CN106866940A - A kind of conjugated polymer for being based on 3,7 naphtho- sulphur dibenzofuran units and preparation method and application - Google Patents

A kind of conjugated polymer for being based on 3,7 naphtho- sulphur dibenzofuran units and preparation method and application Download PDF

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CN106866940A
CN106866940A CN201710030871.1A CN201710030871A CN106866940A CN 106866940 A CN106866940 A CN 106866940A CN 201710030871 A CN201710030871 A CN 201710030871A CN 106866940 A CN106866940 A CN 106866940A
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substitution
naphtho
fluorenes
conjugated polymer
sulphur dibenzofuran
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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 3,7 naphtho- sulphur dibenzofuran units and preparation method and application.The present invention obtains the described conjugated polymer based on 3,7 naphtho- sulphur dibenzofuran units by Suzuki polymerisations.Conjugated polymer of the present invention based on 3,7 naphtho- sulphur dibenzofuran units has preferable dissolubility, after being dissolved using common organic solvents, then by spin coating, inkjet printing or printing film forming, prepares the luminescent layer of light emitting diode.Luminescent layer based on the polymer is for preparing during luminescent device without annealing so that preparation technology is simpler.

Description

A kind of conjugated polymer based on 3,7- naphtho- sulphur dibenzofuran units and preparation method thereof with Using
Technical field
The present invention relates to organic photoelectrical material technical field, and in particular to one kind being total to based on 3,7- naphtho- sulphur dibenzofuran units 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.
3, the 7- naphtho-s sulphur dibenzofuran unit and its polymer that the present invention relates to, because having preferable solubility property, Suitable for solution processing, and preferably fluorescence quantum yield, 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 3,7- naphtho- sulphur dibenzofuran units.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 based on 3,7- naphtho- sulphur dibenzofuran units Preparation Method.
The present invention also aims to provide a kind of conjugated polymer based on 3,7- naphtho- sulphur dibenzofuran units in system Application in the luminescent layer of standby Organic Light Emitting Diode.
Conjugated polymer of the one kind based on 3,7- naphtho- sulphur dibenzofuran units, with following chemical structural formula：
In formula, R is aryl, triphenylamine, the straight or branched alkyl of carbon number 1-20, or is the alkane of carbon number 1-20 Epoxide；0≤x≤1；Polymerization degree n=1-300；
Ar is any one in following structural formula：
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- 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；
Wherein, R is hydrogen, aryl, triphenylamine, the straight chain or branched alkyl of carbon number 1-20, or is carbon number 1- 20 alkoxy.
Described one kind is based on the preparation method of the conjugated polymer of 3,7- naphtho- sulphur dibenzofuran units, comprises the following steps：
By 3,7- naphtho-s sulphur dibenzofuran monomer with 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 3,7- naphtho- sulphur dibenzofuran units 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 based on 3,7- naphtho- sulphur dibenzofuran units is applied to prepare the hair of light emitting diode Photosphere, will based on the conjugated polymer of 3,7- naphtho- sulphur dibenzofuran units with organic solvent dissolve, 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 3,7- naphtho- sulphur dibenzofuran units of the invention, due to larger conjugate length, So there is fluorescence quantum yield higher, be conducive to improving the device efficiency of material；
(2) conjugated polymer for being based on 3,7- naphtho- sulphur dibenzofuran units of the invention, with preferable dissolubility, based on this The luminescent layer of polymer is for preparing during electroluminescent device without annealing so that preparation technology is simpler.
Brief description of the drawings
Fig. 1 is the DSC spectrograms of polymer P 1；
Fig. 2 is uv-visible absorption spectra spectrogram of the polymer P 2 under filminess；
Fig. 3 is photoluminescence spectra spectrogram of the polymer P 3 under filminess；
Fig. 4 is the current density-luminous efficiency spectrogram of the electroluminescent device based on polymer P 4.
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 2-methyl naphthoate of 1- bromines two
Chemical equation is as follows：
Under an argon atmosphere, by bromo- 2- naphthoic acids (10g, 39.83mmol) the addition two-mouth bottles of 1-, 100mL first is added Alcohol, is then added dropwise over 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 saline solution is washed completely, 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.
Embodiment 2
1- borate -2- 2-methyl naphthoates
Chemical equation is as follows：
Under argon atmosphere, the bromo- 2- 2-methyl naphthoates (10g, 37.72mmol) of compound 1- are dissolved in anhydrous THF, Stirred 20 minutes at -78 DEG C, add n-BuLi (21.05g, 113.16mmol), stirred 2 hours at -78 DEG C, then added Enter isopropoxy pinacol ester (9.66g, 150.88mmol), stirred at -78 DEG C 1 hour, react 16 hours at room temperature.Will be anti- Answer mixture to be poured into water, be extracted with ethyl acetate, after organic layer saline solution is washed completely, plus anhydrous magnesium sulfate is dried.It is molten After liquid concentration, crude white solid is obtained, (eluant, eluent selection petroleum ether/dichloromethane=2/1, v/ are purified with silica gel column chromatography V), product obtains white solid, yield 75% in placing refrigerator for a long time.1H NMR、13CNMR, MS and elementary analysis result table Compound obtained by bright is target product.
Embodiment 3
The preparation of 3,7- bis- bromo- S, S- titanium dioxide dibenzothiophens
Chemical equation is as follows：
(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.Be poured into water for reactant after terminating by reaction, 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 20g 4,4 '-'-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%.
Embodiment 4
The preparation of compound M1
Chemical equation is as follows：
Under argon atmosphere, by compound 3,7-S, S ,-dioxydibenze bithiophene (5g, 13.37mmol) and 1- borates- 2- 2-methyl naphthoates (12.52g, 40.10mmol) are added in two-mouth bottle, are added 100ml toluene and are completely dissolved, then are added Enter sodium carbonate (7.08g, 66.84mmol) and four triphenyl phosphorus palladiums (308.93mg, 267.35umol), oil bath is warming up to 110 DEG C, Reaction 16 hours.Reactant mixture is poured into water, is extracted with ethyl acetate, after organic layer saline solution is washed completely, plus nothing Water magnesium sulfate is dried.After solution concentration, crude white solid is obtained, (eluant, eluent selection petroleum ether/bis- are purified with silica gel column chromatography Chloromethanes=2/1, v/v), product obtains white solid, yield 75% in placing refrigerator for a long time.1H NMR、13CNMR, MS and Compound obtained by elementary analysis result shows is target product.
Embodiment 5
The preparation of compound M2
Chemical equation is as follows：
Under argon atmosphere, by M1 (10g, 17.10mmol) 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.
Embodiment 6
The preparation of compound M3
Chemical equation is as follows：
Under argon atmosphere, M2 (5g, 5.19mmol) 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 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 chemical combination Thing is target product.
Embodiment 7
The preparation of compound M4
Chemical equation is as follows：
Under argon atmosphere, M3 (5g, 5.50mmol) is dissolved in 50mL dichloromethane, add iron powder (185.35mg, 3.32mmol), then bromine (1.93g, 12.10mmol) 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.
Embodiment 8
The preparation of 2,7- dibromo fluorenes
Chemical equation is as follows：
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；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.
Embodiment 9
The preparation of 2,7- bis- bromo- 9,9- dioctyl fluorenes
Chemical equation is as follows：
Added in there-necked flask 2,7- dibromos fluorenes (9.7g, 0.03mol), benzyltriethylammoinium chloride (0.07g, 0.3mmol), dimethyl sulfoxide (DMSO) 90mL, 45mL sodium hydrate aqueous solutions (50wt%), at room temperature stirring forms 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.
Embodiment 10
2,7- diborate -9, the preparation of 9- dioctyl fluorenes
Chemical equation is as follows：
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 is placed in refrigerator, obtains white solid, yield 70%.1H NMR、13CNMR, MS and elementary analysis Compound obtained by result shows is target product.
Embodiment 11
The preparation of 3,6- dibromo carbazoles
Chemical equation is as follows：
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, after allowing temperature to rise to room temperature automatically, is reacted 6 hours, reaction solution is added drop-wise in water and is precipitated, and is taken out After filter obtains 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.
Embodiment 12
The preparation of the bromo- N- octylcarbazols of 3,6- bis-
Chemical equation is as follows：
3,6- dibromos carbazole (16.25g, 0.05mmol), toluene 100mL, tetrabutyl phosphonium bromide are added in 250mL there-necked flasks Ammonium (0.8g, 3.5mmol), stirring and dissolving, then be added dropwise 50wt%KOH aqueous solution 11mL, then add bromooctane (19.3g, 0.1mol), reacted 24 hours at 80 DEG C, add water terminating reaction, the organic phase that washing is separated, water is extracted with dichloromethane After taking, merge organic phase, use anhydrous MgSO4Dry, vacuum distillation obtains light yellow solid after removing solvent, is tied again with petroleum ether Crystalline substance obtains white powder solid.Yield 90%.1H NMR、13CNMR, MS and elementary analysis result show that resulting compound is Target product.
Embodiment 13
The preparation of 3,6- bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-diyl)-N- octylcarbazols
Preparation process chemical equation is as follows：
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), stirred 2 hours at -78 DEG C, then temperature is warmed to room temperature, 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%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product.
Embodiment 14
The preparation of polymer P 1
Preparation process chemical equation is as follows：
Under argon atmosphere, by 2,7- diborate -9,9- dioctyl fluorenes (300mg, 272.92 μm of ol) and 3,7- naphtho- Sulphur dibenzofuran (342.92mg, 272.92 μm of ol) is added in 100ml two-mouth bottles, is added 8ml toluene and is completely dissolved, and is added Palladium (2.45mg, 10.92 μm of ol) and tricyclohexyl phosphine (6.12mg, 21.83 μm of ol), are subsequently adding 2ml tetraethyl hydrogen-oxygens Change ammonium, be warming up to 80 DEG C, react 24 hours；It is subsequently adding 30mg phenyl boric acids to be blocked, after 12 hours, then uses 0.1ml bromobenzenes Blocked；Continue to react 12 hours afterwards, product is added dropwise and is precipitated out in methyl alcohol, stir, filtering, then crude product is molten It is fixing phase with 200~300 mesh silica gel in the toluene of 20mL, is that eluant, eluent carries out column chromatography with toluene, then by solvent under reduced pressure After concentration, separate out to come in methyl alcohol again, stirring, filtering obtains polymer solids after vacuum drying；Finally use successively again Methyl alcohol, acetone, tetrahydrofuran are respectively extracted 24 hours, remove small molecule；Sunk during tetrahydrofuran solution after concentration is instilled into methyl alcohol Analysis, the fibrous solids conjugated polymer P1 obtained after vacuum drying.
The DSC spectrograms of the polymer P 1 for obtaining are as shown in figure 1, as shown in Figure 1, the glass transition temperature of polymer P 1 is 127℃。
Embodiment 15
The preparation of polymer P 2
Preparation process chemical equation is as follows：
Under argon atmosphere, by 3,6- bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborinates-diyl)-N- octyl group clicks Azoles (145.01mg, 272.92 μm of ol) and 3,7- naphtho- sulphur dibenzofuran (300mg, 272.92 μm of ol) are added in 100ml two-mouth bottles, then Add 8ml toluene to be completely dissolved, add palladium (2.45mg, 10.92 μm of ol) and tricyclohexyl phosphine (6.12mg, 21.83 μm of ol), 2ml tetraethyl ammonium hydroxides are subsequently adding, 80 DEG C are warming up to, react 24 hours；It is subsequently adding 30mg phenyl boric acids Blocked, after 12 hours, then blocked with 0.1ml bromobenzenes；Continue 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.
UV-visible absorption spectrum of the polymer P 2 for obtaining under filminess is as shown in Fig. 2 as shown in Figure 2, gather Maximum absorption bands of the compound P2 under filminess is located at 320nm and 360nm.
Embodiment 14
The preparation of polymer P 3
Preparation process chemical equation is as follows：
Under argon atmosphere, by indenes fluorenes boric acid (260.66mg, 272.92 μm of ol) and 3,7- naphtho- sulphur dibenzofuran (300mg, 272.92 μm of ol) add 100ml two-mouth bottles in, add 8ml toluene and be completely dissolved, add palladium (2.45mg, 10.92 μm of ol) and tricyclohexyl phosphine (6.12mg, 21.83 μm of ol), 2ml tetraethyl ammonium hydroxides are subsequently adding, it is warming up to 80 DEG C, react 24 hours；It is subsequently adding 30mg phenyl boric acids to be blocked, after 12 hours, then is blocked with 0.1ml bromobenzenes；Continue Be added dropwise for product and be precipitated out in methyl alcohol by reaction for 12 hours afterwards, stirs, filtering, then the toluene that crude product is dissolved in 20mL In, it is fixing phase with 200~300 mesh silica gel, it is that eluant, eluent carries out column chromatography with toluene, then after solvent under reduced pressure is concentrated, further Secondary separating out in methyl alcohol is come, stirring, and filtering obtains polymer solids after vacuum drying；It is last again successively with methyl alcohol, acetone, Tetrahydrofuran is respectively extracted 24 hours, removes small molecule；By precipitating, vacuum drying in the tetrahydrofuran solution instillation methyl alcohol after concentration The fibrous solids conjugated polymer P3 for obtaining afterwards.
UV-visible absorption spectrum of the polymer P 3 for obtaining under filminess is as shown in figure 3, from the figure 3, it may be seen that poly- Maximum emission peaks of the compound P3 under filminess is located at 492nm.
Embodiment 16
The preparation of polymer P 4
Preparation process chemical equation is as follows：
Under argon atmosphere, by naphtho- indenes fluorenes borate (274.33mg, 272.92 μm of ol) and 3,7- naphtho- sulphur dibenzofuran (300mg, 272.92 μm of ol) are added in 100ml two-mouth bottles, are added 8ml toluene and are completely dissolved, and add palladium (2.45mg, 10.92 μm of ol) and tricyclohexyl phosphine (6.12mg, 21.83 μm of ol), is subsequently adding 2ml tetraethyl ammonium hydroxides, rises Temperature is reacted 24 hours to 80 degrees Celsius；It is subsequently adding 30mg phenyl boric acids to be blocked, after 12 hours, then is carried out with 0.1ml bromobenzenes End-blocking；Continue to react 12 hours afterwards, product is added dropwise and is precipitated out in methyl alcohol, stir, filtering, then crude product is dissolved in It is fixing phase with 200~300 mesh silica gel in the toluene of 20mL, is that eluant, eluent carries out column chromatography with toluene, then solvent under reduced pressure is dense After contracting, separate out to come in methyl alcohol again, stirring, filtering obtains polymer solids after vacuum drying；Finally use first successively again Alcohol, acetone, tetrahydrofuran are respectively extracted 24 hours, remove small molecule；By precipitating in the tetrahydrofuran solution instillation methyl alcohol after concentration, The fibrous solids conjugated polymer P4 obtained after vacuum drying.
Embodiment 17
The preparation of the electroluminescent device based on polymer
It is on tin indium oxide (ITO) glass of 20 Ω/, first successively with acetone, washing 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 luminescent material P1, P2, P3, P4 is then spin-coated on PEDOT:PSS films Surface, thickness is 80nm, used as luminescent layer；It is last to be deposited with a thin layer CsF (1.5nm) and 120nm thickness successively on luminescent layer Metal Al layer；Obtaining device architecture is：ITO/PEDOT/EML/CsF/Al.
The current density of the electroluminescent device based on polymer P 4-luminous efficiency spectrogram as shown in figure 4, as shown in Figure 4, The maximum lumen efficiency of the electroluminescent device based on polymer P 4 is 1.88cd/A.
Electroluminescent device to obtaining carries out photoelectric properties test respectively, as a result as shown in table 1.
Table 1 is based on the photoelectric properties index of the electroluminescent device that 1~P4 of polymer P is obtained
As shown in Table 1, luminescent layer is prepared with polymer P 1, P2, P3, P4, prepares device architecture for ITO/PEDOT/EML/ The electroluminescent device of CsF/Al, maximum lumen efficiency is followed successively by 1.12cd/A, 0.85cd/A, 0.61cd/A, 1.31cd/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 (6)

1. one kind is based on the conjugated polymer of 3,7- naphtho- sulphur dibenzofuran units, it is characterised in that with following chemical structural formula：
In formula, R is aryl, triphenylamine, the straight or branched alkyl of carbon number 1-20, or is the alcoxyl of carbon number 1-20 Base；0≤x≤1；Polymerization degree n=1-300；
Ar is any one in following structural formula：
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；
Wherein, R is hydrogen, aryl, triphenylamine, the straight chain or branched alkyl of carbon number 1-20, or is carbon number 1-20's Alkoxy.
2. the one kind described in claim 1 is based on the preparation method of the conjugated polymer of 3,7- naphtho- sulphur dibenzofuran units, its feature It is to comprise the following steps：
Under argon atmosphere, 3,7- naphtho-s sulphur dibenzofuran monomer is passed through into 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 the conjugation based on 3,7- naphtho- sulphur dibenzofuran units and gather Compound.
3. one kind according to claim 2 is based on the preparation method of the conjugated polymer of 3,7- naphtho- sulphur dibenzofuran units, its It is characterised by, the temperature of the Suzuki polymerisations is 80~100 DEG C, and the time is 24~48 hours.
4. one kind according to claim 2 is based on the preparation method of the conjugated polymer of 3,7- naphtho- sulphur dibenzofuran units, 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.
5. a kind of conjugated polymer based on 3,7- naphtho- sulphur dibenzofuran units described in claim 1 is applied to prepare light-emitting diodes The luminescent layer of pipe, it is characterised in that will be dissolved based on the conjugated polymer of 3,7- naphtho- sulphur dibenzofuran units organic solvent, then led to Spin coating, inkjet printing or printing film forming are crossed, the luminescent layer of Light-Emitting Diode is obtained.
6. application according to claim 5, it is characterised in that the organic solvent includes chlorobenzene.
CN201710030871.1A 2017-01-17 2017-01-17 A kind of conjugated polymer for being based on 3,7 naphtho- sulphur dibenzofuran units and preparation method and application Pending CN106866940A (en)

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Application publication date: 20170620