CN114539030B - Method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl by utilizing microchannel reactor - Google Patents
Method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl by utilizing microchannel reactor Download PDFInfo
- Publication number
- CN114539030B CN114539030B CN202011327478.7A CN202011327478A CN114539030B CN 114539030 B CN114539030 B CN 114539030B CN 202011327478 A CN202011327478 A CN 202011327478A CN 114539030 B CN114539030 B CN 114539030B
- Authority
- CN
- China
- Prior art keywords
- tert
- solution
- tetra
- reaction
- dihydroxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 22
- 239000004305 biphenyl Substances 0.000 title claims abstract description 22
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 85
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 51
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 claims abstract description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000005086 pumping Methods 0.000 claims abstract description 5
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 4
- 238000005691 oxidative coupling reaction Methods 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000004880 explosion Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000004811 liquid chromatography Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000005112 continuous flow technique Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005459 micromachining Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- C07C37/11—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
- 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
-
- 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
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
-
- 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
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The method for preparing 2,2' -dihydroxyl-3, 3', 5' -tetra-tert-butyl biphenyl by utilizing a microchannel reactor comprises the steps of preparing 2, 4-di-tert-butyl phenol and alkali liquor into a mixed solution according to a certain proportion, respectively pumping the mixed solution and hydrogen peroxide solution into the microchannel reactor for fully mixing, reacting the mixed material in a first reaction area module of the microchannel reactor, mixing the mixed material with toluene in a second reaction area module, carrying out neutralization reaction with an acid solution in the second reaction area module, separating the obtained product liquid by continuous phase, and obtaining toluene solution D containing 2,2' -dihydroxyl-3, 3', 5' -tetra-tert-butyl biphenyl, and concentrating, crystallizing and washing the toluene solution D to obtain the target product 2,2' -dihydroxyl-3, 3', 5' -tetra-tert-butyl biphenyl. The invention can obviously improve the reaction efficiency, greatly shorten the reaction time, avoid possible explosion risks, facilitate the control of the production process, reduce the production cost, and overcome the defects of high labor intensity, long production period, low product quality and the like in the traditional production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl by utilizing a microchannel reactor.
Background
2,2' -Dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl is an important raw material for synthesizing bidentate phosphine ligands in hydroformylation of carbonyl, and is mainly prepared by oxidative coupling in the industry at present.
According to the different oxidants, the synthesis method is mainly divided into alkali catalytic reactions using hydrogen peroxide, and U.S. Pat. No. 3, 4380676 discloses a synthesis method of 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl, which adopts alkali catalysis and hydrogen peroxide as oxidants, and is characterized in that hydrogen peroxide is slowly dripped at high temperature (80 ℃) to control the reaction speed, ensure the reaction safety, so that the danger is high, and the method is unfavorable for the large-scale production; and the final product is obtained by multi-supplement batch reaction, which has low efficiency.
The use of air or oxygen as the oxidant requires a transition metal (copper or cobalt complex (CN 201911011611.5)) as a catalyst and sometimes an organic as a solvent, which not only results in subsequent separation difficulties, but also reduces the oxidation reaction rate to prevent explosion.
The preparation methods reported at present all use batch reaction modes, and the reaction process is completed in multiple steps, so that an efficient and safe synthesis method needs to be developed to improve the production efficiency of the 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl.
The microchannel reactor (Microreactor/Microchannel reactor) is a continuous flow, pipe reactor, a device manufactured by micromachining technology with feature sizes between 10-1000 microns that controls chemical reactions in minute reaction spaces. The narrow micro-channels in the micro-reactor shorten the distance and time of mass transfer, and the increased specific surface area also provides a larger place for the mass transfer process, so that the rapid mixing of the reaction materials is realized, and the radial complete mixing is realized in the millisecond range. Meanwhile, the micro-channel reactor module has small volume of materials, and the safety of chemical reaction is essentially improved. Therefore, hydrogen peroxide can be used as an oxidant in the microchannel reactor, and the high-temperature rapid chemical reaction can be safely carried out, so that the reaction is safe and controllable; meanwhile, the multi-step intermittent reaction is made into a continuous flow process, so that the labor intensity is reduced, the reaction stability is improved, and the production efficiency is greatly enhanced.
Disclosure of Invention
The invention aims to provide a method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl by utilizing a microchannel reactor, which has the advantages that the reaction rate is remarkably improved, the reaction time is greatly shortened, the danger of intermittent reaction is avoided, and the safety is increased; the production process is more convenient to control, the defects of high labor intensity, long production period and the like in the traditional production are overcome, and the production efficiency is greatly enhanced.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butylbiphenyl using a microchannel reactor, comprising the steps of:
1) 2, 4-di-tert-butylphenol is dissolved in alkali liquor under the heating condition to prepare a mixed solution A, wherein the ratio of the amount of 2, 4-di-tert-butylphenol to the amount of alkali liquor substance is 1:2 to 2.1; the heating temperature is 60-100 ℃;
2) Respectively and simultaneously pumping the mixed solution A and the hydrogen peroxide solution prepared in the step 1) into a first reaction area module of a microchannel reactor to perform oxidative coupling reaction to obtain a solution B; wherein the ratio of the amount of the substances of the 2, 4-di-tert-butylphenol and the hydrogen peroxide is 1: 0.49-0.51, wherein the set temperature of the first reaction area module is 80-100 ℃;
3) The solution B obtained in the step 2) flows into a mixing area module to be mixed with toluene to obtain a solution C, and then the solution C flows into a second reaction area module;
4) Pumping acid solution into a second reaction area module to perform neutralization reaction with the solution C, wherein the temperature of the second reaction area module is set to be 30-50 ℃ to obtain a toluene solution D containing 2,2 '-dihydroxy-3, 3',5 '-tetra-tert-butyl biphenyl and a saline-containing aqueous phase, and separating the continuous phases to obtain the toluene solution D containing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl; wherein the ratio of the mass substances contained in the acid solution to the mass substances of the alkali liquor is 1-1.05: 1, a step of;
5) The toluene solution D containing 2,2 '-dihydroxyl-3, 3',5 '-tetra-tert-butyl biphenyl obtained in the step 4) is concentrated, crystallized and washed to obtain the target product 2,2' -dihydroxyl-3, 3', 5' -tetra-tert-butyl biphenyl.
Preferably, the alkali liquor is sodium hydroxide or potassium hydroxide solution.
Preferably, the mass fraction of the hydrogen peroxide is 30%.
Preferably, the acid solution is sulfuric acid or hydrochloric acid.
Preferably, the reaction residence time of the reaction solution in the microchannel reactor is 50-400 s.
Preferably, the first reaction area, the second reaction area and the mixing area are arranged in the microchannel reactor, and all have forced mixing effect.
Preferably, the liquid holdup of a single module of the microchannel reactor is 0.4-120 ml.
Preferably, the microchannel reactor controls flow through a metering pump and the temperature of the reaction zone module through an external heat exchanger.
The invention adopts a microchannel reactor to prepare a mixed solution of 2, 4-di-tert-butylphenol and alkali liquor, then pumps the mixed solution and hydrogen peroxide solution into a first reaction zone module of the microchannel reactor at the same time for oxidative coupling reaction, after the reaction is completed, a solution B is obtained, then the mixed solution B flows into the mixed zone module to be mixed with toluene, then flows into a second reaction zone module to be subjected to neutralization reaction with acid solution, thus obtaining a toluene solution containing 2,2 '-dihydroxy-3, 3',5 '-tetra-tert-butyl biphenyl and a salt-containing water phase, and the target product 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl is obtained after continuous phase separation, concentration, crystallization and washing.
The microchannel reactor (Microreactor/Microchannel reactor) is a continuous flow, pipe reactor, a feature size between 10 and 1000 microns, made by micromachining technology, and means to control chemical reactions in a small reaction space.
The first reaction area, the second reaction area and the mixing area in the microchannel reactor are all provided with a forced mixing effect, and are similar to U-shaped or heart-shaped templates with unit blocking, so that the water phase and the water phase, the water phase and the organic phase can be fully mixed. And the liquid holdup of a single template is controlled to be 0.4-120 ml so as to improve the safety of the reaction.
The narrow micro-channels in the micro-reactor shorten the distance and time of mass transfer, and the increased specific surface area also provides a larger place for the mass transfer process, so that the rapid mixing of the reaction materials is realized, and the radial complete mixing is realized in the millisecond range. The narrow micro-channel of the micro-reactor increases the temperature gradient and the increased specific surface area greatly enhances the heat transfer capability of the reactor. Therefore, the development of a microchannel reactor technology for synthesizing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl has important practical significance.
The invention has the beneficial effects that:
1) The invention utilizes the continuous flow process of the microchannel reactor, shortens the high-temperature reaction time from the traditional hours to tens of seconds to several minutes, reduces the unit liquid holdup in the kettle reaction, and therefore has the characteristics of high efficiency and safety.
2) The invention adopts the continuous flow process of the micro-channel reactor, has better mixing effect of raw materials, less side reaction, good product selectivity, and is beneficial to improving the yield, meanwhile, the product quality is improved, the reaction selectivity reaches more than 98 percent, and the raw material conversion rate reaches more than 95 percent.
3) The micro-channel reactor equipment occupies small area, flexible production can be realized, and the automation level of production is improved.
Drawings
FIG. 1 is a reaction scheme of an embodiment of the present invention.
Detailed Description
The invention is further described below in connection with specific embodiments and the accompanying drawings, but is not thereby limited.
Example 1
The adopted microchannel reactor adopts G1 reaction equipment of Corning company, a metering pump is used for conveying reaction solution, the temperature of the first reaction area module is set to be 100 ℃, and the temperature of the second reaction area module is set to be 30 ℃.
Solution a was prepared: 400g (10 mol) of sodium hydroxide was dissolved in 2000g of water, and 1030g (5 mol) of 2, 4-di-tert-butylphenol was added under heating until it was sufficiently dissolved.
Solution A was pumped at 15ml/min,30% hydrogen peroxide at 15ml/min, toluene at 30ml/min, sulfuric acid (98%) at 2.6ml/min, respectively, into the corresponding reaction modules. After the reaction is stable, the solution D is taken and detected by liquid chromatography to find that: the conversion rate of the 2, 4-di-tert-butylphenol is 98.6%, and the selectivity of the target product 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butylbiphenyl is 98.2%.
Example 2
The adopted microchannel reactor is G2 reaction equipment of Corning company, a metering pump is used for conveying reaction solution, the temperature of the first reaction area module is set to be 95 ℃, and the temperature of the second reaction area module is set to be 50 ℃.
Solution a was prepared: 400g (10 mol) of sodium hydroxide was dissolved in 2000g of water, and 1030g (5 mol) of 2, 4-di-tert-butylphenol was added under heating until it was sufficiently dissolved.
Solution A was pumped at 45ml/min,30% hydrogen peroxide at 45ml/min, toluene at 90ml/min, sulfuric acid (98%) at 7.8ml/min, respectively, into the corresponding reaction modules. After the reaction is stable, the solution D is taken and detected by liquid chromatography to find that: the conversion rate of the 2, 4-di-tert-butylphenol is 98.1%, and the selectivity of the target product 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butylbiphenyl is 98.7%.
Example 3
The microchannel reactor used was a G1 reaction apparatus from Corning, and the reaction solution was fed using a metering pump. The first reaction zone module temperature was set at 80 ℃ and the second reaction zone module temperature was set at 50 ℃.
Solution a was prepared: 561g (10 mol) of sodium hydroxide was dissolved in 1839g of water, and 1030g (5 mol) of 2, 4-di-tert-butylphenol was added under heating until it was sufficiently dissolved.
Solution A was pumped at 15ml/min,30% hydrogen peroxide at 15ml/min, toluene at 30ml/min, sulfuric acid (98%) at 2.6ml/min, respectively, into the corresponding reaction modules. After the reaction is stable, the solution D is taken and detected by liquid chromatography to find that: the conversion rate of the 2, 4-di-tert-butylphenol is 95.8%, and the selectivity of the target product 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butylbiphenyl is 98.4%.
Example 4
The microchannel reactor used was an LFR reaction apparatus from Corning company, and the reaction solution was fed using a metering pump. The first reaction zone module temperature was set at 85 ℃ and the second reaction zone module temperature was set at 40 ℃.
Solution a was prepared: 561g (10 mol) of sodium hydroxide was dissolved in 1839g of water, and 1030g (5 mol) of 2, 4-di-tert-butylphenol was added under heating until it was sufficiently dissolved.
Solution A was pumped at a flow rate of 1.5ml/min,30% hydrogen peroxide at 1.5ml/min, toluene at 3ml/min, and hydrochloric acid (37%) at 0.4ml/min, respectively, into the corresponding reaction modules. After the reaction is stable, the solution D is taken and detected by liquid chromatography to find that: the conversion rate of the 2, 4-di-tert-butylphenol is 96.9%, and the selectivity of the target product 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butylbiphenyl is 99.1%.
Comparative example 1
The microchannel reactor used was a G1 reaction apparatus from Corning, and the reaction solution was fed using a metering pump, and the temperature of the first zone module was set to 100 ℃.
Solution a was prepared: 400g (10 mol) of sodium hydroxide was dissolved in 2000g of water, and 1030g (5 mol) of 2, 4-di-tert-butylphenol was added under heating until it was sufficiently dissolved.
Solution A was pumped into the corresponding first reaction zone modules at 15ml/min and 30% hydrogen peroxide was collected directly after the reaction was completed at 15 ml/min. 500ml of reaction stabilization section material was collected in a 1000ml flask, after cooling, neutralized to pH neutral with acid in a glass flask, the product was extracted 2-3 times with toluene and the organic phases were combined to give a solution E similar to solution D, which was found by liquid chromatography detection: the conversion rate of the 2, 4-di-tert-butylphenol is 93.5%, and the selectivity of the target product 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butylbiphenyl is 95.2%.
Claims (9)
1. A method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl by utilizing a microchannel reactor, which is characterized by comprising the following steps:
1) 2, 4-di-tert-butylphenol is dissolved in alkali liquor under the heating condition to prepare a mixed solution A, wherein the ratio of the amount of 2, 4-di-tert-butylphenol to the amount of alkali liquor substance is 1:2 to 2.1; the temperature of the heated liquid is 60-100 ℃;
2) Respectively and simultaneously pumping the mixed solution A and the hydrogen peroxide solution prepared in the step 1) into a first reaction area module of a microchannel reactor to perform oxidative coupling reaction to obtain a solution B; wherein the ratio of the amount of the substances of the 2, 4-di-tert-butylphenol and the hydrogen peroxide is 1: 0.49-0.51, wherein the set temperature of the first reaction area module is 80-100 ℃;
3) The solution B obtained in the step 2) flows into a mixing area module to be mixed with toluene to obtain a solution C, and then the solution C flows into a second reaction area module;
4) Pumping acid solution into a second reaction area module to perform neutralization reaction with the solution C, wherein the temperature of the second reaction area module is set to be 30-50 ℃ to obtain a toluene solution D containing 2,2 '-dihydroxy-3, 3',5 '-tetra-tert-butyl biphenyl and a saline-containing aqueous phase, and separating the continuous phases to obtain the toluene solution D containing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl; wherein the ratio of the amount of proton substances contained in the acid solution to the amount of substances in the alkali liquor is 1-1.05: 1, a step of;
5) The toluene solution D containing 2,2 '-dihydroxyl-3, 3',5 '-tetra-tert-butyl biphenyl obtained in the step 4) is concentrated, crystallized and washed to obtain the target product 2,2' -dihydroxyl-3, 3', 5' -tetra-tert-butyl biphenyl.
2. The method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butylbiphenyl using a microchannel reactor according to claim 1, wherein the alkaline solution is sodium hydroxide or potassium hydroxide solution.
3. The method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butylbiphenyl using a microchannel reactor according to claim 1, wherein the hydrogen peroxide mass fraction is 30%.
4. The method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butylbiphenyl using a microchannel reactor according to claim 1, wherein the acid solution is sulfuric acid or hydrochloric acid.
5. The method for producing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butylbiphenyl using a microchannel reactor according to claim 1, wherein the residence time of the reaction solution in the microchannel reactor is 50 to 400s.
6. The method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butylbiphenyl using a microchannel reactor according to any one of claims 1 to 5, wherein a first reaction zone, a second reaction zone and a mixing zone are arranged in the microchannel reactor, and all have a forced mixing effect.
7. The method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butylbiphenyl according to claim 6, wherein the single module liquid holdup of the microchannel reactor is 0.4-120 ml.
8. The method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butylbiphenyl according to claim 6, wherein the micro-channel reactor controls flow rate through a metering pump and controls temperature of a reaction zone module through an external heat exchanger.
9. The method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butylbiphenyl according to claim 7, wherein the micro-channel reactor controls flow rate through a metering pump and controls temperature of a reaction zone module through an external heat exchanger.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011327478.7A CN114539030B (en) | 2020-11-24 | 2020-11-24 | Method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl by utilizing microchannel reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011327478.7A CN114539030B (en) | 2020-11-24 | 2020-11-24 | Method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl by utilizing microchannel reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114539030A CN114539030A (en) | 2022-05-27 |
| CN114539030B true CN114539030B (en) | 2024-06-14 |
Family
ID=81659369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011327478.7A Active CN114539030B (en) | 2020-11-24 | 2020-11-24 | Method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl by utilizing microchannel reactor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114539030B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115745748B (en) * | 2022-12-07 | 2024-03-08 | 山东昆达生物科技有限公司 | Method for continuously producing 3,3',5,5' -tetraalkyl-4, 4' -biphenol |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999046227A1 (en) * | 1998-03-10 | 1999-09-16 | Sumitomo Chemical Company, Limited | Method for producing 2,2'-dihydroxybiphenyls |
| JP2001097908A (en) * | 1999-09-29 | 2001-04-10 | Sumitomo Chem Co Ltd | Method for producing 2,2'-dihydroxybiphenyls |
| CN102432638A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Synthesis method of diphosphite ligand |
| CN110964057A (en) * | 2019-12-25 | 2020-04-07 | 东南大学 | Method for preparing sofosbuvir intermediate by using microfluid reaction device |
| CN111269129A (en) * | 2020-02-19 | 2020-06-12 | 天津科技大学 | Method for preparing 4,4 '-disubstituted-2, 2' -diaminobiphenyl and hydrochloride thereof by continuous flow oxidation coupling method |
-
2020
- 2020-11-24 CN CN202011327478.7A patent/CN114539030B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999046227A1 (en) * | 1998-03-10 | 1999-09-16 | Sumitomo Chemical Company, Limited | Method for producing 2,2'-dihydroxybiphenyls |
| JP2001097908A (en) * | 1999-09-29 | 2001-04-10 | Sumitomo Chem Co Ltd | Method for producing 2,2'-dihydroxybiphenyls |
| CN102432638A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Synthesis method of diphosphite ligand |
| CN110964057A (en) * | 2019-12-25 | 2020-04-07 | 东南大学 | Method for preparing sofosbuvir intermediate by using microfluid reaction device |
| CN111269129A (en) * | 2020-02-19 | 2020-06-12 | 天津科技大学 | Method for preparing 4,4 '-disubstituted-2, 2' -diaminobiphenyl and hydrochloride thereof by continuous flow oxidation coupling method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114539030A (en) | 2022-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108863760B (en) | Method for continuously producing glyoxylic acid by using microchannel reactor | |
| CN111018715A (en) | Microchannel synthesis method of dinitrobenzene | |
| CN112225642B (en) | Method for preparing resorcinol by micro-channel reaction | |
| CN110218139A (en) | A method of biphenyl derivatives are prepared using microchannel continuous flow reactor | |
| CN114539030B (en) | Method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl by utilizing microchannel reactor | |
| CN111039829B (en) | Method for producing p-acetamido benzene sulfonyl chloride by two-temperature zone two-stage method based on continuous flow reaction | |
| CN109180437A (en) | The method that cumyl hydroperoxide decomposition prepares phenol in tubular type continuous flow reactor | |
| CN108516982B (en) | Method for preparing rifampicin by using microchannel reaction device | |
| CN109836334B (en) | Method for continuously preparing cyclopropylamine | |
| CN104496848B (en) | A kind of method of preparing aniline-acetonitrile | |
| CN106278853A (en) | The method of macro work technology continuous synthesis alpha, beta-lonone | |
| CN104418752A (en) | Method for synthesizing single nitro-o-xylene employing catalytic nitration in micro-reactor | |
| CN116162076B (en) | Spirocyclic gamma-butyrolactone containing carboxylic acid tert-butyl ester and 1, 3-indene diketone structure and preparation method thereof | |
| CN109369498B (en) | Method for continuously synthesizing 4-bromo-2-p-chlorophenyl-5-trifluoromethylpyrrole-3-nitrile by using microreactor | |
| CN111620797A (en) | Method for synthesizing m-nitrobenzenesulfonic acid by adopting micro-channel continuous flow reactor | |
| CN107814691B (en) | Method for synthesizing ethylguaiacol | |
| CN116178164A (en) | Method for synthesizing m-dinitrobenzene by adopting microreactor | |
| CN111072515B (en) | Method for continuously synthesizing thiaminoximic acid intermediate | |
| CN111662207B (en) | Method for synthesizing 4-methoxy-3-biphenylhydrazine hydrochloride by adopting micro-channel | |
| CN113527126A (en) | Method for synthesizing 3-nitro-4-methoxyacetanilide by continuous flow microchannel reactor | |
| CN114671808A (en) | Preparation method of caprolactam | |
| CN115745850B (en) | Method for continuous flow production of sodium dodecyl diphenyl ether sulfonate | |
| CN111875503A (en) | Preparation method of 2, 6-dichloro-4-trifluoromethylaniline | |
| CN112961132A (en) | Method for preparing monochlorophthalic anhydride in micro-channel continuous flow reactor | |
| CN109485544B (en) | Method for continuously preparing trimethylolpropane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |