JP5446007B2 - Organic-inorganic hybrid polymer, production method thereof, and molecular weight adjustment method - Google Patents
Organic-inorganic hybrid polymer, production method thereof, and molecular weight adjustment method Download PDFInfo
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Description
本発明は、有機−無機ハイブリッドポリマーとその製造方法ならびに分子量調整方法に関するものである。 The present invention relates to an organic-inorganic hybrid polymer, a production method thereof, and a molecular weight adjustment method.
近年、新たな特性を有する機能性材料の研究が盛んに行われているが、有機−無機ハイブリッドポリマーは、ワイドバンドギャップ半導体デバイス（特許文献１参照）、マイクロレンズ（特許文献２参照）、塗料組成物（特許文献３参照）、光触媒含有塗膜（特許文献４参照）、ガスバリアフィルム（特許文献５参照）などの各種の分野での応用が検討されている。 In recent years, functional materials having new characteristics have been actively researched. Organic-inorganic hybrid polymers include wide bandgap semiconductor devices (see Patent Document 1), microlenses (see Patent Document 2), and paints. Applications in various fields such as a composition (see Patent Document 3), a photocatalyst-containing coating (see Patent Document 4), a gas barrier film (see Patent Document 5), and the like are being studied.
中でも、ビス（ターピリジン）化合物と遷移金属イオンとを錯形成して形成された有機−無機ハイブリッドポリマー（特許文献６、７参照）は、優れたエレクトロクロミック特性を示すことが知られており、電子ペーパーなどの表示材料としての技術展開が期待されている。
しかしながら、このビス（ターピリジン）化合物と遷移金属イオンとからなる有機−無機ハイブリッドポリマーは、各種の分野での応用が期待されている一方で、その実用化は必ずしも十分には進んでいないのが現状である。その要因の一つとして、従来の製法では分子量の調整が困難であること、具体的には分散を小さくし且つ所望の分子量に調整することが困難であることが挙げられる。 However, while the organic-inorganic hybrid polymer composed of the bis (terpyridine) compound and the transition metal ion is expected to be applied in various fields, its practical use is not necessarily sufficiently advanced. It is. One of the factors is that it is difficult to adjust the molecular weight in the conventional production method, and specifically, it is difficult to reduce the dispersion and adjust to the desired molecular weight.
本発明は、以上の通りの事情に鑑みてなされたものであり、ビス（ターピリジン）化合物と遷移金属イオンとからなる有機−無機ハイブリッドポリマーにおいて、分子量の分散が極めて小さい有機−無機ハイブリッドポリマー、および、実用性の高い範囲内の所望の分子量に調整することができ、分子量の分散も極めて小さくすることができる有機−無機ハイブリッドポリマーの製造方法ならびに分子量調整方法を提供することを課題としている。 The present invention has been made in view of the circumstances as described above, and in an organic-inorganic hybrid polymer comprising a bis (terpyridine) compound and a transition metal ion, an organic-inorganic hybrid polymer having a very small molecular weight dispersion, and It is an object of the present invention to provide a method for producing an organic-inorganic hybrid polymer and a method for adjusting the molecular weight, which can be adjusted to a desired molecular weight within a highly practical range, and in which the dispersion of the molecular weight can be extremely reduced.
本発明は、上記の課題を解決するために、以下のことを特徴としている。 The present invention is characterized by the following in order to solve the above problems.
第１：ビス（ターピリジン）化合物と遷移金属イオンとが錯形成して交互に連結している有機−無機ハイブリッドポリマーであって、分子量が８００以上６１８００以下のいずれかであり、その分散値が２．０以下であることを特徴とする有機−無機ハイブリッドポリマー。
First: bis (terpyridine) organic compound and the transition metal ion is linked alternately by complexing - an inorganic hybrid polymer, is either molecular weight of 800 or more 61800 or less, dispersion values of that is An organic-inorganic hybrid polymer characterized by being 2.0 or less.
第２：ビス（ターピリジン）化合物と遷移金属イオンとが錯形成して交互に連結している有機−無機ハイブリッドポリマーの製造方法であって、ビス（ターピリジン）化合物と遷移金属化合物とを溶液中で錯形成反応させて有機−無機ハイブリッドポリマーを合成した後に当該有機−無機ハイブリッドポリマーを溶媒に溶解することにより得られる有機−無機ハイブリッドポリマーの分子量と、当該溶媒に溶解させる有機−無機ハイブリッドポリマーの濃度との分子量−濃度対応関係を予め導出する工程と、ビス（ターピリジン）化合物と遷移金属化合物とを溶液中で錯形成反応させて有機−無機ハイブリッドポリマーを合成した後、予め導出した前記分子量−濃度対応関係に基づき、得ようとする分子量に対応する濃度で有機−無機ハイブリッドポリマーを溶媒に溶解させ、分散値が２．０以下である８００以上６１８００以下のいずれかの分子量の有機−無機ハイブリッドポリマーを得る工程とを含むことを特徴とする有機−無機ハイブリッドポリマーの製造方法。
Second: A method for producing an organic-inorganic hybrid polymer in which a bis (terpyridine) compound and a transition metal ion are complexed and linked alternately, wherein the bis (terpyridine) compound and the transition metal compound are combined in a solution. The molecular weight of the organic-inorganic hybrid polymer obtained by dissolving the organic-inorganic hybrid polymer in the solvent after synthesizing the organic-inorganic hybrid polymer by complex formation reaction, and the concentration of the organic-inorganic hybrid polymer dissolved in the solvent A molecular weight-concentration correspondence relationship with a bis (terpyridine) compound and a transition metal compound in a solution to synthesize an organic-inorganic hybrid polymer, and then the molecular weight-concentration derived in advance. Based on the correspondence, the organic-inorganic hive at a concentration corresponding to the molecular weight to be obtained. Ddoporima is dissolved in a solvent, organic dispersion value is 2.0 or less is more than 800 61800 one of the following molecular weight - the method of producing inorganic hybrid polymer - organic, which comprises a step of obtaining inorganic hybrid polymer .
第３：ビス（ターピリジン）化合物と遷移金属化合物とを錯形成反応させる溶液が酢酸溶液であることを特徴とする上記第２の有機−無機ハイブリッドポリマーの製造方法。 Third: The method for producing the second organic-inorganic hybrid polymer, wherein the solution for complexing the bis (terpyridine) compound and the transition metal compound is an acetic acid solution.
第４：溶液中で錯形成反応させて得られた有機−無機ハイブリッドポリマーを溶解させる溶媒がメタノールであることを特徴とする上記第２または第３の有機−無機ハイブリッドポリマーの製造方法。 Fourth: The method for producing the second or third organic-inorganic hybrid polymer described above, wherein the solvent for dissolving the organic-inorganic hybrid polymer obtained by the complex formation reaction in the solution is methanol.
第５：ビス（ターピリジン）化合物と遷移金属イオンとが錯形成して交互に連結している有機−無機ハイブリッドポリマーの分子量調整方法であって、ビス（ターピリジン）化合物と遷移金属化合物とを溶液中で錯形成反応させて有機−無機ハイブリッドポリマーを合成した後に当該有機−無機ハイブリッドポリマーを溶媒に溶解することにより得られる有機−無機ハイブリッドポリマーの分子量と、当該溶媒に溶解させる有機−無機ハイブリッドポリマーの濃度との分子量−濃度対応関係を予め導出する工程と、ビス（ターピリジン）化合物と遷移金属化合物とを溶液中で錯形成反応させて有機−無機ハイブリッドポリマーを合成した後、予め導出した前記分子量−濃度対応関係に基づき、得ようとする分子量に対応する濃度で有機−無機ハイブリッドポリマーを溶媒に溶解させることにより、有機−無機ハイブリッドポリマーの分子量を分散値が２．０以下である８００以上６１８００以下のいずれかの値に調整する工程とを含むことを特徴とする有機−無機ハイブリッドポリマーの分子量調整方法。
Fifth: A method for adjusting the molecular weight of an organic-inorganic hybrid polymer in which a bis (terpyridine) compound and a transition metal ion are alternately formed by complex formation, wherein the bis (terpyridine) compound and the transition metal compound are in solution. The molecular weight of the organic-inorganic hybrid polymer obtained by dissolving the organic-inorganic hybrid polymer in a solvent after synthesizing the organic-inorganic hybrid polymer with a complex formation reaction, and the organic-inorganic hybrid polymer dissolved in the solvent A step of deriving a molecular weight-concentration correspondence relationship with the concentration in advance, and synthesizing a bis (terpyridine) compound and a transition metal compound in a solution to synthesize an organic-inorganic hybrid polymer. Based on the concentration correspondence, organic-inorganic at a concentration corresponding to the molecular weight to be obtained Lee By Brides polymer is dissolved in a solvent, organic - organic, characterized in that variance molecular weight inorganic hybrid polymer and a step of adjusting the value of any of 2.0 or less is 800 or more 61800 or less - A method for adjusting the molecular weight of an inorganic hybrid polymer.
第６：ビス（ターピリジン）化合物と遷移金属化合物とを錯形成反応させる溶液が酢酸溶液であることを特徴とする上記第５の有機−無機ハイブリッドポリマーの分子量調整方法。 Sixth: The method for adjusting the molecular weight of the fifth organic-inorganic hybrid polymer, wherein the solution for complexing the bis (terpyridine) compound and the transition metal compound is an acetic acid solution.
第７：溶液中で錯形成反応させて得られた有機−無機ハイブリッドポリマーを溶解させる溶媒がメタノールであることを特徴とする上記第５または第６の有機−無機ハイブリッドポリマーの分子量調整方法。 Seventh: The method for adjusting the molecular weight of the fifth or sixth organic-inorganic hybrid polymer described above, wherein the solvent for dissolving the organic-inorganic hybrid polymer obtained by the complex formation reaction in the solution is methanol.
本発明によれば、異常な分子量の成分がなく分子量の分散が極めて小さい有機−無機ハイブリッドポリマーが提供される。 According to the present invention, an organic-inorganic hybrid polymer having no abnormal molecular weight component and extremely low molecular weight dispersion is provided.
また本発明の有機−無機ハイブリッドポリマーの製造方法および分子量調整方法によれば、実用性の高い範囲内の所望の分子量に調整することができ、分子量の分散も極めて小さくすることができる。また、このような分散の小さい所望の分子量の有機−無機ハイブリッドポリマーを量産することも可能である。従って、有機−無機ハイブリッドポリマーの利用に際し、所望の値に揃えた分散の小さい分子量による機能を発揮させることができる。 Moreover, according to the manufacturing method and molecular weight adjustment method of the organic-inorganic hybrid polymer of the present invention, the molecular weight can be adjusted to a desired molecular weight within a highly practical range, and the molecular weight dispersion can be extremely reduced. It is also possible to mass-produce such an organic-inorganic hybrid polymer having a desired molecular weight with small dispersion. Therefore, when using the organic-inorganic hybrid polymer, it is possible to exhibit a function with a molecular weight having a small dispersion and a desired value.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明において、遷移金属化合物との錯形成反応に用いられるビス（ターピリジン）化合物としては、例えば、特願２００５−３０８２９０、特願２００５−３０８２９１、特願２００６−３５６２５５、特願２００６−３５５９６３、特願２００６−３５６１８６、特願２００６−３５６３６５に記載のビス（ターピリジン）化合物を用いることができる。 In the present invention, examples of the bis (terpyridine) compound used for the complex formation reaction with the transition metal compound include, for example, Japanese Patent Application Nos. 2005-308290, 2005-308291, 2006-356255, 2006-355963, Bis (terpyridine) compounds described in Japanese Patent Application Nos. 2006-356186 and 2006-356365 can be used.
具体的には、例えば下記式（I）のビス（ターピリジン）化合物を用いることができる。 Specifically, for example, a bis (terpyridine) compound of the following formula (I) can be used.
式（I）の符号Ｒは、スペーサとしての２価の炭化水素基であり、その具体例としては、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、芳香族複素環基などが挙げられる。中でも、下記式（II）〜（V）のアリーレン基が好ましい。 The symbol R in the formula (I) is a divalent hydrocarbon group as a spacer. Specific examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an aromatic heterocyclic ring. Group and the like. Among these, arylene groups represented by the following formulas (II) to (V) are preferable.
式（I）のＲ1、Ｒ2、Ｒ3、およびＲ4は、それぞれ独立に水素原子または置換基を示し、この置換基の具体例としては、ハロゲン原子、炭化水素基、ヒドロキシル基、アルコキシ基、カルボニル基、カルボン酸エステル基、アミノ基、置換アミノ基、アミド基、置換アミド基、シアノ基、ニトロ基などが挙げられる。R 1 , R 2 , R 3 , and R 4 in the formula (I) each independently represent a hydrogen atom or a substituent. Specific examples of the substituent include a halogen atom, a hydrocarbon group, a hydroxyl group, an alkoxy group Group, carbonyl group, carboxylic acid ester group, amino group, substituted amino group, amide group, substituted amide group, cyano group, nitro group and the like.
本発明に用いられるビス（ターピリジン）化合物は、例えば、下記式（VI）で表されるターピリジン化合物を、下記式（VII）で表わされるホウ素化合物の存在下、好ましくはパラジウム錯体化合物と塩基（Ｋ２ＣＯ３、ＫＨＣＯ３、ＫＯＡｃ、ＫＦ、Ｎａ２ＣＯ３、ＮａＨＣＯ３、ＫＯＨなど）の共存下に、溶媒中において６０〜１２０℃の温度範囲に加熱しながら反応させることで合成することができる。The bis (terpyridine) compound used in the present invention is, for example, a terpyridine compound represented by the following formula (VI), preferably a palladium complex compound and a base (K) in the presence of a boron compound represented by the following formula (VII). 2 CO 3 , KHCO 3 , KOAc, KF, Na 2 CO 3 , NaHCO 3 , KOH, etc.) and can be synthesized by reacting in a solvent while heating to a temperature range of 60 to 120 ° C. .
（式（VI）中のＡ1、Ａ2は、それぞれ独立に上記式（I）のＲを形成する基であり、Ｘはハロゲン原子を示す。Ｒ1、Ｒ2、Ｒ3、およびＲ4は、上記と同義である。）(In the formula (VI), A 1 and A 2 are each independently a group forming R in the formula (I), and X represents a halogen atom. R 1 , R 2 , R 3 , and R 4 Is as defined above.)
（式（VII）中のＲa、Ｒb、Ｒc、およびＲdは炭化水素基を示し、ＲaとＲb、ＲcとＲdは結合して環を形成していてもよい。）
また、本発明に用いられるビス（ターピリジン）化合物は、例えば次の方法で製造することができる。下記式（VIII）で表される２−アセチルピリジン誘導体と、式（IX）で表される２−アセチルピリジン誘導体とをヨウ素およびピリジン中で還流させ、ピリミジウム塩を生成させる。(R a , R b , R c , and R d in formula (VII) represent a hydrocarbon group, and R a and R b , R c and R d may combine to form a ring. )
Moreover, the bis (terpyridine) compound used for this invention can be manufactured, for example with the following method. A 2-acetylpyridine derivative represented by the following formula (VIII) and a 2-acetylpyridine derivative represented by the formula (IX) are refluxed in iodine and pyridine to produce a pyrimidium salt.
（式（VIII）中、Ｒ5は水素原子、アリール基、またはアルキル基を示し、Ｘは臭素などのハロゲン原子を示す。Ｘは末端ピリジンの任意の炭素原子に位置し得るが、好ましくは、窒素原子に隣接して位置する。）(In Formula (VIII), R 5 represents a hydrogen atom, an aryl group, or an alkyl group, and X represents a halogen atom such as bromine. X may be located at any carbon atom of the terminal pyridine, but preferably Located adjacent to the nitrogen atom.)
（式（IX）中、Ｒ8は水素原子、アリール基、またはアルキル基を示す。）
一方、下記式（X）で表されるアリールジアルデヒド誘導体と、式（XI）で表される２−アセチルピリジン誘導体とを、アルカリ溶液中、室温で２４時間以上攪拌しながら反応させる。(In formula (IX), R 8 represents a hydrogen atom, an aryl group, or an alkyl group.)
On the other hand, an aryldialdehyde derivative represented by the following formula (X) and a 2-acetylpyridine derivative represented by the formula (XI) are reacted in an alkaline solution with stirring for 24 hours or more at room temperature.
（式（X）中、Ｒは上記式（II）〜（V）のアリーレン基を示す。） (In formula (X), R represents an arylene group of the above formulas (II) to (V).)
（式（XI）中、Ｒ6およびＲ7は水素原子、アリール基、またはアルキル基を示す。）
得られた反応物を、上記のピリミジウム塩と共に酢酸アンモニウムおよびメタノール中で還流させてこれらを反応させ、これにより下記式（XII）のビス（ターピリジン）化合物が得られる。(In formula (XI), R 6 and R 7 represent a hydrogen atom, an aryl group, or an alkyl group.)
The obtained reaction product is refluxed together with the above pyrimidium salt in ammonium acetate and methanol to react them, whereby a bis (terpyridine) compound of the following formula (XII) is obtained.
（式（XII）中、Ｒ5〜Ｒ8、Ｘ、およびＲは上記と同義である。）
以下、上記のビス（ターピリジン）化合物を用いた本発明の有機−無機ハイブリッドポリマーの製造方法および分子量調整方法について説明する。本発明では、ビス（ターピリジン）化合物と遷移金属化合物とを溶液中で錯形成反応させて有機−無機ハイブリッドポリマーを合成した後、得ようとする分子量に対応する濃度で有機−無機ハイブリッドポリマーを溶媒に溶解させることを特徴としている。(In the formula (XII), R 5 to R 8 , X, and R are as defined above.)
Hereafter, the manufacturing method and molecular weight adjustment method of the organic-inorganic hybrid polymer of this invention using said bis (terpyridine) compound are demonstrated. In the present invention, a bis (terpyridine) compound and a transition metal compound are complexed in a solution to synthesize an organic-inorganic hybrid polymer, and then the organic-inorganic hybrid polymer is dissolved in a solvent at a concentration corresponding to the molecular weight to be obtained. It is characterized by being dissolved in.
有機−無機ハイブリッドポリマーの合成は、ビス（ターピリジン）化合物と、遷移金属化合物とを、好ましくは酢酸中にて、所望により加熱しながら攪拌混合して錯形成反応させることにより行われる。これにより、ビス（ターピリジン）化合物と遷移金属イオンとが錯形成して交互に連結した有機−無機ハイブリッドポリマーが合成される。この有機−無機ハイブリッドポリマーは、例えば下記式（XIII）の構造を有する。 The synthesis of the organic-inorganic hybrid polymer is performed by stirring and mixing a bis (terpyridine) compound and a transition metal compound, preferably in acetic acid, with heating as desired, to cause a complex formation reaction. Thereby, an organic-inorganic hybrid polymer in which a bis (terpyridine) compound and a transition metal ion are complexed and alternately connected is synthesized. This organic-inorganic hybrid polymer has a structure of the following formula (XIII), for example.
（式（XIII）中、Ｒ1〜Ｒ4およびＲは上記式（I）と同義であり、Ｍは遷移金属イオンを示し、ｎは錯形成構造の繰り返し数を示す。）
遷移金属化合物としては、２価または３価の遷移金属イオン化合物、例えば無機酸塩、有機酸塩、錯体等のイオン解離性の化合物が好ましいものとして例示され、遷移金属イオンの具体例としては、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｃｄ、Ｓｎ、Ｍｎ、Ｔｉ、Ｂａ、Ｇｅ、Ｇａ、Ｙ、Ｌａ、Ｅｕ、Ｓｃ、Ｐｄ、Ｐｔ、Ｒｈ、Ｒｕ、Ｂｉ、Ｖ、Ｍｇ、Ｚｎ、Ｓｒ、Ｍｏ、Ｗ、Ｔｅなどの２価または３価のイオンが挙げられる。(In formula (XIII), R 1 to R 4 and R have the same meanings as in the above formula (I), M represents a transition metal ion, and n represents the number of repeating complex-forming structures.)
As the transition metal compound, a divalent or trivalent transition metal ion compound, for example, an ion dissociative compound such as an inorganic acid salt, an organic acid salt, or a complex is exemplified as a preferable example. Fe, Co, Ni, Cu, Cd, Sn, Mn, Ti, Ba, Ge, Ga, Y, La, Eu, Sc, Pd, Pt, Rh, Ru, Bi, V, Mg, Zn, Sr, Mo, Divalent or trivalent ions such as W and Te can be mentioned.
また、非対称型ビス（ターピリジン）化合物を用いることで、隣接する２つのターピリジル基に異種の遷移金属イオンが錯形成した有機−無機ハイブリッドポリマーを合成することもできる。 In addition, by using an asymmetric bis (terpyridine) compound, an organic-inorganic hybrid polymer in which different transition metal ions are complexed to two adjacent terpyridyl groups can be synthesized.
錯形成反応は、好ましくは酢酸溶液中で行われる。反応温度は、例えば常温〜１２０℃、好ましくは６０〜１２０℃である。 The complexing reaction is preferably carried out in an acetic acid solution. The reaction temperature is, for example, normal temperature to 120 ° C, preferably 60 to 120 ° C.
本発明では、上記のようにして合成された有機−無機ハイブリッドポリマーを、得ようとする分子量に対応する濃度で溶媒に溶解させる。溶媒としては、水、メタノール、エタノール等の親水性溶媒、酢酸等の酸性溶媒などが好ましく用いられる。 In the present invention, the organic-inorganic hybrid polymer synthesized as described above is dissolved in a solvent at a concentration corresponding to the molecular weight to be obtained. As the solvent, water, hydrophilic solvents such as methanol and ethanol, and acidic solvents such as acetic acid are preferably used.
例えば、合成後の有機−無機ハイブリッドポリマーの反応液から液分を除去し、乾燥してパウダー状またはフィルム状にしたものを、濃度調整用の溶媒に溶解させることができる。 For example, a solution obtained by removing the liquid from the reaction solution of the organic-inorganic hybrid polymer after synthesis and drying it into a powder or film can be dissolved in a solvent for adjusting the concentration.
本発明者らは、合成後の有機−無機ハイブリッドポリマーを溶媒に溶解することにより、分子量の分散を２．０以下と極めて小さくすることができ、さらに、得られる有機−無機ハイブリッドポリマーの分子量と、当該溶媒に溶解させる有機−無機ハイブリッドポリマーの濃度との間に一定の増減関係があることを見出した。この知見に基づき、合成後の有機−無機ハイブリッドポリマーを溶媒に溶解することにより得られる有機−無機ハイブリッドポリマーの分子量と、当該溶媒に溶解させる有機−無機ハイブリッドポリマーの濃度との分子量−濃度対応関係を予め導出しておくことで、有機−無機ハイブリッドポリマーを合成した後、予め導出した前記分子量−濃度対応関係に基づき、得ようとする分子量に対応する濃度で有機−無機ハイブリッドポリマーを溶媒に溶解させることで、分散値が２．０以下である所望の分子量の有機−無機ハイブリッドポリマーが得られることを見出し本発明を完成するに至った。 The present inventors can reduce the molecular weight dispersion to 2.0 or less by dissolving the synthesized organic-inorganic hybrid polymer in a solvent. Furthermore, the molecular weight of the resulting organic-inorganic hybrid polymer The present inventors have found that there is a certain increase / decrease relationship between the concentration of the organic-inorganic hybrid polymer dissolved in the solvent. Based on this finding, the molecular weight-concentration correspondence between the molecular weight of the organic-inorganic hybrid polymer obtained by dissolving the synthesized organic-inorganic hybrid polymer in the solvent and the concentration of the organic-inorganic hybrid polymer dissolved in the solvent. After synthesizing the organic-inorganic hybrid polymer, the organic-inorganic hybrid polymer is dissolved in the solvent at a concentration corresponding to the molecular weight to be obtained based on the molecular weight-concentration correspondence relationship derived in advance. As a result, it was found that an organic-inorganic hybrid polymer having a desired molecular weight having a dispersion value of 2.0 or less was obtained, and the present invention was completed.
本発明の有機−無機ハイブリッドポリマーは、光、電子、磁気、触媒機能の発現が期待されている発光素子、エネルギー変換材料、薬剤輸送、センサ、高機能触媒、太陽電池等、各種の分野に応用することが可能である。 The organic-inorganic hybrid polymer of the present invention is applied to various fields such as light-emitting elements, energy conversion materials, drug transport, sensors, high-performance catalysts, solar cells, etc. that are expected to exhibit optical, electronic, magnetic, and catalytic functions. Is possible.
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれらの実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all.
以下の実施例において、分子量の分散値は光散乱測定および屈折率測定を用いてＭｗ／Ｍｎとして求めた。In the following examples, the molecular weight dispersion value was determined as M w / M n using light scattering measurement and refractive index measurement.
Ｍｗは、光散乱測定により、以下の式より算出した。
ＫＣ／Ｒ0＝１／Ｍｗ＋２Ａ2Ｃ
（ここで、Ｒ0は散乱角０でのレイリー比、Ｍｗは重量平均分子量、Ｃは溶液の濃度、Ｋは光学定数、Ａ2は第２ビリアル係数を示す。）
Viscotek社製、270 DUAL DETECTORを用い、標準サンプルとして、同社が精製したPolyCALTMPolyethylene Oxide Std-PEO-22K (Ｍｗ=22396)を用いてキャリブレーションを行ってから試料の測定を行った。すなわち、それぞれの濃度に溶解したポリマー試料２０μＬを注入し、長さ１０ｍのコイルを通した後（流速０．２ｍＬ／ｓｅｃ）に測定を行った。Mw was calculated from the following equation by light scattering measurement.
KC / R 0 = 1 / M w + 2A 2 C
(Where R 0 is the Rayleigh ratio at a scattering angle of 0, M w is the weight average molecular weight, C is the concentration of the solution, K is the optical constant, and A 2 is the second virial coefficient.)
Using a 270 DUAL DETECTOR manufactured by Viscotek, calibration was performed using PolyCAL ™ Polyethylene Oxide Std-PEO-22K ( Mw = 22396) purified by the company as a standard sample, and then the sample was measured. That is, 20 μL of a polymer sample dissolved in each concentration was injected, passed through a 10 m long coil (flow rate: 0.2 mL / sec), and measurement was performed.
Ｍｎは、屈折率測定により、以下の式で算出した。M n was calculated by the following formula by refractive index measurement.
１，４−ビス（ターピリジル）ベンゼンと酢酸鉄または酢酸コバルトとを表１に示す割合で混合し、酢酸溶液中、１００℃で２４時間加熱攪拌することで錯形成を行い、１，４−ビス（ターピリジル）ベンゼンと鉄イオンまたはコバルトイオンとが交互に結合した下記に示す構造を持つ有機−無機ハイブリッドポリマー（ＭＥＰＥ）を合成した。 1,4-bis (terpyridyl) benzene and iron acetate or cobalt acetate were mixed in the ratio shown in Table 1, and complex formation was performed by heating and stirring in an acetic acid solution at 100 ° C. for 24 hours. An organic-inorganic hybrid polymer (MEPE) having the structure shown below in which (terpyridyl) benzene and iron ions or cobalt ions are alternately bonded was synthesized.
なお、上記では鉄イオンを無機材とした場合を例示しているが、コバルトイオンを無機材とした場合も有機−無機繰り返し構造は同様である。 In addition, although the case where the iron ion is used as the inorganic material is illustrated above, the organic-inorganic repeating structure is the same when the cobalt ion is used as the inorganic material.
表１に示す物質Ｎｏ．１〜６のＭＥＰＥそれぞれについて、表２に示すようにメタノール溶媒に溶解させ、１時間室温で攪拌することにより、表２に示す通りの分子量とその分散値をもったＭＥＰＥを得た。 Substance No. shown in Table 1 Each MEPE of 1 to 6 was dissolved in a methanol solvent as shown in Table 2 and stirred for 1 hour at room temperature to obtain MEPE having the molecular weight and dispersion value shown in Table 2.
有機材と無機材とを等量混合して合成した物質Ｎｏ．１、２では、溶媒中のポリマー濃度が高くなるにつれ分子量の著しい増加が観測された。分子量の分散値は１．３程度に収束した。物質Ｎｏ．１、２のそれぞれについて、ハイブリッドポリマーの分子量と溶媒濃度との関係を図１および表３に示す。 Substance No. synthesized by mixing equal amounts of organic and inorganic materials In 1 and 2, a significant increase in molecular weight was observed as the polymer concentration in the solvent increased. The molecular weight dispersion value converged to about 1.3. Substance No. The relationship between the molecular weight of the hybrid polymer and the solvent concentration is shown in FIG.
以上の結果より、溶媒中のポリマー濃度を変更するだけで、所望の分子量を有する有機−無機ハイブリッドポリマーが得られることが明らかとなった。 From the above results, it has been clarified that an organic-inorganic hybrid polymer having a desired molecular weight can be obtained simply by changing the polymer concentration in the solvent.
一方、有機材と無機材の混合比（モル比）を０．９５、０．９０として合成した物質Ｎｏ．３、４、５、６においても、溶媒の濃度と分子量との関係に一定の増減傾向が見られた。さらに、合成時の１，４−ビス（ターピリジル）ベンゼンと金属イオンとのモル比を等量より変更することで、メタノール溶媒への溶解濃度が高い場合であっても分子量の著しい増加を防ぐことができ、所望の範囲の分子量をもつポリマーが得られることが明らかとなった。また分散値も１．３程度となった。物質Ｎｏ．６について、ハイブリッドポリマーの分子量と溶媒濃度との関係を図２および表４に示す。 On the other hand, the substance No. synthesized with the mixing ratio (molar ratio) of the organic material and the inorganic material being 0.95 and 0.90. Also in 3, 4, 5, and 6, the fixed increase / decrease tendency was seen by the relationship between the density | concentration of a solvent, and molecular weight. Furthermore, by changing the molar ratio of 1,4-bis (terpyridyl) benzene and metal ions during synthesis from an equivalent amount, a significant increase in molecular weight can be prevented even when the concentration in methanol solvent is high. It was revealed that a polymer having a molecular weight in a desired range can be obtained. The dispersion value was also about 1.3. Substance No. 6 and FIG. 4 show the relationship between the molecular weight of the hybrid polymer and the solvent concentration.
Claims (7)
ビス（ターピリジン）化合物と遷移金属化合物とを溶液中で錯形成反応させて有機−無機ハイブリッドポリマーを合成した後に当該有機−無機ハイブリッドポリマーを溶媒に溶解することにより得られる有機−無機ハイブリッドポリマーの分子量と、当該溶媒に溶解させる有機−無機ハイブリッドポリマーの濃度との分子量−濃度対応関係を予め導出する工程と、
ビス（ターピリジン）化合物と遷移金属化合物とを溶液中で錯形成反応させて有機−無機ハイブリッドポリマーを合成した後、予め導出した前記分子量−濃度対応関係に基づき、得ようとする分子量に対応する濃度で有機−無機ハイブリッドポリマーを溶媒に溶解させ、分散値が２．０以下である８００以上６１８００以下のいずれかの分子量の有機−無機ハイブリッドポリマーを得る工程とを含むことを特徴とする有機−無機ハイブリッドポリマーの製造方法。 A method for producing an organic-inorganic hybrid polymer in which a bis (terpyridine) compound and a transition metal ion are complexed and alternately connected,
Molecular weight of the organic-inorganic hybrid polymer obtained by complex-forming a bis (terpyridine) compound and a transition metal compound in a solution to synthesize an organic-inorganic hybrid polymer and then dissolving the organic-inorganic hybrid polymer in a solvent And a step of deriving in advance a molecular weight-concentration correspondence relationship between the concentration of the organic-inorganic hybrid polymer dissolved in the solvent,
After synthesizing a bis (terpyridine) compound and a transition metal compound in a solution to synthesize an organic-inorganic hybrid polymer, the concentration corresponding to the molecular weight to be obtained based on the previously derived molecular weight-concentration correspondence And an organic-inorganic hybrid polymer is dissolved in a solvent to obtain an organic-inorganic hybrid polymer having a molecular weight of 800 to 61800 having a dispersion value of 2.0 or less. A method for producing a hybrid polymer.
ビス（ターピリジン）化合物と遷移金属化合物とを溶液中で錯形成反応させて有機−無機ハイブリッドポリマーを合成した後に当該有機−無機ハイブリッドポリマーを溶媒に溶解することにより得られる有機−無機ハイブリッドポリマーの分子量と、当該溶媒に溶解させる有機−無機ハイブリッドポリマーの濃度との分子量−濃度対応関係を予め導出する工程と、
ビス（ターピリジン）化合物と遷移金属化合物とを溶液中で錯形成反応させて有機−無機ハイブリッドポリマーを合成した後、予め導出した前記分子量−濃度対応関係に基づき、得ようとする分子量に対応する濃度で有機−無機ハイブリッドポリマーを溶媒に溶解させることにより、有機−無機ハイブリッドポリマーの分子量を分散値が２．０以下である８００以上６１８００以下のいずれかの値に調整する工程とを含むことを特徴とする有機−無機ハイブリッドポリマーの分子量調整方法。 A method for adjusting the molecular weight of an organic-inorganic hybrid polymer in which a bis (terpyridine) compound and a transition metal ion are complexed and alternately connected,
Molecular weight of the organic-inorganic hybrid polymer obtained by complex-forming a bis (terpyridine) compound and a transition metal compound in a solution to synthesize an organic-inorganic hybrid polymer and then dissolving the organic-inorganic hybrid polymer in a solvent And a step of deriving in advance a molecular weight-concentration correspondence relationship between the concentration of the organic-inorganic hybrid polymer dissolved in the solvent,
After synthesizing a bis (terpyridine) compound and a transition metal compound in a solution to synthesize an organic-inorganic hybrid polymer, the concentration corresponding to the molecular weight to be obtained based on the previously derived molecular weight-concentration correspondence And adjusting the molecular weight of the organic-inorganic hybrid polymer to any value of 800 or more and 61800 or less having a dispersion value of 2.0 or less by dissolving the organic-inorganic hybrid polymer in a solvent. A method for adjusting the molecular weight of the organic-inorganic hybrid polymer.
The method for adjusting the molecular weight of an organic-inorganic hybrid polymer according to claim 5 or 6, wherein the solvent for dissolving the organic-inorganic hybrid polymer obtained by the complex formation reaction in the solution is methanol.
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