CN106905512A - A kind of conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit and preparation method and application - Google Patents

A kind of conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit and preparation method and application Download PDF

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CN106905512A
CN106905512A CN201710101433.XA CN201710101433A CN106905512A CN 106905512 A CN106905512 A CN 106905512A CN 201710101433 A CN201710101433 A CN 201710101433A CN 106905512 A CN106905512 A CN 106905512A
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substitution
fluorenes
heteroaromatics
conjugated polymer
indenes
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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 conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit and preparation method and application.The conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit of the invention, due to larger conjugate length, so there is fluorescence quantum yield higher, being conducive to improving the device efficiency of material；Meanwhile, the polymer solubility is relatively good, is appropriate for solution processing and typographical display.Conjugated polymer of the present invention based on two heteroaromatics and indenes fluorenes unit is prepared by Suzuki polymerisations.It is of the invention to be based on two heteroaromatics and the conjugated polymer of indenes fluorenes can be used to prepare the luminescent layer of Organic Light Emitting Diode.

Description

A kind of conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit and preparation method thereof with Using
Technical field
The present invention relates to organic photoelectrical material technical field, and in particular to a kind of to be based on being total to for two heteroaromatics and indenes fluorenes unit Conjugated polymer and preparation method and application.
Background technology
In the past thirty years, organic electronic and photoelectronic industry, including organic/polymer LED, it is organic The fields such as field-effect transistor, organic solar batteries have obtained swift and violent development, and gradually realize 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 The material of stabilization 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.
Two heteroaromatics and indenes fluorenes unit and its polymer that the present invention relates to, because having preferable solubility property, Suitable for solution processing, and fluorescence quantum yield higher, its luminescent device not only efficient stable, and be more blue saturation Blue light, can simultaneously realize the raising of the luminous efficiency and service life of luminescent device, can meet the requirement of full-color display.Institute There is huge development potentiality and prospect with organic electronic display field.
The content of the invention
It is an object of the invention to be directed to current polymer LED (PLED) problems faced, there is provided one kind is based on The conjugated polymer of two heteroaromatics and indenes fluorenes unit.The conjugated polymer can be used as luminescent material, and with preferable dissolubility, Fluorescence quantum yield higher, is suitable for solution processing and inkjet printing, with good development prospect.
System the present invention also aims to provide a kind of conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit Preparation Method.
The present invention also aims to provide a kind of conjugated polymer of two heteroaromatics and indenes fluorenes unit that is based in system Application in the luminescent layer of standby Organic Light Emitting Diode.
A kind of conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit, with following chemical structural formula：
In formula, Ar1It is hexa-atomic heteroaromatic；R is aryl, triphenylamine, the straight or branched alkyl of carbon number 1-20, halogen Element, cyano group, alkoxy or fluoroalkyl；0≤x≤1；Polymerization degree n=1-300；
Ar is any one in following structure：
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- substitution-dithieno thiophenes are coughed up；
2,6- substitution-dithieno cyclopentadiene；
2,5- substituted pyridines；
2,6- substituted pyridines；
3,5- substituted pyridines；
3,5- double (4- substituted 4-phenyls) -4- base -1,2,4- triazoles；
3,5- double (4- substituted 4-phenyls) -1,2,4- oxadiazoles；
4,7- double (5- substitution -4- alkylthrophenes bases) -2,1,3- diazosulfide；
4,7- double (5- substitution -4- alkylthrophenes bases) 2,1,3- selenoles；
4,7- -5,6- of substitution alkyl -2,1,3- diazosulfide；
4,7- -5,6- of substitution alkyl -2,1,3- selenole；
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；
S, S- dioxydibenze bithiophene；
Wherein, R1For hydrogen, aryl, triphenylamine, carbon number 1-20 straight chain or branched alkyl, or be carbon number 1- 20 alkoxy.
A kind of preparation method of described conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit, comprises the following steps：
By two heteroaromatics and indenes fluorenes unit and the boric acid ester monomer containing Ar structures by after Suzuki polymerisations, then successively End capping reaction is carried out using phenyl boric acid and bromobenzene, the conjugated polymer based on two heteroaromatics and indenes fluorenes unit is obtained.
Further, the temperature of the Suzuki polymerisations is 80~100 DEG C, and the time is 24~48 hours.
Further, the temperature for carrying out end capping reaction using phenyl boric acid and bromobenzene is 80~100 DEG C, and the time is 12~ 24 hours.
A kind of described conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit is applied to prepare the hair of light emitting diode Photosphere, the conjugated polymer that will be based on two heteroaromatics and indenes fluorenes unit is dissolved with organic solvent, then by spin coating, inkjet printing or Printing film forming, obtains the luminescent layer of the light emitting diode；Light emitting diode based on the luminescent layer can be used to preparing flat board and show Show device.
Further, the organic solvent includes chlorobenzene.
Compared with prior art, the present invention has advantages below：
(1) conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit of the invention, due to long with larger conjugation Degree, so there is fluorescence quantum yield higher, is conducive to improving the device efficiency of material；
(2) conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit of the invention, with preferable dissolubility, based on this The luminescent layer of polymer is when electroluminescent device is prepared without annealing so that preparation technology is simpler.
Brief description of the drawings
Fig. 1 is uv-visible absorption spectra spectrogram of the polymer P 1 under filminess；
Fig. 2 is uv-visible absorption spectra spectrogram of the polymer P 2 under filminess；
Fig. 3 is the current density-luminous efficiency music score of Chinese operas figure of the electroluminescent device based on polymer P 3.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
The preparation of 2,7- dibromo fluorenes
In 250mL there-necked flasks, fluorenes (24.5g, 0.1mol), iron powder (88mg, 1.57mmol) and chloroform are added 100mL；Ice-water bath is cooled down, and bromine (17.6g, 0.1mol)/chloroform mixed solution 35mL is added dropwise, and temperature does not surpass in bottle during dropwise addition Cross 5 DEG C；Reaction is finished, filtering, Gossypol recrystallized from chloroform, obtains white solid 20.3g, yield 83%.1HNMR、13CNMR, MS and element Compound obtained by analysis result shows is target product.Chemical equation is as follows：
Embodiment 2
The preparation of 2,7- bis- bromo- 9,9- dioctyl fluorenes
Added in there-necked flask 2,7- dibromos fluorenes (9.7g, 0.03mol), benzyltriethylammoinium chloride (0.07g, 0.3mmol), dimethyl sulfoxide (DMSO) 90mL and 45mL sodium hydrate aqueous solutions (50wt%), at room temperature stirring form suspension；Add 1- bromines normal octane (12.5g, 65mmol), after continuing to stir 3 hours, are extracted with ether；Second is washed with saturated sodium-chloride water solution Ether phase, anhydrous magnesium sulfate is dried；Solvent is boiled off, product petroleum ether makees the purification of eluant, eluent column chromatography, obtains white solid.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product.The following institute of chemical equation Show：
Embodiment 3
2,7- diborate -9, the preparation of 9- dioctyl fluorenes
Under an argon atmosphere, bromo- 9, the 9- dioctyl fluorenes (5g, 9.12mmol) of 2,7- bis- are dissolved in the refined THF of 180mL In, 1.6mol.L is gradually added dropwise at -78 DEG C-1N-BuLi 28mL, react 2 hours, be subsequently adding 2- isopropoxy -4,4, 5,5- tetramethyl -1,3,2- dioxaborinate 25mL continue to react 1 hour at -78 DEG C, then heat to room temperature reaction 24 small When；Reactant mixture is poured into water, is extracted with ethyl acetate, after organic layer saline solution is washed completely, plus anhydrous magnesium sulfate Dry；After solution concentration, thick pale yellow shape crude product is obtained, (eluant, eluent selection petroleum ether/acetic acid second is purified with silica gel column chromatography Ester=15/1, v/v), product obtains white solid, yield 70% in placing refrigerator for a long time.1H NMR、13CNMR, MS and element Compound obtained by analysis result shows is target product.Chemical equation is as follows：
Embodiment 4
The bromo- 2- quinoxalines methyl formates of 1-
Under an argon atmosphere, by bromo- 2- quinoxalines formic acid (10g, 39.73mmol) the addition two-mouth bottles of 1-, add 100mL methyl alcohol, is then added dropwise over the concentrated sulfuric acid (39.06mg, 397.29umol), is heated to 110 DEG C, reacts 18h；Reaction is mixed Compound is poured into water, and is extracted with ethyl acetate, and after organic layer saline solution is washed completely, plus anhydrous magnesium sulfate is dried；Solution is dense After contracting, crude white solid is obtained, (eluant, eluent selects petroleum ether/dichloromethane=3/1, v/v) is purified with silica gel column chromatography, produced Thing obtains white solid, yield 85% in placing refrigerator for a long time.1H NMR、13CNMR, MS and elementary analysis result show gained The compound for arriving is target product.Chemical equation is as follows：
Embodiment 5
The preparation of compound M1
Under argon atmosphere, by 2,7- diborate -9,9- dioctyl fluorenes (5g, 7.78mmol) and the bromo- 2- naphthoic acids of 1- Methyl esters (6.19g, 23.54mmol) is added in two-mouth bottle, is added 100ml toluene and is completely dissolved, and adds sodium carbonate (4.12g, 38.91mmol), TBAB (312.01mg, 967.86umol) and four triphenyl phosphorus palladiums (179.84mg, 155.63umol), 18h is reacted at 110 DEG C；Reactant mixture is poured into water, is extracted with ethyl acetate, organic layer salt After water is washed completely, plus anhydrous magnesium sulfate is dried；After solution concentration, (eluant, eluent selection petroleum ether/bis- are purified with silica gel column chromatography Chloromethanes=8/1, v/v), finally give white solid, yield 80%.1H NMR、13CNMR, MS and elementary analysis result show Resulting compound is target product.Chemical equation is as follows：
Embodiment 6
The preparation of compound M2
Under argon atmosphere, by M1 (10g, 13.07mmol) addition single port bottles, the anhydrous THF of 50ml are added until complete CL；Reaction solution is reacted into 1h at 0 DEG C again, then is added dropwise over C8H17MgBr (n-octyl magnesium bromide), mixed liquor is in room temperature Lower reaction 18h；Add water to that reaction is quenched in reaction solution, be extracted with ethyl acetate, organic layer saline solution is washed completely Afterwards, plus anhydrous magnesium sulfate dry；After solution concentration, (eluant, eluent selection petroleum ether/dichloromethane=3/ is purified with silica gel column chromatography 1, v/v), product obtains white solid, yield 80% in placing refrigerator for a long time.1H NMR、13CNMR, MS and elementary analysis knot Compound obtained by fruit shows is target product.Chemical equation is as follows：
Embodiment 7
The preparation of compound M3
Under argon atmosphere, M2 (5g, 8.58mmol) is dissolved in 50ml dichloromethane, trifluoro is added dropwise at room temperature Change borate ether solution (588.67mg, 8.68mmol), react 18h；It is extracted with ethyl acetate, organic layer saline solution is washed completely Afterwards, plus anhydrous magnesium sulfate dry；After solution concentration, (eluant, eluent selection petroleum ether) is purified with silica gel column chromatography, product is for a long time White solid, yield 90% are obtained in placement refrigerator.1H NMR、13CNMR, MS and elementary analysis result show resulting change Compound is target product.Chemical equation is as follows：
Embodiment 8
The preparation of compound M4
Under argon atmosphere, M3 (5g, 4.38mmol) is dissolved in 50mL dichloromethane, add iron powder (185.35mg, 4.38mmol), then bromine (1.50g, 9.41mmol) is added dropwise over, 18h is reacted at room temperature；It is extracted with ethyl acetate, it is organic After layer saline solution is washed completely, 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.Change Learn reaction equation as follows：
Embodiment 9
The preparation of compound M5
Under an argon atmosphere, M4 (10g, 7.75mmol) is dissolved in the refined THF of 180mL, is gradually dripped at -78 DEG C Plus the n-BuLi 32mL of 1.6mol L-1, react 2 hours, it is then quickly added into 2- isopropoxy -4,4,5,5- tetramethyl -1, 3,2- dioxaborinate 28mL, continue to react 1 hour at -78 DEG C, are to slowly warm up to room temperature reaction 24 hours；Reaction is mixed Compound is poured into water, and is extracted with ethyl acetate, and after organic layer saline solution is washed completely, plus anhydrous magnesium sulfate is dried；Solution is dense After contracting, thick pale yellow shape crude product is obtained, (eluant, eluent selection petrol ether/ethyl acetate=20/1, v/ are purified with silica gel column chromatography V), product obtains white solid, yield 70% in placing refrigerator for a long time.1H NMR and GC-MASS test are shown to be target product Thing.Chemical equation is as follows：
Embodiment 10
The preparation of 3,6- dibromo carbazoles
In 500mL two-mouth bottles add carbazole (24.7g, 0.1mol), dimethylformamide 200mL, stirring to completely it is molten Solution, NBS (49.84g, 0.28mol) 120ml DMFs dissolve, and ice bath is added dropwise NBS solution, instead to 0 DEG C Should, lucifuge, after completion of dropping, temperature rises to room temperature automatically, reacts 6 hours, reaction solution is added drop-wise in water and is precipitated, and suction filtration is obtained To after crude product, suction filtration thing is recrystallized with absolute ethyl alcohol, dried, obtained precious color needle-like solid, yield 85%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product.The following institute of chemical equation Show：
Embodiment 11
The bromo- N- octylcarbazols of 3,6- bis-
3,6- dibromos carbazole (16.25g, 0.05mmol), toluene 100mL and tetrabutyl bromine are added in 250mL there-necked flasks Change ammonium (0.8g, 3.5mmol) stirring and dissolving, 50wt%KOH aqueous solution 11mL are then added dropwise, then add bromooctane (19.3g, 0.1mol), reacts 24 hours at 80 DEG C, and add water terminating reaction, the organic phase that washing is separated, and water is mutually with two After chloromethanes extraction, merge organic phase, use anhydrous MgSO4Dry, vacuum distillation obtains light yellow solid after removing solvent, uses stone Oily ether is recrystallized to give white powder solid.Yield 90%.1H NMR、13CNMR, MS and elementary analysis result show resulting Compound is target product.Chemical equation is as follows：
Embodiment 12
3,6- bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-diyl)-N- octylcarbazols
The bromo- N- octylcarbazols (13.11g, 30mmol) of 3,6- bis-, the new ether 250mL for steaming, stirring are added in there-necked flask It is completely dissolved to clear, reaction solution is cooled to -78 DEG C, it is then disposable to add 2- isopropoxies-(4,4,5,5- tetra- Methyl) -1,3,2- ethylenedioxy borates (37mL, 180mmol), stir 2 hours, then temperature is warmed to room temperature at -78 DEG C Reaction terminates reaction after 24 hours；Extracted with ether, saturated common salt water washing 4 times, then dried with anhydrous magnesium sulfate, after filtering, Solvent, product petrol ether/ethyl acetate (10 is distilled off:1) for eluant, eluent column chromatography is purified, white solid, yield are obtained 45%.Chemical equation is as follows：
Embodiment 13
The preparation of 3,7- bis- bromo- S, S- titanium dioxide dibenzothiophens
(1) 5g biphenyl is dissolved in 80mL dichloromethane in the round-bottomed flask of 150mL, 11.8g is added at room temperature Bromo-succinimide, then reacts 48 hours at room temperature；After reaction terminates, reactant is poured into water, is extracted with dichloromethane Take, then wash with water；Anhydrous magnesium sulfate is dried, and solvent is evaporated off, and is then recrystallized with petroleum ether.White solid 5.65g is obtained, Yield 75%.
(2) add 20g4,4 '-'-dibromobiphenyl to be dissolved in 50mL chloroforms in 150mL there-necked flasks, be added dropwise 11.4mL chlorosulfonic acids, maintenance reaction system is reacted 3 hours below 50 DEG C；After reaction terminates, reactant is poured into 500mL broken In ice, neutrality is adjusted to Na2CO3 solution after ice-out, filters out insoluble matter, Recrystallisation from acetic acid is used after washing and drying, obtain white Color needle-like solid 6g, yield：12%.
Chemical equation is as follows：
Embodiment 14
The preparation of polymer P 1
Under argon atmosphere, by compound M4 (300mg, 297.88 μm of ol), quinoxaline and indenes fluorenes (163.18mg, 178.73umol) added in 100ml two-mouth bottles with bromo- 9, the 9- dioctyl fluorenes of 2,7- bis- (65.35mg, 119.15 μm of ol), then added Enter 8ml toluene to be completely dissolved, substitute gas three times；Add palladium (2.68mg, 11.92 μm of ol) and tricyclohexyl phosphine (6.68mg, 23.82 μm of ol), substitute gas three times；2ml tetraethyl ammonium hydroxides are subsequently adding, 80 degrees Celsius, reaction 24 are warming up to Hour；It is subsequently adding 30mg phenyl boric acids to be blocked, after 12 hours, then is blocked with 0.1ml bromobenzenes, continues to react 12 hours Afterwards, product is added dropwise and is precipitated out in methyl alcohol, stirred, then be dissolved in crude product in the toluene of 20mL by filtering, with 200~ 300 mesh silica gel are fixing phase, are that eluant, eluent carries out column chromatography with toluene, then after solvent under reduced pressure is concentrated, again in methyl alcohol Separate out and, stirring, filtering obtains polymer solids after vacuum drying.It is last each with methyl alcohol, acetone, tetrahydrofuran successively again Extracting 24 hours, removes small molecule.By precipitating, the fibre obtained after vacuum drying in the tetrahydrofuran solution instillation methyl alcohol after concentration Dimension shape solid conjugated polymer P1.Chemical equation is as follows：
The polymer P 1 for obtaining is in filminess uv-visible absorption spectra spectrogram as shown in figure 1, can from figure Go out, the maximum absorption band of polymer P 1 is located at 290nm.
Embodiment 15
The preparation of polymer P 2
Under argon atmosphere, by M4 (300mg, 297.88 μm of ol), quinoxaline and indenes fluorenes (163.18mg, 178.73umol) Added in 100ml two-mouth bottles with N- octylcarbazols (52.09mg, 119.15 μm of ol), add 8ml toluene and be completely dissolved, Substitute gas three times；Palladium (2.68mg, 11.92 μm of ol) and tricyclohexyl phosphine (6.68mg, 23.82 μm of ol) are added, is substituted Gas three times；2ml tetraethyl ammonium hydroxides are subsequently adding, 80 degrees Celsius are warming up to, reacted 24 hours；It is subsequently adding 30mg phenyl boric acids Blocked, after 12 hours, then blocked with 0.1ml bromobenzenes, continued to react 12 hours afterwards, product is added dropwise in methyl alcohol It is precipitated out, stirs, filtering, then crude product is dissolved in the toluene of 20mL, it is fixing phase with 200~300 mesh silica gel, use toluene For eluant, eluent carries out column chromatography, then after solvent under reduced pressure is concentrated, separate out to come in methyl alcohol again, stirring, filtering, vacuum is done Polymer solids are obtained after dry.Finally respectively extracted 24 hours with methyl alcohol, acetone, tetrahydrofuran successively again, remove small molecule.Will be dense Tetrahydrofuran solution after contracting instills precipitating, the fibrous solids conjugated polymer P2 obtained after vacuum drying in methyl alcohol.Chemistry Reaction equation is as follows：
The polymer P 2 for obtaining is in filminess uv-visible absorption spectra spectrogram as shown in Fig. 2 can from figure Go out, the maximum absorption band of polymer P 2 is located at 300nm.
Embodiment 16
The preparation of polymer P 3
Under argon atmosphere, by M4 (300mg, 297.88 μm of ol), quinoxaline and indenes fluorenes (163.18mg, 178.73umol) With the bromo- S of 3,7- bis-, in S- dioxydibenzes bithiophene (44.57mg, 119.15 μm of ol) addition 100ml two-mouth bottles, 8ml is added Toluene is completely dissolved, and substitutes gas three times；Add palladium (2.68mg, 11.92 μm of ol) and tricyclohexyl phosphine (6.68mg, 23.82 μm of ol), substitute gas three times；2ml tetraethyl ammonium hydroxides are subsequently adding, 80 degrees Celsius, reaction 24 are warming up to Hour；It is subsequently adding 30mg phenyl boric acids to be blocked, after 12 hours, then is blocked with 0.1ml bromobenzenes, continues to react 12 hours Afterwards, product is added dropwise and is precipitated out in methyl alcohol, stirred, then be dissolved in crude product in the toluene of 20mL by filtering, with 200~ 300 mesh silica gel are fixing phase, are that eluant, eluent carries out column chromatography with toluene, then after solvent under reduced pressure is concentrated, again in methyl alcohol Separate out and, stirring, filtering obtains polymer solids after vacuum drying.It is last each with methyl alcohol, acetone, tetrahydrofuran successively again Extracting 24 hours, removes small molecule.By precipitating, the fibre obtained after vacuum drying in the tetrahydrofuran solution instillation methyl alcohol after concentration Dimension shape solid conjugated polymer P3.Chemical equation is as follows：
The current density of the polymer P 3 for obtaining-luminous efficiency spectrogram, as shown in Figure 3.It can be seen that electroluminescent hair Optical device structure is ITO/PEDOT/EMITTER/CsF/Al, the current density-stream of the electroluminescent device based on polymer P 3 Obvious results rate spectrogram is as shown in figure 3, it can be seen that maximum lumen efficiency is 1.82cd/A.
The preparation of the electroluminescent device based on conjugated polymer
It is on tin indium oxide (ITO) glass of 20 Ω/, acetone, washing first to be used successively in the square resistance of well in advance Agent, deionized water and isopropanol are cleaned by ultrasonic, plasma treatment 10 minutes；Spin coating 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；The chlorobenzene solution (1wt%) of polymer P 1, P2 and P3 is then spin-coated on PEDOT respectively:The table of PSS films Face, thickness is 80nm, used as luminescent layer；It is last to be deposited with the thick gold of a thin layer CsF (1.5nm) and 120nm successively on luminescent layer Al layers of category.
The EL device structure for obtaining is ITO/PEDOT/EMITTER/CsF/Al, the electroluminescent hair based on polymer P 3 The current density of optical device-luminous efficiency spectrogram is as shown in figure 3, it can be seen that maximum lumen efficiency is 1.82cd/A.
The photoelectric properties of the electroluminescent device based on polymer P 1, P2 and P3 are as shown in table 1.
Table 1 is based on the photoelectric properties index of the conjugated polymer of two heteroaromatics and indenes fluorenes unit
As shown in Table 1, EL device structure is ITO/PEDOT/EMITTER/CsF/Al, based on polymer P 1, P2 Maximum lumen efficiency with the electroluminescent device of P3 is followed successively by 1.62cd/A, 1.47cd/A, 1.82cd/A.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment Limitation, other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification all should It is equivalent substitute mode, is included within protection scope of the present invention.

Claims (7)

1. a kind of conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit, it is characterised in that chemical structural formula is as follows：
In formula, Ar1It is hexa-atomic heteroaromatic；R is aryl, triphenylamine, the straight or branched alkyl of carbon number 1-20, halogen, cyanogen Base, alkoxy or fluoroalkyl, or be the alkoxy of carbon number 1-20；0≤x≤1；Polymerization degree n=1-300.
2. a kind of conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit according to claim 1, it is characterised in that Ar It is any one in following structure：
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- substitution-dithieno thiophenes are coughed up；
2,6- substitution-dithieno cyclopentadiene；
2,5- substituted pyridines；
2,6- substituted pyridines；
3,5- substituted pyridines；
3,5- double (4- substituted 4-phenyls) -4- base -1,2,4- triazoles；
3,5- double (4- substituted 4-phenyls) -1,2,4- oxadiazoles；
4,7- double (5- substitution -4- alkylthrophenes bases) -2,1,3- diazosulfide；
4,7- double (5- substitution -4- alkylthrophenes bases) 2,1,3- selenoles；
4,7- -5,6- of substitution alkyl -2,1,3- diazosulfide；
4,7- -5,6- of substitution alkyl -2,1,3- selenole；
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；
S, S- dioxydibenze bithiophene；
Wherein, R1For hydrogen, aryl, triphenylamine, carbon number 1-20 straight chain or branched alkyl, or be carbon number 1-20's Alkoxy.
3. a kind of described in claim 1 is based on the preparation method of the conjugated polymer of two heteroaromatics and indenes fluorenes unit, its feature It is to comprise the following steps：
Under argon atmosphere, by two heteroaromatics, simultaneously indenes fluorenes unit passes through Suzuki polymerisations with the boric acid ester monomer containing Ar structures Afterwards, then successively end capping reaction is carried out using phenyl boric acid and bromobenzene, obtains being total to based on two heteroaromatics and indenes fluorenes unit unit Conjugated polymer.
4. the preparation method of a kind of conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit according to claim 3, its It is characterised by, the temperature of the Suzuki polymerisations is 80~100 DEG C, and the time is 24~48 hours.
5. the preparation method of a kind of conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit according to claim 3, its It is characterised by, the temperature for carrying out end capping reaction using phenyl boric acid and bromobenzene is 80~100 DEG C, and the time is 12~24 hours.
6. a kind of described in claim 1 is based on two heteroaromatics and the conjugated polymer of indenes fluorenes unit is applied to prepare light-emitting diodes The luminescent layer of pipe, it is characterised in that the organic solvent of the conjugated polymer based on two heteroaromatics and indenes fluorenes unit is dissolved, then is led to Spin coating, inkjet printing or printing film forming are crossed, the luminescent layer of the light emitting diode is obtained.
7. application according to claim 6, it is characterised in that the organic solvent includes chlorobenzene.
CN201710101433.XA 2017-02-24 2017-02-24 A kind of conjugated polymer for being based on two heteroaromatics and indenes fluorenes unit and preparation method and application Pending CN106905512A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105384917A (en) * 2015-11-10 2016-03-09 华南理工大学 Conjugated polymer with side chain containing sulfonic acid or sulfonate and plane-inverted organic/inorganic hybrid perovskite solar cell prepared from conjugated polymer
CN105924629A (en) * 2016-06-27 2016-09-07 华南理工大学 Conjugated polymer based on naphthoindenofluorene unit as well as preparation method and application thereof
CN106243329A (en) * 2016-07-29 2016-12-21 华南理工大学 One is based on S, S dioxydibenze thiophthene derivative replaces conjugated polymer luminescent material and preparation method and application to receptor type

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105384917A (en) * 2015-11-10 2016-03-09 华南理工大学 Conjugated polymer with side chain containing sulfonic acid or sulfonate and plane-inverted organic/inorganic hybrid perovskite solar cell prepared from conjugated polymer
CN105924629A (en) * 2016-06-27 2016-09-07 华南理工大学 Conjugated polymer based on naphthoindenofluorene unit as well as preparation method and application thereof
CN106243329A (en) * 2016-07-29 2016-12-21 华南理工大学 One is based on S, S dioxydibenze thiophthene derivative replaces conjugated polymer luminescent material and preparation method and application to receptor type

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