CN107141452A - The conjugated polymer of one kind based on phenanthro- S, S dioxydibenze bithiophene unit and preparation method and application - Google Patents

The conjugated polymer of one kind based on phenanthro- S, S dioxydibenze bithiophene unit and preparation method and application Download PDF

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CN107141452A
CN107141452A CN201710271730.9A CN201710271730A CN107141452A CN 107141452 A CN107141452 A CN 107141452A CN 201710271730 A CN201710271730 A CN 201710271730A CN 107141452 A CN107141452 A CN 107141452A
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phenanthro
substitution
dioxo
fluorenes
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 a kind of conjugated polymer based on phenanthro- S, S dioxydibenze bithiophene unit and preparation method and application.The present invention obtains described based on phenanthro- S, the conjugated polymer of S dioxydibenze bithiophene units by Suzuki polymerisations.Conjugated polymer of the present invention based on phenanthro- S, S dioxydibenze bithiophene unit has preferable dissolubility, after being dissolved using common organic solvents, then by spin coating, inkjet printing or printing film forming, prepares the luminescent layer of light emitting diode.Luminescent layer based on the polymer is when preparing luminescent device without annealing so that preparation technology is simpler.

Description

One kind based on phenanthro--S, S- dioxo-dibenzothiophene unit conjugated polymer and its Preparation method and application
Technical field
The invention belongs to organic photoelectrical material field, and in particular to one kind is based on phenanthro--S, S- dioxo-dibenzothiophene list Conjugated polymer of member and preparation method and application.
Background technology
In the past thirty years, organic electronic and photoelectronic industry, including organic/polymer LED (PLED), organic field effect tube, the field such as organic solar batteries has obtained swift and violent development, and gradually realizes industry Change.Organic electronic product has cheap, and body is light the advantages of take.Make it have great market potential.Therefore exploitation has The organic electronic product for having market attractiveness has attracted the concern of numerous research institutions and Research Team in the world, and this its In, developing the material of new and effective 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.
Phenanthro--S, the S- dioxo-dibenzothiophene unit and its polymer that the present invention relates to, because with preferable Solubility property, it is adaptable to which solution is processed, and preferably fluorescence quantum yield, its luminescent device not only efficient stable, Er Qiewei More blue saturation blue light, the raising of the luminous efficiency and service life of luminescent device can be realized simultaneously, can meet full-color aobvious The requirement shown.So there is huge development potentiality and prospect in organic electronic display field.
The content of the invention
It is an object of the invention to for current polymer LED problems faced there is provided one kind based on phenanthro-- The conjugated polymer of S, S- dioxo-dibenzothiophene unit.The conjugated polymer can be used as luminescent material, and with preferably molten Xie Xing, higher fluorescence quantum yield is suitable for solution processing and inkjet printing, with good development prospect.
The present invention also aims to provide a kind of conjugation for being based on phenanthro--S, S- dioxo-dibenzothiophene unit The preparation method of polymer.
The present invention also aims to provide a kind of conjugation for being based on phenanthro--S, S- dioxo-dibenzothiophene unit Application of the polymer in the luminescent layer of light emitting diode is prepared.
One kind is based on the conjugated polymer of phenanthro--S, S- dioxo-dibenzothiophene unit, with following chemical structural formula：
In formula, R1-R4For hydrogen, aryl, triphenylamine, carbon number 1-20 straight or branched alkyl, or for carbon number 1- 20 alkoxy；0≤x≤1, polymerization degree n is 1-300；
Ar is any one in following structure：
2,7- substituted fluorenes；
3,6- substituted fluorenes；
2,7- substitution silicon fluorenes；
3,6- substitution silicon fluorenes；
2,7- substitution spiro fluorenes；
3,6- substitution spiro fluorenes；
2,7- substitution -9,9- dialkoxy phenyl fluorenes；
3,6- substitution -9,9- dialkoxy phenyl fluorenes；
2,7- substituted carbazoles；
3,6- substituted carbazoles；
2,6- 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-phenanthro- thiadiazoles；
4,9- -6,7- of substitution alkyl-phenanthro- selenium diazole；
Naphtho- indenes fluorenes；
Wherein, R is H, aryl, triphenylamine, carbon number 1-20 straight chain or branched alkyl, or is carbon number 1-20 Alkoxy.
The method that described one kind is based on the conjugated polymer of phenanthro--S, S- dioxo-dibenzothiophene unit is prepared, including Following steps：
By phenanthro--S, S- dioxo-dibenzothiophenes monomer is polymerize instead with the boric acid ester monomer of the structure containing Ar by Suzuki Ying Hou, then successively using phenyl boric acid and bromobenzene progress end capping reaction, obtain described based on phenanthro--S, S- dioxo-dibenzothiophene The conjugated polymer of unit.
Further, the phenanthro--S, S- dioxo-dibenzothiophenes monomer and mole of the boric acid ester monomer of the structure containing Ar Than for 1:1~1:5.
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 conjugated polymer that described one kind is based on phenanthro--S, S- dioxo-dibenzothiophene unit is luminous applied to preparing The luminescent layer of diode, will be dissolved based on the conjugated polymer of phenanthro--S, S- dioxo-dibenzothiophene unit with organic solvent, Again by spin coating, inkjet printing or printing film forming, the luminescent layer of the light emitting diode is obtained；Luminous two based on the luminescent layer Pole pipe can be used for preparing flat-panel monitor.
Further, the organic solvent includes chlorobenzene.
Compared with prior art, the present invention has advantages below：
(1) it is of the invention based on phenanthro--S, the conjugated polymer of S- dioxo-dibenzothiophene units, due to larger Conjugate length, so there is higher fluorescence quantum yield, be conducive to improving the device efficiency of material；
(2) it is of the invention based on phenanthro--S, the conjugated polymer of S- dioxo-dibenzothiophene units, with preferably molten Xie Xing, the luminescent layer based on the polymer is when preparing electroluminescent device without annealing so that preparation technology is simpler.
Brief description of the drawings
Fig. 1 is the Thermal Chart of polymer P 1；
Fig. 2 is photoluminescence spectra figure of the polymer P 2 under filminess；
Fig. 3 is current density-luminous efficiency spectrogram of the electroluminescent device based on polymer P 3.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
The preparation of the phenanthrenecarboxylic acid methyl esters of 1- bromines two
Under an argon atmosphere, the bromo- 2- phenanthrenecarboxylic acids (10g, 37.83mmol) of 1- are added in two-mouth bottle, adds 100mL first Alcohol, is then added dropwise the concentrated sulfuric acid (39.06mg, 378.29umol), 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, product is placed In refrigerator, white solid, yield 85% are obtained.1H NMR、13CNMR, MS and elementary analysis result show resulting compound For target product, preparation process 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, add 0.5g (275mg, 1.09) elemental iodine, in the case of lucifuge, be added dropwise bromine (38.16g, 238.80mmol), reaction solution is stirred 2 hours under 0 DEG C of ice bath, is then stirred at room temperature 2 hours, adds the sulfurous acid of saturation Bromine is quenched in hydrogen sodium, and 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, 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, and preparation process chemical equation is as follows It is shown：
Embodiment 3
The preparation of 2- borate dibenzothiophens
Under an argon atmosphere, 2- bromines dibenzothiophen (10g, 29.24mmol) is dissolved in the refined tetrahydrofurans (THF) of 180mL In, 1.6mol L-1 n-BuLi 28mL is gradually added dropwise at -78 DEG C, reacts 2 hours, is then quickly added into 2- isopropyl oxygen Base -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 nothing Water magnesium sulfate is dried.After solution concentration, thick pale yellow shape crude product is obtained, (eluant, eluent selection oil is purified with silica gel column chromatography Ether/ethyl acetate=20/1, v/v), in product placing box, obtain white solid, yield 70%.1H NMR and GC-MASS are tested Target product is shown to be, preparation process chemical equation is as follows：
Embodiment 4
Compound M1 preparation
Under argon atmosphere, by 2- borates dibenzothiophen (5g, 10.46mmol) and the bromo- 2- phenanthrenecarboxylic acids methyl esters of 1- (7.6g, 28.66mmol) be added in two-mouth bottle, add 100ml toluene and be completely dissolved, add 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 washing 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 M1, and preparation process chemical equation is as follows：
Embodiment 5
Compound M2 preparation
Under argon atmosphere, compound M1 (10g, 23.89mmol) 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, obtains white solid, yield 80%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product M2, and preparation process chemical equation is such as Shown in lower：
Embodiment 6
Compound M3 preparation
Under argon atmosphere, compound M2 (5g, 4.09mmol) 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 in refrigerator, obtain white solid, yield 90%.1H NMR、13CNMR, MS and elementary analysis result show resulting change Compound is target product M3, and preparation process chemical equation is as follows：
Embodiment 7
Compound M4 preparation
Under argon atmosphere, compound M3 (5g, 4.50mmol) is dissolved in 50mL dichloromethane, iron powder is added (185.35mg, 3.32mmol), then bromine (1.93g, 12.10mmol) is added dropwise, 18h is reacted at room temperature；Use acetic acid second Ester is extracted, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried；After solution concentration, purified with silica gel column chromatography (eluant, eluent selection petroleum ether), yield 70%.1H NMR、13CNMR, MS and elementary analysis result show that resulting compound is Target product M4, preparation process chemical equation is as follows：
Embodiment 8
Compound M5 preparation
Under argon atmosphere, compound M4 (10g, 13.25mmol) is added in 250ml two-mouth bottles, 100mL second is added Acid is dissolved, and adds hydrogen peroxide (1.35g, 39.75mmol, H2O2), 80 DEG C are heated to, is reacted 16 hours；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 75%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is mesh Product M5 is marked, preparation process chemical equation is as follows：
Embodiment 9
Compound M6 preparation
Under an argon atmosphere, compound M5 (10g, 18.24mmol) is dissolved in the refined THF of 180mL, at -78 DEG C Under 1.6mol/L n-BuLi 28mL is gradually added dropwise, react 2 hours, be then quickly added into 2- isopropoxies -4,4,5,5- tetra- Methyl isophthalic acid, 3,2- dioxaborinate 25mL continue to react 1 hour at -78 DEG C, are to slowly warm 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, obtains white solid, yield 70%.1H NMR and GC-MASS test are shown to be target Product M6, preparation process chemical equation is as follows：
Embodiment 10
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, and preparation process chemical equation is as follows：
Embodiment 11
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 12
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 13
The preparation of 3,6- dibromo carbazoles
Carbazole (24.7g, 0.1mol) is added in 500mL two-mouth bottles, dimethylformamide 200mL is stirred to completely molten Solution, N-bromosuccinimide (NBS, 49.84g, 0.28mol) 120ml DMFs dissolve, ice bath to 0 DEG C, it is added dropwise after NBS solution, reaction, lucifuge, completion of dropping, allows temperature to rise to automatically after room temperature, reacts 6 hours, by reaction solution It is added drop-wise in water and precipitates, suction filtration obtains after crude product, suction filtration thing is recrystallized with absolute ethyl alcohol, dries, obtain precious color pin Shape solid, yield 85%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product, system Standby process chemistry reaction equation is as follows：
Embodiment 14
The preparation of 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, wash the organic phase separated, aqueous phase 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, preparation process chemical equation is as follows：
Embodiment 15
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, v/v) purified for eluant, eluent column chromatography, obtain white solid Body, yield 45%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product, is prepared Journey chemical equation is as follows：
Embodiment 16
The preparation of polymer P 1
Under argon atmosphere, by 2,7- diborates -9,9- dioctyl fluorene (300mg, 272.92 μm of ol) and phenanthro--S, S- Dioxy-and benzothiophene (342.92mg, 272.92 μm of ol) are added in 100ml two-mouth bottles, add 8ml toluene carry out it is 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 polymer P 1 of preparation is in Thermal Chart as shown in figure 1, it can be seen that the decomposition temperature of polymer P 1 (temperature when weightless 5%) is 412 DEG C.
Embodiment 17
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 (145.01mg, 272.92 μm of ol) and phenanthro--S, S- dioxy-and benzothiophene (300mg, 272.92 μm of ol) add 100ml In two-mouth bottle, add 8ml toluene and be completely dissolved, add palladium (2.45mg, 10.92 μm of ol) and tricyclohexyl phosphine (6.12mg, 21.83 μm of ol), then add 2ml tetraethyl ammonium hydroxides, are warming up to 80 DEG C, react 24 hours；Then add 30mg phenyl boric acids are blocked, after 12 hours, then are blocked with 0.1ml bromobenzenes；Continue after reacting 12 hours, product is dripped Plus be precipitated out in methyl alcohol, stir, filtering, then crude product is dissolved in 20mL toluene, it is solid using 200~300 mesh silica gel Determine phase, be that eluant, eluent carries out column chromatography with toluene, then after solvent under reduced pressure is concentrated, separate out to come in methyl alcohol again, stirring, Filtering, polymer solids are obtained after vacuum drying；Finally respectively extracted 24 hours, removed with methanol, acetone, tetrahydrofuran successively again Small molecule；Tetrahydrofuran solution after concentration is instilled into precipitating in methanol, the fibrous solids conjugation obtained after vacuum drying is poly- Compound P2.
Luminescence generated by light spectrogram of the polymer P 2 of preparation under filminess as indicated with 2, it can be seen that polymer P2 maximum emission peak is located at 556nm.
Embodiment 18
The preparation of polymer P 3
Under argon atmosphere, the benzo thiophene by indenes fluorenes boric acid (260.66mg, 272.92 μm of ol) and phenanthro--S, S- dioxy- Fen (300mg, 272.92 μm of ol) is added in 100ml two-mouth bottles, is added 8ml toluene and is completely dissolved, adds palladium (2.45mg, 10.92 μm of ol) and tricyclohexyl phosphine (6.12mg, 21.83 μm of ol), then adds 2ml tetraethyl ammonium hydroxides, rises Temperature is reacted 24 hours to 80 DEG C；Then addition 30mg phenyl boric acids are blocked, after 12 hours, then are sealed with 0.1ml bromobenzenes End；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 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 obtains polymer solids after vacuum drying；Finally use first successively again Alcohol, acetone, tetrahydrofuran are respectively extracted 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.
Embodiment 19
The preparation of electroluminescent device based on small molecule
It is that on 20 Ω/ tin indium oxide (ITO) glass, acetone, washing are first used successively in the square resistance of well in advance Agent, deionized water and isopropanol are cleaned by ultrasonic, plasma treatment 10 minutes；Spin coating, 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；Bipolarity small molecule emitter material P1, P2, P3 chlorobenzene solution (1wt%) is then spin-coated on PEDOT respectively: The surface of PSS films, thickness is 80nm, is used as luminescent layer；It is last be deposited successively on luminescent layer a thin layer CsF (1.5nm) and Metal Al layer thick 120nm.
Polymer P 3 is based on device architecture：ITO/PEDOT/EML/CsF/Al current density-luminous efficiency spectrogram such as Fig. 3 It is shown, it can be seen that the maximum lumen efficiency of the device based on polymer P 3 is 1.87cd/A.
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 seen from table, polymer P 1, P2 and P3 are based on device architecture：ITO/PEDOT/EML/CsF/Al max-flow obvious results Rate is followed successively by 1.12cd/A, 1.47cd/A and 1.87cd/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 (7)

1. one kind is based on the conjugated polymer of phenanthro--S, S- dioxo-dibenzothiophene unit, it is characterised in that with followingization Learn structural formula：
In formula, R1-R4For hydrogen, aryl, triphenylamine, carbon number 1-20 straight or branched alkyl, or for carbon number 1-20 Alkoxy；0≤x≤1, polymerization degree n is 1-300；
Ar is any one in following structure：
2,7- substituted fluorenes；
3,6- substituted fluorenes；
2,7- substitution silicon fluorenes；
3,6- substitution silicon fluorenes；
2,7- substitution spiro fluorenes；
3,6- substitution spiro fluorenes；
2,7- substitution -9,9- dialkoxy phenyl fluorenes；
3,6- substitution -9,9- dialkoxy phenyl fluorenes；
2,7- substituted carbazoles；
3,6- substituted carbazoles；
2,6- 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-phenanthro- thiadiazoles；
4,9- -6,7- of substitution alkyl-phenanthro- selenium diazole；
Naphtho- indenes fluorenes；
Wherein, R is H, aryl, triphenylamine, carbon number 1-20 straight chain or branched alkyl, or is carbon number 1-20 alkane Epoxide.
2. prepare the side that one kind described in claim 1 is based on the conjugated polymer of phenanthro--S, S- dioxo-dibenzothiophene unit Method, it is characterised in that comprise the following steps：
By phenanthro--S, after the boric acid ester monomer of S- dioxo-dibenzothiophenes monomer and the structure containing Ar is by Suzuki polymerisations, End capping reaction is carried out using phenyl boric acid and bromobenzene successively again, obtains described based on phenanthro--S, S- dioxo-dibenzothiophene unit Conjugated polymer.
3. a kind of system of conjugated polymer based on phenanthro--S, S- dioxo-dibenzothiophene unit according to claim 2 Preparation Method, it is characterised in that the phenanthro--S, S- dioxo-dibenzothiophenes monomer rubs with the boric acid ester monomer of the structure containing Ar You are than being 1:1~1:5.
4. a kind of system of conjugated polymer based on phenanthro--S, S- dioxo-dibenzothiophene unit according to claim 2 Preparation Method, it is characterised in that the temperature of the Suzuki polymerisations is 80~100 DEG C, the time is 24~48 hours.
5. a kind of system of conjugated polymer based on phenanthro--S, S- dioxo-dibenzothiophene unit according to claim 2 Preparation 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 hours.
6. the conjugated polymer that one kind described in claim 1 is based on phenanthro--S, S- dioxo-dibenzothiophene unit is applied to system The luminescent layer of preparation optical diode, it is characterised in that the conjugated polymers of phenanthro--S, S- dioxo-dibenzothiophene unit will be based on Thing organic solvent dissolves, then by spin coating, inkjet printing or printing film forming, obtains the luminescent layer of the light emitting diode.
7. application according to claim 6, it is characterised in that the organic solvent includes chlorobenzene.
CN201710271730.9A 2017-04-24 2017-04-24 The conjugated polymer of one kind based on phenanthro- S, S dioxydibenze bithiophene unit and preparation method and application Pending CN107141452A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108424344A (en) * 2018-04-11 2018-08-21 华南协同创新研究院 Monomer and polymer containing luxuriant and rich with fragrance five yuan and ring element and the preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101712674A (en) * 2009-11-13 2010-05-26 华南理工大学 Alkyl substituted-S,S-dioxo-dibenzothiophene monomer, preparation method and polymer thereof
CN105924629A (en) * 2016-06-27 2016-09-07 华南理工大学 Conjugated polymer based on naphthoindenofluorene unit as well as preparation method and application thereof
CN106243329A (en) * 2016-07-29 2016-12-21 华南理工大学 One is based on S, S dioxydibenze thiophthene derivative replaces conjugated polymer luminescent material and preparation method and application to receptor type

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101712674A (en) * 2009-11-13 2010-05-26 华南理工大学 Alkyl substituted-S,S-dioxo-dibenzothiophene monomer, preparation method and polymer thereof
CN105924629A (en) * 2016-06-27 2016-09-07 华南理工大学 Conjugated polymer based on naphthoindenofluorene unit as well as preparation method and application thereof
CN106243329A (en) * 2016-07-29 2016-12-21 华南理工大学 One is based on S, S dioxydibenze thiophthene derivative replaces conjugated polymer luminescent material and preparation method and application to receptor type

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108424344A (en) * 2018-04-11 2018-08-21 华南协同创新研究院 Monomer and polymer containing luxuriant and rich with fragrance five yuan and ring element and the preparation method and application thereof

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Application publication date: 20170908