Compound, polymer, electrolyte membrane, fuel cell, and electrolysis device

Abstract

Provided are a compound capable of producing a polymer having excellent alkali durability, a polymer containing the compound as a monomer, an electrolyte membrane using the polymer and having excellent alkali durability, and a fuel cell and an electrolysis device using the electrolyte membrane. A compound represented by formula (1), and a polymer containing the compound as a monomer. (X1-) 2Ar1 (-L1-RN +) n (Ac-) n / c... (1) (In the formula, X1 is a hydrogen atom or a halogen atom, Ar1 is a 2 + n-valent group having an aromatic ring, L1 is a single bond or a divalent hydrocarbon group, RN + is a group having a ring structure including N +, Ac-is a c-valent counter anion, n is an integer of 1 or more, and c is 1 or 2.

Description

Technical Field

[0001] The present disclosure relates to a compound, a polymer, an electrolyte membrane, a fuel cell, and an electrolysis device. Background Art

[0002] In various fuel cells such as a polymer electrolyte fuel cell and a solid alkaline fuel cell, or various electrolysis technologies such as water electrolysis, an electrolyte membrane and an electrolyte ionomer are used. The electrolyte membrane is required to have excellent ionic conductivity and chemical and mechanical durability capable of withstanding long-term use. In addition, the electrolyte ionomer is required to have high chemical durability and high fuel gas permeability.

[0003] The inventors of the present application disclosed a proton-conductive material in Patent Document 1. The proton-conductive material is a proton-conductive material for an electrolyte membrane having high anti-swelling property and high proton conductivity of a high-density aggregated ion-exchange group, and has a specific hydrophilic part and a specific hydrophobic part, and has a repeating unit containing a specific cyclic compound in at least one of the hydrophilic part and the hydrophobic part. The proton-conductive material has a structure in which the hydrophilic part and the hydrophobic part are bonded by an ether bond.

[0004] A proton-conductive material having an ether bond in the main chain has a problem of deterioration due to cleavage of the ether bond, particularly in an alkaline environment.

[0005] The inventors of the present application disclosed a polymer having no ether bond in the main chain and a method for producing the same in Patent Document 2. The electrolyte membrane using the polymer of Patent Document 2 has excellent chemical durability and membrane strength. On the other hand, the inventors of the present application have conducted research to further improve the durability.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2016-44242

[0009] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2021-42351 Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] An object of the present disclosure is to provide a compound capable of producing a polymer having excellent alkali durability, a polymer containing the compound as a monomer, an electrolyte membrane having excellent alkali durability using the polymer, a fuel cell using the electrolyte membrane, and an electrolysis device.

[0012] Means for Solving the Problems

[0013] The compound of the present disclosure is a compound represented by the following formula (1).

[0014] (X 1 -) 2 Ar 1 (-L 1 -R N+ )n ( A c- ) n / c …(1)

[0015] Among them,

[0016] X 1 is a hydrogen atom or a halogen atom,

[0017] Ar 1 is a (2 + n)-valent group having an aromatic ring,

[0018] L 1 is a single bond or a divalent hydrocarbon group,

[0019] R N+ is a group having a ring structure containing N + in it,

[0020] A c- is a c-valent counter anion,

[0021] n is an integer of 1 or more,

[0022] c is 1 or 2.

[0023] In one embodiment of the above compound, the L 1 is an alkylene group having 1 to 20 carbon atoms.

[0024] In one embodiment of the above compound, the R N+ is a group represented by the following formula (N1) to formula (N8).

[0025] [Chemical formula 1]

[0026]

[0027] Among them,

[0028] R 4 is an alkyl group having 1 to 6 carbon atoms,

[0029] * is the bonding site with L 1 .

[0030] In one embodiment of the above compound, the (X 1 -) 2 Ar 1 (-L 1 -R N+ ) nIt is a compound represented by the following formula (a1) to formula (a12).

[0031] [Chemical formula 2]

[0032]

[0033] Among them,

[0034] R a is a hydrogen atom, a group without an ionic functional group, or L 1 -R N+ R a in which at least one is L 1 -R N+ .

[0035] The polymer of the present disclosure is a polymer having a structural unit represented by the following formula (2).

[0036] [Chemical formula 3]

[0037]

[0038] Among them,

[0039] Ar 2 is a divalent group having an aromatic ring,

[0040] R 11 is a group represented by the following formula (11),

[0041] (*-) 2 AR 1 (-L 1 -R N+ ) n (A c- ) n / c …(11)

[0042] Ar 1 is a (2 + n)-valent group having an aromatic ring,

[0043] L 1 is a single bond or a divalent hydrocarbon group,

[0044] R N+ is a group having a ring structure containing N + .

[0045] A c- is a c-valent counter anion,

[0046] n is an integer of 1 or more,

[0047] c is 1 or 2,

[0048] * is the bonding site with Ar 2 .

[0049] In one embodiment of the above polymer, the (*-) 2 Ar 1 (-L 1 -R N+ ) n is represented by the following formula (a21) to formula (a32).

[0050] [Chemical formula 4]

[0051]

[0052] Wherein,

[0053] R a is a hydrogen atom, a group having no ionic functional group, or L 1 -R N+ , and at least one of R a is L 1 -R N+ .

[0054] * is the bonding site with Ar 2 .

[0055] The present disclosure provides an electrolyte membrane containing the polymer.

[0056] In addition, the present disclosure provides a fuel cell and an electrolysis device having the above electrolyte membrane.

[0057] Advantages of the Invention

[0058] Through the present disclosure, it is possible to provide a compound capable of manufacturing a polymer with excellent alkali durability, a polymer containing the compound as a monomer, an electrolyte membrane with excellent alkali durability using the polymer, a fuel cell using the electrolyte membrane, and an electrolysis device. Brief Description of the Drawings

[0059] Figure 1 is the 1 H-NMR spectrum of compound i.

[0060] Figure 2 is the 1 H-NMR spectrum of compound ii.

[0061] Figure 3 is the 1 H-NMR spectrum of Qin.

[0062] Figure 4 is the 1 H-NMR spectrum of TMA.

[0063] Figure 5 is the1 1H-NMR spectrum.

[0064] Figure 6 is that of DiPrM 1 1H-NMR spectrum.

[0065] Figure 7 is that of Pyr 1 1H-NMR spectrum.

[0066] Figure 8 is that of Pep 1 1H-NMR spectrum.

[0067] Figure 9 is that of DMOc 1 1H-NMR spectrum.

[0068] Figure 10 is that of Polymer I 1 1H-NMR spectrum.

[0069] Figure 11 is that of Polymer II 1 1H-NMR spectrum.

[0070] Figure 12 is that of Polymer III 1 1H-NMR spectrum.

[0071] Figure 13 is a graph showing the results of the alkali durability test of the compound.

[0072] Figure 14 is a graph showing the results of the alkali durability test of the electrolyte membrane.

[0073] Figure 15 is that of Pep-C6-H 1 1H-NMR spectrum.

[0074] Figure 16 is that of Pyr-C6-H 1 1H-NMR spectrum.

[0075] Figure 17 is that of QIN-C6-H 1 1H-NMR spectrum.

[0076] Figure 18 is that of Pep-C10-H 1 1H-NMR spectrum.

[0077] Figure 19 is that of Pyr-C10-H 1 1H-NMR spectrum.

[0078] Figure 20It is the 1 1H-NMR spectrum of QIN-C10-H. Detailed implementation manners

[0079] Hereinafter, the compounds, polymers, electrolyte membranes, fuel cells, and electrolysis devices of the present disclosure will be described.

[0080] It should be noted that in this specification, unless otherwise specified, "polymer" includes "copolymer".

[0081] In this specification, "ionic functional group" means a functional group having dissociability and capable of ion exchange.

[0082] In this specification, unless otherwise specified, "~" indicating a numerical range means including the numerical values described before and after it as the lower limit value and the upper limit value.

[0083] In this specification, "the compound represented by formula (1)" is sometimes denoted as "compound (1)". The same applies to compounds, substituents, etc. represented by other formulas.

[0084] In this specification, "the structural unit represented by formula (2)" is sometimes denoted as "structural unit (2)". The same applies to structural units represented by other formulas.

[0085] In addition, in the case of having the same symbol in a chemical formula, the same symbol is not limited to the symbol representing the same substituent, and may also be substituents different from each other within the range defined by the symbol.

[0086] 1. Compounds

[0087] The compounds of the present disclosure are compounds represented by the following formula (1).

[0088] (X 1 -) 2 Ar 1 (-L 1 -R N+ ) n (A c- ) n / c …(1)

[0089] Among them,

[0090] X 1 is a hydrogen atom or a halogen atom,

[0091] Ar 1 is a (2 + n)-valent group having an aromatic ring,

[0092] L 1 is a single bond or a divalent hydrocarbon group,

[0093] RN+ is a group having a ring structure containing N + and

[0094] A c- is a c-valent counter anion,

[0095] n is an integer of 1 or more,

[0096] and c is 1 or 2.

[0097] In the above compound (1), the N that constitutes the quaternary ammonium group as an ionic functional group + constitutes a ring structure, whereby the durability in an alkaline aqueous solution at a relatively high temperature of about 80 °C is greatly improved. Therefore, deterioration of the electrolyte membrane containing a polymer having the compound (1) as a monomer is suppressed even at a high temperature during the operation of a fuel cell or an electrolysis device.

[0098] Ar 1 is a (2 + n)-valent group having an aromatic ring. For the aromatic ring in Ar 1 , in addition to a benzene ring, it may be a condensed ring such as a naphthalene ring or an anthracene ring. Further, it may be a heterocyclic ring (such as thiophene) containing an oxygen atom (O), a nitrogen atom (N), or a sulfur atom (S). Additionally, it may be a group in which a plurality of aromatic rings are connected by a single bond or a linking group (a group having an aromatic ring). As a group in which a plurality of aromatic rings are connected by a single bond, for example, biphenyl, terphenyl, fluorene, etc. can be cited. Further, as the linking group, for example, a spiro atom, or a linear or branched alkylene group that may have a double bond can be cited. As a specific example of the alkylene group, -CH 2 -, -CH(-) 2 , -CH=CH-, etc. can be cited. In the specific examples, H may also be substituted with a group that does not have an ionic functional group described later, L 1 -R N+ , etc. Further, as Ar 1 having a spiro atom as a linking group, structures such as the following formula (a11) and formula (a12) can be exemplified. As a group in which a plurality of aromatic rings are connected by a linking group, for example, diphenylmethane, triphenylmethane, stilbene, etc. can be cited. From the viewpoint of the durability of the obtained polymer, etc., Ar 1 is preferably a group composed of aromatic rings, or a group in which a plurality of aromatic rings are connected by a single bond, and more preferably a (2 + n)-valent residue of benzene, naphthalene, anthracene, biphenyl, terphenyl, or fluorene. The aromatic ring possessed by Ar 1 may also have substituents other than X 1 and L 1 -R N+ described later. As the substituent, R aGroups without ionic functional groups, etc. in. It should be noted that in the following R a hydrogen atoms and groups without ionic functional groups are included in Ar 1 .

[0099] X 1 is a halogen atom (halo group) or a hydrogen atom. Examples of the halogen atom include F, Cl, Br, and I. From the viewpoint of facilitating the synthesis of the polymers described later, X 1 is preferably Br (bromo group) or I (iodo group), more preferably the bromo group. In addition, the two Xs in formula (1) 1 may be the same or different, but from the viewpoint of ease of polymer synthesis, X 1 is preferably the same.

[0100] When X 1 is a halogen atom, it is preferably directly bonded to the carbon atom of the aromatic ring constituting Ar 1 . By bonding X 1 to the carbon atom of the aromatic ring constituting Ar1, in the polymers described later, the carbon atom of the aromatic ring of Ar 1 is directly bonded to the carbon atom of the aromatic ring of Ar 2 , and the durability of the polymer is excellent.

[0101] L 1 is a single bond or a divalent hydrocarbon group. When L 1 is a single bond, Ar 1 is directly bonded to R N+ . When L 1 is a divalent hydrocarbon group, Ar 1 is connected to R N+ through L 1 . As the divalent hydrocarbon group, an alkylene group having a straight-chain or branched structure is preferred, and a straight-chain alkylene group is more preferred, and an alkylene group having 1 to 20 carbon atoms is even more preferred. The number of carbon atoms of the alkylene group can be appropriately adjusted according to the physical properties required for the resulting polymer. For example, by making the number of carbon atoms of the alkylene group 20 or less, preferably 16 or less, more preferably 12 or less, the ion exchange group capacity of this polymer increases. On the other hand, by making the number of carbon atoms of the alkylene group 2 or more, preferably 4 or more, more preferably 6 or more, a polymer with excellent solubility and anti-swelling properties can be obtained. In addition, from the viewpoint of alkali durability, it is preferred that L 1 is not bonded to the carbon atom constituting Ar 1 through a hetero element such as an ether.

[0102] R N+ is a group having a ring structure containing N + and is a quaternary ammonium group. By having R N+, the resulting polymer has anionic conductivity and excellent alkali durability. As R N+ , groups represented by the following formula (3) can be exemplified.

[0103] *-R 1 N+R 2 R 3 R 4 …(3)

[0104] Among them,

[0105] R 1 is a single bond or a group that forms a ring structure containing N 4 by connecting to R + .

[0106] R 2 is an alkyl group or a group that forms a ring structure containing N 3 by connecting to R 3 or connecting to R 4 and R + .

[0107] R 3 is an alkyl group or a group that forms a ring structure containing N 2 by connecting to R 2 or connecting to R 4 and R + .

[0108] R 4 is an alkyl group or a group that forms a ring structure containing N 1 by connecting to R 2 or connecting to R 3 and R + .

[0109] * is the bonding site with L 1 or Ar 1 .

[0110] When R 1 is a single bond, R 2 connects to R 3 , or R 2 , R 3 and R 4 connect to form a ring structure containing N+.

[0111] When R 1 is a single bond, N + bonds directly to L 1 or Ar 1 .

[0112] When R 1 connects to R 4formed by connection to form a ring structure containing N + In the case of, R N+ For example, as shown in the following formulas (N6) to (N8), etc., a ring structure is present on the L 1 side. In the case where R 1 is connected to R 4 , this R 1 -R 4 is preferably an alkylene group having 4 or 5 carbon atoms. Among them, this alkylene group has a bonding site bonded to L 1 .

[0113] In the case where R 2 is connected to R 3 to form a ring structure containing N + , R N+ For example, as shown in the following formulas (N1), (N2), (N6) to (N8), etc., a ring structure is present on the terminal side. In the case where R 2 is connected to R 3 , this R 2 -R 3 is preferably an alkylene group having 4 or 5 carbon atoms.

[0114] In the case where R 2 , R 3 and R 4 are connected to form a ring structure containing N + , R N+ For example, as shown in the following formulas (N3) to (N5), etc., a bridged ring structure is present on the terminal side. Except for N + , the bridged ring is preferably a hydrocarbon. The number of carbon atoms of the bridged ring is preferably 6 to 18, more preferably 6 to 12.

[0115] In the case where R 2 , R 3 or R 4 is an alkyl group, this alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.

[0116] From the viewpoint of the durability of the present compound and the polymers described later, among them, it is preferred that R 2 is connected to R 3 to form a ring structure containing N + , and among them, R N+ is more preferably a group represented by the following formulas (N1) to (N8).

[0117] [Chemical formula 5]

[0118]

[0119] Among them,

[0120] Here, R4 is an alkyl group having 1 to 6 carbon atoms,

[0121] * is the bonding site with L 1 of.

[0122] R in compound (1) N+ The number (i.e., n) only needs to be 1 or more, and from the viewpoints of ionic conductivity and polymer stability, it is preferably 1 to 2.

[0123] Ar 1 The aromatic ring of may have other substituents in addition to X 1 and L 1 -R N+ Other than. As such other substituents, groups not having an ionic functional group are preferred. As the group not having an ionic functional group, for example, an alkyl group having 1 to 20 carbon atoms which may have a substituent, a phenyl group which may have a substituent, etc. can be mentioned. It should be noted that in the present specification, an ionic functional group means a substituent capable of exhibiting ion exchangeability, and means a sulfo group, a carboxyl group, a phosphoric acid group (-HPO 3 ), a quaternary ammonium group.

[0124] As specific examples of the above alkyl group, alkyl groups such as methyl, ethyl, propyl, n-butyl, tert-butyl, pentyl, hexyl, octyl, etc. can be mentioned, and a phenyl group etc. can also be used as a substituent. In addition, as the substituents that the above phenyl group may have, alkyl groups having 1 to 6 carbon atoms etc. can be mentioned.

[0125] The said A c- is a monovalent or divalent counter anion. A c- is not particularly limited, a monovalent anion is preferred, and an inorganic anion is preferred. As the inorganic anion, chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ), hydrogen carbonate ion (HCO 3 - ), carbonate ion (CO 3 2- ), and hydroxide ion (OH - ) etc. can be mentioned.

[0126] As the preferred structure of (X 1 -) 2 Ar 1 (-L 1 -R N+ ) n in compound (1), the structures represented by the following formulas (a1) to (a12) can be mentioned.

[0127] [Chemical formula 6]

[0128]

[0129] Among them,

[0130] R a is a hydrogen atom, a group having no ionic functional group, or L 1 -R N+ R a in which at least one of them is L 1 -R N+ .

[0131] The method for synthesizing the compound represented by the formula (1) is not particularly limited. For example, a halide containing Ar 1 and an amine having a desired ring structure can be prepared, and the synthesis method described in the following Examples, JP-A-2020-169287, and JP-A-2021-042351 can be referred to.

[0132] 2. Polymer

[0133] The polymer of the present disclosure has a structural unit represented by the following formula (2).

[0134] [Chemical formula 7]

[0135]

[0136] Among them,

[0137] Ar 2 is a divalent group having an aromatic ring,

[0138] R 11 is a group represented by the following formula (11),

[0139] (*-) 2 Ar 1 (-L 1 -R N+ ) n (A c- ) n / c …(11)

[0140] Ar 1 is a (2 + n)-valent group having an aromatic ring,

[0141] L 1 is a single bond or a divalent hydrocarbon group,

[0142] R N+ is a group having a ring structure containing N + ,

[0143] A c- is a c-valent counter anion,

[0144] n is an integer of 1 or more,

[0145] c is 1 or 2,

[0146] * is the bonding site with Ar 2 of.

[0147] The polymer of the present disclosure (hereinafter also referred to as polymer (A)) is a polymer having at least one of the above structural units (2), and may have other structural units within the scope of achieving the effects of the present disclosure. This polymer is a linear polymer having the above structural unit (2) in which R 11 and Ar 2 are alternately arranged, and other structural units as required. In addition, it is preferable that the aromatic ring of R 11 and the aromatic ring of Ar 2 are bonded by a single bond to form the main chain. According to this structure, there are no ether oxygen (-O-), sulfonyl (-S(=O) 2 -), and carbonyl (-C(=O)-) bonds in the main chain skeleton, and the chemical durability, especially the alkali durability, is excellent.

[0148] R 11 is a group represented by the above formula (11), and each symbol in the formula (11) is the same as that in the formula (1), and the preferred modes are also the same.

[0149] Ar 2 is a divalent group having an aromatic ring. Ar 2 preferably does not have an ionic functional group. As Ar 2 , from the viewpoint of chemical durability, examples include an aromatic ring not having an ionic functional group, or a group in which two or more aromatic rings not having an ionic functional group are connected by a single bond or a spiro atom. Examples of the aromatic ring of Ar 2 include the same aromatic rings as those of the above Ar 1 . In addition, the aromatic ring of Ar 2 may also have a substituent other than a group containing an ionic functional group. Examples of such a substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, a phenyl group that may have a substituent, etc. Examples of the halogen atom include F, Cl, Br, I, but from the synthetic viewpoint, F is preferred. Specific examples of the above alkyl group include alkyl groups such as methyl, ethyl, propyl, n-butyl, tert-butyl, pentyl, hexyl, octyl, etc., and may also have a phenyl group as a substituent. In addition, examples of the substituent that the above phenyl group may have include an alkyl group having 1 to 6 carbon atoms.

[0150] From the viewpoints of excellent mechanical strength, chemical durability, and film-forming property of the polymer (A), the above Ar 2Preferably, a divalent aromatic group having substituents other than groups containing ionic functional groups is used, and among them, a group represented by any one of the following formulas (b1) to (b10) is preferable.

[0151] It should be noted that in the polymer, when there are a plurality of Ar 2 they may be the same as or different from each other.

[0152] [Chemical formula 8]

[0153]

[0154] Among them, R b are each independently a hydrogen atom or a group not having an ionic functional group, and * represents a bonding site bonded to R 11 bonding site.

[0155] In addition, from the viewpoint of easily producing a polymer having a high molecular weight, it is preferable that a fluorine atom is present at the α-position in terms of the bonding site with R 11 . By using this polymer having a high molecular weight, a film having more excellent mechanical strength can be formed.

[0156] As Ar having a fluorine atom at the α-position 2 , among them, a group represented by any one of the following formulas (c1) to (c9) is preferable.

[0157] [Chemical formula 9]

[0158]

[0159] Among them, R b are each independently a hydrogen atom or a group not having an ionic functional group, and * represents a bonding site bonded to R 11 bonding site.

[0160] [Other structural units]

[0161] The polymer of the present disclosure may also have other structures within the scope of achieving the effects of the present disclosure. As other structural units, for example, a structural unit represented by the following formula (3) can be cited.

[0162] [Chemical formula 10]

[0163]

[0164] Among them,

[0165] Ar 2 is a divalent group having an aromatic ring,

[0166] R 21 is a divalent group having an aromatic ring.

[0167] Regarding Ar in the structural unit (3) 2 , Ar identical to that in the structural unit (2) can be exemplified 2 . In addition, regarding R 2 , a group that does not have a ring structure containing N 21 in R of the structural unit (2) can be exemplified 11 . R + can have, for example, a structure represented by the following formula (21). 21

[0168] (*-) 2 Ar 1 (-R 22 ) m …(21)

[0169] Among them, Ar 1 is a (2 + m)-valent group having an aromatic ring

[0170] R 22 is a group that does not have an ionic functional group

[0171] and m is an integer of 0 or more

[0172] Regarding Ar in the formula (21) 1 , it is the same as Ar in the formula (11) 1 , except that n is replaced by m. Regarding R 22 , for example, an alkyl group having 1 to 20 carbon atoms that can have a substituent, a phenyl group that can have a substituent, etc., other than an ionic functional group, can be exemplified

[0173] The weight-average molecular weight of the polymer (A) can be appropriately adjusted. For example, it can be set in the range of 10,000 to 1,000,000. However, from the viewpoints of film-forming properties and film strength, etc., it is preferably 50,000 or more, and more preferably 100,000 or more. It should be noted that the weight-average molecular weight is a value in terms of polystyrene measured by GPC (gel permeation chromatography).

[0174] Regarding the proportion of the structural unit (2) in the polymer (A), it is preferably 50% by mass or more based on the total mass of the polymer

[0175] <Manufacturing method of polymer (A)>

[0176] The manufacturing method of the polymer (A) is not particularly limited. For example, it preferably includes at least a step of reacting the compound represented by the formula (1) with a compound represented by H-Ar 2 -H (hereinafter also referred to as compound (4)). In addition, in the compound represented by the formula (1), a part of -L 1 -R N+ can be replaced with -L​1 -X 2 (X 2 is a halogen atom), after polymer synthesis, X 2 is replaced with R N+ .

[0177] In addition, as Ar of compound (4) 2 , by using a substance having a fluorine atom at the α-position of H (for example, the following formulas (d1) to (d9)), the reactivity of X of compound (1) 1 with the hydrogen atom of H-Ar 2 -H is excellent, and an ion-conductive polymer with a high molecular weight (for example, a weight-average molecular weight of 100,000 or more) can be synthesized relatively easily.

[0178] [Chemical formula 11]

[0179]

[0180] Among them, R b are each independently a hydrogen atom or a substituent without an ionic functional group.

[0181] The polymerization of compound (1) and compound (4) can be carried out, for example, by reacting compound (1) and compound (4) in a solvent in the presence of a Pd complex, a ligand, a carboxylic acid (RCO 2 H) and a base. It should be noted that various substances can be used for the Pd complex, ligand, carboxylic acid, base and solvent in this reaction step. Among them, it is particularly preferable to use Pd 2 (dba) 3 ·CHCl 3 , P(o-C 6 H 4 -OMe) 3 , pivalic acid (PivOH), Cs 2 CO 3 , and dry THF. Among them, dba refers to dibenzylideneacetone. In addition, the reaction time and reaction temperature in the above reaction step can also be set appropriately. For example, they can be set to 1 to 48 hr, 80 to 140 °C.

[0182] Next, when X N+ is replaced at the position of R 2 of compound (1), by introducing a desired R N+ after polymerization, polymer (A) is obtained. For the method of introducing R N+ , refer to the methods described in the following examples, Japanese Patent Application Laid-Open No. 2020-169287, and Japanese Patent Application Laid-Open No. 2021-042351.

[0183] 3. Electrolyte membrane

[0184] The electrolyte membrane of the present disclosure is characterized by containing the above polymer (A). The electrolyte membrane using the polymer (A) has excellent chemical durability, ion conductivity, and mechanical strength of the membrane, and can be suitably used as an electrolyte membrane for fuel cells and electrolysis devices. In addition, since this polymer having an ionic functional group can be easily dissolved in solvents (such as alcohols, or a mixed solvent of alcohol and water, etc.) commonly used when preparing a membrane electrode assembly (MEA) of a fuel cell, and also has excellent gas permeability, it can also be used as an electrolyte ionomer in these cells and electrolysis devices.

[0185] It should be noted that the ionic functional group density (IEC) of this polymer (A) is high, showing a high ion conductivity. The IEC of this polymer is preferably 0.5 meq·g -1 or more and 4.0 meq·g -1 or less. In addition, the ion conductivity of this polymer is preferably 50 mS / cm or more at 80 °C and saturated humidity. It should be noted that generally, polymers with high ion conductivity have a high water content and tend to swell significantly in the water-containing state, but this polymer also has good anti-swelling properties.

[0186] The manufacturing method of the electrolyte membrane can apply general film-forming methods. For example, it can be dissolved in a solvent (such as dimethyl sulfoxide, alcohol, or an aqueous alcohol solution, etc.) in which the above polymer (A) can be dissolved to prepare a polymer solution, and a coating film is formed using a known coating means and then dried to manufacture the electrolyte membrane.

[0187] 4. Fuel Cell

[0188] The fuel cell of the present disclosure is characterized by including the above electrolyte membrane. The above electrolyte membrane can also be applied to either a solid alkaline fuel cell or a polymer electrolyte fuel cell.

[0189] When applying the above electrolyte membrane to a solid alkaline fuel cell, an anion-conductive electrolyte membrane is used as the electrolyte membrane. The structure of the solid alkaline fuel cell can be an existing well-known structure.

[0190] For example, a membrane electrode complex is formed with a cathode disposed on one surface of the electrolyte membrane and an anode disposed on the other surface, oxygen is supplied to the cathode, and fuel is supplied to the anode, so that OH - moves through the electrolyte membrane to the anode, and water is generated here, thereby generating electricity.

[0191] The fuel can be appropriately selected from existing well-known fuels, and examples include hydrogen, methanol, ethanol, ethylene glycol, formate, hydrazine, sodium borohydride, ammonia, etc., but are not limited thereto.

[0192] As representatives, the reactions at each electrode when using hydrogen, methanol, and formate as fuels are shown.

[0193] · Fuel cell using hydrogen

[0194] Anode: 2OH - +H 2 →2H 2 O

[0195] Cathode: O 2 +2H 2 O + 4e - →4OH -

[0196] · Fuel cell using methanol

[0197] Anode: 6OH - +CH 3 OH → CO 2 +5H 2 O

[0198] Cathode: O 2 +2H 2 O + 4e- → 4OH-

[0199] · Fuel cell using formate

[0200] Anode: HCOO - +30H - →2H 2 O + CO 3 2- +2e -

[0201] Cathode: O 2 +2H 2 O + 4e - →4OH -

[0202] In addition, when the electrolyte membrane is applied to a polymer electrolyte fuel cell, a proton-conductive electrolyte membrane is used as the electrolyte membrane. The structure of the polymer electrolyte fuel cell can be a structure that is publicly known.

[0203] For example, a membrane electrode assembly is formed with a cathode disposed on one surface of the electrolyte membrane and an anode disposed on the other surface. Oxygen is supplied to the cathode and fuel is supplied to the anode. As a result, protons generated at the anode move through the electrolyte membrane to the cathode, and water is generated here, thereby generating electricity.

[0204] The fuel can be appropriately selected from publicly known fuels, and specifically, the same fuels as those exemplified in the solid alkaline fuel cell can be listed.

[0205] As a representative, the reactions at each electrode when using hydrogen as fuel are shown.

[0206] Anode: H 2 →2H + +2e -

[0207] Cathode: O 2 +4H + +4e - →2H 2 O

[0208] 5. Electrolysis device

[0209] In addition, the electrolyte membrane of the present disclosure can be applied to water electrolysis or other electrolysis technologies (electrolysis methods), as well as electrolysis devices using these electrolysis methods. For example, the electrolysis device can have a structure with the electrolyte membrane, anode, and cathode of the present disclosure in an electrolytic cell, and perform electrolysis (oxidation-reduction reaction) on the object through the electrolyte membrane of the present disclosure, thereby obtaining the target substance.

[0210] When applying the electrolyte membrane to water electrolysis, a proton-conductive or anion-conductive electrolyte membrane is used as the electrolyte membrane. For example, an anode is arranged on one surface of the proton-conductive electrolyte membrane, and a cathode is arranged on the other surface, so that the protons generated at the anode move through the electrolyte membrane to the cathode and bond with electrons at the cathode to obtain hydrogen. The reaction formulas at each electrode are as follows.

[0211] Anode: 2H 2 O→O 2 +4H + +4e -

[0212] Cathode: 2H + +2e - →H 2

[0213] In addition, as another electrolysis technology, an electrolysis technology for generating formic acid by electrolyzing carbon dioxide can be cited. For example, the protons generated at the anode can move through the electrolyte membrane to the cathode and react with the carbon dioxide supplied to the cathode to obtain formic acid. The reaction formulas at each electrode are as follows.

[0214] Anode: 2H 2 O→O 2 +4H + +4e -

[0215] Cathode: CO 2 +2H + +2e - →HCOOH

[0216] Example

[0217] Hereinafter, examples and comparative examples will be given to illustrate the present invention in more detail. It should be noted that the present invention is not limited by these descriptions.

[0218] [Synthesis Example 1: Synthesis of Compound i]

[0219] [Chemical Formula 12]

[0220]

[0221] In a two-necked flask, tetrabutylammonium chloride (556 mg) was added to an aqueous solution of sodium hydroxide (150 g) (300 mL), and the mixture was stirred under nitrogen. 2,7-Dibromofluorene (4.86 g, 15 mmol) was heated and dissolved in 1,10-dichlorodecane (31.7 g, 150 mmol), and this solution was added to the two-necked flask using a syringe.

[0222] After reacting at 95 °C under nitrogen for 120 minutes, the solution was cooled to room temperature. The organic phase was extracted with dichloromethane (300 mL) and washed with 1 M hydrochloric acid (50 mL) and water (200 mL × 2). Dichloromethane was evaporated using an evaporator, and unreacted 1,10-dichlorodecane was removed under reduced pressure at 90 °C. The resulting residue was subjected to a silica gel column (developing solvent: hexane) to obtain the target compound i (2,7-dibromo, 9,9'-(10-chlorodecane), 8.14 g, 12.1 mmol).

[0223] (of Compound i 1 1H-NMR spectrum (see Figure 1 ))

[0224] 1 1H-NMR (400 MHz, CDCl 3 ): 7.52 (2H, m), δ7.45 (4H, m), δ3.50 (4H, t), δ1.91 (4H, t), δ1.73 (4H, m), δ1.37 (4H, m), δ1.20 (8H, m), δ1.05 (12H, m), δ0.58 (4H, m).

[0225] [Synthesis Example 2: Synthesis of Compound ii]

[0226] [Chemical Formula 13]

[0227]

[0228] Dissolve 2,7-dibromo,9,9'-(10-chlorodecane) (6.73 g, 10 mmol) in acetone (100 mL), add sodium iodide (7.5 g, 50 mmol), and stir at 70 °C for 12 hours. Remove the solvent using an evaporator, add chloroform to the residue, filter, and then remove chloroform using an evaporator. Subject the residue to a silica gel column (developing solvent: hexane), and remove hexane using an evaporator. Add acetone (100 mL) and sodium iodide (7.5 g, 50 mmol) again to the obtained residue, and stir at 70 °C for 12 hours. Perform the same purification operation as above, and subject it to a silica gel column (developing solvent: hexane), thereby obtaining the target compound ii (2,7-dibromo,9,9'-(10-chlorodecane), 6.51 g, 7.6 mmol).

[0229] (1H-NMR spectrum of compound ii (see 1 )) Figure 2 )

[0230] 1 1H-NMR (400 MHz, CDCl 3 3): 7.53 (2H, m), δ 7.46 (4H, m), δ 3.18 (4H, t), δ 1.93 (4H, t), δ 1.80 (4H, m), δ 1.34 (4H, m), δ 1.24 (8H, m), δ 1.07 (12H, m), δ 0.61 (4H, m).

[0231] [Example 1: Synthesis of Qin]

[0232] [Chemical formula 14]

[0233]

[0234] Add quinuclidine (222 mg, 2 mmol) and 1,4-dioxane (10 ml) to 2,7-dibromo,9,9'-(10-chlorodecane) (202 mg, 0.3 mmol), and react at 70 °C for 3 hours. Then, add methanol (10 ml), and react at 70 °C for 18 hours. Remove the solvent using an evaporator and dry it under vacuum to obtain the target compound (Qin, 260 mg). (1H-NMR spectrum of Qin (see 1 )) Figure 3 )

[0235] 1H-NMR (400 MHz, DMSO-d6): 7.79 (2H, d), δ 7.67 (2H, s), δ 7.53 (2H, d), δ 3.24 (12H, t), δ 3.03 (4H, s), δ 2.03 (6H, m), δ 1.82 (12H, m), δ 1.56 (4H, m), δ 1.18 (12H, m), δ 0.99 (12H, m), δ 0.41 (4H, m).

[0236] [Comparative Example 1: Synthesis of TMA]

[0237] [Chemical Formula 15]

[0238]

[0239] To 2,7-dibromo, 9,9'-(10-iododecane) (257 mg, 0.3 mmol) was added 25% trimethylamine methanol solution (1 mg, 3.2 mmol) and 1,4-dioxane (15 ml), and the reaction was carried out at 70 °C for 3 hours. Then, methanol (10 ml) was added, and the reaction was carried out at 70 °C for 12 hours. The solvent was removed with an evaporator and dried under vacuum to obtain the target compound (TMA, 278 mg). (The 1 H-NMR spectrum (see Figure 4 ))

[0240] 1 H-NMR (400 MHz, DMSO-d6): 7.79 (2H, d), δ 7.68 (2H, s), δ 7.52 (2H, d), δ 3.24 (4H, t), δ 3.03 (18H, s), δ 1.98 (4H, t), δ 1.60 (4H, m), δ 1.18 (12H, m), δ 1.00 (12H, m), δ 0.42 (4H, m).

[0241] [Comparative Example 2: Synthesis of TEA]

[0242] [Chemical Formula 16]

[0243]

[0244] In the above Comparative Example 1, triethylamine (300 mg, 3 mmol) was used instead of trimethylamine, and the target compound (TEA, 302 mg) was obtained by carrying out the same reaction and purification operations.

[0245] (The 1 H-NMR spectrum (see Figure 5 ))

[0246] 1H-NMR (400 MHz, DMSO-d6): 7.79 (2H, d), δ 7.68 (2H, s), δ 7.52 (2H, d), δ 3.21 (4H, t), δ 3.08 (12H, q), δ 2.00 (4H, t), δ 1.52 (8H, m), δ 1.15 (26H, m), δ 1.00 (12H, m), δ 0.43 (4H, m).

[0247] [Comparative Example 3: Synthesis of DiPrM]

[0248] [Chemical Formula 17]

[0249]

[0250] In the above Comparative Example 2, dimethylpropylamine (230 mg, 2 mmol) was used instead of triethylamine, and the same reaction was carried out. After the reaction, the solvent was removed with an evaporator, hexane was added, and after washing, it was dried under vacuum to obtain the target compound (DiPrM, 287 mg).

[0251] (of DiPrM 1 H-NMR spectrum (see Figure 6 ))

[0252] 1 H-NMR (400 MHz, DMSO-d6): 7.79 (2H, d), δ 7.68 (2H, s), δ 7.52 (2H, d), δ 3.13 (12H, m), δ 2.92 (6H, s), δ 2.00 (4H, t), δ 1.61 (12H, m), δ 1.18 (8H, m), δ 1.12 (4H, m), δ 1.00 (12H, m), δ 0.88 (12H, m), δ 0.42 (4H, m).

[0253] [Example 2: Synthesis of Pyr]

[0254] [Chemical Formula 18]

[0255]

[0256] 1-Methylpyrrolidine (170 mg, 2 mmol) and 1,4-dioxane (15 ml) were added to 2,7-dibromo, 9,9'-(10-iododecane) (257 mg, 0.3 mmol), and the reaction was carried out at 70 °C for 3 hours. Then, methanol (10 ml) was added, and the reaction was carried out at 70 °C for 12 hours. After removing the solvent with an evaporator, hexane was added, and after washing, it was dried under vacuum to obtain the target compound (Pyr, 277 mg).

[0257] (of Pyr 11H-NMR spectrum (see Figure 7 ))

[0258] 1 1H-NMR (400 MHz, DMSO-d6): 7.79 (2H, d), δ 7.68 (2H, s), δ 7.53 (2H, d), δ 3.43 (8H, m), δ 3.24 (4H, t), δ 2.94 (6H, s), δ 2.06 (8H, m), δ 2.00 (4H, t), δ 1.62 (4H, m), δ 1.20 (8H, m), δ 1.13 (4H, m), δ 1.00 (12H, m), δ 0.41 (4H, m).

[0259] [Example 3: Synthesis of Pep]

[0260] [Chemical Formula 19]

[0261]

[0262] Using 1-methylpiperidine (198 mg, 2 mmol) instead of 1-methylpyrrolidine in Example 2, the same reaction was carried out. After the reaction, the solvent was removed by an evaporator, hexane was added, and after washing, it was dried under vacuum to obtain the target compound (Pep, 281 mg).

[0263] (1H-NMR spectrum of Pep 1 see Figure 8 ))

[0264] 1 1H-NMR (400 MHz, DMSO-d6) 7.79 (2H, d), δ 7.68 (2H, s), δ 7.52 (2H, d), δ 3.26 (12H, m), δ 2.94 (6H, s), δ 2.00 (4H, t), δ 1.74 (8H, m), δ 1.59 (4H, m), δ 1.53 (4H, m), δ 1.20 (8H, m), δ 1.13 (4H, m), δ 1.00 (12H, m), δ 0.41 (4H, m).

[0265] [Comparative Example 4: Synthesis of DMOc]

[0266] [Chemical Formula 20]

[0267]

[0268] Using dimethyloctylamine (314 mg, 2 mmol) instead of trimethylamine in Comparative Example 1 above, the same reaction was carried out. After the reaction, the solvent was removed by an evaporator, hexane was added, and after washing, it was dried under vacuum to obtain the target compound (DMOc, 309 mg).

[0269] (1H-NMR spectrum of DMOc (see 1 )) Figure 9 ))

[0270] 1 1H-NMR (400 MHz, DMSO-d6): δ 7.79 (2H, d), δ 7.68 (2H, s), δ 7.52 (2H, d), δ 3.20 (8H, m), δ 2.96 (12H, s), δ 2.00 (4H, t), δ 1.58 (8H, m), δ 1.25 (20H, m), δ 1.18 (8H, m), δ 1.12 (4H, m), δ 1.00 (12H, m), δ 0.85 (6H, t), δ 0.42 (4H, m).

[0271] [Synthesis Example 3: Synthesis of Polymer I]

[0272] [Chemical Formula 21]

[0273]

[0274] 2,7-Dibromo-9,9'-(10-chlorodecane) (1346 mg, 2 mmol), cesium carbonate (1.96 g, 6 mmol), pivalic acid (204 mg, 2 mmol), tris(2-methoxyphenyl)phosphine (14 mg), Pd 2 (dba) 3 ·CHCl 3 complex (10.4 mg) were added to a two-necked flask, and then dehydrated tetrahydrofuran (3 mL) was added and stirred under nitrogen. Tetrafluorophenylene (309 mg, 2.06 mmol) was dissolved in tetrahydrofuran (1 mL), and then added to the two-necked flask by syringe in a manner that minimized air entry. After reacting for 45 minutes at room temperature under nitrogen, the reaction was carried out at 80 °C for 24 hours.

[0275] 1M hydrochloric acid and chloroform were added to the obtained solid, and after stirring at 40 °C for about 1 hour, the organic phase was extracted with a separatory funnel. After washing the organic phase with water, it was dried and solidified with an evaporator. The obtained residue was dissolved in chloroform and reprecipitated in methanol. After filtering the precipitate, it was washed with hexane. The obtained solid was dried under vacuum to obtain the target Polymer I (1271 mg).

[0276] (1H-NMR spectrum of Polymer I (see 1 )) Figure 10 ))

[0277] 1H-NMR (CDCl3, 400 MHz): δ 7.92 (2H, m), δ 7.57 (4H, m), δ 3.50 (4H, t), δ 2.06 (4H, t), δ 1.73 (4H, m), δ 1.37 (4H, m), δ 1.17 (20H, m), δ 0.78 (4H, m)

[0278] [Synthesis Example 4: Synthesis of Polymer II]

[0279] [Chemical Formula 22]

[0280]

[0281] Dissolve the said Polymer I (1.0 g) in chlorobenzene (50 ml), add tetrabutylammonium bromide (322.3 mg, 1 mmol) and 1,2-dibromoethane (3.76 g, 20 mmol), and stir at 130 °C for 12 hours. After concentrating the solvent with an evaporator, reprecipitate the polymer in methanol. Filter the obtained solid and dry it under vacuum to obtain the target Polymer II (1010 mg).

[0282] (1H-NMR spectrum of Polymer II (see 1 )) Figure 11 ))

[0283] 1 H-NMR (CDCl3, 400 MHz): δ 7.91 (2H, m), δ 7.57 (4H, m), δ 3.37 (4H, t), δ 2.06 (4H, t), δ 1.81 (4H, m), δ 1.36 (4H, m), δ 1.17 (20H, m), δ 0.79 (4H, m)

[0284] [Example 4: Synthesis of Polymer III]

[0285] [Chemical Formula 23]

[0286]

[0287] Dissolve Polymer I (200 mg) in chlorobenzene (15 ml), add quinuclidine (222 mg, 2 mmol), and stir at 105 °C for 3 hours. Then, add dimethyl sulfoxide (15 ml) and stir for 12 hours. After removing the solvent with an evaporator, wash the polymer with water and hexane and dry it under vacuum to obtain the target Polymer III (205 mg). The 1H-NMR spectrum of Polymer III is as shown in 1 Figure 12 shown.

[0288] [Example 5: Synthesis of Polymer IV] ​

[0289] [Chemical formula 24]

[0290]

[0291] Polymer II (200 mg) was dissolved in chlorobenzene (15 ml), 1-methylpiperidine (298 mg, 3 mmol) was added, and the mixture was stirred at 80 °C for 2 hours. Then, dimethyl sulfoxide (15 ml) was added and stirred for 6 hours. After removing chlorobenzene with an evaporator, dimethyl sulfoxide (15 ml) and 1-methylpiperidine (99 mg, 1 mmol) were added and stirred for 6 hours. After removing the solvent with an evaporator, it was washed with water and hexane to obtain the target polymer IV (198 mg).

[0292] [Comparative Example 5: Synthesis of Polymer V]

[0293] [Chemical formula 25]

[0294]

[0295] Except for using trimethylamine instead of quinuclidine in Example 4, the others were the same as in Example 4, thereby obtaining Polymer V.

[0296] [Evaluation]

[0297] [Alkali Durability Test of Compounds]

[0298] The alkali durability tests were conducted on the compounds of Examples 1 to 3 and Comparative Examples 1 to 4. Specifically, each compound (0.03 mmol) was added to 5 ml of 4 M NaOH solution (1 ml of water, 4 ml of methanol) and placed in a constant temperature bath at 80 °C. After a specified time, a part of the reaction solution was sampled and neutralized by adding hydrochloric acid. After removing the solvent by vacuum drying, the obtained residue was extracted with dichloromethane and ethanol. After removing the solvent with an evaporator and vacuum drying the residue, the 1H-NMR spectrum of the obtained compound was measured and compared with the spectrum before the test, thereby evaluating the residual rate of ionic functional groups in the model compound. The results are as Figure 13 shown.

[0299] [Alkali Durability Test of Electrolyte Membrane]

[0300] The polymers of Example 4 and Comparative Example 5 were separately dissolved in dimethyl sulfoxide, and the solutions were dropped onto a glass substrate at 100 °C to prepare electrolyte membranes (membrane thickness: 25 μm). After each of the obtained electrolyte membranes was immersed in a 1 M NaOH solution for 24 hours, then immersed in pure water for 6 hours, the ionic conductivity of the electrolyte membrane was measured under the conditions of 40 °C and RH 95%. Next, the electrolyte membrane was immersed in an 8 M NaOH solution and left at 80 °C. After a specified time, the membrane was taken out and immersed in pure water for 3 hours. After measuring the ionic conductivity of the membrane under the conditions of 40 °C and RH 95%, it was immersed in an 8 M NaOH solution, and the same operation was repeated. The results are as Figure 14 shown.

[0301] As Figure 13 shown, the compounds of Examples 1 to 3 in which the ionic functional group has a ring structure containing N + showed a higher residual rate of the ionic functional group and more excellent alkali durability than the compounds of Comparative Examples 1 to 4 in an alkaline solution. In addition, as Figure 14 shown, the electrolyte membrane of the polymer of Example 4 in which the ionic functional group has a ring structure containing N + showed that even in a high-temperature and strong-alkali environment, a decrease in ionic conductivity can be suppressed.

[0302] Thus, the polymer of the present disclosure can be particularly suitable for use as an electrolyte membrane in fuel cells and electrolysis devices.

[0303] ·Synthesis of Compound (1)

[0304] In addition, various compounds (1) were synthesized. The compounds of Examples 6 to 11 below all have excellent alkali durability.

[0305] [Examples 6 to 8]

[0306] In a two-necked flask, tetrabutylammonium bromide (645 mg) was added to an aqueous solution (300 mL) of sodium hydroxide (150 g), and the mixture was stirred under nitrogen. Fluorene (3.32 g, 20 mmol) was heated and dissolved in 1,6-dibromohexane (48.7 g, 200 mmol), and this solution was added to the two-necked flask using a syringe. After reacting at 90 °C under nitrogen for 90 minutes, the solution was cooled to room temperature, and the organic layer was extracted with dichloromethane (300 mL) and washed with 1 M hydrochloric acid (50 mL) and water (200 mL × 2). Dichloromethane was evaporated using an evaporator, and unreacted 1,6-dibromohexane was removed under reduced pressure at 90 °C. The obtained residue was subjected to a silica gel column (developing solvent: hexane: chloroform = 9:1) to obtain the following target compound A (6.45 g, 13.1 mmol).

[0307] [Chemical Formula 26]

[0308]

[0309] Each time, 492 mg (1 mmol) of the above-mentioned compound A was weighed and added to 5 ml of 1,4-dioxane, and the following three amines (10 mmol) were added respectively, and the reaction was carried out at 80 °C for 2 hours. Then, 10 ml of ethanol was added, and the reaction was carried out for another 2 hours. After removing the solvent under reduced pressure, the residue was washed with hexane to obtain the following three compounds.

[0310] The above-mentioned amines used were 1-methylpiperidine (Pep), 1-methylpyrrolidine (Pyr), and quinuclidine (Qin).

[0311] [Chemical formula 27]

[0312]

[0313] (For Pep-C6-H 1 1H-NMR spectrum (see Figure 15 ))

[0314] 1 1H-NMR (400 MHz, DMSO-d6): 7.81 (2H, m), δ 7.43 (2H, m), δ 7.32 (4H, m), δ 3.24 (8H, m), δ 3.15 (4H, t), δ 2.89 (6H, s), δ 2.00 (4H, m), δ 1.90 (8H, m) δ 1.72 - 1.40 (8H, m), δ 1.04 (8H, m), δ 0.50 (4H, m).

[0315] (For Pyr-C6-H 1 1H-NMR spectrum (see Figure 16 ))

[0316] 1 1H-NMR (400 MHz, DMSO-d6): 7.81 (2H, m), δ 7.44 (2H, m), δ 7.32 (4H, m), δ 3.42 (8H, m), δ 3.15 (4H, t), δ 2.88 (6H, s), δ 2.02 (12H, m), δ 1.45 (4H, m), 1.03 (8H, m), δ 0.50 (4H, m). (For Qin-C6-H 1 1H-NMR spectrum (see Figure 17 ))

[0317] 1H-NMR (400 MHz, DMSO-d6): δ 7.81 (2H, m), δ 7.44 (2H, m), δ 7.32 (4H, m), δ 3.26 (12H, t), δ 2.94 (4H, t), δ 2.02 (2H, t), δ 1.96 (4H, m), δ 1.80 (12H, m), δ 1.39 (4H, m), δ 1.01 (8H, m), δ 0.47 (4H, m).

[0318] [Examples 9 - 11]

[0319] In a two-necked flask, tetrabutylammonium chloride (554 mg) was added to an aqueous solution of sodium hydroxide (150 g) in water (300 mL), and the mixture was stirred under nitrogen. Fluorene (3.32 g, 20 mmol) was heated and dissolved in 1,10-dichlorodecane (42.2 g, 200 mmol), and this solution was added to the two-necked flask using a syringe. After reacting for 90 minutes under nitrogen at 90 °C, the solution was cooled to room temperature. The organic layer was extracted with dichloromethane (300 mL) and washed with 1 M hydrochloric acid (50 mL) and water (200 mL × 2). The dichloromethane was evaporated using an evaporator, and unreacted 1,10-dichlorodecane was removed under reduced pressure at 110 °C. The resulting residue was subjected to a silica gel column (developing solvent: hexane), thereby obtaining the target compound B below (7.53 g, 14.6 mmol).

[0320] [Chemical Formula 28]

[0321]

[0322] To compound B (5.16 g, 10 mmol), acetone (50 ml) and sodium iodide (5 g) were added, and the mixture was reacted at 70 °C for 12 hours. After evaporating the solvent, it was extracted with chloroform and filtered. The filtrate was subjected to a short silica gel column (developing solvent: hexane) to remove hexane. Acetone (50 ml) and sodium iodide (5 g) were added again to the residue, and the mixture was stirred at 70 °C for 12 hours. The same purification operation was carried out and treated using a short column, and the resulting compound was dried under vacuum, thereby obtaining the target compound C below (4.26 g, 6.1 mmol).

[0323] [Chemical Formula 29]

[0324]

[0325] Each time, 699 mg (1 mmol) of the above-mentioned compound C was weighed and added to 5 ml of 1,4-dioxane, and then three amines (10 mmol) described in Examples 6 to 9 were added respectively. The reaction was carried out at 80 °C for 2 hours. Then, 10 ml of ethanol was added and the reaction was continued for 2 hours. After removing the solvent under reduced pressure, the residue was washed with hexane to obtain the following three compounds.

[0326] [Chemical formula 30]

[0327]

[0328] (Pep-C10-H's 1 1H-NMR spectrum (see Figure 18 ))

[0329] 1 1H-NMR (400 MHz, DMSO-d6): 7.80 (2H, m), δ7.41 (2H, m), δ7.32 (4H, m), δ3.26 (12H, m), δ2.95 (6H, s), δ1.96 (4H, m), δ1.76 (8H, m) δ1.58 - 1.45 (8H, m), δ1.19 (8H, m), δ1.12 (4H, m), δ0.99 (12H, m), δ0.46 (4H, m).

[0330] (Pyr-C10-H's 1 1H-NMR spectrum (see Figure 19 ))

[0331] 1 1H-NMR (400 MHz, DMSO-d6): 7.810 (2H, m), δ7.42 (2H, m), δ7.32 (4H, m), δ3.42 (8H, m), δ3.25 (4H, t), δ2.95 (6H, s), δ2.06 (8H, m), δ1.97 (4H, m), δ1.62 (4H, m), δ1.19 (8H, m), δ1.12 (4H, m), δ0.99 (12H, m), δ0.47 (4H, m).

[0332] (Qin-C10-H's 1 1H-NMR spectrum (see Figure 20 ))

[0333] 11H-NMR (400 MHz, DMSO-d6): δ 7.80 (2H, d), δ 7.41 (2H, s), δ 7.31 (4H, d), δ 3.3 (12H, t), δ 3.03 (4H, t), δ 2.04 (2H, t), δ 1.96 (4H, m), δ 1.82 (12H, m), δ 1.56 (4H, m), δ 1.16 (12H, m), δ 0.98 (12H, m), δ 0.45 (4H, m).

[0334] This application claims priority based on Japanese Patent Application No. 2022-164813 filed on October 13, 2022, and incorporates the entire contents disclosed therein into this application.

Claims

1. A compound, wherein, the compound is represented by the following formula (1), (X 1 -) 2 Ar 1 (-L 1 -R N+ ) n (A c- ) n / c …(1) wherein, X 1 is a hydrogen atom or a halogen atom, Ar 1 is a 2+n-valent group having an aromatic ring, L 1 is a single bond or a divalent hydrocarbon group, R N+ is a group having a ring structure containing N + and A c- is a counteranion with a c valence, n is an integer of 1 or more, c is 1 or 2.

2. The compound according to claim 1, wherein, The L 1 is an alkylene group having 1 to 20 carbon atoms.

3. The compound according to claim 1, wherein, The R N+ is a group represented by the following formulas (N1) to (N8), [Chemical formula 1] wherein, R 4 is an alkyl group having 1 to 6 carbon atoms, * is the bonding site with L 1 ​ 4. The compound according to claim 1, wherein, The (X 1 -) 2 Ar 1 (-L 1 -R N+ ) n is a compound represented by the following formulas (a1) to (a12), [Chemical formula 2] wherein, R a is a hydrogen atom, a group without an ionic functional group, or L 1 -R N+ and at least one of R a is L 1 -R N+ .

5. A polymer, wherein, the polymer has a structural unit represented by the following formula (2), [Chemical formula 3] wherein, Ar 2 is a divalent group having an aromatic ring, R 11 is a group represented by the following formula (11), (*-) 2 Ar 1 (-L 1 -R N+ ) n (A c- ) n / c …(11) Ar 1 is a 2 + n-valent group having an aromatic ring, L 1 is a single bond or a divalent hydrocarbon group, R N+ is a group having a ring structure containing N + and A c- is the counteranion of c valence n is an integer of 1 or more, c is 1 or 2, * is the bonding site with Ar 2 .

6. The polymer according to claim 5, wherein, The said (*-) 2 Ar 1 (-L 1 -R N+ ) n is shown by the following formulas (a21) to (a32). [Chemical formula 4] wherein, R a is a hydrogen atom, a group without ionic functional groups, or L 1 -R N+ and at least one of R a is L 1 -R N+ and * is the bonding site with Ar 2 .

7. An electrolyte membrane, wherein, the electrolyte membrane contains the polymer according to claim 5 or 6.

8. A fuel cell, wherein, the fuel cell includes the electrolyte membrane according to claim 7.

9. An electrolysis device, wherein, the electrolysis device includes the electrolyte membrane according to claim 7.

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