KR20170031600A - Charge Storage Material, Electrode Active Material and Secondary Battery - Google Patents

Abstract

It is an objective of the present invention to provide materials which have charge storing properties and which, when used as electrode active materials, can provide high-performance batteries that possess high capacity, high rate characteristics, and high cycle characteristics. The materials having charge-storing properties may be made variously of dipyridine-fused benzoquinones of formula (1) or derivatives thereof, dipyridine-fused benzoquinones of formula (4) or derivatives thereof, or dipyridine-fused benzoquinone skeleton-containing polymers. In the formulas, Ar^1 and Ar^2 are each independently a pyridine ring that forms together with two carbon atoms on a benzoquinone skeleton, or a derivative thereof.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a charge storage material, an electrode active material,

The present invention relates to a charge storage material, an electrode active material, and a secondary battery.

The organic secondary battery is a battery using an organic charge storage material as an electrode active material in a secondary battery, and attracts a great deal of attention due to characteristics such as a high rate characteristic, a high capacity retention ratio depending on a charge / discharge cycle, a light weight thin film, and a flexibility. As organic charge storage materials, compounds containing a nitroxy radical group are frequently used (Non-Patent Documents 1 and 2, Patent Document 1), Organic Sulfur Polymers (Non-Patent Documents 3 and 4), Quinone Polymers (Patent Document 2) Based materials (Patent Documents 3, 4 and 5), polycarbonate-based materials (Patent Document 6), and lubeanic acid-based materials (Patent Document 7).

In recent years, by using the lithium secondary battery in coexistence with an inorganic electrode active material, it is possible to improve the capacity and voltage holding ratio (hereinafter referred to as rate characteristics) at the time of high-speed charging and discharging of the lithium ion battery, Property) can be improved (Non-Patent Document 5), and applications and methods of application are being expanded.

Japanese Patent Application Laid-Open No. 2002-117852 Japanese Patent Application Laid-Open No. 2009-217992 Japanese Patent Laid-Open No. 2010-44882 Japanese Patent Laid-Open No. 2010-55923 Japanese Patent Laid-Open No. 2010-80343 Japanese Patent Application Laid-Open No. 2010-212152 Japanese Patent Application Laid-Open No. 2008-147015

Chem. Phys. Lett., Vol. 359, pp. 351-354, 2002 Electrochem. Soc. Interface, vol. 14, pp. 32-36, 2005 J. Electrochem. Soc., Vol. 136, pp. 661-664, 1989 Electrochimica Acta, vol. 46, pp. 2305-2312, 2001 Scientific Reports, vol. 4, pp. 4315-4321, 2014

However, when a battery using a nitroxilicradical charge storage material as an electrode active material has a smaller charge storage capacity than that using an inorganic electrode active material and an organic charge storage material having a high capacity such as an organic sulfur polymer is used, The stability is low, sufficient cycle characteristics can not be obtained, and the voltage is low. In addition to the above-mentioned problems, in addition to the above-mentioned problems, in addition to the above-mentioned problems, in the case of using other organic charge storage materials as a single electrode active material or in combination with an inorganic electrode active material, Conductive property, binding property with an inorganic electrode active material or a current collector and the like are insufficient, so that a sufficient performance as a secondary battery, particularly a lithium ion battery, has not been obtained in some cases.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a material having a charge storage property which can give a high performance battery having high voltage, high capacity, high rate property and high cycle property when used as an electrode active material .

As a result of intensive investigations to achieve the above object, the present inventors have found that a polymer containing a diphyridine dicyclopentadienoquinone or a derivative thereof and a diphyridine dicyclopentadienoquinone skeleton functions as a charge storage material, It has been found that a secondary battery exhibiting a high voltage, a high capacity and a high rate characteristic is provided by overcoming the above problems when used. In addition, it is possible to obtain a derivative by quaternizing nitrogen on the pyridine phase forming the hydrogenated structure, thereby providing a high-performance secondary battery that further increases the voltage and suppresses elution into the electrolyte solution, , Thereby completing the present invention.

That is, the present invention provides the following charge storage material, electrode active material, and secondary battery.

1. A charge storage material comprising a dihydridine cyclic benzoquinone represented by the following formula (1) or a derivative thereof.

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed together with two carbon atoms on the benzoquinone skeleton)

2. The charge storage material according to 1, wherein the dyepyridine dicyclopentadienoquinone or a derivative thereof is represented by the following formula (1-1), (1-2) or (1-3)

(Wherein R ¹ to R ³ each independently represent an alkyl group having 1 to 12 carbon atoms, a propargyl group, a methylstyrene or a norbornene, each of R ⁴ to R ²¹ independently represents a hydrogen atom, a halogen atom, , A mercapto group, an amino group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 12 carbon atoms, An aryl group, a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted A monoalkylamino group, a dialkylamino group in which each alkyl group is independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, a nitro group, a cyano group, a sulfonic acid group, Group, an aminocarbonyl group, or It represents an alkylamino-carbonyl group of a carbon number of 2 to 12.)

3. A charge storage material comprising a dye-containing cyclic benzoquinone skeleton-containing polymer comprising a repeating unit represented by the following formula (2) and / or (3).

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed with two carbon atoms on the benzoquinone skeleton, and each X independently represents a single bond or a divalent group.)

4. The charge storage material of 3, wherein the dipyridyl cyclized benzoquinone skeleton-containing polymer comprises a repeating unit represented by the following formula (2-1), (2-2) and / or (3-1).

(Wherein R ²² represents an alkyl group having 1 to 12 carbon atoms, a propargyl group, a norbornene or a methylstyrene, R ²³ to R ⁴⁰ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, A substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 12 carbon atoms, a substituted or unsubstituted aryl group having 3 to 12 carbon atoms, A substituted or unsubstituted heteroaryl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted monoalkylamino group having 1 to 12 carbon atoms, A dialkylamino group whose alkyl group is independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, a nitro group, a cyano group, a sulfonic acid group, a phosphonic acid group, a carboxyl group, an aminocarbonyl group, Or an alum having 2 to 12 carbon atoms Or a quinoxycarbonyl group.

5. A charge storage material comprising a diphyridine dicyclopentadienoquinone represented by the following formula (4) or a derivative thereof.

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed together with two carbon atoms on the benzoquinone skeleton)

6. The charge storage material of 5, wherein the dipyridinyl cyclic benzoquinone or a derivative thereof is represented by the following formula (4-1), (4-2), or (4-3).

(Wherein R ⁴¹ to R ⁴³ each independently represent an alkyl group having 1 to 12 carbon atoms, a propargyl group, a methylstyrene or a norbornene, R ⁴⁴ to R ⁶¹ each independently represent a hydrogen atom, a halogen atom, , A mercapto group, an amino group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 12 carbon atoms, An aryl group, a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted A monoalkylamino group, a dialkylamino group in which each alkyl group is independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, a nitro group, a cyano group, a sulfonic acid group, Group, an aminocarbonyl group, Represents an alkylamino-carbonyl group of a carbon number of 2 to 12.)

7. A charge storage material comprising a polymer comprising a dipyridene cyclic benzoquinone skeleton containing a repeating unit represented by the following formula (5) and / or (6).

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed together with two carbon atoms on the benzoquinone skeleton, each X independently represents a single bond or a divalent group, Represents -OCH ₂ - or -CH ₂ -.

8. The charge storage material of 7, wherein the dipyridyl cyclized benzoquinone skeleton-containing polymer comprises a repeating unit represented by the following formula (5-1) and / or (6-1).

(Wherein, X and A are the same as above, R ⁶² ~ R ⁷⁰ are independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, an amino group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, having 2 each A substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted monoalkylamino group having 1 to 12 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, A dialkylamino group which is an alkyl group, an alkylcarbonyl group of 2 to 12 carbon atoms, a nitro group, a cyano group, a sulfonic acid group, a phosphonic acid group, a carboxyl group, an aminocarbonyl group or an alkylaminocarbonyl group of 2 to 12 carbon atoms. )

9. A charge storage material comprising a polymer comprising a dipyridene cyclic benzoquinone skeleton containing a repeating unit represented by the following formula (7).

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed with two carbon atoms on the benzoquinone skeleton, and X 'represents a single bond or a divalent group.)

10. The charge storage material of 9, wherein the polymer containing dipyridazine cyclic benzoquinone skeleton comprises a repeating unit represented by the following formula (7-1).

(Wherein, X 'is the same as above, R ⁷¹ - R ⁷⁶ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, an amino group, having 1 to 12 carbon atoms substituted or unsubstituted alkyl group, having 2 to a A substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms, A substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted monoalkylamino group having 1 to 12 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms A nitro group, a cyano group, a sulfonic acid group, a phosphonic acid group, a carboxyl group, an aminocarbonyl group, or an alkylaminocarbonyl group having 2 to 12 carbon atoms.

11. An electrode active material comprising any one of the charge storage materials.

12. An electrode slurry comprising an electrode active material and a solvent.

13. A thin film comprising an electrode active material.

14. A thin film made from an electrode slurry of 12.

15. An electrode comprising an electrode active material.

16. An electrode comprising a thin film of 13 or 14.

17. A secondary battery comprising 15 or 16 electrodes.

18. A lithium ion battery comprising 15 or 16 electrodes.

19. An air cell comprising 15 or 16 electrodes.

20. A diphyridine-dibenzoquinone represented by the following formula (1) or a derivative thereof.

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed together with two carbon atoms on the benzoquinone skeleton)

21. A polymer comprising a repeating unit represented by the following formula (2) and / or (3): ???????? Dipyridine dicyclic benzoquinone skeleton

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed with two carbon atoms on the benzoquinone skeleton, and each X independently represents a single bond or a divalent group.)

22. Dipyridine-dibenzoquinone represented by the following formula (4) or a derivative thereof.

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed together with two carbon atoms on the benzoquinone skeleton)

23. A polymer comprising a repeating unit represented by the following formula (5) and / or (6), wherein the polymer has a dipyridene ring-substituted benzoquinone skeleton.

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed together with two carbon atoms on the benzoquinone skeleton, each X independently represents a single bond or a divalent group, Represents -OCH ₂ - or -CH ₂ -.

24. A polymer comprising a dipyridene cyclic benzoquinone skeleton containing a repeating unit represented by the following formula (7).

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed with two carbon atoms on the benzoquinone skeleton, and X 'represents a single bond or a divalent group.)

The above-mentioned dipyridyl cyclized benzoquinone and its derivatives, and the polymer comprising the diphyridine cyclized benzoquinone skeleton, have a dipyridyl cyclized benzoquinone skeleton as a main body of charge storage, and the resulting anion radical has two pyridine It is stabilized by a bicyclic structure and thus has high electrochemical stability and is useful as a charge storage material. In addition, since the two-electron reduction proceeds to form a stable dianion, when it is used as an electrode active material for a battery, high stability and high capacity are both satisfied.

In addition, the pyridine ring can be derivatized by the bond formation with carbon and can be a quaternary pyridinium salt. Thereby, the potential shifts to a higher side, and when the positive electrode active material is used as a positive electrode active material of the secondary battery, it is possible to make the voltage higher. It is also possible to form a polymer obtained by grafting dipyridazine cyclic benzoquinone or a derivative thereof by reacting a diphyridine dicyclopentadienoquinone or a derivative thereof with another polymer. As a result, it is possible to exhibit elution resistance, swelling property, ionic conductivity, binding property with an inorganic electrode active material or a current collector to a suitable electrolyte solution.

By using the above-mentioned dipyridine cyclic benzoquinone or a derivative thereof, or a polymer containing the dipyridazine cyclic benzoquinone skeleton as an electrode active material, a secondary battery having a high rate characteristic, a high capacity, It is possible to produce. The above-mentioned dipyridinyl cyclized benzoquinone and derivatives thereof, and the polymer comprising the dipyridyl cyclized benzoquinone skeleton are particularly suitable as electrode active materials for lithium ion batteries. In a general secondary battery, an inorganic material or a carbon material is used as an electrode active material. Either the positive electrode or the negative electrode may be substituted for the electrode containing the charge storage material of the present invention, or an inorganic material or a carbon material- It may be used in combination with an active material.

1 is a schematic view of a beaker cell produced in the embodiment.
Fig. 2 is a cyclic voltammogram of the carbon composite electrode produced in Example 9. Fig.
3 is a cyclic voltammogram of the carbon composite electrode produced in Example 10. Fig.
4 is a cyclic voltammogram of the carbon composite electrode produced in Example 11. Fig.
5 is a cyclic voltammogram of an anthraquinone solution and a solution of a diphyridine-dibenzoquinone solution.
FIG. 6 is a cyclic voltammogram of a solution of a diphyridine-cyclized benzoquinone solution, a solution of a diphyridine-cyclized benzoquinone derivative C, and a solution of a diphyridine-dibenzoquinone derivative D. FIG.
7 is a cyclic voltammogram of a solution of a diphyridine-dibenzoquinone derivative E;
8 is a cyclic voltammogram of the carbon composite electrode manufactured in Example 16. Fig.
9 is a graph showing a measurement result of a potential difference with the reference electrode when the charge / discharge capacity of the half-cell fabricated in Example 16 is changed.
10 is a cyclic voltammogram of the carbon composite electrode produced in Example 17. Fig.
11 is a graph showing a measurement result of a potential difference between the lithium ion battery manufactured in Example 17 and the reference electrode when the charge / discharge capacity is changed.
12 is a cyclic voltammogram of the carbon composite electrode produced in Example 18. Fig.
13 is a graph showing the measurement results of the potential difference with the reference electrode when the charge / discharge capacity in the half-cell fabricated in Example 18 is changed.

[Charge storage material]

The first form of the charge storage material of the present invention is composed of a diphyridine-dibenzoquinone represented by the following formula (1) or a derivative thereof. Further, the charge storage material is a material capable of storing electric charges, and this is useful, for example, as an electrode active material of a secondary battery.

Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed together with two carbon atoms on the benzoquinone skeleton.

Such a diphyridine-dibenzoquinone or derivative thereof is preferably represented by the following formula (1-1), (1-2) or (1-3).

In the formulas, R ¹ to R ³ each independently represent an alkyl group having 1 to 12 carbon atoms, a propargyl group, methylstyrene or norbornene. R ⁴ to R ²¹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, an amino group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, A substituted or unsubstituted aryl group having 3 to 12 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms A substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group in which each alkyl group is independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, A nitro group, a cyano group, a sulfonic acid group, a phosphonic acid group, a carboxyl group, an aminocarbonyl group, or an alkylaminocarbonyl group having 2 to 12 carbon atoms.

A second aspect of the charge storage material of the present invention is a polymer comprising a dipyridyl cyclic benzoquinone skeleton-containing polymer containing a repeating unit represented by the following formula (2) and / or (3).

In the formulas, Ar ¹ and Ar ² are the same as described above. X each independently represents a single bond or a divalent group. Among them, X is preferably a single bond and is bonded to a nitrogen atom on the pyridine ring.

Specific examples of the bivalent group include an alkylene group having 1 to 12 carbon atoms, an alkyleneoxy group having 1 to 12 carbon atoms, an alkylenethoxy group having 1 to 12 carbon atoms, an alkylenamino group having 1 to 12 carbon atoms, a dialkyl A dialkylthioether group having 2 to 12 carbon atoms, a dialkylenamino group having 2 to 12 carbon atoms, an alkylenedioxy group having 1 to 12 carbon atoms, an alkylenedioxy group having 1 to 12 carbon atoms, an alkylenedioxy group having 1 to 12 carbon atoms (= O) -O- group, a -OC (= O) - group, an -NH-C (= O) An alkylenecarbonyl group having 2 to 12 carbon atoms, an alkylenethiocarbonyl group having 2 to 12 carbon atoms, an alkylenaminocarbonyl group having 2 to 12 carbon atoms, an alkylenecarbonyl group having 2 to 12 carbon atoms, An oxyalkylene carbonyl group having 2 to 12 carbon atoms, a thioalkylene carbonyl group having 2 to 12 carbon atoms, an aminoalkylene carbonyl group having 2 to 12 carbon atoms, an arylene group having 6 to 20 carbon atoms, an aryleneoxy group having 6 to 20 carbon atoms , Aryl having 6 to 20 carbon atoms An arylene group having 6 to 20 carbon atoms, a diarylene ether group having 6 to 20 carbon atoms, a diarylene thioether group having 6 to 20 carbon atoms, a diarylene amino group having 6 to 20 carbon atoms, An arylene dithio group having 6 to 20 carbon atoms, an arylene diamino group having 6 to 20 carbon atoms, an aryleneaminocarbonyl group having 6 to 20 carbon atoms, an aryleneoxycarbonyl group having 6 to 20 carbon atoms, an aryl An arylenecarbonyl group having 6 to 20 carbon atoms, an oxyarylene carbonyl group having 6 to 20 carbon atoms, a thioarylene carbonyl group having 6 to 20 carbon atoms, an arylenecarbonyl group having 6 to 20 carbon atoms, an arylenecarbonyl group having 6 to 20 carbon atoms, An aminoarylenecarbonyl group having from 1 to 20 carbon atoms, a combination of these groups, and the like. In addition, some or all of hydrogen atoms bonded to these carbon atoms may be substituted with an arbitrary monovalent group.

As such a dipyridazine cyclized benzoquinone skeleton-containing polymer, for example, it is preferable to include a repeating unit represented by the following formula (2-1), (2-2), or (3-1).

In the formula, R ²² represents an alkyl group having 1 to 12 carbon atoms, a propargyl group, methylstyrene or norbornene. R ²³ to R ⁴⁰ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, an amino group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, A substituted or unsubstituted aryl group having 3 to 12 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms A substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group in which each alkyl group is independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, Or an alkylaminocarbonyl group having 2 to 12 carbon atoms.

The content of the repeating unit represented by the formula (2) and / or the repeating unit represented by the formula (3) is preferably 10 to 100 mol%, more preferably 50 to 100 mol%, of the total repeating units in the polymer containing dipyridazine cyclic benzoquinone skeleton , And still more preferably 80 to 100 mol%.

A third embodiment of the charge storage material of the present invention comprises a diphyridine-dibenzoquinone represented by the following formula (4) or a derivative thereof.

(Wherein Ar ¹ and Ar ² are as defined above).

Such a dipyridine-dicarboxylic benzoquinone or a derivative thereof is preferably represented by the following formula (4-1), (4-2) or (4-3).

In the formulas, R ⁴¹ to R ⁴³ each independently represent an alkyl group having 1 to 12 carbon atoms, a propargyl group, a methylstyrene or a norbornene, R ⁴⁴ to R ⁶¹ each independently represent a hydrogen atom, a halogen atom, An amino group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms A substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted monoalkyl group having 1 to 12 carbon atoms Alkylamino group, a dialkylamino group in which each alkyl group is independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, a nitro group, a cyano group, a sulfonic acid group, a phosphonic acid group, , An aminocarbonyl group, and Represents an alkylaminocarbonyl group having 2 to 12 carbon atoms.

A fourth aspect of the charge storage material of the present invention is a polymer comprising a dipyridene cyclic benzoquinone skeleton-containing polymer containing a repeating unit represented by the following formula (5) and / or (6).

Wherein Ar ¹ , Ar ² and X are the same as defined above. Among them, X is preferably a divalent group and is preferably bonded to a carbon atom on the pyridine ring. A is -OCH ₂ each independently - indicates - or -CH _2.

As such a dipyridazine cyclic benzoquinone skeleton-containing polymer, for example, it is preferable to include a repeating unit represented by the following formula (5-1) or (6-1).

Wherein X and A are the same as described above. R ⁶² to R ⁷⁰ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, an amino group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, A substituted or unsubstituted aryl group having 3 to 12 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms A substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group in which each alkyl group is independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, A nitro group, a cyano group, a sulfonic acid group, a phosphonic acid group, a carboxyl group, an aminocarbonyl group, or an alkylaminocarbonyl group having 2 to 12 carbon atoms.

The content of the repeating unit represented by the formula (5) and / or the repeating unit represented by the formula (6) is preferably 10 to 100% by mole, more preferably 50 to 100% by mole in the total repeating units in the polymer containing dipyridyl cyclized benzoquinone skeleton , And still more preferably 80 to 100 mol%.

A fifth aspect of the charge storage material of the present invention is a polymer comprising a dipyridyl cyclic benzoquinone skeleton-containing polymer containing a repeating unit represented by the following formula (7).

In the formulas, Ar ¹ and Ar ² are the same as described above. X 'represents a single bond or a divalent group. Examples of the bivalent group include the same groups as those described in the explanation of X, and an alkylene group having 1 to 5 carbon atoms is preferable. Specific examples thereof include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, Butylene group and the like are preferable. It is preferable that X 'is bonded to a nitrogen atom on the pyridine ring.

As such a dipyridazine cyclic benzoquinone skeleton-containing polymer, it is preferable to include, for example, a repeating unit represented by the following formula (7-1).

Wherein, X 'is the same as above, R ⁷¹ ~ R ⁷⁶ are independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, an amino group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, having a carbon number of 2 to 12, respectively A substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkynyl group having 6 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms, A substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted monoalkylamino group having 1 to 12 carbon atoms, and a substituted or unsubstituted alkylthio group in which each alkyl group is independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms A dialkylamino group, an alkylcarbonyl group having 2 to 12 carbon atoms, a nitro group, a cyano group, a sulfonic acid group, a phosphonic acid group, a carboxyl group, an aminocarbonyl group or an alkylaminocarbonyl group having 2 to 12 carbon atoms.

The content of the repeating unit represented by the formula (7) in the polymer containing the diphyridine-conjugated benzoquinone skeleton is preferably 10 to 100% by mole, more preferably 50 to 100% by mole, And even more preferably 100 mol%.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl group may be any of linear, branched and cyclic, and examples thereof include a methyl group, ethyl group, n-propyl group, i-propyl group, c-propyl group, n- Methyl-c-propyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, Propyl group, a 1-methyl-c-butyl group, a 2-methyl-c-butyl group, a 3-methyl- Propyl group, a 2-ethyl-c-propyl group, an n-hexyl group, a 2-ethyl- Pentyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, Dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3- Dimethyl-n-butyl group, 1- N-propyl group, 1, 2-trimethyl-n-propyl group, 1-ethyl-1-naphthyl group, Methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, c-hexyl group, Butyl group, a 1-ethyl-c-butyl group, a 2-ethyl-c-butyl group, a 3-ethyl- Butyl group, a 2,2-dimethyl-c-butyl group, a 2,3-dimethyl-c-butyl group, a 2,4-dimethyl- , 1-propyl-c-propyl group, 2-n-propyl-c-propyl group, Propyl group, a 2,2,3-trimethyl-c-propyl group, a 1-ethyl-2-methyl- Ethyl-3-methyl-c-propyl group, n-heptyl group, n-octyl group, n N-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like.

The alkenyl group may be linear, branched or cyclic. Examples of the alkenyl group include an ethynyl group, a 1-propenyl group, a 2-propenyl group, a 1-methyl- Methyl-1-propenyl group, a 1-methyl-1-propenyl group, a 1- Propenyl group, 1-n-propenyl group, 1-n-pentenyl group, 2-n-pentenyl group, methyl-2-n-butenyl group, 2-methyl-1-n-butenyl group, 2-n-butenyl group, 3-methyl-3-n-butenyl group, 1-n-propenyl group, 1, 2-dimethyl-2-n-propenyl group, 2-n-hexenyl group, 3-n-hexenyl group, 4-n-pentenyl group, Hexenyl Methyl-2-n-pentenyl group, 1-methyl-3-n-pentenyl group, 1-methyl- Methyl-2-n-pentenyl group, 2-methyl-3-n-pentenyl group, 2-methyl-4-pentenyl group, n-propenyl group, 3-methyl-2-n-pentenyl group, 3-methyl-3-n-pentenyl group, Methyl-2-n-pentenyl group, 4-methyl-1-n-butenyl group, Methyl-4-n-pentenyl group, a 1,1-dimethyl-2-n-butenyl group, a 1,1- Dimethyl-1-n-butenyl group, a 1,2-dimethyl-2-n-butenyl group, a 1,2- Propenyl group, a 1-s-butylheptenyl group, a 1,3-dimethyl-1-n-butenyl group, a 1,3- -Butenyl group, a 2,2-dimethyl-3-n-butenyl group, a 2,3-dimethyl-1-n-butenyl group, n- Propyl-2-n-propenyl group, a 3,3-dimethyl-1-n-butenyl group, a 1-ethyl- 1-n-propyl-1-n-propenyl group, 1-n-propyl-2-n-butylnitroyl group, Propenyl group, a 2-ethyl-1-n-butenyl group, a 2-ethyl-2-n-butenyl group, Propyl group, 1-ethyl-2-methyl-1-n-propenyl group, 1-ethyl- Propyl-2-n-propenyl group, a 1-methyl-2-c-pentenyl group, a 1-methyl- Methyl-1-c-pentenyl group, 2-methyl-2-c-pentenyl group, Methyl-2-c-pentenyl group, 3-methyl-3-c-pentenyl group, 3-methyl-4-pentenyl group, methyl-5-c-pentenyl group, 3-methylene-c-pentyl group, 1-c-hexenyl group, 2-c- Group there may be mentioned 3-c- hexenyl.

The alkynyl group may be any of linear, branched and cyclic. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-n-butynyl group, n-pentynyl group, 4-n-pentynyl group, 1-methyl-2-n-pentynyl group, Methyl-3-n-butynyl group, a 1-methyl-3-n-butynyl group, Ethyl-2-propynyl group, 1-n-hexynyl group, 2-n-hexynyl group, 3-n-hexynyl group, Methyl-3-n-pentynyl group, 2-methyl-4-n-pentynyl group, 3-methyl 1-n-pentynyl group, 4-methyl-2-n-pentynyl group, 1,1-dimethyl-2- n-butynyl group, a 2,2-dimethyl-3-n-butynyl group, a 2,3-n-butynyl group, Dimethyl-1-butynyl group, 1-ethyl-2- Methyl-1-ethyl-2-propynyl group, 1-i-propynyl group, -Propyl-2-propynyl group and the like.

Examples of the aryl group include a phenyl group, an a-naphthyl group, a -naphthyl group, an o-biphenyl group, an m-biphenyl group, Phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.

Examples of the heteroaryl group include a 2-furyl group, a 3-furyl group, a 2-thienyl group, a 3-thienyl group, a 1-pyrrolyl group, A 2-imidazolyl group, a 4-imidazolyl group, and the like.

The alkoxy group may be linear, branched or cyclic. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a c- n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, Butoxy group, 1,1-dimethyl-n-propoxy group, c-pentyloxy group, 2-methyl-c-butoxy group, n-hexyloxy group, n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a c-hexyloxy group, a 1-ethyl- N-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-pentyloxy group, Decyloxy group, n-undecyloxy group, n-dodecyloxy group and the like.

The alkylthio group may be linear, branched or cyclic. Examples of the alkylthio group include methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, s- Butyltrimethyltrimethyltrimethyltrimethyltrimethyltrimethyltrimethyltrimethyltrimethyltrimethyltrimethyltrimethyltrimethyltrimethyltrimethyltrimethoxytrimethyltrimethyltrimethoxytrimethyltrimethyltrimethoxytrimethyltrimethyltrimethoxytrimethyltrimethyltrimethoxytrimethyltrimethyltrimethoxytrimethyltrimethyltrimethoxytrimethyltrimethyltrimethoxytrimethyltrimethyltrimethyltrimethyltrimethoxytrimethyltrimethyltrimethyltrimethoxytrimethyltrimethyltrimethoxytrimethyltrimethyltrimethoxytrimethyltrimethyltrimethoxytrimethyltrimethoxytetruate N-pentylthio, 2-methyl-n-pentylthio, 1,1-dimethyl-n-butylthio, N-heptylthio group, n-heptylthio group, n-heptylthio group, n-octylthio group, 2-ethyl- N-decylthio, n-undecylthio, n-dodecylthio, and the like.

The monoalkylamino group may be any of linear, branched and cyclic, and examples thereof include a methylamino group, ethylamino group, n-propylamino group, i-propylamino group, c-propylamino group, n- Butylamino group, a tert-butylamino group, a c-butylamino group, a 1-methyl-c-propylamino group, a 2-methyl- Dimethyl-n-propylamino group, a 2,2-dimethyl-n-propylamino group, a 2,2-dimethyl-n-butylamino group, Propylamino group, a c-pentylamino group, a 1-methyl-c-butylamino group, a 2-methyl-c-butylamino group, a 3-methyl- Propylamino group, 2-ethyl-c-propylamino group, n-hexylamino group, 1-methyl-n-pentylamino group Methyl-n-pentylamino group, a 1,1-dimethyl-n-butylamino group, a 1,2-dimethyl-n-butyl An amino group, a 1,3-dimethyl-n-butylamino group, a 2,2-dimethyl-n-butylamino group, a 2,3- Ethyl-n-butylamino group, 2-ethyl-n-butylamino group, 1,1,2-trimethyl-n-propylamino group, 1,2,2- Propylamino group, a c-hexylamino group, a 1-methyl-c-pentylamino group, a 2-methyl-c-pentylamino group, a 3-methyl-c Ethyl-c-butylamino group, 3-ethyl-c-butylamino group, 1,2-dimethyl-c-butylamino group, 1,3-dimethyl- dimethyl-c-butylamino group, a 2,4-dimethyl-c-butylamino group, a 3,3-dimethyl-c- View Propylamino group, 2-i-propyl-c-propylamino group, 1, 2-propyl-c- Propylamino group, a 2-trimethyl-c-propylamino group, a 1-ethyl-2-methyl- Ethyl-1-methyl-c-propylamino group, 2-ethyl-2-methyl-c-propylamino group and 2-ethyl-3-methyl-c-propylamino group.

The dialkylamino group may be any of linear, branched and cyclic, and examples thereof include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a di- Di-tert-butylamino group, di-tert-butylamino group, di-tert-butylamino group, di- Di-n-butylamino group, di- (2-methyl-n-butyl) amino group, di- (3- (1,2-dimethyl-n-propyl) amino group, di- (2,2-dimethyl- (1-ethyl-n-propyl) amino group, a di-c-pentylamino group, a di- Amino group, a di- (3-methyl-c-butyl) amino group, a di- (1,2 (1-ethyl-c-propyl) amino group, di- (2-ethyl-c- (1-methyl-n-pentyl) amino group, a di- (3-methyl- (1, 2-dimethyl-n-butyl) amino group, di- (1, Dimethyl-n-butyl) amino group, a di- (2,2-dimethyl-n-butyl) amino group, (1-ethyl-n-butyl) amino group, a di- (1-ethyl-n-butyl) amino group, (1-ethyl-2-methyl-n-propyl) amino group, a di- ) Amino group, di-c-hexylamino group, di- (1-methyl- (1-ethyl-c-butyl) amino group, di- (2-ethyl-c-pentyl) amino group, di- dimethyl-c-butyl) amino group, di- (3-ethyl-c-butyl) amino group, di- Di- (2,2-dimethyl-c-butyl) amino group, di- (2,3-dimethyl- Di- (1-n-propyl-c-propyl) amino group, di- propyl) amino group, a di- (1,2-trimethyl-c-propyl) amino group, Dimethyl-c-propyl) amino group, di- (2,2,3-trimethyl-c-propyl) amino group, di- Ethyl-1-methyl-c-propyl) amino group, di- (2-ethyl- Ropil) amino group, di-there may be mentioned (2-ethyl-3-methyl -c- propyl) amino group and the like.

Examples of the alkylcarbonyl group include methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, i-propylcarbonyl, c-propylcarbonyl, n- Propylcarbonyl group, a n-pentylcarbonyl group, a 1-methyl-n-butylcarbonyl group, a 1-methyl-n-butylcarbonyl group, N-propylcarbonyl group, a 1,2-dimethyl-n-propylcarbonyl group, a 2,2-dimethyl-n-butylcarbonyl group, Dimethyl-n-propylcarbonyl group, 1-ethyl-n-propylcarbonyl group, c-pentylcarbonyl group, 1-methyl- Dimethyl-c-propylcarbonyl group, a 1-ethyl-c-propylcarbonyl group, a 2-ethyl-c-propylcarbonyl group n-hexylcarbonyl group, 1-methyl-n-pentylcarbonyl group, 2-methyl-n-pentylcarbonyl group, 3-methyl- N-butylcarbonyl group, a 1,2-dimethyl-n-butylcarbonyl group, a 1,3-dimethyl-n-butylcarbonyl group, Dimethyl-n-butylcarbonyl group, a 3-dimethyl-n-butylcarbonyl group, a 1-ethyl-n-butylcarbonyl group, n-propylcarbonyl group, 1, 2-trimethyl-n-propylcarbonyl group, 1-ethyl-1-methyl-n-propylcarbonyl group Methyl-c-pentylcarbonyl group, 3-methyl-c-pentylcarbonyl group, 3-methyl- Butylcarbonyl group, a 2-ethyl-c-butylcarbonyl group, a 3-ethyl-c-butylcarbonyl group, a 1,2- dimethyl-c-butylcarbonyl group, a 2,4-dimethyl-c-butylcarbonyl group, a 3,3-dimethylcyclohexylcarbonyl group, Dimethyl-c-butylcarbonyl group, 1-n-propyl-c-propylcarbonyl group, 2-n- 1-propyl-c-propylcarbonyl group, 2-i-propyl-c-propylcarbonyl group, 1,2,2-trimethyl-c-propylcarbonyl group, Propylcarbonyl group, 2-ethyl-1-methyl-c-propylcarbonyl group, 2-ethyl- Ethyl-2-methyl-c-propylcarbonyl group, 2-ethyl-3-methyl-c-propylcarbonyl group and the like.

Examples of the alkylaminocarbonyl group include a methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, i-propylaminocarbonyl group, c-propylaminocarbonyl group, n-butylaminocarbonyl group, Butylaminocarbonyl group, a c-butylaminocarbonyl group, a 1-methyl-c-propylaminocarbonyl group, a 2-methyl-c-propylaminocarbonyl group, a n-pentyl Aminocarbonyl group, a 1-methyl-n-butylaminocarbonyl group, a 2-methyl-n-butylaminocarbonyl group, a 3-methyl-n-butylaminocarbonyl group, Propylaminocarbonyl group, a c-pentylaminocarbonyl group, a 1-methylpropylaminocarbonyl group, a 1-methyl-n-propylaminocarbonyl group, butylaminocarbonyl group, 2-methyl-c-butylaminocarbonyl group, 3-methyl-c-butylaminocarbonyl group, 1,2-dimethyl- Ethyl-c-propylaminocarbonyl group, n-hexylaminocarbonyl group, 1-methyl-n-propylaminocarbonyl group, N-pentylaminocarbonyl group, 4-methyl-n-pentylaminocarbonyl group, 1,1-dimethyl-n-butylamino N-butylaminocarbonyl group, a 2,2-dimethyl-n-butylaminocarbonyl group, a 2,3-di Methyl-n-butylaminocarbonyl group, 3,3-dimethyl-n-butylaminocarbonyl group, 1-ethyl-n-butylaminocarbonyl group, 2-ethyl- Propylaminocarbonyl group, 1-ethyl-1-methyl-n-propylaminocarbonyl group, 1-ethyl-2-methyl- propylaminocarbonyl group, a c-hexylaminocarbonyl group, a 1-methyl-c-pentylaminocarbonyl group, a 2-methyl- ethyl-c-butylaminocarbonyl group, 3-ethyl-c-butylaminocarbonyl group, 3-ethyl- Butylaminocarbonyl group, a 1,2-dimethyl-c-butylaminocarbonyl group, a 1,3-dimethyl-c-butylaminocarbonyl group, a 2,2- butylaminocarbonyl group, a 1-n-propyl-c-propylaminocarbonyl group, a 2-tert-butylaminocarbonyl group, propylaminocarbonyl group, 1,2-trimethyl-c-propylaminocarbonyl group, 1,2-trimethyl-c-propylaminocarbonyl group, Propylaminocarbonyl group, a 1-ethyl-2-methyl-c-propylaminocarbonyl group, a 2-methyl- Ethyl-1-methyl-c-propylaminocarbonyl group, 2-ethyl-2-methyl-c-propylaminocarbonyl group, 2- Methyl-c-propylaminocarbonyl group and the like.

Of these, R ¹ to R ³ , R ²² and R ⁴¹ to R ^{43 are preferably} methyl, ethyl, n-propyl, i-propyl, n-butyl or s Butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, methylbutyl, 1-ethylbutyl, 1,1,2-trimethylpropyl and the like are preferable, and methyl, ethyl, n-butyl, , n-propyl group, i-propyl group, n-butyl group, s-butyl group and t-butyl group are more preferable. R ⁴ to R ²¹ , R ²³ to R ⁴⁰ and R ⁴⁴ to R ^{76 each represent a} hydrogen atom, a chlorine atom, a methyl group, an ethyl group, a n-propyl group, an i- Methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 1-methylbutyl group, Methylpentyl, 1,1-dimethylbutyl, 1-ethylbutyl, 1,1,2-trimethylpropyl, methylcarbonyl, nitro, cyano, sulfone A methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, More preferably a methyl group, a t-butyl group, a t-butyl group, a methylcarbonyl group, a nitro group, a cyano group, a sulfonic acid group, a phosphonic acid group, a carboxyl group, an aminocarbonyl group or a methylaminocarbonyl group. R ⁴ to R ²¹ and R ²³ to R ⁴⁰ are most preferably hydrogen atoms.

In addition, some or all of the hydrogen atoms bonded to the carbon atoms of the aforementioned groups may be substituted with a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a hydroxyl group, a mercapto group, an amino group, an alkoxy group having 1 to 11 carbon atoms, a haloalkoxy group having 1 to 11 carbon atoms, An alkylthio group having 1 to 11 carbon atoms, a monoalkylamino group having 1 to 11 carbon atoms, and each alkyl group is independently a dialkylamino group having 1 to 11 carbon atoms, a glycidoxy group, an alkylcarbonyl group having 2 to 11 carbon atoms, An alkynylcarbonyl group having 3 to 11 carbons, an alkynylcarbonyl group having 3 to 11 carbons, an alkylcarbonyloxy group having 2 to 11 carbons, an alkenylcarbonyloxy group having 3 to 11 carbons, an alkynylcarbonyloxy group having 3 to 11 carbons, A halogenated aryl group having 6 to 11 carbon atoms, a heteroaryl group having 3 to 11 carbon atoms, a halogenated heteroaryl group having 3 to 11 carbon atoms, and the like. However, when the above substituents are present, the upper limit of the total number of carbon atoms in R ¹ to R ⁷⁶ is 12 respectively.

Examples of the alkoxy group having 1 to 11 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, c-propoxy group, n-butoxy group, propoxy group, a n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, n-butoxy group, 1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2- Propoxy group, a c-pentyloxy group, a 1-methyl-c-butoxy group, a 2-methyl-c-butoxy group, a 3-methyl- Propyl group, a dimethyl-c-propoxy group, a 2,3-dimethyl-c-propoxy group, a 1-ethyl- Pentyloxy group, a methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl- 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl- N-butoxy group, a 1-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-butoxy group, N-propoxy group, 1-ethyl-2-methyl-n-propoxy group, c-hexyl group, Methyl-c-pentyloxy group, a 1-ethyl-c-butoxy group, a 2-ethyl-c-butoxy group, Dimethyl-c-butoxy group, a 2,2-dimethyl-c-butoxy group, a 2,3-dimethyl- Dimethyl-c-butoxy group, a 2-n-propyl-c-butoxy group, a 2,4-dimethyl- c-propoxy group, 1-i-propyl-c-propoxy group, 2-i-propyl- Methyl-c-propoxy group, 2-ethyl-1-methyl-c-propoxy group, 2-ethyl-2-methyl-c-propyl N-hexyloxy group, n-hexyloxy group, n-hexyloxy group, n-hexyloxy group, n-hexyloxy group, have.

Examples of the haloalkoxy group having 1 to 11 carbon atoms include a difluoromethoxy group, a trifluoromethoxy group, a bromodifluoromethoxy group, a 2-chloroethoxy group, a 2-bromoethoxy group, a 1,1- Trifluoromethoxy group, difluoroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, 2-chloro-1,1,2-trifluoroethoxy group A pentafluoroethoxy group, a 3-bromopropoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 1,1,2,3,3,3-hexafluoropropoxy group , 1,1,1,3,3,3-hexafluoropropen-2-yloxy group, 3-bromo-2-methylpropoxy group, 4-bromobutoxy group, perfluoropentyloxy group and the like .

Examples of the alkylthio group having 1 to 11 carbon atoms include methylthio group, ethylthio group, n-propylthio group, i-propylthio group, c-propylthio group, n-butylthio group, methyl-c-propylthio group, n-pentylthio group, 1-methyl-n-butylthio group, -Butylthio group, 2-methyl-n-butylthio group, 3-methyl-n-butylthio group, 1,1-dimethyl-n-propylthio group, , 2-methyl-n-propylthio group, 1-ethyl-n-propylthio group, c-pentylthio group, Dimethyl-c-propylthio group, 1-ethyl-c-propylthio group, 2-ethyl- methyl-n-pentylthio, 3-methyl-n-pentylthio, 4-methyl-n-pentylthio, , 1,1-dimethyl-n-butylthio group, 1,2-dimethyl-n -Butylthio group, 3-dimethyl-n-butylthio group, 2,2-dimethyl-n-butylthio group, 2,3- n-butyllithium, 1-ethyl-n-butyllithium, 2-ethyl-n-butyllithium, 1,1,2-trimethyl- methyl-n-propylthio group, 1-ethyl-2-methyl-n-propylthio group, c-hexylthio group, 1-methyl- , 2-methyl-c-pentylthio group, 3-methyl-c-pentylthio group, 1-ethyl-c-butylthio group, , 1,2-dimethyl-c-butyrylthio, 1,3-dimethyl-c-butytilty, 2,2-dimethyl-c-butytilty, 2,3- Propylthio group, 2-n-propyl-c-propylthio group, 2-n-propyl-c-butylthio group, Propylthio, 2-i-propyl-c-propylthio, 1,2,2-trimethyl-c-propylthio, 1,2,3-trimethyl -c Propylthio group, 2-ethyl-1-methyl-c-propylthio group, 2- Propylthio group, n-heptylthio group, n-octylthio group, n-nonylthio group, n-decylthio group, and n-undecylthio group.

Examples of the monoalkylamino group having 1 to 11 carbon atoms include methylamino, ethylamino, n-propylamino, i-propylamino, c-propylamino, Propylamino group, a 2-methyl-n-butylamino group, a 1-methyl-n-butylamino group, a 2-methyl- Dimethyl-n-propylamino group, a 2,2-dimethyl-n-propylamino group, a 1-ethyl-n-propylamino group, Butylamino group, 2-methyl-c-butylamino group, 3-methyl-c-butylamino group, 1,2-dimethyl-c-propylamino group, Propylamino group, a 2-ethyl-c-propylamino group, an n-hexylamino group, a 1-methyl-n-pentylamino group, a 2-methyl- , 3-methyl n-butylamino group, a 1-dimethyl-n-butylamino group, a 1-dimethyl-n-butylamino group, Butylamino group, a 3-dimethyl-n-butylamino group, a 1-ethyl-n-butylamino group, a 2-ethyl- n-propylamino group, 1-ethyl-1-methyl-n-propylamino group, 1-ethyl- Propylamino group, a 2-methyl-n-propylamino group, a c-hexylamino group, a 1-methyl- Dimethyl-c-butylamino group, a 2-ethyl-c-butylamino group, a 3-ethyl- Butylamino group, a 2,3-dimethyl-c-butylamino group, a 2,4-dimethyl-c-butylamino group, a 3,3- Propylamino group, a 2-i-propyl-c-propylamino group, a 1,2,2-trimethyl-c-propylamino group, Propylamino group, a 1-ethyl-2-methyl-c-propylamino group, a 2-ethyl-1-methyl-c -Propylamino group, 2-ethyl-2-methyl-c-propylamino group, 2-ethyl-3-methyl-c-propylamino group and the like.

Examples of the dialkylamino group having 1 to 11 carbon atoms in each of the above alkyl groups are a dimethylamino group, a diethylamino group, a di-n-propylamino group, a di-i-propylamino group, di-tert-butylamino group, di-tert-butylamino group, di-tert-butylamino group, di- Di-n-pentylamino group, di- (1-methyl-n-butyl) amino group, n-propyl) amino group, di- (2,2-dimethyl-n-propyl) amino group, Propyl) amino group, di- (1-ethyl-n-propyl) amino group, di- Di- (3-methyl-c-butyl) amino group, di- (1,2 (1-ethyl-c-propyl) amino group, di- (2-ethyl-c- (1-methyl-n-pentyl) amino group, a di- (3-methyl- (1, 2-dimethyl-n-butyl) amino group, di- (1, Dimethyl-n-butyl) amino group, a di- (2,2-dimethyl-n-butyl) amino group, (1-ethyl-n-butyl) amino group, a di- (1-ethyl-n-butyl) amino group, (1-ethyl-2-methyl-n-propyl) amino group, a di- ) Amino group, di-c-hexylamino group, di- (1-methyl- (1-ethyl-c-butyl) amino group, di- (2-ethyl-c-pentyl) amino group, di- dimethyl-c-butyl) amino group, di- (3-ethyl-c-butyl) amino group, di- Di- (2,2-dimethyl-c-butyl) amino group, di- (2,3-dimethyl- Di- (1-n-propyl-c-propyl) amino group, di- propyl) amino group, a di- (1,2-trimethyl-c-propyl) amino group, Dimethyl-c-propyl) amino group, di- (2,2,3-trimethyl-c-propyl) amino group, di- Ethyl-1-methyl-c-propyl) amino group, di- (2-ethyl- Ropil) amino group, di-there may be mentioned (2-ethyl-3-methyl -c- propyl) amino group and the like.

Examples of the alkylcarbonyl group having 2 to 11 carbon atoms include methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, i-propylcarbonyl, c-propylcarbonyl, n-butylcarbonyl, methyl-c-propylcarbonyl group, an n-pentylcarbonyl group, a 1-methyl-n-butylcarbonyl group, a tert-butylcarbonyl group, Methyl-n-butylcarbonyl group, a 1,1-dimethyl-n-propylcarbonyl group, a 1,2-dimethyl-n-propylcarbonyl group Butylcarbonyl group, a 2-methyl-c-butylcarbonyl group, a 2-methyl-n-propylcarbonyl group, Propylcarbonyl group, a 1-ethyl-c-propylcarbonyl group, a 2-ethyl-c-butylcarbonyl group, n-hexylcarbonyl group, 1-methyl-n-pentylcarbonyl group, 2-methyl-n-pentylcarbonyl group, 3-methyl- Methyl-n-pentylcarbonyl group, a 1,1-dimethyl-n-butylcarbonyl group, a 1,2-dimethyl-n-butylcarbonyl group, N-propylcarbonyl group, a 3-dimethyl-n-butylcarbonyl group, a 1-ethyl-n-butylcarbamoyl group, N-propylcarbonyl group, 1-ethyl-1-methyl-n-butylcarbonyl group, propylcarbonyl group, a 1-methyl-c-pentylcarbonyl group, a 2-methyl-c-pentylcarbonyl group, a 3-methyl- butylcarbonyl group, a 1-ethyl-c-butylcarbonyl group, a 1-ethyl-c-butylcarbonyl group, a 3-ethyl- Dimethyl-c-butylcarbonyl group, 2,2-dimethyl-c-butylcarbonyl group, 2,3-dimethyl-c-butylcarbonyl group, 2,4- , 3,3-dimethyl-c-butylcarbonyl group, 1-n-propyl-c-propylcarbonyl Propylcarbonyl group, a 2-n-propyl-c-propylcarbonyl group, a 1-i-propyl- Propylcarbonyl group, a 1-ethyl-2-methyl-c-propylcarbonyl group, a 2-ethyl-2-methylpropylcarbonyl group, Methyl-c-propylcarbonyl group, 2-ethyl-2-methyl-c-propylcarbonyl group and 2-ethyl-3-methyl-c-propylcarbonyl group.

Examples of the alkenylcarbonyl group having 3 to 11 carbon atoms include an ethynylcarbonyl group, a 1-propenylcarbonyl group, a 2-propenylcarbonyl group, a 1-methyl-1-ethenylcarbonyl group, Methyl-2-propenylcarbonyl group, a 1-ethylethenylcarbonyl group, a 1-methyl-1-propenylcarbonyl group, a 2-methylbutylcarbonyl group, Propenylcarbonyl group, a 3-pentenylcarbonyl group, a 4-pentenylcarbonyl group, a 1-n-propylcarbonyl group, Methyl-2-butenylcarbonyl group, 2-ethyl-2-propenylcarbonyl group, 2-ethyl-2-propenylcarbonyl group, Methyl-2-butenylcarbonyl group, 3-methyl-1-butenylcarbonyl group, 3-methyl-2-t-butenylcarbonyl group, Methyl-3-butenylcarbonyl group, 1,1-dimethyl-2-propenylcarbonyl group, 1-i-propylethenylcarbonyl group, 1,2 1-propenylcarbonyl group, 2-c-pentenylcarbonyl group, 3-c-pentenylcarbamoyl group, 1-hexenylcarbonyl, 2-hexenylcarbonyl, 3-hexenylcarbonyl, 4-hexenylcarbonyl, 5-hexenylcarbonyl, 1-methyl-1-pentenylcarbonyl, 1- Methyl-3-pentenylcarbonyl group, 1-methyl-4-pentenylcarbonyl group, 1-n-butylethenylcarbonyl group, 2-methyl-1-pentenylcarbamoyl group, Methyl-2-pentenylcarbonyl group, 2-methyl-3-pentenylcarbonyl group, 2- Methyl-3-pentenylcarbonyl group, 3-methyl-4-pentenylcarbonyl group, 3-ethyl-3-butenylcarbonyl group, Methyl-1-pentenylcarbonyl group, 4-methyl-2-pentenylcarbonyl group, 4-methyl-3-pentenylcarbonyl group, Dimethyl-2-butenylcarbonyl group, 1,1-di 3-butenylcarbonyl group, a 1,2-dimethyl-1-butenylcarbonyl group, a 1,2-dimethyl-2-butenylcarbonyl group, Methyl-2-ethyl-2-propenylcarbonyl group, 1-s-butylethenylcarbonyl group, 1,3- Tert-butylcarbonyl group, 2,2-dimethyl-3-butenylcarbonyl group, 2,3-dimethyl-1-naphthylcarbonyl group, 2-propenyl-2-propenylcarbonyl group, 3,3-dimethyl-3-butenylcarbonyl group, Ethyl-1-butenylcarbonyl group, 1-ethyl-3-butenylcarbonyl group, 1-n-propyl- Propylcarbonyl group, 2-ethyl-2-butenylcarbonyl group, 2-ethyl-3-butenyl Carbonyl group, 1,1,2-trimethyl-2-propenylcarbonyl group, 1-t- Methyl-1-ethyl-2-propenylcarbonyl group, 1-ethyl-2-methyl-1-propenylcarbonyl group, propylcarbonyl group, 1-methyl-2-c-pentenylcarbonyl group, 1-methyl-3-c-pentenylcarbonyl group Methyl-2-c-pentenylcarbonyl group, 2-methyl-1-c-pentenylcarbonyl group, Methyl-2-c-pentenylcarbonyl group, 3-methyl-1-c-pentenylcarbonyl group, 3-methyl- Methyl-4-c-pentenylcarbonyl group, 3-methyl-5-c-pentenylcarbonyl group, 3-methylene-c-pentylcarbonyl group, , 1-c-hexenylcarbonyl group, 2-c-hexenylcarbonyl group, 3-c-hexenylcarbonyl group and the like.

Examples of the alkynylcarbonyl group having 3 to 11 carbon atoms include an ethynylcarbonyl group, an 1-propynylcarbonyl group, a 2-propynylcarbonyl group, a 1-butynylcarbonyl group, a 2-butynylcarbonyl group, 2-propynylcarbonyl group, 2-pentynylcarbonyl group, 3-pentynylcarbonyl group, 4-pentynylcarbonyl group, 1-methyl- Methyl-3-butynylcarbonyl group, 3-methyl-1-butynylcarbonyl group, 1,1-dimethyl-2-propynylcarbonyl group , 2-propynylcarbonyl, 1-hexynylcarbonyl, 2-hexynylcarbonyl, 3-hexynylcarbonyl, 4-hexynylcarbonyl, 5-hexynylcarbonyl, Methyl-4-pentynylcarbonyl group, 2-methyl-3-pentynylcarbonyl group, 2-methyl-4-pentynylcarbonyl group, Methyl-1-pentynylcarbonyl group, 3-methyl-4-pentynylcarbonyl group, 4-methyl-1-pentynylcarbonyl group, Dimethyl-2-butynylcarbonyl group, 1,1-dimethyl-3-butynylcarbonyl group, 1,2-dimethyl-3-butynylcarbonyl group, 2,2- Butynylcarbonyl group, a 1-ethyl-3-butynylcarbonyl group, a 1-n-propylcarbonyl group, Propylcarbonyl group, 2-ethyl-3-butynylcarbonyl group, 1-methyl-1-ethyl-2-propynyl group and 1-i-propyl-2-propynylcarbonyl group.

Examples of the alkylcarbonyloxy group having 2 to 11 carbon atoms include methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, i-propylcarbonyloxy, c-propylcarbonyloxy, Butylcarbonyloxy group, a tert-butylcarbonyloxy group, a 1-methyl-c-propylcarbonyloxy group, a 2-methyl-c-propylcarbonyloxy group, N-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group, 3-methyl- N-propylcarbonyloxy group, 1-ethyl-n-propylcarbonyloxy group, c-pentylcarbonyloxy group, Methyl-c-butylcarbonyloxy group, a 1,2-dimethyl-c-propylcarbonyloxy group, a 2-methylcyclohexylcarbonyloxy group, , 3-dimethyl-c-propylcarbonyloxy group, 1- Propylcarbonyloxy group, an n-hexylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 3-ethyl- 1-dimethyl-n-butylcarbonyloxy group, a 1,2-dimethyl-n-butylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, N-butylcarbonyloxy group, 2,2-dimethyl-n-butylcarbonyloxy group, 2,3-dimethyl-n-butylcarbonyloxy group, 3,3- Butylcarbonyloxy group, a 1-ethyl-n-butylcarbonyloxy group, a 2-ethyl-n-butylcarbonyloxy group, a 1,1,2- Methyl-n-propylcarbonyloxy group, a c-hexylcarbonyloxy group, a 1-methyl-n-propylcarbonyloxy group, ethyl-c-butylcarbonyloxy group, 2-ethyl-c-butylcarbonyloxy group, 2-methyl-c-pentylcarbonyloxy group, Butylcarbonyloxy group, 1,3-dimethyl-c-butylcarbonyloxy group, 2,2-dimethyl-c-butylcarbonyloxy group, Dimethyl-c-butylcarbonyloxy group, 3,3-dimethyl-c-butylcarbonyloxy group, 1- propyl-c-propylcarbonyloxy group, 2-n-propyl-c-propylcarbonyloxy group, Trimethyl-c-propylcarbonyloxy group, a 1,2,3-trimethyl-c-propylcarbonyloxy group, a 2,2,3-trimethyl- Ethyl-2-methyl-c-propylcarbonyloxy group, 2-ethyl-1-methyl-c-propylcarbonyloxy group, -c-propylcarbonyloxy group and the like.

Examples of the alkenylcarbonyloxy group having 3 to 11 carbon atoms include an ethenylcarbonyloxy group, a 1-propenylcarbonyloxy group, a 2-propenylcarbonyloxy group, a 1-methyl-1-ethenylcarbonyloxy group, Propenylcarbonyloxy group, a 2-methyl-2-propenylcarbonyloxy group, a 1-ethyl-2-propenylcarbonyloxy group, 1-propenylcarbonyloxy group, 1-pentenylcarbonyloxy group, 2-pentenylcarbonyloxy group, 3-pentenylcarbonyloxy group, Methyl-1-butenylcarbonyloxy group, a 1-methyl-2-butenylcarbonyloxy group, a 1-methylpropylcarbonyloxy group, a 1-methylpropylcarbonyloxy group, Propenylcarbonyloxy group, 2-methyl-1-butenylcarbonyloxy group, 2-methyl-2-butenylcarbonyloxy group, 2-methyl- -Butenyl carbonyloxy group, 3-methyl-1-butenylcarbonyloxy Methyl-2-butenylcarbonyloxy group, a 3-methyl-3-butenylcarbonyloxy group, a 1,1- , A 1,2-dimethyl-1-propenylcarbonyloxy group, a 1,2-dimethyl-2-propenylcarbonyloxy group, a 1-c-pentenylcarbonyloxy group, , A 3-c-pentenylcarbonyloxy group, a 1-hexenylcarbonyloxy group, a 2-hexenylcarbonyloxy group, a 3-hexenylcarbonyloxy group, a 4-hexenylcarbonyloxy group, a 5-hexenylcarbonyloxy group Methyl-1-pentenylcarbonyloxy group, 1-methyl-2-pentenylcarbonyloxy group, 1-methyl- methyl-2-pentenylcarbonyloxy group, a 2-methyl-3-pentenylcarbonyloxy group, a 2-methyl-1-pentenylcarbonyloxy group, 2-propenylcarbonyloxy group, 3-methyl-1-pentenylcarbonyloxy group, 3-methyl-2-pentenyl Methyl-3-pentenylcarbonyloxy group, 3-methyl-3-butenylcarbonyloxy group, 4-methyl-1-pentenylcarbonyloxy group, Methyl-2-pentenylcarbonyloxy group, 4-methyl-4-pentenylcarbonyloxy group, 1,1-dimethyl- 1-dimethyl-3-butenylcarbonyloxy group, 1,2-dimethyl-1-butenylcarbonyloxy group, Methyl-2-ethyl-2-propenylcarbonyloxy group, 1-s-butylheptenylcarbonyloxy group, 1,3-dimethyl- Butylcarbonyloxy group, a 1-i-butylhexylcarbonyloxy group, a 2,2-dimethyl-2-butenylcarbonyloxy group, a 1,3- Dimethyl-3-butenylcarbonyloxy group, 2,3-dimethyl-1-butenylcarbonyloxy group, 2,3-dimethyl- Butenylcarbonyloxy Ethyl-1-butenylcarbonyloxy group, 1-ethyl-2-naphthylcarbonyloxy group, 1-ethyl-2-propenylcarbonyloxy group, Propenylcarbonyloxy group, 1-n-propyl-2-propenylcarbonyloxy group, 2-ethyl-1-propenylcarbonyloxy group, Ethyl-2-butenylcarbonyloxy group, a 1,1,2-trimethyl-2-propenylcarbonyloxy group, a 1- methyl-1-ethyl-2-propenylcarbonyloxy group, 1-ethyl-2-methyl-1-propenylcarbonyloxy group, 1-ethyl- 1-propyl-2-propenylcarbonyloxy group, 1-methyl-2-c-pentenylcarbonyloxy group, 1-propyl- 2-methyl-2-c-pentenylcarbonyloxy group, 2-methyl-3-c-pentenecarbonyloxy group, 2- A thienylcarbonyloxy group, a 2- Pentylcarbonyloxy group, 2-methyl-5-c-pentenylcarbonyloxy group, 2-methylene-c-pentylcarbonyloxy group, 3-methyl- Methyl-2-c-pentenylcarbonyloxy group, 3-methyl-3-c-pentenylcarbonyloxy group, 3-methyl- A 3-methylene-c-pentylcarbonyloxy group, a 1-c-hexenylcarbonyloxy group, a 2-c-hexenylcarbonyloxy group, a 3-c-hexenylcarbonyloxy group, .

Examples of the alkynylcarbonyloxy group having 3 to 11 carbon atoms include ethynylcarbonyloxy, 1-propynylcarbonyloxy, 2-propynylcarbonyloxy, 1-butynylcarbonyloxy, 2- Propynylcarbonyloxy group, a 2-pentynylcarbonyloxy group, a 3-pentynylcarbonyloxy group, a 4-pentynylcarbonyloxy group, a 3-pentynylcarbonyloxy group, Methyl-2-butynylcarbonyloxy group, 2-methyl-3-butynylcarbonyloxy group, 3-methyl-1-butynylcarbo 2-propynylcarbonyloxy group, 1-hexynylcarbonyloxy group, 2-hexynylcarbonyloxy group, 3-hexynyl Methyl-2-pentynylcarbonyloxy group, a 1-methyl-3-pentynylcarbonyloxy group, a 1-methyl-4- Pentynylcarbonyloxy group, 2-methyl-3-pentynylcarbonyloxy group Methyl-4-pentynylcarbonyloxy group, 4-methyl-1-pentynylcarbonyloxy group, 4-methyl-1-pentynylcarbonyloxy group, Dimethyl-2-butynylcarbonyloxy group, 1,1-dimethyl-3-butynylcarbonyloxy group, 1,2-dimethyl-3- Butynylcarbonyloxy group, 1-ethyl-2-butynylcarbonyloxy group, 1-ethyl-2-butynylcarbonyloxy group, Ethyl-3-butynylcarbonyloxy group, 1-methyl-1-ethyl-2-propynyl group, 1-propylcarbonyloxy group, -i-propyl-2-propynylcarbonyloxy group and the like.

Examples of the aryl group having 6 to 11 carbon atoms, the halogenated aryl group having 6 to 11 carbon atoms, the heteroaryl group having 3 to 11 carbon atoms, and the halogenated heteroaryl group having 3 to 11 carbon atoms include phenyl, o-chlorophenyl, A fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a chloromethyl group, a chloromethyl group, a chloromethyl group, a phenyl group, a p- An imidazolyl group, a chlorimidazolyl group, a fluoroimidazolyl group, and the like can be given.

The dipyridazine cyclic benzoquinone skeleton-containing polymer containing the repeating unit represented by the formula (2) and / or (3) may further contain a repeating unit represented by the following formula (8).

Wherein Y represents a halogen atom. As the halogen atom, chlorine ion, bromine ion, iodine ion and the like are preferable.

The content of the repeating unit represented by the formula (8) is preferably 0 to 90 mol%, more preferably 0 to 50 mol%, still more preferably 0 to 20 mol%, of the total repeating units.

The dipyridine cyclized benzoquinone skeleton-containing polymer containing the repeating unit represented by the formula (2) and / or (3) may further contain a repeating unit represented by the following formula (9).

Wherein Z represents an alkoxy group such as a methoxy group or an ethoxy group, an alkyl group such as a methyl group or ethyl, an alkylthio group, an acyl group, an alkylamino group, a polyalkylene ether group such as polyethylene glycol or the like, A phenylene group, a phenylene group, a phenylene group, a phenylene group,

The content of the repeating unit represented by the formula (9) is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, still more preferably 0 to 1 mol%, of the total repeating units.

The dipyridazine cyclic benzoquinone skeleton-containing polymer containing the repeating unit represented by the formula (2) and / or (3) may further contain a repeating unit represented by the following formula (9 ').

Wherein, Z 'is _{-O- (CH 2) a -O-,} - (CH 2) a -, -S- (CH 2) a -S-, -C (= O) - (CH 2) b -C (= O) -, -NH- (CH 2) a -NH-, -O- (RO) c -, -NH- (R-NH) c - , or represents a phenylene group, R is c 1 -C A represents an integer of 1 to 12, b represents an integer of 1 to 10, and c represents an integer of 2 to 4.

The content of the repeating unit represented by the formula (9 ') is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, still more preferably 0 to 1 mol%, of the total repeating units.

The dipyridazine cyclic benzoquinone skeleton-containing polymer containing the repeating unit represented by the formula (5) and / or (6) may further contain a repeating unit represented by the following formula (8 ').

Wherein A is as defined above. Y 'represents an amino group, an amide group or an alkylaminocarboxy group, preferably an amino group.

The content of the repeating unit represented by the formula (8 ') is preferably 0 to 90 mol%, more preferably 0 to 50 mol%, still more preferably 0 to 20 mol%, of the total repeating units.

Next, a method for synthesizing a dipyridine cyclic benzoquinone skeleton-containing polymer comprising the dipyridine cyclic benzoquinone represented by the formula (1), a derivative thereof, and the repeating unit represented by the formula (2) and / or (3) Will be described.

The diphyridine-dibenzoquinone represented by the formula (1) can be synthesized by a known method (Synthesis, 1988, p.388). The diphyridine dicyclic benzoquinone derivative can be synthesized by a known alkylation reaction, coupling reaction, or the like using a diphyridine dicyanobenzoquinone. As known alkylation reagents or coupling reaction substrates, for example, methyl iodide, propyl halide, chloromethyl styrene, trimethyl oxonium tetrafluoroborate and the like can be used.

An example of a method for synthesizing a polymer containing a repeating unit represented by the formula (2) and / or (3) with a diphyridine cyclized benzoquinone skeleton will be described.

First, as shown in Scheme A, epihalohydrins in the solvent are subjected to ring-opening polymerization to synthesize a polymer comprising a repeating unit represented by formula (8) as a main chain. Alternatively, commercially available polyepihalohydrins can be used.

(Wherein Y is as defined above).

The conditions for the ring-opening polymerization may be conventionally known methods. It is also possible to incorporate a position isomer which is a by-product in the synthesis. As the polymer comprising the repeating unit represented by the formula (8), a commercially available product may be used. Commercially available products may be subjected to precipitation purification to improve purity.

The dipyridazine cyclic benzoquinone skeleton-containing polymer comprising a repeating unit represented by the formula (2) and / or (3) and a repeating unit represented by the formula (8) has a repeating unit represented by the formula (8) Can be synthesized by reacting a polymer containing the compound represented by the formula (1) with a dihydridine cyclic benzoquinone represented by the formula (1) or a derivative thereof. At this time, the diphyridine-dibenzoquinone represented by the formula (1) or a derivative thereof may be used singly or in combination of two or more.

For example, the dipyridyl cyclized benzoquinone skeleton-containing polymer comprising the repeating unit represented by the formula (2-2) and the repeating unit represented by the formula (8) 8) with a dipyridine dicyclohexylcarbodiimide derivative represented by the formula (1-2). In Scheme B, R ¹ and R ²² in formulas (1-2) and (2-2) are methyl groups, and R ¹⁰ to R ¹⁵ and R ²⁹ to R ³⁴ are hydrogen atoms. In this case, .

Wherein Y is as defined above. m and n represent a content ratio (molar ratio) of the repeating units, and are positive numbers satisfying 0.01? m? 1.0, 0? n? 0.99 and 0.01? m + n?

The dipyridyl cyclic benzoquinone skeleton-containing polymer comprising a repeating unit represented by the formula (2-1), a repeating unit represented by the formula (3-1), and a repeating unit represented by the formula (8) As shown in C, the polymer can be synthesized by reacting a polymer comprising a repeating unit represented by the formula (8) in a solvent with a dipyridine decyclic benzoquinone represented by the formula (1-1). In the scheme C, the case where R ⁴ to R ⁹ in the formula (1-1), R ²³ to R ^{28 in the} formula (2-1) and R ³⁵ to R ⁴⁰ in the formula (3-1) However, this is not the only case.

Wherein Y is as defined above. m1, m2 and n1 represent the content ratio (molar ratio) of the repeating unit, and 0 <m1 <1.0, 0 <m2 <1.0, 0? n1? 0.99, 0.01? m1 + m2? 1.0 and 0.01? Lt; = 1.0.

(2) or (3) can be synthesized by reacting a repeating unit represented by the formula (8) with a dipyridine cyclic benzoquinone or a derivative thereof in an equivalent amount or an excess amount of the repeating unit represented by the formula You may. Further, by reacting a less amount of the quaternary quinone derivative with respect to the repeating unit represented by the formula (8), it is possible to leave an unsubstituted halogenated alkyl substituted ethylene oxide moiety.

In the case of synthesizing a polymer containing only the repeating unit represented by the formula (2) or (3), the amount of the dipyridine decyclic benzoquinone or its derivative represented by the formula (1) Is preferably 1 to 10 moles, more preferably 1 to 5 moles, and still more preferably 1 to 2 moles per 1 mole. In the case of synthesizing a polymer including a repeating unit represented by the formula (8) in addition to the repeating unit represented by the formula (2) or (3), the dipyridine dicyclopentadienoquinone represented by the formula (1) Is preferably 0.01 to 1 mole, more preferably 0.1 to 0.9 mole, and still more preferably 0.5 to 0.8 mole, per mole of the repeating unit represented by the formula (8).

The solvent used in the reactions shown in schemes B and C is not particularly limited as long as it does not adversely affect the reaction and has sufficient solubility in the reagents and products used in the synthesis. Examples of the solvent include dichloromethane, 1,2-di (DMF), dimethylacetamide (DMAc), dimethylformamide (DMF), dimethylformamide (DMF), tetrahydrofuran, dioxane, N-methyl-2-pyrrolidone (NMP), water, acetonitrile and the like can be used.

In the reaction represented by Scheme B or C, the reaction temperature is usually about 20 to 100 캜, preferably 75 to 100 캜. The reaction time is usually about 1 to 1,000 hours, preferably 20 to 72 hours.

When the repeating unit represented by the formula (9) is included in addition to the repeating unit represented by the formula (2) or (3), the polymer obtained by the reaction shown in Scheme B or C is reacted with hexamethylenediamine, polystyreneimine May be reacted. The amount of the compound to be reacted at this time is preferably 0 to 0.1 mol, more preferably 0 to 0.05 mol, still more preferably 0 to 0.01 mol, per 1 mol of the repeating unit represented by the formula (8).

The reaction conditions such as the solvent, the reaction temperature and the reaction time used at this time may be the same as those described in the reaction shown in Scheme B or C.

A description will be given of a method for synthesizing a dipyridine cyclized benzoquinone skeleton-containing polymer represented by formula (4), a derivative thereof, and a repeating unit represented by formula (5) and / or formula (6) do.

Dipyridine-dibenzoquinone represented by the formula (4) may be a commercially available product, or may be synthesized by reference to Organic Letter, 2004, 6, 1091. [ The diphyridine dicyclic benzoquinone derivative can be synthesized by a known alkylation reaction, coupling reaction, or the like using a diphyridine dicyanobenzoquinone. As known alkylation reagents or coupling reaction substrates, for example, methyl iodide, propyl halide, chloromethyl styrene, trimethyl oxonium tetrafluoroborate and the like can be used.

An example of a method for synthesizing a dipyridyl cyclized benzoquinone skeleton-containing polymer containing repeating units represented by the formula (5) and / or (6) wherein A is -CH ₂ - will be described.

First, as shown in Scheme D below, an allyl compound in a solvent is polymerized to synthesize a polymer comprising a repeating unit represented by the formula (8 '') to become a main chain.

(Wherein Y 'is as defined above).

The polymerization is not particularly limited, and radical polymerization, anionic polymerization, cation polymerization and the like can be employed. As the conditions for the polymerization, conventionally known methods may be used. As the polymer comprising the repeating unit represented by the formula (8 ''), a commercially available product may be used. Commercially available products may be subjected to precipitation purification to improve purity.

The dipyridazine cyclic benzoquinone skeleton-containing polymer comprising the repeating unit represented by the formula (5) and / or the repeating unit represented by the formula (8 '') is represented by the formula (8 ' And a dipyridine dicyclohexylbenzoquinone represented by the formula (4) or a derivative thereof. At this time, the diphyridine-dibenzoquinone represented by the formula (1) or a derivative thereof may be used singly or in combination of two or more.

For example, the dipyridyl cyclized benzoquinone skeleton-containing polymer comprising a repeating unit represented by the formula (5-1) and a repeating unit represented by the formula (8 '') can be obtained by reacting a repeating unit represented by the formula Can be synthesized by reacting a polymer comprising a repeating unit represented by the formula (8 '') with a dipyridine dicyclohexylcarbodiimide derivative represented by the formula (4-1 ').

(Wherein R ⁴⁴ to R ⁴⁹ are as defined above), X "is a group capable of forming X by reacting with Y '.

In the formulas, m 'and n' represent the content ratio (molar ratio) of the repeating units and are positive numbers satisfying 0.01? M'? 1.0, 0? N'0.99 and 0.01? M '+ n'?

(5) or (6) is obtained by reacting a repeating unit represented by the formula (8 &quot;) with a dipyridine cyclic benzoquinone or its derivative having an equivalent or excess amount of a substance . In addition, by reacting a less amount of dipyridyl cyclic benzoquinone or a derivative thereof with respect to the repeating unit represented by the formula (8 &quot;), an unsubstituted alkylated alkylene oxide moiety can be left unreacted.

In the case of synthesizing a polymer containing only the repeating unit represented by the formula (5) or (6), the amount of the dipyridine decyclic benzoquinone represented by the formula (4) or the derivative thereof is expressed by the formula (8 ' Is preferably 1 to 10 moles, more preferably 1 to 5 moles, and still more preferably 1 to 2 moles per 1 mole of the repeating unit. In the case of synthesizing a polymer including a repeating unit represented by the formula (8 '') in addition to the repeating unit represented by the formula (5) or (6), the dipyridine decyclic benzoquinone represented by the formula (4) The amount of the derivative to be used is preferably 0.01 to 1 mole, more preferably 0.1 to 0.9 mole, and still more preferably 0.5 to 0.8 mole per mole of the repeating unit represented by the formula (8 '').

The solvent used in the reaction shown in Scheme E is not particularly limited as long as it does not adversely affect the reaction and has sufficient solubility for the reagents and products used in the synthesis and may be dichloromethane, 1,2-dichloroethane (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (DMF), N, N'-dicyclohexylcarbodiimide Methyl-2-pyrrolidone (NMP), water, acetonitrile, and the like.

In the reaction represented by Scheme E, the reaction temperature is usually about 20 to 100 캜, preferably 75 to 100 캜. The reaction time is usually about 1 to 1,000 hours, preferably 20 to 72 hours.

The polymer containing the repeating unit represented by the formula (7) can be synthesized, for example, by reacting a compound represented by the formula (4) and a compound represented by the formula (10) in a solvent.

(Wherein X 'is the same as the above, and Hal represents a halogen atom.)

Of these, the polymer containing the repeating unit represented by the formula (7-1) is obtained by polymerizing a compound represented by the formula (4-1 ') and a compound represented by the formula (10) in a solvent, And the like.

(Wherein R ⁷¹ to R ⁷⁶ , X 'and Hal are as defined above)

In the reaction represented by Scheme F, the amount of the compound represented by the formula (10) is preferably 0.5 to 5 moles, more preferably 0.5 to 2.5 moles per 1 mole of the repeating unit represented by the formula (4-1 ') , And even more preferably 1 to 2 moles.

The solvent used in the reaction represented by Scheme F is not particularly limited as long as it does not adversely affect the reaction and has sufficient solubility for the reagents and products used in the synthesis and includes dichloromethane, 1,2-dichloroethane (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (DMF), N, N'-dicyclohexylcarbodiimide Methyl-2-pyrrolidone (NMP), water, acetonitrile, and the like.

In the reaction represented by Scheme F, the reaction temperature is usually about 25 to 100 캜, preferably 80 to 100 캜. The reaction time is usually about 10 to 50 hours, preferably 20 to 30 hours.

The weight average molecular weight (Mw) of the dipyridazine cyclic benzoquinone skeleton-containing polymer used in the present invention is preferably 1,000 or more, more preferably 100,000 or more, and still more preferably 500,000 or more, from the viewpoint of inhibiting elution into the electrolytic solution desirable. Mw is preferably 5,000,000 or less, more preferably 3,000,000 or less, and still more preferably 2,000,000 or less, from the viewpoint of solubility in a solvent for an electrode slurry described later. In the present invention, Mw is a polystyrene reduced value measured by gel permeation chromatography (GPC).

[Secondary Battery]

The secondary battery of the present invention is characterized in that a charge storage material made of the above-described charge storage material is used as an electrode active material, and other constituent members of the battery element may be appropriately selected from conventionally known ones.

As an example, a general secondary battery will be described.

The secondary battery generally comprises a positive electrode layer, a negative electrode layer, a separator layer disposed between the positive electrode layer and the negative electrode layer, and an electrolyte solution filled in the battery element including both of them. The positive electrode layer and the negative electrode layer may be formed on the substrate as a current collector by using an electrode active material and, if necessary, a conductive additive composed of carbon or the like for improving the conductivity of the electrode layer and further improving the uniformity of film formation, And a thin film containing a binder for suppressing elution. The electrolytic solution is composed of an electrolyte comprising a salt which is a body of ion conduction, a solvent, and the like.

The charge storage material of the present invention is used as the electrode active material of the positive electrode layer or the negative electrode layer. The electrode active material used in any of the electrode layers of the positive electrode layer and the negative electrode layer is not particularly limited and is determined by the relative potential of the electrode. The electrode active material may be used for both electrodes.

The form of the secondary battery, the type of the electrode active material and the electrolytic solution are not particularly limited, and any of a lithium ion battery, a nickel hydrogen battery, a manganese battery, and an air battery may be used. The lamination method and the production method are not particularly limited either.

The electrode layer can be prepared by preparing an electrode slurry by mixing the charge storage material of the present invention, a solvent, a conductive auxiliary agent, a binder, and other conventionally known electrode active materials, etc., and forming a thin film on the substrate using the electrode slurry. The method of forming the thin film is not particularly limited, and various conventionally known methods can be used. For example, various printing methods such as offset printing using a solution or suspension or slurry in which a material containing a charge storage material is dissolved or suspended in a solvent, screen printing, gravure printing, dip coating, spin coating, , A slit (die) coating method, and an ink jet method.

As the current collector used for the base of the electrode layer, for example, a metal foil or substrate such as aluminum, copper, lithium, stainless steel, iron, chromium, platinum or gold, an alloy foil or substrate made of any combination of these metals, An oxide substrate such as an oxide (ITO), an indium zinc oxide (IZO), an antimony tin oxide (ATO) or the like or a carbon substrate such as a glazicarbon, a pyrolytic graphite or a carbon felt, And the like.

Examples of the conductive additive include carbon materials such as graphite, carbon black, acetylene black, vapor grown carbon fiber (VGCF), carbon nanotubes, carbon nanohorns and graphenes, polyaniline, polypyrrole, polythiophene, polyacetylene, polyacene And the like. The conductive additives may be used alone or in combination of two or more.

Examples of the binder include polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, vinylidene fluoride-hexafluoropropylene copolymer, polyvinyl chloride, polycarbonate, polystyrene, polyacrylic acid, polyacrylic acid salt, polyacrylic acid ester , Polymethacrylic acid, polymethacrylic acid salt, polymethacrylic acid ester, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy An aerosol consisting of a resin, a polyamide, ethylcellulose, a vinyl acetate, an ABS resin, an SBR resin, a polyurethane resin, a melamine resin, an unsaturated polyester resin, an alkyd resin, an epoxy resin, a silicone resin, And a blend polymer.

Examples of the solvent for the electrode slurry include NMP, dimethylsulfoxide, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate,? -Butyrolactone, THF, dioxolane, sulfolane, DMF, DMAc And the like.

When the electrode active material containing the charge storage material of the present invention is used for the positive electrode layer, examples of the negative electrode active material contained in the negative electrode layer include graphite, carbon black, acetylene black, vapor grown carbon fiber (VGCF), carbon nanotube, yes lithium alloy such as a carbon material, Li, Li-Al, Li-Si, Li-Sn, such as pins, Si, SiO, SiO _2, Si-SiO ₂ composite, Sn, SnO, SnO _2, PbO, PbO ₂ , GeO ₂ , GeO ₂ , WO ₂ , MoO ₂ , Fe ₂ O ₃ , Nb ₂ O ₅ , TiO ₂ , Li ₄ Ti ₅ O ₁₂ and Li ₂ Ti ₃ O ₇ . When the electrode active material containing the charge storage material of the present invention is used for the negative electrode layer, it may be used in coexistence with these negative electrode active materials.

When the electrode active material containing the charge storage material of the present invention is used for the negative electrode layer, the positive electrode active material contained in the positive electrode layer may be a compound containing a nitroxy radical group, an organic sulfur polymer, a quinone polymer other than the charge storage material of the present invention, (LiCoO ₂₎ , LiMn ₂ O ₄ , LiNiO ₂ , LiNi _0.5 Mn _0.5 O ₂ , LiFePO ₄ , LiMnPO ₄ , LiCoPO ₄ , and Fe ₂ ( SO ₄ ) ₃ , LiMnSiO ₄ , V ₂ O ₅ and the like. When an electrode active material containing the charge storage material of the present invention is used for the positive electrode layer, the positive electrode active material may be used in coexistence with these positive electrode active materials.

The electrode active material containing the charge storage material of the present invention may be used as an air cell as an air electrode (positive electrode). In this case, as the negative electrode active material contained in the negative electrode layer, sodium, magnesium, aluminum, calcium, zinc and the like can be used in addition to the above-mentioned negative electrode active material.

When the positive electrode is used as an air cell, an inorganic material such as manganese oxide or a nitroxide radical material such as TEMPO polymer may be used in combination with the charge storage material of the present invention as an oxidation-reduction auxiliary material contained in the positive electrode layer .

The thickness of the electrode layer is not particularly limited, but is preferably about 0.01 to 1,000 μm, and more preferably about 0.1 to 100 μm.

Examples of the material used for the separator layer include porous polyolefins, polyamides, and polyesters.

Examples of the electrolyte constituting the electrolyte _{LiPF 6, LiBF 4, LiN (} C 2 F 5 SO 2) 2, LiAsF 6, LiSbF 6, LiAlF 4, LiGaF 4, LiInF 4, LiClO 4, LiN (CF 3 SO _{2) 2, LiCF 3 SO 3} , LiSiF 6, LiN (CF 3 SO 2) (C 4 F 9 SO 2) such as a lithium salt, LiI, NaI, KI, CsI, CaI _2, such as of metal iodides, quaternary Iodide salts of imidazolium compounds, iodide salts and perchlorates of tetraalkylammonium compounds, and metal bromides such as LiBr, NaBr, KBr, CsBr and CaBr ₂ .

It is also possible to use a thiolic acid-based material such as a polyethylene oxide-based material and Li ₂ SP ₂ S ₅ or a material such as hexafluoropropylene, tetrafluoroethylene, trifluoroethylene, ethylene, propylene, acrylonitrile, vinylidene chloride, , Or a polymer compound obtained by polymerizing or copolymerizing monomers such as methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, styrene, vinylidene fluoride, etc. may be used.

The solvent constituting the electrolytic solution is not particularly limited as long as it dissolves the electrolyte, not deteriorating the performance by causing corrosion or decomposition of the material constituting the battery. Examples of the non-aqueous solvent include cyclic esters such as ethylene carbonate, propylene carbonate, butylene carbonate and? -Butyrolactone; Ethers such as THF and dimethoxyethane; And chain esters such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate. These solvents may be used singly or in combination of two or more.

[ Example ]

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples. The apparatus used and measurement conditions are as follows.

(1) ¹ H-NMR

(Manufactured by Nihon Denshi Co., Ltd.), nuclear magnetic resonance apparatus ECX-500 (solvent CDCl ₃ , internal standard substance TMS)

(2) ¹³ C-NMR

(Manufactured by Nihon Denshi Co., Ltd.), nuclear magnetic resonance apparatus ECX-500 (solvent CDCl ₃ , internal standard substance TMS)

(3) ¹³ C-CP / MAS NMR

Manufactured by Nihon Denshi Co., Ltd., nuclear magnetic resonance apparatus ECA-400

(4) GC-MS

Gas chromatograph mass spectrometer JMS-GCmate II manufactured by Nihon Denshi Co., Ltd.

(5) MALDI-TOFMS

MALDI-TOF mass spectrometer autoflex III manufactured by Bruker

(6) Elemental analysis

Elemental analysis device PE2400 II manufactured by Perkin Elmer

(7) CV measurement

ALS Model Dual Electrochemical Analyzer manufactured by BAE Co., Ltd.

(8) Characteristic evaluation of battery

16ch battery charge / discharge system made by Hokuto Denko Co., Ltd. HJ1001SD8

[1] Synthesis of Dipyridine-Reductive Benzoquinone and Its Derivatives

[Example 1] Synthesis of Dipyridine-Reducing Benzoquinone

According to the following scheme, a diphyridine-dibenzoquinone was synthesized.

Under an argon atmosphere, 6 mL of hexamethylphosphoric triamide and 70 mL of tetrahydrofuran (THF) were added to a 500 mL eggplant-shaped flask and the tube was sealed with a plug. This was cooled to -78 deg. C in a dry ice-methanol bath and 27 ml (54 mmol, 3.0 eq) of lithium diisopropyl amide (2.0 mol / L THF heptane ethylbenzene solution) was added thereto. Lt; / RTI &gt; Subsequently, 3.2 mL (18 mmol, 1.0 eq) of N, N-diethyl nicotinamide prepared in an argon atmosphere in THF (5 mL) was added dropwise from the syringe. After returning to room temperature for 20 hours, 100 mL of pure water was added to stop the reaction. THF was distilled off under reduced pressure using this distributor, and the product was extracted from dichloromethane and aqueous sodium chloride solution using a separatory funnel. After washing with hexane, purification was carried out on a silica gel column using diethylether / dichloromethane (3/7 (volume ratio)) as a spiraling solvent. Recrystallization from chloroform / hexane (1/20 (volume ratio)) and vacuum drying gave 1.89 g (9.0 mmol) of an ocher-colored solid (yield 50%).

_{^{1 H-NMR (CDCl 3,}} 500 MHz, ppm): σ = 9.59 (d, 2H), 9.19 (d, 2H), 8.11 (dd, 2H)

¹³ C-NMR (CDCl ₃ , 500 MHz, ppm):? = 182.1, 156.4, 149.9, 138.0, 125.8, 119.1

Mass: m / z = 211.0 (found), 210.0 (calcd)

Elemental analysis: (found) C68.4 H2.7 N13.3%, (calcd) C68.6 H2.9 N13.3%

[Example 2] Synthesis of Dipyridine-Reductive Benzoquinone Derivative

According to the following scheme, dipyridinediylbenzoquinone derivatives A and B were synthesized.

200 mg (0.95 mmol, 1.2 eq) of dipyridine dicyclohexylbenzoquinone and 15 mL of acetonitrile were added to a 100 mL eggplant-shaped flask and dissolved by heating at 75 캜. 49.4 μL (0.79 mmol, 1.0 eq) of methyl iodide was added dropwise thereto from the syringe, followed by reaction for 2 hours. After completion of the reaction, the acetonitrile was distilled off under reduced pressure using the same distributor, followed by washing with dichloromethane and vacuum drying to obtain 251 mg (0.71 mmol) of a dark red green solid (dipyridinyl cyclized benzoquinone derivative A) Yield 90%).

_{^{1 H-NMR (CDCl 3,}} 500 MHz, ppm): σ = 9.81 (s, 1H), 9.55 (s, 1H), 9.34 (brs, 1H), 9.20 (brs, 1H), 8.79 (d, 1H) , 8.26 (d, 1 H), 4.63 (s, 3 H)

Mass: m / z = 225.1 (found), 225.1 (calcd)

100 mg (0.28 mmol, 1.0 eq) of dipyridyl cyclic benzoquinone derivative A and 10 mL of DMF were added to a 30 mL flask and dissolved by heating at 100 ° C. Thereafter, 275 μL (2.8 mmol, 10 eq) of methyl iodide was added and reacted at 100 ° C. for 20 hours. After completion of the reaction, the precipitated solid was recovered by filtration, and purified by recrystallization using water at 80 캜 to obtain 69 mg (0.14 mmol) of a purple solid (dipyridinyl cyclized benzoquinone derivative B) (yield: 50%).

Mass: m / z = 493.8 (found), 247.0 (calcd)

[Example 3] Synthesis of Dipyridine-Reductive Benzoquinone Derivative

According to the following scheme, dipyridinyl cyclized benzoquinone derivatives C and D were synthesized.

300 mg (1.43 mmol, 1.2 eq) of dipyridine dicyclohexylbenzoquinone and 20 mL of nitromethane were added to a 50 mL eggplant-shaped flask and dissolved by heating at 40 占 폚. A nitromethane solution (3 mL) of 176 mg (1.19 mmol, 1.0 eq) of trimethyloxonium tetrafluoroborate was added dropwise while stirring in a nitrogen atmosphere or an atmosphere, followed by reaction at 40 ° C for 30 minutes. After completion of the reaction, the reaction mixture was concentrated under reduced pressure using this distributor, precipitation purification with diethyl ether, purification by recrystallization using water at 80 캜, and vacuum drying to obtain 130 mg of a yellowish green solid (dipyridinyl cyclized benzoquinone derivative C) (0.41 mmol) (yield: 29%).

_{^{1 H-NMR (CD 3 CN}} , 500 MHz, ppm): σ = 9.57 (s, 1H), 9.52 (s, 1H), 9.26 (d, 1H), 9.08 (d, 1H), 8.67 (d, 1H ), 8.14 (d, IH), 2.14 (s, IH), 1.95-1.93 (m, 2H)

Mass: m / z = 224.7 (found), 225.1 (calcd)

300 mg (1.43 mmol, 1.0 eq) of dipyridine dicyclohexylbenzoquinone and 20 mL of nitromethane were added to a 50 mL eggplant-shaped flask and dissolved by heating at 40 ° C. A nitromethane solution (10 mL) of 630 mg (4.29 mmol, 3.0 eq) of trimethyloxonium tetrafluoroborate was added dropwise while stirring in a nitrogen atmosphere or an atmosphere, and the reaction was carried out at 40 ° C for 30 minutes. After completion of the reaction, the reaction mixture was concentrated under reduced pressure using this distributor, precipitation purification with diethylether, purification by recrystallization using water at 80 캜, and vacuum drying to obtain a pale pink solid (dipyridyl cyclized benzoquinone derivative D) 227 mg (0.55 mmol) was obtained (yield: 38%).

¹ H-NMR (CD ₃ OH, 500 MHz, ppm):? = 9.62 (s, IH), 9.24 (d, IH), 8.62 ), 5.96 (d, 1H) (aromatic region)

Mass: m / z = 271.1 (found), 271.0 (calcd: [compound D-HBF ₄ ] ⁺ )

[Example 4] Synthesis of Dipyridine-Reductive Benzoquinone Derivative

According to the following scheme, a dihydridine ring-substituted benzoquinone derivative E was synthesized.

100 mg (0.48 mmol, 1.0 eq) of 1,10-phenanthroline-5,6-dione (manufactured by Sigma Aldrich) and 10 mL of nitromethane were added to a 30 mL eggplant-shaped flask and dissolved by heating at 40 ° C. A nitromethane solution (5 mL) of 210 mg (1.42 mmol, 3.0 eq) of trimethyloxonium tetrafluoroborate was added dropwise while stirring in a nitrogen atmosphere or an atmosphere, and the mixture was reacted at 40 ° C for 1 hour. After completion of the reaction, purification was carried out by precipitation with diethyl ether, purification by recrystallization using water at 40 ° C, and vacuum drying to obtain 25 mg (0.03 mmol) of a yellowish brown solid (dipyridinyl cyclized benzoquinone derivative E) 6%).

[2] Synthesis of Dipyridine-Reducing Benzoquinone Skeleton-Containing Polymer

[Example 5] Synthesis of dipyridyl cyclized benzoquinone skeleton-containing polymer A

According to the following scheme, a polymer A containing a dihydridine cyclic benzoquinone skeleton was synthesized.

A 30 mL eggplant-shaped flask was precipitated and purified using a benzene-methanol solvent, and 38 mg (0.32 mmol, 1.0 eq) of vacuum-dried polyepichlorohydrin (Sigma Aldrich, weight average molecular weight 700,000) and 10 mL of acetonitrile Lt; 0 &gt; C. To this was added 100 mg (0.32 mmol, 1.0 eq) of dipyridazine cyclic benzoquinone derivative C, and the mixture was reacted by heating under reflux for 60 hours. After completion of the reaction, the filtrate was concentrated under reduced pressure using this distributor, precipitation purification with diethyl ether, and vacuum drying to obtain a black-green colored solid (polymer A). As a result of the electrochemical measurement, the values of m and n in the scheme were m = 0.5 and n = 0.5.

[Example 6] Synthesis of Dipyridine dicarbonylbenzoquinone skeleton-containing polymer B

According to the following scheme, a polymer B containing a dihydridine cyclic benzoquinone skeleton was synthesized.

A 30 mL eggplant-shaped flask was precipitated and purified using 100 mg (0.48 mmol, 2.0 eq) of dipyridine dicyclohexylbenzoquinone and a benzene-methanol solvent, and vacuum dried polyepichlorohydrin (Sigma Aldrich, weight average molecular weight 700,000) 3 ml of a DMF solution of 5 mass% polyepichlorohydrin prepared using the above was added and reacted at 100 ° C for 72 hours. After completion of the reaction, the reaction mixture was subjected to vacuum distillation with the use of a distributor, redissolution with acetone, and precipitation purification with diethylether to obtain a dark brown solid (polymer B).

[Example 7] Synthesis of polymer C containing a diphyridine dicarboxylic benzoquinone skeleton

According to the following scheme, a polymer C containing a dipyridinyl ring-substituted benzoquinone skeleton was synthesized.

200 mg (0.96 mmol, 1.0 eq) of 2,9-dimethyl-9,10-phenanthroline and 230 mg (1.93 mmol, 2.0 eq) of potassium bromide were added to a 30 mL eggplant-shaped flask. 4 ml of sulfuric acid and 2 ml of nitric acid were slowly added dropwise thereto and dissolved, followed by reflux at 190 캜 for 15 hours. After completion of the reaction, the solution was added dropwise to ice water, and the precipitated solid was collected by filtration, washed with pure water and vacuum dried to obtain a yellow solid (5,6-dioxo-5,6-dihydro- [ Dicarboxylic acid) (yield: 70%).

300 mg (1 mmol, 1.0 eq) of 5,6-dioxo-5,6-dihydro- [1,10] phenanthroline-2,9-dicarboxylic acid, 4- (1.2 mmol, 1.2 eq), 4-dimethylaminopyridine 50 mg (0.4 mmol, 0.4 eq) and DMF &lt; RTI ID = 0.0 & 10 mL was added to dissolve. 15.6 mg (0.5 mmol, 0.5 eq) of methylamine was slowly added dropwise thereto, and the reaction was allowed to proceed at room temperature for 24 hours. After completion of the reaction, the reaction product was purified by precipitation with acetone and vacuum drying to obtain a yellowish green solid (9-methylcarbonyl-5,6-dioxo-5,6-dihydro- [1,10] phenanthroline- 229 mg (0.74 mmol) of the title compound was obtained (yield: 74%).

To a 30 mL eggplant-shaped flask was added 100 mg (0.32 mmol, 1.0 eq) of 9-methylcarbonyl-5,6-dioxo-5,6-dihydro- [1,10] phenanthroline- (Weight average molecular weight: 25,000, manufactured by Nitto Boseki Co., Ltd.) and 105 mg of 4- (4,6-dimethoxy-1,3,5-triazin- 0.38 mmol, 1.2 eq), 4-dimethylaminopyridine (15.6 mg, 0.13 mmol, 0.4 eq) and DMF (10 mL) were added and reacted at room temperature for 24 hours. After the completion of the reaction, purification was carried out by precipitation with methanol, Soxhlet refining with methanol, and vacuum drying to obtain 37 mg of a brownish solid (polymer C containing a dipyridinyl ring-substituted benzoquinone skeleton).

[Example 8] Synthesis of dipyridyl cyclized benzoquinone skeleton-containing polymer D

According to the following scheme, a polymer D containing a dipyridyl cyclic benzoquinone skeleton was synthesized.

100 mg (0.48 mmol, 1.0 eq) of 1,10-phenanthrolinequinone, 500 μL (2.3 mmol, 4.8 eq) of dibromopropane and 5 mL of DMF were added to a 30 mL eggplant type flask and reacted at 90 ° C. for 24 hours. After the completion of the reaction, 54 mg (0.13 mmol) of a black solid (polymer D containing a dipyridinyl ring-substituted benzoquinone skeleton) (yield: 40%) was obtained through precipitation purification with acetonitrile, supersaturation with acetonitrile, and vacuum drying. .

[3] Evaluation of electrodes and batteries including polymer containing dipyridine cyclic benzoquinone skeleton

[Example 9] CV measurement of carbon composite electrode using polymer A containing dipyridine cyclic benzoquinone skeleton

CV was measured in a nitrogen atmosphere using the beaker cell shown in Fig.

20 mg of a carbon powder and 2.5 mg of a polyvinylidene fluoride binder dissolved in 120 mg of NMP were added to 2.5 mg of the dipyridyl cyclized benzoquinone skeleton-containing polymer A synthesized in Example 5, and the mixture was kneaded using a revolving rotary mixer. Mixed for about 20 minutes was coated on a GC substrate and heated at 60 캜 for 18 hours under vacuum to obtain a carbon composite electrode 11.

Next, the obtained electrode was immersed in an electrolytic solution, and an electrolyte solution was introduced into the voids in the electrode. As the electrolytic solution, a? -Butyrolactone solution of 1 mol / L lithium perchlorate was used.

The thin film electrode 11 is used as a working electrode, the platinum electrode 12 is used as a counter electrode, and the Ag / AgCl electrode 13 is used as a reference electrode. These electrodes are placed in a beaker, Was added to the beaker cell 1 to produce a beaker cell 1 as shown in Fig.

Using this beaker cell 1, a CV measurement was carried out at a scan rate of 1 mV / sec. The results are shown in Fig. As shown in FIG. 2, the carbon composite electrode produced by using the polymer A containing a dipyridine cyclic benzoquinone skeleton exhibited a reversible redox wave at E _1/2 = + 0.10 V.

[Example 10] Evaluation of characteristics of an air secondary battery using a polymer B having a dipyridine cyclic benzoquinone skeleton as an electrode

An air cell was fabricated using the prepared carbon composite electrode as a negative electrode, an oxygen reduction catalyst (MnO _x / Carbon, manufactured by Electric Fuel Co., Ltd.) as a positive electrode, a 10 mol / L NaOH aqueous solution as an electrolytic solution and a glass filter as a separator did. CV was measured at a scan rate of 10 mV / sec. The results are shown in Fig.

[Example 11] Evaluation of characteristics of a lithium ion battery using a polymer B containing dipyridine cyclic benzoquinone skeleton as an electrode

20 mg of a carbon powder and 2.5 mg of a polyvinylidene fluoride binder dissolved in 120 mg of NMP were added to 2.5 mg of polymer B and kneaded using a rotary mixer. 20 minutes, and the mixture was heated on vacuum at 60 ° C for 20 hours to obtain a thin-film electrode.

Next, an assembled battery was produced using the above electrode according to the following procedure. All of these were carried out under an argon atmosphere.

First, a thickness of the cell guard 3501 in which the above electrode was provided on the current collector of the case and impregnated with a solution of 1.0 mol / L of lithium hexafluorophosphate in ethylene carbonate / diethyl carbonate (1/1 (volume ratio)) solution A separator of 25 m was placed above the electrode. Subsequently, a metal lithium foil was laminated, a weight made of stainless steel was laminated, and a solution of 1.0 mol / L of lithium hexafluorophosphate in ethylene carbonate / diethyl carbonate (1/1 (volume ratio)) was injected into the internal space , A metallic spring was placed thereon, and a gasket was placed on the peripheral edge thereof to form an assembled battery. CV measurement was performed at a scan rate of 1 mV / sec. The results are shown in Fig.

[Examples 12 to 14, Comparative Example 1]

(Example 12), the diphyridine-dodecylbenzoquinone derivative C (Example 13), the diphyridine-dodecylbenzoquinone derivative D (Example 14), and the commercially available anthraquinone (Comparative Example The cyclic voltammogram of 1) is shown in Figs. 5 and 6. Fig. In the CV measurement, 0.1 mol / L tetrabutylammonium acetate / acetonitrile solution was used as the electrolytic solution and the scan rate was 50 mV / sec. From FIG. 5, it was found that the dipyridine cyclized benzoquinone of the present invention shifted to the higher oxidation-reduction potential side compared with anthraquinone, and the voltage was higher when it was used as the positive electrode of the secondary battery. From FIG. 6, the dipyridyl cyclized benzoquinone derivative C and the diphyridine cyclized benzoquinone derivative D are shifted to a higher side as compared with the diphyridine dicyclopentadienoquinone, and when used as the positive electrode of the secondary battery, Could know.

[Example 15] CV measurement of diphyridine-cyclized benzoquinone derivative E solution

A 0.1-mol / L lithium perchlorate solution of gamma -butyrolactone with a concentration of dipyridazine cyclotetra benzoquinone derivative E of 1 mM was prepared. CV was measured in a beaker cell using Ag / AgCl as a reference electrode, a GC electrode as a working electrode, a platinum electrode as a counter electrode, and a reference electrode.

CV was measured at a scan rate of 0.1 V / sec. The results are shown in Fig.

[Example 16] CV measurement of carbon composite electrode using polymer C containing dipyridine cyclic benzoquinone skeleton

20 mg of carbon powder and 2.5 mg of a polyvinylidene fluoride binder dissolved in 0.25 mL of NMP were added to 2.5 mg of the polymer C containing dipyridinyl cyclized benzoquinone skeleton and kneaded using a ball mill. Mixed at 50 Hz for about 15 minutes, and applied to a GC substrate. The mixture was heated and vacuum-dried at 60 DEG C overnight to obtain a carbon composite electrode.

Next, the obtained electrode was immersed in an electrolytic solution, and an electrolyte solution was introduced into the voids in the electrode. As the electrolytic solution, a? -Butyrolactone solution of 1 mol / L lithium perchlorate was used.

A beaker cell was fabricated using the carbon composite electrode as a working electrode, the platinum electrode as a counter electrode, and the Ag / AgCl electrode as a reference electrode.

CV was measured at a scan rate of 10 mV / sec. The results are shown in Fig. The measurement result of the potential difference with the reference electrode when the charge / discharge capacity is changed is shown in Fig.

[Example 17] Evaluation of characteristics of a lithium ion battery using a polymer C containing a dipyridine cyclic benzoquinone skeleton as an electrode

40 mg of carbon powder and 5.0 mg of polyvinylidene fluoride binder dissolved in 0.50 mL of NMP were added to 5.0 mg of polymer C and kneaded using a ball mill. 50 Hz for 15 minutes, and the mixture was heated and vacuum-dried at 60 ° C overnight to obtain a carbon composite electrode.

Next, an assembled battery was produced by using the above electrode according to the following procedure. All of these were carried out under an argon atmosphere.

First, a separator having a thickness of 25 占 퐉 and comprising a cell guard 3501 in which the above electrode was provided on the collector of the case and impregnated with a? -Butyrolactone solution of 1 mol / L lithium perchlorate was provided above the electrode. Subsequently, a metal lithium foil was laminated, a weight made of stainless steel was laminated, a 1-mol / L lithium perchlorate solution of? -Butyrolactone was injected into the internal space, a metallic spring was placed thereon, With the gasket disposed therebetween to produce an assembled battery.

CV measurement was performed at a scan rate of 1 mV / sec. The results are shown in Fig. The measurement result of the potential difference with the reference electrode when the charge / discharge capacity is changed is shown in Fig.

[Example 18] CV measurement of a carbon composite electrode using a polymer D containing a dipyridine cyclic benzoquinone skeleton

20 mg of carbon powder and 2.5 mg of polyvinylidene fluoride binder dissolved in 0.25 mL of NMP were added to 2.5 mg of dipyridyl cyclized benzoquinone skeleton-containing polymer D and kneaded using a ball mill. Mixed at 50 Hz for about 15 minutes, and applied to a GC substrate. The mixture was heated and vacuum-dried at 60 DEG C overnight to obtain a carbon composite electrode.

Next, the obtained electrode was immersed in an electrolytic solution, and an electrolyte solution was introduced into the voids in the electrode. As the electrolytic solution, a? -Butyrolactone solution of 1 mol / L lithium perchlorate was used.

A beaker cell was fabricated using the carbon composite electrode as a working electrode, the platinum electrode as a counter electrode, and the Ag / AgCl electrode as a reference electrode.

CV was measured at a scan rate of 5 mV / sec. The results are shown in Fig. The measurement result of the potential difference with the reference electrode when the charge / discharge capacity is changed is shown in Fig.

One… Beaker cell
11 ... Working pole
12 ... Antipode
13 ... Reference pole
14 ... Electrolyte

Claims (24)

A charge storage material comprising a diphyridine dicyclopentadienoquinone represented by the following formula (1) or a derivative thereof.

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed together with two carbon atoms on the benzoquinone skeleton) The charge storage material according to claim 1, wherein the dyepyridine ring-substituted benzoquinone or a derivative thereof is represented by the following formula (1-1), (1-2) or (1-3).

(Wherein R ¹ to R ³ each independently represent an alkyl group having 1 to 12 carbon atoms, a propargyl group, a methylstyrene or a norbornene, each of R ⁴ to R ²¹ independently represents a hydrogen atom, a halogen atom, , A mercapto group, an amino group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 12 carbon atoms, An aryl group, a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted A monoalkylamino group, a dialkylamino group in which each alkyl group is independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, a nitro group, a cyano group, a sulfonic acid group, Group, an aminocarbonyl group, or It represents an alkylamino-carbonyl group of a carbon number of 2 to 12.) A charge storage material comprising a polymer comprising a dipyridene cyclic benzoquinone skeleton containing a repeating unit represented by the following formula (2) and / or (3).

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed with two carbon atoms on the benzoquinone skeleton, and each X independently represents a single bond or a divalent group.) 4. The polymerizable composition according to claim 3, wherein the dipyridyl cyclized benzoquinone skeleton-containing polymer comprises a repeating unit represented by the following formula (2-1), (2-2) and / or (3-1) Charge storage material.

(Wherein R ²² represents an alkyl group having 1 to 12 carbon atoms, a propargyl group, a norbornene or a methylstyrene, R ²³ to R ⁴⁰ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, A substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 12 carbon atoms, a substituted or unsubstituted aryl group having 3 to 12 carbon atoms, A substituted or unsubstituted heteroaryl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted monoalkylamino group having 1 to 12 carbon atoms, A dialkylamino group whose alkyl group is independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, a nitro group, a cyano group, a sulfonic acid group, a phosphonic acid group, a carboxyl group, an aminocarbonyl group, Or an alum having 2 to 12 carbon atoms Or a quinoxycarbonyl group. A charge storage material comprising a diphyridine dicyclopentadienoquinone represented by the following formula (4) or a derivative thereof.

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed together with two carbon atoms on the benzoquinone skeleton) The charge storage material according to claim 5, wherein the diphyridine-dendrified benzoquinone or a derivative thereof is represented by the following formula (4-1), (4-2) or (4-3).

(Wherein R ⁴¹ to R ⁴³ each independently represent an alkyl group having 1 to 12 carbon atoms, a propargyl group, a methylstyrene or a norbornene, R ⁴⁴ to R ⁶¹ each independently represent a hydrogen atom, a halogen atom, , A mercapto group, an amino group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 12 carbon atoms, An aryl group, a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted A monoalkylamino group, a dialkylamino group in which each alkyl group is independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, a nitro group, a cyano group, a sulfonic acid group, Group, an aminocarbonyl group, Represents an alkylamino-carbonyl group of a carbon number of 2 to 12.) A charge storage material comprising a polymer containing a dipyridyl cyclic benzoquinone skeleton containing a repeating unit represented by the following formula (5) and / or (6).

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed together with two carbon atoms on the benzoquinone skeleton, each X independently represents a single bond or a divalent group, Represents -OCH ₂ - or -CH ₂ -. The charge storage material according to claim 7, wherein the dipyridyl cyclized benzoquinone skeleton-containing polymer comprises a repeating unit represented by the following formula (5-1) and / or (6-1).

(Wherein, X and A are the same as above, R ⁶² ~ R ⁷⁰ are independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, an amino group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, having 2 each A substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted monoalkylamino group having 1 to 12 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, A dialkylamino group which is an alkyl group, an alkylcarbonyl group of 2 to 12 carbon atoms, a nitro group, a cyano group, a sulfonic acid group, a phosphonic acid group, a carboxyl group, an aminocarbonyl group or an alkylaminocarbonyl group of 2 to 12 carbon atoms. ) A charge storage material comprising a polymer containing a dipyridyl cyclic benzoquinone skeleton containing a repeating unit represented by the following formula (7).

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed with two carbon atoms on the benzoquinone skeleton, and X 'represents a single bond or a divalent group.) The charge storage material according to claim 9, wherein the dipyridyl cyclized benzoquinone skeleton-containing polymer comprises a repeating unit represented by the following formula (7-1).

(Wherein, X 'is the same as above, R ⁷¹ - R ⁷⁶ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, an amino group, having 1 to 12 carbon atoms substituted or unsubstituted alkyl group, having 2 to a A substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms, A substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted monoalkylamino group having 1 to 12 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms A nitro group, a cyano group, a sulfonic acid group, a phosphonic acid group, a carboxyl group, an aminocarbonyl group, or an alkylaminocarbonyl group having 2 to 12 carbon atoms. An electrode active material comprising the charge storage material according to any one of claims 1 to 10. An electrode slurry comprising the electrode active material according to claim 11 and a solvent. 11. A thin film comprising the electrode active material according to claim 11. A thin film produced from the electrode slurry according to claim 12. An electrode comprising the electrode active material according to claim 11. An electrode comprising the thin film according to claim 13 or 14. A secondary battery comprising the electrode according to claim 15 or 16. A lithium ion battery comprising the electrode according to claim 15 or 16. An air cell comprising the electrode according to claim 15 or 16. Dipyridine dicyclohexylbenzoquinone represented by the following formula (1) or a derivative thereof.

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed together with two carbon atoms on the benzoquinone skeleton) A polymer comprising a dipyridene cyclic benzoquinone skeleton containing a repeating unit represented by the following formula (2) and / or (3).

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed with two carbon atoms on the benzoquinone skeleton, and each X independently represents a single bond or a divalent group.) A dihydridine ring-substituted benzoquinone represented by the following formula (4) or a derivative thereof.

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed together with two carbon atoms on the benzoquinone skeleton) A polymer comprising a repeating unit represented by the following formula (5) and / or (6): a dyepyridine dicyclic benzoquinone skeleton.

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed together with two carbon atoms on the benzoquinone skeleton, each X independently represents a single bond or a divalent group, Represents -OCH ₂ - or -CH ₂ -. A polymer comprising a dipyridine cyclic benzoquinone skeleton containing a repeating unit represented by the following formula (7).

(Wherein Ar ¹ and Ar ² each independently represent a pyridine ring or a derivative thereof formed with two carbon atoms on the benzoquinone skeleton, and X 'represents a single bond or a divalent group.)

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