CN101250120B - Method for preparing 4,4-di(2,4-diamino phenoxy) diphenylmethane - Google Patents
Method for preparing 4,4-di(2,4-diamino phenoxy) diphenylmethane Download PDFInfo
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- CN101250120B CN101250120B CN2008100354759A CN200810035475A CN101250120B CN 101250120 B CN101250120 B CN 101250120B CN 2008100354759 A CN2008100354759 A CN 2008100354759A CN 200810035475 A CN200810035475 A CN 200810035475A CN 101250120 B CN101250120 B CN 101250120B
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- diamino phenoxy
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Abstract
The invention relates to a preparation method of 4, 4'-bis (2, 4-diamino phenoxy) diphenylmethane, which comprises reacting 4, 4'-bis (2, 4-dinitro phenoxy) diphenylmethane in a system of palladium/charcoal, hydrazine hydrate solution and saturated fatty alcohol, at 80-90DEG C for 1-5h, filtering immediately, cooling the mother liquor, adding pure water, precipitating crystal product, filtering, drying in vacuum and obtaining 4, 4'-bis (2, 4-diamino phenoxy) diphenylmethane crystal. The invention has simple operation, eliminated following refining and extraction, low time consumption, high product yield and high purity (at least 99%), which 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 preparation method of 4,4 '-two (2, the 4-diamino phenoxy) ditane.
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) ditane 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) ditane also is the important raw and processed materials of synthetic More Malay imide resin.
4,4 '-two (2, the 4-diamino phenoxy) ditane 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) ditane, 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) ditane of the present invention comprises the steps:
4,4 '-two (2,4-2,4-dinitrophenoxy base) ditane, in palladium/charcoal, hydrazine hydrate solution and saturated fatty alcohol solvent system in 80 ℃～90 ℃ temperature range internal reactions after 1～5 hour, 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) ditane 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) ditanes and palladium/charcoal is 100: 1～20.
The mol ratio of described 4,4 '-two (2,4-2,4-dinitrophenoxy base) ditanes and hydrazine hydrate is 1: 20～50.
The weightmeasurement ratio of described 4,4 '-two (2,4-2,4-dinitrophenoxy base) ditanes 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) ditane;
(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) ditane.
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 53.2 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) ditane, 0.5 gram palladium mass percent are that palladium/charcoal of 15%, 800 milliliters of ethanol 1600ml 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 80 ℃～90 ℃ temperature range, continued stirring reaction 5 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 38.9 grams 4,4 '-two (2, the 4-diamino phenoxy) ditane crystal, purity is 99.8%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) ditane and theoretical amount (41.2 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) ditane is 94.5%.
Embodiment 2
With 53.2 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) ditane, 10.0 gram palladium mass percents are that 1% palladium/charcoal, 100ml ethylene glycol and 2000ml 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 3.5 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 37.6 grams 4,4 '-two (2, the 4-diamino phenoxy) ditane crystal, purity is 99.7%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) ditane and theoretical amount (41.2 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) ditane is 91.2%.
Embodiment 3
With 53.2 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) ditane, 5.0 gram palladium mass percents are that 5% 200 milliliters of ethanol of palladium/charcoal and 1000ml 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 1 hour, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 32.2 grams 4,4 '-two (2, the 4-diamino phenoxy) ditane crystal, purity is 99.4%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) ditane and theoretical amount (41.2 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) ditane is 78.2%.
Embodiment 4
With 53.2 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) ditane, 4.1 gram palladium mass percents are palladium/charcoal of 10%, 800 milliliters of ethanol and 1000ml 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 3.5 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 37.2 grams 4,4 '-two (2, the 4-diamino phenoxy) ditane crystal, purity is 99.6%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) ditane and theoretical amount (41.2 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) ditane is 90.4%.
Embodiment 5
With 53.2 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) ditane, 5.0 gram palladium mass percents are that 10% palladium/charcoal, 100ml methyl alcohol and 1000ml 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 3.5 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 37.7 grams 4,4 '-two (2, the 4-diamino phenoxy) ditane crystal, purity is 99.6%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) ditane and theoretical amount (41.2 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) ditane is 91.6%.
Embodiment 6
With 53.2 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base) ditane, 1.7 gram palladium mass percents are palladium/charcoal of 15%, 900 milliliters of ethanol and 1000ml 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 4.5 hours, cold slightly, filtered while hot, cooling mother liquor, add pure water, separate out crystallized product, filter vacuum-drying, obtain 38.2 grams 4,4 '-two (2, the 4-diamino phenoxy) ditane crystal, purity is 99.8%, according to 4 of reality acquisition, the amount of 4 '-two (2, the 4-diamino phenoxy) ditane and theoretical amount (41.2 gram) calculate 4, the yield of 4 '-two (2, the 4-diamino phenoxy) ditane is 92.7%.
Claims (2)
1. one kind 4, the preparation method of 4 '-two (2, the 4-diamino phenoxy) ditane, comprise the steps: 4,4 '-two (2,4-2,4-dinitrophenoxy base) ditane, in the hydrazine hydrate solution of palladium/charcoal, 60wt%～85wt% and saturated fatty alcohol solvent system in 80 ℃～90 ℃ temperature range internal reactions after 1～5 hour, 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) ditane;
The palladium mass percent of described palladium/charcoal is 1%～15%, 4, and the weight ratio of 4 '-two (2,4-2,4-dinitrophenoxy base) ditanes and palladium/charcoal is 100: 1～20; The mol ratio of 4,4 '-two (2,4-2,4-dinitrophenoxy base) ditanes and hydrazine hydrate is 1: 20～50; 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.
2. according to claim 14, the preparation method of 4 '-two (2, the 4-diamino phenoxy) ditane is characterized in that: described 4, the weightmeasurement ratio of 4 '-two (2,4-2,4-dinitrophenoxy base) ditanes and saturated fatty alcoholic solvent is 1 gram: 15 milliliters～100 milliliters.
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| CN2008100354759A CN101250120B (en) | 2008-04-02 | 2008-04-02 | Method for preparing 4,4-di(2,4-diamino phenoxy) diphenylmethane |
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| CN2008100354759A CN101250120B (en) | 2008-04-02 | 2008-04-02 | Method for preparing 4,4-di(2,4-diamino phenoxy) diphenylmethane |
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| CN101250120B true CN101250120B (en) | 2011-06-08 |
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| CN103131371B (en) * | 2013-03-11 | 2014-07-02 | 东华大学 | 4,4'-bis(2,4-diamidophenoxy)diphenylmethane high-temperature-resistant epoxy adhesive and preparation method thereof |
| CN109722211A (en) * | 2018-12-21 | 2019-05-07 | 东华大学 | A kind of BDADDM type silicon-containing adhesive and preparation method thereof |
| CN109722208A (en) * | 2018-12-21 | 2019-05-07 | 东华大学 | A kind of 12BDAPB type silicon-containing adhesive and preparation method thereof |
| CN109722209A (en) * | 2018-12-21 | 2019-05-07 | 东华大学 | A kind of YASI organic imides silica gel and preparation method thereof |
| CN109722210A (en) * | 2018-12-21 | 2019-05-07 | 东华大学 | A kind of TADE type silicon-containing adhesive and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1472193A (en) * | 2003-07-11 | 2004-02-04 | 南通探索科技有限公司 | Preparation of 2,2-bi-[4-(4-aminophenoxy)phenyl]propane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1472193A (en) * | 2003-07-11 | 2004-02-04 | 南通探索科技有限公司 | Preparation of 2,2-bi-[4-(4-aminophenoxy)phenyl]propane |
Non-Patent Citations (3)
| Title |
|---|
| CA文献号82:124950CA入库号1975:124950.1975, * |
| 虞鑫海等.1 3-双(4-氨基苯氧基)苯的合成及其聚酰亚胺.绝缘材料39卷 3期.2006 |
| 虞鑫海等.1,3-双(4-氨基苯氧基)苯的合成及其聚酰亚胺.绝缘材料39卷 3期.2006,39卷(3期),1-4+8. * |
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