CN108383980A - A kind of thermal induction delayed fluorescence polymer and preparation method thereof of main chain silicon containing diphenyl and carbazole unit - Google Patents
A kind of thermal induction delayed fluorescence polymer and preparation method thereof of main chain silicon containing diphenyl and carbazole unit Download PDFInfo
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Abstract
The present invention provides the thermal induction delayed fluorescence polymer and preparation method thereof of main chain silicon containing diphenyl and carbazole unit with formula (I) structure, by detecting the energy gap very little between the first singlet excited and the first triplet excited state that find polymer of the present invention, there is thermal induction delayed fluorescence emission characteristic.The introducing of diphenyl silicon and carbazole unit makes polymer have high triplet energy level, can effectively shield the quenching effect between luminescence unit, so that the polymer has efficient thermal induction delayed fluorescence emission characteristic.When the polymer is applied to electroluminescent, it is expected to realize Full color and realizes the high-efficiency fluorescence transmitting under pure membrane stage；In addition, the preparation method of polymer of the present invention is simple, and such polymer is expected to be applied to the electroluminescent device of solution processing.
Description
Technical field
The invention belongs to luminous organic material fields more particularly to the heat of a kind of main chain silicon containing diphenyl and carbazole unit to lure
Lead delayed fluorescence polymer and preparation method thereof.
Background technology
Small molecular organic compounds with thermal induction delayed fluorescence emission characteristic are swashed due to that can efficiently use triplet
Son, and it is widely used in organic electroluminescence device.Such as document Nature, 2012,492,234；Nature Photon,
2014,8,326；Adv.Mater.2015,27,2096；CN201310413578；CN201310733731；
CN201310739678 and CN201080055404 etc., which reports the small molecule with thermal induction delayed fluorescence emission characteristic, to be had
The electroluminescent properties of machine compound.Using this kind of compound be luminescent materials electroluminescent device can with by a huge sum of money
Belong to the device performance that compound phosphor material makes to compare favourably, however, when micromolecular compound is applied to luminescent device, often need
It to be made by way of vapor deposition, complex process, to make cost increase, be unfavorable for the following commercial applications.
Relatively, when polymerization species luminescent material is applied to luminescent device, since spin coating and inkjet printing etc. can be used
Simple solution processing method is easily achieved large scale and shows and the outstanding features such as Flexible Displays, thus by academia and production
The extensive concern of industry and research.But traditional polymer luminescent material is difficult to realize thermal induction delayed fluorescence, is measured outside device
Sub- efficiency only up to reach 5~6%, can not meet practical requirement.In the recent period, our seminar's designs have synthesized a series of
" main chain-donor/side group-receptor " type polymer, i.e. polymer have main chain be donor monomer, connection side group be receptor unit
Molecular structure, realize the transmitting of efficient thermal induction delayed fluorescence, the wherein electroluminescent hair of polymer P APTC solution processing and fabricating
Optical device external quantum efficiency is up to 12.6% (Macromolecules 2016,49,4373).On this basis, pass through " main chain
The thinking of doping ", chromophore is connected in polycarbazole main chain, its content is adjusted and is quenched with inhibition concentration, significantly improve hair
Light efficiency at the same reduce electroluminescent device efficiency roll-off (J.Mater.Chem. C, 2018,6,568；
Adv.Funct.Mater.2018,1706916).Nevertheless, the triplet energy level of presently disclosed polymer is still relatively low,
It is difficult to realize Full color, while affecting making full use of for the triplet exciton that electricity generates.Therefore, polymerization species heat is improved to lure
The triplet energy level for leading delayed fluorescence material be it is current be badly in need of solving key technical problem (J.Am.Chem.Soc., 2017,
139,11073)。
Invention content
In view of this, technical problem to be solved by the present invention lies in a kind of main chain silicon containing diphenyl of offer and carbazole units
Thermal induction delayed fluorescence polymer and preparation method thereof, polymer provided by the invention has high triplet energy level, and makes
Preparation Method is simple.
The present invention provides the thermal induction delayed fluorescence polymer of a kind of main chain silicon containing diphenyl and carbazole unit, have formula
(I) structure shown in,
Wherein, R1、R2Independently selected from the alkyl of C1~C20 or the aromatic radical of C6~C30；
A is the fluorescent dye unit containing electron donor/receptor distorted-structure unit；
X is 0 x≤0.6 ＜；
N is 2~200.
Preferably, the R1Alkyl selected from C3~C15, C6~C30 without substituent group aromatic radical or be connected with C1~
The aromatic radical of the alkyl of C20 and/or the alkoxy of C1~C20.
Preferably, the R1Selected from methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, phenyl, p-methylphenyl, pyrrole
Pyridine.
Preferably, the R2Alkyl selected from C1~C20, C6~C30 without substituent group aromatic radical or be connected with C1~
The aromatic radical of the alkyl of C20 and/or the alkoxy of C1~C20.
Preferably, the R2Selected from hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,
Myristyl, pentadecyl, cetyl, heptadecyl, butyl phenyl, hexyl phenyl, octyl phenyl, decyl phenyl, 11
Alkyl phenyl, tridecyl phenyl, heptadecyl phenyl, Hexyloxy-phenyl, octyloxyphenyl, decyloxy phenyl, hendecane oxygen
Base phenyl, tridecane epoxide phenyl, heptadecane epoxide phenyl.
Preferably, the A is the fluorescence for connecting electrophilic unit by electron unit of carbazole, acridine or diphenylamines and obtaining
Dye units.
Preferably, the A is formula (II -1-a), formula (II -1-b), formula (II -1-c), formula (II -1-d), formula (II -1-
E), formula (II -1-f), formula (II -1-g), formula (II -1-h), formula (II -1-i), formula (II -1-j), formula (II -1-k), formula (II -
1-l), formula (II -1-m), formula (II -1-n), formula (II -1-o), formula (II -2-a), formula (II -2-b), formula (II -2-c), formula (II -
2-d), formula (II -2-e), formula (II -2-f), formula (II -2-g), formula (II -2-h), formula (II -2-i), formula (II -2-j), formula (II -
2-k), formula (II -2-l), formula (II -2-m), formula (II -2-n), formula (II -2-o)), formula (II -3-a), formula (II -3-b), formula
(II -3-c), formula (II -3-d), formula (II -3-e), formula (II -3-f), formula (II -3-g), formula (II -3-h), formula (II -3-i) or
Formula (II -3-j),
Wherein, R3、R5Independently selected from the alkyl of C1~C20 or the aromatic radical of C6~C30；M is 0 or 1；Y is oxygen atom
Or sulphur atom.
Preferably, the x is 0.002≤x≤0.5.
Preferably, formula (I) compound be specially formula (I-1), formula (I-2), formula (I-3), formula (I-4), formula (I-5),
Formula (I-6), formula (I-7), formula (I-8), formula (I-9), formula (I-10), formula (I-11), formula (I-12), formula (I-13) or formula (I-
14)。
The present invention also provides a kind of thermal induction of main chain silicon containing diphenyl of the present invention and carbazole unit delay is glimmering
The preparation method of photopolymer, including：
Monomer with formula (III), formula (IV) and formula (V) structure is copolymerized, polymer shown in formula (I) is obtained,
Wherein, R1、R2Independently selected from the alkyl of C1~C20 or the aromatic radical of C6~C30；
A is the fluorescent dye unit containing electron donor/receptor distorted-structure unit；
X is 0 x≤0.6 ＜；
N is 2~200.
Compared with prior art, main chain silicon containing diphenyl and carbazole unit provided by the invention with formula (I) structure
Thermal induction delayed fluorescence polymer, the experimental results showed that, which not only has efficient thermal induction delayed fluorescence emissivity
Matter, and there is high triplet energy level, so that when the polymer is applied to electroluminescent, it can realize Full color；This
Outside, the preparation method of polymer of the present invention is simple, it is easy to accomplish industrialized production.
Description of the drawings
Fig. 1 is the film state emission spectrum of the polymer of Examples 1 to 7；
Fig. 2 is the film state emission spectrum of the polymer of embodiment 8~14；
Fig. 3 is absorption, fluorescence and the antenna effect spectrum of the polymer toluene solution of comparative example 1.
Specific implementation mode
The present invention provides the thermal induction delayed fluorescence polymer of a kind of main chain silicon containing diphenyl and carbazole unit, have formula
(I) structure shown in,
Wherein, R1、R2Independently selected from the alkyl of C1~C20 or the aromatic radical of C6~C30；
A is the fluorescent dye unit containing electron donor/receptor distorted-structure unit；
X is 0 x≤0.6 ＜；
N is 2~200.
In the present invention, the R1Preferably the alkyl of C1~C4, C6~C30 without substituent group aromatic radical or be connected with
It is the aromatic radical of the alkyl of C1~C20 and/or the alkoxy of C1~C20, more preferably methyl, ethyl, propyl, butyl, phenyl, right
Tolyl, to methoxybenzene, pyridine.
In the present invention, the R2Preferably the alkyl of C6~C20, be connected with the alkyl of C4~C20 and/or the alkane of C4~C20
The aromatic radical of oxygroup, more preferably hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, 14
Alkyl, pentadecyl, cetyl, heptadecyl, butyl phenyl, hexyl phenyl, octyl phenyl, decyl phenyl, undecyl
Phenyl, tridecyl phenyl, heptadecyl phenyl, Hexyloxy-phenyl, octyloxyphenyl, decyloxy phenyl, hendecane epoxide benzene
Base, tridecane epoxide phenyl, heptadecane epoxide phenyl.
In the present invention, the A preferably connects electrophilic unit as electron unit using carbazole, acridine or diphenylamines and obtains
Fluorescent dye unit, more preferably formula (II -1-a), formula (II -1-b), formula (II -1-c), formula (II -1-d), formula (II -1-
E), formula (II -1-f), formula (II -1-g), formula (II -1-h), formula (II -1-i), formula (II -1-j), formula (II -1-k), formula (II -1-
L), formula (II -1-m), formula (II -1-n), formula (II -1-o), formula (II -2-a), formula (II -2-b), formula (II -2-c), formula (II -
2-d), formula (II -2-e), formula (II -2-f), formula (II -2-g), formula (II -2-h), formula (II -2-i), formula (II -2-j), formula
(II -2-k), formula (II -2-l), formula (II -2-m), formula (II -2-n), formula (II -2-o)), formula (II -3-a), formula (II -3-b),
Formula (II -3-c), formula (II -3-d), formula (II -3-e), formula (II -3-f), formula (II -3-g), formula (II -3-h), formula (II -3-i)
Or formula (II -3-j),
Wherein, R3、R5Independently selected from the alkyl of C1~C20 or the aromatic radical of C6~C30；M is 0 or 1；Y is oxygen atom
Or sulphur atom.Specifically, the R3Preferably the alkyl of C1~C8, C6~C30 without substituent group aromatic radical or be connected with C1
The aromatic radical of the alkyl of~C20 and/or the alkoxy of C1~C20, more preferably methyl, ethyl, propyl, normal-butyl, tertiary fourth
Base, amyl, hexyl, octyl, phenyl, butyl phenyl, hexyl phenyl, octyl phenyl, decyl phenyl, undecyl phenyl, own oxygen
Base phenyl, octyloxyphenyl, decyloxy phenyl, hendecane epoxide phenyl；The R5Preferably the alkyl of C1~C8, without substitution
The aromatic radical of C6~C30 of base or the aromatic radical for being connected with the alkyl of C1~C20 and/or the alkoxy of C1~C20, more preferably first
Base, ethyl, propyl, normal-butyl, tertiary butyl, amyl, hexyl, octyl, phenyl, aminomethyl phenyl, butyl phenyl, hexyl phenyl, first
Phenyl, butoxy phenyl.
In addition, symbolIt is the link position of substituent group and agent structure for connecting key.
In the present invention, the x is preferably 0.002≤x≤0.60, more preferably 0.005≤x≤0.50, most preferably
0.01≤x≤0.40, most preferably 0.05≤x≤0.35, most preferably 0.1≤x≤0.3.
More specifically, formula (I) compound is specially formula (I-1), formula (I-2), formula (I-3), formula (I-4), formula (I-
5), formula (I-6), formula (I-7), formula (I-8), formula (I-9), formula (I-10), formula (I-11), formula (I-12), formula (I-13) or formula (I-
14),
The present invention also provides a kind of thermal induction of main chain silicon containing diphenyl described in claim 1 and carbazole unit delays
The preparation method of fluorescent polymer, including：
Monomer with formula (III), formula (IV) and formula (V) structure is copolymerized, polymer shown in formula (I) is obtained,
Wherein, R1、R2Independently selected from the alkyl of C1~C20 or the aromatic radical of C6~C30；
A is the fluorescent dye unit containing electron donor/receptor distorted-structure unit；
X is 0 x≤0.6 ＜；
N is 2~200.
According to the present invention, the monomer with formula (III), formula (IV) and formula (V) structure is copolymerized by the present invention, obtains formula (I)
Shown in polymer, wherein the present invention does not have particular/special requirement, copolymerization process well known in the art, institute to the condition of copolymerization
The catalyst for stating copolymerization is preferably palladium catalyst, more preferably tris(dibenzylideneacetone) dipalladium and 2- dicyclohexyl phosphine -2',
6'- dimethoxy-biphenyls.
The thermal induction delayed fluorescence of main chain silicon containing diphenyl and carbazole unit provided by the invention with formula (I) structure is poly-
Object is closed, the experimental results showed that, the energy gap between the first singlet excited and the first triplet excited state of the polymer light-emitting unit
Very little has efficient thermal induction delayed fluorescence emission characteristic.The introducing of diphenyl silicon and carbazole unit makes main polymer chain have
High triplet energy level can effectively shield the quenching effect between luminescence unit, so that the polymer has efficient heat
Induce delayed fluorescence emission characteristic.When the polymer is applied to electroluminescent, it can realize Full color and realize pure membrane stage
Under high-efficiency fluorescence transmitting；In addition, the preparation method of polymer of the present invention is simple, and such polymer is expected to be applied to
The electroluminescent device of solution processing.
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
The every other embodiment that technical staff is obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1：The synthesis of polymer I-1
The preparation of (1) two (4- bromophenyls) diphenyl silicon
Shown in the following reaction equation of preparation flow：
The specific steps are：250ml is added in paradibromobenzene (9.44g, 40.0mmol) and dry 100ml tetrahydrofurans to burn
In bottle, gas, argon gas protection, dry ice acetone bath are substituted.Take 16ml n-BuLis (2.5M) in constant pressure funnel, to stirring
Reaction solution is slowly added dropwise, and is added dropwise.After keeping low-temp reaction 1h, diphenyl silicon dichloride (4.2ml, 20.0mmol) is injected
In reaction solution, it is back to room temperature naturally, reaction is overnight.Reaction solution is poured into 200ml water, 100ml ether is extracted twice, and collection has
Machine phase, saturated common salt water washing, anhydrous sodium sulfate drying, filtering, revolving remove solvent.100ml ethyl alcohol is added into crude product,
Ultrasonic 10min, 70 DEG C of heating stirring 20min are filtered, and are collected filter cake, are repeated twice, and are dried, are obtained 8.2g white powders, yield
84%.1H NMR(CDCl3,500MHz):7.46-7.44 (m, 8H), 7.40 (t, 7.6Hz, 2H), 7.33-7.30 (m, 8H), matter
Spectrum test is 494.1 (M+)。
(2) preparation of 3,6- hypoboric acid pinacol ester -9- octylcarbazols
Shown in the following reaction equation of preparation flow：
The specific steps are：The tetrahydrofuran that bis- bromo- 9- octylcarbazols (11.0g, 25.0mmol) of 3,6- and 120ml are dried
It is added in 250ml flasks, substitutes gas, argon gas protection, dry ice acetone bath.Take 28ml n-BuLis (2.5M, 70mmol) in constant pressure
In dropping funel, it is slowly added dropwise, is added dropwise to the reaction solution of stirring.After keeping low-temp reaction 1h, by isopropoxy boric acid frequency
In any alcohol ester (18ml, 88mmol) injection reaction solution, it is back to room temperature reaction naturally overnight.Reaction solution is poured into 200ml water,
100ml ether is extracted twice, and collects organic phase, and saturated salt solution washed once, anhydrous sodium sulfate drying, filtering, and revolving removes
Solvent.Ethyl alcohol recrystallization is to get to 8.2g white solids, yield 61%.Mass spectrometric measurement is 531.3 (M+)。
(3) preparation of bis- bromo- 9- of 3,6- (4- (4', 6'- di-t-butyl -1,3,5- triazines)) phenyl carbazole
Shown in the following reaction equation of preparation flow：
The specific steps are：By 9- (4- (4', 6'- di-t-butyl -1,3,5- triazines)) phenyl carbazole (2.17g,
5.0mmol), N- bromo-succinimides (1.78g, 10.0mmol) are protected from light and 10h are stirred at room temperature in 50ml tetrahydrofurans.It will
Reaction solution pours into 100ml water, and ethyl acetate is extracted twice, and washing twice, collects organic phase, and anhydrous sodium sulfate drying is filtered,
Revolving removes solvent, and ethyl alcohol recrystallization obtains white solid 2.6g, yield 90%.Mass spectrometric measurement is 592.0 (M+)。
(4) preparation of polymer I-1
Shown in the following reaction equation of preparation flow：
Specific step is：Weigh two (4- bromophenyls) diphenyl silicon (0.198g, 0.4mmol), 3,6-, bis- bromo- 9- (4-
(4', 6'- di-t-butyl -1,3,5-triazines)) phenyl carbazole (0.059g, 0.1mmol), 3,6- hypoboric acid pinacol esters -9- be pungent
Base carbazole (0.329g, 0.5mmol), tris(dibenzylideneacetone) dipalladium (4mg, 0.05mmol) and 2- dicyclohexyl phosphine -2',
6'- dimethoxy-biphenyls (8mg, 0.2mmol) substitute gas, argon gas protection in flask.Again by the tetrahydrofuran of deoxygenation (8ml)
It is added in flask with potassium phosphate solution (2M, 1.5ml), substitutes gas, under argon gas protection, 80 DEG C of return stirrings are for 24 hours.It will be dissolved in
The phenyl boric acid (0.015g, 0.1mmol) of 2ml tetrahydrofurans is injected into reaction solution, reacts 5h, then the bromobenzene that will be dissolved in 2ml toluene
(0.1ml) is injected into reaction solution, reacts 5h；The diethylamino bamic acid sodium (1g) being dissolved in 20ml water is added to reaction
In liquid, continue stirring for 24 hours；It is cooled to room temperature, dichloromethane and water extract three times, collection organic phase, concentrated by rotary evaporation to 2ml or so,
It is dripped in methanol, polymer is precipitated, filtered, washing, acetone extraction for 24 hours, collects residue, and it is solid to obtain 0.33g whites
Body, yield 80%.Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 12000, molecular weight distributing index
PDI is 2.2.
Embodiment 2：The synthesis of polymer I-2
(1) preparation of bis- bromo- 9- of 3,6- (4- (4', 6'- phenyl -1,3,5- triazines)) phenyl carbazole
The specific steps are：By 3,6- dibromos carbazole (1.30g, 4.0mmol), 2- (4- fluorophenyls) diphenyl-1-4,6-,
3,5- triazines (1.14g, 3.5mmol) and cesium carbonate (2.60g, 8.0mmol) are substituted in 30ml n,N-Dimethylformamide
Gas, the lower 150 DEG C of stirrings 20h of argon gas protection.It is cooled to room temperature, reaction solution is poured into 200ml water, a large amount of solids are precipitated, filters, water
It washes, collects filter cake and be scattered in 30ml ethyl alcohol, ultrasonic 5min, 70 DEG C of heating stirring 10min are filtered, be repeated twice, and are dried, are obtained
To faint yellow solid 2.0g, yield 90%.Mass spectrometric measurement is 630.0 (M+)。
(2) synthesis of polymer I-2
Specific step is identical as polymer I-1, by monomer 3, bis- bromo- 9- of 6- (4- (4', 6'- di-t-butyl -1,3,5-
Triazine)) phenyl carbazole replaces with bis- bromo- 9- of 3,6- (4- (4', 6'- phenyl -1,3,5- triazines)) phenyl carbazole.Obtain 0.34g
Faint yellow solid, yield 80%.Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 12000, molecular weight
Profile exponent PDI is 2.3.
Embodiment 3：The synthesis of polymer I-3
(1) bis- bromo- 9- of 3,6- (4- benzoyloxy phenyls) carbazole
Shown in the following reaction equation of preparation flow：
Specific steps in embodiment 1 (3) prepare it is identical.
(2) synthesis of polymer I-3
Shown in the following reaction equation of preparation flow：
Specific step is identical as polymer I-1, by monomer 3, bis- bromo- 9- of 6- (4- (4', 6'- di-t-butyl -1,3,5-
Triazine)) phenyl carbazole replaces with 3,6- bis- bromo- 9- (4- benzoyloxy phenyls) carbazole.Obtain 0.32g faint yellow solids, yield
80%.Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 11000, and molecular weight distributing index PDI is
2.1。
Embodiment 4：The synthesis of polymer I-4
(1) bis- bromo- 9- of 3,6- (4- (4 '-pyridinecarboxylic) phenyl) carbazole
Shown in the following reaction equation of preparation flow：
Specific steps in embodiment 1 (3) prepare it is identical.
(2) synthesis of polymer I-3
Shown in the following reaction equation of preparation flow：
Specific step is identical as polymer I-1, by monomer 3, bis- bromo- 9- of 6- (4- (4', 6'- di-t-butyl -1,3,5-
Triazine)) phenyl carbazole replaces with bis- bromo- 9- of 3,6- (4- (4 '-pyridinecarboxylic) phenyl) carbazole.0.32g yellow solids are obtained, are produced
Rate 82%.Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 11000, and molecular weight distributing index PDI is
2.1。
Embodiment 5：The synthesis of polymer I-5
(1) preparation of bis- bromo- 9- of 3,6- (4- (4 '-trifluoromethylbenzoyl) phenyl) carbazole
Shown in the following reaction equation of preparation flow：
Specific steps in embodiment 1 (3) prepare it is identical.
(2) synthesis of polymer I-5
Shown in the following reaction equation of preparation flow：
Specific step is identical as polymer I-1, by monomer 3, bis- bromo- 9- of 6- (4- (4', 6'- di-t-butyl -1,3,5-
Triazine)) phenyl carbazole replaces with bis- bromo- 9- of 3,6- (4- (4 '-trifluoromethylbenzoyl) phenyl) carbazole.Obtain 0.32g yellow
Solid, yield 83%.Obtained polymer is detected, it is 12000 that GPC, which measures number-average molecular weight Mn, and molecular weight distribution refers to
Number PDI is 2.3.
Embodiment 6：The synthesis of polymer I-6
(1) synthesis of 2- (3,6- dibromos carbazole) -10,10- dioxy thioxanthones
Shown in the following reaction equation of preparation flow：
Specific steps in embodiment 1 (3) prepare it is identical.
(2) synthesis of polymer I-6
Shown in the following reaction equation of preparation flow：
Specific step is identical as polymer I-1, by monomer 3, bis- bromo- 9- of 6- (4- (4', 6'- di-t-butyl -1,3,5-
Triazine)) phenyl carbazole replaces with 2- (3,6- dibromos carbazole) -10,10- dioxy thioxanthones.Obtain 0.33g yellow solids, yield
82%.Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 11000, and molecular weight distributing index PDI is
2.3。
Embodiment 7：The synthesis of polymer I-7
(1) synthesis of N- (4- tert-butyl-phenyls) -4- (3,6- dibromos carbazole) phthalimide
Shown in the following reaction equation of preparation flow：
Specific steps in embodiment 1 (3) prepare it is identical.
(2) synthesis of polymer I-7
Shown in the following reaction equation of preparation flow：
Specific step is identical as polymer I-1, by monomer 3, bis- bromo- 9- of 6- (4- (4', 6'- di-t-butyl -1,3,5-
Triazine)) phenyl carbazole replaces with N- (4- tert-butyl-phenyls) -4- (3,6- dibromos carbazole) phthalimide.Obtain 0.33g oranges
Yellow solid, yield 80%.Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 12000, molecular weight point
Cloth indices P DI is 2.1.
Embodiment 8：The synthesis of polymer I-8
(1) bis- bromo- 9,9- dimethyl -10- of 2,7- (6- (4', 6'- di-t-butyl -1,3,5- triazines)) phenyl -9,10-
The synthesis of acridan
Shown in the following reaction equation of preparation flow：
Specific steps in embodiment 1 (3) prepare it is identical.
(2) synthesis of polymer I-8
Shown in the following reaction equation of preparation flow：
Specific step is identical as polymer I-1, by monomer 3, bis- bromo- 9- of 6- (4- (4', 6'- di-t-butyl -1,3,5-
Triazine)) phenyl carbazole replaces with bis- bromo- 9,9- dimethyl -10- of 2,7- (6- (4', 6'- di-t-butyl -1,3,5- triazines)) benzene
Base-acridan.Obtain 0.33g yellow solids, yield 83%.Obtained polymer is detected, gpc measurement number
Average molecular weight Mn is 13000, and molecular weight distributing index PDI is 2.2.
Embodiment 9：The synthesis of polymer I-9
(1) synthesis of bis- bromo- 9,9- dimethyl -10- (4- benzoylphenyls)-acridans of 2,7-
Shown in the following reaction equation of preparation flow：
Specific steps in embodiment 1 (3) prepare it is identical.
(2) synthesis of polymer I-9
Shown in the following reaction equation of preparation flow：
Specific step is identical as polymer I-1, by monomer 3, bis- bromo- 9- of 6- (4- (4', 6'- di-t-butyl -1,3,5-
Triazine)) phenyl carbazole replaces with bis- bromo- 9,9- dimethyl -10- (4- benzoyls) phenyl-acridan of 2,7-.
To 0.32g yellow solids, yield 82%.Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 12000, point
Son amount profile exponent PDI is 2.3.
Embodiment 10：The synthesis of polymer I-10
(1) bis- bromo- 9,9- dimethyl -10- of 2,7- (4- (10 ', 10 '-dioxy thioxanthones) phenyl)-acridan
Synthesis
Shown in the following reaction equation of preparation flow：
Specific steps in embodiment 1 (3) prepare it is identical.
(2) synthesis of polymer I-10
Shown in the following reaction equation of preparation flow：
Specific step is identical as polymer I-1, by monomer 3, bis- bromo- 9- of 6- (4- (4', 6'- di-t-butyl -1,3,5-
Triazine)) phenyl carbazole replaces with bis- bromo- 9,9- dimethyl -10- of 2,7- (4- (10 ', 10 '-dioxy thioxanthones) phenyl) -9,10-
Acridan.Obtain 0.33g orange/yellow solids, yield 80%.Obtained polymer is detected, the equal molecule of gpc measurement number
It is 11000 to measure Mn, and molecular weight distributing index PDI is 2.2.
Embodiment 11：The synthesis of polymer I-11
(1) bis- bromo- 9,9- dimethyl -10- of 2,7- (4- (N- tert-butyl-phenyls phthalimide) phenyl) -9,10- two
The synthesis of hydrogen acridine
Shown in the following reaction equation of preparation flow：
Specific steps in embodiment 1 (3) prepare it is identical.
(2) synthesis of polymer I-11
Shown in the following reaction equation of preparation flow：
Specific step is identical as polymer I-1, by monomer 3, bis- bromo- 9- of 6- (4- (4', 6'- di-t-butyl -1,3,5-
Triazine)) phenyl carbazole replaces with bis- bromo- 9,9- dimethyl -10- of 2,7- (4- (N- tert-butyl-phenyls phthalimide) benzene
Base)-acridan.Obtain 0.33g orange/yellow solids, yield 80%.Obtained polymer is detected, gpc measurement
Number-average molecular weight Mn is 11000, and molecular weight distributing index PDI is 2.1.
Embodiment 12：The synthesis of polymer I-12
(1) conjunction of 4- (bis- bromo- 9,9- diphenyl-acridans of 2,7-)-N- tert-butyl-phenyl -1,8- naphthalene imines
At
Shown in the following reaction equation of preparation flow：
Specific steps in embodiment 1 (3) prepare it is identical.
(2) synthesis of polymer I-12
Shown in the following reaction equation of preparation flow：
Specific step is identical as polymer I-1, by monomer 3, bis- bromo- 9- of 6- (4- (4', 6'- di-t-butyl -1,3,5-
Triazine)) phenyl carbazole replaces with 4- (bis- bromo- 9,9- diphenyl-acridans of 2,7-)-N- tert-butyl-phenyls -1,8-
Naphthalene imines.Obtain 0.34g red solids, yield 81%.Obtained polymer is detected, gpc measurement number-average molecular weight Mn
It is 12000, molecular weight distributing index PDI is 2.3.
Embodiment 13：The synthesis of polymer I-13
(1) synthesis of 3- (bis- p-bromophenyl amine of 4-) phenyl-Oxoxanthone
Shown in the following reaction equation of preparation flow：
Specific steps in embodiment 1 (3) prepare it is identical.
(2) synthesis of polymer I-13
Shown in the following reaction equation of preparation flow：
Specific step is identical as polymer I-1, by monomer 3, bis- bromo- 9- of 6- (4- (4', 6'- di-t-butyl -1,3,5-
Triazine)) phenyl carbazole replaces with 3- (bis- p-bromophenyl amine of 4-) phenyl-Oxoxanthone.Obtain 0.33g yellow solids, yield 83%.
Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 13000, and molecular weight distributing index PDI is 2.4.
Embodiment 14：The synthesis of polymer I-14
(1) synthesis of 2- (bis- p-bromophenyl amine of 4-) phenyl -10,10- dioxy thioxanthones
Shown in the following reaction equation of preparation flow：
Specific steps in embodiment 1 (3) prepare it is identical.
(2) synthesis of polymer I-14
Shown in the following reaction equation of preparation flow：
Specific step is identical as polymer I-1, by monomer 3, bis- bromo- 9- of 6- (4- (4', 6'- di-t-butyl -1,3,5-
Triazine)) phenyl carbazole replaces with 2- (bis- p-bromophenyl amine of 4-) phenyl -10,10- dioxy thioxanthones.It is solid to obtain 0.33g red
Body, yield 83%.Obtained polymer is detected, it is 12000 that GPC, which measures number-average molecular weight Mn, molecular weight distributing index
PDI is 2.3.
Comparative example 1：The synthesis of polymer PC TPSi
Weigh two (4- bromophenyls) diphenyl silicon (0.248g, 0.5mmol), 3,6- hypoboric acid pinacol ester -9- octyl clicks
Azoles (0.329g, 0.5mmol), tris(dibenzylideneacetone) dipalladium (4mg, 0.05mmol) and 2- dicyclohexyl phosphines -2', 6'- bis-
Methoxyl biphenyl (8mg, 0.2mmol) substitutes gas, argon gas protection in flask.Again by the tetrahydrofuran of deoxygenation (8ml) and phosphoric acid
Potassium solution (2M, 1.5ml) is added in flask, substitutes gas, under argon gas protection, 80 DEG C of return stirrings are for 24 hours.2ml tetrahydrochysene furans will be dissolved in
The phenyl boric acid (0.015g, 0.1mmol) muttered is injected into reaction solution, reacts 5h, then the bromobenzene (0.1ml) for being dissolved in 2ml toluene is noted
Reaction solution is injected, 5h is reacted；The diethylamino bamic acid sodium (1g) being dissolved in 20ml water is added in reaction solution, is continued
Stirring is for 24 hours；It is cooled to room temperature, dichloromethane and water extraction three times, collect organic phase, concentrated by rotary evaporation to 2ml or so is dripped to first
In alcohol, polymer is precipitated, filters, washing, acetone extraction for 24 hours, collects residue, obtains 0.35g white solids, yield 85%.
Obtained polymer is detected, gpc measurement number-average molecular weight Mn is 15000, and molecular weight distributing index PDI is 2.3.
Embodiment 15
Luminosity test, the result is shown in Figure 1~Fig. 2 are carried out to the polymer that the embodiment of the present invention 1~14 obtains, wherein
Fig. 1 is the film state emission spectrum of the polymer of Examples 1 to 7, and Fig. 2 is that the film state of the polymer of embodiment 8~14 emits light
Spectrum.
The polymer test result that embodiment 1~14 obtains is as shown in table 1.Wherein λmaxFor film state fluorescent emission peak value；
HOMO energy levels are measured by cyclic voltammetry, and lumo energy is then by E (LUMO)=E (HOMO)-EoptIt is calculated, wherein Eopt
For optical band gap；ΔESTIt is obtained by phosphorescence spectrum test；PLQY is the luminous quantum efficiency in its film state argon atmosphere.From
Test result can see, and select suitable dye units and suitable rate of charge, so that it may to realize from 460 to the glimmering of 620nm
Light emitting, and these polymer all have the Δ E of very little on the basis of keeping higher PLQYST, it is sufficient to realize it is efficient
Thermal induction delayed fluorescence.The T of the unit and fluorescence unit of each polymer simultaneously1Energy level (E as shown in table 1T)。
Polymer film state luminosity described in 1. embodiment of the present invention 1~14 of table
Luminescent spectrum test carried out to the polymer (i.e. polymer PC TPSi) of comparative example 1, it is the absorption of toluene solution, glimmering
Shown in light and the following reaction equation of antenna effect spectrum 3；The T of polymer can be calculated from phosphorescence spectrum1Energy level is
2.68eV(463nm).And the T of luminescence unit1Energy level is as shown in table 1, both less than 2.68eV, therefore the backbone structure is enough to inhibit
Quenching effect in the present invention between chemical doping unit and fluorescence unit therein.
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.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 improvement and modification are also fallen within the protection scope of the claims of the present invention.
Claims (10)
1. the thermal induction delayed fluorescence polymer of a kind of main chain silicon containing diphenyl and carbazole unit has structure shown in formula (I),
Wherein, R1、R2Independently selected from the alkyl of C1~C20 or the aromatic radical of C6~C30；
A is the fluorescent dye unit containing electron donor/receptor distorted-structure unit；
X is 0 x≤0.6 ＜；
N is 2~200.
2. polymer according to claim 1, which is characterized in that the R1Alkyl selected from C1~C15 is free of substituent group
C6~C30 aromatic radical or be connected with the aromatic radical of the alkyl of C1~C20 and/or the alkoxy of C1~C20.
3. polymer according to claim 1, which is characterized in that the R1Selected from methyl, ethyl, propyl, butyl, amyl,
Hexyl, octyl, phenyl, p-methylphenyl, pyridine.
4. polymer according to claim 1, which is characterized in that the R2Alkyl selected from C1~C20 is free of substituent group
C6~C30 aromatic radical or be connected with the aromatic radical of the alkyl of C1~C20 and/or the alkoxy of C1~C20.
5. polymer according to claim 1, which is characterized in that the R2Selected from hexyl, heptyl, octyl, nonyl, decyl,
Undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, butyl phenyl, hexyl
Phenyl, octyl phenyl, decyl phenyl, undecyl phenyl, tridecyl phenyl, heptadecyl phenyl, Hexyloxy-phenyl, pungent oxygen
Base phenyl, decyloxy phenyl, hendecane epoxide phenyl, tridecane epoxide phenyl, heptadecane epoxide phenyl.
6. polymer according to claim 1, which is characterized in that the A is using carbazole, acridine or diphenylamines as electron
The fluorescent dye unit that unit connection electrophilic unit obtains.
7. polymer according to claim 1, which is characterized in that the A is formula (II-1-a), formula (II-1-b), formula
(II-1-c), formula (II-1-d), formula (II-1-e), formula (II-1-f), formula (II-1-g), formula (II-1-h), formula (II-1-i), formula
(II-1-j), formula (II-1-k), formula (II-1-1), formula (II-1-m), formula (II-1-n), formula (II-1-o), formula (II-2-a), formula
(II-2-b), formula (II-2-c), formula (II-2-d), formula (II-2-e), formula (II-2-f), formula (II-2-g), formula (II-2-h), formula
(II-2-i), formula (II-2-j), formula (II-2-k), formula (II-2-1), formula (II-2-m), formula (II-2-n), formula (II-2-o)),
Formula (II-3-a), formula (II-3-b), formula (II-3-c), formula (II-3-d), formula (II-3-e), formula (II-3-f), formula (II-3-g),
Formula (II-3-h), formula (II-3-i) or formula (II-3-j),
Wherein, R3、R5Independently selected from the alkyl of C1~C20 or the aromatic radical of C6~C30；M is 0 or 1；Y is that oxygen atom or sulphur are former
Son.
8. polymer according to claim 1, which is characterized in that the x is 0.002≤x≤0.5.
9. polymer according to claim 1, which is characterized in that formula (I) compound is specially formula (I-1), formula (I-
2), formula (I-3), formula (I-4), formula (I-5), formula (I-6), formula (I-7), formula (I-8), formula (I-9), formula (I-10), formula (I-11),
Formula (I-12), formula (I-13) or formula (I-14),
10. a kind of system of the thermal induction delayed fluorescence polymer of main chain silicon containing diphenyl described in claim 1 and carbazole unit
Preparation Method, including：
Monomer with formula (III), formula (IV) and formula (V) structure is copolymerized, polymer shown in formula (I) is obtained,
Wherein, R1、R2Independently selected from the alkyl of C1~C20 or the aromatic radical of C6~C30；
A is the fluorescent dye unit containing electron donor/receptor distorted-structure unit；
X is 0 x≤0.6 ＜；
N is 2~200.
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