CN116715612A - Continuous flow production process of 4,4' -dichlorodiphenyl sulfone - Google Patents
Continuous flow production process of 4,4' -dichlorodiphenyl sulfone Download PDFInfo
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- dichlorodiphenyl sulfone
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- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 32
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 26
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 229940098779 methanesulfonic acid Drugs 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 9
- 239000012044 organic layer Substances 0.000 claims description 6
- 238000005112 continuous flow technique Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000413 hydrolysate Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 2
- 108010009736 Protein Hydrolysates Proteins 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 29
- 239000011521 glass Substances 0.000 description 11
- 238000001514 detection method Methods 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 3
- RJWBTWIBUIGANW-UHFFFAOYSA-N 4-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C=C1 RJWBTWIBUIGANW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 4-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(S(Cl)(=O)=O)C=C1 ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 229940008406 diethyl sulfate Drugs 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a continuous flow production process of 4,4' -dichlorodiphenyl sulfone, which comprises the following steps: (1) Mixing chlorobenzene and methanesulfonic acid uniformly at 20-25 ℃ to obtain a solution A; (2) Dropwise adding sulfur trioxide into dimethyl sulfate to obtain a solution B; (3) And (3) conveying the solution A and the solution B into a silicon carbide microchannel reactor by adopting a first feed pump and a second feed pump respectively for reaction, receiving materials at an outlet of the reactor into a reaction container, and carrying out hydrolysis, cooling crystallization, filtration and drying to obtain the product 4,4' -dichlorodiphenyl sulfone. According to the method, chlorobenzene, sulfur trioxide, dimethyl sulfate and methylsulfonic acid are used as raw materials, the solution A and the solution B are prepared, and simultaneously the solution A and the solution B are introduced into the silicon carbide microchannel reactor for continuous reaction to obtain the 4,4' -dichlorodiphenyl sulfone.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a continuous flow production process of 4,4' -dichlorodiphenyl sulfone.
Background
The 4,4' -dichloro diphenyl sulfone (DDS for short) is an important organic synthesis product, is a main raw material for manufacturing engineering plastics such as polysulfone, polyethersulfone and the like (such as bisphenol A type polysulfone, polyphenylether sulfone, polyamide sulfone and other resins), is also an intermediate of medicines, dyes, pesticides and the like, and has wide application in the fields of engineering plastics, fine chemical engineering and the like.
At present, the synthesis method of 4,4' -dichloro diphenyl sulfone mainly comprises the following steps:
(1) Chlorosulfonic acid method: chlorobenzene, sulfuric acid and chlorosulfonic acid are used as main raw materials, chlorobenzene and sulfuric acid react at high temperature to generate p-chlorobenzenesulfonic acid, then the p-chlorobenzenesulfonyl chloride is generated by reacting with chlorosulfonic acid under the action of a catalyst, and then the p-chlorobenzenesulfonyl chloride reacts with chlorobenzene to generate the product 4,4' -dichlorodiphenyl sulfone. The method has the advantages of complicated synthetic route, complex process, multiple devices, high cost and environment pollution caused by a large amount of acid gas generated by reaction.
The reaction equation is:
(2) Diethyl sulfate process: US 341687 describes a process for the synthesis of 4,4' -dichlorodiphenyl sulfone starting from sulfur trioxide, diethyl sulfate and chlorobenzene, which process is prone to the production of the isomer 2, 4-dichlorodiphenyl sulfone, has a poor selectivity, a low product content and a difficult purification.
The reaction equation is:
(3) Sulfuric acid process: the method takes chlorobenzene and sulfuric acid as raw materials to sulfonate and synthesize p-chlorobenzenesulfonic acid, and then the p-chlorobenzenesulfonic acid is condensed with excessive chlorobenzene to obtain the product 4,4' -dichlorodiphenyl sulfone. The method has the advantages of 46-47% of yield, lower yield, reaction temperature higher than 200 ℃, serious equipment corrosion, poor crude product purity, deep color and the like, and can obtain a qualified product only by refining and decoloring.
The reaction equation is:
(4) Sulfoxide chloride process: performing Friedel-crafts reaction on chlorobenzene and thionyl chloride under the action of a catalyst, purifying to obtain 4,4' -dichlorobenzene sulfoxide, dissolving the 4,4' -dichlorobenzene sulfoxide in glacial acetic acid, and oxidizing the solution by hydrogen peroxide to obtain the product 4,4' -dichlorobenzene sulfone. The Friedel-crafts reaction method generates a large amount of hydrogen chloride gas, aluminum trichloride and thionyl chloride are decomposed to generate a large amount of sulfur dioxide gas, the environmental pollution is serious, and the aluminum trichloride treatment generates a large amount of high COD wastewater which is difficult to treat.
The reaction equation is as follows:
the existing synthesis method of 4,4' -dichlorodiphenyl sulfone has the problems of complex process operation, high raw material toxicity, serious environmental pollution, severe reaction conditions, serious equipment corrosion, low product yield and the like.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a continuous flow production process of 4,4' -dichlorodiphenyl sulfone, which has the advantages of simple and easily obtained raw materials, simple procedure operation, controllable reaction process, high product purity and high yield.
The invention is realized by the following technical scheme:
a continuous flow process for producing 4,4' -dichlorodiphenyl sulfone, comprising the steps of:
(1) Mixing chlorobenzene and methanesulfonic acid uniformly at 20-25 ℃ to obtain a solution A;
(2) Dropwise adding sulfur trioxide into dimethyl sulfate, and stirring at 40-60 ℃ for 2-4 hours to obtain a solution B;
(3) And conveying the solution A to a silicon carbide micro-channel reactor by adopting a first feed pump, conveying the solution B to the silicon carbide micro-channel reactor by adopting a second feed pump, controlling the temperature of the silicon carbide micro-channel reactor to be 40-60 ℃, and controlling the volume flow rate ratio of the first feed pump to the second feed pump to be (2.58-3.45): 1, receiving the materials at the outlet of the reactor into a reaction vessel, adding a hydrolysate to hydrolyze, separating a water layer after the hydrolysis is completed, cooling an organic layer to 5-10 ℃ to precipitate crystals, filtering, and drying to obtain the product 4,4' -dichlorodiphenyl sulfone.
Preferably, the mass of the methylsulfonic acid in the step (1) is 1% -3% of the mass of the chlorobenzene.
Preferably, the mass ratio of sulfur trioxide to dimethyl sulfate in the step (2) is (0.9-1.1): 1.
preferably, in the step (3), the temperature of the silicon carbide micro-channel reactor is controlled to be 48-52 ℃.
Preferably, the reaction mass is held in the silicon carbide microchannel for a residence time of 9 to 11 minutes. The invention can control the residence time of the reaction liquid in the reaction tube by adjusting the flow of the feed pump.
Preferably, the volumetric flow rate of the first feed pump in the step (3) is controlled to be 800-1000mL/min; the volumetric flow rate of the second feed pump was controlled between 290-310mL/min.
Preferably, the hydrolysate is prepared from chlorobenzene and water according to a mass ratio of 1: (1-1.5).
Preferably, the hydrolysis step comprises: after the hydrolysate is added, the temperature is raised to 70-90 ℃ and stirred for 2-4 hours to hydrolyze. Further, the hydrolysis temperature is preferably 75 to 85 ℃.
The reaction equation of the preparation method of 4,4' -dichlorodiphenyl sulfone is as follows:
compared with the prior art, the invention has the following beneficial effects:
according to the method, chlorobenzene, sulfur trioxide, dimethyl sulfate and methylsulfonic acid are used as raw materials, the solution A and the solution B are prepared, and simultaneously the solution A and the solution B are introduced into the silicon carbide microchannel reactor for continuous reaction to obtain the 4,4' -dichlorodiphenyl sulfone.
The method can effectively inhibit the formation of isomer 2, 4-dichlorodiphenyl sulfone, and has high product yield and purity.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by those skilled in the art without departing from the spirit of the invention, which falls within the scope of the invention.
The reagents used in the examples and comparative examples of the present invention are all commercially available, but are not limited to these materials.
Chlorobenzene: shanghai Miclin Biochemical technologies Co., ltd;
sulfur trioxide: cucurbit island brocade petrochemical industry products trade company;
dimethyl sulfate: shanghai Miclin Biochemical technologies Co., ltd;
methanesulfonic acid: shanghai Miclin Biochemical technologies Co., ltd;
the method for testing the purity of the product comprises the following steps:
the device comprises: high performance liquid chromatography, ultraviolet detector, electronic balance precision 0.1mg;
chromatographic column: nucleosil C18, 150mm 4.6mm 5um;
mobile phase: acetonitrile: methanol: water = 2:1:1;
analysis conditions: the flow rate is 0.5ml/min, the column temperature is 30 ℃, the wavelength is 260nm, the sample injection is 1ul, and the time is 40min;
the sample was fixed to a volume of 10ml with acetonitrile at 0.04 g.
Example 1
(1) 20kg of chlorobenzene and 0.2kg of methylsulfonic acid are added into a 50L glass kettle A, and the mixture is stirred for 30 minutes at 25 ℃ to be uniformly mixed to obtain a solution A;
(2) Adding 5kg of dimethyl sulfate into a 50L glass kettle B, slowly dropwise adding 5kg of liquid sulfur trioxide for about 3 hours, and then stirring at 50 ℃ for 2 hours to obtain a solution B;
(3) The method comprises the steps of adopting a silicon carbide micro-channel reactor with a pipeline volume of 12L, conveying a solution A to the silicon carbide micro-channel reactor at a volume flow rate of 900mL/min by a first feed pump, conveying a solution B to the silicon carbide micro-channel reactor at a volume flow rate of 300mL/min by a second feed pump, controlling the reaction temperature of materials in the silicon carbide micro-channel reactor at 50 ℃, keeping the reaction materials in the silicon carbide micro-channel for 10 minutes, receiving materials at an outlet of the reactor into a 100L glass reaction kettle C, adding 25kg of water and 20kg of chlorobenzene, heating to 80 ℃ and stirring for 2 hours, removing a lower layer of water, cooling and crystallizing an upper layer of organic layer, carrying out suction filtration at 5 ℃ to obtain white solid, drying at 80 ℃, and obtaining 7.03kg of 4,4' -dichlorodiphenyl sulfone, wherein the liquid phase detection content is 99.90%, the melting point is 148.8 ℃, and the isomer 2, 4-dichlorodiphenyl sulfone content is 0.07%.
Example 2
The difference with example 1 is that the reaction temperature of the materials in the silicon carbide micro-channel reactor is controlled to be 40 ℃, other conditions are the same, 6.58kg of target product 4,4' -dichlorodiphenyl sulfone is prepared, the liquid phase detection content is 99.86%, the melting point is 148.7 ℃, and the isomer 2, 4-dichlorodiphenyl sulfone content is 0.08%.
Example 3
The difference with example 1 is that the reaction temperature of the materials in the silicon carbide micro-channel reactor is controlled to be 60 ℃, other conditions are the same, 6.24kg of target product 4,4' -dichlorodiphenyl sulfone is prepared, the liquid phase detection content is 99.73%, the melting point is 148.4 ℃, and the isomer 2, 4-dichlorodiphenyl sulfone content is 0.20%.
Example 4
(1) 20kg of chlorobenzene and 0.5kg of methylsulfonic acid are added into a 50L glass kettle A, and the mixture is stirred for 30 minutes at 25 ℃ to be uniformly mixed to obtain a solution A;
(2) 5kg of dimethyl sulfate is added into a 50L glass kettle B, 5.5kg of liquid sulfur trioxide is slowly dripped, after the dripping is completed for about 3 hours, the mixture is stirred at 50 ℃ for 2 hours, and a solution B is obtained;
(3) Adopting a silicon carbide micro-channel reactor with the pipe volume of 12L, conveying a solution A to the silicon carbide micro-channel reactor at the volume flow of 1000mL/min by a first feeding pump, conveying a solution B to the silicon carbide micro-channel reactor at the volume flow of 290mL/min by a second feeding pump, controlling the reaction temperature of materials in the silicon carbide micro-channel reactor at 52 ℃, keeping the reaction materials in the silicon carbide micro-channel for 9 minutes, receiving materials at an outlet of the reactor into a 100L glass reaction kettle C, adding 25kg of water and 20kg of chlorobenzene, heating to 75 ℃ and stirring for 2 hours, removing a lower layer of water, cooling and crystallizing an upper layer of organic layer, carrying out suction filtration at 5 ℃ to obtain white solid, drying at 80 ℃, and obtaining 6.98kg of 4,4' -dichlorodiphenyl sulfone, the liquid phase detection content of 99.87%, the melting point of 148.5 ℃ and the isomer 2, 4-dichlorodiphenyl sulfone content of 0.10%.
Example 5
(1) 20kg of chlorobenzene and 0.2kg of methylsulfonic acid are added into a 50L glass kettle A, and the mixture is stirred for 30 minutes at 25 ℃ to be uniformly mixed to obtain a solution A;
(2) 5kg of dimethyl sulfate is added into a 50L glass kettle B, 4.5kg of liquid sulfur trioxide is slowly dripped, after the dripping is completed for about 3 hours, the mixture is stirred at 50 ℃ for 2 hours, and a solution B is obtained;
(3) Adopting a silicon carbide micro-channel reactor with the pipe volume of 12L, conveying a solution A to the silicon carbide micro-channel reactor at the volume flow rate of 800mL/min by a first feeding pump, conveying a solution B to the silicon carbide micro-channel reactor at the volume flow rate of 310mL/min by a second feeding pump, controlling the reaction temperature of materials in the silicon carbide micro-channel reactor at 48 ℃, keeping the reaction materials in the silicon carbide micro-channel for 11 minutes, receiving materials at an outlet of the reactor into a 100L glass reaction kettle C, adding 25kg of water and 20kg of chlorobenzene, heating to 85 ℃ and stirring for 2 hours, removing a lower layer of water, cooling and crystallizing an upper layer of organic layer, carrying out suction filtration at 5 ℃ to obtain white solid, drying at 80 ℃, and obtaining 7.05kg of 4,4' -dichlorodiphenyl sulfone, wherein the liquid phase detection content is 99.82%, the melting point is 148.3 ℃, and the isomer 2, 4-dichlorodiphenyl sulfone content is 0.16%.
Comparative example 1
The difference with example 1 is that the reaction temperature of the materials in the silicon carbide micro-channel reactor is controlled to be 30 ℃, other conditions are the same, 3.62kg of target product 4,4' -dichlorodiphenyl sulfone is prepared, the liquid phase detection content is 99.70%, the melting point is 148.5 ℃, and the isomer 2, 4-dichlorodiphenyl sulfone content is 0.23%.
Comparative example 2
The difference with example 1 is that the reaction temperature of the materials in the silicon carbide micro-channel reactor is controlled to be 70 ℃, other conditions are the same, 4.72kg of target product 4,4' -dichlorodiphenyl sulfone is prepared, the liquid phase detection content is 96.85%, the melting point is 146.3 ℃, and the isomer 2, 4-dichlorodiphenyl sulfone content is 3.02%.
Comparative example 3
The difference with example 1 is that the volume flow rate of the solution A feed is 1000mL/min, the volume flow rate of the solution B feed is 200mL/min, and the other conditions are the same, so that 4.26kg of target product 4,4' -dichlorodiphenyl sulfone is prepared, the liquid phase detection content is 99.89%, the melting point is 148.8 ℃, and the isomer 2, 4-dichlorodiphenyl sulfone content is 0.09%.
Comparative example 4
The difference with example 1 is that the volume flow rate of the solution A feed is 800mL/min, the volume flow rate of the solution B feed is 400mL/min, and other conditions are the same, so that 5.75kg of target product 4,4' -dichlorodiphenyl sulfone is prepared, the liquid phase detection content is 96.33%, the melting point is 146.0 ℃, and the isomer 2, 4-dichlorodiphenyl sulfone content is 3.47%.
Comparative example 5
5kg of dimethyl sulfate was added to 50L of glass kettle B, 5kg of liquid sulfur trioxide was slowly dropped, the dropping was completed for about 3 hours, and then stirred at 50℃for 2 hours to obtain solution B. Adding 20kg of chlorobenzene and 0.2kg of methanesulfonic acid into another 100L glass reaction kettle, stirring for 30 minutes at 25 ℃ to uniformly mix the materials to obtain a solution A, dropwise adding the solution B into the solution A at 48-52 ℃ for 3-4 hours, stirring for 4 hours at 50 ℃ after the dropwise adding, adding 25kg of water, 20kg of chlorobenzene, heating to 80 ℃ and stirring for 2 hours, separating a lower layer of water, cooling an upper organic layer for crystallization, carrying out suction filtration at 5 ℃ to obtain a white solid, and drying at 80 ℃ to obtain 5.82kg of 4,4' -dichlorodiphenyl sulfone, wherein the liquid phase detection content is 99.66%, the melting point is 148.1 ℃, and the isomer 2, 4-dichlorodiphenyl sulfone content is 0.32%.
Claims (8)
1. A continuous flow process for the production of 4,4' -dichlorodiphenyl sulfone comprising the steps of:
(1) Mixing chlorobenzene and methanesulfonic acid uniformly at 20-25 ℃ to obtain a solution A;
(2) Dropwise adding sulfur trioxide into dimethyl sulfate, and stirring at 40-60 ℃ for 2-4 hours to obtain a solution B;
(3) And conveying the solution A to a silicon carbide micro-channel reactor by adopting a first feed pump, conveying the solution B to the silicon carbide micro-channel reactor by adopting a second feed pump, controlling the temperature of the silicon carbide micro-channel reactor to be 40-60 ℃, and controlling the volume flow rate ratio of the first feed pump to the second feed pump to be (2.58-3.45): 1, receiving the materials at the outlet of the reactor into a reaction vessel, adding a hydrolysate to hydrolyze, separating a water layer after the hydrolysis is completed, cooling an organic layer to 5-10 ℃ to precipitate crystals, filtering, and drying to obtain the product 4,4' -dichlorodiphenyl sulfone.
2. The continuous flow production process of 4,4' -dichlorodiphenyl sulfone according to claim 1, wherein the mass of the methanesulfonic acid in the step (1) is 1% -3% of the mass of the chlorobenzene.
3. The continuous flow production process of 4,4' -dichlorodiphenyl sulfone according to claim 1, wherein the mass ratio of sulfur trioxide and dimethyl sulfate in the step (2) is (0.9-1.1): 1.
4. the continuous flow process for producing 4,4' -dichlorodiphenyl sulfone according to claim 1, wherein the silicon carbide micro-channel reactor temperature is controlled to 48-52 ℃ in the step (3).
5. The continuous flow process for producing 4,4' -dichlorodiphenyl sulfone according to claim 1, wherein the residence time of the reaction mass in the silicon carbide micro-channel is 9-11 minutes.
6. The continuous flow process for producing 4,4' -dichlorodiphenyl sulfone according to claim 1, wherein the volumetric flow rate of the first feed pump in step (3) is controlled to 800-1000mL/min; the volumetric flow rate of the second feed pump was controlled between 290-310mL/min.
7. The continuous flow production process of 4,4' -dichlorodiphenyl sulfone according to claim 1, wherein the hydrolysate is prepared from chlorobenzene and water according to a mass ratio of 1: (1-1.5).
8. The continuous flow production process of 4,4' -dichlorodiphenyl sulfone according to claim 1, wherein after adding the hydrolysate, heating to 70-90 ℃ and stirring for 2-4h to hydrolyze; preferably, the hydrolysis temperature is 75-85 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310570122.3A CN116715612A (en) | 2023-05-19 | 2023-05-19 | Continuous flow production process of 4,4' -dichlorodiphenyl sulfone |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566180A (en) * | 2015-12-14 | 2016-05-11 | 河北旭隆化工有限公司 | Preparation method of 4,4-dichlorodiphenyl sulfone |
| CN109912469A (en) * | 2019-03-15 | 2019-06-21 | 常州杰铭新材料科技有限公司 | A kind of preparation process of 4,4 '-dichloro diphenyl sulfones |
| CN113149870A (en) * | 2021-02-02 | 2021-07-23 | 武汉青江化工黄冈有限公司 | Synthesis method of 2,4, 5-trichlorobenzene sulfonic acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566180A (en) * | 2015-12-14 | 2016-05-11 | 河北旭隆化工有限公司 | Preparation method of 4,4-dichlorodiphenyl sulfone |
| CN109912469A (en) * | 2019-03-15 | 2019-06-21 | 常州杰铭新材料科技有限公司 | A kind of preparation process of 4,4 '-dichloro diphenyl sulfones |
| CN113149870A (en) * | 2021-02-02 | 2021-07-23 | 武汉青江化工黄冈有限公司 | Synthesis method of 2,4, 5-trichlorobenzene sulfonic acid |
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