CN1623982A - Method for preparing 4,4'-dichloride diphenyl sulfone - Google Patents
Method for preparing 4,4'-dichloride diphenyl sulfone Download PDFInfo
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- CN1623982A CN1623982A CN 200310109009 CN200310109009A CN1623982A CN 1623982 A CN1623982 A CN 1623982A CN 200310109009 CN200310109009 CN 200310109009 CN 200310109009 A CN200310109009 A CN 200310109009A CN 1623982 A CN1623982 A CN 1623982A
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- catalyzer
- sulphur trioxide
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- diphenyl sulfone
- chlorobenzene
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Abstract
A process for preparing 4,4'-dichlorodiphenyl sulfone features that the coupling agent of SO3 is used to lower the free enthalpy of sulfonating and condensating reactions and the catalyst of sulfonating and condensating reactions is used to lower the activating energy of reaction, resulting in low reaction temp, short time and high quality of product.
Description
Technical field
The present invention relates to a kind of sulfone family macromolecule polymerization starting material 4, the preparation method of 4 '-dichloro diphenyl sulfone, particularly this raw-material three oxygen sulphur manufactured processes.
Background technology
Sulfone family macromolecule material such as polysulfones, polyethersulfone, polyarylsulphone are because it has good resistance toheat, physical and mechanical properties, insulating property, chemical resistance, therefore in each essential industry field and daily life, used widely, 4,4 '-dichloro diphenyl sulfone is as sulfone family macromolecule material synthetic starting material, and its manufacturing cost and quality product are the bases of sulfone family macromolecule material development.
Present widely used 4, the manufacture method of 4 '-dichloro diphenyl sulfone comprises sulfuric acid process, sulfuric chlorohydrin method, sulfuryl chloride method, the temperature of reaction height of these methods, reaction time are long, supplies consumption is big, strong to the corrodibility of production unit, and the impurity that the product color of being produced is dark, side reaction produces is many, manufacturing cost is high, three wastes quantity is big.With 4 of these methods manufacturings, 4 '-dichloro diphenyl sulfone has limited the development of sulfone family macromolecule material as the starting material of synthetic sulfone family macromolecule material.
Summary of the invention
The technical issues that need to address of the present invention are that disclosing a kind of is sulphonating agent preparation 4 with the sulphur trioxide, the method of 4 '-dichloro diphenyl sulfone, to overcome prior art in the defective that shows aspect manufacturing cost and the quality product, 4,4 '-dichloro diphenyl sulfone product performance are reliable, manufacture method simple, low production cost.
Design of the present invention is such:
The present invention's imagination, reduce the free enthalpy (Δ G) of sulfonation, condensation reaction with the couplant of sulphur trioxide, reduce the activation energy (Δ E) of reaction with the catalyzer of sulfonation, condensation reaction, the temperature of building-up reactions is obviously reduced, the time shortens dramatically, the products obtained therefrom quality significantly improves, and the three wastes of generation are formed the few and easy processing of simple quantity.
The present invention 4, and the preparation of 4 '-dichloro diphenyl sulfone comprises the steps:
(1) sulphur trioxide can discharge the preparation of solution:
At first sulphur trioxide is dissolved in the couplant with the method for mixing or absorb, and airtightly under 0 ℃～120 ℃ temperature leaves standstill slaking, obtain sulphur trioxide and can discharge solution, preferred temperature is 30 ℃～40 ℃;
Said couplant comprises a kind of and composition thereof in methyl-sulfate, methylcarbonate, methyl nitrate or the tributyl phosphate, preferably methyl-sulfate.
The mass concentration that said sulphur trioxide can discharge sulphur trioxide in the solution is 25%～90%, and preferred concentration is 40%～75%;
(2) figuration of catalyzer:
Catalyzer is dispersed in said sulphur trioxide can discharges in solution or the chlorobenzene, stir, be incubated, obtain the figuration function solution of catalyzer;
Holding temperature is 15 ℃～150 ℃, and preferred temperature is 25 ℃～30 ℃, and soaking time is 5～600 minutes, and the preferred time is 15～25 minutes;
The catalyzer of being addressed comprises a kind of and composition thereof in metal, the nonmetal and oxide compound, preferably a kind of in gac, aluminum oxide, boron oxide or the atlapulgite;
Said catalyzer is 0.01%～10% in the mass concentration that sulphur trioxide can discharge in solution or the chlorobenzene, and preferred concentration is 0.1%～1.0%;
(3) product is synthetic:
Chlorobenzene is added drop-wise in the figuration function solution of catalyzer and reacts, temperature is 15 ℃～160 ℃, and preferred temperature is 40 ℃～75 ℃, reaction times is 5～600 minutes, the preferred time is 120～250 minutes, collects-4 then from reaction product, 4 '-dichloro diphenyl sulfone.
According to the preferred scheme of the present invention, reaction product can be cooled to 10 ℃～-15 ℃, filter, obtain xln, washing, drying can obtain meeting that the polymerization of sulfone family macromolecule material uses 4,4 '-dichloro diphenyl sulfone;
According to the preferred scheme of the present invention, can will reclaim 4, the reaction product recycling behind 4 '-dichloro diphenyl sulfone.
Resulting 4, the fusing point of 4 '-dichloro diphenyl sulfone 〉=147 ℃, form and aspect≤30AHPA, Fe
3+≤ 1.0 * 10-5 (quality).
Adopt method preparation 4 of the present invention, 4 '-dichloro diphenyl sulfone, temperature of reaction is low, reaction time is short, supplies consumption is little, and product color is shallow, isomer is few, and yield height, the essentially no three wastes are convenient to suitability for industrialized production.
Embodiment
Embodiment 1
Absorb 800 gram sulphur trioxides (A) with 400 gram methyl-sulfates down at 35 ℃.
7 gram gacs are dispersed among the A with decollator, and 28 ℃ of following stirrings obtained catalyzer figuration function solution B in 20 minutes.
1100 gram chlorobenzenes are added drop-wise among the B under 70 ℃, reach home, obtain reactant C through reaction in 190 minutes.Slowly cool off C to-5 ℃ of after-filtration with water coolant, gained xln D obtains 1000 gram products 4,4 '-dichloro diphenyl sulfone with clean water washing after drying.
Resulting 4, the fusing point of 4 '-dichloro diphenyl sulfone is 147.8 ℃, and form and aspect are 20AHPA, Fe
3+Be 0.8 * 10-5 (mass ratio).
Embodiment 2
Mix (A) with 800 gram sulphur trioxides with 350 gram methyl-sulfates down at 25 ℃.
8 gram aluminium sesquioxides are dispersed in the 120 gram chlorobenzenes with decollator, and 35 ℃ of following stirrings obtained catalyzer figuration function solution B in 20 minutes.
B and A are added drop-wise to 85 gram recovery 4 respectively under 40 ℃, through in fractionation by distillation vitriolic reaction product and the 870 gram chlorobenzenes, after being added dropwise to complete temperature are adjusted to 75 ℃ behind 4 '-dichloro diphenyl sulfone, reach home, obtain reactant C through reaction in 180 minutes.Slowly cool off C to-8 ℃ of after-filtration with water coolant, gained xln D obtains 1000 gram products 4,4 '-dichloro diphenyl sulfone with clean water washing after drying.
Resulting 4, the fusing point of 4 '-dichloro diphenyl sulfone is 147.6 ℃, and form and aspect are 25AHPA, Fe
3+Be 0.7 * 10-5 (mass ratio).
Claims (8)
1. one kind 4, the preparation method of 4 '-dichloro diphenyl sulfone is characterized in that, comprises the steps:
(1) sulphur trioxide is dissolved in the couplant;
Said couplant comprises a kind of and composition thereof in methyl-sulfate, methylcarbonate, methyl nitrate or the tributyl phosphate;
The mass concentration that sulphur trioxide can discharge sulphur trioxide in the solution is 25%～90%;
(2) catalyzer is dispersed in said sulphur trioxide and can discharges in solution or the chlorobenzene, stir, be incubated, obtain the figuration function solution of catalyzer;
The catalyzer of being addressed comprises a kind of and composition thereof in metal, the nonmetal and oxide compound;
(3) chlorobenzene is added drop-wise in the figuration function solution of catalyzer and reacts, temperature is 15 ℃～160 ℃, and the reaction times is 5～600 minutes, collects-4 then from reaction product, 4 '-dichloro diphenyl sulfone.
2. method according to claim 1 is characterized in that, sulphur trioxide is dissolved in the couplant, and airtightly under 0 ℃～120 ℃ temperature leaves standstill slaking.
3. method according to claim 2 is characterized in that, airtightly under 30 ℃～40 ℃ temperature leaves standstill slaking.
4. method according to claim 1 is characterized in that, the mass concentration that sulphur trioxide can discharge sulphur trioxide in the solution is 40%～75%.
5. method according to claim 1 is characterized in that, catalyzer is dispersed in said sulphur trioxide and can discharges in solution or the chlorobenzene, insulation, and holding temperature is 15 ℃～150 ℃, soaking time is 5～600 minutes.
6. method according to claim 1 is characterized in that, catalyzer is a kind of in gac, aluminum oxide, boron oxide or the atlapulgite.
7. method according to claim 1 is characterized in that, catalyzer is 0.01%～10% in the mass concentration that sulphur trioxide can discharge in solution or the chlorobenzene.
8. according to each described method of claim 1～7, it is characterized in that, can reclaim 4, the reaction product behind 4 '-dichloro diphenyl sulfone is added drop-wise in the figuration function solution of catalyzer simultaneously with chlorobenzene after treatment reacts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109009 CN1623982A (en) | 2003-12-02 | 2003-12-02 | Method for preparing 4,4'-dichloride diphenyl sulfone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109009 CN1623982A (en) | 2003-12-02 | 2003-12-02 | Method for preparing 4,4'-dichloride diphenyl sulfone |
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| CN1623982A true CN1623982A (en) | 2005-06-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200310109009 Pending CN1623982A (en) | 2003-12-02 | 2003-12-02 | Method for preparing 4,4'-dichloride diphenyl sulfone |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011067649A2 (en) | 2009-12-01 | 2011-06-09 | Hemant Ratanakar Bandodkar | Process for the production of a sulfone monomer |
| CN102304072A (en) * | 2011-08-25 | 2012-01-04 | 吴江市北厍盛源纺织品助剂厂 | Method for preparing 4.4-dichlorodiphenyl sulfone by using sulfur trioxide |
| CN102304071A (en) * | 2011-08-25 | 2012-01-04 | 吴江市北厍盛源纺织品助剂厂 | Method for synthesizing 4.4-dichlorodiphenyl sulfone by two-step process |
| CN102304073A (en) * | 2011-08-25 | 2012-01-04 | 吴江市北厍盛源纺织品助剂厂 | Method for preparing 4.4-dichlorodiphenyl sulfone by using sulfuric acid |
| CN102351760A (en) * | 2011-08-25 | 2012-02-15 | 吴江市北厍盛源纺织品助剂厂 | Modified chlorosulfonic acid method of 4,4-dichlorodiphenyl sulfone |
| CN102351752A (en) * | 2011-08-25 | 2012-02-15 | 吴江市北厍盛源纺织品助剂厂 | Chlorosulfonic acid optimization method for preparing 4,4-dichlorodiphenyl sulfone |
| CN102858737A (en) * | 2010-04-22 | 2013-01-02 | 巴斯夫欧洲公司 | Method for the production of 4,4'-dichlorodiphenyl sulfone |
| CN103619810A (en) * | 2011-04-18 | 2014-03-05 | 索维特殊聚合物有限责任公司 | Process for the manufacture of dihalodiphenylsulfones |
| 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 |
| US10745348B2 (en) | 2015-06-09 | 2020-08-18 | Vertellus Holdings Llc | Process for making diaryl sulfones |
| CN115650888A (en) * | 2022-10-18 | 2023-01-31 | 山东东方宏业化工有限公司 | Preparation method of high-purity 4, 4-dichlorodiphenyl sulfone |
-
2003
- 2003-12-02 CN CN 200310109009 patent/CN1623982A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011067649A2 (en) | 2009-12-01 | 2011-06-09 | Hemant Ratanakar Bandodkar | Process for the production of a sulfone monomer |
| DE112010004627T5 (en) | 2009-12-01 | 2013-01-17 | Ratanakar Hemant Bandodkar | Process for the preparation of a sulfone monomer |
| CN102858737A (en) * | 2010-04-22 | 2013-01-02 | 巴斯夫欧洲公司 | Method for the production of 4,4'-dichlorodiphenyl sulfone |
| CN103619810B (en) * | 2011-04-18 | 2017-02-15 | 索维特殊聚合物有限责任公司 | Process for the manufacture of dihalodiphenylsulfones |
| CN103619810A (en) * | 2011-04-18 | 2014-03-05 | 索维特殊聚合物有限责任公司 | Process for the manufacture of dihalodiphenylsulfones |
| CN102304073A (en) * | 2011-08-25 | 2012-01-04 | 吴江市北厍盛源纺织品助剂厂 | Method for preparing 4.4-dichlorodiphenyl sulfone by using sulfuric acid |
| CN102351752A (en) * | 2011-08-25 | 2012-02-15 | 吴江市北厍盛源纺织品助剂厂 | Chlorosulfonic acid optimization method for preparing 4,4-dichlorodiphenyl sulfone |
| CN102351760A (en) * | 2011-08-25 | 2012-02-15 | 吴江市北厍盛源纺织品助剂厂 | Modified chlorosulfonic acid method of 4,4-dichlorodiphenyl sulfone |
| CN102304071A (en) * | 2011-08-25 | 2012-01-04 | 吴江市北厍盛源纺织品助剂厂 | Method for synthesizing 4.4-dichlorodiphenyl sulfone by two-step process |
| CN102304072A (en) * | 2011-08-25 | 2012-01-04 | 吴江市北厍盛源纺织品助剂厂 | Method for preparing 4.4-dichlorodiphenyl sulfone by using sulfur trioxide |
| US10745348B2 (en) | 2015-06-09 | 2020-08-18 | Vertellus Holdings Llc | Process for making diaryl sulfones |
| 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 |
| CN115650888A (en) * | 2022-10-18 | 2023-01-31 | 山东东方宏业化工有限公司 | Preparation method of high-purity 4, 4-dichlorodiphenyl sulfone |
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