Process for the preparation of a molecularly imprinted polymer catalyst for the synthesis of p-tert-butyl ethylbenzene
By preparing molecularly imprinted polymer catalysts, the problems of catalyst corrosion and activity reduction in existing technologies have been solved, achieving highly selective and stable synthesis of tert-butylethylbenzene, reducing production costs and expanding production capacity.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- JIANGSU ZHENGDAN CHEM IND CO LTD
- Filing Date
- 2024-04-29
- Publication Date
- 2026-08-04
AI Technical Summary
Existing technologies for synthesizing p-tert-butylethylbenzene suffer from problems such as catalyst corrosion of equipment, environmental pollution, rapid decline in catalyst activity, and deep cracking due to high reaction temperatures. Furthermore, existing catalysts are difficult to achieve high selectivity and stability.
A molecularly imprinted polymer catalyst preparation method was adopted. By constructing a tetraisobutyl titanate-manganese acetate sol system and using a microwave chemical device, combined with molecular imprinting technology and membrane catalysis technology, Co-MnTiO3 sol was prepared as a crosslinking agent for the synthesis of p-tert-butylethylbenzene.
It improves the activity and stability of the catalyst, with an ethylbenzene conversion rate of ≥30% and a selectivity for tert-butylethylbenzene of ≥99%, reducing production costs and expanding production capacity, making it suitable for industrial production.
Smart Images
Figure BDA0004817782780000051 
Figure BDA0004817782780000052 
Figure BDA0004817782780000091
Abstract
Description
Technical Field
[0001] This invention relates to an alkylation catalyst, specifically to a method for preparing an alkylation catalyst for the synthesis of p-tert-butylethylbenzene, belonging to the field of chemical technology. Background Technology
[0002] p-tert-butylethylbenzene is an important chemical raw material, mainly used for the dehydrogenation production of p-tert-butylstyrene, a special monomer for chemical materials, and its downstream polymers, which are used in high-end coatings, clothing and other fields. It can also be used to prepare thermosetting resins.
[0003] Currently, the methods reported both domestically and internationally for synthesizing p-tert-butylethylbenzene involve catalytic alkylation of ethylbenzene with tert-butanol or isobutene.
[0004] US3631213 and US4982034 disclose methods for synthesizing tert-butylethylbenzene by alkylation of isobutylene and ethylbenzene under the action of acidic catalysts such as H2SO4 and AlCl3. However, the use of liquid acids such as concentrated sulfuric acid and aluminum trichloride as catalysts can lead to serious corrosion of production equipment, inability to recycle catalysts, and environmental pollution.
[0005] US469908 discloses a reaction method using ZSM-12 zeolite as a catalyst, with a reaction temperature of 190℃~300℃, a reaction pressure of 300psig, an isobutylene conversion of 95%, a tert-butylethylbenzene selectivity of 90%, and a p-tert-butylethylbenzene to m-tert-butylethylbenzene ratio of approximately 9:1. Although these alkylation reactions achieve high selectivity under the action of zeolite-type catalysts, due to the high alkylation temperature of aromatics, deep cracking of the reaction products and oligomerization of isobutylene occur.
[0006] The Chinese Journal of Catalysis (2013) 2:294-304 reported the synthesis of tert-butylethylbenzene from ethylbenzene and tert-butanol catalyzed by ZSM-5 zeolite. The effects of ZSM-5 catalysts with different crystallinities on the para-position of tert-butylation of ethylbenzene were discussed, but the catalyst activity decreased rapidly.
[0007] CN114591129A discloses a synthesis process for tert-butylethylbenzene, comprising the following steps: pyrolyzing methyl tert-butyl ether in a pyrolysis reactor; separating and purifying the pyrolysis product to obtain isobutylene; drying the isobutylene; then mixing the isobutylene with ethylbenzene and feeding it into an alkylation reactor for alkylation; part of the alkylation product is returned to the alkylation reactor, and the other part is separated and purified to obtain tert-butylethylbenzene; in the alkylation reaction, the alkylation catalyst is prepared by mixing modified β-zeolite and H-MCM-22 zeolite. The isobutylene from the pyrolysis of methyl tert-butyl ether is alkylated with ethylbenzene to produce tert-butylethylbenzene, with an isobutylene conversion rate greater than 97% and a tert-butylethylbenzene selectivity greater than 93%.
[0008] CN115872824A discloses a method for preparing p-tert-butylethylbenzene. Using ethylbenzene and isobutylene as raw materials, multiple catalyst beds are employed, each filled with an MWW-type molecular sieve catalyst. The process includes: ethylbenzene is fed entirely from the bottom of the bottom catalyst bed, while isobutylene is fed in stages from the bottom of each catalyst bed. Ethylbenzene and the staged isobutylene are sequentially contacted with the MWW-type molecular sieve catalyst in each catalyst bed from bottom to top under liquid phase conditions to undergo an alkylation reaction, thus preparing p-tert-butylethylbenzene. Using this method to prepare p-tert-butylethylbenzene from isobutylene and ethylbenzene can improve the single-pass conversion rate of isobutylene and the shape selectivity of p-tert-butylethylbenzene, while reducing the ethylbenzene recycling ratio.
[0009] CN115838315A discloses a process for producing tert-butyl ethylbenzene with a low aromatic ratio and the tert-butyl ethylbenzene produced using this process. By employing a multi-stage reaction process, the tert-butyl ethylbenzene output concentration is high, and the amount of recycled ethylbenzene is low, achieving energy saving. Simultaneously, the reaction process controls the feed primarily to the alkylation reaction of ethylbenzene and isobutylene, reducing the amount of di-tert-butyl ethylbenzene generated and maintaining a low aromatic molar ratio of ethylbenzene / isobutylene of 3.0–4.0. This ensures that the concentration ratio of di-tert-butyl ethylbenzene to tert-butyl ethylbenzene in the reaction product is below 0.2%, eliminating the need for a "re-hydrocarbonation" reactor. Summary of the Invention
[0010] To overcome the shortcomings of the prior art, the purpose of this invention is to provide a method for preparing a molecularly imprinted polymer catalyst for the synthesis of p-tert-butylethylbenzene.
[0011] This allows it to be used as an alkylation catalyst in the synthesis of p-tert-butylethylbenzene, which can improve catalyst activity and product yield, reduce energy consumption, meet the need for further expansion of production capacity, and has low production cost and improved production efficiency.
[0012] Therefore, the present invention provides a method for preparing a molecularly imprinted polymer catalyst for the synthesis of p-tert-butylethylbenzene, comprising the following steps:
[0013] (1) Construction of tetraisobutyl titanate-manganese acetate sol system using glacial acetic acid
[0014] An ethanol solution of tetraisobutyl titanate was prepared, and glacial acetic acid was added as a stabilizer. Simultaneously, manganese acetate was dissolved in deionized water, and the deionized water containing the dissolved manganese acetate was added dropwise to the ethanol solution of tetraisobutyl titanate while stirring. The mixture was thoroughly mixed to obtain a clear, transparent sol. Glacial acetic acid or ammonia was then added dropwise to adjust the pH of the solution to weakly acidic or neutral. The solution was then kept at a constant temperature in a water bath to obtain a MnTiO3 sol. The molar ratio of tetraisobutyl titanate to manganese acetate was 1:(0.95–1.05).
[0015] (2) Microwave-assisted sol-gel method for preparing Co-MnTiO3 sol
[0016] Co(NO3)4 and sodium citrate were dissolved in distilled water, and then polyethylene glycol 200 (PEG200) and the MnTiO3 sol obtained in step (1) were added. The mixed solution was stirred in a microwave chemical apparatus to obtain Co-MnTiO3 sol. The polyethylene glycol 200 was used as a pore-forming agent for Co-MnTiO3 sol, and the amount used was 2% to 4% of the total volume of the reaction solution. The sodium citrate was used to adjust the pH value of the reaction solution. The mass ratio of Co(NO3)4, MnTiO3 sol and sodium citrate used was 0.25:(0.9 to 1.1):(0.25 to 0.35). The temperature of the microwave chemical apparatus was 70 to 80°C and the pressure was 3.5 to 4.5 MPa.
[0017] (3) Preparation of molecularly imprinted polymer catalysts
[0018] First, p-tert-butylethylbenzene and hydroxyethyl methacrylate (HEMA) in a molar ratio of (0.5:1) to (1:1.1) are mixed in a flask. Then, the Co-MnTiO3 sol obtained in step (3) is added and stirred to polymerize. The Co-MnTiO3 sol is used as a crosslinking agent and its amount is 35-45 times the mass of hydroxyethyl methacrylate. After vacuum drying and grinding, polymer particles are obtained. Then, after annealing and calcination, and cooling to room temperature, molecularly imprinted polymer catalyst (MCMTO) is obtained.
[0019] Further, in step (1), the amount of ethanol used is 90 to 100 times the mass of tetraisobutyl titanate, the amount of glacial acetic acid used is 0.85 to 1 times the mass of tetraisobutyl titanate, and the molar ratio of manganese acetate to tetraisobutyl titanate is 1:(0.9 to 1.1).
[0020] Furthermore, in step (1), the water bath temperature is 20°C; and the pH value of the solution is controlled between 3.6 and 5.0.
[0021] Furthermore, in step (2), the deionized water dispersion time is 1 hour, the reaction time is 30 minutes, and the stirring time is 30 minutes.
[0022] Furthermore, in step (2), the microwave chemical device has a temperature of 75°C and a pressure of 4.0 MPa.
[0023] Furthermore, in step (3), the stirring temperature is 50-55°C; the stirring polymerization time is 12-24 hours; and the vacuum drying temperature is 60-65°C.
[0024] Furthermore, the calcination annealing temperature in step (3) is 650-700℃; then, the temperature is maintained at room temperature for 2 hours.
[0025] In the above technical solution, sodium citrate is used to adjust the pH of the catalytic surface; PEG200 is used as a sol pore-forming agent; Co-MnTiO3 is used as the catalytic active center, crosslinking agent for molecularly imprinted catalytic polymers, and catalyst support; p-tert-butylethylbenzene is used as the template molecule for the catalyst; and hydroxyethyl methacrylate is used as the functional monomer for the catalyst.
[0026] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0027] (1) The alkylation catalyst of the present invention utilizes a sol-gel process to construct a tetraisobutyl titanate-manganese acetate-glacial acetic acid sol system, and successfully prepares a catalytically active MnTiO3 sol. By introducing Co atoms, the particle structure is consolidated and its catalytic activity is increased.
[0028] (2) By combining molecular imprinting technology with membrane catalysis technology, the catalytically active component is used as a crosslinking agent in the preparation of molecular imprinted polymers. This not only stabilizes the molecular imprinted recognition cavity, but also increases the catalytic activity and stability of the molecular imprinted polymer catalyst.
[0029] (3) The catalyst synthesized by the present invention can be used in the synthesis of p-tert-butylethylbenzene. It uses ethylbenzene and tert-butanol / isobutene as the main raw materials. Under the action of the catalyst, p-tert-butylethylbenzene is obtained by alkylation reaction. The conversion rate of ethylbenzene is ≥30%, the selectivity of p-tert-butylethylbenzene is ≥99%, the catalyst activity is stable and the life is long, and it can be used in the industrial production of p-tert-butylethylbenzene. Detailed Implementation
[0030] The invention will be further explained below with reference to specific implementation examples.
[0031] The method for evaluating the activity of the catalyst is as follows:
[0032] A catalyst of a certain size or weight was loaded into a fixed reaction bed. The effects of factors such as feed rate, space velocity, pressure, reaction temperature, and preheating temperature on the catalyst utilization and catalytic efficiency in the synthesis of tert-butylethylbenzene from ethylbenzene and tert-butanol / isobutene were controlled. After the reaction, the reaction solution was analyzed by gas chromatography (GC), and the ethylbenzene conversion (A%) and target analyte selectivity (S%) were calculated based on the results.
[0033]
[0034]
[0035] Among them, C0 (%) and Ct The percentages (%) represent the concentrations of ethylbenzene before and after the reaction, C1 (%) represents the concentration of p-tert-butylethylbenzene produced, and C2 (%) represents the concentration of m-tert-butylethylbenzene produced.
[0036] Example 1
[0037] The preparation method of the molecularly imprinted polymer catalyst for the synthesis of p-tert-butylethylbenzene is carried out according to the following steps:
[0038] (1) Construction of tetraisobutyl titanate-manganese acetate sol system using glacial acetic acid
[0039] First, tetraisobutyl titanate was added to 100 mL of ethanol solution, along with an appropriate amount of glacial acetic acid as a stabilizer. Then, manganese acetate was weighed according to a ratio of n(tetraisobutyl titanate):n(manganese acetate) = 1:1, dissolved in an appropriate amount of deionized water, and added dropwise to the tetraisobutyl titanate ethanol solution with stirring. The mixture was thoroughly mixed to obtain a clear, transparent sol. Finally, glacial acetic acid or ammonia was added to adjust the pH of the solution to 3.8. The sol was then kept at a constant temperature in a water bath to obtain MnTiO3 sol, which was then stored in an ethanol solution for later use.
[0040] (2) Preparation of molecularly imprinted crosslinking agent Co-MnTiO3 sol
[0041] Co-MnTiO3 sol was prepared using a microwave-assisted sol-gel method. The specific procedure was as follows: 4.0 g of Co(NO3)4 and 4.8 g of sodium citrate were dissolved in 100 mL of distilled water, then 3 mL of PEG200 and MnTiO3 sol were added. The mixture was stirred at 75 °C for 10 h in a microwave-assisted sol-gel apparatus to obtain the Co-MnTiO3 sol.
[0042] (3) Preparation of molecularly imprinted polymer catalysts
[0043] First, p-tert-butylethylbenzene and the functional monomer hydroxyethyl methacrylate were added to a mixing reaction flask at a molar ratio of 0.75:1. Then, the crosslinking agent Co-MnTiO3 sol was added to the mixture, with the amount of crosslinking agent being 35-45 times the mass of hydroxyethyl methacrylate. The mixture was stirred and polymerized at 50°C for 12 h, dried at 80°C, and the resulting polymer was ground to obtain p-tert-butylethylbenzene imprinted catalytic polymer particles (MCMTO). Finally, the MCMTO was annealed and calcined at 700°C, cooled to room temperature, and then kept in air for 2 hours.
[0044] Comparative Experiment: Preparation of Non-Molecularly Imprinted Polymer Catalysts
[0045] The difference from Example 1 is that in step (3), p-tert-butylethylbenzene is not added. Instead, Co-MnTiO3 sol is stirred and polymerized at 50°C for 12 hours, dried at 80°C, and the resulting polymer is ground to obtain a non-molecularly imprinted polymer catalyst (CMTO). Finally, CMTO is annealed and calcined at 700°C, cooled to room temperature, and kept in air for 2 hours.
[0046] The catalyst was loaded in a fixed reaction bed. The catalyst's activity evaluation length was 20 cm and its inner diameter was 40 mm. The catalyst loading amount for each reaction was 105 g, i.e., the catalyst height was 10 cm. The molar ratio of ethylbenzene to tert-butanol was 4:1. The alkylation reaction temperature was 220 °C, the space velocity was 2.0 h⁻¹, and the pressure was 1.5 MPa. After 20 days of continuous reaction, the catalytic activity evaluation data were recorded as follows:
[0047] Table 1.1 Catalytic activity evaluation data of MCMTO
[0048] 4 34.2 100 8 33.6 100 12 33.8 100 24 34.1 100 48 32.2 99.8 72 32.2 99.5 120 33.7 99.2 168 32.6 99.2 240 32.3 99.2 360 31.9 99.0 480 31.7 99.0
[0049] Table 1.2 Catalytic activity evaluation data of CMTO
[0050] 4 15.6 98.8 8 14.8 98.5 12 14.4 98.2 24 14.3 96.7 48 14.1 94.3 72 13.2 93.1 120 12.9 90.8 168 12.6 86.5 240 11.8 85.2 360 10.7 84.1 480 10.3 82.2
[0051] The results showed that after 20 days of continuous reaction, the ethylbenzene conversion of MCMTO was ≥30%, and the selectivity for tert-butylethylbenzene was ≥99%, indicating that the molecularly imprinted polymer catalyst had good catalytic activity and stability. Compared with CMTO, the molecularly imprinted polymer catalyst exhibited better catalytic activity and stability than the non-molecularly imprinted polymer catalyst.
[0052] Example 2:
[0053] In Example 1, step (1) was changed to "adding glacial acetic acid or ammonia to adjust the pH of the solution to 5.0", and the rest was the same as in Example 1. The catalytic activity of MCMTO is shown in Table 2.1 below, and the catalytic activity of CMTO is shown in Table 2.2.
[0054] Table 2.1 Catalytic activity evaluation data of MCMTO
[0055] 4 26.2 100 8 25.4 100 12 25.2 99.9 24 25.1 99.9 48 23.6 99.7 72 22.2 99.6 120 21.5 99.4 168 21.4 99.1 240 21.1 99.1 360 20.6 98.9 480 20.4 98.8
[0056] Table 2.2 Catalytic activity evaluation data of CMTO
[0057] 4 10.5 95.2 8 10.1 95.3 12 10.3 94.2 24 9.5 94.5 48 9.9 94.1 72 8.7 93.3 120 8.5 87.3 168 8.5 83.5 240 8.5 82.1 360 8.4 80.2 480 8.3 79.9
[0058] The results showed that adjusting the pH value during the gelation of MnTiO3 sol reduced the catalytic activity of the catalyst. This is because the change in gelation pH leads to a change in the particle structure, resulting in a smaller internal pore size of the catalyst. However, with the help of molecularly imprinted polymers, the catalytic selectivity was not reduced.
[0059] Example 3:
[0060] In step (3) of Example 1, "p-tert-butylethylbenzene and the functional monomer hydroxyethyl methacrylate were added in a molar ratio of 0.5:1", and the rest was the same as in Example 1. The catalytic activity of MCMTO is shown in the table below.
[0061] Table 3. Catalytic activity evaluation data of MCMTO
[0062] 4 31.2 100 8 30.4 99.4 12 30.1 99.1 24 29.5 99.0 48 28.7 98.8 72 27.6 98.5 120 25.5 98.5 168 24.3 98.4 240 23.4 98.4 360 22.5 98.3 480 22.1 98.2
[0063] The results showed that the catalytic activity and stability of the prepared catalyst were reduced. This was because fewer template molecules were added during the molecular imprinting process, resulting in fewer and less stable molecular imprinted cavities. This led to greater resistance and slower conversion when the reaction entered the catalyst channels, which easily caused blockage and thus reduced catalytic stability.
[0064] Example 4:
[0065] In step (3) of Example 1, "adding p-tert-butylethylbenzene and the functional monomer hydroxyethyl methacrylate in a molar ratio of 1:1" was used instead, and the rest was the same as in Example 1. The catalytic activity of MCMTO is shown in the table below.
[0066] Table 4. Catalytic activity evaluation data of MCMTO
[0067]
[0068]
[0069] The results showed that the catalytic activity and stability of the prepared catalyst decreased. This was because a larger number of template molecules were added during the molecular imprinting process, and the increased accumulation of the molecularly imprinted polymer led to smaller and more easily destroyed internal pores in the catalyst. As the reaction continued, the internal pores of the catalyst were destroyed and enlarged, resulting in a decrease in its catalytic activity and stability.
[0070] Based on Examples 3 and 4, the molar ratio of p-tert-butylethylbenzene to hydroxyethyl methacrylate was screened, and the results are shown in Table 5 below:
[0071] Table 5. Catalytic activity evaluation data of MCMTO
[0072]
[0073] Table 5 shows that when the molar ratio of p-tert-butylethylbenzene to hydroxyethyl methacrylate is preferably (0.5:1) to (1:1.1), a lower template molecule content results in larger internal pores in the catalyst, shorter residence time of the reaction solution within the catalyst, leading to lower feed conversion, fewer molecularly imprinted recognition cavities, and poorer selectivity for p-tert-butylethylbenzene. Conversely, as the content of template molecules and functional monomers increases, more molecularly imprinted polymers accumulate, resulting in smaller internal pores in the catalyst, making it more difficult for the reaction solution to enter the catalyst, thus reducing the feed conversion. However, the selectivity remains above 99% under the influence of the molecularly imprinted recognition cavities.
[0074] Example 5:
[0075] In Example 1, step (3) was changed to "polymerization at 50°C for 24 hours with stirring", and the rest was the same as in Example 1. The catalytic activity of MCMTO is shown in the table below.
[0076] Table 6. Catalytic activity evaluation data of MCMTO
[0077] 4 30.1 100 8 29.7 99.8 12 29.1 99.5 24 28.7 99.1 48 28.4 99.0 72 28.0 98.8 120 27.3 98.5 168 26.9 98.1 240 26.6 97.9 360 25.9 97.5 480 24.8 97.1
[0078] The results showed that adjusting the molecularly imprinted polymerization time reduced catalytic activity and stability. This was because an excessively long molecularly imprinted polymerization time resulted in a thicker polymer layer on the catalyst surface, which could not be completely removed during annealing and calcination, thus leading to smaller pore sizes and fewer molecular recognition sites.
[0079] Example 6:
[0080] Based on Example 1, the volume ratio of PEG200 was screened, and the results are shown in Table 7 below:
[0081] Table 7. Catalytic activity evaluation data of MCMTO
[0082]
[0083]
[0084] Table 7 shows that the preferred volume ratio of PEG200 is 2% to 4%. Adding too little PEG200 will result in fewer pores and smaller pore sizes, which is detrimental to the reaction and reduces the conversion rate and selectivity of the reactants. Adding too much pore-forming agent will result in more pores and larger pore sizes, leading to a shorter residence time of the reaction solution as the reaction proceeds, which also reduces the conversion rate and selectivity of the reactants.
[0085] Example 7:
[0086] The catalyst activity evaluation was modified to have a length of 20 cm, an inner diameter of 40 mm, and a catalyst loading of 89 g per reaction, i.e., a catalyst height of 8 cm. Other parameters are the same as in Example 1. The catalytic activity of MCMTO is shown in the table below.
[0087] Table 8. Catalytic activity evaluation data of MCMTO
[0088] 4 33.2 100 8 32.6 100 12 32.4 99.9 24 32.2 99.8 48 32.0 99.7 72 31.9 99.4 120 31.6 99.0 168 31.5 99.0 240 31.3 98.7 360 30.7 98.5 480 30.1 98.2
[0089] The results showed that although reducing the catalyst packing height, i.e. reducing the amount of catalyst stacked, did not affect the alkylation reaction, it weakened the separation effect of tert-butylethylbenzene in the reaction solution within the bed, ultimately reducing the catalyst's effectiveness in alkylating ethylbenzene and tert-butanol, thus decreasing the catalyst's stability.
[0090] Example 8:
[0091] The molar ratio of ethylbenzene to isobutylene was changed to 4:1, the alkylation reaction temperature was 220°C, the space velocity was 2.0 h⁻¹, and the pressure was 1.5 MPa. All other parameters were the same as in Example 1. The catalytic activity of MCMTO is shown in the table below.
[0092] Table 9. Catalytic activity evaluation data of MCMTO
[0093] 4 30.2 100 8 30.0 100 12 29.8 100 24 29.6 99.9 48 29.5 99.9 72 29.4 99.6 120 29.2 99.4 168 29.0 99.1 240 28.7 99.0 360 28.5 98.8 480 28.2 98.6
[0094] The results showed that when isobutylene was used as the feedstock, the conversion rate of ethylbenzene and the selectivity for tert-butylethylbenzene decreased slightly compared to using tert-butanol as the feedstock in the alkylation reaction. Using isobutylene as the feedstock still maintained certain catalytic activity and stability, and after 20 days of continuous reaction, the conversion rate of ethylbenzene was ≥28%, and the selectivity for tert-butylethylbenzene was ≥98.5%.
[0095] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. A method for preparing a molecularly imprinted polymer catalyst for the synthesis of p-tert-butyl ethylbenzene, characterized in that Includes the following steps: (1) Construction of tetraisobutyl titanate-manganese acetate sol system with the aid of glacial acetic acid An ethanol solution of tetraisobutyl titanate was prepared, and glacial acetic acid was added as a stabilizer. Simultaneously, manganese acetate was dissolved in deionized water, and the deionized water containing the dissolved manganese acetate was added dropwise to the ethanol solution of tetraisobutyl titanate while stirring. The mixture was thoroughly mixed to obtain a clear, transparent sol. Glacial acetic acid or ammonia was then added dropwise to adjust the pH of the solution to weakly acidic or neutral. The solution was then kept at a constant temperature in a water bath to obtain a MnTiO3 sol. The molar ratio of tetraisobutyl titanate to manganese acetate was 1:(0.95-1.05). (2) Preparation of Co-MnTiO3 sol by microwave chemical apparatus-assisted sol-gel method Co(NO3)4 and sodium citrate were dissolved in distilled water, and then polyethylene glycol 200 and the MnTiO3 sol obtained in step (1) were added. The mixed solution was stirred in a microwave chemical apparatus to obtain Co-MnTiO3 sol. The polyethylene glycol 200 was used as a pore-forming agent for Co-MnTiO3 sol, and the amount used was 2%-4% of the total volume of the solution. The sodium citrate was used to adjust the pH value in the reaction solution. The mass ratio of Co(NO3)4, MnTiO3 sol and sodium citrate used was 0.25:(0.9-1.1):(0.25-0.35). The temperature of the microwave chemical apparatus was 70-80℃ and the pressure was 3.5-4.5MPa. (3) Preparation of molecularly imprinted polymer catalysts First, p-tert-butylethylbenzene and hydroxyethyl methacrylate in a molar ratio of (0.5:1)-(1:1.1) are mixed in a flask. Then, the Co-MnTiO3 sol obtained in step (3) is added and mixed and stirred to polymerize. The Co-MnTiO3 sol is used as a crosslinking agent and its amount is 35-45 times the mass of hydroxyethyl methacrylate. After vacuum drying and grinding, polymer particles are obtained. Then, after calcination and annealing, and cooling to room temperature, a molecularly imprinted polymer catalyst is obtained.
2. The method for preparing a molecularly imprinted polymer catalyst for the synthesis of p-tert-butylethylbenzene according to claim 1, characterized in that: In step (1), the amount of ethanol used is 90-100 times the mass of tetraisobutyl titanate, the amount of glacial acetic acid used is 0.85-1 times the mass of tetraisobutyl titanate, and the molar ratio of manganese acetate to tetraisobutyl titanate is 1:(0.9-1.1).
3. The method for preparing a molecularly imprinted polymer catalyst for the synthesis of p-tert-butylethylbenzene according to claim 1, characterized in that: The water bath temperature in step (1) is 20°C; the pH value of the solution is controlled between 3.6 and 5.
0.
4. The method for preparing a molecularly imprinted polymer catalyst for the synthesis of p-tert-butylethylbenzene according to claim 1, characterized in that: The microwave chemical device in step (2) has a temperature of 75°C and a pressure of 4.0 MPa.
5. The method for preparing a molecularly imprinted polymer catalyst for the synthesis of p-tert-butylethylbenzene according to claim 1, characterized in that: The stirring temperature in step (3) is 50-55℃; the stirring polymerization time is 12h-24h; and the vacuum drying temperature is 60-65℃.
6. The method for preparing a molecularly imprinted polymer catalyst for the synthesis of p-tert-butylethylbenzene according to claim 1, characterized in that: The calcination and annealing temperature in step (3) is 650-700℃; then, the temperature is maintained at room temperature for 2 hours.