JPS5842866B2 - Method for producing 2,2'↓-bis[4↓-(1,1,3,3↓-tetramethylbutyl)phenol] sulfide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a light stabilizer, a polyolefin modifier, a lubricating oil additive, and intermediates thereof. -Relating to a method for producing phenol sulfide (1,3,3-tetramethylbutyl).

More specifically, 4-(1,1,3,3-tetramethylbutyl)phenol and sulfur dichloride are mixed in an aromatic hydrocarbon solvent at a temperature range of -10 to 20°C without a catalyst or in the presence of a Lewis acid catalyst. The present invention relates to a method for producing 2,2'-bis[4-(1,1-3,3-tetramethylbutyl)phenol) sulfide, which is characterized by the following reaction.

In general, the production of 2,2'-bis(4-substituted phenol) monosulfide is carried out by reacting the corresponding 4-substituted phenol with sulfur dichloride, and sulfide is added to the 6-position of the monosulfide. While the reactions proceed simultaneously to produce polynuclear bodies, sulfur dichloride (I
) Due to the fact that a chemical equilibrium exists as shown in the formula, the reaction becomes more complicated, and polysulfur-containing compounds such as disulfides are produced as by-products, so the target product is often obtained as a resin-like product, and the target product is It has the disadvantage of low yield.

Conventionally, 2,2'-bis[4-(1
・For the production of phenol sulfide (1,3,3-tetramethylbutyl), 4(1,1,3,3-
It has been carried out by the reaction of phenol (tetramethylbutyl) with sulfur dichloride.

For example, a method is described in which a reaction is carried out in carbon tetrachloride at 7° C., and then the reaction mixture is diluted with a large amount of petroleum ether and crystallized to obtain the desired product as a precipitate [US Pat. No. 2,971,968 (1961); Chemical Abstracts 1vol. ．．
55.14385 (1961)).

Furthermore, in recent years, a method has been proposed (German Patent No. 1275067 (1968)) in which the reaction is carried out in a hydrocarbon solvent at 50 to 63° C., and then the precipitate is separated by cooling.

However, both methods leave a large amount of by-products in solution through post-treatment operations such as dilution and cooling crystallization, and only the monosulfide compound, which is the target product, is separated from the reaction mixture.

Both isolated 2・/-bis[4-(1-1・3・3
Although the purity of -tetramethylbutyl)phenol sulfide is relatively high, the yield is 40% for the former and 17% for the latter.
It is as low as ~40%, which is not economical, and cannot be said to be an industrially advantageous method.

In view of these state of the art, the reaction between the phenol and sulfur dichloride substantially suppresses the production of by-products, improves the production rate of the original monosulfide itself, and furthermore, by normal post-treatment operations, It is an industrially desired problem to produce 2,2'-bisC4=(1,1,3,3-tetramethylbutyl)phenol sulfide relatively easily and in good yield.

The present inventors have discovered that 2,2'-bisC4-(1,1,3-3
-Tetramethylbutyl)phenol sulfide, as a result of intensive studies aimed at providing an industrially advantageous manufacturing method, we found that 4-(1.1.3.3-tetramethylbutyl)phenol (hereinafter referred to as raw material phenol) The present invention was based on the discovery that it can be produced extremely easily by reacting sulfur dichloride (abbreviated) with sulfur dichloride in an aromatic hydrocarbon solvent in the temperature range of -10 to 20°C without a catalyst or in the presence of a Lewis acid catalyst. I have reached the point where I have completed the .

According to the method of the present invention, after the reaction is completed, the solvent is distilled off by steam distillation and the crude product is isolated as a solid; b;
The distilled off solvent, ie, the organic phase, can be reused, if necessary, with purification treatment, for example, by distillation.

This not only serves to save solvent, which leads to lower costs compared to the known technology, but it is also advantageous that it poses fewer environmental protection-related problems.

The solvent used in the method of the present invention is an aromatic hydrocarbon solvent, such as benzene, toluene, xylene, ethylbenzene, cumene, xylene, chlorobenzene, 0-dichlorobenzene, and the like.

In particular, benzene, toluene and chlorobenzene are used.

These solvents can also be used as a mixture.

The amount of solvent used can vary within a wide range, but
Generally, 0.5 to 10, preferably about 2 to 5 parts by volume of solvent is used per 1 part by weight of raw phenol.

In the present invention, it is preferable to react 1 mole of sulfur dichloride with 2 moles of raw material phenol, but 0.8 to 1.
A range of 5 moles is also acceptable.

When reacting raw material phenol and sulfur dichloride, it is preferable for the purpose of the present invention to drop sulfur dichloride into a solution of raw material phenol and an organic solvent.

The rate of addition is preferably adjusted so that hydrogen chloride gas, which causes the reaction, is constantly generated.

In some cases, a mixture of sulfur dichloride and an organic solvent may be added dropwise.

In the present invention, the reaction temperature must be in the range of -10 to 20°C.

If the reaction temperature is lower than 110°C, the reaction will take a long time, while if the reaction temperature is higher than 20°C, the purity and yield of the product will be extremely reduced.

A more preferable reaction temperature is 0 to 10°C.

When the reaction is carried out at the above reaction temperature, the reaction time is 1 to 5 hours after the completion of the dropwise addition of sulfur dichloride, and the reaction is almost completed.

In the present invention, although the reaction occurs without a catalyst, it is also a feature of the present invention that when a Lewis acid is used as a catalyst, the reaction proceeds extremely smoothly and the purity and yield of the crude product are further improved.

In the absence of a catalyst, the reaction completes within 1 to 5 hours after the dropwise addition of sulfur dichloride is completed, whereas in the case of using a catalyst, the sulfur dichloride is consumed at the same time as the dropwise addition, and the reaction is completed at the end of the dropwise addition. .

For example, when a reaction is carried out in the temperature range of 0 to 10°C using benzene as a solvent, in the absence of a catalyst, the reaction remains in a solution state even after the reaction is completed, but in the presence of a catalyst, approximately half the desired amount of sulfur dichloride is added dropwise. At this point, the target product begins to precipitate as crystals from the reaction solution, and becomes suspended at the end of the dropwise addition.

Furthermore, the purity of the crude product obtained by distilling off the solvent is improved, so that the crystallinity is even better, and the yield is also more satisfactory.

Examples of the Lewis acid used include aluminum chloride, zinc chloride, stannic chloride, and ferric chloride, with zinc chloride being particularly preferred.

The amount of the catalyst to be used is only a small amount, and is usually about 0.00 to 0.1 mole per mole of sulfur dichloride.

In carrying out the method of the present invention, the raw material phenol is generally dissolved in the above-mentioned solvent, and sulfur dichloride is gradually added dropwise to the solution while maintaining the temperature at -10 to 20 DEG C. without or in the presence of a catalyst.

After the dropwise addition is completed, the mixture is stirred at the same temperature for 1 to 5 hours, and then the hydrogen chloride gas dissolved in the solvent is expelled by blowing air.

Then, the solvent is removed by steam distillation, the mixture is allowed to cool to room temperature, and the precipitate is filtered, washed with water, and dried.

In some cases, the precipitate may be pulverized and then filtered.

If the crude crystals are suspended and stirred at room temperature using a small amount of a low-boiling aliphatic hydrocarbon such as petroleum ether or n-hexane, a high purity product (usually 95% or more) can be obtained with a good yield. be able to.

If necessary, the desired product can be obtained with extremely high purity by recrystallization.

The method of the invention will be explained in further detail by the following examples.

The purity of the product was analyzed by high performance liquid chromatography or gas chromatography.

Example 1 4-(1,1,3,3-tetramethylbutyl)phenol 41.2f (0.2 mol) was added to benzene 150rfLA
Dissolve in.

Add sulfur dichloride 11 to this while keeping the temperature between 0 and 10℃.
．． 3P (0.11 mol) is added dropwise over about 1.5 hours.

Then, stir at the same temperature for 2 hours.

After blowing air to drive out the hydrogen chloride gas, benzene was distilled off by steam distillation, and the mixture was allowed to cool to room temperature.

The precipitate was filtered, washed with water, and dried to give 2,2'-bis[4-(
1,1-3,3-tetramethylbutyl)phenol sulfide (purity: 85.3% by weight) is obtained.

Yield 43.8S' (theoretical yield 44.2SF).

Melting point 115-123°C. 43 g of this crude crystal was suspended in 50 ml of n-hexane, stirred at room temperature for 5 minutes, filtered through a sieve, dried, and the 2,2'-bisC4-
(1-1-3.3-tetramethylbutyl)phenol sulfide was obtained.

Yield: 35-5y (80% yield). Melting point 133-135℃
.

In addition, pure white needle-like crystals were obtained by recrystallization from cyclohexane.

Melting point 135-136°C. Elemental analysis C (%) H (%) S (%) Calculated value 75.97 9.56 7.24 Empress value 76
．． 05 9.63 7.23 Example 2 The same operation as in Example 1 is carried out except that 0.51% of zinc chloride is added as a catalyst.

Crude crystals 43.7S' with purity 92.5% (theoretical yield 44.
2P) is obtained.

Melting point 130-135°C.

This crude crystal 43.7P was suspended in 50 TL of 71-hexane in the same manner as in Example 1, and 2,2'-bis[4-(1,1,3,3- Tetramethylbutyl)phenol sulfide was obtained.

Yield 39.65' (yield 89.5%), melting point 134-1
35℃.

Example 3 The same operation as in Example 2 was performed except that 150 ml of toluene was used instead of benzene, and 43.5 f? of crude crystals with a purity of 92.0% were obtained. I got it.

Melting point 129-135°C.

This coarse crystal 43.5f? was suspended in 50rrL of n-hexane in the same manner as in Example 1 to obtain a purity of 98.0%.
2,2'-bis(4-(1-1,3,3-tetramethylbutyl)phenol sulfide) was obtained.

Yield: 39.3S' (yield: 89.0%). Melting point 134-1
35℃.

Example 4 The same operation as in Example 1 was performed with the addition of stannic chloride to obtain crude crystal 43-8f with a purity of 91.5%.

Melting point: 127-131°C. 43.8f of this crude crystal was suspended in 50TrL of n-hexane in the same manner as in Example 1, and 2,2'-bis[4(1,1,3-
3-Tetramethylbutyl)phenol sulfide was obtained.

Yield 39. Of (yield 88.2%) melting point 134-135
℃.

Example 5 Same procedure as Example 2 except that 150 ml of chlorobenzene was used instead of benzene (purity 91,
0% coarse crystals 44. Of? I got it.

Melting point 127-128°C.

44.0y of this crude crystal was suspended in 50ml of n-hexane in the same manner as in Example 1, and 2
-2'-bis[4-(1.1.3.3-tetramethylbutyl)phenol sulfide was obtained.

Yield: 39.2 y (yield: 88.7%), melting point: 134~
135℃.

Example 6 The same operation as in Example 1 was carried out except that 159 mA' of chlorobenzene was used instead of benzene, and the purity was 83.
．． 0% crude crystals of 43.5S' were obtained.

Melting point: 108-120°C.

This coarse crystal 43.5f? n-hexane 50! 2.nl with a purity of 97% was obtained by suspension treatment in the same manner as in Example 1.
2-bis(4-(1.1.3.3-tetramethylbutyl)phenol sulfide was obtained.

Yield 34.8S' (yield 78.7%), melting point 133-1
35℃.

Claims (1)

[Claims] 14-(1,1-3,3-tetramethylbutyl)phenol and sulfur dichloride are dissolved in an aromatic hydrocarbon solvent and heated at -10 to 20°C without or in the presence of a catalyst. 2,2'-bisC4-(1,
A method for producing phenol sulfide (1,3,3-tetramethylbutyl). 2. The method according to claim 1, which uses a Lewis acid as a catalyst.