SU1776256A3 - Process for production of dicumol peroxide - Google Patents

Description

UNION OF SOVIET

SOCIALIST

REPUBLIC

SU1776256 АЗ (51) 5 С 07 С 409/16

STATE COMMITTEE

BY INVENTIONS AND DISCOVERIES

FOR ΓΚΗΤ USSR

DESCRIPTION OF THE INVENTION

TO PATENT (21) 4742435/04 (22) 24.11.89 (31) R-276346 (32) 12.12.88 (33) PL (46) 15.11.92. Bul. No. 42 (71) Polytechnic Slonskaim. V. Petrovskogo, Osrodek Vdrazhanya Postempu Technically Organizationalgo in Przemyslje Hemichesky and Lekkim (PL). ... , (72) Jan Zawadiak, Zbigniew Stac, Zdzislaw Kulicki, Aleksandra Burghard, Bronislaw Staniowski, Riszard Yuzwicki and Grazyna Stolarchyk (PL) (56) Polish Patent Ns 105264, cl. C07 C 179/06, 1960.

US Patent N "2994719.

cl. 260-610, publ. 1961.

(54) METHOD FOR PRODUCING DICUMYL PEROXIDE (57) The invention relates to the production of tertiary alkylaromatic peroxides, in particular the production of dicumene peroxide, which is used in organic synthesis. The goal is to increase the yield of the target product, simplify the process. For this, cumene hydroperoxide in the presence of a catalyst - a metal salt with variable valence, is reacted with an excess of cumene in the presence of an alkylammonium halide in an amount of 0.05-100% by weight of the catalyst at 70-85 ° C. Under these conditions, the yield is increased from 47.5-58 to 60-61% at a concentration of the target product of 2929.5 instead of 4.5-10% according to the known method.

This invention relates to an improved process for the preparation of tertiary alkyl aromatic peroxides, in particular, dicumyl peroxide, which is used in organic synthesis.

A known method of producing dicumyl peroxide from cumene and cumene hydroperoxide in the presence of catalysts - metal salts with variable valence.

Copper tetra-8-picolinrodanides, cobalt or manganese (I) naphthenate or in the presence of cobalt naphthenate at a temperature of 90105 ° C for 1-5 hours are used as a catalyst.

The weight ratio of hydroperoxide to cumene is 0.05-0.24: 1.

The concentration of dicumyl peroxide in the reaction mixture is ~ 4.5 ~ 10%.

The product yield after crystallization is 47.4-58%.

The disadvantage of this method is the relatively low yield of the target product.

The aim of the invention is to increase the yield of the target product and increase the speed of the process.

This goal is achieved by the method of producing dicumyl peroxide by the interaction of cumene hydroperoxide with cumene in the presence of a metal salt with variable valence at a temperature of 70-85 ° C in the presence of an alkylammonium halide taken in an amount of 0.05-100% of the weight of the catalyst, the distinctive feature of which is that the process lead in the presence of alkylammonium halide. taken in an amount of 5-10% by weight of catalytic

1776256 AZ ra at a temperature of 70-85 ° C. The yield of dicumyl peroxide after recrystallization is 60-61%, the concentration of the target product in the reaction mixture is 29%. The ratio of hydroperoxide to cumene is 0.92: 1.

The proposed method is illustrated by the examples below.

In an example, a reactor equipped with a mixer, a thermometer, a reflux condenser and tubes supplying nitrogen (20 l / h) and cumene hydroperoxide is charged with 162 g of cumene and, with the mixer turned on, 4 g of anhydrous copper chloride CuCl2 and 0.2 g of cetyltrimethylammonium bromide are added.

After heating the contents of the reactor to 70 °, 350 g (360 cm ³ ) of a 70% solution of cumene hydroperoxide was dosed into cumene with a technical degree of frequency, at a rate of 2 cm ³ / min, while maintaining 70 ° C in the reactor. After the introduction of the entire amount of hydroperoxide, the contents of the reactor were kept at a temperature of 70 ° C for 15 minutes. As a result of filtering off the catalyst, 512 g of a product containing 29% dicumyl peroxide were obtained with a hydroperoxide conversion of 98%. The product yield (according to analysis) is 68%.

From the reaction product, cumene, dimethylphenylcarbinol, acetophenone, and other volatile compounds were distilled off under vacuum (1. mm Hg).

Distillation yielded 165 g of a residue containing 90% dicumyl peroxide, which was crystallized from 85% ethyl alcohol. Received 130 g of peroxide with a purity of 99% (yield after crystallization 60%).

PRI me R 2. As alkylammonium halide used 0.2 g of benzyltriethylammonium chloride. Other reagents and process parameters were the same as in example 1. The same results were obtained as in example 1.

Examplez. As the alkylammonium halide, 0.2 g of tetrabutylammonium bromide was used; the cumene hydroperoxide solution was dosed at a rate of 2.7 cm ³ / h. Other reagents and process parameters are the same as in example 1..

As a result of the filtration of the catalyst, 512 g of a product was obtained containing 29.5% of dicumyl peroxide at a conversion of the hydroperoxide of 99%, the product yield (according to analysis) 70%.

As a result of distillation of the product, 168 g of a residue with a content of 91% of dicumyl peroxide was obtained, from which, after crystallization, 133 g of dicumyl peroxide with a frequency of 99% were obtained (yield after crystallization of 61%).

PRI me R 4. As a catalyst used 2 g of cobalt stearate and 0.2 g of tetrabutylammonium bromide. The amounts of cumene and cumene hydroperoxide solution, as well as the dosage rate of the cumene hydroperoxide solution were the same as in example 1.

The reaction was carried out at a temperature of 85 ° C. After the introduction of the entire amount of the cumene hydroperoxide solution, the contents of the reactor were kept at a temperature of 85 ° C for 15 minutes.

Received 502 g of a mixture; obtained after the reaction containing 29% of dycumyl peroxide, the product yield according to the analysis of 67%.

Example 5. The alkylammonium halide used was 0.02 g of tetrabutylammonium bromide. Dosing rate 1.5 cm ³ / min.

The amounts of substances and other process parameters are the same as in the first example,

The results obtained are as in example 1,

Example 6. As the alkylammonium halide, 4 g of tetrabutylammonium bromide were used. The number of substrates and process parameters are the same as in example 1. As a result of filtration of the catalyst, 512 g of a product containing 28% of dicumyl peroxide were obtained at a conversion of 98%. Product yield (based on analysis) 66%. By distilling off such by-products as before, 160 g of a product containing 90% dicumyl peroxide were obtained, which crystallized twice from 85% ethanol.

Received 130 g of peroxide 99% purity (yield after crystallization 59%).

The proposed method allows you to obtain a product with a yield of 60-61% instead of 47.5-58% with a concentration according to the known method of 29-29.5% instead of 4.5-10%, while the process is carried out at a lower temperature with a smaller excess of cumene.

The proposed method also allows you to speed up the process, although the process is carried out at a lower temperature. So in the proposed method at a temperature, for example, 85 ° C, the process is carried out for 180 minutes, in the known one at a temperature of 90-95 ° C, the process duration is 300 minutes.

Claims (1)

Claim A method of producing dicumyl peroxide by the interaction of cumene hydroperoxide with cumene in the presence of a metal salt catalyst with variable valence at an elevated temperature, characterized in that, in order to increase the yield and accelerate the process, the latter is carried out in the presence of an alkylammonium halide taken in an amount of 0.05-100% from the weight of the catalyst, at 70-85 ° C.