公开(公告)号：JPS6019736A

公开(公告)日：1985-01-31

申请号：JP12599583

申请日：1983-07-13

Applicant: TORAY INDUSTRIES

Inventor： SUEMATSU MASAAKI ,  OOTOMO SHIGERU ,  NAKAOKA KENJI

IPC: C07C27/12 ,  B01J23/00 ,  B01J27/08 ,  C07B61/00 ,  C07C27/00 ,  C07C45/00 ,  C07C47/542 ,  C07C51/00 ,  C07C63/04 ,  C07C63/06 ,  C07C67/00

Abstract: PURPOSE:To produce the titled compounds in high purity and yield, by oxidizing p-t-butyltoluene with molecular oxygen under specific condition, separating the reaction product liquid into layers with water, separating the titled aldehyde from he oily layer by distillation, and separating the titled benzoic acid derivative from the residue by crystallization. CONSTITUTION:p-t-Butyltoluene is oxidized with an O2-containing gas in acetic acid solvent in the presence of a catalyst containing a cobalt compound and a bromine compound, and the reaction product liquid is added with water in an amount to cause the phase separation. The upper layer composed mainly of an oily component is distilled to obtain the fraction composed mainly of p-t-butylbenzaldehyde, and the distillation residue is mixed with the above raw material and cooled to crystallize p-t-butylbenzoic acid, which is separated by the solid-liquid separation. The above aldehyde and benzoic acid derivative useful as intermediates of pharmaceuticals, etc. can be oxidized in high selectivity, and the products can be separated from each other high yield and purity.

公开(公告)号：JPS5980637A

公开(公告)日：1984-05-10

申请号：JP19080782

申请日：1982-11-01

Applicant: TORAY INDUSTRIES

Inventor： SUEMATSU MASAAKI ,  UEDA TATSUO ,  NAKAOKA KENJI

IPC: C07B61/00 ,  B01J27/00 ,  B01J27/06 ,  B01J31/00 ,  B01J31/04 ,  B01J31/26 ,  C07C67/00 ,  C07C201/00 ,  C07C201/12 ,  C07C205/57 ,  C07C205/59

Abstract: PURPOSE:To obtain the titled compound in good hue, by oxidizing p-nitrotoluene with molecular oxygen in acetic acid solvent in the presence of a catalyst constituted of metallic compounds of cobalt, manganese and cerium and a bromine compound. CONSTITUTION:p-Nitrotoluene is oxidized with a gas containing molecular oxygen in acetic acid solvent in the presence of a catalyst constituted of a cobalt compound and a bromine compound as main constituent components and further a manganese compound and/or cerium compound to give the aimed p-nitrobenzoic acid. In the process, a zirconium compound, e.g. zirconium bromide, is further present as the catalyst. The amount of the zirconium compound is preferably 0.5-50wt% based on the cobalt metal used as the catalyst constituent component. The aimed compound in good hue is obtained at a high reaction rate with a small amount of the catalyst with prevented formation of coloring impurities by the above-mentioned oxidative reaction.

公开(公告)号：JPS5829740A

公开(公告)日：1983-02-22

申请号：JP12774381

申请日：1981-08-17

Applicant: TORAY INDUSTRIES

Inventor： SUEMATSU MASAAKI ,  NAKAOKA KENJI

IPC: C07C63/15 ,  B01J27/00 ,  B01J27/08 ,  B01J31/00 ,  B01J31/04 ,  C07C51/00 ,  C07C51/265 ,  C07C63/307 ,  C07C67/00

Abstract: PURPOSE:In oxidizing a 9C aromatic distillate in the reaction product by a heterogeneous reaction of a catalytic reforming oil of naphtha, etc. with a molecular oxygen-containing gas in a solvent of acetic acid, to obtain the titled mixture advantageously, by using a cobalt, manganese, and bromine type catalyst with a specific concentration composition. CONSTITUTION:In oxidizing a 9C aromatic distillate contained in the reaction product obtained by making a catalytic reforming oil or an aromatic hydrocarbon heterogeneous, isomerizing or dealkylating it with a molecular oxygen-containing gas in a solvent of acetic acid in the presence of a catalyst consisting essentially of a cobalt compound, manganese compound, and a bromine compound, 0.01-0.2wt% based on the solvent of acetic acid of the cobalt metal in the catalyst, 1-50wt% based on the cobalt metal of the manganese metal and bromine atom in an amount to give 6-20 times that of the cobalt metal are used to give economically the titled compound having characteristics such as heat resistance, volatility resistance, etc. equal to those of trimellitic acid anhydride as a raw material for a high-quality plasticizer.

公开(公告)号：JPS5821642A

公开(公告)日：1983-02-08

申请号：JP11785781

申请日：1981-07-29

Applicant: TORAY INDUSTRIES

Inventor： SUEMATSU MASAAKI ,  NAKAOKA KENJI

IPC: C07C55/14 ,  B01J23/00 ,  B01J23/74 ,  B01J31/00 ,  B01J31/04 ,  C07B61/00 ,  C07C51/00 ,  C07C51/31 ,  C07C67/00

Abstract: PURPOSE:To obtain adipic acid in high reaction yield in high selectivity, by using inexpensive CH3CHO as a reaction accelerator, oxidizing cyclohexane in a specific amount of acetic acid solvent in the presence of a specified amount of a Co compound catalyst with feeding CH3CHO continuously. CONSTITUTION:Cyclohexane is oxidized with a molecular oxygen-containing gas in a solvent of acetic acid in the presence of a Co compound (e.g., cobalt acetate, cobalt carbonate, etc.) and a reaction accelerator, to give adipic acid. In the reaction, acetaldehyde is used as the reaction accelerator, the amount of acetic acid used is 1-5 times, preferably 1.5-3 times the cyclohexane amount, the amount of the cobalt metal used is 0.1-1.0wt%, preferably 0.2-0.5wt% based on acetic acid, the amount of acetaldehyde used is 0.05-0.3 that of cyclohexane, and the oxidation reaction is carried out at a reaction temperature of 80-120 deg.C at a reaction pressure of 5-30atm with feeding acetaldehyde continuously.

公开(公告)号：JPS57167942A

公开(公告)日：1982-10-16

申请号：JP5244481

申请日：1981-04-09

Applicant: TORAY INDUSTRIES

Inventor： SUEMATSU MASAAKI ,  NAKAOKA KENJI

IPC: C07C63/307 ,  B01J23/00 ,  B01J23/84 ,  B01J27/00 ,  B01J27/08 ,  C07B61/00 ,  C07C51/00 ,  C07C51/265 ,  C07C67/00

Abstract: PURPOSE:To prepare the titled compound, in high purity and yield, by the two- stage continuous oxidation reaction of pseudocumene at a specific temperature using a catalyst comprising Co, Mn and Br at a specific concentration, keeping the concentration of the raw material in the produced liquid at the first stage below a specific level. CONSTITUTION:Trimellitic acid is prepared by the continuous oxidation of pseudocumene with an O2-containing gas in an acetic acid solvent in the presence of a catalyst composed mainly of a Co compound, an Mn compound and a bromine compound. In the above process, the first stage reaction is carried out at 120-180 deg.C keeping the amount of Co to 0.01-0.09wt% of the acetic acid solvent, that of Mn to 1-50wt% of Co, and that of Br atom to 6-20 times the weight of Co, and reducing the concentration of the residual pseudocumene in the produced liquid to

公开(公告)号：JPS5683443A

公开(公告)日：1981-07-08

申请号：JP15926879

申请日：1979-12-10

Applicant: TORAY INDUSTRIES

Inventor： TORIGATA HAJIME ,  SUEMATSU MASAAKI ,  NAKAOKA KENJI

IPC: C07C51/487 ,  C07C51/00 ,  C07C63/26 ,  C07C67/00

Abstract: PURPOSE:To prepare purified terephthalic acid useful for the direct polymerization, by oxidizing an alkaline aqueous solution of terephthalic acid with a permanganate, optionally treating the oxidized solution with activated charcoal, precipitating with an acid, and washing with water-containing acetic acid at a high temperature. CONSTITUTION:An alkaline aqueous solution of crude terephthalic acid containing impurities which decrease the transmittance of light at the wavelength of 340nm, is subjected to oxidation treatment by adding a permanganate thereto. After the oxidation, the solution is optionally treated with activated charcoal, and added with an acid to precipitate terephthalic acid, which is washed with water-containing acetic acid at 170-250 deg.C to obtain terephthalic acid free of impurities and having improved particle shape. The water-containing acetic acid is pref. a mixture of water and acetic acid at a weight ratio of 1:99-50:50. The amount of the water- containing acetic acid is 2-6 times weight of the terephthalic acid to be purified. The time for the treatment with the water-containing acetic acid is usually 0.5-3hr.

公开(公告)号：JPS5681534A

公开(公告)日：1981-07-03

申请号：JP15812579

申请日：1979-12-07

Applicant: TORAY INDUSTRIES

Inventor： SUEMATSU MASAAKI ,  NAKAOKA KENJI

IPC: C07C63/26 ,  C07C51/00 ,  C07C51/265 ,  C07C67/00

Abstract: PURPOSE:To obtain terephthalic acid by oxidizing p-xylene in the presence of an acetic acid solvent, a cobalt catalyst, and a reaction promotor, e.g., paraaldehyde, etc., to bring a mother liquid from which the desired substance is removed into contact with an active carbon so that impurity substances to be readily colored are removed, and to circulate the mother liquid to the reaction system. CONSTITUTION:p-Xylene is oxidized in the presence of a solvent of acetic acid, a cobalt compound catalyst and a reaction promotor of paraaldehyde and/or acetaldehyde to give terephthalic acid, and a mother liquid from which terephthalic acid is removed is brought into contact with active carbon, and circulated to the oxidation reaction system. Both powdery and granular active carbon can be used, the mother liquid is brought into contact with the active carbon in a temperature range from room temperature to the boiling point of the solvent in a stirring tank in the case of powdery active carbon and in a packed column in the case of granular one. The active carbon can be recovered by calcination or by bringing it into contact with an alkali solution, washing, and drying, etc. EFFECT:A high-quality terephthalic acid can be prepared advantageously and stably.

公开(公告)号：JPS5651436A

公开(公告)日：1981-05-09

申请号：JP12813179

申请日：1979-10-04

Applicant: TORAY INDUSTRIES

Inventor： NAKAOKA KENJI ,  HASEGAWA SAKIE ,  UEDA CHIAKI

IPC: C07C69/76 ,  C07C69/78

Abstract: PURPOSE:To prepare the titled compound useful as a raw material of pharmaceuticals, polymer modifiers, etc., by partially saponifying dimethyl terephthalate, and without converting to carboxylic acid, reacting with a chlorinating agent. CONSTITUTION:A methanol solution of dimethyl terephthalate is added with a methanol solution containing 1.0-1.5mol, based on 1mol of dimethyl terephthalate, of potassium hydroxide, and made to react with heating. The formed potassium salt of monomethyl terephthalate crystal is filtered, and reacted with a chlorinating agent selected from thionyl chloride, phosphorus pentachloride, phosphorus trichloride, and phosphorus oxychloride, to obtain p-chlorocarbonylbenzoic acid methyl ester. The process for the preparation of monomethyl terephthalate by saponifying a monometal salt of monomethyl terephthalate followed by acid treatment, which is essential in the conventional procedure, can be eliminated by this process.

公开(公告)号：JPS5640640A

公开(公告)日：1981-04-16

申请号：JP11517479

申请日：1979-09-10

Applicant: TORAY INDUSTRIES

Inventor： TORIGATA HAJIME ,  NAKAOKA KENJI

IPC: C07C63/26 ,  C07C51/00 ,  C07C51/487 ,  C07C67/00

Abstract: PURPOSE:To obtain the purified terephthalic acid useful as a raw material for fibers readily, by the specific oxidation of impure terephthalic acid. CONSTITUTION:A solution of terephthalic acid containing an impurity to deteriorate the light transmittance at 340nm, is oxidized by an oxidizing agent consisting of a hypochlorite and hydrogen peroxide in a molar amount of 0.2 or more that of the hypochlorite, to obtain the purified terephthalic acid. Crude or recovered terephthalic acid containing the impurity, is purified much more effectively in simultaneous use of both the oxidizing agent components than in separate use, and readily purified due to its operation in the homogeneous liquid phase.

公开(公告)号：JPS55124741A

公开(公告)日：1980-09-26

申请号：JP3226579

申请日：1979-03-22

Applicant: TORAY INDUSTRIES

Inventor： SUEMATSU MASAAKI ,  NAKAOKA KENJI

IPC: C07C69/82 ,  C07C67/313

Abstract: PURPOSE:To prepare the title compound useful as a raw material of medicines, polymer modifiers, etc., in high purity, by partially hydrolyzing dimethyl terephthalate in methanol in the presence of a specific amount of KOH, thereby suppressing the production of terephthalic acid which is difficult to separate. CONSTITUTION:Dimethyl terephthalate (1mol) is dissolved in hot methanol. A methanol solution of KOH (1.0-1.5mol) is added to the above solution, and the mixture is heated and refluxed to obtain monomethyl monopotassium terephthalate crystal. The crystal is filtered and dissolved in water, and then the remaining dimethyl terephthalate dispersed in the solution as white powder is removed by filtration. The objective compound can be crystallized by adding an acid to the clear and colorless filtrate obtained above. Since monomethyl monopotassium terephthalate is hardly soluble in hot methanol and precipitates as crystal, the excessive hydrolysis to dipotassium salt can be suppressed and the objective compound is obtained in high purity.