CN108912310A - Polyfluorene derivative, luminescent layer of light emitting diode and preparation method thereof - Google Patents

Polyfluorene derivative, luminescent layer of light emitting diode and preparation method thereof Download PDF

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CN108912310A
CN108912310A CN201810372184.2A CN201810372184A CN108912310A CN 108912310 A CN108912310 A CN 108912310A CN 201810372184 A CN201810372184 A CN 201810372184A CN 108912310 A CN108912310 A CN 108912310A
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dibenzothiophene
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dioxo
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CN108912310B (en
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应磊
钟知鸣
彭沣
黄飞
曹镛
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Dongguan volt ampere Photoelectric Technology Co., Ltd
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South China Institute of Collaborative Innovation
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Abstract

The present invention discloses polyfluorene derivative, luminescent layer of light emitting diode and preparation method thereof.S, the fluorenes of S- dioxo-dibenzothiophene unit are carried out Suzuki polymerization reaction by the present invention, obtain the side chain containing S, the polyfluorene derivative of S- dioxo-dibenzothiophene unit or S- oxygen-dibenzothiophene unit or dibenzothiophenes and its derivative.The present invention modifies electron-transport unit in the side chain of polyfluorene derivative, with hole transport account for leading main chain formed it is complementary, main chain not with inhale electrical S, S- dioxo-dibenzothiophene is directly conjugated, make polymer due to containing electron-transport unit and hole transporting unit simultaneously, and maintain the spectral purity and stability of polymer, is conducive to the raising of device efficiency, there is good dissolubility simultaneously, can be used for the preparation of polymer LED luminescent layer.

Description

Polyfluorene derivative, luminescent layer of light emitting diode and preparation method thereof
Technical field
The invention belongs to organic photoelectric technical fields, and in particular to polyfluorene derivative, light emitting diode luminescent layer and its Preparation method.
Background technique
Nineteen ninety, univ cambridge uk's all one's life laboratory have delivered first using conjugated polymer PPV preparation Polymer Thin Film Electroluminescent Devices, to formally pull open the prelude of polymer LED (PLED) research.With small point Sub- light emitting diode is compared, and polymer LED has the advantage that：(1) the methods of solution spin coating, roll-to-roll can be passed through Prepare large area film；(2) electronic structure of the conjugated polymers, luminescent color be easy to the change by chemical structure and modify into Row is adjusted；(3) conjugated polymer can be to avoid crystallization by modification, and then improves device stability.
PLED device is made of cathode, anode and the organic layer of centre, and organic layer generally comprises electron transfer layer, luminescent layer And hole transmission layer, electrons and holes are injected from yin-yang the two poles of the earth respectively first, and are migrated in functional layer respectively, then electric Son and hole form exciton in place, and exciton is migrated in a certain range, last excitonic luminescence.
Main chain contains S, and the polymer luminescent material of S- dioxo-dibenzothiophene is star's material of PLED research field.Poplar Big and Martin R.Bryce project has been combined into a series of based on S, and the high efficiency electroluminescent of S- dioxo-dibenzothiophene is poly- Close object [Chem.Mater.2008,20,4499-4506；Advanced Functional Materials,2013,23,4366- 4376；Macromolecules,2010,43,4481-4488；J.Mater.Chem.C,2014,2,5587–5592].However it is big It is based partially on S, the polymer of S- dioxo-dibenzothiophene is all that greater efficiency is obtained under bi-layer devices structure, is usually existed PEDOT:Hole transmission layer is re-introduced into PSS and luminescent layer.Reason is S, and the introducing of S- dioxo-dibenzothiophene unit is being dropped While the lumo energy of low polymer and the electronic transmission performance for improving polymer, it can also be substantially reduced the HOMO energy of polymer Grade improves hole injection barrier, reduces hole transport performance so that carrier transport is uneven in polymer, device efficiency and Stability is limited.Strong simultaneously to inhale electrical S, the introducing of S- dioxo-dibenzothiophene unit can make to form ICT state in main chain, no Conducive to the raising of photoluminescence efficiency, therefore improving carrier transport balance to improve photoluminescence efficiency is to improve S, S- dioxy- The key point of dibenzothiophenes quasi polymer device efficiency.
Summary of the invention
Primary and foremost purpose of the invention is to provide a kind of polyfluorene derivative and preparation method thereof, and secondary objective of the invention is to mention For a kind of luminescent layer and preparation method thereof of light emitting diode.
For achieving the above object, technical scheme is as follows,
The side chain of a kind of polyfluorene derivative, the polyfluorene derivative contains S, S- dioxo-dibenzothiophene unit or S- oxygen-two Benzothiophene unit or dibenzothiophenes and its derivative, the chain chemistry formula of the polyfluorene derivative is such as shown in (I)：
In formula, x1、x2For the molar fraction of unit component, and 0<x1<0.5,0≤x2<0.5, x1+x2≤0.5；
N is repetitive unit, the integer between n=10~1000；
R1、R2For the alkyl of carbon atom number 6~30, the alcoxyl of the naphthenic base of carbon atom number 6~30 or carbon atom number 6~30 Base substituted-phenyl；
Ar1、Ar2For the R1Or S, S- dioxo-dibenzothiophene unit or substituted S, S- dioxo-dibenzothiophene list Member；Ar3For the aromatic hydrocarbyl of atomicity 6~60 or the aromatic heterocycle of carbon atom number 3~60.
Preferably, the Ar1And Ar2It is selected from the R1Or such as following chemical structural formula or such as following chemical structural formula Any one of derivative：
* it is connected on the 9th carbon of fluorenes；
R3~R5For hydrogen atom, D-atom, fluorine atom, cyano, the alkyl of carbon atom number 1~30, carbon atom number 1~30 Any one of naphthenic base or the alkoxy substituted phenyl of carbon atom number 1~30.
Preferably, the Ar3Any in derivative selected from following chemical structural formula or comprising following chemical structural formula Kind：
* connection site is represented；
Wherein, R6For 3~30 naphthenic base of alkyl or carbon atom number of carbon atom number 1~30.
A kind of preparation method of polyfluorene derivative, includes the following steps：
Dibenzothiophene derivatives and fluorenes or Fluorenone or fluorenol are reacted, taking for the unit containing dibenzothiophene derivatives is made For fluorenes, then the substituted fluorene oxidation of the unit containing dibenzothiophene derivatives is made and contains S, S- dioxo-dibenzothiophene spreads out Biological unit Ar1And Ar2Substituted fluorene, then described will contain S, S- dioxo-dibenzothiophene derivative unit Ar1And Ar2Substitution Fluorenes contains R1、R2Substituted fluorene and Ar3After unit passes through Suzuki polymerization reaction, sequentially adds phenyl boric acid and bromobenzene is sealed End reaction obtains the side chain containing S, S- dioxo-dibenzothiophene unit or S- oxygen-dibenzothiophene unit or dibenzothiophenes And its polyfluorene derivative of derivative.
Preferably, the temperature of the Suzuki polymerization reaction is 80~85 DEG C, and the time is 24~48 hours.
Preferably, the temperature of the end capping reaction is 80~85 DEG C, and the time is 4~8 hours.
A kind of luminescent layer of light emitting diode, the luminescent layer include that the side chain of any one of claims 1 to 3 contains S, The polyfluorene derivative of S- dioxo-dibenzothiophene unit or S- oxygen-dibenzothiophene unit or dibenzothiophenes and its derivative.
Side chain is contained S, S- dioxo-dibenzothiophene unit or S- by a kind of preparation method of the luminescent layer of light emitting diode The polyfluorene derivative of oxygen-dibenzothiophene unit or dibenzothiophenes and its derivative is dissolved with organic solvent, passes through spin coating, spray The method of ink printing or printing film forming, obtains the luminescent layer of the light emitting diode.
Preferably, the organic solvent is any in dimethylbenzene, chlorobenzene, dichloro-benzenes.
Compared with prior art, the present invention has the following advantages and beneficial effect：
(1) present invention modifies electron-transport unit in the side chain of polyfluorene derivative, accounts for leading main chain shape with hole transport At complementation, make polymer due to containing electron-transport unit and hole transporting unit simultaneously, while avoiding the reduction of main chain energy level With the generation for inhibiting ICT state, so that carrier transport be made more to balance, so that more holes and electronics effectively compound generate are swashed Son, and then improve the luminous efficiency of material.Electron-transport unit is connected on polymer lateral chain, to main polymer chain conjugate length Influence is smaller, not will form strong Intramolecular electron transfer, smaller on the influence of polymer light-emitting spectrum, can preferably keep poly- Close excitation purity, spectral purity and the stability of object.
(2) side chain of the invention contains S, and the polyfluorene derivative of S- dioxo-dibenzothiophene unit has double carriers transmission Characteristic and good dissolubility, can simplify device preparation technology, can be used as luminescent layer and obtain compared with high-fluorescence quantum yield Single polymer layer luminescent device is conducive to the electroluminescent properties and device efficiency that improve polymer LED.
Detailed description of the invention
Fig. 1 is the UV-visible absorption spectrum of 1 film of polymer P.
Fig. 2 is the photoluminescence spectra figure of 1 film of polymer P.
Fig. 3 is 1 cyclic voltammetric of polymer P (CV) spectrogram.
Fig. 4 is 1 electroluminescent light spectrogram of polymer P.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
The preparation of compound M1
(1) preparation of compound 1：Dibenzothiophenes (11g, 60mmol), iron powder are added in 100ml there-necked flask (0.17g, 3mmol) and bromine simple substance (3.1mL, 60mmol), under nitrogen atmosphere, stirring at normal temperature is reacted 16 hours, then uses sulfurous Sour hydrogen sodium water solution quenching reaction, is then extracted with dichloromethane three times, solvent is removed under reduced pressure, and obtains crude product, then crosses column Purifying, yield about 80%.
(2) preparation of compound 2：Under nitrogen protection into 100ml there-necked flask be added compound 1 (3.3g, It 12.5mmol) is dissolved in dry tetrahydrofuran, butyl lithium (3.3g, 12.5mmol) then is added, under nitrogen atmosphere, -78 Degree Celsius stirring 2 hours, then be added 1- bromine n-hexane (7.4g, 45mmol) the reaction was continued 1 hour, then be added water quenching go out instead It answers, is then extracted with dichloromethane three times, solvent is removed under reduced pressure, obtain crude product, then cross column purification, yield about 70%.
(3) preparation of compound M1：2,7- dibromo fluorenone (3.38g, 10mmol), chemical combination are added in 100ml there-necked flask Object 2 (5.53g, 30mmol), methane sulfonic acid (0.96g, 10mmol) and 50ml carbon tetrachloride under condition of nitrogen gas, are heated to 90 DEG C Reaction 12 hours；Product is extracted with dichloromethane in end of reaction, washs organic phase, anhydrous slufuric acid with saturated sodium-chloride water solution Magnesium is dry, boils off solvent, crude product petroleum ether：Methylene chloride=6：The mixed solvent of 1 (v/v) is made eluant, eluent column chromatography and is mentioned It is pure, obtain white solid 7.62g, yield 89%, (mass spectrum：856.8).
Chemical equation is as follows：
The preparation of compound M2
(1) preparation of compound 3：Prepare 2,4- dimethyl benzene magnesium bromide first, by bromo- 2, the 4- dimethylbenzene of 1- (0.56g, 3mmol), magnesium chips (2.92g, 120mmol) and 2ml anhydrous tetrahydro furan are added in 300ml two-mouth bottle, under nitrogen protection, are added Heat causes grignard reaction, then 100ml is slowly added dropwise dissolved with the anhydrous tetrahydro furan of bromo- 2, the 4- dimethylbenzene (17.95g, 97mmol) of 1- It mutters solution, is added dropwise, heating reaction 1 hour, obtains 2,4- dimethyl benzene magnesium bromide at 60 DEG C, spare；
2,7- dibromo fluorenone (10.14g, 30mmol) and 100ml anhydrous tetrahydro furan are added into 300ml two-mouth bottle, drops Extremely -78 DEG C of temperature are stirred 1 hour, and 2, the 4- dimethyl benzene bromide solution (60ml, 60mmol) prepared is added to reaction flask In, continuation is reacted 1 hour at -78 DEG C, and reaction is quenched with water, product is extracted with dichloromethane, uses saturated sodium-chloride water solution Organic phase is washed, anhydrous magnesium sulfate is dry, boils off solvent, crude product petroleum ether：Ethyl acetate=6：The mixing of 1 (v/v) is molten Eluant, eluent column Chromatographic purification is made in agent, obtains faint yellow solid 7.98g, yield 60%, (mass spectrum：444.2).
(2) preparation of compound M2：Compound 3 (4.44g, 10mmol), compound 2 are added in 150ml two-mouth bottle Boron trifluoride ether (2.13g, 15mmol) is added after stirring 1 hour in (4.03g, 15mmol) and 80ml anhydrous methylene chloride, after It is continuous to be stirred at room temperature 12 hours；Reaction is quenched with water, product is extracted with dichloromethane, has been washed with saturated sodium-chloride water solution Machine phase, anhydrous magnesium sulfate is dry, boils off solvent, crude product petroleum ether：Methylene chloride=6：The mixed solvent of 1 (v/v) is washed De- agent column Chromatographic purification, obtains white solid 4.59g, yield 66%, (mass spectrum：694.6).
Chemical equation is as follows：
The preparation of compound M3
Compound M2 (2.08g, 3mmol) is dissolved in 15ml acetic acid, 20ml hydrogen peroxide is added, is heated to reflux 6 Hour；It reacts and stops, after cooling, being extracted with deionized water ethyl acetate, organic phase is hanged and is dissolved in 10ml toluene, and precipitating after doing In methanol (300ml), filtering, after dry, crude product successively uses methanol, acetone, n-hexane extracting, is dissolved and is polymerize with toluene Object carries out column Chromatographic purification with neutral alumina using toluene as eluent；The toluene solution of concentrated polymer, precipitating exists again In methanol solution, filter, it is dry, obtain light yellow solid 1.64g, yield 75%, (mass spectrum：726.6).
Chemical equation is as follows：
Embodiment 1
The preparation of polymer P 1
The synthesis of polymer P 1：Under nitrogen protection, by 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryl) - 9,9- bis- (4- (2- ethyl hexane oxygroup) phenyl) fluorenes (248.0mg, 0.3mmol), bis- (4- (the 2- ethyl hexyls of the bromo- 9,9- of 2,7- bis- Alkoxy) phenyl) fluorenes (175.8mg, 0.24mmol) and compound M3 (48.6mg, 0.06mmol) be dissolved in 10mL toluene, Add tetraethyl aqueous hydroxylamine solution (1ml, wt%=25%), palladium acetate (1mg) and tricyclohexyl phosphine (2mg)；It is heated to 80 DEG C reaction 24 hours after, be added phenyl boric acid (20mg) block 6 hours, add 80 degrees Celsius of bromobenzene (0.2ml) block 6 hours； Reaction stops, and after cooling, by organic phase precipitating in methanol (200ml), filtering, after dry, crude product successively uses methanol, third Ketone, n-hexane extracting carry out column Chromatographic purification with neutral alumina using toluene as eluent with toluene dissolution polymer；Concentration The toluene solution of polymer, precipitating filters in methanol solution again, dry, obtains white fibrous polymer.GPC：Mn= 109KDa, PDI=2.32, the polymer have very high molecular weight, are conducive to improve luminescent properties.
The uv-visible absorption spectra spectrogram of 1 film of polymer P is as shown in Figure 1, as shown in Figure 1, the maximum of polymer P 1 Absorbing wavelength is 393nm；
The luminescence generated by light spectrogram of 1 film of polymer P is as shown in Fig. 2, as shown in Figure 2, the maximum emission wavelength of polymer is 438nm；
Cyclic voltammetric (CV) spectrogram of polymer P 1 as shown in figure 3, from the figure 3, it may be seen that the HOMO energy level of polymer P 1 be- 5.73eV, lumo energy are -2.14eV；
1 electroluminescent light spectrogram of polymer P is as shown in figure 4, as shown in Figure 4, maximum emission wavelength 433nm.
Embodiment 2
The preparation of polymer P 2
The synthesis condition of polymer P 2 is identical as polymer P 1, and difference is：
Polymer P 2：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryl) bis- (4- (2- ethyl hexyls of -9,9- Alkoxy) phenyl) fluorenes (248.0mg, 0.3mmol), bis- (4- (the 2- ethyl hexane oxygroup) phenyl) fluorenes of the bromo- 9,9- of 2,7- bis- (175.8mg, 0.24mmol) and compound M1 (41.7mg, 0.06mmol).GPC：Mn=97KDa, PDI=3.21.
Embodiment 3
The preparation of light emitting diode and its luminescent layer
Take well in advance square resistance be 10 Ω tin indium oxide (ITO) glass, successively with acetone, detergent, go from Sub- water and isopropanol ultrasonic cleaning, plasma treatment 10 minutes；The polyethoxy for having polystyrolsulfon acid is mixed in spin coating on ITO Thiophene (PEDOT:PSS=1:1, w/w) film, with a thickness of 40nm；PEDOT:PSS film is 8 hours dry at 80 DEG C in vacuum drying oven； The xylene solution (1.5wt.%) of the PFO bought and polymer P 1 is then spin-coated on PEDOT:The surface of PSS film, thickness For 80nm, as luminescent layer.
The metal Al layer of CsF and the 120nm thickness of one layer of 1.5nm thickness, device architecture are finally successively deposited on the light-emitting layer： ITO/PEDOT:PSS/ polymer/CsF/Al.
1 polymer electroluminescent device performance of table
Polymer P 1 and classical PFO possess identical backbone structure, and contrast table 1 is in single polymer layer luminescent device Number is it has been found that introduce S, S- dioxo-dibenzothiophene unit side chain compared to polymer P FO, P1 without electron-transport unit The device performance of polymer P 1 be obviously improved, show as opening bright voltage be decreased obviously, maximum lumen efficiency, maximum brightness Have to be obviously improved and illustrates that side chain is introduced into electron-transport unit and property of the polyfluorene derivative in monolayer luminescence device can be improved Can, while having substantially no effect on the electroluminescent spectrum of polymer.
The implementation of the present invention is not limited to this, and above content according to the invention is known using the ordinary skill of this field Knowledge and customary means, under the premise of not departing from above-mentioned basic fundamental thought of the invention, the present invention can also make other a variety of shapes Modification, replacement or the change of formula, all fall within rights protection scope of the present invention.

Claims (9)

1. a kind of polyfluorene derivative, which is characterized in that the side chain of the polyfluorene derivative contains S, S- dioxo-dibenzothiophene unit Or S- oxygen-dibenzothiophene unit or dibenzothiophenes and its derivative, the chain chemistry formula of the polyfluorene derivative is such as (I) shown in：
In formula, x1、x2For the molar fraction of unit component, and 0<x1<0.5,0≤x2<0.5, x1+x2≤0.5；
N is repetitive unit, the integer between n=10~1000；
R1、R2Alkoxy for the alkyl of carbon atom number 6~30, the naphthenic base of carbon atom number 6~30 or carbon atom number 6~30 takes For phenyl；
Ar1、Ar2For the R1Or S, S- dioxo-dibenzothiophene unit or substituted S, S- dioxo-dibenzothiophene unit；Ar3 For the aromatic hydrocarbyl of atomicity 6~60 or the aromatic heterocycle of carbon atom number 3~60.
2. polyfluorene derivative according to claim 1, which is characterized in that the Ar1And Ar2It is selected from the R1Or it is as follows Any one of the derivative of column chemical structural formula or such as following chemical structural formula：
* it is connected on the 9th carbon of fluorenes；
R3~R5For hydrogen atom, D-atom, fluorine atom, cyano, the alkyl of carbon atom number 1~30, carbon atom number 1~30 cycloalkanes Any one of base or the alkoxy substituted phenyl of carbon atom number 1~30.
3. polyfluorene derivative according to claim 1, which is characterized in that the Ar3Selected from following chemical structural formula or comprising Any one of the derivative of following chemical structural formula：
* connection site is represented；
Wherein, R6For 3~30 naphthenic base of alkyl or carbon atom number of carbon atom number 1~30.
4. a kind of preparation method of polyfluorene derivative, which is characterized in that include the following steps：
Dibenzothiophene derivatives and fluorenes or Fluorenone or fluorenol are reacted to the substituted fluorene that the unit containing dibenzothiophene derivatives is made, Then the substituted fluorene oxidation of the unit containing dibenzothiophene derivatives is made and contains S, S- dioxo-dibenzothiophene derivative list First Ar1And Ar2Substituted fluorene, then described will contain S, S- dioxo-dibenzothiophene derivative unit Ar1And Ar2Substituted fluorene, contain R1、R2Substituted fluorene and Ar3After unit passes through Suzuki polymerization reaction, sequentially adds phenyl boric acid and bromobenzene block instead Answer, obtain the side chain containing S, S- dioxo-dibenzothiophene unit or S- oxygen-dibenzothiophene unit or dibenzothiophenes and its The polyfluorene derivative of derivative.
5. the preparation method according to claim 4, which is characterized in that the temperature of the Suzuki polymerization reaction is 80~85 DEG C, the time is 24~48 hours.
6. the preparation method according to claim 4, which is characterized in that the temperature of the end capping reaction is 80~85 DEG C, when Between be 4~8 hours.
7. a kind of luminescent layer of light emitting diode, which is characterized in that the luminescent layer includes the institute of any one of claims 1 to 3 Side chain is stated containing S, S- dioxo-dibenzothiophene unit or S- oxygen-dibenzothiophene unit or dibenzothiophenes and its derivative Polyfluorene derivative.
8. a kind of preparation method of the luminescent layer of light emitting diode, which is characterized in that side chain is contained S, S- dioxo-dibenzothiophene The polyfluorene derivative of unit or S- oxygen-dibenzothiophene unit or dibenzothiophenes and its derivative is dissolved with organic solvent, is led to The method for crossing spin coating, inkjet printing or printing film forming, obtains the luminescent layer of the light emitting diode.
9. preparation method according to claim 8, which is characterized in that the organic solvent is selected from dimethylbenzene, chlorobenzene, dichloro It is any in benzene.
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