CN101560166B - Method for preparing 1,3-di(2-trifluoromethyl-4-aminophenoxy) benzene - Google Patents
Method for preparing 1,3-di(2-trifluoromethyl-4-aminophenoxy) benzene Download PDFInfo
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Abstract
The invention relates to a method for preparing 1,3-di(2-trifluoromethyl-4-aminophenoxy) benzene, which comprises the following steps: adding 1,3-di(2-trifluoromethyl-4-nitrophenoxy) benzene, an organic solvent and a catalyst into a high-pressure reaction kettle; introducing hydrogen to the reaction kettle, and stirring the mixture to replace out residual air; introducing the hydrogen continuously, heating the reaction kettle to raise the temperature to between 40 and 80 DEG C, keeping the pressure in the reaction kettle to between 0.4 and 1.2 MPa, maintaining the reaction for 2 to 5 hours, cooling the reaction system to room temperature, relieving the pressure slowly, and introducing nitrogen to the reaction kettle to replace out the residual hydrogen so as to ensure the inert atmosphere in the high-pressure reaction kettle; filtering the mixture, recycling filter residues, leaving and taking the mother liquor, and dropping deionized water into the mother liquor while stirring to separate out a white solid product; and filtering, washing and drying the solid product to obtain the 1,3-di(2-trifluoromethyl-4-aminophenoxy) benzene solid. The method has the advantages of simple process, low cost, environmental protection, high purity and yield, and suitability 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 1, the preparation method of two (2-trifluoromethyl-4-aminophenoxyl) benzene of 3-.
Background technology
Aromatic polyimide has excellent thermostability, chemical stability, good mechanical property, electric property and organic solvent resistance, is widely applied in space flight and aviation, electronics microelectronics, the field such as electric.Because the characteristics such as it these are high temperature resistant, high strength, 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.In addition, its specific inductivity, dielectric loss and water-intake rate are all lower.
The fluorinated polyimide material has important using value in some field, such as 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, electric insulation deielectric-coating of flexible printed circuit board etc.
Yu Xinhai [New Chemical Materials, 2003,31 (10): 24～27,31] discloses two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa and the fluorinated polyimide material preparation methods thereof of 2,2-.
Yu Xinhai [insulating material, 2007,40 (4): 1～5,8] disclose 2, the preparation method of two (3-amino-4-hydroxylphenyl) HFC-236fa 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 2,2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] preparation method of HFC-236fa, 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-236fa 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 the preparation method of two [3-amino-4-(2, the 4-dinitrophenoxy) phenyl] HFC-236fa of 2,2-, and it also is the important source material of preparation fluorinated polyimide resin.
Two (2-trifluoromethyl-4-aminophenoxyl) benzene of 1,3-are one of important source material of synthetic aroma family fluorinated polyimide macromolecular material.
Chinese patent CN1361097A discloses 1, the preparation method of two (2-trifluoromethyl-4-aminophenoxyl) benzene of 3-, it is characterized in that: in 1000 ml flasks, add 170 part 1, two (2-trifluoromethyl-4-nitrophenoxy) benzene of 3-, 100 parts of iron powders and 150 parts of aqueous ethanolic solutions.Slowly splash into 8 parts of aqueous hydrochloric acids at rapid stirring with under refluxing, refluxed 2 hours.Then add ammoniacal liquor, transfer solution to neutral, stirred 0.5 hour.Solids removed by filtration, then the filtrate distillation and concentration was placed 10 hours.Filter, crystal absolute ethanol washing three times are then dry, obtain two (2-trifluoromethyl-4-aminophenoxyl) benzene of 1,3-.
K.Xie, J.G.Liu, et al.[Soluble fluoro-polyimides derived from 1,3-bis (4-amino-2-trifluoromethylphenoxy) benzene and dianhydrides, Polymer, 2001,42:7267-7274] disclose 1, the preparation method of two (2-trifluoromethyl-4-aminophenoxyl) benzene of 3-, it is characterized in that: concentrated hydrochloric acid aqueous solution, 50% aqueous ethanolic solution, 1, two (2-trifluoromethyl-4-nitrophenoxy) benzene of 3-, reduced iron powder mixture back flow reaction added 10% ammoniacal liquor, heat filtering after 2 hours, cool off in the mother liquor ice-water bath, add 5% dilute hydrochloric acid solution, separate out the dihydrochloride of two (2-trifluoromethyl-4-aminophenoxyl) benzene of 1,3-.At 1 of dichloromethane solvent, add in the dihydrochloride of two (2-trifluoromethyl-4-aminophenoxyl) benzene of 3-ammoniacal liquor separate out pure 1, two (2-trifluoromethyl-4-aminophenoxyl) the benzene solids of 3-, 41.2 ℃ of (DSC methods of fusing point, air atmosphere), yield 62%.But the shortcoming of the method is: (1) serious three wastes; (2) yield is too low; (3) industrialization prospect is dim.
Wonbong Jang, Ho-Seong Lee, Seokkyu Lee, Seunghyuk Choi, Daeyong Shin, Haksoo Han[The optical and dielectric characterization of light-colored fluorinated polyimides based on1,3-bis (4-amino-2-trifluoromethylphenoxy) benzene, Materials Chemistry and Physics, 2007,104:342-349] disclose 1, the preparation method of two (2-trifluoromethyl-4-aminophenoxyl) benzene of 3-, it is characterized in that: 1, ethanol/ethyl acetate (volume ratio 1: 1) suspension liquid of two (2-trifluoromethyl-4-nitrophenoxy) benzene of 3-and 10% palladium/charcoal, stirring at room 30min, be heated to 60 ℃ and continue reaction 3 hours, filtered while hot, remove palladium/charcoal, the distillation and concentration mother liquor, solid product is separated out in 80 ℃ of vacuum-dryings, obtain lurid 1, two (2-trifluoromethyl-4-aminophenoxyl) benzaldehyde products (yield 88.5%) of 3-, and 18 ℃ of fusing points (the DSC method, 5 ℃ of temperature rise rates/min).But the shortcoming of the method is: (1) product color is partially dark, fusing point is also low, and purity too low (true qualities of two (2-trifluoromethyl-4-aminophenoxyl) benzene of 1,3-are white) is described, can't directly do polymerization and use, also need further make purification process; (2) yield is too low; (3) according to the technical scheme of describing in the literary composition, can not repeat out target product through experiment confirm, can not repeat out the described technique effect of the technical program, possible this technical scheme is omitted to some extent; (4) industrialization prospect is dim.
Summary of the invention
It is a kind of 1 that technical problem to be solved by this invention provides, the preparation method of two (2-trifluoromethyl-4-aminophenoxyl) benzene of 3-, and the method technique is simple, cost is low, environmental friendliness, purity and yield are high, is applicable to industrial production.
Chemical equation of the present invention is as follows:
Of the present invention a kind of 1, the preparation method of two (2-trifluoromethyl-4-aminophenoxyl) benzene of 3-comprises:
With 1, two (2-trifluoromethyl-4-nitrophenoxy) benzene of 3-, organic solvent, catalyzer adds autoclave, logical hydrogen stirs, and displaces residual air, continue logical hydrogen, heat to 40 ℃～80 ℃, keep reacting kettle inner pressure 0.4MPa～1.2MPa, keep reaction after 2～5 hours, cooling reaction system is to room temperature, slowly release, and logical nitrogen guarantees to be in the autoclave inert atmosphere to displace all remaining hydrogen, filter, reclaim filter residue (catalyzer), leave and take mother liquor, and in mother liquor, drip while stirring deionized water, separate out white solid product, filter washing, drying, obtain two (2-trifluoromethyl-4-aminophenoxyl) the benzene solids of 1,3-;
Wherein, the envelope-bulk to weight ratio of two (2-trifluoromethyl-4-nitrophenoxy) benzene of organic solvent and 1,3-is 5 milliliters～15 milliliters: 1 gram; The weight ratio of two (2-trifluoromethyl-4-nitrophenoxy) benzene of catalyzer and 1,3-is 1: 30～100; The volume ratio of deionized water and organic solvent must be strict controlled in 1: in the scope of 0.5-2.
Described organic solvent is selected from one or more mixtures in methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol, 1,2-PD, the 1,3-PD;
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 ℃ temperature ranges, with resulting 1, two (2-trifluoromethyl-4-aminophenoxyl) the benzene solids of 3-and equimolar pyromellitic acid anhydride react, obtained high thick polyamic acid solution, its limiting viscosity is up to 2.0dL/g; Film, hot imidization obtains tough and tensile transparent Kapton, and tensile strength is up to 126MPa, and second-order transition temperature is 241.4 ℃.
Beneficial effect
(1) preparation method of the present invention is simple to operate, to equipment without particular requirement; Reaction process is carried out under normal pressure, and raw material sources are convenient, and cost is low, does not relate to also not producing corrosives (such as raw materials such as hydrazine hydrates); Organic solvent uses kind few, but iterative cycles usefulness again is environmentally friendly;
(2) the method need not recrystallization operation, has simplified technique, and the fusing point of product is 88.3 ℃, and yield is up to more than 95%, and purity is applicable to suitability for industrialized production up to 99.8%.
Description of drawings
Fig. 1 is the molecular structure of two (2-trifluoromethyl-4-aminophenoxyl) benzene of 1,3-;
Fig. 2 is differential scanning calorimeter (DSC) scanning spectra of two (2-trifluoromethyl-4-aminophenoxyl) benzene of 1,3-;
Fig. 3 is the fourier transform infrared spectrometry FTIR collection of illustrative plates of two (2-trifluoromethyl-4-aminophenoxyl) benzene of 1,3-;
Fig. 4 is the fourier transform infrared spectrometry FTIR collection of illustrative plates of two (2-trifluoromethyl-4-aminophenoxyl) benzene/pyromellitic acid anhydride-Kaptons of 1,3-.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention 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 limited range equally.
Embodiment 1
With 48.8 gram (0.10 moles) 1, two (2-trifluoromethyl-4-nitrophenoxy) benzene of 3-, 488 ml methanol solvents, 0.8 restrain 10% Pd/carbon catalyst adding autoclave, logical hydrogen, stir, displace residual air, continue logical hydrogen, heat to 40 ℃～80 ℃, keep reacting kettle inner pressure 0.4MPa～1.2MPa, keep reaction after 4.5 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 while stirring 600 ml deionized water, and separate out white solid product, filter, with deionized water wash 2～3 times, 25 ℃ of vacuum-dryings obtain 1 of 40.6 gram (product yield is 95%) whites, two (2-trifluoromethyl-4-aminophenoxyl) the benzene pressed powders of 3-(theoretical yield: 42.8 grams), purity 99.8%, 88.3 ℃ of fusing points, (DSC method, nitrogen atmosphere, 10 ℃ of temperature rise rates/min), as shown in Figure 2; Its fourier transform infrared spectrometry figure as shown in Figure 3.
At 30 milliliters of N, in the N-dimethylacetamide solvent, in 0 ℃～10 ℃ temperature ranges, with resulting 1, taking out 4.28 grams (0.01 mole) in two (2-trifluoromethyl-4-aminophenoxyl) the benzene solids of 3-reacted 5 hours with 2.18 gram (0.01 mole) pyromellitic acid anhydrides, obtained high thick polyamic acid solution, its limiting viscosity is 2.0dL/g.Above-mentioned polyamic acid solution evenly is coated on the clean sheet glass, puts into convection oven, hot imidization, concrete technology is: begin to be heated to 80 ℃ from room temperature, be incubated 1 hour; Continue to be warming up to 140 ℃, be incubated 1 hour; Continue to be warming up to 220 ℃, be incubated 1 hour; Continue to be warming up to 280 ℃, be incubated 0.5 hour; Naturally cool to room temperature, demoulding obtains tough and tensile transparent Kapton, and tensile strength is 126MPa, and second-order transition temperature is 241.4 ℃.The fourier transform infrared spectrometry figure of two (2-trifluoromethyl-4-aminophenoxyl) benzene/pyromellitic acid anhydride-Kaptons of 1,3-as shown in Figure 4.
Embodiment 2
With 48.8 gram (0.10 moles) 1, two (2-trifluoromethyl-4-nitrophenoxy) benzene of 3-, 500 milliliters of ethanol and 232 ml methanol solvents, 1.2 restrain 10% Pd/carbon catalyst adding autoclave, logical hydrogen, stir, displace residual air, continue logical hydrogen, heat to 40 ℃～80 ℃, keep reacting kettle inner pressure 0.4MPa～1.2MPa, keep reaction after 2 hours, cooling reaction system is to room temperature, slowly release, and logical nitrogen guarantees to be in the autoclave inert atmosphere to displace all remaining hydrogen, filter, reclaim filter residue (catalyzer), leave and take mother liquor, and in mother liquor, drip while stirring 366 ml deionized water, separate out white solid product, filter, use deionized water wash 2～3 times, 25 ℃ of vacuum-dryings, obtain 1 of 39.4 gram (product yield is 92%) whites, two (2-trifluoromethyl-4-aminophenoxyl) the benzene pressed powders of 3-(theoretical yield: 42.8 grams).
Embodiment 3
With 48.8 gram (0.10 moles) 1, two (2-trifluoromethyl-4-nitrophenoxy) benzene of 3-, 200 milliliters of ethylene glycol and 44 ml methanol solvents, 1.6 restrain 1% Pd/carbon catalyst adding autoclave, logical hydrogen, stir, displace residual air, continue logical hydrogen, heat to 40 ℃～80 ℃, keep reacting kettle inner pressure 0.4MPa～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 to displace all remaining hydrogen, filter, reclaim filter residue (catalyzer), leave and take mother liquor, and in mother liquor, drip while stirring 488 ml deionized water, separate out white solid product, filter, use deionized water wash 2～3 times, 25 ℃ of vacuum-dryings, obtain 1 of 34.2 gram (product yield is 80%) whites, two (2-trifluoromethyl-4-aminophenoxyl) the benzene pressed powders of 3-(theoretical yield: 42.8 grams).
Embodiment 4
With 48.8 gram (0.10 moles) 1, two (2-trifluoromethyl-4-nitrophenoxy) benzene of 3-, 400 milliliters of alcohol solvents, 0.5 restrain 10% Pd/carbon catalyst adding autoclave, logical hydrogen, stir, displace residual air, continue logical hydrogen, heat to 40 ℃～80 ℃, keep reacting kettle inner pressure 0.4MPa～1.2MPa, keep reaction after 4 hours, cooling reaction system is to room temperature, slowly release, and logical nitrogen guarantees to be in the autoclave inert atmosphere to displace all remaining hydrogen, filter, reclaim filter residue (catalyzer), leave and take mother liquor, and in mother liquor, drip while stirring 500 ml deionized water, separate out white solid product, filter, use deionized water wash 2～3 times, 25 ℃ of vacuum-dryings, obtain 1 of 38.5 gram (product yield is 90%) whites, two (2-trifluoromethyl-4-aminophenoxyl) the benzene pressed powders of 3-(theoretical yield: 42.8 grams).
Embodiment 5
With 48.8 gram (0.10 moles) 1, two (2-trifluoromethyl-4-nitrophenoxy) benzene of 3-, 500 milliliters of alcohol solvents, 1.0 restrain 5% Pd/carbon catalyst adding autoclave, logical hydrogen, stir, displace residual air, continue logical hydrogen, heat to 40 ℃～80 ℃, keep reacting kettle inner pressure 0.4MPa～1.2MPa, keep reaction after 3 hours, cooling reaction system is to room temperature, slowly release, and logical nitrogen guarantees to be in the autoclave inert atmosphere to displace all remaining hydrogen, filter, reclaim filter residue (catalyzer), leave and take mother liquor, and in mother liquor, drip while stirring 700 ml deionized water, separate out white solid product, filter, use deionized water wash 2～3 times, 25 ℃ of vacuum-dryings, obtain 1 of 39.8 gram (product yield is 93%) whites, two (2-trifluoromethyl-4-aminophenoxyl) the benzene pressed powders of 3-(theoretical yield: 42.8 grams).
Claims (1)
1. one kind 1, the preparation method of two (2-trifluoromethyl-4-aminophenoxyl) benzene of 3-comprises:
With two (2-trifluoromethyl-4-nitrophenoxy) benzene of 48.8 grams, 1,3-, 488 ml methanol solvents, 0.8 restrain 10% Pd/carbon catalyst adding autoclave, logical hydrogen, stir, displace residual air, continue logical hydrogen, heat to 40 ℃ ~ 80 ℃, keep reacting kettle inner pressure 0.4MPa ~ 1.2MPa, keep reaction after 4.5 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, leave and take mother liquor, and in mother liquor, drip while stirring 600 ml deionized water, and separate out white solid product, filter, with deionized water wash 2 ~ 3 times, 25 ℃ of vacuum-dryings obtain 1 of 40.6 gram whites, two (2-trifluoromethyl-4-nitrophenoxy) benzene of 3-, purity 99.8%, 88.3 ℃ of fusing points.
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| 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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Non-Patent Citations (2)
| Title |
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| Wonbong Jang et al..The optical and dielectric characterization of light-colored fluorinated polyimides based on 1,3-bis(4-amino-2-trifluoromethylphenoxy)benzene.《Materials Chemistry and Physics》.2007,第104卷342-349. * |
| WonbongJangetal..Theopticalanddielectriccharacterizationoflight-coloredfluorinatedpolyimidesbasedon1 3-bis(4-amino-2-trifluoromethylphenoxy)benzene.《Materials Chemistry and Physics》.2007 |
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