JP2003183228A - Method for producing flurorine-containing alicyclic diamine compound - Google Patents
Method for producing flurorine-containing alicyclic diamine compoundInfo
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- JP2003183228A JP2003183228A JP2001386662A JP2001386662A JP2003183228A JP 2003183228 A JP2003183228 A JP 2003183228A JP 2001386662 A JP2001386662 A JP 2001386662A JP 2001386662 A JP2001386662 A JP 2001386662A JP 2003183228 A JP2003183228 A JP 2003183228A
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- fluorine
- diamine compound
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- metal hydroxide
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (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ア
ミン化合物を核水素化して含フッ素脂環式ジアミン化合
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 diamine compound by nuclear hydrogenation of a fluorine-containing aromatic diamine compound.
【０００２】[0002]
【従来の技術】フッ素を含有するジアミン化合物は、例
えば電子材料や光学材料用のポリアミド、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。BACKGROUND OF THE INVENTION Fluorine-containing diamine compounds are useful as raw materials for 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−アミノフェニル）−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
脂環式のジアミン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ア
ミン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-aminophenyl) -hexafluoropropane have been used. However, compounds having an aromatic ring generally have a high electron density, and as a result,
In particular, there are drawbacks such as a high dielectric constant in a high frequency region and strong intermolecular packing between aromatic rings, resulting in low light transmittance. Therefore, for example, an alicyclic diamine compound having no aromatic ring has been studied as a novel material. However, a method for efficiently producing such an alicyclic diamine compound containing fluorine has not been heretofore 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
アミン化合物を、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 easily and efficiently producing such a fluorine-containing alicyclic diamine 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、容易に含フッ素脂環式ジアミン化
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. Thus, the inventors have found that a fluorinated alicyclic diamine compound can be easily produced, 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アミン化合物（式中Ｒは水素原
子またはメチル基を表す）をロジウム触媒を使用し、ア
ルカリ金属水酸化物および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
含フッ素脂環式ジアミン化合物（式中Ｒは水素原子また
はメチル基を表す）の製造方法である。That is, the present invention uses a rhodium catalyst to prepare a fluorine-containing aromatic diamine compound represented by the following general formula (1) (wherein R represents a hydrogen atom or a methyl group) using an alkali metal hydroxide and A method for producing a fluorine-containing alicyclic diamine compound represented by the general formula (2) (wherein R represents a hydrogen atom or a methyl group), which comprises nuclear hydrogenation in the presence of an ether solvent. is there.
【０００７】[0007]
【化３】 [Chemical 3]
【０００８】[0008]
【化４】 [Chemical 4]
【０００９】[0009]
【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アミン化合物（式中Ｒは水素原子
またはメチル基を表す）を、ロジウム触媒を使用し、ア
ルカリ金属水酸化物および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 comprises a fluorine-containing aromatic diamine compound represented by the following general formula (1) (wherein R represents a hydrogen atom or a methyl group) using a rhodium catalyst and alkali metal water. It is characterized by nuclear hydrogenation in the presence of an oxide and an ether solvent.
【００１０】[0010]
【化５】 [Chemical 5]
【００１１】本発明の出発原料とする一般式（１）の含
フッ素芳香族ジアミン化合物としては、例えば、２，２
−ビス（４−アミノフェニル）−ヘキサフルオロプロパ
ン、２，２−ビス（３−アミノフェニル）−ヘキサフル
オロプロパン、２，２−ビス（３−アミノ−４−メチル
フェニル）−ヘキサフルオロプロパン、２，２−ビス
（３−メチル−４−アミノフェニル）−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−アミノフェニル）−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 diamine compound of the general formula (1) used as the starting material of the present invention include 2,2
-Bis (4-aminophenyl) -hexafluoropropane, 2,2-bis (3-aminophenyl) -hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) -hexafluoropropane, 2 , 2-bis (3-methyl-4-aminophenyl) -hexafluoropropane and the like. Among these, in the present invention, it can be preferably carried out particularly when 2,2-bis (4-aminophenyl) -hexafluoropropane is used as a raw material.
【００１２】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
触媒が挙げられるが、含フッ素芳香族ジアミン化合物を
水素化対象物とする場合、ロジウム触媒を使用した場合
において最も転化率、選択率が高くなることが見出され
た。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、通常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,
Examples include metal catalysts such as palladium, ruthenium, rhodium, and platinum.However, when a fluorine-containing aromatic diamine compound is used as a hydrogenation target, it can be seen that the conversion rate and the selectivity are highest when the rhodium catalyst is used. Was issued. 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. As the inert carrier, for example, 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 usual method such as an impregnation method or a precipitation method. The amount of rhodium supported at this time is not particularly limited, but is usually preferably about 0.5 to 10% by weight. . Further, in the present invention, a carbon-supported rhodium catalyst,
Alternatively, a supported catalyst commercially available as an alumina-supported rhodium catalyst or the like can be used as it is.
【００１３】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０．０１〜２重量％の範囲が好ましく、０．０
５〜１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 0.01 to 2% by weight based on the weight of the raw material, and 0.0
More preferably, it is 5 to 1% 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.
【００１４】本発明では上記ロジウム触媒と同時に、助
触媒としてアルカリ金属水酸化物を使用することを特徴
とする。アルカリ金属水酸化物をロジウム触媒と組み合
わせて使用することにより、ロジウム触媒を単独で使用
する場合に比較して、目的の核水素化物の選択率や反応
速度を格段に改善することができる。使用するアルカリ
金属水酸化物としては、例えば、水酸化リチウム、水酸
化ナトリウム、水酸化カリウム等が挙げられるが、本発
明では目的の核水素化物への選択性が最も高い点で水酸
化リチウムが特に好ましい。アルカリ金属水酸化物の使
用量は特に限定されないが、その添加効果が十分に得ら
れる範囲、および経済的観点から通常は原料の含フッ素
芳香族ジアミン化合物の重量に対し０．５〜１０重量％
の範囲が好ましい。The present invention is characterized in that an alkali metal hydroxide is used as a cocatalyst at the same time as the above rhodium catalyst. By using the alkali metal hydroxide in combination with the rhodium catalyst, the selectivity and reaction rate of the target nuclear hydride can be significantly improved as compared with the case where the rhodium catalyst is used alone. Examples of the alkali metal hydroxide used include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide and the like, but in the present invention, lithium hydroxide is the highest in the selectivity to the desired nuclear hydride. Particularly preferred. The amount of the alkali metal hydroxide used is not particularly limited, but is usually 0.5 to 10% by weight based on the weight of the raw material fluorine-containing aromatic diamine compound in the range where the effect of addition thereof is sufficiently obtained and from the economical viewpoint.
Is preferred.
【００１５】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アミン化合物の重量に対し、０．
５〜２０重量倍の範囲で使用することが好ましく、２〜
１０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. Although the amount of the reaction solvent used is not particularly limited, it is usually 0.
It is preferable to use 5 to 20 times by weight,
It is more preferably 10 times by weight.
【００１６】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１３０〜２００℃の範
囲、好ましくは１５０〜１９０℃の範囲が採用され、水
素圧３０〜２００kg／cm2・Ｇの範囲、好ましくは７０〜
１８０kg／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２〜２０時間程度である。The reaction temperature and reaction pressure (hydrogen pressure) in the present invention are not particularly limited, but under low temperature and low pressure conditions, the selectivity of the hydrogenation reaction is high, but the reaction rate is slow, and at high temperature and high pressure conditions. Below, the reaction rate improves but the selectivity tends to decrease. Therefore, these conditions may be selected within a range where an appropriate reaction rate and selectivity can be obtained. Usually, a reaction temperature of 130 to 200 ° C, preferably 150 to 190 ° C, is adopted, and a hydrogen pressure of 30 is used. ~ 200 kg / cm 2 · G range, preferably 70 ~
The range of 180 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 2 to 20 hours.
【００１７】以上のような本発明の方法を実施すること
によって、含フッ素脂環式ジアミン化合物を高濃度に含
む反応液が得られ、当該反応液から、触媒および溶媒を
分離すれば容易に目的の製品とすることができる。本発
明によれば、通常、原料からの選択率８０％以上で目的
の核水素化物が得られる。なお、反応生成物には少量の
水素化分解物や反応中間体が含まれるため、これらは必
要に応じて通常の蒸留あるいは再結晶等の手段により精
製することにより、更に高純度の含フッ素脂環式ジアミ
ン化合物を得ることができる。By carrying out the method of the present invention as described above, a reaction solution containing a fluorine-containing alicyclic diamine compound in a high concentration can be obtained, and if the catalyst and the solvent are separated from the reaction solution, the purpose can be easily obtained. Can be a product of According to the present invention, the target nuclear hydride is usually obtained with a selectivity of 80% or more from the raw materials. Since the reaction product contains a small amount of hydrogenolysis products and reaction intermediates, they can be further purified by a means such as ordinary distillation or recrystallization to obtain a fluorine-containing resin having a higher purity. A cyclic diamine compound can be obtained.
【００１８】[0018]
【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.
【００１９】（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−アミノフェニル）−ヘキサ
フルオロプロパン１００ｇ、テトラヒドロフラン５００
ｇ、５％ロジウム／カーボン担持触媒（エヌイーケムキ
ャット社製）１７ｇ、および水酸化リチウム・１水和物
４．２５ｇ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１８０℃、水素圧１
５０kg/cm2・Ｇで水素化反応を行った。水素吸収は約７
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-aminophenyl) -hexafluoropropane and 500 of tetrahydrofuran.
g, 5% rhodium / carbon-supported catalyst (manufactured by NE Chemcat) 17 g, and 4.25 g of lithium hydroxide monohydrate were added, the system was replaced with nitrogen and then with hydrogen, and then the contents were stirred. Reaction temperature 180 ℃, hydrogen pressure 1
The hydrogenation reaction was carried out at 50 kg / cm 2 · G. Hydrogen absorption is about 7
Although the reaction was stopped at that time, the reaction was terminated by continuing stirring for 1 hour. The reaction solution was cooled to room temperature and then filtered to separate the catalyst.
【００２０】得られた反応液の組成をガスクロマトグラ
フにより分析した結果、水素化生成物中の２，２−ビス
（４−アミノシクロヘキシル）−ヘキサフルオロプロパ
ンの選択率は９５．９％であった。As a result of analyzing the composition of the obtained reaction liquid by gas chromatography, the selectivity of 2,2-bis (4-aminocyclohexyl) -hexafluoropropane in the hydrogenated product was 95.9%. .
【００２１】また、反応液から単蒸留によりテトラヒド
ロフランを留去し、ついで残留物を塔頂温度１６０〜１
７０℃／１０ｍｍＨｇの条件で蒸留精製したした結果、
純度９８．５％の２，２−ビス（４−アミノシクロヘキ
シル）−ヘキサフルオロプロパンが得られた。Tetrahydrofuran was distilled off from the reaction solution by simple distillation, and then the residue was heated to a top temperature of 160 to 1
As a result of purification by distillation under the conditions of 70 ° C./10 mmHg,
2,2-bis (4-aminocyclohexyl) -hexafluoropropane having a purity of 98.5% was obtained.
【００２２】（比較例１）実施例１において水酸化リチ
ウム・１水和物を添加しなかった以外は実施例１と同様
にして水素化反応を行った。Comparative Example 1 A hydrogenation reaction was carried out in the same manner as in Example 1 except that lithium hydroxide monohydrate was not added.
【００２３】得られた反応液の組成をガスクロマトグラ
フにより分析した結果、水素化生成物中の２，２−ビス
（４−アミノシクロヘキシル）−ヘキサフルオロプロパ
ンの選択率は２７％であった。As a result of analyzing the composition of the obtained reaction liquid by gas chromatography, the selectivity of 2,2-bis (4-aminocyclohexyl) -hexafluoropropane in the hydrogenated product was 27%.
【００２４】[0024]
【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アミン
化合物を、簡便に効率よく製造することができる。According to the present invention, a fluorine-containing alicyclic diamine 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 早▲崎▼ 渉 千葉県市原市惣社４−11−14 (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 AC52 BA03 BA24 BA29 BB15 BB25 BE20 4H039 CA40 CA71 CB10 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Wataru Hayasaki 4-11-14 Sousha, Ichihara City, Chiba Prefecture (72) Inventor Kazuhiko Maeda 3-7-1 Kandanishikicho, Chiyoda-ku, Tokyo F-term (reference) 4H006 AA02 AC11 AC52 BA03 BA24 BA29 BB15 BB25 BE20 4H039 CA40 CA71 CB10
Claims (4)
アミン化合物（式中Ｒは水素原子またはメチル基を表
す）をロジウム触媒を使用し、アルカリ金属水酸化物お
よび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アミ
ン化合物（式中Ｒは水素原子またはメチル基を表す）の
製造方法。 【化１】 【化２】 1. A fluorine-containing aromatic diamine compound represented by the general formula (1) (wherein R represents a hydrogen atom or a methyl group) using a rhodium catalyst, and containing an alkali metal hydroxide and an ether solvent. A process for producing a fluorine-containing alicyclic diamine compound represented by the general formula (2) (wherein R represents a hydrogen atom or a methyl group), which comprises nuclear hydrogenation in the presence. [Chemical 1] [Chemical 2]
ある請求項１記載の製造方法。2. The method according to claim 1, wherein the alkali metal hydroxide is lithium hydroxide.
びジオキサンから選択された少なくとも１種である請求
項１または２記載の製造方法。3. The method according to claim 1, wherein the ether solvent is at least one selected from tetrahydrofuran and dioxane.
アミン化合物が、２，２−ビス（４−アミノフェニル）
−ヘキサフルオロプロパンである請求項１ないし３記載
の製造方法。4. The fluorine-containing aromatic diamine compound represented by the general formula (1) is 2,2-bis (4-aminophenyl).
-The production method according to claims 1 to 3, which is hexafluoropropane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257045A (en) * | 2005-03-18 | 2006-09-28 | Arakawa Chem Ind Co Ltd | Method for producing cyclic diamine compound |
| CN112624930A (en) * | 2020-12-21 | 2021-04-09 | 上海如鲲新材料有限公司 | Preparation method of 2, 2-bis (4-aminophenyl) hexafluoropropane |
-
2001
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257045A (en) * | 2005-03-18 | 2006-09-28 | Arakawa Chem Ind Co Ltd | Method for producing cyclic diamine compound |
| CN112624930A (en) * | 2020-12-21 | 2021-04-09 | 上海如鲲新材料有限公司 | Preparation method of 2, 2-bis (4-aminophenyl) hexafluoropropane |
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