CN114394885A - Method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by using microchannel reactor - Google Patents
Method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by using microchannel reactor Download PDFInfo
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Abstract
The invention discloses a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor, which is characterized by comprising the following steps of: pumping the 2, 6-dimethylphenol melt and the acetone-acid solution into a reactor respectively by adopting a corning high-flux continuous flow microchannel reactor, and preheating in a first module-a direct-flow preheating module which is independent from each other and has the temperature of 120-150 ℃; then respectively entering a second module, namely an enhanced mass transfer type mixing module, through an inlet A or an inlet B of the reactor, carrying out mixing reaction at the temperature of 120-150 ℃ for 80-270 s, collecting effluent liquid of the reactor, and recrystallizing to obtain the 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane. The method has the advantages of short time, high efficiency, few byproducts, safety, stability and controllability, and the synthesized 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane is suitable for pharmaceutical and chemical intermediates.
Description
Technical Field
The invention belongs to the preparation of organic compounds, and relates to a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor. The 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane prepared by the invention is used as an organic synthesis intermediate and a medical intermediate, is suitable for producing various high polymer materials such as polycarbonate, polysulfone resin, bifunctional polyphenyl ether resin and the like, and can also be used in fine chemical products such as plasticizers, flame retardants, heat stabilizers, coatings and the like.
Background
2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane is an important organic synthesis intermediate and a medical intermediate, and is mainly used for producing various high polymer materials such as polycarbonate, polysulfone resin, bifunctional polyphenylene oxide resin and the like. Can also be used in fine chemical products such as plasticizers, flame retardants, heat stabilizers, coatings and the like. The market demand is large, the synthesis method is divided into different types by using different raw materials and different synthesis means, and in the prior art, the synthesis method of the 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane mainly comprises the condensation of 2, 6-dimethylphenol and acetone and the substitution of 2, 2-bis (4-hydroxyphenyl) propane by halogenated hydrocarbon. However, the existing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane synthesis process has the problems and disadvantages of use of expensive reactants or catalysts, complex process operation, long reaction time, high reaction temperature, low yield and the like.
In the prior art, CN 112010737a discloses a "method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane", which is a method for synthesizing a target compound from 2, 6-dimethylphenol and paraformaldehyde under the action of a sulfonic acid type MCM-41 mesoporous solid acid as a catalyst, and the method has the advantages of high yield, but the sulfonic acid type MCM-41 mesoporous solid acid catalyst is high in price, and simultaneously generates a large amount of wastewater. A method for synthesizing a target product by using 2, 6-dimethylphenol and aldehyde or ketone under the condition of not needing a solvent is reported in European patent (WO2017100164A1), but the method has the defects of complicated operation and long reaction time in a plurality of reaction processes with different temperature sections in the synthesis process. Document 1(Singh D, Deota P. eco-free Solvent-free Route to Alkyl-and Aryl-Bisphenols catalyst by Perchloric Acid-Silica [ J]Organic Preparations and products International,2020,52(4):1-7) using 2, 6-dimethylphenol with aldehydes or ketones in HClO4-SiO2The method does not need a solvent, but needs to dissolve the product in an organic solvent after the reaction and separate the catalyst by filtration, thereby having complex operation and increasing waste liquidAnd the discharge amount of waste gas and solid waste, and the practicability is poor.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by using a microchannel reactor. The invention makes the melted 2, 6-dimethylphenol and acetone react by means of the kinetic energy of the fluid, thereby providing the method for synthesizing the 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting the microchannel reactor, which has the advantages of short reaction time, high production efficiency, simple operation, safe, stable and controllable reaction process.
The content of the invention is as follows: the method for synthesizing the 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting the microchannel reactor is characterized by comprising the following steps of:
a. preparation of reactor and feed:
preparing a corning high-flux continuous flow microchannel reactor (namely, a microchannel reactor) as a reactor, wherein the corning high-flux continuous flow microchannel reactor comprises a direct-current preheating module, an enhanced mass transfer type mixing module, an inlet A, an inlet B and an outlet;
taking raw material molten state (or called molten solution and molten liquid) 2, 6-dimethylphenol and acetone, taking catalyst acid, and dissolving the catalyst acid in the acetone to obtain acetone-catalyst acid mixed solution for later use;
b. synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane:
respectively pumping the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution into the corning high-flux continuous flow microchannel reactor by adopting a corning high-flux continuous flow microchannel reactor, and preheating in a first module, namely a direct-current preheating module, which is at the temperature of 120-150 ℃ and is independent from each other; and then respectively entering a second module, namely an enhanced mass transfer type mixing module, through an inlet A or an inlet B of the corning high-flux continuous flow microchannel reactor, carrying out mixing reaction for 80-270 s at the reaction temperature of 120-150 ℃, allowing the reacted mixed liquid to flow out of an outlet of the corning high-flux continuous flow microchannel reactor, collecting effluent liquid (of the microchannel reactor), cooling the effluent liquid to room temperature, and recrystallizing to obtain the 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane. The yield is 81-94%, and the liquid phase purity is 99.2-99.5%.
The invention comprises the following steps: the structure of the mass transfer enhancement type mixing module in the step a can be one of a T-shaped channel structure (corresponding to a T-shaped micro-channel mass transfer enhancement type mixing module), a spherical channel structure (corresponding to a spherical micro-channel mass transfer enhancement type mixing module) or a heart-shaped channel structure (corresponding to a heart-shaped micro-channel mass transfer enhancement type mixing module).
The invention comprises the following steps: the Corning high-flux continuous flow microchannel reactor in the step a comprises a direct-flow preheating module and an enhanced mass transfer type mixing module, which can be a direct-flow (microchannel) preheating module and a T-shaped microchannel enhanced mass transfer type mixing module respectively, or a direct-flow (microchannel) preheating module and a spherical microchannel enhanced mass transfer type mixing module, or a direct-flow (microchannel) preheating module plus a heart-shaped microchannel enhanced mass transfer type mixing module.
The invention comprises the following steps: the structure of the direct-current type preheating module in the step a is a direct-current type tubular channel structure, and the diameter of the channel is preferably 0.5-10.0 mm.
The invention comprises the following steps: in the step a, the module (and the fittings) is preferably made of stainless steel metal or polytetrafluoroethylene coated with a monocrystalline silicon layer, a special glass layer and a corrosion-resistant layer.
The invention comprises the following steps: the catalyst acid in step a can be one or a mixture of more than two of hydrochloric acid, sulfuric acid, phosphoric acid and organic acid.
The invention comprises the following steps: in the step b, the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution are respectively pumped into a corning high-flux continuous flow microchannel reactor, preferably, the flow rate of the 2, 6-dimethylphenol (metering pump) is set to be 35.0-67.0 mL/min, the flow rate of the acetone-catalyst acid mixed solution (metering pump) is set to be 13.0mL/min, and the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution are respectively pumped into the corning high-flux continuous flow microchannel reactor.
The invention comprises the following steps: the flow rate of the 2, 6-dimethylphenol (molten liquid) in the step b is preferably 42.0 to 54.0 mL/min.
The invention comprises the following steps: the molar ratio of the acid to 2, 6-dimethylphenol in step a is preferably 1: 100.
The invention comprises the following steps: in the step b, the mixed reaction is carried out at the reaction temperature of 120-150 ℃ for 80-270 s, preferably at the temperature of 138-145 ℃ for 150-200 s.
The invention comprises the following steps: the solvent for recrystallization in step b is preferably one of methanol and toluene.
The chemical reaction equation of the method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting the microchannel reactor is as follows:
compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) the invention adopts the existing corning high-flux continuous flow micro-channel reactor as a reactor, and the micro-channel reactor is a continuous flow pipeline type small reaction system manufactured by micro-processing and fine processing technologies, has unique integral design of multilayer structure, and has large surface area to volume ratio compared with the conventional tubular reactor, thereby having extremely high mixing efficiency and heat exchange capacity, leading the mixing effect of the total heat exchange rate and fluid to have incomparable advantages compared with the traditional kettle type reactor, not only greatly shortening the reaction period, but also simplifying the synthesis steps and improving the reaction efficiency; in addition, because the size of the channel of the process fluid in the microchannel reactor is very small, the on-line material retention of each reaction module is small, and the materials are instantly and uniformly mixed in an accurate proportion, the reaction process is safer and more efficient; meanwhile, the microchannel reactor can realize the amplification of the process through the parallel connection of the devices, does not need a pilot test, has good repeatability and almost no amplification effect, and can improve the flexibility and the safety of production;
(2) the invention synthesizes 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by taking a molten solution of 2, 6-dimethylphenol and an aldehyde or ketone solution as raw materials in a continuous microchannel reactor; the condensation reaction is completed only by the kinetic energy of the fluid without adopting a conventional kettle type mechanical stirring reactor, the reaction time is short, the working procedure is simple and convenient, the operation is easy, the production efficiency is high, and the reaction process is safer, more stable and controllable;
(3) the preparation method has the advantages of simple preparation process, easy operation, short time, high efficiency, few byproducts, safety, stability and controllability, and the synthesized 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane is suitable for pharmaceutical and chemical intermediates and has strong practicability.
Drawings
FIG. 1 is a scheme for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane in example 11H NMR nuclear magnetic spectrum; the figure illustrates that: 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane is successfully synthesized by adopting a corning high-flux continuous flow microchannel reactor;
FIG. 2 is a schematic diagram showing the connection structure of a Corning high-throughput continuous-flow microchannel reactor used in the present invention;
FIG. 3 is a schematic diagram of a DC-type micro-channel structure of a DC-type preheating module in a Corning high-throughput continuous-flow micro-channel reactor used in the embodiments of the present invention;
FIG. 4 is a schematic diagram of the (3) configurations of the second modular mixing module in the corning high throughput continuous flow microchannel reactor employed in the present invention and embodiments;
Detailed Description
The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.
Example 1:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor comprises the following steps:
a. preparation of reactor and feed:
preparing a corning high-flux continuous flow microchannel reactor (a direct-flow microchannel preheating module and a T-shaped microchannel enhanced mass transfer type mixing module) as a reactor, determining the number of the mixing reaction modules according to the flow velocity and the reaction residence time, and using heat transfer oil as a heat exchange medium;
the corning high-flux continuous flow microchannel reactor comprises (i.e. comprises) a direct-current type preheating module (i.e. a direct-current type microchannel preheating module), an enhanced mass transfer type mixing module (i.e. a T-shaped microchannel enhanced mass transfer type mixing module), an inlet A, an inlet B and an outlet;
taking molten 2, 6-dimethylphenol and acetone as raw materials, taking hydrochloric acid with the mass fraction of 37% as a catalyst, and dissolving the hydrochloric acid in the acetone to prepare an acetone-acid solution for later use;
b. synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane:
adopting a Corning high-flux continuous flow microchannel reactor, respectively setting the flow rate of a prepared 2, 6-dimethylphenol molten solution metering pump and the flow rate of an acetone-acid solution metering pump to 35.0mL/min and 13.0mL/min for the prepared 2, 6-dimethylphenol molten solution metering pump, respectively pumping the 2, 6-dimethylphenol molten solution and the acetone-acid solution into the Corning high-flux continuous flow microchannel reactor, respectively preheating the molten solution and the acetone-acid solution in a first independent module, namely a direct-current preheating module, at the temperature of 120 ℃; then respectively entering a second module, namely an enhanced mass transfer type mixing module, through an inlet A or an inlet B of the corning high-flux continuous flow microchannel reactor, carrying out mixing reaction for 80s at the reaction temperature of 120 ℃, enabling the mixed liquid after the reaction to flow out from an outlet of the corning high-flux continuous flow microchannel reactor, collecting effluent liquid of the microchannel reaction device, cooling the effluent liquid to room temperature, and recrystallizing the effluent liquid by using methanol to prepare the 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane with the yield of 81% and the liquid phase purity of 99.4%.
Example 2:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor comprises the following steps:
a. preparation of reactor and feed:
preparing a corning high-flux continuous flow microchannel reactor (a direct-flow microchannel preheating module and a spherical microchannel enhanced mass transfer type mixing module) as a reactor, determining the number of the mixed reaction modules according to the flow rate and the reaction residence time, and using heat transfer oil as a heat exchange medium;
the corning high-flux continuous flow microchannel reactor comprises (i.e. comprises) a direct-current type preheating module (i.e. a direct-current type microchannel preheating module), an enhanced mass transfer type mixing module (i.e. a spherical microchannel enhanced mass transfer type mixing module), an inlet A, an inlet B and an outlet;
taking molten 2, 6-dimethylphenol and aldehyde or ketone solution as raw materials, taking hydrochloric acid with the mass fraction of 37% as a catalyst, and dissolving the hydrochloric acid in acetone to prepare acetone-acid solution for later use;
b. synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane:
adopting a Corning high-flux continuous flow microchannel reactor, respectively setting the flow rate of a prepared 2, 6-dimethylphenol molten solution metering pump and the flow rate of an acetone-acid solution metering pump to be 42.0mL/min and the flow rate of the acetone-acid solution metering pump to be 13.0mL/min, respectively pumping the 2, 6-dimethylphenol molten solution and the acetone-acid solution into the Corning high-flux continuous flow microchannel reactor, wherein the temperature of the molten solution and the acetone-acid solution is 138 ℃, and the molten solution and the acetone-acid solution are preheated in a first independent module, namely a direct-current preheating module; then respectively entering a second module, namely an enhanced mass transfer type mixing module, through an inlet A or an inlet B of the corning high-flux continuous flow microchannel reactor, carrying out mixing reaction for 110s at the reaction temperature of 138 ℃, enabling the mixed liquid after the reaction to flow out from an outlet of the corning high-flux continuous flow microchannel reactor, and collecting effluent liquid of a microchannel reaction device; cooling the effluent to room temperature, and recrystallizing with methanol to obtain 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane with yield of 90% and liquid phase purity of 99.3%.
Example 3:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor comprises the following steps:
a. preparation of reactor and feed:
preparing a corning high-flux continuous flow microchannel reactor (a direct-flow microchannel preheating module and a heart-shaped microchannel enhanced mass transfer type mixing module) as a reactor, determining the number of the mixing reaction modules according to the flow velocity and the reaction residence time, and using heat transfer oil as a heat exchange medium;
the corning high-flux continuous flow microchannel reactor comprises (i.e. comprises) a direct-current type preheating module (i.e. a direct-current type microchannel preheating module), an enhanced mass transfer type mixing module (i.e. a heart-shaped microchannel enhanced mass transfer type mixing module), an inlet A, an inlet B and an outlet;
taking molten 2, 6-dimethylphenol and acetone as raw materials, taking sulfuric acid as a catalyst, and dissolving the sulfuric acid in the acetone to prepare an acetone-acid solution for later use;
b. synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane:
adopting a Corning high-flux continuous flow microchannel reactor, respectively setting the flow rate of a 2, 6-dimethylphenol molten solution metering pump and the flow rate of an acetone-acid solution metering pump to be 53.0mL/min and the flow rate of a 2, 6-dimethylphenol molten solution metering pump to be 13.0mL/min, respectively pumping the 2, 6-dimethylphenol molten solution and the acetone-acid solution into the Corning high-flux continuous flow microchannel reactor, wherein the temperature of the 2, 6-dimethylphenol molten solution and the acetone-acid solution are 140 ℃ and are preheated in a first independent module, namely a direct-current preheating module; then respectively entering a second module, namely an enhanced mass transfer type mixing module, through an inlet A or an inlet B of the corning high-flux continuous flow microchannel reactor, carrying out mixing reaction for 150s at the reaction temperature of 140 ℃, enabling the mixed liquid after the reaction to flow out from an outlet of the corning high-flux continuous flow microchannel reactor, and collecting effluent liquid of a microchannel reaction device; cooling the effluent to room temperature, and recrystallizing with methanol to obtain 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane with yield of 94% and liquid phase purity of 99.5%.
Example 4:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor comprises the following steps:
a. preparation of reactor and feed:
preparing a corning high-flux continuous flow microchannel reactor (a direct-flow microchannel preheating module and a T-shaped microchannel enhanced mass transfer type mixing module) as a reactor, determining the number of the mixing reaction modules according to the flow velocity and the reaction residence time, and using heat transfer oil as a heat exchange medium;
the corning high-flux continuous flow microchannel reactor comprises (i.e. comprises) a direct-current type preheating module (i.e. a direct-current type microchannel preheating module), an enhanced mass transfer type mixing module (i.e. a T-shaped microchannel enhanced mass transfer type mixing module), an inlet A, an inlet B and an outlet;
taking molten 2, 6-dimethylphenol and acetone as raw materials, taking acetic acid as a catalyst, and dissolving the acetic acid in the acetone to prepare an acetone-acid solution for later use;
b. synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane:
adopting a Corning high-flux continuous flow microchannel reactor, respectively setting the flow rate of a prepared 2, 6-dimethylphenol molten solution metering pump and the flow rate of an acetone-acid solution metering pump to be 60.0mL/min and 13.0mL/min for the prepared 2, 6-dimethylphenol molten solution metering pump, respectively pumping the 2, 6-dimethylphenol molten solution and the acetone-acid solution into the Corning high-flux continuous flow microchannel reactor, wherein the temperature of the 2, 6-dimethylphenol molten solution and the acetone-acid solution are 145 ℃ and are respectively preheated in a first independent module, namely a direct-current preheating module; then respectively entering a second module, namely an enhanced mass transfer type mixing module, through an inlet A or an inlet B of the corning high-flux continuous flow microchannel reactor, carrying out mixing reaction for 200s at the reaction temperature of 145 ℃, enabling the mixed liquid after the reaction to flow out from an outlet of the corning high-flux continuous flow microchannel reactor, and collecting effluent liquid of a microchannel reaction device; cooling the effluent to room temperature, and recrystallizing with methanol to obtain 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane with yield of 93% and liquid phase purity of 99.3%.
Example 5:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor comprises the following steps:
a. preparation of reactor and feed:
preparing a corning high-flux continuous flow microchannel reactor (a direct-flow microchannel preheating module and a spherical microchannel enhanced mass transfer type mixing module) as a reactor, determining the number of the mixed reaction modules according to the flow rate and the reaction residence time, and using heat transfer oil as a heat exchange medium;
the corning high-flux continuous flow microchannel reactor comprises (i.e. comprises) a direct-current type preheating module (i.e. a direct-current type microchannel preheating module), an enhanced mass transfer type mixing module (i.e. a spherical microchannel enhanced mass transfer type mixing module), an inlet A, an inlet B and an outlet;
taking molten 2, 6-dimethylphenol and acetone as raw materials, taking acetic acid as a catalyst, and dissolving the acetic acid in the acetone to prepare an acetone-acid solution for later use;
b. synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane:
adopting a Corning high-flux continuous flow microchannel reactor, respectively setting the flow rate of a prepared 2, 6-dimethylphenol molten solution metering pump and the flow rate of an acetone-acid solution metering pump to be 67.0mL/min and 13.0mL/min for the prepared 2, 6-dimethylphenol molten solution metering pump, respectively pumping the 2, 6-dimethylphenol molten solution and the acetone-acid solution into the Corning high-flux continuous flow microchannel reactor, respectively preheating the molten solution and the acetone-acid solution in a first module, namely a direct-current preheating module, which are at 150 ℃ and independent from each other; then respectively entering a second module, namely an enhanced mass transfer type mixing module, through an inlet A or an inlet B of the corning high-flux continuous flow microchannel reactor, carrying out mixing reaction for 270s at the reaction temperature of 150 ℃, enabling the mixed liquid after the reaction to flow out from an outlet of the corning high-flux continuous flow microchannel reactor, and collecting effluent liquid of a microchannel reaction device; cooling the effluent to room temperature, and recrystallizing with methanol to obtain 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane with yield of 85% and liquid phase purity of 99.2%.
Example 6:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor comprises the following steps:
a. preparation of reactor and feed:
preparing a corning high-flux continuous flow microchannel reactor as a reactor, wherein the corning high-flux continuous flow microchannel reactor comprises a direct-current preheating module, an enhanced mass transfer type mixing module, an inlet A, an inlet B and an outlet;
taking the raw materials in a molten state (or called molten solution and molten liquid, and then the same is applied to the raw materials) 2, 6-dimethylphenol and acetone, taking the catalyst acid, and dissolving the catalyst acid in the acetone to obtain an acetone-catalyst acid mixed solution for later use;
b. synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane:
respectively pumping the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution into the corning high-flux continuous flow microchannel reactor by adopting a corning high-flux continuous flow microchannel reactor, and preheating in a first module, namely a direct-current preheating module, which is at the temperature of 120 ℃ and is independent from each other; then respectively entering a second module, namely an enhanced mass transfer type mixing module, through an inlet A or an inlet B of the corning high-flux continuous flow microchannel reactor, carrying out mixing reaction for 270 seconds at the reaction temperature of 120 ℃, enabling the mixed liquid after the reaction to flow out from an outlet of the corning high-flux continuous flow microchannel reactor, collecting effluent liquid (of the microchannel reactor), cooling the effluent liquid to room temperature, and recrystallizing to obtain the 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane.
Example 7:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor comprises the following steps:
a. preparation of reactor and feed:
preparing a corning high-flux continuous flow microchannel reactor as a reactor, wherein the corning high-flux continuous flow microchannel reactor comprises a direct-current preheating module, an enhanced mass transfer type mixing module, an inlet A, an inlet B and an outlet;
taking molten raw materials of 2, 6-dimethylphenol and acetone, taking catalyst acid, and dissolving the catalyst acid in the acetone to obtain an acetone-catalyst acid mixed solution for later use;
b. synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane:
respectively pumping the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution into the corning high-flux continuous flow microchannel reactor by adopting a corning high-flux continuous flow microchannel reactor, and preheating in a first module, namely a direct-current preheating module, which is at the temperature of 150 ℃ and is independent from each other; then respectively entering a second module, namely an enhanced mass transfer type mixing module, through an inlet A or an inlet B of the corning high-flux continuous flow microchannel reactor, carrying out mixing reaction for 80s at the reaction temperature of 150 ℃, enabling the reacted mixed liquid to flow out from an outlet of the corning high-flux continuous flow microchannel reactor, collecting effluent liquid (of the microchannel reactor), cooling the effluent liquid to room temperature, and recrystallizing to obtain the 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane.
Example 8:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor comprises the following steps:
a. preparation of reactor and feed:
preparing a corning high-flux continuous flow microchannel reactor as a reactor, wherein the corning high-flux continuous flow microchannel reactor comprises a direct-current preheating module, an enhanced mass transfer type mixing module, an inlet A, an inlet B and an outlet;
taking molten raw materials of 2, 6-dimethylphenol and acetone, taking catalyst acid, and dissolving the catalyst acid in the acetone to obtain an acetone-catalyst acid mixed solution for later use;
b. synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane:
respectively pumping the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution into the corning high-flux continuous flow microchannel reactor by adopting a corning high-flux continuous flow microchannel reactor, and preheating in a first module, namely a direct-current preheating module, which is at the temperature of 135 ℃ and is independent from each other; then respectively entering a second module, namely an enhanced mass transfer type mixing module, through an inlet A or an inlet B of the corning high-flux continuous flow microchannel reactor, carrying out mixing reaction for 170s at the reaction temperature of 135 ℃, enabling the reacted mixed liquid to flow out from an outlet of the corning high-flux continuous flow microchannel reactor, collecting effluent liquid (of the microchannel reactor), cooling the effluent liquid to room temperature, and recrystallizing to obtain the 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane.
Example 9:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor comprises the following steps:
a. preparation of reactor and feed:
preparing a corning high-flux continuous flow microchannel reactor as a reactor, wherein the corning high-flux continuous flow microchannel reactor comprises a direct-current preheating module, an enhanced mass transfer type mixing module, an inlet A, an inlet B and an outlet;
taking molten raw materials of 2, 6-dimethylphenol and acetone, taking catalyst acid, and dissolving the catalyst acid in the acetone to obtain an acetone-catalyst acid mixed solution for later use;
b. synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane:
respectively pumping the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution into the corning high-flux continuous flow microchannel reactor by adopting a corning high-flux continuous flow microchannel reactor, and preheating in a first module, namely a direct-current preheating module, which is at the temperature of 138 ℃ and is independent from each other; then respectively entering a second module, namely an enhanced mass transfer type mixing module, through an inlet A or an inlet B of the corning high-flux continuous flow microchannel reactor, carrying out mixing reaction for 200s at the reaction temperature of 138 ℃, enabling the reacted mixed liquid to flow out from an outlet of the corning high-flux continuous flow microchannel reactor, collecting effluent liquid (of the microchannel reactor), cooling the effluent liquid to room temperature, and recrystallizing to obtain the 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane.
Example 10:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor comprises the following steps:
a. preparation of reactor and feed:
preparing a corning high-flux continuous flow microchannel reactor as a reactor, wherein the corning high-flux continuous flow microchannel reactor comprises a direct-current preheating module, an enhanced mass transfer type mixing module, an inlet A, an inlet B and an outlet;
taking molten raw materials of 2, 6-dimethylphenol and acetone, taking catalyst acid, and dissolving the catalyst acid in the acetone to obtain an acetone-catalyst acid mixed solution for later use;
b. synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane:
respectively pumping the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution into the corning high-flux continuous flow microchannel reactor by adopting a corning high-flux continuous flow microchannel reactor, and preheating in a first module, namely a direct-current preheating module, which is at the temperature of 145 ℃ and is independent from each other; then respectively entering a second module, namely an enhanced mass transfer type mixing module, through an inlet A or an inlet B of the corning high-flux continuous flow microchannel reactor, carrying out mixing reaction for 150s at the reaction temperature of 145 ℃, enabling the reacted mixed liquid to flow out from an outlet of the corning high-flux continuous flow microchannel reactor, collecting effluent liquid (of the microchannel reactor), cooling the effluent liquid to room temperature, and recrystallizing to obtain the 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane.
Example 11:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor comprises the following steps:
a. preparation of reactor and feed:
preparing a corning high-flux continuous flow microchannel reactor as a reactor, wherein the corning high-flux continuous flow microchannel reactor comprises a direct-current preheating module, an enhanced mass transfer type mixing module, an inlet A, an inlet B and an outlet;
taking molten raw materials of 2, 6-dimethylphenol and acetone, taking catalyst acid, and dissolving the catalyst acid in the acetone to obtain an acetone-catalyst acid mixed solution for later use;
b. synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane:
respectively pumping the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution into the corning high-flux continuous flow microchannel reactor by adopting a corning high-flux continuous flow microchannel reactor, and preheating in a first module, namely a direct-current preheating module, which is at the temperature of 141 ℃ and is independent from each other; then respectively entering a second module, namely an enhanced mass transfer type mixing module, through an inlet A or an inlet B of the corning high-flux continuous flow microchannel reactor, carrying out a mixing reaction for 175s at the reaction temperature of 141 ℃, allowing the reacted mixed liquid to flow out from an outlet of the corning high-flux continuous flow microchannel reactor, collecting effluent liquid (of the microchannel reactor), cooling the effluent liquid to room temperature, and recrystallizing to obtain the 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane.
Example 12:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor is adopted, wherein in the step b, the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution are respectively pumped into a corning high-flux continuous flow microchannel reactor, the flow rate of the 2, 6-dimethylphenol (a metering pump) is set to be 35.0mL/min, the flow rate of the acetone-catalyst acid mixed solution (the metering pump) is set to be 13.0mL/min, and the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution are respectively pumped into the corning high-flux continuous flow microchannel reactor; the same as in any of examples 6 to 11, except that the above-mentioned process was omitted.
Example 13:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor is adopted, wherein in the step b, the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution are respectively pumped into a corning high-flux continuous flow microchannel reactor, the flow rate of the 2, 6-dimethylphenol (a metering pump) is set to be 67.0mL/min, the flow rate of the acetone-catalyst acid mixed solution (the metering pump) is set to be 13.0mL/min, and the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution are respectively pumped into the corning high-flux continuous flow microchannel reactor; the same as in any of examples 6 to 11, except that the above-mentioned process was omitted.
Example 14:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor is adopted, wherein in the step b, the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution are respectively pumped into a corning high-flux continuous flow microchannel reactor, the flow rate of the 2, 6-dimethylphenol (a metering pump) is set to be 51.0mL/min, the flow rate of the acetone-catalyst acid mixed solution (the metering pump) is set to be 13.0mL/min, and the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution are respectively pumped into the corning high-flux continuous flow microchannel reactor; the same as in any of examples 6 to 11, except that the above-mentioned process was omitted.
Example 15:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor is adopted, wherein in the step b, the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution are respectively pumped into a corning high-flux continuous flow microchannel reactor, the flow rate of the 2, 6-dimethylphenol (a metering pump) is set to be 42.0mL/min, the flow rate of the acetone-catalyst acid mixed solution (the metering pump) is set to be 13.0mL/min, and the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution are respectively pumped into the corning high-flux continuous flow microchannel reactor; the same as in any of examples 6 to 11, except that the above-mentioned process was omitted.
Example 16:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor is adopted, wherein in the step b, the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution are respectively pumped into a corning high-flux continuous flow microchannel reactor, the flow rate of the 2, 6-dimethylphenol (a metering pump) is set to be 54.0mL/min, the flow rate of the acetone-catalyst acid mixed solution (the metering pump) is set to be 13.0mL/min, and the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution are respectively pumped into the corning high-flux continuous flow microchannel reactor; the same as in any of examples 6 to 11, except that the above-mentioned process was omitted.
Example 17:
a method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor is adopted, wherein in the step b, the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution are respectively pumped into a corning high-flux continuous flow microchannel reactor, the flow rate of the 2, 6-dimethylphenol (a metering pump) is set to be 48.0mL/min, the flow rate of the acetone-catalyst acid mixed solution (the metering pump) is set to be 13.0mL/min, and the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution are respectively pumped into the corning high-flux continuous flow microchannel reactor; the same as in any of examples 6 to 11, except that the above-mentioned process was omitted.
In examples 6 to 11 above: the structure of the direct-current type preheating module in the step a is a direct-current type tubular channel structure, and the diameter of the channel can be any one of 0.5 mm-10.0 mm.
In examples 6 to 11 above: the catalyst acid in the step a is one or a mixture of more than two of hydrochloric acid, sulfuric acid, phosphoric acid and organic acid.
In examples 6 to 11 above: the solvent for recrystallization in the step b is methanol or toluene.
In examples 6 to 11 above: the structure of the mass transfer enhancement type mixing module in the step a can be one of a T-shaped channel structure (corresponding to a T-shaped micro-channel mass transfer enhancement type mixing module), a spherical channel structure (corresponding to a spherical micro-channel mass transfer enhancement type mixing module) or a heart-shaped channel structure (corresponding to a heart-shaped micro-channel mass transfer enhancement type mixing module).
In examples 6 to 11 above: the Corning high-flux continuous flow microchannel reactor in the step a comprises a direct-flow preheating module and an enhanced mass transfer type mixing module, which can be a direct-flow (microchannel) preheating module and a T-shaped microchannel enhanced mass transfer type mixing module respectively, or a direct-flow (microchannel) preheating module and a spherical microchannel enhanced mass transfer type mixing module, or a direct-flow (microchannel) preheating module plus a heart-shaped microchannel enhanced mass transfer type mixing module.
In the above embodiment: the molar ratio of the acid to the 2, 6-dimethylphenol in step a is 1: 100.
In the above embodiment: in the step a, the module (and accessories) is made of stainless steel metal or polytetrafluoroethylene coated with a monocrystalline silicon layer, a special glass layer and a corrosion-resistant layer.
In the above embodiment: the percentages used, not specifically indicated, are percentages by weight or known to those skilled in the art; the proportions used, not specifically noted, are mass (weight) proportions; the parts by weight may each be grams or kilograms.
In the above embodiment: the process parameters (temperature, time, etc.) and the numerical values of the components in each step are in the range, and any point can be applicable.
The present invention and the technical contents not specifically described in the above examples are the same as those of the prior art, and the raw materials are all commercially available products.
The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.
Claims (10)
1. A method for synthesizing 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane by adopting a microchannel reactor is characterized by comprising the following steps:
a. preparation of reactor and feed:
preparing a corning high-flux continuous flow microchannel reactor as a reactor, wherein the corning high-flux continuous flow microchannel reactor comprises a direct-current preheating module, an enhanced mass transfer type mixing module, an inlet A, an inlet B and an outlet;
taking molten raw materials of 2, 6-dimethylphenol and acetone, taking catalyst acid, and dissolving the catalyst acid in the acetone to obtain an acetone-catalyst acid mixed solution for later use;
b. synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane:
respectively pumping the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution into a Corning high-flux continuous flow microchannel reactor, and preheating in a first module, namely a direct-current preheating module, which is independent of each other and has the temperature of 120-150 ℃; and then respectively entering a second module, namely an enhanced mass transfer type mixing module, through an inlet A or an inlet B of the corning high-flux continuous flow microchannel reactor, carrying out mixing reaction for 80-270 s at the reaction temperature of 120-150 ℃, allowing the reacted mixed liquid to flow out of an outlet of the corning high-flux continuous flow microchannel reactor, collecting the effluent, cooling the effluent to room temperature, and recrystallizing to obtain the 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane.
2. The process of claim 1 for the synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane using a microchannel reactor, wherein: the structure of the mass transfer enhancement type mixing module in the step a is one of a T-shaped channel structure, a spherical channel structure or a heart-shaped channel structure.
3. The process of claim 1 for the synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane using a microchannel reactor, wherein: the structure of the direct-current type preheating module in the step a is a direct-current type tubular channel structure, and the diameter of the channel is 0.5-10.0 mm.
4. The process of claim 1 for the synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane using a microchannel reactor, wherein: the module in the step a is made of stainless steel metal or polytetrafluoroethylene coated with a monocrystalline silicon layer, a special glass layer and a corrosion-resistant layer.
5. A process for the synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane using a microchannel reactor as claimed in claim 1, 2, 3 or 4, wherein: the catalyst acid in the step a is one or a mixture of more than two of hydrochloric acid, sulfuric acid, phosphoric acid and organic acid.
6. A process for the synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane using a microchannel reactor as claimed in claim 1, 2, 3 or 4, wherein: and b, respectively pumping the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution into the corning high-flux continuous flow microchannel reactor, setting the flow rate of the 2, 6-dimethylphenol to be 35.0-67.0 mL/min and the flow rate of the acetone-catalyst acid mixed solution to be 13.0mL/min, and respectively pumping the molten 2, 6-dimethylphenol and the acetone-catalyst acid mixed solution into the corning high-flux continuous flow microchannel reactor.
7. The process of claim 6 for the synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane using a microchannel reactor, wherein: the flow rate of the 2, 6-dimethylphenol in the step b is 42.0-54.0 mL/min.
8. A process for the synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane using a microchannel reactor as claimed in claim 1, 2, 3, 4 or 7, wherein: the molar ratio of the acid to 2, 6-dimethylphenol in step a is 1: 100.
9. A process for the synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane using a microchannel reactor as claimed in claim 1, 2, 3, 4 or 7, wherein: in the step b, the mixed reaction is carried out for 80-270 s at the reaction temperature of 120-150 ℃, and the mixed reaction is carried out for 150-200 s at the temperature of 138-145 ℃.
10. A process for the synthesis of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane using a microchannel reactor as claimed in claim 1, 2, 3, 4 or 7, wherein: and the solvent for recrystallization in the step b is one of methanol and toluene.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101128257A (en) * | 2004-11-12 | 2008-02-20 | 万罗赛斯公司 | Process using microchannel technology for conducting alkylation or acylation reaction |
| CN107488108A (en) * | 2016-06-13 | 2017-12-19 | 上海泰禾国际贸易有限公司 | A kind of synthetic method of chloro phenoxy acetic acid or chlorophenol |
| CN110003012A (en) * | 2019-05-05 | 2019-07-12 | 山东豪迈化工技术有限公司 | A kind of preparation method nitrifying organic matter and the nitrification organic matter being prepared |
| CN110627622A (en) * | 2019-09-12 | 2019-12-31 | 广东省石油与精细化工研究院 | Preparation method of high-purity tetramethyl bisphenol A |
| CN111253262A (en) * | 2019-12-27 | 2020-06-09 | 山东华科化工有限公司 | Continuous flow industrial production method of o-nitro-p-methylphenol |
-
2022
- 2022-01-12 CN CN202210029302.6A patent/CN114394885A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101128257A (en) * | 2004-11-12 | 2008-02-20 | 万罗赛斯公司 | Process using microchannel technology for conducting alkylation or acylation reaction |
| CN107488108A (en) * | 2016-06-13 | 2017-12-19 | 上海泰禾国际贸易有限公司 | A kind of synthetic method of chloro phenoxy acetic acid or chlorophenol |
| CN110003012A (en) * | 2019-05-05 | 2019-07-12 | 山东豪迈化工技术有限公司 | A kind of preparation method nitrifying organic matter and the nitrification organic matter being prepared |
| CN110627622A (en) * | 2019-09-12 | 2019-12-31 | 广东省石油与精细化工研究院 | Preparation method of high-purity tetramethyl bisphenol A |
| CN111253262A (en) * | 2019-12-27 | 2020-06-09 | 山东华科化工有限公司 | Continuous flow industrial production method of o-nitro-p-methylphenol |
Non-Patent Citations (2)
| Title |
|---|
| DEEPAK SINGH等, 《TETRAHEDRON》/AROMATICS TO BIS-TRIQUINANE: A TANDEM OXIDATIVE DEAROMATIZATION OF BIS-PHENOL, CYCLOADDITION, PHOTOREARRANGEMENT AND A RAPID ENTRY INTO CARBOCYCLIC FRAMEWORK OF XEROMPHALINONE E, vol. 70, no. 30, pages 4490 * |
| R. F. CURTIS, 《JOURNAL OF THE CHEMICAL SOCIETY》/"DIPHENYLCYCLOBUTANE DERIVATIVE": 6, 6′-DIHYDROXY-3, 3, 3′, 3′-TERAMETHYL-1, 1′-SPIROBI-INDANE AND A RELATED COMPOUND, vol. 472, pages 223 * |
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