JP2013159686A - New arylamine polymer, and production method and application of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a new arylamine polymer having a high excited triplet level and having a glass transition temperature higher than that of the conventional arylamine polymers; a method for producing the arylamine polymer; and an electronic element using the arylamine polymer.SOLUTION: A new arylamine polymer is represented by general formula (1) (wherein Ar is an aromatic group or a heteroaromatic group; and R, R, and Rare each independently a hydrogen atom, alkyl, alkoxy, or phenyl).

Description

  The present invention relates to a novel arylamine polymer, a method for producing the same, and an electronic device using the same.

  The organic electroluminescent element has a light emitting layer as a main component, and has a basic configuration of two electrodes, a carrier transport layer that transports holes or electrons, a cathode, and an anode.

  As materials for the light emitting layer and the carrier transport layer, various low molecular weight materials and high molecular weight materials are used, and in particular, the technical development of various materials and elements is advanced in the low molecular weight materials. For this reason, organic electroluminescence elements using low molecular weight materials have already been put into practical use in applications such as mobile phone display devices. An organic electroluminescent element made of a low molecular weight material is usually subjected to film formation by vapor deposition, and therefore has a problem of low material utilization efficiency and high cost. Therefore, conversion from vapor deposition film formation to coating film formation is required, and development of polymer materials suitable for manufacturing processes such as coating film formation has been performed.

  For example, PEDOT-PSS, polyarylamine, and the like have been proposed as polymer-based hole injection materials, hole transport materials, and host materials. As the polyarylamine, a non-conjugated arylamine polymer (for example, see Patent Document 1 or 2), a conjugated arylamine polymer (for example, see Patent Document 3 or 4), and the like have been reported.

  Since such conventionally known arylamine polymers have low solubility in organic solvents, there is room for improvement in handling properties and film thickness adjustment during thin film formation. Further, in order to improve the device life, further improvement of the glass transition temperature of the material is required.

In recent years, organic electroluminescence devices using phosphorescent materials have been actively developed in order to achieve high luminous efficiency. For example, a tris (2-phenylpyridine) iridium complex [Ir (ppy) ₃ ] is generally known as a green phosphorescent material, and has a high excitation triplet level (2.5 eV) or more possessed by the iridium complex. Development of a carrier transport material having an excited triplet level is desired.

  Thus, development of an arylamine polymer having a high glass transition temperature and a high excited triplet level is desired.

JP-A-11-292828 Japanese Patent Laid-Open No. 13-98023 JP 2004-292882 A Special table 2001-527102

  The present invention has been made in view of the above-described background art, and an object of the present invention is to provide a novel arylamine polymer having an excited triplet level higher than 2.5 eV and a high glass transition temperature, a production method thereof, and the aryl An organic electroluminescence device comprising an amine polymer is provided.

  As a result of intensive studies to solve the above problems, the present inventors have found that an arylamine polymer having a repeating structure represented by the following general formula (1) has an excited triplet level of 2.5 eV or more. And it discovered that it had a high glass transition temperature compared with the past, and came to complete this invention.

  That is, this invention relates to the arylamine polymer which has 1 type, or 2 or more types of repeating structure represented by following General formula (1), its manufacturing method, and the electronic device using the said arylamine polymer.

(In formula, Ar < ¹ > and Ar < ² > are respectively independently the C1-C18 aromatic group which may have two or more C1-C18 substituents, or C1-C18 substitution. Represents a heteroaromatic group having 4 to 20 carbon atoms which may have a plurality of groups, Ar ³ represents an arylene group having 6 to 24 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms, or carbon Represents a heteroarylene group having 4 to 20 carbon atoms, which may have a plurality of substituents having 1 to 18. R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a C 1-18 carbon atom. A phenyl group which may have 1 to 5 substituents having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a represents an integer of 0 to 4. b and c Each independently represents an integer of 0 to 3. n represents 0 or 1.)

Since the arylamine polymer of the present invention has a high excited triplet level, it can be used in combination with a phosphorescent material such as tris (2-phenylpyridine) iridium complex [Ir (ppy) ₃ ] to provide an organic compound having excellent luminous efficiency. An electroluminescent element can be provided. Moreover, since the glass transition temperature of the arylamine polymer of the present invention is significantly higher than that of conventionally known arylamine polymers, the life of the organic electroluminescent device can be extended. Since the arylamine polymer of the present invention is suitable for the coating process, it can improve the material utilization rate during device production compared to the vapor deposition process.

  In addition, the arylamine polymer of the present invention is extremely effective as a hole transport material because it is excellent in luminous efficiency and current efficiency in the case of an organic electroluminescent device.

  Furthermore, the arylamine polymer of the present invention is a conductive polymer used not only for organic electroluminescent devices but also for electronic devices such as field effect transistors, optical functional devices, and dye-sensitized solar cells because of its structure and physical properties. Since it is considered useful as a material, the present invention is extremely significant industrially.

Reaction of 3,10-dibromo-4bα, 8bβ, 13,14-tetrahydrodiindeno [1,2-a: 2 ′, 1′-b] indene) with 4-n-butylaniline (Example 1) IR chart of things. IR chart of the arylamine polymer (20) obtained in Example 1.

  The present invention relates to an arylamine polymer having one or more repeating structures represented by the general formula (1) (hereinafter also referred to as “the present arylamine polymer”), a production method thereof, and the arylamine polymer. This is the electronic device used.

(In formula, Ar < ¹ > and Ar < ² > are respectively independently the C1-C18 aromatic group which may have two or more C1-C18 substituents, or C1-C18 substitution. Represents a heteroaromatic group having 4 to 20 carbon atoms which may have a plurality of groups, Ar ³ represents an arylene group having 6 to 24 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms, or carbon Represents a heteroarylene group having 4 to 20 carbon atoms, which may have a plurality of substituents having 1 to 18. R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a C 1-18 carbon atom. A phenyl group which may have 1 to 5 substituents having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a represents an integer of 0 to 4. b and c Each independently represents an integer of 0 to 3. n represents 0 or 1.)
In the present arylamine polymer, Ar ¹ and Ar ² each have a plurality of aromatic groups having 6 to 24 carbon atoms or a plurality of substituents having 1 to 18 carbon atoms, which may have a plurality of substituents having 1 to 18 carbon atoms. The C4-C20 heteroaromatic group which may have is represented.

The substituent having 1 to 18 carbon atoms in Ar ¹ and Ar ² may contain a halogen atom and / or a hetero atom, and is not particularly limited. For example, a methyl group, an ethyl group, n -Propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, cyclohexyl, cyclohexadienyl, octyl, decyl, dodecyl, methoxy, ethoxy Group, tert-butoxy group, cyano group, tetrahydrofuranyl group, trifluoromethyl group, trifluoromethoxy group, trimethylsilyl group, phenyl group, tolyl group, chlorophenyl group, acetylphenyl group, cyanophenyl group, methylthiophenyl group, methoxycarbonyl Phenyl group, N, N-dimethylaminophenyl group, biphenyl Group, a naphthyl group, a benzyl group, a phenethyl group, a phenoxy group, a furyl group, a pyridyl group, and a diphenylamino group. Among these, a methyl group, an ethyl group, a cyclohexyl group, a methoxy group, a cyano group, a trifluoromethyl group, a phenyl group, and a pyridyl group are preferable from the viewpoint of easy availability of raw materials. A plurality of substituents having 1 to 18 carbon atoms may be bonded to an aromatic group having 6 to 24 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms within a range not impairing the effects of the present invention. The number of substituents having 1 to 18 carbon atoms is preferably in the range of 1 to 3. When a plurality of substituents having 1 to 18 carbon atoms are bonded, each of them may be the same or different.

Although it does not specifically limit as a C6-C24 aromatic group in Ar < ¹ > and Ar < ² >, For example, a phenyl group, a naphthyl group, an anthryl group, a phenanthrenyl group, a fluorenyl group etc. can be mentioned. Among these, a phenyl group and a fluorenyl group are preferable in terms of easy availability of raw materials.

Ar ^1, and the hetero-aromatic group having 4 to 20 carbon atoms in Ar ^2, it is not particularly limited, for example, a pyridyl group, a carbazolyl group, a thienyl group, bithienyl group, a furyl group, a dibenzofuryl group, dibenzo A thienyl group etc. can be illustrated.

In the present arylamine polymer, Ar ¹ and Ar ² may be the same or different. However, considering the ease of synthesis, Ar ¹ and Ar ² are preferably the same.

In the present arylamine polymer, Ar ³ may have an arylene group having 6 to 24 carbon atoms, which may have a plurality of substituents having 1 to 18 carbon atoms, or a plurality of substituents having 1 to 18 carbon atoms. Represents a heteroarylene group having 4 to 20 carbon atoms.

The substituent having 1 to 18 carbon atoms in Ar ^3, in particular but not limited to, for example, can indicate the same groups as substituents of 1 to 18 carbon atoms shown by Ar ¹ and Ar ^2. A plurality of the substituents having 1 to 18 carbon atoms may be bonded to an arylene group having 6 to 24 carbon atoms or a heteroarylene group having 4 to 20 carbon atoms within a range not impairing the effects of the present invention. The number of substituents having 1 to 18 carbon atoms is preferably in the range of 1 to 3. When a plurality of substituents having 1 to 18 carbon atoms are bonded, each of them may be the same or different.

The arylene group having 6 to 24 carbon atoms in Ar ³ is not particularly limited, and examples thereof include a phenylene group, a naphthylene group, an anthracenediyl group, a phenanthrene diyl group, and a fluorenediyl group. Among these, a phenylene group and a fluorenediyl group are preferable in terms of easy synthesis.

The heteroaromatic group having 4 to 20 carbon atoms in Ar ^3, is not particularly limited, for example, pyridinediyl group, carba sole diyl group, a thiophene-diyl group, bis thiophenediyl group, furandiyl group, dibenzofuran-diyl Group, dibenzothiophene diyl group and the like.

In the present arylamine polymer, R ¹ , R ² , and R ³ each have 1 to 5 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a substituent having 1 to 18 carbon atoms. Even more represents a phenyl group.

The R ^{1, R 2,} and alkyl group having 1 to 18 carbon atoms in ^{R 3,} is not particularly limited, for example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 2-ethylbutyl group, 3,3-dimethylbutyl group, Examples include cyclohexyl group, n-heptyl group, cyclohexylmethyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, trifluoromethyl group and the like. It may be preferable to introduce a long-chain alkyl group from the viewpoint of improving the applicability of the material.

R ^{1, R 2,} and the alkoxy group having 1 to 18 carbon atoms in ^{R 3,} is not particularly limited, for example, a methoxy group, an ethoxy group, n- Puropiropokishi group, isopropoxy group, n- butoxy group , Isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group, tert-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, 2-ethylbutoxy Group, 3,3-dimethylbutoxy group, cyclohexyloxy group, n-heptyloxy group, cyclohexylmethoxy group, n-octyloxy group, tert-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group Group, trifluoromethoxy group and the like. In some cases, it is preferable to introduce a long-chain alkoxyl group in terms of improving the applicability of the material.

In the phenyl group which may have 1 to 5 substituents having 1 to 18 carbon atoms in R ¹ , R ² and R ^3, the substituent having 1 to 18 carbon atoms is not particularly limited. , for example, it can indicate the same groups as substituents of 1 to 18 carbon atoms shown by Ar ¹ and Ar ^2. The number of C1-C18 substituents should just be a range which does not impair the effect of this invention. When a plurality of substituents having 1 to 18 carbon atoms are bonded, each of them may be the same or different.

  a represents an integer of 0 to 4, and b and c each independently represents an integer of 0 to 3. Among these, it is preferable that all of a, b, and c are 0 in terms of easy production. On the other hand, it is preferable that a is an integer of 1 to 4 and b and c are integers of 1 to 3 in terms of improving the coatability of the arylamine polymer.

In addition, when this arylamine polymer contains 2 or more types of repeating structures, in each repeating structure, Ar ¹ , Ar ² , Ar ³ , R ¹ , R ² , R ³ , a, b, c, and n are These may be the same or different between the repeating structures. However, when all are the same, it indicates that the repeating structure is one kind.

  The arylamine polymer is preferably a substituent represented by the following general formula (2) on at least one side, preferably both polymer ends, from the viewpoints of luminescent properties and durability.

(In the formula, each Ar ⁴ independently has an aromatic group having 6 to 24 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms, or a plurality of substituents having 1 to 18 carbon atoms. And represents a heteroaromatic group having 4 to 20 carbon atoms.)
The substituent having 1 to 18 carbon atoms in the Ar ^4, in particular but not limited to, for example, can indicate the same groups as substituents of 1 to 18 carbon atoms shown by Ar ¹ and Ar ^2. A plurality of substituents having 1 to 18 carbon atoms may be bonded to an aromatic group having 6 to 24 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms within a range not impairing the effects of the present invention. When a plurality of substituents having 1 to 18 carbon atoms are bonded, each of them may be the same or different. However, it is preferable that the said C1-C18 substituent does not contain a halogen atom and a hetero atom from the point of the luminescent property of this arylamine polymer, and durability.

The aromatic group having 6 to 24 carbon atoms in the Ar ^4, is not particularly limited, for example, can indicate the same groups as aromatic groups having 6 to 24 carbon atoms shown by Ar ¹ and Ar ² .

The heteroaromatic group having 4 to 20 carbon atoms in the Ar ^4, is not particularly limited, for example, indicate the same groups as heteroaromatic group having 4 to 20 carbon atoms shown by Ar ¹ and Ar ² I can do it.

  The arylamine polymer of the present invention is not particularly limited as long as it falls within the above definition, but it is relatively easy to synthesize and has physical properties such as luminous efficiency and lifetime of the organic electroluminescence device. The structures represented by the following general formulas (16) to (19) are particularly preferable.

(In the formula, each of R ^{17 to} R ³⁷ independently has 1 to 5 hydrogen atoms, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a substituent having 1 to 18 carbon atoms. Represents a phenyl group.
The alkyl group having 1 to 18 carbon atoms in R ¹⁷ to R ^37, in particular but not limited to, for ^example, R 1, ^{R 2,} and the same group as the alkyl group having 1 to 18 carbon atoms indicated by ^{R 3} Can be mentioned.

The alkoxy group having 1 to 18 carbon atoms in R ¹⁷ to R ^37, in particular but not limited to, for ^example, R 1, ^{R 2,} and the same group as the alkoxy group having 1 to 18 carbon atoms indicated by ^{R 3} Can be mentioned.

In the phenyl group which may have 1 to 5 substituents having 1 to 18 carbon atoms in R ^{17 to} R ^37, the substituent having 1 to 18 carbon atoms is not particularly limited. it can indicate the same groups as substituents of 1 to 18 carbon atoms indicated by ¹ and Ar ^2. The number of substituents having 1 to 18 carbon atoms may be in a range that does not impair the effects of the present invention. When a plurality of substituents having 1 to 18 carbon atoms are bonded, each of them may be the same or different. However, it is preferable that the said C1-C18 substituent does not contain a halogen atom and a hetero atom from the point of the luminescent property of this arylamine polymer, and durability.

  Next, the manufacturing method of the arylamine polymer of this invention is demonstrated.

  Although this arylamine polymer is not specifically limited, For example, it can manufacture by the polymerization reaction shown by the following (Reaction Formula 1)-(Reaction Formula 3).

  More specifically, in the presence of a palladium catalyst and a base, a polymerization reaction of one or more triquinane dihalide compounds and one or more arylamine compounds (Reaction Formula 1), one or two kinds Polymerization reaction (reaction formula 2) of the above arylene halide compounds and one or more triquinanediamine compounds, or one or more triquinane dihalide compounds and one or more N, N It can be produced by a polymerization reaction of a '-bisarylarylenediamine compound (Scheme 3) (these reactions are referred to as “polymerization reactions”).

(In the formula, Ar ¹ , Ar ² , Ar ³ , R ¹ , R ² , and R ³ have the same definition as in the general formula (1). X ¹ , X ² , X ³ , and X ⁴ are independent of each other. And represents a chlorine atom, a bromine atom, or an iodine atom.)
Although it does not specifically limit as said triquinane dihalide compound and a triquinanediamine compound, For example, what was synthesize | combined according to the generally well-known method can be used. In addition, the example of a synthesis | combination is later mentioned in detail as a synthesis example of a compound (B-3).

  The arylamine compound, arylene halide compound, and N, N′-bisarylarylenediamine compound are not particularly limited, but are commercially available or synthesized in accordance with generally known methods. Can be used.

  In the polymerization reaction of one or more triquinane dihalide compounds and one or more arylamine compounds (reaction formula 1), the mixing ratio of the triquinane dihalide compound and the arylamine compound is not particularly limited. However, for example, the arylamine compound is used in a range of 0.5 to 2.0 times mol for 1 mol of the triquinane dihalide compound. Among these, the range of 0.75-1.5 times mole is preferable.

  In the polymerization reaction (reaction formula 2) of one or more arylene halide compounds and one or more triquinanediamine compounds, the mixing ratio of the arylene halide compound and the triquinanediamine compound is particularly limited. Although it is not a thing, for example, a triquinanediamine compound is performed in the range of 0.5-2.0 times mole with respect to 1 mol of arylene halide compounds. Among these, the range of 0.75-1.5 times mole is preferable.

    In the polymerization reaction (reaction formula 3) of one or more triquinane dihalide compounds and one or two or more N, N′-bisarylarylenediamine compounds, the triquinane dihalide compound and N, N′-bis The mixing ratio of the aryl arylenediamine compound is not particularly limited. For example, the N, N′-bisaryl arylenediamine compound is 0.5 to 2.0 times mol per mol of the triquinane dihalide compound. Done in a range. Among these, the range of 0.75-1.5 times mole is preferable.

  Furthermore, with respect to the present arylamine polymer obtained by the above polymerization reaction, in the presence of a palladium catalyst and a base, the following general formula (14)

(In the formula, each Ar ⁵ independently has an aromatic group having 6 to 24 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms, or a plurality of substituents having 1 to 18 carbon atoms. And represents a heteroaromatic group having 4 to 20 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom.)
And / or the general formula (15)

(In the formula, Ar ⁶ and Ar ⁷ are each independently an aromatic group having 6 to 24 carbon atoms or a substituent having 1 to 18 carbon atoms, which may have a plurality of substituents having 1 to 18 carbon atoms. Represents a heteroaromatic group having 4 to 20 carbon atoms which may have a plurality of
(These reactions are referred to as “protection reactions”), and at least one of the terminals of the polymer is preferably a substituent represented by the general formula (2). The arylamine polymer described above can be produced.

  In the protection reaction, the protection reaction using an aryl halide compound and the protection reaction using a diarylamine compound can be carried out at the same time. However, in terms of the reaction efficiency of terminal protection of the arylamine, they are different from each other. It is preferable to carry out. In the case where the protection reaction is performed separately, either the protection reaction using an aryl halide compound or the protection reaction using a diarylamine compound may be performed first.

Ar ⁵ , Ar ⁶ , and Ar ⁷ in the general formula (14) and the general formula (15) each independently have 6 to 24 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms. It represents an aromatic group or a heteroaromatic group having 4 to 20 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms. These substituents are not particularly limited. For example, the substituents have a plurality of aromatic groups having 6 to 24 carbon atoms represented by Ar ¹ and Ar ² described above, or a plurality of substituents having 1 to 18 carbon atoms. Or the same group as the heteroaromatic group having 4 to 20 carbon atoms. When one or more substituents having 1 to 18 carbon atoms are bonded, each of them may be the same or different. However, it is preferable that the said C1-C18 substituent does not contain a halogen atom and a hetero atom from the point of the luminescent property of this arylamine polymer, and durability.

  Although it does not specifically limit as an aryl halide compound represented by the said General formula (14), Specifically, bromobenzene (bromobenzene, 2-bromotoluene, 3-bromo which may have a substituent is mentioned. Bromotoluene, 4-bromotoluene, 2-bromo-m-xylene, 2-bromo-p-xylene, 3-bromo-o-xylene, 4-bromo-o-xylene, 4-bromo-m-xylene, 5- Bromo-m-xylene, 1-bromo-2-ethylbenzene, 1-bromo-4-ethylbenzene, 1-bromo-4-propylbenzene, 1-bromo-4-n-butylbenzene, 1-bromo-4-t- Butylbenzene, 1-bromo-5- (trifluoromethoxy) benzene, 2-bromoanisole, 3-bromoanisole, 4-bromoanisole, 1-bromona Talen, 2-bromonaphthalene, 2-bromobiphenyl, 3-bromobiphenyl, 4-bromobiphenyl, 9-bromoanthracene, 9-bromophenanthrene, N-methyl-3-bromocarbazole, N-ethyl-3-bromo Carbazole, N-propyl-3-bromocarbazole, N-butyl-3-bromocarbazole, 2-bromofluorene, 2-bromo-9,9-dimethyl-fluorene, 2-bromo-9,9-diethyl-fluorene, 2 -Bromo-9,9-diisopropyl-fluorene, 2-bromo-9,9-di-n-butyl-fluorene, 2-bromo-9,9-di-t-butyl-fluorene, 2-bromo-9,9 -Di-sec-butyl-fluorene, 2-bromo-9,9-di-n-hexyl-fluorene, 2-bromo-9,9- -N-octyl-fluorene etc.), chlorobenzenes which may have a substituent (chlorobenzene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, 2-chloro-m-xylene, 2-chloro-p -Xylene, 3-chloro-o-xylene, 4-chloro-o-xylene, 4-chloro-m-xylene, 5-chloro-m-xylene, 1-chloro-2-ethylbenzene, 1-chloro-4-ethylbenzene 1-chloro-4-propylbenzene, 1-chloro-4-n-butylbenzene, 1-chloro-4-t-butylbenzene, 1-chloro-5- (trifluoromethoxy) benzene, 2-chloroanisole, 3-chloroanisole, 4-chloroanisole, 1-chloronaphthalene, 2-chloronaphthalene, 2-chlorobiphenyl, 3-chlorobiphenyl Phenyl, 4-chlorobiphenyl, 9-chloroanthracene, 9-chlorophenanthrene, N-methyl-3-chlorocarbazole, N-ethyl-3-chlorocarbazole, N-propyl-3-chlorocarbazole, N-butyl- 3-chlorocarbazole, 2-chlorofluorene, 2-chloro-9,9-dimethyl-fluorene, 2-chloro-9,9-diethyl-fluorene, 2-chloro-9,9-diisopropyl-fluorene, 2-chloro- 9,9-di-n-butyl-fluorene, 2-chloro-9,9-di-t-butyl-fluorene, 2-chloro-9,9-di-sec-butyl-fluorene, 2-chloro-9, 9-di-n-hexyl-fluorene, 2-chloro-9,9-di-n-octyl-fluorene, etc.) and an iodo optionally having a substituent Benzenes (iodobenzene, 2-iodotoluene, 3-iodotoluene, 4-iodotoluene, 2-iodo-m-xylene, 2-iodo-p-xylene, 3-iodo-o-xylene, 4-iodo-o -Xylene, 4-iodo-m-xylene, 5-iodo-m-xylene, 1-iodo-2-ethylbenzene, 1-iodo-4-ethylbenzene, 1-iodo-4-propylbenzene, 1-iodo-4- n-butylbenzene, 1-iodo-4-t-butylbenzene, 1-iodo-5- (trifluoromethoxy) benzene, 2-iodoanisole, 3-iodoanisole, 4-iodoanisole, 1-iodonaphthalene, 2 -Iodonaphthalene, 2-iodobiphenyl, 3-iodobiphenyl, 4-iodobiphenyl, 9-iodoanthracene, 9 Iodophenanthrene, N-methyl-3-iodocarbazole, N-ethyl-3-iodocarbazole, N-propyl-3-iodocarbazole, N-butyl-3-iodocarbazole, 2-iodofluorene, 2-iodo- 9,9-dimethyl-fluorene, 2-iodo-9,9-diethyl-fluorene, 2-iodo-9,9-diisopropyl-fluorene, 2-iodo-9,9-di-n-butyl-fluorene, 2- Iodo-9,9-di-t-butyl-fluorene, 2-iodo-9,9-di-sec-butyl-fluorene, 2-iodo-9,9-di-n-hexyl-fluorene, 2-iodo- 9,9-di-n-octyl-fluorene and the like).

  Although it does not specifically limit as a diarylamine compound represented by the said General formula (15), Specifically, diphenylamine, di-p-tolylamine, N-phenyl-1-naphthylamine, N-phenyl-2 -A naphthylamine etc. can be illustrated.

  The polymerization reaction and the protection reaction are both characterized in that they are carried out in the presence of a palladium catalyst comprising a palladium compound and a ligand and a base, and the reaction conditions are not particularly limited, Also, the following can be used.

  Although it does not specifically limit as a palladium compound which is a structural component of a palladium catalyst, For example, tetravalent palladium compounds (For example, sodium hexachloropalladium (IV) acid tetrahydrate, hexachloropalladium (IV) acid potassium Divalent palladium compounds (for example, palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium (II) acetylacetonate, dichlorobis (benzonitrile) palladium (II), dichlorobis) (Acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium (II) trifluoroacete And zero-valent palladium compounds (for example, tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform complex, tetrakis (triphenylphosphine) palladium (0)) Etc.).

  The ligand that is a constituent component of the palladium catalyst is not particularly limited, and any ligand that can coordinate to palladium, such as trialkylphosphines, arylphosphines, carbene ligands, and the like. Can be mentioned.

  Although it does not specifically limit as trialkyl phosphine, For example, a triethyl phosphine, a tricyclohexyl phosphine, a triisopropyl phosphine, a tri-n-butyl phosphine, a triisobutyl phosphine, a tri-sec-butyl phosphine, a tri-tert- And butylphosphine. Of these, tri-tert-butylphosphine is preferably used because of its particularly high reaction activity as a catalyst.

  The aryl phosphines are not particularly limited, and examples thereof include triphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, and 2,2′-bis. (Diphenylphosphino) -1,1′-binaphthyl (BINAP), trimesitylphosphine, diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinoferrocene and the like.

  Examples of the carbene-based ligand include 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene hydrochloride.

  The amount of the ligand in the palladium catalyst is not particularly limited, but it may be used usually in the range of 0.01 to 10000 times mol of 1 mol of the palladium compound. Since a carbene-type ligand is used, it is preferably in the range of 0.1 to 10 times mol per mol of the palladium compound.

  Although the usage-amount of the palladium catalyst in a polymerization reaction is not specifically limited, It is 0.00001-20 normally in conversion of a palladium atom with respect to 1 mol of halogen atoms of the triquinane dihalide compound or arylene halide compound which is a raw material. It is preferably in the range of mol%. Of these, from the viewpoint of catalytic activity and the use of expensive palladium compounds, it is usually more preferably in the range of 0.001 to 5 mol%.

  The amount of the palladium catalyst used in the protection reaction is not particularly limited, but in terms of palladium atom relative to 1 mol of the halogen atom of the aryl halide compound as a raw material or the present arylamine polymer having a halogen group at the terminal. Usually, it is preferably in the range of 0.00001 to 20 mol%. Of these, from the viewpoint of catalytic activity and the use of expensive palladium compounds, it is usually more preferably in the range of 0.001 to 5 mol%.

  The method for adding the palladium catalyst in the polymerization reaction and the protection reaction is not particularly limited, but each component constituting the palladium catalyst may be added to the reaction system for the polymerization reaction or the protection reaction, You may add what was previously mixed with these catalyst components and prepared in the form of a palladium complex.

  The base used for the polymerization reaction and the protection reaction is not particularly limited. For example, an alkali metal hydroxide such as sodium or potassium, an inorganic base such as carbonate or alkoxide, or an organic such as tertiary amine. A base. Of these, preferred are alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide, and the like. It can be added as it is to the system, or it can be prepared in situ by subjecting an alkali metal, alkali metal hydride or alkali metal hydroxide and alcohol to the reaction system. More preferred is a method in which an alkali metal tertiary alkoxide such as lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide or the like is added to the reaction system as it is.

  The amount of base used in the polymerization reaction and the protection reaction is not particularly limited, but is usually a triquinane dihalide compound, an arylene halide compound, an aryl halide compound used as a raw material, and the present arylamine polymer having a halogen group at the terminal. It is 1.0 times mol or more with respect to 1 mol of halogen atoms. Among these, the range of 1 to 20 times mol is more preferable in consideration of the post-treatment operation after completion of the reaction.

  Both the polymerization reaction and the protecting reaction are usually preferably carried out in the presence of an inert solvent. The solvent used is not particularly limited as long as it does not significantly inhibit this reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane. A solvent, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphotriamide, etc. can be mentioned. Of these, aromatic hydrocarbon solvents such as benzene, toluene and xylene are preferred.

  The polymerization reaction and the protection reaction are preferably carried out under normal pressure and in an inert gas atmosphere such as nitrogen and argon, but can be carried out even under pressurized conditions.

  The reaction temperature in the polymerization reaction and the protection reaction is not particularly limited as long as the reaction proceeds at an economically acceptable rate, but is usually 20 to 300 ° C, preferably 50 to 200 ° C. Preferably it is the range of 100-150 degreeC.

  The reaction time in the polymerization reaction and the protection reaction is not particularly limited because it is not constant depending on the arylamine polymer to be produced, the palladium catalyst and / or the reaction temperature, etc., but in many cases, it is several minutes to 72 hours. Select from a range. Preferably it is less than 24 hours.

  The protection reaction may be carried out continuously after the polymerization reaction in the same reaction vessel without changing the palladium catalyst, with the addition of the raw material and the base, or the present arylamine polymer obtained by the polymerization reaction. After recovering, the reaction may be performed again in another reaction vessel.

  The arylamine polymer produced by the polymerization reaction or the polymerization reaction and the protection reaction can be separated from the unreacted low molecular weight compound by reprecipitation or the like and purified. In addition, an adsorption treatment with silica gel, activated alumina or the like can be performed to remove impurities such as a palladium catalyst.

  The weight average molecular weight of the arylamine polymer is not particularly limited, but is in the range of 1,000 to 1,000,000 in terms of polystyrene, more preferably in the range of 5,000 to 100,000. .

  The arylamine polymer is used as a conductive polymer material in electronic devices such as field effect transistors, optical functional devices, dye-sensitized solar cells, and organic electroluminescent devices. In particular, it is extremely useful as a hole injection material, a hole transport material, a light emitting material, a light emitting material host material, a buffer material, etc.

  If the organic electroluminescent element of this invention is equipped with the organic layer containing this arylamine polymer, an element structure will not be specifically limited. Since the present arylamine polymer is excellent in solubility, for example, the present arylamine polymer itself, or a solution, a mixed solution, or a melt thereof, is used for spin coating method, casting method, dipping method, bar coating method. The element having an organic layer containing the arylamine polymer can be produced by a conventionally known coating method such as a roll coating method. Moreover, the said element provided with the organic layer containing this arylamine polymer can be produced also by the inkjet method, Langmuir-Blodgett method, etc.

  Examples of the present invention are shown below, but the present invention is not limited to these Examples.

  Polymer molecular weight: THF-based GPC (HLC-8220 (manufactured by Tosoh Corp.), column was coupled with TSKgel-SuperH3000, TSKgel-SuperH2000, TSKgel-SuperH1000 (both manufactured by Tosoh Corp.)), and molecular weight measurement of the synthesized polymer. Went. The molecular weight is shown in terms of standard polystyrene.

  Glass transition temperature: Measured using a Netch DSC200F3.

  HOMO level: Measured using an atmospheric photoelectron spectrometer measuring apparatus AC-3 (manufactured by Riken Keiki Co., Ltd.).

  LUMO level: The energy gap (Eg) was calculated from the absorption edge of the UV-vis absorption spectrum and subtracted from HOMO.

  Elemental analysis: Analysis was performed using a fully automatic elemental analyzer 2400II (manufactured by PerkinElmer).

Synthesis Example 1 Synthesis of Compound (B-1) In a 1 L three-necked flask equipped with a stirrer in a nitrogen atmosphere, 21.2 g (144 mmol) of 1,3-indandione, 250 mL of acetonitrile, 42.0 g of potassium fluoride ( 723 mmol) and stirred at room temperature for 10 minutes. A solution prepared by dissolving 72.6 g (290 mmol) of p-bromobenzyl bromide in 250 mL of acetonitrile was added dropwise to this solution over 90 minutes. After completion of dropping, the mixture was further stirred at room temperature for 7 hours. After completion of the reaction, 600 mL of pure water was added and stirred at room temperature for 1 hour. The precipitated yellow powder was collected by filtration and washed with 500 mL of pure water. Further, the obtained yellow powder was recrystallized and purified with ethanol to obtain 62.1 g of a pale yellow powder (yield 89%, purity 99.8%). ^{From the 1} H-NMR and ¹³ C-NMR analyses, it was confirmed that the obtained pale yellow powder was the target compound (B-1).

¹ H-NMR (CDCl ₃ ) δ (ppm) = 3.18 (s 4H), 6.83 to 6.87 (d 4H), 7.12 to 7.16 (d 4H), 7.56 to 7 .68 (m 4H)
¹³ C-NMR (CDCl ₃ ) δ (ppm) = 40.69, 61.64, 120.90, 122.55, 131.17, 131.52, 134.08, 135.64, 142.45, 202 .84
Synthesis Example 2 Synthesis of Compound (B-2) In a 1 L three-necked flask equipped with a stirrer in a nitrogen atmosphere, 15.0 g (31.0 mmol) of compound (B-1), 150 mL of tetrahydrofuran, and 150 mL of methanol were added. Stir at room temperature for 10 minutes. To this solution, 8.8 g (233 mmol) of sodium borohydride was slowly added over 1 hour, and further stirred at room temperature for 1 hour. After completion of the reaction, the reaction vessel was cooled to 0 ° C., and 75 mL of 10% aqueous hydrogen chloride solution was slowly added. 250 mL of pure water was added and extracted with 300 mL of dichloromethane. The obtained organic layer was washed and separated with 500 mL of pure water and then with saturated brine, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain 14.9 g of a yellow oil (yield 99%, purity 99.6%). The resulting yellow oil was recrystallized with a mixed solution of isopropanol / tetrahydrofuran to isolate one diastereomer as white crystals. ^{From the 1} H-NMR and ¹³ C-NMR analyses, it was confirmed that the obtained white crystals were the target compound (B-2).

¹ H-NMR (CDCl ₃ ) δ (ppm) = 1.46 to 1.49 (d 2H), 2.89 (s 4H), 5.10 to 5.13 (d 2H), 7.04 to 7 .35 (m 12H)
¹³ C-NMR (CDCl ₃ ) δ (ppm) = 37.16, 55.91, 78.82, 120.11, 124.16, 128.79, 131.13, 132.16, 137.71, 142 .80
Synthesis Example 3 Synthesis of Compound (B-3) Under a nitrogen atmosphere, 4.0 g (41 mmol) of sulfuric acid and 200 mL of dichloromethane were added to a 500 mL three-necked flask equipped with a stirrer, and stirred at room temperature for 5 minutes. A solution prepared by dissolving 10 g (29 mmol) of the compound (B-2) in 70 mL of dichloromethane was added dropwise to this solution over 1 hour. After completion of dropping, the mixture was further stirred at 45 ° C. for 20 hours. After completion of the reaction, 200 mL of pure water was added and the solution was separated. Further, after washing and separating with saturated brine, the obtained organic layer was concentrated under reduced pressure to distill off the solvent. Furthermore, the obtained residue was purified by silica gel column chromatography and recrystallized from toluene to obtain 7.1 g of a white solid (yield 77%, purity 99.9%). ^{From 1} H-NMR and ¹³ C-NMR analysis, it was confirmed that the obtained white solid was the target compound (B-3).

¹ H-NMR (CDCl ₃ ) δ (ppm) = 3.03 to 3.30 (4H), 4.40 (s 2H), 7.02 to 7.06 (d 2H), 7.19 to 7. 36 (m 6H), 7.48 (s 2H)
¹³ C-NMR (CDCl ₃ ) δ (ppm) = 43.71, 61.77, 63.73, 120.53, 124.56, 126.39, 127.77, 130.13, 141.37, 143 .20, 145.95
Example 1 Synthesis of Arylamine Polymer (20) In a 200 ml four-necked round bottom flask equipped with a condenser and a thermometer, compound (B-3); 3,10-dibromo-4bα, 8bβ, 13, 14-tetrahydrodiindeno [1,2-a: 2 ′, 1′-b] indene) 4.00 g (8.85 mmol), 4-n-butylaniline 1.39 g (9.29 mmol), sodium-tert -6.80 g (70.8 mmol) of butoxide and 74.1 g of o-xylene were charged. To this mixed solution, 40.6 mg (0.044 mmol) of tris (dibenzylideneacetone) dipalladium prepared in advance in a nitrogen atmosphere and 71.6 mg (0.354 mmol) of tri-tert-butylphosphine o-xylene (0. 29 g) The solution was added. Thereafter, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the mixture was aged for 3 hours while heating and stirring at 120 ° C.

  Thereafter, 0.276 g (1.76 mmol) of bromobenzene was added, and the reaction was further performed for 3 hours. Thereafter, 0.892 g (5.28 mmol) of diphenylamine was added, and the reaction was further performed for 3 hours.

  After completion of the reaction, the reaction mixture allowed to cool to about 80 ° C. was slowly added into a stirring solution of 90% aqueous ethanol (1000 mL) to precipitate a solid. The solid was collected by filtration and washed in the order of ethanol, water, and ethanol, and then dried under reduced pressure to obtain a white solid (yield 79%).

  The obtained arylamine polymer (20) had a weight average molecular weight of 11,000 and a number average molecular weight of 4,300 (dispersity 2.6) in terms of polystyrene.

  The glass transition temperature was 234 ° C.

  The HOMO level was 5.65 eV, and the LUMO level was 2.31 eV.

  Table 1 shows the results of elemental analysis.

Example 2 Synthesis of Arylamine Polymer (21)
An arylamine polymer (21) was obtained in the same manner as in Example 1 except that p-toluidine 1.00 (9.29 mmol) was used instead of 4-n-butylaniline in Example 1. Rate 77%).

  The obtained arylamine polymer (21) had a weight average molecular weight of 9,000 and a number average molecular weight of 3,200 (dispersity 2.8) in terms of polystyrene.

  The glass transition temperature was 249 ° C.

  The HOMO level was 5.62 eV, and the LUMO level was 2.30 eV.

  The measurement results of elemental analysis are shown in Table 2.

Example 3 Synthesis of Arylamine Polymer (22)
The same operation as in Example 1 was carried out except that p-anisidine 1.14 (9.29 mmol) was used instead of 4-n-butylaniline in Example 1, to obtain an arylamine polymer (22). Rate 57%).

  The obtained arylamine polymer (22) had a weight average molecular weight of 3,700 and a number average molecular weight of 2,800 (dispersity: 1.3) in terms of polystyrene.

  The glass transition temperature was 240 ° C.

  The HOMO level was 5.60 eV, and the LUMO level was 2.27 eV.

  Table 3 shows the measurement results of elemental analysis.

Example 4 Synthesis of arylamine polymer (23) In a 200 ml four-necked round bottom flask equipped with a condenser and a thermometer, at room temperature, 4.50 g (9.95 mmol) of compound (20-a), 4-n- 4.45 g (29.85 mmol) of butylaniline, 3.82 g (39.8 mmol) of sodium-tert-butoxide and 67.4 g of o-xylene were charged. To this mixed solution was added a solution of 44.7 mg (0.199 mmol) of palladium acetate prepared in advance in a nitrogen atmosphere and 161 mg (0.796 mmol) of tri-tert-butylphosphine in o-xylene (0.64 g). Thereafter, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the mixture was aged for 3 hours while heating and stirring at 120 ° C.

  After completion of the reaction, 50 g of pure water was added to the reaction solution which was allowed to cool to 80 ° C., and then allowed to cool to room temperature with stirring. Extraction was performed by adding 200 mL of toluene to the obtained reaction mixture. The obtained organic layer was washed with 200 mL of saturated brine. The organic layer was passed through silica gel column chromatography. Toluene was removed by distillation under reduced pressure to obtain a residue. The residue was purified by recrystallization using ethanol as a solvent, and 0.53 g of compound (23-a; 3,10-bis (4-bromophenyl) amino-4bα, 8bβ, 13,14-tetrahydrodiindeno [ 1,2-a: 2 ′, 1′-b] indene).

  In a 100 ml four-necked round bottom flask equipped with a condenser and a thermometer, at room temperature, compound (23-a) 0.50 g (0.85 mmol), 1,4-diiodobenzene 0.27 g (0.81 mmol) Sodium tert-butoxide 0.62 g (6.48 mmol) and o-xylene 20 g. To this mixed liquid, 7.8 mg (0.0085 mmol) of tris (dibenzylideneacetone) dipalladium prepared in advance in a nitrogen atmosphere and 13.8 mg (0.068 mmol) of tri-tert-butylphosphine o-xylene (55. 0 mg) solution was added. Thereafter, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the mixture was aged for 3 hours while heating and stirring at 120 ° C.

  Thereafter, 25.1 mg (0.16 mmol) of bromobenzene was added, and the reaction was further performed for 3 hours. Thereafter, 0.287 g (1.70 mmol) of diphenylamine was added, and the reaction was further performed for 3 hours.

  After completion of the reaction, the reaction mixture allowed to cool to about 80 ° C. was slowly added into a stirring solution of 90% aqueous ethanol (1000 mL) to precipitate a solid. The solid was collected by filtration, washed in the order of ethanol, water, and ethanol, and then dried under reduced pressure to obtain a white solid (yield 71%).

  The obtained arylamine polymer (23) had a weight average molecular weight of 10,200 and a number average molecular weight of 3,200 (dispersion degree 3.1) in terms of polystyrene.

  The glass transition temperature was 212 ° C.

  The HOMO level was 5.40 eV, and the LUMO level was 2.09 eV.

  Table 4 shows the measurement results of elemental analysis.

Example 5 Measurement of triplet level of arylamine polymer (20) In a sample tube for UV-Vis spectrum measurement, 1 mg of arylamine polymer (20) and 1 mL of 2-methyltetrahydrofuran were mixed well to prepare a uniform solution. did. The solution was degassed by bubbling with nitrogen gas for 10 minutes, and then the sample tube was sealed and the phosphorescence spectrum was measured. The triplet level of the arylamine polymer (20) calculated from the phosphorescence spectrum was 2.91 eV.
Example 6 Measurement of triplet level of arylamine polymer (21) The phosphorescence spectrum was measured in the same manner as in Example 5 except that arylamine polymer (21) was used instead of arylamine polymer (20). As a result, the triplet level of the arylamine polymer (21) was 2.91 eV.
Example 7 Measurement of triplet level of arylamine polymer (22) The phosphorescence spectrum was measured in the same manner as in Example 5 except that arylamine polymer (22) was used instead of arylamine polymer (20). As a result, the triplet level of the arylamine polymer (22) was 2.91 eV.
Example 8 Measurement of triplet level of arylamine polymer (23) The phosphorescence spectrum was measured in the same manner as in Example 5 except that arylamine polymer (23) was used instead of arylamine polymer (20). As a result, the triplet level of the arylamine polymer (23) was 2.67 eV.

Example 9 (Preparation and evaluation of organic electroluminescence device)
A glass substrate having a transparent ITO electrode having a thickness of 200 nm was sequentially ultrasonically washed with acetone and isopropyl alcohol, then boiled and washed with isopropyl alcohol, and then dried. Further, UV / ozone treatment was performed.

On this substrate, 0.5 wt. Of poly-N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl) benzidine (ADS254BE: manufactured by American Die Source) was formed by spin coating. A% chlorobenzene solution was formed to a thickness of 30 nm and dried at 160 ° C. for 3 hours. On top of that, a 0.5 wt% toluene solution of the arylamine polymer (20) was formed into a film having a thickness of 50 nm by spin coating, and dried at 160 ° C. for 3 hours. Next, tris (8-quinolinolato) aluminum (Alq ₃ , 50 nm) was deposited. The vapor deposition was performed under the conditions of a degree of vacuum of 1.0 × 10 ⁻⁴ Pa and a film formation rate of 0.3 nm / second. Further, lithium fluoride (0.8 nm) and aluminum (150 nm) were deposited in this order under the conditions of a vacuum degree of 1.0 × 10 ⁻⁴ Pa and a film formation rate of 0.3 nm / second. Further, a protective glass substrate was stacked in a nitrogen atmosphere, and was bonded and sealed using an organic EL sealing agent (80 ° C.-3 hours).

The device manufactured as described above was applied with a current of 20 mA / cm ² with the ITO electrode as the positive electrode and the LiF-Al electrode as the negative electrode, and the light emission characteristics (driving voltage, light emission efficiency, current efficiency) of the device. Examined. The emission characteristics are shown in Table 5.

Example 10 (Preparation and evaluation of organic electroluminescence device)
In Example 9, a device was prepared in the same manner as in Example 9 except that the arylamine polymer (21) was used instead of the arylamine polymer (20), and the light emission characteristics of the device were examined. The emission characteristics are shown in Table 5.

Example 11 (Preparation and evaluation of organic electroluminescence device)
In Example 9, a device was prepared in the same manner as in Example 9 except that the arylamine polymer (22) was used instead of the arylamine polymer (20), and the light emission characteristics of the device were examined. The emission characteristics are shown in Table 5.

Example 12 (Preparation and evaluation of organic electroluminescence device)
In Example 9, a device was produced in the same manner as in Example 9 except that the arylamine polymer (23) was used instead of the arylamine polymer (20), and the light emission characteristics of the device were examined. The emission characteristics are shown in Table 5.

Comparative Example 1
In Example 9, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPB) was deposited instead of depositing the arylamine polymer (20) by spin coating. A device was prepared in the same manner as in Example 9 except that the film was formed, and the light emission characteristics of the device were examined. Α-NPB was formed under the conditions of a degree of vacuum of 1.0 × 10 ⁻⁴ Pa and a film formation rate of 0.3 nm / second. The emission characteristics are shown in Table 5.

Claims (9)

The following general formula (1)

(In formula, Ar < ¹ > and Ar < ² > are respectively independently the C1-C18 aromatic group which may have two or more C1-C18 substituents, or C1-C18 substitution. Represents a heteroaromatic group having 4 to 20 carbon atoms which may have a plurality of groups, Ar ³ represents an arylene group having 6 to 24 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms, or Represents a heteroarylene group having 4 to 20 carbon atoms, which may have a plurality of substituents having 1 to 18 carbon atoms, R ¹ , R ² , and R ³ each independently represent a hydrogen atom, 1 to carbon atoms 18 represents an alkyl group, an alkoxy group having 1 to 18 carbon atoms, or a phenyl group which may have 1 to 5 substituents having 1 to 18 carbon atoms, a represents an integer of 0 to 4. b and c each independently represents an integer of 0 to 3. n represents 0 or 1.)
An arylamine polymer containing one or more types of repeating structures represented by: The arylamine polymer according to claim 1, wherein Ar ¹ is a phenyl group which may have 1 to 5 substituents having 1 to 18 carbon atoms. The arylamine polymer according to claim 1 or 2, wherein the weight average molecular weight is in a range of 1,000 to 1,000,000 in terms of polystyrene. The arylamine polymer according to any one of claims 1 to 3, wherein at least one terminal is represented by the following general formula (2).

(In the formula, Ar ⁴ is an aromatic group having 6 to 24 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms, or a carbon number which may have a plurality of substituents having 1 to 18 carbon atoms. Represents 4 to 20 heteroaromatic groups.)
An arylamine polymer, which is a substituent represented by the formula: In the presence of a palladium catalyst and a base, the general formula (4)

(Wherein R ¹ , R ² , and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a substituent having 1 to 18 carbon atoms) Represents a phenyl group which may have 1 to 5. X ¹ and X ² each independently represent a chlorine atom, a bromine atom or an iodine atom, and a represents an integer of 0 to 4. b and c each independently represents an integer of 0 to 3.)
One or more triquinane dihalide compounds represented by general formula (5)

(In the formula, each Ar ¹ independently has an aromatic group having 6 to 24 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms, or a plurality of substituents having 1 to 18 carbon atoms. And represents a heteroaromatic group having 4 to 20 carbon atoms.)
Or one or more arylamine compounds represented by the general formula (6)

(In formula, Ar < ¹ > and Ar < ² > are respectively independently the C1-C18 aromatic group which may have two or more C1-C18 substituents, or C1-C18 substitution. Represents a heteroaromatic group having 4 to 20 carbon atoms which may have a plurality of groups, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents an alkoxy group having 1 to 18 carbon atoms or a phenyl group that may have 1 to 5 substituents having 1 to 18 carbon atoms, a represents an integer of 0 to 4. b and c are each independently And represents an integer of 0 to 3.)
One or more triquinanediamine compounds represented by the general formula (7)

(In the formula, each Ar ³ independently has a plurality of arylene groups having 6 to 24 carbon atoms or a plurality of substituents having 1 to 18 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms. And represents an optionally substituted heteroarylene group having 4 to 20 carbon atoms, X ³ and X ⁴ each independently represents a chlorine atom, a bromine atom, or an iodine atom.)
The arylamine polymer production method according to any one of claims 1 to 3, wherein one or two or more arylene halide compounds represented by the formula (1) are reacted. An arylamine polymer obtained by the production method according to claim 5 and a general formula (14) in the presence of a palladium catalyst and a base.

(In the formula, Ar ⁵ is an aromatic group having 6 to 24 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms, or a carbon number which may have a plurality of substituents having 1 to 18 carbon atoms. Represents a heteroaromatic group of 4 to 20. X represents a chlorine atom, a bromine atom, or an iodine atom.)
One or two or more aryl halide compounds represented by the general formula (15)

(In the formula, Ar ⁶ and Ar ⁷ are each independently an aromatic group having 6 to 24 carbon atoms or a substituent having 1 to 18 carbon atoms, which may have a plurality of substituents having 1 to 18 carbon atoms. Represents a heteroaromatic group having 4 to 20 carbon atoms which may have a plurality of
The method for producing an arylamine polymer according to claim 4, wherein one or more diarylamine compounds represented by the formula (1) are reacted. An electronic device comprising the arylamine polymer according to any one of claims 1 to 4. The electronic device according to claim 7, wherein the electronic device is an organic electroluminescent device. The arylamine polymer according to any one of claims 1 to 4 is included in any one or more of a hole transport layer, a hole injection layer, and a light emitting layer in an organic electroluminescent device. The electronic device according to claim 8.

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