layer) to prepare a permeation test sample.
  • a mixture gas of carbon dioxide (CO 2 ): methane (CH 4 ) of 13:87 (volume ratio) is used with a gas permeation rate measuring device manufactured by GTR Tech Co., Ltd.
  • the total pressure on the gas supply side is 5 MPa (CO 2 ) Pressure: 0.65 MPa), flow rate 500 mL / min, adjusted to 40 ° C. and supplied.
  • the permeated gas was analyzed by gas chromatography.
  • the gas permeability of the membranes was compared by calculating the gas permeation rate as the gas permeability (Permeance).
  • Gas separation selectivity was calculated as the transmission rate R CO2 ratio of CO 2 to permeation rate R CH4 of CH 4 of the film (R CO2 / R CH4).
  • STP is Standard Temperature and pressure
  • 1 ⁇ 10 ⁇ 6 cm 3 (STP) is the volume of gas at 1 atmosphere and 0 ° C.
  • the values of carbon dioxide permeation rate (R CO2 ) and permeation rate ratio (R CO2 / R CH4 ) were applied to the following evaluation criteria to evaluate gas permeability and gas separation selectivity.
  • Test Example 2 Evaluation of plasticization resistance
  • the gas separation membrane used in the above-mentioned Test Example 1 was placed in a stainless steel container containing a petri dish covered with a toluene solvent, and the gas separation membranes prepared in Examples and Comparative Examples were placed. , Closed system. Thereafter, the composite film was stored for 20 minutes at 25 ° C. to expose the composite membrane to toluene vapor, and then the gas separation selectivity was evaluated in the same manner as in [Test Example 1].
  • the gas separation membranes of Examples 1 to 9 are excellent in gas permeability and excellent in plasticization resistance. That is, it can be seen that, by using the gas separation membrane of the present invention, efficient gas separation can be continuously performed even in the presence of a plasticizing component.

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Abstract

L'invention concerne : une membrane de séparation de gaz ayant une excellente perméabilité aux gaz et capable d'exprimer de manière durable une sélectivité de séparation de gaz souhaitée même lors de la mise en contact d'un composant plastifiant tel que le toluène; un module de séparation de gaz utilisant la membrane de séparation de gaz; un dispositif de séparation de gaz; et un procédé de séparation de gaz. L'invention concerne également un composé polyimide approprié en tant que matériau constitutif de la membrane de séparation. La membrane de séparation de gaz a une couche de séparation de gaz contenant un composé polyimide ayant un groupe pentafluorosulfanyle comme matériau constitutif, le module de séparation de gaz et le dispositif de séparation de gaz sont chacun pourvus de la membrane de séparation de gaz, et le procédé de séparation de gaz utilise la membrane de séparation de gaz. Le composé polyimide est un composé approprié pour la membrane de séparation de gaz.
PCT/JP2018/026649 2017-08-29 2018-07-17 Membrane de séparation de gaz, module de séparation de gaz, dispositif de séparation de gaz, procédé de séparation de gaz, et composé de polyimide WO2019044215A1 (fr)

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WO2013084860A1 (fr) * 2011-12-06 2013-06-13 宇部興産株式会社 Procédé pour la production d'acide pentafluorosulfanylbenzoïque
WO2016104677A1 (fr) * 2014-12-25 2016-06-30 宇部興産株式会社 Procédé de production d'un composé de pentafluorosulfanylbenzène contenant de l'azote

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