JP2008081418A - 9,9-bis(4-aminophenyl)fluorene compound - Google Patents

9,9-bis(4-aminophenyl)fluorene compound Download PDF

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JP2008081418A
JP2008081418A JP2006260827A JP2006260827A JP2008081418A JP 2008081418 A JP2008081418 A JP 2008081418A JP 2006260827 A JP2006260827 A JP 2006260827A JP 2006260827 A JP2006260827 A JP 2006260827A JP 2008081418 A JP2008081418 A JP 2008081418A
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bis
aminophenyl
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Ikuo Ito
育夫 伊藤
Takakuni Suzuki
高国 鈴木
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Air Water Inc
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a new diamine producing a polyamide and a polyimide having excellent mechanical strength, heat resistance, optical characteristics, processability, etc., having a fluorene skeleton and free of a halogen and to provide a method for producing the diamine. <P>SOLUTION: The new 9,9-bis(4-aminophenyl)fluorene compound having a structure represented by general formula (1) (wherein, R represents a 1-4C alkyl group; and A represents hydrogen or a 1-3C alkyl group) is provided. The method for producing the compound is provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、ポリアミドやポリイミドの原料として有用な９，９−ビス（４−アミノフェニル）フルオレン化合物に関する。   The present invention relates to a 9,9-bis (4-aminophenyl) fluorene compound useful as a raw material for polyamide and polyimide.

芳香族型の高分子化合物において、主鎖中に嵩高い分子構造を導入することにより、溶媒溶解性、耐熱性、光学特性や機械的特性に改善効果を期待する試みがなされている。このような目的のために、嵩高い分子構造を有する芳香族ジアミンとして、カルド構造を有する９，９−ビス(４−アミノフェニル)フルオレンが知られている。（特許文献１）

Figure 2008081418
In aromatic polymer compounds, attempts have been made to improve the solvent solubility, heat resistance, optical properties, and mechanical properties by introducing a bulky molecular structure in the main chain. For this purpose, 9,9-bis (4-aminophenyl) fluorene having a cardo structure is known as an aromatic diamine having a bulky molecular structure. (Patent Document 1)
Figure 2008081418

また、フルオレン骨格の２，７−に臭素原子を有する９，９−ビス(４−アミノフェニル)−２，７−ジブロモフルオレンが知られている。（特許文献２、非特許文献１及び２）

Figure 2008081418
Further, 9,9-bis (4-aminophenyl) -2,7-dibromofluorene having a bromine atom in 2,7- of the fluorene skeleton is known. (Patent Document 2, Non-Patent Documents 1 and 2)
Figure 2008081418

高分子材料に対して諸特性の一層の向上要望がますます強くなっており、その要望に応えるべく、新規な樹脂の骨格構造を形成する為の新規なジアミン化合物が求められている。とりわけハロゲンを有するフルオレン骨格のジアミン誘導体は優れた性能を有するが、ハロゲンに起因する問題点を提起するため、ハロゲンを含有しない嵩高い分子構造を有する化合物が要望されている。
特開平５−３１３４１号公報 特表２００４−５００４６３号公報 Polymer Preprints, 41 [1],105(2000) Macromolecules，38，745 (2005) There is a growing demand for further improvements in various properties of polymer materials, and in order to meet these demands, a new diamine compound for forming a new resin skeleton structure is required. In particular, a fluorene skeleton diamine derivative having a halogen has excellent performance, but in order to raise problems due to the halogen, a compound having a bulky molecular structure not containing a halogen is desired.
Japanese Patent Laid-Open No. 5-31341 JP-T-2004-500463 Polymer Preprints, 41 [1], 105 (2000) Macromolecules, 38, 745 (2005)

近年新たな特性の付与や諸特性の一層の向上という観点から、新規な樹脂の骨格構造を形成するための新規なジアミン化合物が求められているので、本発明はこのような要請に応えるためになされたものである。本発明の目的とするところは、機械的強度、耐熱性、光学特性、加工性等に優れたポリアミドおよびポリイミドを製造することが可能な、フルオレン骨格を有しハロゲンを含有しない新規なジアミンを提供することにある。   In recent years, a new diamine compound for forming a new resin skeleton structure has been demanded from the viewpoint of imparting new characteristics and further improving various characteristics. It was made. An object of the present invention is to provide a novel diamine having a fluorene skeleton and containing no halogen, which can produce polyamides and polyimides having excellent mechanical strength, heat resistance, optical properties, workability, etc. There is to do.

本発明は、下記一般式（１）で表される構造を有する９，９−ビス（４−アミノフェニル）フルオレン化合物を提供する。

Figure 2008081418
（式中、Ｒは炭素数１〜４のアルキル基を表し、Ａは水素、炭素数１〜３のアルキル基を表す。） The present invention provides a 9,9-bis (4-aminophenyl) fluorene compound having a structure represented by the following general formula (1).
Figure 2008081418
 (In the formula, R represents an alkyl group having 1 to 4 carbon atoms, A represents hydrogen and an alkyl group having 1 to 3 carbon atoms.)

本発明はまた、下記式（２）で表される９，９−ビス(４−アミノフェニル)−２，７−ジブロモフルオレンの臭素原子を炭素数１〜４のアルコキシ基に置換することによって請求項１に記載の９，９−ビス(４−アミノフェニル)−２，７−ジアルコキシフルオレン化合物を製造する方法を提供する。

Figure 2008081418
（式中、Ａは水素、炭素数１〜３のアルキル基を表す。） The present invention also claims by substituting the bromine atom of 9,9-bis (4-aminophenyl) -2,7-dibromofluorene represented by the following formula (2) with an alkoxy group having 1 to 4 carbon atoms. A method for producing the 9,9-bis (4-aminophenyl) -2,7-dialkoxyfluorene compound according to Item 1 is provided.
Figure 2008081418
 (In the formula, A represents hydrogen or an alkyl group having 1 to 3 carbon atoms.)

さらに本発明は、下記式（３）で表される２，７−ジアルコキシ−９−フルオレノンをアニリン誘導体と縮合させることによって、請求項１に記載の９，９−ビス(４−アミノフェニル)−２，７−ジアルコキシフルオレン化合物を製造する方法を提供する。

Figure 2008081418
（式中、Ｒは炭素数１〜４のアルキル基を表す。） Furthermore, the present invention provides 9,9-bis (4-aminophenyl) according to claim 1 by condensing 2,7-dialkoxy-9-fluorenone represented by the following formula (3) with an aniline derivative. A method for producing a -2,7-dialkoxyfluorene compound is provided.
Figure 2008081418
 (In the formula, R represents an alkyl group having 1 to 4 carbon atoms.)

本発明によれば、ポリアミド、ポリイミドの原料として有用な新規な９，９−ビス（４−アミノフェニル）フルオレン化合物が提供される。
本発明により、機械的強度、耐熱性、光学特性、加工性等に優れたポリアミドおよびポリイミドを製造することが可能な、フルオレン骨格を有しハロゲンを含有しない新規なジアミンが提供される。
本発明により、新規な９，９−ビス（４−アミノフェニル）フルオレン化合物を製造することができる有用は方法が提供される。 According to the present invention, a novel 9,9-bis (4-aminophenyl) fluorene compound useful as a raw material for polyamide and polyimide is provided.
According to the present invention, there is provided a novel diamine having a fluorene skeleton and containing no halogen, which can produce a polyamide and a polyimide excellent in mechanical strength, heat resistance, optical properties, workability and the like.
According to the present invention, a useful method capable of producing a novel 9,9-bis (4-aminophenyl) fluorene compound is provided.

本発明は、フルオレン骨格の２，７位にアルコキシ基を有する上記一般式（１）で表される構造を有する新規な９，９−ビス（４−アミノフェニル）フルオレン化合物を提供する。   The present invention provides a novel 9,9-bis (4-aminophenyl) fluorene compound having a structure represented by the above general formula (1) having an alkoxy group at positions 2 and 7 of the fluorene skeleton.

上記一般式（１）で表される９，９−ビス（４−アミノフェニル）フルオレン化合物において、Ｒは炭素数１〜４のアルキル基を表し、Ａは水素、炭素数１〜３のアルキル基を表す。
Ｒの好ましい例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基などを挙げることができる。
Ａの好ましい例としては、水素、メチル基、エチル基、ｎ−プロピル基、イソプロピル基などを挙げることができる。 In the 9,9-bis (4-aminophenyl) fluorene compound represented by the general formula (1), R represents an alkyl group having 1 to 4 carbon atoms, A represents hydrogen, and an alkyl group having 1 to 3 carbon atoms. Represents.
Preferred examples of R include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group and the like.
Preferred examples of A include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group and the like.

本発明の上記一般式（１）で表される９，９−ビス（４−アミノフェニル）フルオレン化合物の好ましい化合物としては、９，９−ビス（４−アミノフェニル）−２，７−ジメトキシフルオレン、９，９−ビス（４−アミノフェニル）−２，７−ジエトキシフルオレン、９，９−ビス（４−アミノフェニル）−２，７−ジプロピルオキシフルオレン、９，９−ビス（４−アミノフェニル）−２，７−ジイソプロピルオキシフルオレン、９，９−ビス（４−アミノフェニル）−２，７−ジｎ−ブチルオキシフルオレン、９，９−ビス（４−アミノ−３−メチルフェニル）−２，７−ジメトキシフルオレン、９，９−ビス（４−アミノ−２−メチルフェニル）−２，７−ジメトキシフルオレン、９，９−ビス（４−アミノ−３−エチルフェニル）−２，７−ジエトキシフルオレン、９，９−ビス（４−アミノ−３−イソプロピルフェニル）−２，７−ジｓｅｃ−ブチルオキシフルオレン等を挙げることができる。   As a preferable compound of the 9,9-bis (4-aminophenyl) fluorene compound represented by the general formula (1) of the present invention, 9,9-bis (4-aminophenyl) -2,7-dimethoxyfluorene is preferable. 9,9-bis (4-aminophenyl) -2,7-diethoxyfluorene, 9,9-bis (4-aminophenyl) -2,7-dipropyloxyfluorene, 9,9-bis (4- Aminophenyl) -2,7-diisopropyloxyfluorene, 9,9-bis (4-aminophenyl) -2,7-di-n-butyloxyfluorene, 9,9-bis (4-amino-3-methylphenyl) -2,7-dimethoxyfluorene, 9,9-bis (4-amino-2-methylphenyl) -2,7-dimethoxyfluorene, 9,9-bis (4-amino-3-ethylphenyl) 2,7 diethoxy fluorene, mention may be made of 9,9-bis (4-amino-3-isopropyl-phenyl) -2,7-di-sec- butyloxy fluorene.

本発明の上記一般式（１）で表される９，９−ビス（４−アミノフェニル）フルオレン化合物を合成する方法として、以下の（１）〜（３）の方法を挙げることができる。（式中Ｒ及びＡは、前記と同じ意味を表す。）
（１）下記に式２，７−ジブロモフルオレンの臭素原子をアルコキシ基に置換した後、酸化して２，７−ジアルコキシ−９−フルオレノンとし、その後アニリン誘導体と縮合して９，９−ビス(４−アミノフェニル)−２，７−ジアルコキシフルオレン化合物を得る方法（下記反応式参照）、

Figure 2008081418
Examples of the method for synthesizing the 9,9-bis (4-aminophenyl) fluorene compound represented by the general formula (1) of the present invention include the following methods (1) to (3). (Wherein R and A represent the same meaning as described above.)
(1) Substitution of the bromine atom of the formula 2,7-dibromofluorene with an alkoxy group below, followed by oxidation to 2,7-dialkoxy-9-fluorenone, followed by condensation with an aniline derivative, 9,9-bis A method of obtaining (4-aminophenyl) -2,7-dialkoxyfluorene compound (see the following reaction formula),
Figure 2008081418

（２）９，９−ビス(４−アミノフェニル)−２，７−ジブロモフルオレンの臭素原子をアルコキシ基に置換して９，９−ビス(４−アミノフェニル)−２，７−ジアルコキシフルオレン化合物を得る方法、及び

Figure 2008081418
(2) 9,9-bis (4-aminophenyl) -2,7-dialkoxyfluorene by replacing the bromine atom of 9,9-bis (4-aminophenyl) -2,7-dibromofluorene with an alkoxy group A method of obtaining a compound, and
Figure 2008081418

（３）９，９−ビス(４−アミノフェニル)−２，７−ジヒドロキシフルオレンの水酸基をハロゲン化アルキルやアルキル硫酸等で処理して９，９−ビス(４−アミノフェニル)−２，７−ジアルコキシフルオレン化合物を得る方法。 (3) 9,9-bis (4-aminophenyl) -2,7 by treating the hydroxyl group of 9,9-bis (4-aminophenyl) -2,7-dihydroxyfluorene with an alkyl halide, alkylsulfuric acid or the like. A method for obtaining a dialkoxyfluorene compound.

以下に実施例によって本発明をさらに詳細に説明するが、本発明はこれらの例によって何ら制限されるものではない。   The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

（実施例１）
９，９−ビス（４−アミノフェニル）−２，７−ジブロモフルオレンから９，９−ビス（４−アミノフェニル）−２，７−ジメトキシフルオレンの合成：
３００ｍｌに４首フラスコにメタノール５０ｍｌを入れ、氷冷下ナトリウムメトキシド１２．７ｇ(２３０ミリモル)を加え溶解させ、ピリジン１００ｍｌを加えた。この液に、Bo Liら、Polymer Preprints, 41 [1], 105 (2000)に記載の方法で調製した９，９−ビス（４−アミノフェニル）−２，７−ジブロモフルオレン１０ｇ(１９．７ミリモル)とヨウ化銅（Ｉ）７．５ｇ(３９．３ミリモル)を加え、還流下１５時間攪拌した。反応液を室温まで冷却し、反応液を水２００ｍｌ中に注ぎ、クロロホルム２００ｍｌを加え、不溶物を吸引濾過で濾別した。得られた濾液を分液して有機層を回収し、水２００ｍｌで４回洗浄した。その後無水硫酸マグネシウムで脱水した後、濃縮乾固した。乾固物をシリカゲルクロマトグラフ(溶媒クロロホルム)で精製し薄黄色固体１．２５ｇを得た。収率は１６％であった。得られた薄黄色固体の分析結果を下記に示す。１Ｈ−ＮＭＲ分析チャートを図１に示した。
スペクトル
（ａ）１Ｈ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ３）
δ:3.83(s,6H)、6.51(d,J=8.1Hz,4H)、6.86-6.80(m,4H) 6.96(d,J=8.7Hz,4H)、7.51(d, J=8.1Hz,2H)、
（ｂ）質量スペクトル ＥＳＩ＋ ４０９（Ｍ＋１）＋
（ｃ）融点 ＤＳＣ １１８．２℃ (Example 1)
Synthesis of 9,9-bis (4-aminophenyl) -2,7-dimethoxyfluorene from 9,9-bis (4-aminophenyl) -2,7-dibromofluorene:
To 300 ml, 50 ml of methanol was placed in a four-necked flask, 12.7 g (230 mmol) of sodium methoxide was added and dissolved under ice cooling, and 100 ml of pyridine was added. To this solution, 10 g (19.7) of 9,9-bis (4-aminophenyl) -2,7-dibromofluorene prepared by the method described in Bo Li et al., Polymer Preprints, 41 [1], 105 (2000). Mmol) and 7.5 g (39.3 mmol) of copper (I) iodide were added, and the mixture was stirred for 15 hours under reflux. The reaction solution was cooled to room temperature, poured into 200 ml of water, 200 ml of chloroform was added, and insoluble matters were separated by suction filtration. The obtained filtrate was separated, and the organic layer was collected and washed four times with 200 ml of water. Thereafter, it was dehydrated with anhydrous magnesium sulfate and concentrated to dryness. The dried product was purified by silica gel chromatography (solvent chloroform) to obtain 1.25 g of a light yellow solid. The yield was 16%. The analysis result of the obtained pale yellow solid is shown below. The 1 H-NMR analysis chart is shown in FIG.
Spectrum (a) 1 H-NMR (300 MHz, solvent CDCl 3 )
δ: 3.83 (s, 6H), 6.51 (d, J = 8.1Hz, 4H), 6.86-6.80 (m, 4H) 6.96 (d, J = 8.7Hz, 4H), 7.51 (d, J = 8.1Hz, 2H),
(B) Mass spectrum ESI + 409 (M + 1) +
(C) Melting point DSC 118.2 ° C

（実施例２）
（１）２，７−ジメトキシフルオレンから２，７−ジメトキシ−９−フルオレノンの合成
２５ｍｌのナスフラスコにHe1mut G. A1tら、Journal of Organometa11ic Chemistry, 552, 39 (1996)に記載の方法で調製した２，７−ジメトキシフルオレン２００ｍｇ(０．８８ミリモル)を仕込み、ジメチルスルホキシド８．８ｍｌを加えて溶解し、ナトリウムメトキシド４７ｍｇ(０．８８ミリモル)を加え、空気を吹き込み室温で１時間攪拌した。反応液に水１５ｍｌ、飽和食塩水５ｍｌを加え、酢酸エチル２０ｍｌで抽出した。有機層を水５ｍｌで３回洗浄、無水硫酸マグネシウムで脱水し、減圧下で濃縮乾固した。乾固物を薄層クロマトグラフィー(ヘキサン/酢酸エチル:３／１)で精製し、９０ｍｇの燈色固体を得た収率は４２％であった。得られた燈色固体のＮＭＲ分析結果を下記に示す。
１Ｈ−ＮＭＲ分析チャートを図２に示した。
スペクトル
（ａ）１Ｈ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ３）
δ:3.83(s,6H)、6.93(dd,J=2.4,8.1Hz,2H)、7.16(d,J=2.4Hz,2H)、7.28(d,J=8.4Hz,2H) (Example 2)
(1) Synthesis of 2,7-dimethoxy-9-fluorenone from 2,7-dimethoxyfluorene A 25 ml eggplant flask was prepared by the method described in He1mut G. A1t et al., Journal of Organometa11ic Chemistry, 552 , 39 (1996). 200 mg (0.88 mmol) of 2,7-dimethoxyfluorene was charged, 8.8 ml of dimethyl sulfoxide was added and dissolved, 47 mg (0.88 mmol) of sodium methoxide was added, air was blown in, and the mixture was stirred at room temperature for 1 hour. 15 ml of water and 5 ml of saturated brine were added to the reaction solution, and the mixture was extracted with 20 ml of ethyl acetate. The organic layer was washed 3 times with 5 ml of water, dehydrated with anhydrous magnesium sulfate, and concentrated to dryness under reduced pressure. The dried product was purified by thin layer chromatography (hexane / ethyl acetate: 3/1) to obtain 90 mg of amber solid. The yield was 42%. The NMR analysis result of the obtained amber solid is shown below.
The 1 H-NMR analysis chart is shown in FIG.
Spectrum (a) 1 H-NMR (300 MHz, solvent CDCl 3 )
δ: 3.83 (s, 6H), 6.93 (dd, J = 2.4, 8.1Hz, 2H), 7.16 (d, J = 2.4Hz, 2H), 7.28 (d, J = 8.4Hz, 2H)

（２）２，７−ジメトキシ−９−フルオレノンから９，９−ビス(４−アミノフェニル)−２，７−ジメトキシフルオレンの合成
１０ｍｌのナスフラスコに２，７−ジメトキシ−９−フルオレノン２００ｍｇ(０．８３ミリモル)、アニリン塩酸塩１６０ｍｇ(１．２３ミリモル)を仕込み、アニリン１．１ｍｌを加えて溶解し、１５０℃で９時間攪拌した。室温まで放冷した後、水５ｍｌ、飽和食塩水５ｍｌを加え、酢酸エチル１０ｍｌで抽出した有機層を無水硫酸マグネシウムで脱水し、減圧下で濃縮乾固した。乾固物にジエチルエーテルを加え、析出した固体を、吸引濾過で慮別し、５０℃で減圧乾燥し、１３０ｍｇの紫色固体を得た。収率は３８％であった。得られた固体の１Ｈ−ＮＭＲスペクトルは図１と同一であった。 (2) Synthesis of 9,9-bis (4-aminophenyl) -2,7-dimethoxyfluorene from 2,7-dimethoxy-9-fluorenone 200 mg (0 mg of 2,7-dimethoxy-9-fluorenone in a 10 ml eggplant flask .83 mmol) and 160 mg (1.23 mmol) of aniline hydrochloride were added, 1.1 ml of aniline was added and dissolved, and the mixture was stirred at 150 ° C. for 9 hours. After allowing to cool to room temperature, 5 ml of water and 5 ml of saturated brine were added, and the organic layer extracted with 10 ml of ethyl acetate was dehydrated with anhydrous magnesium sulfate and concentrated to dryness under reduced pressure. Diethyl ether was added to the dried product, and the precipitated solid was collected by suction filtration and dried under reduced pressure at 50 ° C. to obtain 130 mg of a purple solid. The yield was 38%. The 1 H-NMR spectrum of the obtained solid was the same as FIG.

本発明により、ポリアミド、ポリイミドの原料として有用な新規な９，９−ビス（４−アミノフェニル）フルオレン化合物が提供される。
本発明により機械的強度、耐熱性、光学特性、加工性等に優れたポリアミドおよびポリイミドを製造することが可能な、フルオレン骨格を持ちハロゲンを含有しない新規なジアミンが提供される。 The present invention provides a novel 9,9-bis (4-aminophenyl) fluorene compound useful as a raw material for polyamide and polyimide.
The present invention provides a novel diamine having a fluorene skeleton and containing no halogen, which can produce polyamides and polyimides excellent in mechanical strength, heat resistance, optical properties, workability, and the like.

実施例１で得られた９，９−ビス（４−アミノフェニル）−２，７−ジメトキシフルオレンの１Ｈ−ＮＭＲスペクトルである。1 is a 1 H-NMR spectrum of 9,9-bis (4-aminophenyl) -2,7-dimethoxyfluorene obtained in Example 1. 実施例２で得られた２，７−ジメトキシ−９−フルオレノンの１Ｈ−ＮＭＲスペクトルである。2 is a 1 H-NMR spectrum of 2,7-dimethoxy-9-fluorenone obtained in Example 2.

Claims (3)

下記一般式（１）で表される構造を有する９，９−ビス（４−アミノフェニル）フルオレン化合物。
Figure 2008081418
 （式中、Ｒは炭素数１〜４のアルキル基を表し、Ａは水素、炭素数１〜３のアルキル基を表す。） A 9,9-bis (4-aminophenyl) fluorene compound having a structure represented by the following general formula (1).
Figure 2008081418
 (In the formula, R represents an alkyl group having 1 to 4 carbon atoms, A represents hydrogen and an alkyl group having 1 to 3 carbon atoms.) 下記式（２）で表される９，９−ビス(４−アミノフェニル)−２，７−ジブロモフルオレンの臭素原子を炭素数１〜４のアルコキシ基に置換することによって請求項１に記載の９，９−ビス(４−アミノフェニル)−２，７−ジアルコキシフルオレン化合物を製造する方法。
Figure 2008081418
 （式中、Ａは水素、炭素数１〜３のアルキル基を表す。） The 9-bis (4-aminophenyl) -2,7-dibromofluorene represented by the following formula (2) is substituted with an alkoxy group having 1 to 4 carbon atoms according to claim 1. A method for producing a 9,9-bis (4-aminophenyl) -2,7-dialkoxyfluorene compound.
Figure 2008081418
 (In the formula, A represents hydrogen or an alkyl group having 1 to 3 carbon atoms.) 下記式（３）で表される２，７−ジアルコキシ−９−フルオレノンをアニリン誘導体と縮合させることによって、請求項１に記載の９，９−ビス(４−アミノフェニル)−２，７−ジアルコキシフルオレン化合物を製造する方法。
Figure 2008081418
 （式中、Ｒは炭素数１〜４のアルキル基を表す。） The 9,9-bis (4-aminophenyl) -2,7- according to claim 1, wherein 2,7-dialkoxy-9-fluorenone represented by the following formula (3) is condensed with an aniline derivative. A method for producing a dialkoxyfluorene compound.
Figure 2008081418
 (In the formula, R represents an alkyl group having 1 to 4 carbon atoms.)
JP2006260827A 2006-09-26 2006-09-26 9,9-bis(4-aminophenyl)fluorene compound Pending JP2008081418A (en)

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JPWO2016140245A1 (en) * 2015-03-02 2017-12-21 富士フイルム株式会社 Curable composition, cured product, optical member, lens and compound
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JP2019131571A (en) * 2015-03-02 2019-08-08 富士フイルム株式会社 Curable composition, cured product, optical member, lens, and compound
US10604623B2 (en) 2016-02-24 2020-03-31 Fujifilm Corporation Polycarbonate resin, molded article, optical member, and lens
CN110437078A (en) * 2019-08-30 2019-11-12 常州市阳光药业有限公司 The preparation method of bis- [4- aminophenyl] fluorene derivatives of 9,9-

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