JP2002030136A - New multibranched copolymer, its production method and organic semiconductor material made by using it - Google Patents
New multibranched copolymer, its production method and organic semiconductor material made by using itInfo
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- JP2002030136A JP2002030136A JP2000213421A JP2000213421A JP2002030136A JP 2002030136 A JP2002030136 A JP 2002030136A JP 2000213421 A JP2000213421 A JP 2000213421A JP 2000213421 A JP2000213421 A JP 2000213421A JP 2002030136 A JP2002030136 A JP 2002030136A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は新規なポリアミン系
共重合体、その製造方法及びそれを用いた有機半導体材
料に関するものである。The present invention relates to a novel polyamine-based copolymer, a method for producing the same, and an organic semiconductor material using the same.
【０００２】[0002]
【従来の技術】従来、トリフェニルアミンを構成単位と
して有する化合物は電気化学的活性を示すとともに、エ
レクトロクロミック現象を利用した表示材料として注目
されている。酸化により陰イオンがドーピングされｐ型
半導体となり、この性質を用いて電極材料への応用、及
び酸化・還元時の色変化を用いた表示材料としての応用
が可能である。しかしながら、従来知られている化合物
及びそれを製造する方法はポリトリフェニルアミンの原
料となるＡＢ２型モノマーを合成する必要があり製造工
程上煩雑さを避けることが困難であった（Chemical Com
munications, 1997, 2063)。2. Description of the Related Art Heretofore, compounds having triphenylamine as a constitutional unit exhibit electrochemical activity and have attracted attention as display materials utilizing the electrochromic phenomenon. An anion is doped by oxidation to become a p-type semiconductor, and by using this property, application to an electrode material and application to a display material using color change at the time of oxidation and reduction are possible. However, a method of producing compound and it has been known conventionally has been difficult to avoid raw material becomes must synthesize the AB 2 type monomer manufacturing processes on complexity of polytriphenylamine (Chemical Com
munications, 1997, 2063).
【０００３】[0003]
【発明が解決しようとする課題】本発明は、汎用の有機
溶媒に可溶で、成形加工性に優れたトリフェニルアミン
系重合体、及び原料モノマーとしてＡＢ２型モノマーを
経由することなく一段階の重縮合反応によりトリフェニ
ルアミン系重合体を製造する方法を提供することを目的
とする。さらに本発明は、汎用の有機溶媒に可溶で、成
形加工性に優れたポリアミン系の有機半導体を提供する
ことを目的とする。DISCLOSURE OF THE INVENTION The present invention provides a triphenylamine polymer which is soluble in a general-purpose organic solvent and has excellent moldability, and a one-step process without passing through an AB type 2 monomer as a raw material monomer. It is an object of the present invention to provide a method for producing a triphenylamine-based polymer by a polycondensation reaction of A further object of the present invention is to provide a polyamine-based organic semiconductor that is soluble in a general-purpose organic solvent and has excellent moldability.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記課題
を克服すべく鋭意研究を行った結果、トリス（4-ハロゲ
ン化フェニル）アミンとベンゼン-1,4-ジボロニックア
シッドとの脱ハロゲン化重縮合により得られる規則的な
枝分かれを有する（以下、多分岐という）ある種のトリ
フェニルアミン系共重合体がその目的に適合することを
見出し、この知見に基づき本発明をなすに至った。すな
わち本発明は、（１）下記式（Ｉ）Means for Solving the Problems The present inventors have conducted intensive studies in order to overcome the above-mentioned problems, and as a result, have found that tris (4-halogenated phenyl) amine and benzene-1,4-diboronic acid can be used. It has been found that certain triphenylamine-based copolymers having regular branching (hereinafter referred to as hyperbranched) obtained by dehalogenation polycondensation are suitable for the purpose, and based on this finding, the present invention has been achieved. Reached. That is, the present invention provides (1) the following formula (I)
【０００５】[0005]
【化６】 Embedded image
【０００６】で表される繰り返し単位を有してなること
を特徴とする重合体、（２）下記式（II）A polymer comprising a repeating unit represented by the following formula (2):
【０００７】[0007]
【化７】 Embedded image
【０００８】（式中、Ｘはハロゲン原子を示す。）で表
される化合物と、下記式（III）Wherein X represents a halogen atom; and a compound represented by the following formula (III):
【０００９】[0009]
【化８】 Embedded image
【００１０】で表される化合物を脱ハロゲン化重縮合さ
せることを特徴とする、下記式（Ｉ）Wherein the compound represented by the formula (I) is dehalogenated and polycondensed.
【００１１】[0011]
【化９】 Embedded image
【００１２】で表される繰り返し単位を有してなる重合
体の製造方法、（３）下記式（Ｉ）A method for producing a polymer having a repeating unit represented by the following formula (3):
【００１３】[0013]
【化１０】 Embedded image
【００１４】で表される繰り返し単位を有してなる重合
体に、陰イオンをドーピングさせてなることを特徴とす
る有機半導体材料、及び（４）前記陰イオンが、テトラ
フルオロホウ酸イオン、過塩素酸イオン、ヘキサフルオ
ロリン酸イオン、硫酸イオン、硫酸水素イオン、トリフ
ルオル酢酸イオン又はｐ−トルエンスルホン酸イオンで
あることを特徴とする（３）項記載の有機半導体材料を
提供するものである。An organic semiconductor material obtained by doping an anion into a polymer having a repeating unit represented by the following formula: and (4) the anion is a tetrafluoroborate ion, (3) The organic semiconductor material according to (3), which is chlorate ion, hexafluorophosphate ion, sulfate ion, hydrogen sulfate ion, trifluoroacetate ion or p-toluenesulfonic acid ion.
【００１５】[0015]
【発明の実施の形態】本発明の、前記式(Ｉ)で表される
繰り返し単位を有してなるトリフェニルアミン系多分岐
共重合体は新規化合物であって、クロロホルム、テトラ
ヒドロフランなどの有機溶媒に可溶であるので、フィル
ムなどに容易に成形することができ、例えば容易にキャ
ストフィルムなどを作成することができる。このトリフ
ェニルアミン系多分岐共重合体は前記式（II）で表され
る化合物と前記式（III）で表される化合物とを芳香族
系溶媒中、パラジウム触媒存在下、不活性雰囲気で重縮
合することにより一段階で製造することができる。前記
式（II）で表される化合物において、Ｘとして塩素、臭
素又はヨウ素原子が好ましく、臭素又はヨウ素原子がよ
り好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The triphenylamine-based multibranched copolymer having a repeating unit represented by the above formula (I) of the present invention is a novel compound and is an organic solvent such as chloroform and tetrahydrofuran. Since it is soluble in water, it can be easily formed into a film or the like. For example, a cast film or the like can be easily formed. This triphenylamine-based multibranched copolymer is prepared by polymerizing a compound represented by the formula (II) and a compound represented by the formula (III) in an aromatic solvent in the presence of a palladium catalyst in an inert atmosphere. It can be produced in one step by condensation. In the compound represented by the formula (II), X is preferably a chlorine, bromine or iodine atom, more preferably a bromine or iodine atom.
【００１６】この重縮合の際に用いられる芳香族系溶媒
としてはベンゼン、トルエン、キシレンなどが挙げられ
る。パラジウム触媒としてはテトラキス（トリフェニル
ホスフィン）パラジウムなどが用いられる。パラジウム
触媒の使用量は、上記式（II）で表される化合物に対し
て、好ましくは０．１〜１０モル％、より好ましくは
０．２〜５モル％である。反応温度としては好ましくは
50〜150℃、より好ましくは80〜120℃である。また、反
応は不活性雰囲気、例えばアルゴン、窒素中などで行な
うのが好ましい。このように不活性雰囲気下で行えば、
副生物の生成を抑制することができる。The aromatic solvent used in the polycondensation includes benzene, toluene, xylene and the like. As the palladium catalyst, tetrakis (triphenylphosphine) palladium or the like is used. The amount of the palladium catalyst to be used is preferably 0.1 to 10 mol%, more preferably 0.2 to 5 mol%, based on the compound represented by the above formula (II). The reaction temperature is preferably
It is 50 to 150 ° C, more preferably 80 to 120 ° C. The reaction is preferably performed in an inert atmosphere, for example, in argon or nitrogen. If you run under an inert atmosphere like this,
The generation of by-products can be suppressed.
【００１７】本発明の製造方法において、前記式（II）
で表される化合物と前記式（III）で表される化合物
は、好ましくは等モルの割合で用いられる。本発明の製
造方法では、前記式（II）と式(III)との反応でＸＢ
（ＯＨ）２が離脱し、目的とする重合体が得られる。こ
のＸＢ（ＯＨ）２に由来する副生物は、ホウ酸と同様に
水、アルコール等の溶媒に可溶である。したがって、反
応終了後に、得られた反応混合物をこれらの溶媒に投入
し、副生物を溶媒に溶解させて除去することができる。In the production method of the present invention, the above formula (II)
The compound represented by the formula (III) and the compound represented by the formula (III) are preferably used in an equimolar ratio. In the production method of the present invention, the reaction of the formula (II) with the formula (III) is carried out by XB
(OH) 2 is released to obtain the desired polymer. The by-product derived from XB (OH) 2 is soluble in a solvent such as water and alcohol, like boric acid. Therefore, after completion of the reaction, the obtained reaction mixture can be introduced into these solvents, and by-products can be dissolved in the solvent and removed.
【００１８】本発明の前記式（I）で表される繰り返し
単位を有してなる重合体は、赤外吸収スペクトルで、1,
4-ジ置換ベンゼンの面外変角振動、Ｃ−Ｎ結合の伸縮振
動に帰属されるバンドが、それぞれ812, 1269cm−１に
観測される。本発明の前記式（I）で表される繰り返し
単位を有してなる重合体は下記式によって表される。な
お、下記式は説明的に示すものであり繰り返し単位の数
を示すものでなく、通常、末端にさらに上記の繰り返し
単位が結合しているものである。また、最終末端には水
素原子又はハロゲン原子が結合する。The polymer having a repeating unit represented by the formula (I) of the present invention has an infrared absorption spectrum of 1,
Bands attributable to out-of-plane bending vibration of 4-disubstituted benzene and stretching vibration of C—N bond are observed at 812 and 1269 cm −1 , respectively. The polymer of the present invention having the repeating unit represented by the formula (I) is represented by the following formula. Note that the following formulas are illustrative and do not indicate the number of repeating units, but are usually those in which the above-mentioned repeating units are further bonded to the ends. Further, a hydrogen atom or a halogen atom is bonded to the final terminal.
【００１９】[0019]
【化１１】 Embedded image
【００２０】本発明の重合体の重量平均分子量は、通常
1500〜50000、好ましくは2500〜50000である。The weight average molecular weight of the polymer of the present invention is usually
It is 1500 to 50000, preferably 2500 to 50000.
【００２１】本発明の前記式（I）で表される繰り返し
単位を有してなる重合体はそのままでは電気的に絶縁体
であるが、テトラフルオロホウ酸イオン、過塩素酸イオ
ン、ヘキサフルオロリン酸イオン、硫酸イオン、硫酸水
素イオン、トリフルオル酢酸イオンまたはp-トルエンス
ルホン酸イオンなどの陰イオンをドーピングすることに
より半導体としての性質をもつ。本発明において、ドー
ピング量は、通常、式（Ｉ）で示される繰り返し単位か
らなる重合体に対し、繰り返し単位当り好ましくは５モ
ル％以上、より好ましくは、１０〜５０モル％である。The polymer of the present invention having the repeating unit represented by the above formula (I) is an electrically insulating material as it is, but is not limited to tetrafluoroborate ion, perchlorate ion and hexafluorophosphate. By doping an anion such as an acid ion, a sulfate ion, a hydrogen sulfate ion, a trifluoroacetate ion or a p-toluenesulfonate ion, it has properties as a semiconductor. In the present invention, the doping amount is usually 5 mol% or more, more preferably 10 to 50 mol%, per repeating unit based on the polymer comprising the repeating unit represented by the formula (I).
【００２２】このような陰イオンのドーピングを行なっ
た本発明の前記式（I）で表される繰り返し単位を有し
てなる重合体は、特に、薄膜状態では緑色を示し、陰イ
オンを脱ドープすれば黄褐色を示す。このようなエレク
トロクロミック現象を利用して表示素子としての応用が
可能である。本発明の重合体によれば、前記のように、
容易にキャストフィルムを作成することができる。白金
板上あるいは透明ガラス電極上に作成したフィルムを、
上記陰イオンを含む、支持電解質を溶解した溶液中に浸
し、電位を印加することにより陰イオンをドーピングす
ることができる。また、電位を０Ｖに戻せば、陰イオン
は脱ドーピングし、この脱着現象は印加電位の調節によ
り繰り返し行うことができる。これを利用して電極材料
としての応用が可能である。The polymer having a repeating unit represented by the formula (I) of the present invention, which has been doped with such an anion, shows a green color in a thin film state, and dedopes the anion. If it shows yellowish brown. The application as a display element is possible by utilizing such an electrochromic phenomenon. According to the polymer of the present invention, as described above,
A cast film can be easily created. A film made on a platinum plate or a transparent glass electrode,
An anion can be doped by immersing it in a solution in which a supporting electrolyte containing the anion is dissolved and applying a potential. If the potential is returned to 0 V, the anion is dedoped, and this desorption phenomenon can be repeated by adjusting the applied potential. By utilizing this, application as an electrode material is possible.
【００２３】[0023]
【発明の効果】本発明のトリフェニルアミン系重合体
は、汎用の有機溶媒に可溶で、成形加工性に優れてい
る。また、本発明のトリフェニルアミン系重合体の製造
方法によれば、原料モノマーとしてＡＢ２型モノマーを
経由することなく一段階の重縮合反応により目的の重合
体を製造することができる。さらに本発明のポリアミン
系の有機半導体は、汎用の有機溶媒に可溶で、成形加工
性に優れており、電極材料及び表示材料として好適に用
いられる。The triphenylamine-based polymer of the present invention is soluble in general-purpose organic solvents and has excellent moldability. Further, according to the method for producing a triphenylamine-based polymer of the present invention, a target polymer can be produced by a one-stage polycondensation reaction without passing through an AB 2- type monomer as a raw material monomer. Further, the polyamine-based organic semiconductor of the present invention is soluble in a general-purpose organic solvent, has excellent moldability, and is suitably used as an electrode material and a display material.
【００２４】[0024]
【実施例】次の実施例により本発明を更に詳細に説明す
る。 実施例１ 還流冷却器、マグネチックスターラー付き50ml三頸フラ
スコに、トリス（4-ブロモフェニル）アミン0.482g（1.
0ミリモル）、ベンゼン-1,4-ジボロニックアシッド0.16
5g（1.0ミリモル）、テトラキス（トリフェニルホスフ
ィン）パラジウム（0）11.6mg（0.01ミリモル）、２Ｍ
炭酸ナトリウム水溶液8ml、ベンゼン10ml、エタノール1
0mlを加え、アルゴン雰囲気下、20時間還流させた。反
応混合物から溶媒を除去して、アセトン50mlに投入後、
１Ｎ塩酸25mlで洗浄し真空乾燥した。淡黄色粉末303mg
（95％）を得た。このポリマーの赤外吸収スペクトルを
図１に示す。これより812, 1269cm−１にバンドが観測
され、それぞれ、1,4-ジ置換ベンゼンの面外変角振動、
Ｃ−Ｎ結合の伸縮振動に帰属され、〔化１１〕に示す重
合体であることが確認された。ＧＰＣによる重量平均分
子量は、カラムをTSKgel G3000HＸＬ、溶媒をテトラヒ
ドロフランで測定したところ5.4×10３であった。The present invention will be described in more detail with reference to the following examples. Example 1 In a 50 ml three-necked flask equipped with a reflux condenser and a magnetic stirrer, 0.482 g of tris (4-bromophenyl) amine (1.
0 mmol), benzene-1,4-diboronic acid 0.16
5 g (1.0 mmol), 11.6 mg (0.01 mmol) of tetrakis (triphenylphosphine) palladium (0), 2M
Sodium carbonate aqueous solution 8ml, benzene 10ml, ethanol 1
0 ml was added, and the mixture was refluxed for 20 hours under an argon atmosphere. After removing the solvent from the reaction mixture and pouring into 50 ml of acetone,
It was washed with 25 ml of 1N hydrochloric acid and dried under vacuum. 303mg pale yellow powder
(95%). FIG. 1 shows the infrared absorption spectrum of this polymer. From this, bands were observed at 812 and 1269 cm −1, and out-of-plane bending vibration of 1,4-disubstituted benzene,
The polymer was assigned to the stretching vibration of the C—N bond, and was confirmed to be a polymer represented by Chemical Formula 11. The weight average molecular weight measured by GPC was 5.4 × 10 3 when the column was measured with TSKgel G3000H XL and the solvent was measured with tetrahydrofuran.
【００２５】実施例２ 実施例１において得られたポリマーをテトラヒドロフラ
ンに溶解し、白金板（1×1＝1cm２）上に塗布、乾燥さ
せてフィルムを作成した。この白金板を作用電極、銀線
を参照電極として、炭酸プロピレン中、0.1Ｍテトラフ
ルオロホウ酸テトラフルオロボレートを支持電解質とし
て、20mV/ｓの掃引速度で0〜1.4Ｖ（vsAg）の範囲でサ
イクリックボルタモグラムを測定すると、1.2Ｖにポリ
マーが中性状態から、酸化状態への変化を示すピークが
認められた。したがって、この得られたポリマーは、1.
2Ｖの条件下で酸化反応が可能であることがわかる。Example 2 The polymer obtained in Example 1 was dissolved in tetrahydrofuran, applied on a platinum plate (1 × 1 = 1 cm 2 ), and dried to form a film. This platinum plate is used as a working electrode, a silver wire as a reference electrode, 0.1 M tetrafluoroborate tetrafluoroborate in propylene carbonate as a supporting electrolyte, and a sweep rate of 20 mV / s in a range of 0 to 1.4 V (vsAg). When the click voltammogram was measured, a peak indicating a change from a neutral state to an oxidized state of the polymer was observed at 1.2 V. Thus, the resulting polymer is 1.
It can be seen that an oxidation reaction is possible under the condition of 2V.
【図１】実施例１により得られたトリフェニルアミン系
多分岐共重合体の赤外吸収スペクトル図。FIG. 1 is an infrared absorption spectrum of a triphenylamine-based hyperbranched copolymer obtained in Example 1.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 磯 智昭 茨城県結城市鹿窪189 茨城県工業技術セ ンター内 Ｆターム(参考） 4J032 CA04 CB07 CC01 CD01 CE03 CF02 CG01 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tomoaki Iso 189 Shikabo, Yuki-shi, Ibaraki F-term in the Industrial Technology Center, Ibaraki Prefecture (reference) 4J032 CA04 CB07 CC01 CD01 CE03 CF02 CG01
Claims (4)
重合体。1. A compound represented by the following formula (I): A polymer having a repeating unit represented by the formula:
と、下記式（III） 【化３】 で表される化合物を脱ハロゲン化重縮合させることを特
徴とする、下記式（Ｉ） 【化４】 で表される繰り返し単位を有してなる重合体の製造方
法。2. A compound represented by the following formula (II): (Wherein X represents a halogen atom), and a compound represented by the following formula (III): Wherein the compound represented by the formula (I) is dehalogenated and polycondensed. A method for producing a polymer having a repeating unit represented by the formula:
ンをドーピングさせてなることを特徴とする有機半導体
材料。3. A compound represented by the following formula (I): An organic semiconductor material obtained by doping a polymer having a repeating unit represented by the formula (1) with an anion.
イオン、過塩素酸イオン、ヘキサフルオロリン酸イオ
ン、硫酸イオン、硫酸水素イオン、トリフルオル酢酸イ
オン又はｐ−トルエンスルホン酸イオンであることを特
徴とする請求項３記載の有機半導体材料。4. The method according to claim 1, wherein the anion is tetrafluoroborate, perchlorate, hexafluorophosphate, sulfate, hydrogensulfate, trifluoroacetate or p-toluenesulfonate. The organic semiconductor material according to claim 3, wherein
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008139839A1 (en) | 2007-05-09 | 2008-11-20 | Kyushu University, National University Corporation | Carbon nanotube solubilizer |
| JP2011001462A (en) * | 2009-06-18 | 2011-01-06 | Ricoh Co Ltd | Novel hole transporting multibranched copolymer, and method for producing the same |
| EP2423241A1 (en) * | 2010-07-24 | 2012-02-29 | Blücher GmbH | Unit with porous organic polymers and use of same |
| JP2012126813A (en) * | 2010-12-15 | 2012-07-05 | Tosoh Corp | New arylamine dendrimer-like compound, and method for producing the same and application of the same |
| CN102695557A (en) * | 2009-11-25 | 2012-09-26 | 日产化学工业株式会社 | Carbon nano-tube dispersant |
-
2000
- 2000-07-13 JP JP2000213421A patent/JP3386781B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008139839A1 (en) | 2007-05-09 | 2008-11-20 | Kyushu University, National University Corporation | Carbon nanotube solubilizer |
| JP2011001462A (en) * | 2009-06-18 | 2011-01-06 | Ricoh Co Ltd | Novel hole transporting multibranched copolymer, and method for producing the same |
| CN102695557A (en) * | 2009-11-25 | 2012-09-26 | 日产化学工业株式会社 | Carbon nano-tube dispersant |
| CN102695557B (en) * | 2009-11-25 | 2015-10-21 | 日产化学工业株式会社 | Carbon nano-tube dispersant |
| EP2423241A1 (en) * | 2010-07-24 | 2012-02-29 | Blücher GmbH | Unit with porous organic polymers and use of same |
| JP2012126813A (en) * | 2010-12-15 | 2012-07-05 | Tosoh Corp | New arylamine dendrimer-like compound, and method for producing the same and application of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3386781B2 (en) | 2003-03-17 |
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