JPH04210674A - Production of m-diisopropylbenzenedihydroperoxide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

[00011

[Industrial Field of Application] The present invention relates to a method for producing m-diisopropylbenzene dihydroperoxide. The high-grade m-diisopropylbenzene dihydroperoxide obtained by the present invention can be optimally utilized, especially as a raw material for producing resorcinol. Resorcinol is an extremely useful compound as a raw material for adhesives, pharmaceutical and agricultural intermediates, dye intermediates, and the like. [0002] [0002] When m-diisopropylbenzene is oxidized, m-diisopropylbenzene dihydroperoxide, m-di(2-hydroxy-2-propyl)cumene hydroperoxide and m-(2-hydroxy-2-propyl) are produced. It is known that reaction mixtures containing benzene and the like can be obtained. However, no method is known for efficiently producing, separating and recovering high-grade m-diisopropylbenzene dihydroperoxide from m-diisopropylbenzene. [0003]

[Problems to be Solved by the Invention] Under the current circumstances, the problem to be solved by the present invention is to provide a method for obtaining m-diisopropylbenzene dihydroperoxide from m-diisopropylbenzene in good yield, and to The object of the present invention is to provide a method for producing m-diisopropylbenzene dihydroperoxide, which has the advantage that benzene dihydroperoxide is of high quality and can therefore be suitably used as a raw material for producing high-grade resorcinol in good yield. . [0004]

[Means for Solving the Problems] That is, the present invention relates to a method for producing m-diisopropylbenzene dihydroperoxide, which is characterized by comprising the following first to fourth steps. First step: By oxidizing m-diisopropylbenzene, m-diisopropylbenzene dihydroperoxide, m-(2-hydroxy-2-propyl)cumene hydroperoxide and m-di(2-hydroxy-2-propyl)benzene are produced. obtaining a reaction mixture containing Second step: From the reaction mixture obtained in the first step,
By removing m-diisopropylbenzene dihydroperoxide, a methyl isobutyl ketone solution containing m-(2-hydroxy-2-propyl)cumene hydroperoxide and m-di(2-hydroxy-2-propyl)benzene as main components is obtained. The process of obtaining. Third step: The methyl isobutyl ketone solution obtained in the second step was converted into m-(2
By subjecting hydroxy-2-propyl)cumene hydroperoxide and m-(2-hydroxy-2-propyl)benzene to an oxidation reaction until the combined reaction conversion reaches 60 to 90%, m-diisopropylbenzene dihydroperoxide is produced. A process of obtaining a mixture having main components. Fourth step: A step of obtaining m-diisopropylbenzene dihydroperoxide by extracting the mixture obtained in the third step with alkaline water and then with methyl isobutyl ketone. [0005] This will be explained in detail below. The first step of the present invention is m-diisopropylbenzene (hereinafter referred to as rm-DC
It is written as J. ) by oxidizing m-diisopropylbenzene dihydroperoxide (hereinafter referred to as rm-D
HPO”. Lm-(2-hydroxy-2-propyl)cumene hydroperoxide (hereinafter referred to as rm-CH
PO”. ) and m-di(2-hydroxy-2-propyl)benzene (hereinafter referred to as rm-DKAJ).
This is a step of obtaining a reaction mixture containing. A known method (for example, see Japanese Unexamined Patent Publication No. 49-42624) is applied to this step. That is, to give an example, unreacted m-DC and m-diisopropylbenzene monohydroperoxide (
Hereinafter, it will be referred to as rm-MHPOJ. ) is supplemented with the raw material m-DC as the feedstock for the oxidation reaction, and oxidized in the liquid phase with air under heat and pressure while maintaining the mMHPO concentration in the reaction system within an appropriate range. , m-DHPO
A method for continuous production is shown. [00061 The second step of the present invention is to remove m-DHPO from the reaction mixture obtained in the first step.
This is a step of obtaining a methyl isobutyl ketone (hereinafter referred to as rMIBKJ) solution containing HPO and m-DKA as main components. This step can be carried out using known methods (for example,
JP-A-49-20135, JP-A-51-2945
(Refer to Publication No. 7) shall be applied. That is, by contacting the reaction mixture obtained in the first step with an aqueous solution of caustic soda, m-D HPOlm-CHPO and m-DKA
An extracted aqueous layer containing as the main component is obtained. In addition, the oil layer is m-M
HPO and m-DC are the main components and are recycled to the first step. Next, by bringing the extracted water layer into contact with MIBK, an extracted oil layer containing most of m-CHPO and m-DKA and some m-DHPO, and most of m-DHP
An extracted aqueous layer containing O is obtained. This extracted aqueous layer containing m-DHPO is further extracted and purified with MIBK to recover a highly purified m-DHPO/MIBK liquid, which is used as a raw material for resorcin production. On the other hand, the above m-
The extracted oil layer rich in CHPO and m-DKA is brought into contact with a caustic soda aqueous solution to remove a small amount of m-DH contained in the extracted oil layer.
PO can be transferred to and removed from the aqueous layer. Thus,
The resulting oil layer can be obtained as a MIBK solution containing m-CHPO and m-DKA as main components. Usually, the m-DHPO remaining in the mixture is 2 to 10% by weight relative to m-CHPO. Note that the mixture may be used in the next step after being washed with water and concentrated, if necessary. [00071 The third step of the present invention is the MI obtained in the second step.
By subjecting the BK solution to an oxidation reaction using hydrogen peroxide in the presence of an acidic catalyst in a heterogeneous system until the combined reaction conversion of m-CHPO and m-DKA reaches 60 to 90%. , is a process for obtaining a mixture containing m-DHPO as a main component. The amount of hydrogen peroxide used is preferably 0.8 to 2 mol, more preferably 1.8 to 2 mol per mol of carbinol group of m-CHPO and m-DKA used in the reaction.
It is 0 to 1.6 mol. If the amount is less than 0.8 mol, the dehydration reaction of the carbinol group and the acid decomposition reaction of the hydroperoxide group will increase, and the target m-DH per pass will increase.
The yield of PO is low, which is not preferable. On the other hand, if it is used in an amount exceeding 2 moles, the yield of m-DHPO will be low, which is not preferable. Note that hydrogen peroxide is used as a 20 to 70% by weight aqueous solution. The reaction temperature is preferably 40 to 60°C, more preferably 45 to 55°C. If the temperature is less than 40°C, the reaction rate is slow, while if it exceeds 60°C, side reactions will increase, which is not preferred. The acidic catalyst is preferably sulfuric acid or sulfuric anhydride, and the amount used is preferably 1 to 20% by weight, more preferably 2 to 15% by weight, based on m-CHPO equivalent hydroperoxide. If it is less than 1% by weight, the reaction rate is slow;
If it exceeds 5% by weight, side reactions will increase, which is not preferable. The reaction may be continuous or batchwise. The reaction pressure is not particularly limited, but the reaction is usually carried out under atmospheric pressure. In this step, it is necessary to perform the acidic reaction until the combined reaction rate of m-CHPO and m-DKA reaches 60 to 90%. Controlling the reaction within such a range is one of the greatest features of the present invention. If the reaction rate is less than 60%,
If the yield of m-DHPO, which is the target product, per one pass is small, and the reaction rate exceeds 90%, side reactions such as acid decomposition reactions of hydroperoxide groups and dehydration reactions of carbinol groups increase, The quality of the m-DHPO obtained is reduced. [00081 The fourth step of the present invention is a step of obtaining m-DHPO by extracting the mixture obtained in the third step with alkaline water and then with methyl isobutyl ketone. Note that the method for obtaining m-DHPO is carried out in the same manner as the third step. The incorporation of the fourth step in the present invention is one of the characteristics of the present invention. That is, through this process, it is possible to make m-DHPO of high quality, and when resorcinol is produced using such high-quality m-DHPO as a raw material, high-quality resorcinol can be obtained with good yield. It can be done. In addition, in order to obtain resorcinol using m-DHPO obtained by the present invention, a known method, for example, the method described in JP-A-49-72220, can be used. That is, for example,
By bringing an MIBK solution of m-DHPO into contact with a small amount of an acid catalyst while heating, high-quality resorcinol can be obtained from m-DHPO in good yield. [0009]

[Examples] Next, the present invention will be specifically explained with reference to Examples. Example-1 First Step and Second Step A MIBK solution containing m-CHPO and m-DKA as main components was obtained by the method described below. 3 kg/cm2G at a temperature of 95°C using a cylindrical stainless steel oxidation reactor
55,000 standard volume parts per hour of pressurized air, m-DC
is on average 39.1% by weight and m-MHPO is on average 40.1% by weight.
The reaction raw material contained in the weight percent was 146 parts by weight/Hr, 0.
Oxidation was carried out while continuously supplying 18 parts by weight/hr of 5% by weight caustic soda water to obtain an oxidation reaction solution. Subsequently, the liquefied reaction liquid was brought into contact with 8% caustic soda water, and m
161 parts by weight/Hr of an aqueous layer containing an average of 13.5% by weight of -DHPO, an average of 2.6% by weight of m-CHPO, and an average of 0.3% by weight of m-DKA was obtained. Next, the aqueous layer was heated at 30°C.
m-CHPO and m-DKA
An extracted oil layer containing most of m-DHPO and a part of m-DHPO was obtained. Further, the oil layer was brought into contact with 8% caustic soda water at 30°C to remove the migrated m-DHPO. The MIBK solution containing m-CHPO and m-DKA as main components thus obtained was washed with water and then concentrated to produce m-CHPO26,
3% by weight, m-DKA 3.5% by weight and m-DHPO
16 parts by weight/hr of MIBK liquid containing 1.2% by weight was obtained. 30% by weight hydrogen peroxide solution in a reactor with a stirrer 43.8
g and 6.0 g of concentrated sulfuric acid were added, and 200 g of MIBK liquid obtained in the second step was added dropwise at room temperature using a dropping funnel.
The temperature was raised to .degree. C. and the reaction was continued for 3.5 hours. The molar ratio of hydrogen peroxide and carbinol group at this time was 1.2. After the reaction was completed, the aqueous layer was removed and neutralized with aqueous sodium bicarbonate to obtain a reaction solution. The obtained reaction solution was subjected to gas chromatography (GC) analysis and liquid chromatography (LC) analysis. As a result, m-DHPO23.4% by weight, m-
CHPO was 6.0% by weight, and m-DKA was 0.0% by weight. In addition, the combined reaction conversion rate of m-CHPO and m-DKA was 80.2%, and the selectivity of m-DHPO was 85%.
．． 3%, the yield of m-DHPO per hydrogen peroxide is 55
．． It was 2%. Fourth step: 100 g of the reaction solution obtained in the third step was extracted in two stages at 30°C using 143 g of an 8% by weight aqueous sodium hydroxide solution, and m-D
168 g of an aqueous layer containing 13.5% by weight of HPO and 1.5% by weight of m-CHPO was obtained. Next, the obtained aqueous layer was mixed with MIBK53
Two-stage extraction was carried out at 30°C using m-DHPOll, 3
161 g of aqueous layer containing 3% by weight of m-CHPOO
I got it. Subsequently, the aqueous layer was diluted with 331 g of MIBK for 6 hours.
Three-stage extraction at 0°C, m-DHPO4.9% by weight, m-C
348 g of MIBK liquid containing HPOo, 06% by weight was obtained. [00101 Examples 2 and 3 and Comparative Examples 1 and 2 The same procedure as Example 1 was performed except that the conditions shown in Table 1 were used. The results are shown in Table 1. [0011] Reference Example Using the MIBK solution obtained in the fourth step of Example 1, resorcinol was obtained. That is, the MIBK solution was washed with water, and then 4
Concentrated twice, m-DHPO is 20.0% by weight, m-CH
80g of concentrated liquid containing 0.2% by weight of PO and 0.5% by weight of PO
1.6 g of anhydrous sulfuric acid acetone solution was charged, and the reaction was carried out at 60° C. for 10 minutes. Next, it was neutralized with stoichiometric caustic soda water to obtain 83.0 g of a decomposed and neutralized solution. G.C., L.C.
As a result of analysis, resorcinol was contained in an amount of 8.9% by weight, and the yield was 94.9%. [0012] Comparative Reference Example The MIBK solution obtained in the third step of Example 1 was washed with water and dehydrated without being subjected to the fourth step, and the concentration was adjusted to obtain a raw material. m-DHPO17.5% by weight, m-CHPO
Except for using 80g of MIBK liquid containing 4.6% by weight.
Resorcinol was obtained by the same method as in Reference Example. As a result, 83.3 g of decomposed and neutralized oil contained 5.6% by weight of resorcinol, and the yield of resorcinol was 68.2%, indicating that heavy products were significantly produced. [0013] Table 1 Example Comparative Example Third Step 43.8 36.5
58.5 43.8 43.830wt% H2
O2g '1.2 1.0 1.6 1.2
1.2H202/carbinol mol 50
50 50 50 50 hours
Hr 3.5 3.0 4.0 1.
5 10 Results m-DHPOwt% 23.4 21.9 25.
3 18.4 20.1m-CHPOwt% 6
．． 0 7.5 4.5 13.1 1.7m
-DKAwt% o, o o, o o, o
o, o o,. (m-DHPO+m-DKA) Conversion rate % 80.2
75.0 85.2 56.4 94.3m-D
HPO selectivity 85.3 85.3 87.2
94.1 62.0m-DHPO yield (1)
55.2 59.3 47.7 50.3
44.0 Fourth process result
(2) (3) MIBK liquid g 348
345 365 320m-DHPOwt%
4.9 4.7 5.0 3.7m-CHPO
wt% 0.06 0.12 0.05 0.
09(1))L! Yield per 02. (2) When extracting m-CHPO from the aqueous layer with MIBK,
The required amount of MIBK was 2.5 times that of Example 1. (3) There were many by-products, and the extraction operation was difficult. [0014]

[Effect of the invention] As explained above, according to the present invention, m
- A method for obtaining m-DHPO from DC in a high yield, and since the m-DHPO obtained is of high quality, it has the advantage that it can be suitably used as a raw material for producing high-grade resorcinol. It was possible to provide a method for producing m-DHPO having the following.

Claims (1)

[Claims] 1. A method for producing m-diisopropylbenzene dihydroperoxide, which comprises the following steps 1 to 4. First step: By oxidizing m-diisopropylbenzene, m-diisopropylbenzene dihydroperoxide, m-(2-hydroxy-2-propyl)cumene hydroperoxide and m-di(2-hydroxy-2-propyl)benzene are produced. obtaining a reaction mixture containing Second step: From the reaction mixture obtained in the first step,
By removing m-diisopropylbenzene dihydroperoxide, a methyl isobutyl ketone solution containing m-(2-hydroxy-2-propyl)cumene hydroperoxide and m-di(2-hydroxy-2-propyl)benzene as main components is obtained. The process of obtaining. Third step: The methyl isobutyl ketone solution obtained in the second step was converted into m-(2
-Hydroxy-2-propyl)cumene hydroperoxide and m-(2-hydroxy-2-propyl)benzene are subjected to an oxidation reaction until the combined reaction conversion rate is 60 to 90%, resulting in m-diisopropylbenzene dihydroperoxide. A process of obtaining a mixture containing as the main component. Fourth step: A step of obtaining m-diisopropylbenzene dihydroperoxide by extracting the mixture obtained in the third step with alkaline water and then with methyl isobutyl ketone.