JP4229262B2 - Photoresponsive polymer, method for producing ammonium carboxylate crystal, and method for producing layered crystal of polymer having carboxyl group and amine - Google Patents

Description

【００４９】
で示すように、アンモニウムカルボキシレート基を有する共役ジエンとしての（Ｚ，Ｚ）−ムコン酸アンモニウムの結晶が生成する。
【００５０】
（Ｚ，Ｚ）−ムコン酸アンモニウムの結晶は、図１の（ａ）に示すように、（Ｚ，Ｚ）−ムコン酸アンモニウム分子１がスタッキングしてできるカラム構造がみられる。すなわち、（Ｚ，Ｚ）−ムコン酸アンモニウムの結晶は、（Ｚ，Ｚ）−ムコン酸アニオン分子３と第２級アンモニウムイオン（ＲＣＨ₂ＮＨ₃ ⁺）分子２とが層状に配列された状態でイオン結合することで、形成されている。（Ｚ，Ｚ）−ムコン酸アンモニウムの結晶内では、互いに平行な複数の平面（層）上にそれぞれ複数の（Ｚ，Ｚ）−ムコン酸アニオン分子３の中心が揃い、共役π平面を形成する。また、各（Ｚ，Ｚ）−ムコン酸アニオン分子３および各第２級アンモニウムイオン分子２は、上記平面に対して垂直に配向する。
【００５１】
（Ｚ，Ｚ）−ムコン酸の結晶は、アミン（Ａ）との接触面積を大きくして反応速度を高めるために結晶サイズを小さくすることが望ましい。したがって、（Ｚ，Ｚ）−ムコン酸の結晶と第１級アミンとの混合方法としては、乳鉢中ですりつぶしながら混合する方法が好ましい。混合時間は、特に限定されるものではなく、例えば、乳鉢中ですりつぶしながら混合する場合には３０分間程度で十分である。
【００５２】
（Ｚ，Ｚ）−ムコン酸とアミン（Ａ）との使用量の比は、理論量比、すなわちムコン酸１モル当たりのアミン（Ａ）の使用量が２モルとなるような比にすることが好ましい。
【００５３】
次に、第２のステップでは、次に、第２のステップでは、アンモニウムカルボキシレート基を有する共役ジエンとしての（Ｚ，Ｚ）−ムコン酸アンモニウムの結晶を、結晶状態に保持しながら固相で重合させる。これにより、（Ｚ，Ｚ）−ムコン酸アンモニウムがラジカル連鎖反応機構で重合し、次式
【００５４】
【化２】

【００５５】
で示すように、２，５−ポリムコン酸アンモニウムが生成する。なお、上記式中、ｎは繰り返し構造単位の数を表す。ｎは、ＧＰＣ（ゲル浸透クロマトグラフィー）により確認でき、一般に１０〜１０，０００，０００の範囲内、典型的には、１００〜１００，０００である。
【００５６】
このとき、（Ｚ，Ｚ）−ムコン酸アンモニウムの結晶内では、前述したようにムコン酸アニオン分子３が層状に配列されている。そのため、重合反応は、この層状配列（結晶格子）の支配下で、単量体分子が結晶内において最小限の動きを伴って重合するトポケミカル(topochemical)重合となる。その結果、高分子量で、かつ、繰り返し構造単位中の立体中心が全て制御された、高度な立体規則性を持つ２，５−ポリムコン酸アンモニウムの層状結晶が生成する。したがって、上記固相重合により得られる重合体（２，５−ポリムコン酸アンモニウム）の結晶は、単量体（（Ｚ，Ｚ）−ムコン酸アンモニウム）の結晶と同一の空間対称性を持ち、また、この重合体中の繰り返し構造単位の重心は、単量体の重心とほぼ一致する。
【００５７】
上記の２，５−ポリムコン酸アンモニウムの層状結晶は、図１の（ｂ）に示すように、２，５−ポリムコン酸アニオン（カルボキシレートイオン）分子４で形成された複数の層（ポリカルボン酸層）の間に第２級アンモニウムイオン（カウンターアンモニウムカチオン）分子２がインターカレートされ、第２級アンモニウムイオン分子２が完全配向した構造を持つ。このとき、２，５−ポリムコン酸アンモニウムの層状結晶の層間隔ｄ１は、アミン（Ａ）の炭素鎖の長さに応じて変化する。
【００５８】
上記重合体の結晶中には、単量体の結晶構造内に形成されている水素結合ネットワークと同様の規則正しい水素結合ネットワークが形成される。この水素結合ネットワークは、結晶構造解析の結果より確認されており、また、幾つかのパターンに分類できることが分かっている（J. Am. Chem. Soc., 121(48), 11122-11129 (1999)参照）。
【００５９】
以上のように、分子間の相互作用を利用して、ジエン部分が重合に都合の良いようにスタッキングするよう分子配列をデザインしたトポケミカル重合により、立体規則性だけでなく二次元構造も制御された重合体を合成できる。
【００６０】
上記固相重合はＸ線照射により非常に速く進行するが、イメージプレートやＣＣＤ（電荷結合素子）カメラシステムを搭載した迅速解Ｘ線結晶構造解析により、固相重合前後の結晶構造の変化を解析することが可能である。この迅速解Ｘ線結晶構造解析とＮＭＲ（核磁気共鳴）スペクトル測定の結果より、得られる重合体は、メゾ−ジイソタクチックトランス−２，５−構造を持つ立体規則性重合体であることが確認されている。
【００６１】
上記固相重合は、アンモニウムカルボキシレート基を有する共役ジエンとしての（Ｚ，Ｚ）−ムコン酸アンモニウムの結晶に対し、固相で放射線を照射する方法（以下、「放射線重合法」と称する）で行ってもよく、アンモニウムカルボキシレート基を有する共役ジエンとしての（Ｚ，Ｚ）−ムコン酸アンモニウムの結晶をその結晶状態を保ちながら熱重合させる方法（以下、「熱重合法」と称する）で行ってもよく、これらを併用してもよい。放射線重合法と熱重合法とを比較すると、得られる結晶の純度の点では放射線重合法（特にＸ線やγ線を用いた場合）が有利である。一方、熱重合法は、放射線重合法と比べて、大掛かりな反応装置を必要としない、Ｘ線やγ線等を用いた場合のような被爆の危険性が全くなく安全性が高い、といった利点がある。
【００６２】
上記放射線重合法に用いる放射線としては、紫外線、Ｘ線、γ線等が挙げられる。透過性の高いＸ線やγ線を用いた場合、結晶全体で均一に開始反応が起こり、歪みや欠陥が特に少ない重合体結晶が作成できる。
【００６３】
また、上記熱重合法における加熱温度は、（Ｚ，Ｚ）−ムコン酸アンモニウムが重合を開始する温度であればよいが、（Ｚ，Ｚ）−ムコン酸アンモニウムの融点または分解温度より低いことが好ましい。これにより、（Ｚ，Ｚ）−ムコン酸アンモニウムを結晶状態に保持したまま熱重合を行うことができる。ここで、上記モノマーの融点より低い温度は、（Ｚ，Ｚ）−ムコン酸アンモニウムが融解を開始する温度より低いことが好ましい。さらに、（Ｚ，Ｚ）−ムコン酸アンモニウムの分解温度より低い温度は、（Ｚ，Ｚ）−ムコン酸アンモニウムが分解を開始する温度より低いことが好ましい。さらに、熱重合における温度は、（Ｚ，Ｚ）−ムコン酸アンモニウムが分解を開始する温度以上の場合には、（Ｚ，Ｚ）−ムコン酸アンモニウムの重合の速度が速く、かつ上記重合の速度と分解の速度と差が大きい温度であることが好ましい。
【００６４】
次に、第３ステップでは、アンモニウムカルボキシレート基を有する共役ジエンとしての２，５−ポリムコン酸アンモニウムの結晶を加熱することにより熱分解させる。これにより、次式
【００６５】
【化３】

【００６６】
で示すように、アンモニウムイオンがアミンとして脱離し、２，５−ポリムコン酸アンモニウムの結晶が、カルボキシル基を有する共役ジエンの重合体の層状結晶としての２，５−ポリムコン酸の層状結晶に変換される。
【００６７】
なお、２，５−ポリムコン酸アンモニウムの結晶を２，５−ポリムコン酸の層状結晶に変換する方法としては、塩酸等の酸を用いて加水分解する方法などを採用してもよいが、液体媒質を使用しない点で、上記の熱分解による方法が好ましい。酸を用いて加水分解する方法としては、例えば、２，５−ポリムコン酸アンモニウムの結晶を塩酸のメタノール溶液（水を含む）または水溶液に含浸させる方法がある。
【００６８】
上記の変換により得られた２，５−ポリムコン酸の層状結晶は、図１の（ｃ）に示すように、多数のポリマーシート４’からなり、アンモニウムイオンを可逆的に出し入れできる有機インターカレーション化合物として機能する。すなわち、２，５−ポリムコン酸の層状結晶は、種々のアミンをゲストとして取り込むことができる有機インターカレーションのホスト化合物（有機インターカレーション化合物）として有用である。一般的なインターカレート材料（インターカレーションに用いられる材料）は、グラファイト、金属酸化物、粘度鉱物等に代表される無機材料であるが、本発明に係る２，５−ポリムコン酸の層状結晶は、そのような一般的なインターカレート材料とは異なり、有機物質のみで構成されたインターカレート材料である。
【００６９】
最後に、第４のステップでは、２，５−ポリムコン酸の層状結晶と、前記のアミン（Ｂ）とを、液体媒質の非存在下で混合する。これにより、次式
【００７０】
【化４】

【００７１】
で示すように、アンモニウムカルボキシレート基を有する共役ジエンの重合体の結晶（アンモニウムイオンを層間にインターカレートした層状結晶）としての、２，５−ポリムコン酸アンモニウムの結晶が再度生成する。
【００７２】
この２，５−ポリムコン酸アンモニウムの結晶は、図１の（ｄ）に示すように、２，５−ポリムコン酸アニオン（カルボキシレートイオン）分子４で形成された複数の層の間に、アミン（Ｂ）の分子５’が第２級アンモニウムイオン分子５としてインターカレートされた層状結晶構造を持つ。
【００７３】
２，５−ポリムコン酸の結晶とアミン（Ｂ）との使用量の比は、収率の向上のためには２，５−ポリムコン酸のカルボキシル基１モル当たりのアミン（Ｂ）の使用量が２モル以上となるような比にすることが好ましく、アミン（Ｂ）理論量比、すなわち２，５−ポリムコン酸のカルボキシル基１モル当たりのアミン（Ｂ）の使用量が２モルとなるような比にすることが最も好ましい。
【００７４】
このとき、アミン（Ｂ）の炭素鎖の長さを変えると、２，５−ポリムコン酸アンモニウムの層状結晶の層間隔ｄ２もそれに応じて変化する。したがって、例えば、アミン（Ｂ）の炭素鎖の長さがアミン（Ａ）の炭素鎖の長さより短い場合、第４のステップで得られる層状結晶の層間隔ｄ２は、図１の（ｄ）に示すように、第２のステップで得られる層状結晶の層間隔ｄ１より短くなる。
【００７５】
上記の第４ステップのインターカレーションによれば、アミン（Ｂ）として、特定の機能を発現する官能基を有するアミンを使用することで、特定の機能を発現する官能基を２，５−ポリムコン酸結晶（図２のポリマーシート４’）内に導入することができる。特定の機能を発現する官能基を有するアミンを２，５−ポリムコン酸の層状結晶内に導入した結晶は、様々な機能性高分子結晶としての応用が考えられ、例えば、光学分割、分子認識、有機磁性体、イオン伝導性材料、光応答性材料、刺激応答性材料、光反応性材料などとしての展開が期待できる。
【００７６】
具体的には、アミン（Ｂ）として、キラル炭素を持つアミンを用いると、キラル炭素を持つアミンが２，５−ポリムコン酸の層状結晶の層間にインターカレートされた機能性高分子結晶が得られる。例えば、図２に示すように、式（１）（式中、Ｒ¹およびＲ²は互いに異なる炭化水素基、Ｘは炭化水素二価基を表す）で表される、キラル炭素に結合した水酸基を持つアミンを用いると、このアミンが層状結晶（図２の２，５−ポリムコン酸アニオン分子４）の層間にインターカレートされた機能性高分子結晶が得られる。この機能性高分子結晶は、（Ｒ）−アルコールと（Ｓ）−アルコールとの混合物から、どちらか一方のアルコールのみを取り出す光学分割や、分子認識などに使用できると考えられる。
【００７７】
また、アミン（Ｂ）として、大きな磁性モーメントを持つアミン、例えば、図２に示すように、式（２）（式中、Ｘは炭化水素二価基を表す）で表される、アミンオキシド部分を持つアミンを用いると、このアミンが２，５−ポリムコン酸の層状結晶の層間にインターカレートされた機能性高分子結晶が得られる。この機能性高分子結晶は、有機磁性体として使用できると考えられる。
【００７８】
また、アミン（Ｂ）として、ポリオキシエチレン鎖等のポリオキシアルキレン鎖を持つアミン、例えば、図２に示すように、式（３）（式中、Ｘは炭化水素二価基、ｎは２以上の整数を表す）で表される、ポリオキシエチレン鎖を持つ第１級アミンを用いると、このアミンが２，５−ポリムコン酸の層状結晶の層間にインターカレートされた機能性高分子結晶が得られる。この機能性高分子結晶は、Ｌｉイオン等のイオンを伝導するイオン伝導性材料や、導電性材料として使用できると考えられる。
【００７９】
また、アミン（Ｂ）として、窒素−窒素二重結合を持つアミン、例えば、図２に示すように、式（４）（式中、Ｘは炭化水素二価基を表す）で表される、アゾ基を持つアミンを用いると、このアミンが２，５−ポリムコン酸の層状結晶の層間にインターカレートされた機能性高分子結晶が得られる。この機能性高分子結晶は、図２に示すように、光エネルギーによって、インターカレートされたアミン（アンモニウムイオン）の配向が変化し、層間距離が変化すると考えられる。したがって、機能性高分子結晶は、この光応答性材料や刺激応答性材料として使用できると考えられる。すなわち、アミン（Ｂ）として窒素−窒素二重結合を持つアミンを用いることにより、光応答性材料や刺激応答性材料として使用可能な機能性高分子結晶が得られる。この機能性高分子結晶については、後段で詳細に説明する。
【００８０】
また、アミン（Ｂ）として、炭素−炭素不飽和結合を持つアミン、例えば、図２に示すように、式（５）（式中、Ｘは炭化水素二価基、Ｒ³は炭化水素基を表す）で表される、ビニル基を持つアミンを用いると、このアミンが２，５−ポリムコン酸の層状結晶の層間にインターカレートされた機能性高分子結晶が得られる。この機能性高分子結晶は、光反応性材料や、特異な反応場を提供する材料として使用できると考えられる。
【００８１】
以上のようにして、単量体（（Ｚ，Ｚ）−ムコン酸アンモニウム）の合成から、単量体の重合、２，５−ポリムコン酸アンモニウムから２，５−ポリムコン酸への変換、２，５−ポリムコン酸へのアンモニウムイオンのインターカレーション、と全てのステップにおいて、液体媒質を反応に使用することなく、任意のアミン（Ｂ）が層間にインターカレートされた２，５−ポリムコン酸の層状結晶を得ることができる。
【００８２】
なお、ここでは、カルボキシル基を有する共役ジエンとして（Ｚ，Ｚ）−ムコン酸を用いた場合について説明したが、（Ｚ，Ｚ）−ムコン酸に代えて、（Ｅ，Ｅ）−ムコン酸や（Ｅ，Ｚ）−ムコン酸等のような他のα，β−不飽和二塩基性カルボン酸；ソルビン酸等のようなα，β−不飽和一塩基性カルボン酸等を用いることもできる。
【００８３】
（Ｚ，Ｚ）−ムコン酸に代えて（Ｅ，Ｅ）−ムコン酸を用いた場合、第２ステップにおいて、（Ｚ，Ｚ）−ムコン酸を用いた場合と同一の構造の重合体が得られる。これは、第１のステップで同じ方向を向いた単量体がカラム状にスタッキングするためであり、結晶構造のモデルから確認されている。
【００８４】
また、カルボキシル基を有する共役ジエンとして（Ｚ，Ｚ）−ムコン酸に代えて（Ｅ，Ｅ）−ムコン酸またはソルビン酸を用いる場合、アミン（Ａ）として、１−ナフチルメチルアミンを用いることが好ましい。
【００８５】
次に、前記の機能性高分子結晶、すなわち本発明にかかる光応答性高分子について、詳細に説明する。
【００８６】
本発明に係る光応答性高分子は、前述したカルボキシル基を有する共役ジエンの重合体の層状結晶と、アミンおよびアンモニアからなる群より選ばれる少なくとも１種の化合物とを液体媒質の非存在下で混合するカルボン酸アンモニウムの結晶の製造方法において、カルボキシル基を有する共役ジエンの重合体の層状結晶と混合する化合物として、次の一般式
−Ａｒ−Ｎ＝Ｎ−Ａｒ’− …（６）
（上記式中、ＡｒおよびＡｒ’は、それぞれ独立して、芳香族炭化水素２価基を表す）
で表される２価基を持つアミンを用いる方法によって得ることができる。上記方法によれば、上記カルボン酸アンモニウムの結晶として、カルボキシル基を有する共役ジエンの重合体の層状結晶（層状の結晶性高分子）に対して、上記光応答性基を持つアミンがゲスト化合物としてインターカレートされた本発明にかかる光応答性高分子が得られる。
【００８７】
本発明に係る光応答性高分子は、カルボキシル基を有する高分子の層状結晶（層状の結晶性高分子）に対して、前記一般式（６）で表される２価基を持つアミン（以下、「光応答性基含有アミン」と称する）がゲスト化合物としてインターカレートされたものである。
【００８８】
上記のカルボン酸を有する層状の結晶性高分子としては、層状構造をもち、カルボン酸を含む結晶性高分子であれば、特に制限なく用いることができる。すなわち、カルボン酸を有する層状の結晶性高分子は、共役ジエンカルボン酸から誘導される結晶性高分子に限らず、共役ジエンカルボン酸から誘導される結晶性高分子以外の、層状構造をもち、カルボン酸を含む結晶性高分子でもよい。ただし、カルボン酸を有する層状の結晶性高分子としては、共役ジエンカルボン酸から誘導される結晶性高分子（カルボキシル基を有する共役ジエンの重合体の層状結晶）、例えばポリムコン酸結晶やポリソルビン酸結晶、ポリブタジエンカルボン酸結晶などが好ましく、ポリムコン酸結晶およびポリソルビン酸結晶がさらに好ましい。
【００８９】
上記光応答性基含有アミンとしては、インターカレーション反応が起こり易いことから、１級アミンが好ましい。
【００９０】
また、上記光応答性基含有アミンとしては、芳香環に直接アミノ基が結合しているアミン等のような塩基性が低いアミンではインターカレーション反応が起こりにくいことから、前記一般式（６）で表される２価基とアミノ基との間に少なくとも１つの飽和炭化水素二価基がスペーサーとして介在していることが好ましい。これにより、光応答性基含有アミンが十分な塩基性を持ち、インターカレーション反応が進行しやすくなる。
【００９１】
また、前記一般式（６）においてＡｒおよびＡｒ’で示す芳香族炭化水素２価基としては、特に限定されるものではなく、２個以上のベンゼン環がつながったものでもよい。上記ＡｒおよびＡｒ’で示す芳香族炭化水素２価基としては、具体的には、１，４−フェニレン基等のフェニレン基；ビフェニレン基；ナフチレン基等が挙げられるが、１，４−フェニレン基が特に好ましい。
【００９２】
上記光応答性基含有アミンとしては、次の一般式
Ｙ−Ａｒ−Ｎ＝Ｎ−Ａｒ−Ｘ¹−Ｒ⁴−ＮＨ₂
（上記式中、Ｒ⁴は、その位置に炭化水素２価基が存在するか、あるいはその位置に置換基が存在しないことを表し、Ｘ¹は、その位置にヘテロ原子を含む２価基が存在するか、あるいはその位置に置換基が存在しないことを表し、Ｙは、水素原子または任意の置換基を表す）
で表されるモノアミン（以下、「光応答性基含有モノアミン」と称する）、または次の一般式
Ｈ₂Ｎ−Ｒ⁴−Ｘ¹−Ａｒ−Ｎ＝Ｎ−Ａｒ−Ｘ¹−Ｒ⁴−ＮＨ₂
（上記式中、Ｒ⁴は、それぞれ独立して、その位置に炭化水素２価基が存在するか、あるいはその位置に置換基が存在しないことを表し、Ｘ¹は、それぞれ独立して、その位置にヘテロ原子を含む２価基が存在するか、あるいはその位置に置換基が存在しないことを表す）
で表されるジアミン（以下、「光応答性基含有ジアミン」と称する）が特に好ましい。
【００９３】
上記Ｒ⁴における飽和炭化水素２価基は、直鎖の脂肪族飽和炭化水素２価基に代表される脂肪族炭化水素２価基でもよく、シクロヘキシレン基に代表される脂環式炭化水素２価基でもよい。上記Ｒ⁴は、次の一般式
−（ＣＨ２）ｎ−
（上記式中、ｎは０から１８までの整数を表す）
で表される２価基であることが好ましい。すなわち、上記Ｒ⁴は、その位置に炭素数０〜１８の直鎖のアルキレン基（脂肪族飽和炭化水素２価基）が存在するか、あるいはその位置に置換基が存在しないことを表すことが好ましい。さらに、上記ｎは、より好ましくは１以上１２以下である。すなわち、Ｒ⁴の位置には、スペーサー基として直鎖のアルキレン基が存在することが好ましく、スペーサー基の炭素数（メチレン炭素の数）ｎは、１２以下であることが好ましい。
【００９４】
上記Ｘ¹におけるヘテロ原子を含む２価基としては、主鎖にヘテロ原子を含む２価基、例えば、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮＨＣＯ−、−ＮＨＣＯＮＨ−、−ＯＣＯＮＨ−、−ＮＨＣＯＯ−などが好ましい。
【００９５】
上記Ｙは、特に限定されるものではなく、水素原子、アルキル基、アルコキシ基、シアノ基（−ＣＮ）などが挙げられる。上記アルキル基としては、例えば−（ＣＨ₂）_nＣＨ₃（メチレン炭素の数ｎは、０〜１８、より好ましくは１以上１２以下）で表される直鎖のアルキル基が挙げられ、上記アルコキシ基としては、例えば−Ｏ（ＣＨ₂）_nＣＨ₃（メチレン炭素の数ｎは、０〜１８、より好ましくは１以上１２以下）で表される置換基が挙げられる。また、上記Ｙは、−（ＯＣＨ₂ＣＨ₂）_nＯＣＨ₃（メチレン炭素の数ｎは、０〜１８、より好ましくは１以上１２以下）で表される置換基であってもよい。
【００９６】
上記光応答性基含有アミンは、市販されているアゾ基含有化合物から合成することができる。例えば、光応答性基含有モノアミンの１種である４−（フェニルアゾ）ベンジルアミンは、市販のアゾベンゼン−４−カルボニルクロリドから、次のスキーム（Ａ）により製造できる。
【００９７】
【化５】

【００９８】
また、光応答性基含有モノアミンの１種である４−（１１−アミノウンデシルオキシ）アゾベンゼン（別名「１１−［４−（フェニルアゾ）フェニルオキシ］ウンデシルアミン」）は、市販の４−フェニルアゾフェノールと市販の１１−ブロモウンデカン酸とから、次のスキーム（Ｂ）により製造できる。
【００９９】
【化６】

【０１００】
また、光応答性基含有モノアミンの１種であるＮ−（６−アミノヘキシル）アゾベンゼンカルボキサミドは、次のスキーム（Ｃ）に示すように、市販のアゾベンゼン−４−カルボニルクロリドと市販のヘキサメチレンジアミンとを反応させることにより、製造できる。また、他のＮ−（アミノアルキル）アゾベンゼンカルボキサミドも、同様の手法で、対応するアルキレンジアミンを用いて製造できる。
【０１０１】
【化７】

【０１０２】
また、光応答性基含有ジアミンの１種である４，４’−ジ（アミノメチル）アゾベンゼン（別名「４，４’−アゾビス（ベンジルアミン）」）は、次のスキーム（Ｄ）に示すように、市販のアゾベンゼン−４，４’−ジカルボニルジクロリドとアンモニアとを反応させた後、水素化リチウムアルミニウムで還元することにより、製造できる。
【０１０３】
【化８】

【０１０４】
また、光応答性基含有ジアミンの１種であるＮ，Ｎ’−ジ（６−アミノヘキシル）−アゾベンゼン−４，４’−ジカルボキサミド（別名「４，４’−アゾビス［Ｎ−（６−アミノヘキシル）ベンズアミド］」）は、次のスキーム（Ｅ）に示すように、市販のアゾベンゼン−４，４’−ジカルボニルジクロリドと市販のヘキサメチレンジアミンとを反応させることにより、製造できる。また、他の４，４’−アゾビス［Ｎ−（アミノアルキル）ベンズアミド］も、同様の手法で、対応するアルキレンジアミンを用いて製造できる。
【０１０５】
【化９】

【０１０６】
なお、本発明に係る光応答性高分子は、前述した製造方法（カルボキシル基を有する共役ジエンの重合体の層状結晶と、光応答性基含有アミンとを液体媒質の非存在下で混合する方法）で製造することが望ましいが、他の方法で製造することも可能である。
【０１０７】
例えば、前述した製造方法では、溶媒を用いずに液体媒質の非存在下でインターカレーション反応を行っていたが、結晶性高分子（カルボキシル基を有する共役ジエンの重合体の層状結晶）を分散させる分散剤として溶媒を用いてインターカレーション反応を行ってもよい。分散剤として用いる溶媒としては、アミンが溶解し、かつ、結晶性高分子が溶解や膨潤しないものであればどのような溶媒を用いてよく、メタノールやイソプロパノール等のアルコールをはじめとして、アセトンやメチルエチルケトン等のケトン；ｔｅｒｔ−ブチルメチルエーテル等のエーテル；１，２−ジクロロエタン等のハロゲン系溶媒；トルエン等の芳香族炭化水素；ヘキサン等の脂肪族炭化水素等の有機溶媒を用いることができ、さらには水も用いることができる。
【０１０８】
また、光応答性基含有アミンと、共役ジエン部分を持つカルボン酸（特に、ムコン酸やソルビン酸）とを反応させて、共役ジエン部分を持つカルボン酸のアンモニウム塩をあらかじめ調整し、この共役ジエン部分を持つカルボン酸アンモニウム結晶の固相重合によって、前述した製造方法で得られるのと同様の層状構造を持つ結晶性高分子を得てもよい。ただし、固相重合反応性（トポケミカル重合反応性）は、アンモニウム塩誘導体モノマー（共役ジエン部分を持つカルボン酸アンモニウム）の結晶構造、すなわち結晶中でのモノマー分子のパッキング様式によって決まるので、全てのアンモニウム塩誘導体モノマーがトポケミカル重合により層状構造を形成可能なわけではない。したがって、予め調製したカルボン酸を有する層状の結晶性高分子に対して光応答性基を含むアミンをインターカレートさせる前述の製造方法は、本発明に係る光応答性高分子を得るためのより確実な方法である。
【０１０９】
【実施例】
〔実施例１〕
本発明に係る製造方法を用いて、光固相重合が可能な結晶である（Ｚ、Ｚ）−ムコン酸ベンジルアンモニウムの結晶の合成を行った。
【０１１０】
（Ｚ、Ｚ）−ムコン酸の結晶０．９２９１ｇ（６．５４×１０^-3モル）と、常温で液体であるベンジルアミン１．４０１２ｇ（１．３１×１０^-2モル）とを、常温で、乳鉢で３０分すりつぶし反応させた。
【０１１１】
反応により得られた生成物のＩＲスペクトル（赤外吸収スペクトル）は、カルボキシル基に基づく１７１０ｃｍ^-1の吸収ピークが確認されず、カルボキシレートに基づく１５６０ｃｍ^-1の吸収ピークが確認された。また、反応により得られた生成物は、粉末Ｘ線回折測定において、図３（ａ）に示すように、溶媒中での反応後に再結晶によって単離を行う従来の方法で作成した（Ｚ、Ｚ）−ムコン酸ベンジルアンモニウムの結晶の回折パターン（図３（ｂ））と同じ回折パターンを示した。これらにより、反応が定量的に進行し、（Ｚ、Ｚ）−ムコン酸ベンジルアンモニウムの結晶が得られたことが分かった。
【０１１２】
〔実施例２〕
まず、実施例１で合成した（Ｚ、Ｚ）−ムコン酸ベンジルアンモニウムの結晶に対し、高圧水銀灯を用いて３０℃で８時間、紫外線を照射した。これにより、（Ｚ、Ｚ）−ムコン酸ベンジルアンモニウムの光固相重合が進行し、溶媒に不溶の生成物が得られた。照射終了後、メタノールで未反応の単量体（（Ｚ、Ｚ）−ムコン酸ベンジルアンモニウム）を抽出し、生成物を単離した。
【０１１３】
単離された生成物のＩＲスペクトルにおいて、図４の曲線Ａに示すように、共役ジエンによる１５８０ｃｍ^-1の吸収ピークが消失したことにより、（Ｚ、Ｚ）−ムコン酸ベンジルアンモニウムが重合し、２，５−ポリムコン酸ベンジルアンモニウムの結晶が生成したことが確認された。２，５−ポリムコン酸ベンジルアンモニウムの収率は３％であった。なお、紫外線照射時間を８時間から７２時間に変更したところ、２，５−ポリムコン酸ベンジルアンモニウムの収率は、３０％まで向上した。
【０１１４】
次に、２，５−ポリムコン酸ベンジルアンモニウムの結晶を、減圧（真空）下、２５０℃で２時間加熱することにより熱分解させた。
【０１１５】
熱分解により得られた生成物のＩＲスペクトルは、図４の曲線Ｂに示すように、カルボキシレートに基づく１５６０ｃｍ^-1の吸収ピークが確認されず、カルボキシル基に基づく１７１０ｃｍ^-1の吸収ピークが確認された。また、粉末Ｘ線回折測定において、生成物は、従来の方法（（Ｚ、Ｚ）−ムコン酸とベンジルアミンとを溶媒中で混合した後に再結晶により（Ｚ、Ｚ）−ムコン酸ベンジルアンモニウムを単離し、次いで、（Ｚ、Ｚ）−ムコン酸ベンジルアンモニウムを光固相重合し、塩酸を用いて加水分解する方法）で作成した２，５−ポリムコン酸の結晶と同じ回折パターンを示した。これにより、２，５−ポリムコン酸ベンジルアンモニウムの結晶が２，５−ポリムコン酸の結晶に変換され、高度に立体規制された２，５−ポリムコン酸結晶が得られたことが分かった。
【０１１６】
次に、実施例１と同様にして、２，５−ポリムコン酸の結晶０．０６８７ｇに、ベンジルアミン０．１０３６ｇ（２，５−ポリムコン酸の繰り返し構造単位１モル当たり２モルとなる量、つまり２，５−ポリムコン酸のカルボキシル基１モル当たり１モルとなる量）を加え、乳鉢で３０分すりつぶし反応させた。
【０１１７】
反応により得られた生成物のＩＲスペクトルは、図４の曲線Ｃに示すように、カルボキシル基に基づく１７１０ｃｍ^-1の吸収ピークが確認されず、カルボキシレートに基づく１５６０ｃｍ^-1の吸収ピークが確認された。また、反応により得られた生成物は、粉末Ｘ線回折測定において、分散媒中でのインターカレート後に再結晶によって単離を行う従来の方法で作成した、ベンジルアミンが層間にインターカレートされた２，５−ポリムコン酸結晶の回折パターンと同じ回折パターンを示した。
【０１１８】
これらにより、定量的にインターカレーションが進行し、ベンジルアミンが層間にインターカレートされた２，５−ポリムコン酸の結晶、すなわち２，５−ポリムコン酸ベンジルアンモニウムの結晶が得られたことが分かった。
【０１１９】
〔実施例３〕
本発明に係る製造方法を用いて、光固相重合が可能な結晶である（Ｚ、Ｚ）−ムコン酸ドデシルアンモニウム塩の合成を行った。
【０１２０】
（Ｚ、Ｚ）−ムコン酸の結晶０．３２５６ｇ（２．２９×１０^-3モル）と、常温で固体であるドデシルアミン０．８４９３ｇ（４．５８×１０^-3モル）とを、常温で、乳鉢で３０分すりつぶし反応させた。
【０１２１】
反応により得られた生成物のＩＲスペクトルは、カルボキシル基に基づく１７１０ｃｍ^-1の吸収ピークが確認されず、カルボキシレートに基づく１５６０ｃｍ^-1の吸収ピークが確認された。また、粉末Ｘ線回折測定において、溶媒中での反応後に再結晶によって単離を行う従来の方法で作成した（Ｚ、Ｚ）−ムコン酸ドデシルアンモニウムの結晶の回折パターン（図２の（ｂ））と同じ回折パターンを示した。これらにより、反応が定量的に進行し、（Ｚ、Ｚ）−ムコン酸ドデシルアンモニウムの結晶が得られたことが分かった。
【０１２２】
〔実施例４〕
まず、実施例３で合成した（Ｚ、Ｚ）−ムコン酸ドデシルアンモニウムの結晶に対し、高圧水銀灯を用いて３０℃で８時間、紫外線を照射した。これにより、（Ｚ、Ｚ）−ムコン酸ドデシルアンモニウムの光固相重合が進行し、溶媒に不溶の生成物が得られた。照射終了後、メタノールで未反応の単量体（（Ｚ、Ｚ）−ムコン酸ドデシルアンモニウム）を抽出し、生成物を単離した。
【０１２３】
単離された生成物のＩＲスペクトルにおいて、共役ジエンによる１５８０ｃｍ^-1の吸収ピークが消失したことにより、（Ｚ、Ｚ）−ムコン酸ドデシルアンモニウムが重合し、２，５−ポリムコン酸ドデシルアンモニウムの結晶が生成したことが確認された。２，５−ポリムコン酸ドデシルアンモニウムの収率は２４％であった。なお、紫外線照射時間を８時間から７２時間に変更したところ、２，５−ポリムコン酸ドデシルアンモニウムの収率は、８１％まで向上した。
【０１２４】
次に、２，５−ポリムコン酸ドデシルアンモニウムの結晶を、減圧下、２５０℃で２時間加熱することにより熱分解させた。
【０１２５】
熱分解により得られた生成物のＩＲスペクトルは、カルボキシレートに基づく１５６０ｃｍ^-1の吸収ピークが確認されず、カルボキシル基に基づく１７１０ｃｍ^-1の吸収ピークが確認された。また、粉末Ｘ線回折測定において、生成物は、従来の方法（（Ｚ、Ｚ）−ムコン酸とドデシルアミンとを溶媒中で混合した後に再結晶により（Ｚ、Ｚ）−ムコン酸ドデシルアンモニウムを単離し、次いで、（Ｚ、Ｚ）−ムコン酸ドデシルアンモニウムを光固相重合し、塩酸を用いて加水分解する方法）で作成した２，５−ポリムコン酸結晶と同じ回折パターンを示した。これにより、２，５−ポリムコン酸ドデシルアンモニウムが２，５−ポリムコン酸に変換され、高度に立体規制された２，５−ポリムコン酸の結晶が得られたことが分かった。
【０１２６】
次に、実施例３と同様にして、２，５−ポリムコン酸の結晶０．０７７４ｇに、ドデシルアミン０．２０１９ｇ（２，５−ポリムコン酸の繰り返し構造単位１モル当たり２モルとなる量、つまり２，５−ポリムコン酸のカルボキシル基１モル当たり１モルとなる量）を加え、乳鉢で３０分すりつぶし反応させた。
【０１２７】
反応により得られた生成物のＩＲスペクトルは、カルボキシル基に基づく１７１０ｃｍ^-1の吸収ピークが確認されず、カルボキシレートに基づく１５６０ｃｍ^-1の吸収ピークが確認された。また、反応により得られた生成物は、粉末Ｘ線回折測定において、分散媒中でのインターカレート後に再結晶によって単離を行う従来の方法で作成した、ドデシルアミンがインターカレートされた２，５−ポリムコン酸結晶の回折パターンと同じ回折パターンを示した。粉末Ｘ線回折測定の結果によれば、層状結晶（２，５−ポリムコン酸の結晶）の層間距離ｄは、インターカレーション前は４．８Åであったのに対し、ドデシルアミンがインターカレートされた後は３２．６Åであった。
【０１２８】
これらにより、定量的にインターカレーションが進行し、ドデシルアミンがインターカレートされた２，５−ポリムコン酸結晶、すなわち２，５−ポリムコン酸ドデシルアンモニウムの結晶が得られたことが分かった。
【０１２９】
〔実施例５〕
まず、実施例４と同様にして、２，５−ポリムコン酸の結晶を得た。
【０１３０】
次に、実施例４と同様に、２，５−ポリムコン酸の結晶に、２，５−ポリムコン酸のカルボキシル基１モル当たり１モルとなる量のｔｅｒｔ−ブチルアミンを加え、乳鉢で３０分すりつぶし反応させた。
【０１３１】
反応により得られた生成物のＩＲスペクトルは、カルボキシル基に基づく１７１０ｃｍ^-1の吸収ピークが確認されず、カルボキシレートに基づく１５６０ｃｍ^-1の吸収ピークが確認された。このＩＲスペクトル分析の結果と、粉末Ｘ線回折測定の結果とにより、定量的にインターカレーションが進行し、ｔｅｒｔ−ブチルアミンがインターカレートされた２，５−ポリムコン酸結晶、すなわち２，５−ポリムコン酸ｔｅｒｔ−ブチルアンモニウムの結晶が得られたことが分かった。
【０１３２】
〔比較例１〕
まず、実施例４と同様にして、２，５−ポリムコン酸の結晶を得た。
【０１３３】
次に、従来法、すなわち、２，５−ポリムコン酸の結晶をメタノールに分散させ、この分散液にｔｅｒｔ−ブチルアミンを加える方法で、２，５−ポリムコン酸の結晶へのｔｅｒｔ−ブチルアミンのインターカレーションを試みた。
【０１３４】
その結果、反応中にポリマーがメタノールに膨潤あるいは溶解してしまうために目的のアンモニウムの結晶を得ることができなかった。
【０１３５】
以上の実施例５および比較例１から明らかなように、本発明の方法では、従来法では不可能であった２，５−ポリムコン酸の結晶へのｔｅｒｔ−ブチルアミンのインターカレーションが可能となった。
【０１３６】
〔実施例６〕
［４-(フェニルアゾ)ベンジルアミンの合成］
４−（フェニルアゾ）ベンジルアミンは、前述したように、市販のアゾベンゼン−４−カルボニルクロリドから、前記スキーム（Ａ）により製造できる。
【０１３７】
具体的には、まず、市販品のアゾベンゼン−４−カルボニルクロリド（東京化成工業株式会社製）０．１９７ｇを１５ｍＬのジクロロメタンに溶解させた溶液を、２８重量％アンモニア水２ｍＬに、室温下、ゆっくり加えた。一晩、撹拌した後、不溶部をろ別単離し、水で洗浄した。得られた固体をアセトンから再結晶することにより、８５％の収率でアゾベンゼンカルボキサミド（アゾベンゼンカルボン酸アミド）を得た。アゾベンゼンカルボキサミドの構造は、¹Ｈ ＮＭＲスペクトルおよび¹³Ｃ ＮＭＲスペクトルで確認した。
【０１３８】
アゾベンゼンカルボキサミドのＮＭＲスペクトルデータを以下に示す。
¹Ｈ ＮＭＲ（アセトン−ｄ₆）δ ８．１３−８．１５（ｍ，Ａｒ，２Ｈ），７．９５−７．９９（ｍ，Ａｒ，４Ｈ），７．５８−７．６３（ｍ，Ａｒ，３Ｈ），６．８（ｂｒ，ＮＨ₂，２Ｈ）
¹³Ｃ ＮＭＲ（アセトン−ｄ₆）δ １６８．４２（Ｃ＝Ｏ），１５５．１７，１５３．６８，１３７．７７，１３２．９４，１３０．５４，１２９．８７，１２４．０４，１２３．６３（Ａｒ）。
【０１３９】
なお、アゾベンゼンカルボキサミドは、アンモニア水のかわりにアンモニアガスを用いる反応によっても得られた。すなわち、過剰のアンモニアガスをクロロホルム中に吹き込みながら、アゾベンゼン−４−カルボニルクロリドのクロロホルム溶液をゆっくり滴下することによっても、同様の反応収率（８５％）で目的とするアゾベンゼンカルボキサミドが得られた。
【０１４０】
次に、合成したアゾベンゼンカルボン酸アミド０．０７８ｇ、水素化リチウムアルミニウム０．１１９ｇ、および乾燥したジエチルエーテル５ｍＬをフラスコに入れ、３４時間還流した。室温に戻し、１０ｍＬの水を慎重にゆっくりと滴下して、過剰の水素化リチウムアルミニウムと反応させた後、さらに一晩撹拌を行った。１００ｍＬのジエチルエーテルで３回抽出し、エーテルを減圧除去した。その後、残渣をシリカゲルクロマトグラフィ（展開溶媒：メタノール）により精製することにより、目的とする４−（フェニルアゾ）ベンジルアミンを０．０２１ｇ（収率２９％）得た。４−（フェニルアゾ）ベンジルアミンの構造は、¹Ｈ ＮＭＲスペクトルおよび¹³Ｃ ＮＭＲスペクトルで確認した。
【０１４１】
４−（フェニルアゾ）ベンジルアミンのＮＭＲスペクトルデータを以下に示す。
¹Ｈ ＮＭＲ（クロロホルム−ｄ）δ ７．８９−７．９２（ｍ，Ａｒ，４Ｈ），７．２６−７．５４（ｍ，Ａｒ，５Ｈ），３．９４（ｓ，ＣＨ₂，２Ｈ）．
¹³Ｃ ＮＭＲ（クロロホルム−ｄ）δ １５２．６２，１５１．５８，１４６．４２，１３０．８５，１２９．０６，１２７．６６，１２３．０８，１２２．７５（Ａｒ），４６．２１（ＣＨ₂）。
［２，５−ポリムコン酸結晶の調製］
実施例４と同様にして、２，５−ポリムコン酸の結晶を得た。
［インターカレーション反応］
次に、得られた２，５−ポリムコン酸の結晶への４−（フェニルアゾ）ベンジルアミンのインターカレーション反応を行った。
【０１４２】
すなわち、実施例４と同様に、２，５−ポリムコン酸の結晶７９ｍｇ（ムコン酸単位０．５６ｍｍｏｌ）と４−（フェニルアゾ）ベンジルアミン２３６ｍｇ（１．１２ｍｍｏｌ；理論量比、すなわち［−ＮＨ₂］／［−ＣＯ₂Ｈ］＝２）とを、乳鉢中で、３０分間すりつぶしながら混合、撹拌した。その後、５０ｍＬのジエチルエーテルで未反応の４−（フェニルアゾ）ベンジルアミンを洗浄除去すると、４−（フェニルアゾ）ベンジルアミンをインターカレーションした２，５−ポリムコン酸の結晶が４８％収率で得られた。
【０１４３】
インターカレーションの前後における２，５−ポリムコン酸結晶のＩＲスペクトル（赤外吸収スペクトル）の変化を図５に示す（日本分光株式会社製のフーリエ変換赤外分光光度計「ＪＡＳＣＯ Ｈｅｒｓｃｈｅｌ ＦＴ−ＩＲ−４３０」を使用、ＫＢｒ錠剤法による測定）。図５においては、（ａ）が２，５−ポリムコン酸結晶のＩＲスペクトル、（ｂ）が４−（フェニルアゾ）ベンジルアミンをインターカレーションした２，５−ポリムコン酸結晶のＩＲスペクトルを示す。
【０１４４】
反応後、インターカレーションする前の２，５−ポリムコン酸に見られた１７１０ｃｍ^-1のカルボキシル基による吸収が消失し、かわりに１５６０ｃｍ^-1のカルボキシレート（カルボン酸アンモニウム）による吸収が認められた。このことから、２，５−ポリムコン酸結晶へのアミンのインターカレーションにより、カルボキシル基がカルボキシレートに変化していることが分かった。したがって、本発明に係る光応答性高分子としてのポリムコン酸４−（フェニルアゾ）ベンジルアンモニウムの結晶が生成していることがわかった。
［紫外光照射による紫外可視吸収スペルトルの変化］
４−（フェニルアゾ）ベンジルアミンをインターカレーションした２，５−ポリムコン酸結晶に、高圧水銀灯（株式会社東芝製のＳＨＬ−１００−２型ランプ、１００Ｗ）を用いて、室温下、１０ｃｍの距離から紫外光照射を行い、０分から３００分まで照射時間を変化させたときの紫外可視吸収スペクトル（紫外可視拡散反射スペクトル）の変化を測定した。この紫外可視吸収スペクトルは、日本分光株式会社製の紫外可視分光光度計「Ｖ−５５０ＤＳ」に積分球装置を装備して、固体試料の拡散反射を測定することにより行った。紫外可視吸収スペクトル変化の測定結果を図６に示す。図６に示す曲線は、下から順に、照射時間０分、照射時間３０分、照射時間９０分、照射時間１５０分、照射時間３００分の場合を示している。
【０１４５】
その結果、図６に示すように、紫外光照射時間の増加と共に、４５０ｎｍ付近のシス型アゾベンゼン構造に由来する吸収強度が増大していた。したがって、４−（フェニルアゾ）ベンジルアミンは、紫外光照射前にはアゾベンゼン部分がトランス体であるが、紫外光照射によって、アゾベンゼン部分が一部トランス体からシス体へと変化していることがわかった。
［紫外光照射による粉末Ｘ線回折プロファイルの変化］
紫外光照射（３時間および１０時間）による２，５−ポリムコン酸結晶の層状構造の変化を、粉末Ｘ線回折により評価した。測定には、理学電機製粉末Ｘ線回折計「ＲＩＮＴ２１００」（ＣｕＫα、λ＝１．５４１７８Å）を用いた。粉末Ｘ線回折プロファイルを図７に示す。その結果、照射前に見られた、１８度付近の鋭い回折ピークが、照射後にはその強度が低下し、層状構造に変化の生じたことがわかった。また、２θが３度付近のピーク強度が紫外光照射とともに低下し、かわりにさらに低角側に別のピークが現れた。このことから、紫外光照射によって、層状構造の繰返し周期（層間距離ｄ）が光照射前後で変化していることが分かった。
【０１４６】
〔実施例７〕
［４−（１１−アミノウンデシルオキシ）アゾベンゼンの合成］
アゾベンゼンを含む別のアミンの合成例として、４−（１１−アミノウンデシルオキシ）アゾベンゼンを、前記スキーム（Ｂ）により合成した。
【０１４７】
合成の反応の詳細は以下の通りである。
【０１４８】
まず、市販の１１−ブロモウンデカン酸（東京化成工業株式会社製）１０．０ｇと３，４−ジヒドロ−２Ｈ−ピラン（和光純薬株式会社製）３．１７ｇを２０ｍＬのジクロロメタンに溶かし、氷水で冷却しながら、０．９５ｇのｐ−トルエンスルホン酸ピリジニウムを加えた。０℃で３０分間撹拌、さらに室温で２時間撹拌した。重炭酸水素ナトリウム水溶液で洗浄、水で洗浄後、有機層を分離した。有機層からジクロロメタンを減圧除去すると、３、４−ジヒドロ−２Ｈ−ピランで保護された１１−ブロモウンデカン酸エステル、すなわち１１−ブロモウンデカン酸３，４，５，６−テトラヒドロ−２Ｈ−ピラニル（Ｂｒ（ＣＨ₂）₁₀ＣＯＯＲ⁰；Ｒ⁰は３，４，５，６−テトラヒドロ−２Ｈ−ピラニル基）が収率５９％で得られた。１１−ブロモウンデカン酸３，４，５，６−テトラヒドロ−２Ｈ−ピラニルの構造は、¹Ｈ ＮＭＲスペクトルで確認した。
【０１４９】
１１−ブロモウンデカン酸３，４，５，６−テトラヒドロ−２Ｈ−ピラニルの¹Ｈ ＮＭＲスペクトルデータを以下に示す。
¹Ｈ ＮＭＲ（クロロホルム−ｄ）δ ５．９７（ｔ，ＣＨ，１Ｈ），３．９０（ｔ，ＯＣＨ₂，１Ｈ），３．７０（ｔ，ＯＣＨ₂，１Ｈ），３．４０（ｔ，ＢｒＣＨ₂，２Ｈ），２．３５（ｔ，ＣＨ₂ＣＯ₂，２Ｈ），１．２９−１．８８（ｍ，ＣＨ₂，２４Ｈ）。
【０１５０】
上記１１−ブロモウンデカン酸３，４，５，６−テトラヒドロ−２Ｈ−ピラニル７．０３ｇ、および市販の４−（フェニルアゾ）フェノール（東京化成工業株式会社製）２．６２ｇを２５ｍＬの乾燥ジメチルホルムアミドに溶かした。得られた溶液に、炭酸カリウム２．８０ｇと触媒量のヨウ化カリウムとを加え、７０℃で２日間反応を行った。室温に戻した後、５０ｍＬのエーテルで３回抽出し、エーテル溶液を水で洗浄した。エーテルを減圧除去した後、５０ｍＬのテトラヒドロフランと５ｍＬの濃塩酸を加え、室温下、４０分間撹拌した。テトラヒドロフランを減圧除去した後、１００ｍＬのクロロホルムを用いてクロロホルム可溶部を３回抽出し、飽和食塩水ならびに水で洗浄後、濃縮して黄色い固体を得た。この固体を、クロロホルムとヘキサンとの混合溶媒（混合比はクロロホルム／ヘキサンの比が２から５）から再結晶することにより精製して、アゾベンゼン部分とカルボキシル基との間にスペーサー基としてデカメチレンオキシ基（−Ｏ（ＣＨ₂）₁₀−）を持つ化合物、１１−［４−（フェニルアゾ）フェニルオキシ］ウンデカン酸（Ａｚｏｂｅｎｚｅｎｅ−Ｏ−（ＣＨ₂）₁₀ＣＯＯＨ）を収率８２％で得た。１１−［４−（フェニルアゾ）フェニルオキシ］ウンデカン酸の構造は、¹Ｈ ＮＭＲスペクトルおよび¹³Ｃ ＮＭＲスペクトルで確認した。
【０１５１】
１１−［４−（フェニルアゾ）フェニルオキシ］ウンデカン酸のＮＭＲスペクトルデータを以下に示す。
¹Ｈ ＮＭＲ（クロロホルム−ｄ）δ ７．８５−７．９２（ｍ，Ａｒ，４Ｈ），７．４９−７．５１（ｍ，Ａｒ，３Ｈ），６．９８−７．０１（ｍ，Ａｒ，２Ｈ），４．０３（ｔ，ＯＣＨ₂），２．３５（ｔ，ＣＨ₂ＣＯ₂，２Ｈ），１．３１−１．８３（ｍ，ＣＨ₂，１６Ｈ）
¹³Ｃ ＮＭＲ（クロロホルム−ｄ）δ １７９．１０，１６１．７０，１５２．７８，１４６．８４，１３０．２７，１２９．０１，１２４．７３，１２２．５１，１１４．６９，６８．３４，６４．３９，３３．９２，２９．４４，２９．３１，２９．１８，２９．０１，２８．６２，２５．９９，２５．００，２４．００。
【０１５２】
上記１１−［４−（フェニルアゾ）フェニルオキシ］ウンデカン酸１．４９４ｇを１０ｍＬの１，２−ジクロロエタンに溶解させた。得られた溶液に、０．５ｍＬの塩化チオニルとＮ，Ｎ−ジメチルホルムアミド１滴を加え、３．５時間還流して、１１−［４−（フェニルアゾ）フェニルオキシ］ウンデカニルクロリド（Ａｚｏｂｅｎｚｅｎｅ−Ｏ−（ＣＨ₂）₁₀ＣＯＣｌ）を合成した。別のフラスコに１０ｍＬの１，２−ジクロロエタンを入れ、ここにアンモニアガスを５分間吹き込んで、飽和溶液とした。この飽和溶液に、１１−［４−（フェニルアゾ）フェニルオキシ］ウンデカニルクロリドの溶液として、１１−［４−（フェニルアゾ）フェニルオキシ］ウンデカン酸と塩化チオニルとの反応溶液をそのまま、室温に保つために水冷しながら、ゆっくりと滴下した。滴下終了後、アンモニアガスを２時間吹き込み、アミドに変換する反応を行った。反応終了後、反応溶液に少量の水を加えて撹拌後、不溶部をろ別、乾燥して、スペーサー基を含むアゾベンゼンのアミド誘導体、１１−［４−（フェニルアゾ）フェニルオキシ］ウンデカンアミド（Ａｚｏｂｅｎｚｅｎｅ−Ｏ−（ＣＨ₂）₁₀ＣＯＮＨ₂）を黄色固体として得た（収率７４％）。１１−［４−（フェニルアゾ）フェニルオキシ］ウンデカンアミドの構造は、¹Ｈ ＮＭＲスペクトルで確認した。
【０１５３】
１１−［４−（フェニルアゾ）フェニルオキシ］ウンデカンアミドの¹Ｈ ＮＭＲスペクトルデータを以下に示す。
¹Ｈ ＮＭＲ（クロロホルム−ｄ）δ ７．８６−７．９２（ｍ，Ａｒ，４Ｈ），７．４３−７．５１（ｍ，Ａｒ，３Ｈ），６．９９−７．０１（ｍ，Ａｒ，２Ｈ），４．０４（ｔ，ＯＣＨ₂），２．２２（ｔ，ＣＨ₂ＣＯＮＨ₂，２Ｈ），１．３１−１．８２（ｍ，ＣＨ₂，１６Ｈ）。
【０１５４】
１１−［４−（フェニルアゾ）フェニルオキシ］ウンデカンアミドを１．００８ｇ、水素化リチウムアルミニウム０．６２４ｇ、乾燥したジエチルエーテル４０ｍＬをフラスコに入れ、１２時間還流した。室温に戻し、２０ｍＬの水をゆっくりと滴下して、過剰の水素化リチウムアルミニウムと反応させた後、さらに一日撹拌を行った。反応溶液から２００ｍＬのジエチルエーテルで抽出を３回行い、ジエチルエーテルを減圧除去した。その後、残渣をクロロホルムとヘキサンとの混合溶媒より再結晶して精製することにより、目的とするスペーサー基を含む４−（フェニルアゾ）ベンゼンのアミン誘導体、４−（１１−アミノウンデシルオキシ）アゾベンゼン（Ａｚｏｂｅｎｚｅｎｅ−Ｏ−（ＣＨ₂）₁₁ＮＨ₂）を収率７６％で得た。４−（１１−アミノウンデシルオキシ）アゾベンゼンの構造は、¹Ｈ ＮＭＲスペクトルおよび¹³Ｃ ＮＭＲスペクトルで確認した。
【０１５５】
４−（１１−アミノウンデシルオキシ）アゾベンゼンのＮＭＲスペクトルデータを以下に示す。
¹Ｈ ＮＭＲ（クロロホルム−ｄ）δ ７．８６−７．９１（ｍ，Ａｒ，４Ｈ），７．４２−７．５１（ｍ，Ａｒ，３Ｈ），６．９９−７．００（ｍ，Ａｒ，２Ｈ），４．０３（ｔ，ＯＣＨ₂），２．７３（ｔ，ＣＨ₂ＮＨ₂，２Ｈ），１．２９−１．８１（ｍ，ＣＨ₂，１８Ｈ）．
¹³Ｃ ＮＭＲ（クロロホルム−ｄ）δ １６１．７０，１５２．７８，１４６．８４，１３０．２７，１２．０１，１２４．７３，１２２．５１，１１４．６８，６８．３４，４１．２６，３１．８６，２９．５３，２９．３６，２９．１８，２６．７９，２６．００。
［２，５−ポリムコン酸結晶の調製］
実施例４と同様にして、２，５−ポリムコン酸の結晶を得た。
［インターカレーション反応］
次に、得られた２，５−ポリムコン酸の結晶への４−（１１−アミノウンデシルオキシ）アゾベンゼンのインターカレーション反応を行った。
【０１５６】
すなわち、２，５−ポリムコン酸の結晶８０ｍｇ（ムコン酸単位０．５６ｍｍｏｌ）と４−（１１−アミノウンデシルオキシ）アゾベンゼン５４５ｍｇ（１．１２ｍｍｏｌ；理論量比、すなわち［−ＮＨ₂］／［−ＣＯ₂Ｈ］＝２）とを、乳鉢中で、３０分間すりつぶしながら混合、撹拌した。その後、５０ｍＬのジエチルエーテルで未反応の４−（１１−アミノウンデシルオキシ）アゾベンゼンを洗浄除去すると、４−（１１−アミノウンデシルオキシ）アゾベンゼンをインターカレーションした２，５−ポリムコン酸の結晶が５０％収率で得られた。
【０１５７】
実施例６と同様のインターカレーションの前後における２，５−ポリムコン酸結晶のＩＲスペクトルから、本発明に係る光応答性高分子としての２，５−ポリムコン酸１１−［４−（フェニルアゾ）フェニルオキシ］ウンデシルアンモニウムの結晶が生成していることがわかった。
［光応答性］
得られた２，５−ポリムコン酸１１−［４−（フェニルアゾ）フェニルオキシ］ウンデシルアンモニウムの結晶について、実施例６と同様に、紫外線照射による紫外可視吸収スペルトルの変化を観測したところ、光照射前後で層状構造の繰返し周期が変化しており、光応答性を持っていることが分かった。
【０１５８】
【発明の効果】
本発明のカルボン酸アンモニウムの結晶の製造方法は、以上のように、カルボン酸の結晶とアミンおよびアンモニアからなる群より選ばれる少なくとも１種の化合物とを液体媒質の非存在下で混合し、上記カルボン酸の結晶として、カルボキシル基を有する共役ジエンを用い、上記アミンおよびアンモニアからなる群より選ばれる少なくとも１種の化合物として、次式ＲＣＨ ₂ ＮＨ ₂ （式中、Ｒは炭素数５以上の直鎖アルキル基またはアリール基を表す）で表される第１級アミンを用いる方法である。
【０１５９】
上記方法によれば、カルボン酸が結晶状態でアミンおよびアンモニアからなる群より選ばれる少なくとも１種の化合物と反応するため、立体特異的な反応が進行し、単一の生成物を得ることができる。また、上記方法によれば、溶媒や分散媒のような液体媒質を使用しないので、液体媒質の分離操作や再結晶が不要である。したがって、上記方法は、カルボン酸アンモニウムの結晶を簡便に製造することができるという効果を奏する。
【０１６０】
上記方法では、上記カルボン酸として、カルボキシル基を有する共役ジエンを用い、上記アミンおよびアンモニアからなる群より選ばれる少なくとも１種の化合物として、次式
ＲＣＨ₂ＮＨ₂
（式中、Ｒは炭素数５以上の直鎖アルキル基またはアリール基を表す）
で表される第１級アミンを用いると、固相での放射線重合により層状結晶を生成可能なカルボン酸アンモニウムの結晶を得ることができる。
【０１６１】
また、上記カルボン酸の結晶として、カルボキシル基を有する共役ジエンの重合体の結晶を用いると、カルボキシル基を有する共役ジエンの重合体の層状結晶に対して、アミンおよびアンモニアからなる群より選ばれる少なくとも１種の化合物がゲスト化合物としてインターカレートされた（ポリ）カルボン酸アンモニウムの結晶を得ることができる。
【０１６２】
また、上記方法では、上記カルボキシル基を有する共役ジエンの重合体の層状結晶を用い、上記アミンおよびアンモニアからなる群より選ばれる少なくとも１種の化合物として、次式Ｒ’ＮＨ₂（式中、Ｒ’は、官能基を有していてもよい炭化水素基を表す）で表される第１級アミンを用いた場合、カルボン酸アンモニウムの重合体の層状結晶（カルボキシル基を有する重合体とアミンとの層状結晶）を得ることができる。
【０１６３】
また、この場合、液体媒質を用いないことで、従来の分散媒に分散させる方法のように、重合体の結晶が反応中に分散媒によって膨潤したり、溶解したりすることがない。それゆえ、従来の分散媒を用いた方法では実現できなかった、分岐構造を持つアルキル第１級アミンや官能基を含む第１級アミンをカルボン酸の重合体の結晶の層間にインターカレートすることが可能となる。したがって、従来の分散媒を用いた方法では合成できない、分岐構造を持つアルキル第１級アミンや官能基を含む第１級アミンが層状結晶の層間にインターカレートされた状態の新規なカルボン酸アンモニウムの重合体の層状結晶の合成に応用できる。
【０１６４】
また、本発明のカルボキシル基を有する重合体とアミンとの層状結晶の製造方法は、以上のように、カルボキシル基を有する共役ジエンと、次式ＲＣＨ₂ＮＨ₂（式中、Ｒは炭素数５以上の直鎖アルキル基またはアリール基を表す）で表される第１級アミンとを、液体媒質の非存在下で混合し、アンモニウムカルボキシレート基を有する共役ジエンの結晶を得る第１のステップと、アンモニウムカルボキシレート基を有する共役ジエンを固相で重合させ、アンモニウムカルボキシレート基を有する共役ジエンの重合体の層状結晶を得る第２のステップと、アンモニウムカルボキシレート基を有する共役ジエンの重合体の層状結晶を加熱することによりアンモニウムイオンを脱離させ、カルボキシル基を有する共役ジエンの重合体の層状結晶を得る第３のステップと、カルボキシル基を有する共役ジエンの重合体の層状結晶と、次式Ｒ’ＮＨ₂（式中、Ｒ’は、官能基を有していてもよい炭化水素基を表す）で表される第１級アミンとを、液体媒質の非存在下で混合する第４のステップとを含む方法である。
【０１６５】
上記方法では、第４のステップで、カルボン酸アンモニウムの重合体の層状結晶が生成する。
【０１６６】
上記方法によれば、全てのステップで、結晶状態で反応を行うため、立体特異的な反応が進行し、単一の生成物を得ることができる。また、上記方法によれば、全てのステップで溶媒や分散媒のような液体媒質を反応に使用しないので、液体媒質の分離操作や再結晶が不要である。したがって、上記方法は、カルボン酸アンモニウムの重合体の層状結晶を簡便に製造することができるという効果を奏する。
【０１６７】
さらに、上記方法によれば、液体媒質を用いないことで、従来の分散媒に分散させる方法のように、重合体の結晶が反応中に分散媒によって膨潤したり、溶解したりすることがないので、分岐構造を持つアルキル第１級アミンや官能基を含む第１級アミンをカルボン酸の重合体の結晶の層間にインターカレートすることが可能となる。したがって、上記方法は、従来の分散媒を用いた方法では合成できない、分岐構造を持つアルキル第１級アミンや官能基を含む第１級アミンが層状結晶の層間にインターカレートされた状態の新規なカルボン酸アンモニウムの重合体の層状結晶の合成に応用できるという効果も奏する。
【０１６８】
また、本発明の製造方法は、以上のように、カルボキシル基を有する共役ジエンの重合体の層状結晶を用いる上記各方法において、カルボキシル基を有する共役ジエンの重合体の層状結晶と混合する化合物として、次の一般式
−Ａｒ−Ｎ＝Ｎ−Ａｒ’−
（上記式中、ＡｒおよびＡｒ’は、それぞれ独立して、芳香族炭化水素２価基を表す）
で表される２価基を持つアミンを用い、このアミンを層状結晶にインターカレートさせる方法である。これにより、本発明にかかる光応答性高分子を簡便に製造することができる。
【０１６９】
本発明に係る光応答性高分子は、以上のように、カルボキシル基を有する重合体の層状結晶に対して、次の一般式
−Ａｒ−Ｎ＝Ｎ−Ａｒ’−
（上記式中、ＡｒおよびＡｒ’は、それぞれ独立して、芳香族炭化水素２価基を表す）
で表される２価基を持つアミンがインターカレートされたものである。
【０１７０】
上記構成によれば、光応答（光照射に対する応答）をして結晶構造が可逆的に変化しうる新規な結晶性の光機能性高分子を提供できるという効果が得られる。本発明にかかる光機能性高分子は、光照射条件に応じてその層間距離が可逆的に変化するので、光メモリー材料、記録材料に用いる光機能性材料、電気・電子材料に用いる光機能性材料等への応用が期待できる。
【図面の簡単な説明】
【図１】（ａ）〜（ｄ）は、本発明の実施の一形態に係るカルボン酸アンモニウムの重合体の層状結晶の製造工程を模式的に示す図である。
【図２】本発明の製造方法によって得られるカルボン酸アンモニウムの重合体の層状結晶の応用例を模式的に示す図である。
【図３】２，５−ポリムコン酸ベンジルアンモニウムの結晶のＸ線回折スペクトルを表す図であり、（ａ）は本発明の製造方法の一実施例で得られる２，５−ポリムコン酸ベンジルアンモニウムの結晶のＸ線回折スペクトル、（ａ）は従来の製造方法で得られる２，５−ポリムコン酸ベンジルアンモニウムの結晶のＸ線回折スペクトルを表す。
【図４】本発明の製造方法の一実施例で得られる２，５−ポリムコン酸ベンジルアンモニウムおよび２，５−ポリムコン酸のＩＲスペクトルを表す図である。
【図５】本発明の製造方法の一実施例における、光応答性基を有するアミンをインターカレートする前後で２，５−ポリムコン酸の層状結晶のＩＲスペクトルがどのように変化するかを表す図である。
【図６】本発明の一実施例にかかる光応答性高分子を紫外線照射したときの紫外可視吸収スペクトルの変化を表す図である。
【図７】本発明の一実施例にかかる光応答性高分子を紫外線照射したときの粉末Ｘ線回折の変化を表す図である。
【符号の説明】
１ （Ｚ，Ｚ）−ムコン酸アンモニウム分子
２ 第２級アンモニウムイオン分子
３ （Ｚ，Ｚ）−ムコン酸アニオン分子
４ ２，５−ポリムコン酸アニオン分子
４’ ポリマーシート
５ 第２級アンモニウムイオン分子
５’ アミン（Ｂ）の分子[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel photoresponsive polymer in which a guest compound containing a photoresponsive group is intercalated in a layered crystalline polymer, and a method for producing a carboxylic acid ammonium salt crystal suitable for the production thereof. Further, the present invention relates to a method for producing an ammonium carboxylate crystal using a carboxylic acid crystal and at least one compound selected from the group consisting of an amine and ammonia. More specifically, the present invention relates to a layered crystalline polymer having a carboxylic acid in which an amine containing an azo group is intercalated as a guest compound, and the azo group is cis-trans isomerized by light irradiation. The present invention provides a photoresponsive polymer that can be changed in absorption characteristics and structure, and a simple method for producing crystals of ammonium carboxylate salt suitable for the production thereof.
[0002]
[Prior art]
Conventionally, a method for producing an ammonium carboxylate crystal using a carboxylic acid crystal and an amine is known.
[0003]
For example, the inventors of the present application dissolved and mixed muconic acid crystals and linear alkylamine in a solvent such as methanol or water, and then removed the solvent and recrystallized the obtained solid, It has been reported that alkyl ammonium muconate crystals can be obtained.
[0004]
In addition, the inventors of the present application have found that a polymer crystal is formed by solid-phase polymerization in which light, X-rays, γ-rays, etc. are irradiated to the crystal of alkyl ammonium muconate obtained by the above-described method. It has been reported that layered crystals of polymuconic acid can be obtained by removing the solvent after hydrolysis using.
[0005]
  Further, the inventors of the present application have obtained the linear alkylamine and the lamellar crystal of polymuconic acid obtained by the above method in a state of being dispersed in a dispersion medium such as methanol or water.MixedLater, it was reported that linear alkylamines were intercalated between layers of polymuconic acid layered crystals by removing the dispersion medium.
[0006]
[Problems to be solved by the invention]
However, the conventional method using a solvent or a dispersion medium requires a separation operation or recrystallization of the solvent or the dispersion medium, so that crystals of ammonium carboxylate cannot be easily produced.
[0007]
In addition, in the above-described conventional method of performing intercalation using a dispersion medium, depending on the type of amine, the polymer crystals swell or dissolve by the dispersion medium during the reaction, and therefore a polymer having a layered structure. In some cases, crystals could not be obtained. In particular, when alkyl primary amines having a branched structure or primary amines containing functional groups are used, the lamellar crystals of polymuconic acid are swollen or dissolved by the dispersion medium during the reaction. It was not possible to obtain a polymer crystal intercalated with an alkyl primary amine having a branched structure or a primary amine containing a functional group.
[0008]
Conventionally, photoresponsive low molecular weight compounds, photoresponsive polymers, and photoresponsive polymer materials are known. For example, it is well known that an azobenzene derivative (low molecular weight compound) isomerizes to a cis form upon irradiation with ultraviolet light, but has a property of isomerizing to a trans form upon irradiation with visible light or heating (photoresponsiveness). . Also known are photoresponsive polymers in which a substituent containing an azo group is chemically bonded to the side chain of the polymer, and photoresponsive polymer materials in which a low molecular azo compound is dispersed in a polymer matrix. Yes. These are used in the form of a solution or a film-like solid.
[0009]
In addition, many attempts have been made to intercalate amines containing photoresponsive groups such as azo groups in general layered crystals with inorganic layered crystals. Among inorganic layered crystals, clay minerals, silicates, and metal oxides have a negative charge and thus exhibit cation exchange properties. Therefore, inorganic layered crystals of clay minerals, silicates, and metal oxides are known to easily intercalate amines (Quarterly Chemical Review No. 42, Inorganic Organic Nanocomposites, The Chemical Society of Japan, Academic Publishing Center (1999), see pages 33-44). For example, an example in which an amine containing an azo group is intercalated in an inorganic layered crystal has been reported (for example, “Photocontrol of the Basal Spacing of Azobenzene-Magadiite Intercalation Compound”, M. Ogawa, T. Ishii, N. Miyamoto , K. Kuroda, Adv. Mater. 13, 1107-1109 (2001) and “Preparation of a Cationic Azobenzene Derivative-Montmorillonite Intercalation Compound and the Photochemical Behavior”, M. Ogawa, Mater. Chem., 8, 1347-1349 (1996)).
[0010]
However, even when a normal azobenzene derivative (containing no amino group) and a crystalline polymer are mixed, it is difficult to induce a structural change of the crystalline polymer by photoisomerization of the azobenzene derivative. In addition, it is not a little troublesome to chemically bond an azo group directly to the polymer. Therefore, the conventional photoresponsive polymer is difficult to manufacture, and it is more difficult to manufacture a variety of polymers. Further, simply dispersing a low molecular weight azo compound in a matrix is insufficient in stability and function (photoresponsiveness).
[0011]
In addition, a photoresponsive material obtained by intercalating an amine containing a photoresponsive group such as an azo group in an inorganic layered crystal is difficult to use in a solution state or a film-like solid state. There is a drawback of low.
[0012]
The present invention has been made in view of the above-described conventional problems, and an object of the present invention is to provide a novel photoresponsive polymer that can solve the problems of conventional photoresponsive materials, and the production of the photoresponsive polymer. It is an object of the present invention to provide a simple method for producing an ammonium carboxylate crystal suitable for the above.
[0013]
[Means for Solving the Problems]
  In order to solve the above-described problem, the method for producing an ammonium carboxylate crystal of the present invention comprises a carboxylic acid crystal and at least one compound selected from the group consisting of an amine and ammonia in the absence of a liquid medium. mixtureIn addition, a conjugated diene having a carboxyl group is used as the carboxylic acid crystal, and at least one compound selected from the group consisting of the amine and ammonia is represented by the following formula RCH: ₂ NH ₂ (In the formula, R represents a linear alkyl group or aryl group having 5 or more carbon atoms).It is characterized by that.
[0014]
According to the above method, the carboxylic acid reacts with at least one compound selected from the group consisting of amine and ammonia in a crystalline state. Since the reaction in the crystalline state is a reaction in the most controlled reaction field called crystal, a stereospecific reaction proceeds and a single product can be obtained. Further, according to the above method, since a liquid medium such as a solvent or a dispersion medium is not used, separation operation and recrystallization of the liquid medium are unnecessary. Therefore, according to the above method, crystals of ammonium carboxylate can be easily produced.
[0015]
Further, the above method has not only such advantages in synthesis but also an advantage that it does not generate a waste liquid medium and is environmentally friendly because it does not use a liquid medium.
[0016]
In the present specification, “liquid medium” refers to a field (reaction field) in which a chemical reaction is performed without being directly involved in a chemical reaction, as typified by a liquid solvent or a liquid dispersion medium. It refers to the liquid material that does.
[0017]
In the above method, a conjugated diene having a carboxyl group (conjugated diene carboxylic acid; a conjugated diene having at least one carboxyl group) is used as the carboxylic acid, and at least one compound selected from the group consisting of the amine and ammonia is used. ,
RCH₂NH₂
(In the formula, R represents a linear alkyl group or aryl group having 5 or more carbon atoms)
When a primary amine represented by the formula (1) is used, an ammonium carboxylate crystal capable of producing a layered crystal by polymerization in a solid phase can be obtained.
[0018]
  Also,the aboveWhen a crystal of a conjugated diene polymer having a carboxyl group is used, at least one compound selected from the group consisting of an amine and ammonia is used as a guest compound for the layered crystal of a polymer of a conjugated diene having a carboxyl group. Crystals of calated ammonium (poly) carboxylate(Layered crystal of polymer having carboxyl group and amine)Can be obtained.
[0019]
In the above method, a layered crystal of a polymer of a conjugated diene having a carboxyl group is used as the carboxylic acid crystal, and at least one compound selected from the group consisting of the amine and ammonia has the following formula:
R'NH₂
(Wherein R ′ represents a hydrocarbon group which may have a functional group)
When a primary amine represented by the formula (1) is used, a layered crystal of a polymer of ammonium carboxylate can be obtained.
[0020]
Also, in this case, by not using a liquid medium, the polymer crystals are not swollen or dissolved by the dispersion medium during the reaction, unlike the conventional method of dispersing in a dispersion medium. Therefore, an alkyl primary amine having a branched structure or a primary amine containing a functional group, which could not be realized by the conventional method using a dispersion medium, is intercalated between the crystal layers of the carboxylic acid polymer. It becomes possible. Therefore, a novel ammonium carboxylate in a state in which a branched alkyl primary amine or a primary amine containing a functional group is intercalated between layered crystals, which cannot be synthesized by a conventional method using a dispersion medium. It can be applied to the synthesis of layered crystals of polymers.
[0021]
The “functional group” refers to a group other than a hydrocarbon group.
[0022]
  In addition, the present inventionLayered polymer with carboxyl group and amineIn order to solve the above problems, a method for producing a crystal includes a conjugated diene having a carboxyl group, and RCH₂NH₂(Wherein R represents a straight-chain alkyl group or aryl group having 5 or more carbon atoms) and a conjugated diene having an ammonium carboxylate group, mixed in the absence of a liquid medium. A second step of obtaining a layered crystal of a polymer of a conjugated diene having an ammonium carboxylate group by polymerizing in a solid phase a crystal of a conjugated diene having an ammonium carboxylate group; A third step of obtaining a layered crystal of a conjugated diene polymer having a carboxyl group by desorbing ammonium ions by heating the layered crystal of a conjugated diene polymer having a carboxylate group, and a conjugate having a carboxyl group Layered crystals of diene polymer and the following formula R′NH₂(Wherein R ′ represents a hydrocarbon group which may have a functional group), and a fourth step of mixing in the absence of a liquid medium. It is characterized by that.
[0023]
In the above method, a layered crystal of a polymer of ammonium carboxylate is formed in the fourth step.
[0024]
According to the above method, the reaction is performed in a crystalline state in all steps. Since the reaction in the crystalline state is a reaction in the most controlled reaction field called crystal, a stereospecific reaction proceeds and a single product can be obtained.
[0025]
Further, according to the above method, since a liquid medium such as a solvent or a dispersion medium is not used for the reaction in all steps, separation operation and recrystallization of the liquid medium are unnecessary.
[0026]
Therefore, according to the above method, a layered crystal of a polymer of ammonium carboxylate can be easily produced.
[0027]
Further, according to the above method, the polymer crystal is not swollen or dissolved by the dispersion medium during the reaction, unlike the conventional method of dispersing in the dispersion medium, without using the liquid medium. . Therefore, according to the above method, the alkyl primary amine having a branched structure and the primary amine containing a functional group, which could not be realized by the conventional method using a dispersion medium, are converted into the carboxylic acid polymer crystals. It is possible to intercalate between layers. Therefore, the above-mentioned method is a novel method in which a branched alkyl primary amine or a primary amine containing a functional group is intercalated between layers of layered crystals, which cannot be synthesized by a conventional method using a dispersion medium. It can be applied to the synthesis of layered crystals of various ammonium carboxylate polymers.
[0028]
The polymerization in the solid phase in the second step may be performed by irradiating the crystal of the conjugated diene having an ammonium carboxylate group with radiation in the solid phase. The crystal may be subjected to thermal polymerization while maintaining the crystal state.
[0029]
  In addition, the present inventionLayered polymer with carboxyl group and amineCrystallineotherIn order to solve the above-mentioned problem, the production method uses the following general formula -Ar-N = N-Ar'- (in the above formula, as a compound mixed with a layered crystal of a polymer of a conjugated diene having a carboxyl group. Ar and Ar ′ each independently represents an aromatic hydrocarbon divalent group), and an amine having a divalent group represented by a photoresponsive group is used. The amine is intercalated into a layered crystal as a guest compound. It is characterized by making it.
[0030]
According to the above method, ammonium carboxylate in which an amine having the above divalent group is intercalated as a guest compound with respect to a layered crystal (layered crystalline polymer) of a conjugated diene polymer having a carboxyl group. A crystal, that is, a photoresponsive polymer (described later) according to the present invention can be easily produced.
[0031]
In order to solve the above-described problems, the photoresponsive polymer according to the present invention includes the following in a layered crystal (layered crystalline polymer) of a polymer having a carboxyl group (particularly, polymuconic acid or polysorbic acid). General formula of
-Ar-N = N-Ar'-
(In the above formula, Ar and Ar ′ each independently represents an aromatic hydrocarbon divalent group)
An amine having a divalent group represented by the formula (1) as a photoresponsive group is a layered polymer intercalated as a guest compound.
[0032]
According to the above configuration, since an amine having a divalent group containing an azo group (—N═N—) as a photoresponsive group is intercalated, the azo group is cis-trans isomerized by irradiation with light, and By utilizing the structural change of the divalent group, it is possible to cause a change in crystal structure in accordance with the structural change of the divalent group, such as a change in interlayer distance, for the layered crystalline polymer. Therefore, according to the present invention, it is possible to provide a novel crystalline photofunctional polymer capable of reversibly changing the crystal structure by photoresponse (response to light irradiation). In the photofunctional polymer containing an azo group according to the present invention, the interlayer distance reversibly changes depending on the light irradiation conditions. Therefore, the photofunctional polymer can be used for optical memory materials, optical functional materials used for recording materials, and electrical / electronic materials. It is considered that it can be used as an optical functional material to be used.
[0033]
DETAILED DESCRIPTION OF THE INVENTION
An embodiment of the present invention will be described as follows.
[0034]
In the method for producing ammonium carboxylate crystals of the present invention, the amine and the carboxylic acid crystals remain in the crystalline state in the absence of a liquid medium, that is, without being dissolved in a solvent or dispersed in a dispersion medium. Mix with at least one compound selected from the group consisting of ammonia.
[0035]
The carboxylic acid may be solid at room temperature, and may be a monobasic unsaturated carboxylic acid such as sorbic acid, crotonic acid, tiglic acid; muconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic And dibasic unsaturated carboxylic acids such as acids; dibasic saturated carboxylic acids such as malonic acid, succinic acid, adipic acid and oxalic acid. Furthermore, as the carboxylic acid, it is also possible to use a polymer having a carboxyl group, such as polymuconic acid or polysorbic acid.
[0036]
The at least one compound selected from the group consisting of amine and ammonia is not particularly limited (may be solid, liquid or gas at room temperature), methylamine, ethylamine, n-propylamine, n-butylamine, Examples include primary amines such as isobutylamine, octylamine, benzylamine, dodecylamine, 1-naphthylmethylamine; secondary amines; tertiary amines; ammonia and the like.
[0037]
Here, as the carboxylic acid, a carboxylic acid having a conjugated diene moiety (conjugated diene having a carboxyl group) such as sorbic acid or muconic acid is used, and at least one selected from the group consisting of the amine and ammonia is used. As a compound, the following formula
RCH₂NH₂
(In the formula, R represents a linear alkyl group or aryl group having 5 or more carbon atoms)
When a primary amine represented by the formula (hereinafter referred to as amine (A)) is used, ammonium carboxylate crystals capable of forming layered crystals by solid phase polymerization can be obtained.
[0038]
The amine (A) may be liquid, solid, or gas, and is not particularly limited. Examples of the amine (A) include octylamine, benzylamine, dodecylamine, 1-naphthylmethylamine, n-pentylamine, n-hexylamine, n-heptylamine, decylamine and the like. Among these, as the amine (A), an amine having a molecular structure that can easily form a column structure, specifically, at least one compound selected from the group consisting of benzylamine, dodecylamine, and 1-naphthylmethylamine Are preferred, and 1-naphthylmethylamine is particularly preferred.
[0039]
The group represented by R is more preferably a linear alkyl group having 7 or more carbon atoms or an aryl group, and further preferably a linear alkyl group having 9 or more carbon atoms or an aryl group.
[0040]
Further, when a crystal of a polymer of a carboxylic acid having a conjugated diene moiety (conjugated diene having a carboxyl group) such as sorbic acid or muconic acid is used as the carboxylic acid crystal, a carboxyl group as a host species can be obtained. A crystal having a structure in which at least one compound selected from the group consisting of an amine and ammonia is intercalated between the layers of the layered crystal as a guest species (guest compound) with respect to the layered crystal of the conjugated diene polymer. A crystal of ammonium acid polymer) can be obtained.
[0041]
The compound mixed with the layered crystal of the conjugated diene polymer having a carboxyl group is not particularly limited. Primary amine; Secondary amine such as N-methylbenzylamine; N, N-dimethyldodecyl And tertiary amines such as amine, tridodecylamine, N, N-dimethylbenzylamine and the like. Of these, the following formula
R'NH₂
(In the formula, R ′ represents a hydrocarbon group which may have a functional group (one or more carbon atoms)).
The primary amine represented by these is preferable.
[0042]
In addition, a crystal of a polymer of a carboxylic acid having a conjugated diene moiety (a conjugated diene having a carboxyl group), such as sorbic acid or muconic acid, is used as the carboxylic acid crystal. As at least one compound selected, the following formula
R'NH₂
(In the formula, R ′ represents a hydrocarbon group which may have a functional group (one or more carbon atoms)).
When a primary amine represented by the formula (hereinafter referred to as amine (B)) is used, a layered crystal of a polymer of ammonium carboxylate can be obtained.
[0043]
As the amine (B), the above formula
RCH₂NH₂
(In the formula, R represents a linear alkyl group or aryl group having 5 or more carbon atoms)
In addition to the primary amine represented by the formula, linear alkyl primary amines having less than 5 carbon atoms such as methylamine, ethylamine, n-propylamine, n-butylamine and the like; isobutylamine, sec-butylamine, tert- Branched primary amines such as butylamine; primary amines having a cyclic structure such as cyclohexylamine; diamines such as hexamethylenediamine; primary containing functional groups such as ethanolamine and amino acids Amines can also be used.
[0044]
The ratio of the amount of carboxylic acid and amine used is preferably the theoretical amount ratio, that is, the number of carboxyl groups of the carboxylic acid and the number of amino groups of the amine are equal.
[0045]
As a method of mixing the carboxylic acid crystals and the solid or liquid amine at room temperature, a method of mixing while grinding in a mortar is preferable. The mixing time is not particularly limited, and for example, about 30 minutes is sufficient when mixing while grinding in a mortar.
[0046]
Next, a method for obtaining layered crystals of ammonium polycarboxylate in which various primary amines are intercalated between layers from a conjugated diene having a carboxyl group and a primary amine using the method of the present invention. explain. Here, the case where (Z, Z) -muconic acid is used as the conjugated diene having a carboxyl group will be described as an example.
[0047]
First, in the first step, (Z, Z) -muconic acid crystals as a conjugated diene having a carboxyl group and the amine (A) are mixed in the absence of a liquid medium. This gives
[0048]
[Chemical 1]

[0049]
As shown, a crystal of ammonium (Z, Z) -muconate as a conjugated diene having an ammonium carboxylate group is formed.
[0050]
The crystal of (Z, Z) -ammonium muconate has a column structure formed by stacking (Z, Z) -ammonium muconate molecules 1 as shown in FIG. That is, the crystal of (Z, Z) -muconate ammonium is composed of (Z, Z) -muconate anion molecule 3 and secondary ammonium ion (RCH).₂NH_Three ⁺) Molecules 2 are formed by ionic bonding in a state of being arranged in layers. In the crystal of (Z, Z) -muconate ammonium, the centers of a plurality of (Z, Z) -muconate anion molecules 3 are aligned on a plurality of planes (layers) parallel to each other to form a conjugated π plane. . Each (Z, Z) -muconate anion molecule 3 and each secondary ammonium ion molecule 2 are oriented perpendicular to the plane.
[0051]
The crystal of (Z, Z) -muconic acid is desirably reduced in size in order to increase the contact area with the amine (A) and increase the reaction rate. Therefore, as a method of mixing the crystal of (Z, Z) -muconic acid and the primary amine, a method of mixing while grinding in a mortar is preferable. The mixing time is not particularly limited, and for example, about 30 minutes is sufficient when mixing while grinding in a mortar.
[0052]
The ratio of the amount of (Z, Z) -muconic acid to amine (A) used should be a theoretical amount ratio, that is, a ratio such that the amount of amine (A) used per mole of muconic acid is 2 moles. Is preferred.
[0053]
Next, in the second step, next, in the second step, the crystals of ammonium (Z, Z) -muconate as a conjugated diene having an ammonium carboxylate group are maintained in the solid phase while maintaining the crystalline state. Polymerize. As a result, ammonium (Z, Z) -muconate is polymerized by the radical chain reaction mechanism,
[0054]
[Chemical formula 2]

[0055]
As shown in Figure 2, ammonium 2,5-polymuconate is formed. In the above formula, n represents the number of repeating structural units. n can be confirmed by GPC (gel permeation chromatography) and is generally in the range of 10 to 10,000,000, typically 100 to 100,000.
[0056]
At this time, in the crystal of (Z, Z) -ammonium muconate, the muconate anion molecules 3 are arranged in layers as described above. Therefore, the polymerization reaction is topochemical polymerization in which monomer molecules are polymerized with a minimum movement in the crystal under the control of this layered arrangement (crystal lattice). As a result, a layered crystal of ammonium 2,5-polymuconate having a high degree of stereoregularity having a high molecular weight and having all the stereocenters in the repeating structural unit controlled. Therefore, the crystal of the polymer (ammonium 2,5-polymuconate) obtained by the solid phase polymerization has the same spatial symmetry as the crystal of the monomer ((Z, Z) -ammonium muconate), and The center of gravity of the repeating structural unit in this polymer is almost the same as the center of gravity of the monomer.
[0057]
The layered crystal of ammonium 2,5-polymuconate is composed of a plurality of layers (polycarboxylic acid) formed of 2,5-polymuconate anion (carboxylate ion) molecules 4, as shown in FIG. The secondary ammonium ion (counter ammonium cation) molecule 2 is intercalated between the layers), and the secondary ammonium ion molecule 2 has a completely oriented structure. At this time, the layer interval d1 of the layered crystal of ammonium 2,5-polymuconate changes according to the length of the carbon chain of the amine (A).
[0058]
In the polymer crystal, a regular hydrogen bond network similar to the hydrogen bond network formed in the crystal structure of the monomer is formed. This hydrogen bond network has been confirmed from the results of crystal structure analysis and can be classified into several patterns (J. Am. Chem. Soc., 121 (48), 11122-11129 (1999). )reference).
[0059]
As described above, not only stereoregularity but also the two-dimensional structure was controlled by the topochemical polymerization that designed the molecular arrangement so that the diene part would be stacked for convenient polymerization, utilizing the interaction between molecules. A polymer can be synthesized.
[0060]
The above solid-state polymerization proceeds very quickly by X-ray irradiation, but changes in crystal structure before and after solid-phase polymerization are analyzed by rapid solution X-ray crystal structure analysis equipped with an image plate and CCD (charge coupled device) camera system. Is possible. From the results of this rapid solution X-ray crystal structure analysis and NMR (nuclear magnetic resonance) spectrum measurement, the polymer obtained is a stereoregular polymer having a meso-diisotactic trans-2,5-structure. It has been confirmed.
[0061]
The solid phase polymerization is a method of irradiating a crystal of (Z, Z) -ammonium muconate as a conjugated diene having an ammonium carboxylate group in the solid phase (hereinafter referred to as “radiation polymerization method”). It may be carried out by a method of thermally polymerizing crystals of ammonium (Z, Z) -muconate as a conjugated diene having an ammonium carboxylate group while maintaining its crystalline state (hereinafter referred to as “thermal polymerization method”). These may be used in combination. Comparing the radiation polymerization method and the thermal polymerization method, the radiation polymerization method (especially when X-rays or γ-rays are used) is advantageous in terms of the purity of the crystals obtained. On the other hand, the thermal polymerization method does not require a large reactor compared to the radiation polymerization method, and has the advantage that there is no danger of exposure as in the case of using X-rays or γ-rays, and the safety is high. There is.
[0062]
Examples of radiation used in the radiation polymerization method include ultraviolet rays, X-rays, and γ rays. When highly transmissive X-rays or γ-rays are used, a polymer crystal can be produced in which the initiation reaction occurs uniformly throughout the crystal, and the distortion and defects are particularly small.
[0063]
Further, the heating temperature in the thermal polymerization method may be any temperature at which (Z, Z) -ammonium muconate starts polymerization, but may be lower than the melting point or decomposition temperature of (Z, Z) -ammonium muconate. preferable. Thereby, thermal polymerization can be performed while maintaining the (Z, Z) -ammonium muconate in a crystalline state. Here, the temperature lower than the melting point of the monomer is preferably lower than the temperature at which (Z, Z) -ammonium muconate starts melting. Further, the temperature lower than the decomposition temperature of (Z, Z) -ammonium muconate is preferably lower than the temperature at which (Z, Z) -ammonium muconate starts to decompose. Furthermore, when the temperature in thermal polymerization is equal to or higher than the temperature at which (Z, Z) -ammonium muconate starts to decompose, the rate of polymerization of (Z, Z) -ammonium muconate is high, and the rate of the above polymerization It is preferable that the temperature has a large difference between the decomposition rate and the decomposition rate.
[0064]
Next, in the third step, a crystal of ammonium 2,5-polymuconate as a conjugated diene having an ammonium carboxylate group is thermally decomposed by heating. This gives
[0065]
[Chemical 3]

[0066]
As shown, the ammonium ion is eliminated as an amine, and the ammonium 2,5-polymuconate is converted into a layered crystal of 2,5-polymuconic acid as a layered crystal of a conjugated diene polymer having a carboxyl group. The
[0067]
In addition, as a method for converting 2,5-polymuconic acid ammonium crystals into layered crystals of 2,5-polymuconic acid, a method of hydrolysis using an acid such as hydrochloric acid may be employed. In view of not using the above-mentioned method, the above-described thermal decomposition method is preferable. As a method of hydrolyzing with an acid, for example, there is a method of impregnating ammonium 2,5-polymuconate crystal in a methanol solution (including water) of hydrochloric acid or an aqueous solution.
[0068]
The layered crystal of 2,5-polymuconic acid obtained by the above conversion is composed of a large number of polymer sheets 4 ′ as shown in FIG. 1 (c), and is an organic intercalation capable of reversibly taking in and out ammonium ions. Functions as a compound. That is, the layered crystal of 2,5-polymuconic acid is useful as a host compound (organic intercalation compound) for organic intercalation that can incorporate various amines as guests. Common intercalating materials (materials used for intercalation) are inorganic materials typified by graphite, metal oxides, viscous minerals, etc., but layered crystals of 2,5-polymuconic acid according to the present invention. Unlike such a general intercalating material, is an intercalating material composed only of an organic substance.
[0069]
Finally, in the fourth step, the layered crystal of 2,5-polymuconic acid and the amine (B) are mixed in the absence of a liquid medium. This gives
[0070]
[Formula 4]

[0071]
As shown in the figure, crystals of ammonium 2,5-polymuconate are produced again as crystals of a polymer of a conjugated diene having an ammonium carboxylate group (a layered crystal in which ammonium ions are intercalated between layers).
[0072]
As shown in FIG. 1 (d), the crystals of ammonium 2,5-polymuconate have an amine (between a plurality of layers formed of 2,5-polymuconate anion (carboxylate ion) molecules 4). The molecule 5 'of B) has a layered crystal structure intercalated as secondary ammonium ion molecules 5.
[0073]
The ratio of the amount of 2,5-polymuconic acid crystals to amine (B) used is such that the amount of amine (B) used per mole of carboxyl group of 2,5-polymuconic acid is increased in order to improve the yield. The ratio is preferably 2 mol or more, and the theoretical amount ratio of amine (B), that is, the amount of amine (B) used per mol of carboxyl group of 2,5-polymuconic acid is 2 mol. Most preferred is a ratio.
[0074]
At this time, when the length of the carbon chain of the amine (B) is changed, the layer interval d2 of the layered crystal of ammonium 2,5-polymuconate also changes accordingly. Therefore, for example, when the length of the carbon chain of the amine (B) is shorter than the length of the carbon chain of the amine (A), the layer interval d2 of the layered crystal obtained in the fourth step is as shown in (d) of FIG. As shown, it becomes shorter than the layer interval d1 of the layered crystal obtained in the second step.
[0075]
According to the intercalation in the fourth step described above, by using an amine having a functional group that expresses a specific function as the amine (B), the functional group that expresses a specific function is converted to 2,5-polymucon. It can be introduced into acid crystals (polymer sheet 4 'in FIG. 2). A crystal in which an amine having a functional group that expresses a specific function is introduced into a layered crystal of 2,5-polymuconic acid can be applied as various functional polymer crystals. For example, optical resolution, molecular recognition, Development as an organic magnetic material, ion conductive material, photoresponsive material, stimulus responsive material, photoreactive material, etc. can be expected.
[0076]
Specifically, when an amine having a chiral carbon is used as the amine (B), a functional polymer crystal in which an amine having a chiral carbon is intercalated between layers of 2,5-polymuconic acid is obtained. It is done. For example, as shown in FIG. 2, the formula (1) (wherein R¹And R²When an amine having a hydroxyl group bonded to a chiral carbon represented by different hydrocarbon groups and X represents a divalent hydrocarbon group is used, the amine is converted into a layered crystal (2,5-polymuconic acid in FIG. 2). A functional polymer crystal intercalated between the anion molecules 4) is obtained. This functional polymer crystal is considered to be usable for optical resolution, molecular recognition and the like in which only one alcohol is extracted from a mixture of (R) -alcohol and (S) -alcohol.
[0077]
Further, as the amine (B), an amine having a large magnetic moment, for example, an amine oxide moiety represented by the formula (2) (wherein X represents a hydrocarbon divalent group) as shown in FIG. When an amine having the formula is used, a functional polymer crystal in which the amine is intercalated between the layered crystals of 2,5-polymuconic acid is obtained. It is considered that this functional polymer crystal can be used as an organic magnetic substance.
[0078]
In addition, as the amine (B), an amine having a polyoxyalkylene chain such as a polyoxyethylene chain, for example, as shown in FIG. When a primary amine having a polyoxyethylene chain represented by the above formula is used, this amine is intercalated between layers of 2,5-polymuconic acid layered crystals. Is obtained. It is considered that this functional polymer crystal can be used as an ion conductive material that conducts ions such as Li ions or a conductive material.
[0079]
Further, as the amine (B), an amine having a nitrogen-nitrogen double bond, for example, as shown in FIG. 2, is represented by the formula (4) (wherein X represents a hydrocarbon divalent group). When an amine having an azo group is used, a functional polymer crystal in which the amine is intercalated between layered crystals of 2,5-polymuconic acid is obtained. In this functional polymer crystal, as shown in FIG. 2, the orientation of the intercalated amine (ammonium ion) is changed by light energy, and the interlayer distance is considered to change. Therefore, it is considered that the functional polymer crystal can be used as this photoresponsive material or stimulus responsive material. That is, by using an amine having a nitrogen-nitrogen double bond as the amine (B), a functional polymer crystal that can be used as a photoresponsive material or a stimulus-responsive material can be obtained. This functional polymer crystal will be described in detail later.
[0080]
In addition, as the amine (B), an amine having a carbon-carbon unsaturated bond, for example, as shown in FIG. 2, is represented by the formula (5) (wherein X is a hydrocarbon divalent group, R^ThreeWhen an amine having a vinyl group is used, a functional polymer crystal in which this amine is intercalated between the layered crystals of 2,5-polymuconic acid is obtained. It is considered that this functional polymer crystal can be used as a photoreactive material or a material that provides a specific reaction field.
[0081]
As described above, synthesis of the monomer ((Z, Z) -ammonium muconate), polymerization of the monomer, conversion of ammonium 2,5-polymuconate to 2,5-polymuconic acid, 2, Intercalation of ammonium ions into 5-polymuconic acid, and in all steps, 2,5-polymuconic acid intercalated with any amine (B) between layers without using a liquid medium for the reaction. Layered crystals can be obtained.
[0082]
In addition, although the case where (Z, Z) -muconic acid was used as the conjugated diene having a carboxyl group was described here, instead of (Z, Z) -muconic acid, (E, E) -muconic acid or Other α, β-unsaturated dibasic carboxylic acids such as (E, Z) -muconic acid and the like; α, β-unsaturated monobasic carboxylic acids such as sorbic acid and the like can also be used.
[0083]
When (E, E) -muconic acid is used instead of (Z, Z) -muconic acid, in the second step, a polymer having the same structure as when (Z, Z) -muconic acid is used is obtained. It is done. This is because the monomers facing in the same direction in the first step are stacked in a column shape, which is confirmed from the crystal structure model.
[0084]
When (E, E) -muconic acid or sorbic acid is used instead of (Z, Z) -muconic acid as the conjugated diene having a carboxyl group, 1-naphthylmethylamine is used as amine (A). preferable.
[0085]
Next, the functional polymer crystal, that is, the photoresponsive polymer according to the present invention will be described in detail.
[0086]
The photoresponsive polymer according to the present invention comprises a layered crystal of a conjugated diene polymer having a carboxyl group described above and at least one compound selected from the group consisting of an amine and ammonia in the absence of a liquid medium. As a compound to be mixed with a layered crystal of a polymer of a conjugated diene having a carboxyl group in a method for producing an ammonium carboxylate crystal to be mixed, the following general formula
-Ar-N = N-Ar'- (6)
(In the above formula, Ar and Ar ′ each independently represents an aromatic hydrocarbon divalent group)
It can obtain by the method of using the amine which has a bivalent group represented by these. According to the above method, as a crystal of the ammonium carboxylate, an amine having the photoresponsive group is used as a guest compound with respect to a layered crystal (layered crystalline polymer) of a conjugated diene polymer having a carboxyl group. An intercalated photoresponsive polymer according to the present invention is obtained.
[0087]
The photoresponsive polymer according to the present invention is an amine having a divalent group represented by the above general formula (6) (hereinafter, referred to as “layered crystal polymer having a carboxyl group”). , Referred to as “photoresponsive group-containing amine”) as an intercalated guest compound.
[0088]
The layered crystalline polymer having a carboxylic acid may be used without particular limitation as long as it has a layered structure and is a crystalline polymer containing a carboxylic acid. That is, the layered crystalline polymer having a carboxylic acid is not limited to a crystalline polymer derived from a conjugated dienecarboxylic acid, but has a layered structure other than a crystalline polymer derived from a conjugated dienecarboxylic acid, A crystalline polymer containing a carboxylic acid may be used. However, as the layered crystalline polymer having a carboxylic acid, a crystalline polymer derived from a conjugated dienecarboxylic acid (a layered crystal of a polymer of a conjugated diene having a carboxyl group), for example, a polymuconic acid crystal or a polysorbic acid crystal Polybutadiene carboxylic acid crystals are preferred, and polymuconic acid crystals and polysorbic acid crystals are more preferred.
[0089]
As the photoresponsive group-containing amine, a primary amine is preferable because an intercalation reaction easily occurs.
[0090]
In addition, as the photoresponsive group-containing amine, an intercalation reaction is unlikely to occur with an amine having a low basicity such as an amine in which an amino group is directly bonded to an aromatic ring. Therefore, the general formula (6) It is preferable that at least one saturated hydrocarbon divalent group is interposed as a spacer between a divalent group represented by As a result, the photoresponsive group-containing amine has sufficient basicity and the intercalation reaction easily proceeds.
[0091]
Further, the aromatic hydrocarbon divalent group represented by Ar and Ar ′ in the general formula (6) is not particularly limited, and may be one in which two or more benzene rings are connected. Specific examples of the aromatic hydrocarbon divalent group represented by Ar and Ar ′ include a phenylene group such as a 1,4-phenylene group; a biphenylene group; a naphthylene group, and the like. Is particularly preferred.
[0092]
As the photoresponsive group-containing amine, the following general formula
Y-Ar-N = N-Ar-X¹-R^Four-NH₂
(In the above formula, R^FourRepresents a divalent hydrocarbon group at that position or no substituent at that position, X¹Represents that a divalent group containing a hetero atom is present at that position, or that no substituent is present at that position, and Y represents a hydrogen atom or any substituent)
(Hereinafter referred to as “photoresponsive group-containing monoamine”), or the following general formula
H₂N-R^Four-X¹-Ar-N = N-Ar-X¹-R^Four-NH₂
(In the above formula, R^FourEach independently represents a hydrocarbon divalent group at that position or no substituent at that position;¹Each independently represents a divalent group containing a heteroatom at that position or no substituent at that position)
(Hereinafter referred to as “photoresponsive group-containing diamine”) is particularly preferred.
[0093]
R above^FourThe saturated hydrocarbon divalent group in may be an aliphatic hydrocarbon divalent group represented by a linear aliphatic saturated hydrocarbon divalent group, or an alicyclic hydrocarbon divalent group represented by a cyclohexylene group. Good. R above^FourIs the general formula
-(CH2) n-
(In the above formula, n represents an integer from 0 to 18)
It is preferable that it is a bivalent group represented by these. That is, the above R^FourPreferably represents a linear alkylene group having 0 to 18 carbon atoms (aliphatic saturated hydrocarbon divalent group) at that position or no substituent at that position. Furthermore, n is more preferably 1 or more and 12 or less. That is, R^FourIn this position, a linear alkylene group is preferably present as a spacer group, and the number of carbon atoms (number of methylene carbons) n of the spacer group is preferably 12 or less.
[0094]
X above¹As the divalent group containing a hetero atom in the above, a divalent group containing a hetero atom in the main chain, for example, —O—, —S—, —COO—, —OCO—, —CONH—, —NHCO—, —CONHCO -, -NHCONH-, -OCONH-, -NHCOO- and the like are preferable.
[0095]
Y is not particularly limited, and examples thereof include a hydrogen atom, an alkyl group, an alkoxy group, and a cyano group (—CN). Examples of the alkyl group include — (CH₂)_nCH_Three(The number n of methylene carbons is 0 to 18, more preferably 1 or more and 12 or less). Examples of the alkoxy group include —O (CH₂)_nCH_Three(The number n of methylene carbons is 0-18, More preferably, it is 1-12) The substituent represented by this is mentioned. Y represents-(OCH₂CH₂)_nOCH_Three(The number n of methylene carbons may be 0 to 18, more preferably 1 to 12).
[0096]
The photoresponsive group-containing amine can be synthesized from a commercially available azo group-containing compound. For example, 4- (phenylazo) benzylamine, which is one of photoresponsive group-containing monoamines, can be produced from commercially available azobenzene-4-carbonyl chloride by the following scheme (A).
[0097]
[Chemical formula 5]

[0098]
In addition, 4- (11-aminoundecyloxy) azobenzene (also known as “11- [4- (phenylazo) phenyloxy] undecylamine”), which is a kind of photoresponsive group-containing monoamine, is commercially available 4-phenyl. It can be produced by the following scheme (B) from azophenol and commercially available 11-bromoundecanoic acid.
[0099]
[Chemical 6]

[0100]
In addition, N- (6-aminohexyl) azobenzenecarboxamide, which is one of photoresponsive group-containing monoamines, is obtained from commercially available azobenzene-4-carbonyl chloride and commercially available hexamethylenediamine as shown in the following scheme (C). It can manufacture by making these react. In addition, other N- (aminoalkyl) azobenzenecarboxamides can be produced using the corresponding alkylenediamine in the same manner.
[0101]
[Chemical 7]

[0102]
In addition, 4,4′-di (aminomethyl) azobenzene (also known as “4,4′-azobis (benzylamine)”), which is one kind of photoresponsive group-containing diamine, is as shown in the following scheme (D). In addition, it can be produced by reacting commercially available azobenzene-4,4′-dicarbonyldichloride with ammonia and then reducing with lithium aluminum hydride.
[0103]
[Chemical 8]

[0104]
In addition, N, N′-di (6-aminohexyl) -azobenzene-4,4′-dicarboxamide (also known as “4,4′-azobis [N- (6- Aminohexyl) benzamide] ”) can be prepared by reacting commercially available azobenzene-4,4′-dicarbonyl dichloride with commercially available hexamethylenediamine as shown in the following scheme (E). In addition, other 4,4'-azobis [N- (aminoalkyl) benzamide] can be produced in the same manner using the corresponding alkylenediamine.
[0105]
[Chemical 9]

[0106]
The photoresponsive polymer according to the present invention is prepared by the above-described production method (a method of mixing a conjugated diene polymer layered crystal having a carboxyl group and a photoresponsive group-containing amine in the absence of a liquid medium. However, it is also possible to manufacture by other methods.
[0107]
For example, in the above-described production method, an intercalation reaction is performed in the absence of a liquid medium without using a solvent, but a crystalline polymer (a layered crystal of a conjugated diene polymer having a carboxyl group) is dispersed. An intercalation reaction may be performed using a solvent as a dispersing agent. As a solvent used as a dispersant, any solvent can be used as long as it dissolves an amine and does not dissolve or swell a crystalline polymer, and includes alcohols such as methanol and isopropanol, acetone and methyl ethyl ketone. Ketones such as tert-butyl methyl ether; halogen solvents such as 1,2-dichloroethane; aromatic hydrocarbons such as toluene; organic solvents such as aliphatic hydrocarbons such as hexane, and the like. Can also use water.
[0108]
In addition, by reacting a photoresponsive group-containing amine with a carboxylic acid having a conjugated diene moiety (particularly muconic acid or sorbic acid), an ammonium salt of the carboxylic acid having a conjugated diene moiety is prepared in advance, and this conjugated diene is prepared. A crystalline polymer having a layered structure similar to that obtained by the production method described above may be obtained by solid-phase polymerization of ammonium carboxylate crystals having a moiety. However, the solid phase polymerization reactivity (topochemical polymerization reactivity) is determined by the crystal structure of the ammonium salt derivative monomer (ammonium carboxylate having a conjugated diene moiety), that is, the packing mode of the monomer molecules in the crystal. Salt derivative monomers cannot form a layered structure by topochemical polymerization. Therefore, the above-described production method of intercalating an amine containing a photoresponsive group to a layered crystalline polymer having a carboxylic acid prepared in advance is more suitable for obtaining the photoresponsive polymer according to the present invention. It is a sure method.
[0109]
【Example】
[Example 1]
Using the production method according to the present invention, crystals of (Z, Z) -benzylammonium muconate, which is a crystal capable of photosolid phase polymerization, were synthesized.
[0110]
0.9291 g (6.54 × 10 6) crystals of (Z, Z) -muconic acid^-3Mol) and 1.4012 g (1.31 × 10 4) of benzylamine which is liquid at room temperature^-2Mol) was ground and reacted in a mortar at room temperature for 30 minutes.
[0111]
The IR spectrum (infrared absorption spectrum) of the product obtained by the reaction is 1710 cm based on the carboxyl group.^-1Absorption peak of 1560 cm based on carboxylate^-1The absorption peak of was confirmed. In addition, the product obtained by the reaction was prepared by a conventional method of isolation by recrystallization after reaction in a solvent in powder X-ray diffraction measurement as shown in FIG. 3 (a) (Z, The same diffraction pattern as that of the crystal of Z) -benzylammonium muconate (FIG. 3B) was exhibited. Thus, it was found that the reaction proceeded quantitatively and crystals of benzylammonium (Z, Z) -muconate were obtained.
[0112]
[Example 2]
First, the crystals of (Z, Z) -benzylammonium muconate synthesized in Example 1 were irradiated with ultraviolet rays at 30 ° C. for 8 hours using a high-pressure mercury lamp. As a result, photosolid phase polymerization of (Z, Z) -benzylammonium muconate proceeded, and a product insoluble in the solvent was obtained. After the irradiation was completed, unreacted monomer ((Z, Z) -benzylammonium muconate) was extracted with methanol, and the product was isolated.
[0113]
In the IR spectrum of the isolated product, as shown by curve A in FIG.^-1It was confirmed that (Z, Z) -benzylammonium muconate was polymerized and crystals of benzylammonium 2,5-polymuconate were formed. The yield of benzylammonium 2,5-polymuconate was 3%. When the ultraviolet irradiation time was changed from 8 hours to 72 hours, the yield of benzylammonium 2,5-polymuconate was improved to 30%.
[0114]
Next, the crystals of benzylammonium 2,5-polymuconate were thermally decomposed by heating at 250 ° C. for 2 hours under reduced pressure (vacuum).
[0115]
The IR spectrum of the product obtained by pyrolysis is 1560 cm based on carboxylate as shown in curve B of FIG.^-1Absorption peak of 1710 cm based on carboxyl group^-1The absorption peak of was confirmed. In the powder X-ray diffraction measurement, the product was obtained by mixing (Z, Z) -muconic acid benzylammonium by recrystallization after mixing the conventional method ((Z, Z) -muconic acid and benzylamine in a solvent. And then the same diffraction pattern as that of 2,5-polymuconic acid crystal prepared by photosolid phase polymerization of (Z, Z) -benzylammonium muconate and hydrolyzing with hydrochloric acid). As a result, it was found that 2,5-polymuconic acid benzylammonium crystals were converted to 2,5-polymuconic acid crystals, and highly sterically regulated 2,5-polymuconic acid crystals were obtained.
[0116]
Next, in the same manner as in Example 1, 0.0687 g of 2,5-polymuconic acid crystals was added to 0.1036 g of benzylamine (an amount of 2 mol per mole of repeating structural unit of 2,5-polymuconic acid, that is, 2,5-polymuconic acid was added in an amount of 1 mol per mol of carboxyl group), and the mixture was ground and reacted for 30 minutes in a mortar.
[0117]
The IR spectrum of the product obtained by the reaction is 1710 cm based on the carboxyl group, as shown by curve C in FIG.^-1Absorption peak of 1560 cm based on carboxylate^-1The absorption peak of was confirmed. In addition, the product obtained by the reaction was intercalated between layers with benzylamine prepared by a conventional method of isolation by recrystallization after intercalation in a dispersion medium in powder X-ray diffraction measurement. Further, the same diffraction pattern as that of 2,5-polymuconic acid crystal was shown.
[0118]
As a result, it was found that intercalation progressed quantitatively, and crystals of 2,5-polymuconic acid in which benzylamine was intercalated between layers, that is, crystals of benzylammonium 2,5-polymuconate were obtained. It was.
[0119]
Example 3
The production method according to the present invention was used to synthesize (Z, Z) -muconic acid dodecyl ammonium salt, which is a crystal capable of photosolid phase polymerization.
[0120]
0.3256 g (2.29 × 10 6) crystals of (Z, Z) -muconic acid^-3Mol) and 0.8493 g (4.58 × 10 6) of dodecylamine which is solid at room temperature^-3Mol) was ground and reacted in a mortar at room temperature for 30 minutes.
[0121]
The IR spectrum of the product obtained by the reaction is 1710 cm based on carboxyl groups.^-1Absorption peak of 1560 cm based on carboxylate^-1The absorption peak of was confirmed. In addition, in the powder X-ray diffraction measurement, the diffraction pattern of the crystal of (Z, Z) -dodecylammonium muconate prepared by a conventional method of isolation by recrystallization after reaction in a solvent ((b) in FIG. 2) ) Showed the same diffraction pattern. Thus, it was found that the reaction proceeded quantitatively and crystals of (Z, Z) -dodecyl ammonium muconate were obtained.
[0122]
Example 4
First, (Z, Z) -dodecylammonium muconate crystals synthesized in Example 3 were irradiated with ultraviolet rays at 30 ° C. for 8 hours using a high-pressure mercury lamp. As a result, photosolid phase polymerization of (Z, Z) -dodecyl ammonium muconate proceeded, and a product insoluble in the solvent was obtained. After the irradiation, unreacted monomer ((Z, Z) -dodecyl ammonium muconate) was extracted with methanol, and the product was isolated.
[0123]
In the IR spectrum of the isolated product, 1580 cm due to the conjugated diene^-1It was confirmed that (Z, Z) -dodecyl ammonium muconate was polymerized and crystals of dodecyl ammonium 2,5-polymuconate were formed. The yield of 2,5-polymuconate dodecyl ammonium was 24%. In addition, when the ultraviolet irradiation time was changed from 8 hours to 72 hours, the yield of 2,5-polymuconic acid dodecyl ammonium improved to 81%.
[0124]
Next, the crystals of 2,5-polymuconate dodecyl ammonium were thermally decomposed by heating at 250 ° C. for 2 hours under reduced pressure.
[0125]
The IR spectrum of the product obtained by pyrolysis is 1560 cm based on carboxylate.^-1Absorption peak of 1710 cm based on carboxyl group^-1The absorption peak of was confirmed. Further, in the powder X-ray diffraction measurement, the product was obtained by mixing (Z, Z) -mudecate ammonium dodecylammonium by recrystallization after mixing (Z, Z) -muconic acid and dodecylamine in a solvent. The same diffraction pattern as that of 2,5-polymuconic acid crystal prepared by isolation and then photo-solid phase polymerization of (Z, Z) -mudeconic ammonium dodecyl ammonium and hydrolysis using hydrochloric acid) was obtained. Thereby, it was found that dodecyl ammonium 2,5-polymuconate was converted to 2,5-polymuconic acid, and highly sterically regulated 2,5-polymuconic acid crystals were obtained.
[0126]
Next, in the same manner as in Example 3, 0.0774 g of 2,5-polymuconic acid crystals was added to 0.2019 g of dodecylamine (an amount of 2 mol per 1 mol of repeating structural unit of 2,5-polymuconic acid, that is, 2,5-polymuconic acid was added in an amount of 1 mol per mol of carboxyl group), and the mixture was ground and reacted for 30 minutes in a mortar.
[0127]
The IR spectrum of the product obtained by the reaction is 1710 cm based on carboxyl groups.^-1Absorption peak of 1560 cm based on carboxylate^-1The absorption peak of was confirmed. In addition, the product obtained by the reaction was prepared by a conventional method of isolation by recrystallization after intercalation in a dispersion medium in powder X-ray diffraction measurement. The same diffraction pattern as that of 1,5-polymuconic acid crystal was exhibited. According to the result of the powder X-ray diffraction measurement, the interlayer distance d of the layered crystal (2,5-polymuconic acid crystal) was 4.8 mm before the intercalation, whereas dodecylamine was intercalated. It was 32.6cm after being done.
[0128]
As a result, it was found that intercalation progressed quantitatively, and crystals of 2,5-polymuconic acid in which dodecylamine was intercalated, that is, crystals of dodecylammonium 2,5-polymuconate, were obtained.
[0129]
Example 5
First, in the same manner as in Example 4, crystals of 2,5-polymuconic acid were obtained.
[0130]
Next, in the same manner as in Example 4, tert-butylamine in an amount of 1 mol per 1 mol of carboxyl group of 2,5-polymuconic acid was added to 2,5-polymuconic acid crystals, and ground in a mortar for 30 minutes. I let you.
[0131]
The IR spectrum of the product obtained by the reaction is 1710 cm based on carboxyl groups.^-1Absorption peak of 1560 cm based on carboxylate^-1The absorption peak of was confirmed. 2,5-polymuconic acid crystals in which intercalation progresses quantitatively and tert-butylamine is intercalated, that is, 2,5-polymuconic acid crystals, based on the results of IR spectrum analysis and the results of powder X-ray diffraction measurement, It was found that crystals of tert-butylammonium polymuconate were obtained.
[0132]
[Comparative Example 1]
First, in the same manner as in Example 4, crystals of 2,5-polymuconic acid were obtained.
[0133]
Next, a conventional method, that is, a method in which 2,5-polymuconic acid crystals are dispersed in methanol and tert-butylamine is added to the dispersion, whereby tert-butylamine intercalation into 2,5-polymuconic acid crystals is performed. Tried.
[0134]
As a result, since the polymer swells or dissolves in methanol during the reaction, the desired ammonium crystals cannot be obtained.
[0135]
As is clear from Example 5 and Comparative Example 1 described above, the method of the present invention enables intercalation of tert-butylamine into 2,5-polymuconic acid crystals, which was impossible with the conventional method. It was.
[0136]
Example 6
[Synthesis of 4- (phenylazo) benzylamine]
As described above, 4- (phenylazo) benzylamine can be produced from commercially available azobenzene-4-carbonyl chloride by the scheme (A).
[0137]
Specifically, first, a solution obtained by dissolving 0.197 g of commercially available azobenzene-4-carbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 15 mL of dichloromethane was slowly added to 2 mL of 28 wt% aqueous ammonia at room temperature. added. After stirring overnight, the insoluble part was isolated by filtration and washed with water. The obtained solid was recrystallized from acetone to obtain azobenzenecarboxamide (azobenzenecarboxylic amide) with a yield of 85%. The structure of azobenzenecarboxamide is¹1 H NMR spectrum and¹³Confirmed by C NMR spectrum.
[0138]
The NMR spectrum data of azobenzenecarboxamide is shown below.
¹1 H NMR (acetone-d₆) Δ 8.13-8.15 (m, Ar, 2H), 7.95-7.99 (m, Ar, 4H), 7.58-7.63 (m, Ar, 3H), 6.8 (Br, NH₂, 2H)
¹³C NMR (acetone-d₆) 168.42 (C = O), 155.17, 153.68, 137.77, 132.94, 130.54, 129.87, 124.04, 123.63 (Ar).
[0139]
Azobenzenecarboxamide was also obtained by a reaction using ammonia gas instead of ammonia water. That is, the target azobenzenecarboxamide was obtained in the same reaction yield (85%) by slowly dropping a chloroform solution of azobenzene-4-carbonyl chloride while blowing excess ammonia gas into chloroform.
[0140]
Next, 0.078 g of synthesized azobenzenecarboxylic acid amide, 0.119 g of lithium aluminum hydride, and 5 mL of dried diethyl ether were placed in a flask and refluxed for 34 hours. After returning to room temperature, 10 mL of water was carefully added dropwise slowly and reacted with an excess of lithium aluminum hydride, followed by further stirring overnight. Extraction was performed 3 times with 100 mL of diethyl ether, and the ether was removed under reduced pressure. Thereafter, the residue was purified by silica gel chromatography (developing solvent: methanol) to obtain 0.021 g (yield 29%) of the desired 4- (phenylazo) benzylamine. The structure of 4- (phenylazo) benzylamine is¹1 H NMR spectrum and¹³Confirmed by C NMR spectrum.
[0141]
The NMR spectrum data of 4- (phenylazo) benzylamine is shown below.
¹1 H NMR (chloroform-d) δ 7.89-7.92 (m, Ar, 4H), 7.26-7.54 (m, Ar, 5H), 3.94 (s, CH₂, 2H).
¹³C NMR (chloroform-d) δ 152.62, 151.58, 146.42, 130.85, 129.06, 127.66, 123.08, 122.75 (Ar), 46.21 (CH₂).
[Preparation of 2,5-polymuconic acid crystals]
In the same manner as in Example 4, 2,5-polymuconic acid crystals were obtained.
[Intercalation reaction]
Next, an intercalation reaction of 4- (phenylazo) benzylamine was performed on the obtained 2,5-polymuconic acid crystals.
[0142]
That is, as in Example 4, 79 mg of 2,5-polymuconic acid crystals (muconic acid unit 0.56 mmol) and 4- (phenylazo) benzylamine 236 mg (1.12 mmol; stoichiometric ratio, that is, [—NH₂] / [-CO₂H] = 2) were mixed and stirred in a mortar while grinding for 30 minutes. Thereafter, unreacted 4- (phenylazo) benzylamine was removed by washing with 50 mL of diethyl ether to obtain crystals of 2,5-polymuconic acid intercalated with 4- (phenylazo) benzylamine in a yield of 48%. It was.
[0143]
FIG. 5 shows changes in IR spectrum (infrared absorption spectrum) of 2,5-polymuconic acid crystal before and after intercalation (Fourier transform infrared spectrophotometer “JASCO Herschel FT-IR-” manufactured by JASCO Corporation). 430 ", measured by KBr tablet method). In FIG. 5, (a) shows the IR spectrum of 2,5-polymuconic acid crystal, and (b) shows the IR spectrum of 2,5-polymuconic acid crystal intercalated with 4- (phenylazo) benzylamine.
[0144]
1710 cm seen in 2,5-polymuconic acid after reaction and before intercalation^-1Absorption due to carboxyl group disappears, 1560cm instead^-1Absorption by carboxylate (ammonium carboxylate) was observed. From this, it was found that the carboxyl group was changed to a carboxylate by amine intercalation into 2,5-polymuconic acid crystal. Therefore, it was found that crystals of 4- (phenylazo) benzylammonium polymuconate were produced as the photoresponsive polymer according to the present invention.
[Changes in UV-visible absorption spelling by UV irradiation]
From 2,5-polymuconic acid crystal intercalated with 4- (phenylazo) benzylamine, using a high-pressure mercury lamp (SHL-100-2 lamp manufactured by Toshiba Corporation, 100 W) from a distance of 10 cm at room temperature. Irradiation with ultraviolet light was performed, and changes in the ultraviolet-visible absorption spectrum (ultraviolet-visible diffuse reflection spectrum) when the irradiation time was changed from 0 to 300 minutes were measured. This ultraviolet-visible absorption spectrum was obtained by equipping an ultraviolet-visible spectrophotometer “V-550DS” manufactured by JASCO Corporation with an integrating sphere device and measuring the diffuse reflection of a solid sample. The measurement result of ultraviolet visible absorption spectrum change is shown in FIG. The curve shown in FIG. 6 shows the case of irradiation time 0 minutes, irradiation time 30 minutes, irradiation time 90 minutes, irradiation time 150 minutes, and irradiation time 300 minutes in order from the bottom.
[0145]
As a result, as shown in FIG. 6, the absorption intensity derived from the cis-type azobenzene structure near 450 nm increased with the increase of the ultraviolet light irradiation time. Therefore, in 4- (phenylazo) benzylamine, the azobenzene moiety is in the trans form before irradiation with ultraviolet light, but it is found that the azobenzene part is partially changed from the trans form to the cis form by ultraviolet light irradiation. It was.
[Changes in powder X-ray diffraction profile due to UV irradiation]
Changes in the layered structure of 2,5-polymuconic acid crystals due to ultraviolet light irradiation (3 hours and 10 hours) were evaluated by powder X-ray diffraction. For the measurement, a powder X-ray diffractometer “RINT2100” (CuKα, λ = 1.54178 mm) manufactured by Rigaku Corporation was used. The powder X-ray diffraction profile is shown in FIG. As a result, it was found that the sharp diffraction peak near 18 degrees, which was seen before irradiation, was reduced in intensity after irradiation and the layered structure was changed. In addition, the peak intensity when 2θ was around 3 degrees decreased with ultraviolet light irradiation, and another peak appeared on the lower angle side instead. From this, it was found that the repetition period (interlayer distance d) of the layered structure was changed before and after the light irradiation by the ultraviolet light irradiation.
[0146]
Example 7
[Synthesis of 4- (11-aminoundecyloxy) azobenzene]
As a synthesis example of another amine containing azobenzene, 4- (11-aminoundecyloxy) azobenzene was synthesized according to the scheme (B).
[0147]
Details of the synthesis reaction are as follows.
[0148]
First, 10.0 g of commercially available 11-bromoundecanoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.17 g of 3,4-dihydro-2H-pyran (manufactured by Wako Pure Chemical Industries, Ltd.) are dissolved in 20 mL of dichloromethane, and iced water is used. While cooling, 0.95 g of pyridinium p-toluenesulfonate was added. The mixture was stirred at 0 ° C. for 30 minutes and further stirred at room temperature for 2 hours. After washing with aqueous sodium bicarbonate and water, the organic layer was separated. Dichloromethane was removed from the organic layer under reduced pressure, 11-bromoundecanoic acid ester protected with 3,4-dihydro-2H-pyran, ie 11-bromoundecanoic acid 3,4,5,6-tetrahydro-2H-pyranyl (Br (CH₂)_TenCOOR⁰R⁰3,4,5,6-tetrahydro-2H-pyranyl group) was obtained in a yield of 59%. The structure of 11-bromoundecanoic acid 3,4,5,6-tetrahydro-2H-pyranyl is¹Confirmed by 1 H NMR spectrum.
[0149]
Of 11-bromoundecanoic acid 3,4,5,6-tetrahydro-2H-pyranyl¹1 H NMR spectrum data is shown below.
¹1 H NMR (chloroform-d) δ 5.97 (t, CH, 1H), 3.90 (t, OCH₂, 1H), 3.70 (t, OCH₂, 1H), 3.40 (t, BrCH₂, 2H), 2.35 (t, CH₂CO₂, 2H), 1.29-1.88 (m, CH₂, 24H).
[0150]
To 25 mL of dry dimethylformamide, 7.03 g of 11-bromoundecanoic acid 3,4,5,6-tetrahydro-2H-pyranyl and 2.62 g of commercially available 4- (phenylazo) phenol (Tokyo Chemical Industry Co., Ltd.) were added. Melted. To the obtained solution, 2.80 g of potassium carbonate and a catalytic amount of potassium iodide were added and reacted at 70 ° C. for 2 days. After returning to room temperature, extraction was performed 3 times with 50 mL of ether, and the ether solution was washed with water. After removing ether under reduced pressure, 50 mL of tetrahydrofuran and 5 mL of concentrated hydrochloric acid were added, and the mixture was stirred at room temperature for 40 minutes. Tetrahydrofuran was removed under reduced pressure, and then the chloroform-soluble portion was extracted three times with 100 mL of chloroform, washed with saturated brine and water, and concentrated to give a yellow solid. The solid was purified by recrystallization from a mixed solvent of chloroform and hexane (mixing ratio of chloroform / hexane is 2 to 5), and decamethyleneoxy was used as a spacer group between the azobenzene moiety and the carboxyl group. Group (-O (CH₂)_Ten-, A compound having 11- [4- (phenylazo) phenyloxy] undecanoic acid (Azobenzene-O- (CH₂)_TenCOOH) was obtained in a yield of 82%. The structure of 11- [4- (phenylazo) phenyloxy] undecanoic acid is¹1 H NMR spectrum and¹³Confirmed by C NMR spectrum.
[0151]
The NMR spectrum data of 11- [4- (phenylazo) phenyloxy] undecanoic acid is shown below.
¹1 H NMR (chloroform-d) δ 7.85-7.92 (m, Ar, 4H), 7.49-7.51 (m, Ar, 3H), 6.98-7.01 (m, Ar, 2H), 4.03 (t, OCH₂), 2.35 (t, CH₂CO₂, 2H), 1.31-1.83 (m, CH₂, 16H)
¹³C NMR (chloroform-d) δ 179.10, 161.70, 152.78, 146.84, 130.27, 129.01, 124.73, 122.51, 114.69, 68.34, 64. 39, 33.92, 29.44, 29.31, 29.18, 29.01, 28.62, 25.99, 25.00, 24.00.
[0152]
The above 1- [4- (phenylazo) phenyloxy] undecanoic acid 1.494 g was dissolved in 10 mL of 1,2-dichloroethane. To the resulting solution, 0.5 mL of thionyl chloride and 1 drop of N, N-dimethylformamide were added and refluxed for 3.5 hours. 11- [4- (phenylazo) phenyloxy] undecanyl chloride (Azobenzene- O- (CH₂)_TenCOCl) was synthesized. 10 mL of 1,2-dichloroethane was put into another flask, and ammonia gas was blown into the flask for 5 minutes to obtain a saturated solution. In this saturated solution, as a solution of 11- [4- (phenylazo) phenyloxy] undecanyl chloride, the reaction solution of 11- [4- (phenylazo) phenyloxy] undecanoic acid and thionyl chloride is kept as it is at room temperature. Therefore, it was dripped slowly, cooling with water. After completion of the dropwise addition, ammonia gas was blown for 2 hours to carry out a reaction for conversion to amide. After completion of the reaction, a small amount of water was added to the reaction solution and stirred, and then the insoluble part was filtered off and dried, and an amide derivative of azobenzene containing a spacer group, 11- [4- (phenylazo) phenyloxy] undecanamide (Azobenzene). -O- (CH₂)_TenCONH₂) Was obtained as a yellow solid (74% yield). The structure of 11- [4- (phenylazo) phenyloxy] undecanamide is¹Confirmed by 1 H NMR spectrum.
[0153]
Of 11- [4- (phenylazo) phenyloxy] undecanamide¹1 H NMR spectrum data is shown below.
¹1 H NMR (chloroform-d) δ 7.86-7.92 (m, Ar, 4H), 7.43-7.51 (m, Ar, 3H), 6.99-7.01 (m, Ar, 2H), 4.04 (t, OCH₂), 2.22 (t, CH₂CONH₂, 2H), 1.31-1.82 (m, CH₂, 16H).
[0154]
1.008 g of 11- [4- (phenylazo) phenyloxy] undecanamide, 0.624 g of lithium aluminum hydride, and 40 mL of dried diethyl ether were placed in a flask and refluxed for 12 hours. It returned to room temperature, 20 mL of water was dripped slowly, and after making it react with excess lithium aluminum hydride, it stirred for another day. The reaction solution was extracted with 200 mL of diethyl ether three times, and diethyl ether was removed under reduced pressure. Thereafter, the residue is purified by recrystallization from a mixed solvent of chloroform and hexane, whereby an amine derivative of 4- (phenylazo) benzene containing the target spacer group, 4- (11-aminoundecyloxy) azobenzene ( Azobenzene-O- (CH₂)₁₁NH₂) Was obtained in a yield of 76%. The structure of 4- (11-aminoundecyloxy) azobenzene is¹1 H NMR spectrum and¹³Confirmed by C NMR spectrum.
[0155]
The NMR spectrum data of 4- (11-aminoundecyloxy) azobenzene are shown below.
¹H NMR (chloroform-d) δ 7.86-7.91 (m, Ar, 4H), 7.42-7.51 (m, Ar, 3H), 6.99-7.00 (m, Ar, 2H), 4.03 (t, OCH₂), 2.73 (t, CH₂NH₂, 2H), 1.29-1.81 (m, CH₂, 18H).
¹³C NMR (chloroform-d) δ 161.70, 152.78, 146.84, 130.27, 12.01, 124.73, 122.51, 114.68, 68.34, 41.26, 31. 86, 29.53, 29.36, 29.18, 26.79, 26.00.
[Preparation of 2,5-polymuconic acid crystals]
In the same manner as in Example 4, 2,5-polymuconic acid crystals were obtained.
[Intercalation reaction]
Next, an intercalation reaction of 4- (11-aminoundecyloxy) azobenzene was performed on the obtained 2,5-polymuconic acid crystals.
[0156]
That is, 80 mg of 2,5-polymuconic acid crystals (0.56 mmol of muconic acid unit) and 545 mg (1.12 mmol) of 4- (11-aminoundecyloxy) azobenzene;₂] / [-CO₂H] = 2) were mixed and stirred in a mortar while grinding for 30 minutes. Thereafter, unreacted 4- (11-aminoundecyloxy) azobenzene was removed by washing with 50 mL of diethyl ether, and crystals of 2,5-polymuconic acid intercalated with 4- (11-aminoundecyloxy) azobenzene were obtained. Was obtained in 50% yield.
[0157]
From the IR spectra of 2,5-polymuconic acid crystals before and after the same intercalation as in Example 6, 2,5-polymuconic acid 11- [4- (phenylazo) phenyl as a photoresponsive polymer according to the present invention was used. It was found that crystals of oxy] undecylammonium were formed.
[Optical response]
Regarding the obtained crystals of 2,5-polymuconic acid 11- [4- (phenylazo) phenyloxy] undecylammonium, as in Example 6, the change in ultraviolet-visible absorption spectrum due to ultraviolet irradiation was observed. It was found that the repetition period of the layered structure was changed before and after, and it had photoresponsiveness.
[0158]
【The invention's effect】
  As described above, the method for producing an ammonium carboxylate crystal of the present invention comprises mixing a carboxylic acid crystal and at least one compound selected from the group consisting of an amine and ammonia in the absence of a liquid medium.In addition, a conjugated diene having a carboxyl group is used as the carboxylic acid crystal, and at least one compound selected from the group consisting of the amine and ammonia is represented by the following formula RCH: ₂ NH ₂ (In the formula, R represents a linear alkyl group or aryl group having 5 or more carbon atoms).Is the method.
[0159]
According to the above method, since the carboxylic acid reacts with at least one compound selected from the group consisting of amine and ammonia in a crystalline state, a stereospecific reaction proceeds and a single product can be obtained. . Further, according to the above method, since a liquid medium such as a solvent or a dispersion medium is not used, separation operation and recrystallization of the liquid medium are unnecessary. Therefore, the above method has an effect that an ammonium carboxylate crystal can be easily produced.
[0160]
In the method, a conjugated diene having a carboxyl group is used as the carboxylic acid, and at least one compound selected from the group consisting of the amine and ammonia has the following formula:
RCH₂NH₂
(In the formula, R represents a linear alkyl group or aryl group having 5 or more carbon atoms)
When a primary amine represented by the formula (1) is used, an ammonium carboxylate crystal capable of forming a layered crystal by radiation polymerization in a solid phase can be obtained.
[0161]
Further, when a conjugated diene polymer crystal having a carboxyl group is used as the carboxylic acid crystal, the layered crystal of the conjugated diene polymer having a carboxyl group is at least selected from the group consisting of amine and ammonia. A crystal of ammonium (poly) carboxylate in which one compound is intercalated as a guest compound can be obtained.
[0162]
  In the above method,the aboveUsing a layered crystal of a polymer of a conjugated diene having a carboxyl group, at least one compound selected from the group consisting of the amine and ammonia is represented by the following formula R′NH₂(In the formula, R 'represents a hydrocarbon group which may have a functional group) When a primary amine represented by the formula (1) is used, a layered crystal of a polymer of ammonium carboxylate(Layered crystal of polymer having carboxyl group and amine)Can be obtained.
[0163]
Also, in this case, by not using a liquid medium, the polymer crystals are not swollen or dissolved by the dispersion medium during the reaction, unlike the conventional method of dispersing in a dispersion medium. Therefore, an alkyl primary amine having a branched structure or a primary amine containing a functional group, which could not be realized by the conventional method using a dispersion medium, is intercalated between the crystal layers of the carboxylic acid polymer. It becomes possible. Therefore, a novel ammonium carboxylate in a state in which a branched alkyl primary amine or a primary amine containing a functional group is intercalated between layered crystals, which cannot be synthesized by a conventional method using a dispersion medium. It can be applied to the synthesis of layered crystals of polymers.
[0164]
  In addition, the present inventionLayered polymer with carboxyl group and amineAs described above, the crystal production method includes a conjugated diene having a carboxyl group, the following formula RCH:₂NH₂(Wherein R represents a straight-chain alkyl group or aryl group having 5 or more carbon atoms) and a conjugated diene having an ammonium carboxylate group, mixed in the absence of a liquid medium. A second step of obtaining a layered crystal of a polymer of a conjugated diene having an ammonium carboxylate group by polymerizing in a solid phase a conjugated diene having an ammonium carboxylate group, and an ammonium carboxylate A third step of heating the layered crystal of the conjugated diene polymer having a group to desorb ammonium ions to obtain a layered crystal of the polymer of a conjugated diene having a carboxyl group; Polymer layered crystals and the following formula R′NH₂(Wherein R ′ represents a hydrocarbon group which may have a functional group), and a fourth step of mixing in the absence of a liquid medium. Is the method.
[0165]
In the above method, a layered crystal of a polymer of ammonium carboxylate is formed in the fourth step.
[0166]
According to the above method, since the reaction is performed in a crystalline state in all steps, a stereospecific reaction proceeds and a single product can be obtained. Further, according to the above method, since a liquid medium such as a solvent or a dispersion medium is not used for the reaction in all steps, separation operation and recrystallization of the liquid medium are unnecessary. Therefore, the above method has an effect that a layered crystal of a polymer of ammonium carboxylate can be easily produced.
[0167]
Further, according to the above method, the polymer crystal is not swollen or dissolved by the dispersion medium during the reaction, unlike the conventional method of dispersing in the dispersion medium, without using the liquid medium. Therefore, it is possible to intercalate the alkyl primary amine having a branched structure or the primary amine containing a functional group between the crystal layers of the carboxylic acid polymer. Therefore, the above-described method is a novel method in which a branched alkyl primary amine or a primary amine containing a functional group is intercalated between layers of layered crystals, which cannot be synthesized by a conventional method using a dispersion medium. It is also effective in that it can be applied to the synthesis of layered crystals of various ammonium carboxylate polymers.
[0168]
In addition, as described above, the production method of the present invention is a compound that is mixed with the layered crystal of the conjugated diene polymer having a carboxyl group in each of the above methods using the layered crystal of the conjugated diene polymer having a carboxyl group. And the general formula
-Ar-N = N-Ar'-
(In the above formula, Ar and Ar ′ each independently represents an aromatic hydrocarbon divalent group)
In which the amine is intercalated into a layered crystal. Thereby, the photoresponsive polymer concerning this invention can be manufactured simply.
[0169]
As described above, the photoresponsive polymer according to the present invention has the following general formula for a layered crystal of a polymer having a carboxyl group.
-Ar-N = N-Ar'-
(In the above formula, Ar and Ar ′ each independently represents an aromatic hydrocarbon divalent group)
An amine having a divalent group represented by the formula is intercalated.
[0170]
According to the above configuration, it is possible to provide a novel crystalline optical functional polymer capable of reversibly changing the crystal structure by optical response (response to light irradiation). Since the optical functional polymer according to the present invention reversibly changes the interlayer distance depending on the light irradiation conditions, the optical functional material used for optical memory materials, recording materials, and electrical / electronic materials. Application to materials etc. can be expected.
[Brief description of the drawings]
FIGS. 1A to 1D are diagrams schematically showing a production process of a layered crystal of a polymer of ammonium carboxylate according to an embodiment of the present invention.
FIG. 2 is a diagram schematically showing an application example of a layered crystal of an ammonium carboxylate polymer obtained by the production method of the present invention.
FIG. 3 is a diagram showing an X-ray diffraction spectrum of a crystal of benzylammonium 2,5-polymuconate, wherein (a) is a graph of benzylammonium 2,5-polymuconate obtained in an example of the production method of the present invention. X-ray diffraction spectrum of the crystal, (a) shows the X-ray diffraction spectrum of the crystal of benzylammonium 2,5-polymuconate obtained by a conventional production method.
FIG. 4 is a diagram showing an IR spectrum of benzylammonium 2,5-polymuconate and 2,5-polymuconic acid obtained in an example of the production method of the present invention.
FIG. 5 shows how the IR spectrum of a layered crystal of 2,5-polymuconic acid changes before and after intercalating an amine having a photoresponsive group in one embodiment of the production method of the present invention. FIG.
FIG. 6 is a diagram showing a change in an ultraviolet-visible absorption spectrum when a photoresponsive polymer according to an embodiment of the present invention is irradiated with ultraviolet rays.
FIG. 7 is a graph showing changes in powder X-ray diffraction when the photoresponsive polymer according to one example of the present invention is irradiated with ultraviolet rays.
[Explanation of symbols]
1 (Z, Z) -Ammonium muconate molecule
2 Secondary ammonium ion molecule
3 (Z, Z) -muconate anion molecule
4 2,5-polymuconate anion molecule
4 'polymer sheet
5 Secondary ammonium ion molecule
5 'Amine (B) molecule

Claims (5)

Carboxylic acid crystals and at least one compound selected from the group consisting of amine and ammonia are mixed in the absence of a liquid medium ,
A conjugated diene having a carboxyl group is used as the carboxylic acid crystal, and at least one compound selected from the group consisting of the amine and ammonia is represented by the following formula RCH ₂ NH ₂ (wherein R is a carbon atom of 5 or more). A method for producing an ammonium carboxylate crystal, comprising using a primary amine represented by the formula: a linear alkyl group or an aryl group . And layered crystal of a polymer of conjugated diene including a carboxyl group,
A primary amine represented by the following formula R′NH ₂ (wherein R ′ represents a hydrocarbon group which may have a functional group) is mixed in the absence of a liquid medium. A method for producing a layered crystal of a polymer having a carboxyl group and an amine, comprising obtaining a layered crystal of a polymer having a carboxyl group and an amine . A conjugated diene having a carboxyl group and a primary amine represented by the following formula: RCH ₂ NH ₂ (wherein R represents a linear alkyl group or aryl group having 5 or more carbon atoms) A first step of mixing in the presence to obtain crystals of a conjugated diene having ammonium carboxylate groups;
A second step of polymerizing a conjugated diene crystal having an ammonium carboxylate group in a solid phase to obtain a layered crystal of a polymer of a conjugated diene having an ammonium carboxylate group;
A third step of heating the layered crystal of the conjugated diene polymer having an ammonium carboxylate group to desorb ammonium ions to obtain a layered crystal of the conjugated diene polymer having a carboxyl group;
A primary crystal represented by a layered crystal of a polymer of a conjugated diene having a carboxyl group and the following formula R′NH ₂ (wherein R ′ represents a hydrocarbon group which may have a functional group): A method for producing a layered crystal of a polymer having a carboxyl group and an amine, comprising a fourth step of mixing an amine in the absence of a liquid medium . A layered crystal of a polymer of a conjugated diene having a carboxyl group according to claim 2 or 3, wherein the following general formula -Ar-N = N-Ar'- (wherein Ar and Ar 'are respectively A polymer having a carboxyl group, characterized by using an amine having a divalent group represented by (independently representing an aromatic hydrocarbon divalent group) and intercalating the amine into the layered crystal ; A method for producing a layered crystal with an amine . A photoresponsive polymer, which is a layered crystal of a polymer having a carboxyl group and an amine obtained by the production method according to claim 4 .

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