WO2018079262A1

WO2018079262A1 - Polymer, electrode, electric-storage device, and process for producing polymer

Info

Publication number: WO2018079262A1
Application number: PCT/JP2017/036857
Authority: WO
Inventors: 山本　圭一; 相田　一成; 香奈増田; 大地末政; 遠藤　剛
Original assignee: Jsr株式会社
Priority date: 2016-10-24
Filing date: 2017-10-11
Publication date: 2018-05-03
Also published as: JP2021181581A; JP6969570B2; JPWO2018079262A1; CN109863192A; JP7173241B2

Abstract

The present invention relates to a polymer, an electrode, an electric-storage device, and a process for producing the polymer. An embodiment of the polymer has at least one of structures represented by formulae (1) and (2). [In formula (1), the Ar¹ moieties each independently represent an (un)substituted aromatic hydrocarbon group; the Y moieties independently represent a single bond or a divalent linking group or represent two hydrogen atoms or substituents which are respectively bonded to the two Ar¹ moieties; and n indicates an integer of 4 or larger.] [In formula (2), the Ar² moieties each independently represent a group comprising an aromatic ring (provided that not all of the Ar² moieties are biphenyl-4,4'-diyl); a indicates an integer of 1-10; the Ar³ moieties each independently represent a group comprising an aromatic ring; each b independently indicates 1 or 2; and a group bonded to the N of each –Ar³-(N)_b= may be bonded to one of the Ar² moieties to form a ring.]

Description

POLYMER, ELECTRODE, ELECTRIC STORAGE DEVICE, AND METHOD FOR PRODUCING POLYMER

The present invention relates to a polymer, an electrode, an electricity storage device, and a method for producing the polymer.

Aromatic amine polymers such as polyaniline are known as conductive polymers, and they can be used as hole transport materials used in organic EL, organic transistors, solar cells, and electrode materials such as lithium ion secondary batteries. Expected. As such an aromatic amine polymer, for example, a linear polyarylene amine proposed in Patent Document 1 is known in addition to polyaniline.

In addition, it is known that aromatic diamine compounds such as N, N, N ′, N′-tetramethyl-benzidine are useful as electrode active materials for power storage devices (see Patent Document 2).

JP 2008-45142 A JP 2014-222590 A

However, conventionally proposed polyaryleneamines have poor solubility in organic solvents, so that they are difficult to apply to liquid phase processes and cannot be used as hole transport materials. Moreover, when the conventionally proposed aromatic diamine compound is used as an electrode active material for an electricity storage device, satisfactory characteristics may not be obtained.

Therefore, one embodiment of the present invention provides a novel aromatic amine polymer excellent in solubility in an organic solvent and a method for producing the same. In addition, another embodiment of the present invention provides a novel aromatic amine polymer that provides satisfactory characteristics when used as an electrode active material of an electricity storage device, and a method for producing the same.

In view of such circumstances, the present inventors have conducted intensive research and found that the above-mentioned problems can be solved by using a specific aromatic amine-based polymer having a branched chain structure or a network structure. It came to be completed.
A configuration example of the present invention is as follows.

One embodiment of the present invention
A polymer having at least one of the structures represented by the following formulas (1) and (2) (hereinafter also referred to as “the present polymer 1”);
A polymer having a structure represented by the following formulas (3) and (R ′) and having a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of 2,000 or more (hereinafter “present polymer 2”) Or)
A polymer having a structure represented by the following formulas (1) and (6) (hereinafter also referred to as “present polymer 3”) is provided.
These polymers 1 to 3 are also collectively referred to as this polymer A.

Also, one embodiment of the present invention provides an electrode containing the present polymer A, and further provides an electricity storage device comprising the electrode as a positive electrode.

Furthermore, an embodiment of the present invention
In the presence of a base, a method for producing a polymer comprising a step of reacting a compound represented by the following formula (7) with a compound represented by the following formula (8) (hereinafter also referred to as “the present method I”). Or a method for producing a polymer comprising a step of reacting a compound represented by the following formula (9) with a compound represented by the following formula (10) in the presence of a base (hereinafter also referred to as “the present method II”) .)I will provide a.

According to one embodiment of the present invention, an aromatic amine polymer having excellent solubility in an organic solvent can be obtained. Therefore, the polymer is extremely useful as a positive electrode transport material applied to a liquid phase process. Further, by using the polymer, an electricity storage device satisfying satisfactory characteristics, specifically, high discharge capacity, high cycle characteristics, and high rate characteristics can be easily obtained. Therefore, the polymer is extremely useful as an electrode material for an electricity storage device.

This polymer A
The present polymer A is any one of the following present polymers 1 to 3.
The present polymer 1 is represented by the structure represented by the following formula (1) (hereinafter also referred to as “structure (1)”. Other structures may be expressed in the same manner) and the following formula (2). A polymer having at least one of the following structures:

The present polymer 1 having the structure (1) (hereinafter also referred to as “the present polymer 1a”) is particularly excellent in solubility in an organic solvent, and is extremely useful as a positive electrode transport material or the like applied to a liquid phase process. Moreover, when this polymer 1a is used as an electrode material, particularly as an active material, an electricity storage device having excellent cycle characteristics can be easily obtained.

In Formula (1), Ar ¹ is an independently substituted or unsubstituted aromatic hydrocarbon group, and a bond bonded to Ar ¹ is bonded to N.
Examples of the aromatic ring constituting the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a biphenyl ring, and the like, and a benzene ring is preferable.
Examples of the substituent include a hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, a fluoro group, and a carboxy group.
Ar ¹ is preferably an unsubstituted aromatic hydrocarbon group, more preferably a p-phenylene group.

Y independently represents a single bond, a divalent linking group, or two hydrogen atoms or substituents bonded to each of two Ar ¹ groups.
Examples of the linking group include —O—, —NR— (R is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms), —S—, —CO—, an alkylene group having 1 to 4 carbon atoms, and the like. Examples of the substituent include the same groups as the substituent for Ar ¹ .
Y is preferably a single bond, two hydrogen atoms bonded to each of —S— or Ar ¹ .
Several Y in Formula (1) may be the same respectively, and may differ. The same description in this specification shows the same meaning.

N represents an integer of 4 or more, and is preferably an integer such that the weight average molecular weight of the obtained polymer falls within the following range, and more preferably 10 to 100.

Specific examples of the polymer 1a include the following polymers. N in the following polymer has the same meaning as n in the formula (1).

The present polymer 1a is the present polymer 3 having a structure represented by the above formula (1) and the following formula (6) from the viewpoint that a polymer excellent in solubility in an organic solvent is obtained. preferable. In addition, “*” in the following formula (6) represents a bond that bonds to Ar ¹ in the formula (1).

In Formula (6), Ar ⁴ represents a substituted or unsubstituted aromatic hydrocarbon group independently of each other. Examples of aromatic rings and substituents constituting the aromatic hydrocarbon group in Ar ⁴ , and preferred groups are the same as those for Ar ¹ .

R ² independently represents a hydrogen atom, a halo group, a nitro group, a hydroxyl group, a sulfo group, an amino group, or an organic group.
Examples of the organic group include a hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
The halo group is preferably a fluoro group or a bromo group, and more preferably a fluoro group.

When R ² is a polar group such as a halo group, a nitro group, a hydroxyl group, a sulfo group, an amino group, or an alkoxy group, a polymer that can swell in a general electrolyte solution can be obtained. In particular, when used as an active material, an electricity storage device exhibiting high rate characteristics and excellent cycle characteristics can be easily obtained.
When this polymer 3 in which R ² is a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, particularly a hydrogen atom or a methoxy group, is used as an electrode material, particularly an active material, an electricity storage device having excellent cycle characteristics can be easily obtained. Obtainable.
When the polymer 3 in which R ² is a hydrogen atom, a fluoro group or a hydrocarbon group, particularly a fluoro group or a methyl group, is used as an electrode material, particularly an active material, an electricity storage device having a high discharge capacity can be easily obtained. be able to.
R ² is preferably a hydrogen atom, a fluoro group, a bromo group, a methyl group, or a methoxy group.

Z represents a single bond, a divalent linking group, or two hydrogen atoms or substituents bonded to each of two Ar ⁴ groups. Examples of the linking group and substituent in Z, and preferred groups are the same as those for Y.

Specific examples of the structure (6) include the following structures. R in the following structure has the same meaning as R ² in formula (6), and is preferably a hydrogen atom, a methyl group, a methoxy group, a fluoro group, or a bromo group.

The structure (1) preferably has a structure (R ¹ -N =) represented by the following formula (R) from the viewpoint of ease of production of the present polymers 1a and 3.
In addition, Formula (6) shows that R < ¹ > couple | bonds with N of said Formula (1).

[In the formula (R), R ¹ represents a hydrogen atom, a halo group, a nitro group, a hydroxyl group, a sulfo group, an amino group or an organic group. ]

Examples of the organic group for R ¹ include the same groups as the organic group for R ² , and substituted or unsubstituted aromatic hydrocarbon groups. The organic group includes “═N—Ar — **”. [Ar represents a substituted or unsubstituted aromatic hydrocarbon group, and ** represents a bond bonded to N in the structure (1). It is preferably a group other than a group including a structure represented by
R ¹ is preferably a hydrogen atom or a substituted or unsubstituted aromatic hydrocarbon group, and particularly preferably a hydrogen atom.

Specific examples of the present polymer 1a and / or the present polymer 3 include polymers of the following groups (a1) to (a4). N in the following polymer has the same meaning as n in the formula (1).

The present polymer 1 may be a polymer having a structure represented by the following formula (2) (hereinafter also referred to as “present polymer 1b”).
When the polymer 1b is used as an electrode material, particularly as an active material, an electricity storage device that is excellent in balance between discharge capacity and rate characteristics can be easily obtained.

In the formula (2), Ar ² represents a group containing an aromatic ring independently of each other (provided that all of Ar ² are all biphenyl-4,4′-diyl), and Ar ³ represents a mutual group. Independently represents a group containing an aromatic ring.
Examples of the group containing an aromatic ring in Ar ² and Ar ³ include a group in which a plurality of the aromatic hydrocarbon groups are linked by a divalent linking group in addition to the aromatic hydrocarbon group exemplified for Ar ^1. . Examples of the divalent linking group include —O—, —S—, —SO ₂ —, —NH—, —NHCO—, —COO—, a substituted or unsubstituted divalent hydrocarbon group, —N (C ₆ H ₅ ) — and the like. Examples of the substituent include the same groups as the substituent for Ar ¹ .
As Ar ² and Ar ³ , a group containing an unsubstituted benzene ring is preferable, and a group containing 1 to 5 unsubstituted benzene rings is particularly preferable.
Note that a group bonded to N in —Ar ³ — (N) _b ═ may be bonded to Ar ² to form a ring.

a represents an integer of 1 to 10.
b shows 1 or 2 mutually independently.

The present polymer 1b has a structure represented by the following formula (2 ′) from the viewpoint that a discharge capacity and rate characteristics are excellent in balance and an electric storage device having a particularly large discharge capacity can be easily obtained. Polymers are preferred.

[Ar ² and Ar ³ in Formula (2 ′) are independently the same as Ar ² and Ar ^{3 in} Formula (2). ]

Specific examples of the polymer 1b include the following polymers.

This polymer 2 has a structure represented by the following formulas (3) and (R ′), and has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 2,000 or more. It is.
Such a polymer 2 is particularly excellent in solubility in an organic solvent, and is extremely useful as a positive electrode transport material or the like applied to a liquid phase process. Further, the polymer 2 is used as an electrode material, particularly an active material. When used as a substance, an electricity storage device having excellent cycle characteristics can be easily obtained.

In the formula (3), Ar ¹ and Y are independently of one another have the same meanings as defined above Ar ¹ and Y.
m represents an integer of 2 or more.

In the formula (R ′), R ¹ represents a hydrogen atom, a halo group, a nitro group, a hydroxyl group, a sulfo group, an amino group or an organic group (provided that “= N—Ar — **” [Ar represents a substituent Or an unsubstituted aromatic hydrocarbon group, and ** represents a bond bonded to N in the following formula (3).] Is excluded), and the formula (R ′) Indicates that R ¹ is bonded to N in the formula (3).
Examples of the organic group in R ¹ include the same groups as the organic group in R ² , and substituted or unsubstituted aromatic hydrocarbon groups. R ¹ is preferably a hydrogen atom or a substituted or unsubstituted group. An aromatic hydrocarbon group, particularly preferably a hydrogen atom.

This polymer 2 has a repeating unit represented by the following formula (3-1) and a structure represented by the above formula (6) from the viewpoint of obtaining a polymer excellent in solubility in an organic solvent. Is preferred. In the formula (6), “*” represents a bond that bonds to Ar ¹ in the following formula (3-1).
The repeating unit represented by the following formula (3-1) is between the core of the polymer 2 represented by R ¹ — and the terminal of the polymer 2 represented by the formula (6). It means a repeating unit derived from a monomer.
The present polymer 2 preferably has one or more structural units represented by the following formula (3-2) between repeating units represented by the following formula (3-1).

In the formula (3-1) ~ (3-2), Ar 1, Ar 4, R 2, Y and Z are independently of one another have the same meanings as defined above ^{^{^{Ar 1, Ar 4, R 2}}} , Y and Z. In Formula (3-2), * 1 represents a bond that is bonded to N in the repeating unit represented by Formula (3-1) or N in Structure (3-2). Further, in the equation (3-2), * 2 indicates a bond that binds to an Ar ¹ in the formula at least one or the structure of Ar ¹ in the repeating unit represented by (3-1) (3-2).

The present polymer 2 preferably contains 10 to 100 repeating units represented by the formula (3-1).
Specific examples of the present polymer 2 include, for example, the polymers represented by the groups (a1) to (a3), and those represented by the groups (a1) to (a3) in addition to the polymers having n of 2 or more. In the structural formula, a polymer having one or a plurality of structural units represented by the above formula (3-2) between a repeating unit (structural unit enclosed in parentheses) and the repeating unit is given. It is done.

The Mw of the present polymer A is preferably 2, from the viewpoint that, when the polymer A is used as an electrode material, particularly an active material, an electricity storage device having excellent rate characteristics and cycle characteristics can be easily obtained. 000 to 100,000, more preferably 3,000 to 100,000, and particularly preferably 5,000 to 60,000.
Specifically, Mw is measured by the method described in the following examples.

Production Method of Polymer The production method of the present polymer A is not particularly limited, but from the viewpoint that a polymer having a desired structure can be easily produced, the present polymer A is produced by the following method I or this method. It is preferable to manufacture by II.

In the present method I, in the presence of a base, a compound represented by the following formula (7) (hereinafter also referred to as “compound (7)”. Other compounds may be expressed in the same manner) and the following formula (8). The method of reacting with the compound represented by this.
According to this method, a polymer having a branched chain structure such as the present polymer 1a, the present polymer 2 and the present polymer 3, particularly a hyperbranched polymer can be easily produced.

In the formula (7), Ar ¹ and Y have the same meanings as Ar ¹ and Y in the formulas independently of one another (1).
X represents a chloro group, a bromo group, or an iodo group independently of each other, and a bromo group is preferable from the viewpoint that the reaction proceeds more easily.
Compound (7) used in Method I may be one type or two or more types.

Compound (7) may be a commercially available product or may be synthesized by a conventionally known method.
As the compound (7), the following compounds are preferable.

In the formula ^{(8), Ar 4, R} 2 and Z are as defined Ar ^4, R ² and Z in formula independently of one another (6).
Compound (8) used in Method I may be one type or two or more types.

As the compound (8), the following compounds are preferable.

Compound (8) may be a commercially available product, or may be synthesized by a conventionally known method.
Examples of the conventionally known method, for example, a compound represented by R ² -Ar ⁴ -NH ₂ (wherein R ² and Ar ⁴ has the same meaning as R ² and Ar ⁴ in the formula (8).), R ² -Ar ⁴ -X (wherein R ² and Ar ⁴ has the same meaning as R ² and Ar ⁴ in the formula (8), X is a halo group.) and a compound represented by the following Pd (P (t -Bu) ₃ ) A method of reacting in the presence of a catalyst such as _{2, and the} like.
In this method I, instead of the compound (8), a precursor thereof is a compound represented by the R ² —Ar ⁴ —NH ₂ , a compound represented by the R ² —Ar ⁴ —X, May be used.

The base is not particularly limited, and a conventionally known base can be used, but is preferably a strong base, more preferably a base with low nucleophilicity, specifically, a metal alkoxide, Examples thereof include metal amides, preferably sodium t-butoxide, potassium t-butoxide and the like.
The base used in Method I may be one type or two or more types.

In the reaction in the present method I, it is preferable to use a catalyst. As the catalyst, conventionally known catalysts can be used, and specific examples include the following compounds. Of these, a catalyst comprising a trialkylphosphine and a palladium compound is preferable.
When a catalyst is used in Method I, the catalyst may be one type or two or more types.

[In the compound, “Ms” represents a mesylate group, “Cy” represents a cyclohexyl group, “L” represents a ligand, and “iprO” represents an isopropoxy group. ]

The reaction in Method I is usually performed in the presence of a solvent. As the solvent, a conventionally known solvent can be used, and is not particularly limited, but a solvent capable of dissolving the compounds (7) and (8) is preferable, and specifically, an ether solvent such as THF (tetrahydrofuran). And aromatic hydrocarbon solvents such as benzene, toluene and xylene.
When a solvent is used in Method I, the solvent may be one type or two or more types.

The reaction conditions in Method I are not particularly limited, but the reaction temperature is preferably 25 to 150 ° C., and the reaction time is preferably 0.5 to 10 hours. In Method I, the ratio of compound (7) to compound (8) used (compound (7): compound (8)) is preferably in the range of 100: 100 to 90: 100 in terms of molar ratio. .

In the present method I, “NH” in the polymer obtained by the above method is reacted with the compound containing R ¹ such as R ¹ X (X is a halo group) to thereby form the structure. A polymer in which R ¹ is bonded to N in (1) and (3) can be obtained. Examples of the compound represented by R ¹ X include chlorobenzene, bromonaphthalene, bromoanthracene, bromobenzoic acid, and the like.

This method II is a method including a step of reacting a compound represented by the following formula (9) and a compound represented by the following formula (10) in the presence of a base.
According to this method, a network polymer such as the present polymer 1b can be easily produced.

In Formula (9), Ar ⁵ represents a group containing an aromatic ring. Examples of groups containing an aromatic ring in Ar ⁵ and preferred groups are the same as those for Ar ² and Ar ³ .
As the compound (9), when the obtained polymer is used for an electrode, the aromatic ring is excellent in that the discharge capacity and rate characteristics are excellent in balance and an electric storage device having a particularly large discharge capacity can be easily obtained. A compound in which an amino group is bonded to the para-position is preferred.

Compound (9) used in Method II may be one type or two or more types.
Compound (9) may be a commercially available product or may be synthesized by a conventionally known method.
As the compound (9), the following compounds are preferable.

In the formula (10), Ar ⁶ has the same meaning as Ar ^{5 in the} formula (9), and X represents a halo group independently of each other.
As the compound (10), when the polymer obtained is used for an electrode, the aromatic ring is excellent in that the discharge capacity and rate characteristics are excellent in balance and in particular, an electricity storage device having a large discharge capacity can be easily obtained. A compound in which a halo group is bonded to the para-position is preferred.

The compound (10) used in Method II may be one kind or two or more kinds.
Compound (10) may be a commercially available product, or may be obtained by synthesis by a conventionally known method.
As the compound (10), the following compounds are preferable.

The base used in Method II is not particularly limited, and a conventionally known base can be used, but the same bases as those used in Method I can be mentioned.
The base used in Method II may be one kind or two or more kinds.

In the case of the reaction in Method II, it is preferable to use the same catalyst and solvent as in Method I. Each of these catalysts and solvents may be one kind or two or more kinds.
The reaction conditions in this method II also include the same conditions as in this method I. In Method II, the ratio of compound (9) to compound (10) used (compound (9): compound (10)) is preferably in the range of 50:90 to 50: 110 in terms of molar ratio. .

The present polymer A can be suitably used as a hole transport material for an electricity storage device, an organic EL, an organic transistor, a solar cell, etc. It is preferably used as a device, more preferably used as an electrode material, and particularly preferably used as a positive electrode material, specifically as a positive electrode active material.

Electrode The electrode according to one embodiment of the present invention (hereinafter, also referred to as “main electrode”) is not particularly limited as long as it contains one or two or more main polymers A, but the main polymer on the current collector is not limited. An electrode having an active material layer containing A and a binder is preferred.
The present polymer A used for the present electrode can be used as an electrode material as it is, but can also be used as an electrode material after being combined with activated carbon or an inorganic substance. Moreover, this polymer A can also be used as an electrode material with well-known positive electrode active materials, such as lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, and lithium iron phosphate.
In the following, the present polymer A, a composite of the present polymer A and activated carbon, or a mixture of the present polymer A and a known positive electrode active material is also referred to as a present active material.

The active material layer may be manufactured, for example, by preparing a slurry containing the active material and a binder, applying the slurry onto a current collector, and drying the active material layer. You may manufacture by forming a film from the mixture which contains beforehand, and arrange | positioning this film on a collector with a (hot) press or an adhesive agent.

The present electrode is preferably a positive electrode of a non-aqueous electrolyte secondary battery that includes the active material as a positive electrode active material, and includes a positive electrode active material in which the present polymer A is combined with activated carbon. It is also preferable that it is a positive electrode of a double layer capacitor.

The content of the active material in the electrode is not particularly limited, but is preferably 10 to 90% by mass with respect to 100% by mass of the obtained active material layer.
In addition, the active material contained in the electrode of one embodiment of the present invention may be one kind or two or more kinds.

Examples of the material for the current collector include aluminum, stainless steel, copper, and nickel. When the electrode according to an embodiment of the present invention is a positive electrode, aluminum, stainless steel, and the like are preferable. The thickness of the current collector is usually 10 to 50 μm.

Examples of the binder include rubber binders such as styrene-butadiene rubber (SBR) and acrylonitrile-butadiene rubber (NBR); fluorine resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride; polypropylene, polyethylene Other examples include fluorine-modified (meth) acrylic binders disclosed in JP-A-2009-246137.
The binder may be one type or two or more types.

The content of the binder is not particularly limited, but is preferably 1 to 50% by mass, more preferably 5 to 30% by mass with respect to 100% by mass of the active material layer obtained.

In the active material layer, carbon black (acetylene black, ketjen black, etc.), graphite, vapor-grown carbon fiber (VGCF), high surface area activated carbon (MAXSORB), carbon are further added within the range not impairing the effects of the present invention. Conductive agent such as nanotube (SWNT, MWNT, etc.), metal powder, etc .; increase of carboxyl methyl cellulose, its Na salt or ammonium salt, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch or casein You may contain arbitrary components, such as a sticking agent.
Each of the optional components may be one kind or two or more kinds.

The thickness of the active material layer is not particularly limited, but is usually 5 to 500 μm, preferably 10 to 200 μm, particularly preferably 10 to 100 μm.

An electricity storage device according to an embodiment of the present invention (hereinafter also referred to as “the electricity storage device”) includes the electrode as a positive electrode. Examples of the electricity storage device include a nonaqueous electrolyte secondary battery, an electric double layer capacitor, and a lithium ion capacitor. The power storage device usually includes at least a negative electrode and an electrolyte in addition to the main electrode used as a positive electrode.
The configuration and manufacturing method of the electrode according to an embodiment of the present invention used as the positive electrode are as described in the above “electrode”.

The basic configuration and manufacturing method of the negative electrode may be any conventionally known configuration and manufacturing method, and may be the same as described in the “electrode” except for the type of active material.
Examples of the negative electrode active material used include metallic lithium, a carbon-based material doped with lithium (such as graphite and activated carbon), and a lithium alloy. These negative electrode active materials can use 1 type (s) or 2 or more types.

The electrolyte is usually used in the state of an electrolytic solution dissolved in a solvent. The electrolyte is not particularly limited, but is preferably one that can generate lithium ions. Specifically, LiClO ₄ , LiAsF ₆ , LiBF ₄ , LiPF ₆ , LiN (C ₂ F ₅ SO ₂ ) ₂ , Examples thereof include LiN (CF ₃ SO ₂ ) ₂ and LiN (FSO ₂ ) ₂ . These electrolytes can use 1 type (s) or 2 or more types.

The solvent for dissolving the electrolyte is preferably an aprotic organic solvent, and specifically, ethylene carbonate, propylene carbonate, butylene carbonate, 1-fluoroethylene carbonate, 1- (trifluoromethyl) ethylene carbonate, dimethyl Examples thereof include carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, acetonitrile, dimethoxyethane, diglyme, tetraglyme, dioxolane, methylene chloride, sulfolane and the like. These solvents can be used alone or in combination of two or more.

The electrolyte is usually prepared and used in a liquid state as described above, but a gel or a solid may be used for the purpose of preventing leakage or elution of the active material.

When the electrolyte is used in the state of an electrolyte, a separator is usually provided between the positive electrode and the negative electrode so that the positive electrode and the negative electrode are not in physical contact. A conventionally known separator may be used as the separator, and examples thereof include a nonwoven fabric or a porous film made of cellulose rayon, polyethylene, polypropylene, polyamide, polyester, polyimide and the like, paper, glass filter, and the like.

Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

[Example 1]
In a 100 ml eggplant flask, 3.27 g of bis (4-bromophenyl) amine (BPA), 1.69 g of diphenylamine (DPA), 2.88 g of sodium t-butoxide (NaOtBu), and bis (tri-tBuphosphine as a catalyst) ) 5 mg of palladium (0) and 10 ml of toluene were added, and the mixture was heated at 100 ° C. for 6 hours. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 3.3 g of polymer A-1. ^{In 1} H-NMR (CDCl ₃ ), a peak was present only at 6.9 ppm (aromatic). The polystyrene-equivalent Mw measured by GPC (device name: HCL-8320GPC (manufactured by Tosoh Corporation), column: TSKgelsuperHM-H (manufactured by Tosoh Corporation), mobile phase: THF) was 10,000. Further, as a result of analysis by MALDI-TOFMS (Matrix Assisted Laser Desorption / Ionization Time-of-Flight Mass Spectrometer), a mass spectrum indicating the presence of a structure in which R ² is a hydrogen atom in the following formulas (A) to (D) And was confirmed to have a structure represented by the formulas (1), (3), (3-1) to (3-2) and (6).

[Example 2]
In a 100 ml eggplant flask, 3.27 g of BPA, 1.97 g of p, p'-ditolylamine (MPA), 2.88 g of NaOtBu, 51 mg of bis (tri-tBuphosphine) palladium (0) as a catalyst and 10 ml of toluene In addition, the mixture was heated at 100 ° C. for 6 hours. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 3.6 g of polymer A-2. ^{In 1} H-NMR (CDCl ₃ ), peaks were present at 6.9 ppm (aromatic) and 2.5 ppm (methyl group). The Mw in terms of polystyrene measured under the same conditions as described above was 9,000. Further, as a result of analysis by MALDI-TOFMS, a mass spectrum indicating the presence of a structure in which R ² is a methyl group in the formulas (A) to (D) was obtained, and the formulas (1), (3), It was confirmed to have a structure represented by (3-1) to (3-2) and (6).

[Example 3]
In a 100 ml eggplant flask, 3.27 g of BPA, 2.29 g of bis (methoxyphenyl) amine (MOPA), 2.88 g of NaOtBu, 51 mg of bis (tri-tBuphosphine) palladium (0) as a catalyst and 10 ml of THF In addition, the mixture was heated at 70 ° C. for 6 hours. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 3.7 g of polymer A-3. ^{In 1} H-NMR (CDCl ₃ ), peaks were present at 6.7 ppm, 6.9 ppm (aromatic) and 3.8 ppm (methoxy group). The Mw in terms of polystyrene measured under the same conditions as described above was 11,000. Further, as a result of analysis by MALDI-TOFMS, a mass spectrum indicating the presence of a structure in which R ² is a methoxy group in the formulas (A) to (D) was obtained, and the formulas (1), (3), It was confirmed to have a structure represented by (3-1) to (3-2) and (6).

[Example 4]
In a 100 ml eggplant flask, 3.27 g of BPA, 2.05 g of bis (4-fluorophenyl) amine (FPA), 2.88 g of NaOtBu, 51 mg of bis (tri-tBuphosphine) palladium (0) as a catalyst and THF Was added and heated at 70 ° C. for 6 hours. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 3.7 g of polymer A-4. ^{In 1} H-NMR (CDCl ₃ ), peaks were present at 6.7 ppm and 6.9 ppm (aromatic). The polystyrene-equivalent Mw measured under the same conditions as described above was 8,000. Further, as a result of analysis by MALDI-TOFMS, a mass spectrum showing the presence of a structure in which R ² is a fluoro group in the formulas (A) to (D) was obtained, and the formulas (1), (3), It was confirmed to have a structure represented by (3-1) to (3-2) and (6).

[Example 5]
(Production of polymer having structure (2))
In a 100 ml eggplant flask, 0.54 g of paraphenylenediamine (PDA), 2.35 g of 1,4-dibromobenzene, 2.88 g of NaOtBu, 51 mg of bis (tri-tBuphosphine) palladium (0) as a catalyst and toluene Was added and heated at 100 ° C. for 6 hours. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 1.3 g of polymer B-1. It was confirmed by FT-IR that there was no vibration derived from the bond of NH and C—Br.

[Example 6]
(Production of polymer having structure (2))
In a 100 ml eggplant flask, 0.54 g of metaphenylenediamine (MDA), 2.35 g of 1,3-dibromobenzene, 2.88 g of NaOtBu, 51 mg of bis (tri-tBuphosphine) palladium (0) as a catalyst and toluene Was added and heated at 100 ° C. for 6 hours. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 1.3 g of polymer B-2. It was confirmed by FT-IR that there was no vibration derived from the bond of NH and C—Br.

[Example 7]
(Production of polymer having structure (2))
In a 100 ml eggplant flask, 0.54 g of PDA, 1.56 g of 4,4′-dibromobiphenyl, 1.2 g of 1,4-dibromobenzene, 2.88 g of NaOtBu, bis (tri-tBuphosphine) palladium as a catalyst 51 mg of (0) and 10 ml of toluene were added, and the mixture was heated at 100 ° C. for 6 hours. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 1.8 g of polymer B-3. It was confirmed by FT-IR that there was no vibration derived from the bond of NH and C—Br.

[Example 8]
(Production of polymer having structure (2))
To a 100 ml eggplant flask, 2.48 g of 2,4-dibromoaniline, 2.88 g of NaOtBu, 51 mg of bis (tri-tBuphosphine) palladium (0) and 10 ml of toluene were added and heated at 100 ° C. for 6 hours. did. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 0.88 g of polymer B-4. It was confirmed by FT-IR that there was no vibration derived from the bond of NH and C—Br.

[Comparative Example 1]
(Production of linear polyaryleneamine)
To a 100 ml eggplant flask, 1.23 g of paramethoxyaniline, 1.2 g of 1,4-dibromobenzene, 2.88 g of NaOtBu, 51 mg of bis (tri-tBuphosphine) palladium (0) as a catalyst and 10 ml of toluene were added. And heated at 100 ° C. for 6 hours. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 1.9 g of polymer C. It was confirmed by FT-IR that there was no vibration derived from the bond of NH and C—Br.

<Solubility in organic solvents>
The yields of the polymers A-1 to A-4 and the polymer C and the solubility at 25 ° C. in various solvents were confirmed. The results are shown in Table 1. In Table 1, “◎” means that 99 g or more of the polymer was dissolved in 100 g of the solvent, “Δ” means that 20 to 80 g of the polymer was dissolved in 100 g of the solvent, and “x” means that the polymer was dissolved in 100 g of the solvent. It means that less than 20 g was dissolved.

<Cycle characteristics>
Using the polymers A-1 to A-4 and the polymer C, the cycle characteristics were evaluated as follows.
In a polyethylene container, 0.4 g of each polymer as an active material, 0.5 g of acetylene black as a conductive agent, 0.1 g of NMP solution of polyvinylidene fluoride (PVDF) in solid conversion and 2 g of NMP are mixed and mixed. Stir. The obtained black slurry was coated on an aluminum current collector using an applicator. At that time, the gap of the doctor blade was 150 μm. Then, it dried for 10 minutes on a 100 degreeC hotplate, and it dried for 3 hours under vacuum at 100 degreeC in the vacuum dryer, and obtained the electrode sheet. The obtained electrode sheet was cut into a circle and used as the positive electrode of the battery. The obtained positive electrode, GA-100 (glass separator) and lithium foil (negative electrode) were set in a CR2032-type coin cell, and a 1M ethylene carbonate / diethyl carbonate = 30/70 (volume ratio) solution of LiPF ₆ (electrolytic solution) And sealed using a caulking machine to produce a coin cell.
The produced coin cell was subjected to a charge / discharge test using a Toyo System Co., Ltd. TOSCAT-3100 as a charge / discharge tester at a current value of 0.1 C at room temperature and a cut-off potential shown in Table 1. Table 1 shows the capacity retention ratio (the ratio of the discharge capacity at the 50th cycle to the discharge capacity at the 1st cycle) after 50 cycles of charge and discharge.

<Discharge capacity and rate characteristics>
Using the polymers B-1 to B-4 and the polymer C, discharge capacity and rate characteristics were evaluated as follows.
Coin cells were produced in the same manner as in the above <cycle characteristics> except that the polymers B-1 to B-4 were used instead of the polymers A-1 to A-4.
Using the TOSCAT-3500U manufactured by Toyo System Co., Ltd. as a charge / discharge tester, the produced coin cell was subjected to a charge / discharge test at room temperature, with a current value of 0.1 C and 10 C, at the cutoff potential shown in Table 2. . Table 2 shows the discharge capacity at 0.1 C and the rate characteristics (discharge capacity at 10 C × discharge capacity at 100 / 0.1 C).

[Example 9]
A coin cell was prepared in the same manner as in the above <cycle characteristics> except that 0.08 g of polymer A-3 and 0.32 g of lithium iron phosphate (LiFePO ₄ ) were used instead of polymers A-1 to A-4. Produced. About the produced coin cell, the cycle characteristics and the discharge capacity were evaluated in the same manner as in the above <cycle characteristics> and <discharge capacity and rate characteristics>. At this time, the cut-off potential was set to 3.8 to 2.8V. As a result, the capacity retention rate after 50 cycles was 99%, the capacity retention rate after 5000 cycles was 84%, and the discharge capacity was 150 mAh / g.

[Comparative Example 2]
Coin cells were produced in the same manner as in the above <Cycle characteristics> except that 0.4 g of lithium iron phosphate (LiFePO ₄ ) was used instead of the polymers A-1 to A-4. About the produced coin cell, the cycle characteristics and the discharge capacity were evaluated in the same manner as in the above <cycle characteristics> and <discharge capacity and rate characteristics>. At this time, the cut-off potential was set to 3.8 to 2.8V. As a result, the capacity retention rate after 50 cycles was 95%, the capacity retention rate after 5000 cycles was 34%, and the discharge capacity was 150 mAh / g.

The present polymer is considered to be extremely useful as a hole transport material used in organic EL, organic transistors, solar cells, etc., in addition to electrode materials for power storage devices such as electrode active materials and electrode binders.

Claims

A polymer having at least one of the structures represented by the following formulas (1) and (2):

In the formula (1), Ar 1 independently represents a substituted or unsubstituted aromatic hydrocarbon group, and Y independently represents a single bond, a divalent linking group, or two bonded to each of two Ar 1 groups. And n represents an integer of 4 or more;

In the formula (2), Ar 2 represents a group containing an aromatic ring independently of each other, provided that a is 1 to 10 except that all of Ar 2 are biphenyl-4,4′-diyl. Represents an integer, Ar 3 represents a group containing an aromatic ring independently of each other, b represents 1 or 2 independently of each other, and a group bonded to N of —Ar 3 — (N) b ═ is bonded to Ar 2 It may combine to form a ring.
A polymer having a structure represented by the following formulas (1) and (6):

In the formula (1), Ar 1 independently represents a substituted or unsubstituted aromatic hydrocarbon group, and Y independently represents a single bond, a divalent linking group, or two bonded to each of two Ar 1 groups. And n represents an integer of 4 or more;

In the formula (6), Ar 4 represents an independently substituted or unsubstituted aromatic hydrocarbon group, and R 2 represents each independently a hydrogen atom, a halo group, a nitro group, a hydroxyl group, a sulfo group, an amino group or Represents an organic group, Z represents a single bond, a divalent linking group, or two hydrogen atoms or substituents bonded to two Ar 4 groups, and “*” represents a bond to Ar 1 in the formula (1). Indicates the hand to join.
The polymer according to claim 1 or 2, wherein the structure represented by the formula (1) has a structure represented by the following formula (R):

In the formula (R), R 1 represents a hydrogen atom, a halo group, a nitro group, a hydroxyl group, a sulfo group, an amino group, or an organic group.
A polymer having a structure represented by the following formulas (3) and (R ′) and having a polystyrene-equivalent weight average molecular weight of 2,000 or more measured by gel permeation chromatography:

In the formula (3), Ar 1 independently represents a substituted or unsubstituted aromatic hydrocarbon group, and Y independently represents a single bond, a divalent linking group, or two bonded to each of two Ar 1 groups. And m represents an integer of 2 or more;

In the formula (R ′), R 1 represents a hydrogen atom, a halo group, a nitro group, a hydroxyl group, a sulfo group, an amino group or an organic group, provided that the organic group is represented by “= N—Ar — **”. In the formula (3), Ar represents a substituted or unsubstituted aromatic hydrocarbon group, ** represents a bond bonded to N in the following formula (3), and the formula (R ′) is It shows that R 1 is bonded to N in the formula (3).
The polymer according to claim 4, having a repeating unit represented by the following formula (3-1) and a structure represented by the following formula (6):

In the formula (3-1), Ar 1 and Y are independently the same as Ar 1 and Y in the formula (3);

In the formula (6), Ar 4 represents an independently substituted or unsubstituted aromatic hydrocarbon group, and R 2 represents each independently a hydrogen atom, a halo group, a nitro group, a hydroxyl group, a sulfo group, an amino group or Represents an organic group, Z represents a single bond, a divalent linking group, or two hydrogen atoms or substituents bonded to each of two Ar 4 groups, and “*” represents Ar 1 in the formula (3-1). Indicates a bond to be combined with.
The polymer according to any one of claims 1 to 5, wherein the polystyrene-reduced weight average molecular weight measured by gel permeation chromatography is 2,000 to 100,000.
The polymer according to any one of claims 1 to 6, which is used for an electrode material.
An electrode containing the polymer according to any one of claims 1 to 6.
An electricity storage device comprising the electrode according to claim 8 as a positive electrode.
A method for producing a polymer, comprising a step of reacting a compound represented by the following formula (7) and a compound represented by the following formula (8) in the presence of a base:

In the formula (7), Ar 1 independently represents a substituted or unsubstituted aromatic hydrocarbon group, X independently represents a chloro group, a bromo group or an iodo group, Y represents a single bond, divalent group Or two hydrogen atoms or substituents bonded to each of the two Ar 1 groups,

In the formula (8), Ar 4 represents an independently substituted or unsubstituted aromatic hydrocarbon group, and R 2 represents each independently a hydrogen atom, halo group, nitro group, hydroxyl group, sulfo group, amino group or Z represents an organic group, and Z represents a single bond, a divalent linking group, or two hydrogen atoms or substituents bonded to each of two Ar 4 groups.
A method for producing a polymer, comprising a step of reacting a compound represented by the following formula (9) with a compound represented by the following formula (10) in the presence of a base:

In formula (9), Ar 5 represents a group containing an aromatic ring;

In Formula (10), Ar 6 represents a group containing an aromatic ring, and X represents a halo group independently of each other.