CN116768766B - Preparation method of 4,4' -dichlorodiphenyl sulfone - Google Patents
Preparation method 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 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 4-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(S(Cl)(=O)=O)C=C1 ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000047 product Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 238000004321 preservation Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000003930 superacid Substances 0.000 claims description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
- 238000005406 washing Methods 0.000 abstract description 9
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 abstract 1
- 231100000086 high toxicity Toxicity 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 239000002244 precipitate Substances 0.000 description 15
- 238000000227 grinding Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 230000009471 action Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 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
- 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
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method 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
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 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
- 239000000463 material 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
- 239000002245 particle Substances 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
- 238000011112 process operation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin 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
Abstract
The invention discloses a preparation method of 4,4' -dichlorodiphenyl sulfone, which comprises the following steps: mixing chlorobenzene and solid super acidic catalyst uniformly, adding p-chlorobenzenesulfonyl chloride in batches at a temperature of 20-40 ℃, after the p-chlorobenzenesulfonyl chloride is added completely, raising the system temperature to 40-60 ℃ for heat preservation reaction for 3-6 hours, filtering and recovering the solid super acidic catalyst at 40-60 ℃ after the reaction is finished, and washing filtrate, crystallizing, filtering and drying to obtain the product 4,4' -dichlorodiphenyl sulfone. According to the method, chlorobenzene and p-chlorobenzenesulfonyl chloride are used as raw materials, and 4,4' -dichlorodiphenyl sulfone is obtained through one-step reaction under the catalysis of a solid super acidic catalyst. The method of the invention avoids the use of raw materials such as sulfuric acid, dimethyl sulfate, thionyl chloride and the like, solves the problems of large amount of waste acid, harsh reaction conditions, high toxicity of raw materials and the like generated in the traditional process, and is a green synthesis process particularly suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a preparation method 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 the preparation method of the 4,4' -dichlorodiphenyl sulfone, which has the advantages of simple and easily obtained raw materials, simple working procedures, mild reaction conditions, high product purity and high yield.
The invention is realized by the following technical scheme:
a method for preparing 4,4' -dichlorodiphenyl sulfone, comprising the following steps:
mixing chlorobenzene and solid super acidic catalyst uniformly, adding p-chlorobenzenesulfonyl chloride in batches at a temperature of 20-40 ℃, after the p-chlorobenzenesulfonyl chloride is added completely, raising the system temperature to 40-60 ℃ for heat preservation reaction for 3-6 hours, filtering and recovering the solid super acidic catalyst at 40-60 ℃ after the reaction is finished, and washing filtrate, crystallizing, filtering and drying to obtain the target product 4,4' -dichlorodiphenyl sulfone.
Preferably, the solid super acid catalyst is selected from one or more of SO4 2-/TiO2、SO4 2-/CoFe2O4、SO4 2-/Fe2O3 and SO 4 2-/ZrO2, and more preferably SO 4 2-/TiO2.
The solid superacid catalyst of the invention can be obtained commercially or by homemade preparation. The invention provides a preparation method of a solid super acidic catalyst.
The solid superacid catalyst SO 4 2-/TiO2 can be prepared by the following method: adding 12-16% ammonia water into TiCl 4 solution for hydrolysis until the pH value of the solution is 9-10, generating white precipitate, aging for 3-5h, performing suction filtration, drying under an infrared lamp for 6-8 h, and grinding to obtain powdery TiO 2 with the particle size smaller than 200 meshes; the obtained TiO 2 powder is soaked in 0.1-0.2mol/L H 2SO4 solution at the ratio of 10-20mL/g for 10-15H, and is dried by an infrared lamp after suction filtration, and is activated for 2-3H at 450-500 ℃ in a muffle furnace to obtain the solid super acid catalyst SO 4 2-/TiO2.
The solid superacid catalyst SO 4 2-/CoFe2O4 can be prepared by the following method: taking a proper amount of 0.5mol/L ferric trichloride solution, adding Co (NO 3) 2 solution (the mass ratio of substances is nFe: nCo =2:1) and a certain amount of organic alcohol, stirring, slowly dropwise adding 12-16% ammonia water at the constant temperature of 60-80 ℃, when the pH value of the system is 9-10, standing for 8-12h until the precipitation is complete, filtering, and washing the precipitate until NO chloride ions exist. And (3) drying the precipitate in a human oven at 100-120 ℃ for 8-12h, cooling, and grinding to be less than 200 meshes to obtain a CoFeO (OH) 2 precursor powder sample. Then adding 10-20mL of 20-40% ammonium sulfate solution into each gram of CoFeO (OH) 2 for dipping treatment, and carrying out suction filtration after 8-12 hours. And drying the obtained sample under an infrared lamp, grinding, and then placing the dried sample in a muffle furnace for activation for 2-3h at 450-500 ℃ to obtain the solid super-acidic catalyst SO 4 2-/CoFe2O4.
The solid superacid catalyst SO 4 2-/Fe2O3 can be prepared by the following method: adding proper amount of 1mol/LFe (NO 3)3) into 8-12% ammonia water containing a certain amount of organic alcohol slowly, regulating pH to 9-10 to obtain Fe (OH) 3·nH2 O precipitate, aging at-5 ℃ for 18-24H, washing with distilled water until NO NH 4 + is detected, drying the precipitate at 80-100 ℃ and grinding to below 200 meshes to obtain amorphous Fe 2O3, soaking Fe 2O3 with 0.2-0.3mol/L H 2SO4 solution for 1-2H according to 15mL/g ratio, filtering, drying at 100-120 ℃ for 18-24H, and activating at 450-500 ℃ for 2-3H to obtain solid super acid catalyst SO 4 2-/Fe2O3 .
The solid superacid catalyst SO 4 2-/ZrO2 can be prepared by the following method: adding proper amount of 1mol/L Zr (NO 3)4) into 8-12% ammonia water containing a certain amount of organic alcohol slowly, regulating pH to 9-10 to obtain Zr (OH) 4·nH2 O precipitate, aging 18-24H at-5 ℃, washing with distilled water until NO NH 4 + is detected, drying the precipitate at 80-100 ℃ and grinding to below 200 meshes to obtain ZrO 2, soaking ZrO 2 in 4-5mol/L H 2SO4 solution for 1-2H respectively according to 15mL/g ratio, filtering, drying at 100-120 ℃ for 18-24H, and activating at 450-500 ℃ for 2-3H to obtain solid super acid catalyst SO 4 2-/ ZrO2 .
Preferably, the mass ratio of the chlorobenzene to the p-chlorobenzenesulfonyl chloride is (2-3): 1.
Preferably, the addition amount of the solid super acid catalyst is 1-2% of the mass of chlorobenzene.
Preferably, the mass of each addition of the p-chlorobenzenesulfonyl chloride is 10-20% of the total mass of the p-chlorobenzenesulfonyl chloride.
Preferably, the reaction temperature is 45-55 ℃.
As a preferable implementation mode, after the reaction is finished, slowly adding water into the system at the temperature of filtrate being less than 70 ℃, then preserving heat and stirring for 1-2 hours at 60-70 ℃, standing and layering, separating liquid while the liquid is hot, preserving a layer of organic layer, cooling and crystallizing, filtering at 0-10 ℃ to obtain white solid, and drying at 80-100 ℃ to obtain the target product 4,4' -dichlorodiphenyl sulfone.
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:
The invention adopts chlorobenzene and p-chlorobenzenesulfonyl chloride as raw materials, and the raw materials are reacted in one step under the catalysis of a solid super acidic catalyst to obtain 4,4' -dichlorodiphenyl sulfone.
The solid superacid catalytic reaction process of the invention greatly reduces the content of isomer 2, 4-dichlorodiphenyl sulfone, and the prepared product can meet the market demand without further refining treatment.
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 solid superacid catalysts used in the examples and comparative examples of the present invention were prepared by the following method:
Preparation of solid superacid catalyst SO 4 2-/TiO2: adding 14% ammonia water into TiCl 4 solution for hydrolysis until the pH value of the solution is 9, generating white precipitate, aging for 4 hours, carrying out suction filtration, washing the precipitate with distilled water until no Cl - exists, drying 6h under an infrared lamp, and grinding to obtain 100-mesh powdery TiO 2; the obtained TiO 2 powder is soaked in 0.15mol/L H 2SO4 solution for 15H according to the proportion of 15 mL/g, and is dried by an infrared lamp after suction filtration, and is activated for 3H at 470 ℃ in a muffle furnace, SO that the solid super acid catalyst SO 4 2-/TiO2 is obtained.
Preparation of solid superacid catalyst SO 4 2-/CoFe2O4: adding 1L of 0.5mol/L ferric trichloride solution into 1L of 0.25mol/L Co (NO 3）2 solution (the mass ratio of substances is nFe: nCo =2:1) and 200mL of n-propanol, stirring, slowly dropwise adding 12% ammonia water at a constant temperature of 70 ℃, standing for 12 hours when the pH value of the system is 9.0 till the precipitation is complete, filtering, washing the precipitate until NO chloride ions exist, putting the precipitate into an oven at 120 ℃ for drying for 12 hours, cooling, grinding to 100 meshes to obtain a CoFeO (OH) 2 precursor powder sample, adding 15mL of 40% ammonium sulfate solution per gram of CoFeO (OH) 2 for soaking for 12 hours, carrying out suction filtration, drying the obtained sample under an infrared lamp, grinding, and then placing the sample into a muffle furnace for activation for 3 hours at 470 ℃ to obtain a solid super acid catalyst SO 4 2-/CoFe2O4.
Preparation of solid superacid catalyst SO 4 2-/Fe2O3: adding proper amount of 1mol/LFe (NO 3)3) slowly into 10% ammonia water containing a certain amount of organic alcohol, regulating pH to 10 to obtain Fe (OH) 3·nH2 O precipitate, aging at 0 ℃ for 20H, washing with distilled water until NO NH 4 + is detected, drying the precipitate at 90 ℃ and grinding to 100 meshes to obtain amorphous Fe 2O3, soaking Fe 2O3 with 0.3mol/L H 2SO4 solution for 1H according to 15mL/g ratio, filtering, drying at 120 ℃ for 20H, and activating at 470 ℃ for 2H to obtain the catalyst SO 4 2-/Fe2O3.
The preparation of solid superacid catalyst SO 4 2-/ZrO2 comprises slowly adding proper amount of 1mol/L Zr (NO 3)4) into 10% ammonia water containing a certain amount of n-propanol, adjusting pH to 10 to obtain Zr (OH) 4·nH2 O precipitate, aging at 0deg.C for 20H, washing with distilled water until NO NH 4 + is detected, drying the precipitate at 90deg.C and grinding to 100 mesh to obtain ZrO 2, soaking ZrO 2 in 5mol/L H 2SO4 solution respectively at 15mL/g ratio for 2H, filtering, drying at 120deg.C for 20H, and activating at 470 deg.C for 3H to obtain catalyst SO 4 2-/ ZrO2 .
Other 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;
p-chlorobenzenesulfonyl chloride: 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
500G of chlorobenzene is added into a 1L four-mouth bottle, 4 2-/TiO2 g of solid super acid catalyst SO is stirred for 30 minutes at 20-25 ℃, 211.1g of p-chlorobenzenesulfonyl chloride is added in batches at the temperature of 20-40 ℃ under control (the addition amount of each time is about 20 percent of the total amount of the p-chlorobenzenesulfonyl chloride), after the p-chlorobenzenesulfonyl chloride is fully added, the temperature of the system is raised to 50 ℃ for heat preservation reaction for 4 hours, after the reaction is finished, 200g of water is slowly added into the filtrate under 50 ℃ and the control temperature of the system is controlled to be less than 70 ℃, then the temperature is kept to be 65 ℃ for 1 hour, the mixture is stirred for layering while the mixture is hot, a layer of organic layer is reserved, the mixture is cooled and crystallized, the mixture is filtered at 5 ℃ to obtain white solid, the white solid is dried at 80 ℃, 262.8g of 4,4' -dichlorodiphenyl sulfone is obtained, the yield is 91.5%, the liquid phase detection content is 99.77%, the melting point is 148.8 ℃, and the isomer 2, 4-dichlorodiphenyl sulfone content is 0.14%.
Example 2
The difference from example 1 is that the reaction temperature is 40 ℃, other conditions are the same, 255.2g of target product 4.4' -dichlorodiphenyl sulfone is obtained, the yield is 88.9%, the liquid phase detection content is 99.68%, the melting point is 148.2 ℃, and the isomer 2, 4-dichlorodiphenyl sulfone content is 0.23%.
Example 3
The difference from example 1 is that the reaction temperature is 60℃and other conditions are the same, and the target product 4,4' -dichlorodiphenyl sulfone 261.0g is obtained, the yield is 90.9%, the liquid phase detection content is 99.27%, the melting point is 147.5℃and the isomer 2, 4-dichlorodiphenyl sulfone content is 0.61%.
Example 4
The difference with example 1 is that the catalyst adopts the same amount of solid super acid SO 4 2-/CoFe2O4, the reaction condition is the same, 261.9g of target product 4,4' -dichloro diphenyl sulfone is prepared, the yield is 91.2%, the liquid phase detection content is 99.70%, the melting point is 148.6 ℃, and the isomer 2, 4-dichloro diphenyl sulfone content is 0.19%.
Example 5
The difference with example 1 is that the catalyst adopts the same amount of solid super acid SO 4 2-/Fe2O3, the reaction condition is the same, the yield of the target product 4,4' -dichlorodiphenyl sulfone 261.2g is 90.9%, the liquid phase detection content is 99.63%, the melting point is 148.5 ℃, and the isomer 2, 4-dichlorodiphenyl sulfone content is 0.21%.
Example 6
The difference with example 1 is that the catalyst adopts the same amount of solid super acid SO 4 2-/ZrO2, the reaction condition is the same, 261.6g of target product 4,4' -dichlorodiphenyl sulfone is prepared, the yield is 91.1%, the liquid phase detection content is 99.71%, the melting point is 148.5 ℃, and the isomer 2, 4-dichlorodiphenyl sulfone content is 0.19%.
Example 7
Adding 600g of chlorobenzene into a 1L four-mouth bottle, stirring for 30 minutes at 20-25 ℃ by using a solid superacid catalyst SO 4 2-/TiO2 g, adding 211.1g of p-chlorobenzenesulfonyl chloride in batches at a temperature of 20-40 ℃ under control of the temperature (the addition amount of each time is about 10 percent of the total amount of the p-chlorobenzenesulfonyl chloride), raising the system temperature to 45 ℃ after the complete addition of the p-chlorobenzenesulfonyl chloride, carrying out heat preservation for 6 hours, after the reaction is finished, carrying out suction filtration at 45 ℃ to recycle the solid superacid catalyst, slowly adding 200g of water into the filtrate, controlling the system to a temperature of less than 70 ℃, then carrying out heat preservation for 1 hour, stirring at 65 ℃, layering while the mixture is hot, keeping a layer of organic layers, cooling and crystallizing, filtering at 5 ℃ to obtain white solid, drying at 80 ℃ to obtain 262.4g of target product, wherein the yield is 91.4%, the liquid phase detection content is 99.75%, and the isomer 2, 4-dichlorodiphenyl sulfone content is 0.16%.
Comparative example 1
The difference from example 1 is that 211.1g of p-chlorobenzenesulfonyl chloride is added for 2 times on average, the system temperature is up to 80 ℃, after all the p-chlorobenzenesulfonyl chloride is added, the system temperature is controlled to be 50 ℃, the temperature is kept for 4 hours, and other conditions are the same, so that 251.3g of target product 4,4' -dichlorodiphenyl sulfone is prepared, the yield is 87.5%, the liquid phase detection content is 97.17%, the melting point is 145.8 ℃, and the isomer 2, 4-dichlorodiphenyl sulfone content is 2.65%.
Comparative example 2
The difference from example 1 is that the reaction temperature is 70℃and other conditions are the same, and the target product 4,4' -dichlorodiphenyl sulfone 245.9g is obtained, the yield is 85.6%, the liquid phase detection content is 96.35%, the melting point is 144.6℃and the isomer 2, 4-dichlorodiphenyl sulfone content is 3.31%.
Claims (4)
1. The preparation method of the 4,4' -dichloro diphenyl sulfone is characterized by comprising the following steps: mixing chlorobenzene and solid super acidic catalyst uniformly, adding p-chlorobenzenesulfonyl chloride in batches at a temperature of 20-40 ℃, after the p-chlorobenzenesulfonyl chloride is added completely, raising the system temperature to 40-60 ℃ for heat preservation reaction for 3-6 hours, filtering and recovering the solid super acidic catalyst at 40-60 ℃ after the reaction is finished, slowly adding water into the system at a filtrate temperature of less than 70 ℃, then stirring for 1-2 hours at a temperature of 60-70 ℃, standing for layering, separating liquid while hot, keeping a layer of organic layer, cooling for crystallization, filtering at 0-10 ℃ to obtain white solid, and drying at a temperature of 80-100 ℃ to obtain the target product 4,4' -dichlorodiphenyl sulfone;
The solid super acid catalyst is selected from one or more of SO4 2-/TiO2、SO4 2-/CoFe2O4、SO4 2-/Fe2O3 and SO 4 2-/ZrO2, and the addition amount of the solid super acid catalyst is 1% -2% of the mass of chlorobenzene;
The mass of each addition of the p-chlorobenzenesulfonyl chloride is 10-20% of the total mass of the p-chlorobenzenesulfonyl chloride.
2. The method for preparing 4,4' -dichlorodiphenyl sulfone according to claim 1, wherein the solid super acid catalyst is selected from SO 4 2-/TiO2.
3. The method for producing 4,4' -dichlorodiphenyl sulfone according to claim 1, wherein the mass ratio of chlorobenzene to p-chlorobenzenesulfonyl chloride is (2-3): 1.
4. The process for preparing 4,4' -dichlorodiphenyl sulfone according to claim 1, wherein the reaction temperature is 45-55 ℃.
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