CN106883387A - Based on heteroaromatic and 2,8 S, the conjugated polymer of S dioxydibenze bithiophene units and preparation method and application - Google Patents

Based on heteroaromatic and 2,8 S, the conjugated polymer of S dioxydibenze bithiophene units and preparation method and application Download PDF

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CN106883387A
CN106883387A CN201710110654.3A CN201710110654A CN106883387A CN 106883387 A CN106883387 A CN 106883387A CN 201710110654 A CN201710110654 A CN 201710110654A CN 106883387 A CN106883387 A CN 106883387A
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substitution
heteroaromatic
conjugated polymer
carbon number
dioxydibenze
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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 based on heteroaromatic and 2,8 S, conjugated polymer of S dioxydibenze bithiophene units and preparation method and application.Should be based on heteroaromatic and 2, the conjugated polymer of 8 S, S dioxydibenze bithiophene unit is by by heteroaromatic and 2,8 S, the monomer of S dioxydibenze bithiophenes passes through after Suzuki polymerisations with the boric acid ester monomer containing Ar structures, then using phenyl boric acid and bromobenzene to carry out end capping reaction successively prepared.Conjugated polymer of the present invention has preferable dissolubility, is appropriate for solution processing and typographical display, the luminescent layer for preparing Organic Light Emitting Diode；Luminescent layer based on the polymer is when electroluminescent device is prepared without annealing so that preparation technology is simpler.

Description

Based on heteroaromatic simultaneously -2,8-S, the conjugated polymer of S- dioxydibenze bithiophene units And preparation method and application
Technical field
The invention belongs to organic photoelectric technical field, and in particular to one kind based on heteroaromatic simultaneously -2,8-S, S- dioxydibenzes 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 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.
The heteroaromatic that the present invention relates to simultaneously-conjugated polymer of 2,8-S, S- dioxydibenze bithiophene units because With preferable solubility property, it is adaptable to which solution is processed, and preferably fluorescence quantum yield, its luminescent device is not only efficiently steady It is fixed, and be more saturation blue light, the raising of the luminous efficiency and service life of luminescent device can be simultaneously realized, can meet complete The requirement that colour display screen shows.So having huge development potentiality and prospect in 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 miscellaneous based on virtue Ring simultaneously -2,8-S, the conjugated polymer of S- dioxydibenze bithiophene units.The conjugated polymer can be used as luminescent material, and have Preferable dissolubility, fluorescence quantum yield higher is suitable for solution processing and inkjet printing, with good development prospect, Organic electronic device stability and the device lifetime of correlation can be solved the problems, such as.
The present invention also aims to provide described based on heteroaromatic simultaneously -2,8-S, S- dioxydibenze bithiophene units are total to The preparation method of conjugated polymer.
The present invention also aims to provide described based on heteroaromatic simultaneously -2,8-S, S- dioxydibenze bithiophene units are total to Application of the conjugated polymer in the luminescent layer for preparing Organic Light Emitting Diode.
Based on heteroaromatic simultaneously-conjugated polymer of 2,8-S, S- dioxydibenze bithiophene units, with following structural formula：
In formula, Ar1It is heteroaromatic group；R1-R14It is selected from-H ,-F ,-Cl ,-Br ,-I ,-D ,-CN ,-NO2、-CF3, carbon it is former The linear paraffin base of subnumber 1~20, the alkane ether group of carbon number 1~20, the alkane sulfide group of carbon number 1-10；0 ≤x≤1；Polymerization degree n is 1-300；
Ar is electric transmission unit or hole transporting unit, and 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 H, aryl, triphenylamine, the straight or branched alkyl of carbon number 1-20, or is carbon number 1-20's Alkoxy.
Further, the R1~R14It is selected from deuterium, the alkyl of carbon number 1~20, the alcoxyl of carbon number 1~20 Base, the amino of carbon number 1~20, the alkenyl of carbon number 1~20, the alkynyl of carbon number 1~20, carbon number 1~10 Aralkyl, the aryl of carbon number 1~10 or carbon number 1~10 heteroaryl.
It is described based on heteroaromatic simultaneously-preparation method of the conjugated polymer of 2,8-S, S- dioxydibenze bithiophene units, bag Include following steps：
Under argon atmosphere, by heteroaromatic simultaneously-monomer of 2,8-S, S- dioxydibenze bithiophenes and the boric acid containing Ar structures Ester monomer is by after Suzuki polymerisations, then using phenyl boric acid and bromobenzene carries out end capping reaction successively, obtains described based on virtue Heterocycle simultaneously -2,8-S, the conjugated polymer of S- dioxydibenze bithiophene units.
Further, the heteroaromatic simultaneously-monomer of 2,8-S, S- dioxydibenze bithiophenes and the borate containing Ar structures The mol ratio of monomer is 1：1.
Further, the heteroaromatic simultaneously-monomer and the mol ratio of phenyl boric acid of 2,8-S, S- dioxydibenze bithiophenes be 1.1:1。
Further, the phenyl boric acid and the mol ratio of bromobenzene are 1:3.8.
Further, the temperature of the Suzuki polymerisations is 80~100 DEG C, and the time is 24~48 hours.
Further, the temperature that the phenyl boric acid and bromobenzene carry out end capping reaction is 80~100 DEG C, and the time is 12~24 small When.
It is described based on heteroaromatic simultaneously -2,8-S, the conjugated polymer of S- dioxydibenze bithiophene units is applied to prepare luminous The luminescent layer of diode, will based on heteroaromatic simultaneously-conjugated polymer of 2,8-S, S- dioxydibenze bithiophene units is with organic molten Agent is dissolved, then by spin coating, inkjet printing or printing film forming, obtains the luminescent layer of light emitting diode；Hair based on the luminescent layer Optical diode is applied in the preparation of organic electronic device, including prepares flat-panel monitor.
Further, the organic solvent includes chlorobenzene.
Compared with prior art, the invention has the advantages that and beneficial effect：
(1) conjugated polymer of the invention, the backbone structure of conjugation assigns polymer has abundant optically and electrically property Can, including luminescence generated by light, electroluminescent, photovoltaic effect, characteristic of semiconductor and carrier transmission characteristics；
(2) conjugated polymer of the invention, when being applied to prepare complicated Heterolamellar photovoltaic device, using conjugated polymer Solution processing characteristics, prepare luminescent layer, so as to further make by the solution processing technology such as inkjet printing, silk-screen printing or spin coating Standby polymer light electrical part；
(3) conjugated polymer of the invention, due to larger conjugate length, so there is fluorescent quantum higher to produce Rate, is conducive to improving the device efficiency of material；
(4) conjugated polymer of the invention, with preferable dissolubility, the luminescent layer based on the polymer prepare it is electroluminescent Without annealing during luminescent device so that preparation technology is simpler.
Brief description of the drawings
Fig. 1 is photoluminescence spectra figure of the polymer P 1 under filminess；
Fig. 2 is photoluminescence spectra figure of the polymer P 2 under filminess；
Fig. 3 is the Thermal Chart of polymer P 3；
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 bromo- 2- quinoxalines methyl formates of 1-
Under an argon atmosphere, by bromo- 2- quinoxalines formic acid (10g, 37.83mmol) the addition two-mouth bottles of 1-, add 100mL methyl alcohol, is then added dropwise over the concentrated sulfuric acid (39.06mg, 398.29umol), is heated to 110 DEG C, reacts 18h.Reaction is mixed Compound is poured into water, and is extracted with ethyl acetate, and after organic layer saline solution is washed completely, plus anhydrous magnesium sulfate is dried.Solution is dense After contracting, crude white solid is obtained, (eluant, eluent selects petroleum ether/dichloromethane=3/1, v/v) is purified with silica gel column chromatography, produced Thing obtains white solid, yield 85% in placing refrigerator for a long time.1H NMR、13CNMR, MS and elementary analysis result show gained The compound for arriving is target product.Chemical equation is as follows：
Embodiment 2
The preparation of 2,8- dibromo dibenzothiophens
Under argon atmosphere, dibenzothiophen (20g, 108.54mmol) is added in 250ml two-mouth bottles, adds 100ml chlorine It is imitative to be completely dissolved, elemental iodine (550.99mg, 2.17mmol) is added, in the case of lucifuge, it is added dropwise over bromine (38.16g, 238.80mmol), reaction solution is stirred 2 hours under ice bath, is then stirred at room temperature 2 hours, adds saturation Sodium hydrogensulfite is quenched bromine, and reactant mixture is poured into water, and is extracted with ethyl acetate, and organic layer saline solution is washed completely 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
2,8- diborate dibenzothiophens
Under an argon atmosphere, 2,8- dibromos dibenzothiophen (10g, 29.24mmol) are dissolved in the refined tetrahydrofurans of 180mL (THF) in, the n-BuLi 28mL of 1.6mol L-1 is gradually added dropwise at -78 DEG C, reacts 2 hours, be then quickly added into 2- different Propoxyl group -4,4,5,5- tetramethyl -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 saline solution is washed completely, Plus anhydrous magnesium sulfate is dried.After solution concentration, thick pale yellow shape crude product is obtained, (eluant, eluent selection is purified with silica gel column chromatography Petrol ether/ethyl acetate=20/1, v/v), product obtains white solid, yield 70% in placing refrigerator for a long time.1H NMR and GC-MASS tests are shown to be target product.Chemical equation is as follows：
Embodiment 4
The preparation of compound M1
Under argon atmosphere, by 2,8- diborates dibenzothiophen (5g, 11.46mmol) and the bromo- 2- 2-methyl naphthoates of 1- (7.6g, 27.66mmol) is added in two-mouth bottle, is added 100ml toluene and is completely dissolved, and adds sodium carbonate (6.07g, 57.32mmol), TBAB (312.01mg, 967.86umol) and four triphenyl phosphorus palladiums (264.93mg, 229.26umol), 18h is reacted at 110 DEG C.Reactant mixture is poured into water, is extracted with ethyl acetate, organic layer salt After water is washed completely, plus anhydrous magnesium sulfate is dried.After solution concentration, (eluant, eluent selection petroleum ether/bis- are purified with silica gel column chromatography Chloromethanes=7/1, v/v), finally give white solid, yield 80%.1H NMR、13CNMR, MS and elementary analysis result show Resulting compound is target product.Chemical equation is as follows：
Embodiment 5
The preparation of compound M2
Under argon atmosphere, by M1 (10g, 17.50mmol) 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, 20.25g, 116.15mmol), mixed liquor reacts 18h at room temperature.Add water to that reaction is quenched in reaction solution, extracted with ethyl acetate Take, after organic layer saline solution is washed completely, plus anhydrous magnesium sulfate is dried.After solution concentration, (wash-out is purified with silica gel column chromatography Agent selects petroleum ether/dichloromethane=3/1, v/v), product obtains white solid, yield 80% in placing refrigerator for a long time.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product.The following institute of chemical equation Show：
Embodiment 6
The preparation of compound M3
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.Chemical equation is as follows：
Embodiment 7
The preparation of compound M4
Under argon atmosphere, M3 (5g, 5.40mmol) 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.Change Learn reaction equation as follows：
Embodiment 8
The preparation of compound M5
Under argon atmosphere, compound M4 is added in 250ml two-mouth bottles, adds acetic acid to be dissolved, added double Oxygen water (H2O2), 80 DEG C are heated to, react 16 hours.It is extracted with ethyl acetate, after organic layer saline solution is washed completely, plus nothing Water magnesium sulfate is dried.After solution concentration, (eluant, eluent selection petroleum ether) is purified with silica gel column chromatography, yield 75%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product.Chemical equation is as follows：
Embodiment 9
The preparation of 2,7- dibromo fluorenes
In 250mL there-necked flasks, fluorenes (24.5g, 0.1mol), iron powder (88mg, 1.57mmol), chloroform are added 100mL；Ice-water bath is cooled down, and bromine (17.6g, 0.1mol)/chloroform mixed solution 35mL is added dropwise.Temperature does not surpass in bottle during dropwise addition Cross 5 DEG C；Reaction is finished, filtering, Gossypol recrystallized from chloroform, obtains white solid 20.3g, yield 83%.1HNMR、13CNMR, MS and element Compound obtained by analysis result shows is target product.Chemical equation is as follows：
Embodiment 10
The preparation of 2,7- bis- bromo- 9,9- dioctyl fluorenes
Added in there-necked flask 2,7- dibromos fluorenes (9.7g, 0.03mol), benzyltriethylammoinium chloride (0.07g, 0.3mmol), dimethyl sulfoxide (DMSO) 90mL and 45mL sodium hydrate aqueous solutions (50wt%), at room temperature stirring form suspension；Add 1- bromines normal octane (12.5g, 65mmol), after continuing to stir 3 hours, are extracted with ether.Second is washed with saturated sodium-chloride water solution Ether phase, anhydrous magnesium sulfate is dried.Solvent is boiled off, product petroleum ether makees the purification of eluant, eluent column chromatography, obtains white solid.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product.The following institute of chemical equation Show：
Embodiment 11
2,7- diborate -9, the preparation of 9- dioctyl fluorenes
Under an argon atmosphere, bromo- 9, the 9- dioctyl fluorenes (5g, 9.12mmol) of 2,7- bis- are dissolved in the refined THF of 180mL In, 1.6mol.L is gradually added dropwise at -78 DEG C-1N-BuLi 28mL, react 2 hours, be subsequently adding 2- isopropoxy -4,4, 5,5- tetramethyl -1,3,2- dioxaborinate 25mL continue to react 1 hour at -78 DEG C, then heat to room temperature reaction 24 small When.Reactant mixture is poured into water, is extracted with ethyl acetate, after organic layer saline solution is washed completely, plus anhydrous magnesium sulfate Dry.After solution concentration, thick pale yellow shape crude product is obtained, (eluant, eluent selection petroleum ether/acetic acid second is purified with silica gel column chromatography Ester=15/1, v/v), product obtains white solid, yield 70% in placing refrigerator for a long time.1H NMR、13CNMR, MS and element Compound obtained by analysis result shows is target product.Chemical equation is as follows：
Embodiment 12
The preparation of 3,6- dibromo carbazoles
In 500mL two-mouth bottles add carbazole (24.7g, 0.1mol), dimethylformamide 200mL, stirring to completely it is molten Solution, N-bromosuccinimide (NBS, 49.84g, 0.28mol) 120ml DMFs dissolve, ice bath to 0 DEG C, NBS solution is added dropwise, reaction, lucifuge after completion of dropping, allows temperature to rise to room temperature automatically, reacts 6 hours, will react drop Precipitation in water is added to, after suction filtration obtains crude product, suction filtration thing is recrystallized with absolute ethyl alcohol, dried, obtain precious color needle-like Solid, yield 85%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product.Chemistry Reaction equation is as follows：
Embodiment 13
The bromo- N- octylcarbazols of 3,6- bis-
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.Chemical equation is as follows：
Embodiment 14
3,6- bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-diyl)-N- octylcarbazols
The bromo- N- octylcarbazols (13.11g, 30mmol) of 3,6- bis-, the new ether 250mL for steaming, stirring are added in there-necked flask It is completely dissolved to clear, reaction solution is cooled to -78 DEG C, it is then disposable to add 2- isopropoxies-(4,4,5,5- tetra- Methyl) -1,3,2- ethylenedioxy borates (37mL, 180mmol), stir 2 hours, then temperature is warmed to room temperature at -78 DEG C Reaction terminates reaction after 24 hours.Extracted with ether, saturated common salt water washing 4 times, then dried with anhydrous magnesium sulfate, after filtering, Solvent, product petrol ether/ethyl acetate (10 is distilled off:1) for eluant, eluent column chromatography is purified, white solid, yield are obtained 45%.Chemical equation is as follows：
Embodiment 15
The preparation of polymer P 1
Under argon atmosphere, by 2,7- diborate -9,9- dioctyl fluorenes (300mg, 272.92 μm of ol) and M5 (342.92mg, 272.92 μm of ol) are added in 100ml two-mouth bottles, are added 8ml toluene and are completely dissolved, and substitute gas three times, Palladium (2.45mg, 10.92 μm of ol) and tricyclohexyl phosphine (6.12mg, 21.83 μm of ol) are added, gas is substituted three times, then 2ml tetraethyl ammonium hydroxides are added, 80 DEG C are warming up to, reacted 24 hours.It is subsequently adding 30mg phenyl boric acids to be blocked, 12 hours Afterwards, then with 0.1ml bromobenzenes blocked, continue to react 12 hours；Afterwards, product is added dropwise and is precipitated out in methyl alcohol, stirred, Filtering, then crude product is dissolved in the toluene of 20mL, it is fixing phase with 200~300 mesh silica gel, it is that eluant, eluent carries out post with toluene Chromatography, then after solvent under reduced pressure is concentrated, separate out to come in methyl alcohol again, stirring, filtering obtains polymer after vacuum drying Solid.Finally respectively extracted 24 hours with methyl alcohol, acetone, tetrahydrofuran successively again, remove small molecule.By the tetrahydrofuran after concentration Solution instills precipitating, the fibrous solids conjugated polymer P1 obtained after vacuum drying in methyl alcohol.Chemical equation is as follows It is shown：
Luminescence generated by light spectrogram of the polymer P 1 for obtaining under filminess as indicated with 1, it can be seen that polymer The maximum emission peak of P1 is located at 452nm.
Embodiment 16
The preparation of polymer P 2
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 M5 (300mg, 272.92 μm of ol) are added in 100ml two-mouth bottles, add 8ml toluene Be completely dissolved, substituted gas three times, add palladium (2.45mg, 10.92 μm of ol) and tricyclohexyl phosphine (6.12mg, 21.83 μm of ol), substitute gas three times, 2ml tetraethyl ammonium hydroxides are subsequently adding, 80 DEG C are warming up to, react 24 hours.Then plus Enter 30mg phenyl boric acids to be blocked, after 12 hours, then blocked with 0.1ml bromobenzenes, continue to react 12 hours；Afterwards, will produce Thing is added dropwise and is precipitated out in methyl alcohol, stirs, filtering, then crude product is dissolved in the toluene of 20mL, with 200~300 mesh silica gel It is fixing phase, is that eluant, eluent carries out column chromatography with toluene, then after solvent under reduced pressure is concentrated, separates out to come in methyl alcohol again, Stirring, filtering, obtains polymer solids after vacuum drying.It is last that with methyl alcohol, acetone, tetrahydrofuran respectively to extract 24 successively again small When, remove small molecule.By precipitating, the fibrous solids obtained after vacuum drying in the tetrahydrofuran solution instillation methyl alcohol after concentration Conjugated polymer P2.Chemical equation is as follows：
Luminescence generated by light spectrogram of the polymer P 2 for obtaining under filminess as indicated with 2, it can be seen that polymer The maximum emission peak of P2 is located at 530nm.
Embodiment 17
The preparation of polymer P 3
Under argon atmosphere, indenes fluorenes boric acid (260.66mg, 272.92 μm of ol) and M5 (300mg, 272.92 μm of ol) are added Enter in 100ml two-mouth bottles, add 8ml toluene and be completely dissolved, substitute gas three times, add palladium (2.45mg, 10.92 μm of ol) and tricyclohexyl phosphine (6.12mg, 21.83 μm of ol), substitute gas three times, it is subsequently adding 2ml tetraethyl hydroxides Ammonium, is warming up to 80 DEG C, reacts 24 hours.It is subsequently adding 30mg phenyl boric acids to be blocked, after 12 hours, then is entered with 0.1ml bromobenzenes Row end-blocking, continues to react 12 hours；Afterwards, product is added dropwise and is precipitated out in methyl alcohol, stirred, 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 P3 obtained after vacuum drying.Chemical equation is as follows：
The Thermal Chart of the polymer P 3 for obtaining is as shown in figure 3, it can be seen that the heat decomposition temperature of polymer It it is 430 DEG C, polymer P 3 has preferable heat endurance.
Embodiment 18
The preparation of polymer P 4
Under argon atmosphere, by naphtho- indenes fluorenes borate (274.33mg, 272.92 μm of ol) and M5 (300mg, 272.92 μ Mol) add in 100ml two-mouth bottles, add 8ml toluene and be completely dissolved, substitute gas three times, add palladium (2.45mg, 10.92 μm of ol) and tricyclohexyl phosphine (6.12mg, 21.83 μm of ol), substitutes gas three times, is subsequently adding 2ml tetraethyls Ammonium hydroxide, is warming up to 80 DEG C, reacts 24 hours.It is subsequently adding 30mg phenyl boric acids to be blocked, after 12 hours, then uses 0.1ml Bromobenzene is blocked, and continues to react 12 hours；Afterwards, product is added dropwise and is precipitated out in methyl alcohol, stirred, filtering, then will be thick Product is dissolved in the toluene of 20mL, is fixing phase with 200~300 mesh silica gel, is that eluant, eluent carries out column chromatography with toluene, then will be molten After agent is concentrated under reduced pressure, separate out to come in methyl alcohol again, stirring, filtering obtains polymer solids after vacuum drying.Again finally Respectively extracted 24 hours with methyl alcohol, acetone, tetrahydrofuran successively, remove small molecule.Tetrahydrofuran solution after concentration is instilled into first Precipitating in alcohol, the fibrous solids conjugated polymer P4 obtained after vacuum drying.Chemical equation is as follows：
Embodiment 19
The preparation of the electroluminescent device based on polymer
On tin indium oxide (ITO) glass of well in advance, its square resistance is 20 Ω/, and acetone, washing are first used successively Agent, deionized water and isopropanol are cleaned by ultrasonic, plasma treatment 10 minutes.Spin coating 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 double focusing compound luminescent material P1, P2, P3 and P4 is spin-coated on respectively then PEDOT:The surface of PSS films, thickness is 80nm, used as luminescent layer；Finally it is deposited with a thin layer CsF successively on luminescent layer (1.5nm) and 120nm thick metal Al layer.
The current density of the electroluminescent device based on polymer P 4-luminous efficiency spectrogram is as shown in figure 4, can be with from figure Find out, based on device architecture：ITO/PEDOT/EML/CsF/Al, the maximum lumen efficiency of polymer P 4 is 1.32cd/A.
The photoelectric properties index of the electroluminescent device based on 1~P4 of polymer P is as shown in table 1.
Table 1 is based on the photoelectric properties index of the electroluminescent device of 1~P4 of polymer P.
As shown in Table 1, based on quinoxaline simultaneously-conjugated polymer luminescent material of 2,8-S, S- dioxydibenze bithiophene units The electroluminescent device of P1, P2, P3 and P4, based on device architecture：The maximum lumen efficiency of ITO/PEDOT/EML/CsF/Al point Wei not 1.12cd/A, 1.87cd/A, 1.61cd/A, 1.32cd/A.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment Limitation, other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification all should It is equivalent substitute mode, is included within protection scope of the present invention.

Claims (7)

1. based on heteroaromatic simultaneously-conjugated polymer of 2,8-S, S- dioxydibenze bithiophene units, it is characterised in that chemical constitution Formula is as follows：
In formula, Ar1It is heteroaromatic group；R1-R14It is selected from-H ,-F ,-Cl ,-Br ,-I ,-D ,-CN ,-NO2、-CF3, carbon number 1~20 linear paraffin base, the alkane ether group of carbon number 1~20, the alkane sulfide group of carbon number 1-10；0≤x≤ 1；Polymerization degree n is 1-300；
Ar is electric transmission unit or hole transporting unit, and 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- substitutions -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 H, aryl, triphenylamine, the straight or branched alkyl of carbon number 1-20, or is the alcoxyl of carbon number 1-20 Base.
2. it is according to claim 1 based on heteroaromatic simultaneously-conjugated polymer of 2,8-S, S- dioxydibenze bithiophene units, Characterized in that, the R1~R14It is selected from deuterium, the alkyl of carbon number 1~20, the alkoxy of carbon number 1~20, carbon former The amino of subnumber 1~20, the alkenyl of carbon number 1~20, the alkynyl of carbon number 1~20, the aralkyl of carbon number 1~10 The heteroaryl of base, the aryl of carbon number 1~10 or carbon number 1~10.
3. described in claim 1 or 2 based on heteroaromatic simultaneously -2,8-S, the conjugated polymer of S- dioxydibenze bithiophene units Preparation method, it is characterised in that comprise the following steps：
Under argon atmosphere, by heteroaromatic simultaneously-monomer of 2,8-S, S- dioxydibenze bithiophenes and the borate list containing Ar structures Body is by after Suzuki polymerisations, then using phenyl boric acid and bromobenzene carries out end capping reaction successively, obtains described based on heteroaromatic And the conjugated polymer of -2,8-S, S- dioxydibenze bithiophene unit.
4. according to claim 3 based on heteroaromatic simultaneously -2,8-S, the conjugated polymer of S- dioxydibenze bithiophene units Preparation method, it is characterised in that the heteroaromatic simultaneously-monomer of 2,8-S, S- dioxydibenze bithiophenes and the boron containing Ar structures The mol ratio of acid ester monomer is 1：1；The heteroaromatic simultaneously -2,8-S, the monomer of S- dioxydibenze bithiophenes and phenyl boric acid mole Than being 1.1:1；The phenyl boric acid is 1 with the mol ratio of bromobenzene:3.8.
5. according to claim 3 based on heteroaromatic simultaneously -2,8-S, the conjugated polymer of S- dioxydibenze bithiophene units Preparation method, it is characterised in that the temperature of the Suzuki polymerisations be 80~100 DEG C, the time be 24~48 hours；Institute State phenyl boric acid and bromobenzene to carry out the temperature of end capping reaction be 80~100 DEG C, the time is 12~24 hours.
6. described in claim 1 or 2 based on heteroaromatic simultaneously -2,8-S, the conjugated polymer of S- dioxydibenze bithiophene units should Luminescent layer for preparing light emitting diode, it is characterised in that will based on heteroaromatic simultaneously -2,8-S, S- dioxydibenze bithiophene lists The conjugated polymer of unit organic solvent dissolves, then by spin coating, inkjet printing or printing film forming, obtains the hair of light emitting diode Photosphere.
7. application according to claim 6, it is characterised in that the organic solvent includes chlorobenzene.
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Application publication date: 20170623