CN114181052A - Preparation method of high-purity 4, 4' -biphenol - Google Patents
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- CN114181052A CN114181052A CN202111559205.XA CN202111559205A CN114181052A CN 114181052 A CN114181052 A CN 114181052A CN 202111559205 A CN202111559205 A CN 202111559205A CN 114181052 A CN114181052 A CN 114181052A
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- C07C37/16—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 by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
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Abstract
The invention relates to the technical field of organic synthesis, in particular to a preparation method of high-purity 4,4 ' -biphenol, which takes phenol with high cost performance as a raw material, prepares 2, 6-di-tert-butylphenol purified product through tert-butylation, prepares 3,3 ', 5,5 ' -tetra-tert-butylbiphenol through oxidative coupling, prepares high-purity 4,4 ' -biphenol through tert-butyl removal reaction, optimizes process parameters and material proportion, and finally obtains the 4,4 ' -biphenol with the purity of 99.97%.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of high-purity 4, 4' -biphenol.
Background
The 4, 4' -biphenol is an organic compound with a molecular formula of C12H10O 2. White flaky crystal or crystal powder is a high polymer intermediate, has higher melting point and stronger heat resistance, can be used as a rubber antioxidant and a plastic antioxidant, a stabilizer of petroleum products and dyes and a high polymer intermediate, and is also an important monomer for preparing alkoxy substituted biphenyl liquid crystal.
The 4, 4' -biphenol LCP is a liquid crystal polymer material which is the most widely applied and has the highest scale level at present. The liquid crystal polymer has various characteristics, can be made into high-strength fibers by silk imitation and is used for reinforcing optical fibers. The main reason is that 4, 4' -biphenol LCP has a linear symmetrical molecular structure, and the heat resistance and the fluidity of the LCP are the first of LCP, so that the performance is excellent. In addition, 4' -biphenol which is an important raw material for synthesizing the LCP can be prepared from phenol, and has wide sources and low cost.
The existing methods for synthesizing 4, 4' -biphenol mainly comprise a benzidine method, a biphenyl sulfonation alkali dissolution method, a biphenyl halogenation high-pressure hydrolysis method and a 2, 6-di-tert-butylphenol oxidative coupling method. The benzidine method takes benzidine as raw material, and 4, 4' -biphenol can be obtained after diazotization and hydrolysis; the biphenyl sulfonation alkali dissolution method takes biphenyl as a raw material, and obtains a target product 4, 4' -biphenol after reaction processes of sulfonation, alkali dissolution, acidification and the like; the biphenyl halogenation high-pressure hydrolysis method also takes biphenyl as a reaction raw material, and a final product can be obtained by purification after a series of reactions such as halogenation, hydrolysis and the like; the oxidation coupling method of 2, 6-di-tert-butylphenol is to take 2, 6-di-tert-butylphenol as raw material and obtain the required product by three steps of oxidation, reduction and de-isobutyl.
Specifically, CN106928031A discloses a green production process for preparing biphenol from 2, 6-disubstituted phenol. 2, 6-disubstituted phenol is used as a raw material, water is used as a solvent, an emulsifier and a pH regulator are added, oxidation is carried out by an oxidant, namely hydrogen peroxide under the action of a catalyst, and an oxidative coupling reaction is carried out at a certain temperature to generate the 4, 4' -biphenol. The purity of the 4, 4' -biphenol prepared by the method can reach 99%.
CN111960927A discloses a method for preparing 3,3 ', 5,5 ' -tetraalkyl-4 ' 4-diphenol by catalytic hydrogenation, under the condition of catalyst, the hydrogenation raw material 3,3 ', 5,5 ' -tetraalkyl-4 ' 4-diphenol and hydrogen gas pass through a hydrogen mixer and then enter a fixed bed reactor for hydrogenation reaction, and the product stream is degassed, concentrated, dried, ground and the like to finally prepare the 3,3 ', 5,5 ' -tetraalkyl-4 ' 4-diphenol.
The method for synthesizing the 4,4 ' -biphenol has lower purity and complex and uncontrollable production operation due to technical and environmental protection reasons, and the 4,4 ' -biphenol applied to the production of the liquid crystal material needs to have high purity, and the 4,4 ' -biphenol with lower purity cannot meet the application requirement; in addition, biphenyl as a synthetic raw material has large energy consumption in production, can greatly increase the production cost, and has large environmental pollution.
Disclosure of Invention
In order to solve the problems, the invention provides the preparation method of the high-purity 4, 4' -biphenol, which has the advantages of simple process flow, easily controlled process and high product purity, and meets the requirement of mass production.
The technical scheme adopted by the invention is as follows:
a preparation method of high-purity 4, 4' -biphenol comprises the following steps:
s1: preparation of 2, 6-di-tert-butylphenol
Adding phenol and aluminum into a reaction container, raising the temperature to 140-160 ℃, stirring for reaction for 1-2h, reducing the reaction temperature in the reaction container to 110-120 ℃, introducing isobutene into the reaction container, controlling the pressure in the reaction container to be 0.4-0.6 Mpa, continuously reducing the reaction temperature in the reaction container to 50-60 ℃ after reaction for 4-6h, reacting for 1-2h to obtain a crude product of 2, 6-di-tert-butylphenol, adding sodium hydroxide into the crude product of 2, 6-di-tert-butylphenol, reacting for 1-2h at 180-220 ℃, filtering and distilling the reaction product under reduced pressure to obtain a purified product of 2, 6-di-tert-butylphenol;
s2: preparation of 3,3 ', 5, 5' -tetra-tert-butyl biphenyl diphenol by oxidative coupling reaction
Adding the 2, 6-di-tert-butylphenol purified product in the S1 and potassium hydroxide into a reaction vessel, introducing oxygen into the reaction vessel, starting stirring, reacting at 30-40 ℃ for 0.5-1.5 h, raising the temperature to 180-200 ℃, and reacting for 6-8 h to obtain 3,3 ', 5, 5' -tetra-tert-butylbiphenol;
s3: preparation of 4, 4' -biphenol by tert-butyl removal reaction
Adding 3,3 ', 5,5 ' -tetra-tert-butyl diphenol, p-toluenesulfonic acid and benzene solvents in S2 into a reaction vessel, introducing nitrogen into the reaction vessel, heating to 130-140 ℃ through an oil bath, stirring for 5-7 h to obtain a reaction product, filtering the reaction product, dissolving a filter cake obtained by filtering into a hot methanol solution with activated carbon at 50-60 ℃, and recrystallizing the uniformly dissolved solution to finally obtain 4,4 ' -diphenol.
Further, in S1, the aluminum material is at least one of aluminum powder, aluminum chloride, and aluminum trichloride.
Further, in S1, the molar ratio of phenol to aluminum material is 1: 0.02 to 0.025; the molar ratio of the phenol to the isobutene is 1: 2-2.2.
Further, in S1, 0.02-0.04 mol of sodium hydroxide is added into the crude product of 2, 6-di-tert-butylphenol to prepare a sodium hydroxide solution with the mass portion of 15% -25%, and then the mixture is reacted for 1-2 hours at 180-220 ℃.
Further, in S2, adding a mixture of two kinds of organic solvents in a molar ratio of 1: 0.2-0.3 of 2, 6-di-tert-butylphenol purified product and potassium hydroxide, preparing a potassium hydroxide solution with the concentration of 20-30%, and introducing nitrogen to stir for reaction.
Further, in S2, after the temperature is raised to 180-200 ℃ at the temperature raising rate of 1-3 ℃/min, the reaction is carried out for 6-8 h.
Further, in S3, the benzene solvent is toluene, xylene, or m-xylene.
Further, in S3, the molar ratio of 3,3 ', 5, 5' -tetra-tert-butylbiphenol to p-toluenesulfonic acid is 1: 0.04 to 0.08; the molar ratio of the 3,3 ', 5, 5' -tetra-tert-butyl biphenyl diphenol to the benzene solvent is 1: 4 to 8.
Further, in S3, the mass fraction of the activated carbon in the methanol solution is 0.1-0.5%.
Further, in S1, the stirring speed in the reaction process is 200-300 rpm/min;
the oxygen introducing rate in S2 is controlled to be 45-60 ml/min.
The invention has the following beneficial effects:
the preparation method of the high-purity 4,4 ' -biphenol provided by the invention is characterized in that phenol with high cost performance is used as a raw material, 2, 6-di-tert-butylphenol purified product is prepared through tert-butylation, 3 ', 5,5 ' -tetra-tert-butylbiphenol is prepared through oxidative coupling, and high-purity 4,4 ' -biphenol is prepared through tert-butylation reaction, and the purity of the finally prepared 4,4 ' -biphenol can reach 99.97%.
Drawings
FIG. 1 is a flow chart of the preparation in examples 1 to 5 of the present invention.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete. The various starting materials used in the examples are, unless otherwise indicated, conventional commercial products.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The numerical values set forth in the examples of the present invention are approximations, not necessarily values. All values within the error range may be included without limiting to the specific values disclosed in the embodiments of the present invention, where the error or experimental conditions allow.
The numerical ranges disclosed in the examples of the present invention are intended to indicate the relative amounts of the components in the mixture and the ranges of temperatures or other parameters recited in the other method examples.
The preparation method of the high-purity 4, 4' -biphenol provided by the application comprises the following steps:
s1: preparation of 2, 6-di-tert-butylphenol
Adding phenol and aluminum into a reaction container, raising the temperature to 140-160 ℃, stirring for reaction for 1-2h, reducing the reaction temperature in the reaction container to 110-120 ℃, introducing isobutene into the reaction container, controlling the pressure in the reaction container to be 0.4-0.6 Mpa, continuously reducing the reaction temperature in the reaction container to 50-60 ℃ after reaction for 4-6h, reacting for 1-2h to obtain a crude product of 2, 6-di-tert-butylphenol, adding sodium hydroxide into the crude product of 2, 6-di-tert-butylphenol, reacting for 1-2h at 180-220 ℃, filtering and distilling the reaction product under reduced pressure to obtain a purified product of 2, 6-di-tert-butylphenol;
s2: preparation of 3,3 ', 5, 5' -tetra-tert-butyl biphenyl diphenol by oxidative coupling reaction
Adding the 2, 6-di-tert-butylphenol purified product in the S1 and potassium hydroxide into a reaction vessel, introducing oxygen into the reaction vessel, starting stirring, reacting at 30-40 ℃ for 0.5-1.5 h, raising the temperature to 180-200 ℃, and reacting for 6-8 h to obtain 3,3 ', 5, 5' -tetra-tert-butylbiphenol;
s3: preparation of 4, 4' -biphenol by tert-butyl removal reaction
Adding 3,3 ', 5,5 ' -tetra-tert-butyl diphenol, p-toluenesulfonic acid and benzene solvents in S2 into a reaction vessel, introducing nitrogen into the reaction vessel, heating to 130-140 ℃ through an oil bath, stirring for 5-7 h to obtain a reaction product, filtering the reaction product, dissolving a filter cake obtained by filtering into a hot methanol solution with activated carbon at 50-60 ℃, and recrystallizing the uniformly dissolved solution to finally obtain 4,4 ' -diphenol.
Specifically, in S1, the aluminum material is at least one of aluminum powder, aluminum chloride, and aluminum trichloride.
In S1, the molar ratio of phenol to aluminum material is 1: 0.02 to 0.025; the molar ratio of the phenol to the isobutene is 1: 2-2.2.
In S1, 0.02-0.04 mol of sodium hydroxide is added into the crude product of 2, 6-di-tert-butylphenol to prepare a sodium hydroxide solution with the mass portion of 15% -25%, and then the mixture is reacted for 1-2 hours at 180-220 ℃.
In S2, adding a mixture of 1: 0.2-0.3 of 2, 6-di-tert-butylphenol purified product and potassium hydroxide, preparing a potassium hydroxide solution with the concentration of 20-30%, and introducing nitrogen to stir for reaction.
In S2, the temperature is raised to 180-200 ℃ at the temperature raising rate of 1-3 ℃/min, and then the reaction is carried out for 6-8 h.
In S3, the benzene solvent is toluene, xylene or m-xylene.
In S3, the molar ratio of 3,3 ', 5, 5' -tetra-tert-butyl biphenyl diphenol to p-toluenesulfonic acid is 1: 0.04 to 0.08; the molar ratio of the 3,3 ', 5, 5' -tetra-tert-butyl biphenyl diphenol to the benzene solvent is 1: 4 to 8.
In S3, the mass fraction of the activated carbon in the methanol solution is 0.1-0.5%.
In S1, the stirring speed in the reaction process is 200-300 rpm/min;
the oxygen introducing rate in S2 is controlled to be 45-60 ml/min.
The preparation method of the high-purity 4,4 ' -biphenol provided by the invention is characterized in that phenol with high cost performance is used as a raw material, 2, 6-di-tert-butylphenol purified product is prepared through tert-butylation, 3 ', 5,5 ' -tetra-tert-butylbiphenol is prepared through oxidative coupling, and high-purity 4,4 ' -biphenol is prepared through tert-butyl reaction, and technological parameters and material proportion are optimized, so that the purity of the finally prepared 4,4 ' -biphenol can reach 99.97%.
The following are specific examples of the present application:
example 1:
s1: preparation of 2, 6-di-tert-butylphenol
Adding 0.3mol of phenol and 0.006mol of aluminum powder into a reaction vessel, raising the temperature to 150 ℃, stirring at a low speed of 200rpm/min for reaction for 1h, then reducing the reaction temperature in the reaction vessel to 120 ℃, introducing 0.6mol of isobutene into the reaction vessel, controlling the pressure in the reaction vessel to be 0.6Mpa, continuously reducing the reaction temperature in the reaction vessel to 60 ℃ after reacting for 4h, reacting for 1h to obtain a crude product of 2, 6-di-tert-butylphenol, adding 0.02mol of sodium hydroxide into the crude product of 2, 6-di-tert-butylphenol to prepare a sodium hydroxide solution with the mass fraction of 20%, reacting for 1h at 200 ℃, and filtering and distilling the reaction product under reduced pressure to obtain a purified product of 2, 6-di-tert-butylphenol;
s2: preparation of 3,3 ', 5, 5' -tetra-tert-butyl biphenyl diphenol by oxidative coupling reaction
Preparing 0.2mol of 2, 6-di-tert-butylphenol purified product and 0.04mol of potassium hydroxide in S1 into a potassium hydroxide solution with the mass fraction of 20%, adding the potassium hydroxide solution into a reaction container, introducing oxygen into the reaction container, starting stirring, controlling the oxygen introduction rate at 45ml/min, stirring at 400rpm/min, reacting for 1h at 35 ℃, then raising the temperature to 180 ℃, raising the temperature at 2 ℃/min, and reacting for 6h to obtain 3,3 ', 5, 5' -tetra-tert-butylbiphenyl diphenol;
s3: preparation of 4, 4' -biphenol by tert-butyl removal reaction
Adding 0.025mol of 3,3 ', 5,5 ' -tetra-tert-butyl biphenyl diphenol, 0.001mol of p-toluenesulfonic acid and 0.1mol of toluene solvent in S2 into a reaction vessel, introducing nitrogen into the reaction vessel, heating to 130 ℃ through oil bath, stirring at the speed of 300rpm/min, reacting for 7 hours to obtain a reaction product, filtering the reaction product, dissolving a filter cake obtained by filtering into 2mol of 50 ℃ hot methanol solution with 0.1% of activated carbon by mass fraction, and recrystallizing the uniformly dissolved solution to finally obtain the 4,4 ' -biphenyl diphenol.
Example 2:
s1: preparation of 2, 6-di-tert-butylphenol
Adding 0.3mol of phenol and 0.007mol of aluminum chloride into a reaction vessel, raising the temperature to 150 ℃, stirring at a low speed of 250rpm/min for reaction for 1.5h, then reducing the reaction temperature in the reaction vessel to 110 ℃, introducing 0.65mol of isobutene into the reaction vessel, controlling the pressure in the reaction vessel to be 0.5Mpa, continuously reducing the reaction temperature in the reaction vessel to 60 ℃ after reacting for 4h, reacting for 1h to obtain a crude product of 2, 6-di-tert-butylphenol, adding 0.03mol of sodium hydroxide into the crude product of 2, 6-di-tert-butylphenol to prepare a sodium hydroxide solution with the mass fraction of 20%, reacting for 1h at 200 ℃, and filtering and distilling the reaction product under reduced pressure to obtain a purified product of 2, 6-di-tert-butylphenol;
s2: preparation of 3,3 ', 5, 5' -tetra-tert-butyl biphenyl diphenol by oxidative coupling reaction
Preparing 0.2mol of 2, 6-di-tert-butylphenol purified product and 0.04mol of potassium hydroxide in S1 into a potassium hydroxide solution with the mass fraction of 25%, adding the potassium hydroxide solution into a reaction container, introducing oxygen into the reaction container, starting stirring, controlling the oxygen introduction rate at 50ml/min, stirring at 500rpm/min, reacting for 1h at 40 ℃, then raising the temperature to 190 ℃, raising the temperature at 2 ℃/min, and reacting for 6h to obtain 3,3 ', 5, 5' -tetra-tert-butylbiphenyl diphenol;
s3: preparation of 4, 4' -biphenol by tert-butyl removal reaction
Adding 0.025mol of 3,3 ', 5,5 ' -tetra-tert-butyl biphenyl diphenol, 0.001mol of p-toluenesulfonic acid and 0.1mol of toluene solvent in S2 into a reaction vessel, introducing nitrogen into the reaction vessel, heating to 130 ℃ through oil bath, stirring at the speed of 300rpm/min, reacting for 6h to obtain a reaction product, filtering the reaction product, dissolving a filter cake obtained by filtering into 2mol of 50 ℃ hot methanol solution with 0.1% of activated carbon by mass fraction, and recrystallizing the uniformly dissolved solution to finally obtain the 4,4 ' -biphenyl diphenol.
Example 3:
s1: preparation of 2, 6-di-tert-butylphenol
Adding 0.3mol of phenol and 0.007mol of aluminum trichloride into a reaction container, raising the temperature to 160 ℃, stirring at a low speed of 300rpm/min for reaction for 2 hours, then reducing the reaction temperature in the reaction container to 120 ℃, introducing 0.65mol of isobutene into the reaction container, controlling the pressure in the reaction container to be 0.5Mpa, continuously reducing the reaction temperature in the reaction container to 60 ℃ after reacting for 5 hours, reacting for 1 hour to obtain a crude product of 2, 6-di-tert-butylphenol, adding 0.03mol of sodium hydroxide into the crude product of 2, 6-di-tert-butylphenol to prepare a sodium hydroxide solution with the mass fraction of 20%, reacting for 1 hour at 200 ℃, and filtering and distilling the reaction product under reduced pressure to obtain a purified product of 2, 6-di-tert-butylphenol;
s2: preparation of 3,3 ', 5, 5' -tetra-tert-butyl biphenyl diphenol by oxidative coupling reaction
Preparing 0.2mol of 2, 6-di-tert-butylphenol purified product and 0.05mol of potassium hydroxide in S1 into a 25% potassium hydroxide solution by mass percent, adding the potassium hydroxide solution into a reaction vessel, introducing oxygen into the reaction vessel and starting stirring, wherein the oxygen introduction rate is controlled at 60ml/min, the stirring rate is 600rpm/min, the reaction is carried out for 1h at 40 ℃, then the temperature is increased to 200 ℃, the temperature increase rate is 3 ℃/min, and the reaction is carried out for 6h, thus obtaining the 3,3 ', 5, 5' -tetra-tert-butylbiphenyl diphenol;
s3: preparation of 4, 4' -biphenol by tert-butyl removal reaction
Adding 0.025mol of 3,3 ', 5,5 ' -tetra-tert-butyl biphenyl diphenol, 0.0015mol of p-toluenesulfonic acid and 0.1mol of toluene solvent in S2 into a reaction vessel, introducing nitrogen into the reaction vessel, heating to 140 ℃ through an oil bath, stirring at the speed of 400rpm/min, reacting for 5 hours to obtain a reaction product, filtering the reaction product, dissolving a filter cake obtained by filtering into 2mol of 50 ℃ hot methanol solution with 0.3% of activated carbon by mass fraction, and recrystallizing the uniformly dissolved solution to finally obtain the 4,4 ' -biphenyl diphenol.
Example 4:
s1: preparation of 2, 6-di-tert-butylphenol
Adding 0.3mol of phenol and 0.075mol of aluminum trichloride into a reaction container, raising the temperature to 160 ℃, stirring at a low speed of 300rpm/min for reaction for 2 hours, then reducing the reaction temperature in the reaction container to 120 ℃, introducing 0.66mol of isobutene into the reaction container, controlling the pressure in the reaction container to be 0.6Mpa, continuously reducing the reaction temperature in the reaction container to 60 ℃ after reacting for 5 hours, reacting for 1 hour to obtain a crude product of 2, 6-di-tert-butylphenol, adding 0.03mol of sodium hydroxide into the crude product of 2, 6-di-tert-butylphenol to prepare a sodium hydroxide solution with the mass fraction of 20%, reacting for 1 hour at 200 ℃, and filtering and distilling the reaction product under reduced pressure to obtain a purified product of 2, 6-di-tert-butylphenol;
s2: preparation of 3,3 ', 5, 5' -tetra-tert-butyl biphenyl diphenol by oxidative coupling reaction
Preparing 0.2mol of 2, 6-di-tert-butylphenol purified product and 0.06mol of potassium hydroxide in S1 into a potassium hydroxide solution with the mass fraction of 30%, adding the potassium hydroxide solution into a reaction container, introducing oxygen into the reaction container, starting stirring, controlling the oxygen introduction rate at 60ml/min, stirring at 600rpm/min, reacting for 1h at 40 ℃, then raising the temperature to 200 ℃, raising the temperature at 3 ℃/min, and reacting for 6h to obtain 3,3 ', 5, 5' -tetra-tert-butylbiphenyl diphenol;
s3: preparation of 4, 4' -biphenol by tert-butyl removal reaction
Adding 0.025mol of 3,3 ', 5,5 ' -tetra-tert-butyl biphenyl diphenol, 0.002mol of p-toluenesulfonic acid and 0.2mol of toluene solvent in S2 into a reaction vessel, introducing nitrogen into the reaction vessel, heating to 140 ℃ through an oil bath, stirring at the speed of 400rpm/min, reacting for 5 hours to obtain a reaction product, filtering the reaction product, dissolving a filter cake obtained by filtering into 3mol of 55 ℃ hot methanol solution with 0.5% of activated carbon by mass fraction, and recrystallizing the uniformly dissolved solution to finally obtain the 4,4 ' -biphenyl diphenol.
Example 5:
s1: preparation of 2, 6-di-tert-butylphenol
Adding 0.3mol of phenol and 0.0068mol of aluminum powder into a reaction container, raising the temperature to 160 ℃, stirring at a low speed of 300rpm/min for reaction for 2 hours, then reducing the reaction temperature in the reaction container to 120 ℃, introducing 0.63mol of isobutene into the reaction container, controlling the pressure in the reaction container to be 0.55Mpa, continuously reducing the reaction temperature in the reaction container to 60 ℃ after reacting for 4.5 hours, reacting for 1.5 hours to obtain a crude product of 2, 6-di-tert-butylphenol, adding 0.032mol of sodium hydroxide into the crude product of 2, 6-di-tert-butylphenol to prepare a 25 mass percent sodium hydroxide solution, reacting for 1 hour at 200 ℃, filtering and distilling the reaction product under reduced pressure to obtain a purified product of 2, 6-di-tert-butylphenol;
s2: preparation of 3,3 ', 5, 5' -tetra-tert-butyl biphenyl diphenol by oxidative coupling reaction
Preparing 0.2mol of 2, 6-di-tert-butylphenol purified product and 0.048mol of potassium hydroxide in S1 into a potassium hydroxide solution with the mass fraction of 20%, adding the potassium hydroxide solution into a reaction container, introducing oxygen into the reaction container, starting stirring, controlling the oxygen introduction rate at 50ml/min, stirring at 600rpm/min, reacting for 1h at 40 ℃, then raising the temperature to 200 ℃, raising the temperature at 2.5 ℃/min, and reacting for 6h to obtain the 3,3 ', 5, 5' -tetra-tert-butyldiphenol;
s3: preparation of 4, 4' -biphenol by tert-butyl removal reaction
Adding 0.025mol of 3,3 ', 5,5 ' -tetra-tert-butyl biphenyl diphenol, 0.0016mol of p-toluenesulfonic acid and 0.15mol of toluene solvent in S2 into a reaction vessel, introducing nitrogen into the reaction vessel, heating to 140 ℃ through oil bath, stirring at the speed of 350rpm/min, reacting for 5 hours to obtain a reaction product, filtering the reaction product, dissolving a filter cake obtained by filtering into 3mol of 58 ℃ hot methanol solution with 0.35% of activated carbon by mass fraction, and recrystallizing the uniformly dissolved solution to finally obtain the 4,4 ' -biphenyl diphenol.
The purity of 4, 4' -biphenol obtained in examples 1 to 5 is shown in the following table:
| 4, 4' -Biphenyldiphenol | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Purity of | 98.98％ | 99.28％ | 99.89％ | 99.93％ | 99.97％ |
In the above embodiment, specifically illustrating the preparation method provided by the present invention, a suitable aluminum material can be selected by optimizing the ratio of phenol to aluminum material, the three-stage reaction temperature in the process of preparing 2, 6-di-tert-butylphenol, and the concentration and amount of sodium hydroxide are controlled to refine the 2, 6-di-tert-butylphenol purified product, and 3,3 ', 5, 5' -tetra-tert-butylbiphenyl diphenol is accurately prepared by controlling the reaction ratio of 2, 6-di-tert-butylphenol to potassium hydroxide, the concentration of potassium hydroxide solution, the introduction rate of oxygen during the oxidative coupling reaction, the reaction temperature of the reaction system and the heating rate, finally the benzene aromatic ring solution is used as solvent, p-toluenesulfonic acid is used as catalyst, the molar ratio of 3,3 ', 5, 5' -tetra-tert-butylbiphenyl diphenol to catalyst and solvent is regulated to prepare 4,4 ' -biphenol, and further improving the purity of the 4,4 ' -biphenol by controlling the temperature and the concentration of the methanol solution and the mass fraction of the activated carbon, and finally obtaining the 4,4 ' -biphenol with the purity of 99.97 percent, wherein the purity is high, and the application requirement of high purity can be better met.
The preparation method of the high-purity 4,4 ' -biphenol provided by the invention is characterized in that phenol with high cost performance is used as a raw material, 2, 6-di-tert-butylphenol purified product is prepared through tert-butylation, 3 ', 5,5 ' -tetra-tert-butylbiphenol is prepared through oxidative coupling, and high-purity 4,4 ' -biphenol is prepared through tert-butyl reaction, and technological parameters and material proportion are optimized, so that the purity of the finally prepared 4,4 ' -biphenol can reach 99.97%.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the high-purity 4, 4' -biphenol is characterized by comprising the following steps:
s1: preparation of 2, 6-di-tert-butylphenol
Adding phenol and aluminum into a reaction container, raising the temperature to 140-160 ℃, stirring for reaction for 1-2h, reducing the reaction temperature in the reaction container to 110-120 ℃, introducing isobutene into the reaction container, controlling the pressure in the reaction container to be 0.4-0.6 Mpa, continuously reducing the reaction temperature in the reaction container to 50-60 ℃ after reaction for 4-6h, reacting for 1-2h to obtain a crude product of 2, 6-di-tert-butylphenol, adding sodium hydroxide into the crude product of 2, 6-di-tert-butylphenol, reacting for 1-2h at 180-220 ℃, filtering and distilling the reaction product under reduced pressure to obtain a purified product of 2, 6-di-tert-butylphenol;
s2: preparation of 3,3 ', 5, 5' -tetra-tert-butyl biphenyl diphenol by oxidative coupling reaction
Adding the 2, 6-di-tert-butylphenol purified product in the S1 and potassium hydroxide into a reaction vessel, introducing oxygen into the reaction vessel, starting stirring, reacting at 30-40 ℃ for 0.5-1.5 h, raising the temperature to 180-200 ℃, and reacting for 6-8 h to obtain 3,3 ', 5, 5' -tetra-tert-butylbiphenol;
s3: preparation of 4, 4' -biphenol by tert-butyl removal reaction
Adding 3,3 ', 5,5 ' -tetra-tert-butyl diphenol, p-toluenesulfonic acid and benzene solvents in S2 into a reaction vessel, introducing nitrogen into the reaction vessel, heating to 130-140 ℃ through an oil bath, stirring for 5-7 h to obtain a reaction product, filtering the reaction product, dissolving a filter cake obtained by filtering into a hot methanol solution with activated carbon at 50-60 ℃, and recrystallizing the uniformly dissolved solution to finally obtain 4,4 ' -diphenol.
2. The method of claim 1, wherein in S1, the aluminum material is at least one of aluminum powder, aluminum chloride and aluminum trichloride.
3. The method for preparing high-purity 4, 4' -biphenol according to claim 1, wherein in S1, the molar ratio of phenol to aluminum material is 1: 0.02 to 0.025; the molar ratio of the phenol to the isobutene is 1: 2-2.2.
4. The method for preparing high-purity 4, 4' -biphenol according to claim 1, wherein in S1, 0.02-0.04 mol of sodium hydroxide is added into the crude product of 2, 6-di-tert-butylphenol, 15-25% by mass of sodium hydroxide solution is prepared, and then the reaction is carried out at 180-220 ℃ for 1-2 h.
5. The method of claim 1, wherein the step of adding the 4, 4' -biphenol into the reaction vessel in a molar ratio of 1: 0.2-0.3 of 2, 6-di-tert-butylphenol purified product and potassium hydroxide, preparing a potassium hydroxide solution with the concentration of 20-30%, and introducing nitrogen to stir for reaction.
6. The method for preparing high-purity 4, 4' -biphenol according to claim 1, wherein in S2, after the temperature is raised to 180-200 ℃ at a temperature raising rate of 1-3 ℃/min, the reaction is carried out for 6-8 h.
7. The method of claim 1, wherein the benzene-based solvent used in S3 is toluene, xylene or meta-xylene.
8. The method for preparing high-purity 4,4 ' -biphenol according to claim 1, wherein in S3, the molar ratio of 3,3 ', 5,5 ' -tetra-tert-butylbiphenol to p-toluenesulfonic acid is 1: 0.04 to 0.08; the molar ratio of the 3,3 ', 5, 5' -tetra-tert-butyl biphenyl diphenol to the benzene solvent is 1: 4 to 8.
9. The method for preparing high-purity 4, 4' -biphenol according to claim 1, wherein in S3, the mass fraction of activated carbon in the methanol solution is 0.1-0.5%.
10. The method for preparing high-purity 4, 4' -biphenol according to claim 1, wherein in S1, the stirring speed in the reaction process is 200-300 rpm/min;
the oxygen introducing rate in S2 is controlled to be 45-60 ml/min.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805035A (en) * | 2022-06-08 | 2022-07-29 | 四川圣效科技股份有限公司 | Method for purifying 4, 4' -biphenol |
| CN115385818A (en) * | 2022-09-01 | 2022-11-25 | 江苏海洋大学 | Paracetamol impurity and preparation method thereof |
| CN115611709A (en) * | 2022-12-15 | 2023-01-17 | 北京弗莱明科技有限公司 | Synthetic method of 4,4' -dihydroxybiphenyl |
| CN115626866A (en) * | 2022-09-25 | 2023-01-20 | 宿迁思睿屹新材料有限公司 | Industrial synthesis method of high-purity 4,4' -biphenol compound |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3133974A (en) * | 1960-11-23 | 1964-05-19 | Ethyl Corp | Phenol alkylation process |
| US4560809A (en) * | 1984-10-09 | 1985-12-24 | Ethyl Corporation | Alkylation process |
| US5099076A (en) * | 1989-10-06 | 1992-03-24 | Honshu Chemical Industry Co., Ltd. | Method for preparing p,p'-biphenol |
| JPH0812611A (en) * | 1994-06-30 | 1996-01-16 | Dainippon Ink & Chem Inc | Production of 2,6-dialkylphenol |
| JPH11292813A (en) * | 1998-03-11 | 1999-10-26 | Choshun Jinzo Jushisho Kofun Yugenkoshi | New production method of tetraalkyldiphenol |
| US6118029A (en) * | 1997-01-30 | 2000-09-12 | Honshu Chemical Industry Co., Ltd. | Process for producing 3,3',5,5'-tetra-t butylbiphenol |
| KR20020071050A (en) * | 2001-03-02 | 2002-09-12 | 송원산업 주식회사 | Method of preparing 4,4'-biphenol |
| CN1493556A (en) * | 2002-11-01 | 2004-05-05 | ��ѧ����������ҵ�� | Process for continuously producing 3, 3', 5, 5'-tetra-t-butyl-4, 4'-diphenol |
-
2021
- 2021-12-20 CN CN202111559205.XA patent/CN114181052A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3133974A (en) * | 1960-11-23 | 1964-05-19 | Ethyl Corp | Phenol alkylation process |
| US4560809A (en) * | 1984-10-09 | 1985-12-24 | Ethyl Corporation | Alkylation process |
| US5099076A (en) * | 1989-10-06 | 1992-03-24 | Honshu Chemical Industry Co., Ltd. | Method for preparing p,p'-biphenol |
| JPH0812611A (en) * | 1994-06-30 | 1996-01-16 | Dainippon Ink & Chem Inc | Production of 2,6-dialkylphenol |
| US6118029A (en) * | 1997-01-30 | 2000-09-12 | Honshu Chemical Industry Co., Ltd. | Process for producing 3,3',5,5'-tetra-t butylbiphenol |
| JPH11292813A (en) * | 1998-03-11 | 1999-10-26 | Choshun Jinzo Jushisho Kofun Yugenkoshi | New production method of tetraalkyldiphenol |
| KR20020071050A (en) * | 2001-03-02 | 2002-09-12 | 송원산업 주식회사 | Method of preparing 4,4'-biphenol |
| CN1493556A (en) * | 2002-11-01 | 2004-05-05 | ��ѧ����������ҵ�� | Process for continuously producing 3, 3', 5, 5'-tetra-t-butyl-4, 4'-diphenol |
| US20040122263A1 (en) * | 2002-11-01 | 2004-06-24 | Mikio Kawahara | Method for continuously producing 3,3',5,5'-tetra-t-butyl-4,4'-biphenol |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805035A (en) * | 2022-06-08 | 2022-07-29 | 四川圣效科技股份有限公司 | Method for purifying 4, 4' -biphenol |
| CN115385818A (en) * | 2022-09-01 | 2022-11-25 | 江苏海洋大学 | Paracetamol impurity and preparation method thereof |
| CN115385818B (en) * | 2022-09-01 | 2023-09-29 | 江苏海洋大学 | Paracetamol impurity and preparation method thereof |
| CN115626866A (en) * | 2022-09-25 | 2023-01-20 | 宿迁思睿屹新材料有限公司 | Industrial synthesis method of high-purity 4,4' -biphenol compound |
| CN115611709A (en) * | 2022-12-15 | 2023-01-17 | 北京弗莱明科技有限公司 | Synthetic method of 4,4' -dihydroxybiphenyl |
| CN116217343A (en) * | 2023-03-14 | 2023-06-06 | 锦州三丰科技有限公司 | Production process of biphenol |
| CN116120154A (en) * | 2023-04-17 | 2023-05-16 | 东方飞源(山东)电子材料有限公司 | Preparation method of 3,3', 5' -tetramethyl biphenol applied to electronic material |
| CN116444349A (en) * | 2023-06-19 | 2023-07-18 | 北京弗莱明科技有限公司 | Preparation method of 3,3', 5' -tetraalkyl-4, 4' -biphenol |
| CN118724784A (en) * | 2024-08-30 | 2024-10-01 | 北京弗莱明科技有限公司 | Pyrrolidone sulfonate ionic liquid for synthesizing 4,4' -biphenol and preparation method and application thereof |
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