CN107383343A - A kind of blue light frequency-doubling luminescent material based on naphtho- sulphur dibenzofuran unit and preparation method and application - Google Patents

A kind of blue light frequency-doubling luminescent material based on naphtho- sulphur dibenzofuran unit and preparation method and application Download PDF

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CN107383343A
CN107383343A CN201710764977.4A CN201710764977A CN107383343A CN 107383343 A CN107383343 A CN 107383343A CN 201710764977 A CN201710764977 A CN 201710764977A CN 107383343 A CN107383343 A CN 107383343A
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naphtho
substitution
substituted
fluorenes
luminescent material
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应磊
王小君
钟知鸣
马亚威
郭婷
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 blue light frequency-doubling luminescent material based on naphtho- sulphur dibenzofuran unit and preparation method and application.Sulfuryl in naphtho- sulphur dibenzofuran unit is strong electrophilic unit, be advantageous to improve electron affinity, promote the injection and transmission of electronics, with high fluorescence efficiency and chemical stability, and the sulfuryl in naphtho- sulphur dibenzofuran unit is located at the side chain of polymer, there are appropriate conjugate planes, spectrum will not be made to have larger red shift.The present invention obtains the described blue light frequency-doubling luminescent material based on naphtho- sulphur dibenzofuran unit by Suzuki polymerisations has preferable dissolubility, after being dissolved using common organic solvents, pass through spin coating, inkjet printing or printing film forming again, the luminescent layer of light emitting diode is prepared, without annealing when preparing luminescent device based on the luminescent layer, make preparation technology simpler.

Description

A kind of blue light frequency-doubling luminescent material and its preparation side based on naphtho- sulphur dibenzofuran unit Method and application
Technical field
The invention belongs to organic photoelectric technical field, and in particular to a kind of blue light frequency-doubling based on naphtho- sulphur dibenzofuran unit Luminescent material 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 produces Product have cheap, body light the advantages that taking.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, exploitation is new and effective Stable material turns into key.
It is exactly the hair of luminescent device but organic luminescent device technology encounters bottleneck problem in evolution at present 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.
Therefore, exploitation one kind has preferable fluorescence quantum yield, and makes luminescent device not only efficient stable, and for more Blue saturation blue light, can realize that the polymer luminescent material of the raising of the luminous efficiency and service life of luminescent device shows simultaneously Must be particularly important, there are huge development potentiality and prospect in organic electronic display field.
The content of the invention
It is an object of the invention to the deficiency for existing polymer LED (PLED), there is provided one kind is based on naphthalene And the blue light frequency-doubling luminescent material of sulphur dibenzofuran unit.Sulfuryl in naphtho- sulphur dibenzofuran unit is strong electrophilic unit, is advantageous to Electron affinity is improved, promotes the injection and transmission of electronics, there is high fluorescence efficiency and chemical stability, and naphtho- sulphur dibenzofuran list Sulfuryl in member is located at the side chain of polymer, has appropriate conjugate planes, spectrum will not be made to have larger red shift；Meanwhile the base It is used as luminescent material in the blue light frequency-doubling luminescent material of naphtho- sulphur dibenzofuran unit, there is preferable dissolubility, higher fluorescence Quantum yield, is suitable for solution processing and inkjet printing, and luminescent device prepared by the luminescent layer based on the material is not only efficiently steady It is fixed, and be more blue saturation blue light, while the luminous efficiency and service life of higher luminescent device are realized, meet full-color aobvious The requirement shown, there is good development prospect.
The present invention also aims to provide a kind of described blue light frequency-doubling based on naphtho- sulphur dibenzofuran unit luminous material The preparation method of material.
The present invention also aims to provide a kind of described conjugated polymer based on naphtho- sulphur dibenzofuran unit luminous material Expect the application in the luminescent layer of light emitting diode is prepared.
A kind of blue light frequency-doubling luminescent material based on naphtho- sulphur dibenzofuran unit, there is following chemical structural formula：
In formula, R1、R2Aryl, triphenylamine, carbon number 1-20 straight or branched alkyl are independently chosen from, or it is former for carbon Subnumber 1-20 alkoxy；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；
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 bases) -2,1,3- diazosulfide；
4,7- double (5- substitution -4- alkylthrophenes base) 2,1,3- selenoles；
Indenes fluorenes；
Indole carbazole；
2,6- substitutions-dithieno thiophene is coughed up；
2,6- substitutions-dithieno cyclopentadiene；
2,5- substitution -3,4- dialkyl group selenophens；
5,5- -4,4- of substitution dialkyl group-bithiophene；
4,7- bis- (4- substituted-phenyls) -2,1,3- diazosulfides；
4,7- bis- (4- substituted-phenyls) -2,1,3- selenoles；
4,7- bis- (5- substitution -4- alkylthrophene -2- bases) -2,1,3- benzos thiophene two Azoles；
4,7- bis- (5- substitution -4- alkylthrophene -2- bases) -2,1,3- benzos selenium two Azoles；
(N- (4- substituted-phenyls)-N- (the 4- alkylbenzenes of 4,7- bis- Base) amido) -2,1,3- diazosulfides；
(N- (4- substituted-phenyls)-N- (the 4- alkylbenzenes of 4,7- bis- Base) amido) -2,1,3- selenoles；
(4- (N- (the 4- substituted benzenes of 4,7- bis- Base)-N- (4- alkyl phenyls) amido) phenyl) -2,1,3- diazosulfides；
(4,4'- (benzo [c] [1,2,5] selenium Diazole -4,7- diyl) double (N, N- diphenyl aniline))
Wherein, R H, aryl, triphenylamine, carbon number 1-20 straight chain or branched alkyl, or be carbon number 1-20 Alkoxy；Z1、Z2It is independently chosen from H, D, F, CN, alkenyl, alkynyl, itrile group, amido, nitro, acyl group, alkoxy, carbonyl, sulfone Base, the alkyl of carbon number 1~30, the cycloalkyl of carbon number 3~30, the aromatic hydrocarbyl of carbon number 6~60 or carbon are former The aromatic heterocycle of subnumber 3~60.
The method for preparing a kind of described conjugated polymer luminescent material based on naphtho- sulphur dibenzofuran unit, including following step Suddenly：
Under argon atmosphere, R will be contained1And R2Naphtho- sulphur dibenzofuran unit and the boric acid ester units of the structure containing Ar pass through After Suzuki polymerisations, then end capping reaction is carried out using phenyl boric acid and bromobenzene successively, obtain described being based on naphtho- sulphur dibenzofuran list The conjugated polymer luminescent material of member.
Further, the temperature of the Suzuki polymerisations is 80~100 DEG C, and the time is 24~48 hours.
Further, it is 80~100 DEG C to carry out the temperature of end capping reaction using phenyl boric acid and bromobenzene, and the time is 12~ 24 hours.
A kind of described conjugated polymer luminescent material based on naphtho- sulphur dibenzofuran unit is applied to prepare light emitting diode Luminescent layer, the conjugated polymer luminescent material based on naphtho- sulphur dibenzofuran unit is dissolved with organic solvent, then pass through spin coating, spray Ink printing or printing film forming, obtain the luminescent layer of light emitting diode.
Further, the organic solvent includes chlorobenzene, dimethylbenzene or chloroform.
Compared with present technology, the present invention has advantages below：
(1) conjugated polymer luminescent material based on naphtho- sulphur dibenzofuran unit of the invention, due to appropriate conjugation Length, while there is higher fluorescence quantum yield, ensure the blue emission for having preferable excitation again, be advantageous to improve blue light The efficiency of material devices；
(2) conjugated polymer luminescent material based on naphtho- sulphur dibenzofuran unit of the invention, has preferable dissolubility, base Without annealing when the luminescent layer of the polymer is preparing electroluminescent device so that preparation technology is simpler.
Brief description of the drawings
Fig. 1 is the thermogravimetric analysis figure of polymer P 1, P2 and P3；
Fig. 2 is the Thin Films UV-vis optical absorption spectra figure of polymer P 1, P2 and P3；
Fig. 3 is the film luminescence generated by light spectrogram of polymer P 1, P2 and P3.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment and accompanying drawing, but the invention is not restricted to this.
Embodiment 1
Compound M1 synthesis
The preparation of 2- bromines dibenzo [b, d] thiophene
In 500mL there-necked flasks, add dibenzo [b, d] thiophene (20.00g, 108.54mmol), iron powder (0.33g, 6mmol), chloroform 200mL, ice-water bath cooling, bromine (19.08g, 119.40mmol) is injected into flask, drop with syringe Temperature is no more than 5 DEG C in added-time bottle, reacts 12 hours；Stop reaction, filtering, Gossypol recrystallized from chloroform, obtain white solid, yield 62%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product M1, and preparation process is chemical Reaction equation is as follows：
Embodiment 2
Compound M2 synthesis
The preparation of 2- (dibenzo [b, d] thiophene -2- bases) -4,4,5,5- tetramethyl -1,3,2- dioxaborinates
2- bromines dibenzo [b, d] thiophene (10.00g, 45.6mmol) is dissolved in refined anhydrous THF (200mL), 1.6mol/L n-BuLi (3.65g, 57.00mmol) is gradually added dropwise at -78 DEG C, reacts 2 hours, 2- isopropyls is then added dropwise Epoxide -4,4,5,5- tetramethyls -1,3,2- dioxaborinates (14.14g, 76.00mmol), it is small to continue reaction 1 at -78 DEG C When, it is warming up to room temperature reaction 24 hours.Reactant mixture is poured into water, is extracted with ethyl acetate, organic layer saline solution is complete After full washing, anhydrous magnesium sulfate is added to dry.After solution concentration, thick pale yellow shape crude product is obtained, is purified and (washed with silica gel column chromatography De- agent selection petroleum ether/dichloromethane=5/1, v/v), obtain yellow solid, yield 58%.1H NMR、13CNMR, MS and element Compound obtained by analysis result shows is target product M2, and preparation process chemical equation is as follows：
Embodiment 3
Compound M3 synthesis
Bromo- 2 2-methyl naphthoates of 1-
Bromo- 2 naphthoic acids (9.00g, 35.85mmol) of 1- are dissolved in 200ml methanol, and toward being added dropwise to 20ml's in reaction solution The concentrated sulfuric acid, after stirring 12 hours under normal temperature, stop reaction, reaction is quenched with water, is extracted with dichloromethane and uses anhydrous sulphur Sour magnesium is dried, and khaki solid is obtained after solution concentration, and (eluant, eluent selection petroleum ether/dichloromethane is purified with silica gel column chromatography Alkane=5/1, v/v), obtain white solid, yield 95%.1H NMR、13CNMR, MS and elementary analysis result show resulting Compound is target product M3, and preparation process chemical equation is as follows：
Embodiment 4
Compound M4 synthesis
The preparation of methyl 1- (dibenzo [b, d] thiophene -2- bases) -2- naphthoates
In 500mL three-necked flasks, 2- (dibenzo [b, d] thiophene -2- bases) -4,4,5,5- tetramethyls -1,3,2- bis- are added Oxa- borine (9.75g, 31.43mmol), 200mL toluene stirring and dissolvings, then it is separately added into bromo- 2 2-methyl naphthoates of 1- (10.00g, 37.72mmol), Na2CO3(16.66g, 157.17mmol), four butyl bromation amine (4mg, 12.4umol), organic base (tetraethyl ammonium hydroxide) (20mL), deionized water 30mL and catalyst four (triphenylphosphine) close palladium (1.82g, 1.57mmol), 150 DEG C are heated to, reacts 12h.After reaction solution is concentrated, with silica gel column chromatography, (eluant, eluent selects petroleum ether, two Chloromethanes=5/1, v/v), obtain white solid, yield 60%.1H NMR、13CNMR, MS and elementary analysis result show gained The compound arrived is target product M4, and preparation process chemical equation is as follows：
Embodiment 5
Compound M5 synthesis
The preparation of 2- (1- (dibenzo [b, d] thiophene -2- bases) naphthalene -2- bases) heptadecane -9- alcohol
Methyl 1- (dibenzo [b, d] thiophene -2- bases) -2- naphthoates (10.00g, 27.14mmol) are dissolved in refined Anhydrous THF in (150ml), dropwise be added dropwise 1.6mol/L octyls magnesium bromide (59.00g, 271.41mmol), be warming up to 120 DEG C it is heated to reflux, reacts 16h；Room temperature is cooled to, reactant mixture is poured into water, is extracted with ethyl acetate, organic layer food After salt solution washing completely, dried with anhydrous magnesium sulfate；After solution concentration, next step reaction is directly carried out.1H NMR、13CNMR、MS Compound obtained by showing with elementary analysis result is target product M5, and preparation process chemical equation is as follows：
Embodiment 6
Compound M6 synthesis
The preparation of 14,14- dioctyl -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene
2- (1- (dibenzo [b, d] thiophene -2- bases) naphthalane -2- bases) isopropanol (2.3g, 6.24mmol) is dissolved in dichloro In methane 150mL, 0.5mL Eorontrifluoride etherate solution (concentration 46.5wt%) is added, reacts 1h；After solution concentration, silicon is used Plastic column chromatography (eluant, eluent selection petroleum ether, dichloromethane=5/1, v/v) Methods For Purification, obtains white solid；Tied again with ethanol Crystalline substance twice, filters to obtain white crystal 1.8g, yield 82.6%.1H NMR、13Obtained by CNMR, MS and elementary analysis result show Compound be target product M6, preparation process chemical equation is as follows：
Embodiment 7
Compound M7 synthesis
2,8- dibromos 14,14 dioctyl -14H- benzos [b] benzo [5,6] fluorenes simultaneously [1,2-d] thiophene
14,14- dioctyl -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene (900mg, 1.65mmol) is dissolved In 20ml chloroforms, then bromine (657.52mg, 4.11mmol) is added dropwise into reaction solution at twice in ice-water bath, instead Reaction is quenched with saturation sodium hydrogensulfite after answering 24 hours, and is extracted with saturation sodium hydrogensulfite and ethyl acetate, anhydrous slufuric acid After magnesium is dried, (eluant, eluent selection petroleum ether) is purified with silica gel column chromatography, obtains yellow oil.Yield：50%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product M7, and preparation process chemical equation is such as Shown in lower：
Embodiment 8
Compound M8 synthesis
Bromo- 14,14- dioctyls -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene -9,9- dioxide of 2,8- bis- Preparation
By 2,8- dibromos 14,14 dioctyl -14H- benzos [b] benzo [5,6] fluorenes simultaneously [1,2-d] thiophene (300mg, 0.426mmol) it is dissolved in 15ml acetic acid, the aqueous hydrogen peroxide solution that 2ml concentration is 30wt%, heating is added dropwise into reaction solution To 150 DEG C, stirring reaction 5 hours；Extracted with saturated sodium-chloride water solution ethyl acetate, after anhydrous magnesium sulfate is dried, use silica gel (eluant, eluent selects dichloromethane to column chromatography：Petroleum ether=1:1, v/v) purify, obtain yellow solid, yield：50%.1H NMR 、13Compound obtained by CNMR, MS and elementary analysis result show is target product M8, preparation process chemical equation It is as follows：
Embodiment 9
Compound M9 synthesis
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 cools down, and is added dropwise bromine (17.6g, 0.1mol)/chloroform mixed solution 35mL, and temperature does not surpass in bottle during dropwise addition Cross 5 DEG C；Reaction finishes, and 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 M9, and preparation process chemical equation is as follows：
Embodiment 10
Compound M10 synthesis
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 Enter 1- bromines normal octane (12.5g, 65mmol), after continuing stirring 3 hours, extracted with ether；Washed with saturated sodium-chloride water solution Ether phase, anhydrous magnesium sulfate are 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 M10, preparation process chemical reaction side Formula is as follows：
Embodiment 11
Compound M11 synthesis
The preparation of 2,7- diborate -9,9- 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, then add 2- isopropoxies -4,4, 5,5- tetramethyls -1,3,2- dioxaborinate 25mL, continue reaction 1 hour at -78 DEG C, it is small to then heat to room temperature reaction 24 When；Reactant mixture is poured into water, is extracted with ethyl acetate, after organic layer is washed completely with saline solution, adds 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 As a result the compound obtained by showing is target product M11, and preparation process chemical equation is as follows：
Embodiment 12
Compound M12 synthesis
The preparation of 3,6- dibromo carbazoles
Carbazole (24.7g, 0.1mol) and dimethylformamide 200mL are added in 500mL two-mouth bottles, is stirred to complete Dissolving；N- bromo-succinimides (NBS, 49.84g, 0.28mol) 120ml DMFs dissolve, and obtain NBS Solution；To 0 DEG C NBS solution is slowly added dropwise, lucifuge, after being added dropwise, after allowing temperature to rise to room temperature automatically, reaction 6 is small in ice bath When, reaction solution is added drop-wise in water and precipitated, after suction filtration obtains crude product, thing will be filtered and recrystallized with absolute ethyl alcohol, dried, Obtain white needles, yield 85%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is mesh Product M12 is marked, preparation process chemical equation is as follows：
Embodiment 13
Compound M13 synthesis
The preparation of the bromo- 9- octyl groups -9H- carbazoles of 3,6- bis-
3,6- dibromos carbazole (16.25g, 0.05mmol), toluene 100mL and the tetrabutyl are added in 250mL there-necked flasks Ammonium bromide (0.8g, 3.5mmol), stirring and dissolving, 50wt%KOH aqueous solution 11mL are then added dropwise, then add bromooctane (19.3g, 0.1mol), reacted 24 hours at 80 DEG C, add water terminating reaction, wash the organic phase separated, aqueous phase is with two After chloromethanes extraction, merge organic phase, with anhydrous MgSO4Dry, be evaporated under reduced pressure after removing solvent and obtain light yellow solid, use 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 M13, and preparation process chemical equation is as follows：
Embodiment 14
Compound M14 synthesis
The preparation of double (4,4,5,5- tetramethyl -1,3,2- dioxaborolane -2- the bases) -9H- carbazoles of 9- octyl groups -3,6-
The ether 250mL for the bromo- 9- octyl groups -9H- carbazoles (13.11g, 30mmol) of 3,6- bis- are added in there-necked flask, newly steaming, Stirring is completely dissolved to clear, and reaction solution is cooled into -78 DEG C, then disposably add 2- isopropoxies-(4,4,5, 5- tetramethyls) -1,3,2- ethylenedioxy borates (37mL, 180mmol), are stirred 2 hours, then temperature is risen at -78 DEG C Room temperature, reaction terminate reaction after 24 hours；Extracted, saturated common salt water washing 4 times, then dried with anhydrous magnesium sulfate, mistake with ether After filter, solvent, product petrol ether/ethyl acetate (10 is distilled off:1, v/v) purified for eluant, eluent column chromatography, obtain white Solid, yield 45%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product M14, system Standby process chemistry reaction equation is as follows：
Embodiment 15
Polymer P 1 synthesizes
Under argon atmosphere, by 2,7- diborates -9,9- dioctyl fluorene (M11,200mg, 311.25 μm of ol of compound), 2,7- bis- bromo- 9,9- dioctyl fluorenes (M10,136.56mg, 249.00 μm of ol of compound) and naphtho- sulphur dibenzofuran (compound M8, 45.86mg, 62.25 μm of ol) add in 50ml two-mouth bottles, add 8ml toluene and be completely dissolved, add palladium (2.80mg, 12.45 μm of ol) and tricyclohexyl phosphine (6.98mg, 24.90 μm of ol), 2ml tetraethyl ammonium hydroxides are then added, risen Temperature is reacted 24 hours to 80 DEG C；Then 30mg phenyl boric acids are added to be blocked, after 12 hours, then are sealed with 0.3ml bromobenzenes End；After continuing reaction 12 hours, product is added dropwise and is precipitated out in methyl alcohol, stirred, filtering, then crude product is dissolved in 20mL Toluene in, be that eluant, eluent carries out column chromatography with toluene, then solvent under reduced pressure is concentrated using 200~300 mesh silica gel as stationary phase Afterwards, separate out to come in methyl alcohol again, stir, filtering, polymer solids are obtained after vacuum drying；Finally use first successively again Alcohol, acetone, tetrahydrofuran respectively extract 24 hours, remove small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, The fibrous solids conjugated polymer P1 obtained after vacuum drying.1H NMR、13CNMR, MS and elementary analysis result show gained The compound arrived is target product P1, and preparation process chemical equation is as follows：
Embodiment 16
The synthesis of polymer P 2
Under argon atmosphere, by 2,7- diborates -9,9- dioctyl fluorene (M11,200mg, 311.25 μm of ol of compound), 2,7- bis- bromo- 9,9- dioctyl fluorenes (M10,153.63mg, 280.12 μm of ol of compound) and naphtho- sulphur dibenzofuran (compound M8, 22.93mg, 31.12 μm of ol) add in 50ml two-mouth bottles, add 8ml toluene and be completely dissolved, add palladium (2.80mg, 12.45 μm of ol) and tricyclohexyl phosphine (6.98mg, 24.90 μm of ol), 2ml tetraethyl ammonium hydroxides are then added, risen Temperature is reacted 24 hours to 80 DEG C；Then 30mg phenyl boric acids are added to be blocked, after 12 hours, then are sealed with 0.3ml bromobenzenes End；After continuing reaction 12 hours, product is added dropwise and is precipitated out in methyl alcohol, stirred, filtering, then crude product is dissolved in 20mL Toluene in, be that eluant, eluent carries out column chromatography with toluene, then solvent under reduced pressure is concentrated using 200~300 mesh silica gel as stationary phase Afterwards, separate out to come in methyl alcohol again, stir, filtering, polymer solids are obtained after vacuum drying；Finally use first successively again Alcohol, acetone, tetrahydrofuran respectively extract 24 hours, remove small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, The fibrous solids conjugated polymer P2 obtained after vacuum drying.1H NMR、13CNMR, MS and elementary analysis result show gained The compound arrived is target product P2, and preparation process chemical equation is as follows：
Embodiment 17
The synthesis of polymer P 3
Under argon atmosphere, by 2,7- diborates -9,9- dioctyl fluorene (M11,200mg, 311.25 μm of ol of compound), 2,7- bis- bromo- 9,9- dioctyl fluorenes (M10,163.87mg, 298.80 μm of ol of compound) and naphtho- sulphur dibenzofuran (compound M8, 9.17mg, 12.45 μm of ol) add in 50ml two-mouth bottles, add 8ml toluene and be completely dissolved, add palladium (2.80mg, 12.45 μm of ol) and tricyclohexyl phosphine (6.98mg, 24.90 μm of ol), 2ml tetraethyl ammonium hydroxides are then added, risen Temperature is reacted 24 hours to 80 DEG C；Then 30mg phenyl boric acids are added to be blocked, after 12 hours, then are sealed with 0.3ml bromobenzenes End；After continuing reaction 12 hours, product is added dropwise and is precipitated out in methyl alcohol, stirred, filtering, then crude product is dissolved in 20mL Toluene in, be that eluant, eluent carries out column chromatography with toluene, then solvent under reduced pressure is concentrated using 200~300 mesh silica gel as stationary phase Afterwards, separate out to come in methyl alcohol again, stir, filtering, polymer solids are obtained after vacuum drying；Finally use first successively again Alcohol, acetone, tetrahydrofuran respectively extract 24 hours, remove small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, The fibrous solids conjugated polymer P3 obtained after vacuum drying.1H NMR、13CNMR, MS and elementary analysis result show gained The compound arrived is target product P3, and preparation process chemical equation is as follows：
The thermogravimetric analysis figure of polymer P 1, P2 and P3 is as shown in figure 1, as shown in Figure 1, the heat of polymer P 1, P2 and P3 is divided It is 420 DEG C to solve temperature, illustrates that polymer P 1, P2 and P3 are respectively provided with higher heat endurance.
Embodiment 18
The preparation of copolymer electroluminescent device
It is on 15-20 Ω tin indium oxide (ITO) glass, 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, which is mixed, on ITO polystyrolsulfon acid Polyethoxy thiophene (PEDOT:PSS=1：1, w/w) film, thickness 40nm；PEDOT:PSS films are in vacuum drying oven at 180 DEG C Dry 10 minutes, then the PEDOT in spin coating：Add on the ITO of PSS films at spin coating 15nm polyvinylcarbazole (PVK), 120 DEG C Hot 10min；Polymer P 1, P2 and P3 paraxylene solution (1wt.%) are then spin-coated on the surface of PVK films, thickness respectively For 60nm, as luminescent layer；The thick metal Al layers of one layer of 4nm thick Ba and 200nm are finally deposited successively on luminescent layer, obtain Electroluminescent device prepared by the luminescent layer of the blue light frequency-doubling luminescent material based on naphtho- sulphur dibenzofuran unit.
The performance of electroluminescent device based on polymer P 1, P2 and P3 is as shown in table 1.
The performance of electroluminescent device of the table 1 based on polymer P 1, P2 and P3
As shown in Table 1, P1 maximal efficiency is 1.39, and high-high brightness 2450, chromaticity coordinates is (0.171,0.1476)；P2 Maximal efficiency be 0.43, high-high brightness 1825, chromaticity coordinates is (0.1682,0.1101)；P3 maximal efficiency is 1.31, most Big brightness is 3052, and chromaticity coordinates is (0.1654,0.1047)；By the property of the electroluminescent device based on polymer P 1, P2 and P3 Knowable to energy index, luminescent device not only efficient stable, and the transmitting light is more blue saturation blue light.
The uv-visible absorption spectroscopy figure of polymer P 1, P2 and P3 under filminess is as shown in Fig. 2 can by Fig. 2 Know, the maximum absorption band of polymer P 1, P2 and P3 inside film in 375-385nm, wherein, maximums of the P1 inside film Absworption peak is 381nm, and absorption maximums of the P2 inside film is 379nm, and maximum absorption bands of the P3 inside film is 382nm.
The photoluminescence spectra figure of polymer P 1, P2 and P3 under filminess is as shown in figure 3, from the figure 3, it may be seen that P1 is thin Maximum emission peak inside film is 449nm, and maximum emission peaks of the P2 inside film is 445nm, maximums of the P3 inside film Emission peak is 439nm.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, it is other it is any without departing from the present invention Spirit Essences with made under principle change, modification, replacement, combine, simplification all should For equivalent substitute mode, it is included within protection scope of the present invention.

Claims (6)

1. a kind of blue light frequency-doubling luminescent material based on naphtho- sulphur dibenzofuran unit, it is characterised in that there is following chemical constitution Formula：
In formula, R1、R2It is independently chosen from aryl, triphenylamine, carbon number 1-20 straight or branched alkyl, or carbon number 1- 20 alkoxy；0≤x<1；Polymerization degree n is 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；
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 bases) -2,1,3- diazosulfide；
4,7- double (5- substitution -4- alkylthrophenes base) 2,1,3- selenoles；
Indenes fluorenes；
Indole carbazole；
2,6- substitutions-dithieno thiophene is coughed up；
2,6- substitutions-dithieno cyclopentadiene；
2,5- substitution -3,4- dialkyl group selenophens；
5,5- -4,4- of substitution dialkyl group-bithiophene；
4,7- bis- (4- substituted-phenyls) -2,1,3- diazosulfides；
4,7- bis- (4- substituted-phenyls) -2,1,3- selenoles；
4,7- bis- (5- substitution -4- alkylthrophene -2- bases) -2,1,3- diazosulfides；
4,7- bis- (5- substitution -4- alkylthrophene -2- bases) -2,1,3- selenoles；
(N- (4- substituted-phenyls)-N- (4- alkyl phenyls) amine of 4,7- bis- Base) -2,1,3- diazosulfides；
(N- (4- substituted-phenyls)-N- (4- alkyl phenyls) amine of 4,7- bis- Base) -2,1,3- selenoles；
(4- (N- (4- the substituted-phenyls)-N- of 4,7- bis- (4- alkyl phenyls) amido) phenyl) -2,1,3- diazosulfides；
(4,4'- (benzo [c] [1,2,5] selenium diazole- 4,7- diyls) double (N, N- diphenyl aniline))
Wherein, R H, aryl, triphenylamine, carbon number 1-20 straight chain or branched alkyl, or the alkane for carbon number 1-20 Epoxide；Z1、Z2It is independently chosen from H, D, F, CN, alkenyl, alkynyl, itrile group, amido, nitro, acyl group, alkoxy, carbonyl, sulfuryl, carbon The alkyl of atomicity 1~30, the cycloalkyl of carbon number 3~30, the aromatic hydrocarbyl of carbon number 6~60 or carbon number 3~ 60 aromatic heterocycle.
2. a kind of method of blue light frequency-doubling luminescent material based on naphtho- sulphur dibenzofuran unit described in claim 1 is prepared, its It is characterised by, comprises the following steps：
Under argon atmosphere, R will be contained1And R2Naphtho- sulphur dibenzofuran unit and the boric acid ester units of the structure containing Ar gathered by Suzuki After closing reaction, then end capping reaction is carried out using phenyl boric acid and bromobenzene successively, obtain the conjugation based on naphtho- sulphur dibenzofuran unit Polymer luminescent material.
A kind of 3. preparation side of blue light frequency-doubling luminescent material based on naphtho- sulphur dibenzofuran unit according to claim 2 Method, it is characterised in that the temperature of the Suzuki polymerisations is 80~100 DEG C, and the time is 24~48 hours.
A kind of 4. preparation side of blue light frequency-doubling luminescent material based on oxa- sulphur dibenzofuran unit according to claim 2 Method, it is characterised in that the temperature that end capping reaction is carried out using phenyl boric acid and bromobenzene is 80~100 DEG C, and the time is 12~24 Hour.
Lighted 5. a kind of blue light frequency-doubling luminescent material based on naphtho- sulphur dibenzofuran unit described in claim 1 is applied to prepare The luminescent layer of diode, it is characterised in that by the blue light frequency-doubling luminescent material organic solvent based on naphtho- sulphur dibenzofuran unit Dissolving, then by spin coating, inkjet printing or printing film forming, obtain the luminescent layer of light emitting diode.
6. application according to claim 5, it is characterised in that the organic solvent includes chlorobenzene, dimethylbenzene or chloroform.
CN201710764977.4A 2017-08-30 2017-08-30 A kind of blue light frequency-doubling luminescent material based on naphtho- sulphur dibenzofuran unit and preparation method and application Pending CN107383343A (en)

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