Method for preparing odorless cross-linking agent BIPB through condensation reaction
Through the modified Fe3O4 microbead catalyzed condensation reaction method, the existing BIPB synthesis methods are solved, and the efficient, environmentally friendly and sustainable preparation of BIPB is achieved.
Patent Information
- Application Number
- CN202411776474.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-05
- Publication Date
- 2025-03-11
AI Technical Summary
The existing BIPB crosslinking agent synthesis methods have complex steps, high raw material costs, environmental pollution and human health hazards, making it difficult to achieve large-scale safe production.
The odorless crosslinker BIPB was prepared by modifying Fe3O4 microbeads as catalysts, combining tert-butyl hydrogen peroxide and α,α′-dihydroxy-1,3-diisopropylbenzene.
The catalytic capacity and stability of the catalyst are improved, the high content and high purity preparation of BIPB are achieved, the production cost is reduced, the environmental pollution is reduced, and the catalyst is easy to be separated and recovered.
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing an odorless crosslinking agent BIPB through a condensation reaction. Background Art
[0002] Di-tert-butyl peroxide isopropylbenzene (BIPB) is an upgraded product of diisopropylbenzene peroxide (DCP), commonly known as "odorless DCP". It is a dialkyl organic peroxide crosslinker second only to DCP in usage. It is a new type of peroxide product that was industrialized in foreign countries in the early 1960s. The BIPB molecule contains two peroxide bonds and is a diperoxide compound with a molecular formula of C 20 H 34 O4, molecular weight 338. Since the free radicals generated by the thermal decomposition of BIPB have high stability, BIPB can be used as a crosslinking agent for rubbers and plastics such as polyethylene, EPDM rubber, ethylene-vinyl acetate copolymer, silicone rubber, and nitrile rubber. Under the condition of the same crosslinking effect, the added amount is only 2 / 3 of DCP. At the same time, BIPB does not have the odor of DCP crosslinking either in the crosslinking process or in the finished product, and BIPB has high crosslinking efficiency, and the heat resistance, low-temperature flexibility and compressive deformation resistance of the finished product are good.
[0003] At present, there are four main methods for synthesizing the crosslinking agent BIPB: (1) Olefin synthesis method, but its raw material di-(isopropenyl)benzene monomer is easy to polymerize, which is troublesome in industrial production. (2) Dehydrohalogenation synthesis method, but its raw material synthesis method 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 and tert-butyl hydroperoxide (TBHP) are condensed to produce BIPB. The traditional condensation reaction synthesis method not only has a complex synthesis process, cumbersome steps, and high raw material cost, but also toluene is toxic and will cause harm to the environment and human health; sulfuric acid is highly corrosive to stainless steel equipment, and there are many by-products, which will produce a large amount of dark black and red waste sulfuric acid. The wastewater is difficult to treat, which is not conducive to the implementation of green environmental protection measures, and is not conducive to large-scale safe production. Summary of the invention
[0004] The object of the present invention is to provide a method for preparing an odorless crosslinking agent BIPB by condensation reaction, so as to solve one of the technical problems mentioned in the background technology.
[0005] The purpose of the present invention can be achieved through the following technical solutions:
[0006] A method for preparing an odorless crosslinking agent BIPB by condensation reaction comprises the following steps:
[0007] Step 1, adding tert-butyl hydroperoxide into a reactor, and adding a catalyst into the reactor at room temperature for dehydration reaction;
[0008] Step 2, adding α,α′-dihydroxy-1,3-diisopropylbenzene into a reaction kettle for condensation reaction to obtain a reaction material;
[0009] Step 3, washing the reaction material obtained in step 2, separating and filtering to obtain an organic phase solution;
[0010] Step 4, vacuum flash drying the organic phase solution obtained in step 3, cooling and solidifying at room temperature to obtain BIPB;
[0011] Wherein, the catalyst in step 1 is prepared by the following steps:
[0012] The modified Fe3O4 microbeads and concentrated sulfuric acid were added to deionized water, the solution was shaken until uniformly dispersed, and dried in a drying oven at 80°C. The dried solid matter was taken out and calcined under nitrogen protection, and then ground and sieved to obtain a catalyst.
[0013] As a further solution of the present invention, the usage ratio of the modified Fe3O4 microbeads, concentrated sulfuric acid and deionized water is: 1.0-1.2 g: 0.5-0.6 g: 50 mL.
[0014] As a further solution of the present invention, the roasting temperature is 280-310° C., and the roasting time is 3.5-5.5 hours.
[0015] As a further embodiment of the present invention, the modified Fe3O4 microspheres are prepared by the following steps:
[0016] Sucrose is added into deionized water and stirred until uniform. Fe3O4 microbeads are added and dispersed uniformly by ultrasonication. The temperature is then raised to 175-180°C for carbonization reaction for 6.0-6.5 hours. After naturally cooling to room temperature, an external magnetic field is used for separation and sedimentation, washing, and vacuum drying to obtain modified Fe3O4 microbeads.
[0017] As a further embodiment of the present invention, the usage ratio of sucrose, deionized water and Fe3O4 microbeads is 1.0-1.5 g:100 mL:6.0-7.5 g.
[0018] As a further solution of the present invention, the mass fraction of tert-butyl hydroperoxide in step 1 is 70% to 75%.
[0019] As a further embodiment of the present invention, the usage ratio of tert-butyl hydroperoxide, catalyst and α,α′-dihydroxy-1,3-diisopropylbenzene is 130-150 g: 60-85 g: 100-110 g.
[0020] As a further solution of the present invention, the reaction temperature in the condensation reaction in step 2 is 50-55°C, and the reaction time is 35-50 minutes. When the reaction time is short, the materials in the reaction system are not completely reacted, resulting in low reaction yield and purity; when the reaction time is too long, the synthesized BIPB is prone to thermal decomposition at high temperature to generate tert-butyl alcohol and by-products such as alcohols and ketones with higher boiling points, resulting in a decrease in product yield and purity, and the final BIPB product has a yellowish appearance and poor quality.
[0021] As a further solution of the present invention, the specific steps of washing in step 3 are: alkaline washing and water washing in sequence.
[0022] As a further solution of the present invention, the temperature of the vacuum flash drying in step 4 is 50 to 60° C., the pressure is -0.090 to -0.0095 MPa, and the flash time is 1 to 2 hours.
[0023] Beneficial effects of the present invention:
[0024] In the present invention, sucrose is coated on the surface of Fe3O4 microbeads to promote the formation of a mesoporous structure of the catalyst, thereby increasing its specific surface area, thereby facilitating the loading of sulfonic acid groups and improving the catalytic ability of the catalyst. The sulfonated Fe3O4 microbeads have excellent acid activity like concentrated sulfuric acid, and have good thermal stability and chemical stability. In addition, Fe3O4 is easy to separate as a catalyst, and can be quickly aggregated and separated from a reaction mixture under the action of an external magnetic field, thereby achieving efficient recovery and reuse.
[0025] Compared with the toxic and non-recyclable sulfuric acid catalyst, the acid catalyst provided by the present invention has the advantages of being easy to separate and recycle, thereby reducing processing costs and reducing the demand for waste acid treatment.
[0026] When the catalyst provided by the present invention replaces sulfuric acid as a catalyst, it not only improves the catalytic efficiency and stability, but also has multiple advantages such as environmental protection, sustainability and easy operation.
[0027] The present invention provides a method for preparing an odorless crosslinking agent BIPB by a condensation reaction. The BIPB product prepared by the method has high content and purity, is nearly white in color, can be used directly, and does not need to be recrystallized and purified, thereby greatly shortening the production process and reducing production costs. DETAILED DESCRIPTION
[0028] 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.
[0029] The Fe3O4 microspheres used in the embodiments and comparative examples of the present invention are prepared by the following steps:
[0030] Ferrous chloride tetrahydrate, ferric chloride hexahydrate and sodium dodecyl sulfate (wherein the molar ratio of ferrous chloride tetrahydrate, ferric chloride hexahydrate and sodium dodecyl sulfate is 1:2:0.4) are added into deionized water, and the reaction is continued by stirring after ultrasonic dispersion. The temperature is raised to 70°C under the protection of N2 gas, and then ammonia water is slowly added to adjust the pH to 11. The reaction is carried out at a constant temperature for 1.5 hours. After the reaction is completed, Fe3O4 is attracted and precipitated by an external magnetic field, and finally washed with anhydrous ethanol and deionized water for many times until the filtrate is a clear liquid. Finally, Fe3O4 microspheres are obtained after vacuum drying.
[0031] Example 1
[0032] This embodiment provides a catalyst, and the preparation steps are as follows:
[0033] S1. Add 1.0 g of sucrose to 100 mL of deionized water, stir until uniform, add 6.0 g of Fe3O4 microbeads, disperse by ultrasonic until uniform, then heat to 175°C for carbonization reaction for 6.0 h, cool naturally to room temperature, separate and precipitate using an external magnetic field, wash the precipitate, and vacuum dry at 80°C to obtain modified Fe3O4 microbeads;
[0034] S2. Add 1.0 g of modified Fe3O4 microbeads and 0.5 g of concentrated sulfuric acid into 50 mL of deionized water, shake the solution until it is evenly dispersed, and dry it in a drying oven at 80°C. Take out the dried solid matter and calcine it under nitrogen protection. Grind and sieve it to obtain a catalyst.
[0035] Example 2
[0036] The only difference from Example 1 is that:
[0037] S1. Add 1.5 g of sucrose to 100 mL of deionized water, stir until uniform, add 7.5 g of Fe3O4 microbeads, disperse by ultrasonic until uniform, then heat to 175°C for carbonization reaction for 6.0 h, cool naturally to room temperature, separate and precipitate using an external magnetic field, wash the precipitate, and vacuum dry at 80°C to obtain modified Fe3O4 microbeads.
[0038] Example 3
[0039] The only difference from Example 1 is that:
[0040] S2. Add 1.2 g of modified Fe3O4 microbeads and 0.6 g of concentrated sulfuric acid into 50 mL of deionized water, shake the solution until it is evenly dispersed, and dry it in a drying oven at 80°C. Take out the dried solid matter and calcine it under nitrogen protection. Grind and sieve it to obtain a catalyst.
[0041] Example 4
[0042] This embodiment provides a method for preparing an odorless crosslinking agent BIPB by a condensation reaction, comprising the following steps:
[0043] Step 1, adding 130g of tert-butyl hydroperoxide (mass fraction 70%) into a reactor, and adding 60g of the catalyst in Example 1 into the reactor at room temperature for dehydration reaction;
[0044] Step 2, adding 100 g of α,α′-dihydroxy-1,3-diisopropylbenzene (mass fraction of 98%) into a reactor for condensation reaction, wherein the reaction temperature is 50° C. and the reaction time is 45 min to obtain a reaction material;
[0045] Step 3, washing the reaction material obtained in step 2 with alkali and water in sequence, separating and filtering to obtain an organic phase solution;
[0046] Step 4: subjecting the organic phase solution obtained in step 3 to vacuum flash drying, wherein the vacuum flash drying temperature is 50° C., the pressure is -0.090 MPa, the flash time is 1 h, and then cooling and solidifying at room temperature to obtain BIPB.
[0047] Example 5
[0048] The only difference from Example 4 is that:
[0049] The catalyst in Example 1 was replaced by the catalyst in Example 2, and the amount used remained unchanged.
[0050] Example 6
[0051] The only difference from Example 4 is that:
[0052] The catalyst in Example 1 was replaced by the catalyst in Example 3, and the amount used remained unchanged.
[0053] Example 7
[0054] The only difference from Example 4 is that:
[0055] Step 1: Add 145 g of tert-butyl hydroperoxide (mass fraction 70%) into a reactor, and at room temperature, add 80 g of the catalyst in Example 1 into the reactor for dehydration reaction.
[0056] Example 8
[0057] The only difference from Example 4 is that:
[0058] Step 2: Add 100 g of α,α′-dihydroxy-1,3-diisopropylbenzene (mass fraction of 98%) into a reactor for condensation reaction, wherein the reaction temperature is 55° C. and the reaction time is 40 min to obtain a reaction material.
[0059] Example 9
[0060] The only difference from Example 4 is that:
[0061] Step 4: vacuum flash drying the organic phase solution obtained in step 3, wherein the vacuum flash drying temperature is 60° C., the pressure is -0.0092 MPa, the flash time is 1.5 h, and then cooled and solidified at room temperature to obtain BIPB.
[0062] Comparative Example 1
[0063] This comparative example provides a method for preparing an odorless crosslinking agent BIPB by a condensation reaction, comprising the following steps:
[0064] Step 1, add 130g of tert-butyl hydroperoxide (mass fraction 70%) into a reactor, and at room temperature, add 60g of concentrated sulfuric acid into the reactor for dehydration reaction;
[0065] Step 2, adding 100 g of α,α′-dihydroxy-1,3-diisopropylbenzene (mass fraction of 98%) into a reactor for condensation reaction, wherein the reaction temperature is 50° C. and the reaction time is 45 min to obtain a reaction material;
[0066] Step 3, washing the reaction material obtained in step 2 with alkali and water in sequence, separating and filtering to obtain an organic phase solution;
[0067] Step 4: subjecting the organic phase solution obtained in step 3 to vacuum flash drying, wherein the vacuum flash drying temperature is 50° C., the pressure is -0.090 MPa, the flash time is 1 h, and then cooling and solidifying at room temperature to obtain BIPB.
[0068] Comparative Example 2
[0069] The only difference from Example 4 is that:
[0070] 60 g of the catalyst in Example 1 was replaced by 50 g of the catalyst in Example 1.
[0071] Comparative Example 3
[0072] The only difference from Example 4 is that:
[0073] 60 g of the catalyst in Example 1 was replaced by 95 g of the catalyst in Example 1.
[0074] Comparative Example 4
[0075] The only difference from Example 4 is that:
[0076] Step 1: Add 120 g of tert-butyl hydroperoxide (mass fraction 70%) into a reactor, and at room temperature, add 60 g of the catalyst in Example 1 into the reactor for dehydration reaction.
[0077] Comparative Example 5
[0078] The only difference from Example 4 is that:
[0079] Step 2: Add 100 g of α,α′-dihydroxy-1,3-diisopropylbenzene (mass fraction of 98%) into a reactor for condensation reaction, wherein the reaction temperature is 50° C. and the reaction time is 65 min to obtain a reaction material.
[0080] Comparative Example 6
[0081] The only difference from Example 4 is that:
[0082] Step 4: subjecting the organic phase solution obtained in step 3 to vacuum flash drying, wherein the vacuum flash drying temperature is 40° C., the pressure is -0.085 MPa, the flash time is 1 h, and then cooling and solidifying at room temperature to obtain BIPB.
[0083] Performance tests were performed on Examples 4 to 9 and Comparative Examples 1 to 6. The test results are shown in Table 1:
[0084] Table 1
[0085] project Yield (%) purity(%) Whiteness Example 4 96.75 98.95 94.8 Example 5 97.11 99.03 94.6 Example 6 96.68 98.99 95.0 Example 7 96.99 98.90 94.5 Example 8 97.05 98.87 95.1 Example 9 97.06 99.01 94.9 Comparative Example 1 88.45 91.27 89.6 Comparative Example 2 91.35 95.62 90.1 Comparative Example 3 92.04 94.87 90.9 Comparative Example 4 93.11 93.24 91.2 Comparative Example 5 93.24 94.05 90.8 Comparative Example 6 92.78 93.73 90.6
[0086] As can be seen from Table 1, the yield, purity and whiteness of BIPB prepared in Examples 4-9 are higher than those in Comparative Examples 1-6. It can be seen from this that the method for preparing an odorless crosslinking agent BIPB by a condensation reaction provided by the present invention, the BIPB product prepared by the method has high content and purity, is nearly white in color, can be used directly, and does not require recrystallization and purification, thereby reducing production costs. It can be seen from Comparative Example 1 and Examples 4-9 that the catalyst provided by the present invention, when replacing sulfuric acid as a catalyst, not only improves the catalytic efficiency and stability, but also has multiple advantages such as environmental protection, sustainability and easy operation.
[0087] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.
[0088] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.
Claims
1. A method for preparing an odorless crosslinking agent BIPB by condensation reaction, characterized in that: The following steps are involved: Step 1, adding tert-butyl hydroperoxide into a reactor, and adding a catalyst into the reactor at room temperature for dehydration reaction; Step 2, adding α,α′-dihydroxy-1,3-diisopropylbenzene into a reaction kettle for condensation reaction to obtain a reaction material; Step 3, washing the reaction material obtained in step 2, separating and filtering to obtain an organic phase solution; Step 4, vacuum flash drying the organic phase solution obtained in step 3, cooling and solidifying at room temperature to obtain BIPB; Wherein, the catalyst in step 1 is prepared by the following steps: The modified Fe3O4 microbeads and concentrated sulfuric acid were added to deionized water, the solution was shaken until uniformly dispersed, and dried in a drying oven at 80°C. The dried solid matter was taken out and calcined under nitrogen protection, and then ground and sieved to obtain a catalyst.
2. The method for preparing an odorless crosslinking agent BIPB by condensation reaction according to claim 1, characterized in that: The dosage ratio of the modified Fe3O4 microbeads, concentrated sulfuric acid and deionized water is: 1.0-1.2 g: 0.5-0.6 g: 50 mL.
3. The method for preparing an odorless crosslinking agent BIPB by condensation reaction according to claim 1, characterized in that: The calcination temperature is 280-310° C., and the calcination time is 3.5-5.5 hours.
4. The method for preparing an odorless crosslinking agent BIPB by condensation reaction according to claim 1, characterized in that: The modified Fe3O4 microbeads are prepared by the following steps: Sucrose is added into deionized water and stirred until uniform. Fe3O4 microbeads are added and dispersed uniformly by ultrasonication. The temperature is then raised to 175-180°C for carbonization reaction for 6.0-6.5 hours. After naturally cooling to room temperature, an external magnetic field is used for separation and sedimentation, washing, and vacuum drying to obtain modified Fe3O4 microbeads.
5. The method for preparing an odorless crosslinking agent BIPB by condensation reaction according to claim 4, characterized in that: The usage ratio of sucrose, deionized water and Fe3O4 microbeads is 1.0-1.5 g:100 mL:6.0-7.5 g.
6. The method for preparing an odorless crosslinking agent BIPB by condensation reaction according to claim 1, characterized in that: The mass fraction of tert-butyl hydroperoxide in step 1 is 70% to 75%.
7. The method for preparing an odorless crosslinking agent BIPB by condensation reaction according to claim 1, characterized in that: The usage ratio of tert-butyl hydroperoxide, catalyst and α,α′-dihydroxy-1,3-diisopropylbenzene is 130-150g: 60-85g: 100-110g.
8. The method for preparing an odorless crosslinking agent BIPB by condensation reaction according to claim 1, characterized in that: In the condensation reaction in step 2, the reaction temperature is 50-55° C., and the reaction time is 35-50 min.
9. The method for preparing an odorless crosslinking agent BIPB by condensation reaction according to claim 1, characterized in that: The specific steps of washing in step 3 are: alkali washing and water washing in sequence.
10. The method for preparing an odorless crosslinking agent BIPB by condensation reaction according to claim 1, characterized in that: In step 4, the temperature of vacuum flash drying is 50 to 60° C., the pressure is -0.090 to -0.0095 MPa, and the flash time is 1 to 2 hours.