JPH06329584A - Production of 4-biphenylcarboxylic acid - Google Patents
Production of 4-biphenylcarboxylic acidInfo
- Publication number
- JPH06329584A JPH06329584A JP5139318A JP13931893A JPH06329584A JP H06329584 A JPH06329584 A JP H06329584A JP 5139318 A JP5139318 A JP 5139318A JP 13931893 A JP13931893 A JP 13931893A JP H06329584 A JPH06329584 A JP H06329584A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- solvent
- biphenylcarboxylic acid
- reaction
- ethylbiphenyl
- 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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Links
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は液晶原料、ポリマー原料
等として有用な４−ビフェニルカルボン酸の製造方法に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing 4-biphenylcarboxylic acid useful as a raw material for liquid crystals, a raw material for polymers and the like.
【０００２】[0002]
【従来の技術】従来、４−ビフェニルカルボン酸の製造
方法として工業的に可能な方法の一つに４−アシルビフ
ェニルを液相酸化する方法（特開平４−２２１３４１、
特開平４−１５９２４７、特開平４−１２８２５２）が
あるが、以下のような欠点があり、工業的に必ずしも満
足いくものではなかった。すなわち、 ビフェニルをアシル化し４−アシルビフェニルを製造
する際、大量の、再利用が困難な均一系ルイス酸触媒を
必要とし、コスト的に好ましくはなかった。 大量の均一系ルイス酸触媒の使用に伴い、大量の酸性
排水が排出され、環境上問題であった。 液相酸化において、酸化をスムーズに進行させるた
め、アルキルベンゼン等を添加する必要がある。2. Description of the Related Art Conventionally, one of industrially possible methods for producing 4-biphenylcarboxylic acid is a method of liquid-phase oxidation of 4-acylbiphenyl (Japanese Patent Laid-Open No. 222211/1992).
There are JP-A-4-159247 and JP-A-4-128252), but they are not always industrially satisfactory due to the following drawbacks. That is, when a biphenyl is acylated to produce 4-acylbiphenyl, a large amount of a homogeneous Lewis acid catalyst that is difficult to reuse is required, which is not preferable in terms of cost. With the use of a large amount of homogeneous Lewis acid catalyst, a large amount of acidic wastewater was discharged, which was an environmental problem. In liquid phase oxidation, it is necessary to add alkylbenzene or the like in order to make the oxidation proceed smoothly.
【０００３】この方法以外にも、（１）４−ビフェニル
トリフレートを酸化する方法(Tetrahedron Lett., 199
2, 33, 3939-42)、（２）４−ホルミルビフェニルを酸
化する方法(Bull. Chem. Soc. Jpn., 1988, 61, 4464-
6) 、（３）ビフェニルにＣＯ2を挿入する方法(J. Che
m. Soc., Chem. Commun., 1988, 8, 562-4)、等がある
が、（１）、（２）は酸化原料の安価な入手が困難であ
る、（２）、（３）は収率が数％と低い、等の欠点があ
り、先に挙げた４−アシルビフェニルの液相酸化法以上
に工業化が困難な方法であった。In addition to this method, (1) a method of oxidizing 4-biphenyl triflate (Tetrahedron Lett., 199)
2, 33 , 3939-42), (2) Method for oxidizing 4-formylbiphenyl (Bull. Chem. Soc. Jpn., 1988, 61 , 4464-
6), (3) Method of inserting CO 2 into biphenyl (J. Che
m. Soc., Chem. Commun., 1988, 8, 562-4), etc., but (1) and (2) make it difficult to obtain an oxidizing raw material at low cost, (2) and (3). Has a defect that the yield is as low as several%, and is a method that is more difficult to industrialize than the liquid phase oxidation method of 4-acylbiphenyl mentioned above.
【０００４】以上の様に、工業的に比較的容易に得られ
る原料を用いて、液相酸化することにより、収率良く４
−ビフェニルカルボン酸を製造する方法は知られていな
かった。As described above, by using the raw materials that are relatively easily obtained industrially and performing the liquid phase oxidation, the yield is improved.
No method was known to produce biphenylcarboxylic acid.
【０００５】[0005]
【発明が解決しようとする課題】そこで、本発明者ら
は、熱媒用のエチルビフェニル製造の際、生成物より４
−エチルビフェニルを蒸留で分離し、得られた４−エチ
ルビフェニルを液相で空気酸化すれば４−アシルビフェ
ニル等の酸化に比べ容易に４−ビフェニルカルボン酸が
製造できることを見出し、本発明を完成した。従って、
本発明の目的は、４−エチルビフェニルを液相酸化する
ことによる、工業的に有利な４−ビフェニルカルボン酸
製造方法を提供することにある。Therefore, the inventors of the present invention, when producing ethylbiphenyl for a heat transfer medium, use the product to produce 4
It was found that 4-biphenylcarboxylic acid can be easily produced by separating 4-ethylbiphenyl by distillation and air-oxidizing the obtained 4-ethylbiphenyl in a liquid phase as compared with oxidation of 4-acylbiphenyl and the like, and completed the present invention. did. Therefore,
An object of the present invention is to provide an industrially advantageous method for producing 4-biphenylcarboxylic acid by liquid-phase oxidizing 4-ethylbiphenyl.
【０００６】[0006]
【課題を解決するための手段】すなわち本発明は、４−
エチルビフェニル及び／又はその酸化中間体を、炭素数
が３以下の脂肪族モノカルボン酸を少なくとも５０重量
％含有する溶媒に、触媒としての遷移金属及び臭素を溶
解させた溶液中で、分子状酸素含有ガスにより酸化する
に当たり、４−エチルビフェニル、その酸化中間体及び
４−ビフェニルカルボン酸の合計に対して少なくとも２
倍重量の溶媒を使用し、溶媒当たり０．０３重量％以上
のコバルト及び／又はマンガンよりなる遷移金属及び溶
媒当たり０．０１重量％以上の臭素を存在させた溶液中
で、反応温度１１０〜２６０℃、酸素分圧０．１〜２０
ｋｇ／ｃｍ2 ・Ｇの反応条件で酸化し、得られた反応生
成液から４−ビフェニルカルボン酸を分離することを特
徴とする４−ビフェニルカルボン酸の製造方法である。That is, the present invention is
Molecular weight of ethylbiphenyl and / or its oxidation intermediate was measured in a solution prepared by dissolving a transition metal and bromine as a catalyst in a solvent containing at least 50% by weight of an aliphatic monocarboxylic acid having 3 or less carbon atoms. At least 2 with respect to the total of 4-ethylbiphenyl, its oxidation intermediate and 4-biphenylcarboxylic acid upon oxidation by the contained gas.
A reaction temperature of 110 to 260 was used in a solution in which a double weight of a solvent was used and 0.03% by weight or more of a transition metal consisting of cobalt and / or manganese was present per solvent and 0.01% by weight or more of bromine was present per solvent. ℃, oxygen partial pressure 0.1-20
A method for producing 4-biphenylcarboxylic acid, which comprises oxidizing 4-biphenylcarboxylic acid from the obtained reaction product solution by oxidizing under a reaction condition of kg / cm 2 · G.
【０００７】以下、本発明の製造方法について、詳細に
説明する。本発明で酸化原料として用いる４−エチルビ
フェニルは、通常、ビフェニルをフリーデルクラフツ触
媒を用いてエチレン、エチルクロライド、ポリエチルベ
ンゼン等のエチル化剤によりエチル化又はトランスエチ
ル化し、得られたエチル化生成物を蒸留、冷却晶析、圧
力晶析、アダクツ分離等の分離手段を用いて単離するこ
とにより得ることができる。ポリエチルベンゼンによる
トランスエチル化反応生成物からは、蒸留のみで４−エ
チルビフェニルを単離することができ、特に工業的に好
ましい。このほかにも、エチル化されたシクロヘキシル
ベンゼンの脱水素、ベンゼン環の化合物を出発原料にす
るカップリング、等により合成された４−エチルビフェ
ニルを酸化原料に用いても良い。これら４−エチルビフ
ェニルは高純度のものが好ましいが、酸化反応終了後の
生成物を各種方法で精製する際に除去できる程度であれ
ば、４−エチルビフェニルおよびその酸化中間体以外の
他の成分、たとえば３−エチルビフェニル等を含んでい
ても差し支えない。また、４−エチルビフェニルのエチ
ル基がアセチル基またはホルミル基等に酸化された酸化
中間体をこれに混合しても良い。The manufacturing method of the present invention will be described in detail below. 4-Ethylbiphenyl used as an oxidizing raw material in the present invention is usually produced by ethylation or transethylation of biphenyl with an ethylating agent such as ethylene, ethyl chloride or polyethylbenzene using a Friedel-Crafts catalyst. It can be obtained by isolating the product using a separation means such as distillation, cooling crystallization, pressure crystallization, and adduct separation. From the transethylation reaction product with polyethylbenzene, 4-ethylbiphenyl can be isolated only by distillation, which is particularly industrially preferable. In addition to this, 4-ethylbiphenyl synthesized by dehydrogenation of ethylated cyclohexylbenzene, coupling using a compound having a benzene ring as a starting material, or the like may be used as an oxidizing material. These 4-ethylbiphenyls are preferably of high purity, but other components other than 4-ethylbiphenyl and its oxidation intermediate can be used as long as they can be removed when the products after the oxidation reaction are purified by various methods. , For example, 3-ethylbiphenyl may be contained. Further, an oxidation intermediate in which the ethyl group of 4-ethylbiphenyl is oxidized to an acetyl group or a formyl group may be mixed with this.
【０００８】本発明で溶媒として使用する炭素数が３以
下の脂肪族モノカルボン酸としては、蟻酸、酢酸、プロ
ピオン酸、ブロモ酢酸等を挙げることができるが、酢
酸、プロピオン酸又はそれらの混合物が好ましい。そし
て、本発明で用いる溶媒はこれら炭素数が３以下の脂肪
族モノカルボン酸を少なくとも５０重量％、好ましくは
７０重量％含む。Examples of the aliphatic monocarboxylic acid having 3 or less carbon atoms used as a solvent in the present invention include formic acid, acetic acid, propionic acid, bromoacetic acid, and the like, and acetic acid, propionic acid or a mixture thereof. preferable. The solvent used in the present invention contains at least 50% by weight, preferably 70% by weight, of these aliphatic monocarboxylic acids having 3 or less carbon atoms.
【０００９】溶媒中に多量の水分が存在する場合は酸化
反応を阻害するが、少量であればむしろ良い結果をもた
らす場合もある。また、後述するように、生成した４−
ビフェニルカルボン酸の溶媒への溶解度を低下させる目
的からも、反応溶媒中にある程度の水分をあらかじめ混
在させるのが良い。その様な水分濃度としては、反応生
成液中の水分濃度として、５〜４０重量％、好ましくは
５〜３０重量％である。The presence of a large amount of water in the solvent hinders the oxidation reaction, but a small amount may give rather good results. In addition, as described later, the generated 4-
For the purpose of reducing the solubility of the biphenylcarboxylic acid in the solvent, it is preferable that a certain amount of water is mixed in the reaction solvent in advance. As such a water concentration, the water concentration in the reaction product liquid is 5 to 40% by weight, preferably 5 to 30% by weight.
【００１０】本発明で使用する触媒はコバルト及び／又
はマンガンからなる遷移金属並びに臭素であるが、遷移
金属としてニッケル、セリウム等の他の遷移金属が加わ
っても良い。これらの遷移金属を反応系内に存在させる
には、溶媒に可溶な化合物として添加すれば良く、その
様な化合物としては、遷移金属の酢酸塩、プロピオン酸
塩、水酸化物、炭酸塩、臭化物等を挙げることができる
が、好ましくは酢酸塩、プロピオン酸塩、臭化物であ
る。また、臭素も溶媒に可溶な物質であれば何でも良
く、その様な化合物としては、分子状臭素、臭化水素、
金属臭化物、臭化アルキル等を挙げることができるが、
好ましくは臭化コバルト、臭化マンガン、臭化ニッケ
ル、臭化セリウム等の遷移金属臭化物、臭化カリウム、
臭化ナトリウム等のアルカリ金属臭化物である。これら
の触媒の内、コバルト及び／又はマンガンからなる遷移
金属の使用量はその合計濃度が溶媒に対して０．０３重
量％以上、好ましくは０．０６重量％以上、より好まし
くは０．２重量％以上である。臭素の使用量は臭素濃度
が溶媒に対して０．０１重量％、好ましくは０．０３重
量％以上である。ここで、濃度は金属または臭素に換算
した濃度を意味し、反応系内で金属または臭素として存
在することを意味するものではない。The catalyst used in the present invention is a transition metal composed of cobalt and / or manganese and bromine, but other transition metals such as nickel and cerium may be added as transition metals. In order to allow these transition metals to exist in the reaction system, it may be added as a compound soluble in a solvent, and examples of such compounds include transition metal acetates, propionates, hydroxides, carbonates, Bromide and the like can be mentioned, but acetate, propionate and bromide are preferable. Also, bromine may be any substance that is soluble in a solvent, and examples of such a compound include molecular bromine, hydrogen bromide,
Metal bromide, alkyl bromide and the like can be mentioned,
Preferably cobalt bromide, manganese bromide, nickel bromide, transition metal bromides such as cerium bromide, potassium bromide,
It is an alkali metal bromide such as sodium bromide. Among these catalysts, the total amount of the transition metal composed of cobalt and / or manganese used is 0.03% by weight or more, preferably 0.06% by weight or more, more preferably 0.2% by weight, based on the solvent. % Or more. The amount of bromine used is such that the bromine concentration is 0.01% by weight, preferably 0.03% by weight or more, based on the solvent. Here, the concentration means a concentration converted to metal or bromine, and does not mean that it exists as metal or bromine in the reaction system.
【００１１】炭素数が３以下の脂肪族モノカルボン酸を
少なくとも５０重量％含有する溶媒を、４−エチルビフ
ェニル、その酸化中間体及び４−ビフェニルカルボン酸
の合計に対し、２倍重量、好ましくは３倍重量以上用い
る。溶媒量が不足すると４−ビフェニルカルボン酸の収
率が低下すると共に、スラリー濃度が高くなり操作性が
悪くなる。A solvent containing at least 50% by weight of an aliphatic monocarboxylic acid having 3 or less carbon atoms is used in an amount of twice the weight of 4-ethylbiphenyl, its oxidation intermediate and 4-biphenylcarboxylic acid, preferably Use at least 3 times the weight. When the amount of the solvent is insufficient, the yield of 4-biphenylcarboxylic acid is lowered, and the slurry concentration is increased to deteriorate the operability.
【００１２】反応温度は、１１０〜２６０℃、好ましく
は１３０〜２２０℃の範囲である。反応温度が低いと反
応速度の低下により４−ビフェニルカルボン酸の収率が
低下し、反対に高い場合は副反応生成物が増加して、得
られる４−ビフェニルカルボン酸の純度が低下する。The reaction temperature is in the range of 110 to 260 ° C, preferably 130 to 220 ° C. If the reaction temperature is low, the yield of 4-biphenylcarboxylic acid decreases due to the decrease in the reaction rate, and on the contrary, if it is high, the side reaction product increases and the purity of the obtained 4-biphenylcarboxylic acid decreases.
【００１３】本発明で使用する分子状酸素含有ガスとし
ては、酸素ガス、不活性ガスで希釈された分子状酸素等
であり、その酸素濃度は１０〜１００体積％、好ましく
は、１５〜１００体積％である。工業的には空気を使用
するのが有利である。また、酸素分圧は、０．１〜２０
ｋｇ／ｃｍ2 ・Ｇの範囲、好ましくは０．１〜１０ｋｇ
／ｃｍ2 ・Ｇの範囲、更に好ましくは０．５〜５ｋｇ／
ｃｍ2 ・Ｇの範囲である。反応圧力は反応温度において
溶媒が液相に保持されるように設定するが、通常、１０
〜３０ｋｇ／ｃｍ2 ・Ｇ程度が適当である。The molecular oxygen-containing gas used in the present invention is oxygen gas, molecular oxygen diluted with an inert gas or the like, and the oxygen concentration thereof is 10 to 100% by volume, preferably 15 to 100% by volume. %. Industrially, it is advantageous to use air. The oxygen partial pressure is 0.1 to 20.
Range of kg / cm 2 · G, preferably 0.1 to 10 kg
/ Cm 2 · G range, more preferably 0.5-5 kg /
The range is cm 2 · G. The reaction pressure is set so that the solvent is kept in the liquid phase at the reaction temperature, but it is usually 10
Appropriately about 30 kg / cm 2 · G.
【００１４】本発明の反応形式は、完全連続方式、半連
続方式、バッチ方式のいずれでも良いが、副反応を抑制
し、収率、純度良く４−ビフェニルカルボン酸を得るた
めには、完全連続方式、半連続方式が好ましい。The reaction system of the present invention may be a complete continuous system, a semi-continuous system or a batch system, but in order to suppress side reactions and obtain 4-biphenylcarboxylic acid in good yield and purity, it is a complete continuous system. The method and the semi-continuous method are preferable.
【００１５】酸化反応によって生成した４−ビフェニル
カルボン酸は、反応生成物を固液分離することによって
固相側に得ることができる。ただし、４−ビフェニルカ
ルボン酸の溶媒への溶解度がジカルボン酸等に比べ大き
いため、反応終了後の溶液中の水分濃度を高くする、固
液分離時の温度を低くする、等して４−ビフェニルカル
ボン酸の溶媒への溶解度を低くすることが好ましい。The 4-biphenylcarboxylic acid produced by the oxidation reaction can be obtained on the solid phase side by solid-liquid separation of the reaction product. However, since the solubility of 4-biphenylcarboxylic acid in a solvent is higher than that of dicarboxylic acid, 4-biphenylcarboxylic acid is used by increasing the water concentration in the solution after completion of the reaction, lowering the temperature during solid-liquid separation, and the like. It is preferable to lower the solubility of the carboxylic acid in the solvent.
【００１６】反応終了後の溶液中の水分濃度を高くする
場合は、反応生成液中の水分濃度として、５〜４０重量
％、好ましくは５〜３０重量％となるよう、水分をあら
かじめ混在させるのが良い。こうすることによって、た
とえば酢酸を溶媒に用いた場合、８０℃での酢酸に対す
る４−ビフェニルカルボン酸の溶解度は約６重量％であ
るのに対し、２０重量％の水分を含む酢酸水溶液に対す
る８０℃での４−ビフェニルカルボン酸の溶解度は約２
重量％と低くなる。また、反応中は水分濃度を低く保
ち、反応終了後に貧溶媒として水を加える方法でも良
い。When the water concentration in the solution after the reaction is increased, water is mixed in advance so that the water concentration in the reaction product liquid is 5 to 40% by weight, preferably 5 to 30% by weight. Is good. By doing so, for example, when acetic acid is used as a solvent, the solubility of 4-biphenylcarboxylic acid in acetic acid at 80 ° C. is about 6% by weight, while the solubility in acetic acid aqueous solution containing 20% by weight of water is 80 ° C. The solubility of 4-biphenylcarboxylic acid is about 2
It becomes as low as weight%. Alternatively, a method may be used in which the water concentration is kept low during the reaction and water is added as a poor solvent after the reaction is completed.
【００１７】固液分離時の温度を低くして４−ビフェニ
ルカルボン酸の溶媒への溶解度を低くする場合は、７０
℃以下、好ましくは５０℃以下が良い。たとえば、４０
℃での酢酸に対する４−ビフェニルカルボン酸の溶解度
は約２重量％と低くなる。固液分離時の温度を低くする
方法と、反応終了後の溶媒中の水分濃度を高くする方法
を併せて用いれば、さらに効果的である。たとえば、２
０重量％の水分を含む酢酸水溶液に対する４０℃での４
−ビフェニルカルボン酸の溶解度は約０．５重量％にま
で低下し、有利である。When the temperature at the time of solid-liquid separation is lowered to lower the solubility of 4-biphenylcarboxylic acid in the solvent, 70
C. or lower, preferably 50.degree. C. or lower. For example, 40
The solubility of 4-biphenylcarboxylic acid in acetic acid at ° C is as low as about 2% by weight. It is more effective to use both the method of lowering the temperature during solid-liquid separation and the method of increasing the water concentration in the solvent after the completion of the reaction. For example, 2
4 at 40 ° C. for acetic acid aqueous solution containing 0% by weight of water
Advantageously, the solubility of biphenylcarboxylic acid is reduced to about 0.5% by weight.
【００１８】また、４−ビフェニルカルボン酸の収率を
上げるために、４−ビフェニルカルボン酸固液分離後の
溶液より溶媒の一部を除去し、さらに４−ビフェニルカ
ルボン酸を回収することもできる。Further, in order to increase the yield of 4-biphenylcarboxylic acid, a part of the solvent can be removed from the solution after the solid-liquid separation of 4-biphenylcarboxylic acid, and further 4-biphenylcarboxylic acid can be recovered. .
【００１９】以上のような固液分離によって得られた粗
４−ビフェニルカルボン酸は、酢酸等による洗浄、水洗
浄を行うことにより、付着触媒溶液、酸化反応中間体、
および遷移金属錯体を除去することができ、純度アップ
が可能である。さらに必要な場合は、公知の方法として
知られている芳香族カルボン酸精製法を用いれば、極め
て高純度の４−ビフェニルカルボン酸を得ることができ
る。The crude 4-biphenylcarboxylic acid obtained by the solid-liquid separation as described above is washed with acetic acid or the like and washed with water to obtain an attached catalyst solution, an oxidation reaction intermediate,
And the transition metal complex can be removed, and the purity can be increased. Further, if necessary, an extremely high-purity 4-biphenylcarboxylic acid can be obtained by using a known aromatic carboxylic acid purification method.
【００２０】[0020]
【実施例】以下、実施例に基づいて、本発明を具体的に
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。なお、実施例における部及び％はそれ
ぞれ重量部及び重量％を示す。EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. In addition, the part and% in an Example show a weight part and weight%, respectively.
【００２１】実施例１ ポリエチルベンゼン１００００部、ビフェニル５０００
部、触媒としてＹ型ゼオライト３０００部を攪拌器付き
オ−トクレ−ブに仕込み、１８０℃で４時間反応させ
た。ポリエチルベンゼンはジエチルベンゼンとトリエチ
ルベンゼンの混合物である。反応終了後、触媒を固液分
離により除去し、エチルベンゼン類及びエチルビフェニ
ル類混合物を得た。エチルビフェニル類の組成は、ビフ
ェニル３５％、エチルビフェニル４６％、ジエチルビフ
ェニル１５％、トリエチルビフェニル２％、その他２％
であり、エチルビフェニル中の４−エチルビフェニルの
割合は８９％であった。このようにして得られた反応生
成物の内、１２０００部を理論段数７０段の精密蒸留塔
で蒸留した。その結果、純度９９％の４−エチルビフェ
ニルを１１００部得た。電磁攪拌器付きチタン製オ−ト
クレ−ブに、コバルト濃度０．２％、マンガン濃度０．
２％、臭素濃度０．２％の触媒溶液１００部を予め装入
し、反応温度１６０℃、反応圧３０kg/cｍ2 ・G に保持
しながら、この純度９９％の４−エチルビフェニル及び
圧縮空気を連続的に反応器に供給し、酸化反応を行っ
た。コバルトは酢酸コバルトとして、マンガンは酢酸マ
ンガンとして、臭素は臭化ナトリウムとしてそれぞれ添
加し、溶媒には５％の水分を含む酢酸を用いた。４−エ
チルビフェニルは毎時１０部の割合で２時間供給し、４
−エチルビフェニル供給終了後も、反応器の温度と圧力
を保持したまま圧縮空気を１５分間供給した。反応終了
後、反応生成液を３０℃まで冷却し、固液分離した。得
られた結晶を水洗後乾燥し、純度９８％の４−ビフェニ
ルカルボン酸を２０部得た。また、固液分離後の溶液の
水分濃度は１１％であった。Example 1 10000 parts of polyethylbenzene and 5000 of biphenyl
Parts, and 3000 parts of Y-type zeolite as a catalyst were placed in an autoclave equipped with a stirrer and reacted at 180 ° C. for 4 hours. Polyethylbenzene is a mixture of diethylbenzene and triethylbenzene. After completion of the reaction, the catalyst was removed by solid-liquid separation to obtain a mixture of ethylbenzenes and ethylbiphenyls. The composition of ethylbiphenyls is as follows: 35% biphenyl, 46% ethylbiphenyl, 15% diethylbiphenyl, 2% triethylbiphenyl, 2% other.
And the ratio of 4-ethylbiphenyl in ethylbiphenyl was 89%. Of the reaction product thus obtained, 12,000 parts were distilled in a precision distillation column having 70 theoretical plates. As a result, 1100 parts of 4-ethylbiphenyl having a purity of 99% was obtained. A titanium autoclave equipped with an electromagnetic stirrer had a cobalt concentration of 0.2% and a manganese concentration of 0.
100 parts of a catalyst solution of 2% and bromine concentration of 0.2% was charged in advance, and while maintaining the reaction temperature of 160 ° C. and the reaction pressure of 30 kg / cm 2 · G, the 99% pure 4-ethylbiphenyl and compressed air. Was continuously supplied to the reactor to carry out the oxidation reaction. Cobalt was added as cobalt acetate, manganese was added as manganese acetate, bromine was added as sodium bromide, and acetic acid containing 5% water was used as a solvent. 4-Ethylbiphenyl is supplied at a rate of 10 parts per hour for 2 hours and 4
After the ethyl biphenyl feed was completed, compressed air was fed for 15 minutes while maintaining the reactor temperature and pressure. After completion of the reaction, the reaction product liquid was cooled to 30 ° C. and solid-liquid separated. The obtained crystals were washed with water and dried to obtain 20 parts of 4-biphenylcarboxylic acid having a purity of 98%. The water concentration of the solution after solid-liquid separation was 11%.
【００２２】実施例２ 電磁攪拌器付きチタン製オ−トクレ−ブに、コバルト濃
度０．３％、マンガン濃度０．３％、臭素濃度０．３％
の触媒溶液１００部を予め装入し、反応温度１７０℃、
反応圧３０kg/cｍ2 ・G に保持しながら、実施例１で得
た純度９９％の４−エチルビフェニル及び圧縮空気を連
続的に反応器に供給し、酸化反応を行った。コバルトは
酢酸コバルトとして、マンガンは酢酸マンガンとして、
臭素は臭化ナトリウムとしてそれぞれ添加し、溶媒には
１５％の水分を含む酢酸を用いた。４−エチルビフェニ
ルは毎時１０部の割合で２時間供給し、４−エチルビフ
ェニル供給終了後も、反応器の温度と圧力を保持したま
ま圧縮空気を１５分間供給した。反応終了後、反応生成
液を４５℃まで冷却し、固液分離した。得られた結晶を
水洗後乾燥し、純度９８％の４−ビフェニルカルボン酸
を２１部得た。また、固液分離後の溶液の水分濃度は２
１％であった。Example 2 A titanium autoclave equipped with an electromagnetic stirrer was used, and the cobalt concentration was 0.3%, the manganese concentration was 0.3%, and the bromine concentration was 0.3%.
100 parts of the catalyst solution was charged in advance, and the reaction temperature was 170 ° C.,
While maintaining the reaction pressure at 30 kg / cm 2 · G, 99% pure 4-ethylbiphenyl obtained in Example 1 and compressed air were continuously supplied to the reactor to carry out the oxidation reaction. Cobalt is cobalt acetate, manganese is manganese acetate,
Bromine was added as sodium bromide, and acetic acid containing 15% water was used as a solvent. 4-Ethylbiphenyl was supplied at a rate of 10 parts per hour for 2 hours, and after completion of the 4-ethylbiphenyl supply, compressed air was supplied for 15 minutes while maintaining the temperature and pressure of the reactor. After completion of the reaction, the reaction product liquid was cooled to 45 ° C. and solid-liquid separated. The obtained crystals were washed with water and dried to obtain 21 parts of 4-biphenylcarboxylic acid having a purity of 98%. The water concentration of the solution after solid-liquid separation is 2
It was 1%.
【００２３】実施例３ 電磁攪拌器付きチタン製オ−トクレ−ブに、コバルト濃
度０．２％、マンガン濃度０．２％、臭素濃度０．２％
の触媒溶液１００部を予め装入し、反応温度１６０℃、
反応圧３０kg/cｍ2 ・G に保持しながら、実施例１で得
た純度９９％の４−エチルビフェニル及び圧縮空気を連
続的に反応器に供給し、酸化反応を行った。コバルトは
酢酸コバルトとして、マンガンは酢酸マンガンとして、
臭素は臭化ナトリウムとしてそれぞれ添加し、溶媒には
２％の水分を含む酢酸を用いた。４−エチルビフェニル
は毎時１０部の割合で２時間供給し、４−エチルビフェ
ニル供給終了後も、反応器の温度と圧力を保持したまま
圧縮空気を１５分間供給した。反応終了後、反応生成液
を６０℃まで冷却し、さらに溶液中の酢酸：水重量比が
１：１程度となるよう水を添加した後、固液分離した。
得られた結晶を水洗後乾燥し、純度９７％の４−ビフェ
ニルカルボン酸を２２部得た。Example 3 A titanium autoclave equipped with an electromagnetic stirrer was used, and a cobalt concentration of 0.2%, a manganese concentration of 0.2%, and a bromine concentration of 0.2%.
100 parts of the catalyst solution were charged in advance, and the reaction temperature was 160 ° C.
While maintaining the reaction pressure at 30 kg / cm 2 · G, 99% pure 4-ethylbiphenyl obtained in Example 1 and compressed air were continuously supplied to the reactor to carry out the oxidation reaction. Cobalt is cobalt acetate, manganese is manganese acetate,
Bromine was added as sodium bromide, and acetic acid containing 2% of water was used as a solvent. 4-Ethylbiphenyl was supplied at a rate of 10 parts per hour for 2 hours, and after completion of the 4-ethylbiphenyl supply, compressed air was supplied for 15 minutes while maintaining the temperature and pressure of the reactor. After completion of the reaction, the reaction product solution was cooled to 60 ° C., water was added so that the weight ratio of acetic acid: water in the solution was about 1: 1, and then solid-liquid separation was performed.
The obtained crystals were washed with water and dried to obtain 22 parts of 4-biphenylcarboxylic acid having a purity of 97%.
【００２４】実施例４ 電磁攪拌器付きチタン製オ−トクレ−ブに、コバルト濃
度０．２％、マンガン濃度０．２％、臭素濃度０．１％
の触媒溶液１００部を予め装入し、反応温度１７０℃、
反応圧３０kg/cｍ2 ・G に保持しながら、実施例１で得
た純度９９％の４−エチルビフェニル及び圧縮空気を連
続的に反応器に供給し、酸化反応を行った。コバルトは
酢酸コバルトとして、マンガンは酢酸マンガンとして、
臭素は臭化ナトリウムとしてそれぞれ添加し、溶媒には
１％の水分を含む酢酸を用いた。４−エチルビフェニル
は毎時１０部の割合で２時間供給し、４−エチルビフェ
ニル供給終了後も、反応器の温度と圧力を保持したまま
圧縮空気を１５分間供給した。反応終了後、反応生成液
を６０℃まで冷却し、固液分離した。得られた結晶を水
洗後乾燥し、純度９８％の４−ビフェニルカルボン酸を
１８部得た。また、固液分離後の溶液を、その重量が半
分になるまでエバポレートし、析出した結晶を固液分離
した。得られた結晶を水洗後乾燥し、純度９５％の４−
ビフェニルカルボン酸を２部得た。Example 4 A titanium autoclave equipped with an electromagnetic stirrer was charged with a cobalt concentration of 0.2%, a manganese concentration of 0.2%, and a bromine concentration of 0.1%.
100 parts of the catalyst solution was charged in advance, and the reaction temperature was 170 ° C.,
While maintaining the reaction pressure at 30 kg / cm 2 · G, 99% pure 4-ethylbiphenyl obtained in Example 1 and compressed air were continuously supplied to the reactor to carry out the oxidation reaction. Cobalt is cobalt acetate, manganese is manganese acetate,
Bromine was added as sodium bromide, and acetic acid containing 1% of water was used as a solvent. 4-Ethylbiphenyl was supplied at a rate of 10 parts per hour for 2 hours, and after completion of the 4-ethylbiphenyl supply, compressed air was supplied for 15 minutes while maintaining the temperature and pressure of the reactor. After completion of the reaction, the reaction product liquid was cooled to 60 ° C. and solid-liquid separated. The obtained crystals were washed with water and dried to obtain 18 parts of 4-biphenylcarboxylic acid having a purity of 98%. Further, the solution after solid-liquid separation was evaporated until the weight became half, and the precipitated crystal was solid-liquid separated. The obtained crystals were washed with water and dried to give a 95% pure 4-
Two parts of biphenylcarboxylic acid were obtained.
【００２５】比較例１ 電磁攪拌器付きチタン製オ−トクレ−ブに、コバルト濃
度０．０１％、マンガン濃度０．０１％、臭素濃度０．
０１％の触媒溶液１００部を予め装入し、反応温度１７
０℃、反応圧３０kg/cｍ2 ・G に保持しながら、実施例
１で得た純度９９％の４−エチルビフェニル及び圧縮空
気を連続的に反応器に供給し、酸化反応を行った。コバ
ルトは酢酸コバルトとして、マンガンは酢酸マンガンと
して、臭素は臭化ナトリウムとしてそれぞれ添加し、溶
媒には１％の水分を含む酢酸を用いた。４−エチルビフ
ェニルは毎時１０部の割合で２時間供給し、４−エチル
ビフェニル供給終了後も、反応器の温度と圧力を保持し
たまま圧縮空気を１５分間供給した。反応終了後、反応
生成液を７５℃まで冷却し、固液分離した。得られた結
晶を水洗後乾燥し、純度９２％の４−ビフェニルカルボ
ン酸を５部得た。Comparative Example 1 A titanium autoclave equipped with an electromagnetic stirrer was used, in which a cobalt concentration of 0.01%, a manganese concentration of 0.01%, and a bromine concentration of 0.
100 parts of 01% catalyst solution was charged in advance and the reaction temperature was 17
While maintaining at 0 ° C. and a reaction pressure of 30 kg / cm 2 · G, 4-ethylbiphenyl having a purity of 99% obtained in Example 1 and compressed air were continuously supplied to the reactor to carry out an oxidation reaction. Cobalt was added as cobalt acetate, manganese was added as manganese acetate, and bromine was added as sodium bromide. Acetic acid containing 1% of water was used as a solvent. 4-Ethylbiphenyl was supplied at a rate of 10 parts per hour for 2 hours, and after completion of the 4-ethylbiphenyl supply, compressed air was supplied for 15 minutes while maintaining the temperature and pressure of the reactor. After completion of the reaction, the reaction product liquid was cooled to 75 ° C. and solid-liquid separated. The obtained crystals were washed with water and dried to obtain 5 parts of 4-biphenylcarboxylic acid having a purity of 92%.
【００２６】[0026]
【発明の効果】本発明によれば、入手の容易な４−エチ
ルビフェニルを液相酸化することにより効率の良い４−
ビフェニルカルボン酸の製造方法が確立でき、工業的に
有意義である。INDUSTRIAL APPLICABILITY According to the present invention, 4-ethylbiphenyl, which is easily available, is subjected to liquid-phase oxidation to improve the efficiency of 4-
A method for producing biphenylcarboxylic acid can be established and is industrially significant.
Claims (5)
化中間体を、炭素数が３以下の脂肪族モノカルボン酸を
少なくとも５０重量％含有する溶媒に、触媒としての遷
移金属及び臭素を溶解させた溶液中で、分子状酸素含有
ガスにより酸化するに当たり、４−エチルビフェニル、
その酸化中間体及び４−ビフェニルカルボン酸の合計に
対して少なくとも２倍重量の溶媒を使用し、溶媒当たり
０．０３重量％以上のコバルト及び／又はマンガンより
なる遷移金属及び溶媒当たり０．０１重量％以上の臭素
を存在させた溶液中で、反応温度１１０〜２６０℃、酸
素分圧０．１〜２０ｋｇ／ｃｍ2 ・Ｇの反応条件で酸化
し、次いで得られた反応生成液から４−ビフェニルカル
ボン酸を分離することを特徴とする４−ビフェニルカル
ボン酸の製造方法。1. A transition metal and bromine as a catalyst are dissolved in 4-ethylbiphenyl and / or its oxidized intermediate in a solvent containing at least 50% by weight of an aliphatic monocarboxylic acid having 3 or less carbon atoms. In the solution, when oxidized by a gas containing molecular oxygen, 4-ethylbiphenyl,
At least 2 times the weight of the solvent is used with respect to the total amount of the oxidation intermediate and 4-biphenylcarboxylic acid, and 0.03% by weight or more of the transition metal consisting of cobalt and / or manganese per solvent and 0.01 weight per solvent. % Of bromine is present in the solution, the reaction temperature is 110 to 260 ° C., the oxygen partial pressure is 0.1 to 20 kg / cm 2 · G, and the reaction product solution is oxidized to give 4-biphenyl. A method for producing 4-biphenylcarboxylic acid, which comprises separating a carboxylic acid.
％とする請求項１記載の４−ビフェニルカルボン酸の製
造方法。2. The method for producing 4-biphenylcarboxylic acid according to claim 1, wherein the water concentration in the reaction product liquid is 5 to 40% by weight.
ン酸の分離が７０℃以下で行う固液分離である請求項１
記載の４−ビフェニルカルボン酸の製造方法。3. The separation of 4-biphenylcarboxylic acid from the reaction product liquid is solid-liquid separation performed at 70 ° C. or lower.
A method for producing the described 4-biphenylcarboxylic acid.
ランスエチル化反応で得られた反応生成物から蒸留分離
して得られた４−エチルビフェニルを酸化する請求項１
記載の４−ビフェニルカルボン酸の製造方法。4. The 4-ethylbiphenyl obtained by distillation separation from the reaction product obtained by the transethylation reaction of biphenyl and polyethylbenzene is oxidized.
A method for producing the described 4-biphenylcarboxylic acid.
及び／又はマンガン及び溶媒当たり０．０１重量％以上
の臭素を存在させた溶液中で反応する請求項１記載の４
−ビフェニルカルボン酸の製造方法。5. The method according to claim 1, wherein the reaction is carried out in a solution containing 0.2% by weight or more of cobalt and / or manganese per solvent and 0.01% by weight or more of bromine per solvent.
-Method for producing biphenylcarboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13931893A JP3264733B2 (en) | 1993-05-19 | 1993-05-19 | Method for producing 4-biphenylcarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13931893A JP3264733B2 (en) | 1993-05-19 | 1993-05-19 | Method for producing 4-biphenylcarboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06329584A true JPH06329584A (en) | 1994-11-29 |
| JP3264733B2 JP3264733B2 (en) | 2002-03-11 |
Family
ID=15242522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13931893A Expired - Fee Related JP3264733B2 (en) | 1993-05-19 | 1993-05-19 | Method for producing 4-biphenylcarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3264733B2 (en) |
-
1993
- 1993-05-19 JP JP13931893A patent/JP3264733B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3264733B2 (en) | 2002-03-11 |
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