A process for the preparation of 1,3-dihydroperoxy cumene

Abstract

The application provides a method for preparing 1,3-dihydroperoxy cumene. The method comprises: a catalytic reaction of a solution of 3-(1-hydroperoxy-1-methylethyl)-alpha,alpha-dimethyl benzyl alcohol HHP, which is a by-product of air oxidation of m-diisopropylbenzene, and a peroxide to obtain 1,3-dihydroperoxy cumene; wherein the catalyst of the catalytic reaction is alkyl benzene sulfonic acid. The introduction of alkyl benzene sulfonic acid promotes the mass transfer of oil and water two phases, and improves the reaction rate; the alkyl benzene sulfonic acid replaces strong acids such as sulfuric acid, reduces the decomposition of 1,3-dihydroperoxy cumene into m-dihydroxybenzene in the reaction, thereby avoiding the decomposition of hydrogen peroxide caused by m-dihydroxybenzene, improving the utilization rate of hydrogen peroxide; and the concentration of hydrogen peroxide in the reaction is reduced, and the reaction safety is improved.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a method for preparing 1,3-diperoxide isopropylbenzene. Background Technology

[0002] Resorcinol, commonly known as resorcinol, is a colorless or off-white needle-like crystal or powder, soluble in water, and mainly used in the rubber industry, low-temperature wood adhesives, dyes, and pharmaceuticals. Depending on the raw materials used, the main industrialized synthesis methods for resorcinol are: benzene sulfonation alkali fusion method, m-phenylenediamine method, and m-diisopropylbenzene oxidation method. Among these, the benzene sulfonation alkali fusion method uses a large amount of sulfonating agent, is highly corrosive to equipment, produces many byproducts, and causes serious environmental pollution, facing elimination. The m-phenylenediamine method is highly dangerous, with numerous nitro compound explosion accidents, and domestic small factories have limited access to raw materials. Only a few foreign companies possess the technology for the m-diisopropylbenzene oxidation method; the process flow is as follows:

[0003]

[0004] In this process, m-diisopropylbenzene is oxidized in air to prepare peroxide (MHP), 3-(1-hydroperoxy-1-methylethyl)-α,α-dimethylbenzyl alcohol (HHP), and DHP. DHP is then decomposed to generate resorcinol, while HHP can further react with hydrogen peroxide to produce DHP. MHP is returned to the feedstock for further air oxidation to generate DHP. The method for obtaining resorcinol through acidic pyrolysis of DHP can be found in US4339615A and US6350921B1. Since HHP is inevitably generated in this reaction system, the effective utilization of HHP is of great significance. The main research direction is to react HHP with hydrogen peroxide to convert it into DHP.

[0005] Because the reaction between HHP and hydrogen peroxide is a two-phase reaction involving oil and water, the reaction rate is slow. Furthermore, as the reaction proceeds, a large amount of water is generated, further diluting the hydrogen peroxide concentration, causing the reaction rate to slow down even more. Patent US4933506A reports a reaction in the presence of sulfuric acid to convert HHP and hydrogen peroxide into DHP. While sulfuric acid catalyzes this reaction, it also causes DHP to decompose into resorcinol. Resorcinol promotes the decomposition of hydrogen peroxide, posing a significant safety hazard during continuous reactions or start-up and shutdown. In addition, this reaction system contains a large amount of hydrogen peroxide, requiring 16 times the molar amount of HHP.

[0006] Therefore, there is an urgent need in the field for an intrinsically safe, highly efficient and stable method for preparing DHP from HHP. Summary of the Invention

[0007] One of the objectives of this invention is to provide a method for preparing 1,3-disperoxide isocumene, which can accelerate the reaction rate of HHP with hydrogen peroxide, reduce risks, and efficiently produce DHP.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] A method for preparing 1,3-dihydrocumene hydroperoxide, the method comprising: reacting a solution of 3-(1-hydroperoxy-1-methylethyl)-α,α-dimethylbenzyl alcohol (HHP), a byproduct of air oxidation of m-diisopropylbenzene, with a peroxide to obtain 1,3-dihydrocumene hydroperoxide;

[0010] The catalyst for the catalytic reaction is alkylbenzene sulfonic acid.

[0011] In this invention, the introduction of alkylbenzene sulfonic acid promotes mass transfer between the oil and water phases and increases the reaction rate; the substitution of strong acids such as sulfuric acid with alkylbenzene sulfonic acid reduces the decomposition of 1,3-disperoxide cumene into resorcinol in the reaction, thereby avoiding the decomposition of hydrogen peroxide caused by resorcinol, improving the utilization rate of hydrogen peroxide, reducing the concentration of hydrogen peroxide in the reaction, and improving the safety of the reaction.

[0012] In one embodiment of the present invention, the structure of the alkylbenzene sulfonic acid is as follows:

[0013]

[0014] In the formula, alkyl group R is an alkyl group with 10-20 carbon atoms; preferably, the catalyst is 1-5% of the mass of the reaction solution.

[0015] In one embodiment of the present invention, the solvent of the solution is a ketone and / or an alkylbenzene, preferably one or more of toluene, cumene, diisopropylbenzene, acetone, methyl ethyl ketone, and methyl isobutyl ketone (MIBK); preferably, the HHP content in the solution is 1-25 wt%.

[0016] In one embodiment of the present invention, the peroxide is hydrogen peroxide; preferably, the molar amount of the peroxide is 2-10 times that of HHP, more preferably 2-5 times; preferably, the concentration of the aqueous solution of the peroxide is 3-30 wt%, more preferably 5-10 wt%.

[0017] In one embodiment of the present invention, the peroxide is hydrogen peroxide; preferably, the molar amount of the peroxide is 2-10 times that of HHP, and more preferably, the temperature of the catalytic reaction is 20-70°C and the time is 5-30 min.

[0018] Another object of the present invention is to provide 1,3-diperoxyisopropylbenzene.

[0019] A 1,3-disperoxide isocumene, wherein the 1,3-disperoxide isocumene is prepared by the above method.

[0020] Compared with the prior art, the present invention has the following advantages:

[0021] (1) The catalyst has the function of enhancing mass transfer, which can realize the reaction of low concentration hydrogen peroxide with HHP and achieve high yield;

[0022] (2) Low-concentration hydrogen peroxide reaction system improves the inherent safety level of the reaction;

[0023] (3) Avoid using strong inorganic acids such as sulfuric acid to greatly reduce the decomposition of DHP into resorcinol (resorcinol will react with hydrogen peroxide to decompose it). Detailed Implementation

[0024] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.

[0025] Main raw material information:

[0026] m-Diisopropylbenzene, 99% purity, Jiangsu Evergreen Co., Ltd.

[0027] Sodium hydroxide, 98% purity, Shanghai Aladdin Biochemical Technology Co., Ltd.

[0028] Dihydroxy-1,3-diisopropylbenzene (HHP);

[0029] n-Decylbenzenesulfonic acid, 97% purity, Zibo Yujia Chemical Co., Ltd.;

[0030] Hexadecylbenzenesulfonic acid, 97% purity, Zibo Yujia Chemical Co., Ltd.

[0031] Dodecylbenzenesulfonic acid, 96% purity, Saen Chemical Technology (Shanghai) Co., Ltd.

[0032] Concentrated sulfuric acid, 98% purity, Beijing Innocare Co., Ltd.

[0033] Hydrogen peroxide, 27.5% aqueous solution, Luxi Chemical Co., Ltd.;

[0034] Hydrogen peroxide with a concentration higher than 27.5% is produced by distillation, while hydrogen peroxide with a concentration lower than 27.5% is produced by diluting with pure water.

[0035] All other raw materials can be purchased through ordinary commercial channels.

[0036] Detection method:

[0037] (1) HPLC method

[0038] This invention uses high-performance liquid chromatography (HPLC) to analyze reaction conversion and selectivity. The chromatographic analysis conditions are as follows:

[0039] Instrument Model: LC-6A High Performance Liquid Chromatograph (Shimadzu)

[0040] Analytical column: CLC-SIL 150*6.0mm (Shimadzu)

[0041] Preparation column: Zorbax SIL 250*9.4mm (column bonding)

[0042] Mobile phase: Water: Methanol: Isopropanol: Isopropylcyclohexane (60-90℃) = 15:3:3:60 (v / v)

[0043] Flow rate: 0.7 ml / min

[0044] Column temperature: room temperature

[0045] Ultraviolet detector (Shimadzu SPD-6AV UV-Vis spectrophotometer) wavelength: 235nm;

[0046] (2) Peroxide titration

[0047] Refer to national standards GB / T 1616-2014 and GB / T 32102-2015.

[0048] (3) HHP conversion rate calculation method

[0049] HHP conversion rate = (molar amount of HHP feed - molar amount of HHP remaining in the oil phase after reaction) / molar amount of HHP feed * 100%

[0050] (4) Calculation method for hydrogen peroxide utilization rate

[0051] Hydrogen peroxide utilization rate = (molar amount of hydrogen peroxide-1,3-diisopropylbenzene) * 2 / (molar amount of feed H2O2 - molar amount of residual H2O2 in aqueous phase) * 100%

[0052] Example of raw material HHP preparation

[0053] (1) Oxidation reaction stage: Take 5000g of m-diisopropylbenzene, 10g of cumene hydroperoxide, and 2500g of 2wt% alkaline solution, and add them to a 15L high-pressure reactor. Heat to 80℃. Introduce air, control the pressure at 3 barg, and continuously purge at a rate of 1200ml / min. Control the pressure inside the reactor through a back pressure valve. After reacting for 30h, remove the reaction solution, let it stand, separate the oil and water, and measure the HHP concentration in the oil phase to be 20.26wt%.

[0054] (2) Alkali extraction stage: Take the oil phase of the oxidation reaction liquid, add an equal mass of 6wt% sodium hydroxide solution, stir at 20℃, and after 20min the layers are separated. The hydrogen peroxides HHP and DHP produced in the oxidation stage exist in the alkaline phase in the form of ions.

[0055] (3) Back-extraction stage: The alkaline phase from (2) is introduced into the back-extraction tower, and twice the mass of MIBK is added. The mixture is stirred at 20°C for 30 min for back-extraction. The HHP content in the extract is 10.13 wt%. A MIBK solution with 10.13 wt% HHP is thus obtained. HHP concentrations higher than 10.13 wt% are obtained by vacuum distillation, and HHP concentrations lower than 10.13 wt% are obtained by diluting MIBK. If MIBK is replaced with other solvents, distillation and solvent replacement are performed on the basis of this process.

[0056] Example 1

[0057] 1000g of a 1.51wt% HHP solution in MIBK was added to a 5L stainless steel reactor. Subsequently, an aqueous hydrogen peroxide solution (30wt%) was added to the reactor at twice the molar amount of HHP. Decylbenzenesulfonic acid (1% of the reaction solution mass) was added to the reactor. The temperature was raised to 70℃ to initiate the reaction. After 5 minutes, the reaction solution was cooled to room temperature, and the oil and water were separated. The HHP and DHP contents in the oil phase were determined by HPLC, and the remaining hydrogen peroxide content in the aqueous phase was determined by titration. Analysis confirmed that the HHP conversion rate was 99.20%, the DHP content was 1.58wt%, and the DHP yield was 97.01%. The hydrogen peroxide content in the aqueous phase was 13.50wt%, and the hydrogen peroxide utilization rate was 90.21%.

[0058] After the reaction was completed, the reaction solution was heated at the original temperature for another 5 hours. The composition of the oil phase and the aqueous phase was tested by HPLC. The DHP content was 1.58%, the resorcinol content in the aqueous phase was 0.12 wt%, the hydrogen peroxide content was 13.37 wt%, the DHP decomposition in the oil phase was 0.26%, and the hydrogen peroxide decomposition in the aqueous phase was 0.96%.

[0059] Example 2

[0060] 1000g of a 5.06wt% HHP solution in MIBK was added to a 5L stainless steel reactor. Subsequently, an aqueous hydrogen peroxide solution was added to the reactor at a concentration three times the molar amount of HHP, with a hydrogen peroxide concentration of 15wt%. Hexadecylbenzenesulfonic acid was added to the reactor at a concentration of 1% of the reaction solution mass. The mixture was heated to 50℃ to initiate the reaction. After 8 minutes, the reaction solution was cooled to room temperature, and the oil and water were separated. The HHP and DHP contents in the oil phase were determined by HPLC, and the remaining hydrogen peroxide content in the aqueous phase was determined by titration. Analysis confirmed that the HHP conversion rate was 97.51%, the DHP content was 5.12wt%, and the DHP yield was 94.03%; the hydrogen peroxide content in the aqueous phase was 9.03wt%, and the hydrogen peroxide utilization rate was 93.41%.

[0061] After the reaction was completed, the reaction solution was heated at the original temperature for another 5 hours. The composition of the oil phase and the aqueous phase was tested by HPLC. The DHP content was 5.08%, the resorcinol content in the aqueous phase was 0.06 wt%, the hydrogen peroxide content was 8.90 wt%, the DHP decomposition in the oil phase was 0.42%, and the hydrogen peroxide decomposition in the aqueous phase was 1.13%.

[0062] Example 3

[0063] 1000g of a 10.13wt% HHP solution in MIBK was added to a 5L stainless steel reactor. Subsequently, an aqueous hydrogen peroxide solution was added to the reactor at a concentration 8 times the molar amount of HHP, resulting in a hydrogen peroxide concentration of 7.5wt%. Dodecylbenzenesulfonic acid was added to the reactor at a concentration of 4% of the reaction solution mass. The temperature was raised to 35℃ to initiate the reaction. After 10 minutes, the reaction solution was cooled to room temperature, and the oil and water were separated. The HHP and DHP contents in the oil phase were determined by HPLC, and the remaining hydrogen peroxide content in the aqueous phase was determined by titration. Analysis confirmed that the HHP conversion rate was 96.30%, the DHP content was 10.18wt%, and the DHP yield was 93.04%. The hydrogen peroxide content in the aqueous phase was 5.91wt%, and the hydrogen peroxide utilization rate was 96.11%.

[0064] After the reaction was completed, the reaction solution was heated at the original temperature for another 5 hours. The composition of the oil phase and the aqueous phase was tested by HPLC. The DHP content was 10.09%, the resorcinol content in the aqueous phase was 0.03 wt%, the hydrogen peroxide content was 5.85 wt%, the DHP decomposition in the oil phase was 0.96%, and the hydrogen peroxide decomposition in the aqueous phase was 0.93%.

[0065] Example 4

[0066] 1000g of a 15.19wt% HHP solution in MIBK was added to a 5L stainless steel reactor. Subsequently, an aqueous hydrogen peroxide solution was added to the reactor at a concentration 7.5wt%, ten times the molar amount of HHP. Dodecylbenzenesulfonic acid was added to the reactor at a concentration of 4% of the reaction solution mass. The temperature was maintained at 20℃ to initiate the reaction. After 30 minutes, the reaction solution was cooled to room temperature, and the oil and water were separated. The HHP and DHP contents in the oil phase were determined by HPLC, and the remaining hydrogen peroxide content in the aqueous phase was determined by titration. Analysis confirmed that the HHP conversion rate was 95.41%, the DHP content was 14.97wt%, and the DHP yield was 92.01%. The hydrogen peroxide content in the aqueous phase was 6.08wt%, and the hydrogen peroxide utilization rate was 91.80%.

[0067] After the reaction was completed, the reaction solution was heated at the original temperature for another 5 hours. The composition of the oil phase and the aqueous phase was tested by HPLC. The DHP content was 14.83%, the resorcinol content in the aqueous phase was 0.02 wt%, the hydrogen peroxide content was 6.04 wt%, the DHP decomposition in the oil phase was 0.96%, and the hydrogen peroxide decomposition in the aqueous phase was 0.65%.

[0068] Example 5

[0069] 1000g of a 20.38wt% HHP solution in MIBK was added to a 5L stainless steel reactor. Subsequently, an aqueous hydrogen peroxide solution was added to the reactor at a concentration three times the molar amount of HHP, resulting in a hydrogen peroxide concentration of 7.5wt%. Dodecylbenzenesulfonic acid was added to the reactor at a concentration of 4% of the reaction solution mass. The temperature was raised to 35℃ to initiate the reaction. After 10 minutes, the reaction solution was cooled to room temperature, and the oil and water were separated. The HHP and DHP contents in the oil phase were determined by HPLC, and the remaining hydrogen peroxide content in the aqueous phase was determined by titration. Analysis confirmed that the HHP conversion rate was 97.21%, the DHP content was 20.89wt%, and the DHP yield was 95.01%. The hydrogen peroxide content in the aqueous phase was 4.53wt%, and the hydrogen peroxide utilization rate was 90.42%.

[0070] After the reaction was completed, the reaction solution was heated at the original temperature for another 5 hours. The composition of the oil phase and the aqueous phase was tested by HPLC. The DHP content was 20.70%, the resorcinol content in the aqueous phase was 0.07 wt%, the hydrogen peroxide content was 4.48 wt%, the DHP decomposition in the oil phase was 0.92%, and the hydrogen peroxide decomposition in the aqueous phase was 0.38%.

[0071] Example 6

[0072] 1000g of a 25.69wt% HHP solution in MIBK was added to a 5L stainless steel reactor. Subsequently, an aqueous hydrogen peroxide solution was added to the reactor at a concentration three times the molar amount of HHP, resulting in a hydrogen peroxide concentration of 7.5wt%. Dodecylbenzenesulfonic acid was added to the reactor at a concentration of 4% of the reaction solution mass. The temperature was raised to 35℃ to initiate the reaction. After 10 minutes, the reaction solution was cooled to room temperature, and the oil and water were separated. The HHP and DHP contents in the oil phase were determined by HPLC, and the remaining hydrogen peroxide content in the aqueous phase was determined by titration. Analysis confirmed that the HHP conversion rate was 97.83%, the DHP content was 26.77wt%, and the DHP yield was 97.03%. The hydrogen peroxide content in the aqueous phase was 4.51wt%, and the hydrogen peroxide utilization rate was 88.59%.

[0073] After the reaction was completed, the reaction solution was heated at the original temperature for another 5 hours. The composition of the oil phase and the aqueous phase was tested by HPLC. The DHP content was 26.49%, the resorcinol content in the aqueous phase was 0.08 wt%, the hydrogen peroxide content was 4.49 wt%, the DHP decomposition in the oil phase was 1.02%, and the hydrogen peroxide decomposition in the aqueous phase was 0.42%.

[0074] Example 7

[0075] 1000g of a 10.13wt% HHP MIBK solution was added to a 5L stainless steel reactor. Subsequently, an aqueous hydrogen peroxide solution was added to the reactor at a concentration three times the molar amount of HHP, resulting in a hydrogen peroxide concentration of 7.5wt%. Dodecylbenzenesulfonic acid was added to the reactor at a concentration of 4% of the reaction solution mass. The temperature was raised to 35℃ to initiate the reaction. After 10 minutes, the reaction solution was cooled to room temperature, and the oil and water were separated. The HHP and DHP contents in the oil phase were determined by HPLC, and the remaining hydrogen peroxide content in the aqueous phase was determined by titration. Analysis confirmed that the HHP conversion rate was 98.31%, the DHP content was 10.29wt%, and the DHP yield was 94.05%. The hydrogen peroxide content in the aqueous phase was 4.50wt%, and the hydrogen peroxide utilization rate was 89.71%.

[0076] After the reaction was completed, the reaction solution was heated at the original temperature for another 5 hours. The composition of the oil phase and the aqueous phase was tested by HPLC. The DHP content was 10.19%, the resorcinol content in the aqueous phase was 0.08 wt%, the hydrogen peroxide content was 4.49 wt%, the DHP decomposition in the oil phase was 0.99%, and the hydrogen peroxide decomposition in the aqueous phase was 0.29%.

[0077] Comparative Example 1

[0078] This comparative example prepared DHP under the same conditions as Example 5, except that the catalyst, dodecylbenzenesulfonic acid, was replaced with sulfuric acid. Analysis confirmed that the HHP conversion rate was 73.61%, the DHP content was 6.50 wt%, and the DHP yield was 60.21%; the aqueous hydrogen peroxide content was 4.02 wt%, and the hydrogen peroxide utilization rate was 42.2%.

[0079] After the reaction was completed, the reaction solution was heated at the original temperature for another 5 hours. The composition of the oil phase and the aqueous phase was tested by HPLC. The DHP content was 3.35%, the resorcinol content in the aqueous phase was 2.33 wt%, the hydrogen peroxide content was 2.17 wt%, the DHP decomposition in the oil phase was 48.39%, and the hydrogen peroxide decomposition in the aqueous phase was 45.72%.

[0080] Comparative Example 2

[0081] This comparative example prepared DHP under the same conditions as Example 5, except that the catalyst, dodecylbenzenesulfonic acid, was replaced with phosphoric acid. Analysis confirmed that the HHP conversion rate was 58.71%, the DHP content was 4.67 wt%, and the DHP yield was 43.01%; the aqueous hydrogen peroxide content was 3.51 wt%, and the hydrogen peroxide utilization rate was 38.91%.

[0082] After the reaction was completed, the reaction solution was heated at the original temperature for another 5 hours. The composition of the oil phase and the aqueous phase was tested by HPLC. The DHP content was 2.66%, the resorcinol content in the aqueous phase was 1.49 wt%, the hydrogen peroxide content was 1.63 wt%, the DHP decomposition in the oil phase was 43.14%, and the hydrogen peroxide decomposition in the aqueous phase was 53.43%.

[0083] The test results above show that the alkylbenzenesulfonic acid addition scheme of this invention increases the reaction rate and yield in the HHP oxidation process to DHP. The alkylbenzenesulfonic acid addition scheme of this invention significantly improves the utilization rate of hydrogen peroxide, minimizes the decomposition of DHP during the reaction, produces very little resorcinol, further reduces hydrogen peroxide decomposition, and enhances reaction safety.

[0084] The above description is merely an embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing 1,3-disperoxide isocumene, characterized in that, The method comprises: reacting a solution of 3-(1-hydroperoxy-1-methylethyl)-α,α-dimethylbenzyl alcohol (HHP), a byproduct of the air oxidation of m-diisopropylbenzene, with a peroxide to obtain 1,3-dihydroperoxyisopropylbenzene. The catalyst for the catalytic reaction is alkylbenzene sulfonic acid; The structure of the alkylbenzene sulfonic acid is as follows: In the formula, alkyl group R is an alkyl group with 10-20 carbon atoms.

2. The method according to claim 1, characterized in that, The alkylbenzene sulfonic acid catalyst accounts for 1-5% of the mass of the reaction solution.

3. The method according to claim 1 or 2, characterized in that, The solvent of the solution is a ketone and / or an alkylbenzene.

4. The method according to claim 3, characterized in that, The solvent of the solution is one or more of toluene, cumene, diisopropylbenzene, acetone, methyl ethyl ketone, and methyl isobutyl ketone (MIBK). The HHP content in the solution is 1-25 wt%.

5. The method according to claim 1, characterized in that, The peroxide is hydrogen peroxide.

6. The method according to claim 5, characterized in that, The molar amount of peroxide is 2-10 times that of HHP; The concentration of the aqueous solution of peroxide is 3-30 wt%.

7. The method according to claim 6, characterized in that, The molar amount of peroxide is 2-5 times that of HHP; The concentration of the aqueous solution of peroxide is 5-10 wt%.

8. The method according to claim 1, characterized in that, The catalytic reaction is carried out at a temperature of 20-70℃ for 5-30 minutes.

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