CN101260058A - Method for preparing 4,4'-di(2,4-diaminophenoxy)diphenyl ether - Google Patents
Method for preparing 4,4'-di(2,4-diaminophenoxy)diphenyl ether Download PDFInfo
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- CN101260058A CN101260058A CNA2008100360586A CN200810036058A CN101260058A CN 101260058 A CN101260058 A CN 101260058A CN A2008100360586 A CNA2008100360586 A CN A2008100360586A CN 200810036058 A CN200810036058 A CN 200810036058A CN 101260058 A CN101260058 A CN 101260058A
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Abstract
The invention relates to a preparation method for 4,4'-bis(2,4-diamidophenoxyl)diphenyl ether. The steps of the method are as follows: 4,4'-bis(2,4-dinitrophenoxy) diphenyl ether is put in a system of palladium/charcoal, a hydrazine hydrate solution and saturated fat alcohol and reacted for 2 to 8 hours at a temperature of between 80 and 90 DEG C, and the hot solution is filtered, and the mother solution is cooled down and dropwise added in with purified water, and crystal products are separated out, filtered and vacuum-dried, obtaining 4,4'-bis(2,4- diamidophenoxyl)diphenyl ether 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 preparation method of 4,4 '-two (2, the 4-diamino phenoxy) phenyl ether.
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) phenyl ether 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) phenyl ether also is the important raw and processed materials of synthetic More Malay imide resin.
4,4 '-two (2, the 4-diamino phenoxy) phenyl ether 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) phenyl ether, 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) phenyl ether of the present invention comprises the steps:
4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether, in palladium/charcoal, hydrazine hydrate solution and saturated fatty alcohol solvent system in 80 ℃～90 ℃ temperature range internal reactions after 2～8 hours, 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) phenyl ether 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) phenyl ether and palladium/charcoal is 100: 1～20.
The mol ratio of described 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether and hydrazine hydrate is 1: 20～50.
The weightmeasurement ratio of described 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether 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) phenyl ether;
(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) phenyl ether.
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 53.4 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether, 0.6 gram palladium mass percent are that palladium/charcoal of 15%, 600 milliliters of ethanol, 1200ml ethylene glycol add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 60% hydrazine hydrate solution, totally 250.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 80 ℃～90 ℃ temperature range, continued stirring reaction 8 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 39.6 grams 4,4 '-two (2, the 4-diamino phenoxy) phenyl ether crystal, purity is 99.7%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) phenyl ether and theoretical amount (41.4 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) phenyl ether is 95.6%.
Embodiment 2
With 53.4 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether, 8.8 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 8 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 36.8 grams 4,4 '-two (2, the 4-diamino phenoxy) phenyl ether crystal, purity is 99.4%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) phenyl ether and theoretical amount (41.4 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) phenyl ether is 88.9%.
Embodiment 3
With 53.4 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether, 4.0 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 6 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 36.1 grams 4,4 '-two (2, the 4-diamino phenoxy) phenyl ether crystal, purity is 99.5%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) phenyl ether and theoretical amount (41.4 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) phenyl ether is 87.2%.
Embodiment 4
With 53.4 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether, 3.0 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 4 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 34.0 grams 4,4 '-two (2, the 4-diamino phenoxy) phenyl ether crystal, purity is 99.7%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) phenyl ether and theoretical amount (41.4 gram) calculate 4,4 '-) yield of two (2, the 4-diamino phenoxy) phenyl ether is 82.3%.
Embodiment 5
With 53.4 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether, 3.5 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 7 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 36.9 grams 4,4 '-two (2, the 4-diamino phenoxy) phenyl ether crystal, purity is 99.5%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) phenyl ether and theoretical amount (41.4 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) phenyl ether is 89.2%.
Embodiment 6
With 53.4 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether, 1.6 gram palladium mass percents are palladium/charcoal of 15%, 300 milliliters of ethanol and 3000ml 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 8 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 38.8 grams 4,4 '-two (2, the 4-diamino phenoxy) phenyl ether crystal, purity is 99.6%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) phenyl ether and theoretical amount (41.4 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) phenyl ether is 93.7%.
Embodiment 7
With 53.4 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether, 1.2 gram palladium mass percents are that palladium/charcoal of 15%, 5340 milliliters of ethanol add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 60% hydrazine hydrate solution, totally 250.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 80 ℃～90 ℃ temperature range, continued stirring reaction 8 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 37.1 grams 4,4 '-two (2, the 4-diamino phenoxy) phenyl ether crystal, purity is 99.8%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) phenyl ether and theoretical amount (41.4 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) phenyl ether is 90.2%.
Claims (7)
1. one kind 4, the preparation method of 4 '-two (2, the 4-diamino phenoxy) phenyl ether, comprise the steps: 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether, in palladium/charcoal, hydrazine hydrate solution and saturated fatty alcohol solvent system in 80 ℃～90 ℃ temperature range internal reactions after 2～8 hours, 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) phenyl ether.
2. the preparation method of 4,4 '-two (2, the 4-diamino phenoxy) phenyl ether 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) phenyl ether 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 phenyl ether, 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) phenyl ether according to claim 1 and 2 is characterized in that: the weight ratio of described 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether 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) phenyl ether, it is characterized in that: the mol ratio of described 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether 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) phenyl ether is characterized in that: described 4, the weightmeasurement ratio of 4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether and saturated fatty alcoholic solvent is 1 gram: 15 milliliters～100 milliliters.
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| CNA2008100360586A CN101260058A (en) | 2008-04-15 | 2008-04-15 | Method for preparing 4,4'-di(2,4-diaminophenoxy)diphenyl ether |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109628055A (en) * | 2018-12-21 | 2019-04-16 | 东华大学 | A kind of BDADDE type silicon-containing adhesive and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109628055A (en) * | 2018-12-21 | 2019-04-16 | 东华大学 | A kind of BDADDE type silicon-containing adhesive and preparation method thereof |
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Open date: 20080910 |