JP2003012596A - Method for producing fluorine-containing alicyclic dicarboxylic acid compound - Google Patents
Method for producing fluorine-containing alicyclic dicarboxylic acid compoundInfo
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- JP2003012596A JP2003012596A JP2001196971A JP2001196971A JP2003012596A JP 2003012596 A JP2003012596 A JP 2003012596A JP 2001196971 A JP2001196971 A JP 2001196971A JP 2001196971 A JP2001196971 A JP 2001196971A JP 2003012596 A JP2003012596 A JP 2003012596A
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- Prior art keywords
- dicarboxylic acid
- acid compound
- fluorine
- solvent
- alicyclic dicarboxylic
- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は含フッ素芳香族ジカ
ルボン酸化合物を核水素化して含フッ素脂環式ジカルボ
ン酸化合物を製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a fluorine-containing alicyclic dicarboxylic acid compound by nuclear hydrogenation of a fluorine-containing aromatic dicarboxylic acid compound.
【０００２】[0002]
【従来の技術】フッ素を含有するジカルボン酸化合物
は、例えば電子材料や光学材料用のポリエステル、ポリ
ウレタン、ポリアミド、ポリベンゾオキサゾール、ポリ
アミドイミドおよびエポキシ樹脂等の原料として有用で
ある。2. Description of the Related Art Fluorine-containing dicarboxylic acid compounds are useful as raw materials for polyesters, polyurethanes, polyamides, polybenzoxazoles, polyamideimides and epoxy resins for electronic materials and optical materials.
【０００３】従来、このような用途では例えば２，２−
ビス（４−カルボキシフェニル）−ヘキサフルオロプロ
パン等の芳香族化合物が使用されている。しかし、芳香
環を有する化合物は、一般的に電子密度が高く、その結
果、特に高周波域での誘電率が高いといった欠点や、芳
香環どうしの分子間パッキングが強く、光透過率が低く
なるなどの欠点がある。そこで、芳香環を有しない、例
えば脂環式のジカルボン酸化合物が新規な材料として検
討されている。ただし、このようなフッ素を含有する脂
環式ジカルボン酸化合物を効率よく製造する方法は従来
知られておらず、従って、その効率的な製造方法の開発
が望まれていた。Conventionally, in such applications, for example, 2,2-
Aromatic compounds such as bis (4-carboxyphenyl) -hexafluoropropane have been used. However, a compound having an aromatic ring generally has a high electron density, resulting in a high dielectric constant, especially in a high frequency range, and strong intermolecular packing between aromatic rings, resulting in low light transmittance. There is a drawback of. Therefore, for example, an alicyclic dicarboxylic acid compound having no aromatic ring has been studied as a novel material. However, a method for efficiently producing such an alicyclic dicarboxylic acid compound containing fluorine has not heretofore been known, and therefore, the development of an efficient production method thereof has been desired.
【０００４】[0004]
【発明が解決しようとする課題】本発明は上記の問題を
解決し、電子材料として例えば半導体用の低誘電性パッ
ケージ材料や基板材料、あるいは光学材料として例えば
光導波路や光部品などの分野に有用な含フッ素脂環式ジ
カルボン酸化合物を、簡便に効率よく製造する方法を提
供することを目的とする。The present invention solves the above problems and is useful in the field of electronic materials such as low dielectric packaging materials for semiconductors and substrate materials, or optical materials such as optical waveguides and optical components. Another object of the present invention is to provide a method for producing a simple and efficient fluorinated alicyclic dicarboxylic acid compound.
【０００５】[0005]
【課題を解決するための手段】本発明者らは上記課題を
解決するため鋭意検討を行った結果、特定の水素化触媒
および反応溶媒を使用し、含フッ素芳香族化合物を核水
素化することにより、また、この反応液を特定の方法で
精製することにより、容易に含フッ素脂環式ジカルボン
酸化合物を製造できることを見出し本発明を完成した。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a specific hydrogenation catalyst and a reaction solvent are used to nuclear hydrogenate a fluorine-containing aromatic compound. Further, the inventors have found that the fluorinated alicyclic dicarboxylic acid compound can be easily produced by purifying this reaction solution by a specific method, and completed the present invention.
【０００６】すなわち本発明は、下記一般式（１）で表
される含フッ素芳香族ジカルボン酸化合物をロジウム触
媒を使用しエーテル系溶媒の存在下に核水素化すること
を特徴とする、下記一般式（２）で表される含フッ素脂
環式ジカルボン酸化合物の製造方法を提供するものであ
る。That is, the present invention is characterized in that a fluorine-containing aromatic dicarboxylic acid compound represented by the following general formula (1) is subjected to nuclear hydrogenation in the presence of an ether solvent using a rhodium catalyst. The present invention provides a method for producing a fluorine-containing alicyclic dicarboxylic acid compound represented by formula (2).
【０００７】また本発明は、下記一般式（１）で表され
る含フッ素芳香族ジカルボン酸化合物をロジウム触媒を
使用しエーテル系溶媒の存在下に核水素化し、当該反応
液から触媒を分離し、次いで反応液に脂肪族炭化水素系
溶媒を混合して沈殿を析出させ、得られた沈殿を溶媒と
分離することからなる下記一般式（２）で表される含フ
ッ素脂環式ジカルボン酸化合物の製造方法を提供するも
のである。In the present invention, the fluorine-containing aromatic dicarboxylic acid compound represented by the following general formula (1) is subjected to nuclear hydrogenation in the presence of an ether solvent using a rhodium catalyst to separate the catalyst from the reaction solution. Then, a fluorine-containing alicyclic dicarboxylic acid compound represented by the following general formula (2), which comprises mixing an aliphatic hydrocarbon solvent into the reaction solution to precipitate a precipitate, and separating the obtained precipitate from the solvent The present invention provides a method for manufacturing the same.
【０００８】[0008]
【化５】 [Chemical 5]
【０００９】[0009]
【化６】 [Chemical 6]
【００１０】（式中、Ｒは、水素原子または炭素数１〜
３のアルキル基を表す）(In the formula, R represents a hydrogen atom or a carbon number of 1 to
3 represents an alkyl group)
【００１１】[0011]
【発明の実施の形態】本発明は下記一般式（１）で表さ
れる含フッ素芳香族ジカルボン酸化合物を、ロジウム触
媒を使用しエーテル系溶媒の存在下、核水素化すること
を特徴とする。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is characterized in that a fluorine-containing aromatic dicarboxylic acid compound represented by the following general formula (1) is nuclear hydrogenated in the presence of an ether solvent using a rhodium catalyst. .
【００１２】[0012]
【化７】 [Chemical 7]
【００１３】（式中、Ｒは、水素原子または炭素数１〜
３のアルキル基を表す）。(In the formula, R represents a hydrogen atom or a carbon number of 1 to
3 represents an alkyl group).
【００１４】本発明の出発原料とする一般式（１）の含
フッ素芳香族ジカルボン酸化合物としては、例えば、
２，２−ビス（４−カルボキシフェニル）−ヘキサフル
オロプロパン、２，２−ビス（４−メトキシカルボニル
フェニル）−ヘキサフルオロプロパン、２，２−ビス
（４−エトキシカルボニルフェニル）−ヘキサフルオロ
プロパン、２，２−ビス（４−プロポキシカルボニルフ
ェニル）−ヘキサフルオロプロパン等が挙げられる。本
発明ではこれらの中でも特に２，２−ビス（４−カルボ
キシフェニル）−ヘキサフルオロプロパンを原料とする
場合に好適に実施することができる。Examples of the fluorine-containing aromatic dicarboxylic acid compound of the general formula (1) used as the starting material of the present invention include:
2,2-bis (4-carboxyphenyl) -hexafluoropropane, 2,2-bis (4-methoxycarbonylphenyl) -hexafluoropropane, 2,2-bis (4-ethoxycarbonylphenyl) -hexafluoropropane, 2,2-bis (4-propoxycarbonylphenyl) -hexafluoropropane and the like can be mentioned. Among these, in the present invention, it can be preferably carried out particularly when 2,2-bis (4-carboxyphenyl) -hexafluoropropane is used as a raw material.
【００１５】本発明では水素化触媒としてロジウム触媒
を使用する。一般的に水素化触媒としては、ニッケル、
パラジウム、ルテニウム、ロジウムおよび白金等の金属
触媒が使用されるが、本発明ではロジウム触媒を使用し
た場合に最も転化率、選択率が高く好ましい。ロジウム
触媒としては活性金属種としてのロジウムを含むもので
あれば特に限定されないが、取扱いが容易である点で不
活性担体に担持したロジウム担持触媒が推奨される。不
活性担体としては例えばカーボン、シリカ、アルミナ、
シリカアルミナ、マグネシア等が好ましく、カーボンま
たはアルミナが特に好ましい。担体へのロジウムの担持
は含浸法、沈殿法等の通常の方法により可能であり、こ
のときのロジウムの担持量は特に限定されるものではな
いが０．５〜１０重量％程度が好ましい。また、本発明
ではカーボン担持ロジウム触媒、またはアルミナ担持ロ
ジウム触媒等として市販されている担持触媒をそのまま
使用することもできる。In the present invention, a rhodium catalyst is used as the hydrogenation catalyst. Generally, as the hydrogenation catalyst, nickel,
Although metal catalysts such as palladium, ruthenium, rhodium and platinum are used, in the present invention, the use of a rhodium catalyst is preferable because the conversion and selectivity are highest. The rhodium catalyst is not particularly limited as long as it contains rhodium as an active metal species, but a rhodium-supported catalyst supported on an inert carrier is recommended because it is easy to handle. Examples of the inert carrier include carbon, silica, alumina,
Silica-alumina, magnesia and the like are preferable, and carbon or alumina is particularly preferable. Rhodium can be supported on the carrier by a conventional method such as an impregnation method or a precipitation method. The amount of rhodium supported at this time is not particularly limited, but is preferably about 0.5 to 10% by weight. Further, in the present invention, a supported catalyst commercially available as a carbon-supported rhodium catalyst or an alumina-supported rhodium catalyst may be used as it is.
【００１６】水素化反応におけるロジウム触媒の使用量
は特に限定されないが、通常は原料の重量に対し、金属
量として０．００１〜１重量％の範囲が好ましく、０．
０５〜０．５重量％がさらに好ましい。なお、ロジウム
触媒は一般的に高価であるが、本発明では一度使用した
触媒を回収し、そのまま再生処理を施すことなく次回の
水素化反応に使用することができ、このようなリサイク
ル使用を行うことにより触媒コストを低減することが可
能である。The amount of the rhodium catalyst used in the hydrogenation reaction is not particularly limited, but usually, the amount of metal is preferably in the range of 0.001 to 1% by weight based on the weight of the raw material,
More preferably, it is from 05 to 0.5% by weight. Although the rhodium catalyst is generally expensive, in the present invention, the catalyst that has been used once can be recovered and used as it is in the next hydrogenation reaction without being subjected to a regeneration treatment, and such a recycled use is performed. As a result, it is possible to reduce the catalyst cost.
【００１７】本発明では反応溶媒としてエーテル系溶媒
を使用する。エーテル系溶媒としては例えば、メチルタ
ーシャリーブチルエーテル、ジプロピルエーテル、ジブ
チルエーテル、メチラール、ジメトキシエタン、ジエト
キシエタン、テトラヒドロフラン、テトラヒドロピラ
ン、ジオキサン、ジオキソラン等が挙げられ、これらの
中でもテトラヒドロフラン、テトラヒドロピラン、ジオ
キサン、ジオキソラン等の飽和環状エーテル類が好まし
く、テトラヒドロフランまたはジオキサンが特に好まし
い。反応溶媒の使用量は特に限定されないが、通常は原
料の含フッ素芳香族ジカルボン酸化合物の重量に対し
０．５〜１０重量倍の範囲で使用することが好ましく、
１〜５重量倍がさらに好ましい。In the present invention, an ether solvent is used as a reaction solvent. Examples of the ether solvent include methyl tertiary butyl ether, dipropyl ether, dibutyl ether, methylal, dimethoxyethane, diethoxyethane, tetrahydrofuran, tetrahydropyran, dioxane, dioxolane, and the like, and among them, tetrahydrofuran, tetrahydropyran, dioxane. , Saturated cyclic ethers such as dioxolane are preferred, and tetrahydrofuran or dioxane is particularly preferred. The amount of the reaction solvent used is not particularly limited, but normally it is preferably used in the range of 0.5 to 10 times by weight with respect to the weight of the fluorine-containing aromatic dicarboxylic acid compound as a raw material,
It is more preferably 1 to 5 times by weight.
【００１８】本発明における反応温度および反応圧力
（水素圧）は特に限定されないが、低温・低圧の条件下
では水素化反応の選択率が高くなるものの反応速度が遅
くなり、また高温・高圧の条件下では反応速度は向上す
るものの選択率が低下する傾向にある。従って、これら
の条件は適度な反応速度と選択率が得られる範囲で選択
すれば良く、通常は、反応温度９０〜１８０℃の範囲、
好ましくは１１０〜１５０℃の範囲が採用され、水素圧
１０〜１５０kg／cm2・Ｇの範囲、好ましくは３０〜１０
０kg／cm2・Ｇの範囲が採用される。また、水素化反応の
終点、すなわち反応時間は反応系内の水素吸収量の低下
によって判断されるが、上記の条件下における反応時間
は通常１〜１０時間程度である。In the present invention, the reaction temperature and the reaction pressure (hydrogen pressure) are not particularly limited, but under the conditions of low temperature and low pressure, the selectivity of the hydrogenation reaction is high but the reaction rate is slow, and the conditions of high temperature and high pressure are high. Below, the reaction rate improves but the selectivity tends to decrease. Therefore, these conditions may be selected within a range in which an appropriate reaction rate and selectivity can be obtained. Usually, the reaction temperature is in the range of 90 to 180 ° C.
The range of 110 to 150 ° C. is preferably adopted, and the hydrogen pressure is in the range of 10 to 150 kg / cm 2 · G, preferably 30 to 10
The range of 0 kg / cm 2 · G is adopted. The end point of the hydrogenation reaction, that is, the reaction time is determined by the decrease in the amount of hydrogen absorbed in the reaction system, but the reaction time under the above conditions is usually about 1 to 10 hours.
【００１９】以上の水素化反応によって得られた水素化
反応生成物から、触媒および溶媒を分離することによっ
て目的の製品とすることができる。The desired product can be obtained by separating the catalyst and the solvent from the hydrogenation reaction product obtained by the above hydrogenation reaction.
【００２０】水素化反応生成物には通常、目的物である
２つのベンゼン環が完全核水素化されたものの他に、一
方のベンゼン環のみが核水素化されたもの、あるいは部
分水素化されたもの等の水素化中間体、カルボキシル基
等の側鎖が水素化分解された分解物、および未反応原料
等の不純物が含まれる。そこで、本発明では必要に応じ
て、以下の精製方法を実施することによりさらに高純度
の目的物を得ることができる。In the hydrogenation reaction product, usually, two benzene rings, which are the object, are completely nuclear-hydrogenated, and only one benzene ring is nuclear-hydrogenated or partially hydrogenated. Hydrogenated intermediates such as compounds, decomposed products obtained by hydrogenolysis of side chains such as carboxyl groups, and impurities such as unreacted raw materials are included. Therefore, in the present invention, if necessary, the purifying method described below can be carried out to obtain a target compound of higher purity.
【００２１】すなわち本発明の精製方法は、水素化反応
後のエーテル系溶媒を含む反応生成物溶液から濾過等の
手段によって触媒を除去した後、これに脂肪族炭化水素
系溶媒を混合することによって水素化生成物を沈殿とし
て析出させ、析出した沈殿を濾過または遠心分離等の手
段によって溶媒と分離し、乾燥する方法による。That is, in the purification method of the present invention, the catalyst is removed from the reaction product solution containing the ether solvent after the hydrogenation reaction by means such as filtration, and then the mixture is mixed with an aliphatic hydrocarbon solvent. The hydrogenated product is deposited as a precipitate, and the deposited precipitate is separated from the solvent by means such as filtration or centrifugation, and then dried.
【００２２】混合する脂肪族炭化水素系溶媒の種類は特
に限定されないが、分離した沈殿の乾燥性を考慮すると
炭素数５〜８の直鎖状、分枝鎖状または環状のパラフィ
ン溶剤が好ましい。具体的には、ノルマルペンタン、シ
クロペンタン、ノルマルヘキサン、イソヘキサン、シク
ロヘキサン、メチルシクロヘキサン、ノルマルヘプタ
ン、イソヘプタン、ノルマルオクタン、イソオクタンが
好ましく、ノルマルペンタン、ノルマルヘキサン、イソ
ヘキサンが特に好ましい。混合する脂肪族炭化水素系溶
媒の量は、水素化反応溶媒として使用するエーテル系溶
媒の量にもよるが、収率良く目的物の沈殿を得るには、
相対的にエーテル系溶媒の量より多い量を加えることが
好ましく、例えば、エーテル系溶媒の２〜１０重量倍の
範囲が好ましい。また、反応溶媒として使用したエーテ
ル系溶媒をある程度除去して、反応液を濃縮した後に脂
肪族炭化水素系溶媒を混合する方法も好ましい方法であ
る。一般的に、エーテル系溶媒の量が多く脂肪族炭化水
素系溶媒の量が少ない場合は、得られる沈殿の収率は低
下するが純度が高くなり、逆にエーテル系溶媒の量が少
なく脂肪族炭化水素系溶媒の量が多い場合には、得られ
る沈殿の純度はやや低下するが収率が向上する。従っ
て、これらの溶媒量は水素化物の所望の純度や収率によ
って適宜選択すればよい。The type of the aliphatic hydrocarbon solvent to be mixed is not particularly limited, but a linear, branched or cyclic paraffin solvent having 5 to 8 carbon atoms is preferable in consideration of the drying property of the separated precipitate. Specifically, normal pentane, cyclopentane, normal hexane, isohexane, cyclohexane, methylcyclohexane, normal heptane, isoheptane, normal octane and isooctane are preferable, and normal pentane, normal hexane and isohexane are particularly preferable. The amount of the aliphatic hydrocarbon solvent to be mixed depends on the amount of the ether solvent used as the hydrogenation reaction solvent, but in order to obtain a precipitate of the desired product in good yield,
It is preferable to add a relatively larger amount than the amount of the ether solvent, for example, a range of 2 to 10 times the weight of the ether solvent is preferable. Further, a method in which the ether solvent used as the reaction solvent is removed to some extent, the reaction solution is concentrated, and then the aliphatic hydrocarbon solvent is mixed is also a preferable method. In general, when the amount of the ether solvent is large and the amount of the aliphatic hydrocarbon solvent is small, the yield of the obtained precipitate is low but the purity is high, and conversely, the amount of the ether solvent is small and the aliphatic solvent is small. When the amount of the hydrocarbon solvent is large, the purity of the obtained precipitate is slightly lowered but the yield is improved. Therefore, the amount of these solvents may be appropriately selected depending on the desired purity and yield of the hydride.
【００２３】脂肪族炭化水素系溶媒を混合し析出した沈
殿は、濾過、遠心分離等の手段によって溶媒と分離し、
必要に応じて沈殿を少量の脂肪族炭化水素系溶媒で洗浄
し、その後、減圧下に加温して乾燥することによって、
目的の水素化生成物とすることができる。The precipitate formed by mixing the aliphatic hydrocarbon solvent is separated from the solvent by means such as filtration and centrifugation,
If necessary, the precipitate is washed with a small amount of an aliphatic hydrocarbon solvent, and then heated under reduced pressure and dried,
It can be the desired hydrogenation product.
【００２４】以上のような本発明の方法を実施すること
によって、含フッ素脂環式ジカルボン酸化合物を容易に
製造することができる。By carrying out the method of the present invention as described above, the fluorinated alicyclic dicarboxylic acid compound can be easily produced.
【００２５】[0025]
【実施例】以下実施例によって本発明をさらに具体的に
説明するが、本発明はこれらの実施例によって限定され
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.
【００２６】（実施例１）容量１リットルのオートクレ
ーブに、２，２−ビス（４−カルボキシフェニル）−ヘ
キサフルオロプロパン１００ｇ、テトラヒドロフラン３
００ｇ、および５重量％ロジウム／カーボン担持触媒
（エヌイーケムキャット社製）２．５ｇを入れ、系内を
窒素、次いで水素で置換した後、内容物を撹拌しながら
反応温度１３０℃、水素圧８０kg/cm2・Gで水素化反応を
行った。水素吸収は約３時間で停止したが、その後１時
間撹拌を継続し反応を終了した。反応液を室温まで冷却
した後、濾過して触媒を分離した。Example 1 In an autoclave having a volume of 1 liter, 100 g of 2,2-bis (4-carboxyphenyl) -hexafluoropropane and 3 parts of tetrahydrofuran.
00 g and 2.5 g of a 5 wt% rhodium / carbon supported catalyst (manufactured by NE Chemcat) were charged, the system was replaced with nitrogen and then with hydrogen, and then the reaction temperature was 130 ° C. while stirring the contents, and the hydrogen pressure was 80 kg /. The hydrogenation reaction was performed at cm 2 · G. Hydrogen absorption was stopped in about 3 hours, but the stirring was continued for 1 hour thereafter to complete the reaction. The reaction solution was cooled to room temperature and then filtered to separate the catalyst.
【００２７】反応液からテトラヒドロフランを留去し、
得られた反応生成物の組成をガスクロマトグラフで分析
した結果、目的物である２，２−ビス（４−カルボキシ
シクロヘキシル）−ヘキサフルオロプロパンの含有量８
５％、水素化中間体６％、分解物９％であった。なお、
ガスクロマトグラフ分析は、反応生成物を常法によりト
リメチルシラノールでトリメチルシリル化して行った。Tetrahydrofuran was distilled off from the reaction solution,
As a result of analyzing the composition of the obtained reaction product by gas chromatography, the content of 2,2-bis (4-carboxycyclohexyl) -hexafluoropropane, which is the target product, was 8
It was 5%, the hydrogenated intermediate was 6%, and the decomposition product was 9%. In addition,
Gas chromatographic analysis was carried out by trimethylsilylating the reaction product with trimethylsilanol by a conventional method.
【００２８】（実施例２）実施例１と同様の反応条件に
て得られた反応液から触媒を分離した後、これにノルマ
ルヘキサン９００ｇを混合した。この混合液を緩やかに
撹拌しながら１時間放置したところ白色沈殿が析出し
た。混合液を濾過して沈殿を分離し、得られた沈殿をノ
ルマルヘキサン９０ｇで洗浄した後、１２０℃、１０mm
Hg、２．５時間乾燥し、白色粉末８９ｇを得た。Example 2 After separating the catalyst from the reaction solution obtained under the same reaction conditions as in Example 1, 900 g of normal hexane was mixed. When this mixed solution was left for 1 hour with gentle stirring, a white precipitate was deposited. The mixed solution is filtered to separate the precipitate, and the obtained precipitate is washed with 90 g of normal hexane and then at 120 ° C. for 10 mm.
Hg was dried for 2.5 hours to obtain 89 g of a white powder.
【００２９】得られた白色粉末の組成を実施例１と同様
の方法で分析した結果、目的物である２，２−ビス（４
−カルボキシシクロヘキシル）−ヘキサフルオロプロパ
ンの含有量９７％、水素化中間体２％、分解物１％であ
った。The composition of the obtained white powder was analyzed in the same manner as in Example 1, and as a result, 2,2-bis (4
The content of -carboxycyclohexyl) -hexafluoropropane was 97%, the hydrogenated intermediate was 2%, and the decomposition product was 1%.
【００３０】[0030]
【発明の効果】本発明によれば、電子材料や光学材料等
の原料として好適に使用できる含フッ素脂環式ジカルボ
ン酸化合物を、簡便に効率よく製造することができる。INDUSTRIAL APPLICABILITY According to the present invention, a fluorine-containing alicyclic dicarboxylic acid compound which can be suitably used as a raw material for electronic materials, optical materials and the like can be simply and efficiently produced.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 前田 一彦 東京都千代田区神田錦町３−７−１ Ｆターム(参考） 4H006 AA02 AC11 AD15 BA24 BA55 BA61 BB23 BC10 BC11 BC34 BE20 BJ20 BM10 BM71 BS20 4H039 CA40 CB10 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Kazuhiko Maeda 3-7-1 Kandanishikicho, Chiyoda-ku, Tokyo F-term (reference) 4H006 AA02 AC11 AD15 BA24 BA55 BA61 BB23 BC10 BC11 BC34 BE20 BJ20 BM10 BM71 BS20 4H039 CA40 CB10
Claims (3)
カルボン酸化合物をロジウム触媒を使用しエーテル系溶
媒の存在下に核水素化することを特徴とする、一般式
（２）で表される含フッ素脂環式ジカルボン酸化合物の
製造方法。 【化１】 【化２】 （式中Ｒは水素原子または炭素数１〜３のアルキル基を
表す）1. A compound represented by the general formula (2), which comprises subjecting the fluorine-containing aromatic dicarboxylic acid compound represented by the general formula (1) to nuclear hydrogenation in the presence of an ether solvent using a rhodium catalyst. The manufacturing method of the represented fluorine-containing alicyclic dicarboxylic acid compound. [Chemical 1] [Chemical 2] (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms)
カルボン酸化合物をロジウム触媒を使用しエーテル系溶
媒の存在下に核水素化し、当該反応液から触媒を分離
し、次いで反応液に脂肪族炭化水素系溶媒を混合して水
素化生成物を沈殿として析出させ、得られた沈殿を溶媒
と分離することからなる一般式（２）で表される含フッ
素脂環式ジカルボン酸化合物の製造方法。 【化３】 【化４】 （式中、Ｒは、水素原子または炭素数１〜３のアルキル
基を表す）2. A fluorine-containing aromatic dicarboxylic acid compound represented by the general formula (1) is nuclear hydrogenated in the presence of an ether solvent using a rhodium catalyst to separate the catalyst from the reaction solution, and then the reaction solution. A fluorine-containing alicyclic dicarboxylic acid compound represented by the general formula (2), which comprises mixing an aliphatic hydrocarbon solvent with the above to precipitate a hydrogenation product as a precipitate, and separating the obtained precipitate from the solvent. Manufacturing method. [Chemical 3] [Chemical 4] (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms)
びジオキサンから選択された少なくとも１種であり、か
つ脂肪族炭化水素系溶媒が炭素数５〜８の直鎖状、分岐
鎖状または環状のパラフィン溶剤から選択された少なく
とも１種である請求項２記載の製造方法。3. The ether solvent is at least one selected from tetrahydrofuran and dioxane, and the aliphatic hydrocarbon solvent is selected from linear, branched or cyclic paraffin solvents having 5 to 8 carbon atoms. The manufacturing method according to claim 2, which is at least one of
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007307639A (en) * | 2006-05-17 | 2007-11-29 | Toyo Tire & Rubber Co Ltd | Polishing pad |
| JP2007307638A (en) * | 2006-05-17 | 2007-11-29 | Toyo Tire & Rubber Co Ltd | Polishing pad |
| WO2010095678A1 (en) * | 2009-02-20 | 2010-08-26 | セントラル硝子株式会社 | Fluorinated dicarboxylic acid derivative and polymer obtained therefrom |
-
2001
- 2001-06-28 JP JP2001196971A patent/JP3904854B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007307639A (en) * | 2006-05-17 | 2007-11-29 | Toyo Tire & Rubber Co Ltd | Polishing pad |
| JP2007307638A (en) * | 2006-05-17 | 2007-11-29 | Toyo Tire & Rubber Co Ltd | Polishing pad |
| WO2010095678A1 (en) * | 2009-02-20 | 2010-08-26 | セントラル硝子株式会社 | Fluorinated dicarboxylic acid derivative and polymer obtained therefrom |
| JP2010215904A (en) * | 2009-02-20 | 2010-09-30 | Central Glass Co Ltd | Fluorinated dicarboxylic acid derivative and high-molecular compound obtained by using the same |
| KR101290226B1 (en) | 2009-02-20 | 2013-07-30 | 샌트랄 글래스 컴퍼니 리미티드 | Fluorinated dicarboxylic acid derivative and polymer obtained therefrom |
| US8809451B2 (en) | 2009-02-20 | 2014-08-19 | Central Glass Company, Limited | Fluorinated dicarboxylic acid derivative and polymer obtained therefrom |
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| JP3904854B2 (en) | 2007-04-11 |
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