CN101245041B - Process for producing 4,4'-bis(2,4-diaminophenyloxy)diphenyl sulfone - Google Patents
Process for producing 4,4'-bis(2,4-diaminophenyloxy)diphenyl sulfone Download PDFInfo
- Publication number
- CN101245041B CN101245041B CN200810034977XA CN200810034977A CN101245041B CN 101245041 B CN101245041 B CN 101245041B CN 200810034977X A CN200810034977X A CN 200810034977XA CN 200810034977 A CN200810034977 A CN 200810034977A CN 101245041 B CN101245041 B CN 101245041B
- Authority
- CN
- China
- Prior art keywords
- sulfobenzide
- diamino phenoxy
- preparation
- palladium
- hydrazine hydrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 4, 4'-bi (2, 4-diamino phenoxy) sulphone, which comprises the following steps: the 4, 4'-bi (2, 4-dinitro phenoxy) sulphone is reacted in a solvent system of palladium/carbon, hydrazine hydrate solution and saturated fatty alcohol in the temperature range of 80 to 90 DEG C for 1 hour to 5 hours; immediate filtration is carried out when the mixture is still hot; mother liquor is cooled; pure water is dropped and crystal products are precipitated; the 4, 4'-bi (2, 4-diamino phenoxy) sulphone crystalloid is obtained after filtration and vacuum drying. The preparation method is simple in operation, does not need subsequent refining purification technologies, is short in time consumption and high in product yield, has the purity of more than 99 percent and is suitable for industrial production.
Description
Technical field
The invention belongs to the preparation field of the polynary primary amine of aromatic series, particularly relate to a kind of preparation method of 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide.
Background technology
The heteroaromatic polymkeric substance has outstanding thermostability, anti-nuclear radiation, flame retardant resistance, organic solvent resistance and good high cryogenic mechanics performance and electric property, has obtained widespread use in space flight and aviation, electronics microelectronics, automobile boats and ships, electric contour performance field.
Along with the information electronic product towards high performance, lightweight, slimming, the development that becomes more meticulous, the insulating material of flexible copper-clad plate (FCCL) is had higher requirement, high strength heat-resisting, low-k and low-dielectric loss etc. as the needs height.Therefore, polyimide material enjoys favor in the FCCL field.
4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide is one of important source material of synthetic high cladodification polyimide resin, and therefore, it not only can be applicable to the FCCL field, strengthens advanced composite material but also can be applicable to the fire resistant polyimide carbon fiber.In addition, 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide also is the important raw and processed materials of synthetic More Malay imide resin.
4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide is the polynary primary amine of a kind of important aromatic series, but its preparation method do not see patent is arranged, bibliographical information.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide, this method technology is simple, need not follow-up refining purifying technique, and the three wastes are few, and the purity of product and yield height are applicable to suitability for industrialized production.
Chemical equation of the present invention is as follows:
The preparation method of a kind of 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide of the present invention comprises the steps:
4,4 '-two (2,4-2,4-dinitrophenoxy base) sulfobenzide, in palladium/charcoal, hydrazine hydrate solution and saturated fatty alcohol solvent system in 80 ℃～90 ℃ temperature range internal reactions after 1～5 hour, filtered while hot, the cooling mother liquor drips pure water, separate out crystalline product, filter, vacuum-drying obtains 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide crystal.
Described palladium/charcoal, its palladium mass percent is 1%～15%.
The mass percent concentration of described hydrazine hydrate solution is 60%～85%.
Described saturated fatty alcoholic solvent is selected from methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, one or more mixtures in 2-methyl cellosolve, cellosolvo, 2-methyl cellosolve, 3-methoxypropanol, 2-oxyethyl group propyl alcohol, the 3-oxyethyl group propyl alcohol.
The weight ratio of described 4,4 '-two (2,4-2,4-dinitrophenoxy base) sulfobenzides and palladium/charcoal is 100: 1～20.
The mol ratio of described 4,4 '-two (2,4-2,4-dinitrophenoxy base) sulfobenzides and hydrazine hydrate is 1: 20～50.
The weightmeasurement ratio of described 4,4 '-two (2,4-2,4-dinitrophenoxy base) sulfobenzides and saturated fatty alcoholic solvent is 1 gram: 15 milliliters～100 milliliters.
Beneficial effect of the present invention
(1) the present invention is the commercial run of preparation 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide;
(2) three wastes are few, and are environmentally friendly;
(3) consuming time few, obviously energy-saving and cost-reducing;
(4) simple to operate, related industrial chemicals is few;
(5) raw material sources are convenient;
(6) product purity reaches more than 99%, yield is high.
Description of drawings
Figure is 4, the molecular structure of 4 '-two (2, the 4-diamino phenoxy) sulfobenzide.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With 58.2 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) sulfobenzide, 0.8 gram palladium mass percent are that palladium/charcoal of 15%, 800 milliliters of ethanol 1600ml ethylene glycol add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 60% hydrazine hydrate solution (the hydrazine hydrate molecular weight is 50.06), totally 250.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 80 ℃～90 ℃ temperature range, continued stirring reaction 5 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 43.1 grams 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide crystal, purity is 99.5%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) sulfobenzide and theoretical amount (46.2 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) sulfobenzide is 93.2%.
Embodiment 2
With 58.2 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) sulfobenzide, 11.0 gram palladium mass percents are that 1% palladium/charcoal, 100ml ethylene glycol and 4800ml ethanol add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 85% hydrazine hydrate solution, totally 294.1 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 80 ℃～90 ℃ temperature range, continued stirring reaction 4.5 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 41.8 grams 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide crystal, purity is 99.7%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) sulfobenzide and theoretical amount (46.2 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) sulfobenzide is 90.5%.
Embodiment 3
With 58.2 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) sulfobenzide, 5.6 gram palladium mass percents are that palladium/charcoal of 5%, 250 milliliters of ethanol and 1600ml 2-methyl cellosolve add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 80% hydrazine hydrate solution, totally 260.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 80 ℃～90 ℃ temperature range, continued stirring reaction 5 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 41.3 grams 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide crystal, purity is 99.6%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) sulfobenzide and theoretical amount (46.2 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) sulfobenzide is 89.4%.
Embodiment 4
With 58.2 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) sulfobenzide, 3.6 gram palladium mass percents are palladium/charcoal of 10%, 400 milliliters of ethanol and 1200ml 1, the 2-propylene glycol adds in the reaction flask, stir, heat temperature raising to 60 ℃ begins to drip mass concentration and is 80% hydrazine hydrate solution, totally 300.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 80 ℃～90 ℃ temperature range, continued stirring reaction 1 hour, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 39.5 grams 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide crystal, purity is 99.7%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) sulfobenzide and theoretical amount (46.2 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) sulfobenzide is 85.4%.
Embodiment 5
With 58.2 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) sulfobenzide, 5.7 gram palladium mass percents are that 10% palladium/charcoal, 100ml methyl alcohol and 2500ml cellosolvo add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 85% hydrazine hydrate solution, totally 280.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 80 ℃～90 ℃ temperature range, continued stirring reaction 2.5 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 42.8 grams 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide crystal, purity is 99.5%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) sulfobenzide and theoretical amount (46.2 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) sulfobenzide is 92.7%.
Embodiment 6
With 58.2 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) sulfobenzide, 1.2 gram palladium mass percents are palladium/charcoal of 15%, 800 milliliters of ethanol and 1600ml 1, ammediol adds in the reaction flask, stir, heat temperature raising to 60 ℃ begins to drip mass concentration and is 60% hydrazine hydrate solution, totally 260.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 80 ℃～90 ℃ temperature range, continued stirring reaction 3.5 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 43.6 grams 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide crystal, purity is 99.8%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) sulfobenzide and theoretical amount (46.2 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) sulfobenzide is 94.3%.
Claims (7)
1. one kind 4, the preparation method of 4 '-two (2, the 4-diamino phenoxy) sulfobenzide, comprise the steps: 4,4 '-two (2,4-2,4-dinitrophenoxy base) sulfobenzide, in palladium/charcoal, hydrazine hydrate solution and saturated fatty alcohol solvent system in 80 ℃～90 ℃ temperature range internal reactions after 1～5 hour, filtered while hot, cooling mother liquor, drip pure water, separate out crystalline product, filter, vacuum-drying, obtain 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide.
2. the preparation method of 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide according to claim 1, it is characterized in that: the palladium mass percent of described palladium/charcoal is 1%～15%.
3. the preparation method of 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide according to claim 1, it is characterized in that: the mass percent concentration of described hydrazine hydrate solution is 60%～85%.
4. according to claim 14,4 '-two (2, the 4-diamino phenoxy) preparation method of sulfobenzide, it is characterized in that: described saturated fatty alcoholic solvent is selected from methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, one or more mixtures in 2-methyl cellosolve, cellosolvo, 2-methyl cellosolve, 3-methoxypropanol, 2-oxyethyl group propyl alcohol, the 3-oxyethyl group propyl alcohol.
5. the preparation method of 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide according to claim 1 and 2 is characterized in that: the weight ratio of described 4,4 '-two (2,4-2,4-dinitrophenoxy base) sulfobenzides and palladium/charcoal is 100: 1～20.
6. according to the preparation method of claim 1 or 3 described 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzides, it is characterized in that: the mol ratio of described 4,4 '-two (2,4-2,4-dinitrophenoxy base) sulfobenzides and hydrazine hydrate is 1: 20～50.
7. according to claim 1 or 4 described 4, the preparation method of 4 '-two (2, the 4-diamino phenoxy) sulfobenzide is characterized in that: described 4, the weightmeasurement ratio of 4 '-two (2,4-2,4-dinitrophenoxy base) sulfobenzides and saturated fatty alcoholic solvent is 1 gram: 15 milliliters～100 milliliters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810034977XA CN101245041B (en) | 2008-03-21 | 2008-03-21 | Process for producing 4,4'-bis(2,4-diaminophenyloxy)diphenyl sulfone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810034977XA CN101245041B (en) | 2008-03-21 | 2008-03-21 | Process for producing 4,4'-bis(2,4-diaminophenyloxy)diphenyl sulfone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101245041A CN101245041A (en) | 2008-08-20 |
| CN101245041B true CN101245041B (en) | 2010-12-01 |
Family
ID=39945755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810034977XA Expired - Fee Related CN101245041B (en) | 2008-03-21 | 2008-03-21 | Process for producing 4,4'-bis(2,4-diaminophenyloxy)diphenyl sulfone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101245041B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591277B (en) * | 2009-07-03 | 2012-11-28 | 东华大学 | Method for preparing 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone |
| CN102976983B (en) * | 2012-10-25 | 2015-10-21 | 华中科技大学 | A kind of sulfuryl fluorinated diamine compound and polyimide film material and method for making thereof |
| CN103739528A (en) * | 2012-10-25 | 2014-04-23 | 华中科技大学 | Sulfuryl fluorine-containing diamine compound, polyimide film material and preparation method thereof |
| CN109735292A (en) * | 2018-12-21 | 2019-05-10 | 东华大学 | A kind of BDADDS type silicon-containing adhesive and preparation method thereof |
| CN113912522A (en) * | 2020-12-24 | 2022-01-11 | 常州市阳光药业有限公司 | Refining method of 4,4' -bis (3-aminophenoxy) diphenyl sulfone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986526A (en) * | 2005-12-20 | 2007-06-27 | 上海化学试剂研究所 | Preparing process of 4,4-(4-aminophenoxy) diphenyl sulfone |
-
2008
- 2008-03-21 CN CN200810034977XA patent/CN101245041B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986526A (en) * | 2005-12-20 | 2007-06-27 | 上海化学试剂研究所 | Preparing process of 4,4-(4-aminophenoxy) diphenyl sulfone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101245041A (en) | 2008-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101245026A (en) | Process for producing 1,4-(2,4-diaminophenyloxy)-2,5-di-t-butyl benzene | |
| CN101245024A (en) | Process for producing 1,3-bis(2,4-diaminophenyloxy)benzene | |
| CN101284793B (en) | Preparation method of 2,2-di[4-(2,4-diamino phenoxy) phenyl group] propane | |
| CN101245041B (en) | Process for producing 4,4'-bis(2,4-diaminophenyloxy)diphenyl sulfone | |
| CN101245023A (en) | Process for producing 2,2-bis[2,4-diaminophenyloxy)phenyl]hexafluoropropane | |
| CN101250124A (en) | Method for preparing 2,5-di(2,4-diamino phenoxy) toluene | |
| CN101250120B (en) | Method for preparing 4,4-di(2,4-diamino phenoxy) diphenylmethane | |
| CN101293842B (en) | Method for preparing 4,4'-di(2,4-diaminophenyloxy)biphenyl | |
| CN101215241A (en) | Method for preparing 1,4-di(2,4-diaminophenoxy)benzene | |
| CN101260052A (en) | Method for preparing 2,6-di(2,4-diaminophenoxy)toluene | |
| CN101245030B (en) | Process for producing 1,2-bis(2,4-diaminophenyloxy)benzene | |
| CN101250128A (en) | Method for preparing 1,4-di(2,4-diamino phenoxy) naphthalene | |
| CN101260053A (en) | Method for preparing 2,2-di[3-amino-4-(2,4-diaminophenoxy)phenyl]hexafluoropropane | |
| CN101250142A (en) | Method for preparing 4,4'-di(2,4-diamino phenoxy)-3,3',5,5'-tetramethyl diphenyl sulfone | |
| CN101260058A (en) | Method for preparing 4,4'-di(2,4-diaminophenoxy)diphenyl ether | |
| CN101245022A (en) | Process for producing 3,5-bis(2,4-diaminophenyloxy)-2-naphthoic acid | |
| CN101260057A (en) | Method for preparing 1,3,5-tri(2,4-diaminophenoxy)benzene | |
| CN101245028A (en) | Process for producing 2,2-bis[3-amido-4-(4-aminophenoxy)phenyl] hexafluoropropane | |
| CN101265203A (en) | Method for preparing 3,3'-diamino-4,4'-di(2,4-diaminophenoxy)diphenyl | |
| CN101245031A (en) | Process for producing 1,2-bis(2,4-diaminophenyloxy)naphthalin | |
| CN101245025A (en) | Process for producing 1,3-bis(2,4-diaminophenyloxy)naphthalin | |
| CN101289407A (en) | Method for preparing 4,4'-di(2,4- diaminophenyloxy)-3,3',5,5'-tetramethylbiphenyl | |
| CN101260060A (en) | Method for preparing 3,5-di(2,4-diaminophenoxy)toluene | |
| CN101250122A (en) | Method for preparing 2,3-di(2,4-diamino phenoxy) naphthalene | |
| CN101265204A (en) | Method for preparing 3,5-di(2,4-diaminophenoxy)benzoic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101201 Termination date: 20130321 |