CN101591277B - Method for preparing 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone - Google Patents
Method for preparing 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone Download PDFInfo
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- CN101591277B CN101591277B CN2009100543825A CN200910054382A CN101591277B CN 101591277 B CN101591277 B CN 101591277B CN 2009100543825 A CN2009100543825 A CN 2009100543825A CN 200910054382 A CN200910054382 A CN 200910054382A CN 101591277 B CN101591277 B CN 101591277B
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Abstract
The invention relates to a method for preparing 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, which comprises the following steps: adding 4,4'-bis(4-nitro-2-trifluoromethylphenoxy)diphenylsulfone, an organic solvent and a catalyst into a high-pressure reaction kettle; introducing hydrogen into the reaction kettle; stirring the mixture in the reaction kettle; displacing residue air; continuing to introduce hydrogen; heating the mixture to between 95 and 110 DEGC; keeping the pressure in the reaction kettle at 0.8 to 1.2 MPa and keeping the reaction for 4 to 5 hours; cooling the reaction system to room temperature; slowly reliving pressure; filtering the product of the reaction; recovering filter residue, keeping mother solution; adding deionized water into the mother solution with stirring to precipitate a white solid product; filtering the solution; and washing and drying the white solid product to obtain the 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone. The method is simple in process, low in cost and environmentally-friendly. The product of the method has a melting point of from 218.3 to 218.9 DEG C, yield up to more than 97 percent and purity up to 99.8 percent and is suitable for industrial production.
Description
Technical field
The invention belongs to the preparation field of aromatic series fluorinated organic compound, particularly relate to a kind of 4,4 '-preparation method of two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide.
Background technology
Aromatic polyimide has excellent thermostability, chemicalstability, excellent mechanical property, electric property and organic solvent resistance, has obtained widespread use in space flight and aviation, electronics microelectronics, field such as electric.Because characteristics such as it these are high temperature resistant, HS, anticorrosive, good insulating, film-forming process are simple, thereby be a kind of good functional materials, can satisfy the performance requriements of LCD (liquid-crystal display).
The fluorinated polyimide material not only has above-mentioned excellent properties, but also has very excellent optical transparence, flame retardant resistance and good forming process property.In addition, its specific inductivity, dielectric loss and water-intake rate are all lower.
The fluorinated polyimide material has important use and is worth in some field, like the passivating coating of flexible solar radiation protector, liquid crystal orientation film, gas separation membrane, unicircuit or layer insulation medium, the waveguide material of communications connectors, the electric insulation deielectric-coating of flexible printed circuit board etc.
Yu Xinhai [New Chemical Materials, 2003,31 (10): 24～27,31] discloses 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa and the fluorinated polyimide preparation methods thereof of 2-.
Yu Xinhai [insulating material, 2007,40 (4): 1～5; 8] disclose 2; The preparation method of two (the 3-amino-4-hydroxy phenyl) HFC-236fas of 2-, it is not only the important source material of the fluorine-containing polybenzoxazole macromolecular material of preparation, also is the important source material of the fluorine-containing phenolic hydroxy group polyimide resin of preparation.
Chinese patent CN101234991A discloses 2, the preparation method of two [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fas of 2-, and it also is the important source material of preparation fluorinated polyimide resin, particularly prepares the important source material of fluorine-containing high branched polyimide resin.
Chinese patent CN101245028A discloses 2; The preparation method of two [3-amino-4-(4-amino-benzene oxygen) phenyl] HFC-236fas of 2-; It also is the important source material of preparation fluorinated polyimide resin, particularly prepares the important source material of fluorine-containing high branched polyimide resin.
Chinese patent CN101245023A discloses 2, the preparation method of two [3-amino-4-(2, the 4-2,4-dinitrophenoxy base) phenyl] HFC-236fas of 2-, and it also is the important source material of preparation fluorinated polyimide resin.
4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide is one of important source material of synthetic aroma family fluorinated polyimide macromolecular material.
Chin-Ping Yang, Yu-Yang Su and Kuen-Lin Wu [Organosoluble and Light-coloredFluorinated Polyimides from 2,2-Bis [4-(4-amino-2-trifluoromethylphenoxy) phenyl] sulfone andAromatic Dianhydrides, Journal of Polymer Research; 2005,12:257-269] disclose 4,4 '-preparation method of two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide, it is characterized in that: 4; 4 '-two (4-nitro-2-4-trifluoromethylphenopendant) sulfobenzide, alcohol solvent and 10% palladium/charcoal, stir down at 70 ℃-80 ℃, drip Hydrazine Hydrate 80, be added dropwise to complete in the 30min; Be heated to backflow, continue reaction 2 hours, filtered while hot; Remove palladium/charcoal, the distillation concentrated mother liquor is poured liquid concentrator in the water into; Separate out solid product, vacuum-drying obtains 4; 4 '-two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide products (yield 90%), 219 ℃-220 ℃ of fusing points, but the shortcoming of this method is; (1) reductive agent adopts the Hydrazine Hydrate 80 of severe toxicity, is unfavorable for environment protection, also is unfavorable for operator's labour protection; (2) yield is on the low side; (3) industrialization prospect is dim.
Summary of the invention
Technical problem to be solved by this invention provides a kind of 4; 4 '-preparation method of two (4-nitro-2-4-trifluoromethylphenopendant) sulfobenzide; This method technology is simple, cost is low, the fusing point of environmental friendliness, product is 218.3 ℃-218.9 ℃; Yield is up to more than 97%, and purity is applicable to suitability for industrialized production up to 99.8%.
Chemical equation of the present invention is following:
Of the present invention a kind of 4,4 '-preparation method of two (4-nitro-2-4-trifluoromethylphenopendant) sulfobenzide, comprising:
With 4,4 '-two (4-nitro-2-4-trifluoromethylphenopendant) sulfobenzide, organic solvent, catalyzer add in the autoclave, and logical hydrogen stirs; Displace residual air, continue logical hydrogen, heat to 95 ℃-110 ℃, keep reacting kettle inner pressure 0.8MPa-1.2MPa; Keep reaction after 4-5 hour, cooling reaction system is to room temperature, slowly release, and logical nitrogen is to displace all remaining hydrogen; Guarantee to be inert atmosphere in the autoclave, filter, reclaim filter residue, leave and take mother liquor; And in mother liquor, drip deionized water while stirring, and separate out white solid product, filter washing; Drying, obtain 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide solid;
Wherein, organic solvent and 4,4 '-envelope-bulk to weight ratio of two (4-nitro-2-4-trifluoromethylphenopendant) sulfobenzide is 10 milliliters-15 milliliters: 1 gram; Catalyzer and 4,4 '-weight ratio of two (4-nitro-2-4-trifluoromethylphenopendant) sulfobenzide is 1: 10-40; Deionized water must be strict controlled in 1 with the volume of organic solvent ratio: in the scope of 0.8-1.2.
Described organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, terepthaloyl moietie, 1,2-Ucar 35,1, one or more mixtures in the ammediol;
Described catalyzer is selected from raney nickel or palladium/charcoal;
Described palladium/charcoal, its palladium metal quality percentage composition is 1%～10%.
At N; In the N-dimethylacetamide solvent; In 0 ℃～10 ℃ TRs, with resulting 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide solids and equimolar pyromellitic acid anhydride react; Obtained high thick polyamic acid solution, its limiting viscosity is up to 2.1dL/g; Film, hot imidization obtains tough and tensile transparent Kapton, and tensile strength is up to 121MPa, and second-order transition temperature is 299.5 ℃.
In the DMAC N,N solvent, in 0 ℃～10 ℃ TRs; With resulting 4; 4 '-two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide solids and equimolar 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2-react; Obtained high thick polyamic acid solution, its limiting viscosity is up to 1.8dL/g; Film, hot imidization obtains tough and tensile transparent Kapton, and tensile strength is up to 113MPa, and second-order transition temperature is 190.1 ℃.
Beneficial effect
(1) preparation method of the present invention is simple to operate, and raw material sources are convenient, does not relate to also not producing corrosives or highly toxic substance (like raw materials such as Hydrazine Hydrate 80s); Organic solvent uses kind few, and Recycling repeatedly is environmentally friendly;
(2) this method need not recrystallization operation, has simplified technology, and the fusing point of product is 218.3 ℃-218.9 ℃, and yield is up to more than 97%, and purity is applicable to suitability for industrialized production up to 99.8%.
Description of drawings
Fig. 1 is 4,4 '-molecular structure of two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide
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 the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to 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 62.8 gram (0.10 moles) 4,4 '-Pd/carbon catalyst of two (4-nitro-2-4-trifluoromethylphenopendant) sulfobenzide, 940 ml methanol solvents, 2.1 grams 10% adds autoclave, logical hydrogen stirs; Displace residual air, continue logical hydrogen, heat to 95 ℃-110 ℃, keep reacting kettle inner pressure 0.8MPa-1.2MPa; Keep reaction after 4 hours, cooling reaction system is to room temperature, slowly release, and logical nitrogen is to displace all remaining hydrogen; Guarantee to be inert atmosphere in the autoclave, filter, reclaim filter residue (catalyzer); Leave and take mother liquor, and in mother liquor, drip 784 ml deionized water while stirring, separate out white solid product; Filter, with deionized water wash 2～3 times, 25 ℃ of vacuum-dryings; Obtain 4,4 of 55.2 gram (product yield is 97.2%) whites '-two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide pressed powder (theoretical yield: 56.8 gram), purity 99.8%; 218.3 ℃-218.9 ℃ of fusing points (WRR optics fusing point appearance, the initial temperature that is provided with is 215 ℃, 1.0 ℃ of temperature rise rates/min).
At 30 milliliters of N; In the N-dimethylacetamide solvent; In 0 ℃～10 ℃ TRs, with resulting 4,4 '-taking out 5.68 grams (.0.01 mole) in two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide solid reacted 5 hours with 2.18 gram (0.01 mole) pyromellitic acid anhydrides; Obtained high thick polyamic acid solution, its limiting viscosity is 2.1dL/g.
Above-mentioned polyamic acid solution evenly is coated on the clean sheet glass, puts into convection oven, hot imidization, concrete technology is: begin heat temperature raising to 100 ℃ from room temperature, be incubated 2 hours; Continue to be warming up to 170 ℃, be incubated 1.5 hours; Continue to be warming up to 250 ℃, be incubated 0.5 hour; Continue to be warming up to 300 ℃, be incubated 0.5 hour; Naturally cool to room temperature, demoulding obtains tough and tensile transparent Kapton, and tensile strength is 121MPa; 4,4 '-second-order transition temperature of two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide/pyromellitic acid anhydride-Kapton is 299.5 ℃.
In 40 milliliters of DMAC N,N solvents, in 0 ℃～10 ℃ TRs; With resulting 4; 4 '-taking out 5.68 grams (.0.01 mole) and 5.20 gram (0.01 moles) 2 in two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide solid, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2-reacted 5 hours; Obtained high thick polyamic acid solution, its limiting viscosity is 1.8dL/g.
Above-mentioned polyamic acid solution evenly is coated on the clean sheet glass, puts into convection oven, hot imidization, concrete technology is: begin heat temperature raising to 100 ℃ from room temperature, be incubated 1 hour; Continue to be warming up to 180 ℃, be incubated 1 hour; Continue to be warming up to 250 ℃, be incubated 0.5 hour; Naturally cool to room temperature, demoulding obtains tough and tensile transparent Kapton, and tensile strength is 113MPa; 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide/2, the second-order transition temperature of two [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane dianhydride-Kaptons of 2-is 190.1 ℃.
Embodiment 2
With 62.8 gram (0.10 moles) 4,4 '-Pd/carbon catalyst of two (4-nitro-2-4-trifluoromethylphenopendant) sulfobenzide, 628 milliliters of alcohol solvents, 1.6 grams 10% adds autoclave, logical hydrogen stirs; Displace residual air, continue logical hydrogen, heat to 95 ℃-110 ℃, keep reacting kettle inner pressure 0.8MPa-1.2MPa; Keep reaction after 5 hours, cooling reaction system is to room temperature, slowly release; And logical nitrogen guarantees to be in the autoclave inert atmosphere, filtration to displace all remaining hydrogen; Reclaim filter residue (catalyzer), leave and take mother liquor, and in mother liquor, drip 785 ml deionized water while stirring; Separate out white solid product, filter, with deionized water wash 2～3 times; 25 ℃ of vacuum-dryings, obtain 4,4 of 55.4 gram (product yield is 97.5%) whites '-two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide pressed powder (theoretical yield: 56.8 gram).
Embodiment 3
With 62.8 gram (0.10 moles) 4,4 '-Pd/carbon catalyst of two (4-nitro-2-4-trifluoromethylphenopendant) sulfobenzide, 400 milliliters of alcohol solvents, 350 milliliters of ethylene glycol solvents, 4.5 grams 5% adds autoclave, logical hydrogen stirs; Displace residual air, continue logical hydrogen, heat to 95 ℃-110 ℃, keep reacting kettle inner pressure 0.8MPa-1.2MPa; Keep reaction after 4.5 hours, cooling reaction system is to room temperature, slowly release; And logical nitrogen guarantees to be in the autoclave inert atmosphere, filtration to displace all remaining hydrogen; Reclaim filter residue (catalyzer), leave and take mother liquor, and in mother liquor, drip 750 ml deionized water while stirring; Separate out white solid product, filter, with deionized water wash 2～3 times; 25 ℃ of vacuum-dryings, obtain 4,4 of 54.9 gram (product yield is 96.7%) whites '-two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide pressed powder (theoretical yield: 56.8 gram).
Embodiment 4
With 62.8 gram (0.10 moles) 4,4 '-Pd/carbon catalyst of two (4-nitro-2-4-trifluoromethylphenopendant) sulfobenzide, 200 milliliters of alcohol solvents, 550 ml methanol solvents, 6.2 grams 1% adds autoclave, logical hydrogen stirs; Displace residual air, continue logical hydrogen, heat to 95 ℃-110 ℃, keep reacting kettle inner pressure 0.8MPa-1.2MPa; Keep reaction after 5 hours, cooling reaction system is to room temperature, slowly release; And logical nitrogen guarantees to be in the autoclave inert atmosphere, filtration to displace all remaining hydrogen; Reclaim filter residue (catalyzer), leave and take mother liquor, and in mother liquor, drip 750 ml deionized water while stirring; Separate out white solid product, filter, with deionized water wash 2～3 times; 25 ℃ of vacuum-dryings, obtain 4,4 of 52.5 gram (product yield is 92.4%) whites '-two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide pressed powder (theoretical yield: 56.8 gram).
Claims (4)
1. one kind 4,4 '-preparation method of two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide, comprising:
With 4,4 '-two (4-nitro-2-4-trifluoromethylphenopendant) sulfobenzide, organic solvent, catalyzer add in the autoclave, and logical hydrogen stirs; Displace residual air, continue logical hydrogen, heat to 95 ℃-110 ℃, keep reacting kettle inner pressure 0.8MPa-1.2MPa; Keep reaction after 4-5 hour, cooling reaction system is to room temperature, slowly release, and logical nitrogen is to displace all remaining hydrogen; Guarantee to be inert atmosphere in the autoclave, filter, reclaim filter residue, leave and take mother liquor; And in mother liquor, drip deionized water while stirring, and separate out white solid product, filter washing; Drying, obtain 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide solid;
Wherein, organic solvent and 4,4 '-envelope-bulk to weight ratio of two (4-nitro-2-4-trifluoromethylphenopendant) sulfobenzide is 10 milliliters-15 milliliters: 1 gram; Catalyzer and 4,4 '-weight ratio of two (4-nitro-2-4-trifluoromethylphenopendant) sulfobenzide is 1: 10-40; Deionized water must be strict controlled in 1 with the volume of organic solvent ratio: in the scope of 0.8-1.2.
2. according to claim 1 a kind of 4; 4 '-preparation method of two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide; It is characterized in that: described organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, terepthaloyl moietie, 1; 2-Ucar 35,1, one or more mixtures in the ammediol.
3. according to claim 1 a kind of 4,4 '-preparation method of two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide, it is characterized in that: described catalyzer is raney nickel or palladium/charcoal.
4. according to claim 3 a kind of 4,4 '-preparation method of two (4-amino-2-4-trifluoromethylphenopendant) sulfobenzide, it is characterized in that: described palladium/charcoal, its palladium metal quality percentage composition is 1%～10%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3988374A (en) * | 1970-06-29 | 1976-10-26 | Union Carbide Corporation | Polyamide-imides |
| CN101245041A (en) * | 2008-03-21 | 2008-08-20 | 东华大学 | Process for producing 4,4'-bis(2,4-diaminophenyloxy)diphenyl sulfone |
| CN101250142A (en) * | 2008-04-02 | 2008-08-27 | 东华大学 | Method for preparing 4,4'-di(2,4-diamino phenoxy)-3,3',5,5'-tetramethyl diphenyl sulfone |
| CN101429132A (en) * | 2008-12-09 | 2009-05-13 | 上海固创化工新材料有限公司 | Synthesis of 1,3-di(4-aminophenoxy)benzene |
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2009
- 2009-07-03 CN CN2009100543825A patent/CN101591277B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3988374A (en) * | 1970-06-29 | 1976-10-26 | Union Carbide Corporation | Polyamide-imides |
| CN101245041A (en) * | 2008-03-21 | 2008-08-20 | 东华大学 | Process for producing 4,4'-bis(2,4-diaminophenyloxy)diphenyl sulfone |
| CN101250142A (en) * | 2008-04-02 | 2008-08-27 | 东华大学 | Method for preparing 4,4'-di(2,4-diamino phenoxy)-3,3',5,5'-tetramethyl diphenyl sulfone |
| CN101429132A (en) * | 2008-12-09 | 2009-05-13 | 上海固创化工新材料有限公司 | Synthesis of 1,3-di(4-aminophenoxy)benzene |
Non-Patent Citations (2)
| Title |
|---|
| Chin-Ping Yang, et al..Organosoluble and Light-colored Fluorinated Polyimides from 2,2-Bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]sulfone and Aromatic Dianhydrides.《Journal of Polymer Research》.2005,第12卷(第4期),257-269. * |
| Chin-PingYang et al..Organosoluble and Light-colored Fluorinated Polyimides from 2 |
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