JP2002255929A - Bis(hydroxyphenylthio)fluorene compound and method for producing the same - Google Patents
Bis(hydroxyphenylthio)fluorene compound and method for producing the sameInfo
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- JP2002255929A JP2002255929A JP2001052214A JP2001052214A JP2002255929A JP 2002255929 A JP2002255929 A JP 2002255929A JP 2001052214 A JP2001052214 A JP 2001052214A JP 2001052214 A JP2001052214 A JP 2001052214A JP 2002255929 A JP2002255929 A JP 2002255929A
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- Prior art keywords
- bis
- hydroxyphenylthio
- fluorene compound
- producing
- compound
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はビス（ヒドロキシフ
ェニルチオ）フルオレン化合物及びその製造方法に関す
る。The present invention relates to a bis (hydroxyphenylthio) fluorene compound and a method for producing the same.
【０００２】[0002]
【従来の技術】ビス（ヒドロキシフェニル）フルオレン
等の、フルオレン骨格をもち官能基として水酸基をする
化合物は、耐熱性が高い、高屈折率である、収縮率が小
さいといった特長を有しており、エポキシ樹脂、アクリ
ル樹脂、ポリエステル、ポリウレタン、ポリカーボネー
ト、ポリアリレート等の樹脂原料や、酸化防止剤等の樹
脂添加剤、エポキシ樹脂の硬化剤として用いられてい
る。しかしながら、耐熱樹脂用途や光学材料用途の高機
能な材料として用いるためには、耐熱温度、屈折率向上
の点で、さらなる改善が望まれている。2. Description of the Related Art Compounds having a fluorene skeleton and having a hydroxyl group as a functional group, such as bis (hydroxyphenyl) fluorene, have the characteristics of high heat resistance, high refractive index, and low shrinkage. It is used as a resin raw material such as an epoxy resin, an acrylic resin, polyester, polyurethane, polycarbonate, and polyarylate, as a resin additive such as an antioxidant, and as a curing agent for an epoxy resin. However, in order to use it as a high-performance material for heat-resistant resins and optical materials, further improvements are desired in terms of heat-resistant temperature and refractive index.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、樹脂原料、
酸化防止剤、硬化剤などの用途に適した、耐熱性、高屈
折率材料として優れた性能を有する新規なフルオレン化
合物及びその製造方法を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention relates to a resin raw material,
An object of the present invention is to provide a novel fluorene compound suitable for applications such as an antioxidant and a curing agent and having excellent performance as a heat-resistant, high-refractive-index material, and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明は、以下のビス
（ヒドロキシフェニルチオ）フルオレン化合物及びその
製造方法に関する。 項１ 一般式（Ｉ）SUMMARY OF THE INVENTION The present invention relates to the following bis (hydroxyphenylthio) fluorene compound and a method for producing the same. Item 1. General formula (I)
【０００５】[0005]
【化３】 Embedded image
【０００６】〔式中、Ｒ1、Ｒ2、Ｒ3及びＲ4は、同一又
は異なって、水素原子又はＣ１〜Ｃ６の直鎖状乃至分岐
状のアルキル基を示す。ｎは、０〜１０の整数を示
す。〕で表されることを特徴とするビス（ヒドロキシフ
ェニルチオ）フルオレン化合物。 項２ Ｒ1、Ｒ2、Ｒ3及びＲ4が水素原子であり、ｎが０
である項１に記載のビス（ヒドロキシフェニルチオ）フ
ルオレン化合物。 項３ 酸性下でフルオレノン（１）とメルカプトフェノ
ール類（２）とを反応させることを特徴とする一般式
（Ｉ）で表されるビス（ヒドロキシフェニルチオ）フル
オレン化合物の製造方法。[Wherein, R 1 , R 2 , R 3 and R 4 are the same or different and each represent a hydrogen atom or a C 1 -C 6 linear or branched alkyl group. n shows the integer of 0-10. And a bis (hydroxyphenylthio) fluorene compound represented by the formula: Item 2: R 1 , R 2 , R 3 and R 4 are hydrogen atoms, and n is 0
Item 2. The bis (hydroxyphenylthio) fluorene compound according to item 1, wherein Item 3. A method for producing a bis (hydroxyphenylthio) fluorene compound represented by the general formula (I), wherein fluorenone (1) and a mercaptophenol (2) are reacted under acidity.
【０００７】[0007]
【化４】 Embedded image
【０００８】〔式中、Ｒ1、Ｒ2、Ｒ3及びＲ4は、同一又
は異なって、水素原子又はＣ１〜Ｃ６の直鎖状乃至分岐
状のアルキル基を示す。ｎは、０〜１０の整数を示
す。〕項４ 反応温度を１０℃以下として反応させるこ
とを特徴とする項３に記載のビス（ヒドロキシフェニル
チオ）フルオレン化合物の製造方法。[Wherein R 1 , R 2 , R 3 and R 4 are the same or different and each represent a hydrogen atom or a C 1 -C 6 linear or branched alkyl group. n shows the integer of 0-10. Item 4. The process for producing a bis (hydroxyphenylthio) fluorene compound according to Item 3, wherein the reaction is carried out at a reaction temperature of 10 ° C. or lower.
【０００９】[0009]
【発明の実施の形態】本発明において、Ｃ１〜Ｃ６アル
キル基としては、メチル、エチル、ｎ−プロピル、イソ
プロピル、ｎ−ブチル、イソブチル、ｓｅｃ−ブチル、
ｔｅｒｔ−ブチル、ペンチル、ヘキシルなどの直鎖また
は分枝を有するアルキル基が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the C 1 -C 6 alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
Examples thereof include linear or branched alkyl groups such as tert-butyl, pentyl, and hexyl.
【００１０】ｎは０〜１０で、好ましくは０〜６程度
で、さらに好ましくは０〜２である。N is 0 to 10, preferably about 0 to 6, and more preferably 0 to 2.
【００１１】一般式（Ｉ）で示される化合物としては、
Ｒ1、Ｒ2、Ｒ3及びＲ4がいずれも水素原子であって、ｎ
が０又は１の化合物が好ましい。The compound represented by the general formula (I) includes
R 1 , R 2 , R 3 and R 4 are all hydrogen atoms and n
Are preferably 0 or 1.
【００１２】より具体的には、ビス（ヒドロキシフェニ
ルチオ）フルオレン、ビス｛（２−ヒドロキシエトキ
シ）フェニルチオ｝フルオレンが好ましい化合物として
挙げられる。More specifically, bis (hydroxyphenylthio) fluorene and bis {(2-hydroxyethoxy) phenylthio} fluorene are preferred compounds.
【００１３】一般式（Ｉ）で示される化合物は、下記の
＜反応工程式＞に従って製造することができる。 ＜反応工程式＞The compound represented by the general formula (I) can be produced according to the following <reaction scheme>. <Reaction process formula>
【００１４】[0014]
【化５】 Embedded image
【００１５】〔式中、Ｒ1、Ｒ2、Ｒ3及びＲ4及びｎは、
上記に定義した通りである。〕 反応は、溶媒の存在下でも無溶媒でも可能であるが、溶
媒を用いる場合は、トルエン、キシレン、ベンゼンなど
の芳香族炭化水素を用いることができる。溶媒の使用量
は、特に限定されず適宜設定することができるが、通
常、フルオレノン（１）１ｇに対して０．１〜５０ｍｌ
程度である。反応の雰囲気としては、窒素、アルゴン等
の不活性ガス雰囲気が好ましい。反応はフルオレノン化
合物（１）１モルに対しメルカプトフェノール類（２）
２〜４モル程度用いて、酸として硫酸、塩酸、塩酸ガ
ス、ｐ−トルエンスルホン酸、メタンスルホン酸などを
適量使用して行うことができる。反応温度は、通常８０
℃以下であり、反応温度としては室温以下が好ましく、
１０℃以下がさらに好ましい。Wherein R 1 , R 2 , R 3 and R 4 and n are
As defined above. The reaction can be carried out in the presence or absence of a solvent, but when a solvent is used, aromatic hydrocarbons such as toluene, xylene and benzene can be used. The amount of the solvent to be used is not particularly limited and can be appropriately set, but is usually 0.1 to 50 ml per 1 g of fluorenone (1).
It is about. As the reaction atmosphere, an inert gas atmosphere such as nitrogen or argon is preferable. The reaction was carried out with 1 mole of the fluorenone compound (1) and mercaptophenols (2)
Using about 2 to 4 moles, sulfuric acid, hydrochloric acid, hydrochloric acid gas, p-toluenesulfonic acid, methanesulfonic acid and the like can be used in an appropriate amount as an acid. The reaction temperature is usually 80
° C. or less, the reaction temperature is preferably room temperature or less,
10 ° C. or lower is more preferable.
【００１６】反応生成物である一般式（Ｉ）の化合物
は、通常の分離、精製手段、例えば再結晶、溶媒抽出
法、カラムクロマトグラフィー法等を用いて、容易に単
離、精製することができる。The compound of the formula (I), which is a reaction product, can be easily isolated and purified by usual separation and purification means, for example, recrystallization, solvent extraction, column chromatography and the like. it can.
【００１７】本発明の化合物の用途としては、硫黄原子
を分子骨格に有していることから高耐熱性、高屈折率の
特長を有するエポキシ樹脂、アクリル樹脂、ポリエステ
ル、ポリウレタン、ポリカーボネート、ポリアリレート
等の樹脂原料や、酸化防止剤等の樹脂添加剤、エポキシ
樹脂の硬化剤として好ましく用いられる。The compound of the present invention can be used as an epoxy resin, an acrylic resin, a polyester, a polyurethane, a polycarbonate, a polyarylate, etc. having high heat resistance and a high refractive index because of having a sulfur atom in a molecular skeleton. Resin raw materials, resin additives such as antioxidants, and curing agents for epoxy resins.
【００１８】[0018]
【発明の効果】本発明の化合物は、硫黄原子を分子骨格
に有しているので、従来の硫黄原子を分子骨格に有しな
いビスフェノールフルオレン類よりも耐熱性及び屈折率
が向上する。Since the compound of the present invention has a sulfur atom in the molecular skeleton, heat resistance and refractive index are improved as compared with conventional bisphenolfluorenes having no sulfur atom in the molecular skeleton.
【００１９】[0019]
【実施例】次に実施例により本発明をさらに詳細に説明
するが、本発明はこれら実施例によって何ら限定される
ものではない。 実施例１ ３００ｍｌの４つ口フラスコをアルゴン雰囲気とし、フ
ルオレノン４．５ｇ（０．０２５ｍｏｌ）、ｐ−メルカ
プトフェノール１２．６ｇ（０．１ｍｏｌ）、トルエン
５０ｍｌを加えて、容器内を０℃に保持して攪拌し、濃
硫酸４ｍｌを加えて３時間反応させた。その後、５０ｍ
ｌの蒸留水を滴下して、濾過し、固形分１５．８ｇを酢
酸エチル３０ｍｌで再結晶して、固形分を乾燥し、生成
物７．６ｇを得た。得られた生成物の液体クロマトグラ
フィーによる純度は９９．１％であった。分析結果を、
下記に、及び図１〜４に示す。 MSスペクトル分子イオンピーク；M/Z＝４１４（M/Z＝２
８９に認められたピークは、目的物のフラグメントイオ
ンのもの） 赤外線吸収スペクトル（cm-1）； O-H伸縮振動：3400〜3200付近 芳香族C-H伸縮振動：3100〜3000 芳香族カルボン酸C=O伸縮振動：1695 ベンゼン環骨格振動：1600（２本）及び1492 フルオレン骨格振動：1434，742 フェノール又は芳香族カルボン酸のC-O伸縮振動又はO-H
変角振動：1370付近 芳香族カルボン酸C-O伸縮振動、またはO-H変角振動：12
78 フェノールのC-O伸縮振動、またはO-H変角振動：1230 p-二置換ベンゼンのC-H面内変角振動：1168,1093,1041 p-二置換ベンゼンのC-H面外変角振動：8351 H-NMR（d-8テトラヒドロフラン、270MHz）のスペクト
ルにおいて、6.4〜7.5ppmに芳香族のピークと8.4ppmに
一重線の会合したOH基のピークが観測された。不純物と
して、目的物を合成する際に溶剤として用いた酢酸エチ
ルのピークが観測された。13C-NMR（d-8テトラヒドロフ
ラン、270MHz）のスペクトルにおいて、酢酸エチルのピ
ーク以外に、116〜160ppmに10本の芳香族のピークと68.
8ppmには四級脂肪族炭素によるピークが見られた。Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention. Example 1 A 300 ml four-necked flask was set to an argon atmosphere, and 4.5 g (0.025 mol) of fluorenone, 12.6 g (0.1 mol) of p-mercaptophenol, and 50 ml of toluene were added, and the inside of the vessel was kept at 0 ° C. Then, 4 ml of concentrated sulfuric acid was added and reacted for 3 hours. Then 50m
l of distilled water was added dropwise, filtered, and 15.8 g of solid was recrystallized with 30 ml of ethyl acetate, and the solid was dried to obtain 7.6 g of product. The purity of the obtained product by liquid chromatography was 99.1%. Analysis results
Shown below and in FIGS. MS spectrum molecular ion peak; M / Z = 414 (M / Z = 2
Infrared absorption spectrum (cm -1 ); OH stretching vibration: around 3400-3200 Aromatic CH stretching vibration: 3100-3000 Aromatic carboxylic acid C = O stretching Vibration: 1695 Benzene ring skeleton vibration: 1600 (two) and 1492 fluorene skeleton vibration: 1434, 742 CO stretching vibration of phenol or aromatic carboxylic acid or OH
Deflection vibration: around 1370 CO stretching vibration of aromatic carboxylic acid or OH deflection vibration: 12
78 CO stretching vibration of phenol or OH bending vibration: 1230 p-disubstituted benzene in-plane bending vibration: 1168,1093,1041 p-disubstituted benzene out-of-plane bending vibration: 835 1 H-NMR In the spectrum of (d-8 tetrahydrofuran, 270 MHz), an aromatic peak was observed at 6.4 to 7.5 ppm, and a singlet associated OH group peak was observed at 8.4 ppm. As an impurity, a peak of ethyl acetate used as a solvent in synthesizing the target product was observed. In the spectrum of 13 C-NMR (d-8 tetrahydrofuran, 270 MHz), in addition to the peak of ethyl acetate, 10 aromatic peaks at 116 to 160 ppm and 68.
At 8 ppm, a peak due to quaternary aliphatic carbon was observed.
【００２０】得られた生成物０．１ｇをテトラヒドロフ
ラン５ｍｌに溶解させ、該溶液の屈折率をアッベ屈折計
を用いてASTM D542に従って測定した（20℃）。測定し
た結果、THF溶液中での屈折率は1.412であり、得られた
生成物の屈折率が1.77であることが計算により求められ
た。0.1 g of the obtained product was dissolved in 5 ml of tetrahydrofuran, and the refractive index of the solution was measured using an Abbe refractometer according to ASTM D542 (at 20 ° C.). As a result of the measurement, the refractive index in the THF solution was found to be 1.412, and the refractive index of the obtained product was found to be 1.77.
【図１】 実施例１で得られた化合物のＭＳスペクトル
を示す図である。FIG. 1 is a diagram showing an MS spectrum of the compound obtained in Example 1.
【図２】 実施例１で得られた化合物の赤外線吸収スペ
クトルを示す図である。FIG. 2 is a view showing an infrared absorption spectrum of the compound obtained in Example 1.
【図３】 実施例１で得られた化合物の1Ｈ−NMRのスペ
クトル（THF、270MHz）を示す図である。FIG. 3 is a chart showing 1 H-NMR spectrum (THF, 270 MHz) of the compound obtained in Example 1.
【図４】 実施例１で得られた化合物の13Ｃ−NMRのス
ペクトル（THF、270MHz）を示す図である。4 is a chart showing 13 C-NMR spectrum (THF, 270 MHz) of the compound obtained in Example 1. FIG.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｇ 63/68 Ｃ０８Ｇ 63/68 64/08 64/08 (72)発明者 山田 光昭 大阪府大阪市中央区平野町四丁目１番２号 大阪瓦斯株式会社内 Ｆターム(参考） 4H006 AA01 AA02 AB46 AB48 AB49 AB83 AC63 BC10 TA04 TB42 TB72 TC11 TC32 4J029 AA03 AA04 AA10 AB07 AC01 AC02 BF26 BH02 DB05 JE182 4J034 CA04 CB03 CC12 CC23 CC26 CC46 CC54 CC62 CC68 CD08 DC02 DC07 DC12 DC36 DC39 DC43 DD03 4J036 AJ01 AJ19 DD01 4J100 AL66P BA02P BA08P BA51P BC36P BC43P CA01 CA04──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification code FI Theme coat ゛ (Reference) C08G 63/68 C08G 63/68 64/08 64/08 (72) Inventor Mitsuaki Yamada Chuo-ku, Osaka-shi, Osaka 4-1-2 Hiranocho Osaka Gas Co., Ltd. F-term (reference) 4H006 AA01 AA02 AB46 AB48 AB49 AB83 AC63 BC10 TA04 TB42 TB72 TC11 TC32 4J029 AA03 AA04 AA10 AB07 AC01 AC02 BF26 BH02 DB05 JE182 4J034 CA04 CB03 CC12 CC23 CC23 CC54 CC62 CC68 CD08 DC02 DC07 DC12 DC36 DC39 DC43 DD03 4J036 AJ01 AJ19 DD01 4J100 AL66P BA02P BA08P BA51P BC36P BC43P CA01 CA04
Claims (4)
水素原子又はＣ１〜Ｃ６の直鎖状乃至分岐状のアルキル
基を示す。ｎは、０〜１０の整数を示す。〕で表される
ことを特徴とするビス（ヒドロキシフェニルチオ）フル
オレン化合物。1. A compound of the general formula (I) Wherein R 1 , R 2 , R 3 and R 4 are the same or different,
It represents a linear or branched alkyl group of which a hydrogen atom or a C 1 -C 6. n shows the integer of 0-10. And a bis (hydroxyphenylthio) fluorene compound represented by the formula:
ｎが０である請求項１に記載のビス（ヒドロキシフェニ
ルチオ）フルオレン化合物。2. A method according to claim 1 , wherein R 1 , R 2 , R 3 and R 4 are hydrogen atoms.
The bis (hydroxyphenylthio) fluorene compound according to claim 1, wherein n is 0.
フェノール類（２）とを反応させることを特徴とする一
般式（Ｉ）で表されるビス（ヒドロキシフェニルチオ）
フルオレン化合物の製造方法。 【化２】 〔式中、Ｒ1、Ｒ2、Ｒ3及びＲ4は、同一又は異なって、
水素原子又はＣ１〜Ｃ６の直鎖状乃至分岐状のアルキル
基を示す。ｎは、０〜１０の整数を示す。〕3. Bis (hydroxyphenylthio) represented by the general formula (I), wherein fluorenone (1) is reacted with mercaptophenols (2) under acidic conditions.
A method for producing a fluorene compound. Embedded image Wherein R 1 , R 2 , R 3 and R 4 are the same or different,
It represents a linear or branched alkyl group of which a hydrogen atom or a C 1 -C 6. n shows the integer of 0-10. ]
とを特徴とする請求項３に記載のビス（ヒドロキシフェ
ニルチオ）フルオレン化合物の製造方法。4. The method for producing a bis (hydroxyphenylthio) fluorene compound according to claim 3, wherein the reaction is carried out at a reaction temperature of 10 ° C. or lower.
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| JP2008111138A (en) * | 2008-01-31 | 2008-05-15 | Osaka Gas Co Ltd | Fluorene-containing resin |
| JP2009179568A (en) * | 2008-01-29 | 2009-08-13 | Nippon Shokubai Co Ltd | Aromatic backbone-containing alicyclic epoxy compound, method for producing the same, aromatic backbone-containing alicyclic epoxy resin composition, and molded article and optical member of the same |
| JP2013213030A (en) * | 2012-03-09 | 2013-10-17 | Osaka Gas Chem Kk | Polycarboxylic acid having florene skeleton and method for producing the same |
| WO2014157674A1 (en) | 2013-03-29 | 2014-10-02 | 東京応化工業株式会社 | Compound containing structural unit derived from vinyl ether compound |
| WO2014157676A1 (en) | 2013-03-29 | 2014-10-02 | 東京応化工業株式会社 | Vinyl-group-containing fluorene compound |
| WO2014157675A1 (en) | 2013-03-29 | 2014-10-02 | 東京応化工業株式会社 | Composition containing vinyl-group-containing compound |
| JP2014208605A (en) * | 2013-03-25 | 2014-11-06 | 大阪ガスケミカル株式会社 | Sulfur-containing fluorene compound |
| JP2015160914A (en) * | 2014-02-27 | 2015-09-07 | Jsr株式会社 | Polymer, compound, resin composition, resin pellet and resin molding |
| KR101760170B1 (en) | 2015-01-28 | 2017-07-21 | 삼성에스디아이 주식회사 | Novel fluorene-containing (meth)acrylic compound, curable composition comprising the same, optical sheet prepared therefrom, and optical display apparatus comprising the same |
| WO2023011307A1 (en) * | 2021-08-06 | 2023-02-09 | 中国科学院过程工程研究所 | Polycarbonate and preparation method therefor and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60188364A (en) * | 1984-02-03 | 1985-09-25 | チバ−ガイギ− アクチエンゲゼルシヤフト | Di-(substituted hydroxyphenylthio)alkane or cycloalkane stabilizer and composition stabilized therewith |
| JPH0980792A (en) * | 1995-09-14 | 1997-03-28 | Canon Inc | Electrophotographic photoreceptor, process cartridge having the same, and electrophotographic apparatus |
| JPH0990648A (en) * | 1995-09-27 | 1997-04-04 | Canon Inc | Electrophotographic photoreceptor and process cartridge and electrophotographic device |
| JP2000508003A (en) * | 1996-03-21 | 2000-06-27 | ビーエスアイ コーポレイション | Photoactivated chain transfer agent |
| WO2001040175A1 (en) * | 1999-12-02 | 2001-06-07 | Tokuyama Corporation | Process for production of sulfur compounds |
| JP2001316355A (en) * | 1999-06-16 | 2001-11-13 | Mitsui Chemicals Inc | Sulfur-containing unsaturated carboxylic ester compound and use thereof |
-
2001
- 2001-02-27 JP JP2001052214A patent/JP4596663B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60188364A (en) * | 1984-02-03 | 1985-09-25 | チバ−ガイギ− アクチエンゲゼルシヤフト | Di-(substituted hydroxyphenylthio)alkane or cycloalkane stabilizer and composition stabilized therewith |
| JPH0980792A (en) * | 1995-09-14 | 1997-03-28 | Canon Inc | Electrophotographic photoreceptor, process cartridge having the same, and electrophotographic apparatus |
| JPH0990648A (en) * | 1995-09-27 | 1997-04-04 | Canon Inc | Electrophotographic photoreceptor and process cartridge and electrophotographic device |
| JP2000508003A (en) * | 1996-03-21 | 2000-06-27 | ビーエスアイ コーポレイション | Photoactivated chain transfer agent |
| JP2001316355A (en) * | 1999-06-16 | 2001-11-13 | Mitsui Chemicals Inc | Sulfur-containing unsaturated carboxylic ester compound and use thereof |
| WO2001040175A1 (en) * | 1999-12-02 | 2001-06-07 | Tokuyama Corporation | Process for production of sulfur compounds |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003026654A (en) * | 2001-07-10 | 2003-01-29 | Osaka Gas Co Ltd | Bis(halogen-substituted phenylthio)fluorene compound and method for manufacturing the same |
| JP2009179568A (en) * | 2008-01-29 | 2009-08-13 | Nippon Shokubai Co Ltd | Aromatic backbone-containing alicyclic epoxy compound, method for producing the same, aromatic backbone-containing alicyclic epoxy resin composition, and molded article and optical member of the same |
| JP2008111138A (en) * | 2008-01-31 | 2008-05-15 | Osaka Gas Co Ltd | Fluorene-containing resin |
| JP2013213030A (en) * | 2012-03-09 | 2013-10-17 | Osaka Gas Chem Kk | Polycarboxylic acid having florene skeleton and method for producing the same |
| JP2014208605A (en) * | 2013-03-25 | 2014-11-06 | 大阪ガスケミカル株式会社 | Sulfur-containing fluorene compound |
| US9914687B2 (en) | 2013-03-29 | 2018-03-13 | Tokyo Ohka Kogyo Co., Ltd. | Composition containing vinyl-group-containing compound |
| WO2014157675A1 (en) | 2013-03-29 | 2014-10-02 | 東京応化工業株式会社 | Composition containing vinyl-group-containing compound |
| WO2014157676A1 (en) | 2013-03-29 | 2014-10-02 | 東京応化工業株式会社 | Vinyl-group-containing fluorene compound |
| EP2980057A4 (en) * | 2013-03-29 | 2016-04-13 | Tokyo Ohka Kogyo Co Ltd | Compound containing structural unit derived from vinyl ether compound |
| US9902675B2 (en) | 2013-03-29 | 2018-02-27 | Tokyo Ohka Kogyo Co., Ltd. | Vinyl-group-containing fluorene compound |
| WO2014157674A1 (en) | 2013-03-29 | 2014-10-02 | 東京応化工業株式会社 | Compound containing structural unit derived from vinyl ether compound |
| US10233269B2 (en) | 2013-03-29 | 2019-03-19 | Tokyo Ohka Kogyo Co., Ltd. | Compound containing structural unit derived from vinyl ether compound |
| CN105073699B (en) * | 2013-03-29 | 2019-10-25 | 东京应化工业株式会社 | The compound of structural unit containing derived from ethylene base ether compound |
| JP2015160914A (en) * | 2014-02-27 | 2015-09-07 | Jsr株式会社 | Polymer, compound, resin composition, resin pellet and resin molding |
| KR101760170B1 (en) | 2015-01-28 | 2017-07-21 | 삼성에스디아이 주식회사 | Novel fluorene-containing (meth)acrylic compound, curable composition comprising the same, optical sheet prepared therefrom, and optical display apparatus comprising the same |
| WO2023011307A1 (en) * | 2021-08-06 | 2023-02-09 | 中国科学院过程工程研究所 | Polycarbonate and preparation method therefor and application thereof |
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