JP5867699B2 - Ionic conductor - Google Patents

Description

  The present invention relates to an ionic conductor. Moreover, this invention relates to the polymeric compound useful for manufacture of an ion conductor, and the manufacturing method of an ion conductor using the same.

  In order to move ions over a long distance in a polymer constituting an ionic conductor, in addition to local movement of ions in cooperation with local movement of polymer chains, polymer ligands solvated with ions (for example, Exchange of an ion conductive group represented by a polymer represented by a carboxyl group) and a polymer ligand not solvated with the ion is an essential process (Patent Document 1).

JP 2011-38089 A

  There is a demand for further improvement in the lifetime of ion conductors used in the battery field. Although the ionic conductor disclosed in Patent Document 1 can exhibit good ionic conductivity, the degradation reaction gradually proceeds over a long period of use, and the ethylene glycol chain contributing to ionic conductivity is dropped from the polymer. As a result, there is a problem that ion conductivity is lowered.

  Accordingly, an object of the present invention is to provide a novel ionic conductor that is excellent in ionic conductivity and is expected to have a longer lifetime. Moreover, an object of this invention is to provide the polymeric compound useful for manufacture of the said ion conductor, and the manufacturing method of an ion conductor using the same.

The present invention firstly
An ionic conductor comprising a polymer containing a repeating unit having a cyclic organic group,
The repeating unit further has a monovalent ion conductive group represented by the following formula (1):
The ion conductive group is bonded to each of three or more consecutive atoms among the atoms constituting the ring of the cyclic organic group, and the plurality of ion conductive groups may be the same or different. An ionic conductor is provided.

[Where:
k represents an integer of 0 to 50;
R ¹ represents a divalent hydrocarbon group,
Z represents a divalent organic group containing an atom having an unshared electron pair,
Q is the following formula (Q-1), (Q-2), (Q-3), (Q-4), (Q-5), (Q-6), (Q-7), (Q-8) ), (Q-9), (Q-10), (Q-11), (Q-12), (Q-13), (Q-14), (Q-15), (Q-16), A polar group represented by (Q-17), (Q-18), (Q-19), (Q-20), (Q-21), (Q-22) or (Q-23);
A plurality of Z may be the same as or different from each other. ]

[Where:
R ¹⁰ , R ²⁰ , R ²¹ , R ³⁰ , R ⁴⁰ , R ⁴¹ , R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁶⁰ , R ⁷⁰ , R ⁷¹ , R ⁸⁰ , R ¹¹⁰ and R ¹²⁰ are respectively A hydrogen atom, a monovalent hydrocarbon group which may have a substituent, or a metal atom is shown.
X represents an atom having an unshared electron pair. ]

The present invention secondly provides a polymerizable compound represented by the following formula (4), wherein R ¹ is bonded to three or more consecutive atoms among atoms constituting the A ring one by one.

[Where:
U ¹ represents a polymerizable group, A ring represents a cyclic organic group,
k represents an integer of 0 to 50;
R ¹ represents a divalent hydrocarbon group,
Z represents a divalent organic group containing an atom having an unshared electron pair,
Q is the following formula (Q-1), (Q-2), (Q-3), (Q-4), (Q-5), (Q-6), (Q-7), (Q-8) ), (Q-9), (Q-10), (Q-11), (Q-12), (Q-13), (Q-14), (Q-15), (Q-16), A polar group represented by (Q-17), (Q-18), (Q-19), (Q-20), (Q-21), (Q-22) or (Q-23);
n k, R ¹ , Z and Q may be the same as or different from each other;
n represents an integer of 3 or more,
X ¹ represents a divalent hydrocarbon group which may have a substituent, and Y ¹ represents a single bond or a divalent organic group. ]

[Where:
R ¹⁰ , R ²⁰ , R ²¹ , R ³⁰ , R ⁴⁰ , R ⁴¹ , R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁶⁰ , R ⁷⁰ , R ⁷¹ , R ⁸⁰ , R ¹¹⁰ and R ¹²⁰ are respectively A hydrogen atom, a monovalent hydrocarbon group which may have a substituent, or a metal atom is shown.
X represents an atom having an unshared electron pair. ]

Third, the present invention is a method for producing an ion conductor,
Comprising polymerizing one or more polymerizable compounds by living anionic polymerization to produce an ionic conductor composed of a polymer containing a repeating unit represented by the following formula (2);
At least one of the polymerizable compounds is the polymerizable compound of the present invention.
A method for producing an ionic conductor is provided.

[In the formulas, A ^{ring, k, R 1, Z,} Q, n, X 1 and ^{Y 1,} A ring in the formula (4) ^{in, k, R 1, Z,} Q, n, X 1 and Y ¹ represents the same meaning as ^1, and W ¹ represents a trivalent hydrocarbon group. ]

  ADVANTAGE OF THE INVENTION According to this invention, the ion conductor excellent in ionic conductivity can be provided. Moreover, according to this invention, the polymeric compound useful for manufacture of the polymer which comprises an ion conductor, and the manufacturing method of an ion conductor using the same can be provided. Since the ionic conductor of the present invention is not easily decomposed into components contained in the electrolytic solution, particularly alkaline components, it is possible to maintain high ionic conductivity for a long period of time.

It is the schematic which shows one Embodiment of a lithium ion battery. 2 is a ¹ H-NMR chart of the compound obtained in Example 2. FIG. 2 is a ¹ H-NMR chart of a block copolymer (PS ₇₄ -b-PPTEG ₄ ) obtained in Example 4. FIG. It is an AFM (atomic force microscope) photograph of the ion conductive film in Examples 5-7.

  Hereinafter, the present invention will be described in detail.

  In the present specification, the term “aromatic group” means an atomic group excluding one or more hydrogen atoms bonded to an aromatic hydrocarbon ring, or one or more hydrogen atoms bonded to a ring of a heterocyclic compound. It means an atomic group removed, or an atomic group remaining after removing one or more hydrogen atoms bonded to a ring in a compound in which two or more compounds selected from aromatic hydrocarbons and heterocyclic compounds are directly bonded. .

  The present invention relates to an ionic conductor comprising a polymer containing a repeating unit having a cyclic organic group. The repeating unit further has a monovalent ion conductive group represented by the formula (1), and the ion conductive group is a continuous three of the atoms constituting the ring of the cyclic organic group. One atom is bonded to each of the above atoms, and a plurality of the ion conductive groups may be the same or different.

R ¹ in the formula (1) is a divalent hydrocarbon group such as methane, ethane, propane, butane, octane, decane, icosane, triacontane, pentacontan, cycloheptane, and cyclohexane. An alkylene group formed by removing two hydrogen atoms from a saturated hydrocarbon molecule having 1 to 50 carbon atoms, and 6 to 50 carbon atoms such as benzene, naphthalene, anthracene, tetracene, biphenyl, acenaphthylene, phenalene, and pyrene. And an arylene group formed by removing two hydrogen atoms from the aromatic hydrocarbon molecule. From the viewpoint of ion conductivity, R ¹ preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. Among these, as R ¹ , a methylene group and an ethylene group are particularly preferable.

In the formulas (Q-1) to (Q-23) as Q in the formula (1), R ¹⁰ , R ²⁰ , R ²¹ , R ³⁰ , R ⁴⁰ , R ⁴¹ , R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁶⁰ , R ⁷⁰ , R ⁷¹ , R ⁸⁰ , R ¹¹⁰ and R ¹²⁰ each independently represent a hydrogen atom, a monovalent hydrocarbon group or a metal atom which may have a substituent. X represents an atom having an unshared electron pair, for example, an oxygen atom.

Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, an icosyl group, a triacontyl group, a pentacontyl group, a cycloheptyl group, and C1-C50 linear, branched or cyclic alkyl groups such as cyclohexyl groups; benzyl groups, naphthyl groups, anthracenyl groups, tetracenyl groups, biphenyl groups, acenaphthylenyl groups, phenalenyl groups, pyrenyl groups, pyridinyl groups, etc. Aryl group; and the like. As the monovalent hydrocarbon group having a substituent, for example, — (CH ₂ CH ₂ O) _h R ¹³⁰ (where h is an integer of 1 to 80, R ¹³⁰ is a hydrogen atom or a monovalent hydrocarbon group). And — (CH ₂ CH (CH ₃ ) O) _i R ¹³¹ (i is an integer of 1 to 80, R ¹³¹ represents a hydrogen atom or a monovalent hydrocarbon group). Can be mentioned. Examples of the substituent that the monovalent hydrocarbon group may have include a cyano group, — (Si (R ¹⁴⁰ ) ₂ O) _j —R ¹⁴¹ (j is an integer of 1 to 80, and R ¹⁴⁰ is a monovalent hydrocarbon group. , R ¹⁴¹ represents a hydrogen atom or a monovalent hydrocarbon group.), — (OCH ₂ CH ₂ ) _h R ¹³⁰ , and — (OCH ₂ CH (CH ₃ )) _i R ^{131 and the} like.

  Examples of the metal atom include lithium, sodium, potassium, rubidium, cesium and the like. The metal atom is preferably lithium, sodium, or potassium, more preferably lithium or sodium, from the viewpoint of the energy density of the battery and the availability. These metal atoms may be ionically dissociated as metal cations.

R ¹⁰ , R ²⁰ , R ²¹ , R ³⁰ , R ⁴⁰ , R ⁴¹ , R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁶⁰ , R ⁷⁰ in the formulas (Q-1) to (Q-23) R ⁷¹ , R ⁸⁰ , R ¹¹⁰ and R ¹²⁰ are preferably changed as appropriate according to the use of the ion conductor, the type of ions to be conducted, and the like. If conducts protons by an ion conductor, when the hydrogen atoms preferably conducts metal ^{_{ions, - (CH 2 CH 2 O}} ) h R 130, - (CH 2 CH (CH 3) O) i R 131 and conduction A metal atom of the same element as the metal ion to be used is preferable.

  Since Q in the formula (1) is easier to synthesize the polymer according to the ionic conductor of the present invention, the formula (Q-1), (Q-2), (Q-3), (Q -4), (Q-5), (Q-12), (Q-13), (Q-14), (Q-15), (Q-16) or (Q-23) Preferably, it is represented by the formula (Q-1), (Q-2), (Q-3), (Q-12), (Q-13), (Q-14) or (Q-23). More preferably, it is a group.

  In the formula (1), k represents an integer of 0 to 50, and the ionic conductivity is higher, so that it is preferably 1 to 40, and more preferably 2 to 20.

  Z in the formula (1) is preferably a divalent organic group represented by a formula selected from the group consisting of the following formulas (Z-1) to (Z-8). Among these, a group represented by (Z-1), (Z-2), (Z-3), (Z-4) or (Z-5) is more preferred, and a group represented by (Z-3) is more preferred. Further preferred. When Z is any of these organic groups, the content of oxygen atoms capable of coordinating with the cation is increased, so that more excellent ion conductivity characteristics as an ion conductor can be obtained.

The polymer according to the ionic conductor of the present invention is a polymer containing a repeating unit having a cyclic organic group (hereinafter referred to as cyclic organic group A). This repeating unit is represented by the formula (1) 1
As described above, the ion conductive group is bonded to three or more consecutive atoms constituting the ring of the cyclic organic group A.

  The cyclic organic group A is, for example, selected from cyclobutane, cyclopentane, cyclohexane, pyrrolidine, piperidine, cycloheptane, benzene, naphthalene, anthracene, tetracene, biphenyl, acenaphthylene, phenalene, pyrene, furan, thiophene, pyrrole, and pyridine. It is a group formed by removing 4 or more hydrogen atoms from a cyclic compound, and is preferably an aromatic group from the viewpoint of easy synthesis by utilizing various substitution reactions on the aromatic ring. Among these, the cyclic organic group A is preferably a group formed by removing 4 or more hydrogen atoms from benzene, pyridine, biphenyl or acenaphthylene, more preferably 4 or more hydrogen atoms from benzene or pyridine. And is particularly preferably a group formed by removing 4 or more hydrogen atoms from benzene.

For example, when the cyclic organic group A is a group formed by removing four hydrogen atoms from benzene, the ionic conductivity of the formula (1) at least at the 1-position, 2-position and 3-position of the benzene ring, respectively. A group is attached. At this time, a linking group X ¹ described later may be bonded to any of the 4-position, 5-position and 6-position of the benzene ring.

  By the ion conductive group represented by the formula (1), a function of ion conduction is imparted to the polymer. By closely arranging these groups adjacent to each other, the ion conduction characteristics of the ion conductor of the present invention can be made better. The ion conductive group represented by the formula (1) is a continuous 3 to 3 atoms among the atoms constituting the ring of the cyclic organic group A from the viewpoints of both the ion conductive properties and the synthesis of the ion conductor of the present invention. It is preferably bonded to 20 atoms one by one, more preferably bonded to 4 to 8 consecutive atoms one by one, 4 or 5 consecutive, particularly preferably 5 consecutive It is particularly preferable to bond one atom at a time.

  The repeating unit having a cyclic organic group is preferably a group represented by the following formula (2) because ion conductivity can be further improved.

In the formula (2), A ring indicates the cyclic organic group A, ^{k, R} 1, Z and Q k in the formula ^(1), and ^R 1, Z and Q, also preferred embodiments thereof, including N k, R ¹ , Z and Q may be the same as or different from each other, and n represents an integer of 3 or more. X ¹ represents a divalent hydrocarbon group which may have a substituent, Y ¹ represents a single bond or a divalent organic group, and W ¹ represents a trivalent hydrocarbon group.

X ¹ in the formula (2) is a linking group bonded to the cyclic organic group A and further bonded to at least one other atomic group constituting the polymer according to the ion conductor of the present invention. . X ¹ includes, for example, two hydrogen atoms from saturated hydrocarbon molecules having 1 to 50 carbon atoms such as methane, ethane, propane, butane, octane, decane, icosane, triacontane, pentacontan, cycloheptane, and cyclohexane. An alkylene group formed by removing atoms; formed by removing two or more hydrogen atoms from an aromatic hydrocarbon molecule having 1 to 50 carbon atoms such as benzene, naphthalene, anthracene, tetracene, biphenyl, acenaphthylene, phenalene and pyrene. Arylene group; and the like. X ¹ preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. Among these, particularly preferred are phenylene group as X ^1.

When X ¹ is a hydrocarbon group, the bond between the cyclic organic group A and X ¹ becomes inactive, and an effect is obtained in that a durable ion conductor is obtained.

Examples of the divalent organic group represented by Y ¹ include saturated hydrocarbon molecules having 1 to 40 carbon atoms such as methane, ethane, propane, butane, octane, decane, icosane, triacontane, cycloheptane, and cyclohexane. An alkylene group formed by removing two hydrogen atoms from an aromatic hydrocarbon molecule having 6 to 50 carbon atoms such as benzene, naphthalene, anthracene, tetracene, biphenyl, acenaphthylene, phenalene and pyrene; An arylene group formed by removing; the following formulas (E-1), (E-2), (E-3), (E-4), (E-5), (E-6), (E-7) ), (E-8), (E-9) or a group represented by (E-10); Y1 may be a group obtained by arbitrarily combining a plurality of these groups. Y ¹ is particularly preferably a single bond or an alkylene group because the synthesis of the ionic conductor of the present invention is simple and the chemical stability of the ionic conductor of the present invention is easily secured.

In the formulas (E-1) to (E-10), R ^a , R ^b , R ^c , R ^d , R ^e , R ^f and R ^g each independently have a hydrogen atom or a substituent. Or a monovalent hydrocarbon group. Here, the monovalent hydrocarbon group includes one hydrogen atom from a saturated hydrocarbon molecule having 1 to 30 carbon atoms such as methane, ethane, propane, 2-methylpropane, butane, cycloheptane, and cyclohexane. An alkyl group formed by removing; a group formed by removing one hydrogen atom from an aromatic hydrocarbon molecule such as benzene, naphthalene, anthracene, tetracene, biphenyl, acenaphthylene, phenalene, pyrene, and pyridine; It is done.

Examples of the trivalent hydrocarbon group represented by W ¹ include 3 to C 3-30 saturated hydrocarbon molecules such as methane, ethane, propane, 2-methylpropane, butane, cycloheptane, and cyclohexane. Alkanetriyl group formed by removing one hydrogen atom; formed by removing three hydrogen atoms from aromatic hydrocarbon molecules such as benzene, naphthalene, anthracene, tetracene, biphenyl, acenaphthylene, phenalene, pyrene, and pyridine And the like; and the like. The number of carbon atoms in W ¹ is preferably 1-30, more preferably 1-16, and still more preferably 1-8. Among these, as W ¹ , an alkanetriyl group is particularly preferable because of easy polymerization reaction.

  The repeating unit represented by the formula (2) is more preferably a repeating unit represented by the following formula (3) because synthesis is simple.

In the formula (3), Z, k, Q, R ¹ , X ¹ , Y ¹ and W ¹ include Z, k, Q, R ¹ in the formula (2), including preferred embodiments thereof. Synonymous with X ¹ , Y ¹ and W ¹ . The plurality of Z, k, Q, and R ¹ may be the same as or different from each other. T ¹ represents a monovalent ion conductive group represented by the formula (1), a monovalent hydrocarbon group which may have a substituent or a hydrogen atom, and T ² represents the formula (1). And a monovalent hydrocarbon group or a hydrogen atom which may have a substituent.

Examples of the repeating unit represented by the formula (3) include a repeating unit represented by the following formula (3-1). In formula (3-1), R ²⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group. It is.

The number of repeating units (degree of polymerization) constituting the polymer according to the ionic conductor of the present invention is preferably 1 to 1 × 10 ⁷ from the viewpoint of easily ensuring the solubility of the polymer and ensuring the film strength. More preferably, it is 5 to 1 × 10 ⁶ , further preferably 2 × 10 to 1 × 10 ⁶ , and particularly preferably 1 × 10 ^{2 to} 5 × 10 ⁵ .

  The number average molecular weight (Mn) determined by GPC measurement of the polymer according to the ionic conductor of the present invention is preferably 500 to 1000000 from the viewpoint of easily ensuring the solubility of the polymer and ensuring the film strength. More preferably, it is 1000-900000, More preferably, it is 2000-700000. In the GPC measurement, the GPC apparatus uses HBPX 880Pu (trade name) manufactured by JASCO equipped with an RI detector, and performs the measurement by setting the liquid feeding speed to 1.0 mL / min and the column oven to 40 ° C. THF is used as the solvent, and KF-803L and KF-804L (trade name) manufactured by Shodex are used as the analytical column. As a standard sample, polystyrene (1300, 3000, 5000, 11000, 50000, 90000, 200000, 490000, 900000) is used.

When conducting a metal ion with the ion conductor of this invention, it is preferable to disperse | distribute the metal salt of the metal ion made to conduct in the polymer which concerns on the ion conductor of this invention. Examples of the metal ions constituting the metal salt include lithium ions, sodium ions, potassium ions, rubidium ions, and alkali ions such as cesium ions from the viewpoint of the electromotive force of the battery, preferably lithium ions, sodium ions. And potassium ions, more preferably lithium ions and sodium ions. Counter anions constituting the metal salt include CF ₃ SO ₃ ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , N (SO ₂ CF ₃ ) ₂ ⁻ , N (SO ₂ CF ₂ CF ₃ ) ₂ ⁻ , And N (SO ₂ F) ₂ ^{— and the} like. Metal ions constituting the metal salt can contribute to ionic conduction through coordination of ion conductive groups (polar groups) in the polymer. When conducting protons with the ionic conductor, the polymer may be humidified.

  The polymer synthesis method relating to the ionic conductor of the present invention described above includes (i) a method of modifying and introducing a hydrocarbon group substituted with a cyclic organic group A into the polymer, and (ii) a cyclic organic group A. Examples include a method of polymerizing a polymerizable compound having a substituted hydrocarbon group. Of these, the method (ii) is preferred. According to this method, it is possible to synthesize a polymer with controlled ion conduction characteristics by more precisely controlling the molecular weight of the polymer and the introduction rate of ion conductive groups (polar groups).

Examples of the method for synthesizing a polymerizable compound that can be suitably used in the method (ii) include the following methods (I) to (IV). By appropriately combining these methods, a compound having a desired cyclic organic group A can be synthesized.
(I) Hydromethylation of aromatic group using formaldehyde and acid, etc. (II) Hydroxylation after oxidation of alkyl group of aromatic group having alkyl group (III) Acetylene substituted with electron withdrawing group Aromatic ring formation reaction used (reference: Dalton Transactions, 2011, 40, 3748, etc.)
(IV) Aromatic ring formation reaction using acetylene substituted with a polar group (reference: Tetrahedron Letter, 1994, 35, 9323, etc.)

The polymerizable compound is, for example, a compound represented by the following formula (4). U ¹ in the formula (4) represents a polymerizable group. The ring A, k, R ¹ , Z, Q, n, X ¹ , and Y ¹ in the formula (4) are synonymous with the group represented by the formula (2), including preferred embodiments thereof. The n ion conductive groups may be the same as or different from each other.

Examples of the polymerizable group represented by U ¹ include a 1,2-epoxyethyl group and a monovalent hydrocarbon group having an ethylenically unsaturated bond. Examples of the hydrocarbon group having an ethylenically unsaturated bond include vinyl group, allyl group, propenyl group, butenyl group, butazinyl group, styryl group, 2-vinylbenzyl group, 3-vinylbenzyl group, 4-vinylbenzyl group,- COCHCH ₂ group, —COC (CH ₃ ) CH ₂ group and the like can be mentioned. Among these, from the viewpoint of easily ensuring polymerization reactivity, vinyl group, styryl group, 2-vinylbenzyl group, 3-vinylbenzyl group, 4-vinylbenzyl group, —COCHCH ₂ group and —COC (CH ₃ ) CH _Two groups are preferable, and a vinyl group and a styryl group are more preferable.

The polymerizable compound may have a plurality of polymerizable groups on the A ring. For example, the polymerizable compound may have a plurality of groups represented by —X ¹ —Y ¹ —U ¹ bonded to the A ring.

As the polymerizable compound, a polymerizable compound represented by the following formula (6) is preferable. In the formula (6), Z, Q, k, T ¹ , T ² , X ¹ , Y ¹ and U ¹ are synonymous with the polymerizable compound represented by the formula (4) including preferred embodiments thereof. .

Furthermore, as a polymeric compound shown by said Formula (6), the compound shown by following formula (6-1) is mentioned, for example. In formula (6-1), X ¹ and Y ¹ are synonymous with formula (4), including preferred embodiments thereof, and R ²⁰⁰ is defined by formula (3- It is synonymous with 1).

  A method for synthesizing the polymer according to the ionic conductor of the present invention from the polymerizable compound can be appropriately selected according to the type of the polymerizable group and the like. The polymer may be a homopolymer of the polymerizable compound (a polymerizable compound having a hydrocarbon group substituted with a cyclic organic group A), and a copolymer with an appropriately selected copolymer component (comonomer). It may be a coalescence. When the polymer is a copolymer, comonomer-derived characteristics can be imparted to the polymer.

  When the polymerizable group is a monovalent hydrocarbon group having an ethylenically unsaturated bond, the polymerization reaction can be performed by various heating methods such as heat, light, electrolysis, radiation irradiation, oxidation, and light irradiation methods. , Radical generating catalysts, radical polymerization initiators and the like may be used. Among these, a polymerization method using a radical polymerization initiator is preferable. As radical polymerization initiators, organic peroxides such as benzoyl peroxide, inorganic peroxides such as potassium persulfate, and azo radical polymerization initiation such as 2,2′-azobis (2,4-dimethylvaleronitrile) Agents and the like. Moreover, you may use the radical polymerization initiator used by the living radical polymerization method mentioned later.

  The copolymer component is a monomer having sufficient polymerization reactivity, and has an ethylenically unsaturated bond from the viewpoint of copolymerization with the polymerizable compound represented by the formula (6-1). Comonomers are preferred. This comonomer includes, for example, (meth) acrylic acid and salts thereof, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid phenyl, (meth) acrylic 2-hydroxyethyl acid, 2-aminoethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, trifluoromethylmethyl (meth) acrylate, And (meth) acrylic acid monomers such as 2-trifluoromethylethyl (meth) acrylate; styrene, vinyltoluene, α-methylstyrene, chlorostyrene, vinylbenzoic acid and its salts, styrenesulfonic acid and its salts, etc. Styrenic monomers: perfluoroethylene, perfluoropropylene Fluorine-containing vinyl monomers such as vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, and monoalkyl or dialkyl esters of maleic acid, fumarate Maleimide monomers such as acids and monoalkyl or dialkyl esters of fumaric acid, maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide groups such as acrylamide and methacrylamide Vinyl monomers; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; olefin monomers such as ethylene, propylene, and butene; dienes such as butadiene and isoprene Monomers; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, acrolein, methacrolein, and nylphosphonic acid and its salts. These comonomers may be used alone or in combination of two or more for the copolymerization reaction. In addition, (meth) acrylic acid means acrylic acid and methacrylic acid.

  As the polymerization reaction, bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, bulk / suspension polymerization and the like can be selected. In the polymerization reaction of the polymerizable compound, any solvent can be used as long as it does not inhibit the reaction. For example, an aromatic hydrocarbon solvent such as benzene, toluene, xylene, pentane, hexane, heptane, Aliphatic hydrocarbon solvents such as octane, nonane and decane; Alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene; Chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetra Chlorinated hydrocarbon solvents such as chloroethylene; alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol; acetone, methyl ethyl ketone and methyl isobutyl keto Ketone solvents such as ethyl acetate and ester solvents such as dimethyl phthalate; ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole; 1-methyl-2-pyrrolidinone, dimethylformamide Acetic acid and water can be used. These solvents may be used alone or in admixture of two or more. Moreover, it is preferable that the reaction liquid becomes a homogeneous phase by using these solvents, but a plurality of non-uniform phases may be used.

  The polymer according to the ionic conductor of the present invention preferably has a higher-order structure, so that the properties of the comonomer can be introduced while maintaining the ionic conductivity, and thus a material having desired physical properties can be easily obtained. It is a block copolymer. It does not specifically limit regarding the manufacturing method of this block copolymer, A well-known method etc. can be used. The monomer constituting the polymer block (D) is referred to as monomer (d), and the monomer constituting the polymer block (E) is referred to as monomer (e). Hereinafter, as a specific example of the production method, a production method of a block copolymer having the polymer block (D) and the polymer block (E) as components will be described.

  Depending on the type and molecular weight of the monomer constituting the polymer block (D) or (E), the production method of the polymer block (D) or (E) can be radical polymerization, anionic polymerization, cationic polymerization, coordination It selects suitably from the polymerization method etc. A radical polymerization method, an anionic polymerization method, and a cationic polymerization method are preferably selected from the viewpoint of industrial ease. In particular, the so-called living polymerization method is preferable from the viewpoints of molecular weight control, molecular weight distribution control, polymer structure control, ease of bonding between the polymer block (D) and the polymer block (E), and specifically, a living radical polymerization method. The living anionic polymerization method and the living cationic polymerization method are preferable, and the living radical polymerization method and the living anion polymerization method are particularly preferable. Living anionic polymerization is more preferable from the viewpoint of industrial ease, molecular weight, molecular weight distribution, ease of bonding between the polymer block (D) and the polymer block (E), and the like.

Examples of the living anionic polymerization method include the following methods.
(1) After polymerization of the monomer (e) using a dianionic initiator in a tetrahydrofuran solvent, the monomer (d) is sequentially polymerized under a temperature condition of −78 ° C. to obtain a D-E-D type block copolymer. Methods (eg, Macromolecules, (1969), 2 (5), 453-458.).
(2) After bulk polymerization of the monomer (d) using an anionic initiator, the monomer (e) is sequentially polymerized, and then a coupling reaction is performed with a coupling agent such as tetrachlorosilane, (DE) _n Methods for obtaining X-type block copolymers (for example, Kautsch. Gummi, Kunstst., (1984), 37 (5), 377-379. and Polym. Bull., (1984), 12, 71-77. ).
(3) An organic lithium compound in a nonpolar solvent is used as an initiator, and a concentration of 5 to 50% by mass at a temperature of −30 ° C. to 30 ° C. in the presence of a polar compound having a concentration of 0.1 to 10% by mass. The monomer (d) is polymerized, the monomer (e) is polymerized to the resulting living polymer, and then a coupling agent is added to obtain a D-E-D type block copolymer.
(4) A concentration of 5 to 50% by mass at a temperature of −30 ° C. to 30 ° C. in the presence of a polar compound having a concentration of 0.1 to 10% by mass using an organolithium compound in a nonpolar solvent as an initiator. The monomer (d) (monomer constituting the polymer block (D)) is polymerized, the monomer (e) is polymerized to the resulting living polymer, and the resulting monomer (d) polymer block and monomer (e) A method of obtaining a DED type block copolymer by polymerizing a monomer constituting the polymer block (D) to a living polymer of a block copolymer comprising polymer blocks.

As specific examples of the production method, a polymer block (F) having monomer (f) as a main repeating unit, a polymer block (D) comprising monomer (d), and a polymer block (E) comprising monomer (e) A method for producing a block copolymer or graft copolymer having a component as a component is described. In this case, the living anion polymerization method is preferable in view of industrial ease, molecular weight, molecular weight distribution, ease of bonding of polymer blocks (F), (E) and (D), and the following specific synthesis examples Is mentioned.
(5) Monomer (f) is polymerized using an anionic polymerization initiator in a cyclohexane solvent under a temperature condition of 10 to 100 ° C., and then monomer (e) and monomer (d) are sequentially polymerized to produce FE. A method for obtaining a D-type block copolymer.
(6) After polymerizing the monomer (f) under a temperature condition of 10 to 100 ° C. using an anionic polymerization initiator in a cyclohexane solvent, and then sequentially polymerizing the monomer (d) and the monomer (e), A method for obtaining an F-D-E-D-F type block copolymer by adding a coupling agent such as phenyl benzoate.
(7) Monomer (f), monomer (e) and monomer (f) are sequentially polymerized using an anionic polymerization initiator in a cyclohexane solvent under a temperature condition of 10 to 100 ° C. After preparing a copolymer and adding an anionic polymerization initiator system (anionic polymerization initiator / N, N, N ′, N′-tetramethylethylenediamine) to lithiate the monomer (e) unit, the monomer (d) To obtain a FE (-gD) -F type block / graft copolymer. (-G-D) represents a graft site of the block / graft copolymer.
(8) A concentration of 5 to 50% by mass at a temperature of −30 ° C. to 30 ° C. in the presence of a polar compound having a concentration of 0.1 to 10% by mass using an organolithium compound in a nonpolar solvent as an initiator. The monomer (d) is polymerized, and the resulting living polymer is sequentially polymerized with the monomer (e) and the monomer (f) to obtain a D-E-F type block copolymer, and the monomer (d), the monomer (f), A method in which a monomer (e) and a monomer (f) are sequentially polymerized to obtain a D-F-E-D type block copolymer.

Examples of the living radical polymerization method include the following methods.
(I) Nitroxide mediated polymerization (NMP) using a radical scavenger such as a nitroxide compound.
(Ii) Atom transfer radical polymerization (ATRP) using an organic halide or the like as an initiator and a transition metal complex as a catalyst.
Of these, nitroxide-mediated polymerization using a radical scavenger such as a nitroxide compound can be suitably used because the polymerization reaction can be carried out more easily.

(I) Nitroxide-mediated polymerization Nitroxide-mediated polymerization is described in, for example, Chemical Reviews, 2001, Vol. 101, no. A nitroxide compound as disclosed in US Pat. No. 12,3661 can be used as a polymerization initiator. The nitroxide compound refers to a compound having a nitroxy group or a compound that generates a nitroxy group under polymerization reaction conditions. As the nitroxy group, N-tert-butyl-2-methyl-1-phenylpropylamine-N-oxy group, 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) group, 4-hydroxy -2,2,6,6-tetramethylpiperidinyl-1-oxy group, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy group, 3-amino-2,2,5,5 -Tetramethyl-1-pyrrolidinyloxy group, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy group, di-t-butylnitroxy group and the like.

(Ii) Atom transfer radical polymerization Atom transfer radical polymerization is a method in which a polymerizable compound is radically polymerized using an organic halide or a sulfonyl halide compound as a radical polymerization initiator and a metal complex having a transition metal as a central metal as a catalyst. is there. As such a method, for example, Chem. Rev. 101, 2921 (2001), Chem. Rev. 101, 3689 (2001). Examples of the radical polymerization initiator include organic halides and sulfonyl halide compounds. Among these, compounds having a halogen group at the α-position of the carbon-carbon double bond, and at the α-position of the carbon-oxygen double bond. A compound having a halogen group can be preferably used. The carbon-halogen bond of these compounds is suitable as a structure contained in the radical polymerization initiator.

  The transition metal complex used as a catalyst for atom transfer radical polymerization is preferably a metal complex having a group 7 element, group 8, group 9, group 10, or group 11 element as a central metal in the periodic table. More preferred are metal complexes having divalent copper, divalent ruthenium, divalent iron or divalent nickel as the central metal, and particularly preferred are metal complexes having monovalent copper or divalent iron as the central metal. Examples of such a metal complex include monovalent copper as a central metal, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2- Chlorocopper complexes, bromocopper complexes, and cationic copper complexes with nitrogen atom-containing compounds such as aminoethyl) amine; ligands with divalent iron as the central metal and triphenylphosphine, tributylamine, etc. The dichloroiron (II) complex and the dibromoiron (II) complex are preferred.

  The living radical polymerization reaction can be further promoted by using, as a catalyst, Bronsted acid such as acetic acid, sulfuric acid, formic acid, and paratoluenesulfonic acid, and Lewis acid such as acetic anhydride and aluminum chloride.

  In any polymerization reaction of (i) nitroxide-mediated polymerization and (ii) atom transfer radical polymerization, the polymerization temperature may be any temperature at which the radical polymerization reaction proceeds, and the desired polymer of the ionic conductor of the present invention can be used. Although it can be appropriately selected depending on the degree of polymerization, the type and amount of the radical polymerization initiator to be used, the type and amount of the solvent, etc., it is usually -100 ° C to 250 ° C, preferably -50 ° C to 180 ° C. More preferably, it is 0 degreeC-160 degreeC. The polymerization reaction can be performed at any of reduced pressure, normal pressure, and increased pressure. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.

  The polymer according to the ionic conductor of the present invention produced by the above method is isolated by using a known method such as distillation of the solvent used in the polymerization or unreacted monomer or reprecipitation with a non-solvent.

  A macromonomer can also be obtained by living radical polymerization of the polymerizable compound. This macromonomer has a unit structure derived from the polymerizable compound and a polymerization initiation site derived from a radical polymerization initiator, and is represented, for example, by the following formula (8).

In the formula (8), A ^{ring, X 1, Y 1, W} 1, Z, Q, k and n is a preferred embodiment be included synonymous with a group represented by the formula (2). R ³⁰⁰ and R ³⁰¹ represent a radical polymerization initiator residue, and m represents an integer of 1 to 1 × 10 ⁶ . At least one of R ³⁰⁰ and R ³⁰¹ is a polymerizable group, and examples of such a group include a nitroxy group and a halogen atom. The radical polymerization initiator residue indicates a partial structure derived from a radical polymerization initiator. For example, according to living radical polymerization using a radical polymerization initiator represented by the following formula (8-a), A macromonomer represented by the formula (8-b) is obtained. m is preferably 5 to 1 × 10 ⁶ , more preferably 2 × 10 to 1 × 10 ⁶ , and further preferably 1 × 10 ^{2 to} 5 × 10 ⁵ .

  A block copolymer can be obtained by the reaction between the macromonomer and the copolymer component. Such a block copolymer can form a higher order structure, and has characteristics such as high ionic conduction characteristics due to a continuous ionic group portion derived from the higher order structure. Therefore, it can be suitably used as a polymer constituting the ionic conductor.

Examples of the method for synthesizing the polymerizable compound include the following methods (I) to (IV) as described above. By appropriately combining these methods, a polymerizable compound having a desired cyclic organic group can be synthesized. In the case where the A ring is an aromatic ring, the method (II) is preferred from the viewpoint of ease of synthesis.
(I) Hydromethylation of aromatic group using formaldehyde and acid, etc. (II) Hydroxylation after oxidation of alkyl group of aromatic group having alkyl group (III) Acetylene substituted with electron withdrawing group Aromatic ring formation reaction used (reference: Dalton Transactions, 2011, 40, 3748, etc.)
(IV) Aromatic ring formation reaction using acetylene substituted with a polar group (reference: Tetrahedron Letter, 1994, 35, 9323, etc.)

  Below, the example of the synthesis | combining method of the said polymeric compound is shown. In addition, the synthesis | combining method of a polymeric compound is not limited to the reagent shown by the following scheme 1, scheme 2, scheme 3, and scheme 4, reaction time, reaction temperature, etc.

First, an example of the synthesis method of the polymerizable compound of the present invention represented by the following formulas (8-5) and (8-6) will be shown. As shown in the following scheme 1, a compound represented by the formula (8-3) is synthesized by a reaction of acetylene (8-1) substituted with a polar group and an acetate compound (8-2). In Scheme 1, R ⁴⁰¹ represents a monovalent hydrocarbon group which may have a substituent. In Scheme 2, R ⁴⁰² represents R ²⁰⁰ in the repeating unit represented by the formula (3-1). Similar groups are shown. DMAP represents 4- (dimethylamino) pyridine, and DME represents 1,2-dimethoxyethane.

  Then, as shown in Scheme 2, a compound represented by the formula (8-4) is obtained by introducing a polymerizable group into the compound represented by the formula (8-3).

  Next, as shown in Scheme 3, the polymerizable compound of the present invention represented by the formula (8-5) is obtained by reducing the compound represented by the formula (8-4) and introducing a hydroxymethyl group. .

  Next, as shown in Scheme 4, by polymerizing the hydroxymethyl group of the polymerizable compound of the present invention represented by the formula (8-5), the polymerizability of the present invention represented by the formula (8-6) is represented. A compound is obtained.

Examples of the alkylating agent used in the alkylation step include the compounds represented by the following formula (11) including those described above.
Lv- [Z] _k -Q (11)
In formula (11), Lv represents a leaving group, for example, p-toluenesulfonyloxy group, methanesulfonyloxy group, trifluoromethanesulfo group, iodine atom, bromine atom, chlorine atom, or fluorine atom. Z, k, and Q are synonymous with the polymerizable compound represented by the formula (4), including preferred embodiments.

  Next, an example of the synthesis method of the polymerizable compound of the present invention represented by the following formulas (9-5) and (9-6) will be shown. As shown in the following scheme 5, the compound represented by the formula (9-1) is oxidized to obtain a compound represented by the formula (9-2) into which a carboxyl group is introduced, and the ester (9-3) is obtained by esterification. And a compound represented by the formula (9-4) is obtained by introducing a polymerizable group. The compound represented by the formula (9-4) is further reduced to obtain a polymerizable compound of the present invention represented by the formula (9-5) having a hydroxymethyl group, and alkylated to obtain the formula (9-6). The polymerizable compound of the present invention represented by) is obtained.

  Furthermore, an example of the synthesis | combining method of the polymeric compound of this invention represented by following formula (10-4) and (10-5) is shown. As shown in the following scheme 6, a compound represented by the formula (10-1) is synthesized from an acetylene compound having a polar group, is induced to a compound represented by the formula (10-2), and a polymerizable group is introduced. To obtain the compound represented by the formula (10-3). Further, the ester moiety is reduced to a hydroxymethyl group to obtain the polymerizable compound of the present invention represented by the formula (10-4), and further alkylated to represent the polymerizable compound of the present invention represented by the formula (10-5). A compound is obtained.

  The ion conductor of the present invention can be suitably used as an electrolyte for solid polymer fuel cells, lithium ion polymer secondary batteries, sodium ion polymer secondary batteries, and the like. The polymerizable compound according to the present invention is suitable for producing a polymer constituting the ionic conductor of the present invention.

  The ion conductor of the present invention can be used as an ion conductive film. Hereinafter, the ion conductive film containing the ion conductor of the present invention will be described.

  The method for producing the ion conductive membrane of the present invention is not particularly limited, but after the ion conductor is dissolved in a cast solvent to form a polymer solution, the polymer solution is applied to a supporting substrate and dried to form a film. Is preferred. According to such a manufacturing method, an ion conductive film can be easily manufactured. The support substrate is not particularly limited as long as it has durability against the polymer solution. For example, a silicon substrate, a PET (polyethylene terephthalate) film, a glass plate, or a PTFE (polytetrafluoroethylene) plate can be used. .

  Examples of the casting solvent include benzene, toluene, xylene, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, N, N. -Dimethylformamide, dimethyl sulfoxide, acetone, methyl ethyl ketone, acetonitrile, ethyl acetate, methanol, ethanol, isopropyl alcohol, hexane, cyclohexane, and mixtures thereof.

  Examples of the method for applying the polymer solution include spin coating, casting, dip coating, gravure coating, bar coating, roll coating, spray coating, screen printing, flexographic printing, and offset printing. Among these, spin coating and casting Roll coating, spray coating, screen printing, flexographic printing and offset printing are preferred, and roll coating, spray coating and flexographic printing are more preferred.

  Examples of the method for drying the polymer solution applied to the support substrate include air drying, heat drying, reduced pressure drying, heat reduced pressure drying, and drying performed by blowing nitrogen gas. Of these, air drying and heat drying are preferable. Heat drying is more preferable.

  The film thickness of the ion conductive film is not particularly limited, but is preferably 3 nm to 300 μm, more preferably 5 nm to 100 μm, and still more preferably 10 nm to 50 μm. A film thickness of 10 nm or more is preferable because the practical strength is more excellent, and a film thickness of 50 μm or less is preferable because the film resistance decreases and the characteristics of the electrochemical device tend to be further improved. The film thickness of the ion conductive film can be controlled by the solid content concentration of the polymer solution and the coating thickness on the support substrate.

  The ion conductive membrane according to the present embodiment is preferably a first block comprising a repeating unit having a hydrocarbon group substituted with a cyclic organic group A (for example, a repeating unit represented by the formula (2)), and An ionic conductor made of a block copolymer having a second block made of a repeating unit derived from a copolymer component is contained.

  Such an ion conductor can form a microphase separation structure, and can exhibit high ion conduction characteristics due to the microphase separation structure.

  As the copolymer component, a comonomer having an ethylenically unsaturated bond is preferable. The second block having a comonomer having an ethylenically unsaturated bond as a repeating unit is excellent in phase separation from the first block. Therefore, according to the block copolymer having the second block having a comonomer having an ethylenically unsaturated bond as a repeating unit, a microphase separation structure is more reliably formed.

  Examples of the microphase separation structure include a sea-island structure, a cylinder structure, a co-continuous structure, and a lamellar structure. For example, in the sea-island structure, the island region may be mainly configured by a first block, and the sea region may be mainly configured by a second block.

  In the ion conductive membrane of the present invention, by appropriately changing the copolymer component constituting the second block, the functional group of the polymer forming the ion conductor, the cast solvent, etc. Accordingly, an appropriate microphase separation structure can be formed.

  For example, by changing the copolymer composition (content ratio of the first block and the second block) in the block copolymer, the block constituting the sea region and the island region can be reversed, or other microphase separation It can be changed to a structure.

  Moreover, it can change to another micro phase-separation structure by changing a cast solvent and utilizing the difference in solubility of a 1st block and a 2nd block.

As a specific example, a block block having a first block composed of a repeating unit represented by the formula (2) and a second block composed of a repeating unit derived from a comonomer having an ethylenically unsaturated bond described above. A ratio (molar ratio, C ₁ ) between the content C _{1 of the} repeating unit represented by the formula (2) and the content C ₂ of the repeating unit derived from a comonomer having an ethylenically unsaturated bond as described above. : C ₂ ) using an ionic conductor composed of a block copolymer of 100: 1 to 1: 100 (preferably 50: 1 to 1:50, more preferably 20: 1 to 1:20), When a 2 mass% toluene solution of the ion conductor is spin-coated on a silicon substrate, a periodic sea-island microphase separation structure with a width of 30 to 50 nm is formed on the surface of the ion conductive film. At this time, the sea area mainly consists of the second block, and the island area mainly consists of the first area. An ion conductive membrane having such a sea-island structure is more suitable for electrolyte applications such as solid polymer fuel cells and metal ion batteries (particularly lithium ion batteries and sodium ion batteries).

  The ion conductive membrane according to this embodiment can change the surface state of the membrane by a “solvent annealing method” in which the membrane is placed in a closed container filled with organic solvent vapor and exposed to the solvent vapor. By changing the surface state of the membrane in this way, for example, in secondary battery and fuel cell applications, the contact between the membrane and the electrode catalyst can be enhanced. In addition, the battery performance is improved by reducing the interface resistance between the membrane and the electrode catalyst.

  For example, the ion conduction membrane (the first block consisting of a repeating unit represented by the formula (2) and the second block consisting of a repeating unit derived from a comonomer having an ethylenically unsaturated bond described above as a specific example) In the case of a film in which an ionic conductor made of a block copolymer having the above structure is formed), when annealed with toluene, the dot-shaped uneven structure resulting from the microphase separation structure on the film surface can be strengthened. Moreover, when annealed with chloroform or acetone, the dot-like uneven structure resulting from the microphase separation structure on the film surface can be weakened. Here, it is considered that the change in the dot-like uneven structure reflects the change in phase separation in the ion conductive film. Thus, according to the solvent annealing method, the surface of the ion conductive membrane and the microphase separation structure inside the membrane can be appropriately changed according to the purpose of use.

  In the solvent annealing method, the annealing time (time to be exposed to solvent vapor), the type of solvent, the temperature during annealing, etc. are not particularly limited, and is optimal for the purpose of forming a preferred microphase separation structure and surface structure according to the purpose of use. You can choose the conditions.

  The ion conductive membrane according to the present invention may contain, in addition to the ion conductor, plasticizers, stabilizers, mold release agents and the like used for ordinary polymers for the purpose of improving various physical properties of the ion conductive membrane. Good. Alternatively, the ion conductor and another polymer may be combined into a composite alloy by a method such as mixing and casting in the same solvent. In addition, for the purpose of improving the mechanical strength of the ion conductive membrane, it can also be crosslinked by irradiating an electromagnetic wave such as an electron beam or radiation. In addition to these, known methods can be used as long as they are not contrary to the object of the present invention.

  The ion conductive membrane of the present invention can be made into a composite membrane by impregnating a porous base material with a porous base material and improving the mechanical properties such as high strength and flexibility. The compounding can be performed by a known method.

  The porous substrate is not particularly limited as long as it satisfies the above-mentioned purpose of use, and examples thereof include porous membranes, woven fabrics, nonwoven fabrics, and fibrils. The porous substrate can be used regardless of its shape and material. The material of the porous substrate is preferably an aliphatic polymer, an aromatic polymer or a fluorine-containing polymer from the viewpoint of excellent heat resistance and physical strength reinforcement effects.

  The ion conductive membrane of the present invention can be used, for example, as a separator provided between a positive electrode and a negative electrode in a metal ion battery (particularly, a lithium ion battery or a sodium ion battery).

  The positive electrode and the negative electrode in the lithium ion battery are not particularly limited, and ordinary ones can be used. Examples of the negative electrode include an electrode made of lithium metal, an electrode made of an alloy of lithium and aluminum, a carbon electrode that can absorb and release lithium ions, and the like. Examples of the positive electrode include an electrode made of manganese dioxide. FIG. 1 is a schematic view showing an embodiment of a lithium ion battery. A lithium ion battery 1 shown in FIG. 1 includes a battery container 20, a plurality of negative electrodes 2 and positive electrodes 3 disposed alternately in the battery container 20, and an ion conductive film 5 disposed between the negative electrode 2 and the positive electrode 3. And an enclosing member 6 enclosing the battery container. The ion conductive film 5 may include a separator that contains an ion conductor and is impregnated with the ion conductor.

A well-known thing can be used for the positive electrode and negative electrode in a sodium ion battery, respectively. For example, metal sodium is mentioned as a negative electrode. Examples of the positive electrode include marisite type NaMnO ₄ .

  The ion conductive membrane of the present invention can also be used for fuel cells. As a fuel cell, one having a polymer conductive membrane and a catalyst layer is known. As the polymer conductive membrane, the ion conductive membrane according to this embodiment can be used.

  The catalyst layer in the fuel cell contains a catalyst material that can activate the oxidation-reduction reaction with hydrogen or oxygen. As such a catalyst substance, it is preferable to use fine particles of platinum or a platinum-based alloy. The fine particles of platinum or platinum-based alloy may be supported on particulate or fibrous carbon such as activated carbon or graphite.

  The catalyst layer is made of, for example, a catalyst ink obtained by mixing platinum supported on carbon and an alcohol solution of a perfluoroalkyl sulfonic acid resin as a polymer electrolyte together into a paste. Manufactured by. As a specific method, J. Org. Electrochem. Soc. : Known methods such as those described in Electrochemical Science and Technology, 1988, 135 (9), 2209 can be used.

  Next, the catalyst ink according to this embodiment will be described.

  The catalyst ink according to this embodiment contains the ionic conductor of the present invention. According to such a catalyst ink, a catalyst layer containing the ionic conductor of the present invention is formed. And since this catalyst layer contains the ion conductor of this invention, it has the outstanding proton conductivity.

  The catalyst ink according to the present embodiment can appropriately contain components contained in a known catalyst ink. In addition, the catalyst ink according to the present embodiment can be manufactured by replacing part or all of the polymer electrolyte in the known catalyst ink with the ion conductor according to the present embodiment.

  According to the catalyst ink according to the present embodiment, as described above, a fuel cell comprising a catalyst layer and the ion conductive membrane of the present invention, wherein the catalyst layer contains the ion conductor of the present invention. Can be obtained.

  In such a fuel cell, a well-known material can be used also about the electroconductive substance as a collector. As the current collector, a porous carbon woven fabric, carbon non-woven fabric or carbon paper is preferable in that the source gas can be efficiently transported to the catalyst. Moreover, the fuel cell manufactured in this way can be used in various forms using hydrogen gas, reformed hydrogen gas, and methanol as fuel.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

(NMR measurement)
Unless otherwise specified, NMR measurement was performed by dissolving a measurement sample in deuterated chloroform and using an NMR measurement apparatus (trade name: JNM-AL300, manufactured by JEOL Ltd.).

(IR measurement)
Unless otherwise specified, IR measurement is performed by mixing with powder KBr to produce pellets, or by producing a film on a NaCl plate to produce a measurement sample, and an IR measurement device (manufactured by JASCO Corporation, (Trade name: FT / IR-400).

  According to the synthetic route shown in the following scheme 7, polymerizable compound 4 was synthesized by the following procedure.

(Production Example 1) [Synthesis of Compound 1]
Under a stream of argon, a 500 mL three-necked flask was charged with ethyl (4-bromobenzoyl) acetate (3.93 g, 14.5 mmol), 1,2-dimethoxyethane (DME, 340 mL), diethyl acetylenedicarboxylate (6.14 g, 36. 1 mmol) and 4- (dimethylamino) pyridine (DMAP, 0.45 g, 3.7 mmol) were added to prepare a reaction solution, and the reaction solution was stirred at room temperature for 3 hours. After removing the reaction solvent under reduced pressure, the obtained crude product was purified by column chromatography using ethyl acetate / hexane (3: 7, v / v) as a developing solvent. The obtained solid was recrystallized from methanol to obtain colorless polymerizable compound precursor 1 crystals (yield 7.11 g, 83% yield).
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.52 (d, J = 8.4 Hz, 2H), 7.11 (d, J = 8.4 Hz, 2H), 4.39-4 .29 (m, 6H), 4.00 (q, J = 7.2 Hz, 4H), 1.38-1.31 (m, 9H), 0.95 (t, J = 7.2 Hz, 6H) .
¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm): 165.8, 165.4, 165.0, 138.9, 136.2, 134.9, 132.6, 131.6, 131.2 130.1, 122.9, 62.5, 62.4, 61.9, 13.8, 13.7, 13.4.
IR (KBr, cm ⁻¹ ) 2984 (w), 2936 (w), 1743 (vs), 1490 (w), 1470 (w), 1427 (m), 1391 (w), 1374 (w), 1341 ( m), 1326 (w), 1298 (w), 1224 (s), 1206 (s), 1175 (w), 1165 (w), 1139 (w), 1100 (w), 1072 (w), 1018 ( m), 885 (w), 856 (w), 827 (w), 695 (w).

(Production Example 2) [Synthesis of Compound 2]
In a 300 mL three-necked flask under a nitrogen stream, the compound 1 (7.01 g, 11.8 mmol), dry toluene (100 mL), tributylvinyltin (4.85 g, 15.3 mmol), palladium tetra (triphenylphosphine) (0. 20 g, 0.17 mmol) and 2,6-di-tert-butyl-4-cresol (42 mg, 0.19 mmol) were added to prepare a reaction solution, and the reaction solution was heated to reflux for 48 hours. After confirming disappearance of the raw material by ¹ H-NMR spectrum, the reaction solution was cooled to room temperature, 150 mL of 5N KF aqueous solution was added, and the mixture was stirred for 12 hours. The reaction solution was extracted with ethyl acetate and then washed with an aqueous sodium chloride solution. The solution was dried with MgSO ₄ to remove the solvent, and then purified twice by column chromatography using ethyl acetate / hexane (3: 7 v / v) as a developing solvent. The obtained solid was washed with hexane to obtain colorless Compound 2 crystals (yield 2.50 g, yield 40%).
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm): 7.42 (d, J = 8.3 Hz, 2H), 7.18 (d, J = 8.3 Hz, 2H), 6.72 ( dd, J = 17.6 Hz, J ′ = 10.9 Hz, 1H), 5.80 (d, J = 17.6 Hz, 1H), 5.23 (d, J = 10.9 Hz, 1H), 4. 39-4.30 (m, 6H), 3.98 (q, J = 7.1 Hz, 4H), 1.38-1.31 (m, 9H), 0.91 (t, J = 7.1 Hz) , 6H).
¹³ C-NMR (75 MHz, CDCl ₃ ): δ (ppm): 167.0, 165.5, 165.1, 139.9, 137.7, 136.3, 135.9, 135.6, 132. 1, 131.5, 128.6, 125.7, 114.7, 62.4, 62.2, 61.7, 13.7, 13.6, 13.3.
IR (KBr, cm ⁻¹ ): 2984 (w), 2934 (w), 2908 (w), 1738 (vs), 1720 (vs), 1569 (w), 1512 (w), 1468 (w), 1443 (W), 1420 (m), 1402 (w), 1367 (w), 1325 (w), 1299 (w), 1252 (vs), 1218 (vs), 1170 (w), 1116 (w), 1096 (W), 1022 (s), 920 (w), 884 (w), 859 (w), 840 (w), 769 (w), 593 (w).

Example 1 [Synthesis of Polymerizable Compound 3]
The reaction solution obtained by adding the compound 2 (2.16 g, 4.00 mmol) and 500 mL of dehydrated THF to a 1 L three-necked flask under a nitrogen stream condition was cooled to 0 ° C. Thereafter, LiAlH ₄ (1.14 g, 30 mmol) was added to turn the reaction solution brown. The reaction solution was stirred at room temperature for 24 hours, and then the reaction was stopped by sequentially adding H ₂ O (1.5 mL), 15 mass% NaOH aqueous solution (1.5 mL), and H ₂ O (4.5 mL). Thereafter, the reaction solution was filtered through Celite and washed with MeOH. By removing the solvent from the obtained solution, a polymerizable compound 3 having a pale yellow viscosity was obtained.

(Example 2) [Synthesis of polymerizable compound 4]
The polymerizable compound 3 obtained in Example 1 (total amount of the reaction product), dehydrated DMF (20 mL), and NaH (1.44 g, 60 mmol) were added to a 100 mL three-necked flask under a nitrogen stream condition. The prepared reaction solution was stirred at room temperature for 12 hours. Thereafter, triethylene glycol monomethyl ether monotosylate (9.6 g, 30 mmol) was added, and the mixture was further stirred at room temperature for 24 hours. 30 mL of H ₂ O was added to the reaction solution in small portions, followed by extraction with CHCl ₃ and washing with water three times. After drying with MgSO ₄ , the solvent was removed, and column chromatography was performed to obtain a light yellow liquid polymerizable compound 4 (yield 0.42 g, yield 10%).

From the ¹ H-NMR spectrum (FIG. 2) of the obtained polymerizable compound 4, a signal based on the TEG (triethylene glycol) chain is observed, and from the proton integral intensity ratio, the TEG chain is present in all five hydroxymethyl groups. It was confirmed that they were bonded. Moreover, since all signals such as vinyl groups could be clearly assigned, it was found that the target polymerizable compound was obtained.

  Next, the solvent of the reduction reaction was changed to a mixed solvent of 1,4-dioxane and THF, and the reaction of Example 3 below was performed.

Example 3 [Synthesis of Polymerizable Compound 3]
The compound 2 (4.32 g, 8.00 mmol), dehydrated 1,4-dioxane (1 L), and THF (300 mL) are added to a 2 L three-necked flask under a nitrogen stream condition, and the reaction solution is cooled to 0 ° C. did. Thereafter, LiAlH ₄ (2.28 g, 30 mmol) was added, and the reaction solution became brown by warming the reaction temperature to room temperature. The reaction solution was stirred at room temperature for 36 hours, and then the reaction was stopped by sequentially adding H ₂ O (3.0 mL), 15 mass% NaOH aqueous solution (3.0 mL), and H ₂ O (9.0 mL). The reaction solution was neutralized by adding 6N HCl aqueous solution and then filtered through Celite. After removing the solvent from the resulting solution, 20 mL of MeOH was added. After removing a small amount of salt, the solvent was removed again to obtain a polymerizable compound 3 having a pale yellow viscosity (yield 2.62 g, yield 99%).

  The yield was improved by changing the reaction solvent from THF to a mixed solvent of 1,4-dioxane / THF. By using this synthesis method, a polymerizable compound having a TEG chain can be synthesized with high yield.

(Example 4) [Synthesis of PTEG-containing block copolymer (PS-b-PPTEG)]
For the purpose of obtaining a block copolymer having the obtained polymerizable compound 4 (PTEG) as a repeating unit and capable of forming a clear microphase separation, hydrophilic PTEG and hydrophobic styrene are used. A block copolymer was synthesized (Scheme 8). As the polymerization reaction, a living anionic polymerization method was selected that allows precise control of the molecular weight and composition and that can yield a polymer with a narrow molecular weight distribution (see Macromolecules 2009, 42, 8835).

  Dry THF (40 mL) was added to a Schlenk tube with a stopcock under an Ar stream and cooled to -78 ° C. Thereafter, 0.5 mL of a 1N sec-BuLi cyclohexane / n-hexane solution was added to dehydrate the reaction system. Next, the reaction vessel was allowed to stand at room temperature to decompose sec-BuLi, and then cooled again to -78 ° C. After adding 6 drops of 1N sec-BuLi cyclohexane / n-hexane solution to the reaction solution, 0.8 mL of dry styrene was added and stirred for 1 hour under sealed conditions. At that time, the reaction solution turned yellow. Then, the THF solution (4 mL) of the said polymeric compound 4 (0.42g) lyophilized with benzene was added, and it stirred under sealed conditions for 6 hours. At that time, the reaction solution turned red. The reaction was stopped by adding 5 mL of MeOH under Ar flow, and then the polymer was reprecipitated in hexane. The viscous body was taken out with a centrifuge and freeze-dried with benzene to obtain a white powder of polymer (PS-b-PPTEG) (0.6 g).

[Structural analysis of PS-b-PPTEG]
The structure of the polymer was analyzed by ¹ H-NMR spectrum and GPC measurement. The disappearance of the vinyl group was observed in the ¹ H-NMR spectrum (FIG. 3), indicating that the polymerization reaction had proceeded. Polystyrene (PS), the polymer of the polymerizable compound 4 (PPTEG), an aromatic signal based on each component, and a peak based on the TEG chain were found, indicating that a block copolymer was obtained. . Further, from the proton integral intensity ratio of each component of the ¹ H-NMR spectrum, the molar fraction of each component of PS and PPTEG is 0.95 / 0.05, and the weight fraction is 0.68 / 0.32. I understood.

As a result of GPC measurement, the number average molecular weight (Mn) of the polymer was 11800 g / mol, and the molecular weight distribution (PDI) was 1.15.
The GPC device used HBPX 880Pu (trade name) manufactured by JASCO, equipped with an RI detector, and the measurement was performed with the liquid feed rate set to 1.0 mL / min and the column oven set to 40 ° C. THF was used as the solvent, and KF-803L and KF-804L (trade names) manufactured by Shodex were used as the analytical column. As a standard sample, polystyrene (1300, 3000, 5000, 11000, 50000, 90000, 200000, 490000, 900000) was used.

When the degree of polymerization of the polymer was calculated from these results, it was found to be PS ₇₄ -b-PPTEG ₄ . From these facts, it was found that the target block copolymer was obtained. Block copolymers with various molecular weights and compositions can be obtained by changing the amount of initiator and each monomer used in the polymerization reaction, so that microphase-separated structures with various sizes and forms can be prepared according to the purpose. It is.

(Example 5) [Production of ion conductive membrane]
The diblock polymer (PS-b-PPTEG) obtained in Example 4 was dissolved in chloroform to obtain a 1% by weight solution. The solution was formed on a silicon substrate by spin casting (rotation speed: 8000 rpm, 30 seconds) to obtain an ion conductive film. The film thickness was about 50 nm. When the surface was observed with an AFM (atomic force microscope), a slight contrast of light and dark based on microphase separation was observed. An AFM photograph of the ion conductive membrane is shown in FIG.

Example 6 [Annealing Treatment 1 of Ion Conductive Membrane]
Next, in order to clarify the microphase separation structure formed inside the polymer thin film (ion-conducting membrane), microphase separation is performed by performing a solvent annealing method in which the polymer thin film is exposed to various solvent vapors. I tried to control the structure. A polymer thin film was prepared by spin casting a 1% by mass chloroform solution of the polymer under the conditions of 8000 rpm and 30 sec. The thickness of the obtained thin film was about 50 nm. Solvent annealing of the obtained thin film was carried out by allowing the polymer thin film to stand in a solvent reservoir and an upper part having a nitrogen inlet / outlet in a glass container. The degree of swelling of the polymer was controlled by adjusting the flow rate of nitrogen while measuring the film thickness of the thin film with a thin film measuring device (Firmetics, F20). There are three types of solvents used for annealing: xylene, toluene, and chloroform. These solvents are described in T.W. P. Selected based on papers reported by Russell, Ho-Cheol Kim et al. (Adv. Mater. 2004, 16, 226, Nano. Lett. 2005, 5, 2014). The swelling ratio was defined as the ratio of the film thickness during annealing to the film thickness before swelling, and the unswelled state was defined as 100%.

  The ion conductive membrane obtained in Example 5 was allowed to stand until the swelling rate reached 200% under xylene vapor filling conditions. When the surface of the obtained film was observed by AFM, it was observed that the contrast of the microphase separation structure on the film surface was weakened. An AFM photograph with a swelling rate of 200% in xylene is shown in FIG.

(Example 7) [Annealing treatment 2 of ion conductive membrane]
The ion conductive membrane obtained in Example 5 was allowed to stand until the swelling rate reached 150% under toluene vapor full conditions. When the surface of the obtained film was observed by AFM, it was observed that the contrast of the microphase separation structure on the film surface was weakened. An AFM photograph with a swelling rate of 150% in toluene is shown in FIG.

  From the above experimental results, it was confirmed that the surface state of the membrane of the ion conductive membrane of the present invention can be changed by the solvent annealing method. This solvent annealing improves the contact property between the ion conductive membrane and the electrode catalyst and lowers the interface resistance. As a result, the power generation efficiency of an alkaline ion polymer secondary battery or a polymer electrolyte fuel cell comprising the ion conductive membrane of the present invention can be improved.

  ADVANTAGE OF THE INVENTION According to this invention, the ion conductor excellent in ionic conductivity can be provided. Moreover, according to this invention, the compound useful for manufacture of the polymer which comprises the ionic conductor which concerns can be provided. Furthermore, according to this invention, the ion conductive film and metal ion battery (especially lithium ion battery, sodium ion battery) containing the said ion conductor can be provided. Since the ionic conductor of the present invention is hardly decomposed, it is possible to maintain high ionic conductivity for a long time.

  DESCRIPTION OF SYMBOLS 1 ... Lithium ion battery, 2 ... Negative electrode, 3 ... Positive electrode, 5 ... Ion conductive film, 6 ... Enclosing member, 20 ... Battery container.

Claims (12)

An ionic conductor comprising a polymer containing a repeating unit having a cyclic organic group,
The repeating unit further has a monovalent ion-conducting group represented by the following formula (1), and the ion-conducting group is a continuous three of the atoms constituting the ring of the cyclic organic group. An ion conductor in which one atom is bonded to each of the above atoms, and the plurality of ion conductive groups may be the same or different.

[Where:
k represents an integer of 0 to 50;
R ¹ represents a divalent hydrocarbon group,
Z represents the following formula (Z-1), (Z-2), (Z-3), (Z-4), (Z-5), (Z-6), (Z-7) or (Z-8). )
Q is the following formula (Q-1), (Q-2), (Q-3), (Q-4), (Q-5), (Q-6), (Q-7), (Q-8) ), (Q-9), (Q-10), (Q-11), (Q-12), (Q-13), (Q-14), (Q-15), (Q-16), A polar group represented by (Q-17), (Q-18), (Q-19), (Q-20), (Q-21), (Q-22) or (Q-23);
A plurality of Z may be the same as or different from each other. ]

[Where:
R ¹⁰ , R ²⁰ , R ²¹ , R ³⁰ , R ⁴⁰ , R ⁴¹ , R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁶⁰ , R ⁷⁰ , R ⁷¹ , R ⁸⁰ , R ¹¹⁰ and R ¹²⁰ are respectively A hydrogen atom, a monovalent hydrocarbon group which may have a substituent, or a metal atom is shown.
X represents an atom having an unshared electron pair. ]

[Where:
* And ** represent bonding positions, * represents bonding to the R ¹ side, and ** represents bonding to the Q side. ]   Q is the formula (Q-1), (Q-2), (Q-3), (Q-4), (Q-5), (Q-12), (Q-13), (Q The ion conductor according to claim 1, which is a group represented by -14), (Q-15), (Q-16) or (Q-23). The cyclic organic group is an aromatic group which may have a substituent, an ion conductor according to claim 1 or 2. The ion conductor as described in any one of Claims 1-3 whose repeating unit which has the said cyclic organic group is group shown by following formula (2).

[Where:
A ring represents the cyclic organic group,
^{k, R} 1, Z and Q represents k in the formula ^(1), the same meaning as ^R 1, Z and Q, n-number of ^{k, R} 1, Z and Q are each mutually the same or different You can,
n represents an integer of 3 or more,
X ¹ represents a divalent hydrocarbon group which may have a substituent, Y ¹ represents a single bond or a divalent organic group, and W ¹ represents a trivalent hydrocarbon group. ] The ionic conductor according to claim 4 , wherein Y ¹ is a single bond or an alkylene group. The ionic conductor according to claim 4 or 5 , wherein the W ¹ is an alkanetriyl group. The polymer containing a repeating unit having a cyclic organic group is a repeating unit formed by polymerizing a comonomer having an ethylenically unsaturated bond (different from the monovalent ion conductive group represented by the formula (1)). further comprising, ion conductor according to any one of claims 1-6. The ionic conductor according to any one of claims 1 to 7 , wherein the polymer containing a repeating unit having a cyclic organic group is a block copolymer. A polymerizable compound represented by the following formula (4), wherein R ¹ is bonded to three or more consecutive atoms among atoms constituting the A ring one by one.

[Where:
U ¹ represents a polymerizable group, A ring represents a cyclic organic group,
k represents an integer of 0 to 50;
R ¹ represents a divalent hydrocarbon group,
Z represents the following formula (Z-1), (Z-2), (Z-3), (Z-4), (Z-5), (Z-6), (Z-7) or (Z-8). )
Q is the following formula (Q-1), (Q-2), (Q-3), (Q-4), (Q-5), (Q-6), (Q-7), (Q-8) ), (Q-9), (Q-10), (Q-11), (Q-12), (Q-13), (Q-14), (Q-15), (Q-16), A polar group represented by (Q-17), (Q-18), (Q-19), (Q-20), (Q-21), (Q-22) or (Q-23);
n k, R ¹ , Z and Q may be the same as or different from each other;
n represents an integer of 3 or more,
X ¹ represents a divalent hydrocarbon group which may have a substituent, and Y ¹ represents a single bond or a divalent organic group. ]

[Where:
R ¹⁰ , R ²⁰ , R ²¹ , R ³⁰ , R ⁴⁰ , R ⁴¹ , R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁶⁰ , R ⁷⁰ , R ⁷¹ , R ⁸⁰ , R ¹¹⁰ and R ¹²⁰ are respectively A hydrogen atom, a monovalent hydrocarbon group which may have a substituent, or a metal atom is shown.
X represents an atom having an unshared electron pair. ]

[Where:
* And ** represent bonding positions, * represents bonding to the R ¹ side, and ** represents bonding to the Q side. ] A method for producing an ionic conductor, comprising:
Comprising polymerizing one or more polymerizable compounds by living anionic polymerization to produce an ionic conductor composed of a polymer containing a repeating unit represented by the following formula (2);
The method for producing an ionic conductor, wherein at least one of the polymerizable compounds is the polymerizable compound according to claim 9 .

[In the formulas, A ^{ring, k, R 1, Z,} Q, n, X 1 and ^{Y 1,} A ring in the formula (4) ^{in, k, R 1, Z,} Q, n, X 1 and Y ¹ represents the same meaning as ^1, and W ¹ represents a trivalent hydrocarbon group. ] The ion conductive film containing the ion conductor as described in any one of Claims 1-8 . A metal ion battery comprising the ion conductive membrane according to claim 11 .