CN107254033A - Blue light conjugated polymer based on naphtho- 2,7 S, S dioxydibenze bithiophene unit and preparation method and application - Google Patents

Blue light conjugated polymer based on naphtho- 2,7 S, S dioxydibenze bithiophene unit and preparation method and application Download PDF

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CN107254033A
CN107254033A CN201710353907.XA CN201710353907A CN107254033A CN 107254033 A CN107254033 A CN 107254033A CN 201710353907 A CN201710353907 A CN 201710353907A CN 107254033 A CN107254033 A CN 107254033A
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naphtho
substitution
fluorenes
blue light
conjugated polymer
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应磊
赵森
郭婷
杨伟
彭俊彪
曹镛
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South China University of Technology SCUT
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Abstract

The invention discloses blue light conjugated polymer based on naphtho- 2,7 S, S dioxydibenze bithiophene unit and preparation method and application.The present invention obtains the described blue light conjugated polymer based on naphtho- 2,7 S, S dioxydibenze bithiophene unit by Suzuki polymerisations.The present invention is based on naphtho- 2,7 S, the blue light conjugated polymer of S dioxydibenze bithiophene units contains electron deficient S, S dioxydibenze bithiophene unit, with preferable electronic transmission performance, and its connected mode has effectively interrupted the conjugation of main chain, be conducive to obtaining deep blue emission, and its preferable dissolubility is ensure that containing alkyl chain, after being dissolved using common organic solvents, again by spin coating, inkjet printing or printing film forming, the luminescent layer of light emitting diode is prepared.Luminescent layer based on the polymer is when preparing luminescent device without annealing so that preparation technology is simpler.

Description

Based on naphtho- -2,7-S, the blue light conjugated polymer of S- dioxydibenze bithiophene units And preparation method and application
Technical field
The invention belongs to organic photoelectrical material technical field, and in particular to one kind is based on naphtho- -2,7-S, S- dioxydibenzes Blue light conjugated polymer of bithiophene unit and preparation method and application.
Background technology
In the past thirty years, organic electronic and photoelectronic industry, including organic/polymer LED, it is organic Field-effect transistor, the field such as organic solar batteries has obtained swift and violent development, and gradually realizes industrialization.Organic electronic is produced Product have cheap, and body is light the advantages of take.Make it have great market potential.Therefore exploitation has market attractiveness Organic electronic product has attracted the concern of numerous research institutions and Research Team in the world, and among these, develops new and effective Stable material turns into key.
But, current organic luminescent device technology encounters bottleneck problem in evolution, is exactly the hair of luminescent device Light efficiency and service life do not reach practical requirement, which greatly limits the development of OLED technology, for this problem, respectively Individual research institution is all carrying out the research of exploration.Therefore, developing the material of new and effective stabilization is used to improve luminescent device Luminous efficiency and service life are particularly important.
The content of the invention
It is an object of the invention to for current polymer LED (PLED) problems faced, there is provided a kind of base In naphtho- -2,7-S, the blue light conjugated polymer of S- dioxydibenze bithiophene units.The conjugated polymer can be used as blue light emitting Material, and with preferable dissolubility, higher fluorescence quantum yield, preferable excitation is suitable for solution processing and ink-jet Printing, the not only efficient stable of the luminescent device based on the conjugated polymer, can meet the requirement of full-color display, in organic electronic Display field has huge development potentiality and prospect.
The present invention also aims to provide described one kind to be based on naphtho- -2,7-S, S- dioxydibenze bithiophene unit The preparation method of blue light conjugated polymer.
The present invention also aims to provide described one kind to be based on naphtho- -2,7-S, S- dioxydibenze bithiophene unit Application of the blue light conjugated polymer in the luminescent layer of Organic Light Emitting Diode is prepared.
One kind is based on naphtho- -2,7-S, the blue light conjugated polymer of S- dioxydibenze bithiophene units, with following chemistry Structural formula：
In formula, R1-R4For the straight or branched alkyl of hydrogen atom, carbon number 1-20；R5-R6For aryl, triphenylamine, carbon Atomicity 1-20 straight or branched alkyl, or be 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- take Generation -9,9- dialkoxy phenyl fluorenes；2,7- substituted carbazoles；
3,6- substituted carbazoles；
2,6- substitutions-dithieno thiophene is coughed up；
2,6- substitutions-dithieno cyclopentadiene；
2,5- substituted pyridines；
2,6- substituted pyridines；
3,5- substituted pyridines；
3,5- double (4- substituted 4-phenyls) -4- bases -1,2,4- triazoles；
3,5- double (4- substituted 4-phenyls) -1,2,4- oxadiazoles；
4,7- double (5- substitution -4- alkylthrophenes base) -2,1,3- diazosulfide；
4,7- double (5- substitution -4- alkylthrophenes base) 2,1,3- selenoles；
4,7- substitution -5,6- alkyl -2,1,3- diazosulfides；
4,7- substitution -5,6- alkyl -2,1,3- selenoles；
2,5- substitution -3,4- dialkylthiophenes；
2,5- substitution -3,4- dialkyl group selenophens；
5,5- -4,4- of substitution dialkyl group-bithiophene；
Indenes fluorenes；
Indole carbazole；
4,9- -6,7- of substitution alkyl-naphtho- thiadiazoles；
4,9- -6,7- of substitution alkyl-naphtho- selenium diazole；
Naphtho- indenes fluorenes；
Wherein, R is hydrogen, aryl, triphenylamine, carbon number 1-20 straight chain or branched alkyl, or is carbon number 1- 20 alkoxy.
Prepare the side that described one kind is based on the blue light conjugated polymer of naphtho- -2,7-S, S- dioxydibenze bithiophene unit Method, comprises the following steps：
By naphtho- -2,7-S, S- dioxydibenze bithiophene monomers are polymerize with the boric acid ester monomer of the structure containing Ar by Suzuki After reaction, then successively using phenyl boric acid and bromobenzene progress end capping reaction, obtain described based on naphtho- -2,7-S, S- dioxydibenzes are simultaneously The conjugated polymer of thiophene unit.
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.
The blue light conjugated polymer that described one kind is based on naphtho- -2,7-S, S- dioxydibenze bithiophene unit has in preparation Application in the luminescent layer of machine light emitting diode, will be based on naphtho- -2,7-S, the conjugated polymers of S- dioxydibenze bithiophene units Thing organic solvent dissolves, then by spin coating, inkjet printing or printing film forming, obtains the luminous of the Organic Light Emitting Diode Layer；Light emitting diode based on the luminescent layer can be used for preparing flat-panel monitor.
Further, the organic solvent includes chlorobenzene.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) it is of the invention based on naphtho- -2,7-S, the conjugated polymer of S- dioxydibenze bithiophene units, due to containing lacking Electronics S, S- dioxo-dibenzothiophene unit, with preferable electronic transmission performance, and due to the connection of its nonplanarity, has Conjugate length has been interrupted to effect, has been conducive to obtaining deep blue emission.
(2) it is of the invention based on naphtho- -2,7-S, the conjugated polymer of S- dioxydibenze bithiophene units, due to compared with Big conjugate length, so there is higher fluorescence quantum yield, is conducive to improving the device efficiency of material；
(3) it is of the invention based on naphtho- -2,7-S, the conjugated polymer of S- dioxydibenze bithiophene units, with preferable Dissolubility, the luminescent layer based on the polymer is when preparing electroluminescent device without annealing so that preparation technology is simpler It is single.
Brief description of the drawings
Fig. 1 is the DSC spectrograms of polymer P 1；
Fig. 2 is photoluminescence spectra spectrogram of the polymer P 2 under filminess；
Fig. 3 is photoluminescence spectra spectrogram of the polymer P 3 under filminess.
Embodiment
The present invention is described in further detail with reference to specific embodiments and the drawings, but embodiments of the present invention Not limited to this.
Embodiment 1
The 2-methyl naphthoate of 1- bromines two
Under an argon atmosphere, the bromo- 2- naphthoic acids (10g, 39.83mmol) of 1- are added in two-mouth bottle, adds 100mL first Alcohol, is then added dropwise the concentrated sulfuric acid (39.06mg, 398.29umol), is heated to 110 DEG C, reacts 18h.Reactant mixture is fallen Enter in water, be extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.After solution concentration, obtain To crude white solid, (eluant, eluent selects petroleum ether/dichloromethane=3/1, v/v) is purified with silica gel column chromatography, when product is long Between place refrigerator in obtain white solid, yield 85%.1H NMR、13CNMR, MS and elementary analysis result show resulting change Compound is target product, and chemical equation is as follows：
Embodiment 2
The preparation of 2- bromine dibenzothiophens
Under argon atmosphere, dibenzothiophen (20g, 108.54mmol) is added in 250ml two-mouth bottles, 100ml chlorine is added It is imitative to be completely dissolved, 0.5g (275mg, 1.09) grain elemental iodine is added, in the case of lucifuge, bromine is added dropwise (18.16g, 138.80mmol), reaction solution is stirred 2 hours under ice bath, is then stirred at room temperature 2 hours, adds saturation Bromine is quenched in sodium hydrogensulfite, and reactant mixture is poured into water, and is extracted with ethyl acetate, and organic layer is washed completely with saline solution Afterwards, plus anhydrous magnesium sulfate dry.After solution concentration, crude white solid is obtained, then with Gossypol recrystallized from chloroform, 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 3
2- diborate dibenzothiophens
Under an argon atmosphere, 2- bromines dibenzothiophen (10g, 29.24mmol) is dissolved in the refined tetrahydrofurans (THF) of 180mL In, 1.6mol L are gradually added dropwise at -78 DEG C-1N-BuLi 18mL, react 2 hours, be then quickly added into 2- isopropoxies- 4,4,5,5- tetramethyls -1,3,2- dioxaborinate 25mL continue to react 1 hour at -78 DEG C, are to slowly warm up to room temperature reaction 24 hours.Reactant mixture is poured into water, is extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous sulphur Sour magnesium is dried.After solution concentration, thick pale yellow shape crude product is obtained, (eluant, eluent selection petroleum ether/second is purified with silica gel column chromatography Acetoacetic ester=20/1, v/v), product is placed in refrigerator obtain white solid, yield 70% for a long time.1H NMR and GC-MASS are surveyed Examination is shown to be target product, and chemical equation is as follows：
Embodiment 4
Compound M1 preparation
It is under argon atmosphere, compound 2- borates-S, S- dioxydibenze bithiophene (5g, 16.12mmol) and 1- is bromo- 2- 2-methyl naphthoates (4.27g, 16.12mmol) 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 is washed completely with saline solution, 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 is placed in refrigerator obtain white solid, yield 75% for a long time.1H NMR、13CNMR, MS and Compound obtained by elementary analysis result shows is target product M1, and chemical equation is as follows：
Embodiment 5
Compound M2 preparation
Under argon atmosphere, compound M1 (10g, 27.14mmol) is added in single port bottle, the anhydrous THF of 50ml are added Until being completely dissolved；Reaction solution is reacted into 1h at 0 DEG C again, then be added dropwise n-octyl magnesium bromide (25.98g, 119.47mol, C8H17MgBr), mixed liquor reacts 18h at room temperature.Add water in reaction solution that reaction is quenched, be extracted with ethyl acetate, After organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.After solution concentration, (eluant, eluent is purified with silica gel column chromatography Select petroleum ether/dichloromethane=3/1, v/v), product is placed in refrigerator obtain white solid, yield 80% for a long time.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product M2, the following institute of chemical equation Show：
Embodiment 6
Compound M3 preparation
Under argon atmosphere, compound M2 (5g, 8.85mmol) is dissolved in 50ml dichloromethane, added dropwise at room temperature Enter boron trifluoride ether solution (439.59mg, 6.48mmol), react 18h；It is extracted with ethyl acetate, organic layer is complete with saline solution After full washing, plus anhydrous magnesium sulfate is dried.After solution concentration, (eluant, eluent selection petroleum ether), product are purified with silica gel column chromatography Place for a long time in refrigerator and obtain white solid, yield 90%.1H NMR、13Obtained by CNMR, MS and elementary analysis result show Compound be target product M3, chemical equation is as follows：
Embodiment 7
Compound M4 synthesis
Under argon atmosphere, compound M3 (10g, 18.29mmol) is dissolved in acetic acid, 5ml hydrogen peroxide is added, heated To 110 DEG C, react 6 hours；It is extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.It is molten After liquid concentration, (eluant, eluent selection petroleum ether), yield 70% are purified with silica gel column chromatography.1H NMR、13CNMR, MS and element point Compound obtained by analysis result shows is target product M4, and chemical equation is as follows：
Embodiment 8
Compound M5 preparation
Under argon atmosphere, compound M4 (5g, 8.64mmol) is dissolved in 50mL dichloromethane, then N- bromines are added dropwise For succimide (NBS, 1.93g, 22.10mmol), 18h is reacted at room temperature.It is extracted with ethyl acetate, organic layer salt After water washing completely, plus anhydrous magnesium sulfate is dried.After solution concentration, (eluant, eluent selection petroleum ether) is purified with silica gel column chromatography, Yield 70%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product M5, chemical reaction Equation is as follows：
Embodiment 9
Compound M6 preparation
Under argon atmosphere, compound M5 (10g, 15.20mmol) is dissolved in 100ml dichloromethane, it is anti-at 0 DEG C Should, bromine (2.43g, 15.20mmol) is added, is reacted 16 hours.It is extracted with ethyl acetate, organic layer is washed completely with saline solution After washing, plus anhydrous magnesium sulfate is dried.After solution concentration, (eluant, eluent selection petroleum ether), yield 70% are purified with silica gel column chromatography 。1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product M6, and chemical equation is such as Shown in lower：
Embodiment 10
The preparation of 2- bromine fluorenes
In 250mL there-necked flasks, fluorenes (16.6g, 0.1mol), iron powder (88mg, 1.57mmol) and chloroform are added 100mL, ice-water bath cooling, 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 16 hours, filtering, Gossypol recrystallized from chloroform, obtains white solid 19.3g, yield 84%.1H NMR、13CNMR, MS and member Compound obtained by plain analysis result shows is target product, and chemical equation is as follows：
Embodiment 11
The preparation of bromo- 9, the 9- dioctyl fluorenes of 2-
2- bromines fluorenes (7.4g, 0.03mol), benzyltriethylammoinium chloride (0.07g, 0.3mmol), two are added in there-necked flask Methyl sulfoxide 90mL and 45mL sodium hydrate aqueous solution (50wt%), at room temperature stirring form suspension, and 1- bromine normal octanes are added dropwise (12.5g, 65mmol), continues after stirring 3 hours, is extracted with ether.Ether phase, anhydrous sulphur are washed with saturated sodium-chloride water solution Sour magnesium is dried.Solvent is boiled off, product petroleum ether makees the purification of eluant, eluent column chromatography, obtains white solid.1H NMR、13CNMR, MS and Compound obtained by elementary analysis result shows is target product, and chemical equation is as follows：
Embodiment 12
The preparation of 2- borate -9,9- dioctyl fluorenes
Under an argon atmosphere, bromo- 9, the 9- dioctyl fluorenes (5g, 10.65mmol) of 2- are dissolved in the refined THF of 180mL, 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 to react 1 hour at -78 DEG C, are warming up to room temperature reaction 24 hours.Will Reactant mixture is poured into water, and is extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried. After solution concentration, thick pale yellow shape crude product is obtained, purified with silica gel column chromatography (eluant, eluent selection petrol ether/ethyl acetate= 20/1, v/v), product is placed in refrigerator obtain white solid, yield 70% for a long time.1H NMR、13CNMR, MS and elementary analysis As a result the compound obtained by showing is target product, and chemical equation is as follows：
Embodiment 13
The 2-methyl naphthoate of 1- bromines two
Under an argon atmosphere, the bromo- 2- naphthoic acids (10g, 39.83mmol) of 1- are added in two-mouth bottle, adds 100mL first Alcohol, is then added dropwise the concentrated sulfuric acid (39.06mg, 398.29umol), is heated to 110 DEG C, reacts 18h.Reactant mixture is fallen Enter in water, be extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.After solution concentration, obtain To crude white solid, (eluant, eluent selects petroleum ether/dichloromethane=3/1, v/v) is purified with silica gel column chromatography, when product is long Between place refrigerator in obtain white solid, yield 85%.1H NMR、13CNMR, MS and elementary analysis result show resulting change Compound is target product, and chemical equation is as follows：
Embodiment 14
Compound D1 preparation
Under argon atmosphere, by 2- borates -9,9- dioctyl fluorene (5g, 9.68mmol) and the 2-methyl naphthoate of 1- bromines two (2.69g, 10.16mmol) is added in two-mouth bottle, is added 100ml toluene and is completely dissolved, adds sodium carbonate (5.13g, 43.89mmol) and TBAB (312.01mg, 967.86umol), 18h is reacted at 110 DEG C.Will reaction Mixture is poured into water, and is extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.Solution (eluant, eluent selects petroleum ether/dichloromethane=5/1, v/v) after concentration, is purified with silica gel column chromatography, white solid is finally given, Yield 80%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product D1, chemical reaction Equation is as follows：
Embodiment 15
Compound D2 preparation
Under argon atmosphere, compound D1 (5g, 8.70mmol) is added in single port bottle, the anhydrous THF of 50ml are added straight React 1h at 0 DEG C to being completely dissolved, then by reaction solution, then be added dropwise n-octyl magnesium bromide (25.98g, 119.47mol, C8H17MgBr), mixed liquor reacts 18h at room temperature.Add water in reaction solution that reaction is quenched, be extracted with ethyl acetate, After organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.After solution concentration, (eluant, eluent is purified with silica gel column chromatography Select petroleum ether/dichloromethane=3/1, v/v), product is placed in refrigerator obtain white solid, yield 80% for a long time.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product D2, the following institute of chemical equation Show：
Embodiment 16
Compound D3 preparation
Under argon atmosphere, compound D2 (5g, 6.48mmol) is dissolved in 50ml dichloromethane, added dropwise at room temperature Enter boron trifluoride ether solution (439.59mg, 6.48mmol), react 18h；It is extracted with ethyl acetate, organic layer is complete with saline solution After full washing, plus anhydrous magnesium sulfate is dried.After solution concentration, (eluant, eluent selection petroleum ether), product are purified with silica gel column chromatography Place for a long time in refrigerator and obtain white solid, yield 90%.1H NMR、13Obtained by CNMR, MS and elementary analysis result show Compound be target product D3, chemical equation is as follows：
Embodiment 17
The preparation of naphtho- indenes fluorenes (NIF)
Under argon atmosphere, compound D3 (5g, 6.64mmol) is dissolved in 50mL dichloromethane, iron powder is added (185.35mg, 3.32mmol), then bromine (1.06g, 6.64mmol) is added dropwise, 18h is reacted at room temperature.Use ethyl acetate Extraction, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried.After solution concentration, purified and (washed with silica gel column chromatography De- agent selection petroleum ether), yield 70%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is mesh Product NIF is marked, chemical equation is as follows：
Embodiment 18
The preparation of naphtho- indenes fluorenes borate
Under argon atmosphere, naphtho- indenes fluorenes (10g, 10.98mmol) is dissolved in anhydrous 200ml tetrahydrofurans, -78 Stirred at DEG C, add n-BuLi (2.81g, 42.31mmol), reacted 2 hours.Then isopropoxy pinacol ester is added (6.13g, 32.93mmol), reacts 1 hour.It is extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous sulphur Sour magnesium is dried.After solution concentration, (eluant, eluent selection petroleum ether), yield 70% are purified with silica gel column chromatography.1H NMR、13CNMR、 Compound obtained by MS and elementary analysis result show is target product NIF, and chemical equation is as follows：
Embodiment 19
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；Temperature does not surpass in bottle during dropwise addition Cross 5 DEG C；Reaction 16 hours, filtering, Gossypol recrystallized from chloroform, obtains white solid 20.3g, yield 83%.1HNMR、13CNMR, MS and member Compound obtained by plain analysis result shows is target product, and preparation process chemical equation is as follows：
Embodiment 20
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), continues after stirring 3 hours, is 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, preparation process chemical equation It is as follows：
Embodiment 21
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 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 is washed completely with saline solution, 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 As a result the compound obtained by showing is target product, and preparation process chemical equation is as follows：
Embodiment 22
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 completely molten Solution, NBS (49.84g, 0.28mol) 120ml DMFs dissolve, and to 0 DEG C NBS solution is added dropwise, instead in ice bath Answer, lucifuge, after completion of dropping, allow temperature to rise to automatically after room temperature, react 6 hours, reaction solution is added drop-wise in water and precipitated, is taken out Filter is obtained after crude product, and suction filtration thing is recrystallized with absolute ethyl alcohol, is dried, is obtained precious color needle-like solid, yield 85%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product, preparation process chemical equation It is as follows：
Embodiment 23
The preparation of 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), then stirring and dissolving is added dropwise 50wt%KOH aqueous solution 11mL, then adds bromooctane (19.3g, 0.1mol), reacts 24 hours, add water terminating reaction at 80 DEG C, washes the organic phase separated, and aqueous phase uses 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, and preparation process chemical equation is as follows：
Embodiment 24
The preparation of 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- and the ether 250mL newly steamed are added in there-necked flask, is stirred Mix and be completely dissolved to clear, reaction solution is cooled to -78 DEG C, it is then disposable to add 2- isopropoxies-(4,4,5,5- Tetramethyl) -1,3,2- ethylenedioxy borates (37mL, 180mmol), are stirred 2 hours, then temperature is risen into room at -78 DEG C Temperature, reaction terminates reaction after 24 hours；Extracted, saturated common salt water washing 4 times, then dried with anhydrous magnesium sulfate with ether, filtered Afterwards, solvent, product petrol ether/ethyl acetate (10 is distilled off:1) purified for eluant, eluent column chromatography, obtain white solid, produced Rate 45%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product, preparation process chemistry Reaction equation is as follows：
Embodiment 25
The preparation of polymer P 1
Under argon atmosphere, by 2,7- diborates -9,9- dioctyl fluorene (261.69mg, 407.26 μm of ol) and naphtho- - 2,7-S, S- dioxydibenze (300mg, 407.25 μm of ol) are added in 100ml two-mouth bottles, add the progress of 8ml toluene completely molten Solution, adds palladium (2.45mg, 10.92 μm of ol) and tricyclohexyl phosphine (6.12mg, 21.83 μm of ol), then adds 2ml tetra- Ethyl ammonium hydroxide, is warming up to 80 DEG C, reacts 24 hours；Then 30mg phenyl boric acids are added to be blocked, after 12 hours, then are used 0.1ml bromobenzenes are blocked；Continue after reacting 12 hours, product is added dropwise and is precipitated out in methyl alcohol, stir, filtering, then Crude product is dissolved in 20mL toluene, is that eluant, eluent carries out column chromatography with toluene using 200~300 mesh silica gel as stationary phase, then After solvent under reduced pressure is concentrated, separate out to come in methyl alcohol again, stir, filtering obtains polymer solids after vacuum drying；Most Respectively extracted 24 hours with methanol, acetone, tetrahydrofuran successively again afterwards, remove small molecule；By the tetrahydrofuran solution drop after concentration Enter the fibrous solids conjugated polymer P1 obtained after precipitating in methanol, vacuum drying.
The DSC spectrograms of polymer P 1 are as shown in figure 1, it can be seen that the glass transition temperature of polymer P 1 is 125℃。
Embodiment 26
The preparation of polymer P 2
Under argon atmosphere, by 3,6- bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-diyl)-N- octyl group clicks Azoles (216.39mg, 407.26 μm of ol) and compound M6 (300mg, 407.26 μm of ol) are added in 100ml two-mouth bottles, are added 8ml toluene is completely dissolved, and adds palladium (2.45mg, 10.92 μm of ol) and tricyclohexyl phosphine (6.12mg, 21.83 μ Mol), 2ml tetraethyl ammonium hydroxides are then added, 80 DEG C are warming up to, reacted 24 hours；Then 30mg phenyl boric acids are added to be sealed End, after 12 hours, then is blocked with 0.1ml bromobenzenes；Continue after reacting 12 hours, product is added dropwise and is settled out in methyl alcohol Come, stir, filtering, then crude product is dissolved in 20mL toluene, it is elution with toluene using 200~300 mesh silica gel as stationary phase Agent carries out column chromatography, then after solvent under reduced pressure is concentrated, separates out to come in methyl alcohol again, stirs, filtering, after vacuum drying To polymer solids；Finally respectively extracted 24 hours with methanol, acetone, tetrahydrofuran successively again, remove small molecule；After concentration Tetrahydrofuran solution instills precipitating, the fibrous solids conjugated polymer P2 obtained after vacuum drying in methanol.
Photoluminescence spectra spectrogram of the polymer P 2 under filminess is as shown in Fig. 2 it can be seen that polymer P2 maximum emission peak is located at 490nm, positioned at blue light emitting region.
Embodiment 27
The preparation of polymer P 3
Under argon atmosphere, by naphtho- indenes fluorenes borate (409.36mg, 407.26 μm of ol) and M6 (300mg, 407.26 μ Mol) add in 100ml two-mouth bottles, add 8ml toluene and be completely dissolved, add palladium (2.45mg, 10.92 μ Mol) and tricyclohexyl phosphine (6.12mg, 21.83 μm of ol), 2ml tetraethyl ammonium hydroxides are then added, 80 DEG C, reaction are warming up to 24 hours；Then addition 30mg phenyl boric acids are blocked, after 12 hours, then are blocked with 0.1ml bromobenzenes；Continue reaction 12 small When after, product is added dropwise and is precipitated out in methyl alcohol, is stirred, crude product then is dissolved in 20mL toluene, with 200 by filtering ~300 mesh silica gel are stationary phase, are that eluant, eluent carries out column chromatography with toluene, then after solvent under reduced pressure is concentrated, again in methanol In separate out come, stir, filtering, obtain polymer solids after vacuum drying；Finally use methanol, acetone, tetrahydrofuran successively again Each extracting 24 hours, removes small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, obtained after vacuum drying Fibrous solids conjugated polymer P3.
Photoluminescence spectra spectrogram of the polymer P 3 under filminess is as shown in figure 3, it can be seen that polymer P3 maximum emission peak is located at 433nm, positioned at deep blue region.
Embodiment 28
The preparation of electroluminescent device based on polymer
It is on 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 is 150nm；PEDOT:PSS films are in vacuum drying oven at 80 DEG C Dry 8 hours；Polymer luminescent material P1, P2, P3 chlorobenzene solution (1wt%) are then spin-coated on PEDOT respectively:PSS films Surface, thickness is 80nm, is used as luminescent layer；It is last that a thin layer CsF (1.5nm) and 120nm thickness is deposited successively on luminescent layer Metal Al layer.
Photoelectric properties test is carried out respectively to obtained electroluminescent device, as a result as shown in table 1.
Photoelectric properties index of the table 1 based on the obtained electroluminescent devices of 1~P3 of polymer P
As shown in Table 1, with polymer P 1, P2, P3 is the electroluminescent device of luminescent layer, based on device architecture：ITO/ PEDOT/EML/CsF/Al maximum lumen efficiency is followed successively by 1.32cd/A, 1.85cd/A, 1.68cd/A.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention Limitation, it is other it is any without departing from Spirit Essences and the change made under principle of the present invention, modification, replacement, combine, simplification all should For equivalent substitute mode, it is included within protection scope of the present invention.

Claims (6)

1. one kind is based on naphtho- -2,7-S, the blue light conjugated polymer of S- dioxydibenze bithiophene units, it is characterised in that have Following chemical structural formula：
In formula, R1-R4For the straight or branched alkyl of hydrogen atom, carbon number 1-20；R5-R6For aryl, triphenylamine, carbon number 1-20 straight or branched alkyl, or be 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；
2,6- substitutions-dithieno thiophene is coughed up；
2,6- substitutions-dithieno cyclopentadiene；
2,5- substituted pyridines；
2,6- substituted pyridines；
3,5- substituted pyridines；
3,5- double (4- substituted 4-phenyls) -4- bases -1,2,4- triazoles；
3,5- double (4- substituted 4-phenyls) -1,2,4- oxadiazoles；
4,7- double (5- substitution -4- alkylthrophenes base) -2,1,3- diazosulfide；
4,7- double (5- substitution -4- alkylthrophenes base) 2,1,3- selenoles；
4,7- substitution -5,6- alkyl -2,1,3- diazosulfides；
4,7- substitution -5,6- alkyl -2,1,3- selenoles；
2,5- substitution -3,4- dialkylthiophenes；
2,5- substitution -3,4- dialkyl group selenophens；
5,5- -4,4- of substitution dialkyl group-bithiophene；
Indenes fluorenes；
Indole carbazole；
4,9- -6,7- of substitution alkyl-naphtho- thiadiazoles；
4,9- -6,7- of substitution alkyl-naphtho- selenium diazole；
Naphtho- indenes fluorenes；
Wherein, R is hydrogen, aryl, triphenylamine, carbon number 1-20 straight chain or branched alkyl, or is carbon number 1-20's Alkoxy.
2. it is poly- to prepare blue light conjugation of the one kind described in claim 1 based on naphtho- -2,7-S, S- dioxydibenze bithiophene unit The method of compound, it is characterised in that comprise the following steps：
Under argon atmosphere, by naphtho- -2,7-S, S- dioxydibenze bithiophene monomers and the boric acid ester monomer of the structure containing Ar pass through After Suzuki polymerisations, then successively using phenyl boric acid and bromobenzene progress end capping reaction, obtain described based on naphtho- -2,7-S, S- The conjugated polymer of dioxydibenze bithiophene unit.
3. a kind of blue light conjugation based on naphtho- -2,7-S, S- dioxydibenze bithiophene unit according to claim 2 is poly- The preparation method of compound, it is characterised in that the temperature of the Suzuki polymerisations is 80~100 DEG C, the time is 24~48 small When.
4. a kind of blue light conjugation based on naphtho- -2,7-S, S- dioxydibenze bithiophene unit according to claim 2 is poly- The preparation method of compound, 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, when Between be 12~24 hours.
5. one kind described in claim 1 is based on the blue light conjugated polymer of naphtho- -2,7-S, S- dioxydibenze bithiophene unit Application in the luminescent layer of Organic Light Emitting Diode is prepared, it is characterised in that naphtho- -2,7-S will be based on, S- dioxydibenzes are simultaneously The conjugated polymer of thiophene unit is dissolved with organic solvent, then by spin coating, inkjet printing or printing film forming, obtains described organic The luminescent layer of light emitting diode.
6. application according to claim 5, it is characterised in that the organic solvent includes chlorobenzene.
CN201710353907.XA 2017-05-18 2017-05-18 Blue light conjugated polymer based on naphtho- 2,7 S, S dioxydibenze bithiophene unit and preparation method and application Pending CN107254033A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108276562A (en) * 2018-01-23 2018-07-13 华南协同创新研究院 One kind contains S, the polymer and preparation method of S- dioxies-naphtho- [2,1-b] benzothiophene derivative unit and application
CN110790742A (en) * 2018-08-02 2020-02-14 华南理工大学 Small-molecule luminescent material based on naphtho-sulfur-oxygen-fluorene unit and preparation method and application thereof
WO2020232770A1 (en) * 2019-05-21 2020-11-26 武汉华星光电半导体显示技术有限公司 Organic light-emitting material, preparation method therefor, and organic light-emitting device
CN112521934A (en) * 2019-12-31 2021-03-19 华南理工大学 Hyperbranched electroluminescent polymer, and polymerized monomer, preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106588869A (en) * 2016-11-15 2017-04-26 华南理工大学 Dialkyl-substituted naphtho-dioxodibenzothiophene monomer and preparation method thereof and polymer containing dialkyl-substituted naphtho-dioxodibenzothiophene unit and application of polymer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106588869A (en) * 2016-11-15 2017-04-26 华南理工大学 Dialkyl-substituted naphtho-dioxodibenzothiophene monomer and preparation method thereof and polymer containing dialkyl-substituted naphtho-dioxodibenzothiophene unit and application of polymer

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108276562A (en) * 2018-01-23 2018-07-13 华南协同创新研究院 One kind contains S, the polymer and preparation method of S- dioxies-naphtho- [2,1-b] benzothiophene derivative unit and application
CN108276562B (en) * 2018-01-23 2020-03-24 华南协同创新研究院 Polymer containing S, S-dioxo-naphtho [2,1-b ] benzothiophene derivative unit, preparation method and application
CN110790742A (en) * 2018-08-02 2020-02-14 华南理工大学 Small-molecule luminescent material based on naphtho-sulfur-oxygen-fluorene unit and preparation method and application thereof
CN110790742B (en) * 2018-08-02 2023-02-14 华南理工大学 Small-molecule luminescent material based on naphtho-sulfur-oxygen-fluorene unit and preparation method and application thereof
WO2020232770A1 (en) * 2019-05-21 2020-11-26 武汉华星光电半导体显示技术有限公司 Organic light-emitting material, preparation method therefor, and organic light-emitting device
US11387416B2 (en) 2019-05-21 2022-07-12 Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. Organic light emitting material, preparation method thereof, and organic light emitting device
CN112521934A (en) * 2019-12-31 2021-03-19 华南理工大学 Hyperbranched electroluminescent polymer, and polymerized monomer, preparation method and application thereof
CN112521934B (en) * 2019-12-31 2022-07-26 华南理工大学 Hyperbranched electroluminescent polymer, and polymerization monomer, preparation method and application thereof

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Application publication date: 20171017