JP4986004B2 - Polymerizable iridium complex, polymer thereof and production method thereof - Google Patents

Description

〔式中、Ａ、Ｂ、Ｃのうち少なくとも１つは重合性官能基を有する置換基を表し、Ａ、Ｂ、Ｃのうちの残りはそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。Ｒ₁〜Ｒ₁₅はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕
［２］記式（１）におけるＡ、Ｂ、Ｃのうちの少なくとも１つがアクリレート基またはメタクリレート基を有する置換基である［１］に記載の重合性化合物。
【００１３】
［３］前記式（１）におけるＡ、Ｂ、Ｃのうちの１つがアクリレート基またはメタクリレート基を有する置換基である［２］に記載の重合性化合物。
［４］式（２）で示される重合性化合物。
【化２３】

〔式中、Ｒ₁、Ｒ₂はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕
［５］式（２）のＲ₁、Ｒ₂が水素原子である［４］に記載の重合性化合物。
［６］式（３）で示される重合性化合物。
【化２４】

〔式中、Ｒ₁、Ｒ₂はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕
［７］式（３）のＲ₁、Ｒ₂が水素原子である［６］に記載の重合性化合物。
［８］前記式（１）におけるＡ、Ｂ、Ｃのうちの２つがアクリレート基またはメタクリレート基を有する置換基である［２］に記載の重合性化合物。
【００１４】
［９］式（４）で示される重合性化合物。
【化２５】

〔式中、Ｒ₁は水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕
［１０］式（４）のＲ₁が水素原子である［９］に記載の重合性化合物。
【００１５】
［１１］式（５）で示される重合性化合物。
【化２６】

〔式中、Ｒ₁は水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕
［１２］式（５）のＲ₁が水素原子である［１１］に記載の重合性化合物。
［１３］前記式（１）におけるＡ、Ｂ、Ｃのすべてがアクリレート基またはメタクリレート基を有する置換基である［２］に記載の重合性化合物。
【００１６】
［１４］式（６）で示される重合性化合物。
【化２７】

【００１７】
［１５］式（７）で示される重合性化合物。
【００１８】
【化２８】

【００１９】
［１６］式（１）で示される重合性化合物を重合して得られる重合体。
【化２９】

〔式中、Ａ、Ｂ、Ｃのうち少なくとも１つは重合性官能基を有する置換基を表し、Ａ、Ｂ、Ｃのうちの残りはそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。Ｒ₁〜Ｒ₁₅はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕
［１７］前記式（１）におけるＡ、Ｂ、Ｃのうちの少なくとも１つがアクリレート基またはメタクリレート基を有する置換基である［１６］に記載の重合体。
［１８］前記式（１）におけるＡ、Ｂ、Ｃのうちの１つがアクリレート基またはメタクリレート基を有する置換基である［１７］に記載の重合体。
【００２０】
［１９］式（２）で示される重合性化合物を重合して得られる重合体。
【化３０】

〔式中、Ｒ₁、Ｒ₂はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕
［２０］式（２）のＲ₁、Ｒ₂が水素原子である［１９］に記載の重合体。
【００２１】
［２１］式（３）で示される重合性化合物を重合して得られる重合体。
【化３１】

〔式中、Ｒ₁、Ｒ₂はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕
［２２］式（３）のＲ₁、Ｒ₂が水素原子である［２１］に記載の重合体。
［２３］前記式（１）におけるＡ、Ｂ、Ｃのうちの２つがアクリレート基またはメタクリレート基を有する置換基である［１７］に記載の重合体。
【００２２】
［２４］式（４）で示される重合性化合物を重合して得られる重合体。
【化３２】

〔式中、Ｒ₁は水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕
［２５］式（３）のＲ₁が水素原子である［２４］に記載の重合体。
【００２３】
［２６］式（５）で示される重合性化合物を重合して得られる重合体。
【化３３】

〔式中、Ｒ₁は水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕
［２７］式（３）のＲ₁が水素原子である［２６］に記載の重合体。
【００２４】
［２８］前記式（１）におけるＡ、Ｂ、Ｃのすべてがアクリレート基またはメタクリレート基を有する置換基である［１７］に記載の重合体。
【００２５】
［２９］式（６）で示される重合性化合物を重合して得られる重合体。
【化３４】

【００２６】
［３０］式（７）で示される重合性化合物を重合して得られる重合体。
【化３５】

［３１］式（１）〜式（７）のいずれかで示される重合性化合物に由来するモノマー単位を少なくとも１種含むことを特徴とする共重合体。
【００２７】
［３２］式（８）で示されるイリジウム二核錯体と式（９）で示されるフェニルピリジン誘導体を反応させた後、その反応生成物中の反応性置換基と、重合性官能基を有する化合物とを反応させることを特徴とする単核イリジウム錯体部分を含む重合性化合物の製造方法。
【化３６】

〔式中、ＸおよびＹは反応性置換基、あるいは水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表し、Ｒ₁〜Ｒ₂₀はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕
【化３７】

〔式中、Ｚは反応性置換基、あるいは水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表し、Ｒ₁〜Ｒ₅はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。但し、式（８）におけるＸ、Ｙおよび式（９）におけるＺのうち少なくとも１つは反応性置換基である。〕
【００２８】
［３３］式（８）におけるＸ、Ｙがそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基のいずれかであり、式（９）におけるＺが反応性置換基である［３２］に記載の単核イリジウム錯体部分を含む重合性化合物の製造方法。
［３４］式（９）におけるＺが水酸基である［３３］に記載の単核イリジウム錯体部分を含む重合性化合物の製造方法。
［３５］重合性官能基を有する化合物が酸ハロゲン化物である［３４］に記載の単核イリジウム錯体部分を含む重合性化合物の製造方法。
【００２９】
［３６］重合性官能基を有する化合物がイソシアネート化合物である［３４］に記載の単核イリジウム錯体部分を含む重合性化合物の製造方法。
［３７］式（８）におけるＸ、Ｙが反応性置換基であり、式（９）におけるＺが水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基、ヘテロ原子を有してもよい炭素数１〜２０の有機基のいずれかである［３１］に記載の単核イリジウム錯体部分を含む重合性化合物の製造方法。
［３８］式（９）におけるＺが水酸基である［３７］に記載の単核イリジウム錯体部分を含む重合性化合物の製造方法。
【００３０】
［３９］重合性官能基を有する化合物が酸ハロゲン化物である［３８］に記載の単核イリジウム錯体部分を含む重合性化合物の製造方法。
［４０］重合性官能基を有する化合物がイソシアネート化合物である［３７］に記載の単核イリジウム錯体部分を含む重合性化合物の製造方法。
【００３１】
［４１］式（１０）で示されるイリジウム錯体と重合性官能基を有する化合物を一定のモル比で反応させ、未反応の反応性置換基が残存している場合には更に得られた生成物中の反応性置換基と、非重合性化合物とを反応させることを特徴とするイリジウム錯体部分を含む重合性化合物の製造方法。
【化３８】

〔式中、Ｘは反応性置換基、Ｒ₁〜Ｒ₂₄はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕
［４２］式（１０）で示されるイリジウム錯体と重合性官能基を有する化合物のモル比が１：（０．５〜１．５）である［４１］に記載のイリジウム錯体部分を含む重合性化合物の製造方法。
【００３２】
［４３］式（１０）における反応性置換基が水酸基である［４１］または［４２］に記載のイリジウム錯体部分を含む重合性化合物の製造方法。
［４４］重合性官能基を有する化合物が酸ハロゲン化物である［４３］に記載のイリジウム錯体部分を含む重合性化合物の製造方法。
［４５］重合性官能基を有する化合物がイソシアネート化合物である［４３］に記載のイリジウム錯体部分を含む重合性化合物の製造方法。
【００３３】
［４６］式（１０）で示されるイリジウム錯体と重合性官能基を有する化合物のモル比が１：（１．５〜２．５）である［４１］に記載のイリジウム錯体部分を含む重合性化合物の製造方法。
［４７］式（１０）における反応性基が水酸基である［４５］または［４６］に記載のイリジウム錯体部分を含む重合性化合物の製造方法。
［４８］重合性官能基を有する化合物が酸ハロゲン化物である［４７］に記載のイリジウム錯体部分を含む重合性化合物の製造方法。
［４９］重合性官能基を有する化合物がイソシアネート化合物である［４７］に記載のイリジウム錯体部分を含む重合性化合物の製造方法。
【００３４】
［５０］式（１０）で示されるイリジウム錯体と重合性官能基を有する化合物のモル比が１：（２．５以上）である［４１］に記載のイリジウム錯体部分を含む重合性化合物の製造方法。
［５１］式（１０）における反応性基が水酸基である［４９］または［５０］に記載のイリジウム錯体部分を含む重合性化合物の製造方法。
［５２］重合性官能基を有する化合物が酸ハロゲン化物である［５１］に記載のイリジウム錯体部分を含む重合性化合物の製造方法。
［５３］重合性官能基を有する化合物がイソシアネート化合物である［５１］に記載のイリジウム錯体部分を含む重合性化合物の製造方法。
【００３５】
［５４］式（１１）で示される化合物。
【化３９】

〔式中、Ｘ、Ｙ、Ｚの少なくとも１つは水酸基を表し、のこりはそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。Ｒ₁〜Ｒ₁₅はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕
［５５］式（１１）におけるＸ、Ｙ、Ｚのうち１つが水酸基である［５４］に記載の化合物。
【００３６】
［５６］式（１２）で示される化合物。
【化４０】

［５７］式（１１）におけるＸ、Ｙ、Ｚのうち２つが水酸基である［５３］に記載の化合物。
【００３７】
［５８］式（１３）で示される化合物。
【化４１】

【００３８】
［５９］式（１１）におけるＸ、Ｙ、Ｚのすべてが水酸基である［５４］に記載の化合物。
［６０］式（１４）で示される化合物。
【化４２】

【００３９】
【発明の実施の形態】
以下、本発明を具体的に説明する。
本発明により式（１）
【化４３】

〔式中、Ａ、Ｂ、Ｃのうち少なくとも１つは重合性官能基を有する置換基を表し、Ａ、Ｂ、Ｃのうちの残りはそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。Ｒ₁〜Ｒ₁₅はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕で表される重合性化合物が提供される。
【００４０】
式（１）におけるＡ、Ｂ、Ｃのうちの重合性官能基を有する置換基としては、ビニル基、アクリレート基、メタクリレート基、メタクリロイルオキシエチルカルバメート基等のウレタン（メタ）アクリレート基、スチリル基及びその誘導体、ビニルアシド基及びその誘導体などを有する置換基を挙げることができる。これらの重合性官能基の中で、その重合性という観点から、アクリレート基、メタアクリレート基、ウレタン（メタ）アクリレート基が好ましい。また、これらの置換基が結合する位置は、フェニルピリジン配位子のフェニル基の２位、３位、４位、５位のいずれでもよい。
【００４１】
式（１）におけるＡ、Ｂ、Ｃのうちの重合性官能基を有しない置換基、及びＲ₁〜Ｒ₁₅としては水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸メチル等のスルホン酸エステル基、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ターシャリーブチル、アミル、ヘキシル等のアルキル基、またメトキシ、エトキシ、プロポキシ、イソブトキシ、ターシャリーブトキシ等のアルコキシ基、更にはアセトキシ基、プロポキシカルボニル基などのエステル基等の有機基を挙げることができる。また、これらの有機基は、更にハロゲン原子、ニトロ基、アミノ基等の置換基を有していてもよい。
【００４２】
次に、本発明による重合性化合物の合成方法の例を以下に挙げるが、本発明は何らこれらに限定されるものではない。
【００４３】
その第１の合成方法は、式（８）で示されるイリジウムの二核錯体と式（９）で示されるフェニルピリジン誘導体を反応させることにより反応性置換基を有する単核のイリジウム錯体を中間体として得、この中間体の反応性置換基と重合性置換基を有する化合物を反応させることにより単核イリジウム錯体部分を含む重合性化合物を得る方法である。
【００４４】
【化４４】

〔式中、ＸおよびＹは反応性置換基、水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表し、Ｒ₁〜Ｒ₂₀はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕
【化４５】

〔式中、Ｚは反応性置換基、水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表し、Ｒ₁〜Ｒ₅はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。但し、式（８）におけるＸ、Ｙおよび式（９）におけるＺのうち少なくとも１つは反応性置換基である。〕
【００４５】
式（８）のイリジウムの二核錯体は公知の方法（S. Lamansky et al., Inorganic Chemistry, 40, 1704 (2001)）により合成することができる。式（８）のＲ₁〜Ｒ₂₀としては水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸メチル等のスルホン酸エステル基、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ターシャリーブチル、アミル、ヘキシル等のアルキル基、またメトキシ、エトキシ、プロポキシ、イソブトキシ、ターシャリーブトキシ等のアルコキシ基、更にはアセトキシ基、プロポキシカルボニル基などのエステル基等の有機基を挙げることができる。また、これらの有機基は、更にハロゲン原子、ニトロ基、アミノ基等の置換基を有していてもよい。
【００４６】
式（８）のＸ、Ｙおよび式（９）のＺのうち少なくとも１つは反応性置換基であり、水酸基などを例示することができるが、何らこれに限定されるものではない。また、この反応性置換基は保護基で保護されていてもよい。この場合は保護基により保護されたままで反応を行って単核イリジウム錯体を得た後、脱保護により反応性置換基を有する単核イリジウム錯体を中間体として得る。その後、この中間体の反応性置換基と重合性官能基を有する化合物と反応させることにより、単核イリジウム錯体部分を含む重合性化合物を得る。
【００４７】
式（９）の化合物におけるＲ₁〜Ｒ₅としては水素原子、ハロゲン原子、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ターシャリーブチル、アミル、ヘキシル等のアルキル基、またメトキシ、エトキシ、プロポキシ、イソブトキシ、ターシャリーブトキシ等のアルコキシ基、更にはアセトキシ基、プロポキシカルボニル基などのエステル基等の有機基・を挙げることができる。また、これらの置換基は、更にハロゲン原子、ニトロ基、アミノ基等の置換基を有していてもよい。
【００４８】
上記中間体と反応させる重合性官能基を有する化合物における重合性官能基としては、ビニル基、アクリレート基、メタクリレート基、アクリロイルオキシ基、メタクリロイルオキシ基、メタクリロイルオキシエチルカルバメート基等のウレタン（メタ）アクリレート基、スチリル基及びその誘導体、ビニルアシド基及びその誘導体などエチレン性二重結合を有する基を挙げることができる。これらの重合性官能基の中で、その重合性という観点から、アクリレート基、メタアクリレート基、ウレタン（メタ）アクリレート基が好ましい。
【００４９】
上記第１の合成方法において、式（８）で示されるイリジウム二核錯体におけるＸ、Ｙが非反応性置換基であり、式（９）で示されるフェニルピリジン誘導体におけるＺが反応性置換基である場合には、これらの反応により１つの反応性置換基を有する単核イリジウム錯体が中間体として得られ、この中間体と重合性官能基を有する化合物を反応させることにより単核イリジウム錯体部分を含む単官能の重合性化合物が得られる。また、式（８）で示されるイリジウム二核錯体におけるＸ、Ｙが反応性置換基であり、式（９）で示されるフェニルピリジン誘導体におけるＺが非反応性置換基である場合には、これらの反応により２つの反応性置換基を有する単核イリジウム錯体が中間体として得られ、この中間体と重合性官能基を有する化合物を反応させることにより単核イリジウム錯体部分を含む２官能の重合性化合物が得られる。
【００５０】
本発明による重合性化合物の第２の合成方法は、式（１０）で示されるイリジウム錯体を中間体とし、この中間体と重合性官能基を有する化合物を一定のモル比で反応させることにより、重合性官能基を所定の数だけ有するイリジウム錯体部分を含む重合性化合物を得る方法である。
【化４６】

〔式中、Ｘは反応性置換基、Ｒ₁〜Ｒ₂₄はそれぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ基、スルホン酸基、スルホン酸エステル基またはヘテロ原子を有してもよい炭素数１〜２０の有機基を表す。〕
【００５１】
上記の式（１０）で表されるイリジウム錯体における反応性置換基Ｘとしては水酸基、アミノ基などを例示することができるが、何らこれに限定されるものではない。また、式（１０）のイリジウム錯体と反応を行う重合性官能基を有する化合物としては、重合性酸ハロゲン化物や重合性イソシアネートを例示することができるが、何らこれらに限定されるものではない。
【００５２】
次に、この第２の合成方法を重合性酸ハロゲン化物及び／又は重合性イソシアネートを使用する場合について詳述する。
【００５３】
すなわち、式（１０）のイリジウム錯体と重合性酸ハロゲン化物及び／又は重合性イソシアネートのモル比が１：１に近い場合、例えば１：（０．５〜１．５）の場合には主として単官能の重合性化合物が得られ、生成物を精製して単官能の重合性化合物を得る。またこのモル比が１：２に近い場合、例えば１：（１．５〜２．５）の場合には主として二官能の重合性化合物が得られ、生成物を精製して二官能の重合性化合物を得る。更にこのモル比が１：３に近い場合、例えば１：（２．５以上）の場合には主として三官能の重合性化合物が得られ、生成物を精製して三官能の重合性化合物を得る。但し、上記モル比が１：（３以上）の場合には、単官能または二官能のものを除くための精製は必ずしも要らない。尚、単官能と二官能の重合性化合物を合成する場合には、重合性酸ハロゲン化物を所定のモル比で反応させた後、生成物に残留する反応性置換基を非反応性にするための反応を行う。反応性置換基が水酸基の場合について、この目的で使用される非重合性化合物としては、アルキルハライド、カルボン酸、カルボン酸ハロゲン化物、スルホン酸ハロゲン化物、クロロホルメート、イソシアネート等を例示することができるが、何らこれらに限定されるものではない。
【００５４】
この第２の合成方法に用いられる重合性酸ハロゲン化物としてはアクリル酸クロライド、メタクリル酸クロライド等が挙げられ、また非重合性酸ハロゲン化物としてはプロピオン酸クロライド、酢酸クロライド等が挙げられる。重合性イソシアネートとしてはメタクリロイルイソシアネート、メタクリロイルオキシエチルイソシアネート等が挙げられ、また非重合性イソシアネートとしてはヘキシルイソシアネート、ベンジルイソシアネート等が挙げられる。
【００５５】
本発明による重合性化合物は２，２’−アゾビス（イソブチロニトリル）（ＡＩＢＮ）、ベンゾイルパーオキサイド等の熱重合開始剤やベンゾフェノン等の紫外線重合開始剤を用いることにより容易に重合を行うことができ、イリジウム錯体部分を含む重合体を提供することができる。重合体は、本発明による重合性化合物のうちの１種類によるホモ重合体、また本発明の重合性化合物のうちの２種類以上による共重合体、更には本発明の重合性化合物のうちの１種類以上と他の重合性化合物（特に限定はされないが、例示をすればメタクリレート等）の１種類以上との共重合体のいずれであってもよい。
【００５６】
また、本発明による重合性化合物の更に別の合成方法としては、イリジウム（ＩＩＩ）ビス（２−フェニルピリジナート）アセチルアセトナート錯体と前記（９）式で示される反応性置換基を有するフェニルピリジン誘導体を反応させた後、これに重合性置換基を導入することによりイリジウム錯体部分を含む単官能の重合性化合物を得る方法等が挙げられる。
【００５７】
本発明による重合体及び共重合体の重合度としては３〜５０００が好ましい。
【００５８】
【実施例】
以下に本発明について代表的な例を示し、更に具体的に説明する。尚、これらは説明のための単なる例示であって、本発明は何らこれらに限定されるものではない。
【００５９】
＜測定装置等＞
１）¹Ｈ−ＮＭＲ
日本電子（ＪＥＯＬ）製 ＪＮＭ ＥＸ２７０
２７０Ｍｚ 溶媒：重クロロホルムまたは重ジメチルスルホシキド
２）ＧＰＣ測定（分子量測定）
カラム：Ｓｈｏｄｅｘ ＫＦ−Ｇ＋ＫＦ８０４Ｌ＋ＫＦ８０２＋ＫＦ８０１
溶離液：テトラヒドロフラン（ＴＨＦ）
温度 ：４０℃
検出器：ＲＩ（Ｓｈｏｄｅｘ ＲＩ−７１）
３）元素分析装置
ＲＥＣ０社製 ＣＨＮＳ−９３２型
【００６０】
（実施例１）重合性化合物：Ｉｒ（ＭＡ−ＰＰｙ）（ＰＰｙ）₂の合成
常法に従い２−（３−メトキシフェニル）ピリジン（３−ＭｅＯ−ＰＰｙ）を合成した。即ち、スキーム（１Ａ）に示すように、常法によりアルゴン気流下において３−ブロモアニソール２２．４ｇ（１２０ｍｍｏｌ）から脱水テトラヒドロフラン（ＴＨＦ）中でマグネシウム（Ｍｇ）３．４ｇを用いて（３−メトキシフェニル）マグネシウムブロマイドを合成し、これを２−ブロモピリジン１５．８ｇ（１００ｍｍｏｌ）と（１，２−ビス（ジフェニルホスフィノ）エタン）ジクロロニッケル（ＩＩ）（Ｎｉ（ｄｐｐｅ）Ｃｌ₂） １．８ｇの脱水ＴＨＦ溶液に徐々に添加し５０℃で１時間攪拌した。反応液に５％塩酸水溶液２５０ｍｌを加えた後、クロロホルムで目的物を抽出し、有機層を減圧下に蒸留した。無色透明の液体として２−（３−メトキシフェニル）ピリジン（３−ＭｅＯ−ＰＰｙ）を１７．４ｇ（９３．９ｍｍｏｌ）得た。同定はＣＨＮ元素分析、¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 8.68(d, 1H), 7.72(m, 2H), 7.59(s, 1H), 7.54(d, 1H), 7.37(t, 1H), 7.22(d,1H), 6.97(d, 1H), 3.89(s, 3H). Anal. Found: C 77.44, H 6.01, N 7.53. Calcd: C 77.81, H 5.99, N 7.56.
【化４７】

【００６１】
次いでこの３−ＭｅＯ−ＰＰｙのメトキシ基を常法に従い加水分解した。即ち、スキーム（１Ｂ）に示すように、３−ＭｅＯ−ＰＰｙ １６．０ｇ（８６．４ｍｍｏｌ）を濃塩酸中に溶解させ密閉容器中１３０℃で４時間攪拌した。反応後、反応液を炭酸水素ナトリウム水溶液で中和し、目的物をクロロホルムで抽出し、抽出物をクロロホルム/ヘキサン溶液より結晶化させ、無色の結晶として２−（３−ヒドロキシフェニル）ピリジン（３−ＨＯ−ＰＰｙ）１０．４ｇ（６０．７ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 8.66(d, 1H), 7.76(t, 1H), 7.67(d, 1H), 7.56(s, 1H), 7.40(d, 1H), 7.30(t, 1H), 7.26(t,1H), 6.88(d, 1H), 2.08(br, 1H). Anal. Found: C 76.81, H 5.37, N 8.11. Calcd: C 77.17, H 5.30, N 8.18.
【化４８】

【００６２】
次いでこの３−ＨＯ−ＰＰｙの水酸基に常法に従いｔｅｒｔ−ブチルジメチルクロロシラン（ＴＢＤＭＳ−Ｃｌ）を作用させ、水酸基をｔｅｒｔ−ブチルジメチルシリル基で保護した。即ち、スキーム（１Ｃ）に示すように、３−ＨＯ−ＰＰｙ ８．６ｇ（５０．２ｍｍｏｌ）とイミダゾール１０．２ｇとｔｅｒｔ−ブチルジメチルクロロシラン１１．３ｇ（７５．０ｍｍｏｌ）を２００ｍｌのＮ，Ｎ−ジメチルホルムアミドに溶解し、室温で４時間反応させた。反応液をシリカゲルカラムにて精製し、無色透明の液体として２−（３−ｔｅｒｔ−ブチルジメチルシリルオキシフェニル）ピリジン（３−ＳｉＯ−ＰＰｙ） １３．０ｇ（４５．５ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 8.68(d, 1H), 7.74(t, 1H), 7.68(d, 1H), 7.58(d, 1H), 7.48(s, 1H), 7.32(t, 1H), 7.22(t, 1H), 6.89(d, 1H), 1.01(s, 9H), 0.24(s, 6H). Anal. Found: C 71.08, H 8.14, N 4.88. Calcd: C 71.53, H 8.12, N 4.91.
【化４９】

【００６３】
次いでこの３−ＳｉＯ−ＰＰｙを、常法に従い合成したビス（μ-クロロ）テトラキス（２−フェニルピリジン）ジイリジウム（ＩＩＩ）（［Ｉｒ（ｐｐｙ）₂Ｃｌ］₂）とトリフルオロメチルスルホン酸銀（Ｉ）（ＡｇＣＦ₃ＳＯ₃）の存在下に反応させた。即ち、スキーム（１Ｄ）に示すように、アルゴン気流下ＳｉＯ−ＰＰｙ ５．７１ｇ（２０．０ｍｍｏｌ）と［Ｉｒ（ｐｐｙ）₂Ｃｌ］₂ ５．３７ｇ（５．０ｍｍｏｌ）の脱水トルエン懸濁液にＡｇＣＦ₃ＳＯ₃を２．７０ｇ加え、６時間還流した。反応液をシリカゲルカラムで精製した後、溶媒を留去し、黄色粉末として（２−（３−ｔｅｒｔ−ブチルジメチルシリルオキシフェニル）ピリジン）ビス（２−フェニルピリジン）イリジウム（ＩＩＩ）（Ｉｒ（ＰＰｙ）₂（３−ＳｉＯ−ＰＰｙ））２．５３ｇ（３．２ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 7.86(d, 2H), 7.78(d, 1H), 7.64(d, 2H), 7.55(m, 6H), 7.16(s, 1H), 6.85(m,9H), 6.60(d, 1H), 6.45(d, 1H). Anal. Found: C 59.53, H 4.89, N 5.34. Calcd: C 59.67, H 4.88, N 5.35.
【化５０】

【００６４】
次いでこのＩｒ（ＰＰｙ）₂（３−ＳｉＯ−ＰＰｙ）のシリル基を常法に従い加水分解した。即ち、スキーム（１Ｅ）に示すように、Ｉｒ（ＰＰｙ）₂（３−ＳｉＯ−ＰＰｙ） ２．００ｇ（２．５５ｍｍｏｌ）のＴＨＦ溶液にテトラ−ｎ−ブチルアンモニウムフルオライド（ＴＢＡＦ）の１M ＴＨＦ溶液５．１ｍｌを加え、室温で３０分間反応させた。反応液をシリカゲルカラムで精製した後、溶媒を留去し（２−（３−ヒドロキシフェニル）ピリジン）ビス(２−フェニルピリジン)イリジウム（ＩＩＩ）（Ｉｒ（ＰＰｙ）₂（３−ＨＯ−ＰＰｙ））１．６９ｇ（２．５２ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 7.87(d, 2H), 7.78(d, 1H), 7.6(m, 9H), 6.85(m, 10H), 6.63(d, 1H), 4.23(s, 1H). Anal. Found: C 58.64, H 3.74, N 6.17. Calcd: C 59.09, H 3.61, N 6.26.
【化５１】

【００６５】
次いで、スキーム（１Ｆ）に示すように、アルゴン気流下にて、Ｉｒ（ＰＰｙ）₂（３−ＨＯ−ＰＰｙ） １．３４ｇ（２．０ｍｍｏｌ）、脱酸剤としてのトリエチルアミン０．８１ｇ（８．０ｍｍｏｌ）の脱水ＴＨＦ溶液にメタクリル酸クロライド０．２５ｇ（２．４ｍｍｏｌ）を加えて２０℃で５時間反応させた。反応液からトリエチルアミンの塩酸塩を濾別し、濾液をシリカゲルカラムで精製した後、溶媒を留去し（（２−（３−（２−メタクリロイルオキシ）フェニル）ピリジン）ビス（２−フェニルピリジン）イリジウム（ＩＩＩ）（Ｉｒ（３−ＭＡ−ＰＰｙ）（ＰＰｙ）₂）１．２８ｇ（１．７３ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 7.87(d, 2H), 7.78(d, 1H), 7.6(m, 8H), 7.40(s, 1H), 6.8(m, 10H), 6.59(d,1H), 6.35(s, 1H), 5.74(s, 1H), 2.08(s, 3H).Anal. Found: C 59.85, H 3.86, N 5.66. Calcd: C 60.15, H 3.82, N 5.69.
【化５２】

【００６６】
（実施例２）重合性化合物：Ｉｒ（３−ＭＯＩ−ＰＰｙ）（ＰＰｙ）₂の合成
スキーム（２Ａ）に示すように、アルゴン気流下にて、実施例１と同様に合成したＩｒ（ＰＰｙ）₂（３−ＨＯ−ＰＰｙ） １．３４ｇ（２．０ｍｍｏｌ）、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール（ＢＨＴ）９ｍｇ、ジブチル錫(ＩＶ)ジラウレート（ＤＢＴＬ）１３ｍｇの脱水ＴＨＦ溶液にメタクリロイルオキシエチルイソシアネート（ＭＯＩ、昭和電工製）０．３７ｇ（２．３８ｍｍｏｌ）を加えて５０℃で１時間反応させた。反応液をシリカゲルカラムで精製した後、溶媒を留去し（（２−（３−（２−メタクリロイルオキシ）エチルカルバモイルオキシ）フェニル）ピリジン）ビス（２−フェニルピリジン）イリジウム（ＩＩＩ）（Ｉｒ（ＰＰｙ）₂（３−ＭＯＩ−ＰＰｙ））１．４８ｇ（１．７９ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 7.87(d, 2H), 7.80(d, 1H), 7.6(m, 8H), 7.42(s, 1H), 6.8(m, 10H), 6.59(d,1H), 6.14(s, 1H), 5.60(s, 1H), 5.21(br, 1H), 4.28(t, 2H), 3.57(m, 2H), 1.96(s, 3H). Anal. Found: C 57.78, H 4.02, N 6.72. Calcd: C 58.17, H 4.03, N 6.78
【化５３】

【００６７】
（実施例３）重合性化合物：Ｉｒ（４−ＭＡ−ＰＰｙ）₂（ＰＰｙ）の合成
常法に従い４−メトキシフェニルピリジン（４−ＭｅＯ−ＰＰｙ）を合成した。即ち、スキーム（３Ａ）に示すように、常法によりアルゴン気流下において４−ブロモアニソール２２．４ｇ（１２０ｍｍｏｌ）から脱水テトラヒドロフラン（ＴＨＦ）中でマグネシウム（Ｍｇ）３．４ｇを用いて（４−メトキシフェニル）マグネシウムブロマイドを合成し、これを２−ブロモピリジン１５．８ｇ（１００ｍｍｏｌ）と（１，２−ビス（ジフェニルホスフィノ）エタン）ジクロロニッケル（ＩＩ）（Ｎｉ（ｄｐｐｅ）Ｃｌ₂） １．８ｇの脱水ＴＨＦ溶液に徐々に添加し、１時間還流した。反応液に５％塩酸水溶液２５０ｍｌを加えた後、クロロホルムで洗浄した。水層を炭酸水素ナトリウムで中和した後、クロロホルムで目的物を抽出し、有機層を減圧下に蒸留した。蒸留物は室温で直ちに固化し、白色固体として２−（４−メトキシフェニル）ピリジン（４−ＭｅＯ−ＰＰｙ）を１５．１ｇ（８１．５ｍｍｏｌ）得た。同定はＣＨＮ元素分析、¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 8.65(d, 1H), 7.95(d, 2H), 7.71(t, 1H), 7.66(d, 1H), 7.16(t, 1H), 7.00(d, 2H), 3.86(s, 3H). Anal. Found: C 77.52, H 6.10, N 7.40. Calcd: C 77.81, H 5.99, N 7.56.
【化５４】

【００６８】
次いでこの４−ＭｅＯ−ＰＰｙのメトキシ基を常法に従い加水分解した。即ち、スキーム（３Ｂ）に示すように、４−ＭｅＯ−ＰＰｙ １５．０ｇ（８０．１ｍｍｏｌ）を濃塩酸中に溶解させ密閉容器中１３０℃で４時間攪拌した。反応後、反応液を炭酸水素ナトリウム水溶液で中和し、目的物をクロロホルムで抽出し、抽出物をクロロホルム/ヘキサン溶液より結晶化させ、無色の結晶として２−（４−ヒドロキシフェニル）ピリジン（４−ＨＯ−ＰＰｙ）１０．０ｇ（５８．５ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 8.63(d, 1H), 7.82(d, 2H), 7.74(t, 1H), 7.65(d, 1H), 7.20(t, 1H), 6.85(d, 2H). Anal. Found: C 76.91, H 5.39, N 8.02. Calcd: C 77.17, H 5.30, N 8.18.
【化５５】

【００６９】
次いでこの４−ＨＯ−ＰＰｙを常法に従いヘキサクロロイリジウム酸ナトリウムｎ水和物（Ｎａ₃ＩｒＣｌ₆・ｎＨ₂Ｏ）と反応させてビス（μ-クロロ）テトラキス（２−（４−ヒドロキシフェニル）ピリジン）ジイリジウム（ＩＩＩ）（［Ｉｒ（４−ＨＯ−ＰＰｙ）₂Ｃｌ］₂）を合成した。即ち、スキーム（３Ｃ）に示すように、Ｎａ₃ＩｒＣｌ₆・ｎＨ₂Ｏ １０．０ｇを２−エトキシエタノールと水の３：１の混合溶媒４００ｍｌ中に溶解させ、アルゴンガスを３０分間吹き込んだ後に、アルゴン気流下で４−ＨＯ−ＰＰｙ ８．６ｇ（５０．２ｍｍｏｌ）を加えて溶解させ、５時間還流した。反応後、溶媒を留去し、エタノールより再結晶させ、赤橙色の結晶として［Ｉｒ（４−ＨＯ−ＰＰｙ）₂Ｃｌ］₂ ５．８８ｇ（５．１８ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, DMSO-d₆), ppm: 9.66(d, 2H), 9.38(d, 2H), 7.95(m, 8H), 7.61(d, 2H), 7.54(d, 2H), 7.38(t, 2H), 7.26(t, 2H), 6.33(d, 2H), 6.28(d, 2H), 5.67(s, 2H), 5.12(s, 2H). Anal. Found: C 46.33, H 2.51, N 4.76. Calcd: C 46.52, H 2.84, N 4.93.
【化５６】

【００７０】
次いでこの［Ｉｒ（４−ＨＯ−ＰＰｙ）₂Ｃｌ］₂を、常法に従いトリフルオロメチルスルホン酸銀（Ｉ）（ＡｇＣＦ₃ＳＯ₃）の存在下に２−フェニルピリジン（ＰＰｙ）と反応させた。即ち、スキーム（３Ｄ）に示すように、アルゴン気流下にて［Ｉｒ（４−ＨＯ−ＰＰｙ）₂Ｃｌ］₂ ３．９８ｇ（３．５ｍｍｏｌ）とＰＰｙ １５．５ｇ（１０．０ｍｍｏｌ）の脱水トルエン懸濁液にＡｇＣＦ₃ＳＯ₃を１．９８ｇ加え、６時間還流した。反応液をシリカゲルカラムで精製した後、溶媒を留去し、黄色粉末としてビス（２−（４−ヒドロキシフェニル）ピリジン）（２−フェニルピリジン）イリジウム（ＩＩＩ）（Ｉｒ（４−ＨＯ−ＰＰｙ）₂（ＰＰｙ））２．２０ｇ（３．２ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 7.88(d, 1H), 7.78(d, 2H), 7.6(m, 9H), 6.85(m, 8H), 6.64(d, 2H). Anal. Found: C 57.46, H 3.49, N 5.99. Calcd: C 57.71, H 3.52, N 6.12.
【化５７】

【００７１】
次いで、スキーム（３Ｅ）に示すように、アルゴン気流下にて、Ｉｒ（４−ＨＯ−ＰＰｙ）₂（ＰＰｙ） １．３７ｇ（２．０ｍｍｏｌ）、脱酸剤としてのトリエチルアミン０．８１ｇ（８．０ｍｍｏｌ）の脱水ＴＨＦ溶液にメタクリル酸クロライド０．５０ｇ（４．８ｍｍｏｌ）を加えて２０℃で５時間反応させた。反応液からトリエチルアミンの塩酸塩を濾別し、濾液をシリカゲルカラムで精製した後、溶媒を留去し、ビス（（２−（４−（２−メタクリロイルオキシ）フェニル）ピリジン）（２−フェニルピリジン）イリジウム（ＩＩＩ）（Ｉｒ（４−ＭＡ−ＰＰｙ）₂（ＰＰｙ））１．５５ｇ（１．８８ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 7.87(d, 1H), 7.78(d, 2H), 7.6(m, 9H), 6.8(m, 8H), 6.59(s ,2H), 6.35(s, 2H), 5.74(s, 2H), 2.08(s, 6H). Anal. Found: C 59.95, H 3.82, N 5.04. Calcd: C 59.84, H 3.92, N 5.11.
【化５８】

【００７２】
（実施例４）重合性化合物：Ｉｒ（４−ＭＯＩ−ＰＰｙ）₂（ＰＰｙ）の合成
スキーム（４Ａ）に示すように、アルゴン気流下にて、実施例３と同様に合成したＩｒ（４−ＨＯ−ＰＰｙ）₂（ＰＰｙ） １．３７ｇ（２．０ｍｍｏｌ）、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール（ＢＨＴ）１８ｍｇ、ジブチル錫(ＩＶ)ジラウレート（ＤＢＴＬ）２６ｍｇの脱水ＴＨＦ溶液にメタクリロイルオキシエチルイソシアネート（ＭＯＩ、昭和電工製）０．７５ｇ（４．８３ｍｍｏｌ）を加えて５０℃で１時間反応させた。反応液をシリカゲルカラムで精製した後、溶媒を留去し、ビス（（２−（４−（２−メタクリロイルオキシ）エチルカルバモイルオキシ）フェニル）ピリジン）（２−フェニルピリジン）イリジウム（ＩＩＩ）（Ｉｒ（ＭＯＩ−ＰＰｙ）₂（ＰＰｙ））１．６８ｇ（１．６８ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 7.85(d, 1H), 7.81(d, 2H), 7.6(m, 9H), 6.8(m, 8H), 6.58(d, 2H), 6.12(s, 2H), 5.60(s, 2H), 5.21(br, 2H), 4.28(t, 4H), 3.58(m, 4H), 1.96(s, 6H). Anal. Found: C 56.38, H 4.02, N 6.72. Calcd: C 56.62, H 4.25, N 7.02.
【化５９】

【００７３】
（実施例５）重合性化合物：Ｉｒ（３−ＭＡ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂の合成
実施例１のスキーム（１Ａ）と同様にして２−（３−メトキシフェニル）ピリジン（３−ＭｅＯ−ＰＰｙ）を合成した。
【００７４】
次いでこの３−ＭｅＯ−ＰＰｙとトリス（アセチルアセトナート）イリジウム(ＩＩＩ)（Ｉｒ（ａｃａｃ）₃）を下記スキーム（５Ａ）で示す如く、高温で反応させ、トリス（３−メトキシフェニルピリジン）イリジウム(ＩＩＩ)（Ｉｒ（３−ＭｅＯ−ＰＰｙ）₃）を合成した。
【００７５】
即ち、３−ＭｅＯ−ＰＰｙ ５．０ｇ（２７．０ｍｍｏｌ）とＩｒ（ａｃａｃ）₃ ２．０g（４．１ｍｍｏｌ）をグリセロール２００ｍｌ中、２５０℃で９時間反応させ、カラムで精製することにより、蛍光性黄色粉末としてＩｒ（３−ＭｅＯ−ＰＰｙ）₃を０．４０ｇ（０．５４ｍｍｏｌ）得た。同定はＣＨＮ元素分析、¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 7.82(d, 3H), 7.56(t, 3H), 7.53(s, 3H), 7.25(d, 3H), 6.84(t, 3H), 6.67(d,3H), 6.60(d, 3H), 3.80(s, 9H). Anal. Found: C 57.60, H 4.17, N 5.57. Calcd: C 58.05, H 4.06, N 5.64
【化６０】

【００７６】
これらの操作を８回繰り返すことにより、３．２０ｇ（４．３ｍｍｏｌ）のＩｒ（３−ＭｅＯ−ＰＰｙ）₃を得た。
【００７７】
このＩｒ（３−ＭｅＯ−ＰＰｙ）₃を常法に従い、塩酸水溶液中でMeO基を加水分解させ、OH基にし、粉末としてトリス（３−ヒドロキシフェニルピリジン）イリジウム(ＩＩＩ)
（Ｉｒ（３−ＨＯ−ＰＰｙ）₃）を得た（スキーム（５Ｂ））。
【化６１】

【００７８】
次いでＩｒ（３−ＨＯ−ＰＰｙ）₃を下記スキーム（５Ｃ）に従い、メタクリル酸クロライドとモル比１：１で反応させることにより、ＯＨ基の一部分をメタクリル化させＩｒ（３−ＭＡ−ＰＰｙ）（３−ＨＯ−ＰＰｙ）₂が主成分となる錯体を合成した。次いで残りのＯＨ基をプロピオン酸クロライド（ＰｒＣＯＣｌ）と反応させ、Ｉｒ（３−ＭＡ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂が主成分となる錯体を得た。
【００７９】
即ち、反応容器に脱水ＴＨＦ３２ｍｌ、Ｉｒ（３−ＨＯ−ＰＰｙ）₃ ２．８１ｇ（４．０ｍｍｏｌ）、脱酸剤としてトリエチルアミン２．４０ｇ（２３．７ｍｍｏｌ）を仕込んだ後、メタクリル酸クロライド０．４２ｇ（４．０ｍｍｏｌ）を脱水ＴＨＦ１６ｍｌに溶解した溶液を３０分かけて滴下し、２０℃で５時間反応させた。この反応溶液に更にプロピオン酸クロライド１．４８ｇ（１６．０ｍｍｏｌ）を脱水ＴＨＦ１６ｍｌに溶解した溶液を３０分かけて滴下し、２０℃で５時間反応させることにより残りのOH基を反応させ、トリエチルアミンの塩酸塩を濾別した。濾液の溶媒を蒸発乾固し、得られた固形成分はクロロホルム／メタノール混合溶媒にて再結晶を２回行うことにより精製し、目的とするＩｒ（３−ＭＡ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂ ２．３０５ｇ（２．６１ｍｍｏｌ）を粉末として得た。この同定はＣＨＮの元素分析及び¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 7.82(m, 3H), 7.56(m, 6H), 7.26(m, 3H), 6.84(m, 3H), 6.67(m,3H), 6.61(m, 3H), 6.35(s, 1H), 5.74(s, 1H), 2.67(q, 4H), 2.08(s, 3H), 1.42(t, 6H). Anal. Found: C 58.13, H 4.10, N 4.72. Calcd: C 58.49, H 4.11, N 4.76.
【化６２】

【００８０】
（実施例６）重合性化合物：Ｉｒ（３−ＭＡ−ＰＰｙ）₃の合成
実施例５と同様にして合成したモノマー中間体Ｉｒ（３−ＨＯ−ＰＰｙ）₃を下記スキーム（６Ａ）で示す如く、メタクリル酸クロライドとモル比１：３で反応させることにより、すべてのＯＨ基をメタクリル化させＩｒ（３−ＭＡ−ＰＰｙ）₃錯体を合成した。
【００８１】
即ち、反応容器に脱水ＴＨＦ３２ｍｌ、Ｉｒ（３−ＨＯ−ＰＰｙ）₃ ２．８１ｇ（４ｍｍｏｌ）、脱酸剤としてトリエチルアミン２．４０ｇ（２３．７ｍｍｏｌ）を仕込んだ後、メタクリル酸クロライド１．２９ｇ（１２．３ｍｍｏｌ）を脱水ＴＨＦ３２ｍｌに溶解した溶液を９０分かけて滴下し、２０℃で５時間反応させた。沈殿してきたトリエチルアミンの塩酸塩を濾別後、濾液の溶媒を蒸発乾固し、得られた固形成分をヘキサフルオロイソプロパノール／メタノール混合溶媒にて再結晶を２回行うことにより精製し、目的とする三官能性Ｉｒ（３−ＭＡ−ＰＰｙ）₃ ２．８０５ｇ（３．０９ｍｍｏｌ）を粉末として得た。この同定はＣＨＮ元素分析及び¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 7.82(d, 3H), 7.58(t, 3H), 7.55(s, 3H), 7.26(d, 3H), 6.86(t, 3H), 6.67(d,3H), 6.63(d, 3H), 6.36(s, 3H), 5.74(s, 3H), 2.09(s, 9H). Anal. Found: C 59.21, H 3.98, N 4.58. Calcd: C 59.59, H 4.00, N 4.63.
【化６３】

【００８２】
（実施例７）重合性化合物：Ｉｒ（３−ＭＯＩ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂の合成
実施例５と同様にして合成したモノマー中間体Ｉｒ（３−ＨＯ−ＰＰｙ）₃を下記スキーム（７Ａ）で示す如く、メタクリロイルオキシエチルイソシアネート(ＭＯＩ、昭和電工製)とモル比１：１で反応させ、次いで残りのＯＨ基をＰｒＣＯＣｌと反応させ、Ｉｒ（３−ＭＯＩ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂ が主成分となる錯体を得た。
【００８３】
即ち、反応容器に脱水ＴＨＦ３２ｍｌ、Ｉｒ（３−ＨＯ−ＰＰｙ）₃ ２．８１ｇ（４．０ｍｍｏｌ）、ＭＯＩ ０．６２ｇ（４．０ｍｍｏｌ）を仕込み、ジブチルチンジラウレートを触媒量添加し、２０℃で５時間反応させた。この反応溶液に脱酸剤としてトリエチルアミン２．４０ｇ（２３．７ｍｍｏｌ）を加えた後、プロピオン酸クロライド１．４８ｇ（１６．０ｍｍｏｌ）を脱水ＴＨＦ１６ｍｌに溶解させた溶液を３０分かけて滴下し、更に２０℃で５時間反応させることにより残りのＯＨ基を反応させ、トリエチルアミンの塩酸塩を濾別した。濾液の溶媒を蒸発乾固し、得られた固形成分はクロロホルム／メタノール混合溶媒にて再結晶を２回行うことにより精製し、目的とするＩｒ（３−ＭＯＩ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂ ２．６２０g（２．７０ｍｍｏｌ）を粉末として得た。同定はＣＨＮ元素分析及び¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 7.82(m, 3H), 7.56(m, 6H), 7.26(m, 3H), 6.84(m, 3H), 6.67(m,3H), 6.61(m, 3H), 6.14(s, 1H), 5.61(s, 1H), 5.23(br, 1H), 4.29(t, 2H), 3.58(m, 2H), 2.66(q, 4H), 1.95(s, 3H), 1.41(t, 6H). Anal. Found: C 56.58, H 4.25, N 5.72. Calcd: C 56.95, H 4.26, N 5.78.
【化６４】

【００８４】
（実施例８）重合性化合物：Ｉｒ（３−ＭＯＩ−ＰＰｙ）₂（３−ＰｒＣＯ−ＰＰｙ）の合成
実施例５と同様にして合成したモノマー中間体Ｉｒ（３−ＨＯ−ＰＰｙ）₃を下記スキーム（８Ａ）で示す如く、メタクリロイルオキシエチルイソシアネート(ＭＯＩ、昭和電工製)とモル比１：２で反応させ、次いで残りのＯＨ基をＰｒＣＯＣｌと反応させ、Ｉｒ（３−ＭＯＩ−ＰＰｙ）₂（３−ＰｒＣＯ−ＰＰｙ）錯体を得た。
【００８５】
即ち、反応容器に脱水ＴＨＦ４８ｍｌ、Ｉｒ（３−ＨＯ−ＰＰｙ）₃ ２．８１ｇ（４．０ｍｍｏｌ）、ＭＯＩ １．２４ｇ（８．０ｍｍｏｌ）を仕込み、ジブチルチンジラウレートを触媒量添加し、２０℃で５時間反応させた。この反応溶液に脱酸剤としてトリエチルアミン２．４００ｇ（２４．５ｍｍｏｌ）を加えた後、プロピオン酸クロライド０．７４ｇ（８．０ｍｍｏｌ）を脱水ＴＨＦ８ｍｌに溶解させた溶液を３０分かけて滴下し、更に２０℃で５時間反応させることにより残りのＯＨ基を反応させ、トリエチルアミンの塩酸塩を濾別した。濾液の溶媒を蒸発乾固し、得られた固形成分はクロロホルム／メタノール混合溶媒にて再結晶を２回行うことにより精製し、目的とするＩｒ（３−ＭＯＩ−ＰＰｙ）₂（３−ＰｒＣＯ−ＰＰｙ） ２．７５g（２．５７ｍｍｏｌ）を粉末として得た。この同定はＣＨＮ元素分析及び¹Ｈ−ＮＭＲで行った。¹H NMR(270MHz, CDCl₃), ppm: 7.81(m, 3H), 7.54(m, 6H), 7.26(m, 3H), 6.86(m, 3H), 6.68(m,3H), 6.59(m, 3H), 6.13(s, 2H), 5.60(s, 2H), 5.22(br, 2H), 4.27(t, 4H), 3.57(m, 4H), 2.67(q, 2H), 1.95(s, 6H), 1.41(t, 3H). Anal. Found: C 55.86, H 4.37, N 6.51. Calcd: C 56.17, H 4.34, N 6.55.
【化６５】

【００８６】
（実施例９）Ｉｒ（３−ＭＡ−ＰＰｙ）（ＰＰｙ）₂の重合体の合成
反応容器に実施例１で合成したＩｒ（３−ＭＡ−ＰＰｙ）（ＰＰｙ）₂錯体１．１１ｇ（１．５ｍｍｏｌ）、２，２’−アゾビス（イソブチロニトリル）（ＡＩＢＮ）０．０１０ｇ（０．０６１ｍｍｏｌ）、酢酸ブチル１０ｍｌを入れて窒素置換を行った後、８０℃で１０時間反応させた（スキーム（９Ａ））。反応後、反応液をアセトンに滴下して再沈殿を行い、濾過によりポリマーを回収した。回収したポリマーのクロロホルム溶液をメタノール中に滴下して再沈殿させることを更に２回行うことにより精製し、回収後真空乾燥して、目的とするＩｒ（３−ＭＡ−ＰＰｙ）（ＰＰｙ）₂重合体０．９２ｇを粉末として得た。また、得られた重合体のＣＨＮ元素分析はＩｒ（３−ＭＡ−ＰＰｙ）（ＰＰｙ）₂と同じ組成であることを支持していた。また、重合体の重量平均分子量はポリスチレン換算で１２０００（ＧＰＣ測定、溶離液：ＴＨＦ）であった。
【化６６】

【００８７】
（実施例１０）Ｉｒ（３−ＭＯＩ−ＰＰｙ）（ＰＰｙ）₂の重合体の合成
反応容器に実施例２で合成したＩｒ（３−ＭＯＩ−ＰＰｙ）（ＰＰｙ）₂錯体１．１１ｇ（１．５ｍｍｏｌ）、２，２’−アゾビス（イソブチロニトリル）（ＡＩＢＮ）０．０１０ｇ（０．０６１ｍｍｏｌ）、酢酸ブチル１０ｍｌを入れて窒素置換を行った後、８０℃で１０時間反応させた（スキーム（１０Ａ））。反応後、反応液をアセトンに滴下して再沈殿を行い、濾過によりポリマーを回収した。回収したポリマ−のクロロホルム溶液をメタノール中に滴下して再沈殿させることを更に２回行うことにより精製し、回収後真空乾燥して、目的とするＩｒ（３−ＭＯＩ−ＰＰｙ）（ＰＰｙ）₂重合体１．０２ｇを粉末として得た。また、得られた共重合体のＣＨＮ元素分析はＩｒ（３−ＭＯＩ−ＰＰｙ）（ＰＰｙ）₂とほぼ同様の組成であることを支持していた。また、共重合体の重量平均分子量はポリスチレン換算で２００００（ＧＰＣ測定、溶離液：ＴＨＦ）であった。
【化６７】

【００８８】
（実施例１１）Ｉｒ（３−ＭＡ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂の重合体の合成
反応容器に実施例５で合成したＩｒ（３−ＭＡ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂錯体２．２２ｇ（２．５ｍｍｏｌ）、２，２’−アゾビス（イソブチロニトリル）（ＡＩＢＮ）０．０１０ｇ（０．０６１ｍｍｏｌ）、酢酸ブチル３０ｍｌを入れて窒素置換を行った後、８０℃で１０時間反応させた（スキーム（１１Ａ））。反応後、反応液をアセトンに滴下して再沈殿を行い、濾過によりポリマーを回収した。回収したポリマーのクロロホルム溶液をメタノール中に滴下して再沈殿させることを更に２回行うことにより精製し、回収後真空乾燥して、目的とするＩｒ（３−ＭＡ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂重合体１．８５ｇを粉末として得た。また、得られた重合体のＣＨＮ元素分析はＩｒ（３−ＭＡ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂と同じ組成であることを支持していた。また、重合体の重量平均分子量はポリスチレン換算で８０００（ＧＰＣ測定、溶離液：ＴＨＦ）であった。
【化６８】

【００８９】
（実施例１２）Ｉｒ（３−ＭＡ−ＰＰｙ）₃の重合体の合成
反応容器に実施例６で合成したＩｒ（３−ＭＡ−ＰＰｙ）₃錯体２．２８ｇ（２．５ｍｍｏｌ）、２，２’−アゾビス（イソブチロニトリル）（ＡＩＢＮ）０．０１０ｇ（０．０６１ｍｍｏｌ）、酢酸ブチル３０ｍｌを入れて窒素置換を行った後、８０℃で１０時間反応させた（スキーム（１２Ａ））ところ、不溶性のポリマーが沈殿した。このポリマーを濾過により回収し、１００ｍｌのクロロホルム及び１００ｍｌのメタノールで洗浄後、真空乾燥して、目的とするＩｒ（３−ＭＡ−ＰＰｙ）₃重合体２．１０ｇを粉末として得た。また、得られた重合体のＣＨＮ元素分析はＩｒ（３−ＭＡ−ＰＰｙ）₃とほぼ同様の組成であることを支持していた。この重合体は架橋構造をしているものと考えられ、各種溶媒に不溶であり、ＧＰＣによる分子量測定はできなかった。
【化６９】

【００９０】
（実施例１３）Ｉｒ（３−ＭＯＩ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂の重合体の合成
反応容器に実施例７で合成したＩｒ（３−ＭＯＩ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂錯体２．４３ｇ（２．５ｍｍｏｌ）、２，２’−アゾビス（イソブチロニトリル）（ＡＩＢＮ）０．０１０ｇ（０．０６１ｍｍｏｌ）、酢酸ブチル３０ｍｌを入れて窒素置換を行った後、８０℃で１０時間反応させた（スキーム（１３Ａ））。反応後、アセトンに滴下して再沈殿を行い、濾過によりポリマーを回収した。回収したポリマーのクロロホルム溶液をメタノール中に滴下して再沈殿させることを更に２回行うことにより精製し、回収後真空乾燥して、目的とするＩｒ（３−ＭＯＩ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂重合体２．０５ｇを粉末として得た。また、得られた共重合体のＣＨＮ元素分析はＩｒ（３−ＭＯＩ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂とほぼ同様の組成であることを支持していた。また、共重合体の重量平均分子量はポリスチレン換算で１８０００（ＧＰＣ測定、溶離液：ＴＨＦ）であった。
【化７０】

【００９１】
（実施例１４）Ｉｒ（３−ＭＯＩ−ＰＰｙ）₂（３−ＰｒＣＯ−ＰＰｙ）の重合体の合成
反応容器に実施例８で合成したＩｒ（３−ＭＯＩ−ＰＰｙ）₂（３−ＰｒＣＯ−ＰＰｙ）錯体２．４６ｇ（２．５ｍｍｏｌ）、２，２’−アゾビス（イソブチロニトリル）（ＡＩＢＮ）０．０１０ｇ（０．０６１ｍｍｏｌ）、酢酸ブチル３０ｍｌを入れて窒素置換を行った後、８０℃で１０時間反応させた（スキーム（１４Ａ））ところ、不溶性のポリマーが沈殿した。このポリマーを濾過により回収し、１００ｍｌのクロロホルム及び１００ｍｌのメタノールで洗浄後、真空乾燥して、目的とするＩｒ（３−ＭＯＩ−ＰＰｙ）₂（３−ＰｒＣＯ−ＰＰｙ）重合体２．２１ｇを粉末として得た。また、得られた重合体のＣＨＮ元素分析はＩｒ（３−ＭＯＩ−ＰＰｙ）₂（３−ＰｒＣＯ−ＰＰｙ）とほぼ同様の組成であることを支持していた。この重合体は架橋構造をしているものと考えられ、各種溶媒に不溶であり、ＧＰＣによる分子量測定はできなかった。
【化７１】

【００９２】
（実施例１５）Ｉｒ（３−ＭＡ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂／Ｉｒ（３−ＭＡ−ＰＰｙ）₃共重合体の合成
反応容器に実施例５で合成したＩｒ（３−ＭＡ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂錯体１．１１ｇ（１．２５ｍｍｏｌ）、実施例６で合成したＩｒ（ＭＡ−ＰＰｙ）₃錯体１．１４ｇ（１．２５ｍｍｏｌ）、２，２’−アゾビス（イソブチロニトリル）（ＡＩＢＮ）０．０１０ｇ（０．０６１ｍｍｏｌ）、酢酸ブチル３０ｍｌを入れて窒素置換を行った後、８０℃で１０時間反応させた（スキーム（１５Ａ））ところ、不溶性のポリマーが沈殿した。このポリマーを濾過により回収し、１００ｍｌのクロロホルム及び１００ｍｌのメタノールで洗浄後、真空乾燥して、目的とするＩｒ（３−ＭＡ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂／Ｉｒ（３−ＭＡ−ＰＰｙ）₃共重合体２．０５ｇを粉末として得た。また、得られた重合体のＣＨＮ元素分析はＩｒ（３−ＭＡ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂とＩｒ（３−ＭＡ−ＰＰｙ）₃がモル比１：１で共重合していることを支持していた。この共重合体は架橋構造をしているものと考えられ、各種溶媒に不溶であり、ＧＰＣによる分子量測定はできなかった。
【化７２】

【００９３】
（実施例１６）Ｉｒ（３−ＭＯＩ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂／Ｉｒ（３−ＭＯＩ−ＰＰｙ）₂（３−ＰｒＣＯ−ＰＰｙ）共重合体の合成
反応容器に実施例７で合成したＩｒ（３−ＭＯＩ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂錯体１．２１ｇ（１．２５ｍｍｏｌ）、実施例８で合成したＩｒ（３−ＭＯＩ−ＰＰｙ）₂（３−ＰｒＣＯ−ＰＰｙ）１．２３ｇ（１．２５ｍｍｏｌ）、２，２’−アゾビス（イソブチロニトリル）（ＡＩＢＮ）０．０１０ｇ（０．０６１ｍｍｏｌ）、酢酸ブチル３０ｍｌを入れて窒素置換を行った後、８０℃で１０時間反応させた（スキーム（１６Ａ））ところ、不溶性のポリマーが沈殿した。このポリマーを濾過により回収し、１００ｍｌのクロロホルム及び１００ｍｌのメタノールで洗浄後、真空乾燥して、目的とするＩｒ（３−ＭＯＩ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂／Ｉｒ（３−ＭＯＩ−ＰＰｙ）₂（３−ＰｒＣＯ−ＰＰｙ）共重合体２．１８ｇを粉末として得た。また、得られた重合体のＣＨＮ元素分析はＩｒ（３−ＭＯＩ−ＰＰｙ）（３−ＰｒＣＯ−ＰＰｙ）₂とＩｒ（３−ＭＯＩ−ＰＰｙ）₂（３−ＰｒＣＯ−ＰＰｙ）がモル比１：１で共重合していることを支持していた。この共重合体は架橋構造をしているものと考えられ、各種溶媒に不溶であり、ＧＰＣによる分子量測定はできなかった。
【化７３】

【００９４】
【発明の効果】
本発明の新規な重合性化合物はイリジウム錯体部分を含む新規な重合体を与え、これを有機発光素子の発光材料として使用することにより励起三重項状態から高効率で発光し、かつ大面積化が可能で量産に適した有機発光素子を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polymer light emitting material used for a flat display panel and an organic light emitting device (OLED) for a backlight used therein and a polymerizable compound as a precursor thereof.
[0002]
[Prior art]
The organic light-emitting device was manufactured by Kodak C.I. W. Since Tang et al. Showed high-luminance light emission (Appl. Phys. Lett., 51, 913, 1987), material development and device structure improvements have progressed rapidly. Practical use began with telephone displays. In order to further expand the applications of this organic EL, development of materials for improving luminous efficiency and durability, development of full-color display, and the like are being actively carried out. In particular, when considering expansion to medium-sized panels, large-sized panels, or lighting applications, it is necessary to establish a mass production method suitable for further increase in luminance and increase in area by improving luminous efficiency.
[0003]
First, regarding luminous efficiency, what is used in the current luminescent materials is light emission from an excited singlet state, that is, fluorescence. According to Monthly Display, October 1998, separate volume “Organic EL Display”, page 58. For example, since the production ratio of excitons in the excited singlet state and excited triplet state in electrical excitation is 1: 3, the upper limit of the internal quantum efficiency of light emission in organic EL is 25%.
[0004]
In contrast, M.M. A. Baldo et al. Obtained an external quantum efficiency of 7.5% by using an iridium complex that emits phosphorescence from an excited triplet state (an internal quantum efficiency of 37.5% assuming an external extraction efficiency of 20%), and a fluorescent dye is used. It was shown that it was possible to exceed the upper limit of 25% (Appl. Phys. Lett., 75, 4 pages, 1999, WO00 / 70655).
[0005]
Next, as a method for mass production of panels, a vacuum deposition method has been conventionally used. However, this method requires a vacuum facility and can form an organic thin film with a uniform thickness as the area increases. It has problems such as difficulties, and is not necessarily a method suitable for mass production of large-area panels.
[0006]
On the other hand, a manufacturing method using a polymer light emitting material, that is, an ink jet method or a printing method has been developed as a method for easily increasing the area. In particular, the printing method can continuously form a long film and is excellent in large area and mass productivity.
[0007]
As described above, in order to obtain an organic light emitting device with high luminous efficiency and a large area, a phosphorescent polymer material is required. Such phosphorescent polymer materials include those in which a ruthenium complex is incorporated into the main chain or side chain of a polymer (Ng, PK et al., Polymer Preprints., 40 (2), 1212 (1999 )). However, since these are ionic compounds, electrochemiluminescence due to an oxidation-reduction reaction at the electrode occurs when a voltage is applied. This is a very slow response speed on the order of minutes and cannot be used as a normal display panel.
[0008]
Although it cannot be said to be a polymer material in a strict sense, there is a mixture of poly (N-vinylcarbazole) and an iridium complex which is a phosphorescent low-molecular compound (PJ Djurovich et al., Polymer Preprints, 41 (1), 770 (2000)). However, this is inferior in thermal stability to a homogeneous polymer material and may cause phase separation or segregation.
[0009]
[Problems to be solved by the invention]
As described above, there is no practical high-molecular phosphorescent material required for mass-producing organic light-emitting devices having high luminous efficiency and a large area. Accordingly, the present invention provides a polymer light-emitting material for solving the problems of the prior art as described above, and for obtaining an organic light-emitting device capable of large area production with high luminous efficiency and mass production. Is an issue.
[0010]
[Means for Solving the Problems]
As a result of various studies to solve the above problems, the present inventors have succeeded in obtaining a polymerizable compound having an iridium complex portion, and have completed the present invention.
[0011]
That is, the present invention provides a polymerizable compound which is the following novel compound, a polymer obtained by polymerizing them, an intermediate which is a novel compound necessary for the synthesis of these polymerizable compounds, and a method for producing these polymerizable compounds. provide.
[0012]
[1] A polymerizable compound represented by the formula (1).
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[Wherein, at least one of A, B and C represents a substituent having a polymerizable functional group, and the rest of A, B and C each independently represents a hydrogen atom, a halogen atom, a nitro group or an amino group. , A sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. R ₁ ~ R ₁₅ Each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
[2] The polymerizable compound according to [1], wherein at least one of A, B, and C in the formula (1) is a substituent having an acrylate group or a methacrylate group.
[0013]
[3] The polymerizable compound according to [2], wherein one of A, B, and C in the formula (1) is a substituent having an acrylate group or a methacrylate group.
[4] A polymerizable compound represented by the formula (2).
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[In the formula, R ₁ , R ₂ Each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
[5] R in formula (2) ₁ , R ₂ The polymerizable compound according to [4], wherein is a hydrogen atom.
[6] A polymerizable compound represented by the formula (3).
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[In the formula, R ₁ , R ₂ Each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
[7] R in formula (3) ₁ , R ₂ The polymerizable compound according to [6], wherein is a hydrogen atom.
[8] The polymerizable compound according to [2], wherein two of A, B, and C in the formula (1) are substituents having an acrylate group or a methacrylate group.
[0014]
[9] A polymerizable compound represented by the formula (4).
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[In the formula, R ₁ Represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
[10] R in formula (4) ₁ The polymerizable compound according to [9], wherein is a hydrogen atom.
[0015]
[11] A polymerizable compound represented by the formula (5).
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[In the formula, R ₁ Represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
[12] R in formula (5) ₁ The polymerizable compound according to [11], wherein is a hydrogen atom.
[13] The polymerizable compound according to [2], wherein all of A, B, and C in the formula (1) are substituents having an acrylate group or a methacrylate group.
[0016]
[14] A polymerizable compound represented by the formula (6).
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[0017]
[15] A polymerizable compound represented by the formula (7).
[0018]
Embedded image

[0019]
[16] A polymer obtained by polymerizing a polymerizable compound represented by the formula (1).
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[Wherein, at least one of A, B and C represents a substituent having a polymerizable functional group, and the rest of A, B and C each independently represents a hydrogen atom, a halogen atom, a nitro group or an amino group. , A sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. R ₁ ~ R ₁₅ Each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
[17] The polymer according to [16], wherein at least one of A, B, and C in the formula (1) is a substituent having an acrylate group or a methacrylate group.
[18] The polymer according to [17], wherein one of A, B, and C in the formula (1) is a substituent having an acrylate group or a methacrylate group.
[0020]
[19] A polymer obtained by polymerizing a polymerizable compound represented by the formula (2).
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[In the formula, R ₁ , R ₂ Each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
[20] R in formula (2) ₁ , R ₂ The polymer according to [19], wherein is a hydrogen atom.
[0021]
[21] A polymer obtained by polymerizing a polymerizable compound represented by formula (3).
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[In the formula, R ₁ , R ₂ Each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
[22] R in formula (3) ₁ , R ₂ The polymer according to [21], wherein is a hydrogen atom.
[23] The polymer according to [17], wherein two of A, B and C in the formula (1) are substituents having an acrylate group or a methacrylate group.
[0022]
[24] A polymer obtained by polymerizing a polymerizable compound represented by formula (4).
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[In the formula, R ₁ Represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
[25] R in formula (3) ₁ The polymer according to [24], wherein is a hydrogen atom.
[0023]
[26] A polymer obtained by polymerizing a polymerizable compound represented by the formula (5).
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[In the formula, R ₁ Represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
[27] R in formula (3) ₁ The polymer according to [26], wherein is a hydrogen atom.
[0024]
[28] The polymer according to [17], wherein all of A, B and C in the formula (1) are substituents having an acrylate group or a methacrylate group.
[0025]
[29] A polymer obtained by polymerizing a polymerizable compound represented by the formula (6).
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[0026]
[30] A polymer obtained by polymerizing a polymerizable compound represented by the formula (7).
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[31] A copolymer comprising at least one monomer unit derived from the polymerizable compound represented by any one of formulas (1) to (7).
[0027]
[32] A compound having a reactive substituent in the reaction product and a polymerizable functional group after reacting the iridium binuclear complex represented by formula (8) with the phenylpyridine derivative represented by formula (9) And a method for producing a polymerizable compound containing a mononuclear iridium complex portion.
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[Wherein X and Y are reactive substituents, or a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a hetero atom, and an organic group having 1 to 20 carbon atoms. Represents the group R ₁ ~ R ₂₀ Each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
Embedded image

[In the formula, Z represents a reactive substituent, or a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. R ₁ ~ R _Five Each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. However, at least one of X and Y in formula (8) and Z in formula (9) is a reactive substituent. ]
[0028]
[33] X 1 and Y in Formula (8) each independently have a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a hetero atom, and have 1 to 20 carbon atoms The manufacturing method of the polymeric compound containing the mononuclear iridium complex part as described in [32] which is either an organic group and Z in Formula (9) is a reactive substituent.
[34] The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to [33], wherein Z in formula (9) is a hydroxyl group.
[35] The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to [34], wherein the compound having a polymerizable functional group is an acid halide.
[0029]
[36] The method for producing a polymerizable compound containing a mononuclear iridium complex part according to [34], wherein the compound having a polymerizable functional group is an isocyanate compound.
[37] X and Y in the formula (8) are reactive substituents, and Z in the formula (9) is a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group, or a heteroatom. The manufacturing method of the polymeric compound containing the mononuclear iridium complex part as described in [31] which is either the C1-C20 organic group which may have.
[38] The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to [37], wherein Z in formula (9) is a hydroxyl group.
[0030]
[39] The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to [38], wherein the compound having a polymerizable functional group is an acid halide.
[40] The method for producing a polymerizable compound containing a mononuclear iridium complex part according to [37], wherein the compound having a polymerizable functional group is an isocyanate compound.
[0031]
[41] An iridium complex represented by the formula (10) and a compound having a polymerizable functional group are reacted at a constant molar ratio, and when an unreacted reactive substituent remains, a further obtained product A method for producing a polymerizable compound containing an iridium complex part, comprising reacting a reactive substituent therein with a non-polymerizable compound.
Embedded image

[Wherein X is a reactive substituent, R ₁ ~ R _{twenty four} Each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
[42] Polymerizability including an iridium complex moiety according to [41], wherein the molar ratio of the iridium complex represented by formula (10) and the compound having a polymerizable functional group is 1: (0.5 to 1.5). Compound production method.
[0032]
[43] The method for producing a polymerizable compound containing an iridium complex moiety according to [41] or [42], wherein the reactive substituent in formula (10) is a hydroxyl group.
[44] The method for producing a polymerizable compound containing an iridium complex moiety according to [43], wherein the compound having a polymerizable functional group is an acid halide.
[45] The method for producing a polymerizable compound containing an iridium complex moiety according to [43], wherein the compound having a polymerizable functional group is an isocyanate compound.
[0033]
[46] Polymerizability including an iridium complex moiety according to [41], wherein the molar ratio of the iridium complex represented by the formula (10) and the compound having a polymerizable functional group is 1: (1.5 to 2.5). Compound production method.
[47] The method for producing a polymerizable compound containing an iridium complex moiety according to [45] or [46], wherein the reactive group in formula (10) is a hydroxyl group.
[48] The method for producing a polymerizable compound containing an iridium complex moiety according to [47], wherein the compound having a polymerizable functional group is an acid halide.
[49] The method for producing a polymerizable compound containing an iridium complex moiety according to [47], wherein the compound having a polymerizable functional group is an isocyanate compound.
[0034]
[50] Production of a polymerizable compound containing an iridium complex part according to [41], wherein the molar ratio of the iridium complex represented by the formula (10) and the compound having a polymerizable functional group is 1: (2.5 or more). Method.
[51] The method for producing a polymerizable compound containing an iridium complex moiety according to [49] or [50], wherein the reactive group in formula (10) is a hydroxyl group.
[52] The method for producing a polymerizable compound containing an iridium complex moiety according to [51], wherein the compound having a polymerizable functional group is an acid halide.
[53] The method for producing a polymerizable compound containing an iridium complex moiety according to [51], wherein the compound having a polymerizable functional group is an isocyanate compound.
[0035]
[54] A compound represented by the formula (11):
Embedded image

[In the formula, at least one of X, Y and Z represents a hydroxyl group, and each of the residues independently has a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a heteroatom. Or an organic group having 1 to 20 carbon atoms. R ₁ ~ R ₁₅ Each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
[55] The compound according to [54], wherein one of X, Y and Z in the formula (11) is a hydroxyl group.
[0036]
[56] A compound represented by formula (12).
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[57] The compound according to [53], wherein two of X, Y and Z in the formula (11) are hydroxyl groups.
[0037]
[58] A compound represented by formula (13):
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[0038]
[59] The compound according to [54], wherein all of X, Y and Z in the formula (11) are hydroxyl groups.
[60] A compound represented by formula (14).
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[0039]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be specifically described.
According to the invention, the formula (1)
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[Wherein, at least one of A, B and C represents a substituent having a polymerizable functional group, and the rest of A, B and C each independently represents a hydrogen atom, a halogen atom, a nitro group or an amino group. , A sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. R ₁ ~ R ₁₅ Each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. The polymerizable compound represented by this is provided.
[0040]
Examples of the substituent having a polymerizable functional group among A, B, and C in formula (1) include a urethane (meth) acrylate group such as a vinyl group, an acrylate group, a methacrylate group, and a methacryloyloxyethyl carbamate group, a styryl group, and the like. The substituent which has the derivative, a vinyl acid group, its derivative, etc. can be mentioned. Among these polymerizable functional groups, an acrylate group, a methacrylate group, and a urethane (meth) acrylate group are preferable from the viewpoint of polymerizability. In addition, the position at which these substituents are bonded may be any of the 2-position, 3-position, 4-position, and 5-position of the phenyl group of the phenylpyridine ligand.
[0041]
A substituent having no polymerizable functional group among A, B and C in formula (1), and R ₁ ~ R ₁₅ As hydrogen atom, halogen atom, nitro group, amino group, sulfonic acid group, sulfonic acid ester group such as methyl sulfonate, alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, amyl, hexyl, etc. And organic groups such as alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy and tertiary butoxy, and ester groups such as acetoxy group and propoxycarbonyl group. Further, these organic groups may further have a substituent such as a halogen atom, a nitro group, or an amino group.
[0042]
Next, although the example of the synthesis | combining method of the polymeric compound by this invention is given below, this invention is not limited to these at all.
[0043]
In the first synthesis method, a mononuclear iridium complex having a reactive substituent is obtained by reacting a binuclear complex of iridium represented by formula (8) with a phenylpyridine derivative represented by formula (9). And obtaining a polymerizable compound containing a mononuclear iridium complex portion by reacting a reactive substituent of this intermediate with a compound having a polymerizable substituent.
[0044]
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[Wherein X and Y are a reactive substituent, a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group, or an organic group having 1 to 20 carbon atoms which may have a hetero atom. Represents R ₁ ~ R ₂₀ Each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
Embedded image

[In formula, Z represents a C1-C20 organic group which may have a reactive substituent, a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group, or a hetero atom. , R ₁ ~ R _Five Each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. However, at least one of X and Y in formula (8) and Z in formula (9) is a reactive substituent. ]
[0045]
The binuclear complex of iridium of the formula (8) can be synthesized by a known method (S. Lamansky et al., Inorganic Chemistry, 40, 1704 (2001)). R in formula (8) ₁ ~ R ₂₀ As hydrogen atom, halogen atom, nitro group, amino group, sulfonic acid group, sulfonic acid ester group such as methyl sulfonate, alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, amyl, hexyl, etc. And organic groups such as alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy and tertiary butoxy, and ester groups such as acetoxy group and propoxycarbonyl group. Further, these organic groups may further have a substituent such as a halogen atom, a nitro group, or an amino group.
[0046]
At least one of X and Y in formula (8) and Z in formula (9) is a reactive substituent, and examples thereof include a hydroxyl group, but are not limited thereto. Moreover, this reactive substituent may be protected with a protecting group. In this case, the reaction is carried out while protected by the protective group to obtain a mononuclear iridium complex, and then a mononuclear iridium complex having a reactive substituent is obtained as an intermediate by deprotection. Then, the polymeric compound containing a mononuclear iridium complex part is obtained by making it react with the compound which has the reactive substituent of this intermediate body, and a polymeric functional group.
[0047]
R in the compound of formula (9) ₁ ~ R _Five As hydrogen atoms, halogen atoms, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, amyl, hexyl, and alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy, tertiary butoxy, Can include organic groups such as ester groups such as acetoxy group and propoxycarbonyl group. Further, these substituents may further have a substituent such as a halogen atom, a nitro group, or an amino group.
[0048]
Examples of the polymerizable functional group in the compound having a polymerizable functional group to be reacted with the intermediate include urethane (meth) acrylates such as vinyl group, acrylate group, methacrylate group, acryloyloxy group, methacryloyloxy group, and methacryloyloxyethylcarbamate group. And a group having an ethylenic double bond such as a group, a styryl group and a derivative thereof, and a vinyl acid group and a derivative thereof. Among these polymerizable functional groups, an acrylate group, a methacrylate group, and a urethane (meth) acrylate group are preferable from the viewpoint of polymerizability.
[0049]
In the first synthesis method, X and Y in the iridium binuclear complex represented by the formula (8) are non-reactive substituents, and Z in the phenylpyridine derivative represented by the formula (9) is a reactive substituent. In some cases, these reactions yield a mononuclear iridium complex having one reactive substituent as an intermediate, and by reacting this intermediate with a compound having a polymerizable functional group, the mononuclear iridium complex portion is converted. A monofunctional polymerizable compound is obtained. Further, when X and Y in the iridium binuclear complex represented by the formula (8) are reactive substituents, and Z in the phenylpyridine derivative represented by the formula (9) is a non-reactive substituent, As a result, a mononuclear iridium complex having two reactive substituents is obtained as an intermediate, and by reacting this intermediate with a compound having a polymerizable functional group, the bifunctional polymerizability containing the mononuclear iridium complex portion is obtained. A compound is obtained.
[0050]
In the second synthesis method of the polymerizable compound according to the present invention, the iridium complex represented by the formula (10) is used as an intermediate, and the intermediate and the compound having a polymerizable functional group are reacted at a certain molar ratio. This is a method for obtaining a polymerizable compound containing an iridium complex portion having a predetermined number of polymerizable functional groups.
Embedded image

[Wherein X is a reactive substituent, R ₁ ~ R _{twenty four} Each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
[0051]
Examples of the reactive substituent X in the iridium complex represented by the above formula (10) include a hydroxyl group and an amino group, but are not limited thereto. Examples of the compound having a polymerizable functional group that reacts with the iridium complex represented by the formula (10) include polymerizable acid halides and polymerizable isocyanates, but are not limited thereto.
[0052]
Next, the second synthesis method will be described in detail when a polymerizable acid halide and / or polymerizable isocyanate is used.
[0053]
That is, when the molar ratio of the iridium complex of formula (10) and the polymerizable acid halide and / or polymerizable isocyanate is close to 1: 1, for example, 1: (0.5 to 1.5), A functional polymerizable compound is obtained, and the product is purified to obtain a monofunctional polymerizable compound. When this molar ratio is close to 1: 2, for example, 1: (1.5 to 2.5), mainly a bifunctional polymerizable compound is obtained, and the product is purified to obtain a bifunctional polymerizable compound. A compound is obtained. Further, when the molar ratio is close to 1: 3, for example, 1: (2.5 or more), a trifunctional polymerizable compound is mainly obtained, and the product is purified to obtain a trifunctional polymerizable compound. . However, when the molar ratio is 1: (3 or more), purification for removing monofunctional or bifunctional compounds is not necessarily required. In the case of synthesizing monofunctional and bifunctional polymerizable compounds, the reactive substituents remaining in the product are made non-reactive after reacting the polymerizable acid halide at a predetermined molar ratio. Perform the reaction. When the reactive substituent is a hydroxyl group, examples of the non-polymerizable compound used for this purpose include alkyl halides, carboxylic acids, carboxylic acid halides, sulfonic acid halides, chloroformates, and isocyanates. Although it can, it is not limited to these at all.
[0054]
Examples of the polymerizable acid halide used in the second synthesis method include acrylic acid chloride and methacrylic acid chloride, and examples of the non-polymerizable acid halide include propionic acid chloride and acetic acid chloride. Examples of the polymerizable isocyanate include methacryloyl isocyanate and methacryloyloxyethyl isocyanate, and examples of the non-polymerizable isocyanate include hexyl isocyanate and benzyl isocyanate.
[0055]
The polymerizable compound according to the present invention is easily polymerized by using a thermal polymerization initiator such as 2,2′-azobis (isobutyronitrile) (AIBN) or benzoyl peroxide or an ultraviolet polymerization initiator such as benzophenone. And a polymer containing an iridium complex moiety can be provided. The polymer may be a homopolymer of one of the polymerizable compounds according to the present invention, a copolymer of two or more of the polymerizable compounds of the present invention, and further one of the polymerizable compounds of the present invention. It may be any copolymer of at least one kind and one or more kinds of other polymerizable compounds (not particularly limited, but, for example, methacrylate).
[0056]
Further, as another synthesis method of the polymerizable compound according to the present invention, iridium (III) bis (2-phenylpyridinate) acetylacetonate complex and phenyl having a reactive substituent represented by the above formula (9) are used. Examples thereof include a method of obtaining a monofunctional polymerizable compound containing an iridium complex portion by reacting a pyridine derivative and then introducing a polymerizable substituent thereto.
[0057]
The degree of polymerization of the polymer and copolymer according to the present invention is preferably 3 to 5000.
[0058]
【Example】
The present invention will be described in more detail below with typical examples. Note that these are merely illustrative examples, and the present invention is not limited to these.
[0059]
<Measurement equipment, etc.>
1) ¹ H-NMR
JNM EX270 made by JEOL
270Mz Solvent: deuterated chloroform or deuterated dimethyl sulfoxide
2) GPC measurement (molecular weight measurement)
Column: Shodex KF-G + KF804L + KF802 + KF801
Eluent: Tetrahydrofuran (THF)
Temperature: 40 ° C
Detector: RI (Shodex RI-71)
3) Elemental analyzer
CHNS-932 type manufactured by REC0
[0060]
(Example 1) Polymerizable compound: Ir (MA-PPy) (PPy) ₂ Synthesis of
2- (3-methoxyphenyl) pyridine (3-MeO-PPy) was synthesized according to a conventional method. That is, as shown in Scheme (1A), 3-bromoanisole (2.4 mmol, 120 mmol) was used in a conventional manner under an argon stream using 3.4 g of magnesium (Mg) in dehydrated tetrahydrofuran (THF) (3-methoxy Phenyl) magnesium bromide was synthesized, which was converted into 15.8 g (100 mmol) of 2-bromopyridine and (1,2-bis (diphenylphosphino) ethane) dichloronickel (II) (Ni (dppe) Cl ₂ ) Gradually added to 1.8 g of dehydrated THF solution and stirred at 50 ° C. for 1 hour. After adding 250 ml of 5% aqueous hydrochloric acid solution to the reaction solution, the target product was extracted with chloroform, and the organic layer was distilled under reduced pressure. 17.4 g (93.9 mmol) of 2- (3-methoxyphenyl) pyridine (3-MeO-PPy) was obtained as a colorless transparent liquid. Identification is CHN elemental analysis, ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 8.68 (d, 1H), 7.72 (m, 2H), 7.59 (s, 1H), 7.54 (d, 1H), 7.37 (t, 1H), 7.22 (d, 1H), 6.97 (d, 1H), 3.89 (s, 3H). Anal. Found: C 77.44, H 6.01, N 7.53.Calcd: C 77.81, H 5.99, N 7.56.
Embedded image

[0061]
Next, the methoxy group of 3-MeO-PPy was hydrolyzed according to a conventional method. That is, as shown in Scheme (1B), 16.0 g (86.4 mmol) of 3-MeO-PPy was dissolved in concentrated hydrochloric acid and stirred at 130 ° C. for 4 hours in a sealed container. After the reaction, the reaction solution was neutralized with an aqueous sodium hydrogen carbonate solution, the target product was extracted with chloroform, and the extract was crystallized from a chloroform / hexane solution to give 2- (3-hydroxyphenyl) pyridine (3 -HO-PPy) 10.4 g (60.7 mmol) was obtained. Identification is CHN elemental analysis, ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 8.66 (d, 1H), 7.76 (t, 1H), 7.67 (d, 1H), 7.56 (s, 1H), 7.40 (d, 1H), 7.30 (t, 1H), 7.26 (t, 1H), 6.88 (d, 1H), 2.08 (br, 1H). Anal. Found: C 76.81, H 5.37, N 8.11. Calcd: C 77.17, H 5.30, N 8.18.
Embedded image

[0062]
Subsequently, tert-butyldimethylchlorosilane (TBDMS-Cl) was allowed to act on the hydroxyl group of 3-HO-PPy according to a conventional method to protect the hydroxyl group with a tert-butyldimethylsilyl group. That is, as shown in Scheme (1C), 8.6 g (50.2 mmol) of 3-HO-PPy, 10.2 g of imidazole, and 11.3 g (75.0 mmol) of tert-butyldimethylchlorosilane were mixed with 200 ml of N, N— It was dissolved in dimethylformamide and reacted at room temperature for 4 hours. The reaction solution was purified with a silica gel column to obtain 13.0 g (45.5 mmol) of 2- (3-tert-butyldimethylsilyloxyphenyl) pyridine (3-SiO-PPy) as a colorless transparent liquid. Identification is CHN elemental analysis, ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 8.68 (d, 1H), 7.74 (t, 1H), 7.68 (d, 1H), 7.58 (d, 1H), 7.48 (s, 1H), 7.32 (t, 1H), 7.22 (t, 1H), 6.89 (d, 1H), 1.01 (s, 9H), 0.24 (s, 6H). Anal. Found: C 71.08, H 8.14, N 4.88.Calcd: C 71.53, H 8.12, N 4.91.
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[0063]
Next, this 3-SiO-PPy was synthesized from bis (μ-chloro) tetrakis (2-phenylpyridine) diiridium (III) ([Ir (ppy)) ₂ Cl] ₂ ) And silver (I) trifluoromethylsulfonate (AgCF _Three SO _Three ) In the presence of That is, as shown in the scheme (1D), 5.71 g (20.0 mmol) of SiO-PPy and [Ir (ppy) under an argon stream. ₂ Cl] ₂ Add 5.37 g (5.0 mmol) of dehydrated toluene suspension to AgCF _Three SO _Three Was added and refluxed for 6 hours. After the reaction solution was purified with a silica gel column, the solvent was distilled off, and (2- (3-tert-butyldimethylsilyloxyphenyl) pyridine) bis (2-phenylpyridine) iridium (III) (Ir (PPy ) ₂ (3-SiO-PPy)) 2.53 g (3.2 mmol) was obtained. Identification is CHN elemental analysis, ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 7.86 (d, 2H), 7.78 (d, 1H), 7.64 (d, 2H), 7.55 (m, 6H), 7.16 (s, 1H), 6.85 (m, 9H), 6.60 (d, 1H), 6.45 (d, 1H). Anal. Found: C 59.53, H 4.89, N 5.34.Calcd: C 59.67, H 4.88, N 5.35.
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[0064]
Then this Ir (PPy) ₂ The silyl group of (3-SiO-PPy) was hydrolyzed according to a conventional method. That is, as shown in scheme (1E), Ir (PPy) ₂ (3-SiO-PPy) 5.1 ml of a 1M THF solution of tetra-n-butylammonium fluoride (TBAF) was added to 2.00 g (2.55 mmol) of THF solution, and the mixture was reacted at room temperature for 30 minutes. The reaction solution was purified with a silica gel column, and then the solvent was distilled off (2- (3-hydroxyphenyl) pyridine) bis (2-phenylpyridine) iridium (III) (Ir (PPy) ₂ 1.69 g (2.52 mmol) of (3-HO-PPy)) was obtained. Identification is CHN elemental analysis, ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 7.87 (d, 2H), 7.78 (d, 1H), 7.6 (m, 9H), 6.85 (m, 10H), 6.63 (d, 1H), 4.23 (s, 1H). Anal. Found: C 58.64, H 3.74, N 6.17.Calcd: C 59.09, H 3.61, N 6.26.
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[0065]
Then, as shown in Scheme (1F), Ir (PPy) under an argon stream ₂ To a dehydrated THF solution of 1.34 g (2.0 mmol) of (3-HO-PPy) and 0.81 g (8.0 mmol) of triethylamine as a deoxidizing agent, 0.25 g (2.4 mmol) of methacrylic acid chloride was added to add 20 The reaction was carried out at 5 ° C. for 5 hours. Triethylamine hydrochloride was filtered off from the reaction solution, and the filtrate was purified with a silica gel column, and then the solvent was distilled off ((2- (3- (2-methacryloyloxy) phenyl) pyridine) bis (2-phenylpyridine)). Iridium (III) (Ir (3-MA-PPy) (PPy) ₂ ) 1.28 g (1.73 mmol) was obtained. Identification is CHN elemental analysis, ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 7.87 (d, 2H), 7.78 (d, 1H), 7.6 (m, 8H), 7.40 (s, 1H), 6.8 (m, 10H), 6.59 (d, 1H), 6.35 (s, 1H), 5.74 (s, 1H), 2.08 (s, 3H) .Anal. Found: C 59.85, H 3.86, N 5.66.Calcd: C 60.15, H 3.82, N 5.69.
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[0066]
Example 2 Polymerizable Compound: Ir (3-MOI-PPy) (PPy) ₂ Synthesis of
As shown in Scheme (2A), Ir (PPy) synthesized in the same manner as in Example 1 under an argon stream ₂ (3-HO-PPy) 1.34 g (2.0 mmol), 2,6-di-tert-butyl-4-methylphenol (BHT) 9 mg, dibutyltin (IV) dilaurate (DBTL) 13 mg in dehydrated THF solution 0.37 g (2.38 mmol) of methacryloyloxyethyl isocyanate (MOI, Showa Denko) was added and reacted at 50 ° C. for 1 hour. After the reaction solution was purified with a silica gel column, the solvent was distilled off ((2- (3- (2-methacryloyloxy) ethylcarbamoyloxy) phenyl) pyridine) bis (2-phenylpyridine) iridium (III) (Ir ( PPy) ₂ 1.48 g (1.79 mmol) of (3-MOI-PPy)) was obtained. Identification is CHN elemental analysis, ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 7.87 (d, 2H), 7.80 (d, 1H), 7.6 (m, 8H), 7.42 (s, 1H), 6.8 (m, 10H), 6.59 (d, 1H), 6.14 (s, 1H), 5.60 (s, 1H), 5.21 (br, 1H), 4.28 (t, 2H), 3.57 (m, 2H), 1.96 (s, 3H). Anal. Found: C 57.78, H 4.02, N 6.72 Calcd: C 58.17, H 4.03, N 6.78
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[0067]
(Example 3) Polymerizable compound: Ir (4-MA-PPy) ₂ Synthesis of (PPy)
4-Methoxyphenylpyridine (4-MeO-PPy) was synthesized according to a conventional method. That is, as shown in scheme (3A), in the usual manner, 4-bromoanisole was used in an atmosphere of argon from 22.4 g (120 mmol) of 4-bromoanisole in anhydrous tetrahydrofuran (THF) using 3.4 g of magnesium (Mg) (4-methoxy). Phenyl) magnesium bromide was synthesized, which was converted into 15.8 g (100 mmol) of 2-bromopyridine and (1,2-bis (diphenylphosphino) ethane) dichloronickel (II) (Ni (dppe) Cl ₂ ) Slowly added to 1.8 g of dehydrated THF solution and refluxed for 1 hour. 250 ml of 5% aqueous hydrochloric acid solution was added to the reaction solution, and then washed with chloroform. The aqueous layer was neutralized with sodium hydrogen carbonate, the target product was extracted with chloroform, and the organic layer was distilled under reduced pressure. The distillate solidified immediately at room temperature to obtain 15.1 g (81.5 mmol) of 2- (4-methoxyphenyl) pyridine (4-MeO-PPy) as a white solid. Identification is CHN elemental analysis, ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 8.65 (d, 1H), 7.95 (d, 2H), 7.71 (t, 1H), 7.66 (d, 1H), 7.16 (t, 1H), 7.00 (d, 2H), 3.86 (s, Anal. Found: C 77.52, H 6.10, N 7.40.Calcd: C 77.81, H 5.99, N 7.56.
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[0068]
Subsequently, the methoxy group of 4-MeO-PPy was hydrolyzed according to a conventional method. That is, as shown in Scheme (3B), 15.0 g (80.1 mmol) of 4-MeO-PPy was dissolved in concentrated hydrochloric acid and stirred at 130 ° C. for 4 hours in a sealed container. After the reaction, the reaction solution was neutralized with an aqueous sodium hydrogen carbonate solution, the target product was extracted with chloroform, and the extract was crystallized from a chloroform / hexane solution to give 2- (4-hydroxyphenyl) pyridine (4 -HO-PPy) 10.0g (58.5 mmol) was obtained. Identification is CHN elemental analysis, ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 8.63 (d, 1H), 7.82 (d, 2H), 7.74 (t, 1H), 7.65 (d, 1H), 7.20 (t, 1H), 6.85 (d, 2H). Anal. Found: C 76.91, H 5.39, N 8.02.Calcd: C 77.17, H 5.30, N 8.18.
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[0069]
Next, this 4-HO-PPy was converted into sodium hexachloroiridate n hydrate (Na _Three IrCl ₆ ・ NH ₂ O) and reacted with bis (μ-chloro) tetrakis (2- (4-hydroxyphenyl) pyridine) diiridium (III) ([Ir (4-HO-PPy) ₂ Cl] ₂ ) Was synthesized. That is, as shown in Scheme (3C), Na _Three IrCl ₆ ・ NH ₂ 10.0 g of O was dissolved in 400 ml of a 3: 1 mixed solvent of 2-ethoxyethanol and water, and argon gas was blown in for 30 minutes, and then 8.6 g (50.2 mmol) of 4-HO-PPy under an argon stream. Was dissolved and refluxed for 5 hours. After the reaction, the solvent was distilled off and recrystallized from ethanol to give [Ir (4-HO-PPy) as red-orange crystals. ₂ Cl] ₂ 5.88 g (5.18 mmol) were obtained. Identification is CHN elemental analysis, ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, DMSO-d ₆ ), ppm: 9.66 (d, 2H), 9.38 (d, 2H), 7.95 (m, 8H), 7.61 (d, 2H), 7.54 (d, 2H), 7.38 (t, 2H), 7.26 (t, 2H), 6.33 (d, 2H), 6.28 (d, 2H), 5.67 (s, 2H), 5.12 (s, 2H). Anal. Found: C 46.33, H 2.51, N 4.76.Calcd: C 46.52, H 2.84, N 4.93.
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[0070]
This [Ir (4-HO-PPy) ₂ Cl] ₂ In accordance with a conventional method, silver trifluoromethylsulfonate (I) (AgCF _Three SO _Three ) In the presence of 2-phenylpyridine (PPy). That is, as shown in Scheme (3D), [Ir (4-HO-PPy) under an argon stream. ₂ Cl] ₂ AgCF was added to a dehydrated toluene suspension of 3.98 g (3.5 mmol) and PPy 15.5 g (10.0 mmol). _Three SO _Three Was added and refluxed for 6 hours. After the reaction solution was purified with a silica gel column, the solvent was distilled off, and bis (2- (4-hydroxyphenyl) pyridine) (2-phenylpyridine) iridium (III) (Ir (4-HO-PPy) was obtained as a yellow powder. ₂ (PPy)) 2.20 g (3.2 mmol) was obtained. Identification is CHN elemental analysis, ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 7.88 (d, 1H), 7.78 (d, 2H), 7.6 (m, 9H), 6.85 (m, 8H), 6.64 (d, 2H). Anal. Found: C 57.46, H 3.49, N 5.99.Calcd: C 57.71, H 3.52, N 6.12.
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[0071]
Then, as shown in Scheme (3E), Ir (4-HO-PPy) under an argon stream ₂ (PPy) 0.50 g (4.8 mmol) of methacrylic acid chloride was added to a dehydrated THF solution of 1.37 g (2.0 mmol) and triethylamine 0.81 g (8.0 mmol) as a deoxidizer, and the mixture was stirred at 20 ° C. for 5 hours. Reacted. After the triethylamine hydrochloride was filtered off from the reaction solution and the filtrate was purified with a silica gel column, the solvent was distilled off to give bis ((2- (4- (2-methacryloyloxy) phenyl) pyridine) (2-phenylpyridine). ) Iridium (III) (Ir (4-MA-PPy) ₂ (PPy)) 1.55 g (1.88 mmol) was obtained. Identification is CHN elemental analysis, ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 7.87 (d, 1H), 7.78 (d, 2H), 7.6 (m, 9H), 6.8 (m, 8H), 6.59 (s, 2H), 6.35 (s, 2H), 5.74 (s, 2H), 2.08 (s, 6H). Anal. Found: C 59.95, H 3.82, N 5.04.Calcd: C 59.84, H 3.92, N 5.11.
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[0072]
(Example 4) Polymerizable compound: Ir (4-MOI-PPy) ₂ Synthesis of (PPy)
As shown in scheme (4A), Ir (4-HO-PPy) synthesized in the same manner as in Example 3 under an argon stream. ₂ (PPy) 1.37 g (2.0 mmol), 2,6-di-tert-butyl-4-methylphenol (BHT) 18 mg, dibutyltin (IV) dilaurate (DBTL) 26 mg in dehydrated THF solution in methacryloyloxyethyl isocyanate (MOI, Showa Denko) 0.75g (4.83mmol) was added, and it was made to react at 50 degreeC for 1 hour. After the reaction solution was purified with a silica gel column, the solvent was distilled off, and bis ((2- (4- (2-methacryloyloxy) ethylcarbamoyloxy) phenyl) pyridine) (2-phenylpyridine) iridium (III) (Ir (MOI-PPy) ₂ (PPy)) 1.68 g (1.68 mmol) was obtained. Identification is CHN elemental analysis, ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 7.85 (d, 1H), 7.81 (d, 2H), 7.6 (m, 9H), 6.8 (m, 8H), 6.58 (d, 2H), 6.12 (s, 2H), 5.60 (s, 2H), 5.21 (br, 2H), 4.28 (t, 4H), 3.58 (m, 4H), 1.96 (s, 6H). Anal. Found: C 56.38, H 4.02, N 6.72.Calcd: C 56.62, H 4.25, N 7.02.
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[0073]
(Example 5) Polymerizable compound: Ir (3-MA-PPy) (3-PrCO-PPy) ₂ Synthesis of
2- (3-methoxyphenyl) pyridine (3-MeO-PPy) was synthesized in the same manner as in Scheme (1A) of Example 1.
[0074]
Then, this 3-MeO-PPy and tris (acetylacetonato) iridium (III) (Ir (acac)) _Three ) Is reacted at high temperature to give tris (3-methoxyphenylpyridine) iridium (III) (Ir (3-MeO-PPy) as shown in Scheme (5A) below. _Three ) Was synthesized.
[0075]
That is, 3-MeO-PPy 5.0 g (27.0 mmol) and Ir (acac) _Three By reacting 2.0 g (4.1 mmol) in 200 ml of glycerol at 250 ° C. for 9 hours and purifying with a column, Ir (3-MeO-PPy) was obtained as a fluorescent yellow powder. _Three 0.40 g (0.54 mmol) was obtained. Identification is CHN elemental analysis, ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 7.82 (d, 3H), 7.56 (t, 3H), 7.53 (s, 3H), 7.25 (d, 3H), 6.84 (t, 3H), 6.67 (d, 3H), 6.60 (d, 3H), 3.80 (s, 9H). Anal. Found: C 57.60, H 4.17, N 5.57.Calcd: C 58.05, H 4.06, N 5.64
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[0076]
By repeating these operations 8 times, 3.20 g (4.3 mmol) of Ir (3-MeO-PPy) _Three Got.
[0077]
This Ir (3-MeO-PPy) _Three In accordance with a conventional method, the MeO group is hydrolyzed in an aqueous hydrochloric acid solution to form an OH group, and tris (3-hydroxyphenylpyridine) iridium (III) as a powder
(Ir (3-HO-PPy) _Three (Scheme (5B)).
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[0078]
Ir (3-HO-PPy) _Three Is reacted with methacrylic acid chloride at a molar ratio of 1: 1 according to the following scheme (5C) to methacrylate a part of the OH group to give Ir (3-MA-PPy) (3-HO-PPy) ₂ Was synthesized as a main component. The remaining OH groups are then reacted with propionic acid chloride (PrCOCl) to give Ir (3-MA-PPy) (3-PrCO-PPy) ₂ Was obtained as a main component.
[0079]
That is, dehydrated THF 32 ml, Ir (3-HO-PPy) in a reaction vessel _Three After charging 2.81 g (4.0 mmol) and 2.40 g (23.7 mmol) of triethylamine as a deoxidizing agent, a solution of 0.42 g (4.0 mmol) of methacrylic acid chloride in 16 ml of dehydrated THF was added over 30 minutes. The solution was added dropwise and reacted at 20 ° C. for 5 hours. To this reaction solution, a solution of 1.48 g (16.0 mmol) of propionic acid chloride dissolved in 16 ml of dehydrated THF was added dropwise over 30 minutes, and the remaining OH group was reacted by reacting at 20 ° C. for 5 hours to obtain triethylamine. The hydrochloride salt was filtered off. The solvent of the filtrate was evaporated to dryness, and the obtained solid component was purified by recrystallization twice in a chloroform / methanol mixed solvent to obtain the target Ir (3-MA-PPy) (3-PrCO-PPy). ) ₂ 2.305 g (2.61 mmol) was obtained as a powder. This identification is based on the elemental analysis of CHN and ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 7.82 (m, 3H), 7.56 (m, 6H), 7.26 (m, 3H), 6.84 (m, 3H), 6.67 (m, 3H), 6.61 (m, 3H), 6.35 (s, 1H), 5.74 (s, 1H), 2.67 (q, 4H), 2.08 (s, 3H), 1.42 (t, 6H). Anal. Found: C 58.13, H 4.10, N 4.72. Calcd: C 58.49, H 4.11, N 4.76.
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[0080]
(Example 6) Polymerizable compound: Ir (3-MA-PPy) _Three Synthesis of
Monomer intermediate Ir (3-HO-PPy) synthesized in the same manner as in Example 5. _Three As shown in the following scheme (6A), all OH groups are methacrylated by reacting with methacrylic acid chloride at a molar ratio of 1: 3 to give Ir (3-MA-PPy) _Three A complex was synthesized.
[0081]
That is, dehydrated THF 32 ml, Ir (3-HO-PPy) in a reaction vessel _Three After charging 2.81 g (4 mmol) and 2.40 g (23.7 mmol) of triethylamine as a deoxidizer, a solution of 1.29 g (12.3 mmol) of methacrylic acid chloride dissolved in 32 ml of dehydrated THF was added dropwise over 90 minutes. And reacted at 20 ° C. for 5 hours. The precipitated triethylamine hydrochloride is filtered off, the solvent of the filtrate is evaporated to dryness, and the resulting solid component is purified by recrystallization twice with a mixed solvent of hexafluoroisopropanol / methanol. Trifunctional Ir (3-MA-PPy) _Three 2.805 g (3.09 mmol) was obtained as a powder. This identification is based on CHN elemental analysis and ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 7.82 (d, 3H), 7.58 (t, 3H), 7.55 (s, 3H), 7.26 (d, 3H), 6.86 (t, 3H), 6.67 (d, 3H), 6.63 (d, 3H), 6.36 (s, 3H), 5.74 (s, 3H), 2.09 (s, 9H). Anal. Found: C 59.21, H 3.98, N 4.58.Calcd: C 59.59, H 4.00, N 4.63.
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[0082]
(Example 7) Polymerizable compound: Ir (3-MOI-PPy) (3-PrCO-PPy) ₂ Synthesis of
Monomer intermediate Ir (3-HO-PPy) synthesized in the same manner as in Example 5. _Three As shown in the following scheme (7A), methacryloyloxyethyl isocyanate (MOI, manufactured by Showa Denko) was reacted at a molar ratio of 1: 1, and then the remaining OH group was reacted with PrCOCl to give Ir (3-MOI-PPy) (3-PrCO-PPy) ₂ Was obtained as a main component.
[0083]
That is, dehydrated THF 32 ml, Ir (3-HO-PPy) in a reaction vessel _Three 2.81 g (4.0 mmol) and MOI 0.62 g (4.0 mmol) were charged, and a catalytic amount of dibutyltin dilaurate was added, followed by reaction at 20 ° C. for 5 hours. After adding 2.40 g (23.7 mmol) of triethylamine as a deoxidizer to this reaction solution, a solution prepared by dissolving 1.48 g (16.0 mmol) of propionic acid chloride in 16 ml of dehydrated THF was added dropwise over 30 minutes. The remaining OH groups were reacted by reacting at 20 ° C. for 5 hours, and triethylamine hydrochloride was filtered off. The solvent of the filtrate was evaporated to dryness, and the obtained solid component was purified by recrystallization twice in a chloroform / methanol mixed solvent to obtain the target Ir (3-MOI-PPy) (3-PrCO-PPy). ) ₂ 2.620 g (2.70 mmol) was obtained as a powder. Identification includes CHN elemental analysis and ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 7.82 (m, 3H), 7.56 (m, 6H), 7.26 (m, 3H), 6.84 (m, 3H), 6.67 (m, 3H), 6.61 (m, 3H), 6.14 (s, 1H), 5.61 (s, 1H), 5.23 (br, 1H), 4.29 (t, 2H), 3.58 (m, 2H), 2.66 (q, 4H), 1.95 (s, 3H), 1.41 (t, 6H Anal. Found: C 56.58, H 4.25, N 5.72.Calcd: C 56.95, H 4.26, N 5.78.
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[0084]
(Example 8) Polymerizable compound: Ir (3-MOI-PPy) ₂ Synthesis of (3-PrCO-PPy)
Monomer intermediate Ir (3-HO-PPy) synthesized in the same manner as in Example 5. _Three As shown in the following scheme (8A), methacryloyloxyethyl isocyanate (MOI, manufactured by Showa Denko) is reacted at a molar ratio of 1: 2, and then the remaining OH group is reacted with PrCOCl to give Ir (3-MOI-PPy) ₂ A (3-PrCO-PPy) complex was obtained.
[0085]
That is, 48 ml of dehydrated THF, Ir (3-HO-PPy) in a reaction vessel _Three 2.81 g (4.0 mmol) and MOI 1.24 g (8.0 mmol) were charged, and a catalytic amount of dibutyltin dilaurate was added, followed by reaction at 20 ° C. for 5 hours. After adding 2.400 g (24.5 mmol) of triethylamine as a deoxidizer to this reaction solution, a solution prepared by dissolving 0.74 g (8.0 mmol) of propionic acid chloride in 8 ml of dehydrated THF was added dropwise over 30 minutes. The remaining OH groups were reacted by reacting at 20 ° C. for 5 hours, and triethylamine hydrochloride was filtered off. The solvent of the filtrate was evaporated to dryness, and the obtained solid component was purified by performing recrystallization twice with a chloroform / methanol mixed solvent to obtain the target Ir (3-MOI-PPy). ₂ 2.75 g (2.57 mmol) of (3-PrCO-PPy) was obtained as a powder. This identification is based on CHN elemental analysis and ¹ Performed by 1 H-NMR. ¹ H NMR (270MHz, CDCl _Three ), ppm: 7.81 (m, 3H), 7.54 (m, 6H), 7.26 (m, 3H), 6.86 (m, 3H), 6.68 (m, 3H), 6.59 (m, 3H), 6.13 (s, 2H), 5.60 (s, 2H), 5.22 (br, 2H), 4.27 (t, 4H), 3.57 (m, 4H), 2.67 (q, 2H), 1.95 (s, 6H), 1.41 (t, 3H Anal. Found: C 55.86, H 4.37, N 6.51.Calcd: C 56.17, H 4.34, N 6.55.
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[0086]
Example 9 Ir (3-MA-PPy) (PPy) ₂ Synthesis of polymers
Ir (3-MA-PPy) (PPy) synthesized in Example 1 in a reaction vessel ₂ 1.11 g (1.5 mmol) of the complex, 0.010 g (0.061 mmol) of 2,2′-azobis (isobutyronitrile) (AIBN) and 10 ml of butyl acetate were substituted with nitrogen, and then at 80 ° C. The reaction was carried out for 10 hours (Scheme (9A)). After the reaction, the reaction solution was dropped into acetone for reprecipitation, and the polymer was collected by filtration. The recovered polymer in chloroform is added dropwise to methanol and re-precipitated twice to purify, and after recovery, vacuum dried to obtain the desired Ir (3-MA-PPy) (PPy) ₂ 0.92 g of polymer was obtained as a powder. Further, CHN elemental analysis of the obtained polymer was Ir (3-MA-PPy) (PPy) ₂ The same composition was supported. Moreover, the weight average molecular weight of the polymer was 12000 (GPC measurement, eluent: THF) in terms of polystyrene.
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[0087]
(Example 10) Ir (3-MOI-PPy) (PPy) ₂ Synthesis of polymers
Ir (3-MOI-PPy) (PPy) synthesized in Example 2 in a reaction vessel ₂ 1.11 g (1.5 mmol) of the complex, 0.010 g (0.061 mmol) of 2,2′-azobis (isobutyronitrile) (AIBN) and 10 ml of butyl acetate were substituted with nitrogen, and then at 80 ° C. The reaction was carried out for 10 hours (Scheme (10A)). After the reaction, the reaction solution was dropped into acetone for reprecipitation, and the polymer was collected by filtration. The recovered polymer solution in chloroform is added dropwise to methanol and re-precipitated twice to purify, and after recovery, vacuum dried to obtain the target Ir (3-MOI-PPy) (PPy). ₂ 1.02 g of polymer was obtained as a powder. Moreover, CHN elemental analysis of the obtained copolymer is Ir (3-MOI-PPy) (PPy). ₂ And supported that the composition was almost the same. Moreover, the weight average molecular weight of the copolymer was 20000 (GPC measurement, eluent: THF) in terms of polystyrene.
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[0088]
(Example 11) Ir (3-MA-PPy) (3-PrCO-PPy) ₂ Synthesis of polymers
Ir (3-MA-PPy) (3-PrCO-PPy) synthesized in Example 5 in a reaction vessel ₂ Nitrogen substitution was performed by adding 2.22 g (2.5 mmol) of the complex, 0.010 g (0.061 mmol) of 2,2′-azobis (isobutyronitrile) (AIBN) and 30 ml of butyl acetate, and then at 80 ° C. The reaction was carried out for 10 hours (Scheme (11A)). After the reaction, the reaction solution was dropped into acetone for reprecipitation, and the polymer was collected by filtration. The recovered polymer in chloroform was added dropwise to methanol and reprecipitated twice to purify, recovered and vacuum dried to obtain the target Ir (3-MA-PPy) (3-PrCO- PPy) ₂ 1.85 g of polymer was obtained as a powder. Further, CHN elemental analysis of the obtained polymer was Ir (3-MA-PPy) (3-PrCO-PPy). ₂ The same composition was supported. Moreover, the weight average molecular weight of the polymer was 8000 (GPC measurement, eluent: THF) in terms of polystyrene.
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[0089]
(Example 12) Ir (3-MA-PPy) _Three Synthesis of polymers
Ir (3-MA-PPy) synthesized in Example 6 in a reaction vessel _Three 2.28 g (2.5 mmol) of the complex, 0.010 g (0.061 mmol) of 2,2′-azobis (isobutyronitrile) (AIBN) and 30 ml of butyl acetate were substituted with nitrogen, and then at 80 ° C. When reacted for 10 hours (Scheme (12A)), an insoluble polymer was precipitated. The polymer was recovered by filtration, washed with 100 ml of chloroform and 100 ml of methanol, and then vacuum dried to obtain the target Ir (3-MA-PPy). _Three 2.10 g of polymer was obtained as a powder. Further, CHN elemental analysis of the obtained polymer was Ir (3-MA-PPy). _Three And supported that the composition was almost the same. This polymer was considered to have a crosslinked structure, was insoluble in various solvents, and could not be measured for molecular weight by GPC.
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[0090]
(Example 13) Ir (3-MOI-PPy) (3-PrCO-PPy) ₂ Synthesis of polymers
Ir (3-MOI-PPy) (3-PrCO-PPy) synthesized in Example 7 in a reaction vessel ₂ 2.43 g (2.5 mmol) of the complex, 0.010 g (0.061 mmol) of 2,2′-azobis (isobutyronitrile) (AIBN) and 30 ml of butyl acetate were added to perform nitrogen substitution, and then at 80 ° C. The reaction was carried out for 10 hours (Scheme (13A)). After the reaction, it was added dropwise to acetone for reprecipitation, and the polymer was collected by filtration. The recovered polymer chloroform solution is purified by dropping twice into methanol and reprecipitating twice, and after recovery, vacuum drying is performed to obtain the target Ir (3-MOI-PPy) (3-PrCO- PPy) ₂ 2.05 g of polymer was obtained as a powder. Further, CHN elemental analysis of the obtained copolymer was Ir (3-MOI-PPy) (3-PrCO-PPy). ₂ And supported that the composition was almost the same. The weight average molecular weight of the copolymer was 18000 (GPC measurement, eluent: THF) in terms of polystyrene.
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[0091]
(Example 14) Ir (3-MOI-PPy) ₂ Synthesis of (3-PrCO-PPy) polymer
Ir (3-MOI-PPy) synthesized in Example 8 in a reaction vessel ₂ (3-PrCO-PPy) complex 2.46 g (2.5 mmol), 2,2′-azobis (isobutyronitrile) (AIBN) 0.010 g (0.061 mmol), and 30 ml of butyl acetate were added to replace nitrogen. After the reaction, the mixture was reacted at 80 ° C. for 10 hours (Scheme (14A)), whereby an insoluble polymer was precipitated. The polymer was recovered by filtration, washed with 100 ml of chloroform and 100 ml of methanol, and then vacuum-dried to obtain the target Ir (3-MOI-PPy). ₂ 2.21-g of (3-PrCO-PPy) polymer was obtained as a powder. Further, CHN elemental analysis of the obtained polymer was Ir (3-MOI-PPy). ₂ It supported that the composition was almost the same as (3-PrCO-PPy). This polymer was considered to have a crosslinked structure, was insoluble in various solvents, and could not be measured for molecular weight by GPC.
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Example 15 Ir (3-MA-PPy) (3-PrCO-PPy) ₂ / Ir (3-MA-PPy) _Three Copolymer synthesis
Ir (3-MA-PPy) (3-PrCO-PPy) synthesized in Example 5 in a reaction vessel ₂ 1.11 g (1.25 mmol) of complex, Ir (MA-PPy) synthesized in Example 6 _Three 1.14 g (1.25 mmol) of the complex, 0.010 g (0.061 mmol) of 2,2′-azobis (isobutyronitrile) (AIBN) and 30 ml of butyl acetate were substituted with nitrogen, and then at 80 ° C. When reacted for 10 hours (Scheme (15A)), an insoluble polymer was precipitated. The polymer was recovered by filtration, washed with 100 ml of chloroform and 100 ml of methanol, and then vacuum dried to obtain the target Ir (3-MA-PPy) (3-PrCO-PPy). ₂ / Ir (3-MA-PPy) _Three 2.05 g of copolymer was obtained as a powder. Further, CHN elemental analysis of the obtained polymer was Ir (3-MA-PPy) (3-PrCO-PPy). ₂ And Ir (3-MA-PPy) _Three Was copolymerized at a molar ratio of 1: 1. This copolymer is considered to have a crosslinked structure, is insoluble in various solvents, and could not be measured for molecular weight by GPC.
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Example 16 Ir (3-MOI-PPy) (3-PrCO-PPy) ₂ / Ir (3-MOI-PPy) ₂ Synthesis of (3-PrCO-PPy) copolymer
Ir (3-MOI-PPy) (3-PrCO-PPy) synthesized in Example 7 in a reaction vessel ₂ 1.21 g (1.25 mmol) of complex, Ir (3-MOI-PPy) synthesized in Example 8 ₂ (3-PrCO-PPy) 1.23 g (1.25 mmol), 2,2′-azobis (isobutyronitrile) (AIBN) 0.010 g (0.061 mmol), and 30 ml of butyl acetate were added to perform nitrogen substitution. After that, the mixture was reacted at 80 ° C. for 10 hours (Scheme (16A)) to precipitate an insoluble polymer. The polymer was recovered by filtration, washed with 100 ml of chloroform and 100 ml of methanol, and then vacuum-dried to obtain the target Ir (3-MOI-PPy) (3-PrCO-PPy). ₂ / Ir (3-MOI-PPy) ₂ 2.18 g of (3-PrCO-PPy) copolymer was obtained as a powder. Further, CHN elemental analysis of the obtained polymer was Ir (3-MOI-PPy) (3-PrCO-PPy). ₂ And Ir (3-MOI-PPy) ₂ It supported that (3-PrCO-PPy) was copolymerized at a molar ratio of 1: 1. This copolymer is considered to have a crosslinked structure, is insoluble in various solvents, and could not be measured for molecular weight by GPC.
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【Effect of the invention】
The novel polymerizable compound of the present invention gives a novel polymer containing an iridium complex portion, and by using this as a luminescent material of an organic light-emitting device, it emits light from an excited triplet state with high efficiency and has a large area. An organic light-emitting element that is possible and suitable for mass production can be provided.

Claims (34)

A polymerizable compound represented by the formula (1).

[Wherein, at least one of A, B, and C represents a substituent having a polymerizable functional group (excluding a bromine atom), and the rest of A, B, and C are each independently a hydrogen atom, An organic group having 1 to 20 carbon atoms which may have a halogen atom (excluding a bromine atom), a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a hetero atom. R _{1 to} R ₁₅ each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]   The polymerizable compound according to claim 1, wherein at least one of A, B, and C in the formula (1) is a substituent having an acrylate group or a methacrylate group.   The polymerizable compound according to claim 2, wherein one of A, B and C in the formula (1) is a substituent having an acrylate group or a methacrylate group. A polymerizable compound represented by the formula (2).

[Wherein R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a hetero atom, and an organic group having 1 to 20 carbon atoms. Represents. ] The polymerizable compound according to claim 4, wherein R ₁ and R _{2 in} the formula (2) are hydrogen atoms. A polymerizable compound represented by formula (3).

[Wherein R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a hetero atom, and an organic group having 1 to 20 carbon atoms. Represents. ] The polymerizable compound according to claim 6, wherein R ₁ and R _{2 in} the formula (3) are hydrogen atoms.   The polymerizable compound according to claim 2, wherein two of A, B and C in the formula (1) are substituents having an acrylate group or a methacrylate group. A polymerizable compound represented by formula (4).

[Wherein, R ₁ represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ] The polymerizable compound according to claim 9, wherein R _{1 in} formula (4) is a hydrogen atom. A polymerizable compound represented by formula (5).

[Wherein, R ₁ represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ] The polymerizable compound according to claim 11, wherein R _{1 in} formula (5) is a hydrogen atom.   The polymerizable compound according to claim 2, wherein all of A, B, and C in the formula (1) are substituents having an acrylate group or a methacrylate group. A polymerizable compound represented by formula (6).

A polymerizable compound represented by formula (7).

  The polymer obtained by superposing | polymerizing the polymeric compound of any one of Claims 1-15.   A copolymer comprising at least one monomer unit derived from the polymerizable compound according to any one of claims 1 to 15. After reacting the iridium binuclear complex represented by the formula (8) with the phenylpyridine derivative represented by the formula (9), the reactive substituent in the reaction product is reacted with the compound having a polymerizable functional group. A method for producing a polymerizable compound comprising a mononuclear iridium complex portion, characterized by comprising:

[Wherein X and Y are reactive substituents, or a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a hetero atom, and an organic group having 1 to 20 carbon atoms. R _{1 to} R ₂₀ each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group, or an organic group having 1 to 20 carbon atoms that may have a hetero atom. Represents. ]

[In the formula, Z represents a reactive substituent, or a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. R _{1 to} R ₅ each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. . However, at least one of X and Y in formula (8) and Z in formula (9) is a reactive substituent. ] X and Y in the formula (8) are each independently a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. The method for producing a polymerizable compound containing a mononuclear iridium complex part according to claim 18 , wherein Z in formula (9) is a reactive substituent.   The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to claim 19, wherein Z in formula (9) is a hydroxyl group.   X and Y in the formula (8) are reactive substituents, and Z in the formula (9) has a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group, and a hetero atom. The method for producing a polymerizable compound containing a mononuclear iridium complex portion according to claim 18, which is any one of organic groups having 1 to 20 carbon atoms.   The method for producing a polymerizable compound containing a mononuclear iridium complex part according to claim 21, wherein X and Y in formula (8) are hydroxyl groups. When an iridium complex represented by the formula (10) and a compound having a polymerizable functional group (excluding a bromine atom) are reacted at a constant molar ratio, and an unreacted reactive substituent remains, The method for producing a polymerizable compound containing an iridium complex part according to any one of claims 1 to 15, wherein a reactive substituent in the obtained product is reacted with a non-polymerizable compound. .

[Wherein, X is a reactive substituent, R _{1 to} R ₂₄ are each independently a hydrogen atom, a halogen atom (excluding a bromine atom) , a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group, or hetero. The C1-C20 organic group which may have an atom is represented. ]   The production of a polymerizable compound containing an iridium complex part according to claim 23, wherein the molar ratio of the iridium complex represented by formula (10) and the compound having a polymerizable functional group is 1: (0.5 to 1.5). Method.   24. The production of a polymerizable compound containing an iridium complex moiety according to claim 23, wherein the molar ratio of the iridium complex represented by formula (10) and the compound having a polymerizable functional group is 1: (1.5 to 2.5). Method.   The method for producing a polymerizable compound containing an iridium complex part according to claim 23, wherein the molar ratio of the iridium complex represented by the formula (10) and the compound having a polymerizable functional group is 1: (2.5 or more).   27. The method for producing a polymerizable compound containing an iridium complex portion according to any one of claims 23 to 26, wherein the reactive substituent in formula (10) is a hydroxyl group. A compound represented by formula (11):

[In the formula, at least one of X, Y and Z represents a hydroxyl group, and each of the residues independently has a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a heteroatom. Or an organic group having 1 to 20 carbon atoms. R _{1 to} R ₁₅ each independently represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]   The compound according to claim 28, wherein one of X, Y and Z in formula (11) is a hydroxyl group. A compound represented by formula (12):

  29. The compound according to claim 28, wherein two of X, Y and Z in the formula (11) are hydroxyl groups. A compound represented by formula (13):

29. The compound according to claim 28, wherein all of X, Y and Z in the formula (11) are hydroxyl groups.
(11) The compound shown by Formula (14).