CN102295588A - Two-step synthesis process of 4.4-dichlorodiphenyl sulfone - Google Patents
Two-step synthesis process of 4.4-dichlorodiphenyl sulfone Download PDFInfo
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- CN102295588A CN102295588A CN2011102459545A CN201110245954A CN102295588A CN 102295588 A CN102295588 A CN 102295588A CN 2011102459545 A CN2011102459545 A CN 2011102459545A CN 201110245954 A CN201110245954 A CN 201110245954A CN 102295588 A CN102295588 A CN 102295588A
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- chlorobenzene
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- dichlorodiphenyl sulfone
- diphenyl sulfone
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Abstract
The invention discloses a two-step synthesis process of 4.4-dichlorodiphenyl sulfone, comprising the steps of: (1) preparation of p-chlorobenzenesulfonic acid: adding 98% concentrated sulfuric acid and 10% oleum into a reaction pot, stirring for 15min, adding dried chlorobenzene gradually and stirring for reaction at a temperature of 95-100DEG C for 5h, wherein, the concentrated sulfuric acid and oleum are in a volume ratio of 2:1; (2) synthesis of 4.4-dichlorodiphenyl sulfone: with a composite acid as the catalyst, adding chlorobenzene dropwisely at a temperature of 40-60DEG C so as to promote a condensation reaction between p-chlorobenzenesulfonic acid and chlorobenzene for 6-8h, thus obtaining 4.4-dichlorodiphenyl sulfone; and the composite acid consists of polyphosphoric acid and phosphoric pentoxide. Thus, two-step synthesis process of 4.4-dichlorodiphenyl sulfone in the invention can reduce the temperature of the whole reaction so as to reduce the generation of by-products during the reaction and improve the product conversion rate.
Description
Technical field
The present invention relates to a kind of preparation method of 4.4-dichloro diphenyl sulfone.
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 synthetic method of Chang Yong 4.4 – dichloro diphenyl sulfones has: chlorsulfonic acid method, sulfuric acid process and sulphur trioxide method; Wherein, the chlorsulfonic acid legal system is equipped with the production cost height of 4.4 – dichloro diphenyl sulfones, serious three wastes, and quality product is poor, is difficult to reach the specification of quality of polysulfones and polyethersulfone production defined; Sulfuric acid process temperature of reaction height, long reaction time, serious to equipment corrosion, poor product quality, yield is low; The whole operational path of sulphur trioxide method is long, friedel-crafts reaction temperature height, long reaction time, process for refining route complexity.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of two step method synthesis technique of 4.4-dichloro diphenyl sulfone is provided, its earlier synthetic p-chlorobenzenesulfonic acid, and then under the effect of complex acid catalyst condensation reaction takes place with chlorobenzene, generate 4.4-dichloro diphenyl sulfone crude product, after separating treatment, can obtain the 4.4-dichloro diphenyl sulfone, its yield is higher, and product quality is also fine.
For realizing above technical purpose, the present invention will take following technical scheme:
A kind of two step method synthesis technique of 4.4-dichloro diphenyl sulfone, may further comprise the steps: the preparation of (1) p-chlorobenzenesulfonic acid---in reactor, add 98% vitriol oil and 10% oleum, stir 15min, add the exsiccant chlorobenzene gradually, at 95-100 ℃ of stirring reaction 5h, wherein: the volume ratio of the vitriol oil and oleum is 2:1; (2) the 4.4-dichloro diphenyl sulfone is synthetic---and with compound acid is catalyzer, drips chlorobenzene down at 40-60 degree centigrade, and the condensation reaction that impels p-chlorobenzenesulfonic acid and chlorobenzene to take place 6-8 hour generates the 4.4-dichloro diphenyl sulfone; Described compound acid is made up of polyphosphoric acid and Vanadium Pentoxide in FLAKES.
According to above technical scheme, can realize following beneficial effect:
The present invention adopts two-step approach to prepare the 4.4-dichloro diphenyl sulfone, can reduce the temperature of entire reaction, thereby reduces production of by-products in the reaction process, improves the transformation efficiency of product.
Embodiment
Explain technical scheme of the present invention below with reference to embodiment.
The two step method synthesis technique of 4.4-dichloro diphenyl sulfone of the present invention, its earlier synthetic p-chlorobenzenesulfonic acid, and then under the effect of complex acid catalyst condensation reaction takes place with chlorobenzene, generate 4.4-dichloro diphenyl sulfone crude product, after separating treatment, can obtain the 4.4-dichloro diphenyl sulfone, described p-chlorobenzenesulfonic acid is got through sulfonation by chlorobenzene, be specially: in reactor, add 98% vitriol oil and 10% oleum, stir 15min, add the exsiccant chlorobenzene gradually,, check the sulfonation terminal point at 95-100 ℃ of stirring reaction 5h.Reactant acidity is not more than 70% when reaching home, and can dissolve in water fully.
Be catalyzer with compound acid then, drip chlorobenzene down at 40-60 degree centigrade, the condensation reaction that impels p-chlorobenzenesulfonic acid and chlorobenzene to take place 6-8 hour generates the 4.4-dichloro diphenyl sulfone; Described compound acid is made up of polyphosphoric acid and Vanadium Pentoxide in FLAKES.
Claims (1)
1. the two step method synthesis technique of a 4.4-dichloro diphenyl sulfone, it is characterized in that, may further comprise the steps: the preparation of (1) p-chlorobenzenesulfonic acid---in reactor, add 98% vitriol oil and 10% oleum, stir 15min, add the exsiccant chlorobenzene gradually, at 95-100 ℃ of stirring reaction 5h, wherein: the volume ratio of the vitriol oil and oleum is 2:1; (2) the 4.4-dichloro diphenyl sulfone is synthetic---and with compound acid is catalyzer, drips chlorobenzene down at 40-60 degree centigrade, and the condensation reaction that impels p-chlorobenzenesulfonic acid and chlorobenzene to take place 6-8 hour generates the 4.4-dichloro diphenyl sulfone; Described compound acid is made up of polyphosphoric acid and Vanadium Pentoxide in FLAKES.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011102459545A CN102295588A (en) | 2011-08-25 | 2011-08-25 | Two-step synthesis process of 4.4-dichlorodiphenyl sulfone |
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| CN2011102459545A CN102295588A (en) | 2011-08-25 | 2011-08-25 | Two-step synthesis process of 4.4-dichlorodiphenyl sulfone |
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| CN102295588A true CN102295588A (en) | 2011-12-28 |
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| CN2011102459545A Pending CN102295588A (en) | 2011-08-25 | 2011-08-25 | Two-step synthesis process of 4.4-dichlorodiphenyl sulfone |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3501532A (en) * | 1967-09-05 | 1970-03-17 | Continental Oil Co | Process for preparing aromatic sulfones |
| JPS58206551A (en) * | 1982-05-25 | 1983-12-01 | Konishi Kagaku Kogyo Kk | Production of diaryl sulfones |
| GB2135666A (en) * | 1981-08-31 | 1984-09-05 | Mitsui Toatsu Chemicals | Preparation of 4-chlorobenzenesulfonyl chloride and 4,4'-dichlorodiphenyl sulfone |
| US4822916A (en) * | 1987-09-21 | 1989-04-18 | Akzo America Inc. | Preparation of diaryl sulfones |
| US4983773A (en) * | 1988-10-19 | 1991-01-08 | Basf Aktiengesellschaft | Preparation of bis-(4-chlorophenyl) sulfone |
-
2011
- 2011-08-25 CN CN2011102459545A patent/CN102295588A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3501532A (en) * | 1967-09-05 | 1970-03-17 | Continental Oil Co | Process for preparing aromatic sulfones |
| GB2135666A (en) * | 1981-08-31 | 1984-09-05 | Mitsui Toatsu Chemicals | Preparation of 4-chlorobenzenesulfonyl chloride and 4,4'-dichlorodiphenyl sulfone |
| JPS58206551A (en) * | 1982-05-25 | 1983-12-01 | Konishi Kagaku Kogyo Kk | Production of diaryl sulfones |
| US4822916A (en) * | 1987-09-21 | 1989-04-18 | Akzo America Inc. | Preparation of diaryl sulfones |
| US4983773A (en) * | 1988-10-19 | 1991-01-08 | Basf Aktiengesellschaft | Preparation of bis-(4-chlorophenyl) sulfone |
Non-Patent Citations (7)
| Title |
|---|
| 《大连工学院学报》 20070103 李忠义，吴宝庆 4,4'-二氯二苯砜合成新工艺 第98页 第26卷, * |
| 《太原科技》 20030426 黄月君 4,4'-二氯二苯砜的合成研究 第50页1.2目标化合物的合成 , 第2期 * |
| 《辽宁化工》 19951231 高亚彪 4,4'-二氯二苯砜制备技术 第24页1实验部分 1 , 第6期 * |
| 徐克勋: "《精细有机化工原料及中间体手册》", 31 December 2001, article "对氯苯磺酰氯", pages: 646 * |
| 李忠义，吴宝庆: "4,4’-二氯二苯砜合成新工艺", 《大连工学院学报》, vol. 26, 3 January 2007 (2007-01-03), pages 98 * |
| 高亚彪: "4,4’-二氯二苯砜制备技术", 《辽宁化工》, no. 6, 31 December 1995 (1995-12-31), pages 24 - 1 * |
| 黄月君: "4,4’-二氯二苯砜的合成研究", 《太原科技》, no. 2, 26 April 2003 (2003-04-26) * |
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Application publication date: 20111228 |