CN101560165A - Preparation method of 2,2-bi[4-(2-trifluoromethyl-4-aminophenoxyl)phenyl]hexafluoropropane - Google Patents
Preparation method of 2,2-bi[4-(2-trifluoromethyl-4-aminophenoxyl)phenyl]hexafluoropropane Download PDFInfo
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Abstract
The invention relates to a preparation method of 2,2-bi[4-(2-trifluoromethyl-4-aminophenoxyl)phenyl]hexafluoropropane, comprising the steps of adding 2,2-bi[4-(2-trifluoromethyl-4-nitrophenoxyl)phenyl]hexafluoropropane, an organic solvent, active carbon powders and an iron chloride catalyst in a reaction kettle, heating the reaction kettle, stirring, raising temperature to 70-80 DEG C, dripping a hydrazine hydrate aqueous solution, strictly controlling the dripping time within 1.5-2 hours, reacting for 5-8 hours at 70-80 DEG C, filtering when the solution is hot, removing filter residues, maintaining the mother liquid, dripping deionised water into the mother liquid while stirring, separating out white solid product, filtering, washing and drying to obtain 2,2-bi[4-(2-trifluoromethyl-4-aminophenoxyl)phenyl]hexafluoropropane 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 2, the preparation method of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-.
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.
2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-are one of important source material of synthetic aroma family fluorinated polyimide macromolecular material.
CHUN-SHAN WANG, RONG-WEN YANG[Synthesis and Properties ofFluorine-Containing Polyimides, Journal of Applied Polymer Science, 1997,66:609-617] disclose 2, the preparation method of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, it is characterized in that: utilize 2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-, 10% palladium/charcoal and alcohol solvent, drip hydrazine hydrate in 86 ℃, after lasting 30 minutes and being added dropwise to complete, filter, remove palladium/charcoal, remove excessive hydrazine hydrate and alcohol solvent and obtain crude product, obtain 2 with ethyl alcohol recrystallization subsequently, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] the HFC-236fa white needles things (yield 86.1%) of 2-, 159 ℃～160 ℃ of fusing points.But the shortcoming of this method is: (1) 10% Pd/carbon catalyst costs an arm and a leg, and causes product cost higher; (2) need the recrystallization operation, can't a step obtain high purity product; (3) product yield is on the low side.
Wonbong Jang a, Daeyong Shin a, Seunghyuk Choi a, Deng people [Effects of internal linkagegroups of fluorinated diamine on the optical and dielectric properties of polyimide thin films, Polymer 48 (2007) 2130-2143] disclose 2, the preparation method of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, it is characterized in that: utilize 2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-, 10% palladium/charcoal and volume ratio are 1: 1 methanol/ethyl acetate mixed solvent, stirred 30 minutes under the room temperature, heat temperature raising to 60 ℃, logical hydrogen continues to stir 3 hours, filters, remove palladium/charcoal, revolve the inspissation mother liquor that contracts, 80 ℃ of vacuum-dryings obtain faint yellow 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa (yield 87.5%) of 2-, 69 ℃ of fusing points.But the shortcoming of this method is: (1) 10% Pd/carbon catalyst costs an arm and a leg, and causes product cost higher; (2) product colour is dark partially, and purity is on the low side, can't a step obtain high purity product; (3) product yield is on the low side.
CHIN-PING YANG, RUEI-SHIN CHEN, KUEI-HUNG CHEN[Effects of Diaminesand Their Fluorinated Groups on the Color Lightness and Preparation of OrganosolubleAromatic Polyimides from 2,2-Bis[4-(4-amino-2-trifluoromethylphenoxy) phenyl]-hexafluoropropane, Journal of Polymer Science:Part A:Polymer Chemistry, 2003,41:922-938] disclose 2, the preparation method of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, it is characterized in that: utilize 2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-, 10% palladium/charcoal and alcohol solvent, in 70 ℃～80 ℃ temperature ranges, drip hydrazine hydrate while stirring, after lasting 30 minutes and being added dropwise to complete, heat temperature raising, back flow reaction 2 hours, filtered while hot, remove palladium/charcoal, the distillation concentrated mother liquor, remove and desolvate, concentrated solution is poured in the water, to separate out solid product, room temperature vacuum-drying, obtain 2 of white, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] the HFC-236fa products of 2-, 65 ℃～66 ℃ of fusing points.But the shortcoming of this method is: adopt 10% palladium/charcoal as catalyzer, it costs an arm and a leg, and causes product cost higher.
Summary of the invention
It is a kind of 2 that technical problem to be solved by this invention provides, the preparation method of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, and this method technology is simple, cost is low, environmental friendliness, purity and yield height, is applicable to industrial production.
Concrete chemical equation of the present invention is as follows:
Of the present invention a kind of 2, the preparation method of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, comprise: with 2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-, organic solvent, active carbon powder, ferric chloride catalyst adds in the reactor, heating, stir, be warmed up to 70 ℃～80 ℃, drip hydrazine hydrate aqueous solution, the dropping time was strict controlled in 1.5-2 hour, keep reaction after 5～8 hours in 70 ℃～80 ℃ temperature, filtered while hot is removed 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 obtains 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] the HFC-236fa solids of 2-;
Wherein, organic solvent and 2, the envelope-bulk to weight ratio of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-is 5 milliliters～10 milliliters: 1 gram; Active carbon powder and 2, the mass ratio of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-is 1: 5-10; Deionized water is 1-2 with the volume of organic solvent ratio: 1.
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;
The mass percent concentration of described hydrazine hydrate aqueous solution is 80%-85%;
Described hydrazine hydrate aqueous solution, hydrazine hydrate mole number and 2 wherein, the ratio of the mole number of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-is 1: 8-16;
Described ferric chloride catalyst and 2, the weight ratio of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-is 1: 20～80.
At N, in the N-dimethylacetamide solvent, in 0 ℃～10 ℃ temperature ranges, with resulting 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa solids of 2-and equimolar pyromellitic acid anhydride react, obtained high thick polyamic acid solution, its limiting viscosity is up to 1.7dL/g;
Above-mentioned polyamic acid solution is coated on the clean sheet glass equably, put into baking oven, curing process is: rise to 100 ℃ from room temperature, be incubated 1 hour, continue to be warming up to 200 ℃, be incubated 1 hour, continue to be warming up to 250 ℃, be incubated 0.5 hour, naturally cool to room temperature, demoulding obtains 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa/pyromellitic acid anhydrides-Kapton of 2-.
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, adopted ferric chloride catalyst cheaply, substituted expensive Pd/carbon catalyst, 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 product yield is up to more than 96%, and purity is applicable to suitability for industrialized production up to 99.8%.
Description of drawings
Fig. 1 is 2, the molecular structure of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-;
Fig. 2 is 2, the fourier transform infrared spectrometry FTIR collection of illustrative plates of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-;
Fig. 3 is 2, the fourier transform infrared spectrometry FTIR collection of illustrative plates of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa/pyromellitic acid anhydride-polyimide of 2-.
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 71.4 gram (0.10 moles) 2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-, 710 milliliters of alcohol solvents, 7.2 gram active carbon powder, 3.5 the gram ferric chloride catalyst adds in the reactor, heating, stir, be warmed up to 70 ℃～80 ℃, drip 100.0 gram mass percentage concentrations and be 80% hydrazine hydrate aqueous solution, the dropping time was strict controlled in 1.5-2 hour, in 70 ℃～80 ℃ temperature, keep reaction after 5 hours, filtered while hot is removed filter residue, leaves and takes mother liquor, and in mother liquor, drip 710 ml deionized water while stirring, separate out white solid product, filter, washing, dry, obtain 62.8 grams 2, and two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] the HFC-236fa solids of 2-(theoretical yield: 65.4 grams), purity 99.8%, product yield 96%, its fourier transform infrared spectrometry FTIR schemes as shown in Figure 2.
At N, in the N-dimethylacetamide solvent, in 0 ℃～10 ℃ temperature ranges, with resulting 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa solids of 2-and equimolar pyromellitic acid anhydride react, obtained high thick polyamic acid solution, its limiting viscosity is up to 1.7dL/g.
Above-mentioned polyamic acid solution is coated on the clean sheet glass equably, puts into baking oven, curing process is: rise to 100 ℃ from room temperature, be incubated 1 hour, continue to be warming up to 200 ℃, be incubated 1 hour, continue to be warming up to 250 ℃, be incubated 0.5 hour, naturally cool to room temperature, demoulding obtains 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa/pyromellitic acid anhydrides-Kapton of 2-, its fourier transform infrared spectrometry FTIR collection of illustrative plates as shown in Figure 3.
Embodiment 2
With 71.4 gram (0.10 moles) 2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-, 200 milliliters of ethanol and 160 milliliters of ethylene glycol solvents, 14.0 gram active carbon powder, 3.1 the gram ferric chloride catalyst adds in the reactor, heating, stir, be warmed up to 70 ℃～80 ℃, drip 94.0 gram mass percentage concentrations and be 85% hydrazine hydrate aqueous solution, the dropping time was strict controlled in 1.5-2 hour, kept reaction after 6 hours in 70 ℃～80 ℃ temperature, filtered while hot, remove filter residue, leave and take mother liquor, and in mother liquor, drip 720 ml deionized water while stirring, separate out white solid product, filter washing, drying, obtain 61.5 grams 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] the HFC-236fa solids of 2-(theoretical yield: 65.4 grams), purity 99.5%, product yield 94%.
Embodiment 3
With 71.4 gram (0.10 moles) 2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-, 500 milliliters of alcohol solvents, 10.0 gram active carbon powder, 0.9 the gram ferric chloride catalyst adds in the reactor, heating, stir, be warmed up to 70 ℃～80 ℃, drip 47.5 gram mass percentage concentrations and be 85% hydrazine hydrate aqueous solution, the dropping time was strict controlled in 1.5-2 hour, kept reaction after 8 hours in 70 ℃～80 ℃ temperature, filtered while hot, remove filter residue, leave and take mother liquor, and in mother liquor, drip 600 ml deionized water while stirring, separate out white solid product, filter washing, drying, obtain 58.8 grams 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] the HFC-236fa solids of 2-(theoretical yield: 65.4 grams), purity 99.4%, product yield 90%.
Claims (5)
1. one kind 2, the preparation method of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-comprises:
With 2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-, organic solvent, active carbon powder, ferric chloride catalyst adds in the reactor, heating, stir, be warmed up to 70 ℃～80 ℃, drip hydrazine hydrate aqueous solution, the dropping time was strict controlled in 1.5-2 hour, keep reaction after 5～8 hours in 70 ℃～80 ℃ temperature, filtered while hot is removed 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 obtains 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] the HFC-236fa solids of 2-;
Wherein, organic solvent and 2, the envelope-bulk to weight ratio of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-is 5 milliliters～10 milliliters: 1 gram; Active carbon powder and 2, the mass ratio of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-is 1: 5-10; Deionized water is 1-2 with the volume of organic solvent ratio: 1.
2. according to claim 1 a kind of 2, the preparation method of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 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 2, the preparation method of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, it is characterized in that: the mass percent concentration of described hydrazine hydrate aqueous solution is 80%-85%.
4. according to claim 1 a kind of 2, the preparation method of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, it is characterized in that: described hydrazine hydrate aqueous solution, hydrazine hydrate mole number and 2 wherein, the ratio of the mole number of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-is 1: 8-16.
5. according to claim 1 a kind of 2, the preparation method of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, it is characterized in that: described ferric chloride catalyst and 2, the weight ratio of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] HFC-236fa of 2-is 1: 20～80.
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| CN111039802A (en) * | 2019-12-31 | 2020-04-21 | 山东华夏神舟新材料有限公司 | Process for preparing aromatic diether diamine |
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| CN111039802A (en) * | 2019-12-31 | 2020-04-21 | 山东华夏神舟新材料有限公司 | Process for preparing aromatic diether diamine |
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