CN110105176B - TMBP industrial synthesis method - Google Patents
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- CN110105176B CN110105176B CN201910460930.8A CN201910460930A CN110105176B CN 110105176 B CN110105176 B CN 110105176B CN 201910460930 A CN201910460930 A CN 201910460930A CN 110105176 B CN110105176 B CN 110105176B
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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
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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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
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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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
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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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/86—Purification; separation; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification
Abstract
The invention relates to a TMBP industrial synthesis method, which comprises the following steps: (1) dissolving 2, 6-dimethylphenol, sodium dodecyl sulfate and borax in isopropanol to obtain a pre-solution for later use; (2) adding a certain amount of deionized water into a reaction kettle, then adding the pre-solution, heating to a certain temperature, then quickly adding a catalyst, then sealing the reaction kettle, stirring, introducing oxygen, and continuously reacting for a certain time under a certain pressure; (3) after the reaction is finished and the pressure is relieved to normal pressure, a white needle-shaped crystal product, namely TMBP is obtained through cooling, filtering, washing, recrystallization and drying; wherein, a reducing agent is added in the process of recrystallization. The method innovatively uses the pressurized process conditions, greatly reduces the side reaction under the pressurized condition through the selection of the types of raw materials and the adjustment of the process conditions under the synergistic effect, and realizes the double promotion of the TMBP yield (the total yield is more than 85%) and the purity (more than 99.0%) by combining the reduction means.
Description
Technical Field
The invention relates to the technical field of TMBP synthesis, in particular to an industrial TMBP synthesis method.
Background
3, 3',5, 5' -tetramethylbiphenol (3,5,3',5' -Tetramethyl-biphenyl-4,4' -diol, TMBP), is a typical liquid crystal polymer intermediate material. Meanwhile, the modified polycarbonate resin has excellent heat resistance, so that the modified polycarbonate resin is also used as a modified monomer of various products such as polyester, polyurethane, polycarbonate, polysulfone, epoxy resin and the like; and because it has the prevention function to aging caused by oxygen and heat, and has the characteristic of no pollution, it can be used as rubber, latex anti-aging agent and plastic antioxidant, and fuel intermediate or stabilizer of petroleum product, for example, it can be used for light-colored vulcanized rubber product, food packaging rubber, medical dairy product and sulfur oxide product. Among them, the liquid crystal polymer has been used as a raw material in an industrial stage.
The TMBP synthesis methods reported in the literature at present mainly comprise two methods: one method is to take 2, 6-dimethylphenol as a raw material, dissolve the raw material in an aqueous solution with a surfactant, introduce oxygen, add a catalyst, and obtain TMBP after post-treatment; the other method is to take 2, 6-dimethylphenol as a raw material, dissolve the raw material in acetone or acetonitrile, take CuCl as a catalyst, introduce oxygen, and reduce the raw material by sodium hydrosulfite (commonly called sodium hydrosulfite) to obtain TMBP.
However, both of the above methods are in the laboratory stage, and cannot be applied in the mature industry, so that the requirements of industrial mass production cannot be met. Therefore, a TMBP synthesis method applicable to industrial mass production is in urgent need of development to meet the market demand.
Disclosure of Invention
The invention provides an industrial synthesis method of TMBP (tetramethylbenzidine), which solves the problem that the TMBP synthesis process reported in the existing literature is not suitable for industrial large-scale production.
The technical scheme adopted by the invention is as follows:
an industrial synthesis method of TMBP comprises the following steps:
(1) dissolving 2, 6-dimethylphenol, sodium dodecyl sulfate and borax in isopropanol to obtain a pre-solution for later use;
(2) adding a certain amount of deionized water into a reaction kettle, then adding the pre-solution, heating to a certain temperature, then quickly adding a catalyst, then sealing the reaction kettle, stirring, introducing oxygen, and continuously reacting for a certain time under a certain pressure;
(3) after the reaction is finished and the pressure is relieved to normal pressure, a white needle-shaped crystal product, namely TMBP is obtained through cooling, filtering, washing, recrystallization and drying; wherein, a reducing agent is added in the process of recrystallization.
It should be noted that the surfactant selected for use in the present disclosure is sodium lauryl sulfate, but is not limited thereto, and other surfactant types that are similarly suitable for use in the present disclosure but are described herein may also and only should be considered as acceptable.
Further, the catalyst is copper acetate; other copper compounds may also be selected as catalysts, but the effect is less than that of copper acetate in this embodiment.
Further, the reducing agent is sodium hydrosulfite, namely commonly known sodium hydrosulfite.
Furthermore, the dosage of the 2, 6-dimethylphenol, the sodium dodecyl sulfate, the catalyst, the oxygen and the reducing agent is 1: (0.005-0.025): (0.04-0.06): (0.25-0.35): (0.03-0.05); meanwhile, the dosage of the borax is based on the pH value of the reaction solution being 7-12.
Further, in the step 2, the temperature value of the certain temperature is within the range of (80-94) ± 2 ℃; the pressure value range of the certain pressure is 4.5-5.5 Kgf/cm 2; the time value range of the certain time is 6-7 h.
Further, in step 2, the rotation speed of stirring during the reaction is 500 rmp.
Further, in step 3, the washing process is performed by using deionized water.
Further, in step 3, the solvent used in the recrystallization process is any one of methanol, ethanol, toluene and acetone; among them, ethanol is preferably used as a recrystallization solvent for the sake of both safety and cost; meanwhile, in consideration of recrystallization efficiency and effect, the amount of ethanol is 6 times (mass times) that of the TMBP crude product.
Further, in the step 3, in the drying process, the drying temperature is 70-80 ℃.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) the method innovatively uses the pressurized process conditions, greatly reduces the side reaction under the pressurized condition under the synergistic action of the selection of the raw material types and the adjustment of the process conditions, and realizes the double promotion of the TMBP yield (the total yield is more than 85%) and the purity (more than 99.0%) by combining the reduction means;
(2) the invention overcomes the problem that the existing synthesis process can not adapt to industrialized large-scale production, realizes the breakthrough of TMBP industrialized high-efficiency synthesis, and can further improve the industrial production capacity of TMBP so as to meet the requirements of domestic and foreign markets;
(3) the industrial TMBP product obtained by the invention has high purity, and is particularly suitable for diversified use of the TMBP.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description of the present invention is provided with reference to specific examples.
It is to be understood that the components mentioned in the compositions provided in the present disclosure may be selected from the corresponding commercially available materials, and therefore, the sources of the components are not separately described. However, it should be noted that, because the effective contents of the components of the products of different manufacturers are different, the effective amounts recorded in the technical scheme should be converted and used in the using process.
In the following examples, the reaction is carried out in an autoclave according to an industrial production process, and the volume of the autoclave is selected to be 300L (accordingly, the amount of 2, 6-dimethylphenol as a base raw material is generally 40Kg, but is not limited thereto, and can be increased or decreased according to actual needs without departing from the inventive concept), but the invention is not limited thereto, and a skilled person can select an autoclave with a larger or smaller volume according to production needs.
In addition, the selection of raw materials for each component is set forth herein for simplicity in illustrating the process. It is to be understood, however, that the selection of the raw materials for each component is not limited to the sources listed below, and that other sources may be accepted and used without departing from the inventive concept and having equivalent or similar characteristics to the materials selected for use in the invention; in this case, the implementation of the inventive concept is not affected.
The following examples refer to the following table for the selection of the raw materials of the components:
the method comprises the following steps of raw material name specification or local 2, 6-dimethylphenol 99%, borax 95% in Japan, Jiangsu lauryl sodium sulfate super grade, chemical purity of Shanghai copper acetate, self-made oxygen industrial product of Shanghai deionized water, isopropanol 99% in Lanzhou, Liaoning reducing agent 85%, Guangdong alcohol (ethanol) 95% edible grade, and Shandong, wherein the self-made process of the deionized water is carried out by adopting a conventional water purification treatment mode, and the conventional water purification treatment mode comprises but not limited to RO reverse osmosis, EDI continuous electric desalting, anion/cation resin exchange and the like or combination of the treatment modes. Also, it is noted that, generally, deionized water is prepared prior to use and used immediately after preparation; if the product is stored, the components in the product need to be verified before use, and the product can be used after meeting the relevant standards and requirements of deionized water.
Example 1
An industrial synthesis method of TMBP comprises the following steps:
(1) dissolving 2, 6-dimethylphenol, sodium dodecyl sulfate and borax in isopropanol to obtain a pre-solution for later use;
(2) adding a certain amount of deionized water into a reaction kettle, then adding the pre-solution, heating to a certain temperature, then quickly adding a catalyst, then sealing the reaction kettle, stirring, introducing oxygen, and continuously reacting for a certain time under a certain pressure;
(3) after the reaction is finished and the pressure is relieved to normal pressure, a white needle-shaped crystal product, namely TMBP is obtained through cooling, filtering, washing, recrystallization and drying; wherein, a reducing agent is added in the process of recrystallization.
Wherein the catalyst is copper acetate; the reducing agent is sodium hydrosulfite, namely commonly called sodium hydrosulfite. Wherein, the dosage of the 2, 6-dimethylphenol, the sodium dodecyl sulfate, the catalyst, the oxygen and the reducing agent is 1: 0.005: 0.04: 0.25: 0.03; meanwhile, the amount of borax used was such that the pH of the reaction solution became 7.
Meanwhile, in the step 2, the temperature value range of the certain temperature is 80 +/-2 ℃; the pressure value range of the certain pressure is 4.5Kgf/cm 2; the time value range of the certain time is 6 h;
in the step 2, the stirring speed in the reaction process is 500 rmp;
in the step 3, the washing process is carried out by using deionized water;
in the step 3, the solvent used in the recrystallization process is ethanol, and the dosage of the ethanol is 6 times (mass times) of that of the TMBP crude product;
in the step 3, the drying temperature is 70 ℃ in the drying process.
The TMBP obtained in this example was analyzed by infrared spectroscopy. Now, the characteristic peaks appearing in the map are analyzed as follows: the absorption peak at 3389.8cm-1 is the stretching vibration of free OH; the absorption peak at 3060.0cm-1 is the stretching vibration of C-H on the benzene ring; the absorption peaks at 2967.0cm-1 and 2920.1cm-1 are methyl C-H stretching vibration; the absorption peaks at 1603.1cm-1 and 1473.5cm-1 are the vibration of the benzene ring skeleton; the absorption peak at 1391.1cm-1 is methyl bending vibration; the absorption peak at 1195.9cm-1 is the stretching vibration of C-O; 860.1cm-1 absorption peak is the out-of-plane bending vibration of C-H on the benzene ring. The appearance of the characteristic peaks proves that the TMBP prepared by the embodiment meets the characteristic peaks of the standard TMBP sample, and the industrial synthesis method of the embodiment is feasible. Meanwhile, the conclusion is verified by adopting a mass spectrometry method, and the molecular mass of the product reflected by the obtained molecular mass peak is 212 and is consistent with the theoretical molecular weight of TMBP.
The purity of the TMBP obtained in the embodiment is analyzed by adopting a high performance liquid chromatography, and the purity of the product is more than 99 percent and meets the application requirement.
The yield was calculated based on the TMBP product and the actual yield of TMBP was 85.28%.
Example 2
An industrial synthesis method of TMBP comprises the following steps:
(1) dissolving 2, 6-dimethylphenol, sodium dodecyl sulfate and borax in isopropanol to obtain a pre-solution for later use;
(2) adding a certain amount of deionized water into a reaction kettle, then adding the pre-solution, heating to a certain temperature, then quickly adding a catalyst, then sealing the reaction kettle, stirring, introducing oxygen, and continuously reacting for a certain time under a certain pressure;
(3) after the reaction is finished and the pressure is relieved to normal pressure, a white needle-shaped crystal product, namely TMBP is obtained through cooling, filtering, washing, recrystallization and drying; wherein, a reducing agent is added in the process of recrystallization.
Wherein the catalyst is copper acetate; the reducing agent is sodium hydrosulfite, namely commonly called sodium hydrosulfite. Wherein, the dosage of the 2, 6-dimethylphenol, the sodium dodecyl sulfate, the catalyst, the oxygen and the reducing agent is 1: 0.025: 0.06: 0.35: 0.05; meanwhile, the amount of borax used was such that the pH of the reaction solution became 12.
Meanwhile, in the step 2, the temperature value range of the certain temperature is 94 +/-2 ℃; the pressure value range of the certain pressure is 5.5Kgf/cm 2; the time value range of the certain time is 7 h;
in the step 2, the stirring speed in the reaction process is 500 rmp;
in the step 3, the washing process is carried out by using deionized water;
in the step 3, the solvent used in the recrystallization process is ethanol, and the dosage of the ethanol is 6 times (mass times) of that of the TMBP crude product;
in the step 3, the drying temperature is 80 ℃ in the drying process.
The TMBP obtained in this example was analyzed by infrared spectroscopy. Now, the characteristic peaks appearing in the map are analyzed as follows: the absorption peak at 3389.8cm-1 is the stretching vibration of free OH; the absorption peak at 3060.0cm-1 is the stretching vibration of C-H on the benzene ring; the absorption peaks at 2967.0cm-1 and 2920.1cm-1 are methyl C-H stretching vibration; the absorption peaks at 1603.1cm-1 and 1473.5cm-1 are the vibration of the benzene ring skeleton; the absorption peak at 1391.1cm-1 is methyl bending vibration; the absorption peak at 1195.9cm-1 is the stretching vibration of C-O; 860.1cm-1 absorption peak is the out-of-plane bending vibration of C-H on the benzene ring. The appearance of the characteristic peaks proves that the TMBP prepared by the embodiment meets the characteristic peaks of the standard TMBP sample, and the industrial synthesis method of the embodiment is feasible.
Meanwhile, the conclusion is verified by adopting a mass spectrometry method, and the molecular mass of the product reflected by the obtained molecular mass peak is 212 and is consistent with the theoretical molecular weight of TMBP.
The purity of the TMBP obtained in the embodiment is analyzed by adopting a high performance liquid chromatography, and the purity of the product is more than 99 percent and meets the application requirement.
The yield was calculated based on the TMBP product and the actual yield of TMBP was 86.91%.
Example 3
An industrial synthesis method of TMBP comprises the following steps:
(1) dissolving 2, 6-dimethylphenol, sodium dodecyl sulfate and borax in isopropanol to obtain a pre-solution for later use;
(2) adding a certain amount of deionized water into a reaction kettle, then adding the pre-solution, heating to a certain temperature, then quickly adding a catalyst, then sealing the reaction kettle, stirring, introducing oxygen, and continuously reacting for a certain time under a certain pressure;
(3) after the reaction is finished and the pressure is relieved to normal pressure, a white needle-shaped crystal product, namely TMBP is obtained through cooling, filtering, washing, recrystallization and drying; wherein, a reducing agent is added in the process of recrystallization.
Wherein the catalyst is copper acetate; the reducing agent is sodium hydrosulfite, namely commonly called sodium hydrosulfite. Wherein, the dosage of the 2, 6-dimethylphenol, the sodium dodecyl sulfate, the catalyst, the oxygen and the reducing agent is 1: 0.01: 0.045: 0.28: 0.034; meanwhile, the amount of borax used was such that the pH of the reaction solution became 9.
Meanwhile, in the step 2, the temperature value range of the certain temperature is 85 +/-2 ℃; the pressure value range of the certain pressure is 4.8Kgf/cm 2; the time value range of the certain time is 6.3 h;
in the step 2, the stirring speed in the reaction process is 500 rmp;
in the step 3, the washing process is carried out by using deionized water;
in the step 3, the solvent used in the recrystallization process is ethanol, and the dosage of the ethanol is 6 times (mass times) of that of the TMBP crude product;
in the step 3, the drying temperature is 72 ℃ in the drying process.
The TMBP obtained in this example was analyzed by infrared spectroscopy. Now, the characteristic peaks appearing in the map are analyzed as follows: the absorption peak at 3389.8cm-1 is the stretching vibration of free OH; the absorption peak at 3060.0cm-1 is the stretching vibration of C-H on the benzene ring; the absorption peaks at 2967.0cm-1 and 2920.1cm-1 are methyl C-H stretching vibration; the absorption peaks at 1603.1cm-1 and 1473.5cm-1 are the vibration of the benzene ring skeleton; the absorption peak at 1391.1cm-1 is methyl bending vibration; the absorption peak at 1195.9cm-1 is the stretching vibration of C-O; 860.1cm-1 absorption peak is the out-of-plane bending vibration of C-H on the benzene ring. The appearance of the characteristic peaks proves that the TMBP prepared by the embodiment meets the characteristic peaks of the standard TMBP sample, and the industrial synthesis method of the embodiment is feasible.
Meanwhile, the conclusion is verified by adopting a mass spectrometry method, and the molecular mass of the product reflected by the obtained molecular mass peak is 212 and is consistent with the theoretical molecular weight of TMBP.
The purity of the TMBP obtained in the embodiment is analyzed by adopting a high performance liquid chromatography, and the purity of the product is more than 99 percent and meets the application requirement.
The yield was calculated based on the TMBP product and the actual yield of TMBP was 87.52%.
Example 4
An industrial synthesis method of TMBP comprises the following steps:
(1) dissolving 2, 6-dimethylphenol, sodium dodecyl sulfate and borax in isopropanol to obtain a pre-solution for later use;
(2) adding a certain amount of deionized water into a reaction kettle, then adding the pre-solution, heating to a certain temperature, then quickly adding a catalyst, then sealing the reaction kettle, stirring, introducing oxygen, and continuously reacting for a certain time under a certain pressure;
(3) after the reaction is finished and the pressure is relieved to normal pressure, a white needle-shaped crystal product, namely TMBP is obtained through cooling, filtering, washing, recrystallization and drying; wherein, a reducing agent is added in the process of recrystallization.
Wherein the catalyst is copper acetate; the reducing agent is sodium hydrosulfite, namely commonly called sodium hydrosulfite. Wherein, the dosage of the 2, 6-dimethylphenol, the sodium dodecyl sulfate, the catalyst, the oxygen and the reducing agent is 1: 0.02: 0.055: 0.32: 0.045; meanwhile, the amount of borax used was such that the pH of the reaction solution became 10.
Meanwhile, in the step 2, the temperature value range of the certain temperature is 92 +/-2 ℃; the pressure value range of the certain pressure is 5.2Kgf/cm 2; the time value range of the certain time is 6.8 hours;
in the step 2, the stirring speed in the reaction process is 500 rmp;
in the step 3, the washing process is carried out by using deionized water;
in the step 3, the solvent used in the recrystallization process is ethanol, and the dosage of the ethanol is 6 times (mass times) of that of the TMBP crude product;
in the step 3, in the drying process, the drying temperature is 78 ℃.
The TMBP obtained in this example was analyzed by infrared spectroscopy. Now, the characteristic peaks appearing in the map are analyzed as follows: the absorption peak at 3389.8cm-1 is the stretching vibration of free OH; the absorption peak at 3060.0cm-1 is the stretching vibration of C-H on the benzene ring; the absorption peaks at 2967.0cm-1 and 2920.1cm-1 are methyl C-H stretching vibration; the absorption peaks at 1603.1cm-1 and 1473.5cm-1 are the vibration of the benzene ring skeleton; the absorption peak at 1391.1cm-1 is methyl bending vibration; the absorption peak at 1195.9cm-1 is the stretching vibration of C-O; 860.1cm-1 absorption peak is the out-of-plane bending vibration of C-H on the benzene ring. The appearance of the characteristic peaks proves that the TMBP prepared by the embodiment meets the characteristic peaks of the standard TMBP sample, and the industrial synthesis method of the embodiment is feasible. Meanwhile, the conclusion is verified by adopting a mass spectrometry method, and the molecular mass of the product reflected by the obtained molecular mass peak is 212 and is consistent with the theoretical molecular weight of TMBP.
The purity of the TMBP obtained in the embodiment is analyzed by adopting a high performance liquid chromatography, and the purity of the product is more than 99 percent and meets the application requirement.
The yield was calculated based on the TMBP product and the actual yield of TMBP was 87.36%.
Example 5
An industrial synthesis method of TMBP comprises the following steps:
(1) dissolving 2, 6-dimethylphenol, sodium dodecyl sulfate and borax in isopropanol to obtain a pre-solution for later use;
(2) adding a certain amount of deionized water into a reaction kettle, then adding the pre-solution, heating to a certain temperature, then quickly adding a catalyst, then sealing the reaction kettle, stirring, introducing oxygen, and continuously reacting for a certain time under a certain pressure;
(3) after the reaction is finished and the pressure is relieved to normal pressure, a white needle-shaped crystal product, namely TMBP is obtained through cooling, filtering, washing, recrystallization and drying; wherein, a reducing agent is added in the process of recrystallization.
Wherein the catalyst is copper acetate; the reducing agent is sodium hydrosulfite, namely commonly called sodium hydrosulfite. Wherein, the dosage of the 2, 6-dimethylphenol, the sodium dodecyl sulfate, the catalyst, the oxygen and the reducing agent is 1: 0.015: 0.05: 0.3: 0.04; meanwhile, the amount of borax used was such that the pH of the reaction solution was 9.5.
Meanwhile, in the step 2, the temperature value range of the certain temperature is 90 +/-2 ℃; the pressure value range of the certain pressure is 5Kgf/cm 2; the time value range of the certain time is 6.5 hours;
in the step 2, the stirring speed in the reaction process is 500 rmp;
in the step 3, the washing process is carried out by using deionized water;
in the step 3, the solvent used in the recrystallization process is ethanol, and the dosage of the ethanol is 6 times (mass times) of that of the TMBP crude product;
in the step 3, in the drying process, the drying temperature is 78 ℃.
The TMBP obtained in this example was analyzed by infrared spectroscopy. Now, the characteristic peaks appearing in the map are analyzed as follows: the absorption peak at 3389.8cm-1 is the stretching vibration of free OH; the absorption peak at 3060.0cm-1 is the stretching vibration of C-H on the benzene ring; the absorption peaks at 2967.0cm-1 and 2920.1cm-1 are methyl C-H stretching vibration; the absorption peaks at 1603.1cm-1 and 1473.5cm-1 are the vibration of the benzene ring skeleton; the absorption peak at 1391.1cm-1 is methyl bending vibration; the absorption peak at 1195.9cm-1 is the stretching vibration of C-O; 860.1cm-1 absorption peak is the out-of-plane bending vibration of C-H on the benzene ring. The appearance of the characteristic peaks proves that the TMBP prepared by the embodiment meets the characteristic peaks of the standard TMBP sample, and the industrial synthesis method of the embodiment is feasible.
Meanwhile, the conclusion is verified by adopting a mass spectrometry method, and the molecular mass of the product reflected by the obtained molecular mass peak is 212 and is consistent with the theoretical molecular weight of TMBP.
The purity of the TMBP obtained in the embodiment is analyzed by adopting a high performance liquid chromatography, and the purity of the product is more than 99 percent and meets the application requirement.
The yield was calculated based on the TMBP product and the actual yield of TMBP was 88.25%.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (6)
1. An industrial synthesis method of TMBP is characterized by comprising the following steps:
(1) dissolving 2, 6-dimethylphenol, sodium dodecyl sulfate and borax in isopropanol to obtain a pre-solution for later use;
(2) adding deionized water into a reaction kettle, then adding the pre-solution, heating to 80-94 +/-2 ℃, then quickly adding a catalyst copper acetate, then sealing the reaction kettle, stirring, introducing oxygen, and continuously reacting for 6-7 hours under the condition of 4.5-5.5 Kgf/cm 2;
(3) after the reaction is finished and the pressure is relieved to normal pressure, a white needle-shaped crystal product, namely TMBP is obtained through cooling, filtering, washing, recrystallization and drying; wherein, a reducing agent sodium hydrosulfite is added in the recrystallization process.
2. The industrial synthesis method of TMBP according to claim 1, wherein: the dosage of the 2, 6-dimethylphenol, the sodium dodecyl sulfate, the catalyst, the oxygen and the reducing agent is 1: (0.005-0.025): (0.04-0.06): (0.25-0.35): (0.03-0.05); meanwhile, the dosage of the borax is based on the pH value of the reaction solution being 7-12.
3. The industrial synthesis method of TMBP according to claim 1, wherein: in step 2, the stirring speed during the reaction is 500 rmp.
4. The industrial synthesis method of TMBP according to claim 1, wherein: in step 3, the washing process is performed by using deionized water.
5. The industrial synthesis method of TMBP according to claim 1, wherein: in step 3, the solvent used in the recrystallization process is any one of methanol, ethanol, toluene and acetone.
6. The industrial synthesis method of TMBP according to claim 1, wherein: in the step 3, in the drying process, the drying temperature is 70-80 ℃.
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| EP0150967A2 (en) * | 1984-01-23 | 1985-08-07 | Mitsubishi Petrochemical Co., Ltd. | Process for producing 4,4'-dihydroxydiphenyls |
| JPH03227949A (en) * | 1990-02-02 | 1991-10-08 | Toray Ind Inc | Production of 3,3'-5,5'-tetramethylbiphenyl-4,4'diol |
| CN1777570A (en) * | 2003-10-01 | 2006-05-24 | 三菱化学株式会社 | Process for producing 3,3',5,5'-tetraalkyl-4,4'-biphenol |
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