WO1986001200A1 - Process for preparaing tetramethyl biphenyltetracarboxylate - Google Patents

Process for preparaing tetramethyl biphenyltetracarboxylate Download PDF

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Publication number
WO1986001200A1
WO1986001200A1 PCT/JP1985/000447 JP8500447W WO8601200A1 WO 1986001200 A1 WO1986001200 A1 WO 1986001200A1 JP 8500447 W JP8500447 W JP 8500447W WO 8601200 A1 WO8601200 A1 WO 8601200A1
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Prior art keywords
reaction
distillate
dmp
raw material
tetramethyl
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PCT/JP1985/000447
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French (fr)
Japanese (ja)
Inventor
Tsutomu Takeuchi
Mitsumasa Kitai
Yoshio Katsuro
Kunihiro Nakano
Masumi Hino
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Mitsubishi Chemical Industries Limited
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Priority claimed from JP16975984A external-priority patent/JPS6147444A/en
Priority claimed from JP59193497A external-priority patent/JPS6169746A/en
Application filed by Mitsubishi Chemical Industries Limited filed Critical Mitsubishi Chemical Industries Limited
Priority to GB08608582A priority Critical patent/GB2175897B/en
Publication of WO1986001200A1 publication Critical patent/WO1986001200A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring

Definitions

  • the present invention relates to a method for producing biflu-I-n-tetramethyltetracarponic acid (hereinafter referred to as BTCM).
  • BTCM biflu-I-n-tetramethyltetracarponic acid
  • BTCM is an intermediate of biphenyltetracarboxylic dianhydride which is a raw material of a polyimide resin
  • the method of producing the BTCM is as follows.
  • Dimethyl tallate (hereinafter referred to as DMP) ' is produced by performing a dehydrodimerization reaction in the presence of oxygen in the absence of a solvent using a palladium-containing catalyst.
  • the method is known (Japanese Patent Publication No. 48-10454, etc.).
  • the reaction rate of DMP is remarkably low at about 10 to 20%, so that unreacted DMP remains in the reaction mixture after the reaction. That will be.
  • the DMP in the reaction mixture is usually distilled and recovered by distillation, and the recovered DMP needs to be reused as a raw material for the above reaction. .
  • the DMP recovered here is used as it is as a raw material for the above reaction
  • the recovered DMP may be used as the raw material for the reaction, since the reaction growth is greatly deteriorated.
  • the reaction conditions in the patch reaction need to be higher than those in the first reaction, and the reaction must be carried out in a continuous reaction. I am anti If the reaction conditions were kept constant, the content of the reaction would be reduced, so that it was not possible to use it realistically. Disclosure of the invention
  • An object of the present invention is to provide a method for suppressing the deterioration of the reaction content when the recovered DMP is used for a dehydrodimerization reaction.
  • the present invention relates to phthalic acid (hereinafter, referred to as PHA) and / or phthalic anhydride (hereinafter, referred to as PHA) having a boiling point substantially the same as that of DP produced during the reaction or distillation during recovered DMP.
  • PHA phthalic acid
  • PAN phthalic anhydride
  • the purpose of the present invention is achieved by purifying the content of HA and PAN in the recovered DP to a certain value or less, and then reusing it.
  • a reaction mixture obtained by subjecting DMP to a dehydrodimerization reaction in the presence of oxygen using a palladium-containing catalyst is distilled, BTCM is recovered from the residue, and unreacted DM is recovered.
  • a method for producing a BTCM in which a distillate containing P. is reused as a raw material for the reaction the distillate is purified, and PHA and PAN or PAN are produced.
  • the best method for carrying out the invention that summarizes the method of producing BTCM, which is characterized by being reused as a raw material for the above reaction.
  • Examples of the palladium-containing catalyst used in the present invention include: An organic acid salt of palladium such as palladium acetate, and, for example, an acid binder such as soda acetate, cesium acetate or calcium sulfate, and acetic anhydride. Can be used in combination.
  • the amount of the palladium-containing catalyst used is usually from 0.1 to "! 00 mol per mol of DMP.
  • the reaction temperature is usually 50 to 300 ° G
  • the reaction pressure is usually 1 to 300 Kg / d as oxygen partial pressure.
  • This reaction must be carried out in the presence of oxygen, but it is usually desirable to carry out the reaction while supplying air to the reactor liquid unit.
  • the unreacted DMP can be easily recovered by distilling the reaction mixture after the reaction, whereby BTCM can be recovered in the residue and DMP can be recovered in the distillate.
  • the boiling point of DMP at 1 Torr is ⁇ 100 ⁇
  • the boiling point of BTCM generated is 240 CC at 0.3 Torr, so that the two can be easily separated. And can be.
  • This distillation to recover the unreacted DMP may be performed by continuing the treatment of the reaction mixture, but usually separates the palladium-containing catalyst contained in the anti-mixture.
  • the separation of the palladium-containing catalyst, which is preferably performed later, is usually carried out by ripening the reaction mixture to a temperature of 50 to 200; This can be done by depositing the metal component as a palladium black, and then arresting it.
  • the residue obtained by collecting unreacted DMP by distillation from the reaction mixture after the reaction contains BTCM as a target product. This usually involves removing the residue according to known methods. Crystallization is performed in an organic solvent such as methanol, and BTTM is precipitated as a crystal, which is recovered by mistake.
  • the distillate containing unreacted DMP is reused as a raw material for the above-mentioned dimerization reaction
  • the content of PHA and / or PAN contained in the distillate is reduced.
  • the essential requirement is to purify the amount to less than 1 OOO PPm, preferably 100 ppm or less, and more preferably to 50 ppm or less.
  • the distillate collected by the usual method always contains about 0.1 to 2.0% by weight of PHA and / or PAN with respect to DMP, and the PHA and / or PAN is contained as it is. If reused as a raw material for the above dimerization reaction, the reaction growth will deteriorate significantly, so the content of PHA and NO or PAN in the collected distillate However, if the amount is larger than the above range, it is inappropriate as the raw material for the dimerization reaction.
  • a method for purifying the recovered distillate a method of washing the distillate with an aqueous alkali solution or a method of contacting the distillate with a basic ion-exchange resin is usually used. 3 ⁇ 4A method of treatment, and a method of contact treatment with an adsorbent such as molecular sieves or high-porous resin, for example.
  • Alkali in the case of washing with an aqueous solution of alkali is, for example, a primary or secondary grade such as ammonia, 'ethylamine, n-propyl pyramine, and ethylamine. And aliphatic calcium, caustic and carbohydrates, and preferably ammonia.
  • the amount of the aqueous alkali solution can be usually in the range of 0.1 to 20 times the volume of the distillate.
  • the aqueous solution The laper degree is usually 0.1 to 20% by weight 6 and preferably 0.5 to 5% by weight. If the rale degree is too low, the distillation If PHA and PAN in the material cannot be removed effectively, on the other hand, if it is too high, the effect will not change, but the load on waste liquid treatment will increase, and economics will increase. This is not what you want.
  • the amount of ammonia water used is usually 0.1 to 20 times, preferably 0.3 to 1.0 times, the volume of distillate. Can be listed.
  • the temperature of the cleaning treatment is usually 5 to 801; preferably 15 to 35 ° C, and the time of the cleaning treatment is usually 5 to 801 ° C. It can take about 60 minutes.
  • washing method is not particularly limited, a method of adding a distillate and a predetermined amount of ammonia water to a stirring tank and performing a stirring treatment is usually employed.
  • the mixture after washing is separated into an oil phase and a water phase, which is a DMP guideline, and an oil phase is collected.
  • the oily phase is preferably washed with an aqueous hydrochloric acid solution in the same manner as necessary, and then further washed with water.
  • -Also since the DMP collected here contains, for example, 0.5 to 3.5% by weight of water, it is usually used in the range of 80 to 1301%. It is preferable to carry out dehydration treatment by flowing an inert gas such as nitrogen gas under heating or by treating with an adsorbent such as molecular sieves. It is better.
  • the basic ion-exchange resin a commercially available high-polarity, porous or gel-type resin is usually used. Is
  • DMP having a PHA and / or PAN content of 100 ppm or less, preferably 50 ppm or less, is reused as a raw material for the dimerization reaction. Used.
  • the DMP may be used alone as a raw material, or may be used as a raw material by mixing with a new DMP.
  • the mixture was reacted in a hydrogen gas atmosphere at 120 ° C. for 60 minutes to reduce the palladium, and the precipitated palladium black was filtered off.
  • the mixture was distilled at a decompression pressure of 10 mmHg at a temperature of 150 ° G to distill off a distillate 8500 containing unreacted DMP.
  • the content of PHA and PAN contained in this distillate was measured and found to be about 640 ppm as a total amount by fc.
  • a mixed solvent of methanol 197.4Q and toluene 78.7Q is mixed with the residue, and the mixture is cooled and crystallized at a temperature of 15 ° G. Therefore, the BTCM crystals were prayed, filtered, and collected.
  • the distillate collected by the above method was purified by the method shown below, and the contents of PHA and PAN in the purified DMP were measured, as shown in Table 1. .
  • the DMP-containing distillate was washed with 0.3% by volume of 1% ammonia water at 30 ° C. for 30 minutes with stirring, and then 0.3 parts by volume of 196 hydrochloric acid and water each. After washing, the substrate was dehydrated by heating it to 30 ° C and applying 1 JJ / rain of nitrogen gas for 60 minutes.
  • Example 1 3% n-pulp pillamine was used in place of ammonia water.
  • Example 3 Treated with an ion-exchange resin) 0.25 times by weight of a high-poise ion-exchange resin (Diaion HPA25, III) was added, and the mixture was stirred at a temperature of 50 ° G for 60 minutes, and then the resin was separated. Further, the above operation was repeated twice.
  • the DMP was washed by stirring it for 30 minutes at a temperature of 30 with 0.3 times the volume of water.
  • the DMP Table 2 shows the BTCM production rate when the dehydrogenation dimerization reaction was performed.
  • the oil phase and the aqueous phase which were DMP layers, were separated.
  • the dimerization reaction is not inhibited, so that the industrial production of BTCM is possible. It is extremely valuable as a method.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A process for preparaing tetramethyl biphenyltetracarboxylate, which comprises subjecting dimethyl phthalate to dehydrodimerization in the presence of oxygen using a palladium-containing catalyst, distilling the reaction product, recovering a residue containing tetramethyl biphenyletracarboxylate, and re-using the distillate containing unreacted dimethyl phthalate as the starting material, wherein the distillate is purified before the re-use with an alkaline aqueous solution etc. to reduce the content of phthalic acid and/or phthalic anhydride to 1,000 ppm or less.

Description

明 翱 書 ビ フ ヱ 二ルテ 卜 ラ カ ルボ ン酸テ 卜 ラメ チルの製法 技術分野  Technical Documents Biphenyl tetracarboxylate
本発明 は ビ フ I 二ルテ 卜 ラ カ ルポ ン酸テ 卜 ラ メ チル （ 以下 B T C M と 言 う ） の製法 に 関 す る 。 背景技術  The present invention relates to a method for producing biflu-I-n-tetramethyltetracarponic acid (hereinafter referred to as BTCM). Background art
B T C Mは 、 ポ リ イ ミ ド樹脂の原料である ビ フ エ 二ルテ 卜 ラ カ ルポ ン酸二無水物 の中間体であ り 、 該 B T C Mの製造方 法 と し て は 、' オル 卜 一 フ タ ル酸ジ メ チル （ 以下 、 D M P と言 う ） 'をパ ラ ジ ウ ム含有触媒を用 いて 酸素存在下に無溶媒中で 脱水素二量化反応を行な う こ と に よ り 製造する方法が知 ら れ て い る （ 特公昭 4 8 — 1 0 5 4号公報等 ） 。 こ の B T C Mの 製造方法に おい て は 、 D M Pの反応率が 、 1 0〜 2 0 %程度 と 著 し く 低い た め 、 反応後の反応混合物 中 に 未反応の D M P が多暈に残存す る こ と と な る 。  BTCM is an intermediate of biphenyltetracarboxylic dianhydride which is a raw material of a polyimide resin, and the method of producing the BTCM is as follows. Dimethyl tallate (hereinafter referred to as DMP) 'is produced by performing a dehydrodimerization reaction in the presence of oxygen in the absence of a solvent using a palladium-containing catalyst. The method is known (Japanese Patent Publication No. 48-10454, etc.). In this method of producing BTCM, the reaction rate of DMP is remarkably low at about 10 to 20%, so that unreacted DMP remains in the reaction mixture after the reaction. That will be.
そ し て 、 反応後、 反応混合物中 の D M Pは通常、 蒸留 に よ つ て留出回収さ れ、 回収さ れた D M Pは上記反応の原料 と し て 再利用 す る こ と が必要で あ る 。  After the reaction, the DMP in the reaction mixture is usually distilled and recovered by distillation, and the recovered DMP needs to be reused as a raw material for the above reaction. .
と こ ろ が 、 こ こで 回収さ れた D M Pをそ の ま ま 上記反応の 原料 と し て 用 いた 場合に は 、 反応成辏が大幅に 悪化す る た め に 、 回収 し た D M Pを原料 と し て上記反応を実施す る場合 に は 、 パ ッ チ反応に お い て は反応条件を最初 の条件に 比べ て 高 い レ ベル と す る必要があ り 、 ま た 、 連続式反応に お い て は反 応条件を一定に保つ と反応内容が低下 し て く るので、 現実的 に採用 する こ と ができなか っ た 。 発明の 開示 However, if the DMP recovered here is used as it is as a raw material for the above reaction, the recovered DMP may be used as the raw material for the reaction, since the reaction growth is greatly deteriorated. In the case where the above reaction is carried out, the reaction conditions in the patch reaction need to be higher than those in the first reaction, and the reaction must be carried out in a continuous reaction. I am anti If the reaction conditions were kept constant, the content of the reaction would be reduced, so that it was not possible to use it realistically. Disclosure of the invention
本発明 は 、 回収さ れた D M Pを脱水素二量化反応に利用 し た 場合に 、 反応内容が悪化するのを抑制 す る方法を提供する こ とを目 的と するあのである 。  An object of the present invention is to provide a method for suppressing the deterioration of the reaction content when the recovered DMP is used for a dehydrodimerization reaction.
本発明 は 、 回収 D M P中に 、 反応中又は蒸留中 に生成 し た D P と沸点がほぼ同 じである フ タ ル酸 （ 以下、 P H A と言 う ） 及ぴ /又は無水 フ タ ル酸 （ 以下、 P A N と 言 う ） が少量 含有さ れて お り 、 これ ら の成分が脱水素二量化反応 に対 し て 悪影響を及ぼ し て い る と の新規な知見に も とづ く もので あ り 回収 し た D P中の H A及び P A N の含有量をあ る特定の 値以下ま で精製 し た後、 再利用 す る こ と に よ り 本発明の 目 的 が達成さ れる。  The present invention relates to phthalic acid (hereinafter, referred to as PHA) and / or phthalic anhydride (hereinafter, referred to as PHA) having a boiling point substantially the same as that of DP produced during the reaction or distillation during recovered DMP. And PAN), which are based on the new finding that these components have an adverse effect on the dehydrodimerization reaction. The purpose of the present invention is achieved by purifying the content of HA and PAN in the recovered DP to a certain value or less, and then reusing it.
本発明 は 、 D M Pを 、 パラ ジ ゥ ム含有触媒を用 いて酸素存 在下で脱水素二量化反応さ せた後の反応混合物 を蒸留 し 、 残 留物か ら B T C Mを回収 し 、 未反応の D M P.を含有する留 出 物 を '記反応の原料 と し て 再使用 する B T C Mを製造す る方 法に お いて 、 前記留 出物を精製処理 し 、 P H A及びノ又は P A N。の含有量を 1 0 0 0 ppm 以下に調整 し た後、 '前記反応 の原料 と し て再使用 す る こ と を特徴 と する B T C Mの製法を 要旨 と す る 発明 を実施するた め の最良の形態  According to the present invention, a reaction mixture obtained by subjecting DMP to a dehydrodimerization reaction in the presence of oxygen using a palladium-containing catalyst is distilled, BTCM is recovered from the residue, and unreacted DM is recovered. In a method for producing a BTCM in which a distillate containing P. is reused as a raw material for the reaction, the distillate is purified, and PHA and PAN or PAN are produced. After adjusting the content of BTCM to 100 ppm or less, the best method for carrying out the invention that summarizes the method of producing BTCM, which is characterized by being reused as a raw material for the above reaction. Form
本発明で使用 す るパラ ジ ウ ム含有触媒 と し て は 、 搠 えば、 酢酸パラ ジ ウ ム な どのパラ ジ ウ ム の有機酸塩であ り 、 ま た 、 例えば、 酢酸ソ ー ダ、 酢酸セ シ ウ ムあ るい は舴酸カ リ な どの 酸結合剤及び無水酢酸等を併用 し て も差 し 支え ない 。 パラ ジ ゥ ム含有触媒の使用 量は通常、 D M P 1 モルあた り 、 0. 1 〜 "！ 0 0ミ リ モルで あ る 。 Examples of the palladium-containing catalyst used in the present invention include: An organic acid salt of palladium such as palladium acetate, and, for example, an acid binder such as soda acetate, cesium acetate or calcium sulfate, and acetic anhydride. Can be used in combination. The amount of the palladium-containing catalyst used is usually from 0.1 to "! 00 mol per mol of DMP.
反応温度は通常 、 5 0〜 3 00 °Gで あ り 、 ま た 、 反応圧力 は通常、 酸素分圧 と し て 1 〜 3 00 Kg/ dで あ る 。  The reaction temperature is usually 50 to 300 ° G, and the reaction pressure is usually 1 to 300 Kg / d as oxygen partial pressure.
こ の反応は酸素存在下で行う 必要があるが 、 通常、 反応器 液雇部に空気を供給 し な が ら 反応を行 う の が望ま し い 。  This reaction must be carried out in the presence of oxygen, but it is usually desirable to carry out the reaction while supplying air to the reactor liquid unit.
反応後の反応混合物中 に は未反応の D M Pが多量に含有さ れて い る ので 、 こ れを回収 し 再利用 す る必要が あ る 。 未反応 の D M Pの回収 は 、 反応後の反応混合物を蒸留 -す る こ と に よ り 容易に B T C Mを残留物中 に 、 そ し て D M Pを留 出物中 に 回収する こ と ができ る 。 すなわ ち 1 Torrに お け る D M Pの沸 点 は Ί 0 0 Ϊで あ り 、 生成 し た B T C Mの沸点は 0 . 3 Torr で 2 4 0 °Cである た め両者 は簡単 に 分離する こ と ができ る 。  Since a large amount of unreacted DMP is contained in the reaction mixture after the reaction, it is necessary to collect and reuse it. The unreacted DMP can be easily recovered by distilling the reaction mixture after the reaction, whereby BTCM can be recovered in the residue and DMP can be recovered in the distillate. In other words, the boiling point of DMP at 1 Torr is Ί100Ϊ, and the boiling point of BTCM generated is 240 CC at 0.3 Torr, so that the two can be easily separated. And can be.
こ の未反応の D M Pを回収す る た めの蒸留 は 、 反応混合物 を 引 き続き処理 し て も よ いが 、 通常 、 反 ^混合物 中 に 含有さ れるパラ ジ ウ ム含有触媒を分離 し た後 に 行な う のが好 ま し い パラ ジ ウ ム含有触媒の分離 は 、 通常 、 反応混合物を 5 0〜 2 0 01； の'温度に加熟 し 、 水素ガ ス雰囲気下でパラ ジ ウ ム成 分をパラ ジ ウムブラ ッ ク と し て析出さ せ 、 次いで 、 こ れを逮 過す る こ と に よ り 実施す る こ と ができ る 。  This distillation to recover the unreacted DMP may be performed by continuing the treatment of the reaction mixture, but usually separates the palladium-containing catalyst contained in the anti-mixture. The separation of the palladium-containing catalyst, which is preferably performed later, is usually carried out by ripening the reaction mixture to a temperature of 50 to 200; This can be done by depositing the metal component as a palladium black, and then arresting it.
反応後の反応混合物か ら蒸留 に よ り 未反応の D M Pを回収 し た後の残留物中 に は 、 目 的生成物であ る B T C Mが含有さ れて い る 。 こ れ は通常 、 公知の方法に従 っ て 、 前記残留物を メ タ ノ ールな どの有機溶媒中で晶析 し 、 B T 〇 Mを結晶 と し て析出 させ 、 こ れを遽過する こ と に よ り 回収さ れる。 The residue obtained by collecting unreacted DMP by distillation from the reaction mixture after the reaction contains BTCM as a target product. This usually involves removing the residue according to known methods. Crystallization is performed in an organic solvent such as methanol, and BTTM is precipitated as a crystal, which is recovered by mistake.
本発明で は 、 未反応の D M Pを含有す る留出物を 、 上記の 二量化反応の原料と し て再利用 する際に 、 留 出物中 に 含有さ れる P H A及び /又は 、 P A N の含有量を 1 O O O PPm 以下 好ま し く は 1 0 0 ppm 以下、 更 に好ま し く は 5 0 ppm 以下 と な る ま で精製処理する こ と を必須の要件 と す るも ので あ る 。  In the present invention, when the distillate containing unreacted DMP is reused as a raw material for the above-mentioned dimerization reaction, the content of PHA and / or PAN contained in the distillate is reduced. The essential requirement is to purify the amount to less than 1 OOO PPm, preferably 100 ppm or less, and more preferably to 50 ppm or less.
通常の方法で回収 し た留出物中 に は必ず 、 D M Pに対 し て 0 . 1 〜 2 . 0重量％程度の P H A及び /又は P A Nが含有 さ れて お り 、 こ れをその ま ま上記二量化反応の原料 と し て再 使用 し た場合に は、 反応成辏が著 し く 悪化す る こ と と な るの で回収 し た留出物中の P H A及びノ又は P A N の含有量が 、 上記範囲 よ り も多い場合に は上記二量化反応め原料 と し て は 不適切で あ る 。  The distillate collected by the usual method always contains about 0.1 to 2.0% by weight of PHA and / or PAN with respect to DMP, and the PHA and / or PAN is contained as it is. If reused as a raw material for the above dimerization reaction, the reaction growth will deteriorate significantly, so the content of PHA and NO or PAN in the collected distillate However, if the amount is larger than the above range, it is inappropriate as the raw material for the dimerization reaction.
回収 し た留出物 'の精製処理法 と し て は 、 通常、 アルカ リ 水 溶液で留 出物を洗净処理す る方法、 又は、 留 出物を塩基性ィ オ ン交換樹脂で接 ) ¾処理する方法、 更に 、 例えば 、 モ レ キ ュ ラ ー シ ー ブス 、 ハイ ポ ー ラス樹脂な ど の吸着剤で接触処理す る方法な どが挙げ ら れる 。  As a method for purifying the recovered distillate, a method of washing the distillate with an aqueous alkali solution or a method of contacting the distillate with a basic ion-exchange resin is usually used. ¾A method of treatment, and a method of contact treatment with an adsorbent such as molecular sieves or high-porous resin, for example.
アルカ リ 水溶液で洗净す る場合の アルカ リ と し て は 、 例 え ば、 ア ンモ ニア 、' ェチルァ ミ ン 、 n-プ 口 ピルァ ミ ン 、 ジェ チ ルァ ミ ンな どの 1 級又は 2級の脂肪族ァ ミ ン 、 苛性カ リ 、 炭 酸カ リ 等が挙げ ら れ、 好 ま し く は ア ンモニ アが挙げ ら れる 。 こ の場合、 アルカ リ 水溶液の使用量 と し て は 、 留 出物 に対 し て 、 通常 0 . Ί 〜 2 0容量倍の範囲 を挙げる こ と ができる 。  Alkali in the case of washing with an aqueous solution of alkali is, for example, a primary or secondary grade such as ammonia, 'ethylamine, n-propyl pyramine, and ethylamine. And aliphatic calcium, caustic and carbohydrates, and preferably ammonia. In this case, the amount of the aqueous alkali solution can be usually in the range of 0.1 to 20 times the volume of the distillate.
ま た 、 ア ン モニ ア水 に よ る精製処理に お い て 、 そ の水溶液 濂度 と し て は 、 通常、 0. 1 〜 2 0重量 6、 好 ま し く は 0. 5〜 5重量％であ り 、 こ の濂度があ ま り 低すぎる場合に は 、 留出物中の P H A及び P A Nを効果的 に 除去す る こ と が できず 、 逆に 、 あ ま り 高すぎる場合に は 、 効果は変わ ら ない ものの 、 廃液処理の負荷が大き く な る等経済的に 好 ま し く な い こ と と な る 。 In the purification treatment with ammonia water, the aqueous solution The laper degree is usually 0.1 to 20% by weight 6 and preferably 0.5 to 5% by weight. If the rale degree is too low, the distillation If PHA and PAN in the material cannot be removed effectively, on the other hand, if it is too high, the effect will not change, but the load on waste liquid treatment will increase, and economics will increase. This is not what you want.
そ し て 、 ア ンモニ ア水の使用 量 と し て は 、 通常、 留 出物 に 対 し 、 0. 1 〜 2 0容量倍、 好 ま し く は 、 0. 3〜 1 . 0容 量倍の範囲を挙げる こ と ができ る 。  The amount of ammonia water used is usually 0.1 to 20 times, preferably 0.3 to 1.0 times, the volume of distillate. Can be listed.
洗浄処理の温度は 、 通常 5〜 8 01； 、 好 ま し く は 1 5〜 3 5 °Cの範囲を挙げる こ と ができ 、 ま た 、 洗浄処理の時間 と し て は 、 通常、 5〜 6 0分程度を挙げる こ と がで き る 。  The temperature of the cleaning treatment is usually 5 to 801; preferably 15 to 35 ° C, and the time of the cleaning treatment is usually 5 to 801 ° C. It can take about 60 minutes.
洗浄方式 と し て は特に 限定さ れるも のではない が 、 通常 、 攛拌槽に 留 出物 と所定量の ア ン モ ニ ア水 と を加え 拌処理す る方法が採用 さ れる 。  Although the washing method is not particularly limited, a method of adding a distillate and a predetermined amount of ammonia water to a stirring tank and performing a stirring treatment is usually employed.
洗浄後の混合物 は情報 に従 っ て 、 D M P闥であ る油相 と水 相 と を分液 し て 油相 を回収す る 。 こ の 油相 は 、 必要に応 じ て 同様の方法で塩酸水溶液で洗浄 し た後、. 更に 、 水で洗浄する の が好 ま し い 。 - ま た 、 こ こで 回収さ れる D M P中 に は例 えば 、 0. 5〜 3 . 5重量％ の水分が含有さ れて い る為、 こ れを通常 、 8 0 〜 1 3 01； の加熱下 に窒素ガスな どの不活性ガ ス を流通さ せ る か 、 又は 、 モ レ キ ュ ラ ー シ ー ブス な ど の吸着剤で処理す る こ と に よ り 、 脱水処理する の が好 ま し い 。  According to the information, the mixture after washing is separated into an oil phase and a water phase, which is a DMP guideline, and an oil phase is collected. The oily phase is preferably washed with an aqueous hydrochloric acid solution in the same manner as necessary, and then further washed with water. -Also, since the DMP collected here contains, for example, 0.5 to 3.5% by weight of water, it is usually used in the range of 80 to 1301%. It is preferable to carry out dehydration treatment by flowing an inert gas such as nitrogen gas under heating or by treating with an adsorbent such as molecular sieves. It is better.
一方、 塩基性イ オ ン交換樹脂 と し て は 、 通常、 市販さ れて い るハイ ポ ー ラ ス型、 ポ ー ラ ス型又はゲル型の樹脂が用 い ら れる 。 On the other hand, as the basic ion-exchange resin, a commercially available high-polarity, porous or gel-type resin is usually used. Is
上記の よ う な精製処理に よ り 、 P H A及び 又は P A N の 含有量を 1 0 0 0 ppm 以下、 好ま し く は 5 0 ppm 以下 と し た D M Pは上記の二量化反応の原料 と し て再利用 さ れる 。  By the above-mentioned purification treatment, DMP having a PHA and / or PAN content of 100 ppm or less, preferably 50 ppm or less, is reused as a raw material for the dimerization reaction. Used.
本発明で は こ の D M Pは単独で原料 と し て用 い て も 、 ま た 新 し い D M P と混合 し て 原料 と し て 用 いても差 し支えな い 。  In the present invention, the DMP may be used alone as a raw material, or may be used as a raw material by mixing with a new DMP.
次に本発明を実施例 に よ り 更に 詳細 に説明する が 、 本発明 は 、 以下の実施例 に 限定されるもので はない 。  Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
実施例 1 〜 3及び比較例 1 〜 2 Examples 1-3 and Comparative Examples 1-2
[ 第 1 回 目 の反応 ]  [First reaction]
撹拌機及び温度諝節器を有す る 1 5 0 0 ^の流通型反応器 に D M P ( 工業用-試薬 ） 1 0 6 2 g 及び狨媒 と し て 酢酸パラ ジ ゥム 2 0 8 0.g 、 炭酸カ リ ウム 0. 6 4 1 g 及び群酸 2 3 . 8 49 を仕込み、 系内 を空気で加圧 し 酸素分圧を 2 Kg と し た後、 空気を 1 3 0 i / hrで液中 に フ ィ ー ド しつつ 2 0 °Cに昇温後、 酔酸 ： 無水酢酸の 1 ： 1 ( 容量比 ） の混 合液を 5 hrで添加 しつつ 5時間反応を行 っ た 。 こ の反応 に おける B .T C Mの生成率は 7 . 8 モル％であ っ た 。  In a 1500 ^ flow-through reactor equipped with a stirrer and a temperature control device, add 1602 g of DMP (industrial-reagent) and palladium acetate as a solvent. g, potassium carbonate 0.64 1 g and group acid 23.849 were charged, and the system was pressurized with air to adjust the oxygen partial pressure to 2 kg, and then air was reduced to 130 i / hr. After raising the temperature to 20 ° C while feeding into the solution with, the reaction was carried out for 5 hours while adding a mixed solution of 1: 1 (volume ratio) of acetic anhydride and acetic anhydride in 5 hr. . The yield of B.TCM in this reaction was 7.8 mol%.
反応後、 混合物 を水素ガス雰囲気下 、 1 2 0 °Cで 6 0分間 反応を行いパラ ジ ウ ム を還元 し た後、 析出 じたパラジ ウ ムプ ラ ッ ク を濂別 し た 。  After the reaction, the mixture was reacted in a hydrogen gas atmosphere at 120 ° C. for 60 minutes to reduce the palladium, and the precipitated palladium black was filtered off.
次いで 、 こ の混合 ¾を 1 0 mmHgの滅圧下、 1 5 0 °Gの温度 で蒸留 する こ と に よ り 、 未反応の D M Pを含有す る留 出物 8 5 00 を留 出さ せ た 。 こ の留 出物中 に含有さ れる P H A及 び P A N の含有率を測定 し fc と こ ろ合計量 と し て約 6 4 0 0 ppm で あ っ た 。 一方、 メ タ ノ ール 1 9 7 . 4 Q と 卜 ルェ ン 7 8 . 7 Q と の 混合溶媒 と 、 残留物 と を混合 し 、 一 5 °Gの温度で冷却晶析す る こ と に よ り 、 B T C Mの結晶 を祈出 さ せ 、 こ れを瀘別 し 回 収 し た 。 Next, the mixture was distilled at a decompression pressure of 10 mmHg at a temperature of 150 ° G to distill off a distillate 8500 containing unreacted DMP. The content of PHA and PAN contained in this distillate was measured and found to be about 640 ppm as a total amount by fc. On the other hand, a mixed solvent of methanol 197.4Q and toluene 78.7Q is mixed with the residue, and the mixture is cooled and crystallized at a temperature of 15 ° G. Therefore, the BTCM crystals were prayed, filtered, and collected.
[ D M Pの精製 ]  [Purification of DMP]
上記の方法で回収 し た 留 出物を下記に 示す方法で精製処理 を行ない 、 精製後の D M P中 の P H A及び P A N 含有量を測 定 し た と こ ろ第 1 表の通 り で あ っ た 。  The distillate collected by the above method was purified by the method shown below, and the contents of PHA and PAN in the purified DMP were measured, as shown in Table 1. .
第 1 表  Table 1
Figure imgf000009_0001
Figure imgf000009_0001
( 注 ） 精製方法 ：  (Note) Purification method:
0 実施例 1 ( ア ン モニ ア水洗净 ）  0 Example 1 (Ammonia water washing)
D M P含有留出物を 0 ， 3容量倍の 1 %ア ン モニ ア水 で 3 0 の 温度で 3 0分間攪拌 し て 洗净 し 、 次いで 、 0 . 3容量倍の 1 96塩酸、 水で各々願次洗浄 し た後、 • 3 0 °Cに加熱下、 1 JJ / rain で窒素ガ スで 6 0分閩パ プ リ ング し て脱水 し た 。  The DMP-containing distillate was washed with 0.3% by volume of 1% ammonia water at 30 ° C. for 30 minutes with stirring, and then 0.3 parts by volume of 196 hydrochloric acid and water each. After washing, the substrate was dehydrated by heating it to 30 ° C and applying 1 JJ / rain of nitrogen gas for 60 minutes.
0 実施例 2 ( ァ ミ ン水溶液洗浄 ）  0 Example 2 (Amin aqueous solution cleaning)
実施例 1 に お い て ア ン モ ニ ア水のかわ り に 3 %の n -プ 口 ピル ア ミ ン を用 い た 。 O 実施例 3 性イ オ ン交換樹脂処理 ） D M P含有留出物 に対 し て 0. 2 5重量倍のハイ ポ ー ス型陰ィ オ ン交換樹脂 （ ダイ ヤ イ オ ン H P A 2 5 、 三 化成工業株式会社製造、 商標 ） を添加 し 、 5 0 °Gの温 で 6 0分間攪拌処理 し た後、 樹脂を分離 し 、 さ ら に 、 上記の操作を 2 回 く り 返 し た 。 In Example 1, 3% n-pulp pillamine was used in place of ammonia water. O Example 3 Treated with an ion-exchange resin) 0.25 times by weight of a high-poise ion-exchange resin (Diaion HPA25, III) Was added, and the mixture was stirred at a temperature of 50 ° G for 60 minutes, and then the resin was separated. Further, the above operation was repeated twice.
O 比較例 1 ( 水洗浄 ）  O Comparative Example 1 (Washing)
D M Pを 0. 3容量倍の水で 3 0 の温度で 3 0分間 攪拌 し て 洗浄 し た  The DMP was washed by stirring it for 30 minutes at a temperature of 30 with 0.3 times the volume of water.
[ 2回 目 の反応 ]  [2nd reaction]
上記の精製処理を施 し た各 D M P 5 3 1 9 を原料 と し て 、 上述の第 1 回 目 の反応 と同様な条件 （ 但 し 、 スケ ール は 1 / 2 ) に おいて—、 D M Pの脱水素二量化反応を行 っ た場合 の B T C Mの生成率を求め た と こ ろ第 2表に示す結果を得た  Using each of the purified DMPs 53 19 as a raw material under the same conditions as in the first reaction described above (however, the scale is 1/2), the DMP Table 2 shows the BTCM production rate when the dehydrogenation dimerization reaction was performed.
2表  2 tables
Figure imgf000010_0001
Figure imgf000010_0001
参考例 1 〜 7 Reference Examples 1 to 7
種々 の アルカ リ 水溶液の精製効果を示すた め に 、 実施 ^ 1 1 の方法で回収 し た未反応 D M P ( Ρ Η Α及び P A N 含有量 0. 6 4 % ) 9 5 0 «2を 2 攪拌容器に仕込み、 こ れに第 3 表に示す アルカ リ 水溶液を加え 、 3 0 の温度で 5分間攢拌 し つ つ 洗净処理を行ない 、 次いで 、 こ の混合物 を静置分離 しIn order to demonstrate the purification effect of the various alkaline aqueous solutions, the unreacted DMP (Ρ Η Α and PAN content) recovered by the method of (0.64%) 950 <2> was charged into a 2 stirred vessel, an aqueous alkali solution shown in Table 3 was added thereto, and the mixture was washed at a temperature of 30 with stirring for 5 minutes. The mixture is then allowed to stand and separate.
D M P層で ある油相 と水相 と を分液 し た 。 The oil phase and the aqueous phase, which were DMP layers, were separated.
回収 し た D M P中 に 含有さ れる P H A及び P A N の除去率 を求め た と こ ろ第 3表 に 示す結果であ っ た 。  The removal rate of PHA and PAN contained in the recovered DMP was determined, and the results are shown in Table 3.
第 3表  Table 3
Figure imgf000011_0001
Figure imgf000011_0001
* 水の みで洗浄 し た 場合 産業上の利用 可能性  * Industrial applicability when washed with water only
本発明 に よ れば 、 D M Pの脱水素二量化工程 よ り 回収 し た 未反応 D M Pを リ サイ ク ル使用 し て も 前記二量化反応が 阻害 さ れる こ と がないので 、 B T C Mの工業的製造方法 と し て極 め て 価値が髙い 。  According to the present invention, even if the unreacted DMP recovered from the DMP dehydrogenation dimerization step is recycled, the dimerization reaction is not inhibited, so that the industrial production of BTCM is possible. It is extremely valuable as a method.
ま た 、 留 出 回収 し た未反応の粗 D M Pの精製処理は アル 力 リ 水溶液、 特に ア ン モニ ア水に よ る洗浄処理 と い う 極めて 簡 便な手段で効率的に実施できる利点を有する 。 Purification of unreacted crude DMP collected by distillation It has the advantage that it can be carried out efficiently by extremely simple means such as a washing treatment with an aqueous solution, particularly ammonia water.

Claims

請求の範囲 The scope of the claims
. オル 卜一フ タ ル酸ジ メ チルを 、 パラジ ウ ム含有）»媒を用 い 、 酸素存在下で脱水素二量化反応さ せ た後の反応混合物 を蒸留 し 、 ビ フ エ 二ルテ 卜 ラ カ ルポ ン酸テ 卜 ラメ チルを含 有す る残留物 を回収 し 、 未反応の オル 卜 ー フ タ ル酸ジメ チ ルを含有する留出物 を前記反応の原料 と し て再使用 す る ビ フ ェ ニルテ 卜 ラ カ ルポ ン酸テ 卜 ラ メ チルの製法に おい て 、 前記留 出物を精製処理 し 、 フ タ ル酸及び /又は無水フ タ ル 酸の含有量を Ί 0 0 0 PPI8 以下 に調節 し た 後、 前記反応の 原料 と し て 再使用 する こ と を特徴 と す る ビ フ I ニルテ 卜 ラ カ ルボ ン酸テ 卜 ラ メ チルの 製法 。  The reaction mixture after the dehydrodimerization reaction of dimethyl orthophthalate (containing palladium) medium in the presence of oxygen using a solvent is distilled to obtain biphenyl ether. The residue containing tetramethyl lacarponic acid is recovered, and the distillate containing unreacted dimethyl orthophthalate is reused as a raw material for the reaction. In a process for producing tetramethyl biphenyltetracarponic acid, the distillate is purified, and the content of phthalic acid and / or phthalic anhydride is reduced to about 100%. A process for producing bimethyl tert-methyl tetracarbylate, which is adjusted to a PPI of 8 or less and then reused as a raw material for the reaction.
2. 精製処理に よ り 留 出物 中 の フ タ ル酸及び /又は無水フ タ ル酸の含有量を 5 0 PPIB 以下に 調節す る こ と を特徴 と す る 特許請求の範囲第 1 項記載の製法。 . 2. Claim 1 characterized in that the content of phthalic acid and / or phthalic anhydride in the distillate is adjusted to 50 PPIB or less by the purification treatment. The manufacturing method described. .
3 . 精製処理が ア ン モ ニ ア水に よ る洗浄処理であ る こ と を特 徴 と する特許請求の範囲第 1 項記載の製法。 3. The method according to claim 1, wherein the purification treatment is a washing treatment with ammonia water.
4. 精製処理に用 い る ア ン モ ニ ア水の濃度が 0 . 1 〜 2 0重 量％であ る こ と^特徴 と する特許請求の範囲第 3項記載の 製法。  4. The process according to claim 3, wherein the concentration of ammonia water used for the purification treatment is 0.1 to 20% by weight.
5 . ア ン モニ ア水で の洗浄処理が 5〜 8 0 の温度で 5〜 6 0分圊摟拌処理さ れる こ と を特徴 と す る特許請求の範囲 第 3項記載の製法 。  5. The process according to claim 3, wherein the washing treatment with ammonia water is carried out by stirring at a temperature of 5 to 80 for 5 to 60 minutes.
PCT/JP1985/000447 1984-08-14 1985-08-09 Process for preparaing tetramethyl biphenyltetracarboxylate WO1986001200A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4868538A (en) * 1971-12-22 1973-09-18
JPS51101946A (en) * 1975-02-01 1976-09-08 Dynamit Nobel Ag Teifunshiterefutarusanechirengurikooruesuteruoyobisonoseizoho
JPS51101945A (en) * 1975-02-01 1976-09-08 Dynamit Nobel Ag Origomaanoarukirenterefutareetooseizosurutamenohohooyobisochi
JPS5287113A (en) * 1976-01-13 1977-07-20 Mitsubishi Gas Chem Co Inc Production of ester

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4868538A (en) * 1971-12-22 1973-09-18
JPS51101946A (en) * 1975-02-01 1976-09-08 Dynamit Nobel Ag Teifunshiterefutarusanechirengurikooruesuteruoyobisonoseizoho
JPS51101945A (en) * 1975-02-01 1976-09-08 Dynamit Nobel Ag Origomaanoarukirenterefutareetooseizosurutamenohohooyobisochi
JPS5287113A (en) * 1976-01-13 1977-07-20 Mitsubishi Gas Chem Co Inc Production of ester

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