CN101381334B - 4,4'-bis(4-aminophenoxy)phenyl sulfide preparation method - Google Patents
4,4'-bis(4-aminophenoxy)phenyl sulfide preparation method Download PDFInfo
- Publication number
- CN101381334B CN101381334B CN 200810041356 CN200810041356A CN101381334B CN 101381334 B CN101381334 B CN 101381334B CN 200810041356 CN200810041356 CN 200810041356 CN 200810041356 A CN200810041356 A CN 200810041356A CN 101381334 B CN101381334 B CN 101381334B
- Authority
- CN
- China
- Prior art keywords
- diphenyl sulfide
- amino
- benzene oxygen
- 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 method for preparing 4, 4'-bis (4-aminophenoxy) diphenyl sulfide ether, which comprises the following step: 4, 4'-bis (4-nitrophenoxy) diphenyl sulfide ether reacts for 1 to 5 hours in a system formed by palladium/carbon, hydrazine hydrate solution and an organic solvent within the temperature range of between 70 and 85 DEG C, the filtration is performed, mother liquid is cooled to precipitate a product, and the product is subjected to filtration and vacuum drying to obtain the 4, 4'-bis (4-aminophenoxy) diphenyl sulfide ether. The method has simple operation, does not need subsequent refining and purification processes, has small time consumption, and is suitable for industrialized production; and the obtained product has high yield, and the purity of the product reaches more than 99 percent.
Description
Technical field
The invention belongs to the preparation field of phenolic hydroxy group aromatic dicarboxylic primary amine, particularly relate to a kind of preparation method of 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide.
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, is widely applied 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 such as the needs height, low-k and low-dielectric loss etc.Therefore, polyimide material enjoys favor in the FCCL field.
4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide is one of important source material of synthesis of polyimides resin, and therefore, it not only can be applicable to the FCCL field, but also can be applicable to the photo-sensistive polyimide material.In addition, 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide also is the important raw and processed materials of synthesizing glycidol amine type polyfunctional epoxy resin.
4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide is one of a kind of important aromatic dicarboxylic primary amine.The preparation method of aromatic dicarboxylic primary amine has many patents, bibliographical information:
Chinese patent CN1485315A, disclose a kind of 3,4 '-preparation method of diaminodiphenyl oxide;
Chinese patent CN1425644A, disclose a kind of 2, the preparation method of two [4-(4-amino-benzene oxygen) phenyl] propane of 2-;
Japanese Patent JP63-126848, disclose a kind of 4,4 '-two (3-amino-benzene oxygen)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl;
Japanese Patent JP62-248635, disclose a kind of 4,4 '-preparation method of two (3-amino-benzene oxygen) biphenyl;
US Patent No. 4377525, disclose a kind of 1, the preparation method of two (3-amino-benzene oxygen) benzene of 3-;
US Patent No. 4064107, disclose a kind of 4,4 '-preparation method of two (4-amino-benzene oxygen) phenyl ether;
Chinese patent CN1919829A discloses a kind of preparation method of alkyl substituent aromatic diamine;
Chinese patent CN101134730A, disclose a kind of 4,4 '-diamino-4 "-preparation method of hydroxy benzophenone alkane;
Chinese patent CN101157623A discloses the preparation method of a kind of Isosorbide-5-Nitrae-two (4-amino-benzene oxygen) benzene;
Chinese patent CN101117324A, disclose a kind of 2, the preparation method of two (4-amino-benzene oxygen) cyanobenzenes of 6-;
Chinese patent CN101100446A, disclose a kind of 2, the preparation method of two [3-amino-4-(4-cyano-benzene oxygen) phenyl] propane of 2-;
Chinese patent CN101130502A, disclose a kind of 2, two [3-amino-4-(4-nitrophenoxy) phenyl]-1,1,1,3,3 of 2-, the preparation method of 3-HFC-236fa;
Chinese patent CN101186579A, disclose a kind of 4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl;
It is a kind of 1 that the people such as Yu Xinhai [insulating material communication, 1999,32 (5): 1-4] disclose, the preparation method of two (3-amino-benzene oxygen) benzene of 3-, simultaneously, the also synthetic series of heat plastic polyimide that obtained.
That the people such as Yu Xinhai [insulating material, 2001,34 (4): 13-16] disclose is a kind of 3,3 '-preparation method of diaminodiphenyl oxide;
It is a kind of 2 that the people such as Yu Xinhai [insulating material, 2001,34 (6): 3-6] disclose, the preparation method of two [4-(3-amino-benzene oxygen) phenyl] propane of 2-;
It is a kind of 2 that the people such as Yu Xinhai [insulating material, 2002,35 (4): 3-7] disclose, the preparation method of two [4-(4-amino-benzene oxygen) phenyl] propane of 2-;
It is a kind of 2 that Yu Xinhai [New Chemical Materials, 2003,31 (10): 24-27] discloses, two [4-(4-amino-benzene oxygen) phenyl]-1,1,1,3,3 of 2-, the preparation method of 3-HFC-236fa;
That the people such as Yu Xinhai [insulating material, 2006,39 (5): 1-3,6] disclose is a kind of 4,4 '-preparation method of two (3-amino-benzene oxygen) benzophenone;
It is a kind of 1 that the people such as Yu Xinhai [insulating material, 2006,39 (3): 1-4,8] disclose, the preparation method of two (4-amino-benzene oxygen) benzene of 3-;
It is a kind of 2 that the people such as Yu Xinhai [insulating material, 2007,40 (4): 1-5,8] disclose, two (the 3-amino-4-hydroxylphenyls)-1,1,1,3,3 of 2-, the preparation method of 3-HFC-236fa;
That the people such as Yu Xinhai [insulating material, 2008,41 (2): 10-14] disclose is a kind of 4,4 '-preparation method of two (4-amino-benzene oxygen) biphenyl.
But the preparation method of 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide that the purity of and product simple for technique and yield are high does not also have report.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide, the method is simple to operate, need not follow-up refining purifying technique, consuming time few, the three wastes are few, and the purity of product and yield are high, 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 (4-amino-benzene oxygen) diphenyl sulfide of the present invention comprises the following steps:
4,4 '-two (4-nitrophenoxy) diphenyl sulfide, in palladium/charcoal, hydrazine hydrate solution and organic solvent system in 70 ℃ of-85 ℃ of temperature range internal reactions after 1～5 hour, filtered while hot, the cooling mother liquor is separated out the white crystal product, filter, vacuum-drying obtains 4,4 '-two (4-amino-benzene oxygen) white diphenyl sulfide crystal.
Described palladium/charcoal, its palladium mass percent is 1%～15%.
Described hydrazine hydrate solution, its mass percent concentration are 60%～85%.
Described organic solvent is methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, 1, one or more mixtures in 2-propylene glycol, 1,3-PD, 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 (4-nitrophenoxy) diphenyl sulfides and palladium/charcoal is 100: 1～20.
The mol ratio of described 4,4 '-two (4-nitrophenoxy) diphenyl sulfides and hydrazine hydrate is 1: 10～30.
The weightmeasurement ratio of described 4,4 '-two (4-nitrophenoxy) diphenyl sulfides and organic 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 (4-amino-benzene oxygen) diphenyl sulfide;
(2) three wastes are few, and are environmentally friendly;
(3) consuming time few, obviously energy-saving and cost-reducing;
(4) industrial chemicals convenient sources simple to operate, related, kind is few;
(5) product yield and purity are all very high, and purity reaches more than 99%.
Description of drawings
Fig. 1 is 4, the molecular structure of 4 '-two (4-amino-benzene oxygen) diphenyl sulfide.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention 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 limited range equally.
Embodiment 1
With 46.0 gram (0.1 moles) 4,4 '-two (4-nitrophenoxy) diphenyl sulfide, 0.5 gram palladium mass percent are that 15% palladium/charcoal, 90ml ethanol and 600ml ethylene glycol add in the reaction flask, stir, be heated to 60 ℃, begin to drip mass concentration and be 60% hydrazine hydrate solution, totally 160.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-85 ℃ temperature range, continued stirring reaction 1 hour, slightly cold, filtered while hot, the cooling mother liquor, separate out the white crystals product, filter vacuum-drying, obtain 4 of 37.0 gram whites, 4 '-two (4-amino-benzene oxygen) diphenyl sulfide crystal, fusing point is 126.5 ℃, purity is 99.8%, according to 4 of reality acquisition, the amount of 4 '-two (4-amino-benzene oxygen) diphenyl sulfide and theoretical amount (40.0 gram), the yield that calculates 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide is 92.4%.
Embodiment 2
With 46.0 gram (0.1 moles) 4,4 '-two (4-nitrophenoxy) diphenyl sulfide, 9.2 gram palladium mass percents are that 1% palladium/charcoal, 2000ml ethylene glycol and 400ml methyl alcohol add in the reaction flask, stir, be heated to 60 ℃, begin to drip mass concentration and be 85% hydrazine hydrate solution, totally 95.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-85 ℃ temperature range, continued stirring reaction 5 hours, slightly cold, filtered while hot, the cooling mother liquor, separate out the white crystals product, filter vacuum-drying, obtain 4 of 36.0 gram whites, 4 '-two (4-amino-benzene oxygen) diphenyl sulfide crystal, fusing point is 125.4 ℃, purity is 99.7%, according to 4 of reality acquisition, the amount of 4 '-two (4-amino-benzene oxygen) diphenyl sulfide and theoretical amount (40.0 gram), the yield that calculates 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide is 90.0%.
Embodiment 3
With 46.0 gram (0.1 moles) 4,4 '-two (4-nitrophenoxy) diphenyl sulfide, 4.5 gram palladium mass percents are that 5% palladium/charcoal, 800ml ethylene glycol and 200ml 2-methyl cellosolve add in the reaction flask, stir, be heated to 60 ℃, begin to drip mass concentration and be 80% hydrazine hydrate solution, totally 90.6 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-85 ℃ temperature range, continued stirring reaction 3.5 hours, slightly cold, filtered while hot, the cooling mother liquor, separate out the white crystals product, filter, vacuum-drying obtains 4 of 37.8 gram whites, 4 '-two (4-amino-benzene oxygen) diphenyl sulfide crystal, purity is 99.7%, amount and the theoretical amount (40.0 gram) of 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide that obtains according to reality, the yield that calculates 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide is 94.5%.
Embodiment 4
With 46.0 gram (0.1 moles) 4,4 '-two (4-nitrophenoxy) diphenyl sulfide, 3.5 gram palladium mass percents are 10% palladium/charcoal, 200ml ethanol and 1000ml 1, the 2-propylene glycol adds in the reaction flask, stir, be heated to 60 ℃, begin to drip mass concentration and be 80% hydrazine hydrate solution, totally 185.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-85 ℃ temperature range, continued stirring reaction 1 hour, slightly cold, filtered while hot, the cooling mother liquor, separate out the white crystals product, filter, vacuum-drying obtains 4 of 36.2 gram whites, 4 '-two (4-amino-benzene oxygen) diphenyl sulfide crystal, purity is 99.8%, amount and the theoretical amount (40.0 gram) of 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide that obtains according to reality, the yield that calculates 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide is 90.5%.
Embodiment 5
With 46.0 gram (0.1 moles) 4,4 '-two (4-nitrophenoxy) diphenyl sulfide, 4.5 gram palladium mass percents are that 10% palladium/charcoal, 120ml methyl alcohol and 1200ml cellosolvo add in the reaction flask, stir, be heated to 60 ℃, begin to drip mass concentration and be 85% hydrazine hydrate solution, totally 80.6 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-85 ℃ temperature range, continued stirring reaction 2.5 hours, slightly cold, filtered while hot, the cooling mother liquor, separate out the white crystals product, filter, vacuum-drying obtains 4 of 35.8 gram whites, 4 '-two (4-amino-benzene oxygen) diphenyl sulfide crystal, purity is 99.6%, amount and the theoretical amount (40.0 gram) of 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide that obtains according to reality, the yield that calculates 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide is 89.6%.
Embodiment 6
With 46.0 gram (0.1 moles) 4,4 '-two (4-nitrophenoxy) diphenyl sulfide, 1.6 gram palladium mass percents are 15% palladium/charcoal, 200ml ethanol, 1200ml cellosolvo and 800ml 1, ammediol adds in the reaction flask, stir, be heated to 60 ℃, begin to drip mass concentration and be 60% hydrazine hydrate solution, totally 90.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-85 ℃ temperature range, continued stirring reaction 5 hours, slightly cold, filtered while hot, the cooling mother liquor, separate out the white crystals product, filter, vacuum-drying obtains 4 of 34.4 gram whites, 4 '-two (4-amino-benzene oxygen) diphenyl sulfide crystal, purity is 99.5%, amount and the theoretical amount (40.0 gram) of 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide that obtains according to reality, the yield that calculates 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide is 86.0%.
Embodiment 7
With 46.0 gram (0.1 moles) 4,4 '-two (4-nitrophenoxy) diphenyl sulfide, 2.0 gram palladium mass percents are that 15% palladium/charcoal, 4600ml ethanol add in the reaction flask, stir, be heated to 60 ℃, begin to drip mass concentration and be 80% hydrazine hydrate solution, totally 187.5 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-85 ℃ temperature range, continued stirring reaction 3.5 hours, slightly cold, filtered while hot, the cooling mother liquor, separate out the white crystals product, filter, vacuum-drying obtains 4 of 37.8 gram whites, 4 '-two (4-amino-benzene oxygen) diphenyl sulfide crystal, purity is 99.8%, amount and the theoretical amount (40.0 gram) of 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide that obtains according to reality, the yield that calculates 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide is 94.5%.
Claims (1)
1. one kind 4, the preparation method of 4 '-two (4-amino-benzene oxygen) diphenyl sulfide comprises step:
With 46.0g 4,4 '-two (4-nitrophenoxy) diphenyl sulfide, 4.5g palladium mass percent are that palladium/charcoal of 5%, 800ml ethylene glycol and 200ml2-methyl cellosolve add in the reaction flask, stir, be heated to 60 ℃, begin to drip mass concentration and be 80% hydrazine hydrate solution, altogether 90.6g; After hydrazine hydrate is added dropwise to complete, in 70 ℃-85 ℃ temperature range, continue to stir 3.5 hours, slightly cold, filtered while hot, the cooling mother liquor is separated out the white crystals product, filters, vacuum-drying obtains 4,4 ' of 37.8g white-two (4-amino-benzene oxygen) diphenyl sulfide;
Perhaps with 46.0g 4,4 '-two (4-nitrophenoxy) diphenyl sulfide, 2.0g palladium mass percent are that 15% palladium/charcoal, 4600ml ethanol add in the reaction flask, stir, be heated to 60 ℃, begin to drip mass concentration and be 80% hydrazine hydrate solution, altogether 187.5g; After hydrazine hydrate is added dropwise to complete, in 70 ℃-85 ℃ temperature range, continue to stir 3.5 hours, slightly cold, filtered while hot, the cooling mother liquor is separated out the white crystals product, filters, vacuum-drying obtains 4,4 ' of 37.8g white-two (4-amino-benzene oxygen) diphenyl sulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810041356 CN101381334B (en) | 2008-08-04 | 2008-08-04 | 4,4'-bis(4-aminophenoxy)phenyl sulfide preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810041356 CN101381334B (en) | 2008-08-04 | 2008-08-04 | 4,4'-bis(4-aminophenoxy)phenyl sulfide preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101381334A CN101381334A (en) | 2009-03-11 |
| CN101381334B true CN101381334B (en) | 2013-01-02 |
Family
ID=40461415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810041356 Expired - Fee Related CN101381334B (en) | 2008-08-04 | 2008-08-04 | 4,4'-bis(4-aminophenoxy)phenyl sulfide preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101381334B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215241A (en) * | 2007-12-26 | 2008-07-09 | 东华大学 | Method for preparing 1,4-di(2,4-diaminophenoxy)benzene |
-
2008
- 2008-08-04 CN CN 200810041356 patent/CN101381334B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215241A (en) * | 2007-12-26 | 2008-07-09 | 东华大学 | Method for preparing 1,4-di(2,4-diaminophenoxy)benzene |
Non-Patent Citations (1)
| Title |
|---|
| J.V.Crivello,et al..Synthesis and Characterization of Photosensitive Polyimides.《Journal of Polymer Science:Part A:Polymer Chemistry》.1987,第25卷(第12期),3293-3309. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101381334A (en) | 2009-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101245026A (en) | Process for producing 1,4-(2,4-diaminophenyloxy)-2,5-di-t-butyl benzene | |
| CN101284793B (en) | Preparation method of 2,2-di[4-(2,4-diamino phenoxy) phenyl group] propane | |
| CN101245024A (en) | Process for producing 1,3-bis(2,4-diaminophenyloxy)benzene | |
| 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 | |
| CN101245041B (en) | Process for producing 4,4'-bis(2,4-diaminophenyloxy)diphenyl sulfone | |
| 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 | |
| CN101397258B (en) | Process for preparation of 3,3-diamino-4,4-dihydroxybiphenyl | |
| CN101381334B (en) | 4,4'-bis(4-aminophenoxy)phenyl sulfide preparation method | |
| CN101260052A (en) | Method for preparing 2,6-di(2,4-diaminophenoxy)toluene | |
| CN101245030B (en) | Process for producing 1,2-bis(2,4-diaminophenyloxy)benzene | |
| CN101260053A (en) | Method for preparing 2,2-di[3-amino-4-(2,4-diaminophenoxy)phenyl]hexafluoropropane | |
| CN101250128A (en) | Method for preparing 1,4-di(2,4-diamino phenoxy) naphthalene | |
| CN101260057A (en) | Method for preparing 1,3,5-tri(2,4-diaminophenoxy)benzene | |
| 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 | |
| CN101245028A (en) | Process for producing 2,2-bis[3-amido-4-(4-aminophenoxy)phenyl] hexafluoropropane | |
| CN101260055A (en) | Method for preparing 1,6-di(2,4-diaminophenoxy)naphthalene | |
| CN101260054A (en) | Method for preparing 2,2-di[3-amino-4-(2,4-diaminophenoxy)phenyl]propane | |
| CN101260060A (en) | Method for preparing 3,5-di(2,4-diaminophenoxy)toluene | |
| CN101265207A (en) | Method for preparing 2,2-di[4-(2,4-diaminophenoxy)-3,5-dimethylphenyl]hexafluoropropane | |
| CN101260059A (en) | Method for preparing 2,6-dimethyl-1,4-di(2,4-diaminophenoxy)benzene | |
| CN101245031A (en) | Process for producing 1,2-bis(2,4-diaminophenyloxy)naphthalin | |
| CN101245027A (en) | Process for producing 2,2-bis[3-amido-4-(4-aminophenoxy)phenyl]propane |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130102 Termination date: 20150804 |
|
| EXPY | Termination of patent right or utility model |