CN106083612B - 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
- Publication number
- CN106083612B CN106083612B CN201610416353.9A CN201610416353A CN106083612B CN 106083612 B CN106083612 B CN 106083612B CN 201610416353 A CN201610416353 A CN 201610416353A CN 106083612 B CN106083612 B CN 106083612B
- Authority
- CN
- China
- Prior art keywords
- fluorine
- trifluoromethyl
- ethanol
- benzene
- triamine monomer
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to organic chemistry and Material Field, and in particular to a kind of fluorine-containing Triamine monomer and its preparation method and application.The present invention is using 4 hydroxy acetophenones and the nitro-trifluoromethyl toluene of 2 chlorine 5 as raw material, it is substituted reaction and forms 4 (nitro-phenoxy of 2 trifluoromethyl 5) acetophenones, then using ethanol and silicon tetrachloride as composite catalyst, it is catalyzed 4 (nitro-phenoxy of 2 trifluoromethyl 5) acetophenones and condensation reaction formation 1 occurs, 3, 5 three (4 (nitro-phenoxy of 2 trifluoromethyl 4)) benzene, finally using palladium carbon as catalyst, it is catalyzed it and reduces to obtain end-product 1, 3, 5 three (4 (the amido phenoxy group of 2 trifluoromethyl 4)) benzene, i.e. fluorine-containing Triamine monomer, the fluorine-containing Triamine monomer structure is novel, it is a kind of monomer of potential synthesis of super branched fluorinated polyimide, there are great potential research and application value, its structural formula is as follows：
Description
Technical field
The invention belongs to organic chemistry and Material Field, and in particular to a kind of fluorine-containing Triamine monomer and preparation method thereof and should
With.
Background technology
Polyimides (PI) is a series of compounds containing imide ring in molecule structure.Because its 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 come, with integrated circuit (IC) industry it is continuous
Development, heat resistance and dielectric properties to associated materials propose higher requirement, 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 can increase the distance of molecule interchain, reduce molecule due to the introducing of fluorin radical
Between active force, increase the free volume of polymer, solvent molecule can be freely spread in polymer, make 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, so as to improve its processing characteristics.Meanwhile fluorine atom has
Larger electronegativity, the conjugation of electron cloud in PI molecular structures can be cut off, therefore the color of PI products is shallower, has preferable light
Learn the transparency.Simultaneously fluorine atom there is preferable hydrophobicity and relatively low mole of polarizability so that the hydroscopicity of PI products and
Dielectric constant reduces.So these excellent performances cause fluorine-containing PI all to obtain widely should in microelectronic various aspects
With.
Design, synthesis and the development of new PI materials is realized based on new polymerized monomer, and PI performance is very
The property of polymerized monomer is depended in big degree, it is also such for fluorine-containing PI.List of the synthesis with some special natures
Body, such as with photovoltaic reaction, the monomer of heat reactivity group, and assign PI materials corresponding particularity by its polymerization
Can, its property is had traditional insoluble not molten and is difficult to processing and forming and develops into solvable fusible, easy-formation, easily use
Feature, simplify its using technique be always PI research in focus.It is in current functionalization PI researchs on fluorine-containing PI research
One of focus the most noticeable.The special physicochemical properties of fluorine atom impart many unique performances of PI, and these are excellent
Good performance has greatly widened PI application field, and it is shown what is extremely protruded in each application field
Performance.Current fluorine-containing dianhydride, diamine monomer, the species of Triamine monomer are relatively fewer, and industrialized monomeric species just more have
Limit, less monomeric species largely hinder fluorine-containing PI application, it has also become its bottleneck problem developed.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of fluorine-containing Triamine monomer and its preparation method and application, increase
The species of available fluorine-containing Triamine monomer, so as to promote fluorine-containing PI research and development.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of fluorine-containing Triamine monomer is provided, its structural formula is such as
Shown in lower：
The present invention also provides a kind of method for preparing above-mentioned fluorine-containing Triamine monomer, and it comprises the following steps：
The synthesis of S1.4- (2- trifluoromethyl -5- nitro-phenoxies)-acetophenone:Under nitrogen atmosphere, by 4- hydroxy benzenes second
Ketone and potassium carbonate mix with appropriate organic solvent, and condensing reflux simultaneously more than magnetic agitation 3h obtains 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, add toward the mixed liquor is interior
Enter the chloro- 5- nitros-benzotrifluorides of 2- of molal quantity identical with the 4-hydroxyacetophenone, be warming up to 120-125 DEG C, stirring reaction
More than 12h, 60-65 DEG C is naturally cooled to, the mixed solution obtained after reaction is mixed with the ethanol in proper amount aqueous solution, produce yellow
Precipitation, filtering, deionized water washing, ethyl alcohol recrystallization, obtains 4- (2- trifluoromethyl -5- nitro-phenoxies)-acetophenone, specific anti-
Answer equation as follows：
The synthesis of S2.1,3,5- tri- (4- (2- trifluoromethyl-4-nitrophenoxies)) benzene：4- (2- trifluoros prepared by S1
Methyl-5-nitro phenoxy group)-acetophenone is dispersed in ethanol in proper amount (EtOH) to obtain dispersion liquid, it is supreme that appropriate silicon tetrachloride is added dropwise
State in dispersion liquid and quickly stir, react more than 14h after being added dropwise at normal temperatures and obtain mixed liquor, deionized water is added dropwise to mixing
Liquid simultaneously stirs and makes its interior silicon tetrachloride (TCS) complete hydrolysis, reuse sodium hydroxide solution adjust it is mixed after the completion of above-mentioned hydrolysis
Liquid is closed to neutrality, has precipitation to produce in mixed liquor, filtering, washing, dry powder, by obtained powder in ethanol water
Dissolve by heating and condensing reflux purifies, pale yellow powder is filtered to obtain after cooling, is tied again using ethanol and dichloromethane mixed solvent
Crystalline substance, obtains 1,3,5- tri- (4- (2- trifluoromethyl-4-nitrophenoxies)) benzene, and ethanol (EtOH) and silicon tetrachloride (TCS) are compound
Catalyst, the aryl methyl ketone in fcc raw material are condensed to form phenyl ring, and specific reaction equation is as follows：
The synthesis of S3.1,3,5- tri- (4- (2- trifluoromethyl -4- amidos phenoxy group)) benzene:Under nitrogen atmosphere, by S2 systems
Standby (4- (2- the trifluoromethyl-4-nitrophenoxies)) benzene of 1,3,5- tri- is well-dispersed in appropriate absolute ethyl alcohol with catalyst palladium carbon
In dispersion liquid, be heated to 80-85 DEG C of condensing reflux, hydrazine hydrate is added dropwise into dispersion liquid in constant speed, is added dropwise to the hydration of dispersion liquid
The ratio of (4- (2- the trifluoromethyl-4-nitrophenoxies)) benzene of 1,3,5- tri- and absolute ethyl alcohol in hydrazine and dispersion liquid is 20mL:
10-15mmol：90-120mL, after being added dropwise, continue more than condensing reflux 12h, filter while hot, filtrate pours into deionized water
In, there is white precipitate generation, filtering, washing, drying, obtain yellow powder, the as fluorine-containing (4- (2- tri- of Triamine monomer 1,3,5- tri-
Methyl fluoride -4- amidos phenoxy group)) benzene, specific reaction equation is as follows：
On the basis of above-mentioned preparation method, the present invention further can also be embodied or optimized to it, specifically
Content is as follows：
Preferably, the organic solvent described in step S1 is high boiling organic solvent, preferably in DMAC, NMP and DMF
Any, the usage ratio of the organic solvent and the 4-hydroxyacetophenone is 80mL:10mmol.
Specifically, the volume ratio of ethanol and water is 1 in ethanol water described in step S1：9.
Preferably, the usage ratio of (2- trifluoromethyl -5- the nitro-phenoxies)-acetophenones of 4- described in step S2 and ethanol
For 50mmol:40-50mL, the volume ratio of the silicon tetrachloride and ethanol is 14:40-50.
Preferably, the volume fraction for the ethanol water used when condensing reflux purifies in step S2 is 95%, cold
The temperature of the ethanol water is 80 DEG C during solidifying backflow.
Specifically, the mass fraction of sodium hydroxide solution described in step S2 is 10-15%.
Preferably, the volume ratio of ethanol described in step S2 and dichloromethane mixed solvent is 100：1.
Preferably, (4- (2- trifluoromethyl-4-nitrophenoxies)) benzene and catalyst palladium carbon 1,3,5- tri- in step S3
Usage ratio is 10mmol:0.6g, the catalyst palladium carbon are 5% palladium carbon, wherein 5% refer to palladium-carbon catalyst it is effective into
Part content.
Application of the fluorine-containing Triamine monomer in terms of super-branched polyimide synthesis is also claimed in the present invention.
Fluorine-containing Triamine monomer provided by the invention is a kind of new Triamine monomer being not present in the prior art, overcomes mesh
Preceding fluorine-containing dianhydride, diamine monomer, the species of Triamine monomer are relatively fewer so that research and development as fluorinated polyimide
Affected deficiency.It is related to substitution, condensation and reduction reaction in preparation method provided by the invention, is normal in organic synthesis
With technology and reaction condition it is gentle, specially first using 4-hydroxyacetophenone and the chloro- 5- nitros-benzotrifluorides of 2- as raw material, warp
Substitution reaction forms 4- (2- trifluoromethyl -5- nitro-phenoxies)-acetophenone, then using ethanol and silicon tetrachloride as composite catalyzing
Agent, catalysis 4- (2- trifluoromethyl -5- nitro-phenoxies)-acetophenone occur condensation reaction and form 1,3,5- tri- (4- (2- fluoroforms
Base -4-nitrophenoxy)) benzene, finally using palladium carbon as catalyst, it is catalyzed it and reduces to obtain (4- (the 2- fluoroforms of end-product 1,3,5- tri-
Base -4- amidos phenoxy group)) benzene, i.e., fluorine-containing Triamine monomer, Triamine monomer structure provided by the invention is novel, is a kind of potential
The monomer of synthesis of super branched fluorinated polyimide, there are great potential research and application value.
Brief description of the drawings
Fig. 1 is infrared absorpting light spectra, and a, b and c are respectively p prepared by embodiment 1 in figure, p-FNPAP, FTNPOPB and
FTAPOPB infrared absorpting light spectra；
The p that Fig. 2 is prepared for the embodiment of the present invention 1, p-FNPAP nucleus magnetic hydrogen spectrum figure；
Fig. 3 is FTNPOPB prepared by the embodiment of the present invention 1 nucleus magnetic hydrogen spectrum figure；
Fig. 4 is FTAPOPB prepared by the embodiment of the present invention 1 nucleus magnetic hydrogen spectrum figure.
Embodiment
The principle and feature of the present invention are described below in conjunction with drawings and the specific embodiments, example is served only for solving
The present invention is released, is not intended to limit the scope of the present invention.
The method that the present invention uses is not conventional method as specified otherwise, and medicine used in 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-phenoxies)-acetophenone (p, p-FNPAP)：Under nitrogen atmosphere,
0.1mol 4-hydroxyacetophenones and 0.125mol potassium carbonate are added in 250mL three-necked flasks, and it is abundant to add 80mL DMAC
Mixing, mixture condensing reflux under the conditions of 120 DEG C, magnetic agitation 3h obtain mixed liquor.Then 60 DEG C are naturally cooled to, toward mixing
The chloro- 5- nitros-benzotrifluorides of 0.1mol 2- are added in solution, are continuously heating to 120 DEG C, 60 are naturally cooled to after reacting 12h
DEG C, mixed solution is imported into 80mL alcohol-water mixtures, wherein the ratio of ethanol and water is 1:9, there are yellow mercury oxide generation, mistake
It is multiple with deionized water rinsing after filter, obtained product is recrystallized in ethanol, produces p, p-FNPAP, its infared spectrum is such as
In Fig. 1 shown in a, nucleus magnetic hydrogen spectrum it is as shown in Figure 2.
The synthesis (FTNPOPB) of S2.1,3,5- tri- (4- (2- trifluoromethyl-4-nitrophenoxies)) benzene：In tri- mouthfuls of 250mL
In flask, by the p of 50mmol steps S1 preparations, p-FNPAP is distributed in 40mL ethanol.Tail gas absorption is put up with dropping funel to fill
Postpone, 14mL silicon tetrachlorides (TCS) are injected into constant pressure funnel with syringe, are slowly at the uniform velocity added drop-wise to mixed solution
In, and quick magnetic agitation.After being added dropwise 14h is reacted under normal temperature condition.Then instilled several times from the top of condenser pipe
(preventing that hydrolysis is excessively violent) about 100mL deionized waters make silicon tetrachloride complete hydrolysis, after continuing stirring 30 minutes, slowly
The pH for the sodium hydroxide solution regulation solution that mass fraction is 10% is added to neutrality, obtains wine-colored mixed solution, finally
Filtration washing it is dry powder, by obtained powder, 80 DEG C of condensing refluxes purify 30 minutes in 95% ethanol, are taken out after cooling
Filter obtains pale yellow powder, and (volume ratio of ethanol and dichloromethane is 100 in ethanol and dichloromethane mixed solvent：1) in
Recrystallization, product is FTNPOPB, and its infared spectrum is as shown in b in Fig. 1, nucleus magnetic hydrogen spectrum is as shown in Figure 3.
The synthesis (FTAPOPB) of S3.1,3,5- tri- (4- (2- trifluoromethyl -4- amidos phenoxy group)) benzene:In nitrogen atmosphere
Under, FTAPOPB the and 0.6g palladium carbons (Pd/C, 5%) for preparing 0.01mol steps S2 in 250mL three-necked flasks are fully dispersed
In 100mL absolute ethyl alcohols, 80 DEG C of condensing refluxes are heated to, then 20mL hydrazine hydrate is added dropwise 2 small with dropping funel constant speed
When, then proceed to condensing reflux.After 12 hours, mixture is filtered while hot, and filtrate is poured into 800mL deionized waters
In, there is white flock precipitate generation, then filter, wash, drying, it is FTAPOPB to obtain flaxen powder, namely fluorine-containing three
Amine monomers, its infared spectrum is as shown in c in Fig. 1, nucleus magnetic hydrogen spectrum is as shown in Figure 4.
It can be seen in fig. 2 that compared with curve a and b, curve c is in 3458cm-1And 3387cm-1Place and 3223cm-1Place goes out
- NH on phenyl ring is showed2Characteristic absorption peak, 1036cm-1Be in 841cm-1 on curve a, b and c all occur respectively C-F and
C-N characteristic absorption peak, the upper 1350cm of curve a, b-1Locate as-NO2Characteristic absorption peak, be-CH at 14333Characteristic absorption
Peak, the vibration absorption peak for being C=O at 1688cm-1 on curve a, therefore the red spectral absorption curve in Fig. 2 shows, fluorine-containing triamine
FTAPOPB is successfully synthesized.
Fig. 2, Fig. 3 and Fig. 4 are p respectively, and p-FNPAP, FTNPOPB and FTAPOPB nucleus magnetic hydrogen spectrum figure can from figure
Go out, each peak is obtained for ownership in corresponding compound, and occurs without any miscellaneous peak, and it is further demonstrated that, is contained
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-phenoxies)-acetophenone (p, p-FNPAP)：Under nitrogen atmosphere,
0.1mol 4-hydroxyacetophenones and 0.110mol potassium carbonate are added in 250mL three-necked flasks, and it is abundant to add 70mL DMAC
Mixing, mixture condensing reflux under the conditions of 123 DEG C, magnetic agitation 3h obtain mixed liquor.Then 63 DEG C are naturally cooled to, toward mixing
The chloro- 5- nitros-benzotrifluorides of 0.1mol 2- are added in solution, are continuously heating to 123 DEG C, 63 are naturally cooled to after reacting 12h
DEG C, mixed solution is imported into 70mL alcohol-water mixtures, wherein the ratio of ethanol and water is 1:8, there are yellow mercury oxide generation, mistake
It is multiple with deionized water rinsing after filter, obtained product is recrystallized in ethanol, produces p, p-FNPAP.
The synthesis (FTNPOPB) of S2.1,3,5- tri- (4- (2- trifluoromethyl-4-nitrophenoxies)) benzene：In tri- mouthfuls of 250mL
In flask, by the p of 50mmol steps S1 preparations, p-FNPAP is distributed in 50mL ethanol.Tail gas absorption is put up with dropping funel to fill
Postpone, 14mL silicon tetrachlorides (TCS) are injected into constant pressure funnel with syringe, are slowly at the uniform velocity added drop-wise to mixed solution
In, and quick magnetic agitation.After being added dropwise 15h is reacted under normal temperature condition.Then instilled several times from the top of condenser pipe
(preventing that hydrolysis is excessively violent) about 95mL deionized waters make silicon tetrachloride complete hydrolysis, after continuing stirring 30 minutes, slowly
The pH for the sodium hydroxide solution regulation solution that mass fraction is 13% is added to neutrality, obtains wine-colored mixed solution, finally
Filtration washing it is dry powder, by obtained powder, 80 DEG C of condensing refluxes purify 30 minutes in 95% ethanol, are taken out after cooling
Filter obtains pale yellow powder, and (volume ratio of ethanol and dichloromethane is 100 in ethanol and dichloromethane mixed solvent：1) in
Recrystallization, product is FTNPOPB.
The synthesis (FTAPOPB) of S3.1,3,5- tri- (4- (2- trifluoromethyl -4- amidos phenoxy group)) benzene:In nitrogen atmosphere
Under, FTAPOPB the and 0.6g palladium carbons (Pd/C, 5%) for preparing 0.01mol steps S2 in 250mL three-necked flasks are fully dispersed
In 90mL absolute ethyl alcohols, 80 DEG C of condensing refluxes are heated to, then 20mL hydrazine hydrate is added dropwise 2 small with dropping funel constant speed
When, then proceed to condensing reflux.Mixture is filtered while hot after 12h, and filtrate is poured into 800mL deionized waters, is had white
Color flocculent deposit produces, and then filters, washes, drying, it is FTAPOPB to obtain flaxen powder, 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-phenoxies)-acetophenone (p, p-FNPAP)：Under nitrogen atmosphere,
0.1mol 4-hydroxyacetophenones and 0.130mol potassium carbonate are added in 250mL three-necked flasks, and it is abundant to add 90mL DMAC
Mixing, mixture condensing reflux under the conditions of 125 DEG C, magnetic agitation 3h obtain mixed liquor.Then 65 DEG C are naturally cooled to, toward mixing
The chloro- 5- nitros-benzotrifluorides of 0.1mol 2- are added in solution, are continuously heating to 125 DEG C, 65 are naturally cooled to after reacting 14h
DEG C, mixed solution is imported into 100mL alcohol-water mixtures, wherein the ratio of ethanol and water is 1:9, there is yellow mercury oxide generation,
It is multiple with deionized water rinsing after filtering, obtained product is recrystallized in ethanol, produces p, p-FNPAP.
The synthesis (FTNPOPB) of S2.1,3,5- tri- (4- (2- trifluoromethyl-4-nitrophenoxies)) benzene：In tri- mouthfuls of 250mL
In flask, by the p of 50mmol steps S1 preparations, p-FNPAP is distributed in 45mL ethanol.Tail gas absorption is put up with dropping funel to fill
Postpone, 14mL silicon tetrachlorides (TCS) are injected into constant pressure funnel with syringe, are slowly at the uniform velocity added drop-wise to mixed solution
In, and quick magnetic agitation.After being added dropwise 15h is reacted under normal temperature condition.Then instilled several times from the top of condenser pipe
(preventing that hydrolysis is excessively violent) about 110mL deionized waters make silicon tetrachloride complete hydrolysis, after continuing stirring 30 minutes, slowly
The pH for the sodium hydroxide solution regulation solution that mass fraction is 15% is added to neutrality, obtains wine-colored mixed solution, finally
Filtration washing it is dry powder, by obtained powder, 80 DEG C of condensing refluxes purify 30 minutes in 95% ethanol, are taken out after cooling
Filter obtains pale yellow powder, and (volume ratio of ethanol and dichloromethane is 100 in ethanol and dichloromethane mixed solvent：1) in
Recrystallization, product is FTNPOPB.
The synthesis (FTAPOPB) of S3.1,3,5- tri- (4- (2- trifluoromethyl -4- amidos phenoxy group)) benzene:In nitrogen atmosphere
Under, FTAPOPB the and 0.8g palladium carbons (Pd/C, 5%) for preparing 0.015mol steps S2 in 250mL three-necked flasks are fully dispersed
In 120mL absolute ethyl alcohols, 80 DEG C of condensing refluxes are heated to, then 20mL hydrazine hydrate is added dropwise 2 small with dropping funel constant speed
When, then proceed to condensing reflux.After 14 hours, mixture is filtered while hot, and filtrate is poured into 1000mL deionized waters
In, there is white flock precipitate generation, then filter, wash, drying, it is FTAPOPB to obtain flaxen powder, 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-phenoxies)-acetophenone (p, p-FNPAP)：Under nitrogen atmosphere,
0.1mol 4-hydroxyacetophenones and 0.125mol potassium carbonate are added in 250mL three-necked flasks, and it is fully mixed to add 80mL NMP
Close, mixture condensing reflux under the conditions of 120 DEG C, magnetic agitation 3h obtains mixed liquor.Then 60 DEG C are naturally cooled to, it is molten toward mixing
The chloro- 5- nitros-benzotrifluorides of 0.1mol 2- are added in liquid, are continuously heating to 120 DEG C, 60 DEG C are naturally cooled to after reacting 12h,
Mixed solution is imported into 80mL alcohol-water mixtures, wherein the ratio of ethanol and water is 1:9, there is yellow mercury oxide generation, filter
It is multiple with deionized water rinsing afterwards, obtained product is recrystallized in ethanol, produces p, p-FNPAP.
The synthesis (FTNPOPB) of S2.1,3,5- tri- (4- (2- trifluoromethyl-4-nitrophenoxies)) benzene：In tri- mouthfuls of 250mL
In flask, by the p of 50mmol steps S1 preparations, p-FNPAP is distributed in 40mL ethanol.Tail gas absorption is put up with dropping funel to fill
Postpone, 14mL silicon tetrachlorides (TCS) are injected into constant pressure funnel with syringe, are slowly at the uniform velocity added drop-wise to mixed solution
In, and quick magnetic agitation.After being added dropwise 14h is reacted under normal temperature condition.Then instilled several times from the top of condenser pipe
(preventing that hydrolysis is excessively violent) about 100mL deionized waters make silicon tetrachloride complete hydrolysis, after continuing stirring 30 minutes, slowly
The pH for the sodium hydroxide solution regulation solution that mass fraction is 10% is added to neutrality, obtains wine-colored mixed solution, finally
Filtration washing it is dry powder, by obtained powder, 80 DEG C of condensing refluxes purify 30 minutes in 95% ethanol, are taken out after cooling
Filter obtains pale yellow powder, and (volume ratio of ethanol and dichloromethane is 100 in ethanol and dichloromethane mixed solvent：1) in
Recrystallization, product is FTNPOPB.
The synthesis (FTAPOPB) of S3.1,3,5- tri- (4- (2- trifluoromethyl -4- amidos phenoxy group)) benzene:In nitrogen atmosphere
Under, FTAPOPB the and 0.6g palladium carbons (Pd/C, 5%) for preparing 0.01mol steps S2 in 250mL three-necked flasks are fully dispersed
In 100mL absolute ethyl alcohols, 80 DEG C of condensing refluxes are heated to, then 20mL hydrazine hydrate is added dropwise 2 small with dropping funel constant speed
When, then proceed to condensing reflux.After 12 hours, mixture is filtered while hot, and filtrate is poured into 800mL deionized waters
In, there is white flock precipitate generation, then filter, wash, drying, it is FTAPOPB to obtain flaxen powder, 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-phenoxies)-acetophenone (p, p-FNPAP)：Under nitrogen atmosphere,
0.1mol 4-hydroxyacetophenones and 0.130mol potassium carbonate are added in 250mL three-necked flasks, and it is fully mixed to add 90mL DMF
Close, mixture condensing reflux under the conditions of 125 DEG C, magnetic agitation 3h obtains mixed liquor.Then 65 DEG C are naturally cooled to, it is molten toward mixing
The chloro- 5- nitros-benzotrifluorides of 0.1mol 2- are added in liquid, are continuously heating to 125 DEG C, 65 DEG C are naturally cooled to after reacting 14h,
Mixed solution is imported into 100mL alcohol-water mixtures, wherein the ratio of ethanol and water is 1:9, there is yellow mercury oxide generation, filter
It is multiple with deionized water rinsing afterwards, obtained product is recrystallized in ethanol, produces p, p-FNPAP.
The synthesis (FTNPOPB) of S2.1,3,5- tri- (4- (2- trifluoromethyl-4-nitrophenoxies)) benzene：In tri- mouthfuls of 250mL
In flask, by the p of 50mmol steps S1 preparations, p-FNPAP is distributed in 45mL ethanol.Tail gas absorption is put up with dropping funel to fill
Postpone, 14mL silicon tetrachlorides (TCS) are injected into constant pressure funnel with syringe, are slowly at the uniform velocity added drop-wise to mixed solution
In, and quick magnetic agitation.After being added dropwise 15h is reacted under normal temperature condition.Then instilled several times from the top of condenser pipe
(preventing that hydrolysis is excessively violent) about 110mL deionized waters make silicon tetrachloride complete hydrolysis, after continuing stirring 30 minutes, slowly
The pH for the sodium hydroxide solution regulation solution that mass fraction is 15% is added to neutrality, obtains wine-colored mixed solution, finally
Filtration washing it is dry powder, by obtained powder, 80 DEG C of condensing refluxes purify 30 minutes in 95% ethanol, are taken out after cooling
Filter obtains pale yellow powder, and (volume ratio of ethanol and dichloromethane is 100 in ethanol and dichloromethane mixed solvent：1) in
Recrystallization, product is FTNPOPB.
The synthesis (FTAPOPB) of S3.1,3,5- tri- (4- (2- trifluoromethyl -4- amidos phenoxy group)) benzene:In nitrogen atmosphere
Under, FTAPOPB the and 0.8g palladium carbons (Pd/C, 5%) for preparing 0.015mol steps S2 in 250mL three-necked flasks are fully dispersed
In 120mL absolute ethyl alcohols, 80 DEG C of condensing refluxes are heated to, then 20mL hydrazine hydrate is added dropwise 2 small with dropping funel constant speed
When, then proceed to condensing reflux.After 14 hours, mixture is filtered while hot, and filtrate is poured into 1000mL deionized waters
In, there is white flock precipitate generation, then filter, wash, drying, it is FTAPOPB to obtain flaxen powder, namely fluorine-containing three
Amine monomers.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (10)
1. a kind of fluorine-containing Triamine monomer, it is characterised in that structural formula is as follows：
2. a kind of preparation method of fluorine-containing Triamine monomer as claimed in claim 1, it is characterised in that comprise the following steps：
The synthesis of S1.4- (2- trifluoromethyl -5- nitro-phenoxies)-acetophenone:Under nitrogen atmosphere, by 4-hydroxyacetophenone and
Potassium carbonate mixes with appropriate organic solvent, and condensing reflux simultaneously more than magnetic agitation 3h obtains mixed liquor, 4- hydroxyls 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 the mixed liquor with
The chloro- 5- nitros-benzotrifluorides of 2- of the identical molal quantity of the 4-hydroxyacetophenone, are warming up to 120-125 DEG C, stirring reaction 12h
More than, 60-65 DEG C is naturally cooled to, the mixed solution obtained after reaction is mixed with the ethanol in proper amount aqueous solution, yellow is produced and sinks
Form sediment, filtering, deionized water washing, ethyl alcohol recrystallization, obtain 4- (2- trifluoromethyl -5- nitro-phenoxies)-acetophenone, specific reaction
Equation is as follows：
The synthesis of S2.1,3,5- tri- (4- (2- trifluoromethyl-4-nitrophenoxies)) benzene：By S1 prepare 4- (2- trifluoromethyls-
5- nitro-phenoxies)-acetophenone is dispersed in ethanol in proper amount to obtain dispersion liquid, appropriate silicon tetrachloride is added dropwise into above-mentioned dispersion liquid simultaneously
Quick stirring, more than 14h is reacted after being added dropwise at normal temperatures and obtains mixed liquor, deionized water to mixed liquor and stirring, which is added dropwise, makes it
Interior silicon tetrachloride complete hydrolysis, reuse sodium hydroxide solution and adjust mixed liquor after the completion of above-mentioned hydrolysis to neutrality, mixed liquor
In there is precipitation to produce, filtering, washing, dry powder, obtained powder is dissolved by heating in ethanol water and condensed back
Stream purification, filters to obtain pale yellow powder after cooling, recrystallized using ethanol and dichloromethane mixed solvent, obtain 1,3,5- tri- (4-
(2- trifluoromethyl-4-nitrophenoxies)) benzene, specific reaction equation is as follows：
The synthesis of S3.1,3,5- tri- (4- (2- trifluoromethyl -4- amidos phenoxy group)) benzene:Under nitrogen atmosphere, prepared by S2
(4- (2- the trifluoromethyl-4-nitrophenoxies)) benzene of 1,3,5- tri- is well-dispersed in appropriate absolute ethyl alcohol with catalyst palladium carbon and obtained
Dispersion liquid, is heated to 80-85 DEG C of condensing reflux, and hydrazine hydrate is added dropwise into dispersion liquid in constant speed, be added dropwise to the hydrazine hydrate of dispersion liquid with
The ratio of (4- (2- the trifluoromethyl-4-nitrophenoxies)) benzene of 1,3,5- tri- and absolute ethyl alcohol in dispersion liquid is 20mL:10-
15mmol：90-120mL, after being added dropwise, continue more than condensing reflux 12h, filter while hot, filtrate is poured into deionized water, is had
White precipitate produces, and filtering, washing, drying, obtains yellow powder, as fluorine-containing (4- (the 2- fluoroforms of Triamine monomer 1,3,5- tri-
Base -4- amidos phenoxy group)) benzene, specific 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 of DMAC, NMP and DMF, and the usage ratio of the organic solvent and the 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
The volume ratio of ethanol and water is 1 in ethanol water：9.
A kind of 5. preparation method of fluorine-containing Triamine monomer according to claim 2, it is characterised in that 4- described in step S2
The usage ratio of (2- trifluoromethyl -5- nitro-phenoxies)-acetophenone and ethanol is 50mmol:40-50mL, the 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 condensed back in step S2
The volume fraction of the ethanol water used during stream purification is 95%, and the temperature of the ethanol water is during condensing reflux
80℃。
A kind of 7. preparation method 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 with the volume ratio of dichloromethane in the mixed solvent ethanol and dichloromethane：1.
9. the preparation method of a kind of fluorine-containing Triamine monomer according to claim 2, it is characterised in that 1,3,5- in step S3
Three (4- (2- trifluoromethyl-4-nitrophenoxies)) benzene and the usage ratio of catalyst palladium carbon are 10mmol:0.6g, the catalysis
Agent palladium carbon is 5% palladium carbon.
10. a kind of application of fluorine-containing Triamine monomer as claimed in claim 1, it is characterised in that for super-branched polyimide
Synthesis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610416353.9A CN106083612B (en) | 2016-06-14 | 2016-06-14 | A kind of fluorine-containing Triamine monomer and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610416353.9A CN106083612B (en) | 2016-06-14 | 2016-06-14 | A kind of fluorine-containing Triamine monomer and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106083612A CN106083612A (en) | 2016-11-09 |
| CN106083612B true CN106083612B (en) | 2018-02-23 |
Family
ID=57846702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610416353.9A Expired - Fee Related CN106083612B (en) | 2016-06-14 | 2016-06-14 | A kind of fluorine-containing Triamine monomer and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106083612B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2016
- 2016-06-14 CN CN201610416353.9A patent/CN106083612B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| Synthesis and characterization of thermally stable, hydrophobic hyperbranched polyimides derived from a novel triamine;Li Qing等;《High Performance Polymers》;20151231;第27卷(第4期);第428页左栏第2段至右栏第2段，第429页Figure I * |
| 含三(4-氨基苯基)苯的超支化聚酰亚胺的合成及表征;宋佳等;《化学与生物工程》;20111231;第28卷(第3期);第53-56页 * |
| 新型含氟超支化聚合物的合成及性能;高鸿等;《2 0 0 7 年全国高分子学术论文报告会》;20071001;第B-P-031页第1段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106083612A (en) | 2016-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104447869B (en) | It is a kind of containing DOPO and the asymmetric bismaleimide of molecular structure, preparation method and in the application prepared in compound resin | |
| Agag et al. | Synthesis and characterization of benzoxazine resin-SiO2 hybrids by sol-gel process: The role of benzoxazine-functional silane coupling agent | |
| CN105198916B (en) | Functionalization double tower type polyhedral oligomeric silsesquioxane and preparation method thereof | |
| CN102504252B (en) | Amino phenoxy phthalonitrile pre-polymer, condensate and preparation method and application thereof | |
| CN110951076B (en) | Hyperbranched polyetherimide and preparation and application thereof | |
| CN114380947B (en) | Halogen-free phosphorus-free flame-retardant shape memory bismaleimide resin and preparation method thereof | |
| CN105254661A (en) | Cage-shaped oligomerization polyhedral silsesquioxane with eight phenolic hydroxyl groups and preparation method thereof | |
| CN103848993A (en) | Preparation method for hollow TiO2 microsphere surface grafted polyimide composite particles | |
| CN102816327A (en) | Polyimides containing ditrifluoromethyl group and unsymmetrical structure and preparation method thereof | |
| CN105400196B (en) | A kind of method for improving octaphenyl cage-type silsesquioxane dispersive property in polyimide base material | |
| CN106083612B (en) | A kind of fluorine-containing Triamine monomer and its preparation method and application | |
| CN101775138B (en) | Novel polytriazoles imide resin and preparation method thereof | |
| CN104744274A (en) | 2,2'-diaryl-4,4'-diaminodiphenyl ether compound as well as preparation method and applications thereof | |
| CN105175218B (en) | A kind of preparation method of dichloro- paraxylene ring disome | |
| CN104926749A (en) | Benzoxazine monomer comprising vinyl benzene structure, and application and preparation method of benzoxazine monomer | |
| CN105384680A (en) | 9-(2'-aryl benzyl)-3, 6-diamino carbazole compound and preparation method thereof | |
| Sheng et al. | Rare earth centered hybrid materials: Tb 3+ covalently bonded with La 3+, Gd 3+, Y 3+ through sulfonamide bridge and luminescence enhancement | |
| CN111499869A (en) | Fluorinated semi-cage silsesquioxane and preparation method and application thereof | |
| CN106046363B (en) | One kind is containing fluorene structured high dissolubility Nomex of tetramethoxy and preparation method thereof | |
| CN103058917B (en) | Difluoro diketone monomer containing dipyridyl, preparation method of difluoro diketone monomer, and application of difluoro diketone monomer in synthesis of dipyridyl block polyaryletherketone polymer | |
| CN102604101A (en) | Synthesis method for phenyl organosilicon copolymer with uniformly distributed phenyl units | |
| CN101723910B (en) | Synthesis method of 1,3,5-tri-substituted perhydro-s-triazine | |
| JP2002097282A (en) | Method of producing polyamide resin fine powder | |
| CN109970959B (en) | Polycinnoline electrolyte compound and preparation method and application thereof | |
| CN107674171A (en) | A kind of benzoxazine colophony for introducing propargyl and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180223 Termination date: 20190614 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |