JP6146181B2 - Arylamine polymer, production method thereof and use thereof - Google Patents

Description

  The present invention relates to an arylamine polymer, a method for producing the same, and an application thereof.

  In recent years, organic EL devices have begun to be used in various applications such as portable displays and lighting equipment. An organic EL element usually has a structure in which a plurality of organic thin films are sandwiched between a pair of electrodes. Low molecular weight compounds are the current mainstream materials used for the organic thin film layer, but there is a problem that the organic EL element manufacturing cost is high because vacuum deposition is indispensable for forming the organic thin film layer of the low molecular weight compound. there were. Therefore, there is a demand for the development of a high-molecular material that can be applied and manufactured at a low manufacturing cost.

Moreover, in an organic EL element, it is industrially strongly desired to use a phosphorescent material having excellent luminous efficiency. In such phosphorescent organic EL devices, it is generally known that it is necessary to use peripheral materials (a hole transport material and an electron transport material) having a high excited triplet level (T ₁ ).

Examples of the polymer hole injection material, hole transport material, and light emitting host material include PEDOT-PSS, poly- (N, N′-bis (4-butylphenyl) -N, N′-bis ( An arylamine polymer typified by (phenyl) benzidine) and the like has been proposed (for example, see Patent Documents 1 to 6), but T ₁ is not sufficiently high for these conventionally known materials. For this reason, development of an arylamine polymer having a sufficiently high T ₁ suitable for a phosphorescent light emitting device is desired.

JP-A-11-292828 Japanese Patent Laid-Open No. 13-98023 JP 2004-292882 A JP-T-2001-527102 JP-A-56-135448 JP 59-046249 A

  The present invention has been made in view of the above-mentioned background art, and its purpose is to provide an arylamine polymer having a higher excited triplet level than conventionally known ones, a method for producing the same, and an organic electroluminescent device containing the same. It is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have found an arylamine polymer having a skeleton in which at least two repeating structures represented by the following general formula (1) are connected. It came to complete.

  That is, the present invention relates to an arylamine polymer having a skeleton in which at least two repeating structures represented by the following general formula (1) are linked (hereinafter, appropriately referred to as “arylamine polymer (1)”), and a method for producing the arylamine polymer And an organic electroluminescent device using the arylamine polymer (1).

（式中、
Ａｒ^１は炭素数６〜６０の二価芳香族炭化水素基または炭素数４〜２０の二価ヘテロ芳香族基（これらの置換基は、各々独立して、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、フェニル基、炭素数１〜１８のアルキル基を有するフェニル基、炭素数１〜１８のアルコキシ基を有するフェニル基、ハロゲン化フェニル基、及び炭素数１〜６の異なっていてもよいアルキル基からなるジアルキルアミノ基からなる群より選ばれる１種以上の置換基を有していてもよい）を表す。
Ａｒ^２及びＡｒ^３は、各々独立して、炭素数６〜６０の芳香族炭化水素基又は炭素数４〜２０のヘテロ芳香族基（これらの置換基は、各々独立して、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、炭素数６〜６０の芳香族炭化水素基、及び炭素数４〜２０のヘテロ芳香族基からなる群より選ばれる１種以上の置換基を有していてもよい）を表す。
Ｒ^１、Ｒ^２及びＲ^３は、各々独立して、水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、フェニル基、炭素数１〜１８のアルキル基を有するフェニル基、炭素数１〜１８のアルコキシ基を有するフェニル基、または炭素数１〜６の異なっていてもよいアルキル基からなるジアルキルアミノ基を有するフェニル基を表す。
ｎは０または１を表す。）

(Where
Ar ¹ is a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms or a divalent heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, A C1-C18 alkoxy group, a phenyl group, a phenyl group having a C1-C18 alkyl group, a phenyl group having a C1-C18 alkoxy group, a halogenated phenyl group, and a C1-C6 It may have one or more substituents selected from the group consisting of dialkylamino groups that may be different alkyl groups).
Ar ² and Ar ³ are each independently an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently selected from 1 to One or more substituents selected from the group consisting of an 18 alkyl group, an alkoxy group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, and a heteroaromatic group having 4 to 20 carbon atoms. Which may have).
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, a phenyl group, or a phenyl group having an alkyl group having 1 to 18 carbon atoms. A phenyl group having a group, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, or a dialkylamino group composed of an optionally substituted alkyl group having 1 to 6 carbon atoms.
n represents 0 or 1. )

  The arylamine polymer (1) of the present invention has a high excited triplet level as compared with conventionally known polymer compounds. For this reason, the organic EL device using the arylamine polymer (1) of the present invention is expected to be excellent in luminous efficiency, current efficiency, and durability.

  The arylamine polymer (1) of the present invention has a skeleton in which at least two repeating structures represented by the general formula (1) are linked.

In the arylamine polymer (1), Ar ¹ is a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms or a divalent heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently carbon An alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, and a halogenated phenyl group Or may have one or more substituents selected from the group consisting of a phenyl group having a dialkylamino group consisting of an optionally substituted alkyl group having 1 to 6 carbon atoms.

  Although it does not specifically limit as a C6-C60 bivalent aromatic hydrocarbon group, For example, a phenylene group (o-phenylene group, m-phenylene group, p-phenylene group), biphenylylene group, naphthalene dil. A group, anthracenediyl group, pyrenediyl group, terphenylene group, phenanthracenediyl group, perylenediyl group or triphenylenediyl group.

  Although it does not specifically limit as a C4-C20 bivalent hetero aromatic group, For example, a furadyl group, a benzofuranyl group, a dibenzofuranyl group, a thienylene group, a benzothienylene group, a dibenzothienylene group, a pyridylene group, List pyrimidinediyl, pyrazinediyl, quinolinediyl, isoquinolinediyl, acridinediyl, benzothiazolinediyl, quinazolinediyl, quinoxalinediyl, 1,6-naphthyridinediyl, 1,8-naphthyridinediyl I can do it.

  Although it does not specifically limit as a C1-C18 alkyl group, For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl Group, n-hexyl group, cyclohexyl group, cyclohexadienyl group, octyl group, trifluoromethyl group, benzyl group, phenethyl group and the like.

  Although it does not specifically limit as a C1-C18 alkoxy group, For example, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy Group, n-hexyloxy group, cyclohexyloxy group, cyclohexadienyloxy group, octyloxy group, tetrahydrofuranyloxy group, trifluoromethoxy group, benzyloxy group, phenethyloxy group and the like.

  Although it does not specifically limit as a phenyl group which has a C1-C18 alkyl group, For example, o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl Group, p-ethylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group and the like.

  Although it does not specifically limit as a phenyl group which has a C1-C18 alkoxy group, For example, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m -Ethoxyphenyl group, p-ethoxyphenyl group, o-tert-butoxyphenyl group, m-tert-butoxyphenyl group, p-tert-butoxyphenyl group and the like can be mentioned.

  Although it does not specifically limit as a halogenated phenyl group, For example, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a chlorophenyl group, a dichlorophenyl group, a trichlorophenyl group etc. are mentioned.

  Although it does not specifically limit as a phenyl group which has a dialkylamino group which consists of a C1-C6 alkyl group which may differ, For example, a dimethylaminophenyl group, a diethylaminophenyl group, a dibutylaminophenyl group, a dihexyl Aminophenyl group, methylethylaminophenyl group, methylbutylaminophenyl group, methylhexylaminophenyl group and the like can be mentioned.

Ar ¹ has a high excited triplet level, and is an m-phenylene group or a p-phenylene group (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms). Group, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, a halogenated phenyl group, or an optionally substituted alkyl group having 1 to 6 carbon atoms Are preferably 1 or more substituents selected from the group consisting of a phenyl group having a dialkylamino group consisting of: m-phenylene group, p-phenylene group (each independently, More preferably, it may have an alkyl group having 1 to 18 carbon atoms.

In the arylamine polymer (1) of the present invention, Ar ² and Ar ³ are each independently an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents). Are each independently a group consisting of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, and a heteroaromatic group having 4 to 20 carbon atoms. It may have one or more substituents selected from.

With respect to the following substituents represented by Ar ² and Ar ³ , the same substituents as those represented by Ar ¹ can be exemplified.
・ Alkyl group having 1 to 18 carbon atoms ・ Alkoxy group having 1 to 18 carbon atoms The aromatic hydrocarbon group having 6 to 60 carbon atoms in Ar ² and Ar ³ is not particularly limited. , Biphenylyl group, naphthalenyl group, anthracenyl group, pyrenyl group, terphenylenyl group, phenanthracenyl group, perylenyl group, or triphenylenyl group.

The heteroaromatic group having 4 to 20 carbon atoms in the Ar ² and Ar ^3, is not particularly limited, for example, furanyl, benzofuranyl group, a dibenzofuranyl group, Chienireniru group, benzo Chie Nireni group, dibenzo Thienylenyl group, pyridylenyl group, pyrimidinyl group, pyrazinyl group, quinolinyl group, isoquinolinyl group, acridinyl group, benzothiazolyl group, quinazolyl group, quinoxalyl group, 1,6-naphthyridinyl group, 1,8-naphthyridinyl group and the like can be mentioned.

  In addition, “selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, and a heteroaromatic group having 4 to 20 carbon atoms. The “substituent” may be bonded to a plurality of aromatic hydrocarbon groups having 6 to 60 carbon atoms or heteroaromatic groups having 4 to 20 carbon atoms as long as the effects of the present invention are not impaired. Among these, “selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 24 carbon atoms, and a heteroaromatic group having 4 to 20 carbon atoms. The number of “substituents” is preferably in the range of 1 to 3, and the types of substituents may be the same or different.

Ar ² and Ar ³ are each independently a phenyl group, a biphenylyl group, a fluorenyl group, a carbazolyl group, a dibenzothienyl group, a dibenzothienylphenyl group, or an N-dibenzothienylcarbazolyl in terms of excellent hole transport properties. It is more preferable that they are each independently an alkyl group having 1 to 8 carbon atoms as a substituent, and each independently represents a 4-methylphenyl group, 4-n -Butylphenyl group, dibenzothienyl group, dibenzothienylphenyl group, or N-dibenzothienylcarbazolyl group is more preferable.

In the arylamine polymer (1) of the present invention, Ar ² and Ar ³ may be the same or different. However, considering the ease of synthesis, Ar ² and Ar ³ are preferably the same.

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, a phenyl group, or a phenyl group having an alkyl group having 1 to 18 carbon atoms. A phenyl group having a group, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, or a dialkylamino group composed of an optionally substituted alkyl group having 1 to 6 carbon atoms.

As for the following substituents represented by R ¹ , R ² and R ³ , the same substituents as those represented by Ar ¹ can be exemplified.
-C1-C18 alkyl group-C1-C18 alkoxy group-Phenyl group having a C1-C18 alkyl group-Phenyl group having a C1-C18 alkoxy group-C1-C6 The phenyl group R ¹ , R ² and R ³ having a dialkylamino group consisting of an alkyl group which may be different from each other are each independently a hydrogen atom, a methyl group, tert-butyl in terms of excellent polymer production efficiency. Group, a phenyl group, a tolyl group, and a methoxyphenyl group, and each independently more preferably a hydrogen atom, a methyl group, a tert-butyl group, or a phenyl group.

  Moreover, about an arylamine polymer (1), it is preferable that the terminal is a substituent represented by following General formula (2) from the point of luminescent property and durability.

（式中、Ａｒ^４は炭素数６〜６０の芳香族炭化水素基又は炭素数４〜２０のヘテロ芳香族基（これらの置換基は、各々独立して、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、フェニル基、炭素数１〜１８のアルキル基を有するフェニル基、炭素数１〜１８のアルコキシ基を有するフェニル基、ハロゲン化フェニル基、または炭素数１〜６の異なっていてもよいアルキル基からなるジアルキルアミノ基を有するフェニル基からなる群より選ばれる１種以上の置換基を有していてもよい）を表す）
Ａｒ^４で示される下記置換基については、Ａｒ^１及びＡｒ^２又はＡｒ^３で示した置換基と同じ置換基を例示することができる。
・炭素数６〜６０の芳香族炭化水素基（Ａｒ^２又はＡｒ^３で示した例示と同じ）
・炭素数４〜２０のヘテロ芳香族基（Ａｒ^２又はＡｒ^３で示した例示と同じ）
・炭素数１〜１８のアルキル基（Ａｒ^１で示した例示と同じ）
・炭素数１〜１８のアルコキシ基（Ａｒ^１で示した例示と同じ）
・炭素数１〜１８のアルキル基を有するフェニル基（Ａｒ^１で示した例示と同じ）
・炭素数１〜１８のアルコキシ基を有するフェニル基（Ａｒ^１で示した例示と同じ）
・ハロゲン化フェニル基（Ａｒ^１で示した例示と同じ）
・炭素数１〜６の異なっていてもよいアルキル基からなるジアルキルアミノ基を有するフェニル基（Ａｒ^１で示した例示と同じ）
Ａｒ^４については、製造効率に優れる点で、各々独立して、フェニル基（当該フェニル基は、各々独立して、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、フェニル基、炭素数１〜１８のアルキル基を有するフェニル基、炭素数１〜１８のアルコキシ基を有するフェニル基、ハロゲン化フェニル基、または炭素数１〜６の異なっていてもよいアルキル基からなるジアルキルアミノ基を有するフェニル基からなる群より選ばれる１種以上の置換基を有していてもよい）であることが好ましく、各々独立して、ｏ−トリル基、ｍ−トリル基、ｐ−トリル基、又はフェニル基であることがより好ましい。

(In the formula, Ar ⁴ is an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, An alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, a halogenated phenyl group, or an alkyl group having 1 to 6 carbon atoms (It may have one or more substituents selected from the group consisting of phenyl groups having dialkylamino groups consisting of alkyl groups which may be different))
As for the following substituents represented by Ar ⁴ , the same substituents as those represented by Ar ¹ and Ar ² or Ar ³ can be exemplified.
Aromatic hydrocarbon group having 6 to 60 carbon atoms (same as the examples shown for Ar ² or Ar ³ )
-Heteroaromatic group having 4 to 20 carbon atoms (same as the example shown for Ar ² or Ar ³ )
- alkyl group having 1 to 18 carbon atoms (exemplified as the same as shown in Ar ¹⁾
- alkoxy group having 1 to 18 carbon atoms (exemplified as the same as shown in Ar ¹⁾
A phenyl group having an alkyl group having 1 to 18 carbon atoms (same as the example shown for Ar ¹ )
A phenyl group having an alkoxy group having 1 to 18 carbon atoms (same as the example shown for Ar ¹ )
-Halogenated phenyl group (same as the example shown for Ar ¹ )
A phenyl group having a dialkylamino group consisting of an alkyl group having 1 to 6 carbon atoms which may be different (same as the example shown for Ar ¹ )
For Ar ^4, from the viewpoint of excellent production efficiency, each independently, phenyl group (said phenyl group are each independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group A dialkylamino comprising a phenyl group having an alkyl group having 1 to 18 carbon atoms, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, a halogenated phenyl group, or an optionally substituted alkyl group having 1 to 6 carbon atoms It may preferably have one or more substituents selected from the group consisting of a phenyl group having a group, and each independently represents an o-tolyl group, an m-tolyl group, or a p-tolyl group. Or a phenyl group is more preferable.

  That is, the arylamine polymer (1) is preferably an arylamine polymer represented by the following general formula (3).

（式中、Ａｒ^１、Ａｒ^２、Ａｒ^３、Ｒ^１、Ｒ^２、Ｒ^３及びｎは、各々独立して、前述の一般式（１）と同じ定義を示す。Ａｒ^４は、各々独立して、前記一般式（２）と同じ定義を表す。ｍは２以上の整数を表す。）
なお、一般式（３）におけるＡｒ^１、Ａｒ^２、Ａｒ^３、Ｒ^１、Ｒ^２、Ｒ^３、及びＡｒ^４の好ましい範囲については、前述のとおりである。

(In the formula, Ar ¹ , Ar ² , Ar ³ , R ¹ , R ² , R ³ and n each independently represent the same definition as in the general formula (1). Ar ⁴ is independently And m represents an integer of 2 or more.
Note that the preferable range of ^{Ar 1, Ar 2, Ar 3} , R 1, R 2, R 3, and Ar ⁴ in the general formula (3), as described above.

  The arylamine polymer (1) of the present invention is not particularly limited as long as it falls within the above definition, but the following general formulas (4) to (4) are used in terms of physical properties such as luminous efficiency and lifetime of the organic electroluminescent element. It is preferable that it is represented in any one of (11).

（上記一般式（４）〜（１１）中、
Ｒ^１、Ｒ^２及びＲ^３は、前記一般式（１）と同じ定義である。
Ｒ^４及びＲ^５は、各々独立して、水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、炭素数６〜６０の芳香族炭化水素基又は炭素数４〜２０のヘテロ芳香族基を表す。
Ｒ^６、Ｒ^７及びＲ^８は、各々独立して、水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、フェニル基、炭素数１〜１８のアルキル基を有するフェニル基、炭素数１〜１８のアルコキシ基を有するフェニル基、ハロゲン化フェニル基、または炭素数１〜６の異なっていてもよいアルキル基からなるジアルキルアミノ基を有するフェニル基を表す。
ｍは２以上の整数を表す。）
Ｒ^４及びＲ^５で示される下記置換基については、Ａｒ^１及びＡｒ^２又はＡｒ^３で示した置換基と同じ置換基を例示することができる。
・炭素数１〜８のアルキル基（Ａｒ^１で示した例示と同じ）
・炭素数１〜８のアルコキシ基（Ａｒ^１で示した例示と同じ）
・炭素数６〜６０の芳香族炭化水素基（Ａｒ^２又はＡｒ^３で示した例示と同じ）
・炭素数４〜２０のヘテロ芳香族基（Ａｒ^２又はＡｒ^３で示した例示と同じ）
なお、Ｒ^４及びＲ^５は、ポリマーの製造効率に優れる点で、各々独立して、水素原子又は炭素数１〜８のアルキル基であることが好ましく、各々独立して、水素原子又はメチル基であることがより好ましい。

(In the above general formulas (4) to (11),
R ¹ , R ² and R ³ have the same definition as in the general formula (1).
R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, or 4 to 20 carbon atoms. Represents a heteroaromatic group.
R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, or a phenyl group having an alkyl group having 1 to 18 carbon atoms. A phenyl group having a dialkylamino group composed of a group, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, a halogenated phenyl group, or an alkyl group having 1 to 6 carbon atoms which may be different.
m represents an integer of 2 or more. )
As for the following substituents represented by R ⁴ and R ⁵ , the same substituents as those represented by Ar ¹ and Ar ² or Ar ³ can be exemplified.
- an alkyl group having 1 to 8 carbon atoms (exemplified as the same as shown in Ar ¹⁾
- an alkoxy group having 1 to 8 carbon atoms (exemplified as the same as shown in Ar ¹⁾
Aromatic hydrocarbon group having 6 to 60 carbon atoms (same as the examples shown for Ar ² or Ar ³ )
-Heteroaromatic group having 4 to 20 carbon atoms (same as the example shown for Ar ² or Ar ³ )
In addition, R ⁴ and R ⁵ are each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each independently represents a hydrogen atom or a methyl group, from the viewpoint of excellent polymer production efficiency. It is more preferable that

With respect to the following substituents represented by R ⁶ , R ⁷ and R ⁸ , the same substituents as those represented by Ar ¹ can be exemplified.
-C1-C8 alkyl group-C1-C8 alkoxy group-Phenyl group having C1-C18 alkyl group-Phenyl group having C1-C18 alkoxy group-Halogenated phenyl group- A dialkylamino group composed of an alkyl group having 1 to 6 carbon atoms which may be different, wherein R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a methyl group in terms of excellent polymer production efficiency. Preferably there is.

The arylamine polymer (1) preferably has an excited triplet level (T ₁ ) of 2.50 eV or more and 3.25 eV or less from the viewpoint of excellent luminous efficiency of the phosphorescent organic EL.

  Next, the manufacturing method of the arylamine polymer (1) of this invention is demonstrated.

  The arylamine polymer (1) of the present invention is not particularly limited, but various arylene halides and aryleneamines or arylene halides and arylenediamines can be converted to trialkylphosphine and / or palladium as shown in the following reaction formula. It can be synthesized by polymerization in the presence of a catalyst comprising a compound and a base.

（反応式１〜３において、Ａｒ^１、Ａｒ^２、Ａｒ^３、Ｒ^１、Ｒ^２及びＲ^３は上記一般式（１）におけるＡｒ^１、Ａｒ^２、Ａｒ^３、Ｒ^１、Ｒ^２及びＲ^３と同じ定義を表す。Ｘ^１、Ｘ^２、Ｘ^３及びＸ^４は各々独立して、塩素原子、臭素原子、ヨウ素原子のハロゲン原子を表す。ｍは２以上の整数を表す。）
重合工程より得られる一般式（１２ａ）又は一般式（１２ｂ）で表される構造を有する化合物は、通常、末端が二級アミノ基又はハロゲン基、又は二級アミノ基とハロゲン基の両方である。

(In the reaction formula ^{1~3, Ar 1, Ar 2,} Ar 3, R 1, Ar 1 R 2 and ^{R 3} in the general formula ^{(1), Ar 2, Ar} 3, R 1, R 2 and ^{R 3} X ¹ , X ² , X ³ and X ⁴ each independently represent a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, and m represents an integer of 2 or more.)
The compound having a structure represented by the general formula (12a) or the general formula (12b) obtained from the polymerization step is usually a secondary amino group or a halogen group, or both a secondary amino group and a halogen group. .

  In the protection step, in the presence of a palladium catalyst and a base, the compound having the structure represented by the general formula (12a) or the general formula (12b) obtained in the polymerization step and the fragrance represented by the following general formula (13) It is carried out by a reaction with a group halogen compound or an aromatic amine compound represented by the following general formula (14), or both.

（式中、Ａｒ^４は、上記一般式（２）におけるＡｒ^４と同じ定義である。Ｘ^５は、塩素原子、臭素原子、又はヨウ素原子を表す。）

(In the formula, Ar ⁴ has the same definition as Ar ⁴ in the general formula (2). X ⁵ represents a chlorine atom, a bromine atom, or an iodine atom.)

（式中、Ａｒ^４は、各々独立して、上記一般式（２）におけるＡｒ^４と同じ定義である。）
保護化工程の生成物として、下記一般式（３）で表される、反応末端を保護したアリールアミンポリマー（１）を得ることが出来る。

(In the formula, Ar ⁴ each independently has the same definition as Ar ⁴ in the general formula (2).)
As a product of the protection step, an arylamine polymer (1) represented by the following general formula (3) with the reaction terminal protected can be obtained.

（式中、Ａｒ^１、Ａｒ^２、Ａｒ^３、Ｒ^１、Ｒ^２及びＲ^３は、各々独立して、前述の一般式（１）と同じ定義を示す。Ａｒ^４は、各々独立して、前記一般式（２）と同じ定義を表す。）
なお、保護化工程は、重合工程に引き続きワンポットで行なってもよいし、一旦、重合工程の生成物である一般式（１２ａ）又は一般式（１２ｂ）のアリールアミンポリマーを単離した後、別途、パラジウム触媒及び塩基の存在下行なってもよい。

(In the formula, Ar ¹ , Ar ² , Ar ³ , R ¹ , R ^2, and R ³ each independently represent the same definition as in the general formula (1). Ar ⁴ is independently (It represents the same definition as the general formula (2).)
The protection step may be carried out in one pot following the polymerization step, or once the arylamine polymer of the general formula (12a) or the general formula (12b) which is a product of the polymerization step is isolated, , In the presence of a palladium catalyst and a base.

  In the protection step, it is possible to carry out the reaction using the aromatic halogen compound represented by the general formula (13) and the aromatic amine compound represented by the general formula (14) at the same time. In terms of reaction efficiency, the reaction with the aromatic halogen compound and the reaction with the aromatic amine compound are preferably performed separately. In the case of performing the reaction separately, either the reaction using an aromatic halogen compound or the reaction using an aromatic amine compound may be performed first.

  In the protection step, the reaction using the aromatic halogen compound and the reaction using the aromatic amine compound can be carried out continuously in one pot. After one reaction, the reaction product is isolated and separated in a separate batch. The other reaction can also be performed.

  The aromatic halogen compound represented by the general formula (13) is not particularly limited. For example, bromobenzenes which may have a substituent [specifically, bromobenzene, 2-bromotoluene] 3-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 -Tert-butylbenzene, 1-bromo-5- (trifluoromethoxy) benzene, 2-bromoanisole, 3-bromoanisole, 4-bromoanisole, 1 Bromonaphthalene, 2-bromonaphthalene, 2-bromobiphenyl, 3-bromobiphenyl, 4-bromobiphenyl, 9-bromoanthracene, 9-bromophenanthrene, N-methyl-3-bromocarbazole, N-ethyl-3- Bromocarbazole, N-propyl-3-bromocarbazole, N-butyl-3-bromocarbazole, 2-bromofluorene, 2-bromo-9,9-dimethylfluorene, 2-bromo-9,9-diethylfluorene, 2- Bromo-9,9-diisopropylfluorene, 2-bromo-9,9-di-n-butylfluorene, 2-bromo-9,9-di-tert-butylfluorene, 2-bromo-9,9-di-sec -Butylfluorene, 2-bromo-9,9-di-n-hexylfluorene, 2-bromo-9,9 Di-n-octylfluorene, 2-bromodibenzothiophene, 2-bromodibenzofuran, etc.], and optionally substituted chlorobenzenes [specifically, 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-tert-butylbenzene, 1-chlorobenzene Chloro-5- (trifluoromethoxy) benzene, 2-chloroanisole, 3-chloroanisole, 4-chloroanisole, 1- Chloronaphthalene, 2-chloronaphthalene, 2-chlorobiphenyl, 3-chlorobiphenyl, 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-dimethylfluorene, 2-chloro-9,9-diethylfluorene, 2- Chloro-9,9-diisopropylfluorene, 2-chloro-9,9-di-n-butylfluorene, 2-chloro-9,9-di-tert-butylfluorene, 2-chloro-9,9-di-sec -Butyl fluorene, 2-chloro-9,9-di-n-hexyl fluorene, 2-chloro-9,9- -N-octylfluorene, 2-chlorodibenzothiophene, 2-chlorodibenzofuran, etc.] and iodobenzenes which may have a substituent [specifically, 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-tert-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-dimethylfluorene, 2-iodo-9,9-diethylfluorene, 2-iodo-9,9-diisopropylfluorene, 2-iodo-9,9-di-n-butylfluorene, 2-iodo-9,9-di-tert-butylfluorene, 2-iodo-9,9-di -Sec-butylfluorene, 2-iodo-9,9-di-n-hexylfluorene, 2-iodo-9, 9-di-n-octylfluorene, 2-iododibenzothiophene, 2-iododibenzofuran, etc.].

  The aromatic amine compound represented by the general formula (14) is not particularly limited, and examples thereof include diphenylamine, di-p-tolylamine, N-phenyl-1-naphthylamine, and N-phenyl-2-naphthylamine. Etc.

  The polymerization step and the protection step are both carried out in the presence of a palladium catalyst and a base, and the reaction conditions are not particularly limited, but the following may be used. it can. The palladium catalyst usually comprises a palladium compound and a ligand.

  Although it does not specifically limit as a palladium compound which is a structural component of a palladium catalyst, For example, tetravalent palladium compounds [Specifically, sodium hexachloro palladium (IV) acid tetrahydrate, hexachloro palladium (IV Potassium diacid), divalent palladium compounds (for example, palladium chloride (II), palladium bromide (II), palladium acetate (II), 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) trifluoroa Tate etc.], and zero-valent palladium compounds [specifically, 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, but may be any ligand that can coordinate to palladium, such as trialkylphosphines, arylphosphines, carbene-based ligands, and the like. Is 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 used 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 palladium atom in the palladium compound, and expensive trialkyl. Since phosphines, arylphosphines, and carbene-based ligands are used, the range of 0.1 to 10 moles per mole of palladium atom in the palladium compound is preferable.

  The amount of the palladium catalyst used in the polymerization step is not particularly limited. For example, the reaction of an arylene halide represented by the reaction formula (1) with an arylamine, the arylene represented by the reaction formula (2). In the reaction between range halide and arylene diamine, and in the reaction between arylene halide and arylene diamine represented by the reaction formula (3), it is usually 0.0000001 in terms of palladium atom with respect to 1 mole of halogen atom of the raw range arylene halide. It is preferably in the range of ˜0.20 times mole. Of these, from the viewpoint of catalytic activity and the use of an expensive palladium compound, it is usually more preferably in the range of 0.00001 to 0.05 times mole.

  Although the usage-amount of the palladium catalyst in a protection process is not specifically limited, It represents with the aromatic halogen compound represented by General formula (13), or General formula (12a), or General formula (12b). It is preferably in the range of usually 0.0000001 to 0.20 moles in terms of palladium atoms, relative to 1 mole of halogen atoms in the polymer. Of these, from the viewpoint of catalytic activity and the use of expensive palladium compounds, it is usually more preferably in the range of 0.00001 to 0.10 times mole.

  The method for adding the palladium catalyst in the polymerization step and the protection step is not particularly limited, but a palladium compound, a ligand, and other components may be added individually to the reaction system in the polymerization step or the protection step. The catalyst components may be added in advance and mixed in the form of a palladium complex.

  Although it does not specifically limit as a base used for a superposition | polymerization process and a protection process, For example, inorganic bases, such as a hydroxide of alkali metals (specifically sodium, potassium, etc.), carbonate, an alkoxide, or Organic bases such as tertiary amines can be mentioned. 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 step is not particularly limited, but is not particularly limited. For example, the reaction of arylene halide represented by reaction formula (1) with arylamine, reaction formula ( In the reaction of arylene halide represented by 2) and arylene diamine, and the reaction of arylene halide and arylene diamine represented by reaction formula (3), 1 per 1 mole of halogen atom of the raw arylene halide. It is chosen from the range of -1000 times mole. 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.

  The amount of the base used in the protection step is not particularly limited, but is usually in the range of 1 to 1000 times mol with respect to 1 mol of the halogen atom of the aromatic halogen compound represented by the general formula (13), preferably Is in the range of 1 to 20 times mol, or in the range of 1 to 100000 times mol per mol of the halogen atom of the polymer having the structure represented by the general formula (12a) and general formula (12b), preferably 1 to It is chosen from the range of 1000 times mole.

  Both the polymerization step and the protection step are usually preferably carried out in the presence of an inert solvent. The solvent to be 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 step and the protection step are preferably carried out under normal pressure and in an inert gas atmosphere such as nitrogen or argon, but can be carried out even under pressurized conditions.

  The reaction temperature in the polymerization step and the protection step 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 step and the protection step is not particularly limited because it is not constant depending on the arylamine polymer to be produced, the palladium catalyst, the reaction temperature, etc. Just choose. Preferably it is less than 24 hours.

  The arylamine polymer (1) produced by the polymerization step and the protection step can be separated and purified from unreacted low molecular weight compounds by reprecipitation or the like. 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 (1) of the present invention is not particularly limited, but is, for example, in the range of 1,000 to 100,000 in terms of polystyrene, more preferably 1,500 to 50,000. 000 range.

  The arylamine polymer (1) of the present invention is used as a conductive polymer material in electronic devices such as field effect transistors, optical functional devices, dye-sensitized solar cells, and organic electroluminescence devices. In particular, it is extremely useful as a hole transport material, a light emitting material, and a buffer material of an organic electroluminescence device.

  If the organic EL element of this invention is equipped with the organic layer containing the arylamine polymer (1) of this invention, element structure will not be specifically limited.

  Since the arylamine polymer (1) of the present invention is excellent in solubility, for example, a spin coating method, a casting method, a dipping method, a bar coating method using a solution, a mixed solution or a melt of these materials. The element can be easily produced by a conventionally known coating method such as a roll coating method. It can also be easily produced by an inkjet method, a Langmuir Blodget method, or the like.

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

  Polymer molecular weight: THF GPC [HLC-8220 (manufactured by Tosoh Corporation). The columns were TSKgel-SuperH3000, TSKgel-SuperH2000, and TSKgel-SuperH1000 (all manufactured by Tosoh Corporation). ], The molecular weight of the synthesized polymer was measured. The molecular weight is shown in terms of standard polystyrene.

  Glass transition temperature: Measured using DSC200F3 (manufactured by Netch).

  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 (Perkin Elmer).

Example 1
In a 2 L four-necked round bottom flask equipped with a condenser and a thermometer, 5.22 g (18.7 mmol) of 3,6-di-tert-butylcarbazole and 750 mL of acetic acid were mixed at room temperature under a nitrogen atmosphere. Thereafter, a mixture of 6.27 g (39.2 mmol) of bromine and 50 mL of acetic acid was added dropwise to the place where the temperature was raised to 90 ° C. over 0.5 hours. After 3 hours, the reaction mixture was cooled to room temperature. Acetic acid was distilled off from the resulting reaction mixture by distillation under reduced pressure, followed by extraction with 200 g of water and 500 mL of toluene. The organic layer obtained by extraction was passed through silica gel column chromatography, and then toluene was removed by distillation under reduced pressure to obtain a residue. The residue was purified by a recrystallization operation using toluene as a solvent to obtain 8.0 g of the compound (16-a).

温度計を装着した２００ｍＬ四つ口丸底フラスコに、室温下、窒素雰囲気下で化合物（１６−ａ） ５．００ｇ（１１．４ｍｍｏｌ）、ヨードメタン ３．２５ｇ（２２．９ｍｍｏｌ）、粉状の水酸化ナトリウム １．８３ｇ（４５．７ｍｍｏｌ）及びジメチルホルムアミド ５０ｍＬを混合した。その後、４０℃で１７時間加熱した。その後、この反応混合物を室温まで冷却した。得られた反応混合物に水 １００ｇ及びトルエン ２００ｍＬを加えて抽出した。抽出で得られた有機層をシリカゲルカラムクロマトグラフィーに通液後、減圧蒸留によりトルエンを留去し、残渣を得た。トルエンを溶媒とした再結晶操作により前記残渣を精製し、２．３ｇの化合物（１６−ｂ）を取得した。

In a 200 mL four-necked round bottom flask equipped with a thermometer, 5.00 g (11.4 mmol) of compound (16-a), 3.25 g (22.9 mmol) of iodomethane, and powdered water at room temperature under a nitrogen atmosphere Sodium oxide (1.83 g, 45.7 mmol) and dimethylformamide (50 mL) were mixed. Then, it heated at 40 degreeC for 17 hours. The reaction mixture was then cooled to room temperature. The resulting reaction mixture was extracted by adding 100 g of water and 200 mL of toluene. The organic layer obtained by extraction was passed through silica gel column chromatography, and then toluene was removed by distillation under reduced pressure to obtain a residue. The residue was purified by recrystallization using toluene as a solvent to obtain 2.3 g of compound (16-b).

冷却管、温度計を装着した１００ｍＬ四つ口丸底フラスコに、室温下、窒素雰囲気下で化合物（１６−ｂ） ２．００ｇ（４．４３ｍｍｏｌ）、４−ｎ−ブチルアニリン ０．６８ｇ（４．４３ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド ３．４１ｇ（３５．５ｍｍｏｌ）及びｏ−キシレン ２３．０ｇを混合した。反応容器内部に窒素を約２０分間流通させた後、この混合液に予め窒素雰囲気下で調製したトリス（ジベンジリデンアセトン）二パラジウムクロロホルム錯体 ４０．６ｍｇ（４４．３μｍｏｌ）及びＰ（ｔｅｒｔ−ブチル）_３ ２８．７ｍｇ（０．３５５ｍｍｏｌ）のｏ−キシレン（３．０ｍＬ）溶液を追加した。次いで、温度１２０℃で３時間攪拌した。次いで、ブロモベンゼン ０．１６８ｇ（１．０７ｍｍｏｌ）を添加し、１２０℃で更に３時間攪拌した。その後、更にジフェニルアミン ０．３６２ｇ（２．１４ｍｍｏｌ）を添加し、１２０℃更に３時間攪拌した。反応終了後この反応混合物を約６０℃まで冷却した後、水 ５ｇを反応器に添加し、１時間攪拌した。次いで、９０％アセトン水溶液（３００ｍＬ）の攪拌溶液へゆっくり加えた。ろ過により固体をろ別回収し、アセトン、水、アセトンの順番で洗浄した後、減圧乾燥し淡黄色粉末状のアリールアミンポリマー（１６） ０．５７ｇを得た（２９％）。

In a 100 mL four-necked round bottom flask equipped with a condenser and a thermometer, 2.00 g (4.43 mmol) of compound (16-b) and 0.68 g of 4-n-butylaniline at room temperature under a nitrogen atmosphere (4 .43 mmol), 3.41 g (35.5 mmol) of sodium-tert-butoxide and 23.0 g of o-xylene were mixed. After flowing nitrogen through the reaction vessel for about 20 minutes, 40.6 mg (44.3 μmol) of tris (dibenzylideneacetone) dipalladium chloroform complex and P (tert-butyl) prepared in advance in a nitrogen atmosphere were added to this mixed solution. _{3 A} solution of 28.7 mg (0.355 mmol) in o-xylene (3.0 mL) was added. Subsequently, it stirred at the temperature of 120 degreeC for 3 hours. Next, 0.168 g (1.07 mmol) of bromobenzene was added, and the mixture was further stirred at 120 ° C. for 3 hours. Thereafter, 0.362 g (2.14 mmol) of diphenylamine was further added, and the mixture was further stirred at 120 ° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to about 60 ° C., and 5 g of water was added to the reactor and stirred for 1 hour. It was then slowly added to a stirred solution of 90% aqueous acetone (300 mL). The solid was collected by filtration and washed in the order of acetone, water, and acetone, and then dried under reduced pressure to obtain 0.57 g of a light yellow powdery arylamine polymer (16) (29%).

得られたアリールアミンポリマー（１６）は、ポリスチレン換算で重量平均分子量４，０００及び数平均分子量３，３００（分散度１．２）であった。

The obtained arylamine polymer (16) had a weight average molecular weight of 4,000 and a number average molecular weight of 3,300 (dispersion degree 1.2) in terms of polystyrene.

  The glass transition temperature was 121 ° C.

  The HOMO level was 5.52 eV, and the LUMO level was 2.37 eV.

  Table 1 shows the results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

実施例２
冷却管、温度計を装着した５００ｍＬ四つ口丸底フラスコに、室温下、ｐ−ジブロモベンゼン １０．０ｇ（４２．４ｍｍｏｌ）、ｐ−トルイジン １１．４ｇ（１０６ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド ９．８０ｇ（１０２ｍｍｏｌ）及びｏ−キシレン １２０ｇを仕込んだ。

Example 2
In a 500 mL four-necked round bottom flask equipped with a condenser and a thermometer, 10.0 g (42.4 mmol) of p-dibromobenzene, 11.4 g (106 mmol) of p-toluidine, sodium tert-butoxide at room temperature. 80 g (102 mmol) and 120 g of o-xylene were charged.

  To this mixed solution, a solution of 0.19 g (0.85 mmol) of palladium (II) acetate and 0.69 g (3.40 mmol) of tri-tert-butylphosphine prepared in advance in a nitrogen atmosphere in an o-xylene (2.75 g) solution. Was added. Thereafter, the mixture was heated and stirred at 120 ° C. for 4 hours under a nitrogen atmosphere.

  After the completion of the reaction, when the temperature was lowered to 80 ° C. or less by cooling, 100 g of pure water was added to the reaction solution, and then allowed to cool to room temperature with stirring. To the resulting reaction mixture, 200 mL of toluene and 50 mL of tetrahydrofuran were added for extraction. The organic layer was passed through silica gel column chromatography, and then toluene was removed by distillation under reduced pressure to obtain a residue. The product was purified by recrystallization using toluene as a solvent to obtain 8.97 g of compound (17-a).

実施例１において、４−ｎ−ブチルアニリンの代わりに、化合物（１７−ａ） １．２８ｇ（４．４３ｍｍｏｌ）を使用した以外は同様の操作を行ない、アリールアミンポリマー（１７）の淡黄色固体を得た（収率５２％）。

In Example 1, the same operation was carried out except that 1.28 g (4.43 mmol) of the compound (17-a) was used instead of 4-n-butylaniline, and the light yellow solid of the arylamine polymer (17) was obtained. (Yield 52%).

得られたアリールアミンポリマー（１７）は、ポリスチレン換算で重量平均分子量５，２００及び数平均分子量３，０００（分散度１．４）であった。

The obtained arylamine polymer (17) had a weight average molecular weight of 5,200 and a number average molecular weight of 3,000 (dispersion degree: 1.4) in terms of polystyrene.

  The glass transition temperature was 115 ° C.

  The HOMO level was 5.41 eV and the LUMO level was 2.21 eV.

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

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

実施例３
実施例１において３，６−ジ−ｔｅｒｔ−ブチルカルバゾールの代わりに３，６−ジメチルカルバゾール ３．６５ｇ（１８．７ｍｍｏｌ）を使用した以外は同様の操作を行ない４．３５ｇの化合物（１８−ａ）を得た。

Example 3
The same operation as Example 1 was carried out except that 3.65 g (18.7 mmol) of 3,6-dimethylcarbazole was used instead of 3,6-di-tert-butylcarbazole, and 4.35 g of compound (18-a )

実施例１において化合物（１６−ａ）の変わりに化合物（１８−ａ） ４．０２ｇ（１１．４ｍｍｏｌ）を使用した以外は同様の操作を行ない１．７ｇの化合物（１８−ｂ）を得た。

The same operation as Example 1 was carried out except that 4.02 g (11.4 mmol) of the compound (18-a) was used instead of the compound (16-a) to obtain 1.7 g of the compound (18-b). .

実施例１において化合物（１６−ｂ）の変わりに化合物（１８−ｂ） １．６ｇ（４．４３ｍｍｏｌ）を使用した以外は同様の操作を行ない１．５ｇの化合物（１８）を得た。

The same operation as Example 1 was carried out except that 1.6 g (4.43 mmol) of the compound (18-b) was used instead of the compound (16-b) to obtain 1.5 g of the compound (18).

得られたアリールアミンポリマー（１８）は、ポリスチレン換算で重量平均分子量４，８００及び数平均分子量２，５００（分散度１．８）であった。

The obtained arylamine polymer (18) had a weight average molecular weight of 4,800 and a number average molecular weight of 2,500 (dispersity 1.8) in terms of polystyrene.

  The glass transition temperature was 123 ° C.

  The HOMO level was 5.31 eV, and the LUMO level was 2.10 eV.

  Table 3 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

実施例４
実施例１において化合物（１６−ａ）の変わりに１，８−ジクロロカルバゾール ２．６９ｇ（１１．４ｍｍｏｌ）を使用した以外は同様の操作を行ない２．０ｇの化合物（１９−ａ）を得た。

Example 4
The same operation as in Example 1 was performed except that 1.69 g (11.4 mmol) of 1,8-dichlorocarbazole was used instead of the compound (16-a) to obtain 2.0 g of the compound (19-a). .

冷却管、温度計を装着した２００ｍＬ四つ口丸底フラスコに、室温下、化合物（１９−ａ） １．５０ｇ（６．００ｍｍｏｌ）、ｐ−トルイジン １．６１ｇ（１５．０ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド １．３８ｇ（１４．４ｍｍｏｌ）及びｏ−キシレン ３０ｇを仕込んだ。

In a 200 mL four-necked round bottom flask equipped with a condenser and a thermometer, at room temperature, compound (19-a) 1.50 g (6.00 mmol), p-toluidine 1.61 g (15.0 mmol), sodium-tert -1.38 g (14.4 mmol) of butoxide and 30 g of o-xylene were charged.

  To this mixed solution, a solution of 26.8 mg (0.12 mmol) of palladium (II) acetate and 97.4 mg (0.48 mmol) of tri-tert-butylphosphine prepared in advance in a nitrogen atmosphere in an o-xylene (0.38 g) solution. Was added. Thereafter, the mixture was heated and stirred at a temperature of 120 ° C. for 10 hours in a nitrogen atmosphere.

  After the completion of the reaction, when the mixture was allowed to cool to 80 ° C. or less, 50 g of pure water was added to the reaction solution, and then allowed to cool to room temperature with stirring. The obtained reaction mixture was extracted by adding 50 mL of toluene. The organic layer obtained by extraction was passed through silica gel column chromatography, and then toluene was removed by distillation under reduced pressure to obtain a residue. The residue was purified by recrystallization using toluene as a solvent to obtain 1.3 g of compound (19-b).

冷却管、温度計を装着した１００ｍｌ四つ口丸底フラスコに、室温下、窒素雰囲気下で化合物（１９−ｂ） ０．８７ｇ（２．２２ｍｍｏｌ）、１，４−ジブロモベンゼン ０．５２ｇ（２．２２ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド １．７１ｇ（１７．７ｍｍｏｌ）及びｏ−キシレン １１．５ｇを混合した。反応容器内部に窒素を約２０分間流通させた後、この混合液に予め窒素雰囲気下で調製したトリス（ジベンジリデンアセトン）二パラジウム ２０．３ｍｇ（２２．２μｍｏｌ）及びＰ（ｔｅｒｔ−ブチル）_３ ３５．６ｍｇ（０．１７７ｍｍｏｌ）のｏ−キシレン（１．５ｍＬ）溶液を追加した。その後、温度１２０℃で３時間攪拌した。次いで、ブロモベンゼン ８４ｍｇ（０．５３ｍｍｏｌ）を添加し、更に３時間攪拌した。その後、ジフェニルアミン ０．１８１ｇ（１．０７ｍｍｏｌ）を添加し、更に３時間攪拌した。反応終了後この反応混合物を約６０℃まで冷却した後、水 ５ｇを反応器に添加し、１時間攪拌した。その後、９０ｖｏｌ％アセトン水溶液（２００ｍＬ）の攪拌溶液へゆっくり加えた。ろ過により固体をろ別回収し、アセトン、水、アセトンの順番で洗浄した後、減圧乾燥し淡黄色粉末状のアリールアミンポリマー（１９）を得た（２３％）。

A 100 ml four-necked round bottom flask equipped with a condenser and a thermometer was charged with 0.87 g (2.22 mmol) of compound (19-b) and 0.52 g (2 of 2,4-dibromobenzene) at room temperature under a nitrogen atmosphere. .22 mmol), 1.71 g (17.7 mmol) of sodium-tert-butoxide and 11.5 g of o-xylene were mixed. After allowing nitrogen to flow for about 20 minutes inside the reaction vessel, 20.3 mg (22.2 μmol) of tris (dibenzylideneacetone) dipalladium prepared in advance in a nitrogen atmosphere and P (tert-butyl) ₃ 35 An additional solution of .6 mg (0.177 mmol) of o-xylene (1.5 mL) was added. Then, it stirred at the temperature of 120 degreeC for 3 hours. Subsequently, 84 mg (0.53 mmol) of bromobenzene was added, and the mixture was further stirred for 3 hours. Thereafter, 0.181 g (1.07 mmol) of diphenylamine was added, and the mixture was further stirred for 3 hours. After completion of the reaction, the reaction mixture was cooled to about 60 ° C., and 5 g of water was added to the reactor and stirred for 1 hour. Then, it added slowly to the stirring solution of 90 vol% acetone aqueous solution (200 mL). The solid was collected by filtration, washed in the order of acetone, water, and acetone, and then dried under reduced pressure to obtain an arylamine polymer (19) as a pale yellow powder (23%).

得られたアリールアミンポリマー（１９）は、ポリスチレン換算で重量平均分子量５，４００及び数平均分子量３，２００（分散度１．７）であった。

The obtained arylamine polymer (19) had a weight average molecular weight of 5,400 and a number average molecular weight of 3,200 (dispersion degree 1.7) in terms of polystyrene.

  The glass transition temperature was 125 ° C.

  The HOMO level was 5.26 eV and the LUMO level was 2.10 eV.

  Table 4 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

実施例５ アリールアミンポリマー（１６）の励起三重項準位の測定
ＵＶ−Ｖｉｓスペクトル測定用サンプルチューブ内でアリールアミンポリマー（１６） １ｍｇと２−メチルテトラヒドロフラン １ｍＬとをよく混合し、均一な溶液を調製した。この溶液を窒素ガスで１０分間バブリングすることによって脱気した後、このサンプルチューブを密栓し、燐光スペクトルを測定した。燐光スペクトルから算出されたアリールアミンポリマー（１６）の励起三重項準位は、２．６２ｅＶであった。

Example 5 Measurement of excited triplet level of arylamine polymer (16) In a sample tube for UV-Vis spectrum measurement, 1 mg of arylamine polymer (16) and 1 mL of 2-methyltetrahydrofuran were mixed well to obtain a uniform solution. Prepared. 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 excited triplet level of the arylamine polymer (16) calculated from the phosphorescence spectrum was 2.62 eV.

Example 6 Measurement of Excited Triplet Level of Arylamine Polymer (17) The same operation as in Example 5 was performed except that an arylamine polymer (17) was used instead of the arylamine polymer (16) in Example 5. When the phosphorescence spectrum was measured, the excited triplet level of the arylamine polymer (17) was 2.60 eV.

Example 7 Measurement of Excited Triplet Level of Arylamine Polymer (18) The same operation as in Example 5 was performed except that an arylamine polymer (18) was used instead of the arylamine polymer (16) in Example 5. When the phosphorescence spectrum was measured, the excited triplet level of the arylamine polymer (18) was 2.64 eV.

Example 8 Measurement of Excited Triplet Level of Arylamine Polymer (19) The same operation as in Example 5 was performed except that an arylamine polymer (19) was used instead of the arylamine polymer (16) in Example 5. When the phosphorescence spectrum was measured, the excited triplet level of the arylamine polymer (19) was 2.62 eV.

Comparative Example 1 Measurement of excited triplet level of poly- (N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl) benzidine) (ADS254BE: manufactured by American Die Source) Example 5 except that instead of the arylamine polymer (16) in Example 5, commercially available poly- (N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl) benzidine) was used. The phosphorescence spectrum was measured in the same manner as in Example 1, and the excited triplet level of poly- (N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl) benzidine) was 2 .35 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, a suspension of poly (3,4-ethylenedioxythiophene) -polystyrenesulfonic acid (manufactured by Bayer, Baytron P CH8000) is formed into a film with a thickness of 80 nm by a spin coating method (hole injection layer) And dried at 200 ° C. for 1 hour.

  Next, a 0.5 wt% chlorobenzene solution of the arylamine polymer (16) was applied by a spin coating method and dried at 160 ° C. for 3 hours, whereby a hole transport layer made of an arylamine polymer (16) having a thickness of 20 nm. Was deposited.

Next, tris (8-quinolinolato) aluminum (Alq ₃ ) was deposited to form a 50 nm light emitting layer.

  Next, lithium fluoride (0.8 nm) and aluminum (150 nm) were deposited in this order to form an electron transport layer / negative electrode.

  Furthermore, the glass substrate for protection was piled up in nitrogen atmosphere, and it adhered and sealed using the sealing agent for organic EL (80 degreeC, 3 hours).

In addition, all said vapor deposition was performed on the conditions of a vacuum degree of 1.0 * 10 < ^-4 > Pa, and the film-forming speed | rate of 0.3 nm / sec.

The device produced as described above was driven under a constant current density condition of 20 mA / cm ² with the ITO transparent electrode as the positive electrode and the lithium fluoride-aluminum electron transport layer / negative electrode as the negative electrode. The drive voltage, light emission efficiency, and current efficiency at that time are shown in Table 5.
Example 10
In Example 9, a device was fabricated in the same manner as in Example 9, except that a 0.5 wt% chlorobenzene solution of the arylamine polymer (17) was used instead of the 0.5 wt% chlorobenzene solution of the arylamine polymer (16). In the same manner as in Example 9, the driving voltage, light emission efficiency, and current efficiency of the device were examined. The light emission characteristics are shown in Table 5.
Example 11
In Example 9, a device was fabricated in the same manner as in Example 9, except that a 0.5 wt% chlorobenzene solution of the arylamine polymer (18) was used instead of the 0.5 wt% chlorobenzene solution of the arylamine polymer (16). In the same manner as in Example 9, the driving voltage, light emission efficiency, and current efficiency of the device were examined. The light emission characteristics are shown in Table 5.
Example 12
In Example 9, a device was prepared in the same manner as in Example 9 except that a 0.5 wt% chlorobenzene solution of the arylamine polymer (19) was used instead of the 0.5 wt% chlorobenzene solution of the arylamine polymer (16). In the same manner as in Example 9, the driving voltage, light emission efficiency, and current efficiency of the device were examined. The light emission characteristics are shown in Table 5.

Comparative Example 2
In Example 9, instead of a 0.5 wt% chlorobenzene solution of arylamine polymer (16), commercially available poly- (N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl) benzidine ) A device was produced in the same manner as in Example 9 except that a 0.5 wt% chlorobenzene solution (ADS254BE: manufactured by American Die Source) was used. And the current efficiency was investigated. The light emission characteristics are shown in Table 5.

  In Table 5, the results of Examples 9 to 12 are shown as relative values with the measured values of drive voltage, light emission efficiency, and current efficiency of Comparative Example 1 being 100.

  The arylamine polymer (1) of the present invention has a high excited triplet level and high structural durability compared to conventionally known polymer compounds. For this reason, if the arylamine polymer (1) of the present invention is used, it is possible to provide an organic electroluminescent device excellent in luminous efficiency, current efficiency and durability.

Claims (9)

An arylamine polymer having a skeleton in which at least two repeating structures represented by the following general formula (1) are linked.

(Where
Ar ¹ is a C 6-60 divalent aromatic hydrocarbon group or a C 4-20 divalent heteroaromatic group (these substituents are an alkyl group having 1 to 18 carbon atoms, a C 1-18 carbon atom). consisting of an alkoxy group, a phenyl group, a phenyl group, a phenyl group,及 beauty alkyl group which may be different of 1 to 6 carbon atoms having an alkoxy group having 1 to 18 carbon atoms having an alkyl group having 1 to 18 carbon atoms It may have one or more substituents selected from the group consisting of dialkylamino groups.
Ar ² and Ar ³ are each independently an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently selected from 1 to One or more substituents selected from the group consisting of an 18 alkyl group, an alkoxy group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, and a heteroaromatic group having 4 to 20 carbon atoms. Which may have).
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, a phenyl group, or a phenyl group having an alkyl group having 1 to 18 carbon atoms. A phenyl group having a group, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, or a dialkylamino group composed of an optionally substituted alkyl group having 1 to 6 carbon atoms.
n represents 0 or 1. ) The terminal is represented by the following general formula (2)

(In the formula, Ar ⁴ represents an aromatic group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, carbon the number 1 to 18 alkoxy group, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, or also differ with 1 to 6 carbon atoms It may have a phenyl group having a dialkylamino group consisting of a good alkyl group).
The arylamine polymer according to claim 1, wherein the arylamine polymer is an aromatic group represented by: The arylamine polymer according to claim 1 or 2, wherein the arylamine polymer is represented by the following general formula (3).

(Where
Ar ¹ is a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms or a divalent heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, be different with 及 beauty 1 to 6 carbon atoms It may have one or more substituents selected from the group consisting of dialkylamino groups consisting of good alkyl groups).
Ar ² and Ar ³ are each an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, Even if it has 1 or more types of substituents chosen from the group which consists of a C1-C18 alkoxy group, a C6-C60 aromatic hydrocarbon group, and a C4-C20 heteroaromatic group. Good).
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, a phenyl group, or a phenyl group having an alkyl group having 1 to 18 carbon atoms. A phenyl group having a group, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, or a dialkylamino group composed of an optionally substituted alkyl group having 1 to 6 carbon atoms. Ar ² and Ar ³ may be the same substituent or different substituents.
Ar ⁴ is each independently an aromatic group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group) , having a phenyl group, a phenyl group, or dialkylamino group consisting of an alkyl group which may be different of 1 to 6 carbon atoms having an alkoxy group having 1 to 18 carbon atoms having an alkyl group having 1 to 18 carbon atoms Which may have a phenyl group).
n represents 0 or 1.
m represents an integer of 2 or more. ) Ar ² and Ar ³ are each independently a phenyl group, a biphenylyl group, a fluorenyl group, a carbazolyl group, a dibenzothienyl group, a dibenzothienylphenyl group, or an N-dibenzothienylcarbazolyl group (these substituents are each The arylamine polymer according to any one of claims 1 to 3, which may independently have an alkyl group having 1 to 8 carbon atoms as a substituent. Ar ¹ represents an m-phenylene group or a p-phenylene group (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, 1 to 1 carbon atoms). 18 phenyl group having an alkyl group of, from the group consisting of a phenyl group having a phenyl group, consisting of alkyl group which may be different with 及 beauty 1 to 6 carbon atoms dialkylamino group having an alkoxy group having 1 to 18 carbon atoms The arylamine polymer according to any one of claims 1 to 4, which may have one or more selected substituents). An arylamine polymer having a skeleton in which at least two repeating structures represented by the following general formula (1) are linked, and the terminal is a secondary amino group, a halogen atom, or both a secondary amino group and a halogen atom On the other hand, in the presence of a palladium catalyst and a base, an aryl halide represented by the following general formula (13), an arylamine represented by the following general formula (14), or an aryl halide represented by the general formula (13) And the arylamine represented by the general formula (14) are reacted. The method for producing an arylamine polymer according to any one of claims 1 to 5.

(Where
Ar ¹ is a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms or a divalent heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, be different with 及 beauty 1 to 6 carbon atoms It may have one or more substituents selected from the group consisting of dialkylamino groups consisting of good alkyl groups).
Ar ² and Ar ³ are each independently an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently selected from 1 to One or more substituents selected from the group consisting of an 18 alkyl group, an alkoxy group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, and a heteroaromatic group having 4 to 20 carbon atoms. Which may have).
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, a phenyl group, or a phenyl group having an alkyl group having 1 to 18 carbon atoms. A phenyl group having a group, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, or a dialkylamino group composed of an optionally substituted alkyl group having 1 to 6 carbon atoms.
n represents 0 or 1. )

(Where
Ar ⁴ is an aromatic group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, or 1 to 18 carbon atoms). alkoxy group, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, or from an alkyl group which may be different of 1 to 6 carbon atoms Which may have a phenyl group having a dialkylamino group.
X ⁵ represents a chlorine atom, a bromine atom, or an iodine atom. )

(In the formula, Ar ⁴ is each independently an aromatic group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently having 1 to 18 carbon atoms). alkyl group, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, or 1 to 6 carbon atoms A phenyl group having a dialkylamino group composed of an alkyl group which may be different from each other). An electronic device comprising the arylamine polymer according to any one of claims 1 to 5. The electronic device according to claim 7, wherein the electronic device is an organic electroluminescence device. The electronic device according to claim 8, comprising an arylamine polymer in the light emitting layer, the hole transport layer, or the hole injection layer.