Method for preparing bisphenol nitro compound by using continuous tank reactor

By performing multi-stage reaction control and inert gas protection in a continuous kettle reactor, safety hazards and side reaction problems caused by heat in nitration reaction are solved, and efficient and safe preparation of bisphenol nitro compounds is achieved.

CN119504328APending Publication Date: 2025-02-25SHANGHAI XULIU CHEM TECH CO LTD
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Patent Information

Application Number
CN202411660916.X
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2024-11-20
Publication Date
2025-02-25

AI Technical Summary

Technical Problem

In the prior art, when preparing bisphenol nitro compounds, the heat generated by the nitration reaction leads to increased safety hazards and side reactions, and it is difficult for the microchannel reactor to achieve continuous operation of solid-containing slurries.

Method used

Using a continuous kettle reactor, bisphenol compounds and nitric acid are nitrated, and through a multi-stage reactor and an inert gas supply unit, efficient and safe reaction control is achieved, and combined with quenching liquid treatment is ensured to ensure the continuous operation of the reaction liquid. .

Benefits of technology

The nitrification reaction is carried out efficiently and selectively, simplifying the post-treatment steps, improving the purity and yield of the product, and enhancing the safety of the reaction.

✦ Generated by Eureka AI based on patent content.

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Abstract

The invention provides a method for preparing bisphenol nitro compounds by using a continuous tank reactor, and belongs to the field of continuous flow reaction. According to the method for preparing the bisphenol nitro compound by utilizing the continuous tank reactor, the bisphenol compound is used as a raw material, and the bisphenol compound and nitric acid are subjected to nitration reaction by utilizing the continuous tank reactor to prepare the bisphenol nitro compound. The nitration reaction can be realized with high efficiency and high selectivity, the reaction temperature can be effectively controlled, and the safety of the reaction is further ensured.
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Description

Technical Field

[0001] The invention relates to the field of continuous flow reaction, and in particular to a method for preparing bisphenol nitro compounds by utilizing a continuous tank reactor. Background Art

[0002] Bisphenol nitro compounds are important intermediates for many new materials. For example, 2,2-bis(4-hydroxy-3-aminophenyl)propane obtained by reducing 2,2-bis(4-hydroxy-3-nitrophenyl)propane is the raw monomer of polyphenylpropanazole compounds. Polyphenylpropanazole compounds are a kind of photosensitive heat-resistant polymer that can be used in ultra-large-scale integrated circuits and a high-strength high-heat-resistant polymer.

[0003] In the prior art, CN1426390A provides a method for preparing 2,2-bis(4-hydroxy-3-nitrophenyl)propane by a kettle reaction. Although very ideal yield and purity are achieved in gram-level reactions, as the reaction system is scaled up, the large amount of heat released by the nitration reaction not only easily leads to safety problems, but also causes more side reactions in the reaction system, thereby reducing the yield and purity.

[0004] CN11315331A discloses a method for preparing 2,2-bis(4-hydroxy-3-nitrophenyl)hexafluoropropane. Although the method disclosed in the patent is realized by using a microchannel reactor, which can achieve rapid mass transfer and heat exchange and has a small amplification effect, it is difficult to achieve continuous operation of a reaction liquid containing a solid slurry. However, when the applicant repeats the continuous flow process, solids often appear in the system, causing microchannel blockage, making it difficult for the device to operate for a long time. Summary of the invention

[0005] The present invention is made to solve the above problems and aims to provide a method for preparing bisphenol nitro compounds by using a continuous tank reactor, which combines microchannel reaction with tank reaction and can realize continuous operation of solid-containing reaction liquid and is safer and more efficient.

[0006] The present invention provides a method for preparing bisphenol nitro compounds by using a continuous tank reactor, which has the following characteristics: using a bisphenol compound as a raw material, and using a continuous tank reactor to make the bisphenol compound and nitric acid undergo a nitration reaction to prepare the bisphenol nitro compound.

[0007] The reaction formula is:

[0008]

[0009] In the above formula, A is R 1 , R 2are independently selected from H, C1-C3 alkyl and C1-C3 alkyl substituted by at least one halogen; or R 1 , R 2 Together with the carbon atom connected to it, it forms a C5-C6 aliphatic ring;

[0010] Wherein, the continuous tank reactor comprises:

[0011] A raw material kettle, used for containing a bisphenol compound solution;

[0012] A mixed acid kettle, used for containing nitric acid or a mixed acid solution containing at least nitric acid;

[0013] A quenching liquid kettle, used for containing quenching liquid;

[0014] A first reaction kettle, connected to the raw material kettle through a first connecting pipe, and connected to the mixed acid kettle through a second connecting pipe, for receiving the bisphenol compound solution and the nitric acid or mixed acid solution to form a first reaction solution;

[0015] The second reaction kettle is connected to the first reaction kettle and is used to receive the first reaction liquid and form a second reaction liquid;

[0016] A third reaction kettle, connected to the second reaction kettle, for receiving the second reaction liquid and forming a third reaction liquid;

[0017] The fourth kettle is connected to the third reaction kettle and is connected to the quenching liquid kettle through a third connecting pipe, and is used to receive the quenching liquid and the third reaction liquid, and mix the quenching liquid and the third reaction liquid to form a quenched reaction mixed liquid;

[0018] A raw material pump, installed on the first connecting pipe, used to pump the bisphenol compound solution in the raw material kettle into the first reaction kettle;

[0019] A mixed acid pump, installed on the second connecting pipe, used to pump nitric acid or mixed acid solution in the mixed acid kettle into the first reaction kettle;

[0020] A quenching liquid pump, installed on the third connecting pipe, used to pump the quenching liquid into the fourth kettle;

[0021] The method for preparing bisphenol nitro compounds by nitration reaction using a continuous tank reactor comprises the following steps:

[0022] Step 1, charging the bisphenol compound solution into a raw material kettle, charging the mixed acid into the mixed acid kettle, and charging the quenching liquid into the quenching liquid kettle;

[0023] Step 2, simultaneously starting the raw material pump and the mixed acid pump at a certain flow rate, pumping the bisphenol compound solution and the nitric acid or mixed acid solution into the first reactor, and forming a first reaction liquid in the first reactor, after the first reaction liquid is formed and stays for a certain time, the first reaction liquid is transferred to the second reactor at a certain flow rate to obtain a second reaction liquid, after the second reaction liquid is formed and stays for a certain time, the second reaction liquid is transferred to the third reactor at a certain flow rate to obtain a third reaction liquid;

[0024] Step 3, transferring the third reaction liquid into the fourth kettle at a certain flow rate, and at the same time starting the quenching liquid pump to pump the quenching liquid into the fourth kettle to mix the quenching liquid with the third reaction liquid to form a quenched reaction mixture.

[0025] In the method for preparing bisphenol nitro compounds using a continuous tank reactor provided by the present invention, the method may also have the following characteristics: wherein the continuous tank reactor further comprises:

[0026] An inert gas supply unit is connected to the first reaction kettle through an inert gas supply pipe, and provides inert gas into the first reaction kettle to push the reaction liquid to transfer into the second kettle through the connecting pipe;

[0027] The collecting kettle is connected to the fourth kettle and is used to receive the reaction mixture after quenching.

[0028] The method for preparing bisphenol nitro compounds by using a continuous tank reactor provided by the present invention may also have the following characteristics: wherein the inner diameter of the first connecting tube and / or the second connecting tube is 4 to 10 mm, and the outer diameter of the tube is 7 to 12 mm.

[0029] The method for preparing bisphenol nitro compounds by using a continuous tank reactor provided by the present invention may also have the following characteristics: wherein the first reactor, the second reactor, the third reactor and the fourth reactor all have a stirring function to stir the slurry system evenly.

[0030] The method for preparing bisphenol nitro compounds by using a continuous tank reactor provided by the present invention may also have the following characteristics: wherein the bisphenol compound solution is composed of a bisphenol compound, dichloromethane and acetic acid.

[0031] The method for preparing bisphenol nitro compounds by using a continuous tank reactor provided by the present invention may also have the following characteristics: wherein the bisphenol compound solution is composed of 1 part of bisphenol compound, 2.5-3.5 parts of dichloromethane and 2.5-3.5 parts of acetic acid by weight.

[0032] The method for preparing bisphenol nitro compounds by using a continuous tank reactor provided by the present invention may also have the following characteristics: wherein the molar ratio of the bisphenol compound to nitric acid is 1:(1.5-2.5).

[0033] In the method for preparing bisphenol nitro compounds using a continuous tank reactor provided by the present invention, the method may also have the following characteristics: wherein, when the bisphenol compound is 2,2-bis(4-hydroxyphenyl)propane, the bisphenol nitro compound is 2,2-bis(4-hydroxy-3-nitrophenyl)propane, and the reaction formula is as follows:

[0034]

[0035] When the bisphenol compound is 4,4'-dihydroxydiphenyl sulfone, the bisphenol nitro compound is 4-(4-hydroxy-3-nitrobenzenesulfonyl)-2-nitrophenol, the reaction formula is as follows:

[0036]

[0037] When the bisphenol compound is 2,2-bis(4-hydroxyphenyl)hexafluoropropane, and the bisphenol nitro compound is 2,2-bis(4-hydroxy-3-nitrophenyl)hexafluoropropane, the reaction formula is as follows:

[0038]

[0039] When the bisphenol compound is 1,1'-bis(4-hydroxyphenyl)cyclohexane, and the bisphenol nitro compound is 1,1'-bis(4-hydroxy-3-nitrophenyl)cyclohexane, the reaction formula is as follows:

[0040]

[0041] The method for preparing bisphenol nitro compounds by using a continuous tank reactor provided by the present invention may also have the following characteristics: wherein the mixed acid reactor is used to contain a mixed acid solution, and the mixed acid solution is composed of an aqueous nitric acid solution and acetic acid.

[0042] The method for preparing bisphenol nitro compounds using a continuous tank reactor provided by the present invention may also have the following characteristics: wherein the mixed acid solution is composed of 0.8-0.9 parts by weight of a 60wt%-70wt% nitric acid aqueous solution and 1.5-2.5 parts by weight of acetic acid.

[0043] The method for preparing bisphenol nitro compounds by using a continuous tank reactor provided by the present invention may also have the following characteristics: wherein the method for preparing bisphenol compounds by nitration reaction by using a continuous tank reactor further comprises the following steps:

[0044] Step 4, transferring the quenched reaction mixture to a centrifugal device, centrifuging, filtering, eluting, and taking the solid to obtain.

[0045] The method for preparing bisphenol nitro compounds by using a continuous tank reactor provided by the present invention may also have the following characteristics: wherein the method for preparing bisphenol nitro compounds by nitration reaction by using a continuous tank reactor comprises the following steps:

[0046] Step 1, a raw material solution composed of 1 part of a bisphenol compound, 2.5-3.5 parts of dichloromethane and 2.5-3.5 parts of acetic acid is charged into a raw material kettle; a mixed acid solution composed of 0.75-1.0 parts of a 60-70wt% nitric acid aqueous solution and 1-3 parts of acetic acid is charged into the mixed acid kettle; 3.0-5.5 parts of deionized water are added into a quenching liquid kettle;

[0047] Step 2, precooling the raw material solution in the raw material kettle to 15-25°C, precooling the mixed acid solution in the mixed acid kettle to 5-15°C, precooling the first connecting pipe and the second connecting pipe to 0-10°C, opening the inert gas supply part, and opening the valve on the pipeline between the inert gas supply part and the first reactor, precooling the temperature in the first reactor to -20 to -10°C, precooling the temperatures in the second reactor, the third reactor and the fourth reactor to 15-20°C, turning on the raw material pump and the mixed acid pump, controlling the rate of pumping the raw material solution into the first reactor to 350-400mL / min, and the rate of pumping the mixed acid solution into the first reactor to 120-170mL / min;

[0048] Step 3, control the temperature of the material in the first reactor not to exceed 19°C, start transferring the material in the first reactor to the second reactor at 470-570mL / min 15-25min after the material starts to enter the first reactor, control the temperature in the second reactor not to exceed 17°C, transfer the material in the second reactor to the third reactor at 470-570mL / min 15-25min after the material starts to enter the second reactor, control the temperature in the third reactor not to exceed 17°C, transfer the material in the third reactor to the fourth reactor at 470-570mL / min 15-25min after the material starts to enter the third reactor, control the temperature in the fourth reactor not to exceed 17°C, and pass the deionized water in the quenching liquid kettle into the fourth reactor at 200-400mL / min;

[0049] Step 4, continuously running until the raw material solution and the mixed acid solution are completely consumed, when the reaction is completely completed, all the materials are transferred to a collecting kettle, the materials in the collecting kettle are centrifuged, the solids are collected by elution, and dried to obtain bisphenol nitro compounds.

[0050] Functions and Effects of the Invention

[0051] According to the method for preparing bisphenol nitro compounds using a continuous tank reactor involved in the present invention, since a method and device combining a continuous reaction and a tank reaction are adopted, the present invention can not only realize a continuous nitration reaction of a reaction liquid containing solids with high efficiency and high selectivity, which is beneficial to simplifying post-processing, but also can effectively control the reaction temperature, further ensuring the safety of the reaction. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 It is a schematic diagram of the structure of the continuous tank reactor provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0053] In order to make the technical means, creative features, objectives and effects achieved by the present invention easier to understand, the present invention is described in detail below in conjunction with embodiments and drawings.

[0054] In the following examples, unless otherwise specified, all raw materials are commercially available products.

[0055] <Example 1>

[0056] A continuous tank reactor

[0057] The present embodiment provides a continuous tank reactor, including: a raw material tank 11, a mixed acid tank 12, a quenching liquid tank 13, a first reaction tank 14, a second reaction tank 15, a third reaction tank 16, a fourth tank 17, a raw material pump 18, a mixed acid pump 19, a quenching liquid pump 20, a first connecting pipe 21, a second connecting pipe 22, a third connecting pipe 23, an inert gas supply part 24 and a collecting tank 25.

[0058] The raw material kettle 11 is connected to the first reaction kettle 14 through the first connecting pipe 21, and is used to contain the raw material or its solution. In this embodiment, the raw material kettle 11 is used to contain the solution of 2,2-bis(4-hydroxyphenyl)propane.

[0059] The mixed acid kettle 12 is connected to the first reaction kettle 14 through the second connecting pipe 22, and is used to contain nitric acid or a mixed acid solution. In this embodiment, the mixed acid kettle 12 is used to contain a mixed acid solution containing nitric acid and acetic acid.

[0060] The quenching liquid kettle 13 is connected to the fourth kettle 17 through the third connecting pipe 23 and is used to contain the quenching liquid. In this embodiment, the quenching liquid is deionized water.

[0061] The first reaction kettle 14 is connected to the raw material kettle 11 through the first connecting pipe 21, connected to the mixed acid kettle 12 through the second connecting pipe 22, connected to the inert gas supply part 24 through a pipeline with a valve, and connected to the second reaction kettle 15 through a pipeline with a valve.

[0062] The first reactor 14 includes a reactor body, a temperature control element and a stirring element. The reactor body has a cavity for accommodating materials. The temperature control element is wrapped around the outside of the reactor body and is used to adjust the temperature of the materials inside the reactor body, and can be heated or cooled according to actual needs. The stirring element is installed on the reactor body and is used to stir the materials in the reactor body to make them evenly mixed.

[0063] The second reactor 15 is connected to the first reactor 14 through a pipeline with a valve, and is connected to the third reactor 16 through another pipeline with a valve. The structure of the second reactor 15 is the same as that of the first reactor 14, and will not be described in detail.

[0064] The third reactor 16 is connected to the second reactor 15 through a pipeline with a valve, and is connected to the fourth reactor 17 through another pipeline with a valve. The structure of the third reactor 16 is the same as that of the first reactor 14, and will not be described in detail.

[0065] The fourth kettle 17 is connected to the quenching liquid kettle 13 through the third connecting pipe 23, is connected to the third reactor 16 through a pipeline with a valve, and is connected to the collecting kettle 25 through another pipeline with a valve and a pump. The structure of the fourth kettle 17 is the same as that of the first reactor 14, and will not be repeated here.

[0066] In this embodiment, the diameters of the pipes connecting the first reactor 14 and the second reactor 15, the pipes connecting the second reactor 15 and the third reactor 16, the pipes connecting the third reactor 16 and the fourth reactor 17, and the pipes connecting the fourth reactor 17 and the collecting reactor 25 are all 6 mm. In other embodiments, the diameters of the above pipes can be adjusted according to actual needs.

[0067] In this embodiment, the material transfer between the first reactor 14 and the second reactor 15, between the second reactor 15 and the third reactor 16, and between the third reactor 16 and the fourth reactor 17 is achieved by nitrogen pressurization. In other embodiments, the material transfer can also be achieved by installing pumps on the pipeline connecting the first reactor 14 and the second reactor 15, the pipeline connecting the second reactor 15 and the third reactor 16, and the pipeline connecting the third reactor 16 and the fourth reactor 17.

[0068] One end of the first connecting pipe 21 is connected to the raw material kettle 11, and the other end is connected to the first reaction kettle 14. In this embodiment, the first connecting pipe 21 is a coil with a temperature control function, and the material is PFA (polytetrafluoroethylene). The inner diameter of the pipe is 4mm and the outer diameter is 6.35mm.

[0069] One end of the second connecting pipe 22 is connected to the mixed acid kettle 12, and the other end is connected to the first reaction kettle 14. In this embodiment, the second connecting pipe 22 is a coil with a temperature control function, and the material is PFA (polytetrafluoroethylene). The inner diameter of the pipe is 4mm and the outer diameter is 6.35mm.

[0070] One end of the third connecting pipe 23 is connected to the quenching liquid kettle 13, and the other end is connected to the fourth kettle 17. In this embodiment, the third connecting pipe 23 is a PFA tube with an inner diameter of 4 mm and an outer diameter of 6.35 mm.

[0071] The raw material pump 18 is installed on the first connecting pipe 21, and is used to pump the raw material or its solution from the raw material kettle 11 into the first reaction kettle 14. In this embodiment, the raw material pump 18 is a stainless steel pump.

[0072] The mixed acid pump 19 is installed on the second connecting pipe 22, and is used to pump the mixed acid solution or the mixed acid solution from the mixed acid kettle 12 into the first reaction kettle 14. In this embodiment, the mixed acid pump 19 is a PVDF pump.

[0073] The quenching liquid pump 20 is installed on the third connecting pipe 23, and is used to pump the quenching liquid from the quenching liquid kettle 13 into the fourth kettle 17. In this embodiment, the quenching liquid pump 20 is a peristaltic pump.

[0074] The inert gas supply unit 24 is connected to the first reactor 14 through a pipeline with a valve, and is used to provide inert gas protection to the first reactor 14 and the second reactor 15, the third reactor 16, the fourth reactor 17 and the collecting reactor 25 connected to the first reactor 14. In this embodiment, the inert gas supplied by the inert gas supply unit 24 is nitrogen.

[0075] The collecting kettle 25 is connected to the fourth kettle 17 through a pipeline with a valve and a pump, and is used to collect the quenched reaction liquid for further post-processing.

[0076] <Example 2>

[0077] A method for continuously producing 2,2-bis(4-hydroxy-3-nitrophenyl)propane

[0078] This embodiment provides a method for continuously producing 2,2-bis(4-hydroxy-3-nitrophenyl)propane using the continuous tank reactor provided in Example 1, and the reaction formula is as follows:

[0079]

[0080] The steps include:

[0081] Step 1, a raw material solution consisting of 1 kg of 2,2-bis(4-hydroxy-3-nitrophenyl)propane, 3 kg of dichloromethane and 3 kg of acetic acid is charged into a raw material kettle; a mixed acid solution consisting of 0.845 kg of 65 wt% nitric acid aqueous solution and 2 kg of acetic acid is charged into a mixed acid kettle; 0.5 kg of deionized water is added into a quenching liquid kettle;

[0082] Step 2, precooling the raw material solution in the raw material kettle to 20°C, precooling the mixed acid solution in the mixed acid kettle to 10°C, precooling the first connecting pipe and the second connecting pipe to 5°C, opening the inert gas supply part, and opening the valve on the pipeline between the inert gas supply part and the first reactor, precooling the temperature in the first reactor to -15°C, precooling the temperatures in the second reactor, the third reactor and the fourth reactor to 17°C, turning on the raw material pump and the mixed acid pump, and controlling the rate of pumping the raw material solution into the first reactor to 367mL / min, and the rate of pumping the mixed acid solution into the first reactor to 150mL / min;

[0083] Step 3, control the temperature of the material in the first reactor not to exceed 19°C, 20 minutes after the material starts to enter the first reactor, start to transfer the material in the first reactor to the second reactor by nitrogen pressurization at 517mL / min, control the temperature in the second reactor not to exceed 17°C, 20 minutes after the material starts to enter the second reactor, transfer the material in the second reactor to the third reactor by nitrogen pressurization at 517mL / min, control the temperature in the third reactor not to exceed 17°C, 20 minutes after the material starts to enter the third reactor, transfer the material in the third reactor to the fourth reactor by nitrogen pressurization at 517mL / min, when the material enters the fourth reactor, control the temperature in the fourth reactor not to exceed 17°C, and transfer the deionized water in the quenching liquid kettle to the fourth reactor by nitrogen pressurization at 517mL / min;

[0084] Step 4, when the reaction is completed, all the materials in the fourth kettle are transferred to the collecting kettle, the materials in the collecting kettle are centrifuged, the solids are collected and dried to obtain 980g of 2,2-bis(4-hydroxy-3-nitrophenyl)propane with a purity of 99.4%, a single impurity of <0.5%, and a yield of 70.3%.

[0085] <Example 3>

[0086] Selection of raw materials and dosage

[0087] This example is based on Example 2, except that the raw materials and their amounts are adjusted, and the other conditions not mentioned are the same as those in Example 2.

[0088] The results of raw material and dosage screening are shown in Table 1.

[0089] Table 1 Raw materials and dosage screening table

[0090]

[0091]

[0092] In Table 1, bisphenol A is 2,2-bis(4-hydroxyphenyl)propane. When the bisphenol compound is 2,2-bis(4-hydroxyphenyl)propane, the product is 2,2-bis(4-hydroxy-3-nitrophenyl)propane; bisphenol S is 4,4'-dihydroxydiphenyl sulfone. When the bisphenol compound is 4,4'-dihydroxydiphenyl sulfone, the product is 4-(4-hydroxy-3-nitrobenzenesulfonyl)-2-nitrophenol; bisphenol AF is 2,2-bis(4-hydroxyphenyl)hexafluoropropane. When the bisphenol compound is 2,2-bis(4-hydroxyphenyl)hexafluoropropane, the product is 2,2-bis(4-hydroxy-3-nitrophenyl)hexafluoropropane.

[0093] As shown in Table 1, adding dichloromethane to the raw material kettle can greatly improve the purity of the product. According to the analysis of the liquid phase spectrum of the reaction product of No. 3 in the above table, it is found that when dichloromethane is not added, more polynitration products will be produced, resulting in low purity of the final product. At the same time, adding acetic acid to the mixed acid kettle can also appropriately improve the purity of the target product.

[0094] <Comparative Example 1>

[0095] This comparative example is basically the same as Example 2, except that the continuous kettle reactor used is different. The continuous kettle reactor used in this comparative example has only two reactors, namely the first reactor and the second reactor, and does not contain a third reactor. When the material comes out of the second reactor, it is directly passed into the fourth reactor. The residence time of the material in the first reactor and the second reactor and the temperature in the reactor are the same as those in Example 2.

[0096] The yield of the product obtained in this comparative example is 62.8% and the purity is 92.4%.

[0097] <Comparative Example 2>

[0098] This comparative example is basically the same as Example 2, except that the continuous tank reactor used is different. The continuous tank reactor used in this comparative example has only one reactor, namely the first reactor, and does not contain the second reactor and the third reactor. When the material comes out of the first reactor, it is directly passed into the fourth reactor. The residence time of the material in the first reactor and the temperature in the reactor are the same as those in Example 2.

[0099] The yield of the product obtained in this comparative example is 52.3% and the purity is 85.6%.

[0100] Functions and Effects of the Embodiments

[0101] According to the method for preparing bisphenol nitro compounds using a continuous tank reactor involved in the above embodiment, since a method and apparatus combining continuous reaction and tank reaction are adopted, the above embodiment can not only realize the nitration reaction with high efficiency and high selectivity, but also effectively control the reaction temperature to further ensure the safety of the reaction.

[0102] Furthermore, since a solvent system mainly composed of dichloromethane, acetic acid and water is selected, the target product bisphenol nitro compound will continuously precipitate during the reaction process, and the raw materials have good solubility in the solvent system. Therefore, the target product can be separated and purified by only centrifuging the final reaction solution, which greatly saves post-processing steps and improves production efficiency.

[0103] Furthermore, since the target product will precipitate during the reaction, multiple reactors are selected, and the material stays in each reactor for 15-25 minutes, avoiding problems such as pipeline blockage caused by the growth of large-particle crystals of solids in a single reactor, ensuring that the nitrification device can operate stably for a long time.

[0104] Furthermore, since an excessively high temperature in the kettle not only brings certain dangers but also causes the side reaction of polynitration, which further leads to a decrease in yield and purity, the continuous kettle reactor used in the above embodiment has a three-stage reactor, thereby avoiding the accumulation of excessive heat in a single kettle. Therefore, the method provided in the above embodiment not only improves the safety of the reaction, but also helps to improve the purity and yield of the final product.

[0105] Furthermore, in the above embodiment, the material in the raw material kettle consists of bisphenol compounds, dichloromethane and acetic acid, and the material in the mixed acid kettle consists of nitric acid aqueous solution and acetic acid, so the target product with a purity of at least 95% can be obtained with a yield of 73.3% without complicated post-treatment and only after simple centrifugation.

[0106] The above-mentioned embodiments are preferred examples of the present invention and are not intended to limit the protection scope of the present invention.

Claims

1. A method for preparing bisphenol nitro compounds using a continuous tank reactor, characterized in that: Bisphenol compounds are used as raw materials, and bisphenol compounds are subjected to nitration reaction with nitric acid in a continuous tank reactor to prepare bisphenol nitro compounds. The reaction formula is: In the above formula, A is R1 and R2 are independently selected from H, C1-C3 alkyl and C1-C3 alkyl substituted by at least one halogen; or R1, R2 and the adjacent carbon atoms together form a C5-C6 aliphatic ring; Wherein, the continuous tank reactor comprises: A raw material kettle, used for containing a bisphenol compound solution; A mixed acid kettle, used for containing a mixed acid including at least nitric acid or a mixed acid solution including at least nitric acid; A quenching liquid kettle, used for containing quenching liquid; A first reaction kettle, connected to the raw material kettle through a first connecting pipe, and connected to the mixed acid kettle through a second connecting pipe, for receiving the bisphenol compound solution and the mixed acid or mixed acid solution, and forming a first reaction solution; A second reaction kettle, connected to the first reaction kettle, for receiving the first reaction liquid and forming a second reaction liquid; A third reaction kettle, connected to the second reaction kettle, for receiving the second reaction liquid and forming a third reaction liquid; a fourth kettle, connected to the third reaction kettle and connected to the quenching liquid kettle through a third connecting pipe, for receiving the quenching liquid and the third reaction liquid, and mixing the quenching liquid and the third reaction liquid to form a quenched reaction mixed liquid; A raw material pump, installed on the first connecting pipe, used to pump the bisphenol compound solution in the raw material kettle into the first reaction kettle; A mixed acid pump, installed on the second connecting pipe, used to pump the mixed acid or mixed acid solution in the mixed acid kettle into the first reaction kettle; A quenching liquid pump is installed on the third connecting pipe and is used to pump the quenching liquid into the fourth kettle. The method for preparing bisphenol nitro compounds by nitration reaction using the continuous tank reactor comprises the following steps: Step 1, charging the bisphenol compound solution into the raw material kettle, charging the mixed acid or mixed acid solution into the mixed acid kettle, charging the quenching liquid into the quenching liquid kettle; Step 2, respectively starting the raw material pump and the mixed acid pump, pumping the bisphenol compound solution and the mixed acid into the first reactor, and forming a first reaction liquid in the first reactor, after a certain time interval after the first reaction liquid is formed, transferring the first reaction liquid to the second reactor at a certain flow rate to obtain a second reaction liquid, and after a certain time interval after the second reaction liquid is formed, transferring the second reaction liquid to the third reactor at a certain flow rate to obtain a third reaction liquid; Step 3, transferring the third reaction liquid into the fourth kettle at a certain flow rate, and at the same time starting the quenching liquid pump to pump the quenching liquid into the fourth kettle to mix the quenching liquid with the third reaction liquid to form a quenched reaction mixture.

2. The method for preparing bisphenol nitro compounds by using a continuous tank reactor according to claim 1, Features: Wherein, the continuous tank reactor further comprises: an inert gas supply part, connected to the first reaction kettle through an inert gas supply pipe, and used for providing inert gas into the first reaction kettle; The collecting kettle is connected to the fourth kettle and is used to receive the quenched reaction mixture.

3. The method for preparing bisphenol nitro compounds by using a continuous tank reactor according to claim 1, characterized in that: in, The inner diameter of the first connecting tube and / or the second connecting tube is 4-6 mm.

4. The method for preparing bisphenol nitro compounds by using a continuous tank reactor according to claim 1, characterized in that: in, When the bisphenol compound is 2,2-bis(4-hydroxyphenyl)propane, the bisphenol nitro compound is 2,2-bis(4-hydroxy-3-nitrophenyl)propane; When the bisphenol compound is 4,4'-dihydroxydiphenyl sulfone, the bisphenol nitro compound is 4-(4-hydroxy-3-nitrobenzenesulfonyl)-2-nitrophenol; When the bisphenol compound is 2,2-bis(4-hydroxyphenyl)hexafluoropropane, the bisphenol nitro compound is 2,2-bis(4-hydroxy-3-nitrophenyl)hexafluoropropane; When the bisphenol compound is 1,1'-bis(4-hydroxyphenyl)cyclohexane, the bisphenol nitro compound is 1,1'-bis(4-hydroxy-3-nitrophenyl)cyclohexane.

5. The method for preparing bisphenol nitro compounds by using a continuous tank reactor according to claim 1, characterized in that: in, The bisphenol compound solution consists of bisphenol compounds, dichloromethane and acetic acid. Wherein, the mixed acid solution includes nitric acid and acetic acid.

6. The method for preparing bisphenol nitro compounds by using a continuous tank reactor according to claim 5, characterized in that: in, The bisphenol compound solution consists of 1 part of bisphenol compound, 2.5-3.5 parts of dichloromethane and 2.5-3.5 parts of acetic acid by weight.

7. The method for preparing bisphenol nitro compounds by using a continuous tank reactor according to claim 1, characterized in that: in, The molar ratio of the bisphenol compound to nitric acid is 1:(1.5-2.5).

8. The method for preparing bisphenol nitro compounds by using a continuous tank reactor according to claim 1, characterized in that: in, The mixed acid kettle is used to contain a mixed acid solution, and the mixed acid solution includes nitric acid and acetic acid.

9. The method for preparing bisphenol nitro compounds by using a continuous tank reactor according to claim 8, characterized in that: in, The nitric acid solution consists of 0.8-0.9 parts of 60wt%-70wt% nitric acid aqueous solution and 1.5-2.5 parts of acetic acid in parts by weight.

10. The method for preparing bisphenol nitro compounds by using a continuous tank reactor according to claim 1, characterized in that: in, The method for preparing bisphenol compounds by nitration reaction using the continuous tank reactor also includes the following steps: Step 4, transferring the quenched reaction mixture to a centrifugal device, centrifuging, filtering, and washing to obtain a solid.

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  • Continuous reaction or separation equipment

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