WO1986001200A1 - Procede de preparation de biphenyltetracarboxylate de tetramethyle - Google Patents

Procede de preparation de biphenyltetracarboxylate de tetramethyle 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
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
distillate
dmp
raw material
tetramethyl
Prior art date
Application number
PCT/JP1985/000447
Other languages
English (en)
Japanese (ja)
Inventor
Tsutomu Takeuchi
Mitsumasa Kitai
Yoshio Katsuro
Kunihiro Nakano
Masumi Hino
Original Assignee
Mitsubishi Chemical Industries Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP16975984A external-priority patent/JPS6147444A/ja
Priority claimed from JP59193497A external-priority patent/JPS6169746A/ja
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/fr

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Classifications

    • 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

Le procédé consiste à soumettre du diméthyl phthalate à une déshydrodimérisation en présence d'oxygène en utilisant un catalyseur contenant du palladium, à distiller le produit de réaction, à extraire un résidu contenant du biphényltétracarboxylate de tétraméthyle, et à réutiliser le distillat contenant du diméthyl phthalate n'ayant pas réagi en tant que matériau de départ, ce distillent étant purifié avec une solution aqueuse alcaline , etc. avant d'être réutilisé, afin de réduire sa teneur en acide phthalique et/ou anhydride phthalique à une valeur égale ou inférieure à 1000 parties par million.
PCT/JP1985/000447 1984-08-14 1985-08-09 Procede de preparation de biphenyltetracarboxylate de tetramethyle WO1986001200A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB08608582A GB2175897B (en) 1984-08-14 1985-08-09 Process for preparing tetramethyl biphenyltetracarboxylate

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP16975984A JPS6147444A (ja) 1984-08-14 1984-08-14 粗フタル酸ジメチルの精製法
JP59/169759 1984-08-14
JP59/193497 1984-09-14
JP59193497A JPS6169746A (ja) 1984-09-14 1984-09-14 ビフエニルテトラカルボン酸テトラメチルの製法

Publications (1)

Publication Number Publication Date
WO1986001200A1 true WO1986001200A1 (fr) 1986-02-27

Family

ID=26492997

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1985/000447 WO1986001200A1 (fr) 1984-08-14 1985-08-09 Procede de preparation de biphenyltetracarboxylate de tetramethyle

Country Status (3)

Country Link
DE (1) DE3590385T1 (fr)
GB (1) GB2175897B (fr)
WO (1) WO1986001200A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4868538A (fr) * 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 (fr) * 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

Also Published As

Publication number Publication date
DE3590385T1 (de) 1986-08-28
GB2175897B (en) 1987-12-16
GB8608582D0 (en) 1986-05-14
GB2175897A (en) 1986-12-10

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