JP2000239204A - Production method of bisphenols - Google Patents

Abstract

(57) [Problem] To provide a simple and economical method for producing bisphenols having a specific structure with high purity and high yield. In a solvent selected from aliphatic hydrocarbons having 6 to 10 carbon atoms and aromatic hydrocarbons having 6 to 12 carbon atoms,
Formula (II) R ¹ -CHO (II) in the presence of an anionic surfactant selected from sodium monoalkylnaphthalenesulfonate, sodium alkyldiphenyldisulfonate, sodium dialkylbenzenesulfonate and sodium dialkylsulfosuccinate. And an aldehyde of formula (III) A condensation reaction with a dialkylphenol represented by the formula (I): (Wherein, R ¹ represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and R ² and R ³ each independently represent an alkyl group having 1 to 5 carbon atoms).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound of the formula (I)

[0002]

(Wherein R ¹ represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and R ² and R ³ each independently represent an alkyl group having 1 to 5 carbon atoms) About the law.

[0004]

2. Description of the Related Art Bisphenols represented by the above formula (I) have long been known as antioxidants for natural rubbers, synthetic rubbers, lubricating oils, and the like. It is a compound that has attracted attention as an intermediate of an inhibitor (see JP-B-63-46774, JP-B-7-25946, JP-B-7-64786, etc.).

The bisphenols of the formula (I) generally comprise an aldehyde of the formula (II) R ¹ -CHO (II), wherein R ¹ has the same meaning as described above, and a phenol of the formula (III)

[0006] (Wherein R ² and R ³ have the same meaning as described above) (for example, Japanese Patent Publication No. 337-1877, Japanese Patent Publication No.
2-2350, JP-B-52-39029 and JP-B-60-
No. 23097).

[0007]

These known methods are:
In any case, the bisphenols represented by the above formula (I) are isolated by crystallization or the like to obtain high quality. However, considering the use as an intermediate in particular, dissolution loss occurs due to crystallization purification, It is not always satisfactory in production on an industrial scale, for example, requiring a simple filtration and drying process.

[0008] The present inventors have solved these problems,
As a result of intensive research to develop an industrially satisfactory production method as an intermediate material, the aldehyde represented by the formula (II) and the aldehyde represented by the above formula (II) were synthesized using a specific organic solvent and a specific anionic surfactant. By reacting with a dialkylphenol represented by the formula (III), the bisphenols represented by the formula (I) can be obtained in a high purity, a high yield, and conveniently.
It has been found that it can be manufactured economically, leading to the present invention.

[0009]

That is, the present invention provides a method for preparing sodium monoalkylnaphthalenesulfonate in a solvent selected from aliphatic hydrocarbons having 6 to 10 carbon atoms and aromatic hydrocarbons having 6 to 12 carbon atoms. And an aldehyde represented by the formula (II) and an aldehyde represented by the formula (III) in the presence of an anionic surfactant selected from sodium alkyldiphenyldisulfonate, sodium dialkylbenzenesulfonate and sodium dialkylsulfosuccinate. A method for producing a bisphenol represented by the above formula (I) by subjecting a dialkylphenol to a condensation reaction is provided.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the aldehyde of the formula (II) used in the present invention, examples of the alkyl group represented by R ¹ include methyl, ethyl, n-propyl and isopropyl. Therefore, the aldehyde represented by the formula (II) is specifically formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde or isobutyraldehyde.

In the dialkylphenol of the formula (III), the alkyl groups represented by R ² and R ³ include methyl, ethyl, n-propyl, isopropyl, n
-Butyl, isobutyl, sec-butyl, t-butyl, n
-Pentyl, t-pentyl and the like. R ² and R ³ may of course be the same or different.
In particular, R ³ is an alkyl group having a tertiary carbon, that is, t 3
-Butyl or t-pentyl is preferred. Specific examples of the dialkylphenol represented by the formula (III) include 2-4
-Di-t-pentylphenol, 2-4-di-t-butylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-4-ethylphenol, 2-t-
Butyl-4-propylphenol, 2-t-butyl-4
-Isopropylphenol and the like.

Therefore, typical examples of the bisphenols represented by the above formula (I) which are the object of the present invention include:
The following compounds may be mentioned. 2,2'-ethylidenebis (4,6-di-t-pentylphenol), 2,
2'-methylenebis (4,6-di-t-pentylphenol), 2,2'-ethylidenebis (4,6-di-t-phenol)
Butylphenol), 2,2'-methylenebis (4,6
-Di-t-butylphenol), 2,2'-propylidenebis (6-t-butyl-4-methylphenol),
2,2'-ethylidenebis (6-t-butyl-4-methylphenol), 2,2'-methylenebis (6-t-butyl-4-methylphenol), 2,2'-methylenebis (6-t- Butyl-4-ethylphenol), 2,
2'-ethylidenebis (6-t-butyl-4-propylphenol), 2,2'-ethylidenebis (6-t-butyl-4-isopropylphenol).

In the present invention, in the condensation reaction between the aldehyde represented by the formula (II) and the dialkylphenol represented by the formula (III), the solvent is an aliphatic hydrocarbon having 6 to 10 carbon atoms or a solvent having 6 to 12 carbon atoms. Aromatic hydrocarbons are commonly used. Examples of the aliphatic hydrocarbon having 6 to 10 carbon atoms include n
-Hexane, n-heptane, n-octane, n-nonane, n-decane, cyclohexane and the like. Examples of the aromatic hydrocarbon having 6 to 12 carbon atoms include benzene, toluene, xylene, ethylbenzene, cumene, cymene, and chlorobenzene. Of these, aromatic hydrocarbons, especially toluene or xylene, are preferably used. These solvents can be used alone or in combination of two or more. The amount of solvent used is determined by the formula
1 to 100% by weight based on the dialkylphenol of (III)
The degree is preferred. More preferably, it is about 5 to 50% by weight.

Further, in the condensation reaction of the present invention, the use of a surfactant is essential. As a surfactant, usually
An anionic surfactant having a high hydrophilic lipophilic balance (HLB) is used. In particular, the surfactant used in the present invention includes sodium monoalkylnaphthalenesulfonate, sodium alkyldiphenyldisulfonate, sodium dialkylbenzenesulfonate, And sodium dialkyl sulfosuccinate. Commercial products belonging to sodium monoalkylnaphthalenesulfonate include:
For example, there is "Perex NB-L" manufactured by Kao Corporation. A commercially available product belonging to sodium alkyldiphenyldisulfonate is, for example, "Sandet AL" manufactured by Sanyo Chemical Industries, Ltd. As a commercial product belonging to sodium dialkylbenzenesulfonate, for example, "Sendale S" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. is available. As a commercial product belonging to sodium dialkyl sulfosuccinate, there is, for example, "Neoperex OT-P" manufactured by Kao Corporation.

Among these anionic surfactants, sodium monoalkylnaphthalenesulfonate, sodium alkyldiphenyldisulfonate and sodium dialkylbenzenesulfonate are particularly preferably used in the present invention. Commercial products include "Perex NB-L" manufactured by Kao Corporation, "Sandet AL" manufactured by Sanyo Kasei, "Sendale S" manufactured by Daiichi Kogyo Seiyaku, etc.
It is exemplified as particularly preferred.

The amount of the surfactant used is preferably about 0.6 to 3% by weight based on the dialkylphenol of the formula (III).
In addition, nonionic surfactant, cationic surfactant,
Amphoteric surfactants and the like have poor reactivity and are not preferred for use in the condensation reaction of the present invention.

The condensation reaction of the aldehyde of the formula (II) with the dialkylphenol of the formula (III) according to the present invention is usually carried out in the presence of a catalyst and water. As the catalyst, acids, for example, sulfuric acid, hydrochloric acid, mineral acids such as phosphoric acid,
Organic acids such as toluenesulfonic acid can be used, and hydrochloric acid and sulfuric acid are particularly preferably used. The amount of catalyst used is determined by the formula (I
(II) 0.001 to 0.
About 1 mole is preferred. The catalyst may be used whether it is diluted with water or the like or has a high concentration.

The aldehyde is usually used in an amount of about 0.5 to 1 mol per 1 mol of the dialkylphenol. When the amount is less than 0.5 mol, dialkylphenol remains, and when it is more than 0.6 mol, impurities tend to be generated. Therefore, it is preferable to use 0.5 to 0.6 mol times. The aldehyde may be diluted with water or an organic solvent as needed. The aldehyde may be charged together with other raw materials or may be dropped.

This reaction is generally accelerated as the amount of water in the reaction system is reduced. Therefore, by reducing the amount of water present in the system, the desired product can be obtained in a short time and in a high yield.
The temperature of the condensation reaction is preferably in the range of about 30 to 110 ° C, more preferably about 40 to 100 ° C. This reaction is usually performed under atmospheric pressure, but may be performed under pressure. The reaction time varies depending on the type of the aldehyde.
It is sufficient that the time is about 20 hours or more, more preferably about 2 to 10 hours. The progress of the reaction can be monitored by analytical means such as gas chromatography and high performance liquid chromatography.

The bisphenols of the formula (I) obtained by the condensation reaction according to the present invention, without isolation, may be used in the reaction mixture as it is, after adding an appropriate amount of a solvent and neutralizing the catalyst if necessary. By separating and removing the layer and further dehydrating the organic layer, a raw material such as bisphenol monoester can be easily obtained. Of course, the target bisphenols of the formula (I) can also be isolated by crystallization or the like.

[0021]

Next, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples. The percentages and parts in the following examples are by weight unless otherwise specified.

Example 1 2,4-Di-t-pentylphenol 100 was placed in a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device.
Parts, toluene 10 parts, anionic surfactant Perex NB-L (sodium monoalkylnaphthalenesulfonate manufactured by Kao Corporation) 1.0 part, 36% hydrochloric acid 15.1 parts and 30%
Charge 34.5 parts of acetaldehyde aqueous solution and stir
The reaction was maintained for 7 hours at a temperature of 94 to 95 ° C. After completion of the reaction, 154 parts of toluene was added to the reaction mixture, and the aqueous layer was separated and removed. Then, the organic layer was washed with 0.8 part of a 10% aqueous sodium carbonate solution and 50 parts of water, and 2,2'-ethylidenebis ( 4,6
-Di-t-pentylphenol). The results are shown in Table 1.

Example 2 Example 2 was repeated except that Sendale S (a sodium dialkylbenzene sulfonate manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used instead of Perex NB-L in Example 1. The same operation as in Example 1 was performed to obtain a solution of the desired product. The results are shown in Table 1.

Comparative Example 1 The same procedure as in Example 1 was carried out except that acetamine 86 (a stearylamine acetate manufactured by Kao Corporation) was used instead of Perex NB-L in Example 1. The operation was performed to obtain a target solution. The results are shown in Table 1.

Comparative Example 2 The procedure of Example 1 was repeated, except that Neugen EA80 (a polyoxyethylene alkyl phenyl ether manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used instead of Perex NB-L in Example 1. The same operation as in Example 1 was performed to obtain a target solution. The results are shown in Table 1.

Comparative Example 3 The procedure of Example 1 was repeated, except that no surfactant was added, to obtain a solution of the desired product. The results are shown in Table 1.

[0027]

Table 1 Example Surfactant Reaction Time Reaction Yield ^* Example 1 Perex NB-L 7hr 93.6 Example 2 Sendale S 7 93.6 Comparative Example 1 Acetamine 86 7 66.9 Comparative Example 2 Neugen EA80 7 69.4 Comparative Example 3 None 8 63.7 *: Reaction yield based on dialkylphenol (%)

Example 3 A reaction vessel equipped with a thermometer, a stirring device, a reflux condenser and a dropping device was charged with 2,4-di-t-pentylphenol 1172.
Parts, xylene 100 parts, Perex NB-L (Sodium monoalkylnaphthalenesulfonate manufactured by Kao Corporation) 23.5
Parts, 78% concentrated sulfuric acid 47 parts and 30% acetaldehyde aqueous solution
385.5 parts were charged and reacted at a temperature of 90 to 100 ° C. for 7 hours while stirring. After completion of the reaction, 1800 parts of xylene was added to the reaction mixture, the aqueous layer was separated and removed, and the organic layer was washed with water until neutral, and 2,2'-ethylidenebis (4,6-di-t) was added. -Pentylphenol). The results are shown in Table 2.

Example 4 The same operation as in Example 3 was carried out except that Sendale S (sodium dialkylbenzenesulfonate manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used instead of Perex NB-L in Example 3, A solution of the desired product was obtained. The results are shown in Table 2.

Example 5 Example 3 was repeated except that 1031.5 parts of 2,4-di-t-butylphenol was used in place of 2,4-di-t-pentylphenol and toluene was used in place of xylene as a solvent. The same operation as in Example 1 was performed to obtain a solution containing 2,2'-ethylidenebis (4,6-di-t-butylphenol). The results are shown in Table 2.

Example 6 In the same reaction vessel as used in Example 3, 821.5 parts of 2-t-butyl-4-methylphenol, 400 parts of xylene, Sandet AL (sodium alkyldiphenyldisulfonate manufactured by Sanyo Chemical Industries, Ltd.) ) 7 parts, 1.5 parts of 96% concentrated sulfuric acid and 37 parts
Then, 228 parts of a 2% aqueous formaldehyde solution were charged, and the mixture was reacted for 3 hours while maintaining a temperature range of 90 to 95 ° C. with stirring. After the completion of the reaction, 445 parts of xylene was added, and the aqueous layer was separated and removed. The organic layer was washed with water until it became neutral.
A solution containing methylene bis (6-t-butyl-4-methylphenol) was obtained. The results are shown in Table 2.

Example 7 The same procedure as in Example 6 was carried out except that Perex NB-L was used instead of Sandet AL in Example 6, to obtain a solution of the desired product. The results are shown in Table 2.

[0033]

TABLE 2 Percentage Purity (%) Example Surfactant Reaction Time Reaction Yield ^* LC Value GC Value 3 Perex NB-L 7hr 94.0 92.0-4 Sendale S 7 93.9 91.9-5 5 Perex NB-L 7 93.8 94.0- 6 Sandet AL3 94.8-99.8 7. Perex NB-L3 95.8-100.0 *: Reaction yield based on dialkylphenol (%)

Example 8 A reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a dropping device was charged with 194.1 parts of water, 4.2 parts of a 10% aqueous sulfuric acid solution, and 2-t-
Butyl-4-methylphenol 269 parts, Perex NB
After 2.2 parts of -L (sodium monoalkylnaphthalenesulfonate manufactured by Kao Corporation) and 130.5 parts of xylene were charged and heated to 50 ° C, 74.5 parts of a 37% aqueous formaldehyde solution was added dropwise over 0.5 hours. The reaction was performed for 3 hours while maintaining the temperature at 90 to 100 ° C. After completion of the reaction, 137 parts of xylene was added to the reaction mixture, and 2.7 parts by weight of 25% aqueous ammonia was further added to neutralize the mixture. Then, the aqueous layer was separated and removed. The organic layer was washed with water several times to give 2,2'-methylenebis (6-t-butyl-4-.
A solution containing 272.5 parts (methylphenol) (97.7% of the reaction yield based on 2-t-butyl-4-methylphenol) was obtained.

Example 9 130.5 parts of xylene, 4.2 parts of a 10% aqueous sulfuric acid solution, and 2 parts of a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device.
After charging 269.5 parts of t-butyl-4-methylphenol and 2.2 parts of Perex NB-L (sodium monoalkylnaphthalenesulfonate manufactured by Kao Corporation) and raising the temperature to 70 ° C, 67.8 parts of a 37% aqueous formaldehyde solution was applied for 2 hours. And dropped. The reaction was performed for 2 hours while maintaining the temperature at 70 to 80 ° C.
After the completion of the reaction, 150.8 parts of xylene was added to the reaction mixture,
After neutralization with 6 parts by weight of 25% aqueous ammonia, the aqueous layer was separated and removed. The organic layer is washed several times with water,
A solution containing 277.3 parts of -methylenebis (6-tert-butyl-4-methylphenol) (reaction yield based on 2-tert-butyl-4-methylphenol 99.3%) was obtained.

Example 10 A reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device was charged with 23.1 parts of xylene, 230 parts of 2,4-di-t-pentylphenol, and Perex NB-L (manufactured by Kao Corporation). Sodium monoalkylnaphthalenesulfonate) 4.6
And 9.3 parts of 78% concentrated sulfuric acid. To this, 75.9 parts of a 30% acetaldehyde aqueous solution was added dropwise over 1.5 hours, and after the addition was completed, 9
The reaction was carried out for 7 hours while maintaining the temperature at 0 to 100 ° C. After completion of the reaction, 335.3 parts of xylene was added to the reaction mixture, the aqueous layer was separated and removed, and then washed with water until the organic layer became neutral.
A solution containing 227.5 parts of 2,2'-ethylidenebis (4,6-di-t-pentylphenol) (a reaction yield of 93.8% based on 2,4-di-t-pentylphenol) was obtained.

Example 11 A reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a dropping device was charged with 2,4-di-t-pentylphenol 230.
7 parts, Perex NB-L (Kao Corporation sodium monoalkylnaphthalenesulfonate) 2.3 parts, 50% sulfuric acid 14.5
The department was charged. To this, 79.7 parts of a 30% acetaldehyde / xylene solution was added dropwise over 2 hours.
The reaction was carried out for 5 hours while maintaining the temperature at ° C. After completion of the reaction, 312.6 parts of xylene and 115.4 parts of water were added to the reaction mixture, and the aqueous layer was separated and removed, followed by washing with water until the organic layer became neutral.
A solution containing 227.2 parts of 2,2'-ethylidenebis (4,6-di-t-pentylphenol) (93.6% of the reaction yield based on 2,4-di-t-pentylphenol) was obtained.

[0038]

According to the present invention, bisphenols (I) can be produced efficiently and economically with high purity and high yield. Therefore, the method of the present invention is useful as a method for producing bisphenols (I) on an industrial scale.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuaki Yamamoto 2200 Tsuruzaki, Oita-shi, Oita F-term in Sumitomo Chemical Co., Ltd. (reference) 4H006 AA02 AC20 AC25 AC42 AD15 BA35 BA36 BA37 BA52 BA66 BB11 BC10 BC11 BC19 BC31 BN30 FE13 4H039 CA19 CA60 CF30

Claims (8)

[Claims] 1. A solvent selected from aliphatic hydrocarbons having 6 to 10 carbon atoms and aromatic hydrocarbons having 6 to 12 carbon atoms,
In the presence of an anionic surfactant selected from sodium monoalkylnaphthalenesulfonate, sodium alkyldiphenyldisulfonate, sodium dialkylbenzenesulfonate and sodium dialkylsulfosuccinate, the formula (II) R ¹ -CHO (II) Wherein R ¹ represents hydrogen or an alkyl group having 1 to 3 carbon atoms) and an aldehyde represented by the formula (III) (Wherein, R ² and R ³ each independently represent an alkyl group having 1 to 5 carbon atoms). (Wherein, R ¹ , R ² and R ³ have the same meanings as described above). 2. The method according to claim 1, wherein the anionic surfactant is sodium monoalkylnaphthalenesulfonate, sodium alkyldiphenyldisulfonate or sodium dialkylbenzenesulfonate. 3. The method according to claim 1, wherein the anionic surfactant is used in an amount of 0.6 to 3% by weight based on the dialkylphenol (III).
2. The production method according to 2. 4. The process according to claim 1, wherein the reaction solvent is used in an amount of 1 to 100% by weight based on the dialkylphenol (III). 5. The process according to claim 1, wherein the reaction solvent is an aromatic hydrocarbon selected from toluene and xylene. 6. The method according to claim 1, wherein an acid is used as the catalyst. 7. The process according to claim 6, wherein the catalyst is used in an amount of 0.001 to 0.1 mol per mol of the dialkylphenol (III). 8. A bisphenol represented by the formula (I):
2,2'-ethylidenebis (4,6-di-t-pentylphenol), 2,2'-ethylidenebis (4,6-di-t-butylphenol) or 2,2'-methylenebis (6-t -Butyl-4-methylphenol).