CN101250143B - Method for preparing 3,3-diaminodiphenyl sulphone - Google Patents
Method for preparing 3,3-diaminodiphenyl sulphone Download PDFInfo
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- CN101250143B CN101250143B CN2008100547094A CN200810054709A CN101250143B CN 101250143 B CN101250143 B CN 101250143B CN 2008100547094 A CN2008100547094 A CN 2008100547094A CN 200810054709 A CN200810054709 A CN 200810054709A CN 101250143 B CN101250143 B CN 101250143B
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Abstract
The invention relates to a preparation method of 3, 3-diaminodiphenylsulfone, which comprises adding iron powder with solvent in weak acid property, to reduce 3, 3-dinitrodiphenylsulfone into 3, 3-diaminodiphenylsulfone. The inventive method is beneficial for reaction and the reaction is complete, the invention processes purification after the reaction to obtain high-purity white crystal, the mother liquor is deposited, depressurized and distilled to recover solvent for reuse. In the reaction, sulfolane solvent can be added into the reaction to shorten the reaction time to 2-6h, thereby improving reaction selectivity, and sulfolane can be circulated in the preparation while the loss is 5%, to improve solvent utilization and reduce cost.
Description
Technical field
The present invention relates to a kind of 3, the preparation method of 3-diaminodiphenylsulfone(DDS).
Background technology
3, the 3-diaminodiphenylsulfone(DDS) is the important monomer of synthetic polysulphonamide fiber, polysulfonamides fibre (Polysulfonamide fiber) is called for short fragrant sulfone synthetic fibre (PSA), it is a kind of aromatic polyamide fibre that on high polymer main chain, contains sulfuryl (SO 2-), it by 4,4 ' diaminodiphenylsulfone(DDS), 3,3 ' diaminodiphenylsulfone(DDS) and the polycondensation of p-phthaloyl chloride cryogenic fluid, be shaped through wet-spinning, the high temperature drawing-off makes.This fiber is light beige and is rich in gloss, fibre strength is 3.0～4.5g/d, elongation is 20～25%, initial modulus is 760kg/mm2, proportion be 1.416g/cm3. since the existing contraposition of fragrant sulfone synthetic fibre have again between the structure of position, macromole connects and has sulfuryl to exist, so have heat-resisting, flame resistivity, 100 hours strength losses of heating also have good insulation performance and radioresistance less than 5% in 300 ℃ of warm airs.The main protective clothing goods that are applied in, as suit, special uniform, resistant to elevated temperatures goods such as bunker clothing.The insulation aspect is mainly used in electrical machine insulation, and transformer insulated grade wherein insulation paper (H, F) level is a main application facet of fragrant sulfone synthetic fibre material.Cellular structural material be can also make, aircraft interlayer sound-insulating and heat-insulating and self-extinguishing material are used for.
3, the 3-diaminodiphenylsulfone(DDS) is to be used for polysulphonamide fiber (PSA) monomer, so 3, the 3-diaminodiphenylsulfone(DDS) is the important source material of synthetic polysulphonamide fiber (PSA).Adopt present 3,3 of preparation method's preparation of 3-diaminodiphenylsulfone(DDS), the not only impure amount height of 3-diaminodiphenylsulfone(DDS), purity is low, and reaction is not thorough in preparation process, product yield is low.
Summary of the invention
Technical problem to be solved by this invention be reaction thoroughly, the purity that product yield height and foreign matter content are few high 3, the preparation method of 3-diaminodiphenylsulfone(DDS).
The present invention adopts following technical scheme:
The present invention adopts following feed ratio: 1 mole 3, and 3-diphenylsulfone dinitro, 0.1～1.5 mole hydrochloride, 3～8 moles of iron powders, 1～5 mole of solvent, 40～60 mole of water adopt following preparation process: with 0.1～1.5 mole hydrochloride, 3～8 moles of iron powders, 40～60 mole of water, 1～5 mole of solvent is mixed in proportion, under 80～100 ℃ condition, slowly add 1 mole 3, the 3-diphenylsulfone dinitro carries out 2～6 hours back flow reaction, transfers pH value with sodium hydroxide then, makes PH=9-10, filter, filtrate is decoloured at 80～100 ℃, filters, and is cooled to 20 ℃, crystallization can obtain 3,3-diaminodiphenylsulfone(DDS) white crystals.
The used solvent of the present invention is a tetramethylene sulfone.
The used solvent of the present invention is methyl-sulphoxide, gamma-butyrolactone or dimethyl formamide.
Positively effect of the present invention is as follows: preparation method of the present invention utilizes iron powder under solutions of weak acidity, adds the method for solvent, and 3, the 3-diphenylsulfone dinitro is reduced to 3, the 3-diaminodiphenylsulfone(DDS).This method helps reaction and carries out smoothly and react thorough.After reacting completely, carry out purification processes then and obtain the very high white crystals of purity.Mother liquor reclaims solvent through sedimentation, underpressure distillation, reuses.
Above-mentioned 3, among the preparation method of 3-diaminodiphenylsulfone(DDS), used solvent is selected from methyl-sulphoxide, tetramethylene sulfone, gamma-butyrolactone, dimethyl formamide, preferred tetramethylene sulfone.
In preparation 3, adopted solvent sulfolane in the method for 3-diaminodiphenylsulfone(DDS), can be fully with 3 of reaction generation, the 3-diaminodiphenylsulfone(DDS) is dissolved in the solvent, helps successful reaction and carries out, its solubleness:
3, the solubleness of 3-diaminodiphenylsulfone(DDS) in tetramethylene sulfone is as shown in the table:
| 50℃ | 60℃ | 70℃ | 80℃ | 90℃ | 100℃ |
| 58.7 | 65.85 | 74.00 | 83.75 | 95.4 | 100.32 |
3, the solubleness of 3-diaminodiphenylsulfone(DDS) in tetramethylene sulfone and water mixed solution is as shown in the table:
Tetramethylene sulfone: water=1: 2.5
| 50℃ | 60℃ | 70℃ | 80℃ | 90℃ | 98℃ |
| 3.79 | 5.68 | 11.24 | 22.58 | 57.94 | 82.67 |
Adding sulfolane solvent in reaction process can be reaction product 3, the 3-diaminodiphenylsulfone(DDS) separates fully with water, reduced in the reaction residues 3, the residual quantity of 3-diaminodiphenylsulfone(DDS), can make reaction more thoroughly improve yield, make yield reach 75%, can remove the impurity in the product fully simultaneously and obtain highly purified product, through HPLC detection level＞99.5, fusing point＞171 ℃.
Add sulfolane solvent and can make the reaction times shorten to 2～6 hours in reaction process, the selectivity of reaction is improved, tetramethylene sulfone can recycled in preparation process simultaneously, and loss has only 5%, has improved the utilization ratio of solvent, has reduced cost.
Embodiment
Embodiment 1:
In the reaction vessel of 1000ml, add 280g water, 89.8g iron powder, 20g hydrochloric acid, be warmed up to 90 ℃ then, add the 300g tetramethylene sulfone then, adding 125g3 slowly again, 3-diphenylsulfone dinitro reaction 2～3 hours, add sodium hydroxide then, make its solution alkalize, iron mud is precipitated in PH=9～10, remove by filter iron mud, promptly get faint yellow filtrate, add gac, decolour at 80 ℃ ~ 100 ℃, filtration separates gac, reaction soln is cooled to 20 ℃ of crystallizations, and suction filtration is drying to obtain white crystals 3,3-diaminodiphenylsulfone(DDS) 73g, yield are 73%.
Embodiment 2
In the reaction vessel of 1000ml, add 300g water, 134.4g iron powder, 25g hydrochloric acid, be warmed up to 90 ℃ then, add the 300g tetramethylene sulfone then, adding 125g 3 slowly again, 3-diphenylsulfone dinitro reaction 2～3 hours, add sodium hydroxide then, make its solution alkalize, iron mud is precipitated in PH=9～10, remove by filter iron mud, promptly get faint yellow filtrate, add gac, decolour at 80 ℃ ~ 100 ℃, filtration separates gac, reaction soln is cooled to 20 ℃ of crystallizations, and suction filtration is drying to obtain white crystals 3,3-diaminodiphenylsulfone(DDS) 81g, yield are 81%.
Embodiment 3
In the reaction vessel of 1000ml, add 300g water, the 120g iron powder, 25g hydrochloric acid, be warmed up to 90 ℃ then, add the 300g tetramethylene sulfone then, adding 125g 3 slowly again, 3-diphenylsulfone dinitro reaction 2～3 hours, add sodium hydroxide then and make its solution alkalize PH=9～10, with iron mud precipitation, remove by filter iron mud, promptly get faint yellow filtrate adding gac and decolour at 80 ℃ ~ 100 ℃, filtration separates gac, reaction soln is cooled to 20 ℃ of crystallizations, and suction filtration is drying to obtain white crystals 3,3-diaminodiphenylsulfone(DDS) 77g, yield are 77%.
Claims (1)
1. one kind 3, the preparation method of 3-diaminodiphenylsulfone(DDS), it is characterized in that adopting following feed ratio: 1 mole 3,3-diphenylsulfone dinitro, 0.1-1.5 mole hydrochloride, 3-8 mole iron powder, 1-5 mole tetramethylene sulfone, the 40-60 mole of water adopts following preparation process: with the 0.1-1.5 mole hydrochloride, 3-8 mole iron powder, the 40-60 mole of water, 1-5 mole tetramethylene sulfone is mixed in proportion, under 80-100 ℃ condition, slowly add 1 mole 3, the 3-diphenylsulfone dinitro carries out 2-6 hour back flow reaction, uses the sodium hydroxide adjust pH then, makes pH=9-10, filter, filtrate is decoloured at 80-100 ℃, filters, and is cooled to 20 ℃, crystallization can obtain 3,3-diaminodiphenylsulfone(DDS) white crystals.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100547094A CN101250143B (en) | 2008-03-28 | 2008-03-28 | Method for preparing 3,3-diaminodiphenyl sulphone |
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| CN2008100547094A CN101250143B (en) | 2008-03-28 | 2008-03-28 | Method for preparing 3,3-diaminodiphenyl sulphone |
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| CN101250143A CN101250143A (en) | 2008-08-27 |
| CN101250143B true CN101250143B (en) | 2010-11-10 |
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| CN110551046B (en) * | 2019-08-26 | 2021-05-14 | 河北建新化工股份有限公司 | Continuous synthesis method of 3, 3' -diamino diphenyl sulfone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD285347A5 (en) * | 1985-05-21 | 1990-12-12 | Humboldt-Universitaet Zu Berlin,Direktorat Fuer Forschung,Dd | PROCESS FOR THE PREPARATION OF 3,3'-DIAZIDODHENYLSULPHONE |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD285347A5 (en) * | 1985-05-21 | 1990-12-12 | Humboldt-Universitaet Zu Berlin,Direktorat Fuer Forschung,Dd | PROCESS FOR THE PREPARATION OF 3,3'-DIAZIDODHENYLSULPHONE |
Non-Patent Citations (2)
| Title |
|---|
| 孙同华.3 3＇-二氨基二苯基砜合成工艺研究.化工时刊 5.1999 |
| 孙同华.3,3＇-二氨基二苯基砜合成工艺研究.化工时刊 5.1999,(5),32-33. * |
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