CN101260057A - Method for preparing 1,3,5-tri(2,4-diaminophenoxy)benzene - Google Patents
Method for preparing 1,3,5-tri(2,4-diaminophenoxy)benzene Download PDFInfo
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- CN101260057A CN101260057A CNA2008100359983A CN200810035998A CN101260057A CN 101260057 A CN101260057 A CN 101260057A CN A2008100359983 A CNA2008100359983 A CN A2008100359983A CN 200810035998 A CN200810035998 A CN 200810035998A CN 101260057 A CN101260057 A CN 101260057A
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- benzene
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Abstract
The invention relates to a preparation method for 1,3,5-tri(2,4-diamidophenoxyl) benzene. The steps of the method are as follows: 1,3,5-tri(2,4-dinitrophenoxy) benzene is put in a system of palladium/charcoal, a hydrazine hydrate solution and saturated fat alcohol and reacted for 1 to 5 hours at a temperature of between 70 and 85 DEG C, and the hot solution is filtered, and the mother solution is cooled down and is dropwise added with purified water, and crystal products are separated out, filtered and vacuum-dried, obtaining 1,3,5-tri(2,4- diamidophenoxyl) benzene crystals. The invention has the advantages of simple operation, no following refinement and purification processes, short consuming time, high yield of products obtained and high purity(more than 99 percent), and is suitable for the industrialized 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 1,3, the preparation method of 5-three (2, the 4-diamino phenoxy) benzene.
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.
1,3,5-three (2, the 4-diamino phenoxy) benzene is one of important source material of synthetic high branched 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, 1,3,5-three (2, the 4-diamino phenoxy) benzene also is the important raw and processed materials of synthetic More Malay imide resin.
Summary of the invention
The purpose of this invention is to provide a kind of 1,3, the preparation method of 5-three (2, the 4-diamino phenoxy) benzene, 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 1,3, the preparation method of 5-three (2, the 4-diamino phenoxy) benzene comprises the steps:
1,3,5-three (2,4-2,4-dinitrophenoxy base) benzene, in palladium/charcoal, hydrazine hydrate solution and saturated fatty alcohol solvent system in 70 ℃～85 ℃ temperature range internal reactions after 1～5 hour, filtered while hot, the cooling mother liquor drips an amount of pure water, separates out product body product, filter, vacuum-drying obtains 1,3,5-three (2, the 4-diamino phenoxy) benzene 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.
Described 1,3, the weight ratio of 5-three (2,4-2,4-dinitrophenoxy base) benzene and palladium/charcoal is 100: 1～20.
Described 1,3, the mol ratio of 5-three (2,4-2,4-dinitrophenoxy base) benzene and hydrazine hydrate is 1: 20～50.
Described 1,3, the weightmeasurement ratio of 5-three (2,4-2,4-dinitrophenoxy base) benzene and saturated fatty alcoholic solvent is 1 gram: 15 milliliters～100 milliliters.
Beneficial effect of the present invention
(1) the present invention is preparation 1,3, the commercial run of 5-three (2, the 4-diamino phenoxy) benzene;
(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 1,3, the molecular structure of 5-three (2, the 4-diamino phenoxy) benzene.
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 62.4 gram (0.1 moles) 1,3,5-three (2,4-2,4-dinitrophenoxy base) benzene, 1.0 gram palladium mass percents are that 15% palladium/charcoal, 100 ml methanol and 850ml ethylene glycol add in the reaction flask, stir, heat temperature raising to 60 ℃ begins to drip mass concentration and is 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 70 ℃～85 ℃ temperature range, continued stirring reaction 1 hour, cold slightly, filtered while hot, the cooling mother liquor drips an amount of pure water, separates out crystallized product, filters, vacuum-drying obtains 42.5 grams 1,3, and 5-three (2, the 4-diamino phenoxy) benzene crystal, purity are 99.3%, according to 1,3 of reality acquisition, the amount of 5-three (2, the 4-diamino phenoxy) benzene and theoretical amount (44.4 gram) calculate 1,3, the yield of 5-three (2, the 4-diamino phenoxy) benzene is 95.7%.
Embodiment 2
With 62.4 gram (0.1 moles) 1,3,5-three (2,4-2,4-dinitrophenoxy base) benzene, 8.8 gram palladium mass percents are that 1% palladium/charcoal and 6240ml 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 5 hours, cold slightly, filtered while hot, the cooling mother liquor drips an amount of pure water, separates out crystallized product, filters, vacuum-drying obtains 42.3 grams 1,3, and 5-three (2, the 4-diamino phenoxy) benzene crystal, purity are 99.6%, according to 1,3 of reality acquisition, the amount of 5-three (2, the 4-diamino phenoxy) benzene and theoretical amount (44.4 gram) calculate 1,3, the yield of 5-three (2, the 4-diamino phenoxy) benzene is 95.3%.
Embodiment 3
With 62.4 gram (0.1 moles) 1,3,5-three (2,4-2,4-dinitrophenoxy base) benzene, 4.0 gram palladium mass percents are that palladium/charcoal of 5%, 300 milliliters of ethanol and 1000ml 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 4 hours, cold slightly, filtered while hot, the cooling mother liquor drips an amount of pure water, separates out crystallized product, filters, vacuum-drying obtains 42.5 grams 1,3, and 5-three (2, the 4-diamino phenoxy) benzene crystal, purity are 99.7%, according to 1,3 of reality acquisition, the amount of 5-three (2, the 4-diamino phenoxy) benzene and theoretical amount (44.4 gram) calculate 1,3, the yield of 5-three (2, the 4-diamino phenoxy) benzene is 95.8%.
Embodiment 4
With 62.4 gram (0.1 moles) 1,3,5-three (2,4-2,4-dinitrophenoxy base) benzene, 3.0 gram palladium mass percents are palladium/charcoal of 10%, 500 milliliters of ethanol 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 3 hours, cold slightly, filtered while hot, the cooling mother liquor drips an amount of pure water, separates out crystallized product, filters, vacuum-drying obtains 39.0 grams 1,3, and 5-three (2, the 4-diamino phenoxy) benzene crystal, purity are 99.5%, according to 1,3 of reality acquisition, the amount of 5-three (2, the 4-diamino phenoxy) benzene and theoretical amount (44.4 gram) calculate 1,3, the yield of 5-three (2, the 4-diamino phenoxy) benzene is 87.9%.
Embodiment 5
With 62.4 gram (0.1 moles) 1,3,5-three (2,4-2,4-dinitrophenoxy base) benzene, 3.5 gram palladium mass percents are that 10% palladium/charcoal, 320ml 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 (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 2 hours, cold slightly, filtered while hot, the cooling mother liquor drips an amount of pure water, separates out crystallized product, filters, vacuum-drying obtains 40.2 grams 1,3, and 5-three (2, the 4-diamino phenoxy) benzene crystal, purity are 99.5%, according to 1,3 of reality acquisition, the amount of 5-three (2, the 4-diamino phenoxy) benzene and theoretical amount (44.4 gram) calculate 1,3, the yield of 5-three (2, the 4-diamino phenoxy) benzene is 90.5%.
Embodiment 6
With 62.4 gram (0.1 moles) 1,3,5-three (2,4-2,4-dinitrophenoxy base) benzene, 1.6 gram palladium mass percents are palladium/charcoal of 15%, 2800 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 5 hours, cold slightly, filtered while hot, the cooling mother liquor drips an amount of pure water, separates out crystallized product, filters, vacuum-drying obtains 41.2 grams 1,3, and 5-three (2, the 4-diamino phenoxy) benzene crystal, purity are 99.8%, according to 1,3 of reality acquisition, the amount of 5-three (2, the 4-diamino phenoxy) benzene and theoretical amount (44.4 gram) calculate 1,3, the yield of 5-three (2, the 4-diamino phenoxy) benzene is 92.7%.
Claims (7)
1. one kind 1,3, the preparation method of 5-three (2, the 4-diamino phenoxy) benzene, comprise the steps: 1,3,5-three (2,4-2,4-dinitrophenoxy base) benzene, in palladium/charcoal, hydrazine hydrate solution and saturated fatty alcohol solvent system in 70 ℃～85 ℃ temperature range internal reactions after 1～5 hour, filtered while hot, the cooling mother liquor drips an amount of pure water, separates out crystalline product, filter, vacuum-drying obtains 1,3,5-three (2, the 4-diamino phenoxy) benzene.
2. according to claim 11,3, the preparation method of 5-three (2, the 4-diamino phenoxy) benzene, it is characterized in that: the palladium mass percent of described palladium/charcoal is 1%～15%.
3. according to claim 11,3, the preparation method of 5-three (2, the 4-diamino phenoxy) benzene, it is characterized in that: the mass percent concentration of described hydrazine hydrate solution is 60%～85%.
4. according to claim 11,3,5-three (2, the 4-diamino phenoxy) preparation method of benzene, 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. according to claim 1 and 21,3, the preparation method of 5-three (2, the 4-diamino phenoxy) benzene is characterized in that: described 1,3, the weight ratio of 5-three (2,4-2,4-dinitrophenoxy base) benzene and palladium/charcoal is 100: 1～20.
6. according to claim 1 or 3 described 1,3, the preparation method of 5-three (2, the 4-diamino phenoxy) benzene is characterized in that: described 1,3, the mol ratio of 5-three (2,4-2,4-dinitrophenoxy base) benzene and hydrazine hydrate is 1: 20～50.
7. according to claim 1 or 4 described 1,3,5-three (2, the 4-diamino phenoxy) preparation method of benzene is characterized in that: described 1,3, the weightmeasurement ratio of 5-three (2,4-2,4-dinitrophenoxy base) benzene and saturated fatty alcoholic solvent is 1 gram: 15 milliliters～100 milliliters.
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| CNA2008100359983A CN101260057A (en) | 2008-04-14 | 2008-04-14 | Method for preparing 1,3,5-tri(2,4-diaminophenoxy)benzene |
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| CNA2008100359983A CN101260057A (en) | 2008-04-14 | 2008-04-14 | Method for preparing 1,3,5-tri(2,4-diaminophenoxy)benzene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591251B (en) * | 2009-06-19 | 2012-07-04 | 东华大学 | Method for preparing 2-tert-butyl-1,4-di(4-amino-2-trifluoromethylphenoxy) benzene |
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- 2008-04-14 CN CNA2008100359983A patent/CN101260057A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591251B (en) * | 2009-06-19 | 2012-07-04 | 东华大学 | Method for preparing 2-tert-butyl-1,4-di(4-amino-2-trifluoromethylphenoxy) benzene |
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Open date: 20080910 |