JPH08193041A - Method for producing ortho-alkylphenols and method for recovering raw material components thereof - Google Patents

Abstract

(57) [Summary] [Structure] Steaic acid is added to the crude product obtained by reacting phenol and isobutylene in the presence of aluminum phenoxide to deactivate the catalyst, and then the desired product is obtained by distillation. After distilling off the 6,6-di-tert-butylphenol, an organic solvent and an acidic aqueous solution are added to the distillation residue to extract the active ingredient. [Effect] The selectivity to the aromatic nucleus is excellent, and the raw materials can be recovered and reused.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing orthoalkylphenols, and more specifically, orthotert-butylphenol used as a raw material for perfumes and 2,6-diphenol used as a raw material for antioxidants. −
The present invention relates to a method for producing orthoalkylphenols such as tertiary butylphenol, which has good selectivity for the substitution position on the aromatic ring and can efficiently recover raw material components.

[0002]

As a method for producing orthoalkylphenols, for example, JP-B-33-7535 discloses a method of alkylating the ortho position of phenols with a tertiary olefin using aluminum phenoxide. It is mentioned as a method having excellent selectivity to the ortho position of the compound.

However, in this method, when the intended orthoalkylphenols, which are the main products, are separated by distillation, debutylation and disproportionation occur due to heating, resulting in a poor yield.

Therefore, various methods for obtaining the desired orthoalkylphenols with higher purity have been investigated. For example, Japanese Patent Laid-Open No. 153642/1993 discloses adding a monocarboxylic acid to the crude product obtained by the above method. After deactivating the catalyst, distillation is performed to prevent debutylation and disproportionation,
A technique for improving the yield of the target substance is disclosed.

[0005]

However, when attempting to industrially carry out the method described in JP-A-3-153642, the crude product is distilled and purified without separating and removing the catalyst component. However, it has a drawback that a large amount of active ingredients including isobutylene, raw materials such as phenols, and monocarboxylic acid remain in the residue after distillation.

The problem to be solved by the present invention is to produce an orthoalkylphenol by reacting a phenol with an olefin, and it is excellent in the selectivity of the substitution position on the aromatic ring, and is efficient in the purification step. The present invention relates to a method for producing orthoalkylphenol capable of recovering and reusing active ingredients such as raw material ingredients.

[0007]

Means for Solving the Problems As a result of intensive studies in view of the above circumstances, the present inventors have obtained a crude product obtained by reacting phenols and olefins in the presence of aluminum allyl oxide, Then after distilling it,
It was found that the effective component including the raw material components can be effectively recovered by adding an organic solvent to the distillation residue, stirring and separating the liquid, and completed the present invention.

That is, according to the present invention, a crude product obtained by reacting phenols and olefins in the presence of aluminum allyl oxide is 1. Distill to separate ortho-alkylphenols, 2. Add an organic solvent to the residue after distillation, After the oil layer is separated, the oil layer is distilled to recover the raw material components, and the phenols and olefins obtained by the above recovery method are used again as raw materials to react in the presence of aluminum allyl oxide. And a method for producing an ortho-alkylphenol.

The phenols used in the present invention are not particularly limited, but examples thereof include phenol, orthocresol, metacresol, paracresol, orthoethylphenol, metaethylphenol, paraethylphenol, bisphenol F and bisphenol. A
Among them, phenol is preferable.

The olefins are not particularly limited, but tertiary olefins such as isobutylene, isoamine, isooctene and α-methylstyrene have good reactivity with phenols. From the viewpoint, it is preferable, and isobutylene is particularly preferable.

The above-mentioned olefins are preferably tertiary olefins as described above, but the tertiary olefins need not be pure, and may be, for example, a C ₄ mixture obtained by naphtha decomposition. Of course, even if it contains a secondary or primary olefin in addition to the tertiary olefin,
Since the tertiary olefin has higher reactivity than other olefins, the reaction proceeds preferentially, so that it can be used in the present invention.

The aluminum aryl oxide used in the present invention is a salt of phenols and aluminum, and can be easily obtained by adding aluminum pieces to phenols and heating. In the present invention, by using this aluminum aryl oxide as a reaction catalyst, the selectivity to the ortho position as the substitution position on the aromatic ring of olefins becomes extremely good.

The phenols used in the production of the aluminum allyl oxide are the above-mentioned phenols, that is, phenol, orthocresol, metacresol, paracresol, orthoethylphenol, metaethylphenol, paraethylphenol, bisphenol F and bisphenol. Examples thereof include A, and among them, phenol is preferable.

The method of reacting phenols and olefins in the presence of aluminum allyl oxide is not particularly limited, and for example, phenol 100
Aluminum phenoxide is 0.0 with respect to parts by weight.
5 to 30 parts by weight, preferably 1 to 3 parts by weight, reaction temperature 10
To 300 ° C., preferably 50 to 150 ° C., reaction pressure atmospheric pressure to 100 kg / cm 2, preferably 2 to 50 kg / cm 2, and the reaction is usually completed in 0.5 to 10 hours.

In the present invention, if necessary, aluminum phenoxide may be used in combination with other catalyst components such as alkali metal salts of phenols.

The crude product thus obtained is a mixture of various compounds containing the desired ortho-alkylphenols and a monocarboxylic acid. Specifically, unreacted phenols, 2-alkylphenols, 2,6-di-alkylphenols, 2,4,6
-A mixture containing tri-tertiary alkylphenols, a monocarboxylic acid, a catalyst component and the like.

More specifically, for example, when phenol is used as phenols and isobutylene is used as olefins, aluminum is added to phenol at a weight corresponding to 0.001 to 1% by weight, and 150 to 1 is added.
Heat to 70 ° C. to form aluminum phenoxide,
A preferred method is to add isobutylene in an amount corresponding to 1.5 to 3.0 times the molar amount of phenol and react at a temperature of 50 to 120 ° C.

The crude reaction product of phenol and isobutylene by the above-mentioned method is, in addition to the main product 2,6-di-tertiary butylphenol, a small amount of 2-tertiary butylphenol, 2,4,4. A uniform liquid crude product containing 6-tri-tertiary butylphenol, catalyst, etc. is obtained.

The crude product thus obtained may be directly subjected to the subsequent distillation step, but in the present invention, by adding a monocarboxylic acid to the crude product, it is converted to the ortho position. It is preferable because the selectivity and the yield are extremely good.

That is, when aluminum phenoxide is present in the crude product in an active state by distillation, the tertiary alkyl group is eliminated by heating during distillation, or the tertiary alkyl group in the ortho position is para-positioned. Transfer to. Therefore, a monocarboxylic acid is added to deactivate the aluminum aryl oxide, whereby a 2,6-ditertiary alkylphenol can be obtained in good yield.

Specifically, after the monocarboxylic acid is added to the crude product obtained by the above-mentioned method to deactivate the aluminum aryl oxide, it is usually added to 80 to 10
It is preferable to heat at 0 ° C. for 0.5 to 2 hours and then distill.

Examples of the monocarboxylic acid used here include caproic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, naphthenic acid, Benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 4-tertiary-butyl benzoic acid and the like can be mentioned, and also castor oil fatty acid, soybean oil fatty acid, tall oil fatty acid and the like can be mentioned. . Of these, fatty acids having 6 to 25 carbon atoms are preferable because they have low toxicity and are easy to handle.

The amount of monocarboxylic acid added varies depending on the type of aluminum aryl oxide added,
The amount is preferably such that 1 to 3 carboxyl groups per aluminum atom of aluminum aryl oxide in the crude product.

Distillation conditions are slightly different depending on the types of the monocarboxylic acid and aluminum aryl oxide to be added, but generally the distillation is carried out under reduced pressure, and the temperature inside the kettle is 160.
When the temperature exceeds ° C, the introduced tertiary alkyl group is eliminated, so that it is desirable to distill at a reduced pressure of 40 mmHg or less. As a distillation method, both flash distillation and fractional distillation are possible, and both batch and continuous methods can be performed.

Then, after the desired ortho-alkylphenols are removed by the distillation, an organic solvent is added to the distillation residue to uniformly dissolve it, and if necessary, further washing with water is performed to efficiently and almost completely remove the raw material components. Can be collected.

In particular, the above-mentioned monocarboxylic acid is added,
When the aluminum aryl oxide is inactivated and then distilled, it is preferable to add an acidic aqueous solution together with an organic solvent, stir the mixture, and extract and then separate the layers to significantly improve the yield and the recovery rate of the active ingredient.

Specifically, first, an organic solvent and an acidic aqueous solution are added to the distillation residue. Here, the monocarboxylic acid and effective components such as phenols and olefins contained in the residue are extracted into the organic layer.

The organic solvent to be used is not particularly limited, but aromatic hydrocarbons are preferable from the viewpoint of excellent extraction ability of the active ingredient, and xylene or ethylbenzene is particularly preferable. Further, it is preferable to add 30 to 100 parts of the organic solvent to 100 parts of the distillation residue. Moreover, it is preferable that the temperature at the time of dissolution is 60 to 100 ° C. and the dissolution is performed for 0.5 to 3 hours.

The acid that imparts acidity to the acidic aqueous solution includes organic acids and mineral acids. Further, although the strength of the acid is not particularly limited, it is preferably pH 3 or less from the viewpoint of good recovery of the monocarboxylic acid.

As the organic acid, tartaric acid, citric acid and oxalic acid are preferable, and it is preferable to add 100 to 500 parts of acidic aqueous solution as a 5 to 30% aqueous solution to 100 parts of the distillation residue at a pH of 3 or less.

Although various kinds of mineral acids can be used, sulfuric acid is preferably used as a 3 to 20% aqueous solution, and 100 to 500 parts is preferably added to 100 parts of the distillation residue.

The order of adding the organic solvent and the acidic aqueous solution to the distillation residue is not particularly limited, but it is preferable to add the organic solvent and the acidic aqueous solution to the distillation residue in this order. In particular, it is preferable to add the acidic aqueous solution to the distillation residue or the organic solvent mixture continuously or intermittently over 2 hours or more in order to prevent gelation in the system and reduce the loss of the active ingredient.

The temperature at the time of extraction is preferably 60 to 80 ° C. from the viewpoint that the viscosity of the mixed solution is low and the extraction efficiency is excellent. The extraction time is not particularly limited, but
It is preferable that the separation time is ˜5 hours and the liquid separation time is 2-3 hours.

Further, the organic layer after liquid separation is mixed with the same amount of water for 2-3 times.
Wash twice to completely separate and remove the acidic aqueous solution. Also, aluminum becomes aluminum sulfate and is eluted in the aqueous layer. Subsequently, the organic layer is recovered by distillation at atmospheric pressure or reduced pressure in a distillation column having 2 to 10 stages, and stearic acid containing the active ingredient is obtained as a distillation residue.

The active ingredient and stearic acid thus obtained can be used again in the production method of the present invention.

[0036]

EXAMPLES The present invention will be described in more detail with reference to the following examples.

Example 1 300 g of phenol and 0.5 g of aluminum powder were placed in a stainless steel cylindrical pressure-resistant reactor having an inner diameter of 7.5 cm and a capacity of 1000 ml, and heated at 160 ° C. for 30 minutes to prepare a phenol solution of aluminum phenoxide. Prepared.
After cooling the solution to 90 ° C., 355 g of isobutylene was added with stirring for 6 hours and then aged at 90 ° C. for 2 hours. While stirring 650 g of the obtained crude product, 90 ° C.
8 g of stearic acid was added to the mixture while keeping it at 1, and the mixture was reacted for 1 hour. Then, distillation was performed under a reduced pressure of 40 mmHg.
The liquid temperature of the flask during distillation was 160 ° C. Further, no isobutylene gas was generated during the distillation.

The distillate was 610 g and the distillation residue was 40 g.
Most of the distillate was distilled at a steam temperature of 92 to 158 ° C. The content of 2,6-di-tert-butylphenol in 610 g of distillate was 82% by weight.

At the room temperature, the distillation residue was a fluid liquid having a high viscosity, but no solid matter was formed even at room temperature.

Next, 18 g of xylene was added to 40 g of the distillation residue, and the mixture was stirred at 60 ° C. for 1 hour and uniformly dissolved.
The temperature was raised to 0 ° C. After adding 130 g of a 5% sulfuric acid aqueous solution over 2 hours, the mixture was allowed to stand for 2 hours to separate the organic layer and the aqueous layer. Further, 58 g of water was added to the organic layer, washed with water and separated. This operation was repeated twice, and for the obtained organic layer,
When xylene was distilled off, 39 g of an active ingredient containing stearic acid was obtained. In addition, no problem occurred when this recovered active ingredient was used for deactivating aluminum phenoxide in the next reaction.

FIG. 1 shows the process chart of the extraction process in Example 1, and Table 1 shows the component ratios (numerical values when the total amount of distillation residue is 1000) at each stage.

Example 2 Distillate 610 was prepared by the reaction of phenol and isobutylene, addition of stearic acid, and distillation in the same manner as in Example 1.
g, distillation residue 40 was obtained. The content of 2,6-ditert-butylphenol in 610 g of distillate was 82% by weight.

The composition ratio of this distillation residue was as follows. [3.5% by weight of 2-tertiary phenylphenol, 22.1% by weight of 2,6-tertiary chlorophenol, 2.8% by weight of 2,4-tertiary chlorophenol, 0.4% by weight of 2,5-tertiary phenylphenol , 62% by weight of stearic acid, 3% by weight of aluminum, 6.2% by weight of 2,4,6 treater sharphylphenol]

Next, 18 g of ethylbenzene was added to 40 g of the distillation residue, and the mixture was stirred at 60 ° C. for 1 hour, uniformly dissolved and then heated to 80 ° C. After adding 130 g of a 5% sulfuric acid aqueous solution over 2 hours, the mixture was allowed to stand for 2 hours to separate the organic layer and the aqueous layer. Further, 58 g of water was added to the organic layer, washed with water and separated. This operation was repeated twice, and ethylbenzene was distilled off from the obtained organic layer to obtain 38 g of an active ingredient containing stearic acid. In addition, no problem occurred when this recovered active ingredient was used for deactivating aluminum phenoxide in the next reaction.

Comparative Example 1 300 g of phenol and 0.5 g of aluminum powder were placed in a stainless steel cylindrical pressure resistant reactor having an inner diameter of 7.5 cm and a capacity of 1000 ml, and heated at 160 ° C. for 30 minutes to prepare a phenol solution of aluminum phenoxide. Prepared.
After cooling the solution to 90 ° C., 355 g of isobutylene was added with stirring for 6 hours and then aged at 90 ° C. for 2 hours. While stirring 650 g of the obtained crude product, 90 ° C.
8 g of stearic acid was added to the mixture while keeping it at 1, and the mixture was reacted for 1 hour. Then, distillation was performed under a reduced pressure of 40 mmHg.

This distillation residue contained 28.8% by weight of active ingredients including raw material components and 62% by weight of stearic acid. When the distillation residue was discarded, these active ingredients and stearic acid were It turned out to be a loss.

[0047]

[Table 1]

(In Table 1, "OTBP" means 2-tert-chalfylphenol, "26DTBP" means 2,6-octachartyl-tylphenol, "24DTBP".
Represents 2,4-ditertiary sharphylphenol, "25DTBP" represents 2,5-ditertiary sharphytylphenol, and "246TTBP" represents 2,4,6 tritersharfuryl butylphenol. )

[0049]

INDUSTRIAL APPLICABILITY According to the present invention, in producing an orthoalkylphenol by reacting a phenol with an olefin, the selectivity of the substitution position on the aromatic ring is excellent, and almost all the active ingredient containing the raw material is contained. It can be recovered, and the recovered active ingredient can be reused.

[0050]

[Brief description of drawings]

FIG. 1 is a process drawing showing an extraction process of Example 1.

[Brief description of reference numerals]

 A: Distillation residue B: Organic solvent addition process C: Acidic aqueous solution addition process D: Liquid separation process E: Liquid separation process F: Water washing process G: Liquid separation process H: Liquid separation process I: Distillation process J: Stearic acid recovery Process

Claims (7)

[Claims] 1. A crude product obtained by reacting phenols and olefins in the presence of aluminum aryl oxide, 1. Distill to separate ortho-alkylphenols, 2. Add an organic solvent to the residue after distillation, A method for recovering raw material components, which comprises distilling the oil layer after separating the oil layer. 2. A crude product obtained by reacting phenols and olefins in the presence of aluminum aryl oxide is mixed with a monocarboxylic acid, and then 1. 1. Distill to separate ortho-alkylphenols, 2. After the aluminum allyl oxide is taken into the aqueous layer by adding an organic solvent and an acidic aqueous solution to the residue after distillation to separate the oil layer / water layer into two layers, A method for recovering raw material components, which comprises distilling the oil layer after separating the oil layer. 3. The method according to claim 2, wherein the ortho-alkylphenols are ortho-tert-butylphenol or 2,6-di-tert-butylphenol. 4. The recovery method according to claim 1, 2 or 3, wherein the organic solvent is an aromatic organic solvent. 5. The recovery method according to claim 2, wherein the acidic aqueous solution is an aqueous solution of a mineral acid. 6. The recovery method according to claim 5, wherein the acidic aqueous solution has a pH of 3 or less. 7. The ortho-alkylphenols characterized in that the phenols and olefins obtained by the recovery method according to any one of claims 1 to 6 are used again as raw materials and reacted in the presence of aluminum allyl oxide. Production method.