CN106565960A - Block copolymer luminescent material containing dibenzothiophene-S,S-dioxide, preparation method and application thereof - Google Patents
Block copolymer luminescent material containing dibenzothiophene-S,S-dioxide, preparation method and application thereof Download PDFInfo
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- MGNZXYYWBUKAII-UHFFFAOYSA-N C1C=CC=CC1 Chemical compound C1C=CC=CC1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 1
- WYGCJROGCZJRBG-SFHVURJKSA-N C[C@@H](Cc1ccc2-c3ccccc3Cc2c1)[BrH]c(cc1)cc(C2)c1-c(cc1)c2cc1Br Chemical compound C[C@@H](Cc1ccc2-c3ccccc3Cc2c1)[BrH]c(cc1)cc(C2)c1-c(cc1)c2cc1Br WYGCJROGCZJRBG-SFHVURJKSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N c(cc1)ccc1Nc1ccccc1 Chemical compound c(cc1)ccc1Nc1ccccc1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a block copolymer luminescent material containing dibenzothiophene-S,S-dioxide, a preparation method and an application thereof. The block polymer containing dibenzothiophene-S,S-dioxide is an excited-state molecule, and subjected to dipole-dipole passes function with the base-state molecule, so that the excited-state molecule transmits the radiation transition to the base-state molecule directly, the base-state molecule is excited to emit light, so that the carrier transmission balance of the light-emitting polymer is realized, and the light-emitting efficiency of the device is improved. The polymer prepared by the preparation method disclosed by the invention can be used for preparing a light-emitting layer of an organic light-emitting diode. The synthetic method of the prepared polymer is simple, the film forming property and the film morphology stability is good.
Description
Technical field
The invention belongs to organic photoelectric technical field, and in particular to a kind of block copolymer luminescent material and preparation method thereof
With application.
Background technology
Organic Light Emitting Diode (OLED) is because with visual angle width, the response time is short, technical process is simple, be easy to large area system
Standby the advantages of, obtains people and widely pays close attention to.The research of OLED started from the 1950's, until Kodak in 1987
Doctor Deng Qingyun to have developed OLED luminosity under 10V direct voltage drives using sandwich device architecture reachable
To 1000cd m-2, make OLED obtain the development across the epoch.
OLED structure be the organic film deposition of single or multiple lift between two electrodes, when applying between two electrodes
When added electric field, electronics is injected separately into by the anode of the negative electrode, hole and high work function of low work function and is transferred to organic
In luminescent material, electronics and hole migrate under the driving of electric field, finally meet at luminescent layer and form exciton, and exciton is in organic layer
Spread and decay and light.
Luminous efficiency is mainly improved in the research of OLED, driving voltage is reduced, optimizes light excitation, strengthened device and stablize
Property and this several respect of life-span, the wherein electronics of material itself and the balance of hole transport injection affect very big, be on device efficiency
Obtain efficient OLED, it is necessary to the electronics of reasonable adjusting material and the balance of hole transport injection.
The content of the invention
Present invention aims to the deficiencies in the prior art, there is provided one kind contains S, S- dioxies-dibenzo thiophene it is embedding
Section co-polymer luminescent material, the material has good cavity transmission ability, can be with the transmission of equilbrium carrier so that Geng Duo electricity
Son is effectively combined with hole and produces exciton, so as to improve luminous efficiency.
Present invention also offers described contain S, the preparation method of the block copolymer luminescent material of S- dioxies-dibenzo thiophene
And its application in the light emitting diode.
The purpose of the present invention is achieved through the following technical solutions：
One kind contains S, the block copolymer luminescent material of S- dioxies-dibenzo thiophene, and the chemical constitution of the luminescent material is such as
Under：
Or
In formula, x, y is molar fraction, 0 ＜ x≤0.4,0 ＜ y≤0.4；N and m are the degree of polymerization, and 50<n<300,50<m
<200；
R1Be carbon number be 1-20 straight chain or branched alkyl or alkoxyl；
R2Structure be-H ,-F ,-OR or-R, R be carbon number be 1-20 straight chain or branched alkyl；
Ar is functional groups, and the structure of the Ar is any one in following structure：
Wherein, R is the straight chain or branched alkyl or alkoxyl that carbon number is 1-20.
Described one kind contains S, the preparation method of the block copolymer luminescent material of S- dioxies-dibenzo thiophene, including
Suzuki is synthesized single terminated polymer and coupling reaction block polymer synthesis.
Further, the Suzuki is synthesized single terminated polymer and includes containing S, the list of S- dioxies-dibenzo thiophene
The synthesis of end-blocking acceptor polymer and the synthesis of single end-blocking donor polymer：
(1) S, the synthesis of single end-blocking acceptor polymer of S- dioxies-dibenzo thiophene are contained：
By alkyl fluorenes, the bromo- S of 3,7- bis-, S- dibenzothiophene dioxides, tetrakis triphenylphosphine palladium and tricaprylmethyl chlorination
Ammonium is added in the there-necked flask equipped with toluene and tetrahydrofuran (THF), ventilation；The potassium carbonate of 1～3M is added under argon gas protection
The aqueous solution, is heated to reflux, and adds bromobenzene to react 6～12h again after 6～24h of reaction, obtains containing S, S- dioxies-dibenzo thiophene
Single end-blocking acceptor polymer；
What is obtained contains S, and the structural formula of single end-blocking acceptor polymer of S- dioxies-dibenzo thiophene is as follows：
Or
Y is molar fraction, 0 ＜ y≤0.4；
M is the degree of polymerization, 50<m<200；
R1Be carbon number be 1-20 straight chain or branched alkyl or alkoxyl；
R2Structure be-H ,-F ,-OR or-R, R be carbon number be 1-20 straight chain or branched alkyl.
(2) synthesis of single end-blocking donor polymer：
Alkyl fluorenes, Ar structural materials, tetrakis triphenylphosphine palladium and tri-n-octyl methyl ammonium chloride are added to equipped with toluene and
In the there-necked flask of tetrahydrofuran, ventilation；The wet chemical of 1～3M is added under argon gas protection, is heated to reflux, reaction 6～
Add borate ester to react 6～12h again after 24h, obtain single end-blocking donor polymer.
The structural formula of the single end-blocking donor polymer for obtaining is as follows：
In formula, x is molar fraction, 0 ＜ x≤0.4；Ar is functional groups；N is the degree of polymerization, 50<n<300；R1It is that carbon is former
Subnumber is the straight chain or branched alkyl or alkoxyl of 1-20.
Further, in step (1), the alkyl fluorenes and the bromo- S of 3,7- bis-, S- dibenzothiophene dioxides mole
Than for 9：1～6.
Further, in step (1), the tetrakis triphenylphosphine palladium and the bromo- S of 3,7- bis-, S- titanium dioxide dibenzo thiophene
The mol ratio of fen is 1：5～26.
Further, in step (1), the tri-n-octyl methyl ammonium chloride and the bromo- S of 3,7- bis-, S- titanium dioxide dibenzo
The mol ratio of thiophene is 1:10～40.
Further, in step (1), the temperature being heated to reflux is 80～110 DEG C.
Further, in step (1), the bromobenzene and the bromo- S of 3,7- bis-, the mol ratio of S- dibenzothiophene dioxides
For 5～10:1.
Further, in step (2), alkyl fluorenes is 9 with the mol ratio of Ar structural materials：1～6.
Further, in step (2), the tetrakis triphenylphosphine palladium is 1 with the mol ratio of Ar structural materials：5～26.
Further, in step (2), the tri-n-octyl methyl ammonium chloride is 1 with the mol ratio of Ar structural materials:10～
40。
Further, in step (2), the temperature being heated to reflux is 80～110 DEG C.
Further, in step (2), the borate ester is 1 with the mol ratio of Ar structural materials:0.58.
Further, in step (1), (2), toluene is 1 with the volume ratio of tetrahydrofuran:1, the wet chemical
It is 1 with the volume ratio of toluene:1.
Further, the synthesis of the coupling reaction block polymer synthesis comprises the steps：
(1) weigh containing S, single end-blocking acceptor polymer of S- dioxies-dibenzo thiophene and single end-blocking donor polymerization of excess
Thing substitutes gas among two mouthfuls of flasks equipped with toluene；
(2) tetrakis triphenylphosphine palladium and wet chemical are added under argon gas protection, heating stirring, backflow 24～48 is little
When；
(3) the product elder generation precipitating that reaction is obtained is stirred 6～12 hours, again with methanol after filtration in methyl alcohol with complex salt
Precipitating is filtered, and is extracted with acetone, hexamethylene and normal heptane respectively, is dried, obtain it is described contain S, S- dioxies-dibenzo thiophene it is embedding
Section co-polymer luminescent material.
Further, in step (2), the tetrakis triphenylphosphine palladium is sealed with S, the single of S- dioxies-dibenzo thiophene is contained
The mass equivalent ratio of end acceptor polymer is 2%.
Further, in step (2), the wet chemical is 1 with the volume ratio of toluene:1.
Further, in step (2), the temperature of the heating is 80～130 DEG C.
Described one kind contains S, and the block copolymer luminescent material of S- dioxies-dibenzo thiophene is applied to light emitting diode
Luminescent layer, will contain S, and the block polymer material of S- dioxies-dibenzo thiophene is dissolved with organic solvent, then is beaten by spin coating, ink-jet
Print or printing process film forming.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) present invention is by the dipole-dipole effect between donor molecule and acceptor molecule so that excited state molecule is produced
The energy of radiant type transition is directly passed to acceptor molecule, excites acceptor molecule so that more polyelectron is effectively combined with hole
Exciton is produced, so as to improve the luminous efficiency of device.
(2) polymer prepared by the present invention, synthetic method is simple, film forming and film morphology good stability.
Description of the drawings
Fig. 1 is the Current density-voltage-brightness curve of PFSO10-PFTPA10, PFTPA10-BOr and PFSO10-Br.
Fig. 2 is the current density-luminous efficiency curve of PFSO10-PFTPA10, PFTPA10-BOr and PFSO10-Br.
Fig. 3 is the gel permeation chromatography curve of PFSO10-PFTPA10, PFTPA10-BOr and PFSO10-Br.
Fig. 4 for PVK-PFSO10-PFTPA10 film layers, PVK-PFTPA10-BOr and PVK-PFSO10-Br current density-
Voltage-brightness curve.
Fig. 5 for PVK-PFSO10-PFTPA10 film layers, PVK-PFTPA10-BOr and PVK-PFSO10-Br current density-
Luminous efficiency curve.
Specific embodiment
By the following examples the present invention is further described, but the invention is not restricted to listed example.
Embodiment 1
The syntheti c route of PFSO-PFTPA：
The preparation of (1) 2,7- dibromo fluorenes, synthetic route is as follows with step：
60g fluorenes is dissolved in 400ml chloroforms, iron powder 325mg is added, ice bath is cooled to -5 DEG C, be slowly added dropwise 45ml bromines and
50ml chloroform mixed liquors, after dripping, react 3 hours at 30 DEG C；Aqueous solution of sodium bisulfite is added to be washed with niter cake
Wash up to red disappearance, then reactant liquor is poured in distilled water and is extracted with ether, organic layer saturated common salt water washing is simultaneously
Use anhydrous MgSO4It is dried；Solvent is removed, redistillation to be removed and obtain white needles with acetone recrystallization after solvent.Yield：
88%.
The preparation of bromo- 9, the 9- dioctyl fluorenes of (2) 2,7- bis-, synthetic route is as follows with step：
2,7- dibromo fluorenes 15.0g, triethyl benzyl ammonia chloride 0.09g, 200ml dimethyl sulfoxide (DMSO) are put in there-necked flask and are formed
Suspension, instills 50wt% sodium hydrate aqueous solution 15ml, after reaction 1h, then 18.6g bromine octyl group alkane is added dropwise；After dripping, mix
Compound is stirred at room temperature 3 hours, then adds water, and ether is extracted in three times；Merge organic phase, washed with saturated common salt, distillation
Neutrality is washed to, anhydrous magnesium sulfate is dried 6h；After boiling off solvent, column chromatography is carried out with petroleum ether (II)/silica gel, then again third
Recrystallization is carried out in ketone and obtains final product the glutinous thick liquid of white.Yield：81%.
The preparation of double (4,4,5,5- dimethyl -1,3,2- dioxaborinates-diyl) -9, the 9- dioctyl fluorenes of (3) 2,7-, closes
It is as follows with step into route：
Bromo- 9, the 9- dioctyl fluorenes of 2, the 7- bis- of 10.96g are dissolved in 180ml THF, are added dropwise at -78 DEG C
The n-BuLi 28ml of 1.6mol/L, in N22h is reacted under atmosphere, 2- isopropyl -4,4,5,5- tetramethyls are then rapidly joined again
Base -1,3,2- dioxy borine 25ml react 2 hours at -78 DEG C, are slowly increased to room temperature reaction 24 hours；Reactant mixture is fallen
In entering water, and extracted with ether；Merge organic phase, then with saturated common salt water washing to neutrality, anhydrous MgSO4It is dried；Remove molten
Silica gel column chromatography after agent, with recrystallizing methanol white needles crystallization 10.1g is obtained.Yield：79%.
(4) preparation of S, S- dibenzothiophene dioxide, synthetic route is as follows with step：
The dibenzothiophenes of 1.85g is dissolved in 110ml petroleum ethers, after stirring and dissolving, the H of 6ml is added2O2With the first of 6ml
After 40 DEG C of reaction 1h of acid, the H of 3ml is added2O2With the formic acid of 3ml, 70 DEG C of reaction 8h are warming up to；Suction filtration obtains white solid, uses
Neutrality is washed to, white solid 20.5g is recrystallized to give with chloroform after drying.Yield：96%.
The bromo- S of (5) 3,7- bis-, the preparation of S- dibenzothiophene dioxides, synthetic route is as follows with step：
The S of 1.08g is weighed, S- dibenzothiophene dioxides are put in flask, adds the concentrated sulfuric acid of 35ml, stir the S for making,
S- dibenzothiophene dioxides dissolve；N- bromo succinamides (NBS) point of 4 batches of additions of 0.88g are weighed, rear room temperature reaction is added
1h；0.88g NBS and 120r/min stirring 6h, the careful dilute with water concentrated sulfuric acid, suction filtration is added product to be washed till into neutrality, is used again
Vacuum drying after chlorobenzene recrystallization obtains white needles 1.53g.Yield：87%.
(6) syntheti c route of PFSO40-Br：
By double (4,4,5,5- dimethyl -1,3,2- dioxaborinates-the diyl) -9,9- two of 0.321g (0.5mmol) 2,7-
Octyl group fluorenes, the bromo- 9,9- dioctyl fluorenes of 0.055g (0.1mmol) 2,7- bis-, the bromo- S of 0.149g (0.4mmol) 3,7- bis-, S- dioxies
The tri-n-octyl methyl ammonium chloride for changing dibenzothiophenes, 23mg tetrakis triphenylphosphine palladiums and 5mg is added in the there-necked flask of 50ml, is changed
Gas, adds the wet chemical of 4ml toluene, 4mlTHF and 4ml 2M under argon gas protection, and 110 DEG C are heated to reflux；Reaction 12
0.5ml bromobenzenes end-blocking is added after hour, reaction is stopped after 12 hours, be cooled to room temperature, reactant liquor is poured in 100ml methyl alcohol
Precipitation, filters, and is stirred with complex salt and extracted after 6 hours, is then filtered with methanol extraction, again with toluene/alumina column chromatography,
Pour washing lotion into methanol extraction, filter, products therefrom air-dried overnight, be then vacuum dried 24 hours.Yield：70%.
(7) syntheti c route of PFTPA40-BOr：
By double (4,4,5,5- dimethyl -1,3,2- dioxaborinates-the diyl) -9,9- two of 0.321g (0.5mmol) 2,7-
Octyl group fluorenes, the bromo- 9,9- dioctyl fluorenes of 0.055g (0.1mmol) 2,7- bis-, the bromo- 9,9- bis- or three of 0.324g (0.4mmol) 2,7- bis-
The tri-n-octyl methyl ammonium chloride of anilino- fluorenes, 23mg tetrakis triphenylphosphine palladiums and 5mg is added in the there-necked flask of 50ml, ventilation,
The wet chemical of 4ml toluene, 4mlTHF and 4ml 2M is added under argon gas protection, 110 DEG C are heated to reflux；Reaction 12 hours
60mg borate esters end-blocking being added afterwards, reaction being stopped after 12 hours, be cooled to room temperature, reactant liquor is poured in 100ml methyl alcohol
Precipitation, filters, and is stirred with complex salt and extracted after 6 hours, is then filtered with methanol extraction, again with toluene/alumina column chromatography,
Pour washing lotion into methanol extraction, filter, products therefrom air-dried overnight, be then vacuum dried 24 hours.Yield：70%.
(8) S, the synthetic route of the block copolymer PFSO40-PFTPA40 luminescent materials of S- dioxies-dibenzo thiophene are contained：
The PFSO40-Br of PFTPA40-BOr and excess is weighed in being equipped among two mouthfuls of flasks of 6ml toluene, gas is substituted,
Argon gas protection is lower to add the tetrakis triphenylphosphine palladium of 2% mass equivalent ratio and the wet chemical of 4ml 2M, 110 DEG C of heating to stir
Mix, flow back 24 hours；The product elder generation precipitating that reaction is obtained is stirred 8 hours after filtration in methyl alcohol with complex salt, and again with methanol is sunk
Analysis is filtered, and is extracted with acetone, hexamethylene and normal heptane respectively.Yield 80%.
(9) syntheti c route of PFSO15-Br：
By double (4,4,5,5- dimethyl -1,3,2- dioxaborinates-the diyl) -9,9- two of 0.321g (0.5mmol) 2,7-
Octyl group fluorenes, the bromo- 9,9- dioctyl fluorenes of 0.192g (0.35mmol) 2,7- bis-, 0.056g (0.15mmol) 3,7- bis- bromo- S, S- bis-
The tri-n-octyl methyl ammonium chloride of oxidation dibenzothiophenes, 23mg tetrakis triphenylphosphine palladiums and 5mg is added in the there-necked flask of 50ml,
Ventilation, adds the wet chemical of 4ml toluene, 4mlTHF and 4ml 2M under argon gas protection, and 110 DEG C are heated to reflux；Reaction
0.5ml bromobenzenes end-blocking is added after 12 hours, reaction is stopped after 12 hours, be cooled to room temperature, pour reactant liquor into 100ml methyl alcohol
Middle precipitation, filters, and is stirred with complex salt and extracted after 6 hours, is then filtered with methanol extraction, again with toluene/alumina column layer
Analysis, pours washing lotion into methanol extraction, filters, products therefrom air-dried overnight, is then vacuum dried 24 hours.Yield：
71%.
(10) syntheti c route of PFTPA20-BOr：
By double (4,4,5,5- dimethyl -1,3,2- dioxaborinates-the diyl) -9,9- two of 0.321g (0.5mmol) 2,7-
Octyl group fluorenes, the bromo- 9,9- dioctyl fluorenes of 0.165g (0.3mmol) 2,7- bis-, the bromo- 9,9- bis- or three of 0.162g (0.2mmol) 2,7- bis-
The tri-n-octyl methyl ammonium chloride of anilino- fluorenes, 23mg tetrakis triphenylphosphine palladiums and 5mg is added in the there-necked flask of 50ml, ventilation,
The wet chemical of 4ml toluene, 4mlTHF and 4ml 2M is added under argon gas protection, 110 DEG C are heated to reflux；Reaction 12 hours
60mg borate esters end-blocking being added afterwards, reaction being stopped after 12 hours, be cooled to room temperature, reactant liquor is poured in 100ml methyl alcohol
Precipitation, filters, and is stirred with complex salt and extracted after 6 hours, is then filtered with methanol extraction, again with toluene/alumina column chromatography,
Pour washing lotion into methanol extraction, filter, products therefrom air-dried overnight, be then vacuum dried 24 hours.Yield：70%.
(11) S, the synthesis road of the block copolymer PFSO15-PFTPA20 luminescent materials of S- dioxies-dibenzo thiophene are contained
Line：
The PFSO15-Br of PFTPA20-BOr and excess is weighed in being equipped among two mouthfuls of flasks of 6ml toluene, gas is substituted,
Argon gas protection is lower to add the tetrakis triphenylphosphine palladium of 2% mass equivalent ratio and the wet chemical of 4ml 2M, 130 DEG C of heating to stir
Mix, flow back 26 hours；The product elder generation precipitating that reaction is obtained is stirred 6 hours after filtration in methyl alcohol with complex salt, and again with methanol is sunk
Analysis is filtered, and is extracted with acetone, hexamethylene and normal heptane respectively.Yield 78%.
(12) syntheti c route of PFSO10-Br：
By double (4,4,5,5- dimethyl -1,3,2- dioxaborinates-the diyl) -9,9- two of 0.321g (0.5mmol) 2,7-
Octyl group fluorenes, the bromo- 9,9- dioctyl fluorenes of 0.219g (0.4mmol) 2,7- bis-, the bromo- S of 0.037g (0.10mmol) 3,7- bis-, S- dioxies
The tri-n-octyl methyl ammonium chloride for changing dibenzothiophenes, 23mg tetrakis triphenylphosphine palladiums and 5mg is added in the there-necked flask of 50ml, is changed
Gas, adds the wet chemical of 4ml toluene, 4mlTHF and 4ml 2M under argon gas protection, and 110 DEG C are heated to reflux；Reaction 12
0.5ml bromobenzenes end-blocking is added after hour, reaction is stopped after 12 hours, be cooled to room temperature, reactant liquor is poured in 100ml methyl alcohol
Precipitation, filters, and is stirred with complex salt and extracted after 6 hours, is then filtered with methanol extraction, again with toluene/alumina column chromatography,
Pour washing lotion into methanol extraction, filter, products therefrom air-dried overnight, be then vacuum dried 24 hours.Yield：71%.
(13) syntheti c route of PFTPA10-BOr：
By double (4,4,5,5- dimethyl -1,3,2- dioxaborinates-the diyl) -9,9- two of 0.321g (0.5mmol) 2,7-
Octyl group fluorenes, the bromo- 9,9- dioctyl fluorenes of 0.219 (0.4mmol) 2,7- bis-, the triphens of bis- bromo- 9,9- of 0.081g (0.2mmol) 2,7- bis-
The tri-n-octyl methyl ammonium chloride of amido fluorenes, 23mg tetrakis triphenylphosphine palladiums and 5mg is added in the there-necked flask of 50ml, ventilation,
Argon gas protection is lower to add 4ml toluene, the wet chemical of 4mlTHF and 4ml 2M, and 110 DEG C are heated to reflux；After reaction 12 hours
60mg borate esters end-blocking is added, reaction is stopped after 12 hours, be cooled to room temperature, reactant liquor is poured in 100ml methyl alcohol and is sunk
Form sediment, filter, stirred with complex salt and extracted after 6 hours, then filtered with methanol extraction, again with toluene/alumina column chromatography, will
Washing lotion pours methanol extraction into, filters, products therefrom air-dried overnight, is then vacuum dried 24 hours.Yield：72%.
(14) S, the synthesis road of the block copolymer PFSO10-PFTPA10 luminescent materials of S- dioxies-dibenzo thiophene are contained
Line：
The PFSO10-Br of PFTPA10-BOr and excess is weighed in being equipped among two mouthfuls of flasks of 6ml toluene, gas is substituted,
Argon gas protection is lower to add the tetrakis triphenylphosphine palladium of 2% mass equivalent ratio and the wet chemical of 4ml 2M, 80 DEG C of heating to stir
Mix, flow back 48 hours；The product elder generation precipitating that reaction is obtained is stirred 12 hours, again with methanol after filtration in methyl alcohol with complex salt
Precipitating is filtered, and is extracted with acetone, hexamethylene and normal heptane respectively.Yield 76%.
Current density-voltage-the brightness curve of obtained PFSO10-PFTPA10, PFTPA10-BOr and PFSO10-Br is such as
Shown in Fig. 1, in Fig. 1, COP2 represents block conjugated polymer PFSO10-PFTPA10；Known by Fig. 1, block polymer PFSO10-
The brightness of PFTPA10 and current density are higher with respect to PFTPA10-BOr.
The current density of obtained PFSO10-PFTPA10, PFTPA10-BOr and PFSO10-Br-luminous efficiency curve is such as
Shown in Fig. 2, known by Fig. 2, with respect to PFTPA10-BOr, the luminous efficiency of PFSO10-PFTPA10 improves a lot.
Fig. 3 is the gel permeation chromatography curve of obtained PFSO10-PFTPA10, PFTPA10-BOr and PFSO10-Br, by
Fig. 3 knows, the molecular weight of PFSO10-PFTPA10 is substantially big than PFTPA10-BOr and PFSO10-Br, illustrate PFTPA-BOr with
PFSO-Br is coupled, forms block polymer.
Embodiment 2
Based on containing S, the preparation of the electroluminescent device of S- dioxies-dibenzo thiophene block copolymer.
On tin indium oxide (ITO) glass of well in advance, its square resistance is 15 ohm, first successively with acetone, washing
Agent, deionized water and isopropanol are cleaned by ultrasonic, plasma treatment 10min, and spin coating is mixed on ITO the poly- of polystyrolsulfon acid
Ethoxythiophene (PEDOT:PSS) film 40nm, PEDOT:PSS films dry 8h in vacuum drying oven at 80 DEG C, then spin coating 15nm
PVK, subsequently will be based on S be contained, the xylene solution of S- dioxies-dibenzo thiophene block copolymer luminescent material is spin-coated on PVK
Film surface, thickness is finally deposited with successively a thin layer CsF (1.5nm) and metal Al layer for 65nm on luminescent layer.
Fig. 4 is obtained PVK-PFSO10-PFTPA10, PVK-PFTPA10-BOr and PVK- during embodiment
Current density-voltage-the brightness curve of PFSO10-Br film layers, as shown in Figure 4, the brightness of PVK-PFSO10-PFTPA10 film layers
PVK-PFTPA10-BOr relative with current density is higher.
Fig. 5 is the electricity of obtained PVK-PFSO10-PFTPA10, PVK-PFTPA10-BOr and PVK-PFSO10-Br film layer
Current density-luminous efficiency curve, as shown in Figure 5 with respect to PVK-PFTPA10-BOr, the lumen of PVK-PFSO10-PFTPA10 film layers
Efficiency improves a lot.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any Spirit Essences and the changes, modification, replacement made under principle without departing from the present invention, combine, simplification all should
For equivalent substitute mode, it is included within protection scope of the present invention.
Claims (10)
1. one kind contains S, the block copolymer luminescent material of S- dioxies-dibenzo thiophene, it is characterised in that the change of the luminescent material
Learn structure as follows：
In formula, x, y is molar fraction, 0 ＜ x≤0.4,0 ＜ y≤0.4；N and m are the degree of polymerization, and 50<n<300,50<m<
200；
R1Be carbon number be 1-20 straight chain or branched alkyl or alkoxyl；
R2Structure be-H ,-F ,-OR or-R, R be carbon number be 1-20 straight chain or branched alkyl；
Ar is functional groups, and the structure of the Ar is any one in following structure：
Wherein, R is the straight chain or branched alkyl or alkoxyl that carbon number is 1-20.
2. the one kind described in claim 1 contains S, the preparation method of the block copolymer luminescent material of S- dioxies-dibenzo thiophene,
Characterized in that, single terminated polymer and coupling reaction block polymer synthesis is synthesized including Suzuki.
3. one kind according to claim 2 contains S, the preparation of the block copolymer luminescent material of S- dioxies-dibenzo thiophene
Method, it is characterised in that the Suzuki is synthesized single terminated polymer to be included containing S, single envelope of S- dioxies-dibenzo thiophene
The synthesis of end acceptor polymer and the synthesis of single end-blocking donor polymer：
(1) S, the synthesis of single end-blocking acceptor polymer of S- dioxies-dibenzo thiophene are contained：
By alkyl fluorenes, the bromo- S of 3,7- bis-, S- dibenzothiophene dioxides, tetrakis triphenylphosphine palladium and tri-n-octyl methyl ammonium chloride add
Enter in the there-necked flask equipped with toluene and tetrahydrofuran, ventilation；The wet chemical of 1～3M is added under argon gas protection, plus
Heat backflow, adds bromobenzene to react 6～12h again after 6～24h of reaction, obtains containing S, single end-blocking acceptor of S- dioxies-dibenzo thiophene
Polymer；
(2) synthesis of single end-blocking donor polymer：
Alkyl fluorenes, Ar structural materials, tetrakis triphenylphosphine palladium and tri-n-octyl methyl ammonium chloride are added to equipped with toluene and tetrahydrochysene
In the there-necked flask of furans, ventilation；The wet chemical of 1～3M is added under argon gas protection, is heated to reflux, after 6～24h of reaction
Add borate ester to react 6～12h again, obtain single end-blocking donor polymer.
4. one kind according to claim 3 contains S, the preparation of the block copolymer luminescent material of S- dioxies-dibenzo thiophene
Method, it is characterised in that in step (1), the alkyl fluorenes and the bromo- S of 3,7- bis-, the mol ratio of S- dibenzothiophene dioxides is
9:1～6；The tetrakis triphenylphosphine palladium and the bromo- S of 3,7- bis-, the mol ratio of S- dibenzothiophene dioxides is 1：5～26；Institute
Tri-n-octyl methyl ammonium chloride and the bromo- S of 3,7- bis- are stated, the mol ratio of S- dibenzothiophene dioxides is 1:10～40；Toluene and four
The volume ratio of hydrogen furans is 1:1, the wet chemical is 1 with the volume ratio of toluene:1.
5. one kind according to claim 3 contains S, the preparation of the block copolymer luminescent material of S- dioxies-dibenzo thiophene
Method, it is characterised in that in step (1), the temperature being heated to reflux is 80～110 DEG C；The bromobenzene and the bromo- S of 3,7- bis-,
The mol ratio of S- dibenzothiophene dioxides is 5～10:1.
6. one kind according to claim 3 contains S, the preparation of the block copolymer luminescent material of S- dioxies-dibenzo thiophene
Method, it is characterised in that in step (2), alkyl fluorenes is 9 with the mol ratio of Ar structural materials:1～6；Four (triphenylphosphines)
Palladium is 1 with the mol ratio of Ar structural materials：5～26；The tri-n-octyl methyl ammonium chloride is 1 with the mol ratio of Ar structural materials:
10～40.
7. one kind according to claim 3 contains S, the preparation of the block copolymer luminescent material of S- dioxies-dibenzo thiophene
Method, it is characterised in that in step (2), the temperature being heated to reflux is 80～110 DEG C；The borate ester and Ar structures
The mol ratio of material is 1:0.58；Toluene is 1 with the volume ratio of tetrahydrofuran:1, wet chemical is with the volume ratio of toluene
1:1。
8. one kind according to claim 2 contains S, the preparation of the block copolymer luminescent material of S- dioxies-dibenzo thiophene
Method, it is characterised in that the synthesis of coupling reaction block polymer synthesis comprises the steps：
(1) weigh containing S, single end-blocking acceptor polymer of S- dioxies-dibenzo thiophene and single end-blocking donor polymer of excess in
Among equipped with toluene two mouthfuls of flasks, gas is substituted；
(2) wet chemical of tetrakis triphenylphosphine palladium and 1～3M is added under argon gas protection, heating stirring, backflow 24～
48 hours；
(3) the product elder generation precipitating that reaction is obtained is stirred 6～12 hours, again with methanol precipitating after filtration in methyl alcohol with complex salt
Filter, extracted with acetone, hexamethylene and normal heptane respectively, be dried, obtain it is described contain S, the block of S- dioxies-dibenzo thiophene is total to
Polymers luminescent material.
9. one kind according to claim 8 contains S, the preparation of the block copolymer luminescent material of S- dioxies-dibenzo thiophene
Method, it is characterised in that the tetrakis triphenylphosphine palladium blocks acceptor polymer with S, the list of S- dioxies-dibenzo thiophene is contained
Mass equivalent ratio is 2%；The wet chemical is 1 with the volume ratio of toluene:1；The temperature of the heating is 80～130
℃。
10. the one kind described in claim 1 contains S, and the block polymer luminescent material of S- dioxies-dibenzo thiophene is applied to luminous two
The luminescent layer of pole pipe, it is characterised in that S will be contained, the block polymer material of S- dioxies-dibenzo thiophene is dissolved with organic solvent,
Pass through spin coating, inkjet printing or printing process film forming again.
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| CN110034231A (en) * | 2019-03-25 | 2019-07-19 | 华东理工大学 | It is provided simultaneously with macromolecule memristor and its preparation method and the application of storage and calculation function |
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| CN107987255A (en) * | 2017-11-22 | 2018-05-04 | 华南协同创新研究院 | Containing tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring unit polymer and its preparation method and application |
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| CN110034231A (en) * | 2019-03-25 | 2019-07-19 | 华东理工大学 | It is provided simultaneously with macromolecule memristor and its preparation method and the application of storage and calculation function |
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