CN115626866A - Industrial synthesis method of high-purity 4,4' -biphenol compound - Google Patents
Industrial synthesis method of high-purity 4,4' -biphenol compound Download PDFInfo
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- -1 4,4' -biphenol compound Chemical class 0.000 title claims abstract description 24
- 238000001308 synthesis method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 10
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000003377 acid catalyst Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006722 reduction reaction Methods 0.000 claims abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical group [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 229920001429 chelating resin Polymers 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 4
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000013148 Cu-BTC MOF Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000013291 MIL-100 Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000013084 copper-based metal-organic framework Substances 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- QRFMXBKGNQEADL-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical class OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 QRFMXBKGNQEADL-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an industrial synthesis method of a high-purity 4,4' -biphenol compound, which takes 2, 6-di-tert-butylphenol as a raw material, obtains 4,4' -biphenol containing tert-butyl through oxidative coupling reaction and reduction reaction, and then adds a strong acid catalyst to carry out tert-butyl removal reaction to obtain 4,4' -biphenol. The preparation method of the 4,4' -biphenol compound has the advantages of simple steps, mild reaction conditions, low raw material cost, no pollution to the environment, no generation of redundant waste acid in the tert-butyl removal process, easy separation and recovery of the strong acid resin catalyst, less product impurities, simple post-treatment, high yield and purity and suitability for industrial production.
Description
Technical Field
The invention relates to an industrial synthesis method of a high-purity 4,4' -biphenol compound, belonging to the technical field of chemical product preparation.
Background
4,4' -Biphenyldiphenol is an organic compound with the molecular formula C 12 H 10 O 2 White flaky crystals or crystalline powders,the product is a high polymer intermediate, has higher melting point and stronger heat resistance, can be used as a rubber antioxidant, a plastic antioxidant, a petroleum product stabilizer and the like, is a dye stabilizer and a high polymer intermediate, and is also an important precursor for preparing alkoxy substituted biphenyl liquid crystal.
At present, the method for preparing 4,4' -biphenol with industrial production value mainly comprises the following four methods:
1. biphenyl is selected as a raw material, and the biphenyl is prepared through sulfonation, alkali fusion and hydrolysis, and is typified by U.S. Pat. No. 6,000,1023. The method can obtain satisfactory yield, but has high production cost, and causes a large amount of waste and environmental pollution.
2. The catalyst is prepared by a one-step method by taking peroxide as an oxidizing agent in an organic low-boiling point solvent or an aqueous solution, such as Chinese patent CN201010164715.2, but the reaction uses hydrogen peroxide as the oxidizing agent, is not suitable for high-temperature conditions and is easy to explode.
3. The phenol compound is subjected to oxidative coupling and disproportionation reaction, and then the tert-butyl removal reaction is carried out in an aromatic hydrocarbon solvent, such as Chinese patent CN201410203108.0, U.S. Pat. No. 4,4205187 and Japanese patent JPH04338347A, but the reaction yield is not high, and the environment is polluted to a certain extent.
In view of the high demand for 4,4 '-biphenol in the market, it is important to find a more efficient process for preparing 4,4' -biphenol with high purity and high yield.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an industrial synthesis method of a high-purity 4,4 '-biphenol compound, which is used for solving the problems of low purity and low yield in the industrial preparation of 4,4' -biphenol in the prior art.
The purpose of the invention is realized by the following technical scheme:
the invention aims to provide an industrial synthesis method of a high-purity 4,4' -biphenol compound, which comprises the following steps: 2, 6-di-tert-butylphenol is taken as a raw material, the 4,4 '-biphenol containing tert-butyl is obtained through oxidative coupling reaction and reduction reaction, and then a strong acid catalyst is added for carrying out tert-butyl removal reaction, so that the 4,4' -biphenol is obtained.
Further, the oxidative coupling reaction comprises the following steps: adding 2, 6-di-tert-butylphenol, alkali metal or alkaline earth metal hydroxide or weakly acidic alkali metal salt and a catalyst into a reaction kettle, introducing oxygen, wherein the reaction temperature is 100-150 ℃, and the oxidation reaction time is 3-5 h.
Further, the hydroxide or weakly acidic alkali metal salt of alkali metal or alkaline earth metal is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
Further, the catalyst is a copper-iron based catalyst, and the dosage of the copper-iron based catalyst is 5-10% of the weight of 2, 6-di-tert-butylphenol.
Further, the copper-iron based catalyst is MOF material, copper-iron doped carbon material catalyst CuCl 2 、CuSO 4 、FeCl 3 One or more of (a).
Further, the reduction reaction comprises the following steps: adding a reducing agent into the reaction liquid after the oxidative coupling reaction, and stirring for reaction for 1-2 h.
Further, the reducing agent is H 2 SO 3 ,Fe，(NH 4 ) 2 SO 3 ,(NH 4 ) 2 S 2 O 3 ,Na 2 S 2 O 3 One or more of (a).
Furthermore, the strong acid catalyst is strong acid ion exchange resin, and the dosage of the strong acid catalyst is 5-10% of the weight of the 4,4' -biphenol containing tertiary butyl.
Further, the strong acid type ion exchange resin is one or more of AMBERJET1200H, AMBERLITE ER-124 and AMBERLYST-15.
Further, the reaction temperature of the tert-butyl removal reaction is 130-170 ℃, and the reaction time is 3-5 h.
The invention has the outstanding effects that:
the invention relates to an industrial synthesis method of a high-purity 4,4' -biphenol compound, which takes 2, 6-di-tert-butylphenol as a raw material, obtains 4,4' -biphenol containing tert-butyl through oxidative coupling reaction and reduction reaction, and then adds a strong acid catalyst to carry out tert-butyl removal reaction to obtain the 4,4' -biphenol. The preparation method of the 4,4' -biphenol compound has the advantages of simple steps, mild reaction conditions, low raw material cost, no pollution to the environment, no generation of redundant waste acid in the tert-butyl removal process, easy separation and recovery of the strong acid resin catalyst, less product impurities, simple post-treatment, high yield and purity of over 99.5 percent, and suitability for industrial production.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
200kg of 2, 6-di-tert-butylphenol is added into a 1000L stainless steel kettle, 2kg of solid NaOH and 10kg of Cu-MOF material (HKUST-1) are added, a mixed solvent of ethanol and water is added, oxygen is introduced, the temperature is controlled at 100 ℃, and the reaction is carried out for 5 hours. Adding 20kg of Fe for reduction, stirring for reaction for 2 hours, cooling and filtering to obtain a solid product. Dissolving the solid into m-xylene, adding polystyrene sulfonic acid type ion exchange resin-AMBERJET 1200H, controlling the temperature at 130 ℃, stopping the reaction after 5H of reaction, recrystallizing to obtain a high-purity target product, and analyzing by HPLC to obtain the target product with the purity of 99.8% and the yield of 85.6%.
Example 2:
200Kg2, 6-di-tert-butylphenol is added into a 1000L stainless steel kettle, 2kg of solid KOH and 10kg of MIL-100 (Fe) are added, a mixed solvent of ethanol and water is added, oxygen is introduced, the temperature is controlled at 150 ℃, and the reaction is carried out for 3 hours. Adding 20kgH 2 SO 3 Reducing, stirring and reacting for 1h, cooling and filtering to obtain a solid product. Dissolving the solid in m-xylene, adding polystyrene sulfonic acid type ion exchange resin-AMBERLITE-124, and controlling temperatureThe reaction is stopped after 4 hours at 150 ℃, and the high-purity target product is obtained by recrystallization, the purity of the product is up to 99.6 percent by HPLC analysis, and the yield of the product is 83.2 percent.
Example 3:
200Kg2, 6-di-tert-butylphenol is added into a 1000L stainless steel kettle, 2kg of calcium hydroxide + sodium carbonate and 10kg of Cu-MOF material (HKUST-1) are added, a mixed solvent of ethanol and water is added, oxygen is introduced, the temperature is controlled at 120 ℃, and the reaction is carried out for 4 hours. 25kg (NH) were added 4 ) 2 SO 3 Reducing, stirring and reacting for 2h, cooling and filtering to obtain a solid product. Dissolving the solid into m-xylene, adding polystyrene sulfonic acid type ion exchange resin-AMBERLYST-15, controlling the temperature at 130 ℃, stopping the reaction after reacting for 3h, recrystallizing to obtain a high-purity target product, and analyzing by HPLC to obtain the product with the purity of 99.7% and the yield of 84.7%.
Example 4:
200Kg2, 6-di-tert-butylphenol is added into a 1000L stainless steel kettle, 2kg of solid potassium bicarbonate and 20kg of MIL-100 (Fe) are added, a mixed solvent of ethanol and water is added, oxygen is introduced, the temperature is controlled at 100 ℃, and the reaction lasts for 3 hours. Adding 20kgNa 2 S 2 O 3 Reducing, stirring and reacting for 1h, cooling and filtering to obtain a solid product. Dissolving the solid into m-xylene, adding polystyrene sulfonic acid type ion exchange resin-AMBERLYST-15, controlling the temperature at 170 ℃, stopping the reaction after 3h of reaction, recrystallizing to obtain a high-purity target product, and analyzing by HPLC to obtain the product with the purity of 99.5% and the yield of 87.3%.
Comparative example 1
The method disclosed in U.S. Pat. No. 6,10238 selects biphenyl as raw material, and prepares 4,4' -biphenol through sulfonation, alkali fusion and hydrolysis.
Comparative example 2
4,4' -biphenol is prepared by a one-step method by taking peroxide as an oxidant in an organic low-boiling solvent or an aqueous solution by a method described in Chinese patent CN 201010164715.2.
Comparative example 3
The 4,4' -biphenol is prepared by the method described in Chinese patent CN201410203108.0 through oxidative coupling and disproportionation of phenolic compounds and then tert-butyl removal reaction in aromatic hydrocarbon solvent.
Comparative example 4
4,4 '-biphenol is prepared by high-temperature melt-removal of tert-butyl groups from biphenyl diphenols containing tert-butyl substituents in an inert atmosphere by the method described in U.S. Pat. No. 4,4' -biphenol.
The yield and purity of examples 1 to 4 and comparative examples 1 to 4 are shown in table 1 below, and it can be seen that the preparation method provided by the present invention has high yield and high purity, has advantages in yield and purity, and can meet the requirements of market application.
TABLE 1 comparison of yields and purities of examples 1-4 and comparative examples 1-4
| Yield of | Purity of | |
| Example 1 | 85.6％ | 99.8％ |
| Example 2 | 83.2％ | 99.6％ |
| Example 3 | 84.7％ | 99.7％ |
| Example 4 | 87.3％ | 99.5％ |
| Comparative example 1 | 83.1％ | 92.8％ |
| Comparative example 2 | 85.3％ | 94.6％ |
| Comparative example 3 | 75.9％ | 96.6％ |
| Comparative example 4 | 82.9％ | 96.3％ |
Claims (10)
1. An industrial synthesis method of a high-purity 4,4' -biphenol compound is characterized by comprising the following steps: 2, 6-di-tert-butylphenol is used as a raw material, and is subjected to oxidative coupling reaction and reduction reaction to obtain 4,4 '-biphenol containing tert-butyl, and then a strong acid catalyst is added to carry out tert-butyl removal reaction to obtain the 4,4' -biphenol.
2. The industrial synthesis method of a high-purity 4,4' -biphenol compound according to claim 1, characterized in that: the oxidative coupling reaction comprises the following steps: adding 2, 6-di-tert-butylphenol, hydroxide or weakly acidic alkali metal salt of alkali metal or alkaline earth metal and a catalyst into a reaction kettle, introducing oxygen, wherein the reaction temperature is 100-150 ℃, and the oxidation reaction time is 3-5 h.
3. The industrial synthesis method of a high-purity 4,4' -biphenol compound according to claim 2, characterized in that: the hydroxide or weak acidic alkali metal salt of alkali metal or alkaline earth metal is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
4. The industrial synthesis method of a high-purity 4,4' -biphenol compound according to claim 2, characterized in that: the catalyst is a copper-iron based catalyst, and the dosage of the copper-iron based catalyst is 5-10% of the weight of 2, 6-di-tert-butylphenol.
5. The industrial synthesis method of high-purity 4,4' -biphenol compound according to claim 4, characterized in that: the copper-iron based catalyst is MOF material, copper-iron doped carbon material catalyst and CuCl 2 、CuSO 4 、FeCl 3 One or more of (a).
6. The industrial synthesis method of a high-purity 4,4' -biphenol compound according to claim 1, characterized in that: the reduction reaction comprises the following steps: adding a reducing agent into the reaction liquid after the oxidative coupling reaction, and stirring for reaction for 1-2 h.
7. The industrial synthesis method of a high-purity 4,4' -biphenol compound according to claim 6, characterized in that: the reducing agent is H 2 SO 3 ,Fe，(NH 4 ) 2 SO 3 ,(NH 4 ) 2 S 2 O 3 ,Na 2 S 2 O 3 One or more of (a).
8. The industrial synthesis method of a high-purity 4,4' -biphenol compound according to claim 1, characterized in that: the strong acid catalyst is strong acid type ion exchange resin, and the dosage of the strong acid catalyst is 5-10% of the weight of the 4,4' -biphenol containing tertiary butyl.
9. The industrial synthesis method of a high-purity 4,4' -biphenol compound according to claim 8, characterized in that: the strong acid type ion exchange resin is one or more of AMBERJET1200H, AMBERLITE ER-124 and AMBERLYST-15.
10. The industrial synthesis method of a high-purity 4,4' -biphenol compound according to claim 1, characterized in that: the reaction temperature of the tert-butyl removal reaction is 130-170 ℃, and the reaction time is 3-5 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116217343A (en) * | 2023-03-14 | 2023-06-06 | 锦州三丰科技有限公司 | Production process of biphenol |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348047A (en) * | 2015-11-30 | 2016-02-24 | 江门市优巨新材料有限公司 | One-step industrial synthesis method for high-purity dihydroxybiphenyl compound |
| CN105503536A (en) * | 2015-11-30 | 2016-04-20 | 江门市优巨新材料有限公司 | Industrial preparation method of biphenol compounds with high purity |
| CN112142570A (en) * | 2020-09-22 | 2020-12-29 | 威海金泓高分子有限公司 | Preparation method of p-hydroxybiphenyl diphenol |
| CN113416119A (en) * | 2021-06-23 | 2021-09-21 | 四川圣效科技股份有限公司 | Method for synthesizing 4, 4' -dihydroxybiphenyl by adopting loop reactor |
| CN113956135A (en) * | 2021-11-15 | 2022-01-21 | 宁夏清研高分子新材料有限公司 | Preparation method of high-yield 4, 4' -biphenol |
| CN114181052A (en) * | 2021-12-20 | 2022-03-15 | 宁夏清研高分子新材料有限公司 | Preparation method of high-purity 4, 4' -biphenol |
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2022
- 2022-09-25 CN CN202211168938.5A patent/CN115626866A/en active Pending
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| CN105348047A (en) * | 2015-11-30 | 2016-02-24 | 江门市优巨新材料有限公司 | One-step industrial synthesis method for high-purity dihydroxybiphenyl compound |
| CN105503536A (en) * | 2015-11-30 | 2016-04-20 | 江门市优巨新材料有限公司 | Industrial preparation method of biphenol compounds with high purity |
| CN112142570A (en) * | 2020-09-22 | 2020-12-29 | 威海金泓高分子有限公司 | Preparation method of p-hydroxybiphenyl diphenol |
| CN113416119A (en) * | 2021-06-23 | 2021-09-21 | 四川圣效科技股份有限公司 | Method for synthesizing 4, 4' -dihydroxybiphenyl by adopting loop reactor |
| CN113956135A (en) * | 2021-11-15 | 2022-01-21 | 宁夏清研高分子新材料有限公司 | Preparation method of high-yield 4, 4' -biphenol |
| CN114181052A (en) * | 2021-12-20 | 2022-03-15 | 宁夏清研高分子新材料有限公司 | Preparation method of high-purity 4, 4' -biphenol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116217343A (en) * | 2023-03-14 | 2023-06-06 | 锦州三丰科技有限公司 | Production process of biphenol |
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