CN102351758A - New preparation method of 4,4-dichlorodiphenyl sulfone - Google Patents
New preparation method of 4,4-dichlorodiphenyl sulfone Download PDFInfo
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- CN102351758A CN102351758A CN2011102459507A CN201110245950A CN102351758A CN 102351758 A CN102351758 A CN 102351758A CN 2011102459507 A CN2011102459507 A CN 2011102459507A CN 201110245950 A CN201110245950 A CN 201110245950A CN 102351758 A CN102351758 A CN 102351758A
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Abstract
The invention discloses a new preparation method of 4,4-dichlorodiphenyl sulfone. The method comprises the following steps: 1) through using AlCl3 as a catalyst, and chlorobenzene and thionyl chloride as reaction raw materials, performing a Friedel-Crafts reaction at 25-35 DEG C, then hydrolyzing the mother liquor obtained through the Friedel-Crafts reaction, refluxing at 95-100 DEG C for 45-60 minutes, cooling the obtained mother liquor to less than 20 DEG C after refluxing to obtain an organic phase and an aqueous phase; 2) performing reduced pressure distillation on the organic phase, centrifuging, washing the obtained product to be neutral and be used as a product A for later use, wherein the main component of the product A is 4,4-dichlorodiphenyl sulfoxide; and 3) through using the product A and the oxidant hydrogen peroxide as raw materials and acetic acid as satalytic solvent, carrying out an oxidation reaction on the main component 4,4-dichlorodiphenyl sulfoxide of the product A to obtain crude 4,4-dichlorodiphenyl sulfone. Therefore, the existing synthesis method of 4,4-dichlorodiphenyl sulfone is changed, the production cost of 4,4-dichlorodiphenyl sulfone is low, the product quality is good and the reaction time is short.
Description
Technical field
The present invention relates to a kind of preparation method of 4.4 – dichloro diphenyl sulfones.
Background technology
4.4 the – dichloro diphenyl sulfone is called for short DDS, is white crystal, can distil, and is soluble in organic solvents such as benzene, chlorobenzene, DMF; Be slightly soluble in ethanol, methyl alcohol; Water insoluble.Its flash-point is 233 ℃, and boiling point then is 397 ℃.
4.4 the – dichloro diphenyl sulfone has purposes widely at engineering plastics and field of fine chemical, is the main raw material of engineering plastics such as preparation polysulfones, polyethersulfone, also is the intermediate of medicine, dyestuff, agricultural chemicals.
At present, the synthesis method of Chang Yong 4.4 – dichloro diphenyl sulfones has: chlorsulfonic acid method, sulfuric acid process and sulphur trioxide method; Wherein, the production cost that the chlorsulfonic acid legal system is equipped with 4.4 – dichloro diphenyl sulfones is high, serious three wastes, and quality product is poor, is difficult to reach the specification of quality of polysulfones and polyethersulfone production defined; The sulfuric acid process temperature of reaction is high, and long reaction time is serious to equipment corrosion, poor product quality, and yield is low; The whole operational path of sulphur trioxide method is long, and the friedel-crafts reaction temperature is high, long reaction time, and the process for refining route is complicated.
Summary of the invention
The present invention is directed to the deficiency of prior art, a kind of new preparation process of 4.4 – dichloro diphenyl sulfones is provided, it is low that it has a production cost, good product quality, the advantage that the reaction times is short.
For realizing above technical purpose, the present invention will take following technical scheme:
A kind of new preparation process of 4.4 – dichloro diphenyl sulfones; May further comprise the steps: at first; With AlCl3 is catalyzer; Chlorobenzene, thionyl chloride are reaction raw materials, between 25-35 degree centigrade, carry out friedel-crafts reaction, then; Mother liquor after the friedel-crafts reaction end is hydrolyzed; Hydrolysis finishes the back at 95-100 degree centigrade of refluxed 45-60min, reflux finish after, be cooled to and be divided into organic phase and water below 20 ℃; To neutrality, subsequent use as products A, the main composition in the products A is 4.4 – dichloro thionyl benzenes to organic phase through underpressure distillation, centrifuge washing; Then, be raw material with products A, oxidant hydrogen peroxide, acetate is that the catalysis solvent carries out oxidizing reaction to the 4.4 – dichloro thionyl benzenes of the main composition in the products A, synthetic 4.4 – dichloro diphenyl sulfone crude products.
According to above technical scheme, can realize following beneficial effect:
It is reaction raw materials that the present invention adopts chlorobenzene, thionyl chloride earlier; With AlCl3 is catalyzer; Preparing main composition is the products A of 4.4 – dichloro thionyl benzenes, adopts oxidant hydrogen peroxide, oxide catalyst acetate that 4.4 – dichloro thionyl benzenes are carried out oxidation again, obtains 4.4 – dichloro diphenyl sulfone crude products; Hence one can see that, and the present invention changes the synthesis method of existing 4.4 – dichloro diphenyl sulfones, causes the production cost of 4.4 – dichloro diphenyl sulfones low, good product quality, and the reaction times is short.
Embodiment
Below will combine embodiment that technical scheme of the present invention at length is described.
The new preparation process of 4.4 – dichloro diphenyl sulfones of the present invention, the pharmaceutical chemicals of employing has: catalyst A lCl3, chlorobenzene, thionyl chloride, oxidant hydrogen peroxide and catalysis solvent acetic acid; Specifically may further comprise the steps:
The preparation of (1) 4.4 – dichloro thionyl benzene
With AlCl3 is catalyzer; Chlorobenzene, thionyl chloride are reaction raw materials; Between 25-35 degree centigrade, carry out friedel-crafts reaction; Then; Mother liquor after the friedel-crafts reaction end is hydrolyzed; Hydrolysis finishes the back at 95-100 degree centigrade of refluxed 45-60min, reflux finish after, be cooled to and be divided into organic phase and water below 20 ℃; To neutrality, subsequent use as products A, the main composition in the products A is 4.4 – dichloro thionyl benzenes to organic phase through underpressure distillation, centrifuge washing.
1, in the reaction kettle of the dry cleansing that disposes device for absorbing tail gas, metering drops into Benzene Chloride, and stirs cooling;
2, in reaction kettle, drip an amount of sulfur oxychloride earlier, behind the stirring 10min, add required lewis acid alchlor, closed reactor stirs 20min;
3, when reacting liquid temperature during, drip the sulfur oxychloride of metering at 25 degrees centigrade; In this step, need in the whole dropping process of control, reacting liquid temperature is all the time between 25-35 degree centigrade, and the dropping time was controlled between 3.4-4.5 hour;
4, after step 3 finishes, be incubated 40min down at 35-45 degree centigrade, the speed with 1 degree centigrade/min is warming up to 70-80 ℃ then, prepares hydrolysis;
5, in hydrolysis kettle, be metered into tap water, the material that step 4 reaction is good slowly adds in this hydrolysis kettle that fills tap water, behind reinforced the finishing, is warming up to 100 ℃, and backflow 60min allows its abundant hydrolysis; Reflux after the end, be cooled to below 20 ℃, follow blowing, and will tell organic layer in the mother liquor suction separatory still, do distillation and handle, alchlor wastewater collection sale;
6, material carries out centrifugal, washing to neutral, packing.Washing water are made hydrolysis kettle hydrolysis water in next circulation.The product sampling analysis, and put on lot number.This product is 4.4 – dichloro thionyl benzene crude products.
The preparation of (2) 4.4 – dichloro diphenyl sulfones
With products A, oxidant hydrogen peroxide is raw material, and acetate is that the catalysis solvent carries out oxidizing reaction to the 4.4 – dichloro thionyl benzenes of the main composition in the products A, synthetic 4.4 – dichloro diphenyl sulfone crude products; After oxidizing reaction finishes, blowing, suction filtration, tell organic layer, organic layer washing to neutral after drying, packing are got final product.
Claims (1)
1. the new preparation process of a – dichloro diphenyl sulfone; It is characterized in that; May further comprise the steps: at first, be catalyzer with AlCl3, chlorobenzene, thionyl chloride are reaction raw materials; Between 25-35 degree centigrade, carry out friedel-crafts reaction; Then, the mother liquor after the friedel-crafts reaction end is hydrolyzed, hydrolysis finishes the back at 95-100 degree centigrade of refluxed 45-60min; After reflux finishing, be cooled to and be divided into organic phase and water below 20 ℃; To neutrality, subsequent use as products A, the main composition in the products A is 4.4 – dichloro thionyl benzenes to organic phase through underpressure distillation, centrifuge washing; Then, be raw material with products A, oxidant hydrogen peroxide, acetate is that the catalysis solvent carries out oxidizing reaction to the 4.4 – dichloro thionyl benzenes of the main composition in the products A, synthetic 4.4 – dichloro diphenyl sulfone crude products.
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| CN2011102459507A CN102351758A (en) | 2011-08-25 | 2011-08-25 | New preparation method of 4,4-dichlorodiphenyl sulfone |
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| CN2011102459507A CN102351758A (en) | 2011-08-25 | 2011-08-25 | New preparation method of 4,4-dichlorodiphenyl sulfone |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402780A (en) * | 2014-12-12 | 2015-03-11 | 山东凯盛新材料有限公司 | Synthesis process of 4, 4'-dichlorodiphenyl sulfone |
| CN104557626A (en) * | 2014-12-12 | 2015-04-29 | 山东凯盛新材料有限公司 | Process for preparing 4,4'-dichlorodiphenylsulfone employing sulfoxide oxidation method |
| CN105348155A (en) * | 2015-12-14 | 2016-02-24 | 山东凯盛新材料有限公司 | Synthesis process of 4,4'-dichlorodiphenyl sulfone |
| CN106349126A (en) * | 2016-08-25 | 2017-01-25 | 江西金海新能源科技有限公司 | Method for preparing 4,4'-dichloro sulfobenzide |
| CN108047101A (en) * | 2017-12-07 | 2018-05-18 | 九江中星医药化工有限公司 | A kind of synthesis technology of high-efficiency and continuous production 4,4- dichloro diphenyl sulfones |
| CN110642762A (en) * | 2019-09-13 | 2020-01-03 | 辽宁君荣化工有限公司 | Preparation method of 4, 4-dichlorodiphenyl sulfone |
| WO2020161226A1 (en) | 2019-02-08 | 2020-08-13 | Basf Se | A process for obtaining 4,4'-dichlorodiphenyl sulfoxide |
| WO2020161232A1 (en) | 2019-02-08 | 2020-08-13 | Basf Se | Process for producing 4,4'-dichlorodiphenyl sulfoxide |
| WO2020161228A1 (en) | 2019-02-08 | 2020-08-13 | Basf Se | Process for producing 4,4`-dichlorodiphenyl sulfoxide |
| WO2020161225A1 (en) | 2019-02-08 | 2020-08-13 | Basf Se | Process for purifying 4,4'-dichlorodiphenyl sulfoxide |
| WO2020207929A1 (en) | 2019-04-09 | 2020-10-15 | Basf Se | Process for working up a composition comprising solid 4,4'-dichlorodiphenyl sulfoxide and a solvent |
| WO2021037675A1 (en) | 2019-08-27 | 2021-03-04 | Basf Se | Process for producing 4,4'-dichlorodiphenyl sulfone |
| WO2021037672A1 (en) | 2019-08-27 | 2021-03-04 | Basf Se | A process for producing 4,4'-dichlorodiphenyl sulfone |
| WO2021037682A1 (en) | 2019-08-27 | 2021-03-04 | Basf Se | A process for purifying crude 4,4'-dichlorodiphenyl sulfone |
| WO2021037680A1 (en) | 2019-08-27 | 2021-03-04 | Basf Se | A process for obtaining 4,4'-dichlorodiphenyl sulfone |
| WO2021037683A1 (en) | 2019-08-27 | 2021-03-04 | Basf Se | A process for purifying 4,4'-dichlorodiphenyl sulfone |
| DE102020113957A1 (en) | 2020-05-25 | 2021-11-25 | Basf Se | Process for working up carboxylic acid-moist 4,4-dichlorodiphenyl sulfone |
| CN114507165A (en) * | 2022-04-20 | 2022-05-17 | 富海(东营)新材料科技有限公司 | Method for synthesizing 4, 4' -dichlorodiphenyl sulfone by solid acid catalysis |
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402780A (en) * | 2014-12-12 | 2015-03-11 | 山东凯盛新材料有限公司 | Synthesis process of 4, 4'-dichlorodiphenyl sulfone |
| CN104557626A (en) * | 2014-12-12 | 2015-04-29 | 山东凯盛新材料有限公司 | Process for preparing 4,4'-dichlorodiphenylsulfone employing sulfoxide oxidation method |
| CN104402780B (en) * | 2014-12-12 | 2016-04-27 | 山东凯盛新材料有限公司 | 4, the synthesis technique of 4 '-dichloro diphenyl sulfone |
| CN105348155A (en) * | 2015-12-14 | 2016-02-24 | 山东凯盛新材料有限公司 | Synthesis process of 4,4'-dichlorodiphenyl sulfone |
| CN106349126A (en) * | 2016-08-25 | 2017-01-25 | 江西金海新能源科技有限公司 | Method for preparing 4,4'-dichloro sulfobenzide |
| CN106349126B (en) * | 2016-08-25 | 2018-06-01 | 江西金海新能源科技有限公司 | The method for preparing 4,4 '-dichloro diphenyl sulfone |
| CN108047101A (en) * | 2017-12-07 | 2018-05-18 | 九江中星医药化工有限公司 | A kind of synthesis technology of high-efficiency and continuous production 4,4- dichloro diphenyl sulfones |
| WO2020161228A1 (en) | 2019-02-08 | 2020-08-13 | Basf Se | Process for producing 4,4`-dichlorodiphenyl sulfoxide |
| WO2020161232A1 (en) | 2019-02-08 | 2020-08-13 | Basf Se | Process for producing 4,4'-dichlorodiphenyl sulfoxide |
| WO2020161226A1 (en) | 2019-02-08 | 2020-08-13 | Basf Se | A process for obtaining 4,4'-dichlorodiphenyl sulfoxide |
| WO2020161225A1 (en) | 2019-02-08 | 2020-08-13 | Basf Se | Process for purifying 4,4'-dichlorodiphenyl sulfoxide |
| WO2020207929A1 (en) | 2019-04-09 | 2020-10-15 | Basf Se | Process for working up a composition comprising solid 4,4'-dichlorodiphenyl sulfoxide and a solvent |
| WO2021037672A1 (en) | 2019-08-27 | 2021-03-04 | Basf Se | A process for producing 4,4'-dichlorodiphenyl sulfone |
| WO2021037675A1 (en) | 2019-08-27 | 2021-03-04 | Basf Se | Process for producing 4,4'-dichlorodiphenyl sulfone |
| WO2021037682A1 (en) | 2019-08-27 | 2021-03-04 | Basf Se | A process for purifying crude 4,4'-dichlorodiphenyl sulfone |
| WO2021037680A1 (en) | 2019-08-27 | 2021-03-04 | Basf Se | A process for obtaining 4,4'-dichlorodiphenyl sulfone |
| WO2021037683A1 (en) | 2019-08-27 | 2021-03-04 | Basf Se | A process for purifying 4,4'-dichlorodiphenyl sulfone |
| CN110642762A (en) * | 2019-09-13 | 2020-01-03 | 辽宁君荣化工有限公司 | Preparation method of 4, 4-dichlorodiphenyl sulfone |
| DE102020113957A1 (en) | 2020-05-25 | 2021-11-25 | Basf Se | Process for working up carboxylic acid-moist 4,4-dichlorodiphenyl sulfone |
| CN114507165A (en) * | 2022-04-20 | 2022-05-17 | 富海(东营)新材料科技有限公司 | Method for synthesizing 4, 4' -dichlorodiphenyl sulfone by solid acid catalysis |
| CN114507165B (en) * | 2022-04-20 | 2022-07-19 | 富海(东营)新材料科技有限公司 | Method for synthesizing 4, 4' -dichlorodiphenyl sulfone by solid acid catalysis |
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Application publication date: 20120215 |