Synthesis method of high-purity 1, 3-bis (tert-butyldiisopropyl peroxide) benzene
By using supercritical CO2 and MFI-type zeolite molecular sieve in the synthesis of 1,3-bis(tert-butyldiisopropyl peroxide)benzene, the problem of low BIPB purity in the traditional method is solved, and the synthesis of high purity and high yield is achieved, reducing production costs and environmental pollution.
Patent Information
- Application Number
- CN202510141821.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-08
- Publication Date
- 2025-05-13
AI Technical Summary
In the traditional 1,3-bis(tert-butyldiisopropyl peroxide)benzene (BIPB) synthesis method, the purity is low, the side reaction is many, the production cost is high, the environmental pollution and safety risks are large, making it difficult to meet the demand of modern chemicals for high-quality chemicals.
Supercritical CO2 is used as solvent and MFI zeolite molecular sieve as catalyst. By dissolving AATD at 55°C and reacting with TBHB in a reactor, the dissolution and separation characteristics of supercritical CO2 are used to achieve high purity synthesis of BIPB.
It improves the purity and yield of BIPB, reduces production costs and environmental pollution, simplifies the process flow, reduces by-products, and realizes an efficient, low-consumption, green and environmentally friendly synthesis method.
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of 1,3-bis(tert-butyl peroxide diisopropyl)benzene preparation, and in particular to a method for synthesizing high-purity 1,3-bis(tert-butyl peroxide diisopropyl)benzene. Background Art
[0002] In the field of organic chemistry and materials science, 1,3-bis(tert-butylperoxydiisopropyl)benzene (BIPB) has broad application prospects as an important organic synthetic material and crosslinking agent. BIPB is mainly used for crosslinking of rubber, plastics and other polymer materials to improve the strength, heat resistance and chemical corrosion resistance of the materials. With the increasing demand for high-quality chemicals in the global chemical industry, it is particularly important to develop efficient, low-cost and high-purity BIPB synthesis methods.
[0003] Traditional BIPB synthesis methods usually involve complex reaction steps and high reaction conditions, such as high temperature, high pressure and the use of strong acids and bases, which not only increase production costs, but also may cause environmental pollution and safety hazards. In addition, there are many side reactions in traditional methods, resulting in low product yields and low purity, which makes it difficult to meet the demand for high-quality chemicals in modern chemical production. Summary of the invention
[0004] The invention provides a method for synthesizing high-purity 1,3-bis(tert-butylperoxide diisopropyl)benzene, which solves the problem of low purity of 1,3-bis(tert-butylperoxide diisopropyl)benzene in the related art.
[0005] The technical solution of the present invention is as follows:
[0006] The present invention provides a method for synthesizing high-purity 1,3-bis(tert-butylperoxide diisopropyl)benzene, comprising the following synthesis steps:
[0007] S1. A,A'-dihydroxy-1,3-diisopropylbenzene (hereinafter referred to as AATD) was dissolved in ethanol, stirred evenly at 55°C, allowed to stand until no precipitation was generated, and then filtered. The filter material was repeatedly washed with clean water to obtain purified AATD.
[0008] Preferably, the mass fraction of the ethanol is 75%-85%, more preferably 80%.
[0009] Preferably, the usage ratio of AATD to ethanol is 1 g:5 mL.
[0010] In the present invention, impurities are removed from AATD after being treated with ethanol, so that AATD can be purified and its purity is improved, which is beneficial for AATD to participate in the synthesis reaction as a reactant.
[0011] S2. Add MFI zeolite molecular sieve into the reactor, then introduce supercritical CO2, and stir and disperse at the same time to obtain a catalyst solution.
[0012] Preferably, the MFI type zeolite molecular sieve is Silicalite-1 or ZSM-5.
[0013] Preferably, the method of introducing supercritical CO2 is: introducing supercritical CO2 into the reactor at a rate of 3-5 mL / min, while setting the temperature in the reactor to 35-45°C, the pressure to 12-20 MPa, and the amount of supercritical CO2 introduced is the ratio of the amount of MFI zeolite molecular sieve to (400-500) mL:1 g;
[0014] More preferably, the method of introducing supercritical CO2 is: introducing supercritical CO2 into the reactor at a rate of 4 mL / min, while setting the temperature in the reactor to 40°C, the pressure to 15 MPa, and the amount of supercritical CO2 introduced is 450 mL:1 g of the MFI zeolite molecular sieve.
[0015] In the present invention, MFI type zeolite molecular sieve is selected as the catalyst and supercritical CO2 is selected as the solvent. The MFI type zeolite molecular sieve is insoluble in supercritical CO2, but can be evenly dispersed in supercritical CO2 under stirring. When stirring is stopped, it can be precipitated in supercritical CO2, thus facilitating solid-liquid separation.
[0016] S3. Evenly mix the purified AATD and tert-butyl hydroperoxide (hereinafter collectively referred to as TBHB) solution, then put it into the catalyst solution and stir to react. Stop stirring after the reaction changes color, let it stand until no precipitation is produced, drain the upper liquid into a collection device, and reduce the temperature and pressure to release CO2.
[0017] Preferably, the molar mass ratio of the purified AATD to tert-butyl hydroperoxide in the TBHB solution is 1:2, and the mass fraction of tert-butyl hydroperoxide in the TBHB solution is 85%.
[0018] Preferably, the mass ratio of the MFI zeolite molecular sieve to the purified AATD is 1:(35-45); more preferably 1:40.
[0019] Preferably, the initial temperature and pressure conditions in the collection device are the same as those in the reactor, and are reduced to room temperature and pressure when the temperature and pressure are reduced to release CO2.
[0020] In the present invention, purified AATD undergoes a condensation reaction with a TBHB solution, during which water is generated. The MFI zeolite molecular sieve is insoluble in water, and thus the catalytic effect on the condensation reaction is not reduced, thereby avoiding the occurrence of a situation in which the reaction rate is reduced, and allowing the reaction to reach the end point faster. After the reaction is completed, a crude 1,3-bis(tert-butyl peroxide diisopropyl)benzene material dissolved in supercritical CO2 is generated. By stopping stirring, the MFI zeolite molecular sieve can form a precipitate. The supercritical CO2 and the crude 1,3-bis(tert-butyl peroxide diisopropyl)benzene material therein are separated by drainage, thereby achieving complete separation of the catalyst and improving the purity of the 1,3-bis(tert-butyl peroxide diisopropyl)benzene.
[0021] In the present invention, after the upper liquid, i.e., supercritical CO2 and the 1,3-bis(tert-butyl peroxide diisopropyl)benzene crude material therein enter the collecting device, the supercritical CO2 is converted into gaseous CO2 by cooling and reducing the pressure and then released, thereby realizing the separation of 1,3-bis(tert-butyl peroxide diisopropyl)benzene and the solvent. The release rate of the supercritical CO2 converted into gaseous CO2 is high, and a release rate of nearly 100% can be achieved, so that the removal rate of the solvent in 1,3-bis(tert-butyl peroxide diisopropyl)benzene reaches an extremely high level, thereby greatly improving its purity.
[0022] S4. Continue to introduce supercritical CO2 into the reactor while stirring. After stirring, let it stand until no precipitation is produced. Drain the upper liquid into a collection device, and reduce the temperature and pressure to release CO2. Repeat this step 3-5 times.
[0023] Preferably, in step S4, the amount of supercritical CO2 introduced into the reactor each time is the same as the amount of supercritical CO2 introduced in step S2.
[0024] In the present invention, when drainage separation is performed in step S3, a small amount of supercritical CO2 and 1,3-bis(tert-butyl peroxide diisopropyl)benzene therein will remain in the reactor. By repeating the steps in S4, the residual 1,3-bis(tert-butyl peroxide diisopropyl)benzene can be separated and collected, thereby improving the yield of 1,3-bis(tert-butyl peroxide diisopropyl)benzene.
[0025] S5, taking out the product in the collecting device, washing it with hot water, and distilling it to remove water, and finally obtaining 1,3-bis(tert-butylperoxide diisopropyl)benzene;
[0026] Preferably, the temperature of the hot water is 60-80°C, more preferably 70°C.
[0027] Preferably, the obtained 1,3-bis(tert-butylperoxide diisopropyl)benzene is ground into powder and sealed and stored in a cool and dry environment.
[0028] The working principle and beneficial effects of the present invention are:
[0029] 1. In the synthesis method of high-purity 1,3-bis(tert-butylperoxide diisopropyl)benzene of the present invention, supercritical CO2 is selected as the solvent, which not only has good solubility and can promote the synthesis reaction, but also is easy to remove from the product, and CO2 can be recycled without causing pollution to the environment, and has lower cost and is more environmentally friendly.
[0030] 2. In the synthesis method of high-purity 1,3-bis(tert-butylperoxide diisopropyl)benzene of the present invention, MFI type zeolite molecular sieve is selected as the catalyst, which is insoluble in water and supercritical CO2, but can be evenly dispersed in supercritical CO2, so it can play a good catalytic role. At the same time, the water produced during the synthesis reaction will not dissolve the MFI type zeolite molecular sieve, thereby avoiding the phenomenon that the reaction rate decreases due to the decrease in the amount of catalyst, and can promote the reaction to be completed faster; after the reaction is completed, the MFI type zeolite molecular sieve can also be quickly and thoroughly separated from the supercritical CO2, thereby achieving efficient elimination of the catalyst in the product, which is beneficial to improving the purity and yield of the product.
[0031] 3. In the synthesis method of high-purity 1,3-bis(tert-butylperoxide diisopropyl)benzene of the present invention, the whole process is simple and efficient, and no other chemical reagents are required to be put into use or removed in the later stage, which can greatly reduce the raw material cost and the later removal cost. There are very few by-products, which is conducive to improving the purity of the product.
[0032] 4. In the method for synthesizing high-purity 1,3-bis(tert-butylperoxide-diisopropyl)benzene of the present invention, during the process of removing the solvent supercritical CO2, CO2 floats out in the form of gas, which can carry away some impurities in the product 1,3-bis(tert-butylperoxide-diisopropyl)benzene, further improving the purity of the product. DETAILED DESCRIPTION
[0033] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0034] The experimental methods in the following examples, unless otherwise specified, are all conventional methods, and are performed according to the techniques or conditions described in the literature in the field or according to the product instructions. The materials, reagents, etc. used in the following examples, unless otherwise specified, can all be obtained from commercial channels.
[0035] Example 1
[0036] Step 1: Dissolve 1100 g of AATD in 5000 mL of 80% ethanol, stir at 55° C. for 2 h, let stand until no precipitation is produced, filter, and wash the filter material repeatedly with clean water for 3 times to obtain purified AATD.
[0037] Step 2: Add 25 g of ZSM-5 into the reactor, set the temperature in the reactor to 40°C and the pressure to 15 MPa, then introduce 11.25 L of supercritical CO2 into the reactor at a rate of 4 mL / min, stir for 30 min to disperse, and obtain a catalyst solution.
[0038] Step 3: Evenly mix 9700 g (5 mol) of purified AATD and 85% tert-butyl hydroperoxide solution (TBHB content: 10 mol), and then add the mixture into the catalyst solution in step 2 and stir to react. Stop stirring after the reaction changes color, let stand until no precipitation is produced, drain the upper liquid into a collection kettle at a temperature of 40° C. and a pressure of 15 MPa, and then cool and reduce the pressure in the collection kettle to room temperature to release CO2.
[0039] Step 4: Continue to introduce supercritical CO2 into the reactor in step 2, stir for 30 minutes, and then let it stand until no precipitation is produced. Reset the temperature of the collection kettle in step 3 to 40°C and the pressure to 15 MPa, then drain the upper liquid into the collection kettle, and cool and reduce the pressure to room temperature to release CO2. Repeat this step 4 times to obtain 1,3-bis(tert-butylperoxide diisopropyl)benzene crude material in the collection kettle.
[0040] Step 5: Take out the crude 1,3-bis(tert-butylperoxide diisopropyl)benzene from the collecting device, wash it with hot water, and distill to remove water, so as to finally obtain 1,3-bis(tert-butylperoxide diisopropyl)benzene.
[0041] Example 2
[0042] Step 1: Dissolve 1100 g of AATD in 5000 mL of 75% ethanol, stir at 55° C. for 2 h, let stand until no precipitation is produced, filter, and wash the filter material repeatedly with clean water for 3 times to obtain purified AATD.
[0043] Step 2: Add 25 g of ZSM-5 into the reactor, set the temperature in the reactor to 35°C and the pressure to 12 MPa, then introduce 11.25 L of supercritical CO2 into the reactor at a rate of 3 mL / min, stir for 30 min to disperse, and obtain a catalyst solution.
[0044] Step 3: Evenly mix 9700 g (5 mol) of purified AATD and 85% tert-butyl hydroperoxide solution (TBHB content: 10 mol), and then add the mixture into the catalyst solution in step 2 and stir to react. Stop stirring after the reaction changes color, let stand until no precipitation is produced, drain the upper liquid into a collection kettle at a temperature of 40° C. and a pressure of 15 MPa, and then cool and reduce the pressure in the collection kettle to room temperature to release CO2.
[0045] Step 4: Continue to introduce supercritical CO2 into the reactor in step 2, stir for 30 minutes, and then let it stand until no precipitation is produced. Reset the temperature of the collection kettle in step 3 to 35°C and the pressure to 12 MPa, then drain the upper liquid into the collection kettle, and cool and reduce the pressure to room temperature to release CO2. Repeat this step 4 times to obtain 1,3-bis(tert-butylperoxide diisopropyl)benzene crude material in the collection kettle.
[0046] Step 5: Take out the crude 1,3-bis(tert-butylperoxide diisopropyl)benzene from the collecting device, wash it with hot water, and distill to remove water, so as to finally obtain 1,3-bis(tert-butylperoxide diisopropyl)benzene.
[0047] Example 3
[0048] Step 1: Dissolve 1100 g of AATD in 5000 mL of 85% ethanol, stir at 55° C. for 2 h, let stand until no precipitation is produced, filter, and wash the filter material repeatedly with clean water for 3 times to obtain purified AATD.
[0049] Step 2: Add 25 g of ZSM-5 into the reactor, set the temperature in the reactor to 45°C and the pressure to 20 MPa, then introduce 11.25 L of supercritical CO2 into the reactor at a rate of 5 mL / min, stir for 30 min to disperse, and obtain a catalyst solution.
[0050] Step 3: Evenly mix 9700 g (5 mol) of purified AATD and 85% tert-butyl hydroperoxide solution (TBHB content: 10 mol), and then add the mixture into the catalyst solution in step 2 and stir to react. Stop stirring after the reaction changes color, let stand until no precipitation is produced, drain the upper liquid into a collection kettle at a temperature of 40° C. and a pressure of 15 MPa, and then cool and reduce the pressure in the collection kettle to room temperature to release CO2.
[0051] Step 4: Continue to introduce supercritical CO2 into the reactor in step 2, stir for 30 minutes, and then let it stand until no precipitation is produced. Reset the temperature of the collection kettle in step 3 to 45°C and the pressure to 20 MPa, then drain the upper liquid into the collection kettle, and cool and reduce the pressure to room temperature to release CO2. Repeat this step 4 times to obtain 1,3-bis(tert-butylperoxide diisopropyl)benzene crude material in the collection kettle.
[0052] Step 5: Take out the crude 1,3-bis(tert-butylperoxide diisopropyl)benzene from the collecting device, wash it with hot water, and distill to remove water, so as to finally obtain 1,3-bis(tert-butylperoxide diisopropyl)benzene.
[0053] Example 4
[0054] Step 1: Dissolve 1100 g of AATD in 5000 mL of 80% ethanol, stir at 55° C. for 2 h, let stand until no precipitation is produced, filter, and wash the filter material repeatedly with clean water for 3 times to obtain purified AATD.
[0055] Step 2: Add 25 g of Silicalite-1 into the reactor, set the temperature in the reactor to 40°C and the pressure to 15 MPa, then introduce 11.25 L of supercritical CO2 into the reactor at a rate of 4 mL / min, stir for 30 min to disperse, and obtain a catalyst solution.
[0056] Step 3: Evenly mix 9700 g (5 mol) of purified AATD and 85% tert-butyl hydroperoxide solution (TBHB content: 10 mol), and then add the mixture into the catalyst solution in step 2 and stir to react. Stop stirring after the reaction changes color, let stand until no precipitation is produced, drain the upper liquid into a collection kettle at a temperature of 40° C. and a pressure of 15 MPa, and then cool and reduce the pressure in the collection kettle to room temperature to release CO2.
[0057] Step 4: Continue to introduce supercritical CO2 into the reactor in step 2, stir for 30 minutes, and then let it stand until no precipitation is produced. Reset the temperature of the collection kettle in step 3 to 40°C and the pressure to 15 MPa, then drain the upper liquid into the collection kettle, and cool and reduce the pressure to room temperature to release CO2. Repeat this step 4 times to obtain 1,3-bis(tert-butylperoxide diisopropyl)benzene crude material in the collection kettle.
[0058] Step 5: Take out the crude 1,3-bis(tert-butylperoxide diisopropyl)benzene from the collecting device, wash it with hot water, and distill to remove water, so as to finally obtain 1,3-bis(tert-butylperoxide diisopropyl)benzene.
[0059] The purity and yield of 1,3-bis(tert-butylperoxide diisopropyl)benzene obtained in Examples 1-4 were tested, and the test results are listed in Table 1, which is as follows:
[0060] Table 1
[0061] Purity (100%) Yield (100%) Example 1 99.99 99.98 Example 2 99.99 99.78 Example 3 99.99 99.89 Example 4 99.99 99.86
[0062] By analyzing the data in Table 1, it can be learned that the purity of 1,3-bis(tert-butylperoxydiisopropyl)benzene synthesized in Examples 1-4 all reached 99.99%, which is extremely high, and the yield was above 99.7%, which is extremely high, achieving a major breakthrough.
[0063] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.
Claims
1. A method for synthesizing high-purity 1,3-bis(tert-butylperoxide diisopropyl)benzene, characterized in that: The method comprises the following synthesis steps: S1. Dissolve A,A'-dihydroxy-1,3-diisopropylbenzene in ethanol, stir evenly at 55°C, let stand until no precipitation is generated, filter, and repeatedly wash the filter material with clean water to obtain purified AATD; S2, adding MF I type zeolite molecular sieve into the reactor, and then introducing supercritical CO2, while stirring and dispersing, to obtain a catalyst solution; S3, evenly mix the purified AATD and tert-butyl hydroperoxide solution, then add them into the catalyst solution and stir to react, stop stirring after the reaction changes color, let it stand until no precipitation is produced, drain the upper layer of liquid into a collection device, and reduce the temperature and pressure to release CO2; S4, continue to introduce supercritical CO2 into the reactor while stirring, let it stand until no precipitation is produced after stirring, drain the upper liquid into a collection device, and reduce the temperature and pressure to release CO2; repeat this step 3-5 times; S5. The product in the collecting device is taken out, washed with hot water, and water is removed by distillation to finally obtain 1,3-bis(tert-butylperoxide diisopropyl)benzene.
2. The method for synthesizing high-purity 1,3-bis(tert-butylperoxide diisopropyl)benzene according to claim 1, characterized in that: In step S1, the mass fraction of the ethanol is 75%-85%, and the usage ratio of the A,A'-dihydroxy-1,3-diisopropylbenzene to the ethanol is 1 g:5 mL.
3. The method for synthesizing high-purity 1,3-bis(tert-butylperoxide diisopropyl)benzene according to claim 1, characterized in that: In step S2, the MFI type zeolite molecular sieve is Silicali te-1 or ZSM-5.
4. The method for synthesizing high-purity 1,3-bis(tert-butylperoxide diisopropyl)benzene according to claim 1, characterized in that: In step S2, the method of introducing supercritical CO2 is: introducing supercritical CO2 into the reactor at a rate of 3-5 mL / min, while setting the temperature in the reactor to 35-45°C, the pressure to 12-20 MPa, and the amount of supercritical CO2 introduced is the ratio of the amount of MFI zeolite molecular sieve used to (400-500) mL:1 g.
5. The method for synthesizing high-purity 1,3-bis(tert-butylperoxide diisopropyl)benzene according to claim 1, characterized in that: In step S3, the molar mass ratio of the purified AATD to tert-butyl hydroperoxide in the tert-butyl hydroperoxide solution is 1:2, and the mass fraction of tert-butyl hydroperoxide in the tert-butyl hydroperoxide solution is 85%.
6. The method for synthesizing high-purity 1,3-bis(tert-butylperoxide diisopropyl)benzene according to claim 1, characterized in that: In steps S2-S3, the mass ratio of the MF I type zeolite molecular sieve to the purified AATD is 1:(35-45).
7. The method for synthesizing high-purity 1,3-bis(tert-butylperoxide diisopropyl)benzene according to claim 1, characterized in that: In step S3, the initial temperature and pressure conditions in the collection device are the same as those in the reactor, and the temperature and pressure are reduced to room temperature and pressure when CO2 is released.
8. The method for synthesizing high-purity 1,3-bis(tert-butylperoxide diisopropyl)benzene according to claim 1, characterized in that: In step S4, the amount of supercritical CO2 introduced into the reactor each time is the same as the amount of supercritical CO2 introduced in step S2.
9. The method for synthesizing high-purity 1,3-bis(tert-butylperoxide diisopropyl)benzene according to claim 1, characterized in that: In step S5, the temperature of the hot water is 60-80°C.
10. The method for synthesizing high-purity 1,3-bis(tert-butylperoxide diisopropyl)benzene according to claim 1, characterized in that: In step S5, the obtained 1,3-bis(tert-butylperoxydiisopropyl)benzene is ground into powder and sealed and stored in a cool and dry environment.