JP7083793B2 - Method for producing paraterphenyltetracarboxylic acid and paraterphenyltetracarboxylic acid dianhydride - Google Patents
Method for producing paraterphenyltetracarboxylic acid and paraterphenyltetracarboxylic acid dianhydride Download PDFInfo
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Description
本発明は、パラターフェニルテトラカルボン酸およびその二無水物の製造方法に関する。 The present invention relates to a method for producing a paraterphenyltetracarboxylic acid and its dianhydride.
パラターフェニルテトラカルボン酸およびその二無水物は、主にポリイミド樹脂の原料に使用される化合物である。その合成方法については、特許文献１に記載がある。こちらの文献では、ブロモ－オルト－キシレンのグリニャール試薬にパラ－ジクロロベンゼンを反応させて３，４，３”，４”－テトラメチル－パラ－ターフェニルを調製し、さらに過マンガン酸カリウムを用いて酸化することでパラターフェニルテトラカルボン酸を得ている。さらに、得られたパラターフェニルテトラカルボン酸を無水酢酸で無水化することでその二無水物を得ている。しかし、この方法は、カルボン酸を得るまでに２段階の反応を経由しており、工程数が長いこと、低収率であることが課題である。 Paraterphenyltetracarboxylic acid and its dianhydride are compounds mainly used as raw materials for polyimide resins. The synthesis method is described in Patent Document 1. In this document, para-dichlorobenzene is reacted with a Grignard reagent of bromo-ortho-xylene to prepare 3,4,3 ", 4" -tetramethyl-para-terphenyl, and potassium permanganate is used. And oxidize to obtain paraterphenyltetracarboxylic acid. Further, the obtained paraterphenyltetracarboxylic acid is anhydrous with acetic anhydride to obtain the dianhydride. However, this method goes through a two-step reaction until a carboxylic acid is obtained, and has problems that the number of steps is long and the yield is low.
本発明の目的は、従来の方法では満足できなかったパラターフェニルテトラカルボン酸およびその二無水物の工業的に有利な製造方法を提供することにある。 An object of the present invention is to provide an industrially advantageous method for producing paraterphenyltetracarboxylic acid and its dianhydride, which have not been satisfied by conventional methods.
本発明者らは、従来の問題点を解決すべく鋭意検討を重ねた結果、本発明に至った。 The present inventors have reached the present invention as a result of repeated diligent studies to solve the conventional problems.
すなわち本発明は、下記式（１）で表される４－ハロフタル酸を下記式（２）で表される１，４－フェニレンジボロン酸と反応させることで、下記式（３）で表されるパラターフェニルテトラカルボン酸を製造する（第一反応）、さらに、無水化することで、下記式（４）で表されるパラターフェニルテトラカルボン酸二無水物を製造する（第二反応）方法である。
本発明によれば、従来の問題を解決し、かつ工業的規模で経済性に優れた方法でパラターフェニルテトラカルボン酸二無水物を製造することが可能となる。 According to the present invention, it is possible to solve the conventional problems and to produce paraterphenyltetracarboxylic acid dianhydride by an industrial scale and economical method.
次に好ましい実施の形態を挙げて本発明をさらに詳しく説明する。 Next, the present invention will be described in more detail with reference to preferred embodiments.
本発明の第一反応において使用する４－ハロフタル酸は特に限定するものではない。すなわち、４－ハロフタル酸として４－フルオロフタル酸、４－クロロフタル酸、４－ブロモフタル酸、４－ヨードフタル酸を挙げることができる。 The 4-halophthalic acid used in the first reaction of the present invention is not particularly limited. That is, examples of 4-halophthalic acid include 4-fluorophthalic acid, 4-chlorophthalic acid, 4-bromophthalic acid, and 4-iodophthalic acid.
本発明の第一反応では下記のパラジウム系触媒を使用することが好ましい。本発明において使用するパラジウム系触媒としては、テトラキス（トリフェニルホスフィン）パラジウム、ジクロロビス（トリフェニルホスフィン）パラジウム、ジクロロ［ビス（ジフェニルホスフィノ）エタン］パラジウム、ジクロロ［ビス（ジフェニルホスフィノ）プロパン］パラジウム、ジクロロ［ビス（ジフェニルホスフィノ）ブタン］パラジウム、ジクロロ［ビス（ジフェニルホスフィノ）フェロセン］パラジウム等のパラジウム錯体を用いることができる。パラジウム系触媒の使用量は、１，４－フェニレンジボロン酸に対し、０．００１～１０モル％が好ましく、より好ましくは０．００５～２モル％である。 It is preferable to use the following palladium-based catalyst in the first reaction of the present invention. Examples of the palladium-based catalyst used in the present invention include tetrakis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) palladium, dichloro [bis (diphenylphosphino) ethane] palladium, and dichloro [bis (diphenylphosphino) propane] palladium. , Palladium complexes such as dichloro [bis (diphenylphosphino) butane] palladium and dichloro [bis (diphenylphosphino) ferrocene] palladium can be used. The amount of the palladium-based catalyst used is preferably 0.001 to 10 mol%, more preferably 0.005 to 2 mol%, based on 1,4-phenylenediboronic acid.
本発明の第一反応では塩基を使用することが好ましい。本発明の第一反応で使用する塩基としては、炭酸ナトリウム、炭酸カリウム、水酸化ナトリウム、水酸化カリウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸マグネシウム、炭酸カルシウム等の無機塩基を用いることができるが、特に炭酸カリウムが好ましい。塩基の使用量は、１，４－フェニレンジボロン酸に対し、３～２０モル％が好ましく、より好ましくは５～１５モル％である。 It is preferable to use a base in the first reaction of the present invention. As the base used in the first reaction of the present invention, inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, magnesium carbonate, calcium carbonate and the like can be used. , Particularly potassium carbonate is preferred. The amount of the base used is preferably 3 to 20 mol%, more preferably 5 to 15 mol% with respect to 1,4-phenylenediboronic acid.
本発明の第一反応では反応溶媒を使用することが好ましい。本発明の第一反応において使用する反応溶媒としては、水と有機溶媒との混合系を用いることができる。有機溶媒としては、メタノール、エタノール、２－プロパノール等のアルコール類、アセトニトリル、ベンゾニトリル等のニトリル類、ジクロロメタン、１，２－ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ジエチルエーテル、テトラヒドロフラン等のエーテル類、酢酸メチル、酢酸エチル、酢酸ブチル等のエステル類、ヘキサン、ヘプタン、オクタン等の飽和炭化水素類、ベンゼン、トルエン、キシレン等のベンゼン類、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド類などを用いることができる。 It is preferable to use a reaction solvent in the first reaction of the present invention. As the reaction solvent used in the first reaction of the present invention, a mixed system of water and an organic solvent can be used. Examples of the organic solvent include alcohols such as methanol, ethanol and 2-propanol, nitriles such as acetonitrile and benzonitrile, halogen-based solvents such as dichloromethane, 1,2-dichloroethane, chloroform and carbon tetrachloride, diethyl ether and tetrahydrofuran. Ethers, esters such as methyl acetate, ethyl acetate, butyl acetate, saturated hydrocarbons such as hexane, heptane, octane, benzenes such as benzene, toluene, xylene, N, N-dimethylformamide, N, N- Amidos such as dimethylacetoamide can be used.
本発明の第一反応は、窒素等の不活性雰囲気中で行い、１００℃以下の温度で実施することが好ましい。反応終了後は、室温に放冷した反応液中の固形触媒を濾別し、次いで塩酸や硫酸等の酸性水溶液に滴下することで結晶を析出させる。析出した結晶を濾別し、次いで水で洗浄し、乾燥させることでパラターフェニルテトラカルボン酸を得る。 The first reaction of the present invention is preferably carried out in an inert atmosphere such as nitrogen, and is preferably carried out at a temperature of 100 ° C. or lower. After completion of the reaction, the solid catalyst in the reaction solution cooled to room temperature is filtered off, and then the crystals are precipitated by dropping into an acidic aqueous solution such as hydrochloric acid or sulfuric acid. The precipitated crystals are filtered off, then washed with water and dried to obtain paraterphenyltetracarboxylic acid.
本発明の第二反応は、上記の方法で得られたパラターフェニルテトラカルボン酸を無水酢酸と反応させることで実施することができる。無水酢酸の使用量は、パラターフェニル酸テトラカルボン酸に対して、２～５０モル％が好ましく、より好ましくは５～２０モル％である。反応終了後は、室温に放冷したスラリーより固形分を濾別し、次いでトルエン洗浄、乾燥させることでパラターフェニルテトラカルボン酸二無水物を得る。 The second reaction of the present invention can be carried out by reacting the paraterphenyltetracarboxylic acid obtained by the above method with acetic anhydride. The amount of acetic anhydride used is preferably 2 to 50 mol%, more preferably 5 to 20 mol%, based on the tetracarboxylic acid paraterphenylate. After completion of the reaction, the solid content is filtered off from the slurry cooled to room temperature, then washed with toluene and dried to obtain paraterphenyltetracarboxylic acid dianhydride.
本発明の第二反応は、上記の方法で得られたパラターフェニルテトラカルボン酸を加熱脱水することでも実施することができる。加熱温度は１５０～３００℃の温度が好ましく、より好ましくは２００～２５０℃である。 The second reaction of the present invention can also be carried out by heating and dehydrating the paraterphenyltetracarboxylic acid obtained by the above method. The heating temperature is preferably 150 to 300 ° C, more preferably 200 to 250 ° C.
以下に、本発明を実施例により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。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
（実施例１）
攪拌機、温度計、冷却管、窒素導入口を備えた１Ｌ四つ口フラスコに水 ３００ｇ、エタノール ３００ｇ、炭酸カリウム ３００ｇ（１．３０モル）、１，４－フェニレンジボロン酸 １５ｇ（０．０９１モル）、４－ブロモフタル酸 ５３．２ｇ（０．２１７モル）を仕込み、系内を窒素で置換しながら攪拌をした。十分に窒素置換が終わったところで、テトラキス（トリフェニルホスフィン）パラジウム ２．５ｇ（２．１６ミリモル）を加えて、７０℃に昇温し１６時間反応させた。反応完了後、常温まで冷却して、不溶分を濾別し、反応液を回収した。次いで、３５％塩酸 ４７０ｇを仕込んだフラスコを７０℃に加熱し、そこに反応液を徐々に滴下して酸析し、５０℃まで降温した後、濾別して固形分を回収した。回収した固形分を水 ６００ｇで洗浄し、１２０℃で減圧乾燥することでパラターフェニルテトラカルボン酸 ３４．６ｇ（工程収率９４．１％、ＬＣ純度９１．５％）を得た。
(Example 1)
300 g of water, 300 g of ethanol, 300 g of potassium carbonate (1.30 mol), 15 g of 1,4-phenylenediboronic acid (0.091 mol) in a 1 L four-necked flask equipped with a stirrer, thermometer, cooling tube and nitrogen inlet. ), 43.2 g (0.217 mol) of 4-bromophthalic acid was charged, and the inside of the system was stirred while being replaced with nitrogen. When the nitrogen substitution was sufficiently completed, 2.5 g (2.16 mmol) of tetrakis (triphenylphosphine) palladium was added, the temperature was raised to 70 ° C., and the reaction was carried out for 16 hours. After the reaction was completed, the mixture was cooled to room temperature, the insoluble matter was filtered off, and the reaction solution was recovered. Next, a flask containing 470 g of 35% hydrochloric acid was heated to 70 ° C., a reaction solution was gradually added dropwise thereto for acid analysis, the temperature was lowered to 50 ° C., and then the solid content was recovered by filtration. The recovered solid content was washed with 600 g of water and dried under reduced pressure at 120 ° C. to obtain 34.6 g of paraterphenyltetracarboxylic acid (process yield 94.1%, LC purity 91.5%).
（実施例２）
攪拌機、温度計、冷却管、窒素導入口を備えた３００Ｌ四つ口フラスコにパラターフェニルテトラカルボン酸 ３４．６ｇ、無水酢酸 １８０ｇを仕込み、系内を窒素置換しながら加熱攪拌し、１３０℃で４時間反応させた。反応完了後、常温まで冷却して、固形分を濾別した。次いで、固形分をトルエン ２２０ｇで洗浄し、１２０℃で減圧乾燥することでパラターフェニルテトラカルボン酸二無水物 ２７．８ｇ（工程収率８８．２％、ＬＣ純度９２．５％）を得た。
(Example 2)
34.6 g of paraterphenyltetracarboxylic acid and 180 g of acetic anhydride were placed in a 300 L four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen inlet, and the inside of the system was heated and stirred while replacing nitrogen at 130 ° C. The reaction was carried out for 4 hours. After the reaction was completed, the mixture was cooled to room temperature and the solid content was filtered off. Next, the solid content was washed with 220 g of toluene and dried under reduced pressure at 120 ° C. to obtain 27.8 g of paraterphenyltetracarboxylic acid dianhydride (process yield 88.2%, LC purity 92.5%). ..
Claims (7)
前記第一反応で製造した下記式（３）で表されるパラターフェニルテトラカルボン酸を無水酢酸と反応させて無水化する第二反応を有する、下記式（４）で表されるパラターフェニルテトラカルボン酸二無水物の製造方法。
The paraterphenyl represented by the following formula (4) has a second reaction in which the paraterphenyltetracarboxylic acid represented by the following formula (3) produced in the first reaction is reacted with acetic anhydride to make it anhydrous. Method for producing tetracarboxylic acid dianhydride.
前記第一反応で製造した下記式（３）で表されるパラターフェニルテトラカルボン酸を加熱して脱水縮合する第二反応を有する、下記式（４）で表されるパラターフェニルテトラカルボン酸二無水物の製造方法。
The paraterphenyltetracarboxylic acid represented by the following formula (4), which has a second reaction of heating and dehydrating and condensing the paraterphenyltetracarboxylic acid represented by the following formula (3) produced in the first reaction . (2) Method for producing anhydrous product.
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