CN101250142A - Method for preparing 4,4'-di(2,4-diamino phenoxy)-3,3',5,5'-tetramethyl diphenyl sulfone - Google Patents
Method for preparing 4,4'-di(2,4-diamino phenoxy)-3,3',5,5'-tetramethyl diphenyl sulfone Download PDFInfo
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- CN101250142A CN101250142A CNA2008100354778A CN200810035477A CN101250142A CN 101250142 A CN101250142 A CN 101250142A CN A2008100354778 A CNA2008100354778 A CN A2008100354778A CN 200810035477 A CN200810035477 A CN 200810035477A CN 101250142 A CN101250142 A CN 101250142A
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- diphenyl sulfone
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Abstract
The invention relates to a preparation method of 4, 4'-bis (2, 4-diamino phenoxy)-3, 3', 5, 5'-tetramethyl sulfone, which comprises reacting 4, 4'-bis (2, 4-dinitro phenoxy)-3, 3', 5, 5'-tetramethyl sulfone 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 white crystal product, filtering and drying in vacuum to obtain 4, 4'-bis (2, 4-diamino phenoxy)-3, 3', 5, 5'-tetramethyl sulfone crystal. The invention has simple operation, eliminatd 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 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5, the preparation method of 5 '-tetramethyl diphenyl sulfone.
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)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone is one of important source material of synthetic high cladodification 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, 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone also is the important raw and processed materials of synthetic More Malay imide resin.
4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone 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 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5, the preparation method of 5 '-tetramethyl diphenyl sulfone, this method technology is simple, need not follow-up refining purifying technique, 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:
A kind of 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5 of the present invention, the preparation method of 5 '-tetramethyl diphenyl sulfone comprises the steps:
4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 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, obtain 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone 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 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5, the weight ratio of 5 '-tetramethyl diphenyl sulfone and palladium/charcoal is 100: 1～20.
Described 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5, the mol ratio of 5 '-tetramethyl diphenyl sulfone and hydrazine hydrate is 1: 20～50.
Described 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5, the weightmeasurement ratio of 5 '-tetramethyl diphenyl sulfone and saturated fatty alcoholic solvent are 1 gram: 15 milliliters～100 milliliters.
Beneficial effect of the present invention
(1) the present invention is preparation 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5, the commercial run of 5 '-tetramethyl diphenyl sulfone;
(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 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5, the molecular structure of 5 '-tetramethyl diphenyl sulfone.
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 63.8 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 0.7 gram palladium mass percent are that palladium/charcoal of 15%, 1800 milliliters of ethanol 1800ml 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 80 ℃～90 ℃ 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 42.8 grams, 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone crystal, purity is 99.5%, according to 4,4 '-two (2 of reality acquisition, the 4-diamino phenoxy)-3,3 ', 5, the amount of 5 '-tetramethyl diphenyl sulfone and theoretical amount (51.8 gram) calculate 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5, the yield of 5 '-tetramethyl diphenyl sulfone is 82.6%.
Embodiment 2
With 63.8 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 12.0 gram palladium mass percents are that 1% palladium/charcoal, 100ml ethylene glycol and 5800ml 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 80 ℃～90 ℃ 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 43.3 grams, 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone crystal, purity is 99.2%, according to 4,4 '-two (2 of reality acquisition, the 4-diamino phenoxy)-3,3 ', 5, the amount of 5 '-tetramethyl diphenyl sulfone and theoretical amount (51.8 gram) calculate 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5, the yield of 5 '-tetramethyl diphenyl sulfone is 83.5%.
Embodiment 3
With 63.8 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 7.8 gram palladium mass percents are that palladium/charcoal of 5%, 600 milliliters of ethanol and 3600ml 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 80 ℃～90 ℃ 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 44.0 grams, 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone crystal, purity is 99.7%, according to 4,4 '-two (2 of reality acquisition, the 4-diamino phenoxy)-3,3 ', 5, the amount of 5 '-tetramethyl diphenyl sulfone and theoretical amount (51.8 gram) calculate 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5, the yield of 5 '-tetramethyl diphenyl sulfone is 84.9%.
Embodiment 4
With 63.8 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 5.6 gram palladium mass percents are palladium/charcoal of 10%, 400 milliliters of ethanol and 1800ml 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 80 ℃～90 ℃ 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 42.9 grams, 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone crystal, purity is 99.5%, according to 4,4 '-two (2 of reality acquisition, the 4-diamino phenoxy)-3,3 ', 5, the amount of 5 '-tetramethyl diphenyl sulfone and theoretical amount (51.8 gram) calculate 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5, the yield of 5 '-tetramethyl diphenyl sulfone is 82.8%.
Embodiment 5
With 63.8 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 7.7 gram palladium mass percents are that 10% palladium/charcoal, 200ml methyl alcohol and 2800ml 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 80 ℃～90 ℃ 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 47.4 grams, 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone crystal, purity is 99.5%, according to 4,4 '-two (2 of reality acquisition, the 4-diamino phenoxy)-3,3 ', 5, the amount of 5 '-tetramethyl diphenyl sulfone and theoretical amount (51.8 gram) calculate 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5, the yield of 5 '-tetramethyl diphenyl sulfone is 91.6%.
Embodiment 6
With 63.8 gram (0.1 moles) 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 3.2 gram palladium mass percents are palladium/charcoal of 15%, 1800 milliliters of ethanol and 2600ml 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 80 ℃～90 ℃ 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 49.6 grams, 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone crystal, purity is 99.8%, according to 4,4 '-two (2 of reality acquisition, the 4-diamino phenoxy)-3,3 ', 5, the amount of 5 '-tetramethyl diphenyl sulfone and theoretical amount (51.8 gram) calculate 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5, the yield of 5 '-tetramethyl diphenyl sulfone is 95.8%.
Claims (7)
1. one kind 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5, the preparation method of 5 '-tetramethyl diphenyl sulfone, comprise the steps: 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 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, cooling mother liquor, drip pure water, separate out crystalline product, filter vacuum-drying, obtain 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone.
2. 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5 according to claim 1, the preparation method of 5 '-tetramethyl diphenyl sulfone is characterized in that: the palladium mass percent of described palladium/charcoal is 1%～15%.
3. 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5 according to claim 1, the preparation method of 5 '-tetramethyl diphenyl sulfone 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)-3,3 ', 5, the preparation method of 5 '-tetramethyl diphenyl sulfone, 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 24,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5, the preparation method of 5 '-tetramethyl diphenyl sulfone is characterized in that: described 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5, the weight ratio of 5 '-tetramethyl diphenyl sulfone and palladium/charcoal is 100: 1～20.
6. according to claim 1 or 3 described 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5, the preparation method of 5 '-tetramethyl diphenyl sulfone is characterized in that: described 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5, the mol ratio of 5 '-tetramethyl diphenyl sulfone and hydrazine hydrate is 1: 20～50.
7. according to claim 1 or 4 described 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5, the preparation method of 5 '-tetramethyl diphenyl sulfone is characterized in that: described 4,4 '-two (2,4-2,4-dinitrophenoxy base)-3,3 ', 5, the weightmeasurement ratio of 5 '-tetramethyl diphenyl sulfone and saturated fatty alcoholic solvent is 1 gram: 15 milliliters～100 milliliters.
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| CNA2008100354778A CN101250142A (en) | 2008-04-02 | 2008-04-02 | Method for preparing 4,4'-di(2,4-diamino phenoxy)-3,3',5,5'-tetramethyl diphenyl sulfone |
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| CNA2008100354778A CN101250142A (en) | 2008-04-02 | 2008-04-02 | Method for preparing 4,4'-di(2,4-diamino phenoxy)-3,3',5,5'-tetramethyl diphenyl sulfone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591277B (en) * | 2009-07-03 | 2012-11-28 | 东华大学 | Method for preparing 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591277B (en) * | 2009-07-03 | 2012-11-28 | 东华大学 | Method for preparing 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone |
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Open date: 20080827 |