CN106977702A - A kind of cross-linking type conjugated polymer based on diaryl-amine group and preparation method and application - Google Patents

A kind of cross-linking type conjugated polymer based on diaryl-amine group and preparation method and application Download PDF

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CN106977702A
CN106977702A CN201710176385.0A CN201710176385A CN106977702A CN 106977702 A CN106977702 A CN 106977702A CN 201710176385 A CN201710176385 A CN 201710176385A CN 106977702 A CN106977702 A CN 106977702A
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fluorenes
substitution
diaryl
cross
conjugated polymer
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应磊
赵森
郭婷
杨伟
彭俊彪
曹镛
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South China University of Technology SCUT
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Abstract

The invention discloses a kind of cross-linking type conjugated polymer based on diaryl-amine group and preparation method and application.The cross-linking type conjugated polymer based on diaryl-amine group, it is obtained using phenyl boric acid and bromobenzene progress end capping reaction after by the boric acid ester monomer of the monomer of the crosslinked group containing diaryl-amine, alkyl fluorenes monomer and alkyl fluorenes by Suzuki polymerisations, then successively.The cross-linking type conjugated polymer of the present invention has preferable dissolubility, is appropriate for solution processing and typographical display, the luminescent layer for preparing Organic Light Emitting Diode；Luminescent layer based on the crosslinking polymer is when preparing electroluminescent device without annealing so that preparation technology is simpler.

Description

A kind of cross-linking type conjugated polymer based on diaryl-amine group and preparation method thereof with Using
Technical field
The invention belongs to organic photoelectric technical field, and in particular to a kind of cross-linking type conjugated polymers based on diaryl-amine group Thing and preparation method and application.
Background technology
In the past thirty years, organic electronic and photoelectronic industry, including organic/polymer LED, it is organic Field-effect transistor, the field such as organic solar batteries has obtained swift and violent development, and gradually realizes industrialization.Organic electronic is produced Product have cheap, and body is light the advantages of take.Make it have great market potential.Therefore exploitation has market attractiveness Organic electronic product has attracted the concern of numerous research institutions and Research Team in the world, and among these, develops new and effective Stable material turns into key.
But, current organic luminescent device technology encounters bottleneck problem in evolution, is exactly the hair of luminescent device Light efficiency and service life do not reach practical requirement, which greatly limits the development of OLED technology, for this problem, respectively Individual research institution is all carrying out the research of exploration.
The cross-linking type conjugated polymer based on diaryl-amine group that the present invention relates to, because with preferable dissolubility Can, it is adaptable to which solution is processed, and preferably fluorescence quantum yield, its luminescent device not only efficient stable, and be more saturation Blue light, the raising of the luminous efficiency and service life of luminescent device can be realized simultaneously, the requirement of full-color display can be met.Institute To there is huge development potentiality and prospect in organic electronic display field.
The content of the invention
It is an object of the invention to be based on for current polymer LED (PLED) problems faced there is provided one kind The cross-linking type conjugated polymer of diaryl-amine group.The conjugated polymer can be used as luminescent material, and have preferable dissolubility, compared with High fluorescence quantum yield, is suitable for solution processing and inkjet printing, with good development prospect, can solve having for correlation The problem of electromechanical sub- device stability and device lifetime.
The present invention also aims to provide a kind of preparation of cross-linking type conjugated polymer based on diaryl-amine group Method.
The present invention also aims to provide a kind of cross-linking type conjugated polymer based on diaryl-amine group in preparation Application in the luminescent layer of Organic Light Emitting Diode.
A kind of cross-linking type conjugated polymer based on diaryl-amine group, chemical structural formula is as follows：
In formula, Ar is aromatic group；R1-R8Selected from-H ,-F ,-Cl ,-Br ,-I ,-D ,-CN ,-NO2、-CF3, carbon atom The straight or branched alkyl of number 1~20, the alkane ether of carbon number 1~20, carbon number 1-10 alkane thioether；0≤x≤ 1；0≤y≤1；Polymerization degree n is 1-300；
Ar is any one in following structural formula：
9,10- dialkyl group is luxuriant and rich with fragrance；
2,7- substituted fluorenes；
3,6- substituted fluorenes；
2,7- substitution silicon fluorenes；
3,6- substitution silicon fluorenes；
2,7- substitution spiro fluorenes；
3,6- substitution spiro fluorenes；
2,7- substitution -9,9- dialkoxy phenyl fluorenes；3,6- take Generation -9,9- dialkoxy phenyl fluorenes；2,7- substituted carbazoles；
3,6- substituted carbazoles；
2,6- substitutions-dithieno thiophene is coughed up；
2,6- substitutions-dithieno cyclopentadiene；
2,5- substituted pyridines；
2,6- substituted pyridines；
3,5- substituted pyridines；
3,5- double (4- substituted 4-phenyls) -4- bases -1,2,4- triazoles；
3,5- double (4- substituted 4-phenyls) -1,2,4- oxadiazoles；
4,7- double (5- substitution -4- alkylthrophenes base) -2,1,3- diazosulfide；
4,7- double (5- substitution -4- alkylthrophenes base) 2,1,3- selenoles；
4,7- substitution -5,6- alkyl -2,1,3- diazosulfides；
4,7- substitution -5,6- alkyl -2,1,3- selenoles；
2,5- substitution -3,4- dialkylthiophenes；
2,5- substitution -3,4- dialkyl group selenophens；
5,5- -4,4- of substitution dialkyl group-bithiophene；
Indenes fluorenes；
Indole carbazole；
4,9- -6,7- of substitution alkyl-naphtho- thiadiazoles；
4,9- -6,7- of substitution alkyl-naphtho- selenium diazole；
Naphtho- indenes fluorenes；
Two quinoxalines and indenes fluorenes；
Wherein, R is hydrogen, aryl, triphenylamine, carbon number 1-20 straight chain or branched alkyl, or is carbon number 1- 20 alkoxy.
Further, the aromatic hydrocarbon group of the main polymer chain be included hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, The substituent of one or more of alkynyl, aralkyl, aryl and heteroaryl is optionally substituted.
A kind of preparation method of cross-linking type conjugated polymer based on diaryl-amine group, comprises the following steps：
Under argon atmosphere, by the borate list of the monomer of the crosslinked group containing diaryl-amine, alkyl fluorenes monomer and alkyl fluorenes After body is by Suzuki polymerisations, then successively using phenyl boric acid and bromobenzene progress end capping reaction, obtain described based on diaryl-amine The conjugated polymer of group.
Further, the boric acid ester monomer of the monomer of the crosslinked group containing diaryl-amine, alkyl fluorenes monomer and alkyl fluorenes Mol ratio be 1.5:1:2.5.
Further, the temperature of the Suzuki polymerisations is 80~100 DEG C, and the time is 24~48 hours.
Further, the temperature that the phenyl boric acid and bromobenzene carry out end capping reaction is 80~100 DEG C, and the time is 12~ 24 hours.
A kind of cross-linking type conjugated polymer based on diaryl-amine group is applied to prepare the luminescent layer of light emitting diode, Cross-linking type conjugated polymer organic solvent based on diaryl-amine group is dissolved, then by spin coating, inkjet printing or is printed as Film, obtains the luminescent layer of light emitting diode；Light emitting diode based on the luminescent layer is applied in the preparation of organic electronic device, Including preparing flat-panel monitor.
Further, the organic solvent includes chlorobenzene.
Compared with prior art, the invention has the advantages that and beneficial effect：
(1) the cross-linking type conjugated polymer based on diaryl-amine group of the invention, the backbone structure of conjugation assigns polymer Passed with abundant optically and electrically performance, including luminescence generated by light, electroluminescent, photovoltaic effect, characteristic of semiconductor and carrier Defeated characteristic；
(2) the cross-linking type conjugated polymer based on diaryl-amine group of the invention, applied to the complicated multilayer optical electrical equipment of preparation During part, using the solution processing characteristics of conjugated polymer, pass through the solution processing technology such as inkjet printing, silk-screen printing, spin coating Luminescent layer is prepared, so as to further prepare polymer light electrical part；
(3) the cross-linking type conjugated polymer based on diaryl-amine group of the invention, due to larger conjugate length, institute To there is higher fluorescence quantum yield, be conducive to improving the device efficiency of material；
(4) the cross-linking type conjugated polymer based on diaryl-amine group of the invention, it is poly- based on this with preferable dissolubility The luminescent layer of compound is when preparing electroluminescent device without annealing so that preparation technology is simpler.
Brief description of the drawings
Fig. 1 is UV-visible absorption spectrum of the polymer P 1 under filminess；
Fig. 2 is photoluminescence spectra figure of the polymer P 2 under filminess；
Fig. 3 is photoluminescence spectra figure of the polymer P 3 under filminess.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
The preparation of 2- bromine fluorenes
In 250mL there-necked flasks, fluorenes (16.6g, 0.1mol), iron powder (88mg, 1.57mmol), chloroform are added 100mL；Ice-water bath is cooled down, and bromine (17.6g, 0.1mol)/chloroform mixed solution 35mL is added dropwise；Temperature does not surpass in bottle during dropwise addition Cross 5 DEG C.Reaction 16 hours, filtering, Gossypol recrystallized from chloroform, obtains white solid 19.3g, yield 84%.1H NMR、13CNMR, MS and member Compound obtained by plain analysis result shows is target product, and its chemical equation is as follows：
Embodiment 2
The preparation of bromo- 9, the 9- dioctyl fluorenes of 2-
2- bromines fluorenes (7.4g, 0.03mol), benzyltriethylammoinium chloride (0.07g, 0.3mmol), two are added in there-necked flask Methyl sulfoxide 90mL, 45mL sodium hydrate aqueous solution (50wt%), at room temperature stirring form suspension；1- bromine normal octanes are added dropwise (12.5g, 65mmol), continues after stirring 3 hours, is extracted with ether.Ether phase, anhydrous sulphur are washed with saturated sodium-chloride water solution Sour magnesium is dried.Solvent is boiled off, product petroleum ether makees the purification of eluant, eluent column chromatography, obtains white solid.1H NMR、13CNMR, MS and Compound obtained by elementary analysis result shows is target product, and its chemical equation is as follows：
Embodiment 3
The preparation of 2- borate -9,9- dioctyl fluorenes
Under an argon atmosphere, bromo- 9, the 9- dioctyl fluorenes (5g, 10.65mmol) of 2- are dissolved in the refined tetrahydrochysene furans of 180mL Mutter in (THF), 1.6mol.L is gradually added dropwise at -78 DEG C-1N-BuLi 28mL, react 2 hours, then add 2- isopropyl oxygen Base -4,4,5,5- tetramethyls -1,3,2- dioxaborinate 25mL continue to react 1 hour at -78 DEG C, are warming up to room temperature reaction 24 hours.Reactant mixture is poured into water, is extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous sulphur Sour magnesium is dried.After solution concentration, thick pale yellow shape crude product is obtained, (eluant, eluent selection petroleum ether/second is purified with silica gel column chromatography Acetoacetic ester=20/1, v/v), product is placed in refrigerator obtain white solid, yield 70% for a long time.1H NMR、13CNMR, MS and Compound obtained by elementary analysis result shows is target product, and its chemical equation is as follows：
Embodiment 4
The 2-methyl naphthoate of 1- bromines two
Under an argon atmosphere, the bromo- 2- naphthoic acids (10g, 39.83mmol) of 1- are added in two-mouth bottle, adds 100mL first Alcohol, is then added dropwise the concentrated sulfuric acid (39.06mg, 398.29umol), is heated to 110 DEG C, reacts 18h.Reactant mixture is fallen Enter in water, be extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.After solution concentration, obtain To crude white solid, (eluant, eluent selects petroleum ether/dichloromethane=3/1, v/v) is purified with silica gel column chromatography, when product is long Between place refrigerator in obtain white solid, yield 85%.1H NMR、13CNMR, MS and elementary analysis result show resulting change Compound is target product, and its chemical equation is as follows：
Embodiment 5
Compound M1 preparation
Under argon atmosphere, by 2- borates -9,9- dioctyl fluorene (5g, 9.68mmol) and the 2-methyl naphthoate of 1- bromines two (2.69g, 10.16mmol) is added in two-mouth bottle, is added 100ml toluene and is completely dissolved, adds sodium carbonate (5.13g, 43.89mmol) and TBAB (312.01mg, 967.86umol), 18h is reacted at 110 DEG C.Will reaction Mixture is poured into water, and is extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.Solution (eluant, eluent selects petroleum ether/dichloromethane=5/1, v/v) after concentration, is purified with silica gel column chromatography, white solid is finally given, Yield 80%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product, and it chemically reacts Equation is as follows：
Embodiment 6
Compound M2 preparation
Under argon atmosphere, M1 (5g, 8.70mmol) is added in single port bottle, the anhydrous THF of 50ml are added until complete Dissolving.Reaction solution is reacted into 1h at 0 DEG C again, then C is added dropwise8H17MgBr (n-octyl magnesium bromide), mixed liquor is at room temperature React 18h.Add water in reaction solution that reaction is quenched, be extracted with ethyl acetate, after organic layer is washed completely with saline solution, Plus anhydrous magnesium sulfate is dried.After solution concentration, purified with silica gel column chromatography (eluant, eluent selects petroleum ether/dichloromethane=3/1, V/v), product is placed in refrigerator obtain white solid, yield 80% for a long time.1H NMR、13CNMR, MS and elementary analysis result Compound obtained by showing is target product, and its chemical equation is as follows：
Embodiment 7
Compound M3 preparation
Under argon atmosphere, M2 (5g, 6.48mmol) is dissolved in 50ml dichloromethane, trifluoro is added dropwise at room temperature Change borate ether solution (439.59mg, 6.48mmol), react 18h.It is extracted with ethyl acetate, organic layer is washed completely with saline solution Afterwards, plus anhydrous magnesium sulfate dry.After solution concentration, purified with silica gel column chromatography (eluant, eluent selection petroleum ether), product is for a long time Place in refrigerator and obtain white solid, yield 90%.1H NMR、13CNMR, MS and elementary analysis result show resulting chemical combination Thing is target product, and its chemical equation is as follows：
Embodiment 8
The preparation of naphtho- indenes fluorenes (NIF)
Under argon atmosphere, M3 (5g, 6.64mmol) is dissolved in 50mL dichloromethane, add iron powder (185.35mg, 3.32mmol), then bromine (1.06g, 6.64mmol) is added dropwise, 18h is reacted at room temperature.It is extracted with ethyl acetate, it is organic After layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.After solution concentration, (eluant, eluent selection is purified with silica gel column chromatography Petroleum ether), yield 70%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product, its Chemical equation is as follows：
Embodiment 9
The synthesis of compound diphenylamines
Under argon atmosphere, by compound aniline (4.68g, 50.23mmol) and equal trimethyl bromobenzene (10g, 50.23mmol) it is added in 250ml two-mouth bottles, adds sodium tert-butoxide (24.14g, 251.15mmol), adds 100ml toluene Dissolved, palladium (225.54mmol, 1mmol) and tri-butyl phosphine (406.49mmol, 1mmol) are eventually adding, 110 Reacted 18 hours at DEG C.It is extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.Solution After concentration, (eluant, eluent selection petroleum ether), yield 70% are purified with silica gel column chromatography.1H NMR、13CNMR, MS and elementary analysis As a result the compound obtained by showing is target product, and its chemical equation is as follows：
Embodiment 10
Compound M3 synthesis
Under argon atmosphere, compound indenes fluorenes (5g, 5.69mmol) and diphenylamines (2.32g, 10.98mmol) are added to In 250ml two-mouth bottles, sodium tert-butoxide (2.64g, 27.44mmol) is added, 100ml toluene is added and is dissolved, is eventually adding Palladium (44.42mg, 109.77umol) and tri-butyl phosphine (44.42mmol, 219.53umol), 18 are reacted at 110 DEG C Hour.It is extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.After solution concentration, silicon is used Plastic column chromatography purifies (eluant, eluent selection petroleum ether), yield 70%.1H NMR、13CNMR, MS and elementary analysis result show gained The compound arrived is target product, and its chemical equation is as follows：
Embodiment 11
Compound M2 synthesis
Under argon atmosphere, M1 (5g, 4.47mmol) is dissolved in 50mL dichloromethane, add iron powder (238.29mg, 4.27mmol), then bromine (1.50g, 9.39mmol) is added dropwise, 18h is reacted at room temperature.It is extracted with ethyl acetate, it is organic After layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.After solution concentration, (eluant, eluent selection is purified with silica gel column chromatography Petroleum ether), yield 70%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product, its Chemical equation is as follows：
Embodiment 12
Compound M3 synthesis
Under argon atmosphere, compound naphtho- indenes fluorenes (5g, 5.49mmol) and diphenylamines (2.32g, 10.98mmol) are added Enter into 250ml two-mouth bottles, add sodium tert-butoxide (2.64g, 27.44mmol), add 100ml toluene and dissolved, finally Palladium (44.42mg, 109.77umol) and tri-butyl phosphine (44.42mmol, 219.53umol) are added, it is anti-at 110 DEG C Answer 18 hours.It is extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.After solution concentration, (eluant, eluent selection petroleum ether), yield 70% are purified with silica gel column chromatography.1H NMR、13CNMR, MS and elementary analysis result show Resulting compound is target product, and its chemical equation is as follows：
Embodiment 13
Compound M4 synthesis
Under argon atmosphere, M3 (5g, 4.27mmol) is dissolved in 50mL dichloromethane, add iron powder (238.29mg, 4.27mmol), then bromine (1.50g, 9.39mmol) is added dropwise, 18h is reacted at room temperature.It is extracted with ethyl acetate, it is organic After layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.After solution concentration, (eluant, eluent selection is purified with silica gel column chromatography Petroleum ether), yield 70%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product, its Chemical equation is as follows：
Embodiment 14
Compound M5 synthesis
Under argon atmosphere, compound alkyl luxuriant and rich with fragrance (5g, 8.92mmol) and diphenylamines (3.77g, 17.82mmol) are added Into 250ml two-mouth bottles, sodium tert-butoxide (4.29g, 44.61mmol) is added, 100ml toluene is added and is dissolved, finally added Enter palladium (40.06mg, 178.43umol) and tri-butyl phosphine (72.20mmol, 356.86umol), reacted at 110 DEG C 18 hours.It is extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.After solution concentration, use Silica gel column chromatography purifies (eluant, eluent selection petroleum ether), yield 70%.1H NMR、13CNMR, MS and elementary analysis result show institute Obtained compound is target product, and its chemical equation is as follows：
Embodiment 15
Compound M6 synthesis
Under argon atmosphere, M5 (5g, 6.09mmol) is dissolved in 50mL dichloromethane, add iron powder (3.4mg, 60.88umol), then bromine (1.95g, 12.18mmol) is added dropwise, 18h is reacted at room temperature.It is extracted with ethyl acetate, has After machine layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.After solution concentration, (eluant, eluent choosing is purified with silica gel column chromatography Select petroleum ether), yield 70%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product, Its chemical equation is as follows：
Embodiment 17
The preparation of polymer P 1
Under argon atmosphere, by the borate (200mg, 242.20u mol) of fluorenes, divinyl fluorenes (44.59mg, 96.88umol) added with compound M2 (185.93mg, 145.32umol) in 100ml two-mouth bottles, add the progress of 8ml toluene It is completely dissolved, substitutes gas three times, adds palladium (2.17mg, 9.68 μm of ol) and tricyclohexyl phosphine (5.43mg, 19.35 μ Mol), substitute gas three times, then add 2ml tetraethyl ammonium hydroxides, be warming up to 80 DEG C, react 24 hours.Then 30mg is added Phenyl boric acid is blocked, after 12 hours, then is blocked with 0.1ml bromobenzenes, continues to react 12 hours；Afterwards, product is added dropwise It is precipitated out, stirs in methyl alcohol, filtering, then crude product is dissolved in 20mL toluene, using 200~300 mesh silica gel as fixation Phase, is that eluant, eluent carries out column chromatography with toluene, then after solvent under reduced pressure is concentrated, separates out to come in methyl alcohol again, stirring, mistake Filter, polymer solids are obtained after vacuum drying.Finally respectively extracted 24 hours, removed small with methanol, acetone, tetrahydrofuran successively again Molecule.Tetrahydrofuran solution after concentration is instilled into precipitating, the fibrous solids conjugated polymers obtained after vacuum drying in methanol Thing P1.Chemical equation is as follows：
UV-visible absorption spectrum of the obtained polymer P 1 under filminess is as shown in figure 1, can from figure Go out, the maximum absorption band of polymer P 1 is located at 391nm.
Embodiment 18
The preparation of polymer P 2
Under argon atmosphere, by the borate (200mg, 242.20u mol) of fluorenes, divinyl fluorenes (44.59mg, 96.88umol) added with compound M4 (175.93mg, 145.32umol) in 100ml two-mouth bottles, add the progress of 8ml toluene It is completely dissolved, substitutes gas three times, adds palladium (2.17mg, 9.68 μm of ol) and tricyclohexyl phosphine (5.43mg, 19.35 μ Mol), substitute gas three times, then add 2ml tetraethyl ammonium hydroxides, be warming up to 80 DEG C, react 24 hours.Then 30mg is added Phenyl boric acid is blocked, after 12 hours, then is blocked with 0.1ml bromobenzenes, continues to react 12 hours；Afterwards, product is added dropwise It is precipitated out, stirs in methyl alcohol, filtering, then crude product is dissolved in 20mL toluene, using 200~300 mesh silica gel as fixation Phase, is that eluant, eluent carries out column chromatography with toluene, then after solvent under reduced pressure is concentrated, separates out to come in methyl alcohol again, stirring, mistake Filter, polymer solids are obtained after vacuum drying.Finally respectively extracted 24 hours, removed small with methanol, acetone, tetrahydrofuran successively again Molecule.Tetrahydrofuran solution after concentration is instilled into precipitating, the fibrous solids conjugated polymers obtained after vacuum drying in methanol Thing P2.Chemical equation is as follows：
Obtained polymer P 2 under filminess photon luminescent spectrum figure as shown in Fig. 2 it can be seen that polymerization Thing P2 maximum emission peak is located at 451nm.
Embodiment 19
The preparation of polymer P 3
Under argon atmosphere, by the borate (200mg, 242.20u mol) of fluorenes, divinyl fluorenes (44.59mg, 96.88umol) added with compound M6 (155.93mg, 145.32umol) in 100ml two-mouth bottles, add the progress of 8ml toluene It is completely dissolved, substitutes gas three times, adds palladium (2.17mg, 9.68 μm of ol) and tricyclohexyl phosphine (5.43mg, 19.35 μ Mol), substitute gas three times, then add 2ml tetraethyl ammonium hydroxides, be warming up to 80 DEG C, react 24 hours.Then 30mg is added Phenyl boric acid is blocked, after 12 hours, then is blocked with 0.1ml bromobenzenes, continues to react 12 hours；Afterwards, product is added dropwise It is precipitated out, stirs in methyl alcohol, filtering, then crude product is dissolved in 20mL toluene, using 200~300 mesh silica gel as fixation Phase, is that eluant, eluent carries out column chromatography with toluene, then after solvent under reduced pressure is concentrated, separates out to come in methyl alcohol again, stirring, mistake Filter, polymer solids are obtained after vacuum drying.Finally respectively extracted 24 hours, removed small with methanol, acetone, tetrahydrofuran successively again Molecule.Tetrahydrofuran solution after concentration is instilled into precipitating, the fibrous solids conjugated polymers obtained after vacuum drying in methanol Thing P3.Chemical equation is as follows：
Photoluminescence spectra figure of the obtained polymer P 3 under filminess is as shown in figure 3, it can be seen that poly- Compound P3 maximum emission peak is located at 470nm.
Embodiment 20
The preparation of electroluminescent device based on polymer
On tin indium oxide (ITO) glass of well in advance, its square resistance is 20 Ω/, and acetone, washing are first used successively Agent, deionized water and isopropanol are cleaned by ultrasonic, plasma treatment 10 minutes.Spin coating, which is mixed, on ITO polystyrolsulfon acid Polyethoxy thiophene (mass ratio PEDOT:PSS=1:1) film, thickness is 150nm；PEDOT:PSS films are 80 DEG C in vacuum drying oven Lower drying 8 hours；Then double focusing compound luminescent material P1, P2, P3 and P4 chlorobenzene solution (1wt%) are spin-coated on respectively PEDOT:The surface of PSS films, thickness is 80nm, is used as luminescent layer；A thin layer CsF is finally deposited successively on luminescent layer (1.5nm) and 120nm thick metal Al layer.
The photoelectric properties index of electroluminescent device based on 1~P3 of polymer P is as shown in table 1.
The photoelectric properties index of electroluminescent device of the table 1 based on 1~P3 of polymer P
As shown in Table 1, the electroluminescent of cross-linking type conjugated polymer luminescent material P1, P2, P3 based on diaryl-amine group Device, based on device architecture：ITO/PEDOT/EML/CsF/Al maximum lumen efficiency be respectively 1.72cd/A, 0.57cd/A, 1.89cd/A。
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention Limitation, it is other it is any without departing from Spirit Essences and the change made under principle of the present invention, modification, replacement, combine, simplification all should For equivalent substitute mode, it is included within protection scope of the present invention.

Claims (7)

1. a kind of cross-linking type conjugated polymer based on diaryl-amine group, it is characterised in that chemical structural formula is as follows：
In formula, Ar is aromatic group；R1-R8Selected from-H ,-F ,-Cl ,-Br ,-I ,-D ,-CN ,-NO2、-CF3, carbon number 1~ 20 straight or branched alkyl, the alkane ether of carbon number 1~20, carbon number 1-10 alkane thioether；0≤x≤1；0≤ y≤1；Polymerization degree n is 1-300；
Ar is any one in following structural formula：
9,10- dialkyl group is luxuriant and rich with fragrance；
2,7- substituted fluorenes；
3,6- substituted fluorenes；
2,7- substitution silicon fluorenes；
3,6- substitution silicon fluorenes；
2,7- substitution spiro fluorenes；
3,6- substitution spiro fluorenes；
2,7- substitution -9,9- dialkoxy phenyl fluorenes；
3,6- substitution -9,9- dialkoxy phenyl fluorenes；
2,7- substituted carbazoles；
3,6- substituted carbazoles；
2,6- substitutions-dithieno thiophene is coughed up；
2,6- substitutions-dithieno cyclopentadiene；
2,5- substituted pyridines；
2,6- substituted pyridines；
3,5- substituted pyridines；
3,5- double (4- substituted 4-phenyls) -4- bases -1,2,4- triazoles；
3,5- double (4- substituted 4-phenyls) -1,2,4- oxadiazoles；
4,7- double (5- substitution -4- alkylthrophenes base) -2,1,3- diazosulfide；
4,7- double (5- substitution -4- alkylthrophenes base) 2,1,3- selenoles；
4,7- substitution -5,6- alkyl -2,1,3- diazosulfides；
4,7- substitution -5,6- alkyl -2,1,3- selenoles；
2,5- substitution -3,4- dialkylthiophenes；
2,5- substitution -3,4- dialkyl group selenophens；
5,5- -4,4- of substitution dialkyl group-bithiophene；
Indenes fluorenes；
Indole carbazole；
4,9- -6,7- of substitution alkyl-naphtho- thiadiazoles；
4,9- -6,7- of substitution alkyl-naphtho- selenium diazole；
Naphtho- indenes fluorenes；
Two quinoxalines and indenes fluorenes；
Wherein, R is hydrogen, aryl, triphenylamine, carbon number 1-20 straight chain or branched alkyl, or is carbon number 1-20's Alkoxy.
2. a kind of cross-linking type conjugated polymer based on diaryl-amine group according to 1, it is characterised in that the polymerization owner The aromatic hydrocarbon group of chain is included in hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl and heteroaryl More than one substituent is optionally substituted.
3. prepare a kind of method of cross-linking type conjugated polymer based on diaryl-amine group described in claim 1 or 2, its feature It is, comprises the following steps：
Under argon atmosphere, the boric acid ester monomer of the monomer of the crosslinked group containing diaryl-amine, alkyl fluorenes monomer and alkyl fluorenes is led to Cross after Suzuki polymerisations, then successively using phenyl boric acid and bromobenzene progress end capping reaction, obtain described based on diaryl-amine group Conjugated polymer.
4. a kind of preparation method of cross-linking type conjugated polymer based on diaryl-amine group according to claim 3, it is special Levy and be, the mol ratio of the boric acid ester monomer of the monomer of the crosslinked group containing diaryl-amine, alkyl fluorenes monomer and alkyl fluorenes is 1.5:1:2.5。
5. a kind of preparation method of cross-linking type conjugated polymer based on diaryl-amine group according to claim 3, it is special Levy and be, the temperature of the Suzuki polymerisations is 80~100 DEG C, and the time is 24~48 hours；The phenyl boric acid and bromobenzene The temperature for carrying out end capping reaction is 80~100 DEG C, and the time is 12~24 hours.
6. a kind of cross-linking type conjugated polymer based on diaryl-amine group described in claim 1 or 2 is applied to prepare luminous two The luminescent layer of pole pipe, it is characterised in that the cross-linking type conjugated polymer organic solvent based on diaryl-amine group is dissolved, then led to Spin coating, inkjet printing or printing film forming are crossed, the luminescent layer of light emitting diode is obtained.
7. application according to claim 6, it is characterised in that the organic solvent includes chlorobenzene.
CN201710176385.0A 2017-03-23 2017-03-23 A kind of cross-linking type conjugated polymer based on diaryl-amine group and preparation method and application Pending CN106977702A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101712674A (en) * 2009-11-13 2010-05-26 华南理工大学 Alkyl substituted-S,S-dioxo-dibenzothiophene monomer, preparation method and polymer thereof
CN102850528A (en) * 2012-05-29 2013-01-02 华南理工大学 Luminescent polymer containing S,S-dioxo-dibenzothiophene unit, and application thereof
CN103224486A (en) * 2013-04-03 2013-07-31 华南理工大学 S,S-dioxo-dibenzothiophene monomer containing polar substituent groups, water/alcohol soluble polymers thereof, and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101712674A (en) * 2009-11-13 2010-05-26 华南理工大学 Alkyl substituted-S,S-dioxo-dibenzothiophene monomer, preparation method and polymer thereof
CN102850528A (en) * 2012-05-29 2013-01-02 华南理工大学 Luminescent polymer containing S,S-dioxo-dibenzothiophene unit, and application thereof
CN103224486A (en) * 2013-04-03 2013-07-31 华南理工大学 S,S-dioxo-dibenzothiophene monomer containing polar substituent groups, water/alcohol soluble polymers thereof, and application thereof

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