A solvent-free condensation preparation method for BIPB

Abstract

The present invention relates to the technical field of organic synthesis, in particular to IPC C07C407, and more specifically to a solvent-free condensation preparation method of BIPB. In the present invention, tert-butyl hydroperoxide, di-(2-hydroxyisopropyl)benzene, perchlorate, and sulfuric acid are added dropwise to a reaction bottle, and the temperature is controlled to carry out a condensation reaction. Then, the product is obtained by post-treatment and vacuum distillation. The method in the present invention does not add additional solvent, improves the yield and whiteness of the product, reduces reaction by-products, reduces the loss of solvent, and thus reduces costs.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, in particular to IPC C07C407, and more specifically to a solvent-free condensation preparation method of BIPB. Background Art

[0002] Di-tert-butyl peroxide diisopropylbenzene, referred to as BIBP, is a high-temperature organic peroxide-based low-toxic crosslinking agent, widely used in plastics, rubber, petrochemical and other industries. The domestic demand is large, the market is in short supply, and it has a great market prospect.

[0003] According to the document "Research on the Synthesis of a New Cross-linking Agent Di-tert-butyl Diisopropyl Peroxide", there are four main methods for synthesizing the cross-linking agent BIPB in the prior art. (1) Olefin synthesis method, but its raw material di-(isopropyl)benzene monomer is prone to polymerization, which is more troublesome in industrial production. (2) Dehydrohalogenation synthesis method, but the synthesis method of its raw materials is cumbersome and complicated, difficult to operate, and difficult to prepare in large quantities. (3) Metal catalytic synthesis method, this method has problems such as high raw material consumption, low yield, and long reaction time, and it is necessary to find an efficient catalyst. (4) Condensation reaction synthesis method, in the presence of an acidic catalyst, DC is allowed to undergo a condensation reaction with tert-butyl hydroperoxide (TBHP) to generate BIPB. This method has mild conditions and is technically feasible.

[0004] Since several other synthesis methods are difficult to industrialize, we use condensation reaction synthesis as the production method of BIPB. Existing patent CN201210327922.4 discloses a condensation method of mixed meta- and para-bis-(tert-butylperoxyisopropyl)benzene, but this method has a long reaction time, many side reactions, and low reaction yield and product purity. Existing patent CN201510684385.2 discloses a production method of bis(tert-butylperoxyisopropyl)benzene, using di-(2-hydroxyisopropyl)benzene and tert-butyl hydrogen peroxide aqueous solution as raw materials, perchloric acid aqueous solution as catalyst, and toluene as solvent. This production method reduces the loss of raw materials and speeds up the reaction process, but toluene has a high boiling point, poor water separation effect, and it is difficult to remove the solvent in the later stage.

[0005] The current BIPB condensation process mostly uses the process of adding organic solvents. The solvents include xylene, toluene, alkanes, etc. While increasing the cost, the solvent provides the raw materials with more sufficient reaction space, which may lead to more side reactions, thereby reducing the yield and purity. Summary of the invention

[0006] In order to solve the problems in the prior art, the first aspect of the present invention provides a solvent-free condensation preparation method of BIPB, comprising the following steps:

[0007] S1: Adding raw materials: Add tert-butyl hydroperoxide to the reaction bottle, start stirring, then add di-(2-hydroxyisopropyl)benzene and perchlorate in sequence, heat to the set temperature, and add sulfuric acid dropwise after the temperature stabilizes;

[0008] S2: Condensation reaction: After the sulfuric acid is added dropwise, the reaction temperature is raised to 50-60°C and kept warm for 5-15 minutes. After the reaction is completed, stirring is stopped to obtain a reaction solution, which is then separated;

[0009] S3: Secondary feeding reaction: After the separation is completed, sulfuric acid is added dropwise again. After the addition is completed, the temperature of the entire addition process needs to be controlled at 40-60°C, and the temperature is kept for 45-55 minutes. After the reaction time is reached, water is added to terminate the reaction;

[0010] S4: Post-treatment alkali washing: The reaction liquid after the reaction is separated, leaving the upper organic liquid; a second alkali washing is performed, and then a second water washing is performed, and a finished product is obtained after reduced pressure distillation.

[0011] Preferably, the molar ratio of tert-butyl hydroperoxide to di-(2-hydroxyisopropyl)benzene in S1 is 2.90-3.5:1; more preferably, it is 2.90-3.00:1.

[0012] In the present invention, the molar ratio of tert-butyl hydroperoxide and di-(2-hydroxyisopropyl)benzene is 2.90-3.5:1, which not only improves the yield of BIPB, reduces the side reactions in the system, but also improves the whiteness of BIPB. The inventors found that the molar ratio of tert-butyl hydroperoxide and di-(2-hydroxyisopropyl)benzene has a greater influence on the yield of the system. When the amount of tert-butyl hydroperoxide is reduced, as shown in Comparative Example 4, the molar ratio is 2.7:1, and the yield is significantly reduced, and the by-products increase. The inventors speculate that in a solvent-free system, tert-butyl hydroperoxide is reduced, and it is easier to react with di-(2-hydroxyisopropyl)benzene to generate a unilateral peroxide by-product, and the reaction rate of the side reaction system is accelerated, thereby affecting the reaction rate of the main reaction, thereby reducing the yield.

[0013] Preferably, the molar ratio of di-(2-hydroxyisopropyl)benzene to perchlorate in S1 is 1:0.12-0.16, and more preferably 1:0.14.

[0014] Preferably, the di-(2-hydroxyisopropyl)benzene includes dihydroxy-1,4-diisopropylbenzene and dihydroxy-1,3-diisopropylbenzene.

[0015] Preferably, the CAS number of the dihydroxy-1,4-diisopropylbenzene is 2948-46-1, and the CAS number of the dihydroxy-1,3-diisopropylbenzene is 1999-85-5.

[0016] Preferably, the perchlorate includes one or both of sodium perchlorate and potassium perchlorate; further preferably, it is sodium perchlorate.

[0017] In the present invention, by controlling the molar ratio of di-(2-hydroxyisopropyl)benzene to perchlorate to be 1:0.12-0.16, the whiteness of BIPB is greatly improved while maintaining the yield, thereby improving the quality of the product. The inventor unexpectedly found that when the amount of perchlorate in the reaction process is reduced to exceed the range of the present invention, the yield is not much different, but the whiteness is reduced, and the amount of monoperoxide in the system is also increased to a certain extent.

[0018] Preferably, the set temperature in S1 is 40-50°C; more preferably, it is 42-48°C.

[0019] Preferably, the sulfuric acid in S2 and S3 is a 70 wt % sulfuric acid aqueous solution.

[0020] Preferably, the mass ratio of sulfuric acid to di-(2-hydroxyisopropyl)benzene in S2 is 1:3.5-3.9; further preferably, it is 1:3.7.

[0021] Preferably, the mass ratio of sulfuric acid to di-(2-hydroxyisopropyl)benzene in S3 is 1:3.9-5.7; further preferably, it is 1:4.6.

[0022] In the present invention, by controlling the mass ratio of sulfuric acid to di-(2-hydroxyisopropyl)benzene in S2 and S3, the generation of by-products is reduced, and the content of monoperoxide in the system is reduced. The inventors have found that when the concentration of sulfuric acid in the system is too high within the same reaction time, the by-products of the system increase, the whiteness decreases to a certain extent, and the quality of the product decreases, which affects the reaction speed of the entire reaction.

[0023] Preferably, the reaction temperature in S2 is 53-56°C.

[0024] Preferably, the temperature of the entire dropping process in S3 is controlled at 43-53°C.

[0025] Preferably, the specific process of liquid separation in S2 is to separate 55 to 60 g of water from the reaction liquid.

[0026] Preferably, the heat preservation reaction in S2 is 8 to 12 minutes; more preferably, it is 8, 10, or 12 minutes.

[0027] Preferably, the amount of water added to S3 is 55-80 g; more preferably, it is 55 g.

[0028] Preferably, the specific process of alkali washing in S4 is: add 25-50g hot water at 50-55°C and 47-60g sodium hydroxide to the organic liquid, then add 0.5-1g isononanoic acid and stir and keep warm for 10-20min. After the insulation is completed, stop stirring and let the liquid stand to separate the lower layer of alkali liquid and leave the upper layer of organic liquid.

[0029] Preferably, the sodium hydroxide in the alkali washing process is a 30 wt % sodium hydroxide aqueous solution.

[0030] Preferably, the specific process of water washing in S4 is: adding hot water at 50-55° C. to the organic liquid, and stirring at the same temperature for 10-20 minutes.

[0031] Preferably, the amount of hot water added in the first water washing in S4 is 50-70 g, and the amount of hot water added in the second water washing is 100-120 g.

[0032] Preferably, the pressure of the reduced pressure distillation is -0.09 MPa, the heating temperature is 60-65° C., and the reduced pressure time is 30-50 min.

[0033] In the present invention, 70wt% sulfuric acid aqueous solution is added dropwise twice, the first time sulfuric acid is added dropwise and the temperature is kept for 10 minutes, and the second time sulfuric acid is added dropwise and the temperature is kept for 50 minutes, which reduces the water content in the reaction system, speeds up the reaction, and prevents excessive sulfuric acid from being added at one time, which affects the whiteness of the product, thereby improving the quality of BIPB products. The inventor unexpectedly found during the experiment that if the temperature is kept for too long during the first sulfuric acid addition, a large amount of water will be generated, thereby reducing the sulfuric acid concentration and even stopping the reaction. Even after the second acid addition, the yield lost in the reaction during the previous period cannot be compensated.

[0034] Beneficial Effects

[0035] 1. The present invention develops a novel solvent-free condensation preparation method for BIPB, in which no additional solvent is added, reaction by-products are reduced, solvent loss is reduced, and thus solvent costs are reduced. In addition, no solvents such as xylene, toluene, and alkanes are added, which reduces the difficulty of wastewater treatment and reduces the cost of wastewater treatment.

[0036] 2. In the present invention, the molar ratio of tert-butyl hydroperoxide and di-(2-hydroxyisopropyl)benzene is 2.90-3.5:1, which not only improves the yield of BIPB, reduces the by-products in the system, but also improves the whiteness of BIPB.

[0037] 3. In the present invention, by controlling the molar ratio of di-(2-hydroxyisopropyl)benzene to perchlorate to 1:0.12-0.16, the whiteness of BIPB is greatly improved while maintaining the yield, thereby improving the quality of the product.

[0038] 4. In the present invention, by controlling the mass ratio of sulfuric acid to di-(2-hydroxyisopropyl)benzene in S2 and S3, the generation of by-products is reduced, and at the same time, the content of monoperoxide in the system is reduced.

[0039] 5. In the present invention, 70 wt% sulfuric acid aqueous solution is added dropwise twice, the first time sulfuric acid is added dropwise and the temperature is kept for 10 minutes, and the second time sulfuric acid is added dropwise and the temperature is kept for 50 minutes, which reduces the water content in the reaction system and speeds up the reaction. At the same time, it prevents excessive addition of sulfuric acid at one time, which affects the whiteness of the product, thereby improving the quality of BIPB products. DETAILED DESCRIPTION

[0040] Example 1

[0041] S1: Adding raw materials: Add 159g of tert-butyl hydroperoxide to the reaction bottle, start stirring at 300rpm, then add 118g of di-(2-hydroxyisopropyl)benzene and 9.2g of sodium perchlorate in sequence, heat to 42°C, and after the temperature stabilizes, add 32g of 70wt% sulfuric acid aqueous solution dropwise;

[0042] S2: Condensation reaction: After the addition of the aqueous sulfuric acid solution is completed, the reaction temperature is raised to 53°C and the reaction is kept at this temperature for 10 minutes. After the reaction is completed, stirring is stopped to obtain a reaction solution, and the solution is separated to separate 60g of water from the reaction solution;

[0043] S3: Secondary feeding reaction: After the separation is completed, 25.5 g of 70 wt% sulfuric acid aqueous solution is added dropwise again. The temperature of the entire addition process needs to be controlled at 47 ± 5 ° C. The temperature is kept for 50 minutes. After the reaction time is reached, 55 g of water is added to terminate the reaction;

[0044] S4: Post-treatment alkali washing: The reaction liquid after the termination of the reaction is separated, the lower layer of waste acid is separated, and the upper layer of organic liquid is left; 25g of 55℃ hot water and 47g of 30wt% sodium hydroxide aqueous solution are added to the organic liquid, and then 0.5g of isononanoic acid is added and stirred for 10 minutes. After the time is up, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste alkali liquid is separated, leaving the upper layer of organic liquid. After the first alkali washing is completed, the alkali washing is repeated again. After the second alkali washing is completed, 50g of 55℃ hot water is added to the organic liquid and stirred for 10 minutes. After the stirring time is reached, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste water is separated, leaving the upper layer of organic liquid. After the separation is completed, 100g of 55℃ hot water is added and the water washing is repeated. After the second water washing is completed, the organic liquid left is subjected to reduced pressure distillation, the pressure is -0.090MPa, the heating temperature is 60℃, and the time is 30min. The finished product is obtained after reduced pressure distillation.

[0045] Example 2

[0046] S1: Adding raw materials: Add 165g of tert-butyl hydroperoxide to the reaction bottle, start stirring at 300rpm, then add 118g of di-(2-hydroxyisopropyl)benzene and 9.2g of sodium perchlorate in sequence, heat to 42°C, and after the temperature stabilizes, add 32g of 70wt% sulfuric acid aqueous solution dropwise;

[0047] S2: Condensation reaction: After the sulfuric acid aqueous solution is added dropwise, the reaction temperature is raised to 53°C and the reaction is kept warm for 8 minutes. After the reaction is completed, stirring is stopped to obtain a reaction solution, and the solution is separated to separate 55g of water from the reaction solution;

[0048] S3: Secondary feeding reaction: After the separation is completed, 25.5 g of 70 wt% sulfuric acid aqueous solution is added dropwise again. The temperature of the entire addition process needs to be controlled at 47±5°C, and the reaction is kept warm for 55 minutes. After the reaction time is reached, 80 g of water is added to terminate the reaction;

[0049] S4: Post-treatment alkali washing: The reaction liquid after the termination of the reaction is separated, the lower layer of waste acid is separated, and the upper layer of organic liquid is left; 25g of 55℃ hot water and 47g of 30wt% sodium hydroxide aqueous solution are added to the organic liquid, and then 1g of isononanoic acid is added and stirred for 15 minutes. After the time is up, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste alkali liquid is separated, leaving the upper layer of organic liquid. After the first alkali washing is completed, the alkali washing is repeated again. After the second alkali washing is completed, 60g of 55℃ hot water is added to the organic liquid for 15 minutes of insulation and stirring. After the stirring time is reached, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste water is separated, leaving the upper layer of organic liquid. After the separation is completed, 110g of 55℃ hot water is added and the water washing is repeated. After the second water washing is completed, the remaining organic liquid is subjected to reduced pressure distillation, the pressure is -0.090MPa, the heating temperature is 60℃, and the time is 30min. The finished product is obtained after reduced pressure distillation.

[0050] Example 3

[0051] S1: Adding raw materials: Add 163g of tert-butyl hydroperoxide to the reaction bottle, start stirring at 300rpm, then add 118g of di-(2-hydroxyisopropyl)benzene and 9.5g of sodium perchlorate in sequence, heat to 42°C, and after the temperature stabilizes, add 32g of 70wt% sulfuric acid aqueous solution dropwise;

[0052] S2: Condensation reaction: After the sulfuric acid aqueous solution is added dropwise, the reaction temperature is raised to 53°C and the reaction is kept warm for 12 minutes. After the reaction is completed, stirring is stopped to obtain a reaction solution, and the solution is separated to separate 57g of water from the reaction solution;

[0053] S3: Secondary feeding reaction: After the separation is completed, 25.5 g of 70 wt% sulfuric acid aqueous solution is added dropwise again. The temperature of the entire addition process needs to be controlled at 47 ± 5 ° C. The temperature is kept for 50 minutes. After the reaction time is reached, 55 g of water is added to terminate the reaction;

[0054] S4: Post-treatment alkali washing: The reaction liquid after the termination of the reaction is separated, the lower layer of waste acid is separated, and the upper layer of organic liquid is left; 25g of 55℃ hot water and 47g of 30wt% sodium hydroxide aqueous solution are added to the organic liquid, and then 0.5g of isononanoic acid is added and stirred for 10 minutes. After the time is up, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste alkali liquid is separated, leaving the upper layer of organic liquid. After the first alkali washing is completed, the alkali washing is repeated again. After the second alkali washing is completed, 70g of 55℃ hot water is added to the organic liquid and stirred for 20 minutes. After the stirring time is reached, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste water is separated, leaving the upper layer of organic liquid. After the separation is completed, 120g of 55℃ hot water is added and the water washing is repeated. After the second water washing is completed, the remaining organic liquid is subjected to reduced pressure distillation, the pressure is -0.090MPa, the heating temperature is 60℃, and the time is 30min. The finished product is obtained after reduced pressure distillation.

[0055] Comparative Example 1

[0056] S1: Adding raw materials: Add 159g of tert-butyl hydroperoxide to the reaction bottle, start stirring at 300rpm, then add 118g of di-(2-hydroxyisopropyl)benzene and 9.2g of sodium perchlorate in sequence, heat to 42°C, and after the temperature stabilizes, add 32g of 70wt% sulfuric acid aqueous solution dropwise;

[0057] S2: Condensation reaction: After the sulfuric acid aqueous solution is added dropwise, the reaction temperature is raised to 53°C and the reaction is kept warm for 30 minutes. After the reaction is completed, stirring is stopped to obtain a reaction solution, and the solution is separated to separate 55-60g of water from the reaction solution;

[0058] S3: Secondary feeding reaction: After the separation is completed, 25.5 g of 70 wt% sulfuric acid aqueous solution is added dropwise again. The temperature of the entire addition process needs to be controlled at 47 ± 5 ° C. The temperature is kept for 30 minutes. After the reaction time is reached, 55 g of water is added to terminate the reaction;

[0059] S4: Post-treatment alkali washing: The reaction liquid after the termination of the reaction is separated, the lower layer of waste acid is separated, and the upper layer of organic liquid is left; 25g of 55℃ hot water and 47g of 30wt% sodium hydroxide aqueous solution are added to the organic liquid, and then 0.5g of isononanoic acid is added and stirred for 10 minutes. After the time is up, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste alkali liquid is separated, leaving the upper layer of organic liquid. After the first alkali washing is completed, the alkali washing is repeated again. After the second alkali washing is completed, 50g of 55℃ hot water is added to the organic liquid and stirred for 10 minutes. After the stirring time is reached, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste water is separated, leaving the upper layer of organic liquid. After the separation is completed, 100g of 55℃ hot water is added and the water washing is repeated. After the second water washing is completed, the organic liquid left is subjected to reduced pressure distillation, the pressure is -0.090MPa, the heating temperature is 60℃, and the time is 30min. The finished product is obtained after reduced pressure distillation.

[0060] Comparative Example 2

[0061] S1: Adding raw materials: Add 159g of tert-butyl hydroperoxide to the reaction bottle, start stirring at 300rpm, then add 118g of di-(2-hydroxyisopropyl)benzene and 7.2g of sodium perchlorate in sequence, heat to 42°C, and after the temperature stabilizes, add 32g of 70wt% sulfuric acid aqueous solution dropwise;

[0062] S2: Condensation reaction: After the sulfuric acid aqueous solution is added dropwise, the reaction temperature is raised to 53°C and the reaction is kept warm for 10 minutes. After the reaction is completed, stirring is stopped to obtain a reaction solution, and the solution is separated to separate 55-60g of water from the reaction solution;

[0063] S3: Secondary feeding reaction: After the separation is completed, 25.5 g of 70 wt% sulfuric acid aqueous solution is added dropwise again. The temperature of the entire addition process needs to be controlled at 47 ± 5 ° C. The temperature is kept for 50 minutes. After the reaction time is reached, 55 g of water is added to terminate the reaction;

[0064] S4: Post-treatment alkali washing: The reaction liquid after the termination of the reaction is separated, the lower layer of waste acid is separated, and the upper layer of organic liquid is left; 25g of 55℃ hot water and 47g of 30wt% sodium hydroxide aqueous solution are added to the organic liquid, and then 0.5g of isononanoic acid is added and stirred for 10 minutes. After the time is up, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste alkali liquid is separated, leaving the upper layer of organic liquid. After the first alkali washing is completed, the alkali washing is repeated again. After the second alkali washing is completed, 50g of 55℃ hot water is added to the organic liquid and stirred for 10 minutes. After the stirring time is reached, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste water is separated, leaving the upper layer of organic liquid. After the separation is completed, 100g of 55℃ hot water is added and the water washing is repeated. After the second water washing is completed, the organic liquid left is subjected to reduced pressure distillation, the pressure is -0.090MPa, the heating temperature is 60℃, and the time is 30min. The finished product is obtained after reduced pressure distillation.

[0065] Comparative Example 3

[0066] S1: Adding raw materials: Add 159 g of tert-butyl hydroperoxide to the reaction bottle, start stirring at 300 rpm, then add 118 g of di-(2-hydroxyisopropyl)benzene and 9.2 g of sodium perchlorate, heat to 42° C., and after the temperature stabilizes, add 57.5 g of 70 wt % sulfuric acid aqueous solution dropwise;

[0067] S2: Condensation reaction: After the addition of the sulfuric acid aqueous solution is complete, the reaction temperature is raised to 53°C and the reaction is kept at this temperature for 60 minutes. After the reaction is complete, stirring is stopped and 55 g of water is added to terminate the reaction;

[0068] S3: Post-treatment alkali washing: The reaction liquid after the termination of the reaction is separated, the lower layer of waste acid is separated, and the upper layer of organic liquid is left; 25g of 55℃ hot water and 47g of 30wt% sodium hydroxide aqueous solution are added to the organic liquid, and then 0.5g of isononanoic acid is added and stirred for 10 minutes. After the time is up, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste alkali liquid is separated, leaving the upper layer of organic liquid. After the first alkali washing is completed, the alkali washing is repeated again. After the second alkali washing is completed, 50g of 55℃ hot water is added to the organic liquid and stirred for 10 minutes. After the stirring time is reached, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste water is separated, leaving the upper layer of organic liquid. After the separation is completed, 100g of 55℃ hot water is added and the water washing is repeated. After the second water washing is completed, the remaining organic liquid is subjected to reduced pressure distillation, the pressure is -0.090MPa, the heating temperature is 60℃, and the time is 30min. The finished product is obtained after reduced pressure distillation.

[0069] Comparative Example 4

[0070] S1: Adding raw materials: Add 151g of tert-butyl hydroperoxide to the reaction bottle, start stirring at 300rpm, then add 118g of di-(2-hydroxyisopropyl)benzene and 9.2g of sodium perchlorate in sequence, heat to 42°C, and after the temperature stabilizes, add 32g of 70wt% sulfuric acid aqueous solution dropwise;

[0071] S2: Condensation reaction: After the sulfuric acid aqueous solution is added dropwise, the reaction temperature is raised to 53°C and kept warm for 20 minutes. After the reaction is completed, stirring is stopped and the liquid is separated;

[0072] S3: Secondary feeding reaction: After the separation is completed, 25.5 g of 70 wt% sulfuric acid aqueous solution is added dropwise again. The temperature of the entire addition process needs to be controlled at 47 ± 5 ° C. The temperature is kept for 50 minutes. After the reaction time is reached, 55 g of water is added to terminate the reaction;

[0073] S4: Post-treatment alkali washing: The reaction liquid after the termination of the reaction is separated, the lower layer of waste acid is separated, and the upper layer of organic liquid is left; 25g of 55℃ hot water and 47g of 30wt% sodium hydroxide aqueous solution are added to the organic liquid, and then 0.5g of isononanoic acid is added and stirred for 10 minutes. After the time is up, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste alkali liquid is separated, leaving the upper layer of organic liquid. After the first alkali washing is completed, the alkali washing is repeated again. After the second alkali washing is completed, 50g of 55℃ hot water is added to the organic liquid and stirred for 10 minutes. After the stirring time is reached, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste water is separated, leaving the upper layer of organic liquid. After the separation is completed, 100g of 55℃ hot water is added and the water washing is repeated. After the second water washing is completed, the organic liquid left is subjected to reduced pressure distillation, the pressure is -0.090MPa, the heating temperature is 60℃, and the time is 30min. The finished product is obtained after reduced pressure distillation.

[0074] Comparative Example 5

[0075] S1: Adding raw materials: Add 159g of tert-butyl hydroperoxide to the reaction bottle, start stirring at 300rpm, then add 118g of di-(2-hydroxyisopropyl)benzene and 9.2g of sodium perchlorate, heat to 42°C, and after the temperature stabilizes, add 25g of 70wt% sulfuric acid aqueous solution dropwise;

[0076] S2: Condensation reaction: After the sulfuric acid aqueous solution is added dropwise, the reaction temperature is raised to 53°C and the reaction is kept warm for 10 minutes. After the reaction is completed, stirring is stopped to obtain a reaction solution, and the solution is separated to separate 55-60g of water from the reaction solution;

[0077] S3: Secondary feeding reaction: After the separation is completed, 20 g of 70 wt% sulfuric acid aqueous solution is added dropwise again. The temperature of the entire addition process needs to be controlled at 47 ± 5 ° C. The temperature is kept for 50 minutes. After the reaction time is reached, 55 g of water is added to terminate the reaction;

[0078] S4: Post-treatment alkali washing: The reaction liquid after the termination of the reaction is separated, the lower layer of waste acid is separated, and the upper layer of organic liquid is left; 25g of 55℃ hot water and 47g of 30wt% sodium hydroxide aqueous solution are added to the organic liquid, and then 0.5g of isononanoic acid is added and stirred for 10 minutes. After the time is up, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste alkali liquid is separated, leaving the upper layer of organic liquid. After the first alkali washing is completed, the alkali washing is repeated again. After the second alkali washing is completed, 50g of 55℃ hot water is added to the organic liquid and stirred for 10 minutes. After the stirring time is reached, the stirring is stopped and the liquid is allowed to stand for separation, and the lower layer of waste water is separated, leaving the upper layer of organic liquid. After the separation is completed, 100g of 55℃ hot water is added and the water washing is repeated. After the second water washing is completed, the organic liquid left is subjected to reduced pressure distillation, the pressure is -0.090MPa, the heating temperature is 60℃, and the time is 30min. The finished product is obtained after reduced pressure distillation.

[0079] Performance Testing

[0080] The finished products obtained in Examples 1 to 3 and Comparative Examples 1 to 5 were weighed, and the yields were calculated and recorded in Table 1;

[0081] The finished products obtained in Examples 1 to 3 and Comparative Examples 1 to 5 were analyzed by liquid chromatography, and the values ​​of the monoperoxide amount and whiteness were recorded and entered into Table 1.

[0082] Table 1

[0083] Yield % Peroxide content % Whiteness Example 1 96.45 0.74 94.8 Example 2 96.11 1.68 90.3 Example 3 96.48 1.47 92.1 Comparative Example 1 91.37 1.27 88.1 Comparative Example 2 95.40 2.15 89.1 Comparative Example 3 92.36 1.54 89.8 Comparative Example 4 90.77 2.23 90.0 Comparative Example 5 93.20. 2.99 91.9

Claims

1. A solvent-free condensation preparation method of BIPB, characterized in that: The following steps are involved: S1: Adding raw materials: Add tert-butyl hydroperoxide to the reaction bottle, start stirring, then add di-(2-hydroxyisopropyl)benzene and perchlorate in sequence, heat to the set temperature, and add sulfuric acid dropwise after the temperature stabilizes; S2: Condensation reaction: After the sulfuric acid is added dropwise, the reaction temperature is raised to 50-60°C and kept warm for 8-12 minutes. After the reaction is completed, stirring is stopped to obtain the reaction solution, and the solution is separated; S3: Secondary feeding reaction: After the separation is completed, sulfuric acid is added dropwise again. After the addition is completed, the temperature of the entire addition process needs to be controlled at 40-60°C, and the temperature is kept for 45-55 minutes. After the reaction time is reached, water is added to terminate the reaction; S4: Post-treatment alkali washing: the reaction liquid after the reaction is separated, leaving the upper organic liquid; a second alkali washing is performed, and then a second water washing is performed, and a finished product is obtained after reduced pressure distillation; The molar ratio of tert-butyl hydroperoxide to di-(2-hydroxyisopropyl)benzene in S1 is 2.90-3.5:1; The molar ratio of di-(2-hydroxyisopropyl)benzene to perchlorate in S1 is 1:0.12-0.16; The mass ratio of sulfuric acid to di-(2-hydroxyisopropyl)benzene in S2 is 1:3.5-3.9; the mass ratio of sulfuric acid to di-(2-hydroxyisopropyl)benzene in S3 is 1:3.9-5.

7.

2. The solvent-free condensation preparation method of BIPB according to claim 1, characterized in that: The set temperature in S1 is 40-50°C.

3. The solvent-free condensation preparation method of BIPB according to claim 1, characterized in that: The reaction temperature in S2 and S3 is 53-56°C.

4. The solvent-free condensation preparation method of BIPB according to claim 1, characterized in that: The specific process of liquid separation in S2 is to separate 55-60 g of water from the reaction liquid.

5. The solvent-free condensation preparation method of BIPB according to claim 1, characterized in that: The specific process of alkali washing in S4 is: add 25-50g hot water at 55-65°C and 47-60g sodium hydroxide to the organic liquid, then add 0.5-1g isononanoic acid and stir to keep warm for 10-20min. After the insulation is completed, stop stirring and let the liquid stand to separate the lower alkali liquid and leave the upper organic liquid.

6. The solvent-free condensation preparation method of BIPB according to claim 1, characterized in that: The specific process of water washing in S4 is: adding hot water at 55-65° C. to the organic liquid, and stirring at this temperature for 10-20 minutes.