JP4956898B2 - Triarylamine polymer and method for producing the same - Google Patents

Description

  The present invention relates to a novel triarylamine polymer and a method for producing the same, and the triarylamine polymer has carrier transport properties and can be used for a hole transport layer or a hole injection layer of an organic electroluminescence (EL) device. It is.

  The material of the organic EL element is divided into a light emitting layer, a layer for transporting holes or electrons, two electrodes, a cathode and an anode, and other materials.

  As a material for the organic EL element, various low molecular weight materials and high molecular weight materials are used for the light emitting layer and the carrier transporting layer, and many materials have been proposed particularly for the low molecular weight materials.

  On the other hand, in the case of high molecular weight systems, various materials have been studied because they can be easily laminated by a coating method such as spin coating unlike low molecular weight systems. For example, conductive π-conjugated polymers such as poly (p-phenylene vinylene) and polyalkylthiophene are known (see, for example, Patent Document 1). Polymers containing reelamine have been reported (for example, see Patent Documents 2 to 6).

  The present inventors have also developed an efficient method for synthesizing a novel triarylamine polymer containing a triarylamine in the main chain, and have already filed patent applications (see, for example, Patent Documents 7 to 11).

  On the other hand, high-molecular organic EL elements are still not satisfactory from the viewpoint of light emission luminance and lifetime compared to low-molecular elements, and in particular, blue elements are not yet in practical use. One of the causes is that the effect of the hole transport layer as an electron blocking layer is low.

Japanese Patent Laid-Open No. 3-273087 (Claims) JP-A-8-054833 (Claims) JP-A-8-259935 (Claims) JP 11-035687 (Claims) JP-A-11-292828 (Claims) Japanese Patent Laid-Open No. 13-098023 (Claims) JP-A-11-021349 (Claims) JP-A-11-080346 (Claims) Japanese Patent Laid-Open No. 11-080347 (Claims) Japanese Patent Laid-Open No. 11-080348 (Claims) Japanese Patent Laid-Open No. 11-080349 (Claims)

  This invention is made | formed in view of the said subject, The objective is providing the novel triarylamine polymer as a hole transport material or hole injection material use in an organic EL element, and its simple manufacturing method. It is in.

  As a result of diligent studies to solve the above problems, the present inventors have focused on the band energy structure in the use of a hole transport material or a hole injection material, and as a result of optimization, the tria having a wide band gap has been studied. A reelamine polymer was developed and the present invention was completed.

  That is, the present invention provides the following general formula (1)

［式中、Ａｒ^１は無置換若しくは置換基を有する炭素数６〜６０のアリール基、アリールアミノ基又はヘテロアリール基を表し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は各々独立して水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルケニル基、アリール基、アリールアミノ基又はヘテロアリール基である。ただし、少なくとも一つは水素原子以外の置換基である。Ａは直接結合又は下記一般式（２）

[Wherein Ar ¹ represents an unsubstituted or substituted aryl group having 6 to 60 carbon atoms, an arylamino group, or a heteroaryl group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an arylamino group or a heteroaryl group. However, at least one is a substituent other than a hydrogen atom. A is a direct bond or the following general formula (2)

（式中、Ａｒ^２は無置換若しくは置換基を有する炭素数６〜６０のアリール基、アリールアミノ基又はヘテロアリール基を表す。）
で表される基である。ｎは１以上の整数である。］
で表される正孔輸送材及び正孔注入材として使用が期待されるトリアリールアミンポリマーとその簡便な製造方法に関する。

(In the formula, Ar ² represents an unsubstituted or substituted aryl group having 6 to 60 carbon atoms, an arylamino group, or a heteroaryl group.)
It is group represented by these. n is an integer of 1 or more. ]
And a simple production method thereof.

  In the general formula (1), the following general formula (3)

（式中、Ａｒ^１は無置換若しくは置換基を有する炭素数６〜６０のアリール基、アリールアミノ基又はヘテロアリール基を表し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は各々独立して水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルケニル基、アリール基、アリールアミノ基又はヘテロアリール基である。ただし、Ｒ^２、Ｒ^４、Ｒ^５及びＲ^７のうち、少なくとも一つは水素原子以外の置換基である。ｎは１以上の整数である。）
で表されるトリアリールアミンポリマーは広いバンドギャップを与えることから好ましい。

(In the formula, Ar ¹ represents an unsubstituted or substituted aryl group having 6 to 60 carbon atoms, an arylamino group, or a heteroaryl group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^6. , R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an arylamino group or a heteroaryl group, provided that R ² , R ⁴ , R ⁵ and (At least one of R ⁷ is a substituent other than a hydrogen atom. N is an integer of 1 or more.)
Is preferable because it gives a wide band gap.

In the general formulas (1) to (3), Ar ¹ and Ar ² each independently represent an unsubstituted or substituted aryl group having 6 to 60 carbon atoms, an arylamino group, or a heteroaryl group. The structures represented by the general formulas (4) to (9) are particularly preferable.

（式中、Ｒ^９、Ｒ^１０、Ｒ^１１及び^１２は各々独立して水素原子、ハロゲン原子、アルキル基、アルコキシ基又はアルケニル基である。ａは０〜５の整数である。ｂは１又は２である。）
前記一般式（１）において、置換基Ｒ^１〜Ｒ^８としては、前記の定義に該当すれば特に限定されるものではないが、具体的には水素原子の他、ハロゲン原子（フッ素原子、塩素原子、臭素原子等）、アルキル基（メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、シクロペンチル基、ｎ−ヘキシル基、２−エチルブチル基、３，３−ジメチルブチル基、シクロヘキシル基、ｎ−ヘプチル基、４−メチル−シクロヘキシル基、シクロヘキシルメチル基、ｎ−オクチル基、ｔｅｒｔ−オクチル基、２−エチルヘキシル基、ｎ−ノニル基、ｎ−デシル基、トリフルオロメチル基、アダマンチル基等）、アルコキシ基（メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｎ−ペンチルオキシ基、イソペンチルオキシ基、ネオペンチルオキシ基、シクロペンチルオキシ基、ｎ−ヘキシルオキシ基、２−エチルブトキシ基、３，３−ジメチルブトキシ基、シクロヘキシルオキシ基、ｎ−ヘプチルオキシ基、シクロヘキシルメチルオキシ基、ｎ−オクチルオキシ基、２−エチルヘキシルオキシ基、ｎ−ノニルオキシ基、ｎ−デシルオキシ基、トリフルオロメトキシ基等）、アルケニル基（エテニル基、２−プロペニル基、１−メチルエテニル基、３−ブテニル基、１−メチル−２−プロペニル基、４−ペンテニル基等）、アリール基（フェニル基、２−メトキシフェニル基、３−メトキシフェニル基、４−メトキシフェニル基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、２−ヒドロキシフェニル基、３−ヒドロキシフェニル基、４−ヒドロキシフェニル基、２−トリフルオロメチルフェニル基、３−トリフルオロメチルフェニル基、４−トリフルオロメチルフェニル基、２，６−ジメチルフェニル基、３，６−ジメチルフェニル基、２，３−ジメチルフェニル基、３，４−ジメチルフェニル基、２，４−ジメチルフェニル基、３，５−ジメチルフェニル基、３−（トリフルオロメトキシ）フェニル基、４−（トリフルオロメトキシ）フェニル基、３，４−（メチレンジオキシ）フェニル基、２−ビフェニル基、３−ビフェニル基、４−ビフェニル基、４−ターフェニル基、１−ナフチル基、２−ナフチル基、２−メチルナフチル基、４−メチルナフチル基、９−アントラセニル基、９，９二置換−２−フルオレニル基等）、アリールアミノ基（ジフェニルアミノ基、ジ−ｐ−トリルアミノ基、Ｎ−フェニル−１−ナフチルアミノ基、Ｎ−フェニル−２−ナフチルアミノ基等）、及び、ヘテロアリール基（２−フリル基、２−チエニル基、２−ピリジル基等）を挙げることができる。より好ましくは水素原子、アルキル基、アルコキシ基、アリール基、アリールアミノ基のいずれかである。

(Wherein R ⁹ , R ¹⁰ , R ¹¹ and ¹² are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an alkenyl group. A is an integer of 0 to 5. b is 1 or 2)
In the general formula (1), the substituents R ^{1 to} R ⁸ are not particularly limited as long as they fall within the above definition. Specifically, in addition to a hydrogen atom, a halogen atom (fluorine atom, chlorine) Atom, bromine atom, etc.), alkyl group (methyl group, ethyl group, n-propyl group, 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, cyclohexyl group, n-heptyl group, 4-methyl-cyclohexyl group, cyclohexylmethyl group, n- Octyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, trifluoromethyl group, adamant Group), alkoxy group (methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group, cyclopentyl) Oxy group, n-hexyloxy group, 2-ethylbutoxy group, 3,3-dimethylbutoxy group, cyclohexyloxy group, n-heptyloxy group, cyclohexylmethyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, trifluoromethoxy group, etc.), alkenyl group (ethenyl group, 2-propenyl group, 1-methylethenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 4-pentenyl) Group), aryl group (phenyl group, 2-methoxyphenyl group, 3-methyl group) Xiphenyl group, 4-methoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2-trifluoromethyl Phenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 2,6-dimethylphenyl group, 3,6-dimethylphenyl group, 2,3-dimethylphenyl group, 3,4-dimethylphenyl group 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3- (trifluoromethoxy) phenyl group, 4- (trifluoromethoxy) phenyl group, 3,4- (methylenedioxy) phenyl group, 2 -Biphenyl group, 3-biphenyl group, 4-biphenyl group, 4-terphenyl group, 1-naphthyl group, 2 -Naphthyl group, 2-methylnaphthyl group, 4-methylnaphthyl group, 9-anthracenyl group, 9,9 disubstituted-2-fluorenyl group, etc.), arylamino group (diphenylamino group, di-p-tolylamino group, N -Phenyl-1-naphthylamino group, N-phenyl-2-naphthylamino group and the like) and heteroaryl groups (2-furyl group, 2-thienyl group, 2-pyridyl group and the like). More preferably, they are any of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, and an arylamino group.

In the general formulas (4) to (9), R ^{9 to} R ¹² are not particularly limited as long as they fall under the above definition. Specifically, the R ^{9 to} R ¹² in the substituents R ^{1 to} R ⁸ are not limited. Examples include a substituent that satisfies the definition.

The triarylamine polymer represented by the general formula (1) of the present invention is not particularly limited as long as it falls within the above definition, but R ¹ , R ² , R ³ , R ⁴ , R ⁵ , At least one of R ⁶ , R ⁷ and R ⁸ is preferably an alkyl group, an alkoxy group, an aryl group or an arylamino group. In particular, triarylamine polymers having the structures of the following general formulas (10) to (16) are preferable.

（式中、Ｒ^１３、Ｒ^１４、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２１、Ｒ^２２、Ｒ^２４、Ｒ^２５、Ｒ^２６及びＲ^２７は炭素数１〜８の直鎖、分岐、環状のアルキル基若しくはアルコキシ基である。Ｒ^１５、Ｒ^２０、Ｒ^２３及びＲ^２８〜Ｒ^３８は水素原子、炭素数１〜８の直鎖、分岐、環状のアルキル基若しくはアルコキシ基である。）
前記一般式（１０）〜（１６）において、Ｒ^１３〜Ｒ^３８としては、前記の定義に該当すれば特に限定するものではないが、具体的には置換基Ｒ^１〜Ｒ^８の中の前記定義を満たす置換基が挙げられる。

(In the formula, R ¹³ , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²¹ , R ²² , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are linear or branched having 1 to 8 carbon atoms. And R ¹⁵ , R ²⁰ , R ²³ and R ^{28 to} R ³⁸ are a hydrogen atom, a linear, branched or cyclic alkyl group or alkoxy group having 1 to 8 carbon atoms. )
In the general formulas (10) to (16), R ^{13 to} R ³⁸ are not particularly limited as long as they fall under the above definition, but specifically, the substituents in the substituents R ^{1 to} R ⁸ are not limited. Examples include a substituent that satisfies the definition.

  Furthermore, in the general formulas (10) to (16), A is not particularly limited as long as it falls within the above definition, but is preferably a direct bond or the following general formula (17).

（式中、Ｒ^３９は水素原子、炭素数１〜８の直鎖、分岐、環状のアルキル基若しくはアルコキシ基である。）
前記一般式（１７）において、Ｒ^３９としては前記の定義に該当すれば特に限定されるものではないが、具体的には置換基Ｒ^１〜Ｒ^８の中の前記定義を満たす置換基が挙げられる。

(In the formula, R ³⁹ is a hydrogen atom, a linear, branched, or cyclic alkyl group or alkoxy group having 1 to 8 carbon atoms.)
In the general formula (17), R ³⁹ is not particularly limited as long as it falls under the above definition, and specifically, a substituent satisfying the above definition among the substituents R ^{1 to} R ⁸ can be mentioned. It is done.

  The triarylamine polymer represented by the general formula (1) of the present invention has a wide band gap, and the band gap specified by the LUMO level and the HOMO level is 2.5 eV or more 4 0.5 eV or less, preferably 3.0 eV or more and 4.0 eV or less.

  The band gap defined in the present invention is a band energy difference between a material-specific HOMO (highest occupied orbital) level and LUMO (lowest empty orbital) level.

  As a method for obtaining the band gap, for example, the film absorption spectrum of the material is measured, and the energy is converted from the absorption wavelength end. Specifically, in the absorption spectrum, when the wavelength at which the absorption rises from the baseline is λ (nm), the band gap Eg (eV) is obtained by the following conversion formula.

Eg = 1240 / λ
As a method for obtaining HOMO, there are a method of directly measuring by photoelectron spectroscopy, a method of converting an electrochemically measured oxidation potential, a method of calculating by a molecular orbital method, and the like. The photoelectron spectroscopy can be obtained, for example, by using an apparatus (AC-1 or 2) manufactured by Riken Keiki Co., Ltd.

  As a method for obtaining LUMO, a method for converting from the band gap and the HOMO value, a method for converting an electrochemically measured reduction potential, and the like can be used.

  The triarylamine polymer of the present invention can be used as a hole transport material or a hole injection material in an organic EL device. Moreover, the band gap of the light emitting material generally used for the organic EL element is about 1.7 eV (red), about 2.5 eV (green), and about 2.8 eV (blue). Therefore, by using the triarylamine polymer of the present invention having a wide band gap, it is possible to improve the light emission characteristics accompanying the improvement of the electron blocking property. The HOMO level and LUMO level of the hole transport material are preferably higher than the HOMO level and LUMO level of the light emitting material. As a result, it is possible to increase the accumulation and recombination of holes and electrons in the light emitting layer by efficient transport of holes and electron blocking in the hole layer.

  Further, the triarylamine polymer represented by the general formula (1) of the present invention is not particularly limited as long as it falls within the above definition, but the polymer terminal is a phenyl group having no substituent or a substituent. It is particularly preferable from the viewpoint of heat resistance.

  In the present invention, the polystyrene-equivalent weight average molecular weight of the triarylamine polymer is in the range of 500 to 500,000, and preferably in the range of 1,000 to 100,000 from the viewpoint of solubility and film formability.

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

  The triarylamine polymer represented by the general formula (1) of the present invention has the following general formula (18):

（式中、Ｘ^１及びＸ^２はハロゲン原子であり、かつＲ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は各々独立して水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルケニル基、アリール基、アリールアミノ基又はヘテロアリール基である。ただし、少なくとも一つは水素原子以外の置換基である。）
で表される芳香族ジハライドと一般式（１９）

Wherein X ¹ and X ² are halogen atoms, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, An alkyl group, an alkoxy group, an alkenyl group, an aryl group, an arylamino group, or a heteroaryl group, provided that at least one is a substituent other than a hydrogen atom.
Aromatic dihalides represented by general formula (19)

［式中、Ａｒ^１は無置換若しくは置換基を有する炭素数６〜６０のアリール基、アリールアミノ基又はヘテロアリール基である。Ｂは水素原子又は下記一般式（２０）

[Wherein Ar ¹ is an unsubstituted or substituted aryl group having 6 to 60 carbon atoms, an arylamino group, or a heteroaryl group. B is a hydrogen atom or the following general formula (20)

（式中、Ａｒ^２は無置換若しくは置換基を有する炭素数６〜６０のアリール基、アリールアミノ基又はヘテロアリール基を表す。）
で表される基である。］
で表される芳香族一級アミン又は芳香族二級ジアミンを、パラジウム化合物とホスフィンからなる触媒並びに塩基の存在下で重合させることにより、簡便かつ効率的に製造することができる。

(In the formula, Ar ² represents an unsubstituted or substituted aryl group having 6 to 60 carbon atoms, an arylamino group, or a heteroaryl group.)
It is group represented by these. ]
Can be easily and efficiently produced by polymerizing the aromatic primary amine or aromatic secondary diamine represented by the formula (I) in the presence of a catalyst comprising a palladium compound and a phosphine and a base.

  The aromatic dihalide represented by the general formula (18) is not particularly limited, but specific examples thereof include the following general formulas (24) to (38).

（Ｘ^１及びＸ^２は塩素原子、臭素原子、ヨウ素原子を表す。）
前記一般式（１９）で表される芳香族一級アミン又は芳香族二級ジアミンとしては、特に限定するものではないが、具体的には芳香族一級アミン（アニリン、２−フルオロアニリン、３−フルオロアニリン、４−フルオロアニリン、ｏ−トルイジン、ｍ−トルイジン、ｐ−トルイジン、２−エチルアニリン、３−エチルアニリン、４−エチルアニリン、４−ｎ−プロピルアニリン、４−ｉ−プロピルアニリン、４−ｎ−ブチルアニリン、４−ｔｅｒｔ−ブチルアニリン、４−ｓｅｃ−ブチルアニリン、４−ｎ−アミルアニリン、４−ｎ−オクチルアニリン、ｏ−アニシジン、ｍ−アニシジン、ｐ−アニシジン、ｏ−フェネチジン、ｍ−フェネチジン、ｐ−フェネチジン、４−ｎ−ブトキシアニリン、１−アミノナフタレン、２−アミノナフタレン、４−アミノビフェニル、４−アミノベンズトリフルオリド、９−アミノフェナンスレン、４−（Ｎ，Ｎ−ジフェニルアミノ）アニリン等）、芳香族二級ジアミン（Ｎ，Ｎ’−ジフェニルベンジジン、Ｎ，Ｎ’−ジ（２−メトキシフェニル）ベンジジン、Ｎ，Ｎ’−ジ（３−メトキシフェニル）ベンジジン、Ｎ，Ｎ’−ジ（４−メトキシフェニル）ベンジジン、Ｎ，Ｎ’−ジ（２−メチルフェニル）ベンジジン、Ｎ，Ｎ’−ジ（３−メチルフェニル）ベンジジン、Ｎ，Ｎ’−ジ（４−メチルフェニル）ベンジジン、Ｎ，Ｎ’−ジ（４−ｎ−ブチルフェニル）ベンジジン、Ｎ，Ｎ’−ジ（４−ｎ−ブトキシフェニル）ベンジジン、Ｎ，Ｎ’−ジ（２−トリフルオロメチルフェニル）ベンジジン、Ｎ，Ｎ’−ジ（３−トリフルオロメチルフェニル）ベンジジン、Ｎ，Ｎ’−ジ（４−トリフルオロメチルフェニル）ベンジジン、Ｎ，Ｎ’−ジ（３−トリフルオロメトキシフェニル）ベンジジン、Ｎ，Ｎ’−ジ（４−トリフルオロメトキシフェニル）ベンジジン、Ｎ，Ｎ’−ジ（２，６−ジメチルフェニル）ベンジジン、Ｎ，Ｎ’−ジ（３，６−ジメチルフェニル）ベンジジン、Ｎ，Ｎ’−ジ（２，３−ジメチルフェニル）ベンジジン、Ｎ，Ｎ’−ジ（３，４−ジメチルフェニル）ベンジジン、Ｎ，Ｎ’−ジ（２，４−ジメチルフェニル）ベンジジン、Ｎ，Ｎ’−ジ（３，５−ジメチルフェニル）ベンジジン、Ｎ，Ｎ’−ジ（２，４，６−トリメチルフェニル）ベンジジン、Ｎ，Ｎ’−ジ（４−ビフェニル）ベンジジン、Ｎ，Ｎ’−ビス（４−ジフェニルアミノフェニル）ベンジジン、Ｎ，Ｎ’−ジ（１−ナフチル）ベンジジン、Ｎ，Ｎ’−ジ（２−ナフチル）ベンジジン等）を例示することができる。好ましくはフェニル基の４位に炭素数１〜８の直鎖、分岐、環状のアルキル基を有するアニリン誘導体又はベンジジン誘導体である。

^{(X 1} and ^{X 2} represents a chlorine atom, a bromine atom, an iodine atom.)
The aromatic primary amine or aromatic secondary diamine represented by the general formula (19) is not particularly limited. Specifically, the aromatic primary amine (aniline, 2-fluoroaniline, 3-fluoro Aniline, 4-fluoroaniline, o-toluidine, m-toluidine, p-toluidine, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 4-n-propylaniline, 4-i-propylaniline, 4- n-butylaniline, 4-tert-butylaniline, 4-sec-butylaniline, 4-n-amylaniline, 4-n-octylaniline, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m -Phenethidine, p-phenetidine, 4-n-butoxyaniline, 1-aminonaphthalene, 2-aminonaphtha , 4-aminobiphenyl, 4-aminobenztrifluoride, 9-aminophenanthrene, 4- (N, N-diphenylamino) aniline, etc.), aromatic secondary diamine (N, N′-diphenylbenzidine, N , N′-di (2-methoxyphenyl) benzidine, N, N′-di (3-methoxyphenyl) benzidine, N, N′-di (4-methoxyphenyl) benzidine, N, N′-di (2- Methylphenyl) benzidine, N, N′-di (3-methylphenyl) benzidine, N, N′-di (4-methylphenyl) benzidine, N, N′-di (4-n-butylphenyl) benzidine, N , N′-di (4-n-butoxyphenyl) benzidine, N, N′-di (2-trifluoromethylphenyl) benzidine, N, N′-di (3-trifluoromethylphenyl) benzidine N, N′-di (4-trifluoromethylphenyl) benzidine, N, N′-di (3-trifluoromethoxyphenyl) benzidine, N, N′-di (4-trifluoromethoxyphenyl) benzidine, N , N′-di (2,6-dimethylphenyl) benzidine, N, N′-di (3,6-dimethylphenyl) benzidine, N, N′-di (2,3-dimethylphenyl) benzidine, N, N '-Di (3,4-dimethylphenyl) benzidine, N, N'-di (2,4-dimethylphenyl) benzidine, N, N'-di (3,5-dimethylphenyl) benzidine, N, N'- Di (2,4,6-trimethylphenyl) benzidine, N, N′-di (4-biphenyl) benzidine, N, N′-bis (4-diphenylaminophenyl) benzidine, N, N′-di (1- Naphthyl) Benji Gin, N, N′-di (2-naphthyl) benzidine and the like. An aniline derivative or a benzidine derivative having a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms at the 4-position of the phenyl group is preferable.

  In the aromatic secondary diamine in the above reaction formula, in the case of a reaction with an aromatic dihalide using a diamine having an asymmetric structure, the repeating structure may not be regularly arranged.

  Further, the triarylamine polymer represented by the general formula (1) of the present invention has the following general formula (21).

（式中、Ａｒ^１及びＡｒ^２は各々独立して無置換若しくは置換基を有する炭素数６〜６０のアリール基、アリールアミノ基又はヘテロアリール基を表す。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は各々独立して水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルケニル基、アリール基、アリールアミノ基又はヘテロアリール基である。ただし、少なくとも一つは水素原子以外の置換基である。）
で表される芳香族二級ジアミンと４，４’−ジハロビフェニルを、パラジウム化合物とホスフィンからなる触媒並びに塩基の存在下で重合させることによっても同様に合成することができる。

(In the formula, Ar ¹ and Ar ² each independently represent an unsubstituted or substituted aryl group having 6 to 60 carbon atoms, an arylamino group, or a heteroaryl group. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an arylamino group or a heteroaryl group, provided that at least one Is a substituent other than a hydrogen atom.)
Can be synthesized in the same manner by polymerizing an aromatic secondary diamine represented by the formula (4) and 4,4′-dihalobiphenyl in the presence of a catalyst comprising a palladium compound and a phosphine and a base.

  Although it does not specifically limit as aromatic secondary diamine represented by the said General formula (21), Specifically, the following general formula (39)-(48) etc. can be illustrated.

また、本発明の前記一般式（１）で表されるトリアリールアミンポリマーは、その他の合成法として、下記一般式（４９）及び（５０）で表される芳香族ジハライドとボロン酸又はボロン酸エステル類とを反応させることによっても合成できる。

In addition, the triarylamine polymer represented by the general formula (1) of the present invention is prepared by using an aromatic dihalide and a boronic acid or boronic acid represented by the following general formulas (49) and (50) as other synthesis methods. It can also be synthesized by reacting with esters.

触媒成分として使用するパラジウム化合物としては、特に限定するものではないが、例えば、４価のパラジウム化合物類（ヘキサクロロパラジウム（ＩＶ）酸ナトリウム四水和物、ヘキサクロロパラジウム（ＩＶ）酸カリウム等）、２価のパラジウム化合物類（塩化パラジウム（ＩＩ）、臭化パラジウム（ＩＩ）、酢酸パラジウム（ＩＩ）、パラジウムアセチルアセトナート（ＩＩ）、ジクロロビス（ベンゾニトリル）パラジウム（ＩＩ）、ジクロロビス（アセトニトリル）パラジウム（ＩＩ）、ジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）、ジクロロテトラアンミンパラジウム（ＩＩ）、ジクロロ（シクロオクタ−１，５−ジエン）パラジウム（ＩＩ）、パラジウムトリフルオロアセテート（ＩＩ）等）、及び、０価のパラジウム化合物類（トリス（ジベンジリデンアセトン）二パラジウム（０）、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（０）、テトラキス（トリフェニルホスフィン）パラジウム（０）等）を挙げることができる。

Although it does not specifically limit as a palladium compound used as a catalyst component, For example, tetravalent palladium compounds (hexachloro palladium (IV) acid sodium tetrahydrate, hexachloro palladium (IV) acid potassium etc.), 2 Valent palladium compounds (palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium acetylacetonate (II), dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II ), Dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium trifluoroacetate (II), etc.), and zero-valent Pa Indium compounds (tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium chloroform complex (0), tetrakis (triphenylphosphine) palladium (0), and the like) can be mentioned.

  The amount of the palladium compound used is not particularly limited. For example, it is usually in the range of 0.00001 to 20 mol% in terms of palladium with respect to 1 mol of the halogen atom of the aromatic dihalide as a raw material, and expensive palladium. Since the compound is used, it is preferably in the range of usually 0.001 to 5 mol% in terms of palladium with respect to 1 mol of the halogen atom of the aromatic dihalide as a raw material.

  In the method of the present invention, phosphines used as a catalyst component are not particularly limited. For example, triethylphosphine, tricyclohexylphosphine, triisopropylphosphine, tri-n-butylphosphine, triisobutylphosphine, tri- Trialkylphosphine such as sec-butylphosphine and tri-tert-butylphosphine, and triphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, 2,2′- And triarylphosphine such as bis (diphenylphosphino) -1,1′-binaphthyl (BINAP), trimesitylphosphine, diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinoferrocene, etc. It is. Of these, tri-tert-butylphosphine is preferably used because it has a particularly high reaction activity as a catalyst.

  The amount of phosphine to be used is not particularly limited, but it may be used in a range of usually 0.01 to 10000 times mol with respect to the palladium compound, and is preferable in view of expensive trialkylphosphine and triarylphosphine. Is in the range of 0.1 to 10 moles relative to the palladium compound.

  The method for adding the catalyst is not particularly limited, and each catalyst component may be added to the reaction system alone, or may be added after preparing in the form of a complex comprising these catalyst components in advance.

  Although it does not specifically limit as a base, For example, organic bases, such as inorganic bases, such as sodium and potassium carbonate, an alkali metal alkoxide, or a tertiary amine. 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 may be added to the system as it is, or may be prepared in situ from an alkali metal, alkali metal hydride or alkali metal hydroxide and an alcohol and used in the reaction system. More preferably, a 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 the base used is not particularly limited, but is preferably 0.5 times mol or more with respect to the aromatic dihalide and the halogen atom of the aromatic halide to be added to the reaction system. In consideration, it is more preferably in the range of 1 to 5 moles relative to the halogen atom of the aromatic halide.

  Although the polymer obtained in this manner varies depending on the conditions such as the raw material and its charging ratio, the terminal of the terminal is capped from the viewpoint of heat resistance and color resistance because there are halogens derived from the raw material and secondary amine terminal sites. It is preferable to do. Therefore, the general formula (22) corresponding to each of halogen and secondary amine terminals.

（式中、Ａｒ^３及びＡｒ^４は各々独立して無置換若しくは置換基を有する炭素数６〜６０のアリール基、アリールアミノ基又はヘテロアリール基である。）
で表される芳香族二級アミン及び／又は一般式（２３）

(In the formula, Ar ³ and Ar ⁴ are each independently an unsubstituted or substituted aryl group having 6 to 60 carbon atoms, an arylamino group, or a heteroaryl group.)
An aromatic secondary amine represented by the general formula (23)

（式中、Ｘ^３はハロゲン原子であり、かつＡｒ^５は無置換若しくは置換基を有する炭素数６〜６０のアリール基、アリールアミノ基又はヘテロアリール基である。）
で表される芳香族ハライドを更に反応させることにより、安定性を向上させたポリマーの合成を行う。

(Wherein X ³ is a halogen atom, and Ar ⁵ is an unsubstituted or substituted aryl group having 6 to 60 carbon atoms, an arylamino group or a heteroaryl group.)
A polymer with improved stability is synthesized by further reacting with an aromatic halide represented by the following formula.

  The aromatic secondary amine represented by the general formula (22) is not particularly limited, but specifically, diphenylamine, di-p-tolylamine, N-phenyl-1-naphthylamine, N-phenyl- Examples include 2-naphthylamine. Diphenylamine is preferred.

  The aromatic halide represented by the general formula (23) is not particularly limited, but specifically, it is an unsubstituted or substituted bromobenzene (bromobenzene, 2-bromotoluene, 3-bromo). Toluene, 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-butyl Benzene, 1-bromo-5- (trifluoromethoxy) benzene, 2-bromoanisole, 3-bromoanisole, 4-bromoanisole, 1-butyl Monaphthalene, 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-tert-butyl-fluorene, 2-bromo-9,9 -Di-sec-butyl-fluorene, 2-bromo-9,9-di-n-hexyl-fluorene, 2-bromine -9,9-di-n-octyl-fluorene, etc.), unsubstituted or substituted chlorobenzenes (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-chloro-5- (trifluoromethoxy) benzene, 2-chloroanisole, 3-chloroanisole, 4-chloroanisole, 1-chloronaphthalene, 2-chloronaphthalene, 2-chloro Robiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 9-chloroanthracene, 9-chlorophenanthrene, N-methyl-3-chlorocarbazole, N-ethyl-3-chlorocarbazole, N-propyl-3-chloro Carbazole, 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-tert-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 iodobenzenes which are unsubstituted or substituted (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-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-tert-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, etc.). Halobenzene is preferred.

  In the treatment method of the present invention, the aromatic secondary amine represented by the general formula (22) and / or the aromatic halide represented by the general formula (23) is a fragrance represented by the general formula (18). The triarylamine polymer obtained by the reaction with the aromatic dihalide and the aromatic primary amine or aromatic secondary diamine represented by the general formula (19) may be produced and then added, or the triarylamine may be reacted. You may make it react directly in the reactor in the middle of the process which manufactures a polymer. Preferably, it is a method of reacting by sequentially adding into the reactor after a polymerization reaction for a certain time during the production of the polymer.

  In the treatment method of the present invention, the amount of the aromatic secondary amine represented by the general formula (22) and / or the aromatic halide represented by the general formula (23) is the same as that of the triarylamine polymer used in the reaction. Although it is not particularly limited because it is not constant depending on the molecular weight and polymerization reaction conditions, it is 0.01 to 0 with respect to the aromatic dihalide represented by the general formula (18) as a raw material when added directly during polymerization. It is preferably added at a ratio of 8 times mole, more preferably 0.1 to 0.5 times mole.

  In the treatment method of the present invention, the usage amount of the palladium compound, phosphine and base used as the catalyst is not particularly limited because it is not constant depending on the molecular weight of the triarylamine polymer used in the reaction. When the secondary amine and / or aromatic halide is added directly, it is not necessary to add a palladium compound further, and simplification is possible.

  The production of the triarylamine polymer of the present invention is 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 production of the triarylamine polymer of the present invention is preferably carried out under an atmospheric pressure and an inert gas atmosphere such as nitrogen and argon, but it can be carried out even under pressurized conditions.

  In the method of the present invention, the reaction temperature is not particularly limited as long as it is a reaction temperature capable of producing a triarylamine, but is usually 20 to 300 ° C, preferably 50 to 200 ° C, more preferably 100 to 100 ° C. It is in the range of 150 ° C.

  In the method of the present invention, the reaction time is not particularly limited because it is not constant depending on the triarylamine polymer to be produced, but in many cases, it may be selected from the range of several minutes to 72 hours. Preferably it is less than 24 hours.

  The triarylamine polymer of the present invention is extremely useful as a hole transport material, a light emitting material, and a buffer material of an organic electroluminescence device.

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

  Experimental Example 1 (Synthesis of 4,4'-diiodo-2,2'-dimethyl-biphenyl (1-A))

３００ｍｌナスフラスコに、室温下、４，４’−ジアミノ−２，２’−ジメチル−ビフェニル ６．３７ｇ（３０ｍｍｏｌ）、蒸留水６０ｍｌ、塩酸１３．７５ｇ（１３２ｍｍｏｌ）を仕込んだ。この白色懸濁溶液を０℃以下へ冷却した後、亜硝酸ナトリウム４．５５ｇ（６６ｍｍｏｌ）の水（１５ｇ）溶液を内温が０℃以上にならないようにゆっくり滴下し、１時間攪拌した。この水溶液を３００ｍｌセパラブルフラスコ内のヨウ化カリウム１９．９２ｇ（１２０ｍｍｏｌ）、蒸留水（１２０ｍｌ）中へゆっくり滴下し、６０℃で３時間熟成した。室温まで冷却後、ジクロロメタンを用いて有機層を抽出した。硫酸マグネシウムで乾燥、溶媒を減圧留去後、シクロヘキサンのカラムクロマトグラフィーで原点処理を実施した。その後、再結晶（エタノール／クロロホルム）により白色結晶を７．８３ｇ得た（収率６０％）。ＮＭＲ及び赤外分光分析から目的物であることを確認した。

To a 300 ml eggplant flask, 6.37 g (30 mmol) of 4,4′-diamino-2,2′-dimethyl-biphenyl, 60 ml of distilled water, and 13.75 g (132 mmol) of hydrochloric acid were charged at room temperature. After cooling this white suspension to 0 ° C. or lower, a solution of sodium nitrite 4.55 g (66 mmol) in water (15 g) was slowly added dropwise so that the internal temperature would not exceed 0 ° C. and stirred for 1 hour. This aqueous solution was slowly dropped into 19.92 g (120 mmol) of potassium iodide and distilled water (120 ml) in a 300 ml separable flask and aged at 60 ° C. for 3 hours. After cooling to room temperature, the organic layer was extracted with dichloromethane. After drying with magnesium sulfate and distilling off the solvent under reduced pressure, the origin treatment was performed by cyclohexane column chromatography. Thereafter, 7.83 g of white crystals were obtained by recrystallization (ethanol / chloroform) (yield 60%). It was confirmed by NMR and infrared spectroscopic analysis that it was the target product.

¹ H-NMR (CDCl ₃ ): 7.63 (2H; s), 7.55 (2H; d, 8 Hz), 6.79 (2H; d, 8 Hz), 1.99 (6H; s)
IR (KBr): 2919, 1579, 1467, 1381, 1191, 1080, 1001, 877, 863, 827, 806
Example 1 (Synthesis of Compound 52)
In a 100 ml four-necked round bottom flask equipped with a condenser and a thermometer, at room temperature, 4,4′-diiodo-2,2′-dimethylbiphenyl 4.34 g (10 mmol), 4-n-butylaniline 1.64 g (11 mmol), sodium-tert-butoxide 2.31 g (24 mmol; 1.2 equivalents relative to bromine atom) and o-xylene 35 ml were charged. To this mixed solution, 22.9 mg (0.025 mmol; 0.25 mol% with respect to bromine atoms) of tris (dibenzylideneacetone) dipalladium chloroform complex prepared in advance in a nitrogen atmosphere and 0.22 ml of tri-tert-butylphosphine ( A solution of o-xylene (5 ml) in 4 equivalents to palladium atoms 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. After completion of the reaction, the reaction mixture was cooled to about 80 ° C. and then slowly added to a stirred solution of 90% aqueous acetone (200 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 a white powder (91%). When the obtained powder was measured by elemental analysis and infrared spectroscopic analysis, it was confirmed to be a triarylamine polymer represented by the following general formula (51).

続いて冷却管、温度計を装着した１００ｍｌ四つ口丸底フラスコに、室温下一般式（５１）２．９７ｇ、ブロモベンゼン０．７９ｇ（５ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド ０．５８ｇ（６ｍｍｏｌ）及びｏ−キシレン ２５ｍｌを仕込んだ。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１８．３ｍｇ（０．０２ｍｍｏｌ）及びトリ−ｔｅｒｔ−ブチルホスフィン ０．１８ｍｌのｏ−キシレン（５ｍｌ）溶液を添加した。その後窒素雰囲気下、温度を１２０℃まで昇温し、１２０℃で加熱攪拌しながら３時間熟成した。この反応混合物を室温まで冷却した後、蒸留水（１０ｍｌ）を加えて水洗を実施した（３回）。溶媒を一部減圧留去した後、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、減圧乾燥し白色粉体を得た（９４％）。得られた粉体を元素分析及び赤外分光分析により測定したところ、下記一般式（５２）で表されるトリアリールアミンポリマーであることが確認された。元素分析及び赤外分光分析の測定結果をそれぞれ表１及び図１に示す。

Subsequently, in a 100 ml four-necked round bottom flask equipped with a condenser and a thermometer, 2.97 g of general formula (51), 0.79 g (5 mmol) of bromobenzene, and 0.58 g (6 mmol) of sodium tert-butoxide at room temperature. And 25 ml of o-xylene. To this mixture was added a solution of 18.3 mg (0.02 mmol) of tris (dibenzylideneacetone) dipalladium chloroform complex prepared in advance in a nitrogen atmosphere and 0.18 ml of o-xylene (5 ml) of tri-tert-butylphosphine. . 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 cooling the reaction mixture to room temperature, distilled water (10 ml) was added and washed with water (3 times). The solvent was partially distilled off under reduced pressure, and then slowly added to a stirring 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 a white powder (94%). When the obtained powder was measured by elemental analysis and infrared spectroscopic analysis, it was confirmed to be a triarylamine polymer represented by the following general formula (52). The measurement results of elemental analysis and infrared spectroscopic analysis are shown in Table 1 and FIG. 1, respectively.

また、得られたポリマーをＴＨＦ系ＧＰＣ（東ソー（株）製：ＨＬＣ−８２２０；カラム：Ｇ４０００Ｈ_ＸＬ−Ｇ３０００Ｈ_ＸＬ−Ｇ２０００Ｈ_ＸＬ−Ｇ２０００Ｈ_ＸＬ（いずれも東ソー（株）製））にて分析した結果、ポリスチレン換算で重量平均分子量９，７００及び数平均分子量６，５００（分散度１．５）であった。ガラス転移温度は１４９℃を示した。紫外可視分光光度計（（株）日立製作所製）及び光電子分光法（理研計器（株）製、ＡＣ−２）を用い測定した結果、バンドギャップ３．３ｅＶ、ＨＯＭＯ準位５．４ｅＶ、ＬＵＭＯ準位２．１ｅＶであった。

Moreover, as a result of analyzing the obtained polymer in THF-based GPC (manufactured by Tosoh Corporation: HLC-8220; column: G4000H _XL- G3000H _XL- G2000H _XL- G2000H _XL (both manufactured by Tosoh Corporation)), The weight average molecular weight was 9,700 and the number average molecular weight was 6,500 (dispersity 1.5) in terms of polystyrene. The glass transition temperature was 149 ° C. As a result of measurement using an ultraviolet-visible spectrophotometer (manufactured by Hitachi, Ltd.) and photoelectron spectroscopy (manufactured by Riken Keiki Co., Ltd., AC-2), a band gap of 3.3 eV, a HOMO level of 5.4 eV, a LUMO level The position was 2.1 eV.

実験例２（Ｎ，Ｎ’−ビス（４−ｎ−ブチルフェニル）−２，２’−ジメチルベンジジン（２−Ａ）の合成）

Experimental Example 2 (Synthesis of N, N′-bis (4-n-butylphenyl) -2,2′-dimethylbenzidine (2-A))

冷却管、温度計を装着した３００ｍｌ三つ口丸底フラスコに、室温下、４，４’−ジアミノ−２，２’−ジメチルビフェニル １０．６１ｇ（５０ｍｍｏｌ）、４−ブロモ−ｎ−ブチルベンゼン ２１．９５ｇ（１０３ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド １１．５３ｇ（１２０ｍｍｏｌ）及びｏ−キシレン １９０ｍｌを仕込んだ。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２２８．９３ｍｇ（０．２５ｍｍｏｌ）及びトリ−ｔｅｒｔ−ブチルホスフィン ２．２ｍｌ（０．２ｇ／ｍｌトルエン溶液）のｏ−キシレン（１０ｍｌ）溶液を添加した。その後窒素雰囲気下、温度を１２０℃まで昇温し、１２０℃で加熱攪拌しながら３時間熟成した。反応終了後、この反応混合物を室温まで冷却した後、純水を５０ｍｌ加え反応を停止した。有機層を抽出した後、硫酸マグネシウムで乾燥し、溶媒を減圧留去後、トルエン／ヘキサン＝１のカラムクロマトグラフィーで精製し、白色固体を１１．４ｇ得た（４７％）。ＮＭＲから目的物２−Ａであることを確認した。

In a 300 ml three-necked round bottom flask equipped with a condenser and a thermometer, 10.41 g (50 mmol) of 4,4′-diamino-2,2′-dimethylbiphenyl, 4-bromo-n-butylbenzene 21 at room temperature. .95 g (103 mmol), sodium-tert-butoxide 11.53 g (120 mmol) and o-xylene 190 ml were charged. To this mixed solution, 228.93 mg (0.25 mmol) of tris (dibenzylideneacetone) dipalladium chloroform complex and 2.2 ml of tri-tert-butylphosphine (0.2 g / ml toluene solution) prepared in advance in a nitrogen atmosphere were added. -A solution of xylene (10 ml) 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. After completion of the reaction, the reaction mixture was cooled to room temperature, and 50 ml of pure water was added to stop the reaction. The organic layer was extracted, dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography with toluene / hexane = 1 to obtain 11.4 g of a white solid (47%). From NMR, it was confirmed to be the desired product 2-A.

¹ H-NMR (CDCl ₃ ): 6.92-7.12 (14H; m), 5.6 (2H; brs), 2.56 (4H; t, 8 Hz), 2.04 (6H; s) 1.3-1.7 (8H; m), 0.93 (6H; t, 7.4 Hz)
¹³ C-NMR (CDCl ₃ ): 142.54, 140.66, 137.34, 135.79, 130.66, 129.16, 118.61, 118.13, 114.10, 35.03, 33 .94, 22.47, 20.27, 14.10
Example 2 (Synthesis of Compound 53)
In Example 1, 2.04 g (5 mmol) of 4,4′-diiodobiphenyl was used instead of 4.34 g (10 mmol) of 4,4′-diiodo-2,2′-dimethylbiphenyl, and 4-n-butyl was used. A white powder was obtained (quant.) According to the method described in Example 1 except that 2.62 g (5.5 mmol) of 2-A was used instead of 1.64 g (11 mmol) of aniline. When the obtained powder was measured by elemental analysis and infrared spectroscopic analysis, it was confirmed to be a triarylamine polymer represented by the following general formula (53). The measurement results of elemental analysis and infrared spectroscopic analysis are shown in Table 2 and FIG. 2, respectively.

また、得られたポリマーをＴＨＦ系ＧＰＣ（東ソー（株）製：ＨＬＣ−８２２０；カラム：Ｇ４０００Ｈ_ＸＬ−Ｇ３０００Ｈ_ＸＬ−Ｇ２０００Ｈ_ＸＬ−Ｇ２０００Ｈ_ＸＬ（いずれも東ソー（株）製））にて分析した結果、ポリスチレン換算で重量平均分子量２１，５００及び数平均分子量９，８００（分散度２．２）であった。ガラス転移温度は１６４℃を示した。紫外可視分光光度計（（株）日立製作所製）及び光電子分光法（理研計器（株）製、ＡＣ−２）を用い測定した結果、バンドギャップ３．１ｅＶ、ＨＯＭＯ準位５．３ｅＶ、ＬＵＭＯ準位２．２ｅＶであった。

Moreover, as a result of analyzing the obtained polymer in THF-based GPC (manufactured by Tosoh Corporation: HLC-8220; column: G4000H _XL- G3000H _XL- G2000H _XL- G2000H _XL (both manufactured by Tosoh Corporation)), The weight average molecular weight was 21,500 and the number average molecular weight was 9,800 (dispersion degree 2.2) in terms of polystyrene. The glass transition temperature was 164 ° C. As a result of measurement using an ultraviolet-visible spectrophotometer (manufactured by Hitachi, Ltd.) and photoelectron spectroscopy (manufactured by Riken Keiki Co., Ltd., AC-2), a band gap of 3.1 eV, a HOMO level of 5.3 eV, a LUMO level The position was 2.2 eV.

実験例３（４，４’−ビス（４−ｎ−ブチルフェニル）−２，２’−ジメトキシベンジジン（３−Ｄ）の合成）

Experimental Example 3 (Synthesis of 4,4′-bis (4-n-butylphenyl) -2,2′-dimethoxybenzidine (3-D))

冷却管、温度計を装着した５００ｍｌ三つ口丸底フラスコに、室温下３−Ａを１６．３８ｇ（１０７．１ｍｍｏｌ）、亜鉛粉末１９．７ｇ（３０１．４ｍｍｏｌ）、プロパノール２００ｍｌを仕込んだ。この混合溶液を１１５℃にて還流させながら、２０％水酸化ナトリウム水溶液１０６．４ｇ（５３２ｍｍｏｌ）を１時間かけて滴下した後、一晩還流攪拌した。反応終了後、有機層を抽出、硫酸マグネシウムで乾燥し、褐色の粘調オイルとして３−Ｂを１３．７ｇ得た（１００％）。

A 500 ml three-necked round bottom flask equipped with a condenser and a thermometer was charged with 16.38 g (107.1 mmol) of 3-A, 19.7 g (301.4 mmol) of zinc powder, and 200 ml of propanol at room temperature. While this mixed solution was refluxed at 115 ° C., 106.4 g (532 mmol) of a 20% aqueous sodium hydroxide solution was added dropwise over 1 hour, followed by stirring under reflux overnight. After completion of the reaction, the organic layer was extracted and dried with magnesium sulfate to obtain 13.7 g of 3-B as a brown viscous oil (100%).

¹ H-NMR (CDCl ₃ ): 6.36-6.46 (6H; m), 7.11 (2H; dd, 8.4, 8.8 Hz), 5.59 (2H; brs), 3. 74 (6H; s)
¹³ C-NMR (CDCl ₃ ): 160.82, 150.33, 130.13, 105.21, 105.04, 98.37, 55.20
A 500 ml three-necked round bottom flask equipped with a condenser and a thermometer was charged with 13.6 g (56 mmol) of 3-B and 200 ml of ethanol at room temperature and cooled to 0 ° C. in a cooling bath, and then concentrated hydrochloric acid and ethanol A mixed solution of 65 ml (volume ratio of 1: 1) was added dropwise over 1 hour and a half and stirred overnight at room temperature. After completion of the reaction, the resulting precipitate was filtered, neutralized, washed with water, and dried to obtain 4.8 g of 3-C as a white solid (37% from 3-A). It was confirmed to be the desired product 3-C from NMR and melting point.

¹ H-NMR (CDCl ₃ ): 6.76 (2H; d, 7.8 Hz), 6.19 (2H; d, 2.2 Hz), 6.11 (2H; dd, 7.8 Hz, 2.2 Hz) ), 4.28 (4H; brs), 3.59 (6H; s)
Melting point = 187-191 ° C. (literature value: 187-188 ° C.)
The method from 3-C to 3-D was carried out according to the method described in Experimental Example 2 to obtain 6.0 g of 3-D as colorless needle crystals (60%). NMR confirmed that the product was 3-D.

¹ H-NMR (THF): 7.13 (2H; brs), 7.03 (8H; s), 6.97 (2H; d, 8.2 Hz), 6.65 (2H; d, 2 Hz), 6.60 (2H; dd, 8 Hz, 2 Hz), 3.64 (6H; s), 2.54 (4H, t), 1.61 (4H; m), 1.39 (4H; m), 0 .93 (6H, t)
¹³ C-NMR (THF): 158.98, 145.11, 142.61, 135.01, 132.64, 129.57, 120.82, 118.60, 108.89, 101.19, 55. 57, 35.83, 34.99, 23.25, 14.21
Melting point = 128-130 ° C.
Example 3 (Synthesis of Compound 54)
In Example 2, it implemented according to the method of Example 2 except having used said 3-D 3.05g (6 mmol) instead of 2-A 2.62g (5.5 mmol), and obtained white powder. . When the obtained powder was measured by elemental analysis and infrared spectroscopic analysis, it was confirmed to be a triarylamine polymer represented by the following general formula (54). Moreover, the obtained polymer was the weight average molecular weight 16,700 and the number average molecular weight 13,800 (dispersion degree 1.2) in polystyrene conversion. The glass transition temperature was 159 ° C. and the band gap was 2.9 eV.

実験例４（４，４’−ビス（４−ｎ−ブチルフェニル）−３，３’−ジメチルベンジジン（４−Ａ）の合成）

Experimental Example 4 (Synthesis of 4,4′-bis (4-n-butylphenyl) -3,3′-dimethylbenzidine (4-A))

実験例２において、４，４’−ジアミノ−２，２’−ジメチルビフェニルの代わりに４，４’−ジアミノ−３，３’−ジメチルビフェニルを用いる以外は、実験例２に記載した方法に従い実施し、淡黄色結晶として４−Ａを得た（４３％）。ＮＭＲ及び融点から目的物４−Ａであることを確認した。

The same procedure as described in Experimental Example 2 was performed except that 4,4'-diamino-3,3'-dimethylbiphenyl was used instead of 4,4'-diamino-2,2'-dimethylbiphenyl in Experimental Example 2. To give 4-A as pale yellow crystals (43%). From NMR and melting point, it was confirmed to be the desired product 4-A.

¹ H-NMR (THF): 7.40 (2H; s), 7.30 (2H; d, 8.2 Hz), 7.17 (2H; d, 8.2 Hz), 7.00 (4H; d) , 8.4 Hz), 6.86 (4H; d, 8.4 Hz), 6.46 (2H; s), 2.53 (4H; t, 7.4 Hz), 2.27 (6H; s), 1.30-1.61 (8H; m), 0.92 (6H; t, 7.4 Hz)
¹³ C-NMR (THF): 143.61, 141.93, 135.04, 134.62, 129.53, 129.42, 129.33, 125.08, 119.68, 118.20, 35. 81, 35.04, 23.23, 18.38, 14.41
Melting point = 95-96 ° C.
Example 4 (Synthesis of Compound 55)
In Example 2, it implemented according to the method of Example 2 except having used said 4-A 2.86g (6 mmol) instead of 2-A 2.62g (5.5 mmol), and obtained white powder. . When the obtained powder was measured by elemental analysis and infrared spectroscopic analysis, it was confirmed to be a triarylamine polymer represented by the following general formula (55). Moreover, the obtained polymer was the weight average molecular weight 10,600 and the number average molecular weight 7,200 (dispersion degree 1.5) in polystyrene conversion. The glass transition temperature was 162 ° C. and the band gap was 3.0 eV.

実験例５（４，４’−ビス（４−ｎ−ブチルフェニル）−３，３’−ジメトキシベンジジンの合成）

Experimental Example 5 (Synthesis of 4,4′-bis (4-n-butylphenyl) -3,3′-dimethoxybenzidine)

実験例２において、４，４’−ジアミノ−２，２’−ジメチルビフェニルの代わりに４，４’−ジアミノ−３，３’−ジメトキシビフェニルを用いる以外は、実験例２に記載した方法に従い実施し、無色針状結晶として５−Ａを得た（４４％）。ＮＭＲ及び融点から目的物５−Ａであることを確認した。

In Experimental Example 2, the procedure described in Experimental Example 2 was followed, except that 4,4′-diamino-3,3′-dimethoxybiphenyl was used instead of 4,4′-diamino-2,2′-dimethylbiphenyl. To give 5-A as colorless needle crystals (44%). From NMR and melting point, it was confirmed to be the intended product 5-A.

¹ H-NMR (THF): 7.02-7.25 (14H; m), 6.58 (2H; s), 3.91 (6H; s), 2.54 (4H; t, 7.8 Hz) ), 1.30-1.72 (8H; m), 0.93 (6H; t, 7.4 Hz)
¹³ C-NMR (THF): 149.69, 142.02, 135.54, 133.91, 133.21, 129.57, 119.22, 115.47, 109.81, 55.96, 35. 83, 34.97, 23.23, 14.41
Melting point = 108-110 ° C.
Example 5 (Synthesis of Compound 56)
In Example 2, it implemented according to the method of Example 2 except having used said 5-A 3.05g (6 mmol) instead of 2-A 2.62g (5.5 mmol), and obtained white powder. . When the obtained powder was measured by elemental analysis and infrared spectroscopic analysis, it was confirmed to be a triarylamine polymer represented by the following general formula (56). Moreover, the obtained polymer was the weight average molecular weight 18,300 and the number average molecular weight 14,700 (dispersion degree 1.2) in polystyrene conversion. The glass transition temperature was 152 ° C. and the band gap was 2.9 eV.

The infrared-spectroscopy chart of the triarylamine polymer obtained in Example 1 is shown. The infrared-spectroscopy chart of the triarylamine polymer obtained in Example 2 is shown.

Claims (12)

A triarylamine polymer having a band gap represented by the following general formula (1) of 3.0 eV or more and 4.0 eV or less and a polystyrene equivalent weight average molecular weight of 1,000 to 100,000. .

[Wherein Ar ¹ represents an n-butylphenyl group, ^one of R ¹ , R ² , R ³ and R ⁴ is an alkyl group, and 1 of R ⁵ , R ⁶ , R ⁷ and R ^8] One is an alkyl group, and the remaining substituents are all hydrogen atoms. A is a direct bond or the following general formula (2)

(In the formula, Ar ² represents an n-butylphenyl group.)
It is group represented by these. n is an integer of 1 or more. ] The triarylamine polymer according to claim 1, wherein the triarylamine polymer is represented by the following general formula (3) in the general formula (1).

(In the formula, Ar ¹ represents an n-butylphenyl group, ^one of R ¹ , R ² , R ³ , and R ⁴ is an alkyl group, and 1 of R ⁵ , R ⁶ , R ⁷ , and R ⁸ . One is an alkyl group, and the remaining substituents are all hydrogen atoms, and n is an integer of 1 or more.) In General Formula (1), R ¹ , R ³ , R ⁶ and R ⁸ are hydrogen atoms, any one of R ² and R ⁴ is an alkyl group, and any one of R ⁵ and R ⁷ The triarylamine polymer according to claim 1, wherein one is an alkyl group. The triarylamine polymer according to claim 1, wherein the general formula (1) is represented by any one of the following general formulas (10) and (12).

(In the formula, R ¹³ , R ¹⁴ , R ²¹ and R ²² are linear, branched and cyclic alkyl groups having 1 to 8 carbon atoms. R ¹⁵ and R ²³ are n-butyl groups. Is the same.) The triarylamine polymer according to claim 4, wherein A is represented by the following general formula (17).

(In the formula, R ⁴⁰ is an n-butyl group.) The triarylamine polymer according to any one of claims 1 to 5, wherein the terminal of the triarylamine polymer is an unsubstituted or substituted phenyl group. General formula (18)

(In the formula, X ¹ and X ² are halogen atoms, one of R ¹ , R ² , R ³ and R ⁴ is an alkyl group, and 1 of R ⁵ , R ⁶ , R ⁷ and R ⁸ . One is an alkyl group, and the remaining substituents are all hydrogen atoms.)
Aromatic dihalides represented by general formula (19)

[In the formula, Ar ¹ represents an n-butylphenyl group. B is a hydrogen atom or the following general formula (20)

(In the formula, Ar ² represents an n-butylphenyl group.)
It is group represented by these. ]
The tria of any one of claims 1 to 6, wherein the aromatic primary amine or the aromatic secondary diamine represented by the formula is polymerized in the presence of a catalyst comprising a palladium compound and a phosphine and a base. A method for producing a reelamine polymer. In the general formula (1), when A is represented by the general formula (2), the general formula (21)

(In the formula, Ar ¹ and Ar ² each independently represent an n-butylphenyl group. One of R ¹ , R ² , R ³ , and R ⁴ is an alkyl group, and R ⁵ , R ⁶ , R) ⁷ and one of R ⁸ is an alkyl group, and the remaining substituents are all hydrogen atoms.)
2. The triarylamine polymer according to claim 1, wherein the aromatic secondary diamine represented by the formula (4) and 4,4′-dihalobiphenyl are polymerized in the presence of a catalyst comprising a palladium compound and a phosphine and a base. Manufacturing method. For the triarylamine polymer obtained in claim 7 or 8, the general formula (22)

(In the formula, Ar ³ and Ar ⁴ are each independently an unsubstituted or substituted aryl group having 6 to 60 carbon atoms, an arylamino group, or a heteroaryl group.)
An aromatic secondary amine represented by the general formula (23)

(Wherein X ³ is a halogen atom, and Ar ⁵ is an unsubstituted or substituted aryl group having 6 to 60 carbon atoms, an arylamino group or a heteroaryl group.)
The method for producing a triarylamine polymer according to claim 6, wherein the aromatic halide represented by the formula (1) is reacted in the presence of a catalyst comprising a palladium compound and a phosphine and a base. The method for producing a triarylamine polymer according to any one of claims 7 to 9, wherein the phosphine is tri-tert-butylphosphine. The method for producing a triarylamine polymer according to claim 9, wherein the aromatic halide is halobenzene and the aromatic secondary amine is diphenylamine. An organic electroluminescence device, wherein the triarylamine polymer according to claim 1 is used as a hole transport layer or a hole injection layer.

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