A process for the preparation of dihydroperoxyisopropylbenzene from diisopropylbenzene

Abstract

The application provides a method for preparing di-persilicate by using diisopropyl benzene. The method in-situ converts benzyl alcohol generated in the oxidation reaction process of diisopropyl benzene by introducing special additives and ozone into peroxide, thereby greatly simplifying the existing di-persilicate production process, improving the yield, and having a good industrialization prospect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of fine organic synthesis, and particularly relates to a method for preparing di-p-menthane hydroperoxide from p-menthane. BACKGROUND

[0002] The preparation of di-p-menthane hydroperoxide from p-menthane, the acidolysis of di-p-menthane hydroperoxide to prepare phenols and acetone, is one of the main industrial routes for preparing diphenols at present, and can prepare diphenols including phenol, resorcinol, hydroquinone and the like. However, in the process of preparing diphenols by using the route, a part of benzyl alcohol is produced as a by-product in the preparation of peroxide intermediates. In the existing phenol-ketone process, the benzyl alcohol is dehydrated, and then hydrogenated to obtain the raw material p-menthane again. US4283570A prepares di-peroxide from the monobenzyl alcohol monobenzyl alcohol p-menthane hydroperoxide and dibenzyl alcohol produced in the reaction by a secondary oxidation step. Both of the two methods have the problems of long process flow and low conversion efficiency of benzyl alcohol. There is an urgent need for a method for in-situ oxidation of benzyl alcohol to peroxide in an air oxidation reactor.

[0003] CN107660201A provides a method for oxidizing alpha-methyl benzyl alcohol to a mixture of acetophenone; CN104817441B provides a method for obtaining aldehyde ketone by oxidizing benzyl alcohol with a gold catalyst. Since the peroxide group is very unstable, it will decompose into benzyl alcohol / ketone group when encountering alkaline catalyst or high heat. Therefore, these methods oxidize benzyl alcohol to aldehyde ketone compound with air, cannot obtain peroxide, and use solid catalyst which is not suitable for air oxidation p-menthane reactor device.

[0004] At present, there is an urgent need for a method for simply and conveniently converting benzyl alcohol into peroxide. SUMMARY

[0005] One of the purposes of the present application is to provide a method for preparing di-p-menthane hydroperoxide from p-menthane, which can simply and conveniently oxidize benzyl alcohol to peroxide in-situ in an air oxidation p-menthane reactor, and can obtain high conversion rate.

[0006] To achieve the above purposes, the present application adopts the following technical solutions:

[0007] A method for preparing di-p-menthane hydroperoxide from p-menthane, the method comprising the following steps:

[0008] S1: mixing p-menthane with an auxiliary to obtain a reaction oil phase;

[0009] S2: heating, and introducing an oxidation gas source, to obtain di-p-menthane hydroperoxide after reaction;

[0010] The auxiliary in S1 is polychlorobenzene and poly-tert-butylbenzene, and the auxiliary in the present application simultaneously serves as a solvent.

[0011] The present application adopts the complex formed by the chloro group and the peroxide group of polychlorobenzene to inhibit the cleavage of peroxide under reaction conditions, and adopts poly-tert-butylbenzene to improve the solubility of the oxidizing gas source, especially ozone, in the system, to realize the smooth conversion of benzyl alcohol to peroxide, and there is obvious synergistic effect between polychlorobenzene and poly-tert-butylbenzene, so that the benzyl alcohol group in the reaction process is selectively controlled between 0.5-1%.

[0012] In an embodiment of the present application, the diisopropylbenzene in S1 is one or more of ortho-diisopropylbenzene, meta-diisopropylbenzene, and para-diisopropylbenzene.

[0013] In an embodiment of the present application, the polychlorobenzene in S1 is one or more of ortho-dichlorobenzene, 1,3-trichlorobenzene, and 1,4-trichlorobenzene.

[0014] In an embodiment of the present application, the poly-tert-butylbenzene in S1 is one or more of tert-butylbenzene, meta-di-tert-butylbenzene, and para-di-tert-butylbenzene; preferably, the molar ratio of diisopropylbenzene, polychlorobenzene, and poly-tert-butylbenzene is 4:(1-2):(2-3).

[0015] In an embodiment of the present application, the benzyl alcohol in S2 is converted in situ to peroxide.

[0016] In an embodiment of the present application, the oxidizing gas source in S2 is a mixed gas of air and ozone; preferably, the volume ratio of air to ozone is 100:(5-10); preferably, the oxidizing gas source is fed at a rate of 1-2 L / (min*L 反应液 ). The proportion of ozone can be adjusted by those skilled in the art according to the needs of the oxidation reaction.

[0017] In an embodiment of the present application, the reaction temperature in S2 is 70-110°C.

[0018] In an embodiment of the present application, the stirring speed in S2 is 800-1500 r / min.

[0019] In an embodiment of the present application, the reaction pressure in S2 is 2-6 barG; the residence time of the reaction liquid in the kettle is 10-15 h.

[0020] Another object of the present application is to provide a product of dihydroperoxyisopropylbenzene.

[0021] A dihydroperoxyisopropylbenzene is prepared by the above method, and the proportion of the benzyl alcohol group in the dihydroperoxyisopropylbenzene to the sum of the mass of the peroxide and the benzyl alcohol group is less than 1 wt%. The benzyl alcohol group will cause the cleavage yield of the subsequent peroxide group to decrease.

[0022] Unless otherwise specified, the pressure described in the present application is all gauge pressure.

[0023] Compared with the prior art, the present application has the following beneficial effects:

[0024] (1) The conversion rate of the reaction solution in the reaction is 60-70%, the proportion of the benzyl alcohol group in the sum of the peroxide and the benzyl alcohol group in the target product is less than 1%, and the yield of dihydrogen peroxide cumene and monohydrogen peroxide cumene is greater than or equal to 95%.

[0025] (2) The method can simply and in situ oxidize benzyl alcohol to peroxide in the air oxidation cumene reactor. DETAILED DESCRIPTION

[0026] The following examples are further illustrations of the technical solutions provided by the present application, but the present application is not limited to the listed examples, and any other known changes within the scope of the present application are also included.

[0027] Main raw materials:

[0028] m-diisopropylbenzene, Shaanxi Didi Medicine, purity 98%,

[0029] p-diisopropylbenzene, Aradin, 99%,

[0030] p-di-tert-butylbenzene, Aradin, 97%,

[0031] o-dichlorobenzene, Aradin, 97%,

[0032] m-di-tert-butylbenzene, Aradin, 97%,

[0033] 1,3-trichlorobenzene, Aradin, 96%,

[0034] 1,2,4-trichlorobenzene, Aradin, 96%.

[0035] Equipment:

[0036] 2L reaction kettle, Yantai Ailang Machinery Technology Co., Ltd.,

[0037] Ozone generator, Qingdao Guolin.

[0038] Analysis instrument:

[0039] Shimadzu LC-20A liquid chromatograph.

[0040] Analysis method:

[0041] Chromatographic column: Shimadzu phenyl column, mobile phase: water, acetonitrile ratio 1:1, analysis temperature: 30°C, analysis time: 2h.

[0042] Example 1

[0043] 648g of m-diisopropylbenzene, 147g of o-dichlorobenzene, and 380g of p-di-tert-butylbenzene (molar ratio 4:1:2) were stirred at 1000 rpm and heated to 70°C. The gas flow rate was 1 L / (min*kg). 反应液 The reaction was carried out at an air-to-ozone volume ratio of 100:5, a reaction pressure of 2 bar, and a reaction residence time of 10 h. The products obtained were 226 g of cumene dihydroperoxide, 349.2 g of isopropyl monohydroperoxide, 162 g of cumene, 3.36 g of dimethylbenzyl alcohol hydroperoxide, 0.712 g of dimethylbenzyl alcohol hydroperoxide, 7.44 g of isopropyl acetophenone, and 11.64 g of hydroperoxide acetophenone. The proportion of benzyl alcohol groups in the target product (including both peroxide and benzyl alcohol groups) was 0.52 wt%.

[0044] Example 2

[0045] 648g of p-diisopropylbenzene, 273.75g of trichlorobenzene, and 475g of m-di-tert-butylbenzene (molar ratio 4:1.5:2.5) were stirred at 1100 rpm and heated to 90℃. The gas flow rate was 1.5 L / (min*kg). 反应液 The reaction was carried out at an air-to-ozone volume ratio of 100:7.5, a reaction pressure of 4 bar, and a reaction residence time of 12.5 h. The products obtained were 271.2 g of cumene dihydroperoxide, 372.48 g of isopropyl monohydroperoxide, 97.2 g of cumene, 5.04 g of dimethylbenzyl alcohol hydroperoxide, 1.424 g of dimethylbenzyl alcohol hydroperoxide, 8.68 g of isopropyl acetophenone, and 20.952 g of hydroperoxide acetophenone. The benzyl alcohol group accounted for 0.74% of the total peroxide and benzyl alcohol groups in the target product.

[0046] Example 3

[0047] 648g of p-diisopropylbenzene, 362g of trimellibenzene, and 40g of tert-butylbenzene (molar ratio 4:2:3) were stirred at 1200 rpm and heated to 110℃. The gas flow rate was 2 L / (min*kg). 反应液 The reaction was carried out at an air-to-ozone volume ratio of 100:10, a reaction pressure of 6 bar, and a reaction residence time of 15 h. The products obtained were 298.32 g of cumene dihydroperoxide, 375.6 g of isopropyl monohydroperoxide, 64.8 g of cumene, 6.72 g of dimethylbenzyl alcohol hydroperoxide, 2.136 g of dimethylbenzyl alcohol hydroperoxide, 25.92 g of isopropyl acetophenone, and 27.16 g of hydroperoxide acetophenone. The benzyl alcohol group accounted for 0.95% of the total peroxide and benzyl alcohol groups in the target product.

[0048] Comparative Example 1

[0049] Comparing with Example 1, the difference is that no ozone is added during the reaction.

[0050] As a result, the ratio of benzyl alcohol group in the sum of peroxidation and benzyl alcohol group in the target product is 2.3%.

[0051] Comparative Example 2

[0052] Comparing with Example 1, the difference is that no o-dichlorobenzene is added during the reaction, and methanol with the same mass as o-dichlorobenzene in Example 1 is added.

[0053] As a result, the ratio of benzyl alcohol group in the sum of peroxidation and benzyl alcohol group in the target product is 5%.

[0054] Comparative Example 2

[0055] Comparing with Example 1, the difference is that no o-dichlorobenzene is added during the reaction, and methanol with the same mass as o-dichlorobenzene in Example 1 is added.

[0056] As a result, the ratio of benzyl alcohol group in the sum of peroxidation and benzyl alcohol group in the target product is 2.3%.

[0057] Comparative Example 3

[0058] Comparing with Example 1, the difference is that no o-dichlorobenzene, tert-butylbenzene is added during the reaction, and methanol with the same mass as o-dichlorobenzene, tert-butylbenzene in Example 1 is added.

[0059] As a result, the ratio of benzyl alcohol group in the sum of peroxidation and benzyl alcohol group in the target product is 9.6%.

Claims

1. A process for the preparation of di-p-menthane hydroperoxide from diisopropylbenzene, characterized in that, The method comprises the following steps: S1: mixing diisopropylbenzene with an auxiliary to obtain a reaction oil phase; S2: heating, introducing an oxidizing gas source, and obtaining dihydroperoxide isopropylbenzene after reaction; In S1, the auxiliary is polychlorobenzene and poly-tert-butylbenzene.

2. The method of claim 1, wherein, In S1, the diisopropylbenzene is one or more of o-diisopropylbenzene, m-diisopropylbenzene, and p-diisopropylbenzene; In S1, the polychlorobenzene is one or more of o-dichlorobenzene, 1,3-dichlorobenzene, and m-dichlorobenzene; In S1, the poly-tert-butylbenzene is one or more of tert-butylbenzene, m-di-tert-butylbenzene, and p-di-tert-butylbenzene.

3. The method of claim 1, wherein, In S1, the molar ratio of diisopropylbenzene, polychlorobenzene, and poly-tert-butylbenzene is 4:(1-2):(2-3).

4. The method according to claim 1 or 2, characterized in that, In S2, benzyl alcohol is converted into a peroxide in situ; In S2, the oxidizing gas source is a mixture of air and ozone; In S2, the reaction temperature is 70-110°C; In S2, the reaction pressure is 2-6 barG; and the residence time of the reaction liquid in the kettle is 10-15 h.

5. The method of claim 4, wherein, In S2, the volume ratio of air to ozone is 100:(5-10). The rate of feeding the oxidation gas source in S2 is 1-2 L / (min*L 反应液 ).