CN101289405A - Method for preparing 1,4-di(2,4- diaminophenyloxy)-2,3,5-trimethylbenzene - Google Patents
Method for preparing 1,4-di(2,4- diaminophenyloxy)-2,3,5-trimethylbenzene Download PDFInfo
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- CN101289405A CN101289405A CNA2008100382369A CN200810038236A CN101289405A CN 101289405 A CN101289405 A CN 101289405A CN A2008100382369 A CNA2008100382369 A CN A2008100382369A CN 200810038236 A CN200810038236 A CN 200810038236A CN 101289405 A CN101289405 A CN 101289405A
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Abstract
The invention relates to a preparation method of 1, 4-bis (2, 4-diaminophenyloxydisultide)-2, 3, 5-trimethylbenzene, including the following steps: 1, 4-bis (2, 4-dinitro benzene oxyl)-2, 3, 5-trimethylbenzene reacts in the system of palladium or charcoal, hydrazine hydrate solution and saturated fatty alcohol solvent for one to five 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 liquor is cooled and crystal products are precipitated; the crystal of 1, 4-bis (2, 4-diaminophenyloxydisultide)-2, 3, 5-trimethylbenzene is obtained after filtered and vacuum dried,. The method of the invention is simple in operation without the need of 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 1, two (2, the 4-diamino phenoxy)-2,3 of 4-, the preparation method of 5-Three methyl 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, two (2, the 4-diamino phenoxy)-2,3 of 4-, the 5-Three methyl Benzene 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, 1, two (2, the 4-diamino phenoxy)-2,3 of 4-, the 5-Three methyl Benzene also is the important raw and processed materials of synthetic More Malay imide resin.
1, two (2, the 4-diamino phenoxy)-2,3 of 4-, the 5-Three methyl Benzene 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 1, two (2, the 4-diamino phenoxy)-2,3 of 4-, the preparation method of 5-Three methyl 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, two (2, the 4-diamino phenoxy)-2,3 of 4-, the preparation method of 5-Three methyl Benzene comprises the steps:
1, two (2,4-2,4-dinitrophenoxy base)-2 of 4-, 3, the 5-Three methyl 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 is separated out crystalline product, filter, vacuum-drying obtains 1,4-two (2, the 4-diamino phenoxy)-2,3,5-Three methyl 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, two (2,4-2,4-dinitrophenoxy base)-2,3 of 4-, the weight ratio of 5-Three methyl Benzene and palladium/charcoal is 100: 1～20.
Described 1, two (2,4-2,4-dinitrophenoxy base)-2,3 of 4-, the mol ratio of 5-Three methyl Benzene and hydrazine hydrate is 1: 20～50.
Described 1, two (2,4-2,4-dinitrophenoxy base)-2,3 of 4-, the weightmeasurement ratio of 5-Three methyl Benzene and saturated fatty alcoholic solvent is 1 to restrain: 20 milliliters～100 milliliters.
Beneficial effect of the present invention
(1) the present invention is preparation 1, two (2, the 4-diamino phenoxy)-2,3 of 4-, the commercial run of 5-Three methyl 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, two (2, the 4-diamino phenoxy)-2,3 of 4-, the molecular structure of 5-Three methyl 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 48.4 gram (0.1 moles) 1,4-two (2,4-2,4-dinitrophenoxy base)-2,3,5-Three methyl Benzene, 0.5 gram palladium mass percent are that palladium/charcoal of 15%, 368 milliliters of ethanol and 600 milliliters of ethylene glycol add in the reaction flask, stir heat temperature raising to 60 ℃, begin to drip mass concentration and be 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 adds pure water, separate out crystallized product, filter vacuum-drying, obtain 32.1 grams 1, two (2, the 4-diamino phenoxy)-2 of 4-, 3,5-Three methyl Benzene crystal, purity is 99.8%, according to 1 of reality acquisition, two (2, the 4-diamino phenoxy)-2,3 of 4-, the amount of 5-Three methyl Benzene and theoretical amount (36.4 gram), calculate 1, two (2, the 4-diamino phenoxy)-2 of 4-, 3, the yield of 5-Three methyl Benzene is 88.2%.
Embodiment 2
With 48.4 gram (0.1 moles) 1,4-two (2,4-2,4-dinitrophenoxy base)-2,3,5-Three methyl Benzene, 9.6 gram palladium mass percents are that palladium/charcoal and 4840 milliliters of ethanol of 1% 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 70 ℃～85 ℃ temperature range, continued stirring reaction 5 hours, cold slightly, filtered while hot, the cooling mother liquor adds pure water, separate out crystallized product, filter vacuum-drying, obtain 35.6 grams 1, two (2, the 4-diamino phenoxy)-2 of 4-, 3,5-Three methyl Benzene crystal, purity is 99.6%, according to 1 of reality acquisition, two (2, the 4-diamino phenoxy)-2,3 of 4-, the amount of 5-Three methyl Benzene and theoretical amount (36.4 gram), calculate 1, two (2, the 4-diamino phenoxy)-2 of 4-, 3, the yield of 5-Three methyl Benzene is 92.2%.
Embodiment 3
With 48.4 gram (0.1 moles) 1,4-two (2,4-2,4-dinitrophenoxy base)-2,3,5-Three methyl Benzene, 4.8 gram palladium mass percents are that palladium/charcoal of 5%, 600 milliliters of ethanol and 1800 milliliters of 2-methyl cellosolves 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 70 ℃～85 ℃ temperature range, continued stirring reaction 3.5 hours, cold slightly, filtered while hot, the cooling mother liquor adds pure water, separate out crystallized product, filter vacuum-drying, obtain 32.8 grams 1, two (2, the 4-diamino phenoxy)-2 of 4-, 3,5-Three methyl Benzene crystal, purity is 99.6%, according to 1 of reality acquisition, two (2, the 4-diamino phenoxy)-2,3 of 4-, the amount of 5-Three methyl Benzene and theoretical amount (36.4 gram), calculate 1, two (2, the 4-diamino phenoxy)-2 of 4-, 3, the yield of 5-Three methyl Benzene is 90.0%.
Embodiment 4
With 48.4 gram (0.1 moles) 1,4-two (2,4-2,4-dinitrophenoxy base)-2,3,5-Three methyl Benzene, 3.8 gram palladium mass percents are palladium/charcoal of 10%, 1800 milliliters of ethanol and 800 milliliter 1, and 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 70 ℃～85 ℃ temperature range, continued stirring reaction 3 hours, cold slightly, filtered while hot, the cooling mother liquor adds pure water, separate out crystallized product, filter vacuum-drying, obtain 34.1 grams 1, two (2, the 4-diamino phenoxy)-2 of 4-, 3,5-Three methyl Benzene crystal, purity is 99.7%, according to 1 of reality acquisition, two (2, the 4-diamino phenoxy)-2,3 of 4-, the amount of 5-Three methyl Benzene and theoretical amount (36.4 gram), calculate 1, two (2, the 4-diamino phenoxy)-2 of 4-, 3, the yield of 5-Three methyl Benzene is 93.7%.
Embodiment 5
With 48.4 gram (0.1 moles) 1,4-two (2,4-2,4-dinitrophenoxy base)-2,3,5-Three methyl Benzene, 4.2 gram palladium mass percents are that palladium/charcoal, 420 ml methanol and 1200 milliliters of cellosolvos of 10% 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 70 ℃～85 ℃ temperature range, continued stirring reaction 2.5 hours, cold slightly, filtered while hot, the cooling mother liquor adds pure water, separate out crystallized product, filter vacuum-drying, obtain 34.6 grams 1, two (2, the 4-diamino phenoxy)-2 of 4-, 3,5-Three methyl Benzene crystal, purity is 99.5%, according to 1 of reality acquisition, two (2, the 4-diamino phenoxy)-2,3 of 4-, the amount of 5-Three methyl Benzene and theoretical amount (36.4 gram), calculate 1, two (2, the 4-diamino phenoxy)-2 of 4-, 3, the yield of 5-Three methyl Benzene is 95.2%.
Embodiment 6
With 48.4 gram (0.1 moles) 1,4-two (2,4-2,4-dinitrophenoxy base)-2,3,5-Three methyl Benzene, 1.8 gram palladium mass percents are palladium/charcoal of 15%, 1600 milliliters of ethanol and 1200 milliliter 1, and 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 70 ℃～85 ℃ temperature range, continued stirring reaction 5 hours, cold slightly, filtered while hot, the cooling mother liquor adds pure water, separate out crystallized product, filter vacuum-drying, obtain 33.7 grams 1, two (2, the 4-diamino phenoxy)-2 of 4-, 3,5-Three methyl Benzene crystal, purity is 99.5%, according to 1 of reality acquisition, two (2, the 4-diamino phenoxy)-2,3 of 4-, the amount of 5-Three methyl Benzene and theoretical amount (36.4 gram), calculate 1, two (2, the 4-diamino phenoxy)-2 of 4-, 3, the yield of 5-Three methyl Benzene is 92.5%.
Claims (7)
1. one kind 1, two (2, the 4-diamino phenoxy)-2,3 of 4-, the preparation method of 5-Three methyl Benzene comprises the steps: 1, two (2,4-2,4-dinitrophenoxy base)-2 of 4-, 3, the 5-Three methyl 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 is separated out crystalline product, filters, vacuum-drying obtains 1, and 4-two (2, the 4-diamino phenoxy)-2,3,5-Three methyl Benzene.
2. according to claim 11, two (2, the 4-diamino phenoxy)-2,3 of 4-, the preparation method of 5-Three methyl Benzene is characterized in that: the palladium mass percent of described palladium/charcoal is 1%～15%.
3. according to claim 11, two (2, the 4-diamino phenoxy)-2,3 of 4-, the preparation method of 5-Three methyl Benzene is characterized in that: the mass percent concentration of described hydrazine hydrate solution is 60%～85%.
4. according to claim 11,4-two (2, the 4-diamino phenoxy)-2,3, the preparation method of 5-Three methyl Benzene 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, two (2, the 4-diamino phenoxy)-2,3 of 4-, the preparation method of 5-Three methyl Benzene is characterized in that: described 1,4-two (2,4-2,4-dinitrophenoxy base)-2,3, the weight ratio of 5-Three methyl Benzene and palladium/charcoal is 100: 1～20.
6. according to claim 1 or 3 described 1, two (2, the 4-diamino phenoxy)-2,3 of 4-, the preparation method of 5-Three methyl Benzene is characterized in that: described 1,4-two (2,4-2,4-dinitrophenoxy base)-2,3, the mol ratio of 5-Three methyl Benzene and hydrazine hydrate is 1: 20～50.
7. according to claim 1 or 4 described 1,4-two (2, the 4-diamino phenoxy)-2,3, the preparation method of 5-Three methyl Benzene is characterized in that: described 1,4-two (2,4-2,4-dinitrophenoxy base)-2,3, the weightmeasurement ratio of 5-Three methyl Benzene and saturated fatty alcoholic solvent is 1 gram: 20 milliliters～100 milliliters.
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|---|---|---|---|
| CNA2008100382369A CN101289405A (en) | 2008-05-29 | 2008-05-29 | Method for preparing 1,4-di(2,4- diaminophenyloxy)-2,3,5-trimethylbenzene |
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| CNA2008100382369A CN101289405A (en) | 2008-05-29 | 2008-05-29 | Method for preparing 1,4-di(2,4- diaminophenyloxy)-2,3,5-trimethylbenzene |
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Open date: 20081022 |