CN101293843A - Method for preparing 3,3'-diamino--4,4'-di(4-aminophenoxy)biphenyl - Google Patents
Method for preparing 3,3'-diamino--4,4'-di(4-aminophenoxy)biphenyl Download PDFInfo
- Publication number
- CN101293843A CN101293843A CNA2008100386548A CN200810038654A CN101293843A CN 101293843 A CN101293843 A CN 101293843A CN A2008100386548 A CNA2008100386548 A CN A2008100386548A CN 200810038654 A CN200810038654 A CN 200810038654A CN 101293843 A CN101293843 A CN 101293843A
- Authority
- CN
- China
- Prior art keywords
- diamino
- biphenyl
- amino
- benzene oxygen
- preparation
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 3,3'-diamino -4,4'-bis(4-aminophenoxy)biphenyl crystal. The preparation method comprises allowing 3,3'-diamino -4,4'-bis(4-nitrophenoxy)biphenyl to react at 70-85 DEC C in a system of palladium/carbon, hydrazine hydrate solution and alcohol solvent for 10-22 hours, rapidly filtering, cooling mother liquor, adding dropwise appropriate amount of pure water to separate out crystal product, filtering and vacuum drying. The method has simple operation, no requirement of subsequent refining and purifying process, short time, and suitability for industrialized production. The obtained 3,3'-diamino -4,4'-bis(4-aminophenoxy)biphenyl crystal has high yield and high purity of 99% or higher.
Description
Technical field
The invention belongs to the preparation field of the polynary primary amine of aromatic series, particularly relate to a kind of 3,3 '-diamino-4,4 '-preparation method of two (4-amino-benzene oxygen) biphenyl.
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.
3,3 '-diamino-4,4 '-two (4-amino-benzene oxygen) biphenyl is one of important source material of synthetic high cladodification polyimide resin, 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, 3,3 '-diamino-4,4 '-two (4-amino-benzene oxygen) biphenyl also is the important raw and processed materials of synthetic More Malay imide resin.
3,3 '-diamino-4,4 '-two (4-amino-benzene oxygen) biphenyl 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 3,3 '-diamino-4,4 '-preparation method of two (4-amino-benzene oxygen) biphenyl, this method technology is simple, need not follow-up refining purifying technique, the three wastes are few, the purity of product and yield height are applicable to suitability for industrialized production.
Chemical equation of the present invention is as follows:
Of the present invention a kind of 3,3 '-diamino-4,4 '-preparation method of two (4-amino-benzene oxygen) biphenyl, comprise the steps:
3,3 '-diamino-4,4 '-two (4-nitrophenoxy) biphenyl, in palladium/charcoal, hydrazine hydrate solution and alcoholic solvent system in 70 ℃～85 ℃ temperature range internal reactions after 10～22 hours, filtered while hot, the cooling mother liquor drips an amount of pure water, separate out crystalline product, filter, vacuum-drying obtains 3,3 '-diamino-4,4 '-two (4-amino-benzene oxygen) biphenyl crystal.
Described palladium/charcoal, its palladium mass percent is 1%～15%.
The mass percent concentration of described hydrazine hydrate solution is 60%～85%.
Described 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.
Described 3,3 '-diamino-4,4 '-weight ratio of two (4-nitrophenoxy) biphenyl and palladium/charcoal is 100: 1～20.
Described 3,3 '-diamino-4,4 '-mol ratio of two (4-nitrophenoxy) biphenyl and hydrazine hydrate is 1: 8～25.
Described 3,3 '-diamino-4,4 '-weightmeasurement ratio of two (4-nitrophenoxy) biphenyl and alcoholic solvent is 1 gram: 15 milliliters～100 milliliters.
Beneficial effect of the present invention
(1) the present invention be preparation 3,3 '-diamino-4,4 '-commercial run of two (4-amino-benzene oxygen) biphenyl;
(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) 3,3 '-diamino-4,4 '-two (4-nitrophenoxy) biphenyl raw material sources such as (Shanghai EMST Electron Material Co., Ltd stably manufactured) are convenient, help of the present invention 3,3 '-diamino-4,4 '-industrialization of two (4-amino-benzene oxygen) biphenyl product and further applying;
(6) product purity reaches more than 99%, yield is high.
Description of drawings
Figure is 3,3 '-diamino-4,4 '-molecular structure of two (4-amino-benzene oxygen) biphenyl.
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 45.8 gram (0.1 moles) 3,3 '-diamino-4,4 '-two (4-nitrophenoxy) biphenyl, 0.7 gram palladium mass percent are that palladium/charcoal of 15%, 250 milliliters of ethanol and 1000ml ethylene glycol add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 60% hydrazine hydrate solution (hydrazine hydrate molecular weight 50.06), totally 208.3 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 22 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 35.3 grams 3,3 '-diamino-4,4 '-two (4-amino-benzene oxygen) biphenyl crystal, purity is 99.7%, according to 3 of reality acquisition, 3 '-diamino-4,4 '-amount of two (4-amino-benzene oxygen) biphenyl and theoretical amount (39.8 gram), calculate 3,3 '-diamino-4,4 '-yield of two (4-amino-benzene oxygen) biphenyl is 88.7%.
Embodiment 2
With 45.8 gram (0.1 moles) 3,3 '-diamino-4,4 '-two (4-nitrophenoxy) biphenyl, 9.0 gram palladium mass percents are that 1% palladium/charcoal and 4580ml ethanol add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 85% hydrazine hydrate solution, totally 48.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 10 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 31.0 grams 3,3 '-diamino-4,4 '-two (4-amino-benzene oxygen) biphenyl crystal, purity is 99.0%, according to 3 of reality acquisition, 3 '-diamino-4,4 '-amount of two (4-amino-benzene oxygen) biphenyl and theoretical amount (39.8 gram), calculate 3,3 '-diamino-4,4 '-yield of two (4-amino-benzene oxygen) biphenyl is 77.8%.
Embodiment 3
With 45.8 gram (0.1 moles) 3,3 '-diamino-4,4 '-two (4-nitrophenoxy) biphenyl, 4.0 gram palladium mass percents are that palladium/charcoal of 5%, 800 milliliters of ethanol and 1500ml 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 130.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 20 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 37.6 grams 3,3 '-diamino-4,4 '-two (4-amino-benzene oxygen) biphenyl crystal, purity is 99.7%, according to 3 of reality acquisition, 3 '-diamino-4,4 '-amount of two (4-amino-benzene oxygen) biphenyl and theoretical amount (39.8 gram), calculate 3,3 '-diamino-4,4 '-yield of two (4-amino-benzene oxygen) biphenyl is 94.5%.
Embodiment 4
With 45.8 gram (0.1 moles) 3,3 '-diamino-4,4 '-two (4-nitrophenoxy) biphenyl, 3.0 gram palladium mass percents are palladium/charcoal of 10%, 100 milliliters of ethanol and 800ml 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 55.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 20 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 27.0 grams 3,3 '-diamino-4,4 '-two (4-amino-benzene oxygen) biphenyl crystal, purity is 99.8%, according to 3 of reality acquisition, 3 '-diamino-4,4 '-amount of two (4-amino-benzene oxygen) biphenyl and theoretical amount (39.8 gram), calculate 3,3 '-diamino-4,4 '-yield of two (4-amino-benzene oxygen) biphenyl is 67.8%.
Embodiment 5
With 45.8 gram (0.1 moles) 3,3 '-diamino-4,4 '-two (4-nitrophenoxy) biphenyl, 3.5 gram palladium mass percents are that 10% palladium/charcoal, 120ml methyl alcohol and 1500ml cellosolvo add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 85% hydrazine hydrate solution, totally 140.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 18 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 37.1 grams 3,3 '-diamino-4,4 '-two (4-amino-benzene oxygen) biphenyl crystal, purity is 99.8%, according to 3 of reality acquisition, 3 '-diamino-4,4 '-amount of two (4-amino-benzene oxygen) biphenyl and theoretical amount (39.8 gram), calculate 3,3 '-diamino-4,4 '-yield of two (4-amino-benzene oxygen) biphenyl is 93.2%.
Embodiment 6
With 45.8 gram (0.1 moles) 3,3 '-diamino-4,4 '-two (4-nitrophenoxy) biphenyl, 1.6 gram palladium mass percents are 15% palladium/charcoal and 800ml 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 130.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 15 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 31.3 grams 3,3 '-diamino-4,4 '-two (4-amino-benzene oxygen) biphenyl crystal, purity is 99.8%, according to 3 of reality acquisition, 3 '-diamino-4,4 '-amount of two (4-amino-benzene oxygen) biphenyl and theoretical amount (39.8 gram), calculate 3,3 '-diamino-4,4 '-yield of two (4-amino-benzene oxygen) biphenyl is 78.6%.
Claims (7)
1. one kind 3,3 '-diamino-4,4 '-preparation method of two (4-amino-benzene oxygen) biphenyl, comprise the steps: 3,3 '-diamino-4,4 '-two (4-nitrophenoxy) biphenyl, in palladium/charcoal, hydrazine hydrate solution and alcoholic solvent system in 70 ℃～85 ℃ temperature range internal reactions after 10～22 hours, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystalline product, filter, vacuum-drying, obtain 3,3 '-diamino-4,4 '-two (4-amino-benzene oxygen) biphenyl.
2. according to claim 13,3 '-diamino-4,4 '-preparation method of two (4-amino-benzene oxygen) biphenyl, it is characterized in that: the palladium mass percent of described palladium/charcoal is 1%～15%.
3. according to claim 13,3 '-diamino-4,4 '-preparation method of two (4-amino-benzene oxygen) biphenyl, it is characterized in that: the mass percent concentration of described hydrazine hydrate solution is 60%～85%.
4. according to claim 13,3 '-diamino-4,4 '-preparation method of two (4-amino-benzene oxygen) biphenyl, it is characterized in that: described 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. according to claim 1 and 23,3 '-diamino-4,4 '-preparation method of two (4-amino-benzene oxygen) biphenyl, it is characterized in that: described 3,3 '-diamino-4,4 '-weight ratio of two (4-nitrophenoxy) biphenyl and palladium/charcoal is 100: 1～20.
6. according to claim 1 or 3 described 3,3 '-diamino-4,4 '-preparation method of two (4-amino-benzene oxygen) biphenyl, it is characterized in that: described 3,3 '-diamino-4,4 '-mol ratio of two (4-nitrophenoxy) biphenyl and hydrazine hydrate is 1: 8～25.
7. according to claim 1 or 4 described 3,3 '-diamino-4,4 '-preparation method of two (4-amino-benzene oxygen) biphenyl, it is characterized in that: described 3,3 '-diamino-4,4 '-weightmeasurement ratio of two (4-nitrophenoxy) biphenyl and alcoholic solvent is 1 gram: 15 milliliters～100 milliliters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100386548A CN101293843A (en) | 2008-06-06 | 2008-06-06 | Method for preparing 3,3'-diamino--4,4'-di(4-aminophenoxy)biphenyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100386548A CN101293843A (en) | 2008-06-06 | 2008-06-06 | Method for preparing 3,3'-diamino--4,4'-di(4-aminophenoxy)biphenyl |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101293843A true CN101293843A (en) | 2008-10-29 |
Family
ID=40064421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100386548A Pending CN101293843A (en) | 2008-06-06 | 2008-06-06 | Method for preparing 3,3'-diamino--4,4'-di(4-aminophenoxy)biphenyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101293843A (en) |
-
2008
- 2008-06-06 CN CNA2008100386548A patent/CN101293843A/en active Pending
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 | |
| CN101250120B (en) | Method for preparing 4,4-di(2,4-diamino phenoxy) diphenylmethane | |
| CN101245041B (en) | Process for producing 4,4'-bis(2,4-diaminophenyloxy)diphenyl sulfone | |
| 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 | |
| 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 | |
| CN101293843A (en) | Method for preparing 3,3'-diamino--4,4'-di(4-aminophenoxy)biphenyl | |
| CN101260058A (en) | Method for preparing 4,4'-di(2,4-diaminophenoxy)diphenyl ether | |
| CN101250142A (en) | Method for preparing 4,4'-di(2,4-diamino phenoxy)-3,3',5,5'-tetramethyl diphenyl sulfone | |
| CN101289407A (en) | Method for preparing 4,4'-di(2,4- diaminophenyloxy)-3,3',5,5'-tetramethylbiphenyl | |
| CN101245028A (en) | Process for producing 2,2-bis[3-amido-4-(4-aminophenoxy)phenyl] hexafluoropropane | |
| CN101260057A (en) | Method for preparing 1,3,5-tri(2,4-diaminophenoxy)benzene | |
| CN101265205A (en) | Method for preparing 4,4'-diamino-4''-(2,4-diaminophenoxy)triphenylmethane | |
| CN101245027A (en) | Process for producing 2,2-bis[3-amido-4-(4-aminophenoxy)phenyl]propane | |
| CN101265207A (en) | Method for preparing 2,2-di[4-(2,4-diaminophenoxy)-3,5-dimethylphenyl]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 | |
| CN101260059A (en) | Method for preparing 2,6-dimethyl-1,4-di(2,4-diaminophenoxy)benzene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20081029 |