CN111072455B - Method for continuously preparing pentafluorophenol by microreactor - Google Patents
Method for continuously preparing pentafluorophenol by microreactor Download PDFInfo
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- CN111072455B CN111072455B CN201911379804.6A CN201911379804A CN111072455B CN 111072455 B CN111072455 B CN 111072455B CN 201911379804 A CN201911379804 A CN 201911379804A CN 111072455 B CN111072455 B CN 111072455B
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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
- C07C37/01—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
- C07C37/02—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 by substitution of halogen
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Abstract
The invention relates to a method for continuously preparing pentafluorophenol by using a microreactor, belonging to the field of chemical production processes. And respectively pumping hexafluorobenzene and an inorganic alkali aqueous solution into the microchannel reactor by using a metering pump to perform a hydrolysis reaction, keeping the temperature of the reactor at 130-170 ℃, controlling an outlet quantitative pressure control valve to maintain the pipeline pressure at 0.5-1.0Mpa, connecting an outlet of the reactor with a heat exchanger, obtaining an aqueous solution of pentafluorophenylphenol salt from the outlet of the heat exchanger, adding hydrochloric acid water vapor to distill to obtain an oil layer, and rectifying and dehydrating the oil layer to obtain pentafluorophenol. The method has the advantages of simple process, low cost, no amplification effect and capability of realizing continuous production.
Description
Technical Field
The invention relates to a method for continuously preparing pentafluorophenol by a microreactor, belongs to the field of chemical production processes,
background
2,3,4,5, 6-pentafluorophenol, pentafluorophenol for short, is an important fine chemical intermediate, and is mainly used for preparing pentafluorophenyl active ester synthesized by polypeptide so as to promote the formation of peptide bonds; it can also be used as intermediate of medicine, pesticide and liquid crystal material.
At present, the synthesis method of pentafluorophenol mainly comprises the following steps: (1) the patent CN106588577A discloses a catalytic oxidation method, in which pentafluorobenzene is used as a raw material, a high-copper MCM-41 molecular sieve is used as a catalyst, and hydrogen peroxide is used as an oxidant, and pentafluorophenol is generated by reaction. The preparation process of the catalyst is complex, the cost is high, and the catalyst is not suitable for industrial production; (2) and etherification cracking method, for example, CN105016983A uses hexafluorobenzene as raw material, and prepares pentafluorophenol through alkyl etherification and cracking. The process has the advantages that inflammable and explosive gases are easily generated in the cracking process of the lower alkyl ether, the danger is high, and potential safety hazards exist; (3) the hydrolysis method, for example, patent CN102718635A takes 2,3,4,5, 6-pentafluoro-1-substituted benzene as raw material, and obtains pentafluorophenol by lithiation, esterification, hydrolysis and oxidation one-pot reaction, and the method has high raw material cost and low yield, and is not suitable for industrial production; (4) the Grignard reagent method, for example, CN 103420801A, performs Grignard exchange on alkyl magnesium halide and bromopentafluorobenzene to prepare a Grignard reagent, performs esterification reaction on the Grignard reagent and boric acid ester, then acidifies the Grignard reagent, reacts with peroxide to generate pentafluorophenol, and finally rectifies the product to obtain a qualified product. The method has long route, requires an anhydrous and anaerobic system for the Grignard reaction, and has high production cost; (5) the catalytic hydrolysis method, such as patent CN104693010A, uses 2,3,4,5, 6-pentafluoro-1-halogenobenzene to hydrolyze in the presence of catalyst and alkali to obtain 2,3,4,5, 6-pentafluorophenol sodium salt, and then processes in the presence of zeolite catalyst to obtain 2,3,4,5, 6-pentafluorophenol, the preparation of the catalyst is complex, and the product yield is low.
In view of the above situation, the applicant disclosed in patent 201811481959.6 that hexafluorobenzene, strong base and water are placed in a sealed container to prepare a mixed solution, and the mixed solution is subjected to a heat preservation reaction at 100-150 ℃ to obtain a system solution; neutralizing the system solution until the pH value is not higher than 6, extracting a crude product, and rectifying to obtain pentafluorophenol. The method has convenient operation and high yield, but the single impurity in the product is still 0.5-0.8 percent, and the purity requirement of the product as a liquid crystal intermediate can not be met by more than 99.9 percent. The yield is obviously reduced after the product is distilled for many times, and particularly, when the method is amplified to a scale of dozens of kilograms, the polysubstituted phenol by-product is obviously increased.
Therefore, on the basis of the existing synthesis method, the development of a pentafluorophenol production process more suitable for industrial amplification is still needed, and the content of single impurities in the reaction process is reduced so as to meet the requirements of the fields of medicine and liquid crystal on high-purity products.
Disclosure of Invention
In order to solve the problems, the invention provides a method for continuously preparing pentafluorophenol by using a microreactor. And respectively pumping hexafluorobenzene and an inorganic alkali aqueous solution into the microchannel reactor by using a metering pump to perform a hydrolysis reaction, keeping the temperature of the reactor at 130-170 ℃, controlling an outlet quantitative pressure control valve to maintain the pipeline pressure at 0.5-1.0Mpa, connecting an outlet of the reactor with a heat exchanger, obtaining an aqueous solution of pentafluorophenylphenol salt from the outlet of the heat exchanger, adding hydrochloric acid water vapor to distill to obtain an oil layer, and rectifying and dehydrating the oil layer to obtain pentafluorophenol. The invention has simple process, low cost and no amplification effect, and can realize continuous production.
The invention relates to a method for continuously preparing pentafluorophenol by a microreactor, which adopts the technical scheme that the method comprises the following steps:
(1) adding inorganic base and water into a microreactor alkali liquor kettle to prepare a solution;
(2) adding hexafluorobenzene into a microreactor raw material kettle;
(3) simultaneously pumping the solutions obtained in the step (1) and the step (2) into a microchannel reactor for hydrolysis;
(4) adding hydrochloric acid into the system liquid obtained in the step (3) and then distilling with water vapor;
(5) and (4) rectifying and dehydrating the water vapor distillation oil layer in the step (4) to obtain a product.
Further, in the above technical scheme, in the step (1), the mass ratio of the inorganic alkali to the water in the microreactor alkali liquor kettle is 1: 1.4-4.3.
Further, in the above technical solution, the step (1) inorganic base in the present invention is selected from one or more of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, and potassium fluoride.
Further, in the above technical solution, in the step (2), the molar ratio of hexafluorobenzene in the microreactor raw material kettle to the inorganic base in the step (1) is 1: 2-5.
Further, in the above technical solution, in the step (3) of the present invention, the solutions obtained in the step (1) and the step (2) are simultaneously pumped into the microchannel reactor through the metering pump, wherein the flow setting of the alkali solution kettle metering pump and the raw material kettle metering pump is inversely proportional to the volume.
Further, in the above technical solution, in the step (3) of the present invention, the microreactor has a reaction temperature of 130-.
Further, in the above technical solution, in the step (4) of the present invention, the mass fraction of the hydrochloric acid is in the range of 5 to 36%, and the amount of the hydrochloric acid is such that the pH of the steam distillation mother liquor can be maintained to be less than 7.
Further, in the above technical solution, in the step (5) of the present invention, the oil layer is dehydrated by using a rectification method.
Advantageous effects of the invention
Compared with the prior art, the invention has the following remarkable advantages:
(1) the reaction yield is high, and the pentafluorophenol yield is more than 95 percent; the purity is more than 99.90%.
(2) The microchannel continuous reaction inhibits the hydrolysis of other fluorine atoms in the reaction process, thereby facilitating the purification of the product.
(3) The reaction is continuous, the amplification effect is avoided, the production efficiency is high, and the operation is easy.
(4) No catalyst or solvent, low production cost and environmental protection compared with other methods.
Detailed Description
The present invention will be illustrated by, but is not limited to, the following specific examples.
Example 1
52.5g (0.94mol) of potassium hydroxide and 78.0g of water are added into a microreactor alkali liquor kettle to prepare a solution, and 75.0g (0.40mol) of hexafluorobenzene is added into a microreactor raw material kettle. Setting the working temperature of the microreactor to 160 ℃, controlling the outlet of the microreactor channel by a quantitative pressure control valve, and setting the working pressure of the microreactor channel to 0.6 Mpa. The potassium hydroxide aqueous solution and the hexafluorobenzene are all pumped in by a metering pump according to the volume flow ratio of 2:1 within 5 hours, and the residence time in the microreactor is 3 min. Collecting the microreactor heat exchanger outlet system liquid, adding 146g of 30% hydrochloric acid, distilling water vapor to obtain 103g of an oil layer, wherein the oil layer detection system comprises the following components: 30% of water and 70% of pentafluorophenol, and rectifying and dehydrating the mixture to obtain 72.0g of pentafluorophenol. The yield was 97.0% and the purity was 99.95%.
Example 2
271g (4.83mol) of potassium hydroxide and 321g of water are added into a microreactor alkali liquor kettle to prepare a solution, and 300g (1.61mol) of hexafluorobenzene is added into a microreactor raw material kettle. Setting the working temperature of the microreactor to 140 ℃, controlling the outlet of the microreactor channel by a quantitative pressure control valve, and setting the working pressure of the microreactor channel to 0.8 Mpa. The potassium hydroxide aqueous solution and the hexafluorobenzene are all pumped in by a metering pump according to the volume flow ratio of 2.2:1 within 4 hours, and the residence time in the microreactor is 5 min. Collecting the outlet system liquid of the heat exchanger of the microreactor, adding 516g of 30% hydrochloric acid, distilling water vapor to obtain 405g of an oil layer, wherein the oil layer detection system comprises the following components: 30% of water and 70% of pentafluorophenol. Rectifying and dehydrating to obtain 284g of pentafluorophenol. The yield was 95.7% and the purity was 99.96%.
Example 3
95g (1.69mol) of potassium hydroxide, 68g (1.70mol) of sodium hydroxide and 320g of water are added into a microreactor alkali liquor kettle to prepare a solution, and 300g (1.61mol) of hexafluorobenzene is added into a microreactor raw material kettle. Setting the working temperature of the microreactor to be 150 ℃, controlling the outlet of the microreactor channel by a quantitative pressure control valve, and setting the working pressure of the microreactor channel to be 0.8 Mpa. The potassium hydroxide aqueous solution and the hexafluorobenzene are all pumped in by a metering pump according to the volume flow ratio of 2:1 within 4 hours, and the residence time in the microreactor is 5 min. Collecting the outlet system liquid of the heat exchanger of the microreactor, adding 516g of 30% hydrochloric acid, distilling water vapor to obtain 411g of an oil layer, wherein the oil layer detection system comprises the following components: 30% of water and 70% of pentafluorophenol. And rectifying and dehydrating to obtain 288g of pentafluorophenol. The yield was 97.0% and the purity was 99.95%.
Example 4
195g (4.88mol) of sodium hydroxide and 320g of water are added into a microreactor alkali liquor kettle to prepare a solution, and 300g (1.61mol) of hexafluorobenzene is added into a microreactor raw material kettle. Setting the working temperature of the microreactor to be 150 ℃, controlling the outlet of the microreactor channel by a quantitative pressure control valve, and setting the working pressure of the microreactor channel to be 0.8 Mpa. The potassium hydroxide aqueous solution and the hexafluorobenzene are all pumped in by a metering pump according to the volume flow ratio of 2:1 within 4 hours, and the residence time in the microreactor is 5 min. Collecting the outlet system liquid of the heat exchanger of the microreactor, adding 516g of 30% hydrochloric acid, distilling and recovering 45g of front-run hexafluorobenzene and 343g of an oil layer by water vapor distillation, wherein the oil layer detection system comprises the following components: 30% of water and 70% of pentafluorophenol, and rectifying and dehydrating to obtain 240g of pentafluorophenol. The yield was 81% and the purity was 99.95%.
Example 5
180g (1.70mol) of sodium carbonate and 420g of water are added into a microreactor alkali liquor kettle to prepare a solution, and 300g (1.61mol) of hexafluorobenzene is added into a microreactor raw material kettle. Setting the working temperature of the microreactor to be 150 ℃, controlling the outlet of the microreactor channel by a quantitative pressure control valve, and setting the working pressure of the microreactor channel to be 0.8 Mpa. The potassium hydroxide aqueous solution and the hexafluorobenzene are all pumped in by a metering pump according to the volume flow ratio of 3:1 within 5 hours, and the residence time in the microreactor is 5 min. Collecting the outlet system liquid of the heat exchanger of the microreactor, adding 516g of 30% hydrochloric acid, distilling and recovering 225g of front-run hexafluorobenzene and 107g of an oil layer by water vapor distillation, wherein the oil layer detection system comprises the following components: 30% of water and 70% of pentafluorophenol, and rectifying and dehydrating to obtain 73g of pentafluorophenol. The yield was 25% and the purity was 99.92%.
Comparative example 1
271g (4.83mol) of potassium hydroxide and 321g (1.61mol) of water were charged in a 2L autoclave. Keeping the temperature at 140 ℃ for reaction for 25 hours, adding 516g of 30% hydrochloric acid into the system liquid to adjust the pH value to 1-2, and performing steam distillation and rectification to obtain 267g of pentafluorophenol with the yield of 92% and the purity of 99.0%, wherein the yield and the purity of the pentafluorophenol are lower than those of the pentafluorophenol prepared by a microreactor.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. A method for continuously preparing pentafluorophenol by using a microreactor is characterized by comprising the following steps: adding 52.5g of potassium hydroxide and 78.0g of water into a microreactor alkali liquor kettle to prepare a solution, and adding 75.0g of hexafluorobenzene into a microreactor raw material kettle; setting the working temperature of a microreactor to be 160 ℃, controlling the outlet of a microreactor channel by a quantitative pressure control valve, and setting the working pressure of the microreactor channel to be 0.6 Mpa; pumping the potassium hydroxide aqueous solution and the hexafluorobenzene into the micro-reactor for 3min by a metering pump according to the volume flow ratio of 2:1 within 5 hours; collecting the outlet system liquid of the heat exchanger of the microreactor, adding 146g of 30% hydrochloric acid, distilling water vapor to obtain 103g of an oil layer, wherein the oil layer detection system comprises the following components: 30 percent of water and 70 percent of pentafluorophenol are rectified and dehydrated to obtain 72.0g of pentafluorophenol.
2. A method for continuously preparing pentafluorophenol by using a microreactor is characterized by comprising the following steps: adding 271g of potassium hydroxide and 321g of water into a microreactor alkali liquor kettle to prepare a solution, and adding 300g of hexafluorobenzene into a microreactor raw material kettle; setting the working temperature of a microreactor to be 140 ℃, controlling the outlet of a microreactor channel by a quantitative pressure control valve, and setting the working pressure of the microreactor channel to be 0.8 Mpa; the potassium hydroxide aqueous solution and the hexafluorobenzene are all pumped in by a metering pump according to the volume flow ratio of 2.2:1 within 4 hours, and the residence time in the microreactor is 5 min; collecting the outlet system liquid of the heat exchanger of the microreactor, adding 516g of 30% hydrochloric acid, distilling water vapor to obtain 405g of an oil layer, wherein the oil layer detection system comprises the following components: 30% of water and 70% of pentafluorophenol; rectifying and dehydrating to obtain 284g of pentafluorophenol.
3. A method for continuously preparing pentafluorophenol by using a microreactor is characterized by comprising the following steps: adding 95g of potassium hydroxide, 68g of sodium hydroxide and 320g of water into a microreactor alkali liquor kettle to prepare a solution, and adding 300g of hexafluorobenzene into a microreactor raw material kettle; setting the working temperature of the microreactor to be 150 ℃, controlling the outlet of the microreactor channel by a quantitative pressure control valve, and setting the working pressure of the microreactor channel to be 0.8 Mpa; pumping the potassium hydroxide aqueous solution and hexafluorobenzene by a metering pump according to the volume flow ratio of 2:1, wherein the time of use is 4 hours, the residence time in a microreactor is 5min, collecting the microreactor heat exchanger outlet system liquid, adding 516g of 30% hydrochloric acid, distilling water vapor to obtain 411g of an oil layer, wherein the oil layer detection system comprises the following components: 30% of water and 70% of pentafluorophenol; and rectifying and dehydrating to obtain 288g of pentafluorophenol.
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