Efficient catalysis process of phenylimidazole derivative

Abstract

The invention discloses an efficient catalytic process of phenylimidazole derivatives, and belongs to the technical field of 2-phenylimidazole.The efficient catalytic process comprises the steps that a large-specific-surface-area layered structure provided by a zirconium-aluminum layered carrier serves as a carrier, titanium-based MOF is synthesized on the surface through hot water, a zirconium-titanium bimetal layered compound is obtained, the zirconium-titanium bimetal layered compound serves as a main carrier, and the high-efficiency catalytic process of the phenylimidazole derivatives is achieved. The surface of the porous catalyst is coated with resin with cation exchange capacity, the resin contains phosphonic acid groups and sulfonic acid groups, metal ions in copper nitrate and ferric sulfate can be fixed, agglomeration is avoided, the cation exchange resin becomes a porous carbon layer after calcination, and the specific surface area and porosity of the porous catalyst are further increased. And in the process, the coated zirconium-titanium bimetallic layered compound not only provides a large-surface-area carrier effect, but also plays a catalytic role to catalyze the generation of phosphonic acid and sulfonic acid groups.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of 2-phenyl imidazole synthesis, and particularly relates to a high-efficiency catalytic process of a phenyl imidazole derivative. BACKGROUND

[0002] The special structure and properties of imidazole compounds show great development value in many fields such as the biological and medical field, the high-performance composite material field, the metal corrosion prevention field and the like, and the application research thereof attracts great attention of many scholars. As an important imidazole compound, 2-phenyl imidazole is an excellent curing agent for epoxy resin, polyurethane and the like, is an important organic synthesis intermediate for medicines, pesticides and dyes, and is widely applied in the fields of ionic liquid, proton exchange material, organic light-emitting material and the like.

[0003] In recent years, with the rapid development of the downstream industry of 2-phenyl imidazole, the demand for 2-phenyl imidazole is increasing. The Debus method is to obtain 2-phenyl imidazole by one-step reaction of glyoxal, benzaldehyde and ammonia, and has the advantages of wide raw material sources, short process route, mild reaction conditions and simple operation, and is the preferred route of the current domestic 2-phenyl imidazole production plants. However, the production process has problems such as low product yield, by-product generation, serious environmental pollution, difficult separation and purification and insufficient product quality, and cannot meet the requirements of modern enterprise development and market demand, so it is urgent to optimize the production process of 2-phenyl imidazole.

[0004] In recent years, with the needs of industrial production and the improvement of science and technology, especially the advent of more and more catalysts, many scholars introduce catalysts into the reaction system to improve the process. Commonly used catalysts include Lewis acid, molecular iodine, silicotungstic acid, indium trichloride trihydrate, silica gel and zeolite, FeCl3, magnetic nanomaterials, ionic liquids, PEG-400 and the like. The use of these catalysts to some extent makes up for the deficiencies of slow reaction rate, low reaction yield and long reaction time, but at the same time brings problems such as uneven dispersion, complex post-treatment, increased reaction cost, catalyst loss and deactivation and environmental pollution.

[0005] The Chinese patent with the publication number CN111686730B discloses a catalyst preparation method and application for synthesizing 2-phenyl imidazole by the Debus method. In the scheme, the active metal salt is impregnated into the double-metal organic-inorganic framework compound material by the impregnation method, and the active metal / complex oxide porous nanomaterial catalyst is obtained after calcination. However, the impregnation method will cause the aggregation of metal elements, thereby blocking the pores of the porous material. SUMMARY

[0006] The application aims to provide a high-efficiency catalytic process of a phenylimidazole derivative, which uses a large specific surface area layered structure provided by a zirconium aluminum layered carrier as a carrier, a titanium-based MOF synthesized on the surface by hydrothermal synthesis, a zirconium titanium bimetallic layered compound, and a cation exchange resin containing phosphonic acid groups and sulfonic acid groups on the surface of the main carrier, which can fix metal ions in copper nitrate and iron sulfate to avoid agglomeration.

[0007] The application can achieve the above-mentioned purpose through the following technical solutions. A high-efficiency catalytic process of a phenylimidazole derivative, comprising the following steps: Step one: hydrolysis and polycondensation of zirconium n-butylate, urea providing an alkaline environment to promote hydrolysis balance, and alumina as a structure stabilizer embedded in the interlayer to obtain a zirconium aluminum layered carrier; terephthalic acid as a ligand is hydrothermally synthesized on the surface of the zirconium aluminum layered carrier to obtain a titanium-based MOF, and a zirconium titanium bimetallic layered compound.

[0008] Step two: using Lewis acid sites in the zirconium titanium bimetallic layered compound to catalyze the reaction of chloromethylated crosslinked polystyrene resin and triethyl phosphite to obtain a phosphonated resin coated layered compound, which is hydrolyzed and sulfonated into a phosphonic acid group under the action of concentrated sulfuric acid, and a sulfonic acid group is introduced on the resin skeleton to obtain a cation exchange resin coated layered compound.

[0009] Step three: through the cation exchange function of the cation exchange resin coated layered compound, copper salt and iron salt are fixed and then calcined to obtain a porous catalyst.

[0010] Step four: using benzimidazole, 2-methylbromobenzene, potassium carbonate, and a porous catalyst as raw materials, toluene as a solvent, stirring at 20-25 DEG C and 500-600 r / min for 5-6 h to obtain a phenylimidazole derivative.

[0011] Further, the specific preparation steps of the zirconium aluminum layered carrier are as follows: Zirconium n-butylate, urea, and deionized water are added to a reaction kettle, stirred at 60-70 DEG C and 500-600 r / min for 10-12 min, then alumina is added, and stirring is continued for 30-40 min, heated to 120-130 DEG C for aging for 48-50 h, filtered, and the filter cake is washed with deionized water and anhydrous ethanol until the last washing liquid is neutral, and vacuum dried at 60-70 DEG C for 1-2 h to obtain a zirconium aluminum layered carrier.

[0012] Further, the amount ratio of zirconium n-butylate, urea, deionized water, and alumina is 80-90 mL:20-30 g:800-900 mL:22-30 mL.

[0013] Further, the specific preparation steps of the zirconium titanium bimetallic layered compound are as follows: The zirconium-aluminum layered carrier, terephthalic acid and N,N-dimethylformamide are added into a reaction kettle lined with polytetrafluoroethylene, stirred at 20-25℃ and 500-600r / min for 20-30min, then n-butyl titanate is added, continue to stir for 20-30min, then add acetic acid solution, ultrasonic dispersion for 40-50min, heat to 120-130℃, continue to stir for 24-26h, cool to room temperature naturally, filter, wash the filter cake with N,N-dimethylformamide and methanol for 2-4 times respectively, vacuum drying at 60-70℃ for 1-2h, to obtain a zirconium-titanium bimetallic layered compound.

[0014] Further, the use amount ratio of the zirconium-aluminum layered carrier, terephthalic acid, N,N-dimethylformamide, n-butyl titanate and acetic acid solution is 80-90g:100-120g:2-3L:50-60g:100-120mL.

[0015] Further, the specific preparation steps of the phosphinylated resin coated layered compound are as follows: The chloromethylated cross-linked polystyrene resin and 1,2-dichloroethane are added into a reaction kettle, stirred at 20-25℃ and 500-600r / min for 10-12min, then triethyl phosphite and the zirconium-titanium bimetallic layered compound are added, heated to 40-50℃, continue to react for 4-5h, filter, wash the filter cake with N,N-dimethylformamide and methanol for 2-4 times respectively, vacuum drying at 60-70℃ for 1-2h, to obtain a phosphinylated resin coated layered compound.

[0016] Further, the use amount ratio of the chloromethylated cross-linked polystyrene resin, 1,2-dichloroethane, triethyl phosphite and the zirconium-titanium bimetallic layered compound is 22-25g:55-60g:30-40g:70-80g.

[0017] Further, the specific preparation steps of the cation exchange resin coated layered compound are as follows: The phosphinylated resin coated layered compound and 98% sulfuric acid are added into a reaction kettle according to the use amount ratio of 20-22g:45-50mL, stirred at 60-70℃ and 500-600r / min for 2-3h, then heated to 120-130℃, continue to stir for 2-3h, filter, wash the filter cake with deionized water for 2-4 times, vacuum drying at 60-70℃ for 1-2h, to obtain a cation exchange resin coated layered compound.

[0018] Further, the specific preparation steps of the porous catalyst are as follows: The cation exchange resin coated layered compound, copper nitrate, iron sulfate and a methanol solution with a mass fraction of 50-60% are added into a reaction kettle, stirred at 20-25 DEG C and 500-600 r / min for 2-3 h, filtered, the filter cake is washed with methanol for 2-4 times, vacuum dried at 60-70 DEG C for 1-2 h, the product is transferred into a muffle furnace, calcined at 1000-1200 DEG C under nitrogen protection for 6-8 h, and a porous catalyst is obtained.

[0019] Further, the use amount ratio of the cation exchange resin coated layered compound, copper nitrate, iron sulfate and the methanol solution is 50-60 g:10-12 g:10-12 g:200-300 mL.

[0020] Further, the specific preparation steps of the phenylimidazole derivative are as follows: The benzimidazole, 2-methylbromobenzene, potassium carbonate, a porous catalyst and toluene are added into a reaction kettle, stirred at 20-25 DEG C and 500-600 r / min for 5-6 h, the reaction liquid is concentrated and directly separated by silica gel column chromatography after the stirring is completed, vacuum dried at 60-70 DEG C for 1-2 h, and a phenylimidazole derivative is obtained.

[0021] Further, the use amount ratio of the benzimidazole, 2-methylbromobenzene, potassium carbonate, a porous catalyst and toluene is 30-40 g:32-34 g:40-50 g:3-4 g:300-400 mL.

[0022] The beneficial effects of the present application are as follows: 1.The yield of the phenylimidazole derivative prepared by the present application is high, the benzimidazole, 2-methylbromobenzene, potassium carbonate and a porous catalyst are used as raw materials, toluene is used as a solvent, and the catalyst is obtained at room temperature, the specific surface area of the porous catalyst in the catalytic process is large, and the reaction site is active.

[0023] 2.The porous catalyst of the present application uses the large specific surface area layered structure provided by the zirconium-aluminum layered carrier as a carrier, the surface is thermally hydrated with a titanium-based MOF to obtain a zirconium-titanium bimetallic layered compound, the zirconium-titanium bimetallic layered compound is used as a main carrier, the surface is coated with a resin containing cation exchange capacity to obtain a cation exchange resin coated layered compound, the cation exchange resin coated layered compound contains phosphonic acid groups and sulfonic acid groups, can fix the metal ions in the copper nitrate and iron sulfate, avoids agglomeration, and after calcination, the cation exchange resin becomes a porous carbon layer, further increases the specific surface area and porosity of the porous catalyst, and the zirconium-titanium bimetallic layered compound coated in the process not only provides a large surface area carrier effect, but also plays a catalytic role in the generation of phosphonic acid and sulfonic acid groups. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0025] Embodiment 1: A high-efficiency catalytic process of a phenylimidazole derivative, comprising the following steps: S1: 80 mL of n-butyl zirconate, 20 g of urea and 800 mL of deionized water are added into a reaction kettle, stirred at 60 DEG C and 500 r / min for 10 min, then 22 mL of aluminum oxide is added, and stirring is continued for 30 min, heated to 120 DEG C and aged for 48 h, filtered, the filter cake is washed with deionized water and anhydrous ethanol until the last washing liquid is neutral, and vacuum dried at 60 DEG C for 1 h to obtain a zirconium-aluminum layered carrier.

[0026] S2: 80 g of the zirconium-aluminum layered carrier, 100 g of terephthalic acid and 2 L of N,N-dimethylformamide are added into a reaction kettle lined with polytetrafluoroethylene, stirred at 20 DEG C and 500 r / min for 20 min, then 50 g of n-butyl titanate is added, and stirring is continued for 20 min, then 100 mL of acetic acid solution is added, ultrasonic dispersion is carried out for 40 min, heated to 120 DEG C, and stirring is continued for 24 h, and then naturally cooled to room temperature, filtered, the filter cake is washed with N,N-dimethylformamide and methanol respectively for 2 times, and vacuum dried at 60 DEG C for 1 h to obtain a zirconium-titanium bimetallic layered compound.

[0027] S3: 22 g of chloromethylated crosslinked polystyrene resin and 55 g of 1,2-dichloroethane are added into a reaction kettle, stirred at 20 DEG C and 500 r / min for 10 min, then 30 g of triethyl phosphite and 70 g of the zirconium-titanium bimetallic layered compound are added, heated to 40 DEG C, and reaction is continued for 4 h, filtered, the filter cake is washed with N,N-dimethylformamide and methanol respectively for 2 times, and vacuum dried at 60 DEG C for 1 h to obtain a phosphinylated resin coated layered compound.

[0028] S4: 20 g of the phosphinylated resin coated layered compound and 45 mL of 98% mass fraction sulfuric acid are added into a reaction kettle, stirred at 60 DEG C and 500 r / min for 2 h, then heated to 120 DEG C, and stirring is continued for 2 h, filtered, the filter cake is washed with deionized water for 2 times, and vacuum dried at 60 DEG C for 1 h to obtain a cation exchange resin coated layered compound.

[0029] S5: 50 g of cation exchange resin coated layered compound, 10 g of copper nitrate, 10 g of iron sulfate and 200 mL of 50% mass fraction methanol solution were added into a reaction kettle, stirred at 20°C and 500 r / min for 2 h, filtered, the filter cake was washed with methanol for 2 times, vacuum dried at 60°C for 1 h, the product was transferred to a muffle furnace, calcined at 1000°C for 6 h under nitrogen protection, and a porous catalyst was obtained.

[0030] S6: 30 g of benzimidazole, 32 g of 2-methylbromobenzene, 40 g of potassium carbonate, 3 g of porous catalyst and 300 mL of toluene were added into a reaction kettle, stirred at 20°C and 500 r / min for 5 h, after the reaction was completed, the reaction solution was directly separated by silica gel column chromatography, vacuum dried at 60°C for 1 h, and a phenylimidazole derivative was obtained.

[0031] Example 2: An efficient catalytic process of a phenylimidazole derivative, comprising the following steps: S1: 85 mL of n-butyl zirconate, 25 g of urea and 850 mL of deionized water were added into a reaction kettle, stirred at 65°C and 550 r / min for 11 min, then 26 mL of aluminum oxide was added, and the stirring was continued for 35 min, heated to 125°C and aged for 49 h, suction filtered, the filter cake was washed with deionized water and anhydrous ethanol until the last washing liquid was neutral, and vacuum dried at 65°C for 1.5 h to obtain a zirconium-aluminum layered carrier.

[0032] S2: 85 g of zirconium-aluminum layered carrier, 110 g of terephthalic acid and 2.5 L of N,N-dimethylformamide were added into a reaction kettle lined with polytetrafluoroethylene, stirred at 22.5°C and 550 r / min for 25 min, then 55 g of n-butyl titanate was added, and the stirring was continued for 25 min, then 110 mL of acetic acid solution was added, ultrasonic dispersed for 45 min, heated to 125°C, and the stirring was continued for 25 h, and then naturally cooled to room temperature, filtered, the filter cake was washed with N,N-dimethylformamide and methanol for 3 times respectively, and vacuum dried at 65°C for 1.5 h to obtain a zirconium-titanium bimetallic layered compound.

[0033] S3: 23.5 g of chloromethylated crosslinked polystyrene resin and 57.5 g of 1,2-dichloroethane were added into a reaction kettle, stirred at 22.5°C and 550 r / min for 11 min, then 35 g of triethyl phosphite and 75 g of zirconium-titanium bimetallic layered compound were added, heated to 45°C, and the reaction was continued for 4.5 h, filtered, the filter cake was washed with N,N-dimethylformamide and methanol for 3 times respectively, and vacuum dried at 65°C for 1.5 h to obtain a phosphinylated resin coated layered compound.

[0034] S4: 21 g of phosphonated resin-coated layered compound and 47.5 mL of 98% mass fraction sulfuric acid were added into a reaction kettle, stirred at 65 °C and 550 r / min for 2.5 h, then heated to 125 °C, and continued to stir for 2.5 h, filtered, the filter cake was washed with deionized water for 3 times, vacuum dried at 65 °C for 1.5 h, to obtain a cation exchange resin-coated layered compound.

[0035] S5: 55 g of cation exchange resin-coated layered compound, 11 g of copper nitrate, 11 g of iron sulfate and 250 mL of 55% mass fraction methanol solution were added into a reaction kettle, stirred at 22.5 °C and 550 r / min for 2.5 h, filtered, the filter cake was washed with methanol for 3 times, vacuum dried at 65 °C for 1.5 h, the product was transferred to a muffle furnace, calcined at 1100 °C for 7 h under nitrogen protection, to obtain a porous catalyst.

[0036] S6: 35 g of benzimidazole, 33 g of 2-methylbromobenzene, 45 g of potassium carbonate, 3.5 g of porous catalyst and 350 mL of toluene were added into a reaction kettle, stirred at 22.5 °C and 550 r / min for 5.5 h, after the reaction was completed, the reaction solution was directly separated by silica gel column chromatography, vacuum dried at 65 °C for 1.5 h, to obtain a phenylimidazole derivative.

[0037] Example 3: An efficient catalytic process of a phenylimidazole derivative, comprising the following steps: S1: 90 mL of n-butyl zirconate, 30 g of urea and 900 mL of deionized water were added into a reaction kettle, stirred at 70 °C and 600 r / min for 12 min, then 30 mL of aluminum oxide was added, and continued to stir for 40 min, heated to 130 °C and aged for 50 h, suction filtered, the filter cake was washed with deionized water and anhydrous ethanol until the last washing liquid was neutral, vacuum dried at 70 °C for 2 h, to obtain a zirconium-aluminum layered carrier.

[0038] S2: 90 g of zirconium-aluminum layered carrier, 120 g of terephthalic acid and 3 L of N,N-dimethylformamide were added into a reaction kettle lined with polytetrafluoroethylene, stirred at 25 °C and 600 r / min for 30 min, then 60 g of n-butyl titanate was added, continued to stir for 30 min, then 120 mL of acetic acid solution was added, ultrasonic dispersion for 50 min, heated to 130 °C, continued to stir for 26 h, naturally cooled to room temperature, filtered, the filter cake was washed with N,N-dimethylformamide and methanol for 4 times respectively, vacuum dried at 70 °C for 2 h, to obtain a zirconium-titanium bimetallic layered compound.

[0039] S3: 25 g of chloromethylated crosslinked polystyrene resin and 60 g of 1,2-dichloroethane were added into a reaction kettle, stirred at 25 °C and 600 r / min for 12 min, then 40 g of triethyl phosphite and 80 g of zirconium-titanium bimetallic layered compound were added, heated to 50 °C, and continued to react for 5 h, filtered, the filter cake was washed with N,N-dimethylformamide and methanol for 4 times respectively, vacuum dried at 70 °C for 2 h, to obtain a phosphinylated resin coated layered compound.

[0040] S4: 22 g of the phosphinylated resin coated layered compound and 50 mL of 98% mass fraction sulfuric acid were added into a reaction kettle, stirred at 70 °C and 600 r / min for 3 h, then heated to 130 °C, and continued to stir for 3 h, filtered, the filter cake was washed with deionized water for 4 times, vacuum dried at 70 °C for 2 h, to obtain a cation exchange resin coated layered compound.

[0041] S5: 60 g of the cation exchange resin coated layered compound, 12 g of copper nitrate, 12 g of iron sulfate and 300 mL of methanol solution were added into a reaction kettle, stirred at 25 °C and 600 r / min for 3 h, filtered, the filter cake was washed with methanol for 4 times, vacuum dried at 70 °C for 2 h, the product was transferred to a muffle furnace, calcined at 1200 °C for 8 h under nitrogen protection, to obtain a porous catalyst.

[0042] S6: 40 g of benzimidazole, 34 g of 2-methylbromobenzene, 50 g of potassium carbonate, 4 g of the porous catalyst and 400 mL of 60% mass fraction toluene were added into a reaction kettle, stirred at 25 °C and 600 r / min for 6 h, after the end, the reaction solution was directly separated by silica gel column chromatography, vacuum dried at 70 °C for 2 h, to obtain a phenylimidazole derivative.

[0043] Comparative Example 1: on the basis of Example 3, the zirconium-titanium bimetallic layered compound in step S3 was replaced by the zirconium-aluminum layered carrier in step S1.

[0044] Comparative Example 2: on the basis of Example 3, the chloromethylated crosslinked polystyrene resin in step S3 was replaced by polystyrene resin.

[0045] Comparative Example 3: on the basis of Example 3, the cation exchange resin coated layered compound in step S5 was replaced by the zirconium-titanium bimetallic layered compound in step S2.

[0046] The phenylimidazole derivatives prepared in Example 1-Example 3 and Comparative Example 1-Comparative Example 3 were tested for performance, and the results are shown in Table 1: Table 1

[0047] As can be seen from Table 1, the phenylimidazole derivatives prepared in Examples 1-3 have high yield, and the porous catalysts generated by catalyzing the phenylimidazole derivatives have high specific surface area and large average pore size.

[0048] In Comparative Example 1, the zirconium-titanium bimetallic layered compound in step S3 is replaced by the zirconium-aluminum layered carrier in step S1, and the zirconium-aluminum layered carrier is directly used. The lack of Lewis acid sites provided by titanium atoms results in insufficient surface acidity of the carrier. The absence of titanium makes the carrier unable to effectively catalyze the formation of phosphonate groups, resulting in poor resin coating and decreased dispersion of metal loading. The specific surface area of the zirconium-aluminum carrier is significantly lower than that of the zirconium-titanium bimetallic compound, reducing the exposure of active sites.

[0049] In Comparative Example 2, the chloromethylated crosslinked polystyrene resin in step S3 is replaced by a polystyrene resin. The ordinary polystyrene resin does not contain chloromethyl groups and cannot react with triethyl phosphite to form phosphonate groups, resulting in a loss of ion exchange capacity of the resin. The lack of phosphonic acid groups and subsequent sulfonic acid groups generated by sulfonation makes it impossible for copper ions and iron ions to be stably anchored through ion exchange. After calcination, the metal particles are severely agglomerated. The non-functionalized resin forms a dense carbon layer after carbonization, blocking the carrier pores and hindering the mass transfer of reactants.

[0050] In Comparative Example 3, the cation exchange resin coating layer in step S5 is replaced by the zirconium-titanium bimetallic layered compound in step S2. The resin coating layer is not introduced, and after calcination, the hierarchical porous carbon skeleton cannot be formed, the specific surface area is lost, and copper ions and iron ions cannot be stably anchored through ion exchange. After calcination, the metal particles are severely agglomerated.

[0051] Although embodiments of the present application have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and alterations can be made thereto without departing from the principles and spirit of the present application.

Claims

1. A high-efficiency catalytic process for phenylimidazole derivatives, characterized in that, It comprises the following steps: Step one: hydrolysis and polycondensation of n-butyl zirconate, urea provides alkaline environment to promote hydrolysis balance, alumina is embedded into interlayer as structure stabilizer, zirconium aluminum layered carrier is obtained; terephthalic acid as ligand is hydrothermally synthesized on the surface of zirconium aluminum layered carrier to obtain titanium-based MOF, zirconium titanium bimetallic layered compound is obtained; Step two: Lewis acid sites in zirconium titanium bimetallic layered compound are used to catalyze the reaction of chloromethylated crosslinked polystyrene resin and triethyl phosphite to obtain phosphine resin coated layered compound, which is hydrolyzed and sulfonated to phosphonic acid group under the action of concentrated sulfuric acid, and sulfonic acid group is introduced on the resin skeleton to obtain cation exchange resin coated layered compound; Step three: through the cation exchange function of cation exchange resin coated layered compound, copper salt and iron salt are fixed and then calcined to obtain a porous catalyst; Step four: a phenyl imidazole derivative is obtained by using benzimidazole, 2-methyl bromobenzene, potassium carbonate and porous catalyst as raw materials, toluene as solvent, stirring at 20-25℃ and 500-600r / min for 5-6h.

2. A process for the efficient catalysis of phenylimidazole derivatives according to claim 1, characterized in that, The specific preparation steps of the zirconium aluminum layered carrier are as follows: n-butyl zirconate, urea and deionized water are added to the reaction kettle, stirred at 60-70℃ and 500-600r / min for 10-12min, then alumina is added, continue to stir for 30-40min, heat to 120-130℃ and age for 48-50h, filter, wash the filter cake with deionized water and anhydrous ethanol until the last washing liquid is neutral, vacuum drying, to obtain zirconium aluminum layered carrier; The amount ratio of n-butyl zirconate, urea, deionized water and alumina is 80-90mL:20-30g:800-900mL:22-30mL.

3. A process for the efficient catalysis of phenylimidazole derivatives according to claim 1, characterized in that, The specific preparation steps of the zirconium titanium bimetallic layered compound are as follows: The zirconium aluminum layered carrier, terephthalic acid and N,N-dimethylformamide are added to the reaction kettle lined with polytetrafluoroethylene, stirred at 20-25℃ and 500-600r / min for 20-30min, then n-butyl titanate is added, continue to stir for 20-30min, then acetic acid solution is added, ultrasonic dispersion for 40-50min, heat to 120-130℃, continue to stir for 24-26h, natural cooling, filtration, washing, vacuum drying, to obtain zirconium titanium bimetallic layered compound; The amount ratio of the zirconium aluminum layered carrier, terephthalic acid, N,N-dimethylformamide, n-butyl titanate and acetic acid solution is 80-90g:100-120g:2-3L:50-60g:100-120mL.

4. A process for the efficient catalysis of phenylimidazole derivatives according to claim 1, characterized in that, The specific preparation steps of the phosphine resin coated layered compound are as follows: Chloromethylated crosslinked polystyrene resin and 1,2-dichloroethane are added to the reaction kettle, stirred at 20-25℃ and 500-600r / min for 10-12min, then triethyl phosphite and zirconium titanium bimetallic layered compound are added, heated to 40-50℃, continue to react for 4-5h, filtration, washing, vacuum drying, to obtain phosphine resin coated layered compound.

5. A process for the efficient catalysis of phenylimidazole derivatives according to claim 4, characterized in that, The amount ratio of the chloromethylated cross-linked polystyrene resin, 1,2-dichloroethane, triethyl phosphite and zirconium titanium double metal layer compound is 22-25g:55-60g:30-40g:70-80g.

6. A process for the efficient catalysis of phenylimidazole derivatives according to claim 1, characterized in that, The cation exchange resin coated layered compound is prepared by the following steps: The phosphonated resin coated layered compound and 98% sulfuric acid are added into a reaction kettle according to the amount ratio of 20-22g:45-50mL, stirred at 60-70℃ and 500-600r / min for 2-3h, then heated to 120-130℃ and continuously stirred for 2-3h, filtered, washed, vacuum dried to obtain the cation exchange resin coated layered compound.

7. A process for the efficient catalysis of phenylimidazole derivatives according to claim 1, characterized in that, The porous catalyst is prepared by the following steps: The cation exchange resin coated layered compound, copper nitrate, iron sulfate and 50-60% methanol solution are added into a reaction kettle, stirred at 20-25℃ and 500-600r / min for 2-3h, filtered, washed, vacuum dried, and the product is transferred into a muffle furnace, calcined at 1000-1200℃ for 6-8h under nitrogen protection to obtain the porous catalyst.

8. A process for the efficient catalysis of phenylimidazole derivatives according to claim 7, characterized in that, The amount ratio of the cation exchange resin coated layered compound, copper nitrate, iron sulfate and methanol solution is 50-60g:10-12g:10-12g:200-300mL.

9. A process for the efficient catalysis of phenylimidazole derivatives according to claim 1, characterized in that, The phenyl imidazole derivative is prepared by the following steps: The benzimidazole, 2-methylbromobenzene, potassium carbonate, porous catalyst and toluene are added into a reaction kettle, stirred at 20-25℃ and 500-600r / min for 5-6h, and after the reaction is completed, the reaction solution is concentrated and directly separated by silica gel column chromatography, vacuum dried at 60-70℃ for 1-2h to obtain a phenyl imidazole derivative.

10. A process for the efficient catalysis of phenylimidazole derivatives according to claim 1, characterized in that, The amount ratio of the benzimidazole, 2-methylbromobenzene, potassium carbonate, porous catalyst and toluene is 30-40g:32-34g:40-50g:3-4g:300-400mL.

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