CN115650888A - Preparation method of high-purity 4, 4-dichlorodiphenyl sulfone - Google Patents
Preparation method of high-purity 4, 4-dichlorodiphenyl sulfone Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 124
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000003756 stirring Methods 0.000 claims abstract description 51
- 239000000243 solution Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000012043 crude product Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004327 boric acid Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 25
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000012044 organic layer Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 3
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 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 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- RJWBTWIBUIGANW-UHFFFAOYSA-N 4-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C=C1 RJWBTWIBUIGANW-UHFFFAOYSA-N 0.000 description 1
- DFHHQOAUFAUQPV-UHFFFAOYSA-N ClC1=CC=C(C=C1)S(=O)(=O)O.[Cl] Chemical compound ClC1=CC=C(C=C1)S(=O)(=O)O.[Cl] DFHHQOAUFAUQPV-UHFFFAOYSA-N 0.000 description 1
- 206010024229 Leprosy Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006258 high performance thermoplastic Polymers 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000000704 physical effect Effects 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
- 238000004904 shortening Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application provides a preparation method of high-purity 4, 4-dichlorodiphenyl sulfone, relates to the technical field of 4, 4-dichlorodiphenyl sulfone synthesis, and comprises the following steps: dimethyl sulfate and sulfur trioxide are used as raw materials, and the dimethyl sulfate and the sulfur trioxide are mixed, wherein the mixing temperature is kept between 10 and 50 ℃; then adding a boric acid catalyst and continuously stirring for 0.5h to prepare a mixed solution of the pyrosulfate and the sulfur trioxide containing the boric acid catalyst; dripping the mixed solution into a chlorobenzene solution at the temperature of 10-50 ℃; continuously stirring after the dropwise adding is finished, keeping the stirring temperature at 15-50 ℃, and continuously stirring for 1.5h to prepare a crude product; washing the crude product, and drying by using an oven to prepare high-purity 4, 4-dichlorodiphenyl sulfone; the method has the advantages of short reaction flow, low temperature and pressure of each flow, effective simplification of the process flow, adoption of the boric acid catalyst, reaction temperature control and improvement of the reaction efficiency on the premise of reducing the generation of isomers.
Description
Technical Field
The invention relates to the technical field of synthesis of 4, 4-dichlorodiphenyl sulfone, in particular to a preparation method of high-purity 4, 4-dichlorodiphenyl sulfone.
Background
The statements herein merely provide background information related to the present application and may not necessarily constitute prior art.
4, 4-dichlorodiphenyl sulfone (also known as 4, 4-dichlorodiphenyl sulfone) and bis-p-chlorophenyl sulfone, with molecular formula C 12 H 8 C 12 O 2 S has a relative molecular weight of 287.2, is white monoclinic crystal in appearance, has a melting point of 148-149 ℃, can be sublimated, has a relative density of 1.54, is insoluble in water and is slightly soluble in ethanol. 4, 4-dichlorodiphenyl sulfone is a main raw material and an intermediate for manufacturing polysulfone engineering plastics and is also a raw material for synthesizing 4, 4-diaminodiphenyl sulfone which is a medicament for treating leprosy, and since polysulfone is an aromatic amorphous high-performance thermoplastic engineering plastic containing sulfone groups on a molecular main chain, the polysulfone engineering plastic has a plurality of industrially favored physical properties and is widely applied to the industries of electric appliances, electronics, automobiles, aerospace and medicines, and the demand of 4, 4-dichlorodiphenyl sulfone is more and more increased along with the rapid development of polysulfone resins;
at present, the synthesis method of 4, 4-dichlorodiphenyl sulfone mainly comprises the following steps:
1) A sulfuric acid method: the p-chlorobenzenesulfonic acid is prepared by sulfonating chlorobenzene with sulfuric acid, and then condensed with excessive chlorobenzene to synthesize the 4, 4-dichlorodiphenyl sulfone, the reaction time of the method is usually 4-6h, the reaction rate is fast, but the operation temperature needs 240 ℃ and the pressure is 4.5 to 10 DEG C 5 Pa, and the mass ratio of the isomer generated by the method to the 4, 4-dichlorodiphenyl sulfone is (4-10): 1, the defects of harsh reaction conditions and low yield exist;
2) Phosphorus oxychloride method: the method uses chlorobenzene, chlorosulfonic acid and phosphorus oxychloride to react in the presence of a ferric trichloride catalyst to generate 4, 4-dichlorodiphenyl sulfone, and the operating temperature of the method is 60-65 ℃, and the pressure is 3.73 x 10 3 Pa, but the reaction time is too long, and the reaction time is usually over 40h, which is not widely adopted;
3) Chlorosulfonic acid method: the chlorosulfonic acid method is the mainstream synthetic method of 4, 4-dichlorodiphenyl sulfone at present, react with chlorosulfonic acid with chlorobenzene to make 4-chloro benzene sulfonic acid chlorine, condense with chlorobenzene under the existance of aluminium trichloride, get 4, 4-dichlorodiphenyl sulfone finished products by refining; the method has mature technology, the reaction time is about 5 hours, but the operating temperature of the method is 150-180 ℃, the materials need to be put into a negative pressure reaction kettle for further rectification at the later stage of the reaction process, and the defects of high operating temperature and complex process flow exist;
4) The pyrosulfate method: the sulfur trioxide reacts with dimethyl sulfate to prepare pyrosulfate, and then reacts with chlorobenzene to prepare 4, 4-dichlorodiphenyl sulfone. The method needs 80-90 ℃ of reaction temperature, the reaction period is shorter than that of a phosphorus oxychloride method, but still is over 30h, more isomers are produced, and the yield is lower, wherein the mass ratio of the 4, 4-dichlorodiphenyl sulfone to the isomers is (5-10): 1;
namely, the existing synthesis method of 4, 4-dichlorodiphenyl sulfone has the defects of harsh reaction conditions, complex process, long reaction time and more isomer generation.
Disclosure of Invention
In view of the problems in the prior art, the present application provides a method for preparing high-purity 4, 4-dichlorodiphenyl sulfone, so as to simplify the process flow, shorten the reaction time, reduce the production of isomers, improve the yield, and reduce the consumption of raw materials.
The first purpose of the present application is to provide a method for preparing high-purity 4, 4-dichlorodiphenyl sulfone, and one or more embodiments of the present application provide the following technical solutions:
a preparation method of high-purity 4, 4-dichlorodiphenyl sulfone comprises the following steps:
1) Mixing N mol of dimethyl sulfate and M mol of sulfur trioxide by taking dimethyl sulfate and sulfur trioxide as raw materials, and keeping the mixing temperature at 10-50 ℃; adding a catalyst and continuously stirring for 0.5h to prepare a mixed solution of the pyrosulfate and the sulfur trioxide containing the catalyst; the catalyst comprises boric acid;
2) Dripping the mixed solution into a chlorobenzene solution containing L mol of chlorobenzene at the temperature of 10-50 ℃; continuously stirring after the dropwise adding is finished, keeping the stirring temperature at 15-50 ℃, continuously stirring for 1.5 hours until the reaction is finished, and filtering out a reaction product; washing the reaction product to obtain a crude product;
3) Preparing a chlorobenzene cleaning solution, heating the chlorobenzene cleaning solution to 90 ℃, adding the crude product into the chlorobenzene cleaning solution, standing the mixed solution of the crude product and the chlorobenzene cleaning solution until an organic layer is separated; adding activated carbon into the separated organic layer, stirring for 1h, filtering, cooling the filtrate until a product is separated out, and collecting the product;
4) Washing the product with pure water again, and drying the product with an oven to prepare the high-purity 4, 4-dichlorodiphenyl sulfone;
wherein N: m: l =1: (2-2.2): (2-2.2).
Further, the catalyst also comprises one or a mixture of more of trifluoromethanesulfonic acid or organic boric acid compounds.
Further, the mixing method of the dimethyl sulfate and the sulfur trioxide comprises the following steps: under the protection of nitrogen or other inert gases, adding dimethyl sulfate into a flask, dropwise adding sulfur trioxide into the flask within 1h under the stirring condition, and stirring for 0.5h after dropwise adding.
Further, the mixing temperature in step 1 is 25-35 ℃.
Further, the stirring temperature in the step 2 is 30-40 ℃.
Further, the washing process in step 2 is as follows: washing the reaction product with organic solvent, filtering, washing the filtrate with alkaline solution, and washing with pure water.
Further, the organic solvent is one or a mixture of more of isopropanol, chlorobenzene and methanol; the alkaline solution is one or a mixture of more of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a sodium carbonate aqueous solution and a sodium bicarbonate aqueous solution.
Further, the chlorobenzene cleaning solution is prepared by mixing pure water and chlorobenzene according to a mass ratio of 1: 1.
Further, the temperature of the oven drying is 100 ℃.
Advantageous effects of the invention
1. The 4, 4-dichlorodiphenyl sulfone is prepared by mixing and reacting dimethyl sulfate, sulfur trioxide and chlorobenzene, the preparation process is simple, the preparation process is a normal-pressure reaction, the high-temperature and high-pressure environment is not depended on, the vacuum rectification process is not required, the reaction operating temperature is as low as below 50 ℃, even if the phosphorus oxychloride method with the operating temperature of only 60-65 ℃ is adopted, the application also has the advantage of low operating temperature, and the defects of complex process and harsh reaction conditions in the conventional 4, 4-dichlorodiphenyl sulfone preparation process are overcome;
2. the method takes boric acid as a catalyst, further improves the reaction rate, and shortens the reaction period to 3h; even if compared with a sulfuric acid method production process which needs high-temperature and high-pressure driving, the shortest period is more than one fourth shorter, and the yield of the 4, 4-dichlorodiphenyl sulfone is effectively improved;
3. the reaction temperature of dimethyl sulfate, sulfur trioxide and chlorobenzene is preferably 30-40 ℃, and the isomer increasing rate and the mixture reaction rate reach the optimal ratio at the temperature; the reaction rate is effectively improved by using the boric acid catalyst, and the generation time of isomers is shortened; namely, under the action of the special temperature and the catalyst, the isomer production is greatly reduced on the basis of ensuring the yield of the 4, 4-dichlorodiphenyl sulfone, and the isomer production is further reduced by shortening the reaction time, so that the mass ratio of the non-purified isomer to the isomer is (4-10): 1 to (50-65): 1, effectively improving the purity of the 4, 4-dichlorodiphenyl sulfone product; the consumption of corresponding raw materials is greatly reduced, the consumption of the raw materials of a unit product is reduced by more than 8 percent, and the effect of saving materials is achieved;
4. the application comprises the following steps of: sulfur trioxide: the ratio of chlorobenzene is controlled to be 1: (2-2.2): (2-2.2), the dimethyl sulfate can be fully reacted by increasing the mixing amount of sulfur trioxide and chlorobenzene, and the effects of reducing material waste and reducing isomer generation are achieved.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
As introduced in the background art, the synthesis method of 4, 4-dichlorodiphenyl sulfone has the defects of complex process, long reaction time and more isomer generation; accordingly, the present application proposes a method for preparing high-purity 4, 4-dichlorodiphenyl sulfone, comprising the steps of:
1) Taking dimethyl sulfate and sulfur trioxide as raw materials, adding N mol of dimethyl sulfate into a flask, dropwise adding M mol of sulfur trioxide into the flask within 1h under the stirring condition, stirring for 0.5h after dropwise adding is finished, and keeping the temperature at 10-50 ℃ in the mixing process, preferably 25-35 ℃; adding a catalyst, and continuously stirring for 0.5h to prepare a mixed solution of the catalyst-containing disulfate and sulfur trioxide;
specifically, the catalyst comprises boric acid and also comprises one or a mixture of more of trifluoromethanesulfonic acid or organoboron acid compounds;
2) Dropwise adding the mixed solution into a chlorobenzene solution containing L mol of chlorobenzene at the temperature of 10-50 ℃, wherein the chlorobenzene cleaning solution is prepared by mixing pure water and chlorobenzene in a mass ratio of 1: 1; continuously stirring after the dropwise adding is finished, keeping the stirring temperature at 15-50 ℃, preferably 30-40 ℃, continuously stirring for 1.5 hours until the reaction is finished, and filtering out a reaction product; washing the reaction product with an organic solvent, filtering, continuously washing the filtrate with an alkaline solution until the aqueous solution is alkaline, and washing with pure water to obtain a crude product;
specifically, the organic solvent is one or a mixture of more of isopropanol, chlorobenzene and methanol; the alkaline solution is one or a mixture of more of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a sodium carbonate aqueous solution and a sodium bicarbonate aqueous solution;
3) Preparing a chlorobenzene cleaning solution, heating the chlorobenzene cleaning solution to 90 ℃, adding the crude product into the chlorobenzene cleaning solution, standing the mixed solution of the crude product and the chlorobenzene cleaning solution until an organic layer is separated; adding activated carbon into the separated organic layer, stirring for 1h, filtering, cooling the filtrate until a product is separated out, and collecting the product;
4) Washing the product with pure water again, and drying by using an oven at 100 ℃ to obtain the high-purity 4, 4-dichlorodiphenyl sulfone;
wherein N: m: l =1: (2-2.2): (2-2.2).
The present invention is described in further detail below with reference to specific examples, which should be construed as illustrative rather than restrictive.
Example 1
Adding 2.5mol of dimethyl sulfate into a clean flask, dropwise adding 5mol of sulfur trioxide into the flask within 1h under the stirring condition, and mixing, wherein the mixing temperature is kept at 10-50 ℃; then adding boric acid and continuing stirring for 0.5h;
dropwise adding the mixed solution into a chlorobenzene solution containing 5mol of chlorobenzene within 1h at the temperature of 10-50 ℃; continuously stirring after the dropwise adding is finished, keeping the stirring temperature at 15-50 ℃, continuously stirring for 1.5 hours until the reaction is finished, and filtering out a reaction product; washing the reaction product to obtain a crude product;
preparing a chlorobenzene cleaning solution, heating the chlorobenzene cleaning solution to 90 ℃, adding the crude product into the chlorobenzene cleaning solution, standing the mixed solution of the crude product and the chlorobenzene cleaning solution until an organic layer is separated; adding activated carbon into the separated organic layer, stirring for 1h, filtering, cooling the filtrate until a product is separated out, and collecting the product;
the product was washed again with pure water and dried in an oven to obtain 704g of high-purity 4, 4-dichlorodiphenyl sulfone.
Example 2
Adding 2.5mol of dimethyl sulfate into a clean flask, dropwise adding 5mol of sulfur trioxide into the flask within 1h under the stirring condition, and mixing, wherein the mixing temperature is kept at 10-50 ℃; then adding dimethyl sulfoxide and continuing stirring for 0.5h;
dropwise adding the mixed solution into a chlorobenzene solution containing 5mol of chlorobenzene within 1h at the temperature of 10-50 ℃; continuously stirring after the dropwise addition is finished, keeping the stirring temperature at 15-50 ℃, continuously stirring for 1.5 hours until the reaction is finished, and filtering out a reaction product; washing the reaction product to obtain a crude product;
preparing a chlorobenzene cleaning solution, heating the chlorobenzene cleaning solution to 90 ℃, adding the crude product into the chlorobenzene cleaning solution, standing the mixed solution of the crude product and the chlorobenzene cleaning solution until an organic layer is separated; adding activated carbon into the separated organic layer, stirring for 1h, filtering, cooling the filtrate until a product is separated out, and collecting the product;
the product was washed again with pure water and dried in an oven to obtain 460g of high-purity 4, 4-dichlorodiphenyl sulfone.
Example 3
Adding 2.5mol of dimethyl sulfate into a clean flask, dropwise adding 5mol of sulfur trioxide into the flask within 1h under the stirring condition, and mixing, wherein the mixing temperature is kept at 10-50 ℃; then adding boric acid and continuing stirring for 0.5h;
dropwise adding the mixed solution into a chlorobenzene solution containing 5mol of chlorobenzene within 1h at the temperature of 10-50 ℃; continuously stirring after the dropwise adding is finished, keeping the stirring temperature at 55-80 ℃, continuously stirring for 1h until the reaction is finished, and filtering out a reaction product; washing the reaction product to obtain a crude product;
preparing a chlorobenzene cleaning solution, heating the chlorobenzene cleaning solution to 90 ℃, adding the crude product into the chlorobenzene cleaning solution, standing the mixed solution of the crude product and the chlorobenzene cleaning solution until an organic layer is separated; adding activated carbon into the separated organic layer, stirring for 1h, filtering, cooling the filtrate until a product is separated out, and collecting the product;
the product was washed again with pure water and dried in an oven to obtain 665g of high-purity 4, 4-dichlorodiphenyl sulfone.
Example 4
Adding 2.5mol of dimethyl sulfate into a clean flask, dropwise adding 7mol of sulfur trioxide into the flask within 1h under the stirring condition, and mixing, wherein the mixing temperature is kept at 10-50 ℃; then adding boric acid and continuing stirring for 0.5h;
dropwise adding the mixed solution into a chlorobenzene solution containing 7mol of chlorobenzene within 1h at the temperature of 10-50 ℃; continuously stirring after the dropwise adding is finished, keeping the stirring temperature at 15-50 ℃, continuously stirring for 1.5 hours until the reaction is finished, and filtering out a reaction product; washing the reaction product to obtain a crude product;
preparing a chlorobenzene cleaning solution, heating the chlorobenzene cleaning solution to 90 ℃, adding the crude product into the chlorobenzene cleaning solution, standing the mixed solution of the crude product and the chlorobenzene cleaning solution until an organic layer is separated; adding activated carbon into the separated organic layer, stirring for 1h, filtering, cooling the filtrate until a product is separated out, and collecting the product;
the product was washed again with pure water and dried in an oven to obtain 700g of high-purity 4, 4-dichlorodiphenyl sulfone.
Comparative data for reaction products are shown in the following table:
TABLE 1 comparison of reaction products
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A preparation method of high-purity 4, 4-dichlorodiphenyl sulfone is characterized by comprising the following steps:
1) Taking dimethyl sulfate and sulfur trioxide as raw materials, mixing the dimethyl sulfate and the sulfur trioxide, keeping a stable mixing temperature, adding a catalyst, and continuously stirring for 0.5h to prepare a mixed solution of the catalyst-containing pyrosulfate and the sulfur trioxide; the catalyst comprises boric acid;
2) Dripping the mixed solution into a chlorobenzene solution at the temperature of 10-50 ℃; continuously stirring after the dropwise addition is finished, keeping the stable stirring temperature, continuously stirring for 1.5 hours until the reaction is finished, and filtering out a reaction product; washing the reaction product to obtain a crude product;
3) Preparing a chlorobenzene cleaning solution, heating the chlorobenzene cleaning solution to 90 ℃, adding the crude product into the chlorobenzene cleaning solution, standing the mixed solution of the crude product and the chlorobenzene cleaning solution until an organic layer is separated; adding activated carbon into the separated organic layer, stirring for 1h, filtering, cooling the filtrate until a product is separated out, and collecting the product;
4) The product was washed again with pure water and dried in an oven to obtain high-purity 4, 4-dichlorodiphenyl sulfone.
2. The method for preparing high-purity 4, 4-dichlorodiphenyl sulfone according to claim 1, wherein the catalyst further comprises one or more of trifluoromethanesulfonic acid or organoboron acid compounds.
3. The method for preparing high-purity 4, 4-dichlorodiphenyl sulfone according to claim 1, wherein the mixing method of dimethyl sulfate and sulfur trioxide is as follows: under the protection of nitrogen or other inert gases, adding dimethyl sulfate into a flask, dropwise adding sulfur trioxide into the flask within 1h under the stirring condition, and stirring for 0.5h after dropwise adding.
4. The method for preparing high-purity 4, 4-dichlorodiphenyl sulfone according to claim 1, wherein the mixing temperature is 25-35 ℃.
5. The method for preparing high-purity 4, 4-dichlorodiphenyl sulfone according to claim 1, wherein the stirring temperature is 30-40 ℃.
6. The process for preparing high-purity 4, 4-dichlorodiphenyl sulfone according to claim 1, wherein the molar ratio of dimethyl sulfate, sulfur trioxide and chlorobenzene is 1: (2-2.2): (2-2.2).
7. The method for preparing high-purity 4, 4-dichlorodiphenyl sulfone according to claim 1, wherein the washing process in the step 2) is as follows: washing the reaction product with organic solvent, filtering, washing the filtrate with alkaline solution, and washing with pure water.
8. The method for preparing high-purity 4, 4-dichlorodiphenyl sulfone according to claim 7, wherein the organic solvent is one or more of isopropanol, chlorobenzene and methanol; the alkaline solution is one or a mixture of more of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a sodium carbonate aqueous solution and a sodium bicarbonate aqueous solution.
9. The method for preparing high-purity 4, 4-dichlorodiphenyl sulfone according to claim 1, wherein the chlorobenzene cleaning solution is pure water and chlorobenzene in a mass ratio of 1: 1.
10. The method for preparing high-purity 4, 4-dichlorodiphenyl sulfone according to claim 1, wherein the temperature of oven drying is 100 ℃.
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| CN116715611A (en) * | 2023-05-19 | 2023-09-08 | 锦州三丰科技有限公司 | Green synthesis method of 4,4' -dichlorodiphenyl sulfone |
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