CN106928436B - A kind of polymer of main chain unit containing sulfone and its preparation method and application - Google Patents
A kind of polymer of main chain unit containing sulfone and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of polymer of main chain unit containing sulfone, with structure shown in formula (I), polymer provided by the invention is by selecting specific polymerized unit and selecting the ratio of specific polymerized unit, so that the energy level difference between the first excited singlet state and the first excited triplet state of polymer provided by the invention is smaller, there is the transmitting of thermal induction delayed fluorescence；And the polymer, when being applied to electroluminescent device, the external quantum efficiency of obtained electroluminescent device is high, and can effectively inhibit the efficiency roll-off of electroluminescent device.In addition, the preparation method of polymer provided by the invention is simple, and the simple solution processing method preparation such as spin coating and inkjet printing can be used in when obtained polymer is used to prepare device, enormously simplifies the preparation process of electroluminescent device.
Description
Technical field
The present invention relates to the polymer of organic polymer luminescent material field more particularly to a kind of main chain unit containing sulfone and its
Preparation method and application.
Background technique
2012, Adachi seminar reported internal quantum efficiency up to 100% new organic fluorescent material, quilt for the first time
Referred to as thermal induction delayed fluorescence (TADF) material (Nature, 2012,492,234-238).First excitation substance of such material
Energy level difference between state and the first excited triplet state is smaller (< 0.3eV), and triplet exciton can absorb the heat in ambient enviroment
Amount, and singlet excitons are converted to by anti-intersystem crossing, and then radiation transistion generates thermal induction delayed fluorescence；The mechanism can be with
Singlet excitons and triplet exciton are made full use of, internal quantum efficiency reaches as high as 100% when applied to electroluminescent device.Together
When, since such material is pure organic compound, structure is easier to design and modify, and noble metal is not necessarily to, in organic light emission two
The field pole pipe (OLED) has broad application prospects.
In recent years, a large amount of TADF small molecular organic compounds are reported, since it can efficiently utilize triplet exciton
And singlet excitons, electroluminescent device efficiency can compare favourably with the device efficiency of the phosphor material containing heavy metal.But it is small
When molecular compound is applied to luminescent device, the material of main part of doping high triplet energy level is generally required, and pass through vapor deposition side
Formula carries out device preparation, complex process, and is difficult to prepare large scale luminescent device.
Polymer is similar to small molecular organic compounds, can be by change and decorating molecule structural improvement luminosity, together
When can have application advantage in terms of large scale and Flexible Displays using the modes making devices such as spin coating or inkjet printing.So
And traditional polymer, merely with singlet excitons, external quantum efficiency can only achieve 5~6%；Heavy metal is introduced in the polymer
" chemical doping " of complex phosphorescence dye units, can make full use of singlet state and triplet exciton, and external quantum efficiency is reachable
15% or more, but the introducing of phosphorescence unit increases the difficulty of material cost and structural modification.Therefore, will using singlet state and
The TADF dye units " chemical doping " of triplet exciton should be to improve polymer device performance to have efficacious prescriptions into polymer
Method.The utilization of polymer TADF also needs polymer and possesses high triplet energy level, but traditional conjugated polymer have it is big
Conjugation extended system keeps its triplet energy level lower and is difficult to realize delayed fluorescence transmitting.Although being connected by different TADF units
Connect mode, may be implemented polymer TADF transmitting (Adv.Mater.2015,27,7236-7240；Adv.Optical
Mater.2016,4,597-607；Macromolecules,2016,49,5452-5460；Macromolecules 2016,49,
4373-4377；Adv.Mater.2016,28,4019-4024), but its device performance reaches far away desired level, it is difficult to
Small molecular organic compounds TADF material compares favourably.Therefore how to obtain synthetic method simply and there is the polymerization of high triplet energy level
Owner's chain, and then realize that the polymer of efficient TA DF transmitting is the current technical issues that need to address.
Summary of the invention
In view of this, technical problem to be solved by the present invention lies in the polymer for providing a kind of main chain unit containing sulfone and
Preparation method and application, not only preparation method is simple for the polymer of main chain unit containing sulfone provided by the invention, but also the present invention
Obtained polymer is applied to the efficiency roll-off of device external quantum efficiency height and electroluminescent device that electroluminescent device obtains
It is very low.
The present invention provides a kind of polymer of main chain unit containing sulfone, have structure shown in formula (I):
Wherein, R1、R2、R3The independent alkyl selected from C1~C30, the alkoxy of C1~C30 or the aryl of C6~C35；
A is the aryl of C6~C50 containing electron-withdrawing group or the heteroaryl of C3~C45；
X is 0.001 < x < 0.5；
N is 1~200.
Preferably, the x is 0.005≤x≤0.35, preferably 0.01≤x≤0.25.
Preferably, the R1For the substituted aryl of the alkyl of C3~C20, the alkoxy of C3~C20 or C7~C25；
Substituent group on the substituted aryl is one or both of alkyl and alkoxy of C1~C12 of C1~C12.
Preferably, the R2For the substituted aryl of the alkyl of C3~C25, the alkoxy of C3~C25 or C7~C25；
Substituent group on the substituted aryl is one or both of alkyl and alkoxy of C1~C21 of C1~C21.
Preferably, the R3For the substituted aryl of the alkyl of C3~C25, the alkoxy of C3~C25 or C7~C25；
Substituent group on the substituted aryl is one or both of alkyl and alkoxy of C1~C21 of C1~C21.
Preferably, the A is the aryl of C7~C30 containing electron-withdrawing group or the heteroaryl of C4~C25；
Hetero atom is one or more of nitrogen, oxygen, sulphur and boron in the heteroaryl.
Preferably, the A be formula (I-1-a), formula (I-1-b1), formula (I-1-b2), formula (I-1-b3), formula (I-1-c1),
Formula (I-1-c2), formula (I-1-d), formula (I-1-e), formula (I-1-f), formula (I-1-g), formula (I-1-h1), formula (I-1-h2), formula
(I-1-i1), formula (I-1-i2), formula (I-1-i3), formula (I-1-j1), formula (I-1-j2), formula (I-1-k), formula (I-1-l), formula
(I-1-m) or formula (I-1-n)；
Wherein, R4For the aryl of hydrogen, the alkyl of C1~C20 or C6~C30；R5For hydrogen, cyano, fluorine or trifluoromethyl.
Preferably, the polymer be formula (I-a), formula (I-b), formula (I-c), formula (I-d), formula (I-e), formula (I-f) or
Formula (I-g),
Wherein, n is 1~200.
The present invention also provides a kind of preparation methods of the polymer of main chain unit containing sulfone of the present invention, comprising:
There to be the copolymer compound of the compound of formula (II) structure, the compound of formula (III) structure and formula (IV) structure,
Obtain the polymer of structure shown in formula (I)；
Wherein, R1、R2、R3For the substituted aryl of the alkyl of C1~C30, the alkoxy of C1~C30 or C6~C35；
A is the aryl of C6~C50 containing electron-withdrawing group or the heteroaryl of C3~C45；
X is 0.001 < x < 0.5；
N is 1~200.
The present invention also provides a kind of organic electroluminescence devices, including first electrode, second electrode and first electrode
Organic layer between second electrode contains the polymer of main chain unit containing sulfone of the present invention in the organic layer.
Compared with prior art, the present invention provides a kind of polymer of main chain unit containing sulfone, have and tied shown in formula (I)
Structure, polymer provided by the invention pass through the ratio for selecting specific polymerized unit and the specific polymerized unit of selection, so that
Energy level difference between the first excited singlet state and the first excited triplet state of polymer provided by the invention is smaller, has thermal induction
Delayed fluorescence transmitting；And the polymer be applied to electroluminescent device when, the external quantum efficiency of obtained electroluminescent device
Height, and can effectively inhibit the efficiency roll-off of electroluminescent device.The experimental results showed that polymer preparation provided by the invention
The external quantum efficiency of electroluminescent device is 10000cd/m up to 11.9%, and in brightness2When, external quantum efficiency is
11.1%, make its efficiency roll-off only 7%.In addition, the preparation method of polymer provided by the invention is simple, and obtained polymer
The simple solution processing method preparation such as spin coating and inkjet printing can be used when being used to prepare device, enormously simplify electroluminescent hair
The preparation process of optical device.
Detailed description of the invention
Ultraviolet/the visible absorbance and room temperature fluorescence and low temperature of the toluene solution of polymer described in Fig. 1 embodiment of the present invention 1
Phosphorescence spectrum figure；
Ultraviolet/the visible absorbance and room temperature fluorescence and low temperature of the toluene solution of polymer described in Fig. 2 embodiment of the present invention 2
Phosphorescence spectrum figure；
Ultraviolet/the visible absorbance and room temperature fluorescence and low temperature of the toluene solution of polymer described in Fig. 3 embodiment of the present invention 3
Phosphorescence spectrum figure；
Ultraviolet/the visible absorbance and room temperature fluorescence and low temperature of the toluene solution of polymer described in Fig. 4 embodiment of the present invention 4
Phosphorescence spectrum figure；
Ultraviolet/the visible absorbance and room temperature fluorescence and low temperature of the toluene solution of polymer described in Fig. 5 embodiment of the present invention 5
Phosphorescence spectrum figure；
Ultraviolet/the visible absorbance and room temperature fluorescence and low temperature of the toluene solution of polymer described in Fig. 6 embodiment of the present invention 6
Phosphorescence spectrum figure；
Ultraviolet/the visible absorbance and room temperature fluorescence and low temperature of the toluene solution of polymer described in Fig. 7 embodiment of the present invention 7
Phosphorescence spectrum figure；
Ultraviolet/the visible absorbance and Room temperature PL spectrum figure of the film state of polymer described in Fig. 8 embodiment of the present invention 1；
Ultraviolet/the visible absorbance and Room temperature PL spectrum figure of the film state of polymer described in Fig. 9 embodiment of the present invention 2；
Ultraviolet/the visible absorbance and Room temperature PL spectrum figure of the film state of polymer described in Figure 10 embodiment of the present invention 3；
Ultraviolet/the visible absorbance and Room temperature PL spectrum figure of the film state of polymer described in Figure 11 embodiment of the present invention 4；
Ultraviolet/the visible absorbance and Room temperature PL spectrum figure of the film state of polymer described in Figure 12 embodiment of the present invention 5；
Ultraviolet/the visible absorbance and Room temperature PL spectrum figure of the film state of polymer described in Figure 13 embodiment of the present invention 6；
Ultraviolet/the visible absorbance and Room temperature PL spectrum figure of the film state of polymer described in Figure 14 embodiment of the present invention 7；
Figure 15 is the correlation of the current density versus voltage of the electroluminescent device of polymer described in the embodiment of the present invention 3
Figure；
Figure 16 is the correlation of the luminance against voltage characteristic of the electroluminescent device of polymer described in the embodiment of the present invention 3
Figure；
Figure 17 is the external quantum efficiency of the electroluminescent device of polymer described in the embodiment of the present invention 3 to current density spy
Property correlation figure；
Figure 18 is the electroluminescent light spectrogram of the electroluminescent device of polymer described in the embodiment of the present invention 3.
Specific embodiment
The present invention provides a kind of polymer of main chain unit containing sulfone, have structure shown in formula (I):
Wherein, R1、R2、R3The independent alkyl selected from C1~C30, the alkoxy of C1~C30 or the aryl of C6~C35；
A is the aryl of C6~C50 containing electron-withdrawing group or the heteroaryl of C3~C45；
X is 0.001 < x < 0.5；
N is 1~200.
According to the present invention, the R1The preferably substitution virtue of the alkyl of C3~C20, the alkoxy of C3~C20 or C8~C25
Base, the more preferably substituted aryl of the alkyl of C5~C15 or C10~C18, the most preferably alkyl or C12~C16 of C6~C10
Substituted aryl；Substituent group on the substituted aryl is preferably one of the alkyl of C1~C12 and the alkoxy of C1~C12
Or two kinds, more preferably one or both of the alkyl of C3~C10 and the alkoxy of C3~C10, most preferably C5~C8's
One or both of alkyl and the alkoxy of C5~C8；Specifically, the R1Preferably methyl, ethyl, propyl, isopropyl,
Butyl, isobutyl group, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 2- ethylhexyl, phenyl, 4- aminomethyl phenyl, 4- ethylo benzene
Base, 4- propyl phenyl, 4- butyl phenyl, 4- tert-butyl-phenyl, 4- hexyl phenyl, 4- methoxyphenyl, 4- ethoxyl phenenyl, 4-
Propoxyphenyl, 4- butoxy phenyl, 4- tert .- butoxyphenyl, 4- Hexyloxy-phenyl, 4- octane phenyl, 4- decane oxygroup
Phenyl or 4- dodecyloxy phenyl.
According to the present invention, the R2Preferably the alkyl of C3~C25, the alkoxy of C3~C25, C6~C20 it is unsubstituted
The substituted aryl of aryl or C7~C25, the more preferably alkyl of C6~C20, the alkoxy of C6~C20, C10~C15 do not take
For aryl or the substituted aryl of C10~C15；Substituent group on the substituted aryl is preferably the alkyl and C1~C21 of C1~C21
One or both of alkoxy, more preferably one or both of the alkyl of C4~C19 and the alkoxy of C4~C19,
Most preferably one or both of the alkyl of C6~C17 and the alkoxy of C6~C17；Specifically, the R2Preferably methyl,
Ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 2- ethylhexyl, n-octyl, just
Decyl, dodecyl, tridecyl, heptadecyl, phenyl, 4- aminomethyl phenyl, 4- ethylphenyl, 4- propyl phenyl, 4- butyl
Phenyl, 4- tert-butyl-phenyl, 4- hexyl phenyl, 4- methoxyphenyl, 4- ethoxyl phenenyl, 4- propoxyphenyl, 4- butoxy
Phenyl, 4- tert .- butoxyphenyl, 4- Hexyloxy-phenyl, 4- octane phenyl, 4- decane phenyl or 4- dodecyloxy
Phenyl.
According to the present invention, the R3Preferably the alkyl of C3~C25, the alkoxy of C3~C25, C6~C20 it is unsubstituted
The substituted aryl of aryl or C7~C25, the more preferably alkyl of C6~C20, the alkoxy of C6~C20, C10~C15 do not take
For aryl or the substituted aryl of C10~C15；Substituent group on the substituted aryl is preferably the alkyl and C1~C21 of C1~C21
One or both of alkoxy, more preferably one or both of the alkyl of C4~C19 and the alkoxy of C4~C19,
Most preferably one or both of the alkyl of C6~C17 and the alkoxy of C6~C17；Specifically, the R3Preferably methyl,
Ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 2- ethylhexyl, n-octyl, just
Decyl, dodecyl, tridecyl, heptadecyl, phenyl, 4- aminomethyl phenyl, 4- ethylphenyl, 4- propyl phenyl, 4- butyl
Phenyl, 4- tert-butyl-phenyl, 4- hexyl phenyl, 4- methoxyphenyl, 4- ethoxyl phenenyl, 4- propoxyphenyl, 4- butoxy
Phenyl, 4- tert .- butoxyphenyl, 4- Hexyloxy-phenyl, 4- octane phenyl, 4- decane phenyl or 4- dodecyloxy
Phenyl.
According to the present invention, the A preferably heteroaryl of the aryl of C7~C30 containing electron-withdrawing group or C4~C35, more
The preferably heteroaryl of the aryl of C10~C25 or C5~C25, the most preferably heteroaryl of the aryl of C12~C20 or C6~C15
Base；Wherein, hetero atom is one or more of nitrogen, oxygen, sulphur and boron in the heteroaryl；The electron-withdrawing group is preferably carbonyl
One or more of base, sulfuryl and cyano；More specifically, the A is formula (I-1-a), formula (I-1-b1), formula (I-1-
B2), formula (I-1-b3), formula (I-1-c1), formula (I-1-c2), formula (I-1-d), formula (I-1-e), formula (I-1-f), formula (I-1-g),
Formula (I-1-h1), formula (I-1-h2), formula (I-1-i1), formula (I-1-i2), formula (I-1-i3), formula (I-1-j1), formula (I-1-j2),
Formula (I-1-k), formula (I-1-l), formula (I-1-m) or formula (I-1-n)；
Wherein, the R4The aryl of alkyl, C6~C30, the substituted aryl of C7~C35 or C4~C35 selected from C1~C20
Substituted heteroaryl, the preferably substituted aryl of the alkyl of C3~C18 or C8~C25, the more preferably alkyl or C9 of C6~C15
The substituted aryl of~C12；Substituent group on the substituted aryl is preferably in the alkyl of C1~C20 and the alkoxy of C1~C20
One or two, more preferably one or both of the alkyl of C3~C15 and the alkoxy of C3~C15, most preferably C6
One or both of alkyl and the alkoxy of C6~C10 of~C10；Specifically, the R4Selected from methyl, ethyl, propyl, different
Propyl, butyl, isobutyl group, tert-butyl, n-pentyl, n-hexyl, n-heptyl, phenyl, 2- aminomethyl phenyl, 2- methoxyphenyl, 4-
Methoxyphenyl, naphthalene or anthryl；The R5Selected from hydrogen, cyano, fluorine or trifluoromethyl.
According to the present invention, the x is preferably 0.005≤x≤0.35, more preferably 0.01≤x≤0.25, most preferably
0.05≤x≤0.25, most preferably 0.08≤x≤0.20, most preferably 0.10≤x≤0.15.
According to the present invention, the n is preferably 2~150, and more preferably 3~100, most preferably 4~80.The polymer
Number-average molecular weight be preferably 2000~200000, more preferably 3000~100000, most preferably 5000~80000.
More specifically,
The polymer is formula (I-a), formula (I-b), formula (I-c), formula (I-d), formula (I-e), formula (I-f) or formula (I-g),
Wherein, n is 1~200.
The present invention also provides a kind of preparation methods of the polymer of main chain unit containing sulfone of the present invention, comprising:
There to be the copolymer compound of the compound of formula (II) structure, the compound of formula (III) structure and formula (IV) structure,
Obtain the polymer of structure shown in formula (I)；
Wherein, R1、R2、R3For the substituted aryl of the alkyl of C1~C30, the alkoxy of C1~C30 or C6~C35；
A is the aryl of C6~C50 containing electron-withdrawing group or the heteroaryl of C3~C45；
X is 0.001 < x < 0.5；
N is 1~200；
According to the present invention, the present invention will have the compound of formula (II) structure, the compound of formula (III) structure and formula (IV)
The copolymer compound of structure obtains the polymer of structure shown in formula (I)；Wherein, the R in structure1、R2、R3, A, x and n selection
Range is identical as the range of choice of aforementioned polymer；The present invention does not have particular/special requirement to the condition of copolymerization, well known in the art total
Poly- method, the catalyst of the copolymerization are preferably palladium catalyst, more preferably divalent palladium catalyst, and most preferably two (three
O-methyl-phenyl phosphine) palladium chloride catalyst.
The present invention also provides a kind of organic electroluminescence devices, including first electrode, second electrode and first electrode
Organic layer between second electrode, wherein contain the polymer of main chain unit containing sulfone of the present invention in the organic layer；
Organic layer in the electroluminescent device is one or more layers, when organic layer is multilayer, contains this hair at least one layer
The polymer of bright main chain unit containing sulfone.Contain main chain list containing sulfone of the present invention in electroluminescent device of the invention
The organic layer of the polymer of member is the preparation method is as follows: polymer of the present invention is dissolved in chloroform, toluene or chlorobenzene, rotation
Be coated in through polythiofuran derivative: the ito glass surface of poly styrene sulfonate (PEDOT:PSS) modification is prepared into organic layer；?
Device group is loaded onto, after the complete luminescent layer of spin coating can direct evaporation metal electrode, single layer device is made；It can also be in metal electrode and hair
Hole blocking layer or electron transfer layer are added between photosphere, constructs multilayer device.
The present invention provides a kind of polymer of main chain unit containing sulfone, have structure shown in formula (I), provided by the invention
Polymer is by selecting specific polymerized unit and selecting the ratio of specific polymerized unit
Example, so that the energy level difference between the first excited singlet state and the first excited triplet state of polymer provided by the invention
It is smaller, there is the transmitting of thermal induction delayed fluorescence；And the polymer is when being applied to electroluminescent device, obtained electroluminescent cell
The external quantum efficiency of part is high, and can effectively inhibit the efficiency roll-off of electroluminescent device.In addition, polymer provided by the invention
Preparation method it is simple, and the simple solution such as spin coating and inkjet printing can be used in when obtained polymer is used to prepare device
Processing method preparation, enormously simplifies the preparation process of electroluminescent device.
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1: the synthesis of polymer PC SAPTP25
Preparation flow is shown below:
Specific steps are as follows:
Two (4- (the bromo- 6- of 3- (2- ethyl) hexyl carbazole) phenyl) sulfones (139.6mg, 0.15mmol), 2,7- bis- bromo- 9,9-
Dihexyl -10- (4- (4,6- diphenyl -1,3,5-triazines -2- base) phenyl) -9,10- acridan (122.2mg,
0.15mmol), bis- pinacol borate -9- hydrogen carbazole (203.9mg, 0.3mmol) of 9- (4- (dodecyloxy) phenyl) -3,6-
It is added in Schlenk bottles of 100mL with two (three o-methyl-phenyl phosphines) palladium chlorides (2.4mg, 0.003mmol), substitutes gas 3
Secondary, the tetrahydrofuran (10mL) and deoxygenation aqueous potassium phosphate solution (2mL, 2M) of deoxygenation, 80 DEG C of back flow reactions are added in argon gas protection
12h；Reaction solution is added in the phenyl boric acid (69mg, 0.6mmol) for being dissolved in 1mL tetrahydrofuran, reacts 6h, then 1mL bromobenzene is added
Reaction solution reacts 6h；10mL toluene and the diethylamino bamic acid sodium (1.0g) for being dissolved in 10mL water are added to reaction solution
In, return stirring 12h；It is cooled to room temperature, chloroform extraction, anhydrous sodium sulfate is dry, and concentration instills in the methanol of stirring, analyses
Flocculent deposit out is filtered, dry, and acetone extraction for 24 hours, obtains yellow solid 0.285g, and yield 83% is to get arriving polymer
PCSAPTP25。
Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 18320, and molecular weight distributing index PDI is
2.3。
Embodiment 2: the synthesis of polymer PC SAPTP10
Preparation flow is shown below:
Specific steps are as follows:
Two (4- (the bromo- 6- of 3- (2- ethyl) hexyl carbazole) phenyl) sulfones (223.4mg, 0.24mmol), 2,7- bis- bromo- 9,9-
Dihexyl -10- (4- (4,6- diphenyl -1,3,5-triazines -2- base) phenyl) -9,10- acridan (49.0mg,
0.06mmol), bis- pinacol borate -9- hydrogen of 9- (4- (dodecyloxy) phenyl) -3,6--carbazole (203.9mg,
0.3mmol) it is added in Schlenk bottles of 100mL with two (three o-methyl-phenyl phosphines) palladium chlorides (2.4mg, 0.003mmol),
It substitutes gas 3 times, the tetrahydrofuran (10mL) and deoxygenation aqueous potassium phosphate solution (2mL, 2M) of deoxygenation is added in argon gas protection, and 80 DEG C are returned
Stream reaction 12h；Reaction solution is added in the phenyl boric acid (69mg, 0.6mmol) that 1mL tetrahydrofuran will be dissolved in, and reacts 6h, then by 1mL bromine
Reaction solution is added in benzene, reacts 6h；10mL toluene and the diethylamino bamic acid sodium (1.0g) for being dissolved in 10mL water are added to
In reaction solution, return stirring 12h；It is cooled to room temperature, chloroform extraction, anhydrous sodium sulfate is dry, and concentration instills the methanol of stirring
In, flocculent deposit is precipitated, filters, dry, acetone extraction for 24 hours, obtains yellow solid 0.291g, and yield 82% is to get to polymerization
Object PCSAPTP10.
Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 17450, and molecular weight distributing index PDI is
2.4。
Embodiment 3: the synthesis of polymer PC SAPTP5
Preparation flow is shown below:
Specific steps are as follows:
Two (4- (the bromo- 6- of 3- (2- ethyl) hexyl carbazole) phenyl) sulfones (251.4mg, 0.27mmol), 2,7- bis- bromo- 9,9-
Dihexyl -10- (4- (4,6- diphenyl -1,3,5-triazines -2- base) phenyl) -9,10- acridan (24.4mg,
0.03mmol), bis- pinacol borate -9- hydrogen of 9- (4- (dodecyloxy) phenyl) -3,6--carbazole (203.9mg,
0.3mmol) it is added in Schlenk bottles of 100mL with two (three o-methyl-phenyl phosphines) palladium chlorides (2.4mg, 0.003mmol),
It substitutes gas 3 times, the tetrahydrofuran (10mL) and deoxygenation aqueous potassium phosphate solution (2mL, 2M) of deoxygenation is added in argon gas protection, and 80 DEG C are returned
Stream reaction 12h；Reaction solution is added in the phenyl boric acid (69mg, 0.6mmol) that 1mL tetrahydrofuran will be dissolved in, and reacts 6h, then by 1mL bromine
Reaction solution is added in benzene, reacts 6h；10mL toluene and the diethylamino bamic acid sodium (1.0g) for being dissolved in 10mL water are added to
In reaction solution, return stirring 12h；It is cooled to room temperature, chloroform extraction, anhydrous sodium sulfate is dry, and concentration instills the methanol of stirring
In, flocculent deposit is precipitated, filters, dry, acetone extraction for 24 hours, obtains yellow solid 0.298g, and yield 84% is to get to polymerization
Object PCSAPTP5.
Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 15670, and molecular weight distributing index PDI is
2.2。
Embodiment 4: the synthesis of polymer PC SAPTP1
Preparation flow is shown below:
Specific steps are as follows:
Two (4- (the bromo- 6- of 3- (2- ethyl) hexyl carbazole) phenyl) sulfones (273.7mg, 0.294mmol), 2,7- bis- bromo- 9,
9- dihexyl -10- (4- (4,6- diphenyl -1,3,5-triazines -2- base) phenyl) -9,10- acridan (4.9mg,
0.006mmol), bis- pinacol borate -9- hydrogen of 9- (4- (dodecyloxy) phenyl) -3,6--carbazole (203.9mg,
0.3mmol and two (three o-methyl-phenyl phosphines) palladium chlorides (2.4mg, 0.003mmol) are added in Schlenk bottles of 100mL,
It substitutes gas 3 times, the tetrahydrofuran (10mL) and deoxygenation aqueous potassium phosphate solution (2mL, 2M) of deoxygenation is added in argon gas protection, and 80 DEG C are returned
Stream reaction 12h；Reaction solution is added in the phenyl boric acid (69mg, 0.6mmol) that 1mL tetrahydrofuran will be dissolved in, and reacts 6h, then by 1mL bromine
Reaction solution is added in benzene, reacts 6h；10mL toluene and the diethylamino bamic acid sodium (1.0g) for being dissolved in 10mL water are added to
In reaction solution, return stirring 12h；It is cooled to room temperature, chloroform extraction, anhydrous sodium sulfate is dry, and concentration instills the methanol of stirring
In, flocculent deposit is precipitated, filters, dry, acetone extraction for 24 hours, obtains yellow solid 0.295g, and yield 82% is to get to polymerization
Object PCSAPTP1.
Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 15690, and molecular weight distributing index PDI is
2.2。
Embodiment 5: the synthesis of polymer PC SAPTP0.5
Preparation flow is shown below:
Specific steps are as follows:
Two (4- (the bromo- 6- of 3- (2- ethyl) hexyl carbazole) phenyl) sulfones (276.5mg, 0.297mmol), 2,7- bis- bromo- 9,
9- dihexyl -10- (4- (4,6- diphenyl -1,3,5-triazines -2- base) phenyl) -9,10- acridan (2.4mg,
0.003mmol), bis- pinacol borate -9- hydrogen of 9- (4- (dodecyloxy) phenyl) -3,6--carbazole (203.9mg,
0.3mmol) it is added in Schlenk bottles of 100mL with two (three o-methyl-phenyl phosphines) palladium chlorides (2.4mg, 0.003mmol),
It substitutes gas 3 times, the tetrahydrofuran (10mL) and deoxygenation aqueous potassium phosphate solution (2mL, 2M) of deoxygenation is added in argon gas protection, and 80 DEG C are returned
Stream reaction 12h；Reaction solution is added in the phenyl boric acid (69mg, 0.6mmol) that 1mL tetrahydrofuran will be dissolved in, and reacts 6h, then by 1mL bromine
Reaction solution is added in benzene, reacts 6h；10mL toluene and the diethylamino bamic acid sodium (1.0g) for being dissolved in 10mL water are added to
In reaction solution, return stirring 12h；It is cooled to room temperature, chloroform extraction, anhydrous sodium sulfate is dry, and concentration instills the methanol of stirring
In, flocculent deposit is precipitated, filters, dry, acetone extraction for 24 hours, obtains yellow solid 0.294g, and yield 82% is to get to polymerization
Object PCSAPTP0.5.
Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 15370, and molecular weight distributing index PDI is
2.2。
Embodiment 6: the synthesis of polymer PC SAPTT5
Preparation flow is shown below:
Specific steps are as follows:
Two (4- (the bromo- 6- of 3- (2- ethyl) hexyl carbazole) phenyl) sulfones (251.4mg, 0.27mmol), 2,7- bis- bromo- 9,9-
Dihexyl -10- (6- (4,6- di-t-butyls -1,3,5-triazines)) phenyl -9,10- acridan (23.2mg, 0.03mmol), 9-
Two pinacol borate -9- hydrogen of (4- (dodecyloxy) phenyl) -3,6--carbazole (203.9mg, 0.3mmol) and two (three adjacent first
Base Phenylphosphine) palladium chloride (2.4mg, 0.003mmol) is added in Schlenk bottles of 100mL, substitutes gas 3 times, argon gas protection,
The tetrahydrofuran (10mL) and deoxygenation aqueous potassium phosphate solution (2mL, 2M) of deoxygenation, 80 DEG C of back flow reaction 12h are added；1mL will be dissolved in
Reaction solution is added in the phenyl boric acid (69mg, 0.6mmol) of tetrahydrofuran, reacts 6h, then reaction solution is added in 1mL bromobenzene, reacts 6h；
10mL toluene and the diethylamino bamic acid sodium (1.0g) for being dissolved in 10mL water are added in reaction solution, return stirring 12h；
It is cooled to room temperature, chloroform extraction, anhydrous sodium sulfate is dry, and concentration instills in the methanol of stirring, and flocculent deposit is precipitated, it filters,
Dry, acetone extraction for 24 hours, obtains green solid 0.295g, and yield 84% is to get arriving polymer PC SAPTT5.
Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 15870, and molecular weight distributing index PDI is
2.2。
Embodiment 7: the synthesis of polymer PC SAPTN5
Preparation flow is shown below:
Specific steps are as follows:
Two (4- (the bromo- 6- of 3- (2- ethyl) hexyl carbazole) phenyl) sulfones (251.4mg, 0.27mmol), 2- (4- (2,7- bis-
Bromo- -10 (9H)-yl of 9,9- dihexyl acridine) phenyl) thianthrene -5,5,10,10- tetra- oxygen (25.9mg, 0.03mmol), 9- (4-
(dodecyloxy) phenyl) two pinacol borate -9- hydrogen of -3,6--carbazole (203.9mg, 0.3mmol) and two (three adjacent methyl
Phenylphosphine) palladium chloride (2.4mg, 0.003mmol) is added in Schlenk bottles of 100mL, substitutes gas 3 times, and argon gas protection adds
Enter the tetrahydrofuran (10mL) and deoxygenation aqueous potassium phosphate solution (2mL, 2M) of deoxygenation, 80 DEG C of back flow reaction 12h；1mL tetra- will be dissolved in
Reaction solution is added in the phenyl boric acid (69mg, 0.6mmol) of hydrogen furans, reacts 6h, then reaction solution is added in 1mL bromobenzene, reacts 6h；It will
10mL toluene and the diethylamino bamic acid sodium (1.0g) for being dissolved in 10mL water are added in reaction solution, return stirring 12h；It is cold
To room temperature, chloroform extraction, anhydrous sodium sulfate is dry, and concentration instills in the methanol of stirring, and flocculent deposit is precipitated, and filters, and does
Dry, acetone extraction for 24 hours, obtains orange solids 0.298g, and yield 83% is to get arriving polymer PC SAPTN5.
Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 15370, and molecular weight distributing index PDI is
2.2。
Embodiment 8
Luminescent properties test is carried out to the performance for the polymer that the embodiment of the present invention 1~7 obtains.It is specifically shown in Fig. 1~Figure 14,
Ultraviolet/the visible absorbance and room temperature fluorescence and antenna effect spectrum of the toluene solution of polymer described in Fig. 1 embodiment of the present invention 1
Figure；Ultraviolet/the visible absorbance and room temperature fluorescence and antenna effect of the toluene solution of polymer described in Fig. 2 embodiment of the present invention 2
Spectrogram；Ultraviolet/the visible absorbance and room temperature fluorescence and low temperature of the toluene solution of polymer described in Fig. 3 embodiment of the present invention 3
Phosphorescence spectrum figure；Ultraviolet/the visible absorbance and room temperature fluorescence of the toluene solution of polymer described in Fig. 4 embodiment of the present invention 4 and
Antenna effect spectrogram；Ultraviolet/the visible absorbance and room temperature of the toluene solution of polymer described in Fig. 5 embodiment of the present invention 5 are glimmering
Light and antenna effect spectrogram；Ultraviolet/visible absorbance of the toluene solution of polymer described in Fig. 6 embodiment of the present invention 6 and room
Warm fluorescence and antenna effect spectrogram；Ultraviolet/visible absorbance of the toluene solution of polymer described in Fig. 7 embodiment of the present invention 7
And room temperature fluorescence and antenna effect spectrogram；Ultraviolet/visible absorbance of the film state of polymer described in Fig. 8 embodiment of the present invention 1
And Room temperature PL spectrum figure；Ultraviolet/the visible absorbance and room temperature fluorescence of the film state of polymer described in Fig. 9 embodiment of the present invention 2
Spectrogram；Ultraviolet/the visible absorbance and Room temperature PL spectrum figure of the film state of polymer described in Figure 10 embodiment of the present invention 3；Figure
Ultraviolet/the visible absorbance and Room temperature PL spectrum figure of the film state of polymer described in 11 embodiment of the present invention 4；Figure 12 present invention is real
Apply the ultraviolet/visible absorbance and Room temperature PL spectrum figure of the film state of polymer described in example 5；Described in Figure 13 embodiment of the present invention 6
Polymer film state ultraviolet/visible absorbance and Room temperature PL spectrum figure；Polymer described in Figure 14 embodiment of the present invention 7
Ultraviolet/the visible absorbance and Room temperature PL spectrum figure of film state.
Testing result is as shown in table 1, and table 1 is that the luminescent properties of polymer described in the embodiment of the present invention 1~7 test knot
Fruit.
Table 1 is the luminescent properties test result of polymer described in the embodiment of the present invention 1~7
| Polymer | S1/eV | T1/eV | ΔEST/eV | PLQY |
| Embodiment 1 | 2.57 | 2.51 | 0.06 | 0.90 |
| Embodiment 2 | 2.58 | 2.51 | 0.07 | 0.95 |
| Embodiment 3 | 2.59 | 2.51 | 0.07 | 1.00 |
| Embodiment 4 | 2.59 | 2.51 | 0.08 | 0.85 |
| Embodiment 5 | 2.59 | 2.51 | 0.08 | 0.56 |
| Embodiment 6 | 2.66 | 2.58 | 0.08 | 0.79 |
| Embodiment 7 | 2.48 | 2.39 | 0.09 | 0.76 |
Wherein, S1Energy level obtains in the Room temperature PL spectrum figure by the toluene solution of polymer, T1Energy level by polymer first
It is obtained in the 77K phosphorescence spectrum figure of benzole soln.PLQY is that the film aspect product of polymer are measured in an argon atmosphere by integrating sphere
Absolute luminescence quantum efficiency.Need specified otherwise: we from embodiment 7 while can obtain the of main polymer chain
One excited singlet state and the first excited triplet state, value are 3.19eV and 2.69eV respectively, illustrate to introduce in main polymer chain
The first excited triplet state (the first excited triplet state of polycarbazole is 2.60eV) of polymer can be effectively improved after sulfone unit,
So that the energy transfer of main body to object is more effective.
As can be seen from Table 1, the first excited singlet state of the polymer of the series and the first excited triplet state energy level difference compared with
Small (Δ EST< 0.1eV), efficiently realize that thermal induction delayed fluorescence emits so as to ground.Meanwhile it can from Examples 1 to 5 comparison
With discovery: the luminous quantum efficiency of polymer is different with identical doping unit ratio and apparent variation occurs, illustrates to adjust ratio
Example can effectively inhibit the interaction between luminescence unit to improve luminous efficiency.
Embodiment 9
Electroluminescent device is prepared using the polymer described in the embodiment of the present invention 3 with formula (I) structure.Device architecture
Are as follows: ITO/PEDOT:PSS (30nm)/EML (35nm)/TmPyPB (20nm)/LiF (1nm)/Al (100nm).The assembling work of device
Skill is as follows: in the ITO conductive glass surface spin coating conducting polymer polythiofuran derivative of pre-cleaning: poly styrene sulfonate
(PEDOT:PSS) solution obtains the film of 30nm thickness with 3000 revs/min of speed, is put into baking oven in 120 degree of lower heating 30
Natural cooling after minute.Polymer of the present invention with formula (I) structure is dissolved in toluene, the molten of 10mg/mL is made into
Liquid is spin-coated on PEDOT:PSS using 1200 revs/min of speed as luminescent layer (EML), film thickness by step instrument measure for
35nm.After 100 degree of lower annealing, 1,3,5- tri- [(3- pyridyl group) -3- phenyl] benzene of 20nm thickness are deposited on the light-emitting layer
(TmPyPB) it is used as electron transfer layer, upper LiF (1nm)/Al (100nm) electrode is then deposited on the electron transport layer, is deposited
Thickness and deposition rate be monitored and detected by quartz oscillator.It is within cooling 30 minutes after the completion of electrode vapor deposition
It can be taken off device to be tested.As a result as shown in Figure 15~Figure 18, Figure 15 is the electroluminescent of polymer described in the embodiment of the present invention 3
The related figure of the current density versus voltage of luminescent device；Figure 16 is the electroluminescent cell of polymer described in the embodiment of the present invention 3
The related figure of the luminance against voltage characteristic of part；Figure 17 is the outer of the electroluminescent device of polymer described in the embodiment of the present invention 3
Quantum efficiency against current density feature correlation figure；Figure 18 is the electroluminescent device of polymer described in the embodiment of the present invention 3
Electroluminescent light spectrogram.Testing result is shown in Table 2, and table 2 is the electroluminescent device performance of polymer described in the embodiment of the present invention 3
Test result.
Table 2 is the electroluminescent device performance of polymer described in the embodiment of the present invention 3
| Polymer | CE(cd/A) | PE(lm/W) | EQE (%) |
| Maximum value | 34.6 | 17.4 | 11.9 |
| Brightness is in 10000cd/m2When | 32.0 | 14.5 | 11.1 |
Wherein, CE is the current efficiency of electroluminescent device；PE is the power efficiency of electroluminescent device；EQE is electroluminescent
The external quantum efficiency of luminescent device；From Table 2, it can be seen that the efficiency rolling of the luminescent device of polymer preparation provided by the invention
It reduces and high-efficient.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (11)
1. a kind of polymer of main chain unit containing sulfone has structure shown in formula (I):
Wherein, R1、R2、R3The independent alkyl selected from C1~C30, the alkoxy of C1~C30 or the aryl of C6~C35；
A is the aryl of C6~C50 containing electron-withdrawing group or the heteroaryl of C3~C45；
X is 0.001 < x < 0.5；
N is 1~200.
2. polymer according to claim 1, which is characterized in that the x is 0.005≤x≤0.35.
3. polymer according to claim 1, which is characterized in that the x is 0.01≤x≤0.25.
4. polymer according to claim 1, which is characterized in that the R1For the alkyl of C3~C20, the alcoxyl of C3~C20
The substituted aryl of base or C7~C25；
Substituent group on the substituted aryl is one or both of alkyl and alkoxy of C1~C12 of C1~C12.
5. polymer according to claim 1, which is characterized in that the R2For the alkyl of C3~C25, the alcoxyl of C3~C25
The substituted aryl of base or C7~C25；
Substituent group on the substituted aryl is one or both of alkyl and alkoxy of C1~C21 of C1~C21.
6. polymer according to claim 1, which is characterized in that the R3For the alkyl of C3~C25, the alcoxyl of C3~C25
The substituted aryl of base or C7~C25；
Substituent group on the substituted aryl is one or both of alkyl and alkoxy of C1~C21 of C1~C21.
7. polymer according to claim 1, which is characterized in that the A is the aryl of C7~C30 containing electron-withdrawing group
Or the heteroaryl of C4~C25；
Hetero atom is one or more of nitrogen, oxygen, sulphur and boron in the heteroaryl.
8. polymer according to claim 1, which is characterized in that the A is formula (I-1-a), formula (I-1-b1), formula (I-
1-b2), formula (I-1-b3), formula (I-1-c1), formula (I-1-c2), formula (I-1-d), formula (I-1-e), formula (I-1-f), formula (I-1-
G), formula (I-1-h1), formula (I-1-h2), formula (I-1-i1), formula (I-1-i2), formula (I-1-i3), formula (I-1-j1), formula (I-1-
J2), formula (I-1-k), formula (I-1-l), formula (I-1-m) or formula (I-1-n)；
Wherein, R4For the aryl of hydrogen, the alkyl of C1~C20 or C6~C30；R5For hydrogen, cyano, fluorine or trifluoromethyl.
9. polymer according to claim 1, which is characterized in that the polymer is formula (I-a), formula (I-b), formula (I-
C), formula (I-d), formula (I-e), formula (I-f) or formula (I-g),
Wherein, n is 1~200.
10. a kind of preparation method of the polymer of main chain unit containing sulfone described in claim 1, comprising:
There to be the copolymer compound of the compound of formula (II) structure, the compound of formula (III) structure and formula (IV) structure, obtain
The polymer of structure shown in formula (I)；
Wherein, R1、R2、R3For the substituted aryl of the alkyl of C1~C30, the alkoxy of C1~C30 or C6~C35；
A is the aryl of C6~C50 containing electron-withdrawing group or the heteroaryl of C3~C45；
X is 0.001 < x < 0.5；
N is 1~200.
11. a kind of organic electroluminescence device, including between first electrode, second electrode and first electrode and second electrode
Organic layer, which is characterized in that poly- containing main chain unit containing sulfone described in any one of claim 1 to 9 in the organic layer
Close object.
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| WO2014128945A1 (en) * | 2013-02-25 | 2014-08-28 | 株式会社 日立製作所 | Organic light-emitting material and organic light-emitting element |
| CN105038764A (en) * | 2015-06-17 | 2015-11-11 | 中山大学 | Asymmetrical thermal-activation-delayed aggregation-induced emission material based on diphenyl sulfone phenoxazine, as well as synthesis method and application of material |
| KR20160064956A (en) * | 2014-11-28 | 2016-06-08 | 엘지디스플레이 주식회사 | Delayed Fluorescence compound, and Organic light emitting diode device and Display device using the same |
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| CN103483332A (en) * | 2013-09-11 | 2014-01-01 | 中山大学 | Novel piezoluminescence material with thermal activation delayed fluorescence and aggregation-induced emission properties and synthetic method and application of novel piezoluminescence material |
| KR20160064956A (en) * | 2014-11-28 | 2016-06-08 | 엘지디스플레이 주식회사 | Delayed Fluorescence compound, and Organic light emitting diode device and Display device using the same |
| CN105038764A (en) * | 2015-06-17 | 2015-11-11 | 中山大学 | Asymmetrical thermal-activation-delayed aggregation-induced emission material based on diphenyl sulfone phenoxazine, as well as synthesis method and application of material |
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