JP3521150B2 - Method for producing 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to 1,1,3-tris (2
-Methyl-4-hydroxy-5-tert-butylphenyl)
The method for producing butane (hereinafter sometimes referred to as AO-30) is described in detail by treating AO-30 containing an aromatic hydrocarbon solvent as an impurity with a saturated hydrocarbon solvent having a specific boiling point. And a method for producing AO-30 with reduced impurities. 2. Description of the Related Art AO-
Compound No. 30 is a compound widely used as an antioxidant for synthetic polymer materials such as polyolefin, ABS resin, styrene-butadiene copolymer and the like.
It is known that it is produced by reacting 2-tert-butyl-5-methylphenol with crotonaldehyde, as described in JP-A-4469. [0003] The above Japanese Patent Publication No. 39-4469 discloses that
It is described that the compound can be produced by reacting 2-tert-butyl-5-methylphenol with crotonaldehyde in methanol using concentrated hydrochloric acid as a catalyst, and then recrystallizing from an aromatic hydrocarbon solvent such as toluene or xylene. .
However, AO-30 produced by such a method is used.
Contains a considerable amount of solvent, which is not only unfavorable for odor and hygiene, but also causes foaming when compounded with synthetic polymer materials as an antioxidant. Was receiving. In order to avoid such disadvantages, it was necessary to reduce the content of low-boiling impurities to 2% or less. In order to remove the solvent, it is necessary to heat at a high temperature for a long time, but this is not only complicated in the process but also disadvantageous in that the product is colored. [0005] For this reason, Japanese Patent Application Laid-Open No. 56-40629 discloses a method of obtaining AO-30 as a trihydrate by washing the crude product after completion of the reaction with aqueous methanol and then washing with water. Has been proposed. According to this method, no organic solvent is contained, and although odors or hygiene problems can be solved, not only impurities such as raw materials or by-products cannot be sufficiently removed, but also
Since the amount of water combined as crystallization water is very large, about 9% by weight of the product, this water causes foaming, and it was not possible to improve foaming properties when blended in a synthetic polymer material. US Pat. No. 4,467,119 discloses that a crude product after the reaction is recrystallized with an aromatic hydrocarbon solvent such as toluene and then treated with a hydroalcohol to obtain an aromatic hydrocarbon solvent. A with reduced content
A method for producing O-30 has been proposed. However,
In this method, not only the removal of the aromatic hydrocarbon solvent is insufficient, but also the used hydroalcohol is entrapped in AO-30, so that it is not suitable for the purpose of reducing low boiling impurities. [0007] In view of the above-mentioned situation, the present inventors have developed 1,1,1 having a reduced content of low-boiling impurities.
As a result of intensive studies to find a method for producing 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, by treating with a saturated hydrocarbon solvent having a specific boiling point, 1,1,3-Tris (2-methyl-4-) in which the content of low boiling impurities is significantly reduced
The present inventors have found that (hydroxy-5-tert-butylphenyl) butane can be obtained, and have reached the present invention. That is, the present invention relates to 1,1,3-tris (2-methyl-) containing an aromatic hydrocarbon solvent as an impurity.
1,1,3-Tris (2-methyl-methyl) having a reduced impurity, characterized in that 4-hydroxy-5-tert-butylphenyl) butane is treated with a saturated hydrocarbon solvent having a boiling point of 120 to 200 ° C. 4-hydroxy-5-tert-butylphenyl) butane. Hereinafter, the production method of the present invention having the above-mentioned gist will be described in more detail. The 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane treated by the method of the present invention comprises 2-tert-butyl-5-methylphenol and crotonaldehyde. In the present invention, the crude product obtained by removing the reaction solvent from the reaction mixture after the completion of the reaction is recrystallized from an aromatic hydrocarbon solvent such as toluene and xylene. It contains an aromatic hydrocarbon solvent as an impurity. The saturated hydrocarbon solvent used for the treatment in the method of the present invention has a boiling point in the range of 120 to 200 ° C. Those having a boiling point of less than 120 ° C are not preferred because not only are they highly flammable and dangerous for use, but also because the processing temperature is low, impurities cannot be sufficiently removed. Also,
If the boiling point exceeds 200 ° C., the drying step after the treatment requires a long time, and this is unfavorable because it causes coloring of the product. The saturated hydrocarbon solvent used in the present invention includes n-octane, n-nonane, n-decane,
Linear saturated hydrocarbon such as n-undecane and n-dodecane, or 2-methyloctane, 3-methyloctane, 4-
Methyloctane, 2-ethylheptane, 2,2-dimethyl
Luheptane, 2,3-dimethylheptane, 2,4-dimethyl
Tylheptane, 2,2,3-trimethylhexane, 2,
2,4-trimethylhexane, 2,2,5-trimethyl
Hexane, 2-methylnonane, 3-methylnonane, 2,
2-dimethyloctane, 2,2,6-trimethylhepta
, 2,2-dimethyl-4-ethylhexane, etc.
Paraffinic hydrocarbon solvents containing
Or ethylcyclohexane, dimethylcyclohexa
, Methylethylcycloheptane, trimethylcyclope
Naphthenic hydrocarbon solvents such as pentane ;
These may be composed of a single saturated hydrocarbon compound or a mixture of multiple saturated hydrocarbon compounds, and a commercially available saturated hydrocarbon solvent can be used. The saturated hydrocarbon solvent may contain a small amount of an aromatic hydrocarbon solvent, provided that it is included in the above boiling point range. The amount is not more than 30% by weight, more preferably 2% by weight.
It must be less than 0% by weight. When the content of the aromatic hydrocarbon solvent is more than 30% by weight, the amount of AO-30 dissolved increases with the content, not only the yield decreases, but also the solvent used is contained in AO-30. It is not preferable because it may be caused. Since the saturated hydrocarbon solvent hardly dissolves AO-30 and removes only the aromatic hydrocarbons contained therein, a decrease in the yield due to the treatment is hardly recognized. The amount of the saturated hydrocarbon solvent to be used for AO-30 is not particularly limited, but usually 0.5 to 10 times the amount of AO-30 to facilitate stirring during treatment. If the amount of the solvent used is less than 0.5 times, stirring may be difficult, and if it is used more than 10 times, the throughput per batch will be reduced. The treatment can be carried out at any temperature from room temperature to the boiling point of the solvent. In order to carry out the treatment in a short time, it is preferable to carry out the treatment under heating, usually at 60 to 180 ° C. It is preferable to process in the range. AO-30 produced by the method of the present invention comprises:
Aromatic hydrocarbon impurities are significantly reduced, and
Since the saturated hydrocarbon solvent used in the treatment hardly remains, no odor is generated at the time of use, and there is no adverse effect such as foaming when used in a synthetic polymer material as an antioxidant. It has. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. (Production example of AO-30) 2-tert-butyl-
Take 492 g of 5-methylphenol, 350 g of methanol and 175 g of concentrated hydrochloric acid, heat while stirring, and when methanol starts refluxing, crotonaldehyde 70
g was slowly added dropwise, and stirring was further continued for 1 hour after completion of the addition. After a solution prepared by dissolving 26 g of sodium carbonate in 300 g of water was added to neutralize hydrochloric acid, methanol was distilled off, and 1500 g of toluene was slowly added to dissolve the reaction product. After taking the organic layer and washing twice with water,
It was cooled slowly to room temperature with stirring. The precipitated product (1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane) was filtered off and dried. As a result of analysis of the obtained product, the desired product (A
O-30): 84.4%, water: 1.2%, methanol:
It contained 2.7%, toluene: 11.0%, and others: 0.7%. (Example 1) Product 5 obtained in Production Example
0.0 g and an isoparaffinic hydrocarbon solvent having a boiling point of 156 to 175 ° C. (Isopar G: manufactured by Exxon Chemical) 10
0 g was taken and stirred at 120 ° C. for 30 minutes. After cooling, the mixture was filtered and dried at 95 ° C. for 2 hours under reduced pressure of 30 to 10 mmHg to obtain 42.4 g of a processed product as a white powder. As a result of analysis of the treated product, AO-30: 98.7%, water: 0.1%, methanol: 0.1%, toluene 0.2%, and other 0.9%. 99.1%. As a result of differential thermal analysis, the weight loss up to 185 ° C was 1.
1%. (Example 2) The same operation as in Example 1 was carried out except that the amount of the solvent used was changed to 200 g.
42.1 g of a processed product was obtained. Analysis result of processed material, AO-3
0: 99.1%, water: 0.1%, methanol: not detected,
Toluene 0.1%, other 0.7%, AO-30
Was 98.8%. As a result of differential thermal analysis, the weight loss up to 185 ° C. was 0.8%. Example 3 As the hydrocarbon solvent, naphthenic hydrocarbons 26.4%, paraffinic hydrocarbons 58.
Solvent having a composition of 0% and an aromatic hydrocarbon of 15.6% and having a boiling point range of 154 to 197 ° C. (Exxonnaphtha)
No. 5: Exxon Chemical Co.), except that 100 g was used.
6 g were obtained. Analysis result of processed material, AO-30: 98.2
%, Water: 0.2%, methanol: 0.1%, toluene 0.6%, other 0.9%, and the recovery of AO-30 was 96.8%. As a result of differential thermal analysis, 18
The weight loss to 5 ° C. was 1.6%. Comparative Example 1 The product obtained in the Production Example was dried at 95 ° C. for 2 hours under a reduced pressure of 30 to 10 mmHg without treatment. Analysis of the dried product, AO-30: 9
It contained 5.1%, water: 0.4%, methanol: 0.6%, toluene: 3.4%, and others: 0.5%. Further, as a result of differential thermal analysis, the weight loss up to 185 ° C. was 4.
5%. (Comparative Example 2) Product 5 obtained in Production Example
0.0 g and 200 g of an aromatic hydrocarbon solvent (IP150: manufactured by Idemitsu Petrochemical) having a boiling point of 180 to 215 ° C.
After stirring at 120 ° C. for 30 minutes, it was completely dissolved. After cooling, the precipitated powder was filtered and dried at 95 ° C. for 2 hours under a reduced pressure of 30 to 10 mmHg to obtain a processed white powder 42.1.
g was obtained. Analysis result of processed material, AO-30: 89.2
%, Water: 0.2%, methanol: not detected, toluene 0.
It was 2% and others 10.4%, and the recovery of AO-30 was 89.0%. In addition, as a result of differential thermal analysis, 185
Weight loss to 5.0 ° C. was 5.0%. (Comparative Example 3) Product 5 obtained in Production Example
Take 0.0 g and 200 g of 25% aqueous methanol,
Stirred under reflux for 30 minutes. Filtration after cooling, 30-10
It was dried at 95 ° C. for 2 hours under reduced pressure of mmHg to obtain 42.5 g of a processed product as a white powder. Analysis result of processed material, AO-3
0: 95.2%, water: 0.8%, methanol: 2.1
%, Toluene 1.3% and other 0.6%.
The recovery of 30 was 96.0%. As a result of differential thermal analysis, the weight loss up to 185 ° C. was 4.4%. (Comparative Example 4) Product 5 obtained in Production Example
0.0 g and petroleum ether (boiling point 30-70 ° C) 20
0 g was taken and stirred under reflux for 30 minutes. After cooling, the mixture was filtered and dried at 95 ° C. for 2 hours under a reduced pressure of 30 to 10 mmHg to obtain 43.1 g of a processed product as a white powder. As a result of analysis of the treated product, AO-30: 95.9%, water: 0.4%, methanol: 0.1%, toluene 3.1%, and other 0.5%. 97.9%. As a result of differential thermal analysis, the weight loss up to 185 ° C. was 3.
7%. As shown in each of the examples, by treating with a saturated hydrocarbon solvent having a specific boiling point range, the desired 1,1,3-tris (2-methyl-4-hydroxy- It is clear that the content of low-boiling impurities can be significantly reduced without substantially reducing the yield of 5-tert-butylphenyl) butane. On the other hand, the amount of low-boiling impurities cannot be significantly reduced only by drying without treatment. Also, when the treatment is performed using a solvent, the content of toluene can be reduced when an aromatic hydrocarbon is used, but the used aromatic hydrocarbon remains, and conversely, the amount of impurities is reduced. Not only can not be reduced drastically, but also the yield decreases due to the dissolution of the target product, and when using a hydroalcohol that does not dissolve the target product, the yield does not decrease much and the toluene Although the content can be reduced, the content of water and alcohol increases and low-boiling impurities cannot be sufficiently reduced, and when a low-boiling aliphatic hydrocarbon is used, Although the yield is not reduced, the removal of impurities is insufficient. According to the present invention, 1,1,3-tris (2-methyl-4-
By treating (hydroxy-5-tert-butylphenyl) butane with a saturated hydrocarbon solvent having a specific boiling point, low boiling impurities can be removed without reducing the yield.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-301634 (JP, A) JP-A-1-226842 (JP, A) JP-A-56-40629 (JP, A) 4469 (JP, B1) JP 42-533 (JP, B1) JP 32, 426 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 39/00 C07C 37 / 00

Claims (1)

(57) [Claim 1] 1,1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane containing an aromatic hydrocarbon solvent as an impurity, Boiling point 120-2
A process for producing 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane with reduced impurities, characterized by treating with a saturated hydrocarbon solvent at 00 ° C.