JPH0429664B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing 1,3,5-triisopropylbenzene trihydroperoxide (hereinafter referred to as THPO). THPO is well known as a raw material for producing phloroglucin, and its production method involves catalytically reacting 1,3,5-triisopropylbenzene (hereinafter referred to as TIP) with oxygen or an oxygen-containing gas in the coexistence of an aqueous alkaline solution. well known. However, in such conventionally known methods, (1) an induction period is observed at the initial stage of oxidation, and the
This is more noticeable when TIP is used as a raw material. (2) Long oxidation time. (3) The formation of carbinols (hereinafter referred to as THPO carbinols) in which part or all of the hydroperoxide groups of THPO are substituted with hydroxyl groups is remarkable. (This THPO carbinol can be efficiently converted to THPO by treatment with hydrogen peroxide, which the present inventors discovered earlier. Therefore, in the oxidation of TIP, the total yield of THPO and THPO carbinol is is important, but it goes without saying that the higher the THPO yield, the more advantageous it is.) By the way, it has been known that the addition of oxidation initiators such as benzoyl peroxide and azobisisobutyronitrile is effective in shortening the induction period in the oxidation of alkylbenzenes, but the present inventors
As a result of various studies on oxidation initiators in the oxidation reaction of TIP or its derivatives, it was found that the azobis compound specified in the present invention is selectively effective in shortening the induction period in the oxidation reaction, and also improves the oxidation rate. Oxidation time is reduced, resulting in
It was discovered that the carbinolization of THPO was prevented and the yield of THPO was improved, leading to the present invention. That is, the present invention provides a method for producing THPO by contacting TIP or a homolog thereof with oxygen or an oxygen-containing gas in the coexistence of an alkaline aqueous solution,
0.01-5 mol% based on TIP or its homolog
This is a method for producing THPO characterized by adding 1,1'-azobis-(cyclohexane-1-carbonitrile) [hereinafter referred to as AHCN]. In the present invention, TIP congeners are 1,3,5-
It means a THPO precursor such as triisopropylbenzene monohydroperoxide or 1,3,5-triisopropylbenzene dihydroperoxide, and as a raw material in the oxidation reaction of the present invention, TIP, a TIP homologue alone or any of these A mixture of proportions is used. The basic oxidation reaction itself is a conventionally known method and is not particularly limited in the present invention. In the present invention, AHCN is added in such an oxidation reaction, but if the amount added is less than 0.01 mol% with respect to TIP or its homolog, it is difficult to notice the effect, and even if it exceeds 5 mol%, the amount added is Unnecessarily using AHCN without getting the desired effect.
Since there is a tendency to only consume TIP, the amount added is usually 0.01
-5 mol%, preferably 0.05-2 mol%. AHCN may be added in its entirety at the start of the oxidation reaction, or may be added in portions or continuously depending on the consumption rate, and the method is arbitrary. Thus, according to the method of the present invention, excellent effects such as a short induction period in the oxidation reaction, a shortened oxidation time, and an improved THPO yield can be obtained. The present invention will be explained below with reference to Examples. Example 1 204 g of 1,3,5-triisopropylbenzene,
204 g of water and 0.78 g of 1,1'-azobis-(cyclohexane-1-carbonitrile) are charged into a reactor and heated to 94-96°C. While stirring, oxygen was constantly blown into the solution, and at the same time, an oxidation reaction was carried out while adding a concentrated aqueous solution of caustic soda so that the pH of the reaction solution was 9.5±0.4. After the reaction started, the reaction solution was sampled at regular intervals and THPO and THPO carbinol were analyzed to determine the yield at each time, and the results shown in Table 1 were obtained. Comparative Example 1 An oxidation reaction was carried out in the same manner as in Example 1 except that 1,1'-azobis-(cyclohexane-1-carbonitrile) was not added, and the yield at each oxidation time was determined in the same manner. However, the table...
The results shown in 1 were obtained.

[Table] Total yield comparison example 2 In place of 1,1'-azobis-(cyclohexane-1-carbonitrile), 2,2'-azobis-isobutyronitrile and benzoyl peroxide were used for triisopropylbenzene. 0.3 mol%
The oxidation reaction was carried out in the same manner as in Example 1 except for the use of oxidation, and the yield at each oxidation time was determined in the same manner. The results for each reaction were almost the same as in Comparative Example 1. can be,
No effect was observed due to the addition.

Claims (1)

[Claims] 1 1,3,5-triisopropylbenzene or its homolog is reacted with oxygen or oxygen-containing gas in the coexistence of an alkaline aqueous solution to produce 1,3,5-triisopropylbenzene or its analogue.
In the method for producing 5-triisopropylbenzene trihydroperoxide, 0.01 to 5 mol% of 1,1'-azobis(cyclohexane-1-carbonitrile) based on 1,3,5-triisopropylbenzene or its homolog. A method for producing 1,3,5-triisopropylbenzene trihydroperoxide, which comprises adding.