WO2022230196A1 - 陰イオン交換樹脂および電解質膜 - Google Patents
陰イオン交換樹脂および電解質膜 Download PDFInfo
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- WO2022230196A1 WO2022230196A1 PCT/JP2021/017255 JP2021017255W WO2022230196A1 WO 2022230196 A1 WO2022230196 A1 WO 2022230196A1 JP 2021017255 W JP2021017255 W JP 2021017255W WO 2022230196 A1 WO2022230196 A1 WO 2022230196A1
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- Prior art keywords
- group
- divalent
- carbon
- hydrophobic
- anion exchange
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- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/121—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from organic halides
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/42—Non-organometallic coupling reactions, e.g. Gilch-type or Wessling-Zimmermann type
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/516—Charge transport ion-conductive
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- a divalent hydrophobic group represented by the following formula and a single aromatic ring, or a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, or a divalent phosphorus-containing group , a linking group that is a divalent oxygen-containing group or a divalent sulfur-containing group, and/or a plurality of aromatic rings bonded to each other via a carbon-carbon bond, at least among the linking group or the aromatic ring
- One consists of a divalent hydrophilic group bonded to an anion exchange group-containing group, consisting of the hydrophobic group alone, or the hydrophobic group is an ether bond, a thioether bond, or a carbon-carbon bond.
- Patent Document 1 has succeeded in improving electrical properties (anion conductivity) while maintaining high chemical properties (durability, especially alkali resistance).
- electrical properties anion conductivity
- chemical properties durability, especially alkali resistance
- further improvements in chemical and electrical properties have been desired, and there has been the problem of insufficient mechanical properties (thin film flexibility).
- an object of the present invention is to provide an anion-exchange resin capable of producing an electrolyte membrane having excellent chemical, electrical, and mechanical properties, and an electrolyte membrane formed from the anion-exchange resin.
- Alk is the same or different from each other and represents an alkyl group or an aryl group; a, b, c, and d are the same or different from each other and represent an integer of 0 to 4; Indicates an integer of 1 or more.
- Alk' is the same or different and represents an alkyl group or an aryl group
- a', b', c' and d' are the same or different and represent an integer of 0 to 4 and l' represents an integer of 1 or more.
- the hydrophobic group (b) preferably contains a bisphenol residue represented by the following formula (2').
- A is the same or different from each other and represents an anion-exchange group-containing group or a cyclic structure containing an anion-exchange group.
- the electrolyte membrane of the present invention is characterized by containing the anion exchange resin described above.
- the anion exchange resin of the present invention consists of a divalent hydrophobic group (a), a divalent hydrophobic group (b), and a divalent hydrophilic group.
- Alk is the same or different from each other and represents an alkyl group or an aryl group; a, b, c, and d are the same or different from each other and represent an integer of 0 to 4; Indicates an integer of 1 or more.
- c and d are the same or different and represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably c and d are both 0 show.
- Such a hydrophobic group (a) preferably includes a bisphenol residue represented by the following formula (1').
- the divalent hydrophobic group (b) contains a bisphenol residue represented by the following formula (2).
- Alk' is the same or different and represents an alkyl group or an aryl group
- a', b', c' and d' are the same or different and represent an integer of 0 to 4 and l' represents an integer of 1 or more.
- Alk' is the same or different and represents an alkyl group or an aryl group.
- the alkyl group includes the alkyl group represented by the above formula (1)
- the aryl group includes the aryl group represented by the above formula (1).
- a' and b' are the same or different and represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably a' and b' , both indicate 0.
- c' and d' are the same or different and represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably c' and d' , both indicate 0.
- l' represents an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 2 to 6.
- Such a hydrophobic group (b) preferably includes a bisphenol residue represented by the following formula (2').
- the main chain with low intermolecular interaction improves the solubility and flexibility.
- Hydrophilic hydroxide ions and oxidizing agents are less likely to approach the main chain (improved alkali resistance and chemical stability)
- the rigidity of the main chain can be controlled (improved the flexibility of the electrolyte membrane)
- ⁇ Glass transition temperature is low and can be adhered to the catalyst layer (reduced contact resistance)
- ⁇ Gas diffusivity can be controlled (increased oxygen diffusivity when used as a binder)
- the divalent hydrophilic group consists of a single aromatic ring, or a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent A linking group that is a phosphorus-containing group, a divalent oxygen-containing group, or a divalent sulfur-containing group, and/or a plurality of (two or more, preferably two) aromatics linked together via a carbon-carbon bond At least one of the linking group and the aromatic ring is bonded to the anion exchange group-containing group.
- aromatic rings include monocyclic or polycyclic compounds having 6 to 14 carbon atoms such as benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, and phenanthrene ring, and azole, oxol, Heterocyclic compounds such as thiophenes, oxazoles, thiazoles, pyridines and the like are included.
- the aromatic ring is preferably a monocyclic aromatic hydrocarbon having 6 to 14 carbon atoms, more preferably a benzene ring.
- the aromatic ring may optionally be substituted with a substituent such as a halogen atom, an alkyl group, an aryl group, or a pseudohalide.
- Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
- Pseudohalides include trifluoromethyl groups, -CN, -NC, -OCN, -NCO, -ONC, -SCN, -NCS, -SeCN, -NCSe, -TeCN , -NCTe, -N3 .
- alkyl groups examples include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group and octyl group.
- cycloalkyl groups having 1 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups.
- Aryl groups include, for example, a phenyl group, a biphenyl group, a naphthyl group, and a fluorenyl group.
- the aromatic ring is substituted with a substituent such as a halogen atom, an alkyl group, an aryl group, or a pseudohalide
- a substituent such as a halogen atom, an alkyl group, an aryl group, or a pseudohalide
- the number of substituents such as a halogen atom, an alkyl group, an aryl group, or a pseudohalide and the substitution position is appropriately set according to the purpose and application.
- the aromatic ring substituted with halogen atoms more specifically, for example, a benzene ring substituted with 1 to 4 halogen atoms (e.g., a benzene ring substituted with 1 to 4 fluorine atoms, 1 to 4 chlorine atoms, benzene ring substituted with , benzene ring substituted with 1 to 4 bromines, benzene ring substituted with 1 to 4 iodine, etc. 1 to 4 halogen atoms are all the same or different. may be used), etc.
- a benzene ring substituted with 1 to 4 halogen atoms e.g., a benzene ring substituted with 1 to 4 fluorine atoms, 1 to 4 chlorine atoms, benzene ring substituted with , benzene ring substituted with 1 to 4 bromines, benzene ring substituted with 1 to 4 iodine, etc. 1 to 4 halogen
- Divalent hydrocarbon groups include, for example, methylene (--CH.sub.2--), ethylene, propylene, i-propylene (--C(CH.sub.3) .sub.2-- ), butylene, i - butylene, sec-butylene, pentylene (pentene ), i-pentylene, sec-pentylene, hexylene (hexamethylene), 3-methylpentene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, i-decylene, dodecylene, tetradecylene, hexadecylene, octadecylene, carbon Divalent saturated hydrocarbon groups of numbers 1 to 20 can be mentioned.
- the divalent hydrocarbon group is preferably a divalent saturated hydrocarbon group having 1 to 3 carbon atoms, specifically methylene (--CH.sub.2--), ethylene, propylene, i - propylene (--C(CH 3 ) 2 —), more preferably methylene (—CH 2 —), isopropylene (—C(CH 3 ) 2 —), and particularly preferably i-propylene (—C(CH 3 ) 2- ).
- the divalent hydrocarbon group may be substituted with a monovalent residue in the aromatic ring described above.
- the divalent hydrophilic group preferably consists of a single polycyclic compound, or a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing a linking group that is a group, a divalent phosphorus-containing group, a divalent oxygen-containing group, or a divalent sulfur-containing group, and/or a plurality (two or more, preferably 2), wherein at least one of the linking group or the polycyclic compound is bonded to an anion exchange group via a divalent saturated hydrocarbon group having 2 or more carbon atoms.
- polycyclic compounds include naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, phenanthrene ring, carbazole ring, and indole ring, preferably fluorene ring.
- the divalent hydrocarbon group includes the divalent hydrocarbon groups described above.
- the anion-exchange group-containing group may be an anion-exchange group alone or an anion-exchange group bonded via a divalent saturated hydrocarbon group.
- the anion-exchange group-containing group may be bonded to at least one of the connecting groups or aromatic rings of the divalent hydrophilic residue, and may be bonded to a plurality of connecting groups or aromatic rings. It may be attached to a linking group or an aromatic ring. Also, a plurality of anion exchange groups may be bonded to one linking group or aromatic ring.
- the anion-exchange group is introduced into the side chain of the hydrophilic group, and is not particularly limited. Any known anion exchange group such as a class sulfonium group, a quaternary boronium group, a quaternary phosphonium group and a guanidinium group can be employed. From the viewpoint of anion conductivity, a quaternary ammonium group is preferred.
- Preferred anion exchange groups include —N + (CH 3 ) 3 , but also include those having the following structures.
- * indicates a portion that binds to an aromatic ring containing a substituent.
- Alk, Alk', and Alk'' represent the above alkyl groups, and iPr represents an i-propyl group.
- the number of carbon atoms in the divalent saturated hydrocarbon group that binds the linking group or aromatic ring of the divalent hydrophilic residue and the anion exchange group is preferably 2 or more.
- the number of carbon atoms in the divalent saturated hydrocarbon group is more preferably an integer of 2-20, more preferably an integer of 3-10, and particularly preferably an integer of 4-8.
- the divalent saturated hydrocarbon group is preferably methylene (-(CH 2 )-), ethylene (-(CH 2 ) 2 -), trimethylene (-(CH 2 ) 3 -), tetramethylene (-( CH 2 ) 4 -), pentamethylene (-(CH 2 ) 5 -), hexamethylene (-(CH 2 ) 6 -), heptamethylene (-(CH 2 ) 7 -), octamethylene (-(CH 2 ) 8 -) and other linear saturated hydrocarbon groups.
- divalent hydrophilic groups having such a structure include those having a structure represented by the following formula.
- Ion is the same or different from each other and represents an anion-exchange group-containing group, and a is an integer of 0 or more and capable of bonding with an anion-exchange group-containing group (preferably 0 or 1), and n is an integer of 0 or more.
- the divalent hydrophilic group having such a structure includes a fluorene residue represented by the following formula (3).
- A is the same or different from each other and represents an anion-exchange group-containing group or a cyclic structure containing an anion-exchange group.
- the divalent hydrophilic group having such a structure includes those represented by the following formula (3a), the following formula (3b), the following formula (3c), or the following formula (3d). .
- the above hydrophobic group (a) is composed alone, or the above hydrophobic group (a) is repeated via an ether bond, a thioether bond, or a carbon-carbon bond.
- the hydrophobic unit (a) preferably consists of a single hydrophobic group (a), or the hydrophobic group (a) is repeated via a carbon-carbon bond.
- the hydrophobic unit (b) preferably consists of a single hydrophobic group (b), or the hydrophobic group (b) is repeated via a carbon-carbon bond.
- the hydrophilic unit preferably consists of a single hydrophilic group, or is formed by repeating hydrophilic groups via carbon-carbon bonds.
- the units correspond to the blocks of block copolymers that are generally used.
- the hydrophobic unit (a) preferably includes a unit formed by bonding the divalent hydrophobic groups (a) represented by the above formula (1) to each other via a carbon-carbon bond.
- a unit may be formed by combining a plurality of types of divalent hydrophobic groups (a) represented by the above formula (1) with each other in a regular manner such as random or alternating, or in a block.
- Such a hydrophobic unit (a) is represented, for example, by the following formula (4).
- Alk, a, b, c, d, and l have the same meanings as Alk, a, b, c, d, and l in formula (1) above, and q represents 1 to 200. .
- q represents, for example, 1-200, preferably 1-50.
- such a hydrophobic unit (a) includes a unit formed by bonding together via a carbon-carbon bond the divalent hydrophobic groups represented by the above formula (1′). .
- Such a hydrophobic unit (a) is particularly preferably represented by the following formula (4').
- q represents, for example, 1-200, preferably 1-50.
- the hydrophobic unit (b) preferably includes a unit formed by bonding the divalent hydrophobic groups (b) represented by the above formula (2) to each other via a carbon-carbon bond.
- a unit formed by combining a plurality of types of divalent hydrophobic groups (b) represented by the above formula (2) with each other in a regular manner such as random or alternating, or in a block manner may also be used.
- Such a hydrophobic unit (b) is represented, for example, by the following formula (5).
- Alk', a', b', c', d', and l' are the same as Alk', a', b', c', d', and l' in formula (2) above. meaning, q' represents 1 to 200.
- q' represents, for example, 1-200, preferably 1-50.
- such a hydrophobic unit (b) includes a unit formed by binding the divalent hydrophobic groups represented by the above formula (2′) to each other via a carbon-carbon bond. .
- Such a hydrophobic unit (b) is particularly preferably represented by the following formula (5').
- q represents, for example, 1-200, preferably 1-50.
- the hydrophilic unit preferably consists of a single aromatic ring, or a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, or a divalent oxygen-containing group , or a linking group that is a divalent sulfur-containing group, and / or consists of a plurality of aromatic rings bonded to each other via carbon-carbon bonds, at least one of the linking group or the aromatic ring is an anion exchange group Examples include units formed by bonding divalent hydrophilic groups bonded to containing groups to each other via a carbon-carbon bond.
- the hydrophilic unit is more preferably composed of a single polycyclic compound, or a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent A linking group that is an oxygen-containing group or a divalent sulfur-containing group, and/or a plurality of polycyclic compounds that are bonded to each other via carbon-carbon bonds, at least among the linking groups or the polycyclic compounds
- One is a unit formed by bonding a divalent hydrophilic group bonded to an anion exchange group via a divalent saturated hydrocarbon group having 2 or more carbon atoms to each other via a carbon-carbon bond. be done.
- a unit formed by combining a plurality of types of divalent hydrophilic groups in a random manner, in a regular manner such as alternating, or in a block manner may also be used.
- hydrophilic units include units formed by bonding fluorene residues represented by the above formula (3) to each other via a carbon-carbon bond.
- Such a hydrophobic unit is represented, for example, by the following formula (6).
- m represents, for example, 1-200, preferably 1-50.
- hydrophilic unit a unit formed by bonding together hydrophilic groups represented by the above formula (3a) through a carbon-carbon bond, as represented by the following formula (6a), is particularly preferable.
- a unit formed by bonding the hydrophilic groups represented by the above formula (3b) to each other via a carbon-carbon bond as shown in the following formula (6c)
- Hydrophilic groups represented by the above formula (3c) are formed by bonding to each other via a carbon-carbon bond, and as represented by the following formula (6d), hydrophilicity represented by the above formula (3d) Units formed by groups linked together via carbon-carbon bonds are included.
- m represents, for example, 1-200, preferably 1-50.
- the hydrophobic unit (a), the hydrophobic unit (b), and the hydrophilic unit are bonded via an ether bond, a thioether bond, or a carbon-carbon bond. ing.
- the above hydrophobic unit (a), the above hydrophobic unit (b), and the above hydrophilic unit are bonded via a carbon-carbon bond.
- an anion exchange resin preferably, as represented by the following formula (7), the hydrophobic unit (a) represented by the above formula (4) and the hydrophobic unit (b) represented by the above formula (5) ) and a hydrophilic unit represented by the above formula (6) bonded via a carbon-carbon bond.
- Alk, a, b, c, d, and l have the same meanings as Alk, a, b, c, d, and l in the above formula (4), and Alk', a', b' , c', d', and l' have the same meanings as Alk', a', b', c', d', and l' in the above formula (5), and A is the above formula (6) has the same meaning as A of, q, q', and m represent the compounding ratio or the number of repetitions, and represent 1 to 100, and o represents the number of repetitions, and represent 1 to 100.)
- an anion exchange resin more preferably, as represented by the following formula (7′), a hydrophobic unit (a) represented by the above formula (4′) and a hydrophobic unit (a) represented by the above formula (5′)
- anion exchange resins in which the hydrophobic unit (b) and the hydrophilic unit represented by the above formula (6) are bonded via a carbon-carbon bond.
- an anion exchange resin it is particularly preferable to use a hydrophobic unit (a) represented by the above formula (4′) and a hydrophobic unit (a) represented by the above formula (5′), as represented by the following formula (7a).
- the exchange resin as represented by the following formula (7c), is composed of the hydrophobic unit (a) represented by the above formula (4′), the hydrophobic unit (b) represented by the above formula (5′), and the above formula (6c ) and a hydrophilic unit represented by a carbon-carbon bond bonded to an anion exchange resin anion exchange resin, as represented by the following formula (7d), a hydrophobic unit represented by the above formula (4′) ( a), a hydrophobic unit (b) represented by the above formula (5′), and a hydrophilic unit represented by the above formula (6d) are bonded via a carbon-carbon bond.
- l has the same meaning as l in the above formula (4')
- l' has the same meaning as l' in the above formula (5')
- q, q', and m are the blending ratio Alternatively, it represents the number of repetitions and represents 1 to 100, and o represents the number of repetitions and represents 1 to 100.
- l has the same meaning as l in the above formula (4')
- l' has the same meaning as l' in the above formula (5')
- q, q', and m are the blending ratio Alternatively, it represents the number of repetitions and represents 1 to 100, and o represents the number of repetitions and represents 1 to 100.
- l has the same meaning as l in the above formula (4')
- l' has the same meaning as l' in the above formula (5')
- q, q', and m are the blending ratio Alternatively, it represents the number of repetitions and represents 1 to 100, and o represents the number of repetitions and represents 1 to 100.
- l has the same meaning as l in the above formula (4')
- l' has the same meaning as l' in the above formula (5')
- q, q', and m are the blending ratio Alternatively, it represents the number of repetitions and represents 1 to 100, and o represents the number of repetitions and represents 1 to 100.
- the ratio between the number q of repeating units of the hydrophobic group (a) and the number q' of repeating units of the hydrophobic group (b) can be appropriately adjusted so as to obtain the desired properties.
- the hydrophobic group (a) ratio (q/(q+q')) is, for example, 0.05 to 0.95, preferably 0.10 to 0.75, more preferably 0.15 to 0.55.
- the number average molecular weight of such anion exchange resin is, as described above, for example, 10 to 1000 kDa, preferably 30 to 500 kDa.
- the method for producing the anion exchange resin is not particularly limited, and known methods can be adopted. Preferably, a method using a polycondensation reaction is employed.
- an anion exchange resin for example, a monomer for forming a hydrophobic group (a) is prepared, a monomer for forming a hydrophobic group (b) is prepared, and an anion exchange group precursor functional group is prepared.
- the anion-exchange resin can be produced by synthesizing a polymer by allowing the anion-exchange group-precursor functional groups in the polymer to ionize.
- a hydrophobic group (a) forming monomer is prepared, a hydrophobic group (b) forming monomer is prepared, a hydrophilic group forming monomer is prepared, a hydrophobic group (a) forming monomer and a hydrophobic Synthesizing a polymer by polymerizing a group (b)-forming monomer and a hydrophilic group-forming monomer, and introducing a substituent having an anion-exchange group into the polymer to produce an anion-exchange resin. can be done.
- a conventionally known general method can be adopted for the polycondensation reaction. Couplings are preferably employed that form carbon-carbon bonds.
- a compound represented by the following formula (11), which corresponds to the above formula (1) is preferably exemplified.
- Alk, a, b, c, d, and l have the same meanings as Alk, a, b, c, d, and l in formula (1) above, and T is the same or different represents a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative, or a hydrogen atom.
- hydrophobic group (a)-forming monomer examples include compounds represented by the following formula (11') corresponding to the above formula (1').
- T is the same or different from each other and represents a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative, or a hydrogen atom. show.
- hydrophobic group (b)-forming monomer preferably include compounds represented by the following formula (12) corresponding to the above formula (2).
- T which is the same or different from each other, represents a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative, or a hydrogen atom.
- hydrophobic group (b)-forming monomer examples include compounds represented by the following formula (12') corresponding to the above formula (2').
- T is the same or different from each other and represents a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative, or a hydrogen atom. show.
- hydrophilic group-forming monomer having an anion-exchange group-precursor functional group a compound represented by the following formula (13), which corresponds to the above formula (3), is preferably exemplified.
- T is the same or different from each other, it denotes a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative, or a hydrogen atom.
- the hydrophobic group (a)-forming monomer, the hydrophobic group (b)-forming monomer, and the hydrophilic group-forming monomer having an anion exchange group precursor functional group are polymerized by coupling, the blending amount of each monomer are adjusted so that the resulting anion-exchange resin precursor polymer has a desired compounding ratio of the hydrophobic unit (a), the hydrophobic unit (b), and the hydrophilic unit.
- a monomer for forming a hydrophobic group (a), a monomer for forming a hydrophobic group (b) and a monomer for forming a hydrophilic group having an anion exchange group precursor functional group are combined with, for example, N,N-dimethyl
- a known method such as a method of dissolving in a solvent such as acetamide or dimethylsulfoxide and polymerizing using bis(cycloocta-1,5-diene)nickel(0) or the like as a catalyst can be employed.
- the reaction temperature in the coupling reaction is, for example, -100 to 300°C, preferably -50 to 200°C, and the reaction time is, for example, 1 to 48 hours, preferably 2 to 5 hours.
- Alk, a, b, c, d, and l have the same meanings as Alk, a, b, c, d, and l in the above formula (11), and Alk', a', b' , c′, d′, and l′ have the same meanings as Alk′, a′, b′, c′, d′, and l′ of the above formula (12), and Pre is the above formula (13) has the same meaning as Pre, q, q', and m represent the compounding ratio or the number of repetitions, and represent 1 to 100, and o represents the number of repetitions, and represent 1 to 100.)
- the anion exchange group precursor functional group is ionized.
- the ionization method is not particularly limited, and known methods can be employed.
- Known methods such as dissolving the anion exchange resin precursor polymer in a solvent such as N,N-dimethylacetamide or dimethyl sulfoxide and ionizing it using methyl iodide as an alkylating agent can be employed. can.
- the reaction temperature in the ionization reaction is, for example, 0 to 100°C, preferably 20 to 80°C, and the reaction time is, for example, 24 to 72 hours, preferably 48 to 72 hours.
- the anion exchange resin represented by the above formula (7) is obtained by ionizing the anion exchange resin precursor polymer represented by the above formula (17).
- the anion exchange resin represented by the above formula (7') is obtained by ionizing the anion exchange resin precursor polymer represented by the above formula (17').
- the ion exchange group capacity of the anion exchange resin is, for example, 0.1 to 4.0 meq. /g, preferably 0.6 to 3.0 meq. /g.
- the ion exchange group capacity can be determined by the following formula (24).
- [Ion-exchange group capacity (meq./g)] introduction amount of anion-exchange groups per hydrophilic unit ⁇ repeating unit of hydrophilic unit ⁇ 1000/(molecular weight of hydrophobic unit ⁇ number of repeating units of hydrophobic unit + molecular weight of hydrophilic unit ⁇ Number of repeating units of hydrophilic unit + molecular weight of ion-exchange group ⁇ number of repeating units of hydrophilic unit) (24)
- the ion-exchange group introduction amount is defined as the number of ion-exchange groups per unit hydrophilic group.
- the amount of anion-exchange groups introduced is the number of moles (mol) of the anion-exchange groups introduced into the main chain or side chain of the hydrophilic group.
- an anion exchange resin contains a divalent hydrophobic group (a) containing a bisphenol residue represented by the above formula (1) and a bisphenol residue represented by the above formula (2).
- hydrophilic group has a repeating hydrophilic unit through a carbon-carbon bond
- durability such as alkali resistance is excellent because it does not contain an ether bond.
- hydrophilic unit contains an ether bond
- decomposition by hydroxide ions (OH ⁇ ) may occur as described below, resulting in insufficient alkali resistance in some cases.
- the hydrophilic unit of the anion exchange resin having a hydrophilic unit in which the hydrophilic group is repeated via a carbon-carbon bond does not contain an ether bond, so decomposition by the above mechanism does not occur, and as a result As a result, it has excellent durability such as alkali resistance.
- the present invention includes an electrolyte layer (electrolyte membrane) obtained using such an anion exchange resin.
- the electrolyte membrane of the present invention can be applied to various electrochemical applications such as fuel cells, water electrolysis hydrogen generators, and electrochemical hydrogen pumps, and is particularly suitable for use in water electrolysis hydrogen generators.
- an electrolyte membrane is used in a structure in which catalyst layers, electrode substrates and separators are sequentially laminated on both sides.
- the one in which the catalyst layer and the gas diffusion substrate are sequentially laminated on both sides of the electrolyte membrane is a membrane electrode. It is called a composite (MEA), and the electrolyte membrane of the present invention is suitably used as an electrolyte membrane constituting such an MEA.
- the above-described anion exchange resin can be used as the electrolyte membrane (that is, the electrolyte membrane contains the above-described anion exchange resin).
- the electrolyte membrane can be reinforced with a known reinforcing material such as a porous substrate. Various treatments, such as heat treatment, can be applied to control stress.
- a known filler can be added to the electrolyte membrane 4 in order to increase its mechanical strength, and the electrolyte membrane 4 and a reinforcing agent such as glass nonwoven fabric can be combined by pressing.
- various additives that are commonly used in electrolyte membranes such as compatibilizers for improving compatibility, antioxidants for preventing resin deterioration, for example, improving handleability during molding as a film.
- Antistatic agents, lubricants, and the like for improving the properties can be appropriately contained within a range that does not affect the processing and performance of the electrolyte membrane 4 .
- the thickness of the electrolyte membrane is not particularly limited, and is appropriately set according to the purpose and application.
- the thickness of the electrolyte membrane is, for example, 1.2-350 ⁇ m, preferably 5-200 ⁇ m.
- the embodiment of the present invention has been described above, the embodiment of the present invention is not limited to this, and the design can be appropriately modified without changing the gist of the present invention.
- the precipitate recovered by filtration from the mixture was washed with 12 M hydrochloric acid, 0.2 M potassium carbonate aqueous solution, and pure water, and then vacuum-dried overnight (60 ° C.) to obtain an anion exchange resin precursor represented by the following formula.
- Polymer BP 17 A was obtained with a yield of 86%.
- Anion exchange resin precursor polymer BP 17 A (1.24 g) and N,N-dimethylacetamide (13 mL) were added to a 50 mL round-bottom three-necked flask. After stirring this mixture to make a homogeneous solution, dimethyl sulfate (6.44 mL, 67.9 mmol) was added and the reaction was carried out at room temperature for 48 hours. The reaction solution was dropped into pure water. An anion exchange resin QBP 17 A was obtained by vacuum-drying (60° C.) overnight after washing the precipitate collected by filtration from the mixture with pure water.
- IEC ion exchange capacity
- the amount of chloride ions released into the aqueous solution by ion exchange was determined by Mohr's method.
- the chloride ion type membrane was vacuum-dried (60°C) for 12 hours, then quickly transferred to a pre-weighed sample vial and weighed with the lid closed. Calculated using W dry (chloride ion type) obtained by difference and a.
- ⁇ Tensile test> A tensile test was performed on the anion exchange resin membranes obtained in Examples and Comparative Examples. Specifically, the membranes (chloride ion type) of the anion exchange resins obtained in Examples and Comparative Examples were placed in a dumbbell shape (DIN-53504-S3) of 12 mm ⁇ 2 mm (the area of the entire sample: 35 mm ⁇ 6 mm). A measurement sample was cut out from the sample, and a Shimazu universal testing instrument Autograph AGS-J500N equipped with a Toshin Kogyo temperature control unit Bethel-3 was used to perform a tensile test in a chamber controlled to constant temperature and humidity. For the measurement, the sample was held under conditions of 80° C. and 60% RH for 3 hours, then pulled at a rate of 10 mm/min, and the elongation at break was calculated from the obtained stress-strain curve.
- a Shimazu universal testing instrument Autograph AGS-J500N equipped with a Toshin Kogy
- Hydroxide ion conductivity was measured for the anion exchange resin membranes obtained in Examples and Comparative Examples. Specifically, the anion exchange resin membranes obtained in Examples and Comparative Examples were cut into 1 cm wide and 3 cm long pieces as measurement samples, which were placed in a 1 M potassium hydroxide aqueous solution (80° C.) for 48 hours. By immersion, it was made into a hydroxide ion type. Hydroxide ion conductivity measurement was performed by washing a sample taken out of a 1 M potassium hydroxide aqueous solution (80 ° C.) with degassed pure water, followed by an AC four-terminal method (300 mV, 10-100000 Hz). Conducted in water.
- Example 1 Example 3 containing both hydrophobic group (a) and hydrophobic group (b) in Comparative Example 1, Example 1, Example 3, Example 4, and Example 5 having similar IEC , Example 4, and Example 5 exhibit high hydroxide ion conductivity equivalent to Comparative Example 1, which does not contain the hydrophobic group (a). Moreover, the hydroxide ion conductivity tends to decrease as the hydrophobic group (a) ratio (q/(q+q')) increases.
- the water content was measured for the anion exchange resin membranes obtained in Examples and Comparative Examples. Specifically, the anion exchange resin membranes obtained in Examples and Comparative Examples were cut into 1 cm wide and 3 cm long pieces as measurement samples, which were placed in a 1 M potassium hydroxide aqueous solution (80° C.) for 48 hours. By immersion, it was made into a hydroxide ion type.
- the water content (%) was calculated from the following equation using the wet film weight of the film: W wet (g) and the dry film weight: W dry (g).
- Water content (%) (W wet - W dry )/W dry x 100
- W wet the sample was taken out of a 1M potassium hydroxide aqueous solution (80°C) and washed with degassed pure water. The sample was wiped off, quickly transferred to a pre-weighed sample vial, and weighed with the lid closed to determine the difference. W dry was obtained by vacuum-drying (60° C.) for 12 hours the water-containing sample, quickly transferring it to a pre-weighed sample vial, weighing it with the lid on, and calculating the difference.
- ⁇ Durability test> A durability test was performed on the anion exchange resin membranes obtained in Examples and Comparative Examples. Specifically, changes over time in hydroxide ion conductivity were measured when an anion exchange resin membrane (hydroxide ion type) was immersed in an 8 M potassium hydroxide aqueous solution (80° C.). The method for measuring the hydroxide ion conductivity is the same as described above, except that it is performed in pure water at 40° C. by the AC four-terminal method.
- Example 1 has both a high hydroxide ion conductivity and a large elongation at break.
- Example 2 in which the IEC was improved by fixing the hydrophobic group (a) ratio (q / (q + q ')) of Example 1 to 0.17 has a high hydroxide equivalent to Example 1 It exhibits a greater elongation at break than Example 1 while maintaining ionic conductivity. Furthermore, Example 2 showed higher thermal alkali stability than Example 1.
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Abstract
Description
下記式(1)で表されるビスフェノール残基を含む2価の疎水性基(a)と、
下記式(2)で表されるビスフェノール残基を含む2価の疎水性基(b)と、
単数の芳香環からなる、または、2価の炭化水素基、2価のケイ素含有基、2価の窒素含有基、2価のリン含有基、2価の酸素含有基、もしくは2価の硫黄含有基である連結基、および/または炭素-炭素結合を介して互いに結合する複数の芳香環からなり、前記連結基または前記芳香環のうち少なくとも1つが、炭素数2以上の2価の飽和炭化水素基を介して陰イオン交換基と結合した2価の親水性基と
からなり、
前記疎水性基(a)単体からなる、または、前記疎水性基(a)が、エーテル結合、チオエーテル結合、もしくは炭素-炭素結合を介して繰り返される疎水ユニット(a)と、
前記疎水性基(b)単体からなる、または、前記疎水性基(b)が、エーテル結合、チオエーテル結合、もしくは炭素-炭素結合を介して繰り返される疎水ユニット(b)と、
前記親水性基単体からなる、または、前記親水性基が、エーテル結合、チオエーテル結合、もしくは炭素-炭素結合を介して繰り返される親水ユニットと
を有し、
前記疎水ユニット(a)と前記疎水ユニット(b)と前記親水ユニットとが、エーテル結合、チオエーテル結合、または炭素-炭素結合を介して結合していることを特徴とする。
・分子間相互作用の低い主鎖により溶解性・柔軟性が向上する
・撥水性を与え、親水部(イオン交換基周辺)との相分離が発達しイオン導電パスを形成できる
・撥水性により、親水性の水酸化物イオンや酸化剤が主鎖に近づきにくくなる(耐アルカリ性・化学的安定性向上)
・主鎖の剛性を制御できる(電解質膜の柔軟性向上)
・ガラス転移温度が低く、触媒層と接着できる(接触抵抗低下)
・ガス拡散性を制御できる(バインダーとして使用した際の酸素の拡散性増大)
[イオン交換基容量(meq./g)]=親水ユニット当たりの陰イオン交換基導入量×親水ユニットの繰り返し単位×1000/(疎水ユニットの分子量×疎水ユニットの繰り返し単位数+親水ユニットの分子量×親水ユニットの繰り返し単位数+イオン交換基の分子量×親水ユニットの繰り返し単位数) (24)
なお、イオン交換基導入量とは、単位親水性基あたりのイオン交換基の数と定義される。また、陰イオン交換基導入量は、親水性基において主鎖または側鎖に導入された上記陰イオン交換基のモル数(mol)である。
<モノマー1の合成>
窒素インレットおよび冷却管を備えた100mLの丸底三口フラスコに、1,6-ジヨードパーフルオロヘキサン(5.54g、10.0mmol)、3-クロロヨードベンゼン(11.9g、50mmol)、ジメチルスルホキシド(60mL)を加えた。この混合物を撹拌して均一溶液にした後、銅粉末(9.53g、150mmol)を加え、120℃にて48時間反応を行った。反応溶液を0.1M硝酸水溶液中に滴下し反応を停止させた。混合物中からろ過によって回収した析出物をメタノールで洗浄し、ろ液を回収した。同様の操作を繰り返し行った後、合わせたろ液に純水を加えることにより析出した白色固体をろ別回収し、純水とメタノールの混合溶液(純水/メタノール=1/1)で洗浄後、一晩真空乾燥(60℃)させることにより、下記式で示されるモノマー1(白色固体)を収率84%で得た。
窒素インレットおよび冷却管を備えた300mLの丸底三口フラスコに、ビスフェノールAF(18.0g、53.8mmol)、ジクロロトリフェニルホスホラン(36.0g、107mmol)を加え、350℃にて4時間反応を行った。反応混合物に、ジクロロメタン、ヘキサンを加えた後、シリカゲルカラムクロマトグラフィー(展開溶媒:ヘキサン)によって精製した後、一晩真空乾燥(60℃)させることにより、下記式で示されるモノマー2(白色固体)を収率60%で得た。
500mLの丸底三口フラスコに、フルオレン(83.1g、0.50mol)、N-クロロスクシンイミド(167g、1.25mol)、アセトニトリル(166mL)を加えた。この混合物を撹拌して均一溶液にした後、12M塩酸(16.6mL)を加え、室温にて24時間反応を行った。反応溶液中からろ過によって回収した析出物をメタノール、および純水で洗浄後、一晩真空乾燥(60℃)させることにより、下記式で示されるモノマー3(白色固体)を収率65%で得た。
300mLの丸底三口フラスコに、モノマー3(8.23g、35.0mmol)、1,6-ジブロモヘキサン(53mL)を加えた。この混合物を撹拌して均一溶液にした後、テトラブチルアンモニウム(2.26g、7.00mmol)、水酸化カリウム(35.0g)、純水(35mL)の混合溶液を加え、80℃にて1時間反応を行った。反応溶液に純水を加え反応を停止させた。水層から目的物をジクロロメタンで抽出し、合わせた有機層を純水および食塩水で洗浄後、水、ジクロロメタンおよび1、6-ジブロモヘキサンを留去した。粗生成物をシリカゲルカラムクロマトグラフィー(展開溶媒:ジクロロメタン/ヘキサン=1/4)によって精製した後、一晩真空乾燥(60℃)させることにより、下記式で示されるモノマー4(淡黄色固体)を収率75%で得た。
300mLの丸底三口フラスコに、モノマー4(13.2g、23.4mol)、テトラヒドロフラン(117mL)を加えた。この混合物を撹拌して均一溶液にした後、40wt%ジメチルアミン水溶液(58.6mL)を加え、室温にて24時間反応を行った。反応溶液に飽和炭酸水素ナトリウム水溶液を加え反応を停止させた。テトラヒドロフランを除去した後、ヘキサンを加え、目的成分の抽出を行った。有機層を食塩水で洗浄後、水およびヘキサンを留去した。40℃一晩真空乾燥させることにより、下記式で示されるモノマー5(淡黄色固体)を収率75%で得た。
窒素インレットおよび冷却管を備えた100mLの丸底三口フラスコに、モノマー1(208mg、377μmol)、モノマー2(701mg、1.88mmol)、モノマー5(785mg、1.59mmol)、2,2’-ビピリジン(3.07g、19.7mmol)、N,N-ジメチルアセトアミド(13mL)を加えた。この混合物を撹拌して均一溶液にした後、ビス(1,5-シクロオクタジエン)ニッケル(0)(3.00g、10.9mmol)を加え、80℃にて3時間反応させた。反応混合物をメタノールと12M塩酸の混合溶液(メタノール/12M塩酸=1/1)中に滴下し反応を停止させた。混合物中から濾過によって回収した析出物を12M塩酸、0.2M炭酸カリウム水溶液、および純水で洗浄後、一晩真空乾燥(60℃)させることにより、下記式で示される陰イオン交換樹脂前駆体ポリマーBP17Aを収率86%で得た。
50mLの丸底三口フラスコに、陰イオン交換樹脂前駆体ポリマーBP17A(1.24g)、N,N-ジメチルアセトアミド(13mL)を加えた。この混合物を撹拌して均一溶液にした後、硫酸ジメチル(6.44mL、67.9mmol)を加え、室温にて48時間反応を行った。反応溶液を純水中に滴下した。混合物中から濾過によって回収した析出物を純水で洗浄後、一晩真空乾燥(60℃)させることにより、陰イオン交換樹脂QBP17Aを得た。
上記モノマー1、モノマー2、およびモノマー5を用いて、上記と同様の方法で、必要に応じて試薬の仕込み量を変更すること(q:q’:m=0.20:1.00:1.52)により、陰イオン交換樹脂QBP17A-2.5(IEC=2.5meq./g、水酸化物イオン型)の膜を得た。
上記モノマー1、モノマー2、およびモノマー5を用いて、上記と同様の方法で、必要に応じて試薬の仕込み量を変更すること(q:q’:m=1.00:1.00:1.61)により、陰イオン交換樹脂QBP50A(IEC=2.0meq./g、水酸化物イオン型)の膜を得た。
上記モノマー1、モノマー2、およびモノマー5を用いて、上記と同様の方法で、必要に応じて試薬の仕込み量を変更すること(q:q’:m=0.75:0.50:1.04)により、陰イオン交換樹脂QBP60A(IEC=2.0meq./g、水酸化物イオン型)の膜を得た。
上記モノマー1、モノマー2、およびモノマー5を用いて、上記と同様の方法で、必要に応じて試薬の仕込み量を変更すること(q:q’:m=1.00:0.20:1.09)により、陰イオン交換樹脂QBP83A(IEC=2.1meq./g、水酸化物イオン型)の膜を得た。
上記モノマー1を用いずに、上記モノマー2およびモノマー5を用いて、上記と同様の方法で、必要に応じて試薬の仕込み量を変更すること(q’:m=1.00:0.58)により、下記式で示される陰イオン交換樹脂BAF-QAF(IEC=2.0meq./g、水酸化物イオン型)の膜を得た。
上記モノマー2を用いずに、上記モノマー1およびモノマー5を用いて、上記と同様の方法で、必要に応じて試薬の仕込み量を変更すること(q:m=1.00:0.87)により、下記式で示される陰イオン交換樹脂QPAF-4(IEC=2.0meq./g、水酸化物イオン型)の膜を得た。
実施例および比較例で得られた陰イオン交換樹脂の膜に対して、イオン交換容量を測定した。具体的には、イオン交換容量:IEC(meq./g)は、次式より、膜中の対イオンの物質量:a(mmol)、乾燥膜質量:Wdry(水酸化物イオン型)(g)を用いて算出した。
IEC=a/Wdry(水酸化物イオン型)
aは、塩化物イオン型の膜を硝酸ナトリウム水溶液中で撹拌した際、イオン交換によって水溶液中に放出された塩化物イオンの物質量をモール法によって求めた。Wdry(水酸化物イオン型)は、塩化物イオン型の膜を12時間真空乾燥(60℃)した後、予め秤量しておいたサンプル管瓶に素早く移して蓋をした状態で秤量し、差分で求めたWdry(塩化物イオン型)、およびaを用いて算出した。
実施例および比較例で得られた陰イオン交換樹脂の膜に対して、引張試験を行った。具体的には、実施例および比較例で得られた陰イオン交換樹脂の膜(塩化物イオン型)を12mm×2mm(サンプル全体の面積:35mm×6mm)のダンベル型(DIN-53504-S3)に切り出したものを測定サンプルとし、Toshin Kogyo temperature control unit Bethel-3を搭載したShimazu universal testing instrument Autogragh AGS-J500Nを用い、恒温、恒湿に制御されたチャンバー内で引張試験を行った。測定は、サンプルを80℃、60%RHの条件下に3時間保持後、10mm/minの速度で引張り、得られた応力-歪み曲線から破断点伸び率を算出した。
実施例および比較例で得られた陰イオン交換樹脂の膜に対して、水酸化物イオン導電率を測定した。具体的には、実施例および比較例で得られた陰イオン交換樹脂の膜を幅1cm、長さ3cmに切り出したものを測定サンプルとし、これを1M水酸化カリウム水溶液(80℃)に48時間浸漬させることにより水酸化物イオン型とした。水酸化物イオン導電率測定は、1M水酸化カリウム水溶液(80℃)から取り出したサンプルを脱気した純水で洗浄した後、交流四端子法(300mV、10-100000Hz)で、30℃の純水中において実施した。測定装置にはSolartolon1255B/1287を使用し、プローブにはφ1mmの金線を用いた。水酸化物イオン導電率σ(S/cm)は、次式より、プローブ間距離L(1cm)、インピーダンスZ(Ω)、膜断面積A(cm2)から算出した。
σ=(L/Z)×1/A
実施例および比較例で得られた陰イオン交換樹脂の膜に対して、含水率を測定した。具体的には、実施例および比較例で得られた陰イオン交換樹脂の膜を幅1cm、長さ3cmに切り出したものを測定サンプルとし、これを1M水酸化カリウム水溶液(80℃)に48時間浸漬させることにより水酸化物イオン型とした。含水率(%)は、次式より、膜の含水膜質量:Wwet(g)、乾燥膜質量:Wdry(g)を用いて算出した。
含水率(%)=(Wwet-Wdry)/Wdry×100
Wwetは、1M水酸化カリウム水溶液(80℃)から取り出したサンプルを脱気した純水で洗浄した後、サンプルを純水中に室温で24時間以上浸漬した後、サンプル表面の水滴をティッシュで拭き取り、予め秤量しておいたサンプル管瓶に素早く移して蓋をした状態で秤量し、差分で求めた。Wdryは、含水したサンプルを12時間真空乾燥(60℃)した後、予め秤量しておいたサンプル管瓶に素早く移して蓋をした状態で秤量し、差分で求めた。
実施例および比較例で得た陰イオン交換樹脂の膜に対して、耐久試験を行った。具体的には、陰イオン交換樹脂の膜(水酸化物イオン型)を8M水酸化カリウム水溶液(80℃)に浸漬させた際の水酸化物イオン導電率の経時変化を測定した。なお、水酸化物イオン導電率の測定方法は、交流四端子法で40℃の純水中において実施したこと以外は、前述と同様である。
Claims (6)
- 下記式(1)で表されるビスフェノール残基を含む2価の疎水性基(a)と、
下記式(2)で表されるビスフェノール残基を含む2価の疎水性基(b)と、
単数の芳香環からなる、または、2価の炭化水素基、2価のケイ素含有基、2価の窒素含有基、2価のリン含有基、2価の酸素含有基、もしくは2価の硫黄含有基である連結基、および/または炭素-炭素結合を介して互いに結合する複数の芳香環からなり、前記連結基または前記芳香環のうち少なくとも1つが、炭素数2以上の2価の飽和炭化水素基を介して陰イオン交換基と結合した2価の親水性基と
からなり、
前記疎水性基(a)単体からなる、または、前記疎水性基(a)が、エーテル結合、チオエーテル結合、もしくは炭素-炭素結合を介して繰り返される疎水ユニット(a)と、
前記疎水性基(b)単体からなる、または、前記疎水性基(b)が、エーテル結合、チオエーテル結合、もしくは炭素-炭素結合を介して繰り返される疎水ユニット(b)と、
前記親水性基単体からなる、または、前記親水性基が、エーテル結合、チオエーテル結合、もしくは炭素-炭素結合を介して繰り返される親水ユニットと
を有し、
前記疎水ユニット(a)と前記疎水ユニット(b)と前記親水ユニットとが、エーテル結合、チオエーテル結合、または炭素-炭素結合を介して結合していることを特徴とする、陰イオン交換樹脂。
- 前記2価の親水性基が、単数の多環式化合物からなる、または、2価の炭化水素基、2価のケイ素含有基、2価の窒素含有基、2価のリン含有基、2価の酸素含有基、もしくは2価の硫黄含有基である連結基、および/または炭素-炭素結合を介して互いに結合する複数の多環式化合物からなり、前記連結基または前記多環式化合物のうち少なくとも1つが、炭素数2以上の2価の飽和炭化水素基を介して陰イオン交換基と結合していることを特徴とする、請求項1ないし3のいずれか1項に記載の陰イオン交換樹脂。
- 請求項1ないし5のいずれか1項に記載の陰イオン交換樹脂を含むことを特徴とする、電解質膜。
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