JP2002069161A - Tpd polymer ring-condensed with silicon - Google Patents
Tpd polymer ring-condensed with siliconInfo
- Publication number
- JP2002069161A JP2002069161A JP2000258886A JP2000258886A JP2002069161A JP 2002069161 A JP2002069161 A JP 2002069161A JP 2000258886 A JP2000258886 A JP 2000258886A JP 2000258886 A JP2000258886 A JP 2000258886A JP 2002069161 A JP2002069161 A JP 2002069161A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polymer
- independently represent
- compound
- phenazacillin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ケイ素で縮環され
たＴＰＤ（Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−（３−メ
チルフェニル）−１，１’−ビフェニル−４，４’−ジ
アミン）誘導体を主鎖に持つポリマー、即ち、５，１０
−ジヒドロ−５Ｈ−フェナザシリン（以下フェナザシリ
ン）化合物を主鎖骨格とする重合体（フェナザシリン系
重合体）及びその製造方法、その原料となるフェナザシ
リン化合物、さらにその重合体の用途に関するものであ
る。この重合体は、耐熱性を持つとともに、有機薄膜発
光素子の正孔輸送特性を保有する素材として利用でき
る。TECHNICAL FIELD The present invention relates to a TPD (N, N'-diphenyl-N, N '-(3-methylphenyl) -1,1'-biphenyl-4,4'-cycle fused with silicon. Polymer having a diamine) derivative in the main chain, ie, 5,10
TECHNICAL FIELD The present invention relates to a polymer having a main chain skeleton of -dihydro-5H-phenazacillin (hereinafter referred to as phenazacillin) compound (phenazacillin-based polymer), a method for producing the same, a phenazacillin compound as a raw material thereof, and a use of the polymer. This polymer has heat resistance and can be used as a material having the hole transport property of the organic thin film light emitting device.
【０００２】[0002]
【従来の技術】アプライド・フィジックス・レター第５
７巻第６号第５３１ページによると、下式に示すＴＰＤ
について、発光素子の正孔輸送材料として好適に用いら
れることが記載されている。2. Description of the Related Art Applied Physics Letter No. 5
According to Volume 7, Issue 6, page 531, the TPD
Is described as being suitably used as a hole transport material of a light emitting element.
【化３】 一方、ケイ素で縮環されたジフェニルアミン誘導体であ
るフェナザシリンの低分子化合物について、特開平８−
３０２３３９号公報、特開平１０−２１８８８４号公報
で、発光素子の正孔輸送材料として好適に用いられるこ
とが記載されている。また、高いガラス転移温度Ｔｇを
持つことから、発光素子の構成材料として用いた際に、
通常の低分子化合物が時間の経過とともに結晶化し、界
面が凸凹になることから電気短絡を起こすという欠点が
あるのに対し、フェナザシリン化合物は経時変化と共に
結晶化の進行の少ないことが特徴となっていた。一方、
ポリアニリンを初めとする芳香族アミン型ポリマーは、
高い電気活性を示すが、一般の有機溶媒への溶解性が低
いため、膜形成がしにくく、素子化が難しいという問題
を有する。さらに、低分子化合物を発光素子を始めとす
る電子素子の構成材料として用いる場合、真空蒸着装置
等の高価な機器を用いなければならず、簡便な手段によ
って利用できることが求められている。Embedded image On the other hand, a low molecular weight compound of phenazacillin, which is a diphenylamine derivative fused with silicon, is disclosed in
JP-A-302339 and JP-A-10-218884 describe that they are preferably used as a hole transport material of a light emitting element. Further, since it has a high glass transition temperature Tg, when used as a constituent material of a light emitting element,
While ordinary low molecular weight compounds have the disadvantage of crystallizing with the passage of time and causing an electrical short circuit because the interface becomes uneven, phenazacillin compounds are characterized by little progress of crystallization with aging. Was. on the other hand,
Aromatic amine type polymers such as polyaniline,
Although it shows high electrical activity, it has a problem that it is difficult to form a film and it is difficult to make an element due to its low solubility in general organic solvents. Further, when a low-molecular compound is used as a constituent material of an electronic element such as a light-emitting element, expensive equipment such as a vacuum evaporation apparatus must be used, and it is required that the compound can be used by simple means.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、発光素子や
エレクトロクロミック素子用材料として有用な製膜性の
よい重合体、その製造方法及びそのモノマー化合物を提
供することをその課題とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer having good film-forming properties useful as a material for a light-emitting device or an electrochromic device, a method for producing the same, and a monomer compound thereof.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、下記一般式（１）で
表される５，１０−ジヒドロ−５Ｈ−フェナザシリン化
合物を主鎖骨格とする重合体が提供される。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, there is provided a polymer having a main chain skeleton of a 5,10-dihydro-5H-phenazasiline compound represented by the following general formula (1).
【０００５】[0005]
【化４】 （式中、Ｒ１、Ｒ２はそれぞれ独立にアルキル基、アリ
ール基、アルコキシ基またはアリーロキシ基を示し、Ｒ
３〜Ｒ７はそれぞれ独立にアルキル基、アリール基、ア
ルコキシ基、アリーロキシ基または水素原子を示し、ｎ
は数平均重合度で３〜３００００の数字を示す） この重合体は、下記式（ １'）と書きかえる事が可能で
あり、ケイ素で縮環されたＴＰＤ誘導体のポリマーであ
ると言える。Embedded image (Wherein R 1 and R 2 each independently represent an alkyl group, an aryl group, an alkoxy group or an aryloxy group;
3 to R 7 each independently represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydrogen atom;
Represents a number of 3 to 30,000 in terms of the number average degree of polymerization.) This polymer can be rewritten as the following formula (1 ′), and can be said to be a polymer of a TPD derivative fused with silicon.
【化５】 また、本発明によれば、下記一般式（２）で表されるる
フェナザシリン化合物をニッケル錯体を用いて脱ハロゲ
ン化重縮合反応を行うことによって重合することを特徴
とする前記一般式（１）の重合体の製造方法が提供され
る。Embedded image Further, according to the present invention, a phenazacillin compound represented by the following general formula (2) is polymerized by performing a dehalogenation polycondensation reaction using a nickel complex. A method for producing a polymer is provided.
【化６】 （式中、Ｒ１、Ｒ２はそれぞれ独立にアルキル基、アリ
ール基、アルコキシ基またはアリーロキシ基を示し、Ｒ
３〜Ｒ７はそれぞれ独立にアルキル基、アリール基、ア
ルコキシ基、アリーロキシ基または水素原子を示し、Ｘ
１、Ｘ２はそれぞれ独立にハロゲン原子を示す） さらに、本発明によれば、前記一般式（２）で表される
５，１０−ジヒドロ−５Ｈ−フェナザシリン化合物が提
供される。さらにまた、本発明によれば、前記重合体を
構成要素に用いた有機薄膜エレクトロクロミック素子が
提供される。さらにまた、本発明によれば、前記重合体
を構成要素に用いた有機薄膜発光素子が提供される。Embedded image (Wherein R 1 and R 2 each independently represent an alkyl group, an aryl group, an alkoxy group or an aryloxy group;
3 to R 7 each independently represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydrogen atom;
1 and X 2 each independently represent a halogen atom.) Further, according to the present invention, there is provided a 5,10-dihydro-5H-phenazasiline compound represented by the general formula (2). Furthermore, according to the present invention, there is provided an organic thin-film electrochromic device using the polymer as a constituent element. Further, according to the present invention, there is provided an organic thin-film light emitting device using the polymer as a constituent element.
【０００６】[0006]
【発明の実施の形態】前記一般式（１）、（ １'）、
（２）において、Ｒ１〜Ｒ７で表されるアルキル基とし
ては、メチル、エチル、ｎ−またはｉｓｏ−プロピル、
ｎ−、ｉｓｏ−またはｔｅｒｔ−ブチル、ｎ−、ｉｓｏ
−またはｎｅｏ−ペンチル、ｎ−ヘキシル、シクロヘキ
シル、ｎ−ヘプチル、ｎ−オクチル等の直鎖、分岐、環
状の炭素数１〜２０、好ましくは１〜１０のアルキル基
が挙げられる。アルコキシ基としては、メトキシ、エト
キシ、ｎ−またはｉｓｏ−プロポキシ、ｎ−、ｉｓｏ−
またはｔｅｒｔ−ブトキシ、ｎ−、ｉｓｏ−またはｎｅ
ｏ−ペントキシ、ｎ−ヘキソキシ、シクロヘキシソキ
シ、ｎ−ヘプトキシ、ｎ−オクトキシ等の直鎖、分岐、
環状の炭素数１〜２０、好ましくは１〜１０のアルコキ
シ基があげられる。アリール基としては、フェニル基、
ｏ−、ｍ−、ｐ−トリル基、１−および２−ナフチル
基、アントリル基等の炭素数６〜２０、好ましくは６〜
１４のアリール基が挙げられる。アリーロキシ基として
は、フェノキシ基、ｏ−、ｍ−、ｐ−トリロキシ基、１
−および２−ナフトキシ基、アントロキシ基等の炭素数
６〜２０、好ましくは６〜１４のアリーロキシ基が挙げ
られる。BEST MODE FOR CARRYING OUT THE INVENTION The general formulas (1), (1 ′),
In (2), the alkyl group represented by R 1 to R 7 includes methyl, ethyl, n- or iso-propyl,
n-, iso- or tert-butyl, n-, iso
-Or neo-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl and the like, and linear, branched and cyclic alkyl groups having 1 to 20, preferably 1 to 10 carbon atoms. Examples of the alkoxy group include methoxy, ethoxy, n- or iso-propoxy, n-, iso-
Or tert-butoxy, n-, iso- or ne
linear, branched, such as o-pentoxy, n-hexoxy, cyclohexoxy, n-heptoxy, n-octoxy,
A cyclic C1-C20, preferably C1-C10 alkoxy group is mentioned. As the aryl group, a phenyl group,
o-, m-, p-tolyl group, 1- and 2-naphthyl group, anthryl group, etc., having 6 to 20 carbon atoms, preferably 6 to 20 carbon atoms.
14 aryl groups. The aryloxy group includes a phenoxy group, an o-, m-, p-tolyloxy group,
Examples thereof include aryloxy groups having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms, such as-and 2-naphthoxy groups and anthroxy groups.
【０００７】前記一般式（２）において、Ｘ１、Ｘ２で
表されるハロゲン原子としては、塩素原子、臭素原子、
ヨウ素原子が挙げられ、特に臭素原子が好ましい。In the general formula (2), the halogen atoms represented by X 1 and X 2 include a chlorine atom, a bromine atom,
An iodine atom is mentioned, and a bromine atom is particularly preferable.
【０００８】前記一般式（１）で表される重合体は、前
記一般式（２）のハロゲン化されたフェナザシリン化合
物を溶媒に溶かし、このモノマーに対し１〜２０当量の
ニッケル錯体を用いて脱ハロゲン化カップリング反応下
に重合を行うことによって製造することができる。この
場合の反応は下記式（３）で表される。The polymer represented by the general formula (1) is prepared by dissolving the halogenated phenazacillin compound of the general formula (2) in a solvent, and removing the monomer by using 1 to 20 equivalents of a nickel complex with respect to the monomer. It can be produced by performing polymerization under a halogenated coupling reaction. The reaction in this case is represented by the following formula (3).
【０００９】[0009]
【化７】 前記式中、Ｒ１、Ｒ２はそれぞれ独立にアルキル基、ア
リール基、アルコキシ基またはアリーロキシ基を示し、
Ｒ３〜Ｒ７はそれぞれ独立にアルキル基、アリール基、
アルコキシ基、アリーロキシ基または水素原子を示し、
ｎは数平均重合度で３〜３００００の数字を示し、
Ｘ１、Ｘ２はそれぞれ独立にはハロゲン原子を示す。Embedded image In the above formula, R 1 and R 2 each independently represent an alkyl group, an aryl group, an alkoxy group or an aryloxy group;
R 3 to R 7 each independently represent an alkyl group, an aryl group,
Represents an alkoxy group, an aryloxy group or a hydrogen atom,
n shows a number of 3 to 30,000 in the number average degree of polymerization,
X 1 and X 2 each independently represent a halogen atom.
【００１０】ニッケル錯体を用いる脱ハロゲン化重縮合
においては、この種の反応において通常用いられる種々
の溶媒を用いることができる。これを例示すれば、Ｎ，
Ｎ−ジメチルホルムアミド、トルエン、ベンゼン、テト
ラヒドロフラン等である。In the dehalogenation polycondensation using a nickel complex, various solvents commonly used in this type of reaction can be used. To illustrate this, N,
N-dimethylformamide, toluene, benzene, tetrahydrofuran and the like.
【００１１】前記ニッケル錯体としては、従来公知のも
の、例えば、テトラカルボニルニッケル（０）、ジカル
ボニルビス（トリフェニルホスフィン）ニッケル
（０）、ビス（１，５−シクロオクタジエン）ニッケル
（０）、テトラキス（トリフェニルホスフィン）ニッケ
ル（０）、（η２−エチレン）ビス（トリフェニルホス
フィン）ニッケル（０）、テトラキス（イソシアン化ｔ
−ブチル）ニッケル（０）、［（１，２，５，６，８，
１０−η）−ｔｒａｎｓ，ｔｒａｎｓ，ｔｒａｎｓ−
１，５，９−シクロドデカトリエン］ニッケル（０）、
等を例示することができる。ニッケル錯体は、前記
（２）の化合物一当量あたり、０．１〜２０当量、好ま
しくは１〜５当量の割合で用いられる。As the nickel complex, conventionally known ones, for example, tetracarbonylnickel (0), dicarbonylbis (triphenylphosphine) nickel (0), bis (1,5-cyclooctadiene) nickel (0) , tetrakis (triphenylphosphine) nickel (0), (eta 2 - ethylene) bis (triphenylphosphine) nickel (0), tetrakis (isocyanate of t
-Butyl) nickel (0), [(1,2,5,6,8,
10-η) -trans, trans, trans-
1,5,9-cyclododecatriene] nickel (0),
And the like. The nickel complex is used in an amount of 0.1 to 20 equivalents, preferably 1 to 5 equivalents, per equivalent of the compound (2).
【００１２】また、ニッケル錯体には、支持配位子とし
て０．１〜１０当量の２，２’−ビピリジルやトリフェ
ニルホスフィン等の配位子を加えてもよい。その例を挙
げれば、ビス（１，５−シクロオクタジエン）ニッケル
（０）に２，２’−ビピリジルを１当量加えて用いる、
ビス（１，５−シクロオクタジエン）ニッケル（０）に
トリフェニルホスフィンを２当量加えて用いる等であ
る。The nickel complex may contain 0.1 to 10 equivalents of a ligand such as 2,2'-bipyridyl or triphenylphosphine as a supporting ligand. For example, bis (1,5-cyclooctadiene) nickel (0) is used after adding one equivalent of 2,2′-bipyridyl.
For example, bis (1,5-cyclooctadiene) nickel (0) is used after adding 2 equivalents of triphenylphosphine.
【００１３】脱ハロゲン化重縮合反応は、溶媒の融点〜
溶媒の沸点まで種々の温度で実施できるが、特に０℃〜
１００℃程度が望ましい。反応後は、生成物は、再沈等
によって精製できる。本発明のフェナザシリン系重合体
の平均重合度は３〜３００００、好ましくは５〜１００
００である。The dehalogenation polycondensation reaction is carried out at a temperature between the melting point of the solvent and
It can be carried out at various temperatures up to the boiling point of the solvent, especially
About 100 ° C. is desirable. After the reaction, the product can be purified by reprecipitation or the like. The average degree of polymerization of the phenazacillin-based polymer of the present invention is 3 to 30,000, preferably 5 to 100.
00.
【００１４】前記の方法によって得られる重合体は、ス
ピンコートなどの簡便な成形加工手法で薄膜化が出来る
ような素材を提供することができる。それにより、本発
明の重合体を用いた有機薄膜エレクトロクロミック素子
とすることができる。また、本発明の重合体を正孔輸送
層に用いることにより、有機薄膜発光素子とすることが
できる。The polymer obtained by the above method can provide a material that can be formed into a thin film by a simple molding method such as spin coating. Thereby, an organic thin film electrochromic device using the polymer of the present invention can be obtained. Further, by using the polymer of the present invention for the hole transport layer, an organic thin film light emitting device can be obtained.
【００１５】[0015]
【実施例】以下に本発明を実施例により具体的に説明す
るが、本発明はこれらの実施例のみに限定されるもので
はない。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to only these examples.
【００１６】実施例１ 〔２，８−ジブロモ−１０，１０−ジ−ｎ−オクチル−
５−（２，３，４，５，６−ペンタメチルフェニル）−
５，１０−ジヒドロフェナザシリン（一般式２，Ｒ１＝
Ｒ２＝ｎ−オクチル，Ｒ３〜Ｒ７＝メチル，Ｘ１＝Ｘ２
＝Ｂｒ）の合成〕０．５２ｇのトリ（ｔ−ブチルホスフ
ィン）と５．０ｇのペンタメチルヨードベンゼンと２．
７０ｇのジフェニルアミンを６０ｍＬのトルエンに溶か
し、さらに４．６１ｇのナトリウムｔ−ブトキシドと
０．４６ｇのビス（ジベンジリデンアセトン）パラジウ
ム（０）を加えて、１００℃で２４時間撹拌した。反応
液に水を加えて反応を止めて抽出した後、シリカゲルの
カラムで精製することによって２．４０ｇの２，３，
４，５，６−ペンタメチルトリフェニルアミンを得た。
次に、２．１８ｇの２，３，４，５，６−ペンタメチル
トリフェニルアミンを８０ｍＬの四塩化炭素に溶かした
後１．６ｍＬの臭素を加え、２時間撹拌した。さらに、
溶媒を留去した後にシリカゲルのカラムで精製すること
によって３．７１ｇのビス（２，４−ジブロモフェニ
ル）（２，３，４，５，６−ペンタメチルフェニルアミ
ン）を得た。続いて、氷浴中で３１６ｍｇ（０．５ｍｍ
ｏｌ）ビス（２，４−ジブロモフェニル）（２，３，
４，５，６−ペンタメチルフェニルアミン）を５ｍＬの
エーテルに懸濁させた後に０．７ｍＬのｎ−ブチルリチ
ウムのヘキサン溶液（１．６Ｍ）を加えた。懸濁液が均
一になったところでさらにジ−ｎ−オクチルジクロロシ
ランを０．１７ｇ（０．５ｍｍｏｌ）加えた。沈殿が生
成した後に氷浴を外して１２時間かくはんした。反応液
を水を加えてエーテルで抽出した後にシリカゲルのカラ
ムで精製することにより０．２９ｇ（０．４０ｍｍｏ
ｌ）の２，８−ジブロモ−１０，１０−ジ−ｎ−オクチ
ル−５−（２，３，４，５，６−ペンタメチルフェニ
ル）−５，１０−ジヒドロフェナザシリンを単離した。
得られた化合物は文献未記載の新規化合物であった。Example 1 [2,8-Dibromo-10,10-di-n-octyl-
5- (2,3,4,5,6-pentamethylphenyl)-
5,10-dihydrophenazacillin (general formula 2, R 1 =
R 2 = n-octyl, R 3 to R 7 = methyl, X 1 = X 2
= Br)] 0.52 g of tri (t-butylphosphine), 5.0 g of pentamethyliodobenzene and 2.
70 g of diphenylamine was dissolved in 60 mL of toluene, and 4.61 g of sodium t-butoxide and 0.46 g of bis (dibenzylideneacetone) palladium (0) were added, followed by stirring at 100 ° C. for 24 hours. Water was added to the reaction solution to stop the reaction, followed by extraction, followed by purification on a silica gel column to give 2.40 g of 2,3.
4,5,6-pentamethyltriphenylamine was obtained.
Next, after dissolving 2.18 g of 2,3,4,5,6-pentamethyltriphenylamine in 80 mL of carbon tetrachloride, 1.6 mL of bromine was added, and the mixture was stirred for 2 hours. further,
After evaporating the solvent, the residue was purified by a silica gel column to obtain 3.71 g of bis (2,4-dibromophenyl) (2,3,4,5,6-pentamethylphenylamine). Subsequently, 316 mg (0.5 mm
ol) bis (2,4-dibromophenyl) (2,3
After suspending 4,5,6-pentamethylphenylamine) in 5 mL of ether, 0.7 mL of a hexane solution of n-butyllithium (1.6 M) was added. When the suspension became homogeneous, 0.17 g (0.5 mmol) of di-n-octyldichlorosilane was further added. After the precipitate had formed, the ice bath was removed and the mixture was stirred for 12 hours. The reaction solution was added with water, extracted with ether, and purified by a silica gel column to give 0.29 g (0.40 mmol).
1) 2,8-Dibromo-10,10-di-n-octyl-5- (2,3,4,5,6-pentamethylphenyl) -5,10-dihydrophenazacillin was isolated.
The obtained compound was a novel compound not described in the literature.
【００１７】そのＮＭＲスペクトルデータについては以
下の通りである。１ Ｈ−ＮＭＲ（ＣＤＣｌ３）：δ７．５８（ｄ，２
Ｈ），７．１６（ｄｄ，２Ｈ），６．０５（ｄ，２
Ｈ），２．３５（ｓ，６Ｈ），２．２９（ｓ，３Ｈ），
１．８３（ｓ，６Ｈ），０．７−１．５（ｍ，３４Ｈ）１３ Ｃ−ＮＭＲ（ＣＤＣｌ３）：δ１４６．９１，１３
７．３１，１３６．３７，１３５．２１，１３４．７
９，１３３．２１，１３２．４１，１１８．９９，１１
７．７８，１１２．５４，３３．１１，３１．８５，２
９．１７，２９．０６，２３．９１，２２．６５，１
６．９６，１６．８２，１５．４３，１４．４４，１
４．１０２９ Ｓｉ−ＮＭＲ（ＣＤＣｌ３）：δ−２０．７２The NMR spectrum data is as follows. 1 H-NMR (CDCl 3 ): δ7.58 (d, 2
H), 7.16 (dd, 2H), 6.05 (d, 2
H), 2.35 (s, 6H), 2.29 (s, 3H),
1.83 (s, 6H), 0.7-1.5 (m, 34H) 13 C-NMR (CDCl 3 ): δ146.91, 13
7.31, 136.37, 135.21, 134.7
9, 133.21, 132.41, 118.99, 11
7.78, 112.54, 33.11, 31.85, 2
9.17,29.06,23.91,22.65,1
6.96, 16.82, 15.43, 14.44, 1
4.10 29 Si-NMR (CDCl 3 ): δ-20.72
【００１８】実施例２ 〔脱ハロゲン化カップリング反応によるポリ（１０，１
０−ジ−ｎ−オクチル−５−（２，３，４，５，６−ペ
ンタメチルフェニル）−５，１０−ジヒドロフェナザシ
リン−２，８−ジイル）（一般式１，Ｒ１＝Ｒ２＝ｎ−
オクチル，Ｒ３〜Ｒ７＝メチル）の合成〕 窒素雰囲気下でビス（１，５−シクロオクタジエン）ニ
ッケル（０）０．２６ｇ（０．９４ｍｍｏｌ）に１，５
−シクロオクタジエン１ｍＬを加えた後にトルエンを
７．５ｍＬ加えて懸濁させた。更に２，２’−ビピリジ
ル０．１５ｇ（０．９６ｍｍｏｌ）を加えてかくはんし
た。更に５５６ｍｇ（０．７６ｍｍｏｌ）の２，８−ジ
ブロモ−１０，１０−ジ−ｎ−オクチル−５−（２，
３，４，５，６−ペンタメチルフェニル）−５，１０−
ジヒドロフェナザシリンを加えた後に６０℃に昇温して
７４時間かくはんした。反応液をメタノールに注ぎ、得
られた粉末をろ過した。この粉末を水、メタノールの順
で洗浄した後にジクロロメタンに溶かしてメタノールで
再沈殿することにより、３８３ｍｇ（モノマー単位とし
て０．６８ｍｍｏｌ）のポリマーを単離した。得られた
ポリマーはＴＨＦ、クロロホルム等の一般の有機溶媒に
可溶であった。得られたポリマーは文献未記載の新規化
合物であり、数平均分子量は５７００、重量平均分子量
は１３４００であった。Example 2 [Poly (10,1) by dehalogenation coupling reaction
0-di-n-octyl-5- (2,3,4,5,6-pentamethylphenyl) -5,10-dihydrophenazacillin-2,8-diyl (general formula 1, R 1 = R 2 = n-
Synthesis of octyl, R 3 to R 7 = methyl) bis (1,5-cyclooctadiene) nickel (0) was added to 0.26 g (0.94 mmol) of 1,5 under a nitrogen atmosphere.
-After adding 1 mL of cyclooctadiene, 7.5 mL of toluene was added and suspended. Further, 0.15 g (0.96 mmol) of 2,2'-bipyridyl was added and stirred. Further, 556 mg (0.76 mmol) of 2,8-dibromo-10,10-di-n-octyl-5- (2,
3,4,5,6-pentamethylphenyl) -5,10-
After adding dihydrophenazacillin, the mixture was heated to 60 ° C. and stirred for 74 hours. The reaction solution was poured into methanol, and the obtained powder was filtered. The powder was washed with water and methanol in that order, dissolved in dichloromethane, and reprecipitated with methanol to isolate 383 mg (0.68 mmol as a monomer unit) of a polymer. The obtained polymer was soluble in common organic solvents such as THF and chloroform. The obtained polymer was a novel compound not described in any literature, and had a number average molecular weight of 5,700 and a weight average molecular weight of 13,400.
【００１９】そのＮＭＲスペクトルデータについては以
下の通りである。１ Ｈ−ＮＭＲ（ＣＤＣｌ３）：δ７．７５（ｄ，２
Ｈ），７．３６（ｄｄ，２Ｈ），６．２３（ｄ，２
Ｈ），２．３６（ｓ，３Ｈ），２．３０（ｓ，６Ｈ），
１．９１（ｓ，６Ｈ），０．７−１．５（３４Ｈ）１３ Ｃ−ＮＭＲ（ＣＤＣｌ３）：δ１３４．６３，１３
４．４２，１３２．９７，１３２．０３，１２８．２
１，１１５．８８，３３．７２，３１．８６，２９．７
２，２９．２０，２４．２４，２２．６３，１６．８
８，１５．８１，１４．６８，１４．０７２９ Ｓｉ−ＮＭＲ（ＣＤＣｌ３）：δ−２１．７７The NMR spectrum data is as follows. 1 H-NMR (CDCl 3 ): δ 7.75 (d, 2
H), 7.36 (dd, 2H), 6.23 (d, 2
H), 2.36 (s, 3H), 2.30 (s, 6H),
1.91 (s, 6H), 0.7-1.5 (34H) 13 C-NMR (CDCl 3 ): δ 134.63, 13
4.42, 132.97, 132.03, 128.2
1,115.88,33.72,31.86,29.7
2,29.20,24.24,22.63,16.8
8, 15.81, 14.68, 14.07 29 Si-NMR (CDCl 3 ): δ-21.77
【００２０】実施例３ （ポリマーを用いたエレクトロクロミック素子）ポリマ
ーのエレクトロクロミック特性の評価は以下のように行
った。ポリマー１ｍｇを２００μｌのジクロロエタンに
溶かし、電極表面にそのポリマー溶液をキャストし、こ
れを作用極とした。これを対極（白金板）、参照極と共
に石英セル内に配置し、支持電解質として過塩素酸テト
ラブチルアンモニウム、溶媒として脱水アセトニトリル
を用い、電位変化におけるポリマーの色調変化を観察し
た。Example 3 (Electrochromic device using polymer) The evaluation of the electrochromic properties of the polymer was performed as follows. 1 mg of the polymer was dissolved in 200 μl of dichloroethane, and the polymer solution was cast on the electrode surface, and this was used as a working electrode. This was placed in a quartz cell together with a counter electrode (platinum plate) and a reference electrode. Using tetrabutylammonium perchlorate as a supporting electrolyte and dehydrated acetonitrile as a solvent, changes in the color tone of the polymer due to potential changes were observed.
【００２１】ポリ（１０，１０−ジ−ｎ−オクチル−５
−（２，３，４，５，６−ペンタメチルフェニル）−
５，１０−ジヒドロフェナザシリン−２，８−ジイル）
（一般式１，Ｒ１＝Ｒ２＝ｎ−オクチル，Ｒ３〜Ｒ７＝
メチル）を作用極に用いた場合、中性ではポリマーの色
は無色であったがキャストフィルムに引加する電位を高
くすることにより無色から橙色、青黒色と変化した。Poly (10,10-di-n-octyl-5)
-(2,3,4,5,6-pentamethylphenyl)-
5,10-dihydrophenazacillin-2,8-diyl)
(General formula 1, R 1 = R 2 = n-octyl, R 3 to R 7 =
When methyl) was used for the working electrode, the color of the polymer was neutral at neutral, but changed from colorless to orange and blue-black by increasing the potential applied to the cast film.
【００２２】実施例４ （ポリマーを用いた有機発光素子）図１はエレクトロル
ミネッセンス素子（発光素子）の概略断面図を示したも
のである。透明絶縁性の基板１として、厚さ１．１ｍｍ
のガラス板を用い、この上に１２０ｎｍのＩＴＯをスパ
ッタリング法で被膜して陽極２とした。この透明導電性
基板を使用前に水洗、オゾン洗浄、プラズマ洗浄により
十分に洗浄した。正孔輸送層３として、ポリマーを有機
溶媒（１，２−ジクロロエタン、トルエンなど）に溶解
し、陽極２にスピンコート法により４０ｎｍの厚さで成
膜した。Example 4 (Organic Light Emitting Device Using Polymer) FIG. 1 is a schematic sectional view of an electroluminescent device (light emitting device). 1.1 mm thick transparent insulating substrate 1
The above glass plate was used, and 120 nm of ITO was coated thereon by a sputtering method to form an anode 2. Before use, the transparent conductive substrate was sufficiently washed with water, ozone, and plasma. As the hole transport layer 3, a polymer was dissolved in an organic solvent (1,2-dichloroethane, toluene, or the like), and a film having a thickness of 40 nm was formed on the anode 2 by spin coating.
【００２３】次に、有機発光層４としてトリス（８−キ
ノリノール）アルミニウムを６０ｎｍ蒸着し、その上面
に陰極５としてＭｇとＡｇを蒸着速度比１０：１で１５
０ｎｍ蒸着した。最後に、封止層６としてＧｅＯを１．
６μｍ蒸着後、ガラス板７を光硬化性樹脂８で接着し密
封した。なお、図中、９は電源、１０はリード線１１は
陰極端子を示す。Next, tris (8-quinolinol) aluminum is vapor-deposited to a thickness of 60 nm as the organic light-emitting layer 4, and Mg and Ag are deposited on the upper surface thereof as the cathode 5 at a vapor-deposition rate of 10: 1.
0 nm was deposited. Finally, GeO is used as the sealing layer 6.
After vapor deposition of 6 μm, the glass plate 7 was bonded and sealed with a photo-curable resin 8. In the drawing, reference numeral 9 denotes a power source, 10 denotes a lead wire, and 11 denotes a cathode terminal.
【００２４】ポリマーとして、ポリ（１０，１０−ジ−
ｎ−オクチル−５−（２，３，４，５，６−ペンタメチ
ルフェニル）−５，１０−ジヒドロフェナザシリン−
２，８−ジイル）（一般式１，Ｒ１＝Ｒ２＝ｎ−オクチ
ル，Ｒ３〜Ｒ７＝メチル）を用いた場合、この素子は５
Ｖ以上の直流電圧により緑色に発光し、１３Ｖにおける
輝度は２４８０ｃｄ／ｍ２、電流密度は２３７ｍＡ／ｃ
ｍ２であった。As the polymer, poly (10,10-di-
n-octyl-5- (2,3,4,5,6-pentamethylphenyl) -5,10-dihydrophenazacillin-
When 2,8-diyl) (general formula 1, R 1 = R 2 = n-octyl, R 3 to R 7 = methyl) is used,
Green light is emitted by a DC voltage of V or more, the luminance at 13 V is 2480 cd / m 2 , and the current density is 237 mA / c
It was m 2.
【００２５】[0025]
【発明の効果】本発明によれば、新規なフェナザシリン
化合物が提供され、さらに該化合物を高分子化すること
で、成形加工の面で非常に簡単な方法で薄膜化ができる
ような素材の提供が可能であり、さらに発光素子及びエ
レクトロクロミック素子の構成材料として有用な材料を
提供することができる。According to the present invention, a novel phenazacillin compound is provided, and a material which can be formed into a thin film by a very simple method in terms of molding by providing a polymer of the compound. And a material useful as a constituent material of a light-emitting element and an electrochromic element can be provided.
【図１】実施例６で示した発光素子の模式的断面図であ
る。FIG. 1 is a schematic cross-sectional view of a light emitting device shown in Example 6.
１ 基板 ２ 陽極 ３ 正孔注入輸送層 ４ 有機発光層 ５ 陰極 ６ 封止層 ７ ガラス板 ８ 接着性材料層 ９ 電源 １０ リード線 １１ 陰極端子 DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole injection / transport layer 4 Organic light emitting layer 5 Cathode 6 Sealing layer 7 Glass plate 8 Adhesive material layer 9 Power supply 10 Lead wire 11 Cathode terminal
───────────────────────────────────────────────────── フロントページの続き (72)発明者 沖田 晃一 東京都千代田区神田神保町１−３−５ 財 団法人化学技術戦略推進機構内 (72)発明者 林 輝幸 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 (72)発明者 田中 正人 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 Ｆターム(参考） 2K001 AA01 CA22 3K007 AB12 AB14 CA01 CB01 CB03 DB03 FA01 4J032 BA17 BB01 BC03 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Koichi Okita 1-3-5 Kanda Jimbocho, Chiyoda-ku, Tokyo Within the Chemical Technology Strategy Promotion Organization (72) Inventor Teruyuki Hayashi 1-1-1 Higashi, Tsukuba, Ibaraki Kogyo Kogyo (72) Inventor Masato Tanaka 1-1-1 Higashi, Tsukuba, Ibaraki Prefecture F-term (Reference) 2A001 BB01 BC03
Claims (5)
ジヒドロ−５Ｈ−フェナザシリン化合物を主鎖骨格とす
る重合体。 【化１】 （式中、Ｒ１、Ｒ２はそれぞれ独立にアルキル基、アリ
ール基、アルコキシ基またはアリーロキシ基を示し、Ｒ
３〜Ｒ７はそれぞれ独立にアルキル基、アリール基、ア
ルコキシ基、アリーロキシ基または水素原子を示し、ｎ
は数平均重合度で３〜３００００の数字を示す）1. The method according to claim 1, wherein the compound represented by the following general formula (1) is:
A polymer having a dihydro-5H-phenazacillin compound as a main chain skeleton. Embedded image (Wherein R 1 and R 2 each independently represent an alkyl group, an aryl group, an alkoxy group or an aryloxy group;
3 to R 7 each independently represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydrogen atom;
Represents a number of 3 to 30,000 in terms of a number average degree of polymerization)
ジヒドロ−５Ｈ−フェナザシリン化合物。 【化２】 （式中、Ｒ１、Ｒ２はそれぞれ独立にアルキル基、アリ
ール基、アルコキシ基またはアリーロキシ基を示し、Ｒ
３〜Ｒ７はそれぞれ独立にアルキル基、アリール基、ア
ルコキシ基、アリーロキシ基または水素原子を示し、Ｘ
１、Ｘ２はそれぞれ独立にはハロゲン原子を示す）2. The 5,10- compound represented by the following general formula (2):
Dihydro-5H-phenazacillin compound. Embedded image (Wherein R 1 and R 2 each independently represent an alkyl group, an aryl group, an alkoxy group or an aryloxy group;
3 to R 7 each independently represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydrogen atom;
1 and X 2 each independently represent a halogen atom)
５Ｈ−フェナザシリン化合物をニッケル錯体を用いて脱
ハロゲン化重縮合反応させて重合することを特徴とする
請求項１に記載の重合体の製造方法。3. The 5,10-dihydro- according to claim 2.
The method for producing a polymer according to claim 1, wherein the 5H-phenazacillin compound is polymerized by a dehalogenation polycondensation reaction using a nickel complex.
膜エレクトロクロミック素子。4. An organic thin-film electrochromic device using the polymer according to claim 1.
膜発光素子。5. An organic thin-film light emitting device using the polymer according to claim 1.
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| JP2009215334A (en) * | 2008-03-07 | 2009-09-24 | Nagoya City | Phenazacillin polymer having epoxy group in side chain |
| JP2009298921A (en) * | 2008-06-13 | 2009-12-24 | Nagoya City | Phenazasiline polymer and organic thin film transistor using the phenazasiline polymer |
| JP2009298730A (en) * | 2008-06-13 | 2009-12-24 | Nagoya City | Bisphenazasiline compound, process for preparing bisphenazasiline compound and organic thin-film transistor using bisphenazasiline compound |
| JP2011178711A (en) * | 2010-03-01 | 2011-09-15 | Nagoya City | Bis(vinylphenazasiline) compound-derived polymer, method for producing bis(vinylphenazasiline) compound-derived polymer and organic thin film transistor using the bis(vinylphenazasiline) compound-derived polymer |
| KR20190055872A (en) * | 2017-11-15 | 2019-05-24 | 삼성디스플레이 주식회사 | Compound including nitrogen and organic electroluminescence device including the same |
| KR102567881B1 (en) | 2017-11-15 | 2023-08-18 | 삼성디스플레이 주식회사 | Compound including nitrogen and organic electroluminescence device including the same |
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