CN109999912B - Bifunctional heterogeneous ruthenium-based catalyst and method for catalytic synthesis of 3,3,5, 5-tetramethyl biphenol by using same - Google Patents
Bifunctional heterogeneous ruthenium-based catalyst and method for catalytic synthesis of 3,3,5, 5-tetramethyl biphenol by using same Download PDFInfo
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Abstract
A bifunctional heterogeneous ruthenium-based catalyst and a method for synthesizing 3,3,5, 5-tetramethyl diphenol by catalyzing the catalyst. The invention discloses a method for synthesizing 3,3,5, 5-tetramethyl diphenol by a dual-functional ruthenium-based catalyst (Ru @ NH2-MIL-53(Al)) through a green one-pot method, namely, an aluminum-based metal organic framework material (NH2-MIL-53(Al)) is prepared to be used as a carrier, a loaded metal ruthenium nano particle is used as a catalyst, 2, 6-dimethylphenol is used as a reaction substrate, oxygen is used as an oxygen source in an oxidative coupling stage in a tert-butyl alcohol solvent, hydrogen is used as a reducing agent in a reduction hydrogenation stage, and the 3,3,5, 5-tetramethyl diphenol is synthesized through the green one-pot method. The bifunctional ruthenium-based catalyst Ru @ NH2-MIL-53(Al) has high catalytic activity and mild catalytic reaction conditions, can be recycled, has the catalyst dosage of 2.3 percent, and has the yield of 3,3,5, 5-tetramethyl diphenol reaching 81.43 percent under normal pressure.
Description
Technical Field
The invention relates to a catalyst and a method for catalytically synthesizing 3,3,5, 5-tetramethyl diphenol by using the catalyst, in particular to a bifunctional heterogeneous ruthenium-based catalyst and a method for catalytically synthesizing 3,3,5, 5-tetramethyl diphenol by using the catalyst, belonging to the field of catalytic organic synthesis.
Background
3,3,5, 5-tetramethyl biphenyl diphenol (TMBP) can be used as a building block of a polymer electrolyte membrane, a modified intermediate of products such as polyester, polyurethane, epoxy resin, polycarbonate, polysulfone and the like, engineering plastics can be modified to prepare an excellent composite material, and the advantages of oxidation resistance and inhibitory activity of the TMBP are commonly used as an antioxidant of rubber and emulsion and an antioxidant of plastics.
The reported method for synthesizing TMBP mainly comprises the steps of catalyzing and synthesizing 3,3,5, 5-tetramethyl biphenyl Diquinone (DPQ) by using oxydol, potassium permanganate, periodic acid and the like as oxidizing agents through the oxidative coupling reaction of 2, 6-Dimethylphenol (DMP), and then reducing the DPQ into the TMBP by adding a reducing agent. However, these methods have problems that an excessive amount of metal oxidizing agent is added in the oxidation stage, an organic/inorganic reducing agent is added in the reduction stage, and the like, and a large amount of resources are wasted and environmental pollution is caused. Therefore, the development of a green sustainable synthesis technology is a key problem in modern chemical production. The green one-pot synthesis technology of the bifunctional catalyst can reduce the waste of intermediate products, save money and time and avoid environmental pollution. In addition, the use of the heterogeneous catalyst can ensure that the catalyst is easy to recover and recycle, thereby reducing the waste of resources. In recent years, the research of homogeneous transition metal-like catalysts with high catalytic activity and capable of being recycled attracts people's attention.
Metal organic framework Materials (MOFs) are a new class of materials in the field of metal organic materials, and form a 3D coordination network structure by coordination of metal nodes and organic bridging ligands, and are commonly used as carriers of heterogeneous catalysts in recent years. The MOFs as the top branch of organic and inorganic materials has excellent characteristics of high specific surface area, large aperture, low density and the like, and is widely applied to the fields of gas storage, purification, molecular sensing, drug delivery, biomedicine, photocatalysis, heterogeneous catalysis and the like. The characteristic that the inner surface of the gap is easy to functionalize is another interesting place of the MOFs material, and the utilization of the functional group in the organic bridging ligand can be applied to a heterogeneous catalytic system to establish a functional organic site with catalytic activity. Commonly used groups for the functionalization of organic bridging ligands in MOFs are amino, amide, pyridine, etc. Amino-functionalized MOFs have attracted considerable attention in these materials because amino-functionalized organic bridging ligands can serve as sites for interaction with metal nanoparticles to form extremely small, highly dispersible metal nanoparticles, greatly improving the catalytic activity of heterogeneous catalysts.
Disclosure of Invention
In view of the above, the present invention provides a bifunctional heterogeneous ruthenium-based catalyst and a preparation method thereof from the perspective of green chemistry, and a method for preparing the same using a clean gas O at normal pressure2And H2A process for preparing TMBP from O2Selectively promoting oxidative coupling of DMP to form DPQ in an atmosphere, and then in H2DPQ was successfully reduced to TMBP in the atmosphere. Only one by-product water is formed in the process, so that the environmental pollution and the resource waste are reduced. And the catalyst is stable and still has high catalytic activity after being repeatedly used for 5 times. When the amount of the catalyst is 2.3 percent, the yield of the TMBP reaches 83.43 percent.
In order to achieve the purpose, the invention adopts the following technical scheme:
a bifunctional heterogeneous ruthenium-based catalyst has a chemical formula of Ru @ NH2-MIL-53(Al)。
The bifunctional heterogeneous ruthenium-based catalyst adopts metal organic framework material NH2MIL-53(Al) is used as a carrier, the metallic ruthenium is anchored by using nitrogen atoms in the amino groups of the material, and then the ruthenium is reduced into the metallic ruthenium nano-particles by using sodium borohydride. The superfine metal nanoparticles wrapped by the MOFs material are formed, the aluminum-based MOFs material is used as a carrier, the porosity is high, the loading effect is good, the catalyst is excellent in gas-liquid-solid three-phase reaction as a breathing material, the prepared high-dispersion supported ruthenium nanoparticle catalyst is high in stability and good in dispersion effect in an organic solvent, and the catalyst plays a role in an oxidative coupling stage and a catalytic effect in a reductive hydrogenation stage as a bifunctional catalyst, and is mild in reaction conditions and high in stability.
Further, the bifunctional heterogeneous ruthenium-based catalyst is prepared by the following method:
1) adding aluminum nitrate nonahydrate and 2-aminoterephthalic acid into a solvent 1, performing ultrasonic treatment for 10-20 min, stirring for 10-30 min, transferring into an autoclave with a polytetrafluoroethylene inner container, heating to 110-150 ℃, reacting for 3-5 h, filtering after the reaction is finished, washing a product with a solvent 2, and performing vacuum drying at 40-60 ℃ for 1-2 h until the solvent 2 is completely volatilized to obtain yellow powder;
2) transferring the yellow powder into a Soxhlet extractor, washing the yellow powder with a solvent 3 at 110-150 ℃ for 5-8 h, filtering, washing with a solvent 2 again, and drying in vacuum at 40-60 ℃ for 16-24 h to obtain a carrier NH2-MIL-53(Al)；
3) Adding carrier NH2Mixing MIL-53(Al), a ruthenium precursor and a solvent 4, performing ultrasonic treatment for 5-15 min, continuously stirring for 5-8 h, slowly dropwise adding a sodium borohydride solution in an ice bath, continuously performing ice bath reaction for 3-6 h, centrifuging, washing with a solvent 2, and performing vacuum drying at 40-60 ℃ for 16-24 h to obtain the dual-function heterogeneous ruthenium-based catalyst.
The preparation method of the bifunctional heterogeneous ruthenium-based catalyst is simple, the reaction condition is mild, and three wastes are not generated.
Further, the solvent 1 is any one or a mixture of methanol, ethanol and deionized water; the solvent 2 is any one or mixture of methanol, ethanol and acetone; the solvent 3 is any one or a mixture of N, N-dimethylformamide, ethanol and trichloromethane; the solvent 4 is one or more of ethanol, water and methanol.
The further beneficial effects of the adoption of the method are that the synthesized NH2-MIL-53(Al) has complete crystal form, and is quickly dried during filtration, so that the unreacted 2-amino terephthalic acid in the pore channel can be conveniently removed.
Further, the mass ratio of the aluminum nitrate nonahydrate to the 2-amino terephthalic acid in the step 1) is 1: 0.4-0.6, and the amount of the solvent 1 is that the mixture of the aluminum nitrate nonahydrate and the 2-amino terephthalic acid per gram is added into 5-10 ml of the solvent 1; NH described in step 3)2Mix mass ratio of MIL-53(Al), ruthenium precursor, solvent 4Is 1: and 0.1-0.4: 300-400, wherein the adding amount of the sodium borohydride solution is 6-10 times of the molar weight of the sodium borohydride added into the mixed solution as much as that of the metal ruthenium.
The further beneficial effect of the method is that the ultrafine ruthenium nano-particles can be uniformly loaded on the carrier, and the catalytic active sites are increased.
The invention also provides a method for synthesizing 3,3,5, 5-tetramethyl biphenyl diphenol under the catalysis of the bifunctional heterogeneous ruthenium-based catalyst, which comprises the following steps:
taking 2, 6-dimethylphenol as a reaction raw material, carrying out catalytic reaction in a solvent A under the oxygen atmosphere by using the bifunctional heterogeneous ruthenium-based catalyst according to claim 1, cooling to 20-25 ℃, then changing the oxygen atmosphere into the hydrogen atmosphere, and continuing the reaction to obtain the 3,3,5, 5-tetramethyl biphenol.
The 3,3,5, 5-tetramethyl diphenol is synthesized by using Ru @ NH2-MIL-53(Al) catalyst through oxidative coupling and hydrogenation reduction one-pot reaction, the problem that the traditional two-step method has complicated steps, excessive reducing agent is added, and a large amount of water resource waste and environmental pollution are caused is solved by the one-pot method, the catalytic activity of the 3,3,5, 5-tetramethyl diphenol synthesized by using the bifunctional heterogeneous ruthenium-based catalyst is high, the reaction condition is mild, only one byproduct water is generated, the environmental pollution and the resource waste are reduced, the catalyst is stable, the catalytic activity is still high after the catalyst is repeatedly used for 5 times, and when the reaction temperature is 70 ℃, the reaction time is 24 hours, and the using amount of the catalyst is 2.3%, the yield of the 3,3,5, 5-tetramethyl diphenol can reach 81.43%.
Further, the solvent A is any one or a mixture of more of tert-butyl alcohol, toluene and ethanol, and the mass ratio of the 2, 6-dimethylphenol to the solvent A is 1: 45-65.
The method has the further beneficial effects that the reaction substrate can be completely dissolved, the reaction efficiency is increased, and meanwhile, the reaction substrate also has certain solubility on the intermediate product. The reaction temperature is within the boiling point of the solvent, so that the solvent is ensured not to volatilize, and a good dispersion effect can be achieved.
Further, the reaction temperature under the oxygen atmosphere is 40-80 ℃, and the reaction time is 14-26 h; the reaction temperature under the hydrogen atmosphere is 40-60 ℃, and the reaction time is 4-6 h.
Drawings
FIG. 1 is an XRD spectrum of a bifunctional heterogeneous ruthenium-based catalyst and catalyst support according to the present invention;
FIG. 2 is a large angle XRD spectrum of the bifunctional heterogeneous ruthenium-based catalyst and catalyst support of the present invention;
FIG. 3 is an XPS spectrum of a bifunctional heterogeneous ruthenium-based catalyst of the present invention;
FIG. 4 is an SEM image of a support of the bifunctional heterogeneous ruthenium-based catalyst according to the present invention;
FIG. 5 is an SEM image of a bifunctional heterogeneous ruthenium-based catalyst according to the present invention;
FIG. 6 is a TEM image of the bifunctional heterogeneous ruthenium-based catalyst of the present invention at 10 nm.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, a bifunctional heterogeneous ruthenium-based catalyst was prepared by the following steps:
(1) 750.3mgAl (NO) were weighed out3)9H2O and 362.3mgNH2Adding 5ml of deionized water into BDC, performing ultrasonic treatment for 10min, stirring for 30min, transferring to a 100ml polytetrafluoroethylene liner, putting the polytetrafluoroethylene liner into an autoclave, putting the autoclave into an oven, heating to 150 ℃ at room temperature, keeping for 5h, filtering, washing with ethanol and acetone, drying at 40 ℃ in a vacuum drying oven for 2h, and obtaining yellow powder after acetone is volatilized;
(2) the yellow powder was transferred to a Soxhlet extractor and washed with DMF at 150 ℃ for 8h to remove unreacted NH2-BDC, filtered, washed with ethanol and dried under vacuum at 60 ℃ for 24 h.
(3) Weighing 0.2gNH2-MIL-53(Al) was added to a mixed solution of 30ml of water and 30ml of ethanol and sonicated for 10min, 0.0627g of ruthenium trichloride trihydrate was dissolved in 30ml of water and slowly dropped into the former solution and sonicated for 15min to uniformly disperse ruthenium. Stirring in a beaker for 5 h; 151.2mg of sodium borohydride is weighed and dissolved in 40ml of deionized water to prepare a solution, the solution is slowly dripped into the solution under the ice bath condition, the ice bath is continuously stirred for 4 hours, the centrifugation is carried out, the acetone is used for washing, and the vacuum drying is carried out for 24 hours at the temperature of 60 ℃. Obtaining the bifunctional heterogeneous ruthenium-based catalyst.
Wherein, XRD spectra of the bifunctional heterogeneous ruthenium-based catalyst and the catalyst carrier are shown in figure 1, a large-angle XRD spectrum is shown in figure 2, XPS spectra of the bifunctional heterogeneous ruthenium-based catalyst is shown in figure 3, SEM images of the carrier of the bifunctional heterogeneous ruthenium-based catalyst are shown in figure 4, SEM images of the catalyst are shown in figure 5, and TEM images of the bifunctional heterogeneous ruthenium-based catalyst under 10nm are shown in figure 6.
Example 1
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, performing ultrasonic dispersion uniformly, vacuumizing, introducing high-purity oxygen, reacting at 70 ℃ for 24 hours in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, performing ultrasonic dispersion uniformly, centrifuging, and performing rotary evaporation on light yellow supernatant to obtain a crude product of 3,3,5, 5-tetramethylbiphenol, wherein the product yield is 81.43%.
Example 2
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, uniformly dispersing by ultrasonic wave, vacuumizing, charging high-purity oxygen, reacting for 26h at 70 ℃ in oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6h at 60 ℃, and finishing the reactionAfter finishing, adding a triple-filtration methane solvent, performing ultrasonic treatment to uniformly disperse the mixture, centrifuging the mixture, and performing rotary evaporation on light yellow supernatant to obtain a crude product of the 3,3,5, 5-tetramethyl diphenol, wherein the product yield is 74.12%.
Example 3
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, uniformly dispersing by ultrasonic, vacuumizing, introducing high-purity oxygen, reacting for 22 hours at 70 ℃ in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuously reacting for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, uniformly dispersing by ultrasonic, centrifuging, and rotationally evaporating light yellow supernatant to obtain a crude product of the 3,3,5, 5-tetramethylbiphenol, wherein the yield of the product is 70.08%.
Example 4
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, performing ultrasonic dispersion uniformly, vacuumizing, introducing high-purity oxygen, reacting at 70 ℃ for 20h in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6h at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, performing ultrasonic dispersion uniformly, centrifuging, and performing rotary evaporation on light yellow supernatant to obtain a crude product of 3,3,5, 5-tetramethylbiphenol, wherein the product yield is 62.37%.
Example 5
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, performing ultrasonic dispersion uniformly, vacuumizing, charging high-purity oxygen, reacting at 70 ℃ for 18h in an oxygen atmosphere, cooling to room temperature, vacuumizing, and replacing gas with high-purity hydrogenAnd (3) continuously reacting for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, performing ultrasonic treatment to uniformly disperse the triple-filtration methane solvent, centrifuging, and performing rotary evaporation on light yellow supernatant to obtain a crude product of the 3,3,5, 5-tetramethyl diphenol, wherein the product yield is 51.42%.
Example 6
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, uniformly dispersing by ultrasonic, vacuumizing, charging high-purity oxygen, reacting for 16h at 70 ℃ in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6h at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, uniformly dispersing by ultrasonic, centrifuging, and carrying out rotary evaporation on light yellow supernatant to obtain a crude product of the 3,3,5, 5-tetramethylbiphenol, wherein the product yield is 47.69%.
Example 7
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, uniformly dispersing by ultrasonic, vacuumizing, charging high-purity oxygen, reacting for 24 hours at 80 ℃ in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, uniformly dispersing by ultrasonic, centrifuging, and rotationally evaporating light yellow supernatant to obtain a crude product of 3,3,5, 5-tetramethylbiphenol, wherein the product yield is 68.37%.
Example 8
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, uniformly dispersing by ultrasonic wave, vacuumizing, charging high-purity oxygen, reacting at 60 ℃ for 24h in oxygen atmosphere, cooling to room temperatureVacuumizing, replacing gas with high-purity hydrogen, continuously reacting for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, performing ultrasonic treatment to uniformly disperse the triple-filtration methane solvent, centrifuging, and performing rotary evaporation on light yellow supernatant to obtain a crude product of the 3,3,5, 5-tetramethyl diphenol, wherein the product yield is 34.73%.
Example 9
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, uniformly dispersing by ultrasonic, vacuumizing, charging high-purity oxygen, reacting for 24 hours at 50 ℃ in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, uniformly dispersing by ultrasonic, centrifuging, and carrying out rotary evaporation on light yellow supernatant to obtain a crude product of the 3,3,5, 5-tetramethylbiphenol, wherein the product yield is 15.69%.
Example 10
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, uniformly dispersing by ultrasonic, vacuumizing, charging high-purity oxygen, reacting for 24 hours at 40 ℃ in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, uniformly dispersing by ultrasonic, centrifuging, and carrying out rotary evaporation on light yellow supernatant to obtain a crude product of 3,3,5, 5-tetramethylbiphenol, wherein the product yield is 7.23%.
Example 11
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged into a 15ml Schlenk tube, and 0.005g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, uniformly dispersing by ultrasonic wave, vacuumizing, and charging high-purity oxygen and oxygenReacting for 24 hours at 70 ℃ in the atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, performing ultrasonic treatment to uniformly disperse the triple-filtration methane solvent, centrifuging, and performing rotary evaporation on light yellow supernatant to obtain a crude product of the 3,3,5, 5-tetramethyl biphenyl diphenol, wherein the product yield is 30.65%.
Example 12
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.015g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, performing ultrasonic dispersion uniformly, vacuumizing, introducing high-purity oxygen, reacting at 70 ℃ for 24 hours in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, performing ultrasonic dispersion uniformly, centrifuging, and performing rotary evaporation on light yellow supernatant to obtain a crude product of 3,3,5, 5-tetramethylbiphenol, wherein the product yield is 75.69%.
Example 13
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.02g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, uniformly dispersing by ultrasonic, vacuumizing, charging high-purity oxygen, reacting for 24 hours at 70 ℃ in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, uniformly dispersing by ultrasonic, centrifuging, and carrying out rotary evaporation on light yellow supernatant to obtain a crude product of the 3,3,5, 5-tetramethylbiphenol, wherein the product yield is 73.25%.
Example 14
The bifunctional heterogeneous ruthenium-based catalyst after the catalytic synthesis of 3,3,5, 5-tetramethylbiphenol in example 1 was used to catalyze the synthesis of 3,3,5, 5-tetramethylbiphenol again:
0.06g of 2, 6-dimethylphenol was charged into a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium group was addedCatalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, performing ultrasonic dispersion uniformly, vacuumizing, introducing high-purity oxygen, reacting at 70 ℃ for 24 hours in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, performing ultrasonic dispersion uniformly, centrifuging, and performing rotary evaporation on light yellow supernatant to obtain a crude product of 3,3,5, 5-tetramethylbiphenol, wherein the product yield is 80.56%.
Example 15
The bifunctional heterogeneous ruthenium-based catalyst after the catalytic synthesis of 3,3,5, 5-tetramethylbiphenol in example 14 was used to catalyze the synthesis of 3,3,5, 5-tetramethylbiphenol again:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, uniformly dispersing by ultrasonic, vacuumizing, charging high-purity oxygen, reacting for 24 hours at 70 ℃ in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, uniformly dispersing by ultrasonic, centrifuging, and carrying out rotary evaporation on light yellow supernatant to obtain a crude product of the 3,3,5, 5-tetramethylbiphenol, wherein the product yield is 78.47%.
Example 16
The bifunctional heterogeneous ruthenium-based catalyst after the catalytic synthesis of 3,3,5, 5-tetramethylbiphenol in example 15 was used to catalyze the synthesis of 3,3,5, 5-tetramethylbiphenol again:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, performing ultrasonic dispersion uniformly, vacuumizing, introducing high-purity oxygen, reacting at 70 ℃ for 24 hours in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, performing ultrasonic dispersion uniformly, centrifuging, and performing rotary evaporation on light yellow supernatant to obtain a crude product of 3,3,5, 5-tetramethylbiphenol, wherein the product yield is 76.51%.
Example 17
The bifunctional heterogeneous ruthenium-based catalyst after the catalytic synthesis of 3,3,5, 5-tetramethylbiphenol in example 16 was used to catalyze the synthesis of 3,3,5, 5-tetramethylbiphenol again:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of tert-butyl alcohol, uniformly dispersing by ultrasonic, vacuumizing, charging high-purity oxygen, reacting for 24 hours at 70 ℃ in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6 hours at 60 ℃, after the reaction is finished, adding a triple-filtration methane solvent, uniformly dispersing by ultrasonic, centrifuging, and carrying out rotary evaporation on light yellow supernatant to obtain a crude product of the 3,3,5, 5-tetramethylbiphenol, wherein the product yield is 70.36%.
Example 18
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of ethanol, performing ultrasonic dispersion uniformly, vacuumizing, filling high-purity oxygen, reacting at 70 ℃ for 24 hours in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, performing ultrasonic dispersion uniformly, centrifuging, and performing rotary evaporation on light yellow supernatant to obtain a crude product of the 3,3,5, 5-tetramethylbiphenol, wherein the product yield is 34.12%.
Example 19
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of toluene, uniformly dispersing by ultrasonic, vacuumizing, filling high-purity oxygen, reacting for 24 hours at 70 ℃ in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, uniformly dispersing by ultrasonic, centrifuging, and carrying out rotary evaporation on light yellow supernatant to obtain a crude product of 3,3,5, 5-tetramethylbiphenol, namely the productThe yield thereof was found to be 78.23%.
Example 20
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of trichloromethane, performing ultrasonic dispersion uniformly, vacuumizing, introducing high-purity oxygen, reacting at 70 ℃ for 24 hours in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, performing ultrasonic dispersion uniformly, centrifuging, and performing rotary evaporation on light yellow supernatant to obtain a crude product of the 3,3,5, 5-tetramethylbiphenol, wherein the product yield is 24.23%.
Example 21
The bifunctional heterogeneous ruthenium-based catalyst is used for catalyzing and synthesizing 3,3,5, 5-tetramethyl diphenol:
0.06g of 2, 6-dimethylphenol was charged to a 15ml Schlenk tube, and 0.01g of a bifunctional heterogeneous ruthenium-based catalyst (Ru @ NH)2-MIL-53(Al)), adding 3ml of dichloromethane, performing ultrasonic dispersion uniformly, vacuumizing, filling high-purity oxygen, reacting at 70 ℃ for 24 hours in an oxygen atmosphere, cooling to room temperature, vacuumizing, replacing gas with high-purity hydrogen, continuing to react for 6 hours at 60 ℃, adding a triple-filtration methane solvent after the reaction is finished, performing ultrasonic dispersion uniformly, centrifuging, and performing rotary evaporation on light yellow supernatant to obtain a crude product of the 3,3,5, 5-tetramethylbiphenol, wherein the product yield is 30.67%.
Claims (9)
1. A method for catalytically synthesizing 3,3,5, 5-tetramethyl biphenyl diphenol by using a bifunctional heterogeneous ruthenium-based catalyst is characterized by comprising the following steps of:
taking 2, 6-dimethylphenol as a reaction raw material, carrying out catalytic reaction on the 2, 6-dimethylphenol in a solvent A under an oxygen atmosphere by using a bifunctional heterogeneous ruthenium-based catalyst, cooling to 20-25 ℃, then changing the oxygen atmosphere into a hydrogen atmosphere, and continuously reacting to obtain the 3,3,5, 5-tetramethyl diphenol;
wherein the chemical formula of the catalyst is Ru @ NH2-MIL-53(Al), said Ru being metallic ruthenium.
2. The method for catalytically synthesizing 3,3,5, 5-tetramethylbiphenol according to claim 1, wherein the catalyst is prepared by the following steps:
1) adding aluminum nitrate nonahydrate and 2-aminoterephthalic acid into a solvent 1, performing ultrasonic treatment for 10-20 min, stirring for 10-30 min, transferring into an autoclave with a polytetrafluoroethylene inner container, performing heating reaction, filtering after the reaction is finished, washing a product with the solvent 2, and performing vacuum drying until the solvent 2 is completely volatilized to obtain yellow powder;
2) transferring the yellow powder to a Soxhlet extractor, washing with solvent 3, filtering, washing again with solvent 2, and vacuum drying to obtain carrier NH2-MIL-53(Al)；
3) Adding carrier NH2And (3) mixing MIL-53(Al), a ruthenium precursor and a solvent 4, performing ultrasonic treatment, continuously stirring for 5-8 h, slowly dropwise adding a sodium borohydride solution in an ice bath, continuously performing ice bath reaction for 3-6 h, centrifuging, washing with a solvent 2, and performing vacuum drying to obtain the bifunctional heterogeneous ruthenium-based catalyst.
3. The method for catalytically synthesizing 3,3,5, 5-tetramethylbiphenol by using the bifunctional heterogeneous ruthenium-based catalyst according to claim 2, wherein the solvent 1 is any one or a mixture of methanol, ethanol and deionized water;
the solvent 2 is any one or a mixture of methanol, ethanol and acetone;
the solvent 3 is any one or a mixture of N, N-dimethylformamide, ethanol and trichloromethane;
the solvent 4 is any one or a mixture of ethanol, water and methanol.
4. The method for catalytically synthesizing 3,3,5, 5-tetramethylbiphenol by using the bifunctional heterogeneous ruthenium-based catalyst according to claim 2, wherein the mass ratio of the aluminum nitrate nonahydrate to the 2-aminoterephthalic acid in the step 1) is 1: 0.4-0.6, and the solvent 1 is added into 5-10 ml of the solvent 1 per gram of the mixture of the aluminum nitrate nonahydrate and the 2-aminoterephthalic acid;
NH described in step 3)2MIL-53(Al), ruthenium precursor and solvent 4 in a mass ratio of 1: and 0.1-0.4: 300-400, wherein the adding amount of the sodium borohydride solution is 6-10 times of the molar weight of the sodium borohydride added into the mixed solution as much as that of the metal ruthenium.
5. The method for catalytically synthesizing 3,3,5, 5-tetramethylbiphenol by using the bifunctional heterogeneous ruthenium-based catalyst according to claim 2, wherein the heating reaction in the step 1) is heating to a temperature of 110-150 ℃ for 3-5 h; the vacuum drying operation is vacuum drying for 1-2 hours at 40-60 ℃.
6. The method for catalytically synthesizing 3,3,5, 5-tetramethylbiphenol by using the bifunctional heterogeneous ruthenium-based catalyst according to claim 2, wherein the washing operation in the step 2) is washing with a solvent 3 at 110-150 ℃ for 5-8 h; the vacuum drying is carried out for 16-24 hours at 40-60 ℃.
7. The method for catalytically synthesizing 3,3,5, 5-tetramethylbiphenol by using the bifunctional heterogeneous ruthenium-based catalyst according to claim 2, wherein the ultrasonic treatment time in the step 3) is 5-15 min; the vacuum drying operation is vacuum drying for 16-24 hours at 40-60 ℃.
8. The method for catalytically synthesizing 3,3,5, 5-tetramethylbiphenol according to claim 1, wherein the solvent A is any one or a mixture of t-butanol, toluene and ethanol; the mass ratio of the 2, 6-dimethylphenol to the solvent A is 1: 45-65.
9. The method for catalytically synthesizing 3,3,5, 5-tetramethylbiphenol by using the bifunctional heterogeneous ruthenium-based catalyst according to claim 1, wherein the reaction temperature is 40-80 ℃ in an oxygen atmosphere, and the reaction time is 14-26 h; the reaction temperature under the hydrogen atmosphere is 40-60 ℃, and the reaction time is 4-6 h.
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