CN101245026A - Process for producing 1,4-(2,4-diaminophenyloxy)-2,5-di-t-butyl benzene - Google Patents
Process for producing 1,4-(2,4-diaminophenyloxy)-2,5-di-t-butyl benzene Download PDFInfo
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- CN101245026A CN101245026A CNA2008100349731A CN200810034973A CN101245026A CN 101245026 A CN101245026 A CN 101245026A CN A2008100349731 A CNA2008100349731 A CN A2008100349731A CN 200810034973 A CN200810034973 A CN 200810034973A CN 101245026 A CN101245026 A CN 101245026A
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- butylbenzene
- diamino phenoxy
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Abstract
The invention relates to a preparation method of 1,4-double(2,4-diamino phenoxy)-2,5-d-tert-butylbenzene, comprising the steps as following, after being put into the solvent system of the solution of palladium or carbon hydrazine hydrate and saturated fatty alcohol for reaction for 1 to 5 hours with the temperature of 70 to 85 DEG C, the 1,4-double(2,4-dinitro phenoxy)-2,5-d-tert-butylbenzene is filtered when being hot, mother liquor is cooled off, pure water is dripped in, crystal products are precipitated, filtered, and dried in vacuum, and crystals of the 1,4-double(2,4-diamino phenoxy)-2,5-d-tert-butylbenzene are gained. The method has the simple operation, needs no subsequent refining and purifying technique, takes little time, has the products with the high yield and the purity of more than 99 percent, and is suitable for 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 of 4-, the preparation method of 5-di-t-butylbenzene.
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 of 4-, the 5-di-t-butylbenzene 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 of 4-, the 5-di-t-butylbenzene also is the important raw and processed materials of synthetic More Malay imide resin.
1, two (2, the 4-diamino phenoxy)-2 of 4-, the 5-di-t-butylbenzene 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 of 4-, the preparation method of 5-di-t-butylbenzene, 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 of 4-, the preparation method of 5-di-t-butylbenzene comprises the steps:
1, two (2,4-2,4-dinitrophenoxy base)-2 of 4-, the 5-di-t-butylbenzene, 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, separate out crystalline product, filter vacuum-drying, obtain 1, two (2, the 4-diamino phenoxy)-2 of 4-, 5-di-t-butylbenzene 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 of 4-, the weight ratio of 5-di-t-butylbenzene and palladium/charcoal is 100: 1～20.
Described 1, two (2,4-2,4-dinitrophenoxy base)-2 of 4-, the mol ratio of 5-di-t-butylbenzene and hydrazine hydrate is 1: 20～50.
Described 1, two (2,4-2,4-dinitrophenoxy base)-2 of 4-, the weightmeasurement ratio of 5-di-t-butylbenzene and saturated fatty alcoholic solvent is 1 to restrain: 15 milliliters～100 milliliters.
Beneficial effect of the present invention
(1) the present invention is preparation 1, two (2, the 4-diamino phenoxy)-2 of 4-, the commercial run of 5-di-t-butylbenzene;
(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 of 4-, the molecular structure of 5-di-t-butylbenzene.
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 55.4 gram (0.1 moles) 1,4-two (2,4-2,4-dinitrophenoxy base)-2,5-di-t-butylbenzene, 0.6 gram palladium mass percent are that palladium/charcoal of 15%, 200 milliliters of ethanol and 670ml 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 adds pure water, separate out crystallized product, filter, vacuum-drying obtains 41.0 grams 1,4-two (2, the 4-diamino phenoxy)-2,5-di-t-butylbenzene crystal, purity is 99.5%, according to 1 of reality acquisition, two (2, the 4-diamino phenoxy)-2 of 4-, the amount of 5-di-t-butylbenzene and theoretical amount (43.4 gram), calculate 1, two (2, the 4-diamino phenoxy)-2 of 4-, the yield of 5-di-t-butylbenzene is 94.5%.
Embodiment 2
With 55.4 gram (0.1 moles) 1,4-two (2,4-2,4-dinitrophenoxy base)-2,5-di-t-butylbenzene, 11.0 gram palladium mass percents are that 1% palladium/charcoal and 5540ml 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 adds pure water, separate out crystallized product, filter, vacuum-drying obtains 40.6 grams 1,4-two (2, the 4-diamino phenoxy)-2,5-di-t-butylbenzene crystal, purity is 99.3%, according to 1 of reality acquisition, two (2, the 4-diamino phenoxy)-2 of 4-, the amount of 5-di-t-butylbenzene and theoretical amount (43.4 gram), calculate 1, two (2, the 4-diamino phenoxy)-2 of 4-, the yield of 5-di-t-butylbenzene is 93.5%.
Embodiment 3
With 55.4 gram (0.1 moles) 1,4-two (2,4-2,4-dinitrophenoxy base)-2,5-di-t-butylbenzene, 4.0 gram palladium mass percents are that 5% palladium/charcoal 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 adds pure water, separate out crystallized product, filter, vacuum-drying obtains 39.7 grams 1,4-two (2, the 4-diamino phenoxy)-2,5-di-t-butylbenzene crystal, purity is 99.4%, according to 1 of reality acquisition, two (2, the 4-diamino phenoxy)-2 of 4-, the amount of 5-di-t-butylbenzene and theoretical amount (43.4 gram), calculate 1, two (2, the 4-diamino phenoxy)-2 of 4-, the yield of 5-di-t-butylbenzene is 91.5%.
Embodiment 4
With 55.4 gram (0.1 moles) 1,4-two (2,4-2,4-dinitrophenoxy base)-2,5-di-t-butylbenzene, 3.8 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, 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 adds pure water, separate out crystallized product, filter, vacuum-drying obtains 37.7 grams 1,4-two (2, the 4-diamino phenoxy)-2,5-di-t-butylbenzene crystal, purity is 99.4%, according to 1 of reality acquisition, two (2, the 4-diamino phenoxy)-2 of 4-, the amount of 5-di-t-butylbenzene and theoretical amount (43.4 gram), calculate 1, two (2, the 4-diamino phenoxy)-2 of 4-, the yield of 5-di-t-butylbenzene is 86.9%.
Embodiment 5
With 55.4 gram (0.1 moles) 1,4-two (2,4-2,4-dinitrophenoxy base)-2,5-di-t-butylbenzene, 3.5 gram palladium mass percents are that 10% palladium/charcoal, 20ml 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 adds pure water, separate out crystallized product, filter, vacuum-drying obtains 39.6 grams 1,4-two (2, the 4-diamino phenoxy)-2,5-di-t-butylbenzene crystal, purity is 99.6%, according to 1 of reality acquisition, two (2, the 4-diamino phenoxy)-2 of 4-, the amount of 5-di-t-butylbenzene and theoretical amount (43.4 gram), calculate 1, two (2, the 4-diamino phenoxy)-2 of 4-, the yield of 5-di-t-butylbenzene is 91.2%.
Embodiment 6
With 55.4 gram (0.1 moles) 1,4-two (2,4-2,4-dinitrophenoxy base)-2,5-di-t-butylbenzene, 1.6 gram palladium mass percents are 15% palladium/charcoal 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 adds pure water, separate out crystallized product, filter, vacuum-drying obtains 35.7 grams 1,4-two (2, the 4-diamino phenoxy)-2,5-di-t-butylbenzene crystal, purity is 99.5%, according to 1 of reality acquisition, two (2, the 4-diamino phenoxy)-2 of 4-, the amount of 5-di-t-butylbenzene and theoretical amount (43.4 gram), calculate 1, two (2, the 4-diamino phenoxy)-2 of 4-, the yield of 5-di-t-butylbenzene is 82.3%.
Claims (7)
1. one kind 1, two (2, the 4-diamino phenoxy)-2 of 4-, the preparation method of 5-di-t-butylbenzene comprises the steps: 1, and 4-two (2,4-2,4-dinitrophenoxy base)-2, the 5-di-t-butylbenzene, 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, two (2, the 4-diamino phenoxy)-2 of 4-, the 5-di-t-butylbenzene.
2. according to claim 11, two (2, the 4-diamino phenoxy)-2 of 4-, the preparation method of 5-di-t-butylbenzene 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 of 4-, the preparation method of 5-di-t-butylbenzene 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, the preparation method of 5-di-t-butylbenzene, 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, two (2, the 4-diamino phenoxy)-2 of 4-, the preparation method of 5-di-t-butylbenzene is characterized in that: described 1,4-two (2,4-2,4-dinitrophenoxy base)-2, the weight ratio of 5-di-t-butylbenzene and palladium/charcoal is 100: 1～20.
6. according to claim 1 or 3 described 1, two (2, the 4-diamino phenoxy)-2 of 4-, the preparation method of 5-di-t-butylbenzene is characterized in that: described 1,4-two (2,4-2,4-dinitrophenoxy base)-2, the mol ratio of 5-di-t-butylbenzene and hydrazine hydrate is 1: 20～50.
7. according to claim 1 or 4 described 1,4-two (2, the 4-diamino phenoxy)-2, the preparation method of 5-di-t-butylbenzene, it is characterized in that: described 1, two (2,4-2,4-dinitrophenoxy base)-2 of 4-, the weightmeasurement ratio of 5-di-t-butylbenzene and saturated fatty alcoholic solvent are 1 gram: 15 milliliters～100 milliliters.
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2008
- 2008-03-21 CN CNA2008100349731A patent/CN101245026A/en active Pending
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| CN106280455A (en) * | 2016-11-04 | 2017-01-04 | 东华大学 | A kind of 6FDA type BDADTBHQ branched polyimide resin film and preparation method thereof |
| CN106280453A (en) * | 2016-11-04 | 2017-01-04 | 东华大学 | A kind of HQDA type BDADTBHQ branched polyimide resin film and preparation method thereof |
| CN106479182A (en) * | 2016-11-04 | 2017-03-08 | 东华大学 | A kind of BPADA type BDADTBHQ branched polyimide resin film and preparation method thereof |
| CN106479180A (en) * | 2016-11-04 | 2017-03-08 | 东华大学 | A kind of PMDA type BDADTBHQ branched polyimide resin film and preparation method thereof |
| CN106479181A (en) * | 2016-11-04 | 2017-03-08 | 东华大学 | A kind of BPDA type BDADTBHQ branched polyimide resin film and preparation method thereof |
| CN106519227A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | ODPA type BDADTBHQ branched polyimide resin film and preparation method thereof |
| CN106633866A (en) * | 2016-11-04 | 2017-05-10 | 东华大学 | BTDA type BDADTBHQ branched polyimide resin thin film and preparation method thereof |
| CN106751497A (en) * | 2016-12-05 | 2017-05-31 | 东华大学 | A kind of preparation method of crystal waste slag/BDADTBHQ type epoxy matrix resin composites |
| CN109735294A (en) * | 2018-12-21 | 2019-05-10 | 东华大学 | A kind of BDADTBHQ type silicon-containing adhesive and preparation method thereof |
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