CN108864416B - Polymer luminescent material and its preparation method and application - Google Patents

Polymer luminescent material and its preparation method and application Download PDF

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CN108864416B
CN108864416B CN201810621473.1A CN201810621473A CN108864416B CN 108864416 B CN108864416 B CN 108864416B CN 201810621473 A CN201810621473 A CN 201810621473A CN 108864416 B CN108864416 B CN 108864416B
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alkyl
luminescent material
monomer
boron
polymer luminescent
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CN108864416A (en
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任忠杰
刘玉超
闫寿科
孙晓丽
李慧慧
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Beijing University of Chemical Technology
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Abstract

The invention discloses a kind of polymer luminescent materials and its preparation method and application.Alkyl-substituted phenthazine-the dibenzothiophene sulphone of suitable thermal excitation delayed fluorescence unit and main unit are copolymerized by the present invention, to synthesize the regulatable polymer luminescent material of photophysical property.The material can obtain high fluorescence quantum efficiency and device efficiency, the emitting layer material being suitable as in solution processing type organic electroluminescence device.

Description

Polymer luminescent material and its preparation method and application
Technical field
The present invention relates to a kind of polymer luminescent material and its preparation method and application, especially a kind of thermal excitation delay is glimmering The preparation method and purposes of the controllable polymer luminescent material of light.
Background technique
Organic Light Emitting Diode (OLED) is taught Deng Qingyun (Ching W.Tang) by Chinese descendant in America and was being tested in 1979 It is found in room.Have low self-luminous, wide viewing angle, driving voltage, high contrast, reaction speed fast etc. excellent in view of OLED display technology Put and increasingly obtain the extensive concern of people.However, traditional OLED device is limited to the influence that electron spin is prohibited, highest Internal quantum efficiency (IQE) only has 25%.
Then, people develop the organic phosphorescent material for breaking spin forbidden limitation using heavy metal atom effect, thus So that IQE is close to 100%.Due to leading to the higher cost of the material dependent on precious metal elements such as iridium, platinum.In addition, organic phosphorus Luminescent material (especially blue-light device) there are stability it is poor, the service life is short the problems such as.Therefore, the indigo plant based on organic metal phosphor material The exploitation of light and white light parts is always the Research Challenges in the field.
2009, someone was by thermal activities delayed fluorescence (TADF) material based on the anti-intersystem crossing mechanism of triplet state-singlet Material is applied in OLED device, and obtains the green light TADF material of the TADF material and IQE of no metal close to 100% in succession.Always For body, the luminous organic material based on TADF not only has luminescent color is adjustable, raw material sources are extensive, synthesis technology is simple etc. Advantage also has the luminous efficiency for the phosphor material that can match in excellence or beauty, thus referred to as third generation OLED luminescent material.
For the small molecule vacuum evaporation OLED device being widely used at present, solution processing type device has production The advantages that techniques such as inkjet printing prepare large-size device can be used in simple process, advantage of lower cost.With actual production Demand in life to solution processing type OLED device is continuously increased, and how simply and efficiently to be synthesized with the regulatable heat of performance Excitation delayed fluorescence polymer has become the hot spot studied both at home and abroad.In general, will have thermal excitation delayed fluorescence characteristic Small molecule be introduced into polymer chain, and keep the characteristic of its thermal excitation delayed fluorescence, can be obtained the poly- of solution processable Close object thermal excitation delayed fluorescence material.
In general, the selection for the polymer thermal excitation delayed fluorescence material being currently known is still less, it is still desirable to close The polymer thermal excitation delayed fluorescence material of the solution processable of Cheng Xin.
Summary of the invention
In view of this, maximum current efficiency is mentioned it is an object of the present invention to provide polymer luminescent material It is high.
It is another object of the present invention to provide the preparation method of above-mentioned polymer, adjustable thermal excitation delay is glimmering The Photophysics of luminescent material.
Application and organic electroluminescence hair it is yet a further object of the present invention to provide a kind of above-mentioned polymer luminescent material Optical device.
On the one hand, the present invention provides a kind of polymer luminescent material, shown in structure such as formula (1):
Wherein, Host is the main unit with regulation Photophysical Behaviors, and R ' is selected from C5~C15 alkyl；And m be 0.05~ 0.99, n is 10~5000.
Polymer luminescent material according to the present invention, it is preferable that main unit Host is selected from one of flowering structure:
Wherein, R is selected from C5~C15 alkyl.
Polymer luminescent material according to the present invention, it is preferable that R is the straight chained alkyl of C7~C9, and R ' is the branch of C7~C9 Alkyl group.
Polymer luminescent material according to the present invention, it is preferable that m is that 0.1~0.5, n is 10~100.
Polymer luminescent material according to the present invention, it is preferable that shown in its structure such as formula (2):
Wherein, Host is the main unit with regulation Photophysical Behaviors, and it is 10~5000 that m, which is 0.05~0.99, n,.
Polymer luminescent material according to the present invention, it is preferable that the weight average molecular weight Mw of the polymer luminescent material is 5000~30000 dalton, polydispersity coefficient PDI are 1.5~2.5.
On the other hand, the present invention provides a kind of preparation method of above-mentioned polymer luminescent material, includes the following steps:
(1) 2- alkyl -8- phenthazine dibenzothiophene sulphone is obtained into both ends by the bromo-reaction of bromo-succinimide Brominated monomer A；Wherein, the alkyl is C5~C15 alkyl；
(2) the both ends brominated monomer A of step (1) is reacted to obtain both ends boron esterification monomer with bis- (pinacol combined) two boron A'；
(3) by the substituted or unsubstituted carbazole of C5~C15 alkyl, the substituted or unsubstituted triphenylamine of C5~C15 alkyl, C5 The substituted or unsubstituted phenyl carbazole of~C15 alkyl, the substituted or unsubstituted triphenyl phosphorus of C5~C15 alkyl, C5~C15 alkyl Substituted or unsubstituted triphenyl phosphorus oxygen, the substituted or unsubstituted 9,9-dimethylacridan of C5~C15 alkyl, C5~C15 alkyl The substituted or unsubstituted triphenyl phosphorus oxygen carbazole of substituted or unsubstituted fluorenes, C5~C15 alkyl or C5~C15 alkyl replace Or unsubstituted 1- (3- cyano carbazole) -3- carbazyl benzene obtains both ends bromo list by the bromination reaction of bromo-succinimide Body B；
(4) the both ends brominated monomer B of step (3) is reacted to obtain both ends boron esterification monomer with bis- (pinacol combined) two boron B'；
(5) at least two reactants that will be copolymerized are obtained described by Suzuki-palace Pu Suzuki coupling reaction Polymer luminescent material；Wherein, at least two reactants that can be copolymerized are selected from both ends brominated monomer A, both ends boron The group of esterification monomer A ', both ends brominated monomer B and both ends boron esterification monomer B ' composition.
Preparation method according to the present invention, it is preferable that step (2) is in bis- (diphenylphosphino) ferrocene of 1,1'-] dichloride Palladium Pd (dppf) Cl2Catalytic action under carry out；Step (4) is in bis- (diphenylphosphino) ferrocene of 1,1'-] palladium chloride Pd (dppf)Cl2Catalytic action under carry out；Step (5) is in tetrakis triphenylphosphine palladium Pd (PPh3)4Catalytic action under carry out.
Another aspect, the present invention provide above-mentioned polymer luminescent material and are preparing answering in organic electroluminescence device With.
Another aspect, the present invention provide a kind of organic electroluminescence device comprising above-mentioned polymer luminescent material.
Suitable thermal excitation delayed fluorescence (TADF) unit and main body (Host) unit are copolymerized by the present invention, to synthesize light The regulatable polymer luminescent material of physical property.The material can obtain high fluorescence quantum efficiency and device efficiency, be suitble to As the emitting layer material in solution processing type organic electroluminescence device.Preferred technical solution according to the present invention passes through choosing Suitable main unit is selected, Photophysics can be further improved.By taking maximum current efficiency as an example, with unsubstituted dibenzo Thiophene sulfone-phenthazine is the OLED device of luminescence unit, dibenzothiophenes as the alternating polymer luminescent material of main unit It compares, the maximum current efficiency of polymer luminescent material of the invention can be improved by 10.0cd/A to 42.9cd/A.
Detailed description of the invention
Fig. 1 is Current density-voltage-brightness curve of the polymer luminescent material in solution processing type OLED device.
Fig. 2 is external quantum efficiency-brightness curve of the polymer luminescent material in solution processing type OLED device.
Fig. 3 is current efficiency-brightness-power efficiency curve of the polymer luminescent material in solution processing type OLED device.
Fig. 4 is 1 resulting polymers luminescent material of embodiment1H NMR spectra.
Fig. 5 is 2 resulting polymers luminescent material of embodiment1H NMR spectra.
Fig. 6 is 1 resulting polymers luminescent material of comparative example1H NMR spectra.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, but protection scope of the present invention is not limited to This.In the present invention, molal quantity, the relative usage ml being merely representative of between substance, are not intended to limit its absolute dosage.
Polymer luminescent material of the invention can be poly- for a kind of controllable conjugation with thermal excitation delayed fluorescence characteristic Close object luminescent material.The polymer luminescent material includes the thermal excitation delayed fluorescence with electron donor-acceptor (EDA) (D-A) structure (TADF) unit (alkyl-substituted phenthazine-dibenzothiophene sulphone) and main body (Host) unit.Its structure such as formula (1) institute Show:
In formula (1), R ' is solubilizing group, can improve the Photophysics and processability of luminescent material.R ' choosing From C5~C15 alkyl；The preferably branched alkyl of C7~C9.The example of R ' includes but is not limited to amyl, hexyl, heptyl, 2- first Base hexyl, octyl, 2- ethylhexyl, nonyl, decyl etc., for example, 2- ethylhexyl.
According to embodiment of the present invention, shown in the structure of the polymer luminescent material such as formula (2):
In formula (1) and (2), m indicates the molar ratio of TADF unit, selected from 0.05~0.99, preferably 0.1~ 0.5.In formula (1), n indicates the degree of polymerization of polymer, is 10~5000, preferably 10~100.One according to the present invention Embodiment, m are that 0.1~0.5, n is 10~100.
In formula (1) and (2), the weight average molecular weight Mw of the polymer luminescent material can be 5000~30000 Er Dun, polydispersity coefficient PDI are 1.5~2.5.Preferably, Mw is 8000~15000 dalton.Polydispersity coefficient PDI be 2~ 2.2.By molecular weight and polydispersity coefficient control in above range, be conducive to improve photophysical property, such as maximum current efficiency.
In formula (1) and (2), Host is the main unit with regulation Photophysical Behaviors.Host main unit be selected from One of flowering structure:
Wherein, R is selected from C5~C15 alkyl.Preferably, R is the straight chained alkyl of C7~C9.The example of R includes but is not limited to Amyl, hexyl, heptyl, octyl, nonyl, decyl etc., for example, n-heptyl or n-octyl.
According to embodiment of the present invention, shown in the structure of the polymer luminescent material such as formula (3-1):
Wherein, n is 10~5000, preferably 10~100.
According to another implementation of the invention, shown in the structure of the polymer luminescent material such as formula (3-2):
Wherein, n is 10~5000, preferably 10~100.
Above-mentioned polymer luminescent material is prepared using following steps: both ends brominated monomer A synthesis step (1), both ends Boron esterification monomer A ' synthesis step (2), both ends brominated monomer B synthesis step (3), both ends boron esterification monomer B ' synthesis step (4), Polymerization procedure (5).Wherein, step (1)~(4) sequence is not particularly limited.Both ends boron esterification monomer A ' synthesis step (2) It can be only with a step with both ends boron esterification monomer B ' synthesis step (4).
In step (1), 2- alkyl -8- phenthazine dibenzothiophene sulphone is passed through to the bromine of bromo-succinimide (NBS) Generation reaction obtains both ends brominated monomer A.2- alkyl -8- phenthazine dibenzothiophene sulphone can be closed with reference to the method for preparation example At which is not described herein again.The alkyl is C5~C15 alkyl；The preferably branched alkyl of C7~C9.The example of alkyl include but It is not limited to amyl, hexyl, heptyl, 2- methylhexyl, octyl, 2- ethylhexyl, nonyl, decyl etc., for example, 2- ethylhexyl. 2- (2- alkyl) -8- phenthazine dibenzothiophene sulphone is dissolved in dry methylene chloride；In ice-water bath, under the conditions of being protected from light, The dry methylene chloride solution of N- bromo-succinimide is slowly added dropwise thereto；15~30h is stirred at 20~30 DEG C, will be reacted Liquid, which is added to the water, terminates reaction；Then with methylene chloride by organic extractant phase, magnesium sulfate is dry.After being spin-dried for, using volume ratio N-hexane and dichloromethane mixture for 0.5~3:1 are that leacheate carries out column chromatography for separation, obtain both ends brominated monomer A:2- (alkyl) -8- (bis- bromo phenthazine of 3,7-) dibenzothiophene sulphone.For example, by 2- (2- ethylhexyl) -8- phenthazine dibenzo Thiophene sulfone (4mmol) is dissolved in the dry methylene chloride of 50mL.In ice-water bath, under the conditions of being protected from light, NBS is slowly added dropwise thereto The dry methylene chloride solution of (8.4mmol).After stirring 20h at room temperature, reaction solution is added to the water and terminates reaction.Later, With methylene chloride by organic extractant phase, after magnesium sulfate is dry.After being spin-dried for, use volume ratio for the n-hexane of 1:1 and methylene chloride Mixture is that leacheate carries out column chromatography for separation, obtains both ends brominated monomer A:2- (2- ethylhexyl) -8- (3,7- bis- bromo pheno thiophenes Piperazine) dibenzothiophene sulphone.
In step (2), the both ends brominated monomer A of step (1) is reacted to obtain both ends boron with bis- (pinacol combined) two boron Esterification monomer A '.Preferably, step (2) is in bis- (diphenylphosphino) ferrocene of 1,1'-] palladium chloride Pd (dppf) Cl2Urge Change effect is lower to be carried out.In the present invention, bis- (pinacol combined) two boron have the same meaning with double pinacol boron esters.In argon atmospher Under enclosing, by [1,1'- bis- (diphenylphosphinos) of both ends brominated monomer A, potassium acetate KOAc, double pinacol boron esters and catalytic amount Ferrocene] palladium chloride is added in dry Isosorbide-5-Nitrae-dioxane, and 10~20h is stirred at 85~100 DEG C.Reaction terminates Afterwards, add water quenching reaction, and organic phase is extracted with ethyl acetate.After being spin-dried for, use volume ratio for the ethyl acetate of 1~5:10 and Hexane mixture is that leacheate carries out column chromatography for separation, obtains both ends boron esterification monomer A ': 2- (alkyl) -8- (3,7- bis- frequencies Any alcohol ester phenthazine)-dibenzothiophene sulphone.For example, under argon atmosphere, by 2- (2- ethylhexyl) -8- (3,7- bis- bromo phenos Thiazine)-dibenzothiophene sulphone (2mmol), potassium acetate KOAc (12mmol), double pinacol boron esters (6mmol) and catalytic amount [1,1'- bis- (diphenylphosphino) ferrocene] palladium chloride is added in dry Isosorbide-5-Nitrae-dioxane (50mL), and in 90 DEG C Lower stirring 12h.After reaction, add water quenching reaction, and organic phase is extracted with ethyl acetate.After being spin-dried for, use volume ratio for The ethyl acetate and hexane mixture of 1:10 is that leacheate carries out column chromatography for separation, obtains A ': 2- (2- of both ends boron esterification monomer Ethylhexyl) -8- (bis- pinacol ester phenthazine of 3,7-)-dibenzothiophene sulphone.
It is in step (3), the substituted or unsubstituted carbazole of C5~C15 alkyl, C5~C15 alkyl is substituted or unsubstituted Triphenylamine, the substituted or unsubstituted phenyl carbazole of C5~C15 alkyl, the substituted or unsubstituted triphenyl phosphorus of C5~C15 alkyl, C5 The substituted or unsubstituted triphenyl phosphorus oxygen of~C15 alkyl, the substituted or unsubstituted 9,9-dimethylacridan of C5~C15 alkyl, C5 The substituted or unsubstituted triphenyl phosphorus oxygen carbazole of the substituted or unsubstituted fluorenes of~C15 alkyl, C5~C15 alkyl or C5~C15 The substituted or unsubstituted 1- of alkyl (3- cyano carbazole) -3- carbazyl benzene obtains two by the bromination reaction of bromo-succinimide Hold brominated monomer B.The example of above-mentioned C5~C15 alkyl includes but is not limited to amyl, hexyl, heptyl, octyl, nonyl, decyl Deng for example, n-heptyl or n-octyl.
In certain embodiments, in step (3), one of following structural formula compound represented is passed through into bromo fourth two Imido bromination reaction obtains both ends brominated monomer B:
Wherein, R is selected from C5~C15 alkyl.Preferably, R is the straight chained alkyl of C7~C9.The example of R includes but is not limited to Amyl, hexyl, heptyl, octyl, nonyl, decyl etc., for example, n-heptyl or n-octyl.
The alkyl-substituted carbazole of C5~C15 can synthesize in the following way, other monomers can by similar fashion into Row synthesis, which is not described herein again.Carbazole (50mmol) is dissolved in n,N-Dimethylformamide DMF (100mL), and slow in 0 DEG C Slowly the NaH (75mmol) for the 60wt% being scattered in kerosene is added, stirs 3h.After temperature is increased to room temperature naturally, by 1- bromine It is slowly dropped into reaction system for DMF (20mL) solution of normal alkane, such as 1- bromo heptane (55mmol), the reaction was continued 12h.After reaction, add water quenching reaction, and extract organic phase with dichloro hexane.After being spin-dried for, use volume ratio for the two of 1:5 Chloromethanes and hexane mixture are that leacheate carries out column chromatography for separation, and obtaining N- alkyl carbazole, (carbon atom number of alkyl is C5 ~C15), such as N- heptyl alkane carbazole.
N- alkyl carbazole is dissolved in dry methylene chloride.In ice-water bath, under the conditions of being protected from light, slowly it is added dropwise thereto The dry methylene chloride solution of NBS.After stirring 15~30h at room temperature, reaction solution is added to the water and terminates reaction.Later, it uses For methylene chloride by organic extractant phase, magnesium sulfate is dry.After being spin-dried for, use volume ratio for the n-hexane of 0.5~2:5 and methylene chloride Mixture is that leacheate carries out column chromatography for separation, obtains both ends brominated monomer B:N- alkyl -3,6- dibromo carbazole.For example, by N- heptan Base carbazole (50mmol) is dissolved in the dry methylene chloride of 100mL.In ice-water bath, under the conditions of being protected from light, slowly it is added dropwise thereto Dry methylene chloride (100mL) solution of NBS (105mmol).After stirring 20h at room temperature, reaction solution is added to the water termination Reaction.Later, with methylene chloride by organic extractant phase, magnesium sulfate is dry.After being spin-dried for, use volume ratio for the n-hexane of 1:5 and Dichloromethane mixture is that leacheate carries out column chromatography for separation, obtains both ends brominated monomer B:N- heptyl -3,6- dibromo carbazole.
In step (4), the both ends brominated monomer B of step (3) is reacted to obtain both ends boron with bis- (pinacol combined) two boron Esterification monomer B '.Preferably, step (4) is in bis- (diphenylphosphino) ferrocene of 1,1'-] palladium chloride Pd (dppf) Cl2Urge Change effect is lower to be carried out.Under argon atmosphere, by N- alkyl -3,6- dibromo carbazole, KOAc, double pinacol boron esters and catalytic amount [1,1'- bis- (diphenylphosphino) ferrocene] palladium chloride is added in dry Isosorbide-5-Nitrae-dioxane, and at 85~100 DEG C Stir 10~15h.After reaction, add water quenching reaction, and organic phase is extracted with ethyl acetate.After being spin-dried for, using volume ratio Ethyl acetate and hexane mixture for 0.5~2:10 are that leacheate carries out column chromatography for separation, obtain both ends boron esterification monomer Two pinacol boron ester carbazole of B ': N- alkyl -3,6-.For example, under argon atmosphere, by N- heptyl -3,6- dibromo carbazole [bis- (diphenylphosphinos) two of 1,1'- of (10mmol), KOAc (60mmol), double pinacol boron esters (30mmol) and catalytic amount Luxuriant iron] palladium chloride is added in dry Isosorbide-5-Nitrae-dioxane (100mL), and stirs 12h at 90 DEG C.After reaction, Add water quenching reaction, and organic phase is extracted with ethyl acetate.After being spin-dried for, use volume ratio for the ethyl acetate of 1:10 and n-hexane Mixture is that leacheate carries out column chromatography for separation, obtains bis- pinacol boron ester carbazole of N- heptyl -3,6-.
In step (5), at least two reactants that will be copolymerized are anti-by Suzuki-palace Pu Suzuki coupling It answers, obtains the polymer luminescent material；Wherein, at least two reactants that can be copolymerized are selected from both ends bromo list The group of body A, both ends boron esterification monomer A ', both ends brominated monomer B and both ends boron esterification monomer B ' composition.Preferably, step (5) exists Tetrakis triphenylphosphine palladium Pd (PPh3)4Catalytic action under carry out.Both ends brominated monomer A can lead to both ends boron esterification monomer B ' It crosses polymerization procedure (5) and obtains polymer luminescent material.Both ends boron esterification monomer A ' and both ends brominated monomer B can pass through polymerization step Suddenly (5) obtain polymer luminescent material.Both ends brominated monomer A, both ends brominated monomer B and both ends boron esterification monomer B ' can pass through Polymerization procedure (5) obtains polymer luminescent material.Both ends brominated monomer A, both ends boron esterification monomer A ', both ends brominated monomer B can To obtain polymer luminescent material by polymerization procedure (5).
By Pd (PPh3)4, methyl tricapryl ammonium chloride, wet chemical, dry toluene and can be copolymerized at least Two kinds of reactants (both ends brominated monomer A, both ends boron esterification monomer A ', both ends brominated monomer B and/or both ends boron esterification monomer B ') It mixes, under argon atmosphere, 55~100h is reacted at 75~90 DEG C.For reaction mixture by washing, volume ratio is 1~2:1's The mixed extractant solvent of methylene chloride and tetrahydrofuran, concentration, is precipitated in cold methanol, is centrifugated, and filtration drying obtains Polymer luminescent material.For example, by the Pd (PPh of the 6mol% based on reactant total mole number3)4, 10 μ L methyl trioctylphosphine chlorinations The product both ends bromine of ammonium (Aliquat@336), wet chemical (2M, 5mL), dry toluene (20mL) and 1mmol step (1) It is added in 50ml bottle with two necks for the product both ends boron esterification monomer B ' of monomer A, 1mmol step (4).Under argon atmosphere, 85 It is reacted 72 hours at DEG C.Reaction mixture is by washing, mixed solvent (volume ratio 1:1) extraction of methylene chloride and tetrahydrofuran It takes, is concentrated, is precipitated in cold methanol, be centrifugated, filtration drying obtains polymer luminescent material.It for another example, will be based on reaction Pd (the PPh of the 6mol% of object total mole number3)4, 10 μ L methyl tricapryl ammonium chlorides (Aliquat@336), wet chemical The production of product both ends brominated monomer A, the 0.8mmol step (3) of (2M, 5mL), dry toluene (20mL) and 0.2mmol step (1) The product both ends boron esterification monomer B ' of object both ends brominated monomer B and 1mmol step (4) is added in 50ml bottle with two necks.Argon atmospher Under enclosing, reacted 72 hours at 85 DEG C.Reaction mixture is by washing, the mixed solvent (volume of methylene chloride and tetrahydrofuran Than extracting for 1:1), concentration is precipitated in cold methanol, is centrifugated, and filtration drying obtains polymer luminescent material.
The present invention is by the alkyl-substituted phenthazine-dibenzothiophene sulphone of suitable thermal excitation delayed fluorescence unit and main body list Member copolymerization, to synthesize the regulatable polymer luminescent material of photophysical property.Luminescent material of the invention has high fluorescence Quantum efficiency.Therefore, the present invention also provides above-mentioned polymer luminescent materials to prepare the application in organic electroluminescence device.On Stating luminescent material can be used for the luminescent layer of organic electroluminescence device.
The present invention also provides a kind of organic electroluminescence device comprising polymer luminescent material of the invention.This is organic Electroluminescent device has high maximum current efficiency (15~50cd/A) and highest external quantum efficiency (5~18%) etc..It is organic Electroluminescent device can be solution processing type organic electroluminescence device.
Embodiments of the present invention are described further below by way of specific embodiment.
Following embodiment and the test method of comparative example are described as follows:
1H NMR is measured using III 400MHZ type nuclear magnetic resonance chemical analyser of Bruker AVANCE.Molecular weight and its distribution by Waters 515-2410 type gel permeation chromatography measures.
Highest occupies track (HOMO) and is calculated respectively with following formula with lowest unoccupied molecular orbital (LUMO):
Wherein, oxidizing potential is all made of CHI volt-amperes of testers with reduction potential and obtains.
Phosphorescence spectrum is all made of Hitachi F-7000 type Fluorescence Spectrometer and measures under fluorescence spectrum and 77K.
Transient spectrum and absolute quantum yield are all made of FLS980 type transient state Fluorescence Spectrometer and measure.
Electroluminescent spectrum is measured using JYSPEX CCD3000 type spectrometer.
Current density-voltage-brightness curve is measured by 2400 type of Keithley and 2000 type multimeter of Keithley.
The synthesis of preparation example 1:2- (2- ethylhexyl) -8- phenthazine dibenzothiophene sulphone
1) synthesis of 2- bromodiphenylthiophene
Under the conditions of ice-water bath, dibenzothiophenes (0.1mol) is dissolved in the anhydrous CHCl of 100ml in the reactor3 In, then with the anhydrous CHCl of 20ml35.4ml bromine is dissolved in constant pressure funnel, is added dropwise in reactor.Room temperature reaction three days. 30ml is added and is saturated NaHSO3Solution, stirring, until solution is white, extracts organic layer.Then reaction solution is poured into liquid separation leakage Bucket, is extracted with dichloromethane 3 times, then is washed 3 times with saturation NaCl aqueous solution.Organic layer is dried, filtered with anhydrous sodium sulfate, It is spin-dried for, white solid 25.2g, yield 96% is obtained after ethyl alcohol recrystallization.
2) synthesis of the bromo- dibenzothiophenes of 2- (2- ethyl hexyl) -8-
Aluminum trichloride (anhydrous) (120mmol) is added to the anhydrous CH of 100mL2Cl2, -40 DEG C are cooled to, alchlor is obtained Suspension.By 2- ethyl hexanoyl chloro, (100mmol and the resulting 2- bromodiphenylthiophene (80mmol) of step 1) are dissolved in 100mL Anhydrous CH2Cl2In, and be slowly dropped into above-mentioned alchlor suspension.It keeps -40 DEG C of reactions for 24 hours, is then to slowly warm up to room Temperature, the reaction was continued 12h.After reaction, above-mentioned reaction solution is poured into ice water, terminates reaction.After organic layer extraction, drying It is spin-dried for obtaining yellow liquid.Column chromatography point is carried out as leacheate using volume ratio for the n-hexane and dichloromethane mixture of 10:1 From being dried in vacuo to obtain light yellow liquid 24.3g, yield 78%.1H NMR(400MHz,CDCl3): δ 8.70 (d, J=1.1Hz, 1H), 8.38 (d, J=1.8Hz, 1H), 8.08 (dt, J=10.7,5.4Hz, 1H), 7.92 (d, J=8.4Hz, 1H), 7.74 (d, J=8.5Hz, 1H), 7.61 (dd, J=8.5,1.8Hz, 1H), 3.61-3.42 (m, 1H), 1.96-1.46 (m, 6H), 0.89 (dt, J=13.7,7.2Hz, 8H).
3) synthesis of the bromo- dibenzothiophene sulphone of 2- (2- ethylhexyl) -8-
Under condition of ice bath, it is anhydrous that lithium aluminium hydride reduction (100mmol) with alchlor (200mmol) is slowly added into 200mL Suspension is made in THF, and stirs 15 minutes, is cooled to 0 DEG C.Later, 2- (2- ethyl hexyl) -8- step 2) obtained Bromo- dibenzothiophenes (50mmol) is dissolved in the dry THF of 50mL, and is slowly dropped into above-mentioned suspension at 0 DEG C.Room temperature is anti- It is heated after answering 5h, the lower 12h that flows back of argon gas protection.After reaction, it is cooled to room temperature to system, is slowly added to ice water and is quenched instead It answers.By organic extractant phase, be spin-dried for after the hydrogen peroxide that the concentration of 200mL acetic acid and 150mL are 30vol% be added be heated to reflux 12h.It is cooled to room temperature after reaction.Methylene chloride extracts organic phase, is the n-hexane of 3:1 and two with volume ratio after being spin-dried for Chloromethane mixture is that leacheate carries out column chromatography for separation, and ethyl alcohol recrystallization obtains white solid 15.0g, yield 73%.1H NMR (400MHz,CDCl3): δ 7.94 (s, 1H), 7.73 (d, J=7.8Hz, 1H), 7.66 (q, J=8.1Hz, 2H), 7.52 (s, 1H), 7.34 (d, J=7.9Hz, 1H), 2.65 (d, J=7.2Hz, 2H), 1.66-1.59 (m, 1H), 1.29 (dd, J=12.2, 6.1Hz, 8H), 0.90 (dd, J=8.7,5.9Hz, 6H).
4) synthesis of 2- (2- ethylhexyl) -8- phenthazine dibenzothiophene sulphone
Under argon atmosphere, the 2- bromo- dibenzothiophene sulphone of (2- ethylhexyl) -8- (15mmol) that step 3) is obtained, Phenthazine (15.75mmol), Pd (OAc)2(0.375mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (XPhos, 3mmol) and sodium tert-butoxide (22.5mmol) is dissolved in 100mL dry toluene (100mL), reacts 48h at 115 DEG C.Reaction knot System is cooled to room temperature by Shu Hou.Sodium chloride saturated solution is washed three times, methylene chloride extraction.After being spin-dried for, use volume ratio for The n-hexane and dichloromethane mixture of 1:1 carries out column chromatography for separation, obtains light yellow solid 6.9g, yield 88%.1H NMR (400MHz, DMSO-d6): δ 8.11 (dd, J=9.6,5.1Hz, 2H), 7.99 (s, 1H), 7.89 (d, J=7.9Hz, 1H), 7.52-7.44 (m, 2H), 7.29 (dd, J=7.6,1.5Hz, 2H), 7.15 (td, J=7.8,1.5Hz, 2H), 7.06 (td, J= 7.5,1.1Hz, 2H), 6.71 (dd, J=8.1,0.9Hz, 2H), 2.63 (d, J=7.1Hz, 2H), 1.68 (d, J=5.6Hz, 1H), 1.30-1.18 (m, 8H), 0.83 (q, J=7.1Hz, 6H).
The synthesis of preparation example 2:N- heptyl carbazole
Carbazole (50mmol) is dissolved in n,N-Dimethylformamide DMF (100mL), and be slowly added to be scattered in 0 DEG C The NaH (75mmol) of 60wt% in kerosene stirs 3h.After temperature is increased to room temperature naturally, by 1- bromo heptane DMF (20mL) solution of (55mmol) is slowly dropped into reaction system, the reaction was continued 12h.After reaction, water quenching is added to go out instead It answers, and extracts organic phase with dichloro hexane.After being spin-dried for, using volume ratio for the methylene chloride of 1:5 and hexane mixture is leaching Washing lotion carries out column chromatography for separation, obtains yellow solid 11.8g, yield 89%.1H NMR (400MHz, Acetone-d6): δ 8.11 (d, J=7.8Hz, 2H), 7.50 (d, J=8.2Hz, 2H), 7.48-7.36 (m, 2H), 7.18 (t, J=7.4Hz, 2H), 4.34 (t, J=7.2Hz, 2H), 1.37-1.13 (m, 10H), 0.83 (dt, J=13.7,6.8Hz, 3H).
Embodiment 1
(1) conjunction of 2- (2- ethylhexyl) -8- (bis- bromo phenthazine of 3,7-) dibenzothiophene sulphone (both ends brominated monomer A) At
2- (2- ethylhexyl) -8- phenthazine dibenzothiophene sulphone (4mmol) is dissolved in the dry methylene chloride of 50mL. In ice-water bath, under the conditions of being protected from light, the dry methylene chloride solution of NBS (8.4mmol) is slowly added dropwise thereto.It stirs at room temperature After 20h, reaction solution is added to the water and terminates reaction.Later, organic extractant phase after magnesium sulfate is dry, is revolved with methylene chloride It is dry.Using n-hexane and dichloromethane mixture, (volume ratio of the two is that leacheate carries out column chromatography for separation for 1:1), is obtained pale yellow Color solid 2.5g, yield 91%.1H NMR (400MHz, DMSO-d6): δ 8.32 (s, 1H), 8.22 (d, J=8.1Hz, 1H), 8.10 (s, 1H), 8.41-7.68 (m, 8H), 7.92 (d, J=7.9Hz, 1H), 7.65 (d, J=8.1Hz, 1H), 7.48 (d, J= 7.9Hz, 1H), 7.43 (s, 2H), 7.18 (d, J=8.8Hz, 2H), 6.33 (d, J=8.8Hz, 2H), 2.63 (d, J=7.0Hz, 2H), 2.03-1.95 (m, 1H), 1.23 (s, 8H), 0.84 (dd, J=14.4,7.0Hz, 6H).
(2) (boron esterification in both ends is single for 2- (2- ethylhexyl) -8- (bis- pinacol ester phenthazine of 3,7-)-dibenzothiophene sulphone Body A ') synthesis
Under argon atmosphere, by 2- (2- ethylhexyl) -8- (3,7- bis- bromo phenthazine)-dibenzothiophene sulphone (2mmol), with potassium acetate KOAc (12mmol), [bis- (diphenylphosphines of 1,1'- of double pinacol boron esters (6mmol) and catalytic amount Base) ferrocene] palladium chloride is added in dry Isosorbide-5-Nitrae-dioxane (50mL), and stirs 12h at 90 DEG C.Reaction terminates Afterwards, add water quenching reaction, and organic phase is extracted with ethyl acetate.After being spin-dried for, using the mixture (second of ethyl acetate and n-hexane The volume ratio of acetoacetic ester and n-hexane is 1:10) it is that leacheate carries out column chromatography for separation, yellow solid 1.43g is obtained, yield is 92%.1H NMR (400MHz, DMSO-d6): δ 8.38 (d, J=1.6Hz, 1H), 8.27 (d, J=8.1Hz, 1H), 8.14 (s, 1H), 7.92 (d, J=7.9Hz, 1H), 7.68 (dt, J=4.9,2.4Hz, 1H), 7.47 (d, J=8.4Hz, 1H), 7.29 (d, J =1.3Hz, 2H), 7.26-7.21 (m, 2H), 6.25 (d, J=8.2Hz, 2H), 2.61 (d, J=7.1Hz, 2H), 1.70-1.62 (m, 1H), 1.29-1.14 (m, 32H), 0.82 (dd, J=15.4,6.9Hz, 6H).
(3) synthesis of N- heptyl -3,6- dibromo carbazole (both ends brominated monomer B)
N- heptyl carbazole (50mmol) is dissolved in the dry methylene chloride of 100mL.In ice-water bath, under the conditions of being protected from light, Dry methylene chloride (100mL) solution of NBS (105mmol) is slowly added dropwise thereto.After stirring 20h at room temperature, by reaction solution Be added to the water termination reaction.Later, with methylene chloride by organic extractant phase, magnesium sulfate is dry.After being spin-dried for, using n-hexane and The mixture (volume ratio of n-hexane and methylene chloride is 1:5) of methylene chloride is that leacheate carries out column chromatography for separation, obtains yellow Solid 18.5g, yield 88%.1H NMR (400MHz, Acetone-d6): δ 8.46-8.36 (m, 2H), 7.69-7.56 (m, 4H), 4.45 (t, J=7.2Hz, 2H), 1.43-1.20 (m, 10H), 0.92-0.79 (m, 3H).
(4) synthesis of two pinacol boron ester carbazole of N- heptyl -3,6- (both ends boron esterification monomer B ')
Under argon atmosphere, by N- heptyl -3,6- dibromo carbazole (10mmol), KOAc (60mmol), double pinacol boron esters [bis- (diphenylphosphino) ferrocene of 1,1'-] palladium chloride of (30mmol) and catalytic amount is added to dry 1,4- dioxy six In ring (100mL), and 12h is stirred at 90 DEG C.After reaction, add water quenching reaction, and organic phase is extracted with ethyl acetate. After being spin-dried for, use ethyl acetate and n-hexane mixture (volume ratio of ethyl acetate and n-hexane for 1:10) be leacheate into Row column chromatography for separation obtains yellow solid 4.4g, yield 85%.1H NMR (400MHz, Acetone): δ 8.61 (s, 2H), 7.93-7.82 (m, 2H), 7.59 (d, J=8.2Hz, 2H), 4.45 (q, J=7.5Hz, 2H), 1.43-1.19 (m, 34H), 0.84 (t, J=6.9Hz, 3H).
(5) synthesis of polymer luminescent material
By the Pd (PPh of the 6mol% based on reactant total mole number3)4, 10 μ L methyl tricapryl ammonium chloride (Aliquat@ The product both ends brominated monomer A of 336), wet chemical (2M, 5mL), dry toluene (20mL) and 1mmol step (1), The product both ends boron esterification monomer B ' of 1mmol step (4) is added in 50ml bottle with two necks.Under argon atmosphere, reacted at 85 DEG C 72 hours.Reaction mixture is concentrated by washing, mixed solvent (volume ratio 1:1) extraction of methylene chloride and tetrahydrofuran, It is precipitated, is centrifugated in cold methanol, filtration drying obtains polymer luminescent material Cop-50.Through detecting, the road Mw=8241 Er Dun, PDI=2.04, specific performance referring to Fig. 1~3,1H NMR spectra is referring to fig. 4.Optical physics characterize data and device performance Data are referring to table 1 and 2.
Embodiment 2
Other than following steps, other conditions are same as Example 1:
By the Pd (PPh of the 6mol% based on reactant total mole number3)4, 10 μ L methyl tricapryl ammonium chloride (Aliquat@ The product both ends brominated monomer A of 336), wet chemical (2M, 5mL), dry toluene (20mL) and 0.2mmol step (1), The product both ends boron esterification monomer B ' of product both ends brominated monomer B and the 1mmol step (4) of 0.8mmol step (3) is added In 50ml bottle with two necks.Under argon atmosphere, reacted 72 hours at 85 DEG C.Reaction mixture is by washing, methylene chloride and tetrahydro The mixed solvent (volume ratio 1:1) of furans extracts, and concentration is precipitated in cold methanol, is centrifugated, and filtration drying is gathered Close object luminescent material Cop-10.Through detecting, Mw=10441 dalton, PDI=2.17, specific performance referring to Fig. 1~3,1H NMR Spectrogram is referring to Fig. 5.Optical physics characterize data and device performance data are referring to table 1 and 2.
Comparative example 1
Other than following steps, other conditions are same as Example 1:
By the Pd (PPh of the 6mol% based on reactant total mole number3)4, 10 μ L methyl tricapryl ammonium chloride (Aliquat@ The product both ends brominated monomer A of 336), wet chemical (2M, 5mL), dry toluene (20mL) and 0.6mmol step (1), The product both ends boron esterification monomer A ' of 0.6mmol step (2) is added in 50ml bottle with two necks.It is anti-at 85 DEG C under argon atmosphere It answers 72 hours.For reaction mixture by washing, mixed solvent (volume ratio 1:1) extraction of methylene chloride and tetrahydrofuran is dense Contracting, is precipitated in cold methanol, is centrifugated, and filtration drying obtains polymer luminescent material Homo.Through detecting, Mw=11514, PDI=1.44, specific performance referring to Fig. 1~3,1H NMR spectra is referring to Fig. 6.Optical physics characterize data and device performance data ginseng It is shown in Table 1 and 2.
Table 1, optical physics characterize data
Note: sol indicates that solution shape, film indicate filminess.
Table 2, device performance data
As shown in Table 2, device performance data of the invention are significantly improved.For example, maximum current efficiency improve to 42.9cd/A, highest external quantum efficiency are improved to 15.7%.
Present invention is not limited to the embodiments described above, without departing from the essence of the present invention, this field skill Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.

Claims (9)

1. a kind of polymer luminescent material, which is characterized in that shown in its structure such as formula (1):
Wherein, Host is the main unit with regulation Photophysical Behaviors, and R ' is selected from C5~C15 alkyl；And m be 0.05~ 0.99, n is 10~5000；
Main unit Host is selected from one of flowering structure:
Wherein, R is selected from C5~C15 alkyl.
2. polymer luminescent material according to claim 1, which is characterized in that R is the straight chained alkyl of C7~C9, and R ' is C7 The branched alkyl of~C9.
3. polymer luminescent material according to claim 2, which is characterized in that m is that 0.1~0.5, n is 10~100.
4. polymer luminescent material according to claim 1, which is characterized in that shown in its structure such as formula (2):
Wherein, Host is the main unit with regulation Photophysical Behaviors, and it is 10~5000 that m, which is 0.05~0.99, n,.
5. polymer luminescent material according to any one of claims 1 to 4, which is characterized in that the polymer light-emitting material The weight average molecular weight Mw of material is 5000~30000 dalton, and polydispersity coefficient PDI is 1.5~2.5.
6. the preparation method of described in any item polymer luminescent materials according to claim 1~5, which is characterized in that including such as Lower step:
(1) 2- alkyl -8- phenthazine dibenzothiophene sulphone is obtained into both ends bromo by the bromo-reaction of bromo-succinimide Monomer A；Wherein, the alkyl is C5~C15 alkyl；
(2) the both ends brominated monomer A of step (1) is reacted to obtain both ends boron esterification monomer A ' with bis- (pinacol combined) two boron；
(3) by the alkyl-substituted carbazole of C5~C15, the alkyl-substituted triphenylamine of C5~C15, the alkyl-substituted 9,9- of C5~C15 The alkyl-substituted triphenylphosphine of dimethyl acridinium, fluorenes, C5~C15, the alkyl-substituted triphenylphosphine oxide of C5~C15, triphenylphosphine Oxygen carbazole or 1- (3- cyano carbazole) -3- carbazyl benzene obtain both ends bromo list by the bromination reaction of bromo-succinimide Body B；
(4) the both ends brominated monomer B of step (3) is reacted to obtain both ends boron esterification monomer B ' with bis- (pinacol combined) two boron；
(5) at least two reactants that will be copolymerized obtain the polymerization by Suzuki-palace Pu Suzuki coupling reaction Object luminescent material；Wherein, at least two reactants that can be copolymerized are selected from both ends brominated monomer A, both ends boron is esterified The group of monomer A ', both ends brominated monomer B and both ends boron esterification monomer B ' composition.
7. preparation method according to claim 6, which is characterized in that
Step (2) is in [bis- (diphenylphosphino) ferrocene of 1,1'-] palladium chloride Pd (dppf) Cl2Catalytic action under carry out；
Step (4) is in [bis- (diphenylphosphino) ferrocene of 1,1'-] palladium chloride Pd (dppf) Cl2Catalytic action under carry out；
Step (5) is in tetrakis triphenylphosphine palladium Pd (PPh3)4Catalytic action under carry out.
8. described in any item polymer luminescent materials are preparing answering in organic electroluminescence device according to claim 1~5 With.
9. a kind of organic electroluminescence device, which is characterized in that it includes described in any item polymerizations according to claim 1~5 Object luminescent material.
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Citations (1)

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Publication number Priority date Publication date Assignee Title
CN105503766A (en) * 2015-12-18 2016-04-20 昆山国显光电有限公司 Thermal activation delayed fluorescent material and organic electroluminescent device

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Publication number Priority date Publication date Assignee Title
CN105503766A (en) * 2015-12-18 2016-04-20 昆山国显光电有限公司 Thermal activation delayed fluorescent material and organic electroluminescent device

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Efficient triplet utilization in conventional solution-processed phosphorescent organic light emitting diodes using a thermal activated delayed fluorescence polymer as an assistant host;Dianming Sun, et al.;《Journal of Materials Chemistry C》;20180406;第4800-4806页
Rational Design of TADF Polymers Using a Donor–Acceptor Monomer with Enhanced TADF Efficiency Induced by the Energy Alignment of Charge Transfer and Local Triplet Excited States, Supporting Information;Roberto S. Nobuyasu，et al.;《Adv. Optical Mater.》;20160112;第3页
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