CN101591252B - Method for preparing 1,4-bis(4-amino-2-trifluoromethyl phenoxyl)-2,5-diterbutyl benzene - Google Patents
Method for preparing 1,4-bis(4-amino-2-trifluoromethyl phenoxyl)-2,5-diterbutyl benzene Download PDFInfo
- Publication number
- CN101591252B CN101591252B CN2009100539942A CN200910053994A CN101591252B CN 101591252 B CN101591252 B CN 101591252B CN 2009100539942 A CN2009100539942 A CN 2009100539942A CN 200910053994 A CN200910053994 A CN 200910053994A CN 101591252 B CN101591252 B CN 101591252B
- Authority
- CN
- China
- Prior art keywords
- trifluoromethylphenopendant
- butylbenzene
- amino
- organic solvent
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to a method for preparing 1,4-bis(4-amino-2-trifluoromethyl phenoxyl)-2,5-diterbutyl benzene. The method comprises the following steps of: adding 1,4-bis(4-nitryl-2-trifluoromethyl phenoxyl)-2,5-diterbutyl benzene, organic solvent and a catalyst in a high-pressure reaction kettle; introducing hydrogen gas in the reaction kettle; stirring the mixture and heating the reaction kettle to a temperature of between 80 and 90 DEG C; maintaining the reaction for 5 to 6 hours; cooling down the reaction system to the room temperature; filtering the obtained product; recovering filter residue; keeping mother solution; adding deionized water in the mother solution dropwise and stirring the mother solution at the same time; and separating a white solid product out, and filtering, washing and drying the white solid product to obtain the solid of the 1,4-bis(4-amino-2-trifluoromethyl phenoxyl)-2,5-diterbutyl benzene. The method has the advantages of simple process, low cost, and environmental protection; and the melting point of the product is between 215.4 and 215.9 DEG C, the yield is as high as over 94 percent, and the purity is as high as 99.6 percent, so that the method is suitable for the industrialized production.
Description
Technical field
The invention belongs to the preparation field of aromatic series fluorinated organic compound, particularly relate to a kind of 1, two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-, the preparation method of 5-di-t-butylbenzene.
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.
1, two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-, the 5-di-t-butylbenzene is one of important source material of synthetic aroma family fluorinated polyimide macromolecular material.The existence of tertiary butyl in the molecular structure can make macromolecular material have excellent hydrophobic property, excellent especially dielectric properties (like low specific inductivity and low dielectric loss etc.) and good processing properties.
CHIN-PING YANG, FENG-ZHI HSIAO. [Synthesis and Properties of FluorinatedPolyimides Based on 1,4-Bis (4-amino-2-trifluoromethylphenoxy)-2,5-di-tertbutylbenzene andVarious Aromatic Dianhydrides; Journal of Polymer Science:Part A:Polymer Chemistry, Vol.42,2272-2284 (2004)] disclose 1, two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-; The preparation method of 5-di-t-butylbenzene is characterized in that: 1, and two (the 4-nitros-2-4-trifluoromethylphenopendant)-2 of 4-; 5-di-t-butylbenzene, alcohol solvent and 10% palladium/charcoal at 70 ℃ of agitation and dropping Hydrazine Hydrate 80s, is 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, room temperature vacuum-drying obtains 1; Two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-, 5-di-tert-butyl benzaldehyde product (yield 90%), 215 ℃-216 ℃ 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) industrialization prospect is dim.
Summary of the invention
It is a kind of 1 that technical problem to be solved by this invention provides, two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-, and the preparation method of 5-di-t-butylbenzene, 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 1, two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-, the preparation method of 5-di-t-butylbenzene comprises:
With 1, two (the 4-nitros-2-4-trifluoromethylphenopendant)-2 of 4-, 5-di-t-butylbenzene, organic solvent, catalyzer add autoclave, and logical hydrogen stirs; Displace residual air, continue logical hydrogen, heat to 80 ℃～90 ℃, keep reacting kettle inner pressure 0.5MPa～0.8MPa; Keep reaction after 5～6 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 deionized water while stirring, and separate out white solid product, filter washing; Drying obtains 1, two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-, 5-di-t-butylbenzene solid;
Wherein, organic solvent and 1, two (the 4-nitros-2-4-trifluoromethylphenopendant)-2 of 4-, the envelope-bulk to weight ratio of 5-di-t-butylbenzene is 10 milliliters～15 milliliters: 1 gram; Catalyzer and 1, two (the 4-nitros-2-4-trifluoromethylphenopendant)-2 of 4-, the weight ratio of 5-di-t-butylbenzene is 1: 10～31; Deionized water must be strict controlled in 1.0 with the volume of organic solvent ratio: in the scope of 0.5-2.0.
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 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 1; Two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-; 5-di-t-butylbenzene solid and equimolar pyromellitic acid anhydride react, and have obtained high thick polyamic acid solution, and its limiting viscosity is up to 1.9dL/g; Film, hot imidization obtains tough and tensile transparent Kapton, and tensile strength is up to 110MPa, and second-order transition temperature is 288.6 ℃.
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 215.4 ℃-215.9 ℃, and yield is up to more than 94%, and purity is applicable to suitability for industrialized production up to 99.6%.
Description of drawings
Fig. 1 is 1, two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-, the molecular structure of 5-di-t-butylbenzene
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 60.1 gram (0.10 moles) 1, two (the 4-nitros-2-4-trifluoromethylphenopendant)-2 of 4-, the Pd/carbon catalyst of 5-di-t-butylbenzene, 900 ml methanol solvents, 2.0 grams 10% adds autoclave, logical hydrogen; Stir, displace residual air, continue logical hydrogen, heat to 80 ℃～90 ℃; Keep reacting kettle inner pressure 0.5MPa～0.8M.Pa, keep reaction after 6 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, and in mother liquor, drip 450 ml deionized water while stirring, separate out white solid product, filter; With deionized water wash 2～3 times, 25 ℃ of vacuum-dryings, obtain 1 of 50.8 gram (product yield is 94%) whites; Two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-, and 5-di-t-butylbenzene pressed powder (theoretical yield: 54.0 grams), purity 99.6%; 215.4 ℃-215.9 ℃ of fusing points (WRR optics fusing point appearance, the initial temperature that is provided with is 210.0 ℃, 1.0 ℃ of temperature rise rates/min).
At 35 milliliters of N; In the N-dimethylacetamide solvent, in 0 ℃～10 ℃ TRs, with resulting 1; Two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-; Take out 5.4 grams (.0.01 mole) in the 5-di-t-butylbenzene solid and reacted 3 hours with 2.18 gram (0.01 mole) pyromellitic acid anhydrides, obtained high thick polyamic acid solution, its limiting viscosity is 1.9dL/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 1.5 hours; Continue to be warming up to 150 ℃, be incubated 1 hour; Continue to be warming up to 270 ℃, be incubated 1 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 110MPa; 1, two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-, the second-order transition temperature of 5-di-t-butylbenzene/pyromellitic acid anhydride-Kapton is 288.6 ℃.
Embodiment 2
With 60.1 gram (0.10 moles) 1, two (the 4-nitros-2-4-trifluoromethylphenopendant)-2 of 4-, the Pd/carbon catalyst of 5-di-t-butylbenzene, 601 milliliters of alcohol solvents, 3.0 grams 5% adds autoclave, logical hydrogen; Stir, displace residual air, continue logical hydrogen, heat to 80 ℃～90 ℃; Keep reacting kettle inner pressure 0.5MPa～0.8MPa, 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, filtration, recovery filter residue (catalyzer); Leave and take mother liquor, and in mother liquor, drip 601 ml deionized water while stirring, separate out white solid product, filter; With deionized water wash 2～3 times, 25 ℃ of vacuum-dryings, obtain 1 of 49.7 gram (product yield is 92%) whites; Two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-, and 5-di-t-butylbenzene pressed powder (theoretical yield: 54.0 grams), purity 99.5%.
Embodiment 3
With 60.1 gram (0.10 moles) 1, two (the 4-nitros-2-4-trifluoromethylphenopendant)-2 of 4-, the Pd/carbon catalyst of 5-di-t-butylbenzene, 300 milliliters of alcohol solvents, 400 milliliters of alcohol solvents, 6.0 grams 1% adds autoclave, logical hydrogen; Stir, displace residual air, continue logical hydrogen, heat to 80 ℃～90 ℃; Keep reacting kettle inner pressure 0.5MPa～0.8MPa, 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, filtration, recovery filter residue (catalyzer); Leave and take mother liquor, and in mother liquor, drip 600 ml deionized water while stirring, separate out white solid product; Filter, with deionized water wash 2～3 times, 25 ℃ of vacuum-dryings; Obtain 1 of 50.2 gram (product yield is 93%) whites, two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-, 5-di-t-butylbenzene pressed powder (theoretical yield: 54.0 grams).
Claims (3)
1. two (4-amino-2-4-trifluoromethylphenopendant)-2 of a 4-, the preparation method of 5-di-t-butylbenzene comprises:
With 1, two (the 4-nitros-2-4-trifluoromethylphenopendant)-2 of 4-, 5-di-t-butylbenzene, organic solvent, catalyzer add autoclave, and logical hydrogen stirs; Displace residual air, continue logical hydrogen, heat to 80 ℃～90 ℃, keep reacting kettle inner pressure 0.5MPa～0.8MPa; Keep reaction after 5～6 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 deionized water while stirring, and separate out white solid product, filter washing; Drying obtains 1, two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-, 5-di-t-butylbenzene solid; Wherein, 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;
Wherein, organic solvent and 1, two (the 4-nitros-2-4-trifluoromethylphenopendant)-2 of 4-, the envelope-bulk to weight ratio of 5-di-t-butylbenzene is 10 milliliters～15 milliliters: 1 gram; Catalyzer and 1, two (the 4-nitros-2-4-trifluoromethylphenopendant)-2 of 4-, the weight ratio of 5-di-t-butylbenzene is 1: 10～31; Deionized water must be strict controlled in 1.0 with the volume of organic solvent ratio: in the scope of 0.5-2.0.
2. according to claim 1 a kind of 1, two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-, the preparation method of 5-di-t-butylbenzene is characterized in that: described catalyzer is raney nickel or palladium/charcoal.
3. according to claim 2 a kind of 1, two (the 4-amino-2-4-trifluoromethylphenopendant)-2 of 4-, the preparation method of 5-di-t-butylbenzene is characterized in that: described palladium/charcoal, its palladium metal quality percentage composition is 1%～10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100539942A CN101591252B (en) | 2009-06-26 | 2009-06-26 | Method for preparing 1,4-bis(4-amino-2-trifluoromethyl phenoxyl)-2,5-diterbutyl benzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100539942A CN101591252B (en) | 2009-06-26 | 2009-06-26 | Method for preparing 1,4-bis(4-amino-2-trifluoromethyl phenoxyl)-2,5-diterbutyl benzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101591252A CN101591252A (en) | 2009-12-02 |
| CN101591252B true CN101591252B (en) | 2012-11-07 |
Family
ID=41406156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100539942A Expired - Fee Related CN101591252B (en) | 2009-06-26 | 2009-06-26 | Method for preparing 1,4-bis(4-amino-2-trifluoromethyl phenoxyl)-2,5-diterbutyl benzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101591252B (en) |
-
2009
- 2009-06-26 CN CN2009100539942A patent/CN101591252B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| .2004,第42卷(第9期),2272-2284. * |
| Journal of Polymer Science: Part A: Polymer Chemistry> * |
| Yang, Chin-Ping等.Synthesis and properties of fluorinated polyimides based on 1,4-bis(4-amino-2-trifluoromethylphenoxy)-2,5-di-tert-butylbenzene and various aromatic dianhydrides.<Journal of Polymer Science: Part A: Polymer Chemistry>.2004,第42卷(第9期),2272-2284. |
| Yang, Chin-Ping等.Synthesis and properties of fluorinated polyimides based on 1,4-bis(4-amino-2-trifluoromethylphenoxy)-2,5-di-tert-butylbenzene and various aromatic dianhydrides.< * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101591252A (en) | 2009-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101245026A (en) | Process for producing 1,4-(2,4-diaminophenyloxy)-2,5-di-t-butyl benzene | |
| CN101245024A (en) | Process for producing 1,3-bis(2,4-diaminophenyloxy)benzene | |
| CN101284793A (en) | Preparation method of 2,2-di[4-(2,4-diamino phenoxy) phenyl group] propane | |
| CN101245023A (en) | Process for producing 2,2-bis[2,4-diaminophenyloxy)phenyl]hexafluoropropane | |
| CN101560166B (en) | Method for preparing 1,3-di(2-trifluoromethyl-4-aminophenoxy) benzene | |
| CN101580474B (en) | Preparation method of 1,4-bis(2-trifluoromethyl-4-aminophenoxyl)benzene | |
| CN101492381B (en) | Method of preparing 2,2-di(3-amino-4-hydroxyl phenyl) hexafluoroacetore | |
| CN101591252B (en) | Method for preparing 1,4-bis(4-amino-2-trifluoromethyl phenoxyl)-2,5-diterbutyl benzene | |
| CN101293842B (en) | Method for preparing 4,4'-di(2,4-diaminophenyloxy)biphenyl | |
| CN101560163B (en) | Preparation method of 4,4'-bi(2-trifluoromethyl-4-aminophenoxyl)biphenyl | |
| CN101591251B (en) | Method for preparing 2-tert-butyl-1,4-di(4-amino-2-trifluoromethylphenoxy) benzene | |
| CN101591277B (en) | Method for preparing 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone | |
| CN101215241A (en) | Method for preparing 1,4-di(2,4-diaminophenoxy)benzene | |
| CN101560162B (en) | Preparation method of 4,4'-bi(4-amino-2-trifluoromethylphenoxyl)-3,3'5,5'-tetramethylbiphenyl | |
| CN101486660B (en) | Preparation of 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl] propane | |
| CN101397258B (en) | Process for preparation of 3,3-diamino-4,4-dihydroxybiphenyl | |
| CN101560165B (en) | Preparation method of 2,2-bi[4-(2-trifluoromethyl-4-aminophenoxyl)phenyl]hexafluoropropane | |
| CN101560164B (en) | Preparation method of 2,5-bi(2-trifluoromethyl-4-aminophenoxyl)toluene | |
| CN101260052A (en) | Method for preparing 2,6-di(2,4-diaminophenoxy)toluene | |
| CN101250128A (en) | Method for preparing 1,4-di(2,4-diamino phenoxy) naphthalene | |
| CN101245030B (en) | Process for producing 1,2-bis(2,4-diaminophenyloxy)benzene | |
| CN101503360B (en) | Preparation of 2- tertiary butyl-1,4-bis (4-nitro-2-trifluoromethyl phenoxy) benzene | |
| CN101260057A (en) | Method for preparing 1,3,5-tri(2,4-diaminophenoxy)benzene | |
| CN101289406A (en) | Method for preparing 1,4-di(2,4- diaminophenyloxy)-2-tert-butyl benzene | |
| CN101250123A (en) | Method for preparing 2,4-di(2,4-diamino phenoxy) toluene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121107 Termination date: 20150626 |
|
| EXPY | Termination of patent right or utility model |