CN109081771A - A kind of preparation method of 2,4- DI-tert-butylphenol compounds - Google Patents

A kind of preparation method of 2,4- DI-tert-butylphenol compounds Download PDF

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CN109081771A
CN109081771A CN201810228397.8A CN201810228397A CN109081771A CN 109081771 A CN109081771 A CN 109081771A CN 201810228397 A CN201810228397 A CN 201810228397A CN 109081771 A CN109081771 A CN 109081771A
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dtbp
phenol
aluminium oxide
crude product
tert
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郭骄阳
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Jiangsu Jiyi New Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to organic synthesis fields, in particular to a kind of preparation method of 2,4-DTBP, comprising the following steps: the following steps are included: catalyst and methyl tertiary butyl ether(MTBE), stirring is added 1) in the presence of certain pressure and organic solvent；2) phenol is added dropwise into step 1), heats, stirring；3) reaction solution in step 2) is cooled to room temperature, filtered, solvent is evaporated off in filtrate washing；4) the 2,4-DTBP crude product in step 3) is obtained into 2,4-DTBP product after rectifying, dry.Preparation method reaction condition of the invention is mild, and selectivity of product is high, catalyst can be recycled.

Description

A kind of preparation method of 2,4- DI-tert-butylphenol compounds
Technical field
The present invention relates to organic synthesis fields, in particular to a kind of preparation method of 2,4-DTBP.
Background technique
2,4 1 DI-tert-butylphenol compounds (2,4-DTBP) are important fine chemical product and intermediate.2,4-DTBP is main For producing 168,300,3114 antioxidant, also it is used to produce polymerization inhibitor, activator 460, initiator (TIP), light stabilizer, purple Ultraviolet absorbers (UV 326, UV 327, UV 320) and farm chemical emulgent etc..2,4-DTBP can be also added to directly as antioxidant In fuel oil.
Currently, domestic produce antioxidant 168, ultraviolet absorber UV-327 type with 2,4 one DI-tert-butylphenol compounds for raw material Phenolic resin has formed large-scale production device, and product is used widely in the market.With China's ethylene production Ability is continuously increased, synchronous to the consumption of 2,4 one DI-tert-butylphenol compounds to increase.For many years, import is depended on always.Production 2,4 one DI-tert-butylphenol compounds, mostly using phenol, isobutene etc. greatly both at home and abroad is the production technology of raw material.Improving production technology needs Select suitable catalyst.
2,4 one DI-tert-butylphenol compounds of preparation, the acidic catalyst used earliest are reacted using phenol, isobutene as catalytic material It is sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, BF3,AlCl3Equal single component catalysts.One pack system acidic catalyst is that people are universal earliest The method of use forms homogeneous reaction mixed liquor, with alkali neutralization, washing side after addition catalyst is reacted in reactant Formula is except catalytic component in alkylation removal liquid, and then rectifying obtains alkyl phenolic product.The disadvantage of this method be due to neutralize, Water-washing step complicates operating process, increases equipment investment and consumption of raw materials.And since phenol wastewater amount is big, to environment dirt It contaminates more serious, limits the production-scale development of alkyl phenol.In addition, isobutene raw material transport difficult, is difficult to obtain, and operate item Part and control means require stringent.
CN1935763A discloses a kind of preparation method of 2.4- DI-tert-butylphenol compounds alkylation liquid, is 1 by phenol/catalyst : the proportion of 0.01-0.1 weighs phenol and catalyst is sufficiently mixed, the proportion for being then 1: 1.10-1.30 by phenol/isobutene Isobutene is added, and controlling reaction temperature is 70 DEG C -90 DEG C, is alkylated reaction, logical alkene finishes, insulation reaction 0.10- 1.00 hours, filtering removal catalyst was to get 2.4- DI-tert-butylphenol compounds alkylation liquid.The reaction used catalyst is montmorillonite class Catalyst, filtering are more difficult.
CN105198710A is related to the synthetic method of an inter-species tert-butyl phenol, includes the following steps: to tertiary butyl chloride Benzene is raw material, and it is anti-to obtain 2-methyl-2-phenylpropane amine, diazotising, hydrolysis between the chloro- 4- tert-butyl -2- nitrobenzene of 1-, reduction generation by nitrification A tert-butyl phenol should be obtained, the route raw material is cheap and easily-available, and each to walk unit process mild condition, post-processing is simple, and four steps are anti- Answer total recovery high, the prospect with industrialized production.But the reaction has used a large amount of concentrated sulfuric acid and nitric acid, easily causes environment dirty Dye.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, it is mild to provide a kind of reaction condition, selectivity of product is high, The preparation method for the 2,4- DI-tert-butylphenol compounds that catalyst can be recycled.
To achieve the goals above, the present invention provides a kind of preparation method of 2,4-DTBP, which is characterized in that The following steps are included:
1) catalyst and methyl tertiary butyl ether(MTBE) in presence of organic solvent, is added, stirs 5-10 minutes；
2) phenol is added dropwise into step 1), heating is stirred 1-2 hours, obtained containing 2,4-DTBP crude product Reaction solution；
3) reaction solution in step 2) is cooled to room temperature, filtered, filtrate washing is evaporated off solvent and obtains 2,4- di-tert-butyl Phenol crude product；
4) the 2,4-DTBP crude product in step 3) is obtained into 2,4- di-tert-butyl after rectifying, dry Phenolic product.
Further, catalyst described in step 1) is aluminium oxide；The leaching of the mixed liquor of the aluminium oxide phosphoric acid and hydrochloric acid Bubble, then high-temperature roasting 3-5 hours, uses after being cooled to room temperature.
Further, it is 0.2mol/L phosphoric acid that the mixed liquor of the phosphoric acid and hydrochloric acid, which is with concentration, and concentration is 0.3mol/L Hydrochloric acid mixed according to volume ratio for 10-15:1.
The aluminium oxide is commercial alumina powder in the present invention.Inventor has found in the course of the research, without appointing Under the action of the aluminium oxide catalyst of where reason, alkyl can preferential fortified phenol ortho position, but required temperature is higher, 2,4- bis- The selectivity of tert-butyl phenol is lower, is easy to happen disproportionation, turns the side reactions such as alkylation, olefinic polymerization, and catalytic activity is quickly It reduces.Inventor is by the mixed liquid dipping of aluminium oxide phosphoric acid and hydrochloric acid, and then high-temperature roasting 3-5 hours, after being cooled to room temperature It reuses, is found surprisingly that the yield that can greatly improve 2,4-DTBP, and treated aluminium oxide can be with Repeatedly, catalytic activity is not in be substantially reduced for recycling.In the present invention, leaching of the aluminium oxide through peroxophosphoric acid and hydrochloric acid Bubble, high-temperature roasting, while hydrogen ion, phosphate anion, chloride ion three synergistic effect enhance the acidity of aluminium oxide, also greatly The catalytic activity of aluminium oxide is enhanced greatly.Inventor also found in the course of the research, when handling aluminium oxide, change phosphoric acid It is greatly affected with the catalytic activity of the ratio of hydrochloric acid, aluminium oxide, the amount that hydrochloric acid is added is excessive, the catalytic performance meeting of aluminium oxide It is deteriorated.
Further, the temperature of the high-temperature roasting is 400-430 DEG C.
Further, step 1) carries out under the pressure of 0.2-0.4MPa.
In the present invention, the conversion ratio of pressure Pyrogentisinic Acid has important influence.When pressure is 0.2-0.4MPa, phenol Conversion ratio obtain more significantly improving.But when hypertonia, there is decline in the conversion ratio of phenol.Present invention selection Pressure is 0.2-0.4MPa, can both guarantee the higher conversion ratio of phenol, and reaction can also be made to have better choice.
Further, organic solvent described in step 1) is one or both of petroleum ether, methylene chloride.
Further, the organic solvent is petroleum ether.
Further, heating temperature described in step 2) is 60-80 DEG C.
Further, the washing of filtrate described in step 3) is first to be washed with sodium carbonate liquor, then be washed with distilled water.
Further, the molar ratio of phenol and methyl tertiary butyl ether(MTBE) is 1:2.0-2.3.
Further, the mass ratio of catalyst described in step 1) and phenol: 0.01-0.05:1.
It is obtained by the present invention to have the beneficial effect that:
(1) invention uses aluminium oxide catalyst, carries out specially treated to aluminium oxide using preceding, catalysis reaction is in heterogeneous It carries out, Filtration of catalyst after reaction terminating, catalyst can be recycled repeatedly, and catalytic performance is not substantially reduced.
(2) methyl tertiary butyl ether(MTBE) that the present invention uses is cheap and easy to get, can reduce production cost, improves product quality.
(3) preparation method of the invention is selectively good to the purpose product of preparation, and feed stock conversion is high, easy to operate, fits Together in large-scale industrial production.
Specific embodiment
Embodiment 1
1) 300kg petroleum ether is added in a kettle, 0.94kg aluminium oxide is then added, and (aluminium oxide first will using preceding 10L0.2mol/L phosphoric acid solution and the mixing of 1L0.3mol/L hydrochloric acid solution, then aluminium oxide is impregnated 20 minutes in mixed liquor, mistake Aluminium oxide is filtered out, then roasts 5 hours at 400 DEG C in Muffle furnace, is used after being cooled to room temperature), 176kg methyl tertbutyl Ether stirs 5 minutes, reaction pressure 0.2MPa；
2) 94kg phenol is added dropwise into step 1), 60 DEG C are heated to after being added dropwise, stirs 2 hours, obtains containing 2,4- The reaction solution of DI-tert-butylphenol compounds crude product；
3) reaction solution in step 2) is cooled to room temperature, filtered, filtrate is first that 4% sodium carbonate liquor is washed with mass fraction It washs, then is washed with distilled water, solvent is evaporated off and obtains 2,4-DTBP crude product；
4) the 2,4-DTBP crude product in step 3) is obtained into 2,4- di-tert-butyl after rectifying, dry Phenolic product.
Wherein, the reaction solution obtained in step 2) containing 2,4-DTBP crude product is sampled, passes through gas phase Chromatographic quantitative analysis, the conversion ratio of phenol are 99.1%, and the selectivity of 2,4-DTBP is 93.2%.
Embodiment 2
1) 300kg petroleum ether is added in a kettle, 4.7kg aluminium oxide is then added, and (aluminium oxide first will using preceding 15L0.2mol/L phosphoric acid solution and the mixing of 1L0.3mol/L hydrochloric acid solution, then aluminium oxide is impregnated 20 minutes in mixed liquor, mistake Aluminium oxide is filtered out, then roasts 3 hours at 430 DEG C in Muffle furnace, is used after being cooled to room temperature), 202.4kg methyl tertbutyl Ether stirs 10 minutes, reaction pressure 0.4MPa；
2) to 94kg phenol is added dropwise in step 1), it is heated to 80 DEG C after being added dropwise, stirs 1.5 hours, obtains containing 2, The reaction solution of 4- DI-tert-butylphenol compounds crude product；
3) reaction solution in step 2) is cooled to room temperature, filtered, filtrate is first that 4% sodium carbonate liquor is washed with mass fraction It washs, then is washed with distilled water, solvent is evaporated off and obtains 2,4-DTBP crude product；
4) the 2,4-DTBP crude product in step 3) is obtained into 2,4- di-tert-butyl after rectifying, dry Phenolic product.
Wherein, the reaction solution obtained in step 2) containing 2,4-DTBP crude product is sampled, passes through gas phase Chromatographic quantitative analysis, the conversion ratio of phenol are 99.4%, and the selectivity of 2,4-DTBP is 92.5%.
Embodiment 3
1) 300kg petroleum ether is added in a kettle, 1.5kg aluminium oxide is then added, and (aluminium oxide first will using preceding 12L0.2mol/L phosphoric acid solution and the mixing of 1L0.3mol/L hydrochloric acid solution, then aluminium oxide is impregnated 20 minutes in mixed liquor, mistake Aluminium oxide is filtered out, then roasts 4 hours at 430 DEG C in Muffle furnace, is used after being cooled to room temperature), 184.8kg methyl tertbutyl Ether stirs 8 minutes, reaction pressure 0.2MPa；
2) 94kg phenol is added dropwise into step 1), 70 DEG C are heated to after being added dropwise, stirs 2 hours, obtains containing 2,4- The reaction solution of DI-tert-butylphenol compounds crude product；
3) reaction solution in step 2) is cooled to room temperature, filtered, filtrate is first that 4% sodium carbonate liquor is washed with mass fraction It washs, then is washed with distilled water, solvent is evaporated off and obtains 2,4-DTBP crude product；
4) the 2,4-DTBP crude product in step 3) is obtained into 2,4- di-tert-butyl after rectifying, dry Phenolic product.
Wherein, the reaction solution obtained in step 2) containing 2,4-DTBP crude product is sampled, passes through gas phase Chromatographic quantitative analysis, the conversion ratio of phenol are 99.9%, and the selectivity of 2,4-DTBP is 95.1%.
Catalyst reuses performance test: after the aluminium oxide catalyst filtered out in step 3) vacuum drying, according to Aforesaid operations condition, repeatedly the preparation process (is not required to carry out again at this time " first that 12L0.2mol/L phosphoric acid is molten before aluminium oxide use Liquid and the mixing of 1L0.3mol/L hydrochloric acid solution, then aluminium oxide is impregnated 20 minutes in mixed liquor, aluminium oxide is filtered out, is then existed Roast 4 hours at 430 DEG C in Muffle furnace, used after being cooled to room temperature " operation), the repeatable benefit of the visible catalyst of test result With 20 times or more, by chromatogram ration analysis, the conversion ratio of phenol reaches 96-99%, the choosing of 2,4-DTBP Selecting property reaches 91-95%.
Embodiment 4
1) 300kg petroleum ether is added in a kettle, 1.5kg aluminium oxide is then added, and (aluminium oxide first will using preceding 12L0.2mol/L phosphoric acid solution and the mixing of 1L0.3mol/L hydrochloric acid solution, then aluminium oxide is impregnated 20 minutes in mixed liquor, mistake Aluminium oxide is filtered out, then roasts 4 hours at 430 DEG C in Muffle furnace, is used after being cooled to room temperature), 184.8kg methyl tertbutyl Ether stirs 8 minutes, reaction pressure 0.4MPa；
2) 94kg phenol is added dropwise into step 1), 70 DEG C are heated to after being added dropwise, stirs 2 hours, obtains containing 2,4- The reaction solution of DI-tert-butylphenol compounds crude product；
3) reaction solution in step 2) is cooled to room temperature, filtered, filtrate is first that 4% sodium carbonate liquor is washed with mass fraction It washs, then is washed with distilled water, solvent is evaporated off and obtains 2,4-DTBP crude product；
4) the 2,4-DTBP crude product in step 3) is obtained into 2,4- di-tert-butyl after rectifying, dry Phenolic product.
Wherein, the reaction solution obtained in step 2) containing 2,4-DTBP crude product is sampled, passes through gas phase Chromatographic quantitative analysis, the conversion ratio of phenol are 99.8%, and the selectivity of 2,4-DTBP is 94.3%.
Embodiment 5
1) 300kg petroleum ether is added in a kettle, 1.5kg aluminium oxide is then added, and (aluminium oxide first will using preceding 10L0.2mol/L phosphoric acid solution and the mixing of 1L0.3mol/L hydrochloric acid solution, then aluminium oxide is impregnated 20 minutes in mixed liquor, mistake Aluminium oxide is filtered out, then roasts 4 hours at 430 DEG C in Muffle furnace, is used after being cooled to room temperature), 184.8kg methyl tertbutyl Ether stirs 8 minutes, reaction pressure 0.2MPa；
2) 94kg phenol is added dropwise into step 1), 70 DEG C are heated to after being added dropwise, stirs 2 hours, obtains containing 2,4- The reaction solution of DI-tert-butylphenol compounds crude product；
3) reaction solution in step 2) is cooled to room temperature, filtered, filtrate is first that 4% sodium carbonate liquor is washed with mass fraction It washs, then is washed with distilled water, solvent is evaporated off and obtains 2,4-DTBP crude product；
4) the 2,4-DTBP crude product in step 3) is obtained into 2,4- di-tert-butyl after rectifying, dry Phenolic product.
Wherein, the reaction solution obtained in step 2) containing 2,4-DTBP crude product is sampled, passes through gas phase Chromatographic quantitative analysis, the conversion ratio of phenol are 99.1%, and the selectivity of 2,4-DTBP is 93.8%.
Embodiment 6
1) 300kg petroleum ether is added in a kettle, 1.5kg aluminium oxide is then added, and (aluminium oxide first will using preceding 15L0.2mol/L phosphoric acid solution and the mixing of 1L0.3mol/L hydrochloric acid solution, then aluminium oxide is impregnated 20 minutes in mixed liquor, mistake Aluminium oxide is filtered out, then roasts 4 hours at 430 DEG C in Muffle furnace, is used after being cooled to room temperature), 184.8kg methyl tertbutyl Ether stirs 8 minutes, reaction pressure 0.2MPa；
2) 94kg phenol is added dropwise into step 1), 70 DEG C are heated to after being added dropwise, stirs 2 hours, obtains containing 2,4- The reaction solution of DI-tert-butylphenol compounds crude product；
3) reaction solution in step 2) is cooled to room temperature, filtered, filtrate is first that 4% sodium carbonate liquor is washed with mass fraction It washs, then is washed with distilled water, solvent is evaporated off and obtains 2,4-DTBP crude product；
4) the 2,4-DTBP crude product in step 3) is obtained into 2,4- di-tert-butyl after rectifying, dry Phenolic product.
Wherein, the reaction solution obtained in step 2) containing 2,4-DTBP crude product is sampled, passes through gas phase Chromatographic quantitative analysis, the conversion ratio of phenol are 99.9%, and the selectivity of 2,4-DTBP is 93.9%.
Comparative example 1
1) 300kg petroleum ether is added in a kettle, 1.5kg aluminium oxide is then added, and (aluminium oxide is existed using preceding elder generation It is impregnated 20 minutes in 13L0.185mol/L phosphoric acid solution, filters out aluminium oxide, then roasting 4 is small at 430 DEG C in Muffle furnace When, used after being cooled to room temperature), 184.8kg methyl tertiary butyl ether(MTBE) stirs 8 minutes, reaction pressure 0.2MPa；
2) 94kg phenol is added dropwise into step 1), 70 DEG C are heated to after being added dropwise, stirs 2 hours, obtains containing 2,4- The reaction solution of DI-tert-butylphenol compounds crude product；
3) reaction solution in step 2) is cooled to room temperature, filtered, filtrate is first that 4% sodium carbonate liquor is washed with mass fraction It washs, then is washed with distilled water, solvent is evaporated off and obtains 2,4-DTBP crude product；
4) the 2,4-DTBP crude product in step 3) is obtained into 2,4- di-tert-butyl after rectifying, dry Phenolic product.
Wherein, the reaction solution obtained in step 2) containing 2,4-DTBP crude product is sampled, passes through gas phase Chromatographic quantitative analysis, the conversion ratio of phenol are 84.1%, and the selectivity of 2,4-DTBP is 76.7%.
Comparative example 2
1) 300kg petroleum ether is added in a kettle, 1.5kg aluminium oxide is then added, and (aluminium oxide is existed using preceding elder generation It is impregnated 20 minutes in 13L0.023mol/L hydrochloric acid solution, filters out aluminium oxide, then roasting 4 is small at 430 DEG C in Muffle furnace When, used after being cooled to room temperature), 184.8kg methyl tertiary butyl ether(MTBE) stirs 8 minutes, reaction pressure 0.2MPa；
2) 94kg phenol is added dropwise into step 1), 70 DEG C are heated to after being added dropwise, stirs 2 hours, obtains containing 2,4- The reaction solution of DI-tert-butylphenol compounds crude product；
3) reaction solution in step 2) is cooled to room temperature, filtered, filtrate is first that 4% sodium carbonate liquor is washed with mass fraction It washs, then is washed with distilled water, solvent is evaporated off and obtains 2,4-DTBP crude product；
4) the 2,4-DTBP crude product in step 3) is obtained into 2,4- di-tert-butyl after rectifying, dry Phenolic product.
Wherein, the reaction solution obtained in step 2) containing 2,4-DTBP crude product is sampled, passes through gas phase Chromatographic quantitative analysis, the conversion ratio of phenol are 70.4%, and the selectivity of 2,4-DTBP is 61.4%.
Comparative example 3
1) 300kg petroleum ether is added in a kettle, 1.5kg aluminium oxide is then added, and (aluminium oxide first will using preceding 6.5L0.2mol/L phosphoric acid solution and the mixing of 6.5L0.3mol/L hydrochloric acid solution, then aluminium oxide is impregnated 20 points in mixed liquor Clock filters out aluminium oxide, then roasts 4 hours at 430 DEG C in Muffle furnace, uses after being cooled to room temperature), 184.8kg methyl Tertbutyl ether stirs 8 minutes, reaction pressure 0.2MPa；
2) 94kg phenol is added dropwise into step 1), 70 DEG C are heated to after being added dropwise, stirs 2 hours, obtains containing 2,4- The reaction solution of DI-tert-butylphenol compounds crude product；
3) reaction solution in step 2) is cooled to room temperature, filtered, filtrate is first that 4% sodium carbonate liquor is washed with mass fraction It washs, then is washed with distilled water, solvent is evaporated off and obtains 2,4-DTBP crude product；
4) the 2,4-DTBP crude product in step 3) is obtained into 2,4- di-tert-butyl after rectifying, dry Phenolic product.
Wherein, the reaction solution obtained in step 2) containing 2,4-DTBP crude product is sampled, passes through gas phase Chromatographic quantitative analysis, the conversion ratio of phenol are 90.3%, and the selectivity of 2,4-DTBP is 83.2%.
Comparative example 4
1) 300kg petroleum ether is added in a kettle, 1.5kg aluminium oxide is then added, and (aluminium oxide first will using preceding 12L0.2mol/L phosphoric acid solution and the mixing of 1L0.3mol/L hydrochloric acid solution, then aluminium oxide is impregnated 20 minutes in mixed liquor, mistake Aluminium oxide is filtered out, then roasts 4 hours at 430 DEG C in Muffle furnace, is used after being cooled to room temperature), 184.8kg methyl tertbutyl Ether stirs 8 minutes, reaction pressure 2MPa；
2) 94kg phenol is added dropwise into step 1), 70 DEG C are heated to after being added dropwise, stirs 2 hours, obtains containing 2,4- The reaction solution of DI-tert-butylphenol compounds crude product；
3) reaction solution in step 2) is cooled to room temperature, filtered, filtrate is first that 4% sodium carbonate liquor is washed with mass fraction It washs, then is washed with distilled water, solvent is evaporated off and obtains 2,4-DTBP crude product；
4) the 2,4-DTBP crude product in step 3) is obtained into 2,4- di-tert-butyl after rectifying, dry Phenolic product.
Wherein, the reaction solution obtained in step 2) containing 2,4-DTBP crude product is sampled, passes through gas phase Chromatographic quantitative analysis, the conversion ratio of phenol are 92.7%, and the selectivity of 2,4-DTBP is 85.1%.
Comparative example 5
1) 300kg petroleum ether is added in a kettle, 1.5kg aluminium oxide is then added, and (aluminium oxide first will using preceding 12L0.2mol/L phosphoric acid solution and the mixing of 1L0.3mol/L hydrochloric acid solution, then aluminium oxide is impregnated 20 minutes in mixed liquor, mistake Aluminium oxide is filtered out, then roasts 4 hours at 430 DEG C in Muffle furnace, is used after being cooled to room temperature), 94kg phenol stirs 8 points Clock, reaction pressure 0.2MPa；
2) 184.8kg methyl tertiary butyl ether(MTBE) is added dropwise into step 1), 70 DEG C are heated to after being added dropwise, stirs 2 hours, obtains To the reaction solution containing 2,4- DI-tert-butylphenol compounds crude product；
3) reaction solution in step 2) is cooled to room temperature, filtered, filtrate is first that 4% sodium carbonate liquor is washed with mass fraction It washs, then is washed with distilled water, solvent is evaporated off and obtains 2,4-DTBP crude product；
4) the 2,4-DTBP crude product in step 3) is obtained into 2,4- di-tert-butyl after rectifying, dry Phenolic product.
Wherein, the reaction solution obtained in step 2) containing 2,4-DTBP crude product is sampled, passes through gas phase Chromatographic quantitative analysis, the conversion ratio of phenol are 93.6%, and the selectivity of 2,4-DTBP is 90.4%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of preparation method of 2,4-DTBP, which comprises the following steps:
1) catalyst and methyl tertiary butyl ether(MTBE) in presence of organic solvent, is added, stirs 5-10 minutes；
2) phenol is added dropwise into step 1), heating is stirred 1-2 hours, obtained containing the anti-of 2,4-DTBP crude product Answer liquid；
3) reaction solution in step 2) is cooled to room temperature, filtered, filtrate washing, solvent is evaporated off, and to obtain 2,4-DTBP thick Product；
4) by the 2,4-DTBP crude product in step 3) after rectifying, dry, 2,4-DTBP production is obtained Product.
2. the method according to claim 1, wherein catalyst described in step 1) is aluminium oxide；The oxidation The mixed liquid dipping of aluminium phosphoric acid and hydrochloric acid then high-temperature roasting 3-5 hours, uses after being cooled to room temperature.
3. according to the method described in claim 2, it is characterized in that, the temperature of the high-temperature roasting is 400-430 DEG C.
4. the method according to claim 1, wherein step 1) carries out under the pressure of 0.2-0.4MPa.
5. the method according to claim 1, wherein organic solvent described in step 1) is petroleum ether, dichloromethane One or both of alkane.
6. according to the method described in claim 5, it is characterized in that, the organic solvent is petroleum ether.
7. the method according to claim 1, wherein heating temperature described in step 2) is 60-80 DEG C.
8. the method according to claim 1, wherein the washing of filtrate described in step 3) is first to use sodium carbonate liquor Washing, then be washed with distilled water.
9. the method according to claim 1, wherein the molar ratio of phenol and methyl tertiary butyl ether(MTBE) is 1:2.0- 2.3。
10. method described in -9 any one according to claim 1, which is characterized in that catalyst described in step 1) and phenol Mass ratio: 0.01-0.05:1.
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Application publication date: 20181225