Preparation method of ultra-pure 4, 4 '-biphenol

Abstract

The invention discloses a preparation method of ultra-pure 4, 4 '-biphenol, which comprises the following steps: in the presence of air and a first catalyst, carrying out a coupling reaction by using 2, 6-di-tert-butyl phenol as a raw material to obtain 3, 3', 5, 5 '-tetra-tert-butyl-4, 4'-biphenol; and adding a second catalyst into the 3, 3 ', 5, 5'-tetra-tert-butyl-4, 4 '-biphenol, carrying out a heating reaction, after the reaction is finished, filtering to obtain a 4, 4'-biphenol crude product, and recrystallizing and drying to obtain the ultra-pure 4, 4 '-biphenol, the preparation method disclosed by the invention is mild in reaction condition, simple and convenient in post-treatment, easy to operate and excellent in yield, and the product purity reaches 99.99% or above.

Description

Technical Field

[0001] The invention relates to the technical field of 4,4'-biphenyl diphenol preparation, and in particular to a method for preparing ultra-high-purity 4,4'-biphenyl diphenol. Background Art

[0002] 4,4′-Biphenol can be used to make excellent engineering plastics and composite materials. Because it can prevent aging caused by oxygen and heat, it can be used as an antioxidant for rubber and latex. 4,4′-Biphenol has good heat resistance and can be used as a modified monomer for polyester, polyurethane, polycarbonate, polyphenylsulfone and epoxy resin. It can also be used as an additive for petroleum products. 4,4′-Biphenol is also non-polluting and can be used for light-colored vulcanized rubber products, food packaging glue and medical latex products. It is also used for sulfur chloride cold vulcanized products such as medical gloves and condoms. It also has a certain protective effect on harmful metals such as lead. 4,4′-Biphenol can also be used as a dye intermediate and can be used to synthesize photosensitive materials. It has reached the industrial practical stage as a raw material for liquid crystal polymers. This type of liquid crystal polymer has many characteristics and is widely used in many aspects: it can imitate silk, be made into high-strength fibers, and be used for optical fiber reinforcement.

[0003] At present, the synthesis processes of 4,4-dihydroxybiphenyl mainly include the following categories: biphenyl sulfonation alkali fusion method, benzidine method, biphenyl high-pressure hydrolysis method, di-tert-butylphenol oxidative coupling dealkylation method and di-tert-butylphenol oxidative coupling dealkylation continuous reaction method; however, using biphenyl as a raw material, sulfonation, azidation or halogenation to obtain an intermediate product, and then alkalization and hydrolysis to obtain the product, this method not only requires high temperature and high pressure, but also the purity of the obtained product is not high, and it is highly corrosive to the equipment and seriously pollutes the environment; using di-tert-butylphenol oxidative coupling dealkylation method, using transition metal salts The complex formed with organic amine catalyzes the oxidation of di-tert-butylphenol, and then acid-catalyzes dealkylation to obtain the product, but its total yield is only 70%, and the industrial economy is insufficient; in addition, the continuous reaction method of oxidative coupling and dealkylation of di-tert-butylphenol uses a continuous reaction device to continuously oxidatively couple di-tert-butylphenol through air to obtain tetra-tert-butylbiphenol, and then continuously dealkylates in 4-tert-butylphenol to obtain the product. The continuous reaction has high efficiency and is suitable for promotion in industrial production, but the temperature of the dealkylation reaction is above 220°C, and the reaction is prone to produce tar by-products.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] The object of the present invention is to provide a method for preparing ultra-high purity 4,4'-biphenyl diphenol, which has the advantages of mild reaction conditions, high yield, simple treatment, less three wastes, high product purity and low cost.

[0006] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0007] The first aspect of the present invention provides a method for preparing ultra-high purity 4,4'-biphenyl diphenol, the preparation method comprising the following steps:

[0008] (a) carrying out a coupling reaction with 2,6-di-tert-butylphenol as a raw material under the conditions of air and a first catalyst to obtain 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyldiphenol;

[0009] (b) adding a second catalyst to 3,3',5,5'-tetra-tert-butyl-4,4'-biphenol and performing a heating reaction. After the reaction is completed, filtering is performed to obtain a crude 4,4'-biphenol, and then recrystallizing and drying is performed to obtain the ultra-high purity 4,4'-biphenol.

[0010] Preferably, the first catalyst is selected from one of potassium hydroxide / activated alumina, potassium carbonate / activated alumina, sodium carbonate / magnesium oxide, sodium phosphate / magnesium oxide and sodium hydroxide / activated alumina.

[0011] Preferably, the step (a) further comprises a process of filtering and recovering the first catalyst after the reaction is completed.

[0012] Preferably, the coupling reaction temperature is 10-50°C, and the reaction time is 2-5h;

[0013] The solvent used in the coupling reaction is selected from any one of tert-butyl alcohol, methanol, ethanol, isopropanol, xylene and trimethylbenzene.

[0014] Preferably, the addition amount of the first catalyst is 0.1% to 2% of the mass of 2,6-di-tert-butylphenol.

[0015] Preferably, the second catalyst is selected from one of aluminum chloride, ferric chloride, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, perfluorosulfonic acid resin Nafion-H, perfluorosulfonic acid resin Nafion 501, perfluorosulfonic acid resin Nafon xr, perfluorosulfonic acid resin Nafion 425, perfluorosulfonic acid resin Nafion-xr500, sulfonic acid resin Amberlyst 35, sulfonic acid resin Amberlyst15, sulfonic acid resin Amberlyst36, sulfonic acid resin Amberlyst45, sulfonic acid resin amber resin 21 and sulfonic acid resin amber resin 26.

[0016] Preferably, the added amount of the second catalyst is 0.5% to 5% of the mass of 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyl diphenol.

[0017] Preferably, the heating reaction temperature is 80-170° C., and the reaction time is 5-8 hours.

[0018] Preferably, the recrystallization comprises:

[0019] A solvent at 70 to 100° C. is added to the crude 4,4'-biphenol and stirred, and the filtrate is collected by filtration, and the filtrate is cooled and filtered.

[0020] Preferably, the solvent is selected from one of ethyl acetate, benzene, xylene, cyclohexane, cycloheptane, N,N-dimethylformamide, tert-butyl alcohol, trimethylbenzene, methanol, ethanol and ethylene glycol.

[0021] Preferably, the amount of the solvent added is 3 to 10 times the quality of the crude 4,4'-biphenol; and the cooling temperature is 10 to 18°C.

[0022] Compared with the prior art, the beneficial effects of the present invention include at least:

[0023] The preparation method of the invention uses 2,6-tert-butylphenol as a raw material, generates 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyl diphenol in the presence of oxygen and a first catalyst, the reaction conditions are relatively mild, no tar is generated during the reaction process, and then the first catalyst and 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyl diphenol filtrate are separated by filtration; then, 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyl diphenol is dehydrogenated under the action of a second catalyst to obtain 4,4'-biphenyl diphenol; the preparation method of the invention can reduce the operation process and the generation of three wastes, improve the product purity under the premise of ensuring the reaction yield, avoid complicated purification steps, and make the reaction process more suitable for large-scale production; in addition, the catalyst recovered in the preparation method of the invention can be reused after being activated, and the conversion efficiency is basically unchanged; in addition, the preparation method of the invention has mild reaction conditions, simple post-treatment, easy operation, excellent yield and product purity of more than 99.99%. DETAILED DESCRIPTION

[0024] The following embodiments of the technical solution of the present invention are described in detail in conjunction with the embodiments. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and are therefore only used as examples, and cannot be used to limit the protection scope of the present invention.

[0025] It should be noted that, unless otherwise specified, the technical terms or scientific terms used in this application should have the common meanings understood by those skilled in the art to which the invention belongs.

[0026] The embodiment of the present invention provides a method for preparing ultra-high purity 4,4'-biphenyl diphenol, the preparation method comprising the following steps:

[0027] (a) carrying out a coupling reaction with 2,6-di-tert-butylphenol as a raw material under the conditions of air and a first catalyst to obtain 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyldiphenol;

[0028] (b) adding a second catalyst to 3,3',5,5'-tetra-tert-butyl-4,4'-biphenol and performing a heating reaction. After the reaction is completed, filtering is performed to obtain a crude 4,4'-biphenol, and then recrystallizing and drying is performed to obtain the ultra-high purity 4,4'-biphenol.

[0029] The preparation method of the invention uses 2,6-tert-butylphenol as a raw material, generates 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyl diphenol in the presence of oxygen and a first catalyst, the reaction conditions are relatively mild, no tar is generated during the reaction process, and then the first catalyst and 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyl diphenol filtrate are separated by filtration; then, 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyl diphenol is dehydrogenated under the action of a second catalyst to obtain 4,4'-biphenyl diphenol; the preparation method of the invention can reduce the operation process and the generation of three wastes, improve the product purity under the premise of ensuring the reaction yield, avoid complicated purification steps, and make the reaction process more suitable for large-scale production; in addition, the catalyst recovered in the preparation method of the invention can be reused after being activated, and the conversion efficiency is basically unchanged; in addition, the preparation method of the invention has mild reaction conditions, simple post-treatment, easy operation, excellent yield and product purity of more than 99.99%.

[0030] In one embodiment, the first catalyst is selected from one of potassium hydroxide / activated alumina, potassium carbonate / activated alumina, sodium carbonate / magnesium oxide, sodium phosphate / magnesium oxide and sodium hydroxide / activated alumina.

[0031] In one embodiment, the step (a) further comprises a process of filtering and recovering the first catalyst after the reaction is completed.

[0032] In one embodiment, the coupling reaction temperature can be any temperature in the range of 10 to 50° C., and the reaction time can be any time in the range of 2 to 5 hours;

[0033] The solvent used in the coupling reaction is selected from any one of tert-butyl alcohol, methanol, ethanol, isopropanol, xylene and trimethylbenzene.

[0034] In one embodiment, the addition amount of the first catalyst may be 0.1% to 2% of the mass of 2,6-di-tert-butylphenol.

[0035] In one embodiment, the second catalyst is selected from one of aluminum chloride, ferric chloride, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, perfluorosulfonic acid resin Nafion-H, perfluorosulfonic acid resin Nafion 501, perfluorosulfonic acid resin Nafon xr, perfluorosulfonic acid resin Nafion 425, perfluorosulfonic acid resin Nafion-xr500, sulfonic acid resin Amberlyst 35, sulfonic acid resin Amberlyst 15, sulfonic acid resin Amberlyst36, sulfonic acid resin Amberlyst45, sulfonic acid resin amber resin 21 and sulfonic acid resin amber resin 26.

[0036] In one embodiment, the amount of the second catalyst added is 0.5% to 5% of the mass of 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyl diphenol.

[0037] In one embodiment, the heating reaction temperature can be any temperature in the range of 80 to 170° C., and the reaction time can be any time in the range of 5 to 8 hours.

[0038] In one embodiment, the recrystallization comprises:

[0039] A solvent at 70 to 100° C. is added to the crude 4,4'-biphenol and stirred, and the filtrate is collected by filtration, and the filtrate is cooled and filtered.

[0040] In one embodiment, the solvent is selected from one of ethyl acetate, benzene, xylene, cyclohexane, cycloheptane, N,N-dimethylformamide, tert-butyl alcohol, trimethylbenzene, methanol, ethanol and ethylene glycol.

[0041] In one embodiment, the amount of the solvent added is 3 to 10 times the quality of the crude 4,4'-biphenol; and the cooling temperature is 10 to 18°C.

[0042] The technical solution of the present invention is further described in detail below through specific embodiments.

[0043] Potassium hydroxide / activated alumina: Potassium hydroxide activated alumina solid base catalyst was purchased from Qinzhou Yamei Chemical Co., Ltd.

[0044] Example 1

[0045] This embodiment is a method for preparing ultra-high purity 4,4'-biphenyl diphenol, which comprises the following steps:

[0046] (a) adding 206 g of 2,6-di-tert-butylphenol, 1 g of potassium hydroxide / activated alumina and 2 L of ethanol into a reaction kettle, introducing air at a flow rate of 45 mL / min, heating to 20° C. and reacting for 4 hours; filtering after the reaction, the filter cake is the catalyst potassium hydroxide, and the filtrate is 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyldiphenol;

[0047] (b) 3,3',5,5'-tetra-tert-butyl-4,4'-biphenylene glycol was poured into a reaction kettle, and 2 g of perfluorosulfonic acid resin Nafion-H was added, and the temperature was raised to 110° C. for reaction for 5 hours. After the reaction was completed, the reaction was filtered, and 1200 mL of 95% ethanol at 75° C. was added and stirred to dissolve 4,4'-biphenylene glycol. The undissolved perfluorosulfonic acid resin Nafion-H was filtered out, and the filtrate was cooled to 12° C., filtered, and dried to obtain a white solid powder, i.e., 72.22 g of 4,4'-biphenylene glycol, with a yield of 80.02%. The purity was 99.9925% as determined by gas chromatography.

[0048] Example 2

[0049] This embodiment is a method for preparing ultra-high purity 4,4'-biphenyl diphenol, which comprises the following steps:

[0050] (a) 500 g of 2,6-di-tert-butylphenol, 8 g of potassium hydroxide / activated alumina and 1.6 L of methanol were added to a reaction kettle and air was introduced at a flow rate of 130 mL / min, heated to 25° C. and reacted for 3.5 h. After the reaction was completed, the mixture was filtered, and the filter cake was the catalyst sodium hydroxide, and the filtrate was 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyldiphenol;

[0051] (b) 3,3',5,5'-tetra-tert-butyl-4,4'-biphenylene glycol was poured into a reaction kettle, and 5 g of perfluorosulfonic acid resin Nafion-425 was added, and the temperature was raised to 130° C. for reaction for 5 h. After the reaction was completed, the reaction was filtered, and 3000 mL of 95% ethanol at 70° C. was added and stirred to dissolve 4,4'-biphenylene glycol. The undissolved perfluorosulfonic acid resin Nafion-425 was filtered out, and the filtrate was cooled to 15° C., filtered, and dried to obtain a white solid powder, i.e., 179.47 g of 4,4'-biphenylene glycol, with a yield of 79.54%. The purity was 99.9942% as determined by gas chromatography.

[0052] Example 3

[0053] This embodiment is a method for preparing ultra-high purity 4,4'-biphenyl diphenol, which comprises the following steps:

[0054] (a) 1200 g of 2,6-di-tert-butylphenol, 10.8 g of potassium hydroxide / activated alumina and 10 L of xylene were added to a reaction kettle and air was introduced at a flow rate of 3 L / min, heated to 30° C. and reacted for 3.7 h. After the reaction was completed, the mixture was filtered, and the filter cake was the catalyst potassium bicarbonate, and the filtrate was 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyldiphenol;

[0055] (b) 3,3',5,5'-tetra-tert-butyl-4,4'-biphenylene glycol was poured into a reaction kettle, and 12 g of perfluorosulfonic acid resin Nafion-501 was added, and the temperature was raised to 140° C. for reaction for 6 h. After the reaction was completed, the reaction was filtered, and 6000 mL of ethylene glycol at 100° C. was added and stirred to dissolve 4,4'-biphenylene glycol. The undissolved perfluorosulfonic acid resin Nafion-501 was filtered out, and the filtrate was cooled to 16° C., filtered, and dried to obtain a white solid powder, i.e., 439.98 g of 4,4'-biphenylene glycol, with a yield of 81.25%. The purity was 99.9933% as determined by gas chromatography.

[0056] Example 4

[0057] This embodiment is a method for preparing ultra-high purity 4,4'-biphenyl diphenol, which comprises the following steps:

[0058] (a) 700 g of 2,6-di-tert-butylphenol, 10.5 g of potassium hydroxide / activated alumina and 4 L of trimethylbenzene were added to a reaction kettle and air was introduced at a flow rate of 3 L / min, and the mixture was heated to 28° C. and reacted for 3.5 hours. After the reaction was completed, the mixture was filtered, and the filter cake was the catalyst potassium bicarbonate, and the filtrate was 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyldiphenol;

[0059] (b) The filtrate was poured into a reactor, and 17 g of sulfonic acid resin Amberlyst 15 was added, and the temperature was raised to 120° C. for reaction for 6.5 h. After the reaction was completed, the mixture was filtered, and 3000 mL of N,N-dimethylformamide at 100° C. was added and stirred to dissolve 4,4'-biphenol. The undissolved sulfonic acid resin Amberlyst 15 was filtered out, and the filtrate was cooled to 16° C., filtered, and dried to obtain a white solid powder, i.e., 256.25 g of 4,4'-biphenol, with a yield of 81.12%. The purity was 99.9961% as determined by gas chromatography.

[0060] Example 5

[0061] This embodiment is a method for preparing ultra-high purity 4,4'-biphenyl diphenol, which comprises the following steps:

[0062] (a) 100 g of 2,6-di-tert-butylphenol, 1.5 g of potassium hydroxide / activated alumina and 300 mL of tert-butyl alcohol were added to a reaction kettle and air was introduced at a flow rate of 100 mL / min, and the mixture was heated to 45° C. and reacted for 4 h. After the reaction was completed, the mixture was filtered, and the filter cake was the catalyst sodium bicarbonate, and the filtrate was 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyldiphenol;

[0063] (b) 3,3',5,5'-tetra-tert-butyl-4,4'-biphenylene glycol was poured into a reaction kettle, and 5 g of sulfonic acid resin amber resin 21 was added, and the temperature was raised to 100° C. for reaction for 8 h. After the reaction was completed, the reaction was filtered, and 650 mL of tert-butyl alcohol at 80° C. was added and stirred to dissolve 4,4'-biphenylene glycol. The undissolved sulfonic acid resin sulfonic acid resin amber resin 21 was filtered out, and the filtrate was cooled to 12° C., filtered, and dried to obtain a white solid powder, i.e., 36.52 g of 4,4'-biphenylene glycol, with a yield of 80.91%. The purity was 99.9901% as determined by gas chromatography.

[0064] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. These modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention, and they should all be included in the scope of the claims and specification of the present invention.

Claims

1. A method for preparing ultra-high purity 4,4'-biphenyl diphenol, characterized in that: The steps include: (a) carrying out a coupling reaction with 2,6-di-tert-butylphenol as a raw material under the conditions of air and a first catalyst to obtain 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyldiphenol; (b) adding a second catalyst to 3,3',5,5'-tetra-tert-butyl-4,4'-biphenol and performing a heating reaction. After the reaction is completed, filtering is performed to obtain a crude 4,4'-biphenol, and then recrystallizing and drying is performed to obtain the ultra-high purity 4,4'-biphenol.

2. The preparation method according to claim 1, characterized in that: The first catalyst is selected from one of potassium hydroxide / activated alumina, potassium carbonate / activated alumina, sodium carbonate / magnesium oxide, sodium phosphate / magnesium oxide and sodium hydroxide / activated alumina.

3. The preparation method according to claim 1, characterized in that: The coupling reaction temperature is 10-50°C and the reaction time is 2-5h; The solvent used in the coupling reaction is selected from any one of tert-butyl alcohol, methanol, ethanol, isopropanol, xylene and trimethylbenzene.

4. The preparation method according to claim 1, characterized in that: The addition amount of the first catalyst is 0.1% to 2% of the mass of 2,6-di-tert-butylphenol.

5. The preparation method according to claim 1, characterized in that: The second catalyst is selected from one of aluminum chloride, ferric chloride, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, perfluorosulfonic acid resin Nafion-H, perfluorosulfonic acid resin Nafion 501, perfluorosulfonic acid resin Nafon xr, perfluorosulfonic acid resin Nafion 425, perfluorosulfonic acid resin Nafion-xr500, sulfonic acid resin Amberlyst 35, sulfonic acid resin Amberlyst 15, sulfonic acid resin Amberlyst36, sulfonic acid resin Amberlyst45, sulfonic acid resin amber resin 21 and sulfonic acid resin amber resin 26.

6. The preparation method according to claim 1, characterized in that: The added amount of the second catalyst is 0.5% to 5% of the mass of 3,3',5,5'-tetra-tert-butyl-4,4'-biphenyl diphenol.

7. The preparation method according to claim 1, characterized in that: The heating reaction temperature is 80-170° C., and the reaction time is 5-8 hours.

8. The preparation method according to claim 1, characterized in that: The recrystallization comprises: A solvent at 70 to 100° C. is added to the crude 4,4'-biphenol and stirred, and the filtrate is collected by filtration, and the filtrate is cooled and filtered.

9. The preparation method according to claim 8, characterized in that: The solvent is selected from one of ethyl acetate, benzene, xylene, cyclohexane, cycloheptane, N,N-dimethylformamide, tert-butyl alcohol, trimethylbenzene, methanol, ethanol and ethylene glycol.

10. The preparation method according to claim 8, characterized in that: The amount of the solvent added is 3 to 10 times the quality of the crude 4,4'-biphenol; and the cooling temperature is 10 to 18°C.