JPH0597809A - Metal complex diamine compound and its production - Google Patents
Metal complex diamine compound and its productionInfo
- Publication number
- JPH0597809A JPH0597809A JP3255404A JP25540491A JPH0597809A JP H0597809 A JPH0597809 A JP H0597809A JP 3255404 A JP3255404 A JP 3255404A JP 25540491 A JP25540491 A JP 25540491A JP H0597809 A JPH0597809 A JP H0597809A
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- JP
- Japan
- Prior art keywords
- bipyridine
- complex
- diamino
- metal complex
- diamine compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Pyridine Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Polyamides (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
(57)【要約】 （修正有）
【目的】 トリスビピリジン金属錯体を含むポリイミド
およびその前駆体となるポリアミド酸の原料となる金属
ジアミン化合物およびその製造方法を得る。
【構成】 図示一般式で示される５，５´−ジアミノ−
２，２´−ビピリジンを配位子として持つビピリジンル
テニウム(II)錯体，及び５，５´−ジアミノ−２，２´
−ビピリジンと等モルのジハロゲノルテニウム(II)錯体
をアルコール系溶媒中で還流下に加熱して式で示される
ビピリジンルテニウム錯体を製造する方法。
〔式中のＬ１Ｌ２は次の一般式
または
（式中のＲは水素原子、メチル基またはフェニル基を示
す）で表される配位子、Ｘ−はアニオンを示す〕(57) [Summary] (Modified) [Objective] To obtain a polyimide containing a trisbipyridine metal complex, a metal diamine compound as a raw material of a polyamic acid as a precursor thereof, and a method for producing the same. [Structure] 5,5'-diamino-in the general formula shown
Bipyridine ruthenium (II) complex having 2,2'-bipyridine as a ligand, and 5,5'-diamino-2,2 '
A method of producing a bipyridine ruthenium complex represented by the formula by heating an equimolar amount of a dihalogenorthenium (II) complex with bipyridine in an alcohol solvent under reflux. [Wherein L 1 L 2 is the following general formula: Or (R in the formula represents a hydrogen atom, a methyl group or a phenyl group), a ligand represented by X − represents an anion.
Description
【０００１】[0001]
【産業上の利用分野】本発明は新規な金属錯体ジアミン
化合物およびその製造方法に関するものである。FIELD OF THE INVENTION The present invention relates to a novel metal complex diamine compound and a method for producing the same.
【０００２】[0002]
【従来の技術】従来のポリイミドは優れた耐熱性と絶縁
性を有し、半導体などの電子材料や水素分離膜などに広
く工業材料として使用されてきたが、近年ラングミュア
ープロジェット法を用いることにより、ポリイミド超薄
膜を製造する方法が開発された（特開昭６２−２７５１
３５号公報、特開昭６３−６５９８０号公報）。2. Description of the Related Art Conventional polyimide has excellent heat resistance and insulating properties, and has been widely used as an industrial material for electronic materials such as semiconductors and hydrogen separation membranes. In recent years, the Langmuir-Projet method has been used. Has developed a method for producing a polyimide ultra-thin film (JP-A-62-2751).
35, JP-A-63-65980).
【０００３】これにより従来のラングミュアープロジェ
ット膜（ＬＢ膜）より更に薄い分子性超薄膜の製造が行
なえるようになり、分子素子、バイオ素子をめざした研
究が盛んに行われている（特開平１−１０１３３０号公
報、特開平２−１１９０１０号公報）。しかしながら今
後さらに優れた機能を付与したポリイミド材料の開発が
必要である。As a result, it has become possible to manufacture a molecular ultrathin film that is thinner than the conventional Langmuir-Projet film (LB film), and much research has been conducted aiming at molecular devices and biodevices. (Kaihei 1-110330 and Japanese Patent Laid-Open No. 2-119010). However, in the future, it is necessary to develop polyimide materials with even more excellent functions.
【０００４】興味のある化合物として、ビピリジン金属
錯体、特にトリスビピリジン金属錯体がある。たとえば
トリスビピリジンルテニウム錯体は水の光分解や光電変
換機能を有する色素として知られている。しかしながら
このような金属錯体を主鎖に持つポリイミド、ポリアミ
ドは現在のところ知られていない。Compounds of interest are bipyridine metal complexes, especially tris bipyridine metal complexes. For example, a trisbipyridine ruthenium complex is known as a dye having a photolysis function and a photoelectric conversion function for water. However, polyimides and polyamides having such a metal complex in the main chain are not known at present.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的はトリス
ビピリジン金属錯体を含むポリイミドおよびその前駆体
となるポリアミド酸の原料となるジアミン化合物とその
製造方法を提供せんとするにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a polyimide containing a trisbipyridine metal complex, a diamine compound as a raw material for a polyamic acid as a precursor thereof, and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】本発明者らはこのような
新規なジアミン化合物とそれを得る方法について鋭意研
究を重ねた結果、５，５´−ジアミノ−２，２´−ビピ
リジンを配位子として持つビピリジン金属錯体あるいは
その類似体がこの目的に適合することを見い出し、本発
明を達成するに至った。As a result of intensive studies on the novel diamine compound and a method for obtaining the same, the present inventors have coordinated 5,5'-diamino-2,2'-bipyridine. It was found that the bipyridine metal complex or its analog as a child is suitable for this purpose, and the present invention has been accomplished.
【０００７】従って本発明の第１発明は、次の一般式Therefore, the first invention of the present invention is as follows.
【化４】 〔式中のＬ1 ，Ｌ2 は次の一般式[Chemical 4] [Wherein L 1 and L 2 are the following general formulas:
【化５】 または[Chemical 5] Or
【化６】 （式中のＲは水素原子、メチル基またはフェニル基を示
す）で表される配位子、Ｘ- はアニオンを示す〕で表さ
れることを特徴とする金属錯体ジアミン化合物に関する
ものである。また本発明の第２発明は、化４〔式中のＬ
1 ，Ｌ2 は化５または化６（式中のＲは水素原子、メチ
ル基またはフェニル基を示す）で表わされる配位子、Ｘ
- はアニオンを示す〕で表わされる金属錯体ジアミン化
合物を製造するに当り、５，５´−ジアミノ−２，２´
−ビピリジンとＲu2+ Ｌ1 Ｌ2 （Ｘ- )2 を反応させる
ことを特徴とする金属錯体ジアミン化合物の製造方法に
関するものである。[Chemical 6] (Wherein R represents a hydrogen atom, a methyl group or a phenyl group) and X − represents an anion]. The second invention of the present invention is the compound of formula 4 [L in the formula
1 , L 2 is a ligand represented by Chemical formula 5 or Chemical formula 6 (wherein R represents a hydrogen atom, a methyl group or a phenyl group), X
- hits the manufacturing metal complex diamine compound represented by an anion], 5,5'-diamino-2,2'
The present invention relates to a method for producing a metal complex diamine compound, which comprises reacting bipyridine with Ru 2+ L 1 L 2 (X − ) 2 .
【０００８】トリスビピリジン金属錯体をポリイミドま
たはその前駆体であるポリアミド酸に導入するには、２
つのアミノ基を有する金属錯体化合物と酸無水物を反応
させることが一般的に考えられる。金属錯体の配位子と
してもっともよく知られている２，２´−ビピリジンを
考えると、２，２´−ビピリジン環へのアミノ基の導入
位置としては電子密度の最も高い位置に導入するのが効
果的である。２，２´−ビピリジン環の電子密度は高い
方から、５位，４位，３位，６位であるので、５位の位
置にアミノ基を導入することが望ましい。To introduce the trisbipyridine metal complex into the polyimide or its precursor polyamic acid, 2
It is generally considered to react an acid anhydride with a metal complex compound having two amino groups. Considering 2,2'-bipyridine, which is the most well-known ligand of a metal complex, the amino group is introduced into the 2,2'-bipyridine ring at the position with the highest electron density. It is effective. Since the electron density of the 2,2'-bipyridine ring is from the highest position to the 5-position, 4-position, 3-position and 6-position, it is desirable to introduce an amino group at the 5-position.
【０００９】実際、５，５´−ジアミノ−２，２´−ビ
ピリジンを配位子としてもつ金属錯体化合物が上に述べ
た目的に適合する。In fact, metal complex compounds having 5,5'-diamino-2,2'-bipyridine as a ligand are suitable for the purposes mentioned above.
【００１０】５，５´−ジアミノ−２，２´−ビピリジ
ンを配位子としてもつ本発明の化４の金属錯体は、５，
５´−ジアミノ−２，２´−ビピリジンと等モルのＲu
2+ Ｌ1 Ｌ2 （Ｘ- )2（式中のＬ1 Ｌ2 は前記の配位
子、Ｘ- はアニオンを示す) で表わされる化合物、例え
ばＸ- がハロゲン原子を示すジハロゲノルテニウム(II)
錯体をアルコール系溶媒、例えばエタノール中で還流す
ることにより得ることができる。また対イオンを交換す
ることにより溶媒に対する溶解度や脱水のしやすさが変
化する。水和水の無い錯体を得るには対イオンとしてCL
O4 - , BF4 - ,PF6 - などをあげることができるが、特
に PF6 - が好ましい。The metal complex of Chemical formula 4 of the present invention having 5,5'-diamino-2,2'-bipyridine as a ligand is 5,
Ru equimolar to 5'-diamino-2,2'-bipyridine
2+ L 1 L 2 (X − ) 2 (wherein L 1 L 2 represents the above-mentioned ligand and X − represents an anion), for example, dihalogenorthenium (wherein X − represents a halogen atom) II)
It can be obtained by refluxing the complex in an alcoholic solvent such as ethanol. Also, by exchanging the counter ions, the solubility in the solvent and the easiness of dehydration change. To obtain a complex without water of hydration, CL as the counterion
O 4 − , BF 4 − , PF 6 − and the like can be mentioned, but PF 6 − is particularly preferable.
【００１１】[0011]
【実施例】以下実施例、参考例および試験例により本発
明を詳細に説明する。実施例１ ５，５´−ジアミノ−２，２´−ビピリジン−ビス−
２，２´−ビピリジンルテニウムヘキサフルオロフォス
フェートの合成 ジクロロ−ビス−２，２´−ビピリジンルテニウム 2.5
93g(5.0mM)と５，５´−ジアミノ−２，２´−ビピリジ
ン 0.997(5.0mM) をエタノール中に分散させた。この溶
液を窒素通気下、24時間おだやかに還流温度で加熱し
た。反応溶液を熱時ろ過して残渣を取り除いた後、ろ液
にアンモニウムヘキサフルオロフォスフェート飽和水溶
液を加え、０℃で放置した。析出した沈殿をろ過し、冷
水、ジエチルエーテルで洗った。エタノール／アセトン
から再結晶し、赤色の結晶を得た。これを真空下80℃で
５日間乾燥させた。 収量 3.0g(68%) 赤外吸収スペクトル(KBr) 3395 cm-1 (-NH2) The present invention will be described in detail below with reference to Examples, Reference Examples and Test Examples. Example 1 5,5'-diamino-2,2'-bipyridine-bis-
Synthesis of 2,2'-bipyridine ruthenium hexafluorophosphate Dichloro-bis-2,2'-bipyridine ruthenium 2.5
93 g (5.0 mM) and 5,5'-diamino-2,2'-bipyridine 0.997 (5.0 mM) were dispersed in ethanol. This solution was gently heated at reflux temperature for 24 hours under nitrogen bubbling. After the reaction solution was filtered while hot to remove the residue, a saturated aqueous solution of ammonium hexafluorophosphate was added to the filtrate, and the mixture was left at 0 ° C. The deposited precipitate was filtered and washed with cold water and diethyl ether. Recrystallization from ethanol / acetone gave red crystals. It was dried under vacuum at 80 ° C. for 5 days. Yield 3.0 g (68%) Infrared absorption spectrum (KBr) 3395 cm -1 (-NH 2 ).
【００１２】実施例２ ５，５´−ジアミノ−２，２´−ビピリジン−ビス−
５，５´−ジメチル−２−２´−ビピリジンルテニウム
ヘキサフルオロフォスフェートの合成 ビスビピリジン錯体としてジクロロ−ビス−５，５´−
ジメチル−２，２´−ビピリジンルテニウムを用いた以
外は実施例１と同様な方法で上記化合物を得た。 Example 2 5,5'-diamino-2,2'-bipyridine-bis-
Synthesis of 5,5'-dimethyl-2-2'-bipyridine ruthenium hexafluorophosphate Dichloro-bis-5,5'- as bisbipyridine complex
The above compound was obtained in the same manner as in Example 1 except that dimethyl-2,2'-bipyridine ruthenium was used.
【００１３】実施例３ ５，５´−ジアミノ−２，２´−ビピリジン−ビス−
４，７−ジフェニル−１，10−フェナントロリンルテニ
ウムヘキサフルオロフォスフェートの合成 ビスリガンド錯体としてビス−４，７−ジフェニル−
１，10−フェナントロリンルテニウムヘキサフルオロフ
ォスフェートを用いた以外は実施例１と同様な方法で上
記化合物を得た。 Example 3 5,5'-diamino-2,2'-bipyridine-bis-
Synthesis of 4,7-diphenyl-1,10-phenanthroline ruthenium hexafluorophosphate Bis-4,7-diphenyl-as bis ligand complex
The above compound was obtained in the same manner as in Example 1 except that 1,10-phenanthroline ruthenium hexafluorophosphate was used.
【００１４】参考例１ 0.3558g(0.40mM) の５，５´−ジアミノ−２，２´−ビ
ピリジン−ビス２，２−ビピリジンルテニウムヘキサフ
ルオロフォスフェートを２ccの脱水ジメチルスルフォキ
シドに溶解させたのち、0.1177g(0.40mM) の３，４，３
´，４´−ビフェニルテトラカルボン酸二無水物を加え
た。この溶液を乾燥窒素雰囲気下、室温で20時間攪拌し
た後、大量のエタノールに投入して、生じた沈殿をろ過
してポリアミド酸を得た。赤外吸収スペクトルにおいて
アミド結合の吸収が1680cm-1に観測された。 対数粘度数 0.21dl/g (DMSO中 30 ℃、0.5g/dl) Reference Example 1 0.3558 g (0.40 mM) of 5,5'-diamino-2,2'-bipyridine-bis2,2-bipyridine ruthenium hexafluorophosphate was dissolved in 2 cc of dehydrated dimethylsulfoxide. After that, 0.1177g (0.40mM) of 3,4,3
', 4'-Biphenyltetracarboxylic dianhydride was added. The solution was stirred under a dry nitrogen atmosphere at room temperature for 20 hours, poured into a large amount of ethanol, and the generated precipitate was filtered to obtain a polyamic acid. In the infrared absorption spectrum, absorption of an amide bond was observed at 1680 cm -1 . Logarithmic viscosity number 0.21dl / g (30 ° C in DMSO, 0.5g / dl)
【００１５】参考例２ トリス（４−アミノ−２，２´−ビピリジン）ルテニウ
ムヘキサフルオロフォスフェートを用いた以外は参考例
１と同様にしてポリアミド酸の合成を試みたが、反応後
の溶液の赤外吸収スペクトルにおいてアミド結合の吸収
が観測されなかった。そこでトリス（４−アミノ−２，
２´−ビピリジン）ルテニウムヘキサフルオロフォスフ
ェートおよび５，５´−ジアミノ−２，２´−ビピリジ
ン−ビス−２，２´−ビピリジンルテニウムヘキサフル
オロフォスフェートのＨ1-ＮＭＲを測定したところ、ア
ミノ基のＨ1 の化学シフトはそれぞれ 6.79 ppm 、5.95
ppm（ｄ−ＤＭＳＯ中、ＴＭＳ基準）であった。このこ
とからトリス（４−アミノ−２，２´−ビピリジン）ル
テニウムヘキサフルオロフォスフェートにおけるアミノ
基の塩基性が５，５´−ジアミノ−２，２´−ビピリジ
ン−ビス−２，２´−ビピリジンルテニウムヘキサフル
オロフォスフェートにおけるそれに比べて弱いことがわ
かり、この弱い塩基性のため前者が酸無水物と反応しな
いことが推測された。 Reference Example 2 An attempt was made to synthesize a polyamic acid in the same manner as in Reference Example 1 except that tris (4-amino-2,2'-bipyridine) ruthenium hexafluorophosphate was used. No absorption of amide bond was observed in the infrared absorption spectrum. So Tris (4-amino-2,
H 1 -NMR of 2′-bipyridine) ruthenium hexafluorophosphate and 5,5′-diamino-2,2′-bipyridine-bis-2,2′-bipyridine ruthenium hexafluorophosphate was measured and found to be an amino group. H 1 chemical shifts of 6.79 ppm and 5.95 respectively
ppm (in d-DMSO, based on TMS). From this, the basicity of the amino group in tris (4-amino-2,2'-bipyridine) ruthenium hexafluorophosphate is 5,5'-diamino-2,2'-bipyridine-bis-2,2'-bipyridine. It was found to be weaker than that in ruthenium hexafluorophosphate and it was speculated that the former did not react with the acid anhydride due to this weak basicity.
【００１６】試験例 本発明のルテニウム錯体の高分子化やその他の応用のた
めに、機能設計上重要な酸化還元特性をサイクリックボ
ルタメトリーによって測定した。測定は密閉型３極式セ
ルを用いて、五酸化リンで脱水したアセトニトリル中
（支持塩は 0.1Ｍテトラ−ｎ−ブチルアンモニウムヘキ
サフルオロフォスフェート）にて行った。動作電極とし
て直径 0.5mmの白金線、対極として白金線、参照電極と
して銀線を用いた。内部基準としてフェロセン／フェリ
シニウム(Fc0/+) 系を用いて、酸化還元電位はこの系に
対して示した。（Ｅ(Fc0/+) ＝ 0.36 Vvs. SSCE) 。ル
テニウム錯体の濃度は 0.5 mM とした。得られたボルタ
モグラムを図１に示す。用いた測定条件では還元側でビ
ピリジンの還元反応に対応すると考えられる２つの可逆
波、酸化側ではルテニウムを金属イオンの酸化に対応す
る可逆波と、さらに５，５´−ジアミノ−２，２´−ビ
ピリジンを含む錯体に特有な可逆波が観測された。また
測定結果を表１に示した。 Test Example For the polymerization of the ruthenium complex of the present invention and other applications, the redox properties important for functional design were measured by cyclic voltammetry. The measurement was carried out in acetonitrile dehydrated with phosphorus pentoxide (the supporting salt was 0.1 M tetra-n-butylammonium hexafluorophosphate) using a closed three-electrode cell. A platinum wire having a diameter of 0.5 mm was used as a working electrode, a platinum wire was used as a counter electrode, and a silver wire was used as a reference electrode. Using the ferrocene / ferricinium (Fc 0 / + ) system as an internal standard, the redox potential was shown for this system. (E (Fc 0 / + ) = 0.36 Vvs. SSCE). The concentration of ruthenium complex was 0.5 mM. The obtained voltammogram is shown in FIG. Under the measurement conditions used, two reversible waves considered to correspond to the reduction reaction of bipyridine on the reducing side, a reversible wave corresponding to the oxidation of ruthenium on the metal ion on the oxidizing side, and 5,5'-diamino-2,2 ' -A reversible wave peculiar to the complex containing bipyridine was observed. The measurement results are shown in Table 1.
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【発明の効果】本発明は化４で表わされる金属錯体ジア
ミン化合物およびその製造方法を提供する。本発明によ
れば５，５´−ジアミノ−２，２´−ビピリジンを配位
子として持つビピリジン金属錯体あるいはその類似体と
酸性基を持つ化合物と反応させることにより、ポリアミ
ド、ポリイミド等のポリマーにビピリジン金属錯体ある
いはその類似体を直接導入することができる。従って今
後、電気的特性、光学的特性などにおいて新規な機能性
有機材料を提供することができる。The present invention provides a metal complex diamine compound represented by Chemical formula 4 and a method for producing the same. According to the present invention, by reacting a bipyridine metal complex having 5,5′-diamino-2,2′-bipyridine as a ligand or an analogue thereof with a compound having an acidic group, a polymer such as polyamide or polyimide can be obtained. The bipyridine metal complex or its analogue can be introduced directly. Therefore, in the future, a novel functional organic material can be provided in terms of electrical characteristics, optical characteristics and the like.
【図１】〔Ｒu (bpy)2(5,5´-dabpy) 2+のサイクリック
ボルタモグラム線図である。FIG. 1 is a cyclic voltammogram diagram of [Ru (bpy) 2 (5,5′-dabpy) 2+ .
Claims (2)
す）で表される配位子、Ｘ- はアニオンを示す〕で表さ
れることを特徴とする金属錯体ジアミン化合物。1. The following general formula: [Wherein L 1 L 2 is the following general formula: Or [Chemical 3] (R in the formula represents a hydrogen atom, a methyl group or a phenyl group, and X − represents an anion].
（式中のＲは水素原子、メチル基またはフェニル基を示
す）で表される配位子、Ｘ- はアニオンを示す〕で表さ
れる金属錯体ジアミン化合物を製造するに当り、５，５
´−ジアミノ−２，２´−ビピリジンとＲu2+ Ｌ1 Ｌ2
（Ｘ- )2 を反応させることを特徴とする金属錯体ジア
ミン化合物の製造方法。2. Chemical formula 1 [wherein L 1 and L 2 are chemical formulas 2 or 3]
(R in the formula represents a hydrogen atom, a methyl group or a phenyl group, and a ligand represented by X − represents an anion).
′ -Diamino-2,2′-bipyridine and Ru 2+ L 1 L 2
A method for producing a metal complex diamine compound, which comprises reacting (X − ) 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3255404A JPH0597809A (en) | 1991-10-02 | 1991-10-02 | Metal complex diamine compound and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3255404A JPH0597809A (en) | 1991-10-02 | 1991-10-02 | Metal complex diamine compound and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0597809A true JPH0597809A (en) | 1993-04-20 |
Family
ID=17278299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3255404A Pending JPH0597809A (en) | 1991-10-02 | 1991-10-02 | Metal complex diamine compound and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0597809A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7718803B2 (en) | 2003-08-08 | 2010-05-18 | Samsung Electronics Co., Ltd. | Self-dispersible bipyridine-based metal complex and ink composition comprising the same |
| JP2012188517A (en) * | 2011-03-10 | 2012-10-04 | National Institute For Materials Science | Organic/metal hybrid polymer which contains metal whose coordination number is 4 and bisphenanthroline derivative, ligand thereof, and method for producing the same |
| CN103113583A (en) * | 2013-02-07 | 2013-05-22 | 江西师范大学 | High-dielectric-constant polyimide metal complex and preparation method thereof |
| CN105858734A (en) * | 2016-03-20 | 2016-08-17 | 北京工业大学 | Method for compounding Ru complex Ru(bpy)3(NH2)2 with graphene quantum dots |
| CN108690196A (en) * | 2017-03-31 | 2018-10-23 | 长兴材料工业股份有限公司 | Polyimide precursor composition, use thereof, and polyimide prepared therefrom |
-
1991
- 1991-10-02 JP JP3255404A patent/JPH0597809A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7718803B2 (en) | 2003-08-08 | 2010-05-18 | Samsung Electronics Co., Ltd. | Self-dispersible bipyridine-based metal complex and ink composition comprising the same |
| JP2012188517A (en) * | 2011-03-10 | 2012-10-04 | National Institute For Materials Science | Organic/metal hybrid polymer which contains metal whose coordination number is 4 and bisphenanthroline derivative, ligand thereof, and method for producing the same |
| CN103113583A (en) * | 2013-02-07 | 2013-05-22 | 江西师范大学 | High-dielectric-constant polyimide metal complex and preparation method thereof |
| CN105858734A (en) * | 2016-03-20 | 2016-08-17 | 北京工业大学 | Method for compounding Ru complex Ru(bpy)3(NH2)2 with graphene quantum dots |
| CN108690196A (en) * | 2017-03-31 | 2018-10-23 | 长兴材料工业股份有限公司 | Polyimide precursor composition, use thereof, and polyimide prepared therefrom |
| US11034797B2 (en) | 2017-03-31 | 2021-06-15 | Eternal Materials Co., Ltd. | Polyimide precursor composition, use thereof and polyimide made therefrom |
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