Carbon dioxide absorber

Abstract

Provided is a carbon dioxide absorber which contains a polyether compound and which is characterized in that: the polyether compound contains an average of 50 or more repeating units represented by general formula (1) set forth in the description per molecule; and the polyether compound contains repeating units represented by general formula (2) set forth in the description as at least some of the repeating units represented by general formula (1).

Description

Carbon dioxide absorbent

[0001] The present invention relates to a carbon dioxide absorbent, and more particularly to a carbon dioxide absorbent that has excellent carbon dioxide absorbency and is inhibited from falling off from a porous membrane when held in the porous membrane.

[0002] Polyether compounds having cationic groups have ionic conductivity and are therefore known to be used as electrolytes for imparting ionic conductivity between electrodes in electrochemical devices such as secondary batteries, fuel cells, dye-sensitized solar cells, and actuators.

[0003] For example, Patent Document 1 proposes an electrolyte composition characterized by containing a polyalkylene oxide having a side chain with a cationic moiety and a counter ion for the side chain in a polyalkylene oxide main chain, wherein the side chain or the counter ion is liquid crystalline.

[0004] Japanese Patent Application Laid-Open No. 2002-246066

[0005] An object of the present invention is to provide a carbon dioxide absorbent that has excellent carbon dioxide absorption properties and is inhibited from falling off from a porous membrane when held in the porous membrane.

[0006] The present inventors have attempted to use a polyether compound having a cationic group as a carbon dioxide absorbent. However, it has been found that conventional polyether compounds having a cationic group have insufficient carbon dioxide absorption. Furthermore, conventional polyether compounds having a cationic group tend to fall off from a porous membrane when retained therein. Therefore, the present inventors have conducted extensive research to achieve the above object and have found that a carbon dioxide absorbent with excellent carbon dioxide absorption properties can be obtained by using a polyether compound having a specific number or more of repeating units represented by the general formula (1) described below and containing a repeating unit containing a nitrogen-containing cationic group represented by the general formula (2) described below. Furthermore, they have found that the use of such a polyether compound prevents the carbon dioxide absorbent from falling off from a porous membrane when retained therein. The present invention was completed as a result of such investigations.

[0007] That is, according to the present invention, there is provided a carbon dioxide absorbent containing a polyether compound, wherein the polyether compound contains 50 or more repeating units represented by the following general formula (1) as an average number per molecule, and the polyether compound contains a repeating unit represented by the following general formula (2) as at least a part of the repeating units represented by the general formula (1):

[0008] (In general formula (1), A represents a monovalent group.)

[0009] (In the general formula (2), A' ＋ represents a nitrogen-containing cationic group. － represents an anion.)

[0010] In the carbon dioxide absorbent of the present invention, the repeating unit represented by the general formula (2) is preferably a repeating unit represented by the following general formula (3-1), a repeating unit represented by the following general formula (3-2), or a repeating unit represented by the following general formula (4):

[0011] (In the general formula (3-1), R １ ~R ４ each independently represents a hydrogen atom or a substituent, R ２ and R ３ may be bonded to each other. － represents an anion.)

[0012] (In the general formula (3-2), R １１ ~R １５ each independently represents a hydrogen atom or a substituent, R １１ ~R １５ In addition, in the general formula (3-2), two groups arbitrarily selected from X － represents an anion.)

[0013] (In general formula (4), R ５ ~R ７ each independently represents a hydrogen atom or a substituent, R ６ and R ７ may be bonded to each other. － represents an anion.)

[0014] In the carbon dioxide absorbent of the present invention, it is preferable that the polyether compound contains 101 or more repeating units represented by general formula (1) on average per molecule. In the carbon dioxide absorbent of the present invention, it is preferable that the proportion of the repeating units represented by general formula (1) in the polyether compound is 90 to 100 mol % relative to all repeating units of the polyether compound. In the carbon dioxide absorbent of the present invention, it is preferable that the proportion of the repeating units represented by general formula (2) in the polyether compound is 5 to 100 mol % relative to all repeating units represented by general formula (1). It is preferable that the carbon dioxide absorbent of the present invention further contains an ionic liquid or an oxygen-containing polar organic solvent. In the carbon dioxide absorbent of the present invention, －each independently represents a halide ion, a sulfonylimide ion, a carboxylate ion, a sulfonate ion, an OH － , B.F. ４ － , P.F. ６ － , ClO ４ － , B(CN) ４ － , SCN － , (NC) ２ N － Preferably, it represents an anion selected from:

[0015] According to the present invention, there is provided a carbon dioxide absorbent that has excellent carbon dioxide absorption properties and is inhibited from falling off from a porous membrane when held in the porous membrane.

[0016] The carbon dioxide absorbent of the present invention contains a polyether compound described below.

[0017] The polyether compound used in the present invention contains an average of 50 or more repeating units represented by the following general formula (1) per molecule, and is characterized in that at least a part of the repeating units represented by the general formula (1) contains a repeating unit represented by the following general formula (2):

[0018] (In general formula (1), A represents a monovalent group.)

[0019] (In the general formula (2), A' ＋ represents a nitrogen-containing cationic group. － represents an anion.)

[0020] The polyether compound used in the present invention contains a relatively large number of repeating units (oxirane units) represented by general formula (1), with the average number per molecule being 50 or more, and also contains oxirane units containing a nitrogen-containing cationic group represented by general formula (2). By using such a polyether compound, the carbon dioxide absorbent used in the present invention has excellent carbon dioxide absorbency and is inhibited from falling off from a porous membrane when held in the porous membrane.

[0021] The repeating unit represented by general formula (1) is a unit (oxirane monomer unit) obtained by ring-opening polymerization of the oxirane structure portion of a compound containing an oxirane structure. Examples of compounds containing an oxirane structure include aliphatic oxirane monomers such as ethylene oxide, propylene oxide, 1,2-butylene oxide, and 1,2-octylene oxide; aromatic oxirane monomers such as styrene oxide; epihalohydrin monomers such as epichlorohydrin, epibromohydrin, epiiodohydrin, and epifluorohydrin; alkenyl group-containing oxirane monomers such as allyl glycidyl ether; aromatic ether group-containing oxirane monomers such as phenyl glycidyl ether; and (meth)acryloyl group-containing oxirane monomers such as glycidyl acrylate and glycidyl methacrylate. The compounds containing an oxirane structure may be used alone or in combination of two or more.

[0022] The polyether compound used in the present invention contains, as at least a part of the repeating units represented by general formula (1), an oxirane unit containing a nitrogen-containing cationic group represented by general formula (2).

[0023] The repeating unit represented by general formula (2) is usually obtained by substituting at least a portion of the halogen atoms constituting the epihalohydrin monomer units in a polymer containing the epihalohydrin monomer units with nitrogen-containing cationic groups.

[0024] In the general formula (2), A' ＋ represents a nitrogen-containing cationic group. The nitrogen-containing cationic group is preferably bonded to the carbon atom at position "2" in the following general formula via one of the nitrogen atoms constituting the nitrogen-containing cationic group. Furthermore, the nitrogen-containing cationic group may have another nitrogen atom in addition to the nitrogen atom bonded to the carbon atom at position "2" in the following general formula.

[0025]

[0026] A' ＋Examples of the nitrogen-containing cationic group represented by the formula (I) include an amino group, a nitrogen-containing cationic aromatic group, and a nitrogen-containing cationic aliphatic group.

[0027] A' ＋ As the nitrogen-containing cationic aromatic group as the nitrogen-containing cationic aromatic group, a group containing a cationic nitrogen-containing aromatic heterocycle is preferred. The nitrogen-containing aromatic heterocycle in the cationic nitrogen-containing aromatic heterocycle in the group containing a cationic nitrogen-containing aromatic heterocycle may have a nitrogen atom in the ring and have aromaticity, and may have heteroatoms other than nitrogen atoms such as oxygen atoms and sulfur atoms, and some of the atoms constituting the heterocycle may be substituted with substituents. In addition, it may have a polycyclic structure in which two or more rings are condensed. Examples of such nitrogen-containing aromatic heterocyclic structures include five-membered heterocyclic rings such as an imidazole ring, a pyrrole ring, a thiazole ring, an oxazole ring, a pyrazole ring, and an isoxazole ring; six-membered heterocyclic rings such as a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring; and condensed heterocyclic rings such as a quinoline ring, an isoquinoline ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, a purine ring, an indole ring, an isoindole ring, a benzimidazole ring, a benzoxazole ring, and a benzisoxazole ring. Among these, five-membered and six-membered heterocyclic rings are preferred, and an imidazole ring is more preferred.

[0028] The substituent of the nitrogen-containing aromatic heterocycle is not particularly limited, and examples thereof include alkyl groups, cycloalkyl groups, alkenyl groups such as vinyl groups, aryl groups such as phenyl groups, arylalkyl groups, alkylaryl groups, alkoxyl groups, alkoxyalkyl groups, aryloxy groups, alkanol groups, hydroxyl groups, carbonyl groups, alkoxycarbonyl groups, amino groups, imino groups, nitrile groups, alkylsilyl groups, halogen atoms, etc. The number of carbon atoms in these substituents is preferably 0 to 12, more preferably 1 to 8, and even more preferably 1 to 6.

[0029] A' ＋ The nitrogen-containing cationic aliphatic group as may be linear or branched, and may have a non-aromatic ring structure.

[0030] A'＋ Specific examples of the nitrogen-containing cationic group represented by the formula (I) include an ammonium group; mono-substituted ammonium groups containing a cationic nitrogen atom, such as a methylammonium group, a butylammonium group, a cyclohexylammonium group, an anilinium group, a benzylammonium group, or an ethanolammonium group; di-substituted ammonium groups containing a cationic nitrogen atom, such as a dimethylammonium group, a diethylammonium group, a dibutylammonium group, or a nonylphenylammonium group; trimethylammonium group, triethylammonium group, n-butyldimethylammonium group, stearyldimethylammonium group, tributylammonium group, trivinylammonium group, triethanolammonium group, N,N-dimethylethanolammonium group, tri(2-ethoxyethyl)ammonium group, and heterocyclic groups containing a cationic nitrogen atom, such as a piperidinium group, a 1-methylpyrrolidinium group, a 1-butylpyrrolidinium group, an imidazolium group, a 1-methylimidazolium group, a 1-ethylimidazolium group, a 1-butyl-imidazolium group, a benzimidazolium group, a pyrrolium group, a 1-methylpyrrolium group, an oxazolium group, a benzoxazolium group, a pyrazolium group, an isoxazolium group, a pyridinium group, a 2,6-dimethylpyridinium group, a pyrazinium group, a pyrimidinium group, a pyridazinium group, a triazinium group, an N,N-dimethylanilinium group, a quinolinium group, an isoquinolinium group, an indolinium group, a quinoxalium group, and an isoquinoxalium group. Among these, a trisubstituted ammonium group containing a cationic nitrogen atom and a heterocyclic group containing a cationic nitrogen atom are preferred.

[0031] In the general formula (2), X － The anion represented by A' ＋ X is a counter anion of a nitrogen-containing cationic group represented by the formula: － For example, the monovalent anion is F － , Cl － ,Br － , I － Halide ions such as (FSO ２ )２ N － , (CF ３ SO ２ ) ２ N － , (CF ３ CF ２ SO ２ ) ２ N － sulfonylimide ions such as CH ３ COO － , C3H7COO － , C.F. ３ COO － , PhCOO － (Ph represents a phenyl group), and other carboxylate ions; CH ３ SO ３ － , C.F. ３ SO ３ － sulfonate ions such as OH － , B.F. ４ － , P.F. ６ － , ClO ４ － , B(CN) ４ － , SCN － , (NC) ２ N － X － The anion may be a polyvalent anion, or may be a polyanion having two or more monovalent anionic groups in the molecule. For example, the polyvalent anion may be a sulfate ion (SO ４ ２－ ) and carbonate ions (CO ３ ２－ For example, examples of polyanions having two or more monovalent anionic groups in the molecule include: － O ３ SCF2CF2CF2SO ３ － , － O ３ SCF2CF2SO ３ － , C.F. ３ SO ２ N － SO ２CF2CF2OCF2CF2OCF2CF2SO ２ N － SO ２ CF ３ Among them, from the viewpoint of carbon dioxide absorption, sulfonylimide ions, carboxylate ions, BF ４ － is preferred, and sulfonylimide ion, CH ３ COO － , B.F. ４ － is more preferred.

[0032] In the polyether compound used in the present invention, the units represented by the general formula (2) are each independent, and two or more types of units represented by the general formula (2) may be present in the polyether compound. For example, in all of the repeating units represented by the general formula (2) in the polyether compound, A' ＋ All of the nitrogen-containing cationic groups represented by the general formula (2) may be the same kind of nitrogen-containing cationic group, or different kinds of nitrogen-containing cationic groups may be mixed. － All of the anions represented by the formula (I) may be the same kind of anion, or different kinds of anions may be mixed.

[0033] Examples of the repeating unit represented by general formula (2) include the repeating unit represented by the following general formula (3-1): The repeating unit represented by the following general formula (3-1) is an oxirane unit containing an imidazolium structure.

[0034] (In the general formula (3-1), R １ ~R ４ each independently represents a hydrogen atom or a substituent, R ２ and R ３ may be bonded to each other. － represents an anion.)

[0035] In general formula (3-1), R １ ~R ４R each independently represents a hydrogen atom or a substituent. Examples of the substituent include the same as those described above as the substituent of the nitrogen-containing aromatic heterocycle. １ ~R ４ The substituent as R may be linear or branched, and may have a ring structure. １ ~R ４ The substituent as is preferably linear.

[0036] In general formula (3-1), R １ is not particularly limited as long as it is a hydrogen atom or a substituent, but is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrocarbon group, even more preferably an alkyl group or an alkenyl group, particularly preferably an alkyl group or a vinyl group, and most preferably an alkyl group. １ From the viewpoint of carbon dioxide absorption, the number of carbon atoms is preferably 0 to 12, more preferably 0 to 8, even more preferably 1 to 6, still more preferably 1 to 4, particularly preferably 1 to 3, and most preferably 1 or 2.

[0037] In general formula (3-1), R ２ ~R ４ are each independently a hydrogen atom or a substituent and are not particularly limited, but are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or a vinyl group, even more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. ２ ~R ４ From the viewpoint of carbon dioxide absorbency, the number of carbon atoms in each of the groups is preferably 0 to 8, more preferably 0 to 6, even more preferably 0 to 4, still more preferably 0 to 3, particularly preferably 0 to 2, and most preferably 0 to 1.

[0038] In general formula (3-1), R ２ and R ３ may be bonded to each other. ２ and R ３ is bonded, the repeating unit represented by formula (3-1) is ２ -R３ In general formula (3-1), R ２ and R ３ are preferably not bonded to each other.

[0039] In general formula (3-1), R ２ ~R ４ Among R, it is preferable that 1 to 3 represent a hydrogen atom, and more preferable that 2 to 3 represent a hydrogen atom. ２ ~R ４ Preferably, 0 to 2 of these represent a substituent such as a hydrocarbon group, and more preferably, 0 to 1 of these represent a substituent such as a hydrocarbon group.

[0040] X in general formula (3-1) － The anion represented by the formula (2) is X － The preferred embodiments are also the same as those of the anion represented by the formula:

[0041] The repeating unit represented by formula (3-1) preferably contains an imidazolium group, a 1-methylimidazolium group, a 1-butylimidazolium group, a 1-hexylimidazolium group, or a 1-vinylimidazolium group.

[0042] Examples of the repeating unit represented by general formula (2) include the repeating unit represented by the following general formula (3-2): The repeating unit represented by the following general formula (3-2) is an oxirane unit containing a pyridinium structure.

[0043] (In the general formula (3-2), R １１ ~R １５ each independently represents a hydrogen atom or a substituent, R １１ ~R １５ In addition, in the general formula (3-2), two groups arbitrarily selected from X － represents an anion.)

[0044] In general formula (3-2), R １１ ~R １５R each independently represents a hydrogen atom or a substituent. Examples of the substituent include the same as those described above as the substituent of the nitrogen-containing aromatic heterocycle. １１ ~R １５ The substituent as may be linear or branched, and may have a ring structure.

[0045] In general formula (3-2), R １１ ~R １５ are each independently a hydrogen atom or a substituent and are not particularly limited, but are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or a vinyl group, and even more preferably a hydrogen atom or an alkyl group. １１ ~R １５ From the viewpoint of carbon dioxide absorbency, the number of carbon atoms in each of the groups is preferably 0 to 8, more preferably 0 to 6, even more preferably 0 to 4, still more preferably 0 to 3, particularly preferably 0 to 2, and most preferably 0 to 1.

[0046] In general formula (3-2), R １１ ~R １５ Any two selected from the following may be bonded to each other. For example, R １１ and R １２ and are bonded to each other to form -R １１ -R １２ In general formula (3-2), R １１ ~R １５ are preferably not bonded to each other.

[0047] In general formula (3-2), R １１ ~R １５ Among R, preferably 2 to 5 represent hydrogen atoms, more preferably 3 to 5 represent hydrogen atoms, further preferably 4 or 5 represent hydrogen atoms, and particularly preferably all represent hydrogen atoms. １１ ~R １５ Among these, it is preferable that 0 to 3 represent a substituent such as a hydrocarbon group, more preferable that 0 to 2 represent a substituent such as a hydrocarbon group, and even more preferable that 0 to 1 represent a substituent such as a hydrocarbon group.

[0048] X in general formula (3-2) － The anion represented by the formula (2) is X － The preferred embodiments are also the same as those of the anion represented by the formula:

[0049] The repeating unit represented by formula (3-2) preferably contains a pyridinium group, a 2,6-dimethylpyridinium group, a 4-vinylpyridinium group, or a quinolinium group.

[0050] Examples of the repeating unit represented by formula (2) include the repeating unit represented by formula (4) below.

[0051] (In general formula (4), R ５ ~R ７ each independently represents a hydrogen atom or a substituent, R ６ and R ７ may be bonded to each other. － represents an anion.)

[0052] In general formula (4), R ５ ~R ７ R each independently represents a hydrogen atom or a substituent. Examples of the substituent include the same as those described above as the substituent of the nitrogen-containing aromatic heterocycle. Among them, an alkyl group, an aryl group, an arylalkyl group, an alkylaryl group, an alkoxyl group, an alkoxyalkyl group, an aryloxy group, or an alkanol group is preferred, an alkyl group, a cycloalkyl group, a phenyl group, an alkoxyalkyl group, or an alkanol group is more preferred, and an alkyl group or a cycloalkyl group is even more preferred. ５ ~R ７ The substituents as may each independently be linear or branched, and may have a ring structure.

[0053] In general formula (4), R ５ is not particularly limited as long as it is a hydrogen atom or a substituent, but is preferably a linear substituent. ５From the viewpoint of carbon dioxide absorption, the number of carbon atoms is preferably 0 to 12, more preferably 1 to 8, even more preferably 1 to 6, still more preferably 1 to 4, particularly preferably 1 to 3, and most preferably 1 or 2.

[0054] In general formula (4), R ６ ~R ７ are each independently a hydrogen atom or a substituent, and are not particularly limited. ６ and R ７ may or may not be bonded to each other.

[0055] In general formula (4), R ６ and R ７ When R ６ is preferably a linear substituent. ６ The number of carbon atoms in the alkyl group is preferably 0 to 12, more preferably 2 to 8, even more preferably 3 to 6, and particularly preferably 3 to 5, from the viewpoint of carbon dioxide absorption.

[0056] R ６ and R ７ When R ７ is preferably a linear substituent. ７ From the viewpoint of carbon dioxide absorption, the number of carbon atoms is preferably 0 to 12, more preferably 1 to 8, even more preferably 1 to 6, still more preferably 1 to 4, particularly preferably 1 to 3, and most preferably 1 or 2.

[0057] In general formula (4), R ６ and R ７ are bonded to each other, the repeating unit represented by formula (4) is ６ -R ７ -R ６ -R ７ The group represented by - may be linear or branched, and may have a ring structure, but is preferably linear. ６ -R ７The number of carbon atoms in the group represented by - is preferably 1 to 12, more preferably 2 to 8, even more preferably 3 to 6, and particularly preferably 3 to 5, from the viewpoint of carbon dioxide absorption ability.

[0058] X in general formula (4) － The anion represented by the formula (2) is X － The preferred embodiments are also the same as those of the anion represented by the formula:

[0059] The repeating unit represented by general formula (4) preferably contains a trimethylammonium group, a triethylammonium group, an n-butyldimethylammonium group, an n-octyldimethylammonium group, an n-stearyldimethylammonium group, a tributylammonium group, a trivinylammonium group, a 1-methylpyrrolidinium group, an N,N'-dimethylanilinium group, a triethanolammonium group, an N,N'-dimethylethanolammonium group, or a tri(2-ethoxyethyl)ammonium group.

[0060] As the repeating unit represented by general formula (2), a repeating unit represented by general formula (3-1), a repeating unit represented by general formula (3-2), or a repeating unit represented by general formula (4) is preferred, and a repeating unit represented by general formula (3-1) or a repeating unit represented by general formula (4) is more preferred.

[0061] The polyether compound used in the present invention may contain a repeating unit represented by general formula (1) other than the repeating unit represented by general formula (2). Examples of repeating units represented by general formula (1) other than the repeating unit represented by general formula (2) include alkylene oxide monomer units such as ethylene oxide units, propylene oxide units, 1,2-butylene oxide units, and 1,2-octylene oxide units; aromatic oxirane monomer units such as styrene oxide units; epihalohydrin monomer units such as epichlorohydrin units, epibromohydrin units, and epiiodohydrin units; alkenyl group-containing oxirane monomer units such as allyl glycidyl ether units; aromatic ether group-containing oxirane monomer units such as phenyl glycidyl ether units; and (meth)acryloyl group-containing oxirane monomer units such as glycidyl acrylate units and glycidyl methacrylate units. The repeating unit represented by general formula (1) other than the repeating unit represented by general formula (2) is preferably an alkylene oxide monomer unit, an epihalohydrin monomer unit, or a (meth)acryloyl group-containing oxirane monomer unit, and more preferably an ethylene oxide unit, a propylene oxide unit, an epichlorohydrin unit, or a glycidyl methacrylate unit. The polyether compound used in the present invention may contain a single repeating unit represented by general formula (1) other than the repeating unit represented by general formula (2), or may contain two or more of such units.

[0062] The polyether compound used in the present invention may contain a repeating unit other than the repeating unit represented by general formula (1). Examples of repeating units other than the repeating unit represented by general formula (1) include di- or higher-substituted oxirane monomer units such as 2,3-butylene oxide units, and oxirane monomer units containing a ring structure such as cyclohexene oxide. The polyether compound used in the present invention may contain a single type of repeating unit other than the repeating unit represented by general formula (1), or may contain two or more types of such units.

[0063] The polyether compound used in the present invention may contain an oxirane monomer unit having a crosslinkable group. When the polyether compound used in the present invention has a crosslinkable group, a crosslinkable composition can be prepared by adding a crosslinking agent, and the crosslinked product obtained by crosslinking this contains a crosslinked structure, so that when molded into a predetermined shape, it has excellent shape retention. The oxirane monomer unit having a crosslinkable group is not particularly limited, but examples thereof include an epihalohydrin monomer unit, an alkenyl group-containing oxirane monomer unit, and a (meth)acryloyl group-containing oxirane monomer unit.

[0064] The polyether compound used in the present invention may contain two or more types of repeating units. In this case, the distribution pattern of the multiple repeating units is not particularly limited, but it is preferable that the repeating units have a random distribution.

[0065] The chain structure of the polyether compound used in the present invention is not particularly limited, and may be a straight chain or a chain structure having branches such as grafts or radial branches.

[0066] The terminal group of the polyether compound used in the present invention is not particularly limited and can be any monovalent group. Specific examples of the terminal group include a hydrogen atom, a halogen group, an alkyl group, a haloalkyl group, a hydroxyl group, and an azide group. The terminal group can also be a nitrogen-containing cationic group (A') possessed by the repeating unit represented by general formula (2). ＋ ) and anion (X － ) may be a group consisting of

[0067] The polyether compound used in the present invention contains 50 or more repeating units represented by general formula (1) on average per molecule. The number of repeating units represented by general formula (1) in the polyether compound used in the present invention is not particularly limited as long as the average number per molecule is 50 or more, but the average number per molecule is preferably 51 to 2000, more preferably 101 to 1000, and even more preferably 110 to 800. When the number of repeating units represented by general formula (1) is within the above range, the carbon dioxide absorbent of the present invention has even better carbon dioxide absorption properties and is further prevented from falling off from a porous membrane when held in the porous membrane.

[0068] The number average molecular weight (Mn) of the polyether compound used in the present invention is not particularly limited, but is preferably 3,000 to 800,000, more preferably 4,000 to 400,000, and even more preferably 8,000 to 300,000. When the number average molecular weight (Mn) is within the above range, the carbon dioxide absorbent of the present invention has excellent carbon dioxide absorption properties, and is further prevented from falling off from a porous membrane when held by the porous membrane.

[0069] The molecular weight distribution (Mw / Mn) of the polyether compound used in the present invention is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 2.0, and even more preferably 1.0 to 1.5.

[0070] The proportion of the repeating units represented by general formula (1) in the polyether compound used in the present invention is not particularly limited, but is preferably 90 to 100 mol %, more preferably 95 to 100 mol %, and most preferably substantially 100 mol %, relative to all repeating units of the polyether compound. When the proportion of the repeating units represented by general formula (1) is within the above range, the carbon dioxide absorbent of the present invention has even better carbon dioxide absorption properties and is further prevented from falling off from a porous membrane when held in the porous membrane.

[0071] The number of repeating units represented by general formula (2) in the polyether compound used in the present invention is not particularly limited, but the average number per molecule is preferably 8 to 2000, more preferably 15 to 1000, even more preferably 20 to 900, and particularly preferably 25 to 800. When the number of repeating units represented by general formula (2) is within the above range, the carbon dioxide absorbent of the present invention has even more excellent carbon dioxide absorbency and is further prevented from falling off from a porous membrane when held in the porous membrane.

[0072] The proportion of the repeating units represented by general formula (2) in the polyether compound used in the present invention is not particularly limited, but is preferably 5 to 100 mol %, more preferably 8 to 100 mol %, and even more preferably 10 to 100 mol %, relative to all repeating units represented by general formula (1). When the proportion of the repeating units represented by general formula (2) is within the above range, the carbon dioxide absorbent of the present invention has even better carbon dioxide absorbency and is further prevented from falling off from a porous membrane when held in the porous membrane.

[0073] According to the present invention, even when a polyether compound is used that contains an average of 50 or more repeating units represented by general formula (1) per molecule and a relatively small amount (e.g., 14 mol % or 29 mol %) of repeating units represented by general formula (2), the carbon dioxide absorbent of the present invention surprisingly exhibits excellent carbon dioxide absorption. The reason for this is not clear, but it is presumed that the carbon dioxide absorption also depends on the mobility of the repeating units represented by general formula (2).

[0074] When even better carbon dioxide absorption properties are required, the proportion of the repeating units represented by general formula (2) in the polyether compound used in the present invention is preferably 20 to 100 mol %, more preferably 50 to 100 mol %, even more preferably 80 to 100 mol %, particularly preferably 90 to 100 mol %, particularly preferably 95 to 100 mol %, and most preferably substantially 100 mol %, relative to all repeating units represented by general formula (1).

[0075] In the polyether compound used in the present invention, the proportion of the repeating units represented by general formula (1) other than the repeating units represented by general formula (2) is not particularly limited, but is preferably 0 to 95 mol %, more preferably 0 to 92 mol %, and even more preferably 0 to 90 mol %, based on the total repeating units represented by general formula (1).

[0076] When even better carbon dioxide absorption is required, the proportion of repeating units represented by general formula (1) other than repeating units represented by general formula (2) in the polyether compound used in the present invention is preferably 0 to 80 mol %, more preferably 0 to 50 mol %, even more preferably 0 to 20 mol %, particularly preferably 0 to 10 mol %, particularly preferably 0 to 5 mol %, and most preferably substantially 0 mol % based on all repeating units represented by general formula (1).

[0077] The proportion of the oxirane monomer units having a crosslinkable group in the polyether compound used in the present invention is not particularly limited, but is preferably 0 to 50 mol %, and more preferably 0 to 20 mol %, relative to all repeating units of the polyether compound. The lower limit of the proportion of the oxirane monomer units having a crosslinkable group is not particularly limited, but may be 1 mol % or more, from the viewpoint of providing a crosslinked product obtained by forming the polyether compound used in the present invention into a crosslinkable composition and crosslinking this to have excellent shape retention.

[0078] The method for synthesizing the polyether compound used in the present invention is not particularly limited, and any synthesis method can be used as long as it can produce the target polyether compound. As an example of the synthesis method, first, a base polymer (a polyether compound not having a repeating unit represented by general formula (2)) is obtained by the following method (A) or (B).

[0079] (A) A method for obtaining a base polymer by ring-opening polymerization of a monomer containing an oxirane monomer, which includes at least an epihalohydrin such as epichlorohydrin, epibromohydrin, or epiiodohydrin, in the presence of a catalyst comprising an onium salt of a compound containing an atom of Group 15 or 16 of the periodic table and a trialkylaluminum in which all of the alkyl groups contained are linear alkyl groups, as disclosed in JP 2010-53217 A.

[0080] (B) A method of obtaining a base polymer by ring-opening polymerization of a monomer containing an oxirane monomer, which includes at least an epihalohydrin such as epichlorohydrin, epibromohydrin, or epiiodohydrin, in the presence of a catalyst prepared by reacting triisobutylaluminum with phosphoric acid and triethylamine, as disclosed in JP-B-46-27534.

[0081] Then, by reacting the halogen groups constituting the epihalohydrin monomer units of the base polymer obtained by the above method (A) or (B) with an onium-converting agent containing a nitrogen-containing cationic group (onium-converting reaction), at least a part of the halogen groups constituting the epihalohydrin monomer units of the base polymer is converted into onium halide groups containing a nitrogen-containing cationic group, thereby forming an anion (X － ) is a halide ion. If necessary, the obtained polyether compound containing onium halide structural units can be mixed with an anion (X ) other than a halide ion. －) with a salt of a metal cation to carry out an anion exchange reaction, thereby converting the halide ion constituting the onium halide group containing the nitrogen-containing cationic group into an anion other than the halide ion (X － ) can be converted to

[0082] The onium-containing agent containing a nitrogen-containing cationic group used in the reaction of the base polymer with the onium-containing agent containing a nitrogen-containing cationic group is a compound represented by the general formula (2): ＋ For example, by using an imidazole compound corresponding to the imidazolium structure in general formula (3-1) as the onium forming agent, it is possible to form a repeating unit represented by general formula (3-1).

[0083] The method for reacting the base polymer with the onium-conjugating agent is not particularly limited, but a method of mixing the base polymer with the onium-conjugating agent is preferred. The method for mixing the base polymer with the onium-conjugating agent is also not particularly limited, but examples thereof include a method of adding the onium-conjugating agent to a solution containing the base polymer and mixing them, a method of adding the base polymer to a solution containing the onium-conjugating agent and mixing them, and a method of preparing the onium-conjugating agent and the base polymer as separate solutions and mixing the two solutions.

[0084] In the reaction between the base polymer and the onium-forming agent, an inert solvent is preferably used, and may be either nonpolar or polar. Examples of nonpolar solvents include aromatic hydrocarbons such as benzene and toluene; linear saturated hydrocarbons such as n-pentane and n-hexane; and alicyclic saturated hydrocarbons such as cyclopentane and cyclohexane. Examples of polar solvents include ethers such as tetrahydrofuran, anisole, and diethyl ether; esters such as ethyl acetate and ethyl benzoate; ketones such as acetone, 2-butanone, and acetophenone; aprotic polar solvents such as acetonitrile, dimethylformamide, dimethylacetamide, and dimethyl sulfoxide; and protic polar solvents such as ethanol, methanol, and water. Mixtures of these solvents are also preferably used. The amount of solvent used is not particularly limited, but is preferably used so that the base polymer concentration is 1 to 50% by mass, and more preferably 3 to 40% by mass.

[0085] The amount of the onium-forming agent used when reacting the base polymer with the onium-forming agent is not particularly limited and may be determined depending on the content of the repeating unit represented by general formula (2) in the target polyether compound, etc. Specifically, the amount of the onium-forming agent used is usually in the range of 0.01 to 100 mol, preferably 0.02 to 50 mol, more preferably 0.03 to 10 mol, and even more preferably 0.05 to 2 mol, per mol of epichlorohydrin units in the base polymer used.

[0086] The pressure when reacting the base polymer with the onium-containing agent is not particularly limited, but is usually 1 to 500 atm, preferably 1 to 100 atm, and particularly preferably 1 to 50 atm. The temperature during the reaction is also not particularly limited, but is usually 0 to 200°C, preferably 20 to 170°C, and more preferably 40 to 150°C. The reaction time is usually 1 minute to 1,000 hours, preferably 3 minutes to 800 hours, more preferably 5 minutes to 500 hours, and even more preferably 30 minutes to 200 hours.

[0087] A polyether compound containing an onium halide structural unit and an anion other than a halide ion (X － The method for carrying out the anion exchange reaction by reacting a salt of a metal cation with a polyether compound containing an onium halide structural unit and an anion other than a halide ion (X － ) and a salt of a metal cation are mixed and reacted.

[0088] The conditions for carrying out the anion exchange reaction are not particularly limited, and include the steps of: reacting a polyether compound containing an onium halide structural unit with an anion other than a halide ion (X － Alternatively, the reaction may be carried out in the presence of other compounds such as an organic solvent. The amount of the salt used is not particularly limited, but is usually 0.01 to 100 mol, preferably 0.02 to 50 mol, and more preferably 0.03 to 10 mol, per mol of onium halide structural units of the onium halide structural unit-containing polyether compound used.

[0089] An anion other than a halide ion (X － The salt of bis(fluorosulfone)imide (Li(FSO2)2N), lithium (bistrifluoromethylsulfone)imide (Li(CF3SO2)2N), lithium (bispentafluoroethylsulfone)imide (Li(CF3CF2SO2)2N), sodium acetate (CH3COONa), silver acetate (CH3COOAg), lithium butyrate (C3H7COOLi), lithium trifluoroacetate (CF3COOLi), lithium benzoate (PhCOOLi), potassium tetracyanoborate (KB(CN) ４ ), lithium thiocyanate (LiSCN), lithium (biscyano)imide (Li(NC) ２ N), lithium methylsulfonate (LiCH3SO3), lithium trifluoromethylsulfonate (LiCF3SO3), potassium hydroxide (KOH), lithium perchlorate (LiClO4), etc. In the case of salts of polyvalent anions and metal cations, silver sulfate (Ag２ SO ４ ２－ ), sodium carbonate (Na ２ CO ３ ２－ For example, examples of salts of polyanions having two or more monovalent anionic groups in the molecule and metal cations include LiO ３ SCF2CF2CF2SO ３ Li, LiO ３ SCF2CF2SO ３ Li, Li ２ (CF ３ SO ２ NSO ２ CF2CF2OCF2CF2OCF2CF2SO ２ NSO ２ CF ３ ), among others.

[0090] The pressure during the anion exchange reaction is usually 1 to 500 atm, preferably 1 to 100 atm, and particularly preferably 1 to 50 atm. The reaction temperature is usually −30 to 200° C., preferably −15 to 180° C., and more preferably 0 to 150° C. The reaction time is usually 1 minute to 1,000 hours, preferably 3 minutes to 100 hours, more preferably 5 minutes to 10 hours, and even more preferably 5 minutes to 3 hours.

[0091] After the anion exchange reaction is completed, metal cations, halide ions, and salts thereof can be removed by washing with water or membrane separation using a semipermeable membrane, and the mixture containing the polyether compound can be recovered. Alternatively, the mixture containing the polyether compound can be recovered by extracting the polyether compound using a solvent such as methanol. Furthermore, the target polyether compound can be recovered by a conventional method, such as drying under reduced pressure.

[0092] The carbon dioxide absorbent of the present invention contains, in addition to the polyether compound, an ionic liquid; LiPF ６ , alkali metal salts such as LiTFSI and KI; oxygen-containing polar organic solvents; fillers such as carbon materials and inorganic materials; and the like.

[0093] Examples of oxygen-containing polar organic solvents include ethers such as tetrahydrofuran, anisole, diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether; esters such as ethyl acetate and ethyl benzoate; ketones such as acetone, methyl ethyl ketone, diethyl ketone, ethylene carbonate, dimethyl carbonate, and acetophenone; alcohols such as ethanol, methanol, ethylene glycol, diethylene glycol, tetraethylene glycol, polyethylene glycol, and glycerin; and dimethylformamide, dimethylacetamide, and dimethyl sulfoxide. Among these, ethers, ketones, and alcohols are preferred, with methyl ethyl ketone, tetraethylene glycol dimethyl ether, and tetraethylene glycol being more preferred. These may be used alone or in combination of two or more. For example, one or more ethers and one or more ketones may be used in combination.

[0094] When the carbon dioxide absorbent of the present invention contains an oxygen-containing polar organic solvent, the content ratio of the oxygen-containing polar organic solvent is not particularly limited, but is preferably 1 to 4,000 parts by mass, more preferably 5 to 3,000 parts by mass, and more preferably 10 to 2,000 parts by mass, relative to 100 parts by mass of the polyether compound in the carbon dioxide absorbent of the present invention.

[0095] The ionic liquid is not particularly limited as long as it is an organic salt compound having a melting point of 500°C or less, but is preferably an organic salt compound having a melting point of 400°C or less, more preferably an organic salt compound having a melting point of 300°C or less, even more preferably an organic salt compound having a melting point of 150°C or less, particularly preferably an organic salt compound having a melting point of 100°C or less, particularly preferably an organic salt compound having a melting point of 80°C or less, and most preferably an organic salt compound having a melting point of room temperature (25°C) or less. The ionic liquid may be liquid at room temperature or solid at room temperature, but is preferably liquid at room temperature. The ionic liquid is preferably an organic salt compound composed of a cation and an anion, and more preferably an organic salt compound having an organic molecule having only one positive charge as the cation and a counter anion having only one negative charge. The ionic liquid is also sometimes called an ionic liquid or a room temperature molten salt.

[0096] The ionic liquid used in the present invention preferably has a molecular weight (the combined molecular weight of the cation and anion) in the range of 100 to 700, more preferably in the range of 120 to 500. The ionic liquid that is liquid at room temperature (25°C) preferably has a viscosity at 25°C in the range of 10 to 1000 mPa·s, more preferably in the range of 10 to 500 mPa·s.

[0097] Specific examples of cations that form ionic liquids include ammonium ions; mono-substituted ammonium ions containing a cationic nitrogen atom, such as methylammonium ion, butylammonium ion, cyclohexylammonium ion, anilinium ion, benzylammonium ion, and ethanolammonium ion; di-substituted ammonium ions containing a cationic nitrogen atom, such as dimethylammonium ion, diethylammonium ion, dibutylammonium ion, and nonylphenylammonium ion; trimethylammonium ion, triethylammonium ion, n-butyldimethylammonium ion, stearyldimethylammonium ion, tributylammonium ion, trivinylammonium ion, and triethanolammonium ion. tri-substituted ammonium ions containing a cationic nitrogen atom, such as an ammonium ion, an N,N-dimethylethanolammonium ion, a tri(2-ethoxyethyl)ammonium ion, or an N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium ion; and tetra-substituted ammonium ions containing a cationic nitrogen atom, such as a tetramethylammonium ion, a trimethylethylammonium ion, a trimethylpropylammonium ion, a trimethylbutylammonium ion, a trimethylpentylammonium ion, a trimethylhexylammonium ion, a trimethylheptylammonium ion, a trimethyloctylammonium ion, a trimethyldecylammonium ion, or a trimethyldodecylammonium ion.Piperidinium ion, 1-methylpyrrolidinium ion, 1-ethyl-1-methylpyrrolidinium ion, 1-butyl-1-methylpyrrolidinium ion, imidazolium ion, 1-methylimidazolium ion, 1-ethylimidazolium ion, 1-ethyl-3-methylimidazolium ion, 1-butyl-3-methylimidazolium ion, benzimidazolium ion, pyrrolium ion, 1-methylpyrrolium ion, oxazolium ion, benzoxazolium ion, pyrazolium ion, isoxazolium ion, pyridinium ion, 2,6-dimethylpyridinium ion, N-butylpyridinium ion Examples of cationic heterocyclic ions containing a nitrogen atom include, but are not limited to, cationic nitrogen atom-containing heterocyclic ions such as ammonium ion, pyrazinium ion, pyrimidinium ion, pyridazinium ion, triazinium ion, N,N-dimethylanilinium ion, quinolinium ion, isoquinolinium ion, indolinium ion, quinoxalium ion, and isoquinoxalium ion; cationic phosphorus atom-containing ions such as tributyldodecaphosphonium ion and tetrabutylphosphonium ion; and cationic sulfur atom-containing ions such as triphenylsulfonium ion and tributylsulfonium ion. Among these, ions containing a cationic nitrogen atom are preferred, tri-substituted ammonium ions and cationic nitrogen atom-containing heterocyclic ions are more preferred, and tri-substituted ammonium ions, ions containing a pyrrolidinium ring, ions containing an imidazolium ring, and ions containing a pyridinium ring are particularly preferred.

[0098] Specific examples of anions that form an ionic liquid include those represented by the general formula (2) X － Specific examples of the anion represented by the formula (I) include those mentioned above, and the same applies to preferred anions. The anion forming the ionic liquid is an anion represented by the formula (I) of the formula (I) contained in the polyether compound. － It is preferable that the anion is the same as the anion represented by the formula:

[0099] The ionic liquid used in the present invention may be one in which all of the cations and anions are the same ionic species, or one in which two or more ionic species are present as either the cations or the anions, or both. That is, the ionic liquid may be a single ionic liquid or a mixture of two or more ionic species.

[0100] Specific examples of the ionic liquid used in the present invention include N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-methylpyrrolidinium tetrafluoroborate, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, N-butylpyridinium bis(trifluoromethanesulfonyl)imide, tributyldodecaphosphonium bis(trifluoromethanesulfonyl)imide, etc. Of these, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide is preferred.

[0101] When the carbon dioxide absorbent of the present invention contains an ionic liquid, the content ratio of the ionic liquid is not particularly limited, but is preferably 1 to 4,000 parts by mass, more preferably 5 to 3,000 parts by mass, and more preferably 10 to 2,000 parts by mass, relative to 100 parts by mass of the polyether compound in the carbon dioxide absorbent of the present invention.

[0102] Using the carbon dioxide absorbent of the present invention, a carbon dioxide absorbing member containing the carbon dioxide absorbent of the present invention can be obtained.

[0103] The carbon dioxide absorbent of the present invention has excellent carbon dioxide absorption properties. Therefore, by using the carbon dioxide absorbent of the present invention, a carbon dioxide absorbing member with excellent carbon dioxide absorption properties can be obtained. Furthermore, the carbon dioxide absorbent of the present invention is also inhibited from falling off from a porous membrane when held in the porous membrane. Therefore, a carbon dioxide absorbing member in which the carbon dioxide absorbent of the present invention is held in a porous membrane has excellent carbon dioxide absorption properties, is excellent in inhibiting the carbon dioxide absorbent from falling off, and is excellent in durability.

[0104] The carbon dioxide absorbing member containing the carbon dioxide absorbent of the present invention may be, for example, one obtained by casting the carbon dioxide absorbent of the present invention onto a substrate such as a sheet, or one obtained by impregnating the carbon dioxide absorbent of the present invention into a porous body such as a nonwoven fabric or a porous membrane.

[0105] The method for forming the carbon dioxide absorbing member is not particularly limited, but examples thereof include a method in which the carbon dioxide absorbent of the present invention is cast onto a substrate either as is or in a state in which it has been dissolved or dispersed in a solvent to form a liquid composition, to obtain a film-like molded body; and a method in which the carbon dioxide absorbent of the present invention is impregnated into a porous body such as a nonwoven fabric or a porous membrane, either as is or in a state in which it has been dissolved or dispersed in a solvent to form a liquid composition, to obtain a molded body.

[0106] The carbon dioxide absorbent may be blended with additives such as a reinforcing agent, an antioxidant, an ultraviolet absorber, a light resistance stabilizer, a tackifier, a surfactant, a conductivity imparting agent, an electrolyte substance, a colorant (dye or pigment), a flame retardant, or an antistatic agent, and then subjected to molding.

[0107] Furthermore, when the polyether compound contained in the carbon dioxide absorbent of the present invention has a crosslinkable group, a crosslinking agent may be blended with the carbon dioxide absorbent to form a crosslinkable composition, which may then be molded and crosslinked to obtain a carbon dioxide absorbing member.

[0108] The carbon dioxide absorbent of the present invention has excellent carbon dioxide absorption properties and can therefore be suitably used as a component for carbon dioxide separation, a component for carbon dioxide storage, or a component for carbon dioxide transport. The carbon dioxide absorbent of the present invention has excellent carbon dioxide absorption properties both under normal pressure and under high pressure (e.g., 2000 hPa to 150,000 hPa). Therefore, the carbon dioxide absorbent of the present invention can be suitably used, for example, as a component for equipment that performs carbon dioxide separation under normal pressure, or as a component for equipment that performs carbon dioxide separation under high pressure.

[0109] The carbon dioxide absorbent of the present invention is useful for, for example, absorbing carbon dioxide from natural gas, absorbing carbon dioxide from biogas, and ２ / CH ４ Absorption of carbon dioxide from contained gases, CO ２ / N ２ The present invention can be suitably used for applications such as absorbing carbon dioxide from gases containing the carbon dioxide. The gases from which carbon dioxide is absorbed may contain hydrogen sulfide, mercaptans (thiols), disulfides, carbon disulfide, etc.

[0110] The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In the following, "parts" and "%" are by mass unless otherwise specified. Tests and evaluations were carried out according to the following methods.

[0111] [Number Average Molecular Weight (Mn) and Molecular Weight Distribution (Mw / Mn)] (1) The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the base polymer were measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. The measuring instrument used was an HLC-8320 (manufactured by Tosoh Corporation), and four TSKgel SuperMultipore HZH (manufactured by Tosoh Corporation) columns connected in series. The detector used was a differential refractometer RI-8320 (manufactured by Tosoh Corporation). (2) The number average molecular weight (Mn) of the polyether compound was determined as follows. First, the average molecular weight of all repeating units constituting the polyether compound was determined from the average molecular weight of the repeating unit of the base polymer, the average molecular weights of the various monomer units constituting the polyether compound, and the content of the various monomer units determined by (3) below. The number average molecular weight (Mn) of the polyether compound was determined by multiplying the number of repeating units of the base polymer by the average molecular weight of all repeating units constituting the polyether compound. (3) The structures of the base polymer and polyether compound, as well as the contents of various monomer units in the base polymer and polyether compound, were measured using a nuclear magnetic resonance (NMR) spectrometer as follows. First, 30 mg of a sample of the base polymer or polyether compound was added to 1.0 mL of deuterated chloroform or deuterated dimethyl sulfoxide and shaken for 1 hour to achieve uniform dissolution. The resulting solution was then subjected to NMR measurement to obtain a 1H-NMR spectrum, and the structure of the sample was assigned according to a standard method. Furthermore, the content of the repeating unit represented by general formula (2) in a polyether compound containing the repeating unit represented by general formula (2) was calculated using the following method. First, the number of moles B1 of all oxirane monomer units was calculated from the integral value of protons derived from the oxirane monomer units in the main chain. Next, the number of moles B2 of the repeating unit represented by general formula (2) was calculated from the integral value of the protons derived from the onium structure in the repeating unit represented by general formula (2).The ratio (percentage) of B2 to B1 was then calculated as the content of the repeating unit represented by general formula (2) in the polyether compound.

[0112] [Carbon dioxide absorption amount] 1000 mg of a carbon dioxide absorbent (polyether compound or composition) was thinly coated on a glass substrate. Next, the carbon dioxide absorbent together with the glass substrate was dried in a vacuum dryer at 80°C for 24 hours to remove moisture and volatile components. Next, the carbon dioxide absorbent together with the glass substrate was left standing under a carbon dioxide stream at 1000 hPa or 8000 hPa and a temperature of 25°C for 72 hours to allow carbon dioxide to be absorbed into the carbon dioxide absorbent and saturated. The carbon dioxide absorbent saturated with carbon dioxide was transferred together with the glass substrate to a sealed container and introduced into a reaction tube of a temperature programmed desorption gas analyzer (Temperature Programmed Desorption-Mass Spectrometry: TPD-MS; Rigaku Temperature Programmed Desorption Gas Analyzer TPD Type V) filled with helium. After the carbon dioxide absorbent was introduced into the heating furnace, the amount of carbon dioxide detected by the detector was quantified while the temperature was increased, thereby determining the amount of carbon dioxide absorbed per gram of the carbon dioxide absorbent.

[0113] [Test 1 for Carbon Dioxide Absorbent Dropping from Porous Membrane] The carbon dioxide absorbents (polyether compounds) obtained in Examples 1 to 19 and Comparative Examples 1 to 7 were dissolved in dimethyl sulfoxide to prepare a 10 wt% carbon dioxide absorbent solution. Next, a porous membrane substrate (made of polyethylene, membrane thickness 25 micrometers, porosity 40%, average pore size 15 nanometers) was heated to 100 ° C., the carbon dioxide absorbent solution was applied, and the carbon dioxide absorbent solution was allowed to penetrate into the pores. Next, the dimethyl sulfoxide was slowly volatilized, and after removing the solvent, the membrane was immersed in water to scrape off excess carbon dioxide absorbent from the surface. The obtained membrane was dried to obtain a support membrane consisting of a carbon dioxide absorbent and a porous substrate.

[0114] The obtained support membrane was fixed and adhered on a perforated plate (2 cm diameter) having many holes with a diameter of 1 mm. The pressure below the perforated plate (opposite the support membrane) was reduced in two stages to suck the support membrane consisting of the carbon dioxide absorbent and the porous substrate, and the presence or absence of the carbon dioxide absorbent falling off from the porous substrate was visually observed and evaluated according to the following criteria. The pressure above the perforated plate was 1.0 atmospheric pressure.

[0115] When the pressure below the perforated plate was set to 0.9 atmospheres, the case in which some of the carbon dioxide absorbent fell out from the pores of the porous membrane was rated as C. When the pressure below the perforated plate was set to 0.9 atmospheres, the carbon dioxide absorbent did not fall out, but when the pressure below the perforated plate was set to 0.8 atmospheres, the case in which some of the carbon dioxide absorbent fell out from the pores of the porous membrane was rated as B. Furthermore, when the pressure below the perforated plate was set to 0.8 atmospheres, the case in which the carbon dioxide absorbent did not fall out and was retained in the pores of the porous membrane was rated as A.

[0116] [Test 2 for Carbon Dioxide Absorbent Dropping from Porous Membrane] The carbon dioxide absorbents (compositions) obtained in Examples 20 to 30 and Comparative Examples 8 to 11 were applied to a porous substrate (made of polyethylene, film thickness 25 micrometers, porosity 40%, average pore size 15 nanometers) heated to 100°C, and the carbon dioxide absorbent was allowed to penetrate into the pores. Next, the surface of the membrane was wiped to remove excess carbon dioxide absorbent, thereby obtaining a support membrane consisting of the carbon dioxide absorbent and the porous substrate.

[0117] The obtained support membrane was fixed in a vertically hanging state and left to stand for 24 hours under normal pressure at a temperature of 25°C and a humidity of 60%. The presence or absence of carbon dioxide absorbent falling off from the porous substrate was visually observed and judged according to the following criteria. ◯ indicates that the carbon dioxide absorbent was retained in the pores of the porous membrane, and × indicates that some of the carbon dioxide absorbent had fallen off.

[0118] [Production Example A] (Living Anionic Polymerization of Epichlorohydrin) 3.22 g of tetra-n-butylammonium bromide and 50 ml of toluene were added to an argon-purged glass reactor equipped with a stirrer and cooled to 0°C. Next, 1.256 g of triethylaluminum (1.1 equivalents relative to tetra-n-butylammonium bromide) dissolved in 10 ml of normal hexane was added and allowed to react for 15 minutes to obtain a catalyst composition. 10.0 g of epichlorohydrin was added to the obtained catalyst composition, and polymerization was carried out at 0°C. After the start of the polymerization reaction, the viscosity of the solution gradually increased. After 12 hours of reaction, a small amount of water was added to the polymerization reaction solution to terminate the reaction. The resulting polymerization reaction solution was washed with a 0.1 N aqueous hydrochloric acid solution to deash the catalyst residue, and then further washed with ion-exchanged water. The organic phase was then dried under reduced pressure at 50°C for 12 hours. The yield of the resulting colorless, transparent oily substance was 9.9 g. Furthermore, the number average molecular weight (Mn) of the obtained substance measured by GPC was 1,050, the average number of repeating units was 11-mer, and the molecular weight distribution (Mw / Mn) was 1.35. From the above, it can be said that the obtained oily substance is polyepichlorohydrin (base polymer A) composed of epichlorohydrin units having a bromomethyl group at the polymerization initiation end and a hydroxyl group at the polymerization termination end.

[0119] [Production Example B] (Living Anionic Polymerization of Epichlorohydrin) 1.61 g of tetra-n-butylammonium bromide and 50 ml of toluene were added to an argon-purged glass reactor equipped with a stirrer and cooled to 0°C. Next, 0.657 g of triethylaluminum (1.15 equivalents relative to tetra-n-butylammonium bromide) dissolved in 10 ml of normal hexane was added and allowed to react for 15 minutes to obtain a catalyst composition. 10.0 g of epichlorohydrin was added to the obtained catalyst composition, and polymerization was carried out at 0°C. After the start of the polymerization reaction, the viscosity of the solution gradually increased. After 12 hours of reaction, a small amount of water was added to the polymerization reaction solution to terminate the reaction. The resulting polymerization reaction solution was washed with a 0.1 N aqueous hydrochloric acid solution to deash the catalyst residue, and then further washed with ion-exchanged water. The organic phase was then dried under reduced pressure at 50°C for 12 hours. The yield of the resulting colorless, transparent oily substance was 9.9 g. Furthermore, the number average molecular weight (Mn) of the obtained substance measured by GPC was 2,100, the average number of repeating units was 23-mer, and the molecular weight distribution (Mw / Mn) was 1.25. From the above, it can be said that the obtained oily substance is a polyether compound (base polymer B) composed of epichlorohydrin units having a bromomethyl group at the polymerization initiation end and a hydroxyl group at the polymerization termination end.

[0120] [Production Example C] (Living Anionic Polymerization of Epichlorohydrin) 0.644 g of tetra-n-butylammonium bromide and 50 ml of toluene were added to an argon-purged glass reactor equipped with a stirrer and cooled to 0°C. Next, 0.285 g of triethylaluminum (1.25 equivalents relative to tetra-n-butylammonium bromide) dissolved in 10 ml of normal hexane was added and allowed to react for 15 minutes to obtain a catalyst composition. 10.0 g of epichlorohydrin was added to the obtained catalyst composition, and polymerization was carried out at 0°C. After the start of the polymerization reaction, the viscosity of the solution gradually increased. After 12 hours of reaction, a small amount of water was added to the polymerization reaction solution to terminate the reaction. The obtained polymerization reaction solution was washed with a 0.1 N aqueous hydrochloric acid solution to deash the catalyst residue, and then further washed with ion-exchanged water. The organic phase was then dried under reduced pressure at 50°C for 12 hours. The yield of the resulting colorless, transparent oily substance was 9.9 g. Furthermore, the number average molecular weight (Mn) of the obtained substance measured by GPC was 5,390, the average number of repeating units was 58-mer, and the molecular weight distribution (Mw / Mn) was 1.21. From the above, it can be said that the obtained oily substance is a polyether compound (base polymer C) composed of epichlorohydrin units having a bromomethyl group at the polymerization initiation end and a hydroxyl group at the polymerization termination end.

[0121] [Production Example D] (Living Anionic Polymerization of Epichlorohydrin) 0.322 g of tetra-n-butylammonium bromide and 50 ml of toluene were added to an argon-purged glass reactor equipped with a stirrer and cooled to 0°C. Next, 0.148 g of triethylaluminum (1.3 equivalents relative to tetra-n-butylammonium bromide) dissolved in 10 ml of normal hexane was added and allowed to react for 15 minutes to obtain a catalyst composition. 10.0 g of epichlorohydrin was added to the obtained catalyst composition, and polymerization was carried out at 0°C. After the start of the polymerization reaction, the viscosity of the solution gradually increased. After 12 hours of reaction, a small amount of water was added to the polymerization reaction solution to terminate the reaction. The resulting polymerization reaction solution was washed with a 0.1 N aqueous hydrochloric acid solution to decalcify the catalyst residue, and then further washed with ion-exchanged water. The organic phase was then dried under reduced pressure at 50°C for 12 hours. The yield of the resulting colorless, transparent, viscous oily substance was 9.9 g. Furthermore, the number average molecular weight (Mn) of the obtained substance measured by GPC was 10,700, the average number of repeating units was 116-mer, and the molecular weight distribution (Mw / Mn) was 1.18. From the above, it can be said that the obtained oily substance is a polyether compound (base polymer D) composed of epichlorohydrin units having a bromomethyl group at the polymerization initiation end and a hydroxyl group at the polymerization termination end.

[0122] [Production Example E] (Living Anionic Polymerization of Epichlorohydrin) 0.215 g of tetra-n-butylammonium bromide and 50 ml of toluene were added to an argon-purged glass reactor equipped with a stirrer and cooled to 0°C. Next, 0.114 g of triethylaluminum (1.5 equivalents relative to tetra-n-butylammonium bromide) dissolved in 10 ml of normal hexane was added and allowed to react for 15 minutes to obtain a catalyst composition. 10.0 g of epichlorohydrin was added to the resulting catalyst composition, and polymerization was carried out at 0°C. After the start of the polymerization reaction, the viscosity of the solution gradually increased. After 12 hours of reaction, a small amount of water was added to the polymerization reaction solution to terminate the reaction. The resulting polymerization reaction solution was washed with a 0.1 N aqueous hydrochloric acid solution to decalcify the catalyst residue, and then further washed with ion-exchanged water. The organic phase was then dried under reduced pressure at 50°C for 12 hours. The yield of the resulting colorless, transparent, viscous oily substance was 9.7 g. Furthermore, the number average molecular weight (Mn) of the obtained substance measured by GPC was 15,600, the average number of repeating units was 169-mer, and the molecular weight distribution (Mw / Mn) was 1.35. From the above, it can be said that the obtained oily substance is a polyether compound (base polymer E) composed of epichlorohydrin units having a bromomethyl group at the polymerization initiation end and a hydroxyl group at the polymerization termination end.

[0123] [Production Example F] (Living Anionic Polymerization of Epichlorohydrin) 0.107 g of tetra-n-butylammonium bromide and 50 ml of toluene were added to an argon-purged glass reactor equipped with a stirrer and cooled to 0°C. Next, 0.057 g of triethylaluminum (1.5 equivalents relative to tetra-n-butylammonium bromide) dissolved in 10 ml of normal hexane was added and allowed to react for 15 minutes to obtain a catalyst composition. 10.0 g of epichlorohydrin was added to the resulting catalyst composition, and polymerization was carried out at 0°C. After the start of the polymerization reaction, the viscosity of the solution gradually increased. After 12 hours of reaction, a small amount of water was added to the polymerization reaction solution to terminate the reaction. The resulting polymerization reaction solution was washed with a 0.1 N aqueous hydrochloric acid solution to decalcify the catalyst residue, and then further washed with ion-exchanged water. The organic phase was then dried under reduced pressure at 50°C for 12 hours. The yield of the resulting colorless, transparent, viscous oily substance was 9.5 g. Furthermore, the number average molecular weight (Mn) of the obtained substance measured by GPC was 32,500, the average number of repeating units was 351-mer, and the molecular weight distribution (Mw / Mn) was 1.43. From the above, it can be said that the obtained oily substance is a polyether compound (base polymer F) composed of epichlorohydrin units having a bromomethyl group at the polymerization initiation end and a hydroxyl group at the polymerization termination end.

[0124] [Production Example G] (Living Anionic Copolymerization of Epichlorohydrin and Glycidyl Methacrylate) 0.322 g of tetra-normal butylammonium bromide and 50 ml of toluene were added to an argon-purged glass reactor equipped with a stirrer and cooled to 0°C. Next, 0.148 g of triethylaluminum (1.3 equivalents relative to tetra-normal butylammonium bromide) dissolved in 10 ml of normal hexane was added and allowed to react for 15 minutes to obtain a catalyst composition. 9.5 g of epichlorohydrin and 0.5 g of glycidyl methacrylate were added to the obtained catalyst composition, and the polymerization reaction was carried out at 0°C. After 12 hours of reaction, a small amount of water was added to the polymerization reaction solution to terminate the reaction. The resulting polymerization reaction solution was washed with a 0.1 N aqueous hydrochloric acid solution to deash the catalyst residue, and then further washed with ion-exchanged water. The organic phase was then dried under reduced pressure at 50°C for 12 hours. The yield of the resulting colorless, transparent, viscous oily substance was 9.9 g. The number average molecular weight (Mn) of the obtained viscous oily substance measured by GPC was 11,000, the average number of repeating units was 105-mer, and the molecular weight distribution was 1.26. Furthermore, when 1H-NMR measurement was performed on the obtained viscous oily substance, it was confirmed that this rubbery substance contained 97.0 mol% epichlorohydrin units and 3.0 mol% glycidyl methacrylate units. From the above, it can be said that the obtained viscous oily substance is a polyether compound (base polymer G) composed of epichlorohydrin units and glycidyl methacrylate units, which has a bromomethyl group at the polymerization initiation end and a hydroxyl group at the polymerization termination end.

[0125] [Production Example H] (Living Anionic Copolymerization of Epichlorohydrin and Glycidyl Methacrylate) 0.032 g of tetra-normal butylammonium bromide and 5 ml of toluene were added to an argon-purged glass reactor equipped with a stirrer, and the mixture was cooled to 0°C. Next, 0.029 g of triethylaluminum (2.5 equivalents relative to tetra-normal butylammonium bromide) dissolved in 0.25 ml of normal hexane was added, and the mixture was allowed to react for 15 minutes to obtain a catalyst composition. 9.5 g of epichlorohydrin and 0.5 g of glycidyl methacrylate were added to the resulting catalyst composition, and the polymerization reaction was carried out at 0°C. After 12 hours of reaction, a small amount of water was added to the polymerization reaction solution to terminate the reaction. The resulting polymerization reaction solution was washed with a 0.1 N aqueous hydrochloric acid solution to deash the catalyst residue, and then further washed with ion-exchanged water. The organic phase was then dried under reduced pressure at 50°C for 12 hours. The yield of the resulting colorless, transparent, viscous oily substance was 8.3 g. The number average molecular weight (Mn) of the obtained viscous oily substance measured by GPC was 57,000, the average number of repeating units was 606-mer, and the molecular weight distribution was 1.58. Furthermore, when 1H-NMR measurement was performed on the obtained rubbery substance, it was confirmed that this viscous oily substance contained 97.0 mol% epichlorohydrin units and 3.0 mol% glycidyl methacrylate units. From the above, it can be said that the obtained viscous oily substance is a polyether compound (base polymer H) composed of epichlorohydrin units and glycidyl methacrylate units, having a bromomethyl group at the polymerization initiation end and a hydroxyl group at the polymerization termination end.

[0126] [Production Example I] (Production of Epichlorohydrin / Propylene Oxide Random Copolymer) 0.160 g of tetra-n-butylammonium bromide and 60 ml of toluene were added to a glass reactor equipped with a stirrer and cooled to 0°C. A solution of 0.0540 g of trimethylaluminum in 1 ml of n-hexane was then added and the mixture was allowed to react for 15 minutes. 3.0 g of epichlorohydrin and 7.0 g of propylene oxide were added to the resulting mixture, and the polymerization reaction was carried out at 0°C. After the polymerization reaction began, the viscosity of the solution gradually increased. After the reaction time of 1 hour, a small amount of water was added to the polymerization reaction solution to terminate the reaction. The resulting polymerization reaction solution was washed with a 0.1 N aqueous hydrochloric acid solution to decalcify the catalyst residue, and then washed with ion-exchanged water. The organic phase was then dried under reduced pressure at 50°C for 12 hours. The yield of the resulting colorless, transparent, viscous oily substance was 5.6 g. The resulting polymer had a number-average molecular weight (Mn) of 10,600, a weight-average molecular weight (Mw) of 12,200, an average number of repeating units of 171-mer, and a molecular weight distribution (Mw / Mn) of 1.15. The monomer unit composition ratio (molar ratio) of the polymer, determined by 1H-NMR, was epichlorohydrin units:propylene oxide units = 11:89. From the above, it can be said that the resulting viscous oily substance is a polyether compound (base polymer I) having a bromomethyl group at the polymerization initiation end and a hydroxyl group at the polymerization termination end, and composed of epichlorohydrin units and propylene oxide units.

[0127] [Production Example J] (Production of Epichlorohydrin / Ethylene Oxide Random Copolymer) 0.160 g of tetra-n-butylammonium bromide and 60 ml of toluene were added to a glass reactor equipped with a stirrer and cooled to 0°C. A solution of 0.0540 g of trimethylaluminum in 1 ml of n-hexane was then added and the mixture was allowed to react for 15 minutes. 5.0 g of epichlorohydrin and 5.0 g of ethylene oxide were added to the resulting mixture and polymerization was carried out at 0°C. After the polymerization reaction began, the viscosity of the solution gradually increased. After the reaction time of 1 hour, a small amount of water was added to the polymerization reaction solution to terminate the reaction. The resulting polymerization reaction solution was washed with a 0.1 N aqueous hydrochloric acid solution to decalcify the catalyst residue. After further washing with ion-exchanged water, the organic phase was dried under reduced pressure at 50°C for 12 hours. The yield of the resulting colorless, transparent, viscous oily substance was 6.5 g. The resulting polymer had a number-average molecular weight (Mn) of 15,100, a weight-average molecular weight (Mw) of 22,300, an average number of repeating units of 303-mer, and a molecular weight distribution (Mw / Mn) of 1.48. The monomer unit composition ratio (molar ratio) of the polymer, determined by 1H-NMR, was epichlorohydrin units:ethylene oxide units = 12:88. From the above, it can be said that the resulting viscous oily substance is a polyether compound (base polymer J) having a bromomethyl group at the polymerization initiation end and a hydroxyl group at the polymerization termination end, and composed of epichlorohydrin units and ethylene oxide units.

[0128] [Production Example 1'] (Quaternization of epichlorohydrin units in base polymer A with 1-methylimidazole) 8.0 g of base polymer A obtained in Production Example A, 22.0 g of 1-methylimidazole, and 16.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and purged with argon, and heated to 80°C. After reacting at 80°C for 144 hours, the reaction was stopped by cooling to room temperature, and a portion of the resulting reaction solution was withdrawn and dried under reduced pressure at 50°C for 120 hours, yielding 15.0 g of a reddish-brown resinous substance. Regarding this resinous substance, １H-NMR measurement and elemental analysis revealed that the resulting polyether compound was a polyether compound A' having 1-methylimidazolium halide groups, in which the chloro groups in all of the epichlorohydrin units in the base polymer A obtained in Production Example A, which was the starting material, had been substituted with 1-methylimidazolium chloride groups, and the bromo groups in all of the bromomethyl groups at the polymerization initiation terminals had been substituted with 1-methylimidazolium bromide groups. The resulting polyether compound A' had a number average molecular weight (Mn) of 1,980 and an average number of repeating units of 11.

[0129] [Production Example 1″] (Anion exchange of polyether compound A′ having 1-methylimidazolium halide groups with lithium bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water in which 10.0 g of lithium bis(trifluoromethanesulfonyl)imide had been dissolved was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of polyether compound A′ having 1-methylimidazolium halide groups obtained in Production Example 1′ was dissolved in 50 ml of distilled water, and this was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown viscous oily substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The light brown viscous oily substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 11.5 g of a light brown viscous oily substance. Regarding the obtained light brown viscous oily substance: １ H-NMR measurement and elemental analysis revealed that the resulting polyether compound was an imidazolium structure-containing polyether compound A" having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of polyether compound A' having 1-methylimidazolium halide groups, obtained in Production Example 1' (the starting material), and the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminals had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound A" had a number average molecular weight (Mn) of 4,750 and an average number of repeating units of an 11-mer.

[0130] [Production Example 2'] (Quaternization of epichlorohydrin units in base polymer B with 1-methylimidazole) 8.0 g of base polymer B obtained in Production Example B, 22.0 g of 1-methylimidazole, and 16.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and purged with argon, and heated to 80°C. After reacting at 80°C for 144 hours, the reaction was stopped by cooling to room temperature, and a portion of the resulting reaction solution was withdrawn and dried under reduced pressure at 50°C for 120 hours, yielding 15.0 g of a reddish-brown resinous substance. This resinous substance was １ H-NMR measurement and elemental analysis revealed that the resulting compound was identified as polyether compound B' having 1-methylimidazolium halide groups, in which the chloro groups in all of the epichlorohydrin units in base polymer B obtained in Production Example B, which was the starting material, had been substituted with 1-methylimidazolium chloride groups, and the bromo groups in all of the bromomethyl groups at the polymerization initiation terminals had been substituted with 1-methylimidazolium bromide groups. The resulting polyether compound B' had a number average molecular weight (Mn) of 3,960 and an average number of repeating units of 23.

[0131] [Production Example 2''] (Anion exchange of polyether compound B' having 1-methylimidazolium halide groups with lithium bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water in which 10.0 g of lithium bis(trifluoromethanesulfonyl)imide had been dissolved was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of polyether compound B' having 1-methylimidazolium halide groups obtained in Production Example 2' was dissolved in 50 ml of distilled water, and this was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown viscous oily substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The light brown viscous oily substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 11.4 g of a light brown viscous oily substance. Regarding the obtained light brown viscous oily substance: １H-NMR measurement and elemental analysis revealed that the resulting polyether compound was an imidazolium structure-containing polyether compound B" having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of polyether compound B' having 1-methylimidazolium halide groups obtained in Production Example 2', the starting material, and the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminals had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound B" had a number average molecular weight (Mn) of 9,500 and an average number of repeating units of 23-mer.

[0132] [Production Example 3'] (Quaternization of epichlorohydrin units in base polymer C with 1-methylimidazole) 8.0 g of base polymer C obtained in Production Example C, 22.0 g of 1-methylimidazole, and 16.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and purged with argon, and heated to 80°C. After reacting at 80°C for 144 hours, the reaction was stopped by cooling to room temperature, and a portion of the resulting reaction solution was withdrawn and dried under reduced pressure at 50°C for 120 hours, yielding 15.0 g of a reddish-brown resinous substance. Regarding this resinous substance, １ H-NMR measurement and elemental analysis revealed that the resulting compound was identified as polyether compound C' having 1-methylimidazolium halide groups, in which the chloro groups in all of the epichlorohydrin units in base polymer C obtained in Production Example C, which was the starting material, had been substituted with 1-methylimidazolium chloride groups, and the bromo groups in all of the bromomethyl groups at the polymerization initiation terminals had been substituted with 1-methylimidazolium bromide groups. The resulting polyether compound C' had a number average molecular weight (Mn) of 10,200 and an average number of repeating units of 58-mer.

[0133] [Production Example 3''] (Anion exchange of polyether compound C' having 1-methylimidazolium halide groups with lithium bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water in which 10.0 g of lithium bis(trifluoromethanesulfonyl)imide had been dissolved was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of polyether compound C' having 1-methylimidazolium halide groups obtained in Production Example 3' was dissolved in 50 ml of distilled water, and this was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown viscous oily substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The light brown viscous oily substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 11.6 g of a light brown viscous oily substance. Regarding the obtained light brown viscous oily substance: １ H-NMR measurement and elemental analysis revealed that the resulting polyether compound was an imidazolium structure-containing polyether compound C" having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of polyether compound C' having 1-methylimidazolium halide groups, obtained in Production Example 3' (the starting material), and the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminals had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound C" had a number average molecular weight (Mn) of 24,400 and an average number of repeating units of 58-mer.

[0134] [Production Example 4'] (Quaternization of epichlorohydrin units in base polymer D with 1-methylimidazole) 8.0 g of base polymer D obtained in Production Example D, 22.0 g of 1-methylimidazole, and 16.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and purged with argon, and heated to 80°C. After reacting at 80°C for 144 hours, the reaction was stopped by cooling to room temperature, and a portion of the resulting reaction solution was withdrawn and dried under reduced pressure at 50°C for 120 hours, yielding 14.9 g of a reddish-brown resinous substance. Regarding this resinous substance, １H-NMR measurement and elemental analysis revealed that the resulting polyether compound was a polyether compound D' having 1-methylimidazolium halide groups, in which the chloro groups in all of the epichlorohydrin units in the base polymer D obtained in Production Example D (starting material) had been substituted with 1-methylimidazolium chloride groups, and the bromo groups in all of the bromomethyl groups at the polymerization initiation terminals had been substituted with 1-methylimidazolium bromide groups. The resulting polyether compound D' had a number average molecular weight (Mn) of 20,200 and an average number of repeating units of 116.

[0135] [Production Example 4''] (Anion exchange of polyether compound D' having 1-methylimidazolium halide groups with lithium bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water in which 10.0 g of lithium bis(trifluoromethanesulfonyl)imide had been dissolved was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of polyether compound D' having 1-methylimidazolium halide groups obtained in Production Example 4' was dissolved in 50 ml of distilled water, and this was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown viscous oily substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The light brown viscous oily substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 11.5 g of a light brown viscous oily substance. Regarding the obtained light brown viscous oily substance: １ H-NMR measurement and elemental analysis revealed that the resulting polyether compound was an imidazolium structure-containing polyether compound D" having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of the 1-methylimidazolium halide group-containing polyether compound D' obtained in Production Example 4', the starting material, and the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminals had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound D" had a number average molecular weight (Mn) of 48,500 and an average number of repeating units of 116.

[0136] Production Example 5' (Quaternization of epichlorohydrin units in base polymer E with 1-methylimidazole) 8.0 g of base polymer E obtained in Production Example E, 22.0 g of 1-methylimidazole, and 16.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and the atmosphere was purged with argon, and the mixture was heated to 80° C. After reacting at 80° C. for 144 hours, the mixture was cooled to room temperature to terminate the reaction, and a portion of the resulting reaction solution was withdrawn and dried under reduced pressure at 50° C. for 120 hours, yielding 14.9 g of a reddish-brown resinous substance. This resinous substance was subjected to 1H-NMR measurement and elemental analysis, and was identified as polyether compound E' having 1-methylimidazolium halide groups, in which the chloro groups in all of the epichlorohydrin units in base polymer E obtained in Production Example E, which was the starting material, had been substituted with 1-methylimidazolium chloride groups, and the bromo groups in all of the bromomethyl groups at the polymerization initiation terminals had been substituted with 1-methylimidazolium bromide groups. The number average molecular weight (Mn) of the resulting polyether compound E' was 29,400, and the average number of repeating units was 169-mer.

[0137] [Production Example 5''] (Anion Exchange of Polyether Compound E' Having 1-Methylimidazolium Halide Groups with Lithium Bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water containing 10.0 g of lithium bis(trifluoromethanesulfonyl)imide was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of Polyether Compound E' having 1-methylimidazolium halide groups obtained in Production Example 5' was dissolved in 50 ml of distilled water, and this solution was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown viscous oil-like substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The light brown viscous oil-like substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 11.4 g of a light brown viscous oil-like substance. The resulting pale brown viscous oily substance was subjected to 1H-NMR measurement and elemental analysis. The result identified it as imidazolium structure-containing polyether compound E" having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of polyether compound E' having 1-methylimidazolium halide groups, obtained in Production Example 5', the starting material, and the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminals had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound E" had a number average molecular weight (Mn) of 70,700 and an average number of repeating units of 169-mer.

[0138] Production Example 6' (Quaternization of epichlorohydrin units in base polymer F with 1-methylimidazole) 8.0 g of base polymer F obtained in Production Example F, 22.0 g of 1-methylimidazole, and 16.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and the atmosphere was purged with argon, and the mixture was heated to 80° C. After reacting at 80° C. for 144 hours, the mixture was cooled to room temperature to terminate the reaction, and a portion of the resulting reaction solution was withdrawn and dried under reduced pressure at 50° C. for 120 hours, yielding 14.9 g of a reddish-brown resinous substance. This resinous substance was subjected to 1H-NMR measurement and elemental analysis, and was identified as polyether compound F' having 1-methylimidazolium halide groups, in which the chloro groups in all of the epichlorohydrin units in base polymer F obtained in Production Example F, the starting material, had been substituted with 1-methylimidazolium chloride groups, and the bromo groups in all of the bromomethyl groups at the polymerization initiation terminals had been substituted with 1-methylimidazolium bromide groups. The number average molecular weight (Mn) of the resulting polyether compound F' was 61,300, and the average number of repeating units was 351-mer.

[0139] Production Example 6" (Anion Exchange of Polyether Compound F' Having 1-Methylimidazolium Halide Groups with Lithium Bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water containing 10.0 g of lithium bis(trifluoromethanesulfonyl)imide was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of Polyether Compound F' having 1-methylimidazolium halide groups obtained in Production Example 6' was dissolved in 50 ml of distilled water, and this solution was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown viscous oil-like substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The light brown viscous oil-like substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 11.4 g of a light brown viscous oil-like substance. The resulting pale brown viscous oily substance was subjected to 1H-NMR measurement and elemental analysis. The result identified it as imidazolium structure-containing polyether compound F" having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of polyether compound F' having 1-methylimidazolium halide groups, obtained in Production Example 6', which was the starting material, and the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminals had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound F" had a number average molecular weight (Mn) of 147,000 and an average number of repeating units of 351-mer.

[0140] Production Example 7' (Quaternization of epichlorohydrin units in base polymer G with 1-methylimidazole) 8.0 g of base polymer G obtained in Production Example G, 22.0 g of 1-methylimidazole, and 16.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and the atmosphere was purged with argon, and the mixture was heated to 80° C. After reacting at 80° C. for 144 hours, the mixture was cooled to room temperature to terminate the reaction, and a portion of the resulting reaction solution was withdrawn and dried under reduced pressure at 50° C. for 120 hours, yielding 14.6 g of a reddish-brown resinous substance. This resinous substance was subjected to 1H-NMR measurement and elemental analysis, and was identified as polyether compound G' having 1-methylimidazolium halide groups, in which the chloro groups in all of the epichlorohydrin units in base polymer G obtained in Production Example G, the starting material, had been substituted with 1-methylimidazolium chloride groups, and the bromo groups in all of the bromomethyl groups at the polymerization initiation terminals had been substituted with 1-methylimidazolium bromide groups. The number average molecular weight (Mn) of the resulting polyether compound G' was 20,100, and the average number of repeating units was 105-mer.

[0141] Production Example 7" (Anion Exchange of Polyether Compound G' Having 1-Methylimidazolium Halide Groups with Lithium Bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water containing 10.0 g of lithium bis(trifluoromethanesulfonyl)imide was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of Polyether Compound G' having 1-methylimidazolium halide groups obtained in Production Example 7' was dissolved in 50 ml of distilled water, and this solution was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown viscous oil-like substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The light brown viscous oil-like substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 11.1 g of a light brown viscous oil-like substance. The resulting pale brown viscous oily substance was subjected to 1H-NMR measurement and elemental analysis. The result identified it as imidazolium structure-containing polyether compound G" having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of polyether compound G' having 1-methylimidazolium halide groups obtained in Production Example 7', the starting material, and the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminals had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound G" had a number average molecular weight (Mn) of 48,300 and an average number of repeating units of 105-mer.

[0142] Production Example 8' (Quaternization of epichlorohydrin units in base polymer H with 1-methylimidazole) 8.0 g of base polymer H obtained in Production Example H, 22.0 g of 1-methylimidazole, and 16.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and the atmosphere was purged with argon, and the mixture was heated to 80°C. After reacting at 80°C for 144 hours, the mixture was cooled to room temperature to terminate the reaction. A portion of the resulting reaction solution was withdrawn and dried under reduced pressure at 50°C for 120 hours, yielding 14.7 g of a reddish-brown resinous substance. This resinous substance was subjected to 1H-NMR measurement and elemental analysis, and was identified as polyether compound H' having 1-methylimidazolium halide groups, in which the chloro groups in all of the epichlorohydrin units in base polymer H obtained in Production Example H, the starting material, had been substituted with 1-methylimidazolium chloride groups, and the bromo groups in all of the bromomethyl groups at the polymerization initiation terminals had been substituted with 1-methylimidazolium bromide groups. The number average molecular weight (Mn) of the resulting polyether compound H' was 104,000, and the average number of repeating units was 606-mer.

[0143] Production Example 8" (Anion Exchange of Polyether Compound H' Having 1-Methylimidazolium Halide Groups with Lithium Bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water containing 10.0 g of lithium bis(trifluoromethanesulfonyl)imide was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of Polyether Compound H' having 1-methylimidazolium halide groups obtained in Production Example 8' was dissolved in 50 ml of distilled water, and this solution was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown viscous oil-like substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The light brown viscous oil-like substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 11.2 g of a light brown viscous oil-like substance. The resulting pale brown viscous oily substance was subjected to 1H-NMR measurement and elemental analysis. The substance was identified as imidazolium structure-containing polyether compound H" having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of polyether compound H' having 1-methylimidazolium halide groups, obtained in Production Example 8', which was the starting material, and the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminals had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound H" had a number average molecular weight (Mn) of 240,000 and an average number of repeating units of 606-mer.

[0144] [Production Example 9'] (Quaternization of Base Polymer C with 1-normal butylimidazole) 5.0 g of base polymer C obtained in Production Example C, 13.4 g of 1-normal butylimidazole, and 10.0 g of acetonitrile were added to a glass reactor equipped with a stirrer and the atmosphere of the reactor was purged with argon, and the mixture was heated to 80°C. After reacting at 80°C for 144 hours, the mixture was cooled to room temperature to terminate the reaction. The resulting reaction product was washed with an equal mass mixed solution of toluene / methanol / water, and the organic phase containing 1-normal butylimidazole and toluene was removed. The aqueous phase was dried under reduced pressure at 50°C for 12 hours, yielding 11.7 g of a pale red solid. This solid was subjected to 1H-NMR measurement and elemental analysis, and was identified as polyether compound C'9 containing a 1-normal butylimidazolium structure having a halide ion as a counter anion, in which all of the chloro groups in the repeating units of the starting base polymer C had been substituted with 1-normal butylimidazolium chloride groups and all of the bromo groups in the bromomethyl groups at the polymerization initiation terminal had been substituted with 1-normal butylimidazolium bromide groups. The number average molecular weight (Mn) of the resulting polyether compound C'9 was 12,700, and the average number of repeating units was 58-mer.

[0145] [Production Example 9''] (Anion exchange of polyether compound C'9 with lithium bis(trifluoromethanesulfonyl)imide) 5.0 g of polyether compound C'9 obtained in Production Example 9', 10.0 g of lithium bis(trifluoromethanesulfonyl)imide, and 20 mL of ion-exchanged water were added to a glass reactor equipped with a stirrer. After reacting at room temperature for 30 minutes, the mixture was dried under reduced pressure at 50°C for 12 hours. The resulting solid-liquid mixture was washed with water to remove inorganic salts, and the liquid phase was extracted with acetone. The resulting toluene solution was dried under reduced pressure at 50°C for 12 hours, yielding 10.5 g of a viscous liquid substance. The resulting viscous liquid substance was subjected to 1H-NMR spectrum measurement and elemental analysis. The substance was identified as polyether compound C"9 having a 1-normal butylimidazolium structure and having a bis(trifluoromethanesulfonyl)imide anion as the counter anion, in which all of the chloride ions and bromide ions in the starting polyether compound C'9 had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound C"9 had a number average molecular weight (Mn) of 27,100 and an average number of repeating units of 58-mer.

[0146] [Production Example 10'] (Quaternization of Base Polymer D with 1-normal butylimidazole) 5.0 g of base polymer D obtained in Production Example D, 13.4 g of 1-normal butylimidazole, and 10.0 g of acetonitrile were added to a glass reactor equipped with a stirrer and purged with argon, and heated to 80°C. After reacting at 80°C for 144 hours, the reaction was stopped by cooling to room temperature. The resulting reaction product was washed with an equal mass mixed solution of toluene / methanol / water, and the organic phase containing 1-normal butylimidazole and toluene was removed. The aqueous phase was dried under reduced pressure at 50°C for 12 hours, yielding 11.7 g of a pale red solid. This solid was subjected to 1H-NMR measurement and elemental analysis, and was identified as 1-normal butylimidazolium structure-containing polyether compound D'10 having a halide ion as a counter anion, in which all of the chloro groups in the repeating units of the starting base polymer D had been substituted with 1-normal butylimidazolium chloride groups and all of the bromo groups in the bromomethyl groups at the polymerization initiation terminal had been substituted with 1-normal butylimidazolium bromide groups. The number-average molecular weight (Mn) of the resulting polyether compound D'10 was 25,100, and the average number of repeating units was 116-mer.

[0147] [Production Example 10″] (Anion Exchange of Polyether Compound D′10 with Lithium Bis(trifluoromethanesulfonyl)imide) 5.0 g of polyether compound D′10 obtained in Production Example 10′, 10.0 g of lithium bis(trifluoromethanesulfonyl)imide, and 20 mL of ion-exchanged water were added to a glass reactor equipped with a stirrer. After reacting at room temperature for 30 minutes, the mixture was dried under reduced pressure at 50°C for 12 hours. The resulting solid-liquid mixture was washed with water to remove inorganic salts, and the liquid phase was extracted with acetone. The resulting toluene solution was dried under reduced pressure at 50°C for 12 hours, yielding 10.5 g of a viscous liquid substance. The resulting viscous liquid substance was subjected to 1H-NMR spectrum measurement and elemental analysis. The substance was identified as 1-n-butylimidazolium structure-containing polyether compound D"10 having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions and bromide ions in the starting polyether compound D'10 had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound D"10 had a number average molecular weight (Mn) of 53,500 and an average number of repeating units of 116-mer.

[0148] [Production Example 11'] (Quaternization of Base Polymer A with n-butyldimethylamine) 5.0 g of base polymer A obtained in Production Example A, 16.4 g of n-butyldimethylamine, and 10.0 g of acetonitrile were added to a glass reactor equipped with a stirrer and purged with argon, and heated to 80°C. After reacting at 80°C for 144 hours, the reaction was stopped by cooling to room temperature. The resulting reaction product was washed with an equal mass mixed solution of toluene / methanol / water, after which the organic phase containing n-butyldimethylamine and toluene was removed, and the aqueous phase was dried under reduced pressure at 50°C for 12 hours, yielding 10.2 g of a pale red solid. This solid was subjected to 1H-NMR measurement and elemental analysis, and was identified as a polyether compound A'11 having a n-butyldimethylammonium structure and halide ions as counter anions, in which all of the chloro groups in the repeating units of the starting base polymer A had been substituted with n-butyldimethylammonium chloride groups and all of the bromo groups in the bromomethyl groups at the polymerization initiation terminal had been substituted with n-butyldimethylammonium bromide groups. The number-average molecular weight (Mn) of the resulting polyether compound A'11 was 2,120, and the average number of repeating units was 11-mer.

[0149] [Production Example 11″] (Anion Exchange of Polyether Compound A′11 with Lithium Bis(trifluoromethanesulfonyl)imide) 5.0 g of polyether compound A′11 obtained in Production Example 11′, 10.0 g of lithium bis(trifluoromethanesulfonyl)imide, and 20 mL of ion-exchanged water were added to a glass reactor equipped with a stirrer. After reacting at room temperature for 30 minutes, the mixture was dried under reduced pressure at 50°C for 12 hours. The resulting solid-liquid mixture was washed with water to remove inorganic salts, and the liquid phase was extracted with acetone. The resulting toluene solution was dried under reduced pressure at 50°C for 12 hours, yielding 10.5 g of a viscous liquid substance. The resulting viscous liquid substance was subjected to 1H-NMR spectroscopy and elemental analysis, and was identified as n-butyldimethylammonium structure-containing polyether compound A"11 having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions and bromide ions in the starting polyether compound A'11 had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound A"11 had a number-average molecular weight (Mn) of 4,820 and an average number of repeating units of 11.

[0150] [Production Example 12'] (Quaternization of Base Polymer C with n-butyldimethylamine) 5.0 g of base polymer C obtained in Production Example C, 16.4 g of n-butyldimethylamine, and 10.0 g of acetonitrile were added to a glass reactor equipped with a stirrer and purged with argon, and heated to 80°C. After reacting at 80°C for 144 hours, the reaction was stopped by cooling to room temperature. The resulting reaction product was washed with an equal mass mixed solution of toluene / methanol / water, after which the organic phase containing n-butyldimethylamine and toluene was removed, and the aqueous phase was dried under reduced pressure at 50°C for 12 hours, yielding 10.1 g of a pale red solid. This solid was subjected to 1H-NMR measurement and elemental analysis, and was identified as n-butyldimethylammonium structure-containing polyether compound C'12, in which all of the chloro groups in the repeating units of the starting base polymer C had been substituted with n-butyldimethylammonium chloride groups, and all of the bromo groups in the bromomethyl groups at the polymerization initiation terminal had been substituted with n-butyldimethylammonium bromide groups, and which had a halide ion as a counter anion. The resulting polyether compound C'12 had a number average molecular weight (Mn) of 11,200 and an average number of repeating units of 58-mer.

[0151] [Production Example 12''] (Anion Exchange of Polyether Compound C'12 with Lithium Bis(trifluoromethanesulfonyl)imide) 5.0 g of polyether compound C'12 obtained in Production Example 12', 10.0 g of lithium bis(trifluoromethanesulfonyl)imide, and 20 mL of ion-exchanged water were added to a glass reactor equipped with a stirrer. After reacting at room temperature for 30 minutes, the mixture was dried under reduced pressure at 50°C for 12 hours. The resulting solid-liquid mixture was washed with water to remove inorganic salts, and the liquid phase was extracted with acetone. The resulting toluene solution was dried under reduced pressure at 50°C for 12 hours, yielding 10.8 g of a viscous liquid substance. The resulting viscous liquid substance was subjected to 1H-NMR spectrum measurement and elemental analysis, and was identified as n-butyldimethylammonium structure-containing polyether compound C"12 having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions and bromide ions in the starting polyether compound C'12 had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound C"12 had a number average molecular weight (Mn) of 25,400 and an average number of repeating units of 58-mer.

[0152] [Production Example 13'] (Quaternization of Base Polymer D with n-butyldimethylamine) 5.0 g of base polymer D obtained in Production Example D, 16.4 g of n-butyldimethylamine, and 10.0 g of acetonitrile were added to a glass reactor equipped with a stirrer and purged with argon, and heated to 80°C. After reacting at 80°C for 144 hours, the reaction was stopped by cooling to room temperature. The resulting reaction product was washed with an equal mass mixed solution of toluene / methanol / water, after which the organic phase containing n-butyldimethylamine and toluene was removed, and the aqueous phase was dried under reduced pressure at 50°C for 12 hours, yielding 10.0 g of a pale red solid. This solid was subjected to 1H-NMR measurement and elemental analysis, and was identified as n-butyldimethylammonium structure-containing polyether compound D'13, in which all of the chloro groups in the repeating units of the starting base polymer D had been substituted with n-butyldimethylammonium chloride groups, and all of the bromo groups in the bromomethyl groups at the polymerization initiation terminal had been substituted with n-butyldimethylammonium bromide groups, and which had a halide ion as a counter anion. The resulting polyether compound D'13 had a number average molecular weight (Mn) of 22,500 and an average number of repeating units of 116.

[0153] [Production Example 13''] (Anion Exchange of Polyether Compound D'13 with Lithium Bis(trifluoromethanesulfonyl)imide) 5.0 g of polyether compound D'13 obtained in Production Example 13', 10.0 g of lithium bis(trifluoromethanesulfonyl)imide, and 20 mL of ion-exchanged water were added to a glass reactor equipped with a stirrer. After reacting at room temperature for 30 minutes, the mixture was dried under reduced pressure at 50°C for 12 hours. The resulting solid-liquid mixture was washed with water to remove inorganic salts, and the liquid phase was extracted with acetone. The resulting toluene solution was dried under reduced pressure at 50°C for 12 hours, yielding 10.7 g of a viscous liquid substance. The resulting viscous liquid substance was subjected to 1H-NMR spectrum measurement and elemental analysis. The substance was identified as n-butyldimethylammonium structure-containing polyether compound D"13 having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions and bromide ions in the starting polyether compound D'13 had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound D"13 had a number average molecular weight (Mn) of 50,800 and an average number of repeating units of 116.

[0154] [Production Example 14'] (Quaternization of Base Polymer F with n-butyldimethylamine) 5.0 g of base polymer F obtained in Production Example F, 32.8 g of n-butyldimethylamine, and 10.0 g of acetonitrile were added to a glass reactor equipped with a stirrer and purged with argon, and heated to 80°C. After reacting at 80°C for 144 hours, the reaction was stopped by cooling to room temperature. The resulting reaction product was washed with an equal mass mixed solution of toluene / methanol / water, after which the organic phase containing n-butyldimethylamine and toluene was removed, and the aqueous phase was dried under reduced pressure at 50°C for 12 hours, yielding 10.0 g of a pale red solid. This solid was subjected to 1H-NMR measurement and elemental analysis, and was identified as n-butyldimethylammonium structure-containing polyether compound F'14, in which all of the chloro groups in the repeating units of the starting base polymer F had been substituted with n-butyldimethylammonium chloride groups, and all of the bromo groups in the bromomethyl groups at the polymerization initiation terminal had been substituted with n-butyldimethylammonium bromide groups, and which had a halide ion as a counter anion. The resulting polyether compound F'14 had a number average molecular weight (Mn) of 68,000 and an average number of repeating units of 351-mer.

[0155] [Production Example 14''] (Anion Exchange of Polyether Compound F'14 with Lithium Bis(trifluoromethanesulfonyl)imide) 5.0 g of polyether compound F'14 obtained in Production Example 14', 10.0 g of lithium bis(trifluoromethanesulfonyl)imide, and 20 mL of ion-exchanged water were added to a glass reactor equipped with a stirrer. After reacting at room temperature for 30 minutes, the mixture was dried under reduced pressure at 50°C for 12 hours. The resulting solid-liquid mixture was washed with water to remove inorganic salts, and the liquid phase was extracted with acetone. The resulting toluene solution was dried under reduced pressure at 50°C for 12 hours, yielding 10.8 g of a viscous liquid substance. The resulting viscous liquid substance was subjected to 1H-NMR spectrum measurement and elemental analysis. The substance was identified as n-butyldimethylammonium structure-containing polyether compound F"14 having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions and bromide ions in the starting polyether compound F'14 had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound F"14 had a number average molecular weight (Mn) of 154,000 and an average number of repeating units of 351-mer.

[0156] [Production Example 15'] (Quaternization of Base Polymer B with 1-methylpyrrolidine) 4.0 g of Base Polymer B obtained in Production Example B, 11.4 g of 1-methylpyrrolidine, and 8.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and the atmosphere was purged with argon, and the mixture was heated to 80°C. After reacting at 80°C for 144 hours, the mixture was cooled to room temperature to terminate the reaction. The resulting reaction solution was dried under reduced pressure at 50°C for 120 hours, yielding 7.7 g of a light brown resinous substance. This resinous substance was subjected to 1H-NMR measurement and elemental analysis, and was identified as a 1-methylpyrrolidinium structure-containing polyether compound B'15 having a halide ion as a counter anion, in which the chloro groups in all of the epichlorohydrin units of the starting base polymer B had been substituted with 1-methylpyrrolidinium chloride groups, and the bromo groups in all of the bromomethyl groups at the polymerization initiation terminals had been substituted with 1-methylpyrrolidinium bromide groups. The resulting polyether compound B'15 had a number average molecular weight (Mn) of 4,090 and an average number of repeating units of 23.

[0157] [Production Example 15''] (Anion exchange of polyether compound B'15 with lithium bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water containing 26.0 g of lithium bis(trifluoromethanesulfonyl)imide was added to a glass reactor equipped with a stirrer. Separately, 7.7 g of polyether compound B'15 obtained in Production Example 15' was dissolved in 100 ml of distilled water, and this solution was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown rubber-like polyether compound was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The rubber-like substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 18.0 g of a light brown rubber-like substance. The resulting light brown rubber-like substance was subjected to 1H-NMR measurement and elemental analysis, and the substance was identified as a pyrrolidinium structure-containing polyether compound B"15 having a bis(trifluoromethanesulfonyl)imide anion as the counter anion, in which all of the chloride ions of the 1-methylpyrrolidinium chloride groups in the repeating units of polyether compound B'15 obtained in Production Example 15', the starting material, and the bromide ions of the 1-methylpyrrolidinium bromide groups at the polymerization initiation terminal, had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound B"15 had a number average molecular weight (Mn) of 9,710 and an average number of repeating units of 23-mer.

[0158] [Production Example 16'] (Quaternization of Base Polymer C with 1-methylpyrrolidine) 4.0 g of Base Polymer C obtained in Production Example C, 11.4 g of 1-methylpyrrolidine, and 8.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and the atmosphere of the reactor was purged with argon, and the mixture was heated to 80°C. After reacting at 80°C for 144 hours, the mixture was cooled to room temperature to terminate the reaction. The resulting reaction solution was dried under reduced pressure at 50°C for 120 hours, yielding 7.6 g of a light brown resinous substance. This resinous substance was subjected to 1H-NMR measurement and elemental analysis, and was identified as a 1-methylpyrrolidinium structure-containing polyether compound C'16 having a halide ion as a counter anion, in which the chloro groups in all of the epichlorohydrin units of the starting base polymer C had been substituted with 1-methylpyrrolidinium chloride groups, and the bromo groups in all of the bromomethyl groups at the polymerization initiation terminals had been substituted with 1-methylpyrrolidinium bromide groups. The resulting polyether compound C'16 had a number average molecular weight (Mn) of 10,300 and an average number of repeating units of 58-mer.

[0159] [Production Example 16''] (Anion exchange of polyether compound C'16 with lithium bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water containing 26.0 g of lithium bis(trifluoromethanesulfonyl)imide was added to a glass reactor equipped with a stirrer. Separately, 7.7 g of polyether compound C'16 obtained in Production Example 16' was dissolved in 100 ml of distilled water, and this was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown rubber-like substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The rubber-like substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 18.0 g of a light brown rubber-like substance. The resulting light brown rubber-like substance was subjected to 1H-NMR measurement and elemental analysis, and the substance was identified as a pyrrolidinium structure-containing polyether compound C"16 having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions of the 1-methylpyrrolidinium chloride groups in the repeating units of polyether compound C'16 obtained in Production Example 16', the starting material, and the bromide ions of the 1-methylpyrrolidinium bromide groups at the polymerization initiation terminals had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound C"16 had a number average molecular weight (Mn) of 24,500 and an average number of repeating units of 58-mer.

[0160] [Production Example 17'] (Quaternization of Base Polymer D with Pyridine) 4.0 g of base polymer D obtained in Production Example D, 13.6 g of pyridine, and 10.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and purged with argon, and heated to 80°C. After reacting at 80°C for 144 hours, the reaction was stopped by cooling to room temperature. The resulting reaction solution was dried under reduced pressure at 50°C for 120 hours, yielding 7.3 g of a light brown resinous substance. 1H-NMR measurement and elemental analysis of this resinous substance identified it as pyridinium structure-containing polyether compound D'17 having a halide ion as a counter anion, in which the chloro groups in all epichlorohydrin units of the starting base polymer D had been replaced with pyridinium chloride groups, and the bromo groups in all bromomethyl groups at the polymerization initiation terminals had been replaced with pyridinium bromide groups. The resulting polyether compound D'17 had a number average molecular weight (Mn) of 19,800 and an average number of repeating units of 116-mer.

[0161] [Production Example 17″] (Anion exchange of polyether compound D′17 with lithium bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water containing 16.8 g of lithium bis(trifluoromethanesulfonyl)imide was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of polyether compound D′17 obtained in Production Example 17′ was dissolved in 100 ml of distilled water, and this solution was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown rubber-like substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The rubber-like substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 12.1 g of a light brown rubber-like substance. The resulting light brown rubber-like substance was subjected to 1H-NMR measurement and elemental analysis, and the substance was identified as a pyridinium structure-containing polyether compound D"17 having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions of the pyridinium chloride groups in the repeating units of polyether compound D'17 obtained in Production Example 17', the starting material, and the bromide ions of the pyridinium bromide groups at the polymerization initiation terminal, had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound D"17 had a number average molecular weight (Mn) of 48,000 and an average number of repeating units of 116-mer.

[0162] [Production Example 18'] (Quaternization of Base Polymer A with Pyridine) 4.0 g of base polymer A obtained in Production Example A, 13.6 g of pyridine, and 10.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and purged with argon, and heated to 80°C. After reacting at 80°C for 144 hours, the reaction was stopped by cooling to room temperature. The resulting reaction solution was dried under reduced pressure at 50°C for 120 hours, yielding 7.3 g of a light brown resinous substance. 1H-NMR measurement and elemental analysis of this resinous substance identified it as pyridinium structure-containing polyether compound A'18 having a halide ion as a counter anion, in which the chloro groups in all epichlorohydrin units of the starting base polymer A had been replaced with pyridinium chloride groups, and the bromo groups in all bromomethyl groups at the polymerization initiation terminals had been replaced with pyridinium bromide groups. The resulting polyether compound A'18 had a number average molecular weight (Mn) of 1,950 and an average number of repeating units of 11-mer.

[0163] [Production Example 18''] (Anion exchange of polyether compound A'18 with lithium bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water containing 16.8 g of lithium bis(trifluoromethanesulfonyl)imide was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of polyether compound A'18 obtained in Production Example 18' was dissolved in 100 ml of distilled water, and this solution was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown rubber-like substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The rubber-like substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 12.1 g of a light brown rubber-like substance. The resulting light brown rubber-like substance was subjected to 1H-NMR measurement and elemental analysis, and it was identified as pyridinium structure-containing polyether compound A"18 having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions of the pyridinium chloride groups in the repeating units of polyether compound A'18 obtained in Production Example 18', the starting material, and the bromide ions of the pyridinium bromide groups at the polymerization initiation terminal, had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The number average molecular weight (Mn) of the resulting polyether compound A"18 was 4,730, and the average number of repeating units was 11-mer.

[0164] [Production Example 19'] (Partial quaternization of epichlorohydrin units in base polymer D with 1-methylimidazole) 10.0 g of base polymer D obtained in Production Example D, 1.34 g of 1-methylimidazole, and 16.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and purged with argon, and heated to 80°C. After reacting at 80°C for 144 hours, the reaction was stopped by cooling to room temperature, and the resulting reaction solution was dried under reduced pressure at 50°C for 120 hours, yielding 11.3 g of a reddish-brown resinous substance. Regarding this resinous substance, １H-NMR measurement and elemental analysis identified the compound as polyether compound D'19 having 86 mol% of 1-methylimidazolium halide groups and chloromethyl groups, in which the chloro groups in 14 mol% of the epichlorohydrin units in base polymer D obtained in Production Example D, a starting material, had been substituted with 1-methylimidazolium chloride groups, and the bromo groups in all of the bromomethyl groups at polymerization initiation terminals had been substituted with 1-methylimidazolium bromide groups. The number average molecular weight (Mn) of the resulting polyether compound D'19 was 12,100, and the average number of repeating units was 116-mer.

[0165] [Production Example 19''] (Anion Exchange of Polyether Compound D'19 Having 1-Methylimidazolium Halide Groups and Chloromethyl with Lithium Bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water containing 5.0 g of lithium bis(trifluoromethanesulfonyl)imide was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of Polyether Compound D'19 having 1-methylimidazolium halide groups and chloromethyl groups obtained in Production Example 17' was dissolved in 50 ml of distilled water, and this solution was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown viscous oil-like substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The light brown viscous oil-like substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 6.4 g of a light brown viscous oil-like substance. Regarding the obtained light brown viscous oily substance: １H-NMR measurement and elemental analysis revealed that the resulting polyether compound was an imidazolium structure-containing polyether compound D"19 having a bis(trifluoromethanesulfonyl)imide anion as a counter anion, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of the 1-methylimidazolium bromide groups obtained in Production Example 19', the starting material, had been exchanged for bis(trifluoromethanesulfonyl)imide anions, and all of the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminals had been exchanged for bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound D"19 had a number average molecular weight (Mn) of 16,000 and an average number of repeating units of 116.

[0166] Production Example 20' (Partial quaternization of epichlorohydrin units in base polymer D with 1-methylimidazole) 10.0 g of base polymer D obtained in Production Example D, 2.68 g of 1-methylimidazole, and 16.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and the atmosphere was purged with argon, and the mixture was heated to 80°C. After reacting at 80°C for 144 hours, the mixture was cooled to room temperature to terminate the reaction, and the resulting reaction solution was dried under reduced pressure at 50°C for 120 hours, yielding 13.3 g of a reddish-brown resinous substance. This resinous substance was subjected to 1H-NMR measurement and elemental analysis, and was identified as polyether compound D'20 having 71 mol% of 1-methylimidazolium halide groups and chloromethyl groups, in which the chloro groups in 29 mol% of the epichlorohydrin units in base polymer D obtained in Production Example D, the starting material, had been substituted with 1-methylimidazolium chloride groups, and the bromo groups of all bromomethyl groups at polymerization initiation terminals had been substituted with 1-methylimidazolium bromide groups. The number average molecular weight (Mn) of the resulting polyether compound D'20 was 13,500, and the average number of repeating units was 116-mer.

[0167] [Production Example 20''] (Anion Exchange of Polyether Compound D'20 Having 1-Methylimidazolium Halide Groups and Chloromethyl Groups with Lithium Bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water containing 5.0 g of lithium bis(trifluoromethanesulfonyl)imide was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of Polyether Compound D'20 having 1-methylimidazolium halide groups and chloromethyl groups obtained in Production Example 20' was dissolved in 50 ml of distilled water, and this solution was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown viscous oil-like substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The light brown viscous oil-like substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 8.0 g of a light brown viscous oil-like substance. The resulting pale brown viscous oily substance was subjected to 1H-NMR measurement and elemental analysis. The substance was identified as imidazolium structure-containing polyether compound D"20 having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of polyether compound D'20 having 1-methylimidazolium halide groups obtained in Production Example 20', the starting material, and the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminals had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound D"20 had a number average molecular weight (Mn) of 21,700 and an average number of repeating units of 116-mer.

[0168] Production Example 21' (Partial quaternization of base polymer I by quaternization of epichlorohydrin units in base polymer I with 1-methylimidazole) 10.0 g of base polymer I obtained in Production Example I, 1.34 g of 1-methylimidazole, and 16.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and purged with argon, and heated to 80°C. After reacting at 80°C for 144 hours, the mixture was cooled to room temperature to terminate the reaction, and the resulting reaction solution was dried under reduced pressure at 50°C for 120 hours, yielding 11.4 g of a reddish-brown resinous substance. This resinous substance was subjected to 1H-NMR measurement and elemental analysis, and was identified as polyether compound I'21 having 1-methylimidazolium halide groups and 89 mol % of methyl groups derived from propylene oxide units, in which the chloro groups in 11 mol % of the epichlorohydrin units in base polymer I obtained in Production Example I, the starting material, had been substituted with 1-methylimidazolium chloride groups and the bromo groups in all of the bromomethyl groups at the polymerization initiation terminals had been substituted with 1-methylimidazolium bromide groups. The number average molecular weight (Mn) of the resulting polyether compound I'21 was 12,100, and the average number of repeating units was 171-mer.

[0169] Production Example 21" (Anion Exchange of Polyether Compound I'21 Having 1-Methylimidazolium Halide Groups and Methyl Groups Derived from Propylene Oxide Units with Lithium Bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water containing 5.0 g of lithium bis(trifluoromethanesulfonyl)imide was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of polyether compound I'21 having 1-methylimidazolium halide groups and methyl groups derived from propylene oxide units obtained in Production Example 21' was dissolved in 50 ml of distilled water, and this solution was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown viscous oily substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water, and inorganic salts were removed by polymer coagulation. The light brown viscous oily substance obtained by solidification was dried under reduced pressure at 50°C for 12 hours, yielding 6.4 g of a light brown viscous oily substance. H-NMR measurement and elemental analysis of the resulting light brown viscous oily substance revealed that the starting material, polyether compound I'21 having 1-methylimidazolium halide groups and methyl groups derived from propylene oxide units, obtained in Production Example 21', had all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units and the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminal exchanged with bis(trifluoromethanesulfonyl)imide anions; this was imidazolium structure-containing polyether compound I''21 having bis(trifluoromethanesulfonyl)imide anions as counter anions. The resulting polyether compound I''21 had a number average molecular weight (Mn) of 16,000 and an average number of repeating units of 171.

[0170] Production Example 22' (Partial quaternization of base polymer J by quaternization of epichlorohydrin units in base polymer J with 1-methylimidazole) 10.0 g of base polymer J obtained in Production Example J, 1.34 g of 1-methylimidazole, and 16.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and the atmosphere was purged with argon, and the mixture was heated to 80°C. After reacting at 80°C for 144 hours, the mixture was cooled to room temperature to terminate the reaction, and the resulting reaction solution was dried under reduced pressure at 50°C for 120 hours, yielding 12.0 g of a reddish-brown resinous substance. This resinous substance was subjected to 1H-NMR measurement and elemental analysis, and was identified as polyether compound J'22 having 1-methylimidazolium halide groups partially in the ethylene oxide chain, in which the chloro groups in 12 mol % of the epichlorohydrin units in base polymer J obtained in Production Example I, the starting material, had been substituted with 1-methylimidazolium chloride groups, and the bromo groups in all of the bromomethyl groups at the polymerization initiation terminals had been substituted with 1-methylimidazolium bromide groups. The number average molecular weight (Mn) of the resulting polyether compound J'22 was 18,100, and the average number of repeating units was 303-mer.

[0171] Production Example 22" (Anion Exchange of Polyether Compound J'22 Having 1-methylimidazolium Halide Groups Partially in the Ethylene Oxide Chain with Lithium Bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water containing 5.0 g of lithium bis(trifluoromethanesulfonyl)imide was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of Polyether Compound J'22 having 1-methylimidazolium halide groups partially in the ethylene oxide chain, obtained in Production Example 22', was dissolved in 50 ml of distilled water, and this solution was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown viscous oil-like substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The light brown viscous oil-like substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 7.4 g of a light brown viscous oil-like substance. The resulting pale brown viscous oily substance was subjected to 1H-NMR measurement and elemental analysis. The substance was identified as imidazolium structure-containing polyether compound J"22, which had bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of polyether compound J'22 having 1-methylimidazolium halide groups partially in the ethylene oxide chain obtained in Production Example 22' had been exchanged for bis(trifluoromethanesulfonyl)imide anions and all of the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminal had been exchanged for bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound J"22 had a number average molecular weight (Mn) of 26,200 and an average number of repeating units of 303-mer.

[0172] [Production Example 23''] (Anion exchange of polyether compound A' having 1-methylimidazolium halide groups with lithium tetrafluoroborate) 100 ml of distilled water in which 4.0 g of lithium tetrafluoroborate had been dissolved was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of polyether compound A' having 1-methylimidazolium halide groups obtained in Production Example 1' was dissolved in 50 ml of distilled water, and this was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown viscous oil-like substance was recovered and dissolved in acetonitrile. The acetonitrile solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The light brown viscous oil-like substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 6.4 g of a light brown resinous substance. The resulting light brown viscous oily substance was subjected to 1H-NMR measurement and elemental analysis, and was identified as imidazolium structure-containing polyether compound A"23 having tetrafluoroborate anions as counter anions, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of polyether compound A' having 1-methylimidazolium halide groups obtained in Production Example 1', the starting material, and the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminals had been exchanged with tetrafluoroborate anions. The resulting polyether compound A"23 had a number average molecular weight (Mn) of 2,490 and an average number of repeating units of an 11-mer.

[0173] Production Example 24" (Anion Exchange of Polyether Compound C' Having 1-Methylimidazolium Halide Groups with Lithium Tetrafluoroborate) 100 ml of distilled water containing 4.0 g of lithium tetrafluoroborate was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of Polyether Compound C' having 1-methylimidazolium halide groups obtained in Production Example 3' was dissolved in 50 ml of distilled water, and this was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown viscous oil-like substance was recovered and dissolved in acetonitrile. The acetonitrile solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The light brown viscous oil-like substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 6.4 g of a light brown resinous substance. The resulting light brown viscous oily substance was subjected to 1H-NMR measurement and elemental analysis, and was identified as imidazolium structure-containing polyether compound C"24 having tetrafluoroborate anions as counter anions, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of polyether compound C' having 1-methylimidazolium halide groups obtained in Production Example 3', the starting material, and the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminal, had been exchanged with tetrafluoroborate anions. The resulting polyether compound C"24 had a number average molecular weight (Mn) of 13,100 and an average number of repeating units of 58-mer.

[0174] [Production Example 25''] (Anion exchange of polyether compound B' having 1-methylimidazolium halide groups with silver acetate) 600 ml of distilled water in which 4.8 g of silver acetate had been dissolved was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of polyether compound B' having 1-methylimidazolium halide groups obtained in Production Example 2' was dissolved in 50 ml of distilled water, and this was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated silver chloride was removed by centrifugation and filtration, and the water was distilled off. The mixture was further dried under reduced pressure at 50°C for 12 hours, yielding 5.6 g of a light brown resinous substance. The resulting light brown resinous substance was subjected to 1H-NMR measurement and elemental analysis, and the substance was identified as imidazolium structure-containing polyether compound B"25 having acetate anions as counter anions, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of polyether compound B' having 1-methylimidazolium halide groups obtained in Production Example 2', the starting material, and the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminals had been exchanged with acetate anions. The resulting polyether compound B"25 had a number average molecular weight (Mn) of 4,480 and an average number of repeating units of 23-mer.

[0175] [Production Example 26''] (Anion exchange of polyether compound C' having 1-methylimidazolium halide groups with silver acetate) 600 ml of distilled water in which 4.8 g of silver acetate had been dissolved was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of polyether compound C' having 1-methylimidazolium halide groups obtained in Production Example 3' was dissolved in 50 ml of distilled water, and this was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated silver chloride was removed by centrifugation and filtration, and the water was distilled off. The mixture was further dried under reduced pressure at 50°C for 12 hours, yielding 5.6 g of a light brown resinous substance. The resulting light brown resinous substance was subjected to 1H-NMR measurement and elemental analysis, and the substance was identified as imidazolium structure-containing polyether compound C"26 having acetate anions as counter anions, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of polyether compound C' having 1-methylimidazolium halide groups obtained in Production Example 3', the starting material, and the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminals had been exchanged with acetate anions. The resulting polyether compound C"26 had a number average molecular weight (Mn) of 11,500 and an average number of repeating units of 58-mer.

[0176] [Production Example 27'] (Quaternization of Base Polymer H with Pyridine) 4.0 g of base polymer H obtained in Production Example H, 13.6 g of pyridine, and 10.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and purged with argon, and heated to 80°C. After reacting at 80°C for 144 hours, the reaction was stopped by cooling to room temperature. The resulting reaction solution was dried under reduced pressure at 50°C for 120 hours, yielding 7.3 g of a light brown resinous substance. 1H-NMR measurement and elemental analysis of this resinous substance identified it as pyridinium structure-containing polyether compound H'27 having a halide ion as a counter anion, in which the chloro groups in all epichlorohydrin units of the starting base polymer H had been replaced with pyridinium chloride groups, and the bromo groups in all bromomethyl groups at the polymerization initiation terminals had been replaced with pyridinium bromide groups. The resulting polyether compound H'27 had a number average molecular weight (Mn) of 105,700 and an average number of repeating units of 606-mer.

[0177] [Production Example 27″] (Anion exchange of pyridinium structure-containing polyether compound H′27 with silver acetate) 600 ml of distilled water containing 4.9 g of silver acetate was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of pyridinium structure-containing polyether compound H′22,1 obtained in Production Example 27′ was dissolved in 50 ml of distilled water, and this solution was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated silver chloride was removed by centrifugation and filtration, and the water was distilled off. The mixture was further dried under reduced pressure at 50°C for 12 hours, yielding 5.7 g of a light brown resinous substance. The resulting light brown resinous substance was subjected to 1H-NMR measurement and elemental analysis, and was identified as pyridinium structure-containing polyether compound H"27 having acetate anions as counter anions, in which all of the chloride ions of the pyridinium groups in the repeating units of pyridinium structure-containing polyether compound H'27 obtained in Production Example 27', the starting material, and the bromide ions of the pyridinium bromide groups at the polymerization initiation terminal had been exchanged for acetate anions. The resulting polyether compound H"27 had a number average molecular weight (Mn) of 120,000 and an average number of repeating units of 606-mer.

[0178] Production Example 28' (Partial quaternization of epichlorohydrin units in base polymer F with 1-methylimidazole) 10.0 g of base polymer F obtained in Production Example 6, 2.68 g of 1-methylimidazole, and 16.0 g of N,N-dimethylformamide were added to a glass reactor equipped with a stirrer and the atmosphere was purged with argon, and the mixture was heated to 80°C. After reacting at 80°C for 144 hours, the mixture was cooled to room temperature to terminate the reaction, and the resulting reaction solution was dried under reduced pressure at 50°C for 120 hours, yielding 13.3 g of a reddish-brown resinous substance. This resinous substance was subjected to 1H-NMR measurement and elemental analysis, and was identified as polyether compound F'28 having 1-methylimidazolium halide groups and 72 mol% chloromethyl groups, in which the chloro groups in 28 mol% of the epichlorohydrin units in base polymer F obtained in Starting Material Production Example 6 had been substituted with 1-methylimidazolium chloride groups, and the bromo groups of all bromomethyl groups at polymerization initiation terminals had been substituted with 1-methylimidazolium bromide groups. The number average molecular weight (Mn) of the resulting polyether compound F'28 was 41,300, and the average number of repeating units was 351-mer.

[0179] [Production Example 28''] (Anion Exchange of Polyether Compound F'28 Having 1-Methylimidazolium Halide Groups and Chloromethyl with Lithium Bis(trifluoromethanesulfonyl)imide) 300 ml of distilled water containing 5.0 g of lithium bis(trifluoromethanesulfonyl)imide was added to a glass reactor equipped with a stirrer. Separately, 5.0 g of Polyether Compound F'28 having 1-methylimidazolium halide groups and chloromethyl groups obtained in Production Example 28' was dissolved in 50 ml of distilled water, and this solution was added dropwise to the glass reactor and reacted at room temperature for 30 minutes. After the reaction, the precipitated light brown viscous oil-like substance was recovered and dissolved in acetone. The acetone solution was then added dropwise to 300 ml of distilled water to remove inorganic salts by polymer coagulation. The light brown viscous oil-like substance obtained by coagulation was dried under reduced pressure at 50°C for 12 hours, yielding 8.0 g of a light brown viscous oil-like substance. The resulting pale brown viscous oily substance was subjected to 1H-NMR measurement and elemental analysis. The substance was identified as imidazolium structure-containing polyether compound F"28 having bis(trifluoromethanesulfonyl)imide anions as counter anions, in which all of the chloride ions of the 1-methylimidazolium chloride groups in the repeating units of polyether compound F'28 having 1-methylimidazolium halide groups, obtained in Production Example 28', and the bromide ions of the 1-methylimidazolium bromide groups at the polymerization initiation terminals had been exchanged with bis(trifluoromethanesulfonyl)imide anions. The resulting polyether compound F"28 had a number average molecular weight (Mn) of 67,000 and an average number of repeating units of 351-mer.

[0180] [Examples 1 to 19 and Comparative Examples 1 to 7] According to the methods for producing polyether compounds shown in Tables 1 and 2, the type of base polymer and the type of onium-forming agent were selected, and the base polymer was quaternized and then subjected to anion exchange to obtain polyether compounds as carbon dioxide absorbents. Using the obtained carbon dioxide absorbents (polyether compounds), the amount of carbon dioxide absorbed was measured and Test 1 for carbon dioxide absorbent detachment from porous membrane was carried out. The results are shown in Tables 1 and 2.

[0181] [Examples 20 to 30 and Comparative Examples 8 to 11] According to the method for producing a polyether compound shown in Table 3, the type of base polymer and the type of onium-containing agent were selected, and the base polymer was quaternized and then subjected to anion exchange to obtain a polyether compound. The obtained polyether compound, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMImTFSI, viscosity at 25°C: 51 mPa s, molecular weight: 419.36), 1-ethyl-1-methylpyrrolidinium tetrafluoroborate (EMPyBF4, melting point: 294°C, molecular weight: 201.01), N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (N221EtOMeTFSI, melting point: -91°C, specific gravity (density): 1.42 g / cm ３ (25°C, molecular weight 426.397), methyl ethyl ketone, tetraethylene glycol dimethyl ether, and tetraethylene glycol were mixed in the blending ratios shown in Table 3 to obtain a composition as a carbon dioxide absorbent. Using the obtained carbon dioxide absorbent (composition), the amount of carbon dioxide absorbed was measured, and test 2 for carbon dioxide absorbent detachment from porous membrane was performed. The results are shown in Table 3.

[0182] In Tables 1 to 3, the abbreviations for the types of onium-forming agents, the types of counter anions, and the materials blended in the compositions are as follows: MeIm: 1-methylimidazole BuIm: 1-normal butylimidazole nBuMe2N: normal butyldimethylamine Pyridine: pyridine Me-py: 1-methylpyrrolidine TFSI: bis(trifluoromethanesulfonyl)imide anion BF4: tetrafluoroborate anion acetate: acetic acid anion BMImTFSI: 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide N221EtOMeTFSI: N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide EMPyBF4: 1-ethyl-1-methylpyrrolidinium tetrafluoroborate

[0183]

[0184]

[0185] As shown in Tables 1 and 2, carbon dioxide absorbents composed of polyether compounds containing specific repeating units represented by general formula (1) in an average number of 50 or more per molecule and containing a repeating unit containing a nitrogen-containing cationic group represented by general formula (2) had excellent carbon dioxide absorbency and were inhibited from falling off from the porous membrane when held in the porous membrane (Examples 1 to 19).

[0186] On the other hand, carbon dioxide absorbents made of polyether compounds containing an average of less than 50 specific repeating units represented by general formula (1) per molecule were inferior in carbon dioxide absorption ability and were prone to falling off from the porous membrane when held in the porous membrane (Comparative Examples 1 to 7).

[0187]

[0188] As shown in Table 3, carbon dioxide absorbents containing polyether compounds containing specific repeating units represented by general formula (1) in an average number of 50 or more per molecule and repeating units containing a nitrogen-containing cationic group represented by general formula (2) were excellent in carbon dioxide absorption properties and were inhibited from falling off from the porous membrane when held in the porous membrane (Examples 20 to 30).

[0189] On the other hand, carbon dioxide absorbents containing polyether compounds containing less than 50 specific repeating units represented by general formula (1) as an average number per molecule were inferior in carbon dioxide absorption, and when retained in a porous membrane, were prone to falling off from the porous membrane (Comparative Examples 8 to 11).

Claims

1. A carbon dioxide absorbent containing a polyether compound, The polyether compound contains 50 or more repeating units represented by the following general formula (1) on average per molecule, A carbon dioxide absorbent, characterized in that the polyether compound contains a repeating unit represented by the following general formula (2) as at least a part of the repeating units represented by the general formula (1): 【Chemistry 12】 (In general formula (1), A represents a monovalent group.) 【Chemistry 13】 (In the general formula (2), A' ＋ In addition, in the general formula (2), X represents a nitrogen-containing cationic group. － represents an anion.)

2. The repeating unit represented by the general formula (2) is a repeating unit represented by the following general formula (3-1), a repeating unit represented by the following general formula (3-2), or a repeating unit represented by the following general formula (4): The carbon dioxide absorbent according to claim 1. 【Chemistry 14】 (In the general formula (3-1), R １ ~R ４ each independently represents a hydrogen atom or a substituent; R ２ and R ３ may be bonded to each other. － represents an anion.) 【Chemistry 15】 (In the general formula (3-2), R １１ ~R １５ each independently represents a hydrogen atom or a substituent; R １１ ~R １５ In addition, in the general formula (3-2), two of X － represents an anion.) 【Chemistry 16】 (In the general formula (4), R ５ ~R ７ each independently represents a hydrogen atom or a substituent; R ６ and R ７ may be bonded to each other. － represents an anion.)

3. 3. The carbon dioxide absorbent according to claim 1, wherein the polyether compound contains 101 or more repeating units represented by general formula (1) on average per molecule.

4. The carbon dioxide absorbent according to claim 1 or 2, wherein the proportion of the repeating unit represented by the general formula (1) in the polyether compound is 90 to 100 mol % with respect to all repeating units of the polyether compound.

5. The carbon dioxide absorbent according to claim 1 or 2, wherein the proportion of the repeating units represented by the general formula (2) in the polyether compound is 5 to 100 mol % with respect to all repeating units represented by the general formula (1).

6. The carbon dioxide absorbent according to claim 1 or 2, further comprising an ionic liquid or an oxygen-containing polar organic solvent.

7. In the general formula (2), X － each independently represents a halide ion, a sulfonylimide ion, a carboxylate ion, a sulfonate ion, an OH － , B.F. ４ － , P.F. ６ － , ClO ４ － , B (CN) ４ － , S.C.N. － , (NC) ２ N － 3. The carbon dioxide absorbent according to claim 1 or 2, wherein the anion is selected from the group consisting of:

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