WO2002060848A1 - Procede de production de 4,4'-biphenol - Google Patents

Procede de production de 4,4'-biphenol Download PDF

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Publication number
WO2002060848A1
WO2002060848A1 PCT/JP2002/000687 JP0200687W WO02060848A1 WO 2002060848 A1 WO2002060848 A1 WO 2002060848A1 JP 0200687 W JP0200687 W JP 0200687W WO 02060848 A1 WO02060848 A1 WO 02060848A1
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Prior art keywords
biphenol
alkyl
reaction
weight
parts
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Application number
PCT/JP2002/000687
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English (en)
Japanese (ja)
Inventor
Atsushi Higo
Masaaki Toma
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Sumitomo Chemical Company, Limited
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Publication date
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Priority to KR10-2003-7009830A priority Critical patent/KR20030074736A/ko
Publication of WO2002060848A1 publication Critical patent/WO2002060848A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol

Definitions

  • This effort relates to a method for producing 4,4-biphenyl, which is useful as a raw material compound for engineering plastics and the like.
  • 4,4′-biphenol represented by (1) for example, 3,3 ′, 5,5′-tetra-t-butyl-1-4,4′-biphenol can be prepared by adding phenols at atmospheric pressure.
  • a method is known in which a 4,4′-biphenol is formed by a dealkylation reaction to produce 4,4′-biphenol, and the 4,4′-biphenol precipitated at a temperature exceeding the melting point of the phenols and 80 ° C. or lower is separated by filtration. (See JP-A-58-189127).
  • the present invention provides a method for producing 4,4, -biphenol having good hue. Disclosure of the invention
  • alkyl-1,4,4, -bipheno / les such as 3,3,5,5,5'-tetra-t-butyl-4,4, -biphenol are dealkylated to 4,4 'When the method consisting of the following steps (a) and (b) is adopted in the production of -biphenol, 4,4, -biphenol with good hue can be produced. With this finding, the present invention has been completed.
  • the present invention provides a method for producing 4,4, -biphenol, which comprises the following steps (a) and (b).
  • ⁇ represents an alkyl group having 3 to 8 carbon atoms.
  • m and ⁇ represent 0, 1 or 2 each other, and the sum of m and ⁇ is 1-4.
  • the alkyl-4,4'-biphenols represented by are dealkylated in the presence of a phenol selected from the group consisting of phenol, monoalkylphenol, dialkylphenol and trialkylphenol, the ability to react under reduced pressure ⁇ Alternatively, the reaction is carried out under atmospheric pressure until the production amount of monoalkyl 1,4'-biphenols is in the range of 5 to 20 parts by weight per 100 parts by weight of 4,4'-biphenol, and 4,4'-biphenol is obtained. Obtaining a reaction solution containing
  • Biphenols (2) include compounds having 1 to 4 linear or branched alkyl groups having 3 to 8 carbon atoms.
  • Preferred alkyl 1,4,1-biphenyl compounds (2) include those having an alkyl group in which T is alkyl having 3 to 8 carbon atoms and the benzene ring has a tertiary or quaternary carbon atom.
  • Branched alkyl 4,4'-biphenols are preferred.
  • Preferred branched alkyl-1,4'-biphenols include, for example, mono-branched alkyl-1,4, such as 3-i-propyl-14,4,4-biphenol ⁇ 3-t-butyl-4,4, -biphenol. 4, -biphenyl, 3,5-di-1-propyl-1,4,4-biphenol, 3,3,1-propyl-1,4,4-biphenol, 3,5-di-t-butyl
  • Di-branched alkyl-1,4,4'-biphenols such as 4,4, -biphenol and 3,3, -di-t-butyl-4,4, -biphenol, 3,3 ', 5-tri-i-propyl-1,4,4 'Biphenols and 3,3', 5-tri-t-butyl-4,4, -biphenols and other tri-branched alkyl-1,4-,-biphenolenes, or 3,3,5,5'- Tetra i-propyl one, four, four, one biphenol,
  • alkyl-1,4, -biphenols (2) include, for example, 3,3,, 5,5'-tetra-1-i-propinolee 4,4'-biphenol and 3,3, '5,5'-tetra-t Monobutyl-4,4, -biphenol and the like.
  • the above alkyl-1,4, -biphenols can be produced by the method described in JP-A-3-123747. For example, by reacting phenol and t-butylphenol with a dimer reaction, 3_t-butyl-4,4′-biphenyl and 3,5-di-t-butylphenol 4,4, -biphenol are obtained. 3,3'-Gee-Phate / Lae 4,4, -Bi-Henore, 3,3,, 5-Tri-T-Butino-Lee 4,4'-Bi-Henorene by dimerization of t-butylphenol And 3,3,5,5, -tetra-t-butyl-4,4'-biphenol.
  • the alkyl-1,4'-biphenols obtained by such a dimerization reaction may be dealkylated without removal from the dimerization reaction mixture, or may be dealkylated without removal from the dimerization reaction mixture.
  • the biphenyls may be dealkylated, or may be removed from the dimerization reaction mixture, purified and then dealkylated.
  • the dealkynoleidation reaction in step (a) is carried out in the presence of a phenol.
  • phenols examples include phenol; 2-i-propylphenol, 2 Monoalkylphenols such as _t-butynolephenol, 3-i-propylphenol, 3-t-butynolephenol, 4-i-propylphenol, 4-t-butylphenylphenol and cresol; 2, 6- Dialkynolephenols such as G i-propinolephenol and 2,6-di-t-butylphenol; 2, 4, 6-tree i-pin mouth Pinolephenol and 2,4,6-tree trialkyl phenol such as t-butyl phenol; and the like.
  • the above-mentioned phenols are compounds used as raw material compounds for the production of alkyl 1,4′-biphenols, and phenols, i-propylphenols and t-peptides which are contained in the reaction mixture without being reacted. It may be a Norefue nore. Further, the phenols may be phenols by-produced in the production of alkyl 1,4′-biphenols. Such phenols may be used alone or as a mixture of two or more.
  • the above-mentioned phenols alone or in a mixture are preferably used in an amount of from 0.1 to 1 mol: based on 1 mol of the alkyl-1,4, -biphenol. More preferably, the phenols used alone or as a mixture are used in a range of 0.5 to 5 mol.
  • the dealkylation reaction of the alkyl-1,4, -biphenol in the step (a) is preferably carried out in the presence of a dealkylation catalyst.
  • a dealkylation catalyst for example, an inorganic acid or an organic acid such as sulfuric acid or: -toluenesulfonic acid is preferably used.
  • Preferred reaction temperatures for the dealkylation range from 0 to 300 ° C.
  • a more preferred reaction temperature when a dealkylation catalyst is added is in the range of 150 to 300 ° C.
  • a dealkynoleic reaction is carried out in the presence of a phenol selected from the group consisting of phenol, monoalkylphenol, dialkylphenol and 1, real-alkylphenol, by-product alkene reacts with phenol to form 4-i-propylphenol.
  • the de-anolekylation reaction is carried out under reduced pressure, or the amount of mono-a-no-realkyl-1,4'-biphenol in the reaction solution is in the range of 5 to 20 parts by weight per 100 parts by weight of 4,4, -biphenol. React under atmospheric pressure until
  • the dealkylation reaction under reduced pressure is preferably performed in the range of 0.0006 to 0.095 MPa, more preferably in the range of 0.06 to 0.07 MPa.
  • Monoanolequinolene 4,4'-biphenols include, for example, mono-t-butyl-4,4'-biphenol and mono-i-propyl-1,4,4, -biphenol.
  • step (a) The dealkylation reaction in step (a) is carried out batchwise or continuously.
  • a 4,4-biphenyl compound is separated and separated (b) ) May be performed.
  • aromatic hydrocarbon solvent for example, benzene, toluene, xylene, ethylbenzene, jetinobenzene, trimethylenobenzene, monochrome-mouth benzene, dichlorobenzene, aesole, nitrobenzene, cumene, cymene and the like can be mentioned.
  • aliphatic hydrocarbon solvent for example, pentane, hexane, heptane, octane, decane, hexopenedisodibutylene and the like can be mentioned.
  • examples of the aliphatic ketone solvent include acetone-hexanone hexanone.
  • the aromatic hydrocarbon solvent, the aliphatic hydrocarbon solvent and the aliphatic ketone solvent are used alone or in combination of two or more.
  • the amount of the above-mentioned hydrocarbon solvent / ketone solvent per 1 part by weight of the alkyl-1,4'-biphenol is preferably 0.1 To 10 parts by weight, more preferably 0.2 to 2 parts by weight.
  • the temperature of the aromatic hydrocarbon solvent, aliphatic hydrocarbon solvent or aliphatic ketone solvent to be mixed with the reaction solution obtained in the step (a) is usually in a range below the boiling point and above the freezing point, preferably 0 to 200 °. C range.
  • the reaction solution is used during the dealkylation reaction. It may be S or may be cooled appropriately.
  • the time required for the addition is preferably in the range of 1 minute to 30 hours.
  • Step (b) is a step of separating 4,4′-bifunool precipitated from the reaction solution of the above step (a) by filtration or the like.
  • the preferred separation temperature of 4,4, -biphenol is below the boiling point and above the freezing point of the aromatic hydrocarbon solvent, aliphatic hydrocarbon solvent or aliphatic ketone solvent, and the more preferred filtration temperature is in the range of 0 to 200 ° C. It is an enclosure.
  • the 4,4′-biphenole obtained as a filtered product is, for example, water; an aromatic hydrocarbon solvent; an aliphatic hydrocarbon solvent; an aliphatic ketone solvent such as acetone; a lower alcohol such as methanol and ethanol-i-propyl alcohol; And a mixed solvent thereof.
  • a 5% by weight methanol solution of the obtained 4,4'-biphenol was prepared, and its absorbance at 420 nm was measured using a UV-16OA (Shimazu Seisakusho) (cell length: lcm). However, it was 0.057.
  • a reaction solution was obtained in the same manner as in Example 1, except that the reaction was carried out at the same temperature for 2 hours.
  • the reaction mixture was sampled and analyzed by high performance liquid chromatography.
  • the content of 3-t-butyl-4,4, -biphenol was 13 parts by weight with respect to 100 parts by weight of 4,4'-biphenol.
  • Atsuta 65.5 g of toluene was added dropwise to the reaction solution at 200 ° C over 1 hour.
  • the mixture after dropping was cooled to 100 ° C, and further cooled to 60 ° C, and the obtained precipitate was filtered.
  • the filtered material is washed with 65.5 g of toluene, 131 g of a 50% by weight aqueous methanol solution, and then dried in vacuum at 100 ° C. to give 4,9.7′-biphenyl having a purity of 99.7% (percentage area). 52. lg was obtained (87% yield).
  • the resulting 4, 4 to prepare a 5 wt 0/0 methanol Bifuenoru, the absorbance at the wave length of 420 nm, manufactured by Shimadzu Corporation UV-16 OA (a length of a cell l cm) measured using a As a result, it was 0.064.
  • Example 2 After heating to 200 ° C, the reaction was carried out in the same manner as in Example 1 except that the reaction was carried out at the same temperature for 20 hours to obtain a reaction solution.
  • the reaction mixture was sampled and analyzed by high performance liquid chromatography.
  • the content of 3-t-p-tinole-4,4,4-biphenol was 3 parts by weight with respect to 100 parts by weight of 4,4, -biphenol. At the rate of Atsuta.
  • 65.5 g of toluene was added dropwise to the reaction solution at 200 ° C over 1 hour.
  • the mixture after dropping was cooled to 100 ° C, and further cooled to 60 ° C, and the obtained precipitate was filtered.
  • the resulting 4, 4, to prepare a 5 wt 0/0 methanol Bifuenoru the absorbance at the wave length of 420 nm, manufactured by Shimadzu Corporation UV_ 16 OA (a length of a cell l cm) was measured using a However, it was 0.215.
  • Example 2 After heating to 200 ° C, the same operation as in Example 1 was carried out except that the reaction was carried out at the same temperature for 6 hours, to obtain a reaction solution.
  • the reaction mixture was sampled and analyzed by high performance liquid chromatography.
  • the content of 3- (1-butyl) -4,4'-biphenol was 2 parts by weight based on 100 parts by weight of 4,4'-biphenol. It was.
  • 65.5 g of toluene was added dropwise to the reaction solution at 200 ° C over 1 hour.
  • the mixture after the dropwise addition was cooled to 100 ° C, further cooled to 60 ° C, and the obtained precipitate was filtered.
  • the resulting 4, 4 to prepare a 5 wt 0/0 methanol solution one Bifuenoru, measuring the absorbance at the wave length of 420 nm, manufactured by Shimadzu Corporation UV_ 16 OA (a length of a cell l cm) using a The result was 0.174.
  • a 5% by weight methanol solution of the obtained 4,4, -biphenol was prepared, and its absorbance at 420 nm was measured using a UV-16OA (Shimazu Seisakusho, cell length: lcm). , 0.093.
  • 4,4, -biphenol having good hue can be produced industrially and advantageously.

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

Abstract

Procédé de production de 4,4'-biphénol, caractérisé en ce qu'il comprend les étapes (a) et (b) suivantes : (a) désalkylation d'un alkyl-4,4'-biphénol de formule générale (2), en présence d'un phénol choisi dans le groupe comprenant le phénol, les monoalkylphénols, dialkylphénols et trialkylphénols, en ce que la désalkylation est soit effectuée sous pression réduite, soit poursuivie sous la pression atmosphérique jusqu'à ce que la quantité de monoalkyl-4,4'-biphénol formé soit réduite à 5 à 20 parties en poids pour 100 parties en poids de 4,4'-biphénol, et b) précipitation du 4,4'-biphénol à partir du fluide réactionnel obtenu dans l'étape (a), puis séparation du composé précipité. Dans la formule générale (2), T désigne un alkyle ayant de 3 à 8 atomes de carbone, et m et n égalent, chacun, 0, 1 ou 2, la somme de m et n étant comprise entre 1 et 4,1.
PCT/JP2002/000687 2001-01-31 2002-01-30 Procede de production de 4,4'-biphenol WO2002060848A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR10-2003-7009830A KR20030074736A (ko) 2001-01-31 2002-01-30 4,4'-비페놀의 제조방법

Applications Claiming Priority (4)

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JP2001023253 2001-01-31
JP2001-23252 2001-01-31
JP2001-23253 2001-01-31
JP2001023252 2001-01-31

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1440960A1 (fr) * 2003-01-23 2004-07-28 Honshu Chemical Industry Co., Ltd. Procédé pour la préparation de 4,4-biphénol
CN115814854A (zh) * 2022-11-15 2023-03-21 中国海洋石油集团有限公司 一种用于制备2,2'-联苯二酚的催化剂及其制备方法和用途

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5191238A (en) * 1975-02-10 1976-08-10 4*4** jiokishibifueniru no seizoho
JPS58189127A (ja) * 1982-04-30 1983-11-04 Showa Denko Kk Ｐ，ｐ′−ビフエノ−ルの製造法
JPH02169530A (ja) * 1988-12-21 1990-06-29 Honsyu Kagaku Kogyo Kk テトラブチルビフェノールの脱ブチル化方法
EP0421883A2 (fr) * 1989-10-06 1991-04-10 Honshu Chemical Industry Co. Ltd. Procédé de préparation de p,p'-diphénol
EP0571947A1 (fr) * 1992-05-29 1993-12-01 Mitsubishi Chemical Corporation Procédé pour la préparation de 4,4'-biphénol
DE10020272A1 (de) * 1999-04-26 2000-12-14 Sumitomo Chemical Co Verfahren zur Herstellung von p,p'-Biphenol

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5191238A (en) * 1975-02-10 1976-08-10 4*4** jiokishibifueniru no seizoho
JPS58189127A (ja) * 1982-04-30 1983-11-04 Showa Denko Kk Ｐ，ｐ′−ビフエノ−ルの製造法
JPH02169530A (ja) * 1988-12-21 1990-06-29 Honsyu Kagaku Kogyo Kk テトラブチルビフェノールの脱ブチル化方法
EP0421883A2 (fr) * 1989-10-06 1991-04-10 Honshu Chemical Industry Co. Ltd. Procédé de préparation de p,p'-diphénol
EP0571947A1 (fr) * 1992-05-29 1993-12-01 Mitsubishi Chemical Corporation Procédé pour la préparation de 4,4'-biphénol
DE10020272A1 (de) * 1999-04-26 2000-12-14 Sumitomo Chemical Co Verfahren zur Herstellung von p,p'-Biphenol

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1440960A1 (fr) * 2003-01-23 2004-07-28 Honshu Chemical Industry Co., Ltd. Procédé pour la préparation de 4,4-biphénol
CN115814854A (zh) * 2022-11-15 2023-03-21 中国海洋石油集团有限公司 一种用于制备2,2'-联苯二酚的催化剂及其制备方法和用途
CN115814854B (zh) * 2022-11-15 2024-06-07 中国海洋石油集团有限公司 一种用于制备2,2'-联苯二酚的催化剂及其制备方法和用途

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