CN101560166A - 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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- CN101560166A CN101560166A CN 200910051668 CN200910051668A CN101560166A CN 101560166 A CN101560166 A CN 101560166A CN 200910051668 CN200910051668 CN 200910051668 CN 200910051668 A CN200910051668 A CN 200910051668A CN 101560166 A CN101560166 A CN 101560166A
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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-amino-benzene oxygen) benzene of 3-.
Background technology
Aromatic polyimide has excellent thermostability, chemical stability, 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, 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 use and is worth in some field, 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, 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-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, the preparation method of two [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa 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-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 2, the preparation method of two [3-amino-4-(2, the 4-2,4-dinitrophenoxy base) phenyl] HFC-236fa of 2-, and it also is the important source material of preparation fluorinated polyimide resin.
1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 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-amino-benzene oxygen) 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 splashing into 8 parts of aqueous hydrochloric acids under stirring and the backflow fast, refluxed 2 hours.Add ammoniacal liquor then, transfer solution, stirred 0.5 hour to neutral.Solids removed by filtration, the filtrate distillation concentrates, and places then 10 hours.Filter, crystal absolute ethanol washing three times are dry then, obtain 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 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-amino-benzene oxygen) 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, the dilute hydrochloric acid solution of adding 5% separates out 1, the dihydrochloride of two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-.At 1 of dichloromethane solvent, add in the dihydrochloride of two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-ammoniacal liquor separate out pure 1, two (2-trifluoromethyl-4-amino-benzene oxygen) the benzene solids of 3-, 41.2 ℃ of fusing points (DSC method, air atmosphere), yield 62%.But the shortcoming of this method is: (1) serious three wastes; (2) yield is too low; (3) industrialization prospect dimness.
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-amino-benzene oxygen) 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 concentrated mother liquor, solid product is separated out in 80 ℃ of vacuum-dryings, obtain lurid 1, two (2-trifluoromethyl-4-amino-benzene oxygen) 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 this method is: (1) product color is dark partially, and fusing point is also low, and purity too low (1, the true qualities of two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-are white) is described, can't directly do polymerization and use, and 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 dimness.
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-amino-benzene oxygen) benzene of 3-, and this method technology is simple, cost is low, environmental friendliness, purity and yield height, 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-amino-benzene oxygen) 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 deionized water while stirring, separate out white solid product, filter washing, drying, obtain 1, two (2-trifluoromethyl-4-amino-benzene oxygen) the benzene solids of 3-;
Wherein, organic solvent and 1, the envelope-bulk to weight ratio of two (2-trifluoromethyl-4-nitrophenoxy) benzene of 3-is 5 milliliters～15 milliliters: 1 gram; Catalyzer and 1, the weight ratio of two (2-trifluoromethyl-4-nitrophenoxy) benzene of 3-is 1: 30～100; Deionized water must be strict controlled in 1 with the volume of organic solvent ratio: in the scope of 0.5-2.
Described organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol, 1,2-propylene glycol, 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 ℃ temperature ranges, with resulting 1, two (2-trifluoromethyl-4-amino-benzene oxygen) 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, and equipment is not had 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 (as raw materials such as hydrazine hydrates); 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 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 1, the molecular structure of two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-;
Fig. 2 is 1, differential scanning calorimeter (DSC) scanning spectra of two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-;
Fig. 3 is 1, the fourier transform infrared spectrometry FTIR collection of illustrative plates of two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-;
Fig. 4 is 1, the fourier transform infrared spectrometry FTIR collection of illustrative plates of two (2-trifluoromethyl-4-amino-benzene oxygen) benzene/pyromellitic acid anhydride-Kaptons of 3-.
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.
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 600 ml deionized water while stirring, 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-amino-benzene oxygen) 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-amino-benzene oxygen) 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 heat temperature raising 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 ℃.1, the fourier transform infrared spectrometry figure of two (2-trifluoromethyl-4-amino-benzene oxygen) benzene/pyromellitic acid anhydride-Kaptons of 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 366 ml deionized water while stirring, 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-amino-benzene oxygen) 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 488 ml deionized water while stirring, 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-amino-benzene oxygen) 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 Dropwise 5 00 ml deionized water while stirring, 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-amino-benzene oxygen) 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 700 ml deionized water while stirring, 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-amino-benzene oxygen) the benzene pressed powders of 3-(theoretical yield: 42.8 grams).
Claims (4)
1. one kind 1, the preparation method of two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-comprises:
With 1, two (2-trifluoromethyl-4-nitrophenoxy) benzene of 3-, organic solvent, catalyzer adds 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 2～5 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, leave and take mother liquor, and in mother liquor, drip deionized water while stirring, separate out white solid product, filter washing, drying, obtain 1, two (2-trifluoromethyl-4-amino-benzene oxygen) the benzene solids of 3-;
Wherein, organic solvent and 1, the envelope-bulk to weight ratio of two (2-trifluoromethyl-4-nitrophenoxy) benzene of 3-is 5 milliliters～15 milliliters: 1 gram; Catalyzer and 1, the weight ratio of two (2-trifluoromethyl-4-nitrophenoxy) benzene of 3-is 1: 30～100; Deionized water must be strict controlled in 1 with the volume of organic solvent ratio: in the scope of 0.5-2.
2. according to claim 1 a kind of 1, the preparation method of two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-, it is characterized in that: described organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol, 1,2-propylene glycol, 1, one or more mixtures in the ammediol.
3. according to claim 1 a kind of 1, the preparation method of two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-, it is characterized in that: described catalyzer is selected from raney nickel or palladium/charcoal.
4. according to claim 3 a kind of 1, the preparation method of two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-, it is characterized in that: described palladium/charcoal, its palladium metal quality percentage composition is 1%～10%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2453533C1 (en) * | 2011-02-08 | 2012-06-20 | Государственное образовательное учреждение высшего профессионального образования "Ярославский государственный университет им. П.Г. Демидова" | Method of producing 1,3 and 1,4-bis(2-amino-4-(trifluoromethyl)phenoxy)benzene |
| CN115286519A (en) * | 2022-08-08 | 2022-11-04 | 浙江清和新材料科技有限公司 | Preparation method of 4,4' -bis (3-aminophenoxy) biphenyl |
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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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2453533C1 (en) * | 2011-02-08 | 2012-06-20 | Государственное образовательное учреждение высшего профессионального образования "Ярославский государственный университет им. П.Г. Демидова" | Method of producing 1,3 and 1,4-bis(2-amino-4-(trifluoromethyl)phenoxy)benzene |
| CN115286519A (en) * | 2022-08-08 | 2022-11-04 | 浙江清和新材料科技有限公司 | Preparation method of 4,4' -bis (3-aminophenoxy) biphenyl |
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