WO2002060848A1

WO2002060848A1 - Process for production of 4,4'-biphenol

Info

Publication number: WO2002060848A1
Application number: PCT/JP2002/000687
Authority: WO
Inventors: Atsushi Higo; Masaaki Toma
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2001-01-31
Filing date: 2002-01-30
Publication date: 2002-08-08
Also published as: KR20030074736A

Abstract

A process for production of 4,4'-biphenol, characterized by comprising the following steps (a) and (b): the step (a) of dealkylating an alkyl-4,4'-biphenol represented by the general formula (2) in the presence of a phenol selected from the group consisting of phenol, monoalkylphenols, dialkylphenols and trialkylphenols wherein the dealkylation is either conducted under a reduced pressure or continued under atmospheric pressure until the amount of formed monoalkyl -4,4'-biphenol decreases to 5 to 20 parts by weight per 100 parts by weight of 4,4'-biphenol, and the step (b) of precipitating 4,4'-biphenol from the reaction fluid obtained in the step (a) and separating it. (2) [In the general formula, T is alkyl having 3 to 8 carbon atoms; and m and n are each 0, 1, or 2, the sum of m and n ranging from 1 to 4.]

Description

Specification

Method for producing 4,4, -biphenol

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. Background art

The following formula (1)

As a method for producing 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).

However, the above-mentioned known method has a problem that the hue of 4,4, -biphenol obtained is not always satisfactory. The present invention provides a method for producing 4,4, -biphenol having good hue. Disclosure of the invention

As a result of intensive studies, the present inventor has found that 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.

That is, the present invention provides a method for producing 4,4, -biphenol, which comprises the following steps (a) and (b).

(a) Process:

The following formula (2)

(2)

[Wherein, Τ represents an alkyl group having 3 to 8 carbon atoms. m and η represent 0, 1 or 2 each other, and the sum of m and η is 1-4. ]

When 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

(b) a step of precipitating and separating 4,4,1-biphenol from the reaction solution obtained in the step (a). BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, Ryoaki Honaki will be described in detail.

The alkyl-1,4 ′ used as a starting compound in step (a) in the present invention

— 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 ゃ 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,

Compounds such as tetra-branched alkyl-1,4'-biphenols such as 3 ', 5,5, -tetra-t-butyl-4,4'-biphenol are exemplified.

Particularly preferred 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. In the present invention, the dealkynoleidation reaction in step (a) is carried out in the presence of a phenol. Examples of phenols 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.

In the step (a) in the present invention, 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. As the dealkylation catalyst, for example, an inorganic acid or an organic acid such as sulfuric acid or: -toluenesulfonic acid is preferably used. The amount of dealkylation catalyst, alkyl one 4, 4 ⁵ -.. Relative to 1 mole of Bifuenoru acids, preferably 0.0 0 1-0 5 mols, more favorable Mashiku 0 0 It is in the range of 1 to 0.1 mol.

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. When 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. Nore, 4-t-Ptinolephenol, 2,4-Di-i-propizolephenol, 2,4—Di-t-butylphenol, 2,4,6-Tri-i-propylphenol and 2 , Alkyl phenols such as 4,6-tree t-butylphenol are produced. These products are separated from 4,4, -biphenol by the precipitation of 4,4'-biphenol and the separation step (b) described later. The separated alkylphenols can be converted into i-propyl-14,4'-biphenols or t-butyl-14,4'-biphenols by, for example, the above-mentioned dimerization reaction.

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.

Reaction 場合 When the dealkylation reaction is carried out under atmospheric pressure until the amount of mono-alkyl 1,4,4-biphenols formed in the night falls within the range of 5 to 20 parts by weight per 100 parts by weight of 4,4,1-biphenol. For example, the dealkylation reaction can be stopped halfway, for example, by cooling the reaction solution. Monoanolequinolene 4,4'-biphenols include, for example, mono-t-butyl-4,4'-biphenol and mono-i-propyl-1,4,4, -biphenol.

The dealkylation reaction in step (a) is carried out batchwise or continuously.

In the present invention, after the reaction solution obtained in the step (a) is mixed with an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent or an aliphatic ketone solvent, a 4,4-biphenyl compound is separated and separated (b) ) May be performed.

As the 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. As the 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. On the other hand, the reaction solution is used during the dealkylation reaction. It may be S or may be cooled appropriately. When the above-mentioned hydrocarbon solvent / ketone solvent is added to the reaction solution obtained in the step (a), the time required for the addition is preferably in the range of 1 minute to 30 hours.

Thus, by mixing the aromatic hydrocarbon solvent, the monthly aliphatic hydrocarbon solvent or the aliphatic ketone solvent with the reaction solution obtained in the step (a), 4,4,1-biphenol can be precipitated. it can.

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.

Example

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and the like. The present invention is not limited to these Examples.

Example 1

Crude 3,3,, 5,5, -tetra-t-butyl-4,4, -biphenyl 160 g [3,3,, 5,5, -tetra-t-butyl-4,4'-biphenol 0.32 mol and 2,2, Mixture of 0.12 mole of 6-Gee t-Ptinolephenol), 2,6 g-t-Ptinolephenol, 9 g, 4t-Ptinolephenol, 24 g and 2,4 A mixture of 42 g of 6-tree t-butylphenol was heated to 150 ° C., and 3 g of monotonoleenesulfonic acid monohydrate was added at the same temperature. Then, the mixture was heated to 200 ° C. and reacted at the same temperature for 1 hour to obtain a reaction solution. This reaction solution is sampled and As a result of analysis by isomer chromatography, the content of 3-t-butyl-4,4, -biphenol was 9 parts by weight based on 100 parts by weight of 4,4'-biphenol.

After the above sampling, 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 residue was washed with 65.5 g of toluene, washed with 131 g of a 50% by weight methanol / Zk solution, and then dried under vacuum at 100 ° C to obtain 4,4 ′ having a purity of 99.8% (area percentage). Thus, 52.6 g of bibiphenol was obtained (yield: 88%).

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.

Example 2

After heating to 200 ° C., 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. After the above sampling, 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.

Comparative Example 1

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. After the above sampling, 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 residue 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 4,8,4-biphenol having a purity of 99.8% (percentage area). 52. O g was obtained (yield 87%).

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.

Comparative 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. After the above sampling, 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 residue is washed with 65.5 g of toluene, washed with 131 g of a 50% by weight aqueous methanol solution, and then dried in vacuo at 100 ° C. to obtain a 4,9.7-biphenyl compound having a purity of 99.7% (area percentage). 54.9 g were obtained (92% yield).

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.

Example 3

Crude 3,3,, 5,5, -tetra-p-tinole-4,4, -biphenol 160 g [3,3,, 5,5,1-tetra-t-butyl-4,4, -biphenyl 0.32 monole (A mixture of 0.1 mol of 2,6-di-tert-butylphenol), 24 g of 4-t-butynolephenol and 42 g of 2,4,6-tri-tert-butylenophenol The mixture was heated to 151 ° C, and 3 g of p-toluenesulfonic acid hydrate was added at the same temperature. Next, the reaction system was heated to 191 ° C., and the pressure inside the reaction system was reduced to 0.064 MPa. The mixture was heated to 202 ° C under the same pressure and reacted for 3 hours to obtain a reaction solution. This reaction solution To the mixture was added 66 g of toluene over 1 hour, and the resulting precipitate was filtered at 60 ° C. The residue was washed with 66 g of toluene, 132 g of a 50% by weight aqueous methanol solution, and then dried in vacuo at 100 ° C. to give 4,9.9′-biphenyl having a purity of 99.9% (area percentage). 6 g was obtained (93% yield).

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.

Comparative Example 3

Crude 3,3,, 5,5, -tetra-t-butyl-4,4'-biphenol 160 g [3,3,, 5,5,1-tetra-t-butylphenol 1,4,4'-biphenol 0.3 mol and 2 A mixture of 0.14 mole of 6-g-t-butynolephenol)], 22.2 g of 4-t-butynolephenol and 38.8 g of 2,4,6-tree t-butynolephenol The mixture was heated to 150 ° C, and at the same temperature, 2.8 g of p-toluenesulfonic acid monohydrate was added. Next, the mixture was heated to 200 ° C. and reacted at the same temperature for 16 hours to obtain a reaction solution. The reaction solution was cooled to 100 ° C, 60.7 g of toluene was added over 1 hour, and the obtained precipitate was filtered at 60 ° C. The filtrate is washed with 60.7 g of toluene, washed with 121.5 g of a 50% by weight aqueous methanol solution, and then dried in vacuum at 100 ° C. to obtain 4,4 ′ having a purity of 99.6% (area percentage). 48.6 g of bibiphenol was obtained (yield: 88%).

The resulting 4, 4, one 5 weight ^_0/0 methanol solution prepared in Bifuenoru, 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 measured value was 0.179. Industrial applicability

According to the present invention, 4,4, -biphenol having good hue can be produced industrially and advantageously.

Claims

The scope of the claims

1. A method for producing 4,4-biphenol, which comprises the following steps (a) and (b):

(a) process;

The following formula (2)

(T) m (T) n

HO OH

(2)

[Wherein, T represents an alkyl group having 3 to 8 carbon atoms. m and ri represent 0, 1 or 2, respectively, and the sum of m and n is 1-4. ]

Ability to react under reduced pressure when dealkylating alkyl-1,4, -biphenols represented by in the presence of phenols selected from the group consisting of phenols, monoalkynolephenols, dialkylphenols and trialkylphenols \ Or monoalkyl _ 4,4'-biphenols are reacted under atmospheric pressure until the production of 4,4,1-biphenol is in the range of 5 to 20 parts by weight per 100 parts by weight of 4,4,1-biphenol. A step of obtaining a reaction solution containing bibutanol;

(b) process;

A step of precipitating and separating 4,4, -biphenol from the reaction solution obtained in the above step (a).

2. The amount of phenols The method of claim 1 alkyl one 4, 4 per mole of ⁵ Bifuenoru compound is in the range of 0.1 to 1 0 mol.

3. The method according to claim 1, wherein the alkyl-1,4′-biphenol is a compound having 2 to 4 alkyl groups having 3 to 8 carbon atoms.

4. The method according to claim 1, wherein the dealkylation reaction is carried out in the presence of a catalyst.