CN107325276A - Polymer, preparation method and application with both hole and electron migration - Google Patents
Polymer, preparation method and application with both hole and electron migration Download PDFInfo
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- CN107325276A CN107325276A CN201710609189.8A CN201710609189A CN107325276A CN 107325276 A CN107325276 A CN 107325276A CN 201710609189 A CN201710609189 A CN 201710609189A CN 107325276 A CN107325276 A CN 107325276A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
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- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
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Abstract
The invention provides a kind of polymer migrated with both hole and electron, preparation method and application, the triphen amine monomers of class side base containing carbazole are synthesized, monomer two ends have the hydroxyl available for condensation reaction, then, it is polymerize by the hydroxyl on the monomer and 4,4' difluoro benzophenone or 4,4' difluorodiphenyl sulfone, prepare using carbazole ring structure as side chain, triphenylamine and benzophenone polymer or triphenylamine and the polymer that two lauseto neu polymer are main chain；Find that carbazole ring structure is that the triphenylamine of side chain is suitable with the number-average molecular weight of two lauseto neu polymer with the triphenylamine that benzophenone polymer and carbazole ring structure are side chain by gel chromatography test, carbazole ring structure has wider molecular weight distribution for the triphenylamine of side chain with benzophenone polymer, tested and found by dissolubility, the heat decomposition curve of polymer shows that carbazole ring structure has more excellent heat endurance for the triphenylamine of side chain with benzophenone polymer.
Description
Technical field
The present invention relates to polymer arts, more particularly to a kind of polymer migrated with both hole and electron, preparation method and
Using.
Background technology
Compared with inorganic photoelectric material and small molecule organic photoelectric material, polymer photoelectric material has such as film forming
The many merits such as property and processability is fabulous, high mechanical strength, color be can easily be accommodated, stability is got well, as our times various countries
One of Some Questions To Be Researched.Within the quite a long period from now on, Optoelectronic polymers material will all possess before extremely wide application
Scape.
Polyarylether class special engineering plastics have heat-resisting quantity concurrently, and chemical stability is good, the advantages of mechanical performance is outstanding.Such as
Group with photoelectric functional type can be introduced into the polyarylether of excellent combination property by fruit, once it is made with photoelectric functional
High polymer material device, its life-span and the tolerance to extreme condition will have qualitative leap.In addition, excellent mechanical performance meaning
Taste the fiber or film that polymer is made and not only possesses good photoelectric property, can also there is very excellent mechanical strength.
In recent years, due to problem of environmental pollution and lack of energy problem, three based on solar energy, Hydrogen Energy and electric energy are big clear
The clean energy replaces the leading position in the energy such as the petroleum base energy and coal step by step, therefore exploitation is new, can send out
Light, pliability is good, stable, cheap, electroactive material be increasingly becoming the research direction of countries in the world scientists.
In view of gripping polymer altogether, its own possesses π-electronics, and such photoelectric type high polymer material is increasingly becoming electric application field
Substitute, and the visual field of people is appeared in step by step.Scientists are obtained with very high conductivity by acetylene polymerization first
Polyacetylene material, the conjugated structure of polyacetylene material causes the material has in UV-visible range one very strong
Absworption peak.Although scientists first passage polymerization is prepared for conductive polyacetylene material, the material is difficult
Melt-processed is carried out to be dissolved in Conventional solvents, and be difficult to heating, while material is also very unstable under air ambient, it is difficult to enter
Row machine-shaping, can not also be applied to the high-tech areas such as electronic device at present.Then, in the 1980s, various countries
Chemical field expert has carried out the related research of substantial amounts of aromatic polymer, and polyacetylene dissolving is solved by introducing phenyl ring class formation
Property it is poor, be difficult to stability it is poor the problem of.
Polyarylether is a class aromatic thermoplastic special engineering plastics, with good heat resistance, chemical stability, resistance to tired
The performances such as labor, radiation hardness, anti-flammability and dimensional stability, have been widely used in electric, Aero-Space and automobile work
In the various fields such as industry.
And polyarylether is to pass through oxygen bridge with phenylene ring（Ehter bond）And carbonyl（Ketone）Or sulfuryl（Sulfone）One be formed by connecting
The special engineered material of class excellent performance, and obtained extensively in fields such as Aero-Space, electronic apparatus, communications and transportation
Concern.Rigid benzene ring structure is shown as due to having in polyarylether molecule, therefore imparts the excellent high temperature resistant of polyarylether
Property, high-modulus, electrical insulation capability, radiation hardness and resistance toization corrosive nature etc..On the other hand, the ether in polyarylether molecular structure
Key assigns the material with certain flexibility again, therefore can be molded by the processing method of traditional thermoplastic engineering plastic
Processing.In view of the excellent physical-chemical performance of polyarylether, if can will have photoelectric functional monomer to be incorporated into polyarylether skeleton
In, prepared polymeric material can be not only assigned with special photoelectric properties, can also make it have excellent physics-change
Performance etc. is learned, the life-span of boost device and the tolerance to extreme condition etc., are to prepare high added value organic photoelectric macromolecule
One effective route of material.
New material dissolubility especially of the prior art is poor, comes larger tired to process bands such as dissolving processing, molds
Difficulty, and film forming is difficult, is easily come off in organic solvent after film forming.Therefore, prior art needs further improvement
And development.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of polymerization migrated with both hole and electron
Thing, preparation method and application, to provide a kind of new material.
In order to solve the above technical problems, the present invention program includes：
A kind of polymer migrated with both hole and electron, wherein, the polymer includes the triphenylamine that carbazole ring structure is side chain
It is the triphenylamine and two lauseto neu polymer of side chain with benzophenone polymer or carbazole ring structure, carbazole ring structure is side chain
The structural formula of triphenylamine and benzophenone polymer is：
Wherein, n is the positive integer more than 1；
Carbazole ring structure is that the structural formula of the triphenylamine and two lauseto neu polymer of side chain is：
Wherein, n is the positive integer more than 1.
A kind of method for preparing the polymer, it comprises the following steps：
The step of triphen amine monomers including preparing the side base containing carbazole, there are triphen amine monomers two ends and can be used for condensation anti-
The hydroxyl answered；
Including being carried out by the hydroxyl on triphen amine monomers and 4,4'- difluoro benzophenones or 4,4'- difluorodiphenyl sulfones monomer
Polymerization, prepares triphenylamine of the triphenylamine and benzophenone polymer or carbazole ring structure using carbazole ring structure as side chain for side chain
With two lauseto neu polymer be main chain polymer the step of.
Described method, wherein, prepare the side base containing carbazole triphen amine monomers the step of include：
A, by carbazole and p-fluoronitrobenzene under the catalytic action of Anhydrous potassium carbonate, enter in solvent DMF
Row is stirred at reflux fully reaction 8 hours, and room temperature is down to after completion of the reaction, is subsequently poured into water, glassy yellow product is obtained（1）；
B, by resulting glassy yellow product（1）The respective reaction device equipped with reflux condensing tube is added with carbon loaded palladium catalyst
In, add ethanol and carry out return stirring, then addition hydrazine hydrate reduction agent, solution is grass green, with the carry out solution of reaction
Gradually change to bottle green, be finally changed into black completely, fully after 3 hours of reaction, reaction suspension is subjected to hot suction filtration, returned
Carbon loaded palladium catalyst is received, filtrate sealing, which is positioned in refrigerator, to be separated out, and solution is put into single port bottle and is spin-dried for, next day
Ethyl acetate dissolving is added, obtained solution is filtered with diatomite, and product is obtained after finally filtrate is spin-dried for（2）；
C, by product（2）, Anhydrous potassium carbonate, p-fluoronitrobenzene, dimethyl sulfoxide (DMSO), toluene add with water knockout drum respective reaction
In device, 130 DEG C are warming up to, reaction system is the suspension of yellow；Start backflow after half an hour, it is suspended that reaction system is changed into brown
Liquid；After one hour, corresponding container inwall has into salt yellow solid wall built-up；Then reaction system is warming up to 170 DEG C, releases and divide
Toluene in hydrophone, when the toluene in water knockout drum is full of, releases toluene, the toluene solution being repeated several times in cleared water knockout drum is straight
Steamed into water knockout drum there is no toluene, confirm that reaction is abundant by thin-layer chromatography, then stop reaction, reaction solution is added into water
In solution, filtered with separatory funnel and hot suction filtration is carried out after water, obtained product（3）It is put into baking oven and is dried under the conditions of 120 DEG C
It is stand-by；
D, to correspondence reactor in be separately added into product（3）, carbon loaded palladium catalyst and appropriate alcohol solvent, after charging is finished
Stirring is begun to warm up, solution is in yellowish-brown, starts backflow after reaction half an hour, is slowly added to hydrazine hydrate, molten after half an hour
Liquid is in brown color, continues to react after two hours, and observation solution is changed into black, determines that heat is carried out after reaction completely takes out by a plate
Carbon loaded palladium catalyst is reclaimed in filter, and filtrate sealing is put into refrigerator and separated out；Solution is put into single port bottle and is spin-dried for；
And dissolved with ethyl acetate, obtained solution is filtered with diatomite, and is spin-dried for, and obtains product（4）, and by product（4）It is positioned over
It is dried in 60 DEG C of vacuum drying oven；
E, under nitrogen protection by product（4）Ethanol is dissolved in, adds and 8 hours is heated to reflux after parahydroxyben-zaldehyde, stops adding
Heat, keeps ventilation to place a night, and 300ml methanol is added after 24 hours, and filtering, filter residue washes three times with methanol and in vacuum drying oven
80 DEG C of drying, obtain product（5）, i.e., the triphen amine monomers of the described side base containing carbazole；
Described method, wherein, prepare the triphenylamine and benzophenone polymer or carbazole ring knot using carbazole ring structure as side chain
Structure is that the triphenylamine of side chain includes the step of with two lauseto neu polymer being the polymer of main chain：
Trigger the triphen amine monomers and 4,4'- difluoro benzophenones of the above-mentioned side base containing carbazole under the catalysis of potassium carbonate catalyst
Or 4,4'- difluorodiphenyl sulfone carry out condensation polymerization reaction, reaction dissolvent uses DMA；
The mol ratio of the triphen amine monomers of the above-mentioned side base containing carbazole and 4,4'- difluoro benzophenones or 4,4'- difluorodiphenyl sulfones
For 1：1, the mol ratio of the triphen amine monomers of catalyst potassium carbonate and the side base containing carbazole is 3：1, in 145 DEG C, nitrogen ceiling
Reacted 24 hours under part, then raise temperature to 180 DEG C and continue to react 24 hours；After reaction terminates, product is poured into substantial amounts of first
Settled out in alcohol, and the solid of gained is stripped with methanol, chloroform successively, finally mutually gone chloroform
Remove, obtain triphenylamine and benzophenone polymer that carbazole ring structure is side chain or the triphenylamine and two that carbazole ring structure is side chain
Lauseto neu polymer.
A kind of application of the polymer, wherein, polymer as claimed in claim 1 is prepared as hole-injecting material.
A kind of application of the polymer, wherein, polymer as claimed in claim 1 is prepared as electric transmission section bar
Material.
The invention provides a kind of polymer migrated with both hole and electron, preparation method and application, a class is synthesized and has contained
The triphen amine monomers of carbazole side base, triphen amine monomers two ends have the hydroxyl available for condensation reaction, then, pass through triphen
Hydroxyl on amine monomers is polymerize with 4,4'- difluoro benzophenones or 4,4'- difluorodiphenyl sulfone respectively, prepared with
Carbazole ring structure is side chain, and triphenylamine is polymerizeing for main chain with two lauseto neu polymer with benzophenone polymer or triphenylamine
Thing；Find that carbazole ring structure is the triphenylamine of side chain and benzophenone polymer and carbazole ring structure are by gel chromatography test
The triphenylamine of side chain is suitable with the number-average molecular weight of two lauseto neu polymer, and carbazole ring structure is the triphenylamine and hexichol first of side chain
Ketone polymer has wider molecular weight distribution；Tested and found by dissolubility, in addition to toluene, the carbazole ring knot obtained
The triphenylamine and two lauseto neu polymer that structure is the triphenylamine and benzophenone polymer of side chain and carbazole ring structure is side chain exist
Solvent dioxane, chloroform, tetrahydrofuran, 1-METHYLPYRROLIDONE, N,N-dimethylformamide, the N, N- dimethyl second of routine
Extraordinary dissolubility is respectively provided with acid amides and dimethyl sulfoxide (DMSO)；The heat decomposition curve of polymer is shown, in initial decomposition（<~
350℃）, carbazole ring structure has more excellent heat endurance for the triphenylamine of side chain with benzophenone polymer, when temperature pole
Property rise when（>~350℃）, carbazole ring structure is that the triphenylamine and two lauseto neu polymer of side chain have higher thermal decomposition temperature
Degree, and with higher carbon yield.
Brief description of the drawings
Fig. 1 is monomer in the present invention1H-NMR spectrum schematic diagram；
Fig. 2 is monomer in the present invention13C-NMR spectrogram schematic diagrames；
Fig. 3 is the mass spectrogram schematic diagram of monomer in the present invention；
Fig. 4 is the polymer of the PAEK containing carbazole structure in the present invention1H-NMR spectrum；
Fig. 5 is the polymer of the polyether sulphone containing carbazole structure in the present invention1H-NMR spectrum.
Embodiment
The invention provides it is a kind of with both hole and electron migrate polymer and preparation method, for make the purpose of the present invention,
Technical scheme and effect are clearer, clear and definite, and the present invention is described in more detail below.It should be appreciated that described herein
Specific embodiment only to explain the present invention, is not intended to limit the present invention.
Include triphenylamine and benzophenone polymer of the carbazole ring structure for side chain with the polymer that both hole and electron is migrated
Or the triphenylamine and two lauseto neu polymer that carbazole ring structure is side chain, carbazole ring structure is the triphenylamine and benzophenone of side chain
The structural formula of polymer is：
Wherein, n is the positive integer more than 1；
Carbazole ring structure is that the structural formula of the triphenylamine and two lauseto neu polymer of side chain is：
Wherein, n is the positive integer more than 1.
Present invention also offers a kind of method for preparing the above-mentioned polymer migrated with both hole and electron, it includes following step
Suddenly：
The step of triphen amine monomers including preparing the side base containing carbazole, there are triphen amine monomers two ends and can be used for condensation anti-
The hydroxyl answered；
Including being carried out by the hydroxyl on triphen amine monomers and 4,4'- difluoro benzophenones or 4,4'- difluorodiphenyl sulfones monomer
Polymerization, prepares triphenylamine of the triphenylamine and benzophenone polymer or carbazole ring structure using carbazole ring structure as side chain for side chain
With two lauseto neu polymer be main chain polymer the step of.
Further, the step of triphen amine monomers for preparing the side base containing carbazole, specifically includes：
Step A：By carbazole and p-fluoronitrobenzene under the catalytic action of Anhydrous potassium carbonate, in solvent DMF
In be stirred backflow fully reaction 8 hours, room temperature is down to after completion of the reaction, is subsequently poured into water, glassy yellow product is obtained
（1）；
Step B：By resulting glassy yellow product（1）The respective reaction equipped with reflux condensing tube is added with carbon loaded palladium catalyst
In device, add ethanol and carry out return stirring, then addition hydrazine hydrate reduction agent, solution is grass green, molten with the carry out of reaction
Liquid gradually changes to bottle green, is finally changed into black completely, and fully after 3 hours of reaction, reaction suspension is carried out into hot suction filtration,
Carbon loaded palladium catalyst is reclaimed, filtrate sealing, which is positioned in refrigerator, to be separated out, and solution is put into single port bottle and is spin-dried for, secondary
Add ethyl acetate dissolving day, obtained solution is filtered with diatomite, and product is obtained after finally filtrate is spin-dried for（2）；
Step C：By product（2）, Anhydrous potassium carbonate, p-fluoronitrobenzene, dimethyl sulfoxide (DMSO), toluene add it is corresponding with water knockout drum
In reactor, 130 DEG C are warming up to, reaction system is the suspension of yellow；Start backflow after half an hour, reaction system is changed into brown
Suspension；After one hour, corresponding container inwall has into salt yellow solid wall built-up；Then reaction system is warming up to 170 DEG C, put
The toluene gone out in water knockout drum, when the toluene in water knockout drum is full of, releases toluene, the toluene being repeated several times in cleared water knockout drum is molten
Liquid confirms that reaction is abundant by thin-layer chromatography, then stops reaction until steamed in water knockout drum there is no toluene, by reaction solution plus
Enter in the aqueous solution, filtered with separatory funnel and hot suction filtration is carried out after water, obtained product（3）It is put into baking oven under the conditions of 120 DEG C
Drying is stand-by；
Step D：Product is separately added into correspondence reactor（3）, carbon loaded palladium catalyst and appropriate alcohol solvent, fed
Stirring is begun to warm up after finishing, solution is in yellowish-brown, starts backflow after reaction half an hour, is slowly added to hydrazine hydrate, half an hour
Solution is in brown color afterwards, continues to react after two hours, and observation solution is changed into black, determines to carry out after reaction completely by a plate
Hot suction filtration reclaims carbon loaded palladium catalyst, and filtrate sealing is put into refrigerator and separated out；Solution is put into correspondence reactor
It is spin-dried for；And dissolved with ethyl acetate, obtained solution is filtered with diatomite, and solution is put into single port bottle revolved
It is dry, obtain product（4）, and by product（4）It is dried in the vacuum drying oven for being positioned over 60 DEG C；
Step E：Under nitrogen protection by product（4）Ethanol is dissolved in, 8 hours is heated to reflux after adding parahydroxyben-zaldehyde, stops
Only heat, keep ventilation to place a night, 300ml methanol, filtering are added after 24 hours, filter residue is washed three times with methanol and dried in vacuum
80 DEG C of drying, obtain product in case（5）, i.e., the triphen amine monomers of the described side base containing carbazole；
The triphen amine monomers for preparing the above-mentioned side base containing carbazole are prepared to prepare above-mentioned polymer, therefore, are prepared with click
The triphenylamine and two lauseto neus that azoles ring structure is the triphenylamine and benzophenone polymer of side chain or carbazole ring structure is side chain gather
The step of compound is the polymer of main chain specifically includes：
Trigger the triphen amine monomers and 4,4'- difluoro benzophenones of the above-mentioned side base containing carbazole under the catalysis of potassium carbonate catalyst
Or 4,4'- difluorodiphenyl sulfone carry out condensation polymerization reaction, reaction dissolvent uses DMA；
The mol ratio of the triphen amine monomers of the above-mentioned side base containing carbazole and 4,4'- difluoro benzophenones or 4,4'- difluorodiphenyl sulfones
For 1：1, the mol ratio of the triphen amine monomers of catalyst potassium carbonate and the side base containing carbazole is 3：1, in 145 DEG C, nitrogen ceiling
Reacted 24 hours under part, then raise temperature to 180 DEG C and continue to react 24 hours；After reaction terminates, product is poured into substantial amounts of first
Settled out in alcohol, and the solid of gained is stripped with methanol, chloroform successively, finally mutually gone chloroform
Remove, obtain triphenylamine and benzophenone polymer that carbazole ring structure is side chain or the triphenylamine and two that carbazole ring structure is side chain
Lauseto neu polymer.
And above-mentioned polymer can also be prepared as to hole-injecting material or electron-transporting type material.
More detailed embodiment is exemplified below in order to the present invention is described in further detail to illustrate.
The process of the triphen amine monomers of the specific synthetically prepared side base containing carbazole is as follows：
The first step：
By 0.1mol or 16.72g carbazole and 0.11mol or 14.521g p-fluoronitrobenzene（）0.2mol or 27.642g it
Under the catalytic action of Anhydrous potassium carbonate, back flow reaction is stirred in 128ml DMFs 8 hours, reacted
Room temperature is down to after finishing, is subsequently poured into water, obtains glassy yellow product 1.
Second step：
By 0.1 resulting mol or 28.8g glassy yellow products（The three-necked flask of tool return duct is added with carbon loaded palladium catalyst
In, add ethanol and carry out return stirring, then addition hydrazine hydrate reduction agent, solution is grass green, with the carry out solution of reaction
Gradually change to bottle green, be finally changed into black completely.React after 3 hours, reaction suspension is subjected to hot suction filtration, reclaim carbon
Loaded palladium catalyst, filtrate sealing, which is positioned in refrigerator, to be separated out, and solution is put into single port bottle and is spin-dried for, acetic acid is added
Ethyl ester is dissolved, and obtained solution is filtered with diatomite, and product 2 is obtained after finally filtrate is spin-dried for.As infrared spectrum to obtained by
Product 2 analyzed, it can be seen that nitro is converted into amino completely, it was demonstrated that reaction is smoothed out.
3rd step：
By 0.1mol or 25.8g product 2,0.2mol or 27.8g Anhydrous potassium carbonate, 0.22mol or 31.04g to fluorine nitre
The toluene of base benzene, 227mL dimethyl sulfoxide (DMSO) and 76mL（）In the three-necked flask for adding tool water knockout drum, 130 DEG C, reaction are warming up to
System is the suspension of yellow.Start backflow after half an hour, reaction system is changed into brown suspension.After one hour, in flask
Wall has into salt yellow solid wall built-up.Reaction system is warming up to 170 DEG C, the toluene in water knockout drum is released, continues to react, when band water
When toluene in device is full of, toluene is released, the toluene solution in cleared water knockout drum is repeated several times until there is no first in water knockout drum
Benzene is steamed.Confirm that reaction is abundant by a plate, then stop reaction and add reaction solution in the aqueous solution, water is filtered with separatory funnel
After carry out hot suction filtration, obtained product 3 be put into baking oven under the conditions of 120 DEG C dry it is stand-by.
4th step：
0.026 mol product 3,1.1g carbon loaded palladium catalyst and appropriate alcohol solvent are separately added into reactor,
Charging begins to warm up stirring after finishing, solution is in yellowish-brown, starts backflow after reaction half an hour, is slowly added to 13mL hydration
Hydrazine, solution is in brown color after half an hour, continues to react after two hours, and observation solution is changed into black, is determined by a plate anti-
After answering completely, carry out hot suction filtration and reclaim carbon loaded palladium catalyst, filtrate sealing is put into refrigerator and separated out.Solution is put into
It is spin-dried for, and is dissolved with ethyl acetate in single port bottle, obtained solution is filtered with diatomite, is spin-dried for, obtain product 4, will be produced
Thing 4 is positioned in 60 DEG C of vacuum drying oven and is dried.
5th step：
0.026mol product 4 is dissolved in 75ml ethanol under nitrogen protection, add be heated to reflux after parahydroxyben-zaldehyde it is 8 small
When, stop heating, keep ventilation to place a night, next day adds 300ml methanol, filtering, filter residue is washed in 3 times vacuum drying ovens with methanol
80 DEG C of drying, obtain product 5（Monomer）.
Then monomer is carried out1H-NMR、13C-NMR and mass spectrographic analysis, as shown in Figure 1, Figure 2 with shown in Fig. 3, it is determined that
The correctness of product structure.
FT-IR（KBR tablettings, cm-1）:ν=3031 (O-H), 1660 (C=N), 1604,1510 (phenyl ring features
Peak).
1H-NMR (400 MHz, DMSO, ppm) (Fig. 2-5): δ = 10.06(s, 2H, Ar-OH); 8.50(s,
2H, H-C=N);8.21 (d, 2H, carbazoles);6.65-7.93 (H, phenyl ring).
13C-NMR (400 MHz, DMSO, ppm): δ= 160.5(C1), 159.0(C5),147.5(C6), 144.3
(C9), 144.2(C10), 140.2(C14), 132.1(C13), 130.2(C3), 127.5(C4), 126.1(C16),
125.2(C19), 123.8(C18), 123.0(C17), 122.5(C8), 122.0(C7), 120.5(C9), 119.8
(C2), 115.6(C11), 109.7(C15)。
It is as follows on preparing polymer detailed process by above-mentioned monomer：
Trigger the triphen amine monomers and 4,4'- difluoro benzophenones of the above-mentioned side base containing carbazole under the catalysis of potassium carbonate catalyst
Or 4,4'- difluorodiphenyl sulfone carry out condensation polymerization reaction, reaction dissolvent uses DMA；
The mol ratio of the triphen amine monomers of the above-mentioned side base containing carbazole and 4,4'- difluoro benzophenones or 4,4'- difluorodiphenyl sulfones
For 1：1, the mol ratio of the triphen amine monomers of catalyst potassium carbonate and the side base containing carbazole is 3：1, in 145 DEG C, nitrogen ceiling
Reacted 24 hours under part, then raise temperature to 180 DEG C and continue to react 24 hours；After reaction terminates, product is poured into substantial amounts of first
Settled out in alcohol, and the solid of gained is stripped with methanol, chloroform successively, finally by chloroform phase
Remove, obtain triphenylamine that carbazole ring structure is side chain and benzophenone polymer or triphenylamine that carbazole ring structure is side chain with
Two lauseto neu polymer.Carbazole ring structure is the triphenylamine of side chain and benzophenone polymer is 76.4%, carbazole ring structure
The yield of triphenylamine and two lauseto neu polymer for side chain is 60.3%.
As shown in figs. 4 and 5,1H-NMR has carried out table respectively to PAEK and polyether sulphone containing carbazole structure
Levy, and from1In H-NMR spectrum as can be seen that positioned at 10.06ppm locate Ar-OH characteristic peaks be wholly absent, it was demonstrated that product 5 and
The abundant reaction of 4,4'- difluoro benzophenones or 4,4'- difluorodiphenyl sulfone, and do not contain unreacted monomer.
By exclusion chromatography to triphenylamine and benzophenone polymer and click of the resulting carbazole ring structure for side chain
Azoles ring structure has carried out molecular weight test for the triphenylamine and two lauseto neu polymer of side chain, and test result is listed in Table 1 below, table 1
For containing triphenylamine and benzophenone polymer that carbazole ring structure is side chain and triphenylamine and hexichol that carbazole ring structure is side chain
The molecular weight of MSM polymer.From table 1 it follows that containing triphenylamine and benzophenone polymer of the carbazole ring structure for side chain
With carbazole ring structure for side chain triphenylamine it is suitable with the number-average molecular weight of two lauseto neu polymer, respectively 4805 g/mol with
4420g/mol.But carbazole ring structure is the triphenylamine and benzophenone polymer molecular weight wider distribution of side chain, has reached 2.93
（Carbazole ring structure is that the triphenylamine and two lauseto neu polymer of side chain are 1.31）, therefore carbazole ring structure is the triphenylamine of side chain
There is higher weight average molecular weight with benzophenone polymer, about carbazole ring structure is poly- for the triphenylamine and two lauseto neus of side chain
2 times of compound.
Table 1
The dissolubility of polymer is always one of property of Optoelectronic polymers material common concern, is directly connected to the later stage of material
Application, such as dissolving processing, mold.The carbazole ring structure obtained to the present invention gathers for the triphenylamine of side chain with benzophenone
Compound and carbazole ring structure carry out dissolubility test discovery for the triphenylamine of side chain with two lauseto neu polymer, except toluene with
Outside, the triphenylamine that the carbazole ring structure obtained is the triphenylamine and benzophenone polymer of side chain and carbazole ring structure is side chain
With two lauseto neu polymer in conventional solvent dioxane, chloroform, tetrahydrofuran, 1-METHYLPYRROLIDONE, N, N- dimethyl
Extraordinary dissolubility is respectively provided with formamide, DMAC N,N' dimethyl acetamide and dimethyl sulfoxide (DMSO).Table 2 is that carbazole ring structure is side
The triphenylamine of chain is the triphenylamine of side chain and the dissolubility of two lauseto neu polymer with benzophenone polymer and carbazole ring structure；
Table 3 is triphenylamine and benzophenone polymer that carbazole ring structure is side chain and triphenylamine and hexichol that carbazole ring structure is side chain
Temperature of the MSM polymer when 1wt%, 5wt% and 10wt% are decomposed.
Table 2
| Dioxane | Toluene | CHCl3 | THF | NMP | DMF | DMSO | DMAC | |
| PAEK | + | - | + | + | + | + | + | + |
| Polyether sulphone | + | - | + | + | + | + | + | + |
Table 3
As can be seen here, the triphen that carbazole ring structure is the triphenylamine and benzophenone polymer of side chain and carbazole ring structure is side chain
Temperature when 1wt%, 5wt% and 10wt% of amine and two lauseto neu polymer are decomposed is listed in Table 3 below.There it can be seen that decomposing
Initial stage（<~350℃）, carbazole ring structure is that the triphenylamine of side chain and benzophenone polymer have more excellent heat endurance, when
When temperature polarity is raised（>~350℃）, carbazole ring structure is that the triphenylamine and two lauseto neu polymer of side chain have higher heat
Decomposition temperature, this is mainly due to carbazole ring structure to contain S elements, this yuan in triphenylamine and the two lauseto neu polymer of side chain
Element is one of fire retardant element for commonly using in polymer, can suppress the progress decomposed in polymer decomposable process, in burning
During can also promote polymer into carbon, therefore, polyether sulphone has higher carbon yield.
Certainly, described above is only presently preferred embodiments of the present invention, and the present invention is not limited to enumerate above-described embodiment, should
When explanation, any those skilled in the art are all equivalent substitutes for being made, bright under the teaching of this specification
Aobvious variant, all falls within the essential scope of this specification, ought to be protected by the present invention.
Claims (6)
1. a kind of polymer migrated with both hole and electron, it is characterised in that it is side chain that the polymer, which includes carbazole ring structure,
Triphenylamine and benzophenone polymer or triphenylamine and two lauseto neu polymer that carbazole ring structure is side chain, carbazole ring structure
Structural formula for the triphenylamine and benzophenone polymer of side chain is：
Wherein, n is the positive integer more than 1；
Carbazole ring structure is that the structural formula of the triphenylamine and two lauseto neu polymer of side chain is：
Wherein, n is the positive integer more than 1.
2. a kind of method for preparing polymer as claimed in claim 1, it comprises the following steps：
The step of triphen amine monomers including preparing the side base containing carbazole, there are triphen amine monomers two ends and can be used for condensation anti-
The hydroxyl answered；
Including being carried out by the hydroxyl on triphen amine monomers and 4,4'- difluoro benzophenones or 4,4'- difluorodiphenyl sulfones monomer
Polymerization, prepares triphenylamine of the triphenylamine and benzophenone polymer or carbazole ring structure using carbazole ring structure as side chain for side chain
With two lauseto neu polymer be main chain polymer the step of.
3. according to the method described in claim 1, it is characterised in that wrap the step of the triphen amine monomers for preparing the side base containing carbazole
Include：
A, by carbazole and p-fluoronitrobenzene under the catalytic action of Anhydrous potassium carbonate, enter in solvent DMF
Row is stirred at reflux fully reaction 8 hours, and room temperature is down to after completion of the reaction, is subsequently poured into water, glassy yellow product (1) is obtained；
B, the respective reaction device equipped with reflux condensing tube by resulting glassy yellow product (1) and the addition of carbon loaded palladium catalyst
In, add ethanol and carry out return stirring, then addition hydrazine hydrate reduction agent, solution is grass green, with the carry out solution of reaction
Gradually change to bottle green, be finally changed into black completely, fully after 3 hours of reaction, reaction suspension is subjected to hot suction filtration, returned
Carbon loaded palladium catalyst is received, filtrate sealing, which is positioned in refrigerator, to be separated out, and solution is put into single port bottle and is spin-dried for, next day
Ethyl acetate dissolving is added, obtained solution is filtered with diatomite, and product (2) is obtained after finally filtrate is spin-dried for；
C, by product (2), Anhydrous potassium carbonate, p-fluoronitrobenzene, dimethyl sulfoxide (DMSO), toluene add with water knockout drum respective reaction
In device, 130 DEG C are warming up to, reaction system is the suspension of yellow；Start backflow after half an hour, it is suspended that reaction system is changed into brown
Liquid；After one hour, corresponding container inwall has into salt yellow solid wall built-up；Then reaction system is warming up to 170 DEG C, releases and divide
Toluene in hydrophone, when the toluene in water knockout drum is full of, releases toluene, the toluene solution being repeated several times in cleared water knockout drum is straight
Steamed into water knockout drum there is no toluene, confirm that reaction is abundant by thin-layer chromatography, then stop reaction, reaction solution is added into water
In solution, filtered with separatory funnel and hot suction filtration is carried out after water, obtained product (3) is put into baking oven dries under the conditions of 120 DEG C
It is stand-by；
D, into correspondence reactor product (3), carbon loaded palladium catalyst and appropriate alcohol solvent are separately added into, after charging is finished
Stirring is begun to warm up, solution is in yellowish-brown, starts backflow after reaction half an hour, is slowly added to hydrazine hydrate, molten after half an hour
Liquid is in brown color, continues to react after two hours, and observation solution is changed into black, determines that heat is carried out after reaction completely takes out by a plate
Carbon loaded palladium catalyst is reclaimed in filter, and filtrate sealing is put into refrigerator and separated out；Solution is put into correspondence single port bottle and carried out
It is spin-dried for；And dissolved with ethyl acetate, obtained solution is filtered with diatomite, and is spin-dried for, and obtains product (4), and product (4) is put
It is dried in the vacuum drying oven for being placed in 60 DEG C；
E, product (4) is dissolved in ethanol under nitrogen protection, adds and 8 hours are heated to reflux after parahydroxyben-zaldehyde, stop plus
Heat, keeps ventilation to place a night, and 300ml methanol is added after 24 hours, and filtering, filter residue washes three times with methanol and in vacuum drying oven
80 DEG C of drying, obtain product (5), i.e., the triphen amine monomers of the described side base containing carbazole；
4. according to the method described in claim 1, it is characterised in that prepare the triphenylamine and hexichol using carbazole ring structure as side chain
Ketone polymer or carbazole ring structure are that the triphenylamine of side chain includes the step of with two lauseto neu polymer being the polymer of main chain：
Trigger the triphen amine monomers and 4,4'- difluoro benzophenones of the above-mentioned side base containing carbazole under the catalysis of potassium carbonate catalyst
Or 4,4'- difluorodiphenyl sulfone carry out condensation polymerization reaction, reaction dissolvent uses DMA；
The mol ratio of the triphen amine monomers of the above-mentioned side base containing carbazole and 4,4'- difluoro benzophenones or 4,4'- difluorodiphenyl sulfones
For 1：1, the mol ratio of the triphen amine monomers of catalyst potassium carbonate and the side base containing carbazole is 3：1, in 145 DEG C, nitrogen ceiling
Reacted 24 hours under part, then raise temperature to 180 DEG C and continue to react 24 hours；After reaction terminates, product is poured into substantial amounts of first
Settled out in alcohol, and the solid of gained is stripped with methanol, chloroform successively, finally mutually gone chloroform
Remove, obtain triphenylamine and benzophenone polymer that carbazole ring structure is side chain or the triphenylamine and two that carbazole ring structure is side chain
Lauseto neu polymer.
5. a kind of application of polymer as claimed in claim 1, it is characterised in that prepare polymer as claimed in claim 1
For hole-injecting material.
6. a kind of application of polymer as claimed in claim 1, it is characterised in that prepare polymer as claimed in claim 1
For electron-transporting type material.
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| US11233212B2 (en) | 2018-01-03 | 2022-01-25 | Boe Technology Group Co., Ltd. | Polymer, quantum dots film layer and preparation method thereof |
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