CN106083612A - A kind of fluorine-containing Triamine monomer and its preparation method and application - Google Patents
A kind of fluorine-containing Triamine monomer and its preparation method and application Download PDFInfo
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- CN106083612A CN106083612A CN201610416353.9A CN201610416353A CN106083612A CN 106083612 A CN106083612 A CN 106083612A CN 201610416353 A CN201610416353 A CN 201610416353A CN 106083612 A CN106083612 A CN 106083612A
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- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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Abstract
The invention belongs to organic chemistry and Material Field, be specifically related to a kind of fluorine-containing Triamine monomer and its preparation method and application.The present invention is with 4 hydroxy acetophenones and 2 chlorine 5 nitro-trifluoromethyl toluenes as raw material, it is substituted reaction formation 4 (2 trifluoromethyl 5 nitro-phenoxy) acetophenone, then with ethanol and silicon tetrachloride as composite catalyst, catalysis 4 (2 trifluoromethyl 5 nitro-phenoxy) acetophenone generation condensation reaction forms 1, 3, 5 three (4 (2 trifluoromethyl 4 nitro-phenoxy)) benzene, last with palladium carbon as catalyst, it is catalyzed it and reduce to obtain end-product 1, 3, 5 three (4 (2 trifluoromethyl 4 amido phenoxy group)) benzene, i.e. fluorine-containing Triamine monomer, this fluorine-containing Triamine monomer novel structure, it is the monomer of a kind of potential synthesis of super branched fluorinated polyimide, have great potential research and using value, its structural formula is as follows:。
Description
Technical field
The invention belongs to organic chemistry and Material Field, be specifically related to a kind of fluorine-containing Triamine monomer and preparation method thereof and answer
With.
Background technology
Polyimides (PI) is a series of compounds in molecule structure containing imide ring.Owing to it is various excellent
Combination property, such as excellent heat-resisting quantity, resistance to environmental stability and good mechanical performance so that PI Aeronautics and Astronautics,
The fields such as machinery, electrician and electronics are widely used.Especially this year, with integrated circuit (IC) industry continuous
Development, has higher requirement to the heat resistance and dielectric properties of associated materials, and this is polyimides (PI) and over-expense
Change polyimides (HBPI) material and serve good impetus in the application of microelectronic.
Fluorine-containing super-branched polyimide, due to the introducing of fluorin radical, can increase the distance of molecule interchain, reduce molecule
Between active force, increase polymer free volume, solvent molecule can be freely spread in polymer, makes the dissolving of polymer
Performance improves；The introducing of fluorine atom with the regularity of saboteur, can increase the dissolving of the compliance raising polymer of strand
Performance, therefore fluorine atom is greatly improved the dissolubility of polyimides, thus improves its processing characteristics.Meanwhile, fluorine atom has
Bigger electronegativity, can cut off the conjugation of electron cloud in PI molecular structure, and therefore the color of PI goods is shallower, has preferable light
Learn the transparency.Fluorine atom has preferable hydrophobicity and relatively low mole of polarizability simultaneously so that the hydroscopicity of PI goods and
Dielectric constant all reduces.So these excellent performances make fluorine-containing PI all obtain widely should in microelectronic various aspects
With.
The design of novel PI material, synthesis and development are to be polymerized what monomer realized based on novel, and the performance of PI is very
The character being polymerized monomer is depended in big degree, also such for fluorine-containing PI.Synthesis has the list of some special nature
Body, such as the monomer with the group such as photovoltaic reaction, heat reactivity, and be polymerized by it and give PI material corresponding particularity
Can so that it is character have traditional insoluble do not melt and be difficult to processing and forming develop into have solvable fusible, easy-formation, easily use
Feature, simplifies its focus using technique to be always in PI research.It with regard to the research of fluorine-containing PI, is in the research of current functionalization PI
One of the most noticeable focus.The special physicochemical properties of fluorine atom impart the many unique performances of PI, and these are excellent
Good performance has widened the application of PI greatly, and makes it show in each application and extremely highlight
Performance.Current fluorine-containing dianhydride, diamine monomer, Triamine monomer species relatively fewer, industrialized monomeric species just more has
Limit, less monomeric species hinders the application of fluorine-containing PI to a great extent, it has also become the bottleneck problem of its development.
Content of the invention
The technical problem to be solved is to provide a kind of fluorine-containing Triamine monomer and its preparation method and application, increases
The species of available fluorine-containing Triamine monomer, thus promote the research and development of fluorine-containing PI.
The technical scheme is that a kind of fluorine-containing Triamine monomer of offer, its structural formula is such as
Shown in lower:
The present invention also provides a kind of method preparing above-mentioned fluorine-containing Triamine monomer, and it comprises the steps:
The synthesis of S1.4-(2-trifluoromethyl-5-nitro-phenoxy)-acetophenone: under nitrogen atmosphere, by 4-hydroxy benzenes second
Ketone and potassium carbonate mix with appropriate organic solvent, and more than condensing reflux magnetic agitation 3h obtain mixed liquor at 120-125 DEG C,
The mol ratio of 4-hydroxyacetophenone and potassium carbonate is 1:1.1-1.3, after naturally cooling to 60-65 DEG C, adds in described mixed liquor
Enter the 2-chloro-5-nitro-benzotrifluoride of molal quantity identical with described 4-hydroxyacetophenone, be warming up to 120-125 DEG C, stirring reaction
More than 12h, naturally cools to 60-65 DEG C, mixes the mixed solution obtaining after reaction with the ethanol in proper amount aqueous solution, produces yellow
Precipitation, filtration, deionized water washing, ethyl alcohol recrystallization, obtain 4-(2-trifluoromethyl-5-nitro-phenoxy)-acetophenone, specifically instead
Answer equation as follows:
The synthesis of S2.1,3,5-tri-(4-(2-trifluoromethyl-4-nitrophenoxy)) benzene: 4-(2-trifluoro prepared by S1
Methyl-5-nitro phenoxy group)-acetophenone be dispersed in ethanol in proper amount (EtOH) dispersion liquid, drip appropriate silicon tetrachloride supreme
Stating in dispersion liquid and quickly stirring, dropping is reacted more than 14h at normal temperatures and is obtained mixed liquor after finishing, dropping deionized water is to mixing
Liquid stirring make silicon tetrachloride (TCS) complete hydrolysis in it, re-use mixing after sodium hydroxide solution regulation said hydrolyzed completes
Close liquid to neutral, mixed liquor have precipitation produce, filter, washing, dry powder, by the powder that obtains in ethanol water
Heating for dissolving condensing reflux purify, and after cooling, suction filtration obtains pale yellow powder, use ethanol heavily to tie with dichloromethane mixed solvent
Crystalline substance, obtains 1, and 3,5-tri-(4-(2-trifluoromethyl-4-nitrophenoxy)) benzene, ethanol (EtOH) and silicon tetrachloride (TCS) are compound
Catalyst, the aryl methyl ketone condensation in fcc raw material forms phenyl ring, and concrete reaction equation is as follows:
S3.1, the synthesis of 3,5-tri-(4-(2-trifluoromethyl-4-amido phenoxy group)) benzene: under nitrogen atmosphere, by S2 system
Standby 1,3,5-tri-(4-(2-trifluoromethyl-4-nitrophenoxy)) benzene and palladium catalyst carbon are well-dispersed in appropriate absolute ethyl alcohol
In dispersion liquid, be heated to 80-85 DEG C of condensing reflux, in constant speed dropping hydrazine hydrate to dispersion liquid, be added dropwise to the hydration of dispersion liquid
Hydrazine is 20mL with the ratio of 1,3,5-tri-(4-(2-the trifluoromethyl-4-nitrophenoxy)) benzene in dispersion liquid and absolute ethyl alcohol:
10-15mmol:90-120mL, after dropping finishes, continues more than condensing reflux 12h, filters while hot, and filtrate pours deionized water into
In, there is white precipitate to produce, filter, wash, dry, obtain yellow powder, be fluorine-containing Triamine monomer 1,3,5-tri-(4-(2-tri-
Methyl fluoride-4-amido phenoxy group)) benzene, concrete reaction equation is as follows:
On the basis of above-mentioned preparation method, it can also further be embodied or optimized, specifically by the present invention
Content is as follows:
Preferably, the organic solvent described in step S1 is high boiling organic solvent, preferably in DMAC, NMP and DMF
Any one, described organic solvent is 80mL:10mmol with the usage ratio of described 4-hydroxyacetophenone.
Concrete, in the ethanol water described in step S1, ethanol and the volume ratio of water are 1:9.
Preferably, the usage ratio of 4-described in step S2 (2-trifluoromethyl-5-nitro-phenoxy)-acetophenone and ethanol
For 50mmol:40-50mL, described silicon tetrachloride is 14:40-50 with the volume ratio of ethanol.
Preferably, in step S2, the volume fraction of the described ethanol water that condensing reflux is used when purifying is 95%, cold
During solidifying backflow, the temperature of described ethanol water is 80 DEG C.
Concrete, the mass fraction of sodium hydroxide solution described in step S2 is 10-15%.
Preferably, ethanol described in step S2 and the volume ratio of dichloromethane mixed solvent are 100:1.
Preferably, 1,3,5-tri-(4-(2-trifluoromethyl-4-nitrophenoxy)) benzene and palladium catalyst carbon in step S3
Usage ratio is 10mmol:0.6g, and described palladium catalyst carbon is 5% palladium carbon, wherein 5% refers to effective one-tenth of palladium-carbon catalyst
Part content.
The present invention is also claimed application in terms of super-branched polyimide synthesis for the described fluorine-containing Triamine monomer.
The fluorine-containing Triamine monomer that the present invention provides is non-existent novel Triamine monomer in a kind of prior art, overcomes mesh
Before fluorine-containing dianhydride, diamine monomer, Triamine monomer species relatively fewer so that becoming the research and development of fluorinated polyimide
Affected deficiency.The preparation method that the present invention provides relates to replace, be condensed and reduction reaction, be often in organic synthesis
Gentle by technology and reaction condition, it is specially first with 4-hydroxyacetophenone and 2-chloro-5-nitro-benzotrifluoride as raw material, warp
Substitution reaction forms 4-(2-trifluoromethyl-5-nitro-phenoxy)-acetophenone, then with ethanol and silicon tetrachloride as composite catalyzing
Agent, catalysis 4-(2-trifluoromethyl-5-nitro-phenoxy)-acetophenone generation condensation reaction forms 1,3,5-tri-(4-(2-fluoroforms
Base-4-nitrophenoxy)) benzene, it finally with palladium carbon as catalyst, is catalyzed it and reduces to obtain end-product 1,3,5-tri-(4-(2-fluoroform
Base-4-amido phenoxy group)) benzene, i.e. fluorine-containing Triamine monomer, the Triamine monomer novel structure that the present invention provides, is a kind of potential
The monomer of synthesis of super branched fluorinated polyimide, has great potential research and using value.
Brief description
Fig. 1 is infrared absorpting light spectra, in figure a, b and c be respectively embodiment 1 preparation p, p-FNPAP, FTNPOPB and
The infrared absorpting light spectra of FTAPOPB；
Fig. 2 is the p of the embodiment of the present invention 1 preparation, the nucleus magnetic hydrogen spectrum figure of p-FNPAP；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of the FTNPOPB of the embodiment of the present invention 1 preparation；
Fig. 4 is the nucleus magnetic hydrogen spectrum figure of the FTAPOPB of the embodiment of the present invention 1 preparation.
Detailed description of the invention
Being described below in conjunction with principle and feature to the present invention for the drawings and the specific embodiments, example is served only for solving
Release the present invention, be not intended to limit the scope of the present invention.
The method that the present invention uses is conventional method as specified otherwise, and medicine used by the present invention is commercially available prod.
Embodiment 1
A kind of fluorine-containing Triamine monomer, it is prepared by following step:
The synthesis of S1.4-(2-trifluoromethyl-5-nitro-phenoxy)-acetophenone (p, p-FNPAP): under nitrogen atmosphere,
It is added to 0.1mol 4-hydroxyacetophenone and 0.125mol potassium carbonate in 250mL there-necked flask, and add 80mL DMAC abundant
Mixing, mixture condensing reflux under the conditions of 120 DEG C, magnetic agitation 3h obtains mixed liquor.Then 60 DEG C are naturally cooled to, toward mixing
Solution adds 0.1mol 2-chloro-5-nitro-benzotrifluoride, is continuously heating to 120 DEG C, after reaction 12h, naturally cool to 60
DEG C, mixed solution is imported in 80mL alcohol-water mixture, wherein ethanol and the ratio of water are 1:9, have yellow mercury oxide to produce, mistake
After filter with deionized water rinsing repeatedly, recrystallizing the product obtaining in ethanol, obtaining p, p-FNPAP, its infared spectrum is such as
In Fig. 1 shown in a, nucleus magnetic hydrogen spectrum as shown in Figure 2.
The synthesis (FTNPOPB) of S2.1,3,5-tri-(4-(2-trifluoromethyl-4-nitrophenoxy)) benzene: 250mL tri-mouthfuls
In flask, the p for preparing 50mmol step S1, p-FNPAP is distributed in 40mL ethanol.Put up tail gas absorption dress with dropping funel
Postpone, 14mL silicon tetrachloride (TCS) is injected in constant pressure funnel by syringe, be slowly at the uniform velocity added drop-wise to mixed solution
In, and quick magnetic agitation.Dropping reacts 14h after finishing under normal temperature condition.Then instill several times from the top of condenser pipe
(precaution of hydrolysis reaction is excessively violent) about 100mL deionized water makes silicon tetrachloride complete hydrolysis, after continuing stirring 30 minutes, slowly
The pH of the sodium hydroxide solution regulation solution adding mass fraction to be 10%, to neutral, obtains wine-colored mixed solution, finally
Filtration washing is dried to obtain powder, and by the powder obtaining, in the ethanol of 95%, 80 DEG C of condensing refluxes purify 30 minutes, take out after cooling
Filter obtains pale yellow powder, and in ethanol and dichloromethane mixed solvent (ethanol is 100:1 with the volume ratio of dichloromethane)
Recrystallization, product is FTNPOPB, its infared spectrum as shown in b in Fig. 1, nucleus magnetic hydrogen spectrum as shown in Figure 3.
The synthesis (FTAPOPB) of S3.1,3,5-tri-(4-(2-trifluoromethyl-4-amido phenoxy group)) benzene: at nitrogen atmosphere
Under, FTAPOPB and the 0.6g palladium carbon (Pd/C, 5%) prepared 0.01mol step S2 in 250mL there-necked flask is fully dispersed
In 100mL absolute ethyl alcohol, being heated to 80 DEG C of condensing refluxes, then the hydrazine hydrate dropping funel constant speed dropping 2 of 20mL is little
When, then proceed to condensing reflux.After 12 hours, mixture is filtered while hot, and filtrate is poured into 800mL deionized water
In, there is white flock precipitate to produce, then filter, wash, dry, obtaining flaxen powder is FTAPOPB, namely fluorine-containing three
Amine monomers, its infared spectrum as shown in c in Fig. 1, nucleus magnetic hydrogen spectrum as shown in Figure 4.
It can be seen in fig. 2 that compared with curve a and b, curve c is at 3458cm-1And 3387cm-1Place and 3223cm-1Place goes out
Show-NH on phenyl ring2Characteristic absorption peak, 1036cm-1Be on curve a, b and c with 841cm-1 occur in that all respectively C-F and
The characteristic absorption peak of C-N, the upper 1350cm of curve a, b-1Place is-NO2Characteristic absorption peak, at 1433 be-CH3Characteristic absorption
Peak, the vibration absorption peak for C=O at 1688cm-1 on curve a, therefore the red spectral absorption curve in Fig. 2 shows, fluorine-containing triamine
FTAPOPB successfully synthesizes.
Fig. 2, Fig. 3 and Fig. 4 are p respectively, the nucleus magnetic hydrogen spectrum figure of p-FNPAP, FTNPOPB and FTAPOPB, can from figure
Going out, each peak is obtained for ownership in corresponding compound, and does not has any miscellaneous peak to occur, it further demonstrates that, contains
Fluorine triamine successfully prepares.
Embodiment 2
A kind of fluorine-containing Triamine monomer, it is prepared by following step:
The synthesis of S1.4-(2-trifluoromethyl-5-nitro-phenoxy)-acetophenone (p, p-FNPAP): under nitrogen atmosphere,
It is added to 0.1mol 4-hydroxyacetophenone and 0.110mol potassium carbonate in 250mL there-necked flask, and add 70mL DMAC abundant
Mixing, mixture condensing reflux under the conditions of 123 DEG C, magnetic agitation 3h obtains mixed liquor.Then 63 DEG C are naturally cooled to, toward mixing
Solution adds 0.1mol 2-chloro-5-nitro-benzotrifluoride, is continuously heating to 123 DEG C, after reaction 12h, naturally cool to 63
DEG C, mixed solution is imported in 70mL alcohol-water mixture, wherein ethanol and the ratio of water are 1:8, have yellow mercury oxide to produce, mistake
After filter with deionized water rinsing repeatedly, the product obtaining is recrystallized in ethanol, obtain p, p-FNPAP.
The synthesis (FTNPOPB) of S2.1,3,5-tri-(4-(2-trifluoromethyl-4-nitrophenoxy)) benzene: 250mL tri-mouthfuls
In flask, the p for preparing 50mmol step S1, p-FNPAP is distributed in 50mL ethanol.Put up tail gas absorption dress with dropping funel
Postpone, 14mL silicon tetrachloride (TCS) is injected in constant pressure funnel by syringe, be slowly at the uniform velocity added drop-wise to mixed solution
In, and quick magnetic agitation.Dropping reacts 15h after finishing under normal temperature condition.Then instill several times from the top of condenser pipe
(precaution of hydrolysis reaction is excessively violent) about 95mL deionized water makes silicon tetrachloride complete hydrolysis, after continuing stirring 30 minutes, slowly
The pH of the sodium hydroxide solution regulation solution adding mass fraction to be 13%, to neutral, obtains wine-colored mixed solution, finally
Filtration washing is dried to obtain powder, and by the powder obtaining, in the ethanol of 95%, 80 DEG C of condensing refluxes purify 30 minutes, take out after cooling
Filter obtains pale yellow powder, and in ethanol and dichloromethane mixed solvent (ethanol is 100:1 with the volume ratio of dichloromethane)
Recrystallization, product is FTNPOPB.
The synthesis (FTAPOPB) of S3.1,3,5-tri-(4-(2-trifluoromethyl-4-amido phenoxy group)) benzene: at nitrogen atmosphere
Under, FTAPOPB and the 0.6g palladium carbon (Pd/C, 5%) prepared 0.01mol step S2 in 250mL there-necked flask is fully dispersed
In 90mL absolute ethyl alcohol, being heated to 80 DEG C of condensing refluxes, then the hydrazine hydrate dropping funel constant speed dropping 2 of 20mL is little
When, then proceed to condensing reflux.After 12h, mixture is filtered while hot, and filtrate is poured in 800mL deionized water, have white
Look flocculent deposit produces, and then filters, washes, dries, and obtaining flaxen powder is FTAPOPB, namely fluorine-containing Triamine monomer.
Embodiment 3
A kind of fluorine-containing Triamine monomer, it is prepared by following step:
The synthesis of S1.4-(2-trifluoromethyl-5-nitro-phenoxy)-acetophenone (p, p-FNPAP): under nitrogen atmosphere,
It is added to 0.1mol 4-hydroxyacetophenone and 0.130mol potassium carbonate in 250mL there-necked flask, and add 90mL DMAC abundant
Mixing, mixture condensing reflux under the conditions of 125 DEG C, magnetic agitation 3h obtains mixed liquor.Then 65 DEG C are naturally cooled to, toward mixing
Solution adds 0.1mol 2-chloro-5-nitro-benzotrifluoride, is continuously heating to 125 DEG C, after reaction 14h, naturally cool to 65
DEG C, mixed solution is imported in 100mL alcohol-water mixture, wherein ethanol and the ratio of water are 1:9, have yellow mercury oxide to produce,
After filtration with deionized water rinsing repeatedly, the product obtaining is recrystallized in ethanol, obtain p, p-FNPAP.
The synthesis (FTNPOPB) of S2.1,3,5-tri-(4-(2-trifluoromethyl-4-nitrophenoxy)) benzene: 250mL tri-mouthfuls
In flask, the p for preparing 50mmol step S1, p-FNPAP is distributed in 45mL ethanol.Put up tail gas absorption dress with dropping funel
Postpone, 14mL silicon tetrachloride (TCS) is injected in constant pressure funnel by syringe, be slowly at the uniform velocity added drop-wise to mixed solution
In, and quick magnetic agitation.Dropping reacts 15h after finishing under normal temperature condition.Then instill several times from the top of condenser pipe
(precaution of hydrolysis reaction is excessively violent) about 110mL deionized water makes silicon tetrachloride complete hydrolysis, after continuing stirring 30 minutes, slowly
The pH of the sodium hydroxide solution regulation solution adding mass fraction to be 15%, to neutral, obtains wine-colored mixed solution, finally
Filtration washing is dried to obtain powder, and by the powder obtaining, in the ethanol of 95%, 80 DEG C of condensing refluxes purify 30 minutes, take out after cooling
Filter obtains pale yellow powder, and in ethanol and dichloromethane mixed solvent (ethanol is 100:1 with the volume ratio of dichloromethane)
Recrystallization, product is FTNPOPB.
The synthesis (FTAPOPB) of S3.1,3,5-tri-(4-(2-trifluoromethyl-4-amido phenoxy group)) benzene: at nitrogen atmosphere
Under, FTAPOPB and the 0.8g palladium carbon (Pd/C, 5%) prepared 0.015mol step S2 in 250mL there-necked flask is fully dispersed
In 120mL absolute ethyl alcohol, being heated to 80 DEG C of condensing refluxes, then the hydrazine hydrate dropping funel constant speed dropping 2 of 20mL is little
When, then proceed to condensing reflux.After 14 hours, mixture is filtered while hot, and filtrate is poured into 1000mL deionized water
In, there is white flock precipitate to produce, then filter, wash, dry, obtaining flaxen powder is FTAPOPB, namely fluorine-containing three
Amine monomers.
Embodiment 4
A kind of fluorine-containing Triamine monomer, it is prepared by following step:
The synthesis of S1.4-(2-trifluoromethyl-5-nitro-phenoxy)-acetophenone (p, p-FNPAP): under nitrogen atmosphere,
It is added to 0.1mol 4-hydroxyacetophenone and 0.125mol potassium carbonate in 250mL there-necked flask, and add 80mL NMP fully mixed
Closing, mixture condensing reflux under the conditions of 120 DEG C, magnetic agitation 3h obtains mixed liquor.Then 60 DEG C are naturally cooled to, molten toward mixing
Liquid adds 0.1mol 2-chloro-5-nitro-benzotrifluoride, is continuously heating to 120 DEG C, after reaction 12h, naturally cool to 60 DEG C,
Importing to mixed solution in 80mL alcohol-water mixture, wherein ethanol and the ratio of water are 1:9, have yellow mercury oxide to produce, and filter
Afterwards with deionized water rinsing repeatedly, the product obtaining is recrystallized in ethanol, obtain p, p-FNPAP.
The synthesis (FTNPOPB) of S2.1,3,5-tri-(4-(2-trifluoromethyl-4-nitrophenoxy)) benzene: 250mL tri-mouthfuls
In flask, the p for preparing 50mmol step S1, p-FNPAP is distributed in 40mL ethanol.Put up tail gas absorption dress with dropping funel
Postpone, 14mL silicon tetrachloride (TCS) is injected in constant pressure funnel by syringe, be slowly at the uniform velocity added drop-wise to mixed solution
In, and quick magnetic agitation.Dropping reacts 14h after finishing under normal temperature condition.Then instill several times from the top of condenser pipe
(precaution of hydrolysis reaction is excessively violent) about 100mL deionized water makes silicon tetrachloride complete hydrolysis, after continuing stirring 30 minutes, slowly
The pH of the sodium hydroxide solution regulation solution adding mass fraction to be 10%, to neutral, obtains wine-colored mixed solution, finally
Filtration washing is dried to obtain powder, and by the powder obtaining, in the ethanol of 95%, 80 DEG C of condensing refluxes purify 30 minutes, take out after cooling
Filter obtains pale yellow powder, and in ethanol and dichloromethane mixed solvent (ethanol is 100:1 with the volume ratio of dichloromethane)
Recrystallization, product is FTNPOPB.
The synthesis (FTAPOPB) of S3.1,3,5-tri-(4-(2-trifluoromethyl-4-amido phenoxy group)) benzene: at nitrogen atmosphere
Under, FTAPOPB and the 0.6g palladium carbon (Pd/C, 5%) prepared 0.01mol step S2 in 250mL there-necked flask is fully dispersed
In 100mL absolute ethyl alcohol, being heated to 80 DEG C of condensing refluxes, then the hydrazine hydrate dropping funel constant speed dropping 2 of 20mL is little
When, then proceed to condensing reflux.After 12 hours, mixture is filtered while hot, and filtrate is poured into 800mL deionized water
In, there is white flock precipitate to produce, then filter, wash, dry, obtaining flaxen powder is FTAPOPB, namely fluorine-containing three
Amine monomers.
Embodiment 3
A kind of fluorine-containing Triamine monomer, it is prepared by following step:
The synthesis of S1.4-(2-trifluoromethyl-5-nitro-phenoxy)-acetophenone (p, p-FNPAP): under nitrogen atmosphere,
It is added to 0.1mol 4-hydroxyacetophenone and 0.130mol potassium carbonate in 250mL there-necked flask, and add 90mL DMF fully mixed
Closing, mixture condensing reflux under the conditions of 125 DEG C, magnetic agitation 3h obtains mixed liquor.Then 65 DEG C are naturally cooled to, molten toward mixing
Liquid adds 0.1mol 2-chloro-5-nitro-benzotrifluoride, is continuously heating to 125 DEG C, after reaction 14h, naturally cool to 65 DEG C,
Importing to mixed solution in 100mL alcohol-water mixture, wherein ethanol and the ratio of water are 1:9, have yellow mercury oxide to produce, and filter
Afterwards with deionized water rinsing repeatedly, the product obtaining is recrystallized in ethanol, obtain p, p-FNPAP.
The synthesis (FTNPOPB) of S2.1,3,5-tri-(4-(2-trifluoromethyl-4-nitrophenoxy)) benzene: 250mL tri-mouthfuls
In flask, the p for preparing 50mmol step S1, p-FNPAP is distributed in 45mL ethanol.Put up tail gas absorption dress with dropping funel
Postpone, 14mL silicon tetrachloride (TCS) is injected in constant pressure funnel by syringe, be slowly at the uniform velocity added drop-wise to mixed solution
In, and quick magnetic agitation.Dropping reacts 15h after finishing under normal temperature condition.Then instill several times from the top of condenser pipe
(precaution of hydrolysis reaction is excessively violent) about 110mL deionized water makes silicon tetrachloride complete hydrolysis, after continuing stirring 30 minutes, slowly
The pH of the sodium hydroxide solution regulation solution adding mass fraction to be 15%, to neutral, obtains wine-colored mixed solution, finally
Filtration washing is dried to obtain powder, and by the powder obtaining, in the ethanol of 95%, 80 DEG C of condensing refluxes purify 30 minutes, take out after cooling
Filter obtains pale yellow powder, and in ethanol and dichloromethane mixed solvent (ethanol is 100:1 with the volume ratio of dichloromethane)
Recrystallization, product is FTNPOPB.
The synthesis (FTAPOPB) of S3.1,3,5-tri-(4-(2-trifluoromethyl-4-amido phenoxy group)) benzene: at nitrogen atmosphere
Under, FTAPOPB and the 0.8g palladium carbon (Pd/C, 5%) prepared 0.015mol step S2 in 250mL there-necked flask is fully dispersed
In 120mL absolute ethyl alcohol, being heated to 80 DEG C of condensing refluxes, then the hydrazine hydrate dropping funel constant speed dropping 2 of 20mL is little
When, then proceed to condensing reflux.After 14 hours, mixture is filtered while hot, and filtrate is poured into 1000mL deionized water
In, there is white flock precipitate to produce, then filter, wash, dry, obtaining flaxen powder is FTAPOPB, namely fluorine-containing three
Amine monomers.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. a fluorine-containing Triamine monomer, it is characterised in that structural formula is as follows:
2. the preparation method of a fluorine-containing Triamine monomer as claimed in claim 1, it is characterised in that comprise the steps:
The synthesis of S1.4-(2-trifluoromethyl-5-nitro-phenoxy)-acetophenone: under nitrogen atmosphere, by 4-hydroxyacetophenone and
Potassium carbonate mixes with appropriate organic solvent, and more than condensing reflux magnetic agitation 3h obtains mixed liquor, 4-hydroxyl at 120-125 DEG C
The mol ratio of benzoylformaldoxime and potassium carbonate is 1:1.1-1.3, after naturally cooling to 60-65 DEG C, toward add in described mixed liquor with
The 2-chloro-5-nitro-benzotrifluoride of the identical molal quantity of described 4-hydroxyacetophenone, is warming up to 120-125 DEG C, stirring reaction 12h
Above, naturally cool to 60-65 DEG C, the mixed solution obtaining after reaction is mixed with the ethanol in proper amount aqueous solution, produce yellow and sink
Form sediment, filtration, deionized water washing, ethyl alcohol recrystallization, obtain 4-(2-trifluoromethyl-5-nitro-phenoxy)-acetophenone, specifically react
Equation is as follows:
The synthesis of S2.1,3,5-tri-(4-(2-trifluoromethyl-4-nitrophenoxy)) benzene: 4-prepared by S1 (2-trifluoromethyl-
5-nitro-phenoxy)-acetophenone is dispersed in ethanol in proper amount to obtain dispersion liquid, drip appropriate silicon tetrachloride in above-mentioned dispersion liquid simultaneously
Quickly stirring, dropping is reacted more than 14h at normal temperatures and is obtained mixed liquor after finishing, dropping deionized water to mixed liquor stirring make it
Interior silicon tetrachloride complete hydrolysis, re-uses the mixed liquor after sodium hydroxide solution regulation said hydrolyzed completes to neutrality, mixed liquor
In have precipitation to produce, filter, washing, dry powder, by the powder obtaining in ethanol water heating for dissolving condensing back
Stream purifies, and after cooling, suction filtration obtains pale yellow powder, uses ethanol to recrystallize with dichloromethane mixed solvent, obtains 1,3,5-tri-(4-
(2-trifluoromethyl-4-nitrophenoxy)) benzene, concrete reaction equation is as follows:
S3.1, the synthesis of 3,5-tri-(4-(2-trifluoromethyl-4-amido phenoxy group)) benzene: under nitrogen atmosphere, prepared by S2
1,3,5-tri-(4-(2-trifluoromethyl-4-nitrophenoxy)) benzene and palladium catalyst carbon are well-dispersed in appropriate absolute ethyl alcohol
Dispersion liquid, is heated to 80-85 DEG C of condensing reflux, in constant speed dropping hydrazine hydrate to dispersion liquid, be added dropwise to the hydrazine hydrate of dispersion liquid with
The ratio of 1,3,5-tri-(4-(2-the trifluoromethyl-4-nitrophenoxy)) benzene in dispersion liquid and absolute ethyl alcohol is 20mL:10-
15mmol:90-120mL, after dropping finishes, continues more than condensing reflux 12h, filters while hot, and filtrate is poured in deionized water, has
White precipitate produces, and filters, washes, dries, obtains yellow powder, be fluorine-containing Triamine monomer 1,3,5-tri-(4-(2-fluoroform
Base-4-amido phenoxy group)) benzene, concrete reaction equation is as follows:
3. the preparation method of a kind of fluorine-containing Triamine monomer according to claim 2, it is characterised in that described in step S1
Organic solvent is any one in DMAC, NMP and DMF, and described organic solvent with the usage ratio of described 4-hydroxyacetophenone is
80mL:10mmol。
4. the preparation method of a kind of fluorine-containing Triamine monomer according to claim 2, it is characterised in that described in step S1
In ethanol water, ethanol and the volume ratio of water are 1:9.
5. the preparation method of a kind of fluorine-containing Triamine monomer according to claim 2, it is characterised in that 4-described in step S2
(2-trifluoromethyl-5-nitro-phenoxy)-acetophenone is 50mmol:40-50mL with the usage ratio of ethanol, described silicon tetrachloride
Volume ratio with ethanol is 14:40-50.
6. the preparation method of a kind of fluorine-containing Triamine monomer according to claim 2, it is characterised in that condense back in step S2
The volume fraction of the described ethanol water that stream is used when purifying is 95%, and during condensing reflux, the temperature of described ethanol water is
80℃。
7. the preparation method of a kind of fluorine-containing Triamine monomer according to claim 2, it is characterised in that hydrogen described in step S2
The mass fraction of sodium hydroxide solution is 10-15%.
8. the preparation method of a kind of fluorine-containing Triamine monomer according to claim 2, it is characterised in that described in step S2
Ethanol is 100:1 with the volume ratio of ethanol in dichloromethane mixed solvent and dichloromethane.
9. the preparation method of a kind of fluorine-containing Triamine monomer according to claim 2, it is characterised in that in step S3 1,3,5-
Three (4-(2-trifluoromethyl-4-nitrophenoxy)) benzene is 10mmol:0.6g with the usage ratio of palladium catalyst carbon, described catalysis
Agent palladium carbon is 5% palladium carbon.
10. the application of a fluorine-containing Triamine monomer as claimed in claim 1, it is characterised in that be used for super-branched polyimide
Synthesis.
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| CN103467316A (en) * | 2013-09-30 | 2013-12-25 | 湖北大学 | Synthesis of triamine containing truxene structure and polyimide thereof |
| CN105153699A (en) * | 2015-07-31 | 2015-12-16 | 江苏省电力公司泰州供电公司 | Preparation method of hyper branched copolymerized polyimide/zinc oxide (ZnO) hybrid insulated film |
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| CN103467316A (en) * | 2013-09-30 | 2013-12-25 | 湖北大学 | Synthesis of triamine containing truxene structure and polyimide thereof |
| CN105153699A (en) * | 2015-07-31 | 2015-12-16 | 江苏省电力公司泰州供电公司 | Preparation method of hyper branched copolymerized polyimide/zinc oxide (ZnO) hybrid insulated film |
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| CN115724815A (en) * | 2022-11-21 | 2023-03-03 | 安徽国风新材料股份有限公司 | Dianhydride monomer containing amide structure and trifluoromethyl, polyimide film and preparation method thereof |
| CN115724815B (en) * | 2022-11-21 | 2024-05-17 | 安徽国风新材料股份有限公司 | Dianhydride monomer containing amide structure and trifluoromethyl, polyimide film and preparation method thereof |
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