Method of producing 2,6-di-tert-butyl-4-methyl-phenol

FIELD: chemistry.

SUBSTANCE: said compound is a clear phenol antioxidant from 2,6-di-tert-butyl-phenol through successive aminomethylation, hydrogenolysis and extraction of the desired product. The process is carried out in the presence of 2,6-di-tert-butyl-phenol and 2,4-di-tert-butyl-phenol in amount of 0.015-0.04 wt % and 0.1-0.2 wt % respectively, to the initial 2,6-di-tert-butyl-phenol.

EFFECT: method enables to obtain a compound having guaranteed colour index for a long storage period.

1 tbl, 7 ex

 

The invention relates to the petrochemical industry, in particular to the field of receiving light of phenolic antioxidants.

A method of obtaining 2,6-di-tert-butyl-4-methyl-phenol by catalytic hydrogenolysis of N,N-dimethyl-(3,5-di-tert-butyl-4-oxybenzyl) amine (Mannich bases) on the floatable nicolelovestitanic the catalyst for hydrogenating agent in the environment 2,6-di-tert-butyl-4-methyl-phenol at elevated temperature and pressure, and as a hydrogenating agent, a mixture of hydrogen and trimethylamine in the following ratio of the components,% vol.: hydrogen 85-93; trimethylamine 7-15 (RF Patent No. 2147570, SS 39/06, SS 37/50, publ. 20.04.2000).

A method of obtaining 2,6-di-tert-butyl-4-methyl-phenol by hydrogenolysis Mannich bases of hydrogen on the heterogeneous catalyst is an alloy of Nickel, aluminum and molybdenum at a temperature of 120-180C. and a pressure of 1-10 ATA, and the reaction mass obtained by hydrogenolysis, which previously separated the isolated dialkylamino return to the reaction zone, maintaining the concentration of the Mannich bases in the circulating flow within 5-30 wt.% (USSR author's certificate No. 572447, SS 39/06, publ. 15.09.1977).

The disadvantages of these methods of obtaining 2,6-di-tert-butyl-4-methyl-phenol is something that is not guaranteed long svetostoyjkostj obtained product is and when stored.

The closest is a method for 2,6-di-tert-butyl-4-methyl-phenol of 2,6-di-tert-butyl-phenol serial aminomethylpropanol in the presence of 2,6-di-tert-butyl-4-methyl-cyclohexanone in an amount of 1-25 wt.%, by hydrogenolysis and the selection of the target product (RF Patent No. 2137749, SS 39/06, SS 37/11).

This method of obtaining 2,6-di-tert-butyl-4-methyl-phenol as the previous one, does not guarantee svetostoyjkostj received product in a long time storage.

The problem is that light phenolic stabilizers, including 2,6-di-tert-butyl-4-methyl-phenol, during prolonged storage under the influence of air oxygen, temperature oxidized with the formation of colored products. Development of a method of producing 2,6-di-tert-butyl-4-methyl-phenol high svetostoyjkostj (12 months and more) is of great importance for the conservation of consumer properties of commercial products.

The aim of the invention is to improve the quality of 2,6-di-tert-butyl-4-methyl-phenol, namely at the expense of one of its major indicators - svetostoyjkostj.

The problem is solved by implementing a method of producing 2,6-di-tert-butyl-4-methyl-phenol of 2,6-di-tert-butyl-phenol serial aminomethylpropanol, hydrogenolysis derived Mannich bases and the target allocation is the product, where the target product has a guaranteed performance color over a long period of storage.

This is because the synthesis of 2,6-di-tert-butyl-4-methyl-phenol are of 2,6-di-tert-butyl-phenol, containing 0.015 to 0.04 wt.%. 2-sec-butyl-6-tert-butyl-phenol (2 WB-TBF) and 0.1 to 0.2% wt. 2,4-di-tert-butyl-phenol (2,4-dabf).

In the process of synthesis of these impurities in the first place enter into the oxidation reaction, due to the low redox potential and, consequently, high reactivity, forming unpainted products of dimerization.

The effect of impurities is not shown or appears insufficient when the introduction of these additives in quantities less than those specified.

Svetostoyjkostj 2,6-di-tert-butyl-4-methyl-phenol was evaluated by defining the color of the samples after 6 and 12 months of storage. Forecasting svetostoyjkostj was carried out by keeping samples of 2,6-di-tert-butyl-4-methyl-phenol in oxygen atmosphere at a temperature of 60C for 3 days and subsequent measurement of color. Chroma samples 2,6-di-tert-butyl-4-methyl-phenol were determined by known platinumblonde scale Hazen units ARNA.

Under the terms of 2,6-di-tert-butyl-4-methyl-phenol (TU 38.5901237-90) the color of the product at issue should be no more than 25 units ARNA, when the product is stored bolee months permitted to change the color to 50 units ARNA.

Example 1 (the prototype)

In a metal vial load 206 g of 2,6 - di-tert-butyl-phenol, 112 g of bis-(N,N-dimethylamine)methane (bisamine), of 2.06 g of 2,6-di-tert-butyl-4-methyl, 20.6 g of di-tert-butyl-4-methyl-cyclohexanone.

The ampoule is sealed, incubated 3 hours at 120C, hold degassing from light products. Received product carry out the hydrogenolysis reaction, degassing from the volatile products, the stage of distillation of the remaining APS. Get product containing not less than 99,70% wt. 2,6-di-tert-butyl-4-methyl-phenol. The resulting product is subjected to testing on svetostoyjkostj in the atmosphere of oxygen at T=60C for 1, 3 days, after long-term storage within 6-12 months. The test results are shown in table 1.

Examples 2-7 (according to the invention)

Example 2. In a metal vial load 206 g of 2,6-di-tert-butyl-phenol, 0,082 g of 2-sec-butyl-6-tert-butyl-phenol (0,04% 2,6-di-tert-butyl-phenol), 0.4 g of 2,4-di-tert-butyl-phenol (0,2% 2,6-di-tert-butyl-phenol), 112 g bisamine, 45 g of methanol. The ampoule is sealed, incubated at T=120C for 3 hours, cooled, conduct degassing of the reaction mixture from light. The resulting product is subjected to a hydrogenolysis reaction, the catalyst was washed with toluene, combine the washing with toluene product. The resulting mixture Tegaserod distilled off from the toluene. OS is avchina ALKYLPHENOLS subjected to vacuum distillation and crystallization. Get the product with the content of the basic substance is not less 99,70% wt. The resulting product is subjected to testing on svetostoyjkostj in the atmosphere of oxygen at T=60C for 1, 3 days, and after a period of storage Agidol-1 in 6-12 months. The test results are given in table 1.

Example 3. In a metal vial load 206 g of 2,6-di-tert-butyl-phenol, 0,031 g of 2-sec-butyl-6-tert-butyl-phenol (0,015% to 2,6-di-TBP), 0,206 g of 2,4-di-tert-butyl-phenol (0.1% by 2,6-di-TBP), 112 g bisamine, 45 g of methanol. Spend the reaction of aminomethylpyridine and hydrogenolysis by analogy with example 2. The resulting alkyl phenols are subjected to vacuum distillation and crystallization. Get the product with the content of the basic substance is not less 99,70% wt.

The resulting product is subjected to testing on svetostoyjkostj in the atmosphere of oxygen at T=60C for 1, 3 days and after long-term storage in the terms and conditions agreed SPECIFICATIONS, within 6-12 months. The test results are given in table 1.

Example 4. In a metal vial load 206 g of 2,6-di-tert-butyl-phenol, 0,103 g of 2-sec-6-tert-butyl-phenol (0,05% to 2,6-di-TBP), 0,412 g of 2,4-di-TBP (0,2% 2,6-di-TBP), 112 g bisamine, 45 g of methanol. Spend the reaction of aminomethylpyridine and hydrogenolysis. APS is subjected to vacuum distillation and crystallization, get the product with the content of the basic substance is not less 99,70% m is C.

The resulting product is subjected to testing on svetostoyjkostj similar to examples 1-3. The test results in table 1.

Example 5. In a metal vial load 206 g of 2,6-di-tert-butyl-phenol, 0,082 g of 2-sec-6-tert-butyl-phenol (0,04% 2,6-di-tert-butyl-phenol), 0,618 g of 2,4-di-TBP (0,3% 2,6-di-tert-butyl-phenol), 112 g bisamine, 45 g of methanol. Spend the reaction of aminomethylpyridine and hydrogenolysis as in example 1. APS is subjected to vacuum distillation and crystallization. Get the product with the content of the basic substance is not less 99,70% wt.

The product of synthesis is subjected to testing on svetostoyjkostj similar to examples 1-4. The test results in table 1.

Example 6. In a metal vial load 206 g of 2,6-di-tertbutyl-phenol, 0,0206 g of 2-sec-butyl-6-tert-butyl-phenol (0,01% to 2,6-di-tert-butyl-phenol), 0,412 g of 2,4-di-TBP (0,2% 2,6-di-tert-butyl-phenol), 112 g bisamine, 45 g of methanol. Spend the reaction of aminomethylpyridine, hydrogenolysis, stage vacuum distillation and crystallization. Get the product with the content of the basic substance is not less 99,70% wt.

The product of synthesis is subjected to testing on svetostoyjkostj similar to examples 1-5. The test results in table 1.

Example 7. In a metal vial load 206 g of 2,6-di-tert-butyl-phenol, 0,031 g of 2-sec-6-tert-butyl-phenol (0,015% to 2,6-di-tert-butyl-phenol), 0,0206 g 2,di-tert-butyl-phenol (0,01% to 2,6-di-tert-butyl-phenol), 112 g bisamine, 45 g of methanol. Spend the reaction of aminomethylpyridine, hydrogenolysis, stage vacuum distillation and crystallization. Get the product with the content of the basic substance is not less 99,70% wt.

The product of synthesis is subjected to testing on svetostoyjkostj similar to examples 1-6. The test results in table 1.

Thus, from these examples it follows that the implementation of a method of producing 2,6-di-tert-butyl-4-methyl-phenol of 2,6-di-tert-butyl-phenol, containing 0.04 to 0,015% wt. 2-sec-butyl-6-tert-butyl-phenol and 0.1 to 0.2% wt. 2,4-di-tert-butyl-phenol serial aminomethylpropanol, hydrogenolysis and isolation of the desired product 2,6-di-tert-butyl-4-methyl-phenol has guaranteed performance of color over a long period of storage.

Table 1
Indicators of chroma samples Agidol-1 (units ARNA).
ExampleData on color samples at release and after testingData on color samples after storage and after testing
6 months12 months
The original sample1 day3 dayThe original sample1 day3 dayThe original sample
Prototype No. 111,820,027.715,819,839,619,8
Example 211,815,819,811,815,819,811,8
Example 311,815,819,811,815,819,811,8
Example 411,819,823,711,819,823, 13,2
Example 511,819,823,711,819,827,713,2
Example 611,820,027,711,819,827,713,2
Example 711,820.027,711,819,827,713,2

The method of obtaining 2,6-di-tert-butyl-4-methyl-phenol of 2,6-di-tert-butyl-phenol serial aminomethylpropanol, hydrogenolysis and selection of the target product, wherein the process is carried out in the presence of 2-sec-butyl-6-tert-butyl-phenol and 2,4-di-tert-butyl-phenol in the amount of 0.015 to 0.04 wt.% and 0.1-0.2 wt.% accordingly to the original 2,6-di-tert-butyl-phenol.



 

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1 tbl, 7 ex

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