CN101289407A - Method for preparing 4,4'-di(2,4- diaminophenyloxy)-3,3',5,5'-tetramethylbiphenyl - Google Patents
Method for preparing 4,4'-di(2,4- diaminophenyloxy)-3,3',5,5'-tetramethylbiphenyl Download PDFInfo
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- CN101289407A CN101289407A CNA2008100386571A CN200810038657A CN101289407A CN 101289407 A CN101289407 A CN 101289407A CN A2008100386571 A CNA2008100386571 A CN A2008100386571A CN 200810038657 A CN200810038657 A CN 200810038657A CN 101289407 A CN101289407 A CN 101289407A
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Abstract
The invention relates to a preparation method of 4, 4'-bis (2, 4- diaminophenyloxydisultide)-3, 3', 5, 5'-Tetramethylbiphenyl, including the following steps: 4, 4 -bis (2, 4-dinitro benzene oxyl)-3, 3', 5, 5'-diaminophenyloxydisultide reacts in the system of palladium/charcoal, hydrazine hydrate solution and alcohol solvent for 10 to 22 hours within the temperature range of 70 DEG C to 85 DEG C, and then is filtered when the reaction liquid is hot; afterwards, the mother solution is cooled and crystal products are precipitated; the crystal of 4, 4-bis (2, 4-diaminophenyloxydisultide)-3, 3', 5, 5'-Tetramethylbiphenyl is obtained after filtered and vacuum dried. The method of the invention is simple in operation without needing subsequent refined purification technology, less in time-consuming, high in product yield with more than 99 percent of the purity, and applicable to the 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 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-preparation method of tetramethyl 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.
4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl is one of important source material of synthetic high branched 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, 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl also is the important raw and processed materials of synthetic More Malay imide resin.
4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl 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 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl, this method technology is simple, need not follow-up refining purifying technique, 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:
Of the present invention a kind of 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl, comprise the steps:
4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl 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, separate out crystalline product, filter vacuum-drying, obtain 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-the tetramethyl 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 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-weight ratio of tetramethyl biphenyl and palladium/charcoal is 100: 1～20.
Described 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-mol ratio of tetramethyl biphenyl and hydrazine hydrate is 1: 20～50.
Described 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-weightmeasurement ratio of tetramethyl biphenyl and alcoholic solvent is 1 gram: 15 milliliters～100 milliliters.
Beneficial effect of the present invention
(1) the present invention be preparation 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-commercial run of tetramethyl 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) 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl biphenyl raw material sources such as (Shanghai EMST Electron Material Co., Ltd is stably manufactured in batches) are convenient;
(6) product purity reaches more than 99%, yield is high.
Description of drawings
Figure is 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-molecular structure of tetramethyl 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 57.4 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl biphenyl, 0.6 gram palladium mass percent are that palladium/charcoal of 15%, 400 milliliters of ethanol and 800ml ethylene glycol add in the reaction flask, stir, heat temperature raising to 60 ℃ begins to drip mass concentration and is 60% hydrazine hydrate solution, totally 250.0 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, the cooling mother liquor is separated out crystallized product, filter, vacuum-drying obtains 40.9 grams 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-the tetramethyl biphenyl crystal, purity is 99.8%, according to reality obtain 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-amount of tetramethyl biphenyl and theoretical amount (45.4 gram), calculate 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-yield of tetramethyl biphenyl is 90.1%.
Embodiment 2
With 57.4 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl biphenyl, 8.8 gram palladium mass percents are that 1% palladium/charcoal and 5180ml ethanol add in the reaction flask, stir, heat temperature raising to 60 ℃ begins to drip mass concentration and is 85% hydrazine hydrate solution, totally 294.1 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, the cooling mother liquor is separated out crystallized product, filter, vacuum-drying obtains 41.4 grams 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-the tetramethyl biphenyl crystal, purity is 99.7%, according to reality obtain 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-amount of tetramethyl biphenyl and theoretical amount (45.4 gram), calculate 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-yield of tetramethyl biphenyl is 91.2%.
Embodiment 3
With 57.4 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl biphenyl, 4.0 gram palladium mass percents are that 5% palladium/charcoal and 2500ml 2-methyl cellosolve add in the reaction flask, stir, heat temperature raising to 60 ℃ begins to drip mass concentration and is 80% hydrazine hydrate solution, totally 260.0 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, the cooling mother liquor is separated out crystallized product, filter, vacuum-drying obtains 43.7 grams 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-the tetramethyl biphenyl crystal, purity is 99.8%, according to reality obtain 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-amount of tetramethyl biphenyl and theoretical amount (45.4 gram), calculate 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-yield of tetramethyl biphenyl is 96.2%.
Embodiment 4
With 57.4 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl biphenyl, 3.0 gram palladium mass percents are 10% palladium/charcoal, 65ml cellosolvo and 800ml 1, the 2-propylene glycol adds in the reaction flask, stirs heat temperature raising to 60 ℃, begin to drip mass concentration and be 80% hydrazine hydrate solution, totally 300.0 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, the cooling mother liquor is separated out crystallized product, filter, vacuum-drying obtains 40.7 grams 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-the tetramethyl biphenyl crystal, purity is 99.2%, according to reality obtain 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-amount of tetramethyl biphenyl and theoretical amount (45.4 gram), calculate 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-yield of tetramethyl biphenyl is 89.7%.
Embodiment 5
With 57.4 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl biphenyl, 3.5 gram palladium mass percents are that 10% palladium/charcoal, 200ml methyl alcohol and 1000ml cellosolvo add in the reaction flask, stir, heat temperature raising to 60 ℃ begins to drip mass concentration and is 85% hydrazine hydrate solution, totally 280.0 grams.After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 12 hours, cold slightly, filtered while hot, the cooling mother liquor is separated out crystallized product, filter, vacuum-drying obtains 37.8 grams 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-the tetramethyl biphenyl crystal, purity is 99.4%, according to reality obtain 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-amount of tetramethyl biphenyl and theoretical amount (45.4 gram), calculate 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-yield of tetramethyl biphenyl is 83.2%.
Embodiment 6
With 57.4 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl biphenyl, 1.6 gram palladium mass percents are palladium/charcoal of 15%, 500 milliliters of ethanol and 800ml 1, ammediol adds in the reaction flask, stirs heat temperature raising to 60 ℃, begin to drip mass concentration and be 60% hydrazine hydrate solution, totally 260.0 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, the cooling mother liquor is separated out crystallized product, filter, vacuum-drying obtains 41.6 grams 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-the tetramethyl biphenyl crystal, purity is 99.1%, according to reality obtain 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-amount of tetramethyl biphenyl and theoretical amount (45.4 gram), calculate 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-yield of tetramethyl biphenyl is 91.6%.
Claims (7)
1. one kind 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl, comprise the steps: 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl 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 is separated out crystalline product, filter, vacuum-drying obtains 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl.
2. according to claim 14,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl, it is characterized in that: the palladium mass percent of described palladium/charcoal is 1%～15%.
3. according to claim 14,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl, 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)-3,3 ', 5,5 '-preparation method of tetramethyl 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 24,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl, it is characterized in that: described 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-weight ratio of tetramethyl biphenyl and palladium/charcoal is 100: 1～20.
6. according to claim 1 or 3 described 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl, it is characterized in that: described 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-mol ratio of tetramethyl biphenyl and hydrazine hydrate is 1: 20～50.
7. according to claim 1 or 4 described 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl, it is characterized in that: described 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-weightmeasurement ratio of tetramethyl biphenyl and alcoholic solvent is 1 gram: 15 milliliters～100 milliliters.
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| CNA2008100386571A CN101289407A (en) | 2008-06-06 | 2008-06-06 | Method for preparing 4,4'-di(2,4- diaminophenyloxy)-3,3',5,5'-tetramethylbiphenyl |
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| CNA2008100386571A CN101289407A (en) | 2008-06-06 | 2008-06-06 | Method for preparing 4,4'-di(2,4- diaminophenyloxy)-3,3',5,5'-tetramethylbiphenyl |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560162B (en) * | 2009-05-12 | 2012-09-05 | 东华大学 | Preparation method of 4,4'-bi(4-amino-2-trifluoromethylphenoxyl)-3,3'5,5'-tetramethylbiphenyl |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560162B (en) * | 2009-05-12 | 2012-09-05 | 东华大学 | Preparation method of 4,4'-bi(4-amino-2-trifluoromethylphenoxyl)-3,3'5,5'-tetramethylbiphenyl |
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Open date: 20081022 |