CN101560163B - Preparation method of 4,4'-bi(2-trifluoromethyl-4-aminophenoxyl)biphenyl - Google Patents
Preparation method of 4,4'-bi(2-trifluoromethyl-4-aminophenoxyl)biphenyl Download PDFInfo
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Abstract
The invention relates to a preparation method of 4,4'-bi(2-trifluoromethyl-4-aminophenoxyl)biphenyl, comprising the steps of adding 4,4'-bi(2-trifluoromethyl-4-nitrophenoxyl)biphenyl, an organic mixedsolvent containing alcohols, and a catalyst in a high pressure reaction kettle, infusing hydrogen, stirring, substituting residual air, continuously infusing hydrogen, heating and raising temperature , reacting for 2-4 hours, cooling the reaction system to room temperature, slowly discharging pressure, and infusing nitrogen to substitute all residual air so as to ensure that the high pressure reaction kettle is in inert atmosphere, filtering, recovering filter residue, maintaining the mother liquid, condensing the mother liquid such that the solid content of the mother liquid is in the range of 40-80%, cooling, putting the mother liquid aside, separating out white crystal product, filtering, washing and drying to obtain 4,4'-bi(2-trifluoromethyl-4-aminophenoxyl)biphenyl solid. The method has a simple technology, low cost, high purity and yield, and is environment-friendly and suitable for commercial 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 (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl.
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 (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl is one of important source material of synthetic aroma family fluorinated polyimide macromolecular material.
CHIN-PING YANG, SHENG-HUEI HSIAO, MAO-FENG HSU [Organosoluble and Light-Colored Fluorinated Polyimides from 4,4 '-Bis (4-amino-2-trifluoromethylphenoxy) biphenyl and Aromatic Dianhydrides; Journal of Polymer Science:Part A:Polymer Chemistry, 2002,40:524-534] disclose 4,4 '-preparation method of two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl; It is characterized in that: 4,4 '-two (2-trifluoromethyl-4-nitrophenoxy) biphenyl, ethanol, Hydrazine Hydrate 80 and palladium/charcoal, heat temperature raising; Back flow reaction 6 hours, filtered while hot is removed palladium/charcoal; The distillation concentrated mother liquor removes and desolvates, and obtains thick product; Use the alcohol solvent recrystallization, obtain colourless tabular crystal, promptly 4; 4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl products (yield 82%), 155 ℃～156 ℃ of fusing points (the DSC method, 10 ℃/min).But the shortcoming of this method is: Hydrazine Hydrate 80 is used in (1), causes having in the production process a large amount of ammonias to produce, and is unfavorable for environment protection; (2) Hydrazine Hydrate 80 toxicity is big, has increased the labour protection expense of operator and operationlocation; (3) after reaction finishes, produce the waste water that contains Hydrazine Hydrate 80 and by product thereof in a large number, increased the expense of wastewater treatment virtually; (4) yield is on the low side; (5) need the recrystallization purifying operation, can't a step obtain high-purity product.
Summary of the invention
That technical problem to be solved by this invention provides is a kind of 4,4 '-preparation method of two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl, this method technology is simple, cost is low, environmental friendliness, purity and yield are high, is applicable to industrial production.
Chemical equation of the present invention is following:
Of the present invention a kind of 4,4 '-preparation method of two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl, comprising:
With 4,4 '-two (2-trifluoromethyl-4-nitrophenoxy) biphenyl, contain the organic mixed solvent of alcohols, catalyzer adds autoclave, logical hydrogen stirs, and displaces residual air; Continue logical hydrogen, heat to 40 ℃～80 ℃, keep reacting kettle inner pressure 0.2MPa～1.0MPa, keep reaction after 2～4 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, concentrated mother liquor; Its solid content is controlled in the scope of 40%-80%, and cooling is left standstill, and separates out the white crystal product, filters; Washing, drying, obtain 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl solid;
Wherein, contain the organic mixed solvent of alcohols and 4,4 '-envelope-bulk to weight ratio of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl is 20 milliliters～30 milliliters: 1 gram; Catalyzer and 4,4 '-weight ratio of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl is 1: 10～100.
Described to contain the organic mixed solvent of alcohols be alcoholic solvent and the mixture of strong polar non-proton organic solvent, and wherein alcoholic solvent accounts for the volumn concentration of 40%-100%;
Described alcoholic 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 strong polar non-proton organic solvent is selected from N, one or more mixtures in dinethylformamide, DMAC N,N, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, the DMSO 99.8MIN.;
Described catalyzer is raney nickel or palladium/charcoal, and palladium metal quality percentage composition is 1%～15% in palladium/charcoal.
At N; In the N-dimethylacetamide solvent; In 10 ℃～20 ℃ TRs, with resulting 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl solids and equimolar pyromellitic acid anhydride react; Obtained high thick polyamic acid solution, its limiting viscosity is up to 2.4dL/g;
Above-mentioned polyamic acid solution is coated on the clean sheet glass equably, hot imidization, demoulding obtains tough and tensile transparent Kapton, and tensile strength is 120MPa.
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; 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 155.0 ℃, and yield is up to more than 97%, and purity is applicable to suitability for industrialized production up to 99.7%.
Description of drawings
Fig. 1 is 4,4 '-molecular structure of two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl;
Fig. 2 is 4,4 '-differential scanning calorimeter (DSC) scanning spectra of two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl;
Fig. 3 is 4,4 '-the fourier transform infrared spectrometry FTIR collection of illustrative plates of two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl;
Fig. 4 is 4,4 '-the fourier transform infrared spectrometry FTIR collection of illustrative plates of two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl/pyromellitic acid anhydride-polyimide.
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 56.4 gram (0.10 moles) 4,4 '-Pd/carbon catalyst of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl, 700 ml methanol solvents, 700 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 3.2 grams, 10% (the quality percentage composition of palladium metal) adds autoclave, logical hydrogen stirs; Displace residual air, continue logical hydrogen, heat to 40 ℃～80 ℃, keep reacting kettle inner pressure 0.2MPa～1.0MPa; 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; Concentrated mother liquor is controlled in the scope of 40%-80% its solid content, and cooling is left standstill, and separates out the white crystal product; Filter, with deionized water wash 2～3 times, 25 ℃ of vacuum-dryings, obtain 48.9 grams (product yield is 97%) white 4; 4 '-(theoretical yield: 50.4 grams), purity is 99.7% to two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl crystal, and fusing point is 155.0 ℃ of (DSC methods; Nitrogen atmosphere, 10 ℃ of temperature rise rates/min), as shown in Figure 2; Fourier transform infrared spectrometry figure is as shown in Figure 3.
At N; In the N-dimethylacetamide solvent; In 10 ℃～20 ℃ TRs, with resulting 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl crystal and equimolar pyromellitic acid anhydride react; Obtained high thick polyamic acid solution, its limiting viscosity is up to 2.4dL/g.
Above-mentioned polyamic acid solution is coated on the clean sheet glass equably, puts into convection oven, heat temperature raising, hot imidization, concrete technology is: room temperature begins; Be warmed up to 100 ℃, be incubated 1.5 hours, continue to be warmed up to 160 ℃, be incubated 1 hour, continue to be warmed up to 210 ℃; Be incubated 1 hour, continue to be warmed up to 240 ℃, be incubated 0.5 hour, continue to be warmed up to 300 ℃; Be incubated 0.5 hour, close heating system, naturally cool to room temperature, demoulding; Obtain tough and tensile transparent 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl/pyromellitic acid anhydride-Kapton, tensile strength is 120MPa, figure is as shown in Figure 4 for its fourier transform infrared spectrometry.
With 56.4 gram (0.10 moles) 4,4 '-Pd/carbon catalyst of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl, 452 milliliters of alcohol solvents, 678 milliliters of DMAC N,Ns, 5.6 grams, 1% (the quality percentage composition of palladium metal) adds autoclave, logical hydrogen; Stir, displace residual air, continue logical hydrogen, heat to 40 ℃～80 ℃; Keep reacting kettle inner pressure 0.2MPa～1.0MPa, 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, filtration, recovery filter residue (catalyzer); Leave and take mother liquor, concentrated mother liquor is controlled in the scope of 40%-80% its solid content, and cooling is left standstill; Separate out the white crystal product, filter, with deionized water wash 2～3 times; 25 ℃ of vacuum-dryings, obtain 4,4 of 45.3 gram (product yield is 90%) whites '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl crystal (theoretical yield: 50.4 gram).
With 56.4 gram (0.10 moles) 4,4 '-Pd/carbon catalyst of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl, 1000 milliliters of alcohol solvents, 690 milliliters of ethylene glycol solvents, 0.6 gram, 15% (the quality percentage composition of palladium metal) adds autoclave, logical hydrogen stirs; Displace residual air, continue logical hydrogen, heat to 40 ℃～80 ℃, keep reacting kettle inner pressure 0.2MPa～1.0MPa; Keep reaction after 2 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; Concentrated mother liquor is controlled in the scope of 40%-80% its solid content, and cooling is left standstill; Separate out the white crystal product, filter, with deionized water wash 2～3 times; 25 ℃ of vacuum-dryings, obtain 4,4 of 46.9 gram (product yield is 93%) whites '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl crystal (theoretical yield: 50.4 gram).
Embodiment 4
With 56.4 gram (0.10 moles) 4,4 '-Pd/carbon catalyst of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl, 1000 milliliters of alcohol solvents, 200 milliliters of N-N-methyl-2-2-pyrrolidone N-solvents, 4.0 grams, 5% (the quality percentage composition of palladium metal) adds autoclave, logical hydrogen stirs; Displace residual air, continue logical hydrogen, heat to 40 ℃～80 ℃, keep reacting kettle inner pressure 0.2MPa～1.0MPa; Keep reaction after 3 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; Concentrated mother liquor is controlled in the scope of 40%-80% its solid content, and cooling is left standstill; Separate out the white crystal product, filter, with deionized water wash 2～3 times; 25 ℃ of vacuum-dryings, obtain 4,4 of 47.8 gram (product yield is 95%) whites '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl crystal (theoretical yield: 50.4 gram).
With 56.4 gram (0.10 moles) 4,4 '-two (2-trifluoromethyl-4-nitrophenoxy) biphenyl, 1000 milliliters of alcohol solvents, 400 milliliters of ethylene glycol solvents, 5.0 Crays in nickel catalyzators (the quality percentage composition 30% of nickel) add autoclave, logical hydrogen stirs; Displace residual air, continue logical hydrogen, heat to 40 ℃～80 ℃, keep reacting kettle inner pressure 0.2MPa～1.0MPa; 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; Concentrated mother liquor is controlled in the scope of 40%-80% its solid content, and cooling is left standstill; Separate out the white crystal product, filter, with deionized water wash 2～3 times; 25 ℃ of vacuum-dryings, obtain 4,4 of 44.8 gram (product yield is 89%) whites '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl crystal (theoretical yield: 50.4 gram).
Claims (2)
1. one kind 4,4 '-preparation method of two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl, comprising:
With 4,4 '-two (2-trifluoromethyl-4-nitrophenoxy) biphenyl, contain the organic mixed solvent of alcohols, catalyzer adds autoclave, logical hydrogen stirs, and displaces residual air; Continue logical hydrogen, heat to 40 ℃-80 ℃, keep reacting kettle inner pressure 0.2MPa-1.0MPa, keep reaction after 2-4 hour; 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, concentrated mother liquor; Its solid content is controlled in the scope of 40%-80%, and cooling is left standstill, and separates out the white crystal product, filters; Washing, drying, obtain 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl solid;
Wherein, contain the organic mixed solvent of alcohols and 4,4 '-envelope-bulk to weight ratio of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl is 20 milliliters-30 milliliters: 1 gram; Catalyzer and 4,4 '-weight ratio of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl is 1: 10-100;
It is described that to contain the organic mixed solvent of alcohols be alcoholic solvent and the mixture of strong polar non-proton organic solvent; Wherein alcoholic solvent accounts for the volumn concentration of 40%-100%; Alcoholic solvent is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, terepthaloyl moietie, 1; 2-Ucar 35,1, one or more mixtures in the ammediol, strong polar non-proton organic solvent is selected from N; One or more mixtures in dinethylformamide, DMAC N,N, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, the DMSO 99.8MIN.;
Catalyzer is raney nickel or palladium/charcoal.
2. according to claim 1 a kind of 4,4 '-preparation method of two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl, it is characterized in that: in the described Pd/carbon catalyst, its palladium metal quality percentage composition is 1%-15%.
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| CN101205192A (en) * | 2007-12-14 | 2008-06-25 | 常州市阳光精细化工有限公司 | Method for preparing 1,3-di(4-amino-benzene oxygen) benzene |
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Non-Patent Citations (3)
| Title |
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| Chin-Ping Yang et al..Organosoluble and Light-Colored Fluorinated Polyimides from 4,4’-Bis(4-amino-2-trifluoromethylphenoxy)biphenyl and Aromatic Dianhydrides.《Journal of Polymer Science: Part A: Polymer Chemistry》.2002,第40卷524-534. * |
| Chin-PingYangetal..OrganosolubleandLight-ColoredFluorinatedPolyimidesfrom4 4’-Bis(4-amino-2-trifluoromethylphenoxy)biphenyl and Aromatic Dianhydrides.《Journal of Polymer Science: Part A: Polymer Chemistry》.2002 |
| Wonbong Jang et al..Effects of internal linkage groups of fluorinated diamine on the optical and dielectric properties of polyimide thin films.《Polymer》.2007,第48卷2130-2143. * |
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