CN108383980B - Thermally induced delayed fluorescence polymer with main chain containing diphenyl silicon and carbazole units and preparation method thereof - Google Patents

Thermally induced delayed fluorescence polymer with main chain containing diphenyl silicon and carbazole units and preparation method thereof Download PDF

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CN108383980B
CN108383980B CN201810223243.XA CN201810223243A CN108383980B CN 108383980 B CN108383980 B CN 108383980B CN 201810223243 A CN201810223243 A CN 201810223243A CN 108383980 B CN108383980 B CN 108383980B
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程延祥
朱运会
王彦杰
杨一可
战宏梅
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a thermally-induced delayed fluorescence polymer with a structure shown in formula (I), wherein the main chain of the thermally-induced delayed fluorescence polymer contains diphenyl silicon and carbazole units, and a preparation method of the thermally-induced delayed fluorescence polymer. The introduction of the diphenyl silicon and carbazole units enables the polymer to have high triplet state energy level, can effectively shield the quenching effect between the luminescent units, and further enables the polymer to have efficient thermal induction delayed fluorescence emission property. When the polymer is applied to electroluminescence, full-color luminescence and efficient fluorescence emission in a pure film state are expected to be realized; in addition, the preparation method of the polymer is simple, and the polymer is expected to be applied to solution-processed electroluminescent devices.

Description

Thermally induced delayed fluorescence polymer with main chain containing diphenyl silicon and carbazole units and preparation method thereof
Technical Field
The invention belongs to the field of organic luminescent materials, and particularly relates to a thermally-induced delayed fluorescence polymer with a main chain containing diphenyl silicon and carbazole units and a preparation method thereof.
Background
Small molecule organic compounds having a thermally induced delayed fluorescence emission property are widely used in organic electroluminescent devices because they can effectively utilize triplet excitons. Such as the literature Nature,2012,492,234; nature Photon,2014,8, 326; adv.mater.2015,27,2096; CN 201310413578; CN 201310733731; CN201310739678 and CN201080055404 and the like report the electroluminescent property of small molecule organic compounds with heat-induced delayed fluorescence emission property. The electroluminescent device made of the compound as the luminescent material can be compared with the device made of the heavy metal compound phosphorescent material in performance, however, when the small molecular compound is applied to the luminescent device, the small molecular compound is often made in an evaporation mode, and the process is complex, so that the cost is increased, and the future commercial application is not facilitated.
In contrast, when the polymer-based light emitting material is applied to a light emitting device, it has been widely noticed and researched in academia and industry because it can use a simple solution processing method such as spin coating and ink jet printing, and is easy to realize large-size display and flexible display. However, the traditional polymer luminescent material is difficult to realize thermal induction delayed fluorescence, the external quantum efficiency of the device can only reach 5-6% at most, and the practical requirement cannot be met. Recently, we have designed a series of "main chain-donor/side group-acceptor" type polymers, i.e. the polymers have a molecular structure with a main chain as a donor unit and a connected side group as an acceptor unit, and realize high-efficiency thermally-induced delayed fluorescence emission, wherein the external quantum efficiency of the electroluminescent device manufactured by processing the polymer PAPCC solution is as high as 12.6% (Macromolecules 2016,49, 4373). On the basis, a chromophore is connected to a polycarbazole main chain through a main chain doping concept, the content of the chromophore is adjusted to inhibit concentration quenching, the luminous efficiency is obviously improved, and meanwhile, the efficiency roll-off of an electroluminescent device is weakened (J.Mater.chem.C., 2018,6, 568; adv.Funct.Mater.2018, 1706916). Nevertheless, the triplet energy level of the presently disclosed polymers is still low, making it difficult to achieve full color emission while at the same time effecting full utilization of the electrically generated triplet excitons. Therefore, increasing the triplet level of the polymer-based thermally-induced delayed fluorescence material is a critical technical problem to be solved urgently (j.am.chem.soc.,2017,139,11073).
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a thermally induced delayed fluorescence polymer containing diphenylsilicon and carbazole units in the main chain and a preparation method thereof.
The invention provides a thermally induced delayed fluorescence polymer with a main chain containing diphenyl silicon and carbazole units, which has a structure shown in a formula (I),
Figure GDA0001648750100000021
wherein R is1、R2Independently selected from C1-C20 alkyl or C6-C30 aryl;
a is a fluorescent dye unit containing an electron donor/acceptor twisted structural unit;
x is more than 0 and less than or equal to 0.6;
n is 2 to 200.
Preferably, said R is1Is selected from C3-C15 alkyl, C6-C30 aryl without substituent or aryl with C1-C20 alkyl and/or C1-C20 alkoxy.
Preferably, said R is1Selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, phenyl, p-tolyl, pyridine.
Preferably, said R is2Is selected from C1-C20 alkyl, C6-C30 aryl without substituent or aryl with C1-C20 alkyl and/or C1-C20 alkoxy.
Preferably, said R is2Selected from the group consisting of hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, butylphenyl, hexylphenyl, octylphenyl, decylphenyl, undecylphenyl, tridecylphenyl, heptadecylphenyl, hexyloxyphenyl, octyloxyphenyl, decylphenyl, undecyloxyphenyl, tridecoxyphenyl, heptadecylphenyl.
Preferably, A is a fluorescent dye unit obtained by connecting an electron-withdrawing unit with carbazole, acridine or diphenylamine as an electron-donating unit.
Preferably, A is a compound of the formula (II-1-a), the formula (II-1-b), the formula (II-1-c), the formula (II-1-d), the formula (II-1-e), the formula (II-1-f), the formula (II-1-g), the formula (II-1-h), the formula (II-1-i), the formula (II-1-j), the formula (II-1-k), the formula (II-1-l), the formula (II-1-m), the formula (II-1-n), the formula (II-1-o), the formula (II-2-a), the formula (II-2-b), the formula (II-2-c), the formula (II-2-d), the 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),
Figure GDA0001648750100000031
Figure GDA0001648750100000041
Figure GDA0001648750100000051
wherein R is3、R5Independently selected from C1-C20 alkyl or C6-C30 aryl; m is 0 or 1; y is an oxygen atom or a sulfur atom.
Preferably, x is 0.002-0.5.
Preferably, the compound of formula (I) is specifically 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).
Figure GDA0001648750100000061
Figure GDA0001648750100000071
The invention also provides a preparation method of the thermal-induced delayed fluorescence polymer with the main chain containing diphenyl silicon and carbazole units, which comprises the following steps:
copolymerizing monomers with structures of a formula (III), a formula (IV) and a formula (V) to obtain a polymer shown in a formula (I),
Figure GDA0001648750100000081
wherein R is1、R2Independently selected from C1-C20 alkyl or C6-C30 aryl;
a is a fluorescent dye unit containing an electron donor/acceptor twisted structural unit;
x is more than 0 and less than or equal to 0.6;
n is 2 to 200.
Compared with the prior art, the thermal induction delayed fluorescence polymer with the structure shown in the formula (I) and the main chain containing diphenyl silicon and carbazole units has the advantages that experimental results show that the polymer not only has high-efficiency thermal induction delayed fluorescence emission property, but also has high triplet state energy level, so that when the polymer is applied to electroluminescence, full-color luminescence can be realized; in addition, the preparation method of the polymer is simple and easy to realize industrial production.
Drawings
FIG. 1 is a film state emission spectrum of the polymers of examples 1 to 7;
FIG. 2 is a film state emission spectrum of polymers of examples 8 to 14;
FIG. 3 shows absorption, fluorescence and low temperature phosphorescence spectra of the polymer toluene solution of comparative example 1.
Detailed Description
The invention provides a thermally induced delayed fluorescence polymer with a main chain containing diphenyl silicon and carbazole units, which has a structure shown in a formula (I),
Figure GDA0001648750100000091
wherein R is1、R2Independently selected from C1-C20 alkyl or C6-C30 aryl;
a is a fluorescent dye unit containing an electron donor/acceptor twisted structural unit;
x is more than 0 and less than or equal to 0.6;
n is 2 to 200.
In the present invention, R is1Preferably an alkyl group of C1-C4, an aryl group of C6-C30 containing no substituent or an aryl group to which an alkyl group of C1-C20 and/or an alkoxy group of C1-C20 are bonded, and more preferably a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a p-tolyl group, a p-methoxybenzene group or a pyridine.
In the present invention, R is2Preferably an alkyl group having 6 to 20 carbon atoms, an aryl group to which are bonded an alkyl group having 4 to 20 carbon atoms and/or an alkoxy group having 4 to 20 carbon atoms, and more preferably a hexyl group, heptyl group, octyl groupA phenyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, a butylphenyl group, a hexylphenyl group, an octylphenyl group, a decylphenyl group, an undecylphenyl group, a tridecylphenyl group, a heptadecylphenyl group, a hexyloxyphenyl group, an octyloxyphenyl group, a decyloxyphenyl group, an undecyloxyphenyl group, a tridecylphenyl group, a heptadecylphenyl group.
In the present invention, A is preferably a fluorescent dye unit obtained by linking an electron-withdrawing unit to an electron-donating unit using carbazole, acridine or diphenylamine, more preferably a fluorescent dye unit represented by the formula (II-1-a), the formula (II-1-b), the formula (II-1-c), the formula (II-1-d), the formula (II-1-e), the formula (II-1-f), the formula (II-1-g), the formula (II-1-h), the formula (II-1-i), the formula (II-1-j), the formula (II-1-k), the formula (II-1-l), the formula (II-1-m), the formula (II-1-n), the formula (II-1-o), the formula (II-2-a), the formula (II-2-b), A formula (II-2-c), a formula (II-2-d), a formula (II-2-e), a formula (II-2-f), a formula (II-2-g), a formula (II-2-h), a formula (II-2-i), a formula (II-2-j), a formula (II-2-k), a formula (II-2-l), a formula (II-2-m), a formula (II-2-n), a formula (II-2-o)), a formula (II-3-a), a formula (II-3-b), a formula (II-3-c), a formula (II-3-d), a formula (II-3-e), a formula (II-3-f), a formula (II-3-g), Formula (II-3-h), formula (II-3-i) or formula (II-3-j),
Figure GDA0001648750100000101
Figure GDA0001648750100000111
wherein R is3、R5Independently selected from C1-C20 alkyl or C6-C30 aryl; m is 0 or 1; y is an oxygen atom or a sulfur atom. Specifically, the R is3Preferably an alkyl group of C1 to C8, an aryl group of C6 to C30 having no substituent or an aryl group to which an alkyl group of C1 to C20 and/or an alkoxy group of C1 to C20 are bonded, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a phenyl group, a butylphenyl group, a hexylphenyl group, an octylphenyl group, a decylphenyl group, an undecylphenyl group, a hexyloxyphenyl group, an octyloxyphenyl group, a decylphenyl groupOxyphenyl, undecyloxyphenyl; the R is5Preferably an alkyl group of C1 to C8, an aryl group of C6 to C30 having no substituent, or an aryl group to which an alkyl group of C1 to C20 and/or an alkoxy group of C1 to C20 are bonded, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a phenyl group, a methylphenyl group, a butylphenyl group, a hexylphenyl group, a methoxyphenyl group, or a butoxyphenyl group.
In addition, the symbol
Figure GDA0001648750100000122
Is a connecting bond and is the connecting position of a substituent and a main structure.
In the present invention, x is preferably 0.002. ltoreq. x.ltoreq.0.60, more preferably 0.005. ltoreq. x.ltoreq.0.50, most preferably 0.01. ltoreq. x.ltoreq.0.40, most preferably 0.05. ltoreq. x.ltoreq.0.35, most preferably 0.1. ltoreq. x.ltoreq.0.3.
More specifically, the compound of formula (I) is specifically 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),
Figure GDA0001648750100000121
Figure GDA0001648750100000131
Figure GDA0001648750100000141
the invention also provides a preparation method of the thermally induced delayed fluorescence polymer with the main chain containing diphenyl silicon and carbazole units, which comprises the following steps:
copolymerizing monomers with structures of a formula (III), a formula (IV) and a formula (V) to obtain a polymer shown in a formula (I),
Figure GDA0001648750100000142
wherein R is1、R2Independently selected from C1-C20 alkyl or C6-C30 aryl;
a is a fluorescent dye unit containing an electron donor/acceptor twisted structural unit;
x is more than 0 and less than or equal to 0.6;
n is 2 to 200.
According to the invention, the monomers with the structures of the formula (III), the formula (IV) and the formula (V) are copolymerized to obtain the polymer shown in the formula (I), wherein the copolymerization conditions in the invention are not particularly required, the copolymerization method is well known in the art, and the catalyst for the copolymerization is preferably a palladium catalyst, more preferably tris (dibenzylideneacetone) dipalladium and 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl.
The thermal-induced delayed fluorescence polymer with the structure shown in the formula (I) and the main chain containing diphenyl silicon and carbazole units has the advantages that experimental results show that the energy gap between the first singlet excitation state and the first triplet excitation state of the polymer light-emitting unit is very small, and the polymer light-emitting unit has efficient thermal-induced delayed fluorescence emission properties. The introduction of the diphenyl silicon and carbazole units enables the main chain of the polymer to have a high triplet state energy level, can effectively shield the quenching effect between the luminescent units, and further enables the polymer to have efficient thermal-induced delayed fluorescence emission properties. When the polymer is applied to electroluminescence, full-color luminescence can be realized, and efficient fluorescence emission in a pure film state can be realized; in addition, the preparation method of the polymer is simple, and the polymer is expected to be applied to solution-processed electroluminescent devices.
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: synthesis of Polymer I-1
(1) Preparation of bis (4-bromophenyl) diphenylsilicon
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000151
the method comprises the following specific steps: para-dibromobenzene (9.44g,40.0mmol) and dry 100ml tetrahydrofuran were charged to a 250ml flask, purged with air, protected with argon, and a dry ice acetone bath. 16ml of n-butyllithium (2.5M) was slowly dropped into the stirred reaction mixture in a constant pressure dropping funnel, and the dropping was completed. After the reaction was kept at low temperature for 1 hour, diphenyldichlorosilane (4.2ml,20.0mmol) was poured into the reaction mixture, and the mixture was allowed to return to room temperature naturally and reacted overnight. The reaction solution was poured into 200ml of water, extracted twice with 100ml of diethyl ether, the organic phase was collected, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation. Adding 100ml ethanol into the crude product, performing ultrasonic treatment for 10min, heating and stirring at 70 ℃ for 20min, performing suction filtration, collecting a filter cake, repeating the steps twice, and drying to obtain 8.2g of white powder with the yield of 84%.1HNMR(CDCl3500MHz) 7.46-7.44(M,8H),7.40(t,7.6Hz,2H), 7.33-7.30 (M,8H), mass spectrum 494.1 (M)+)。
(2) Preparation of 3, 6-diboronic acid pinacol ester-9-octyl carbazole
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000161
the method comprises the following specific steps: 3, 6-dibromo-9-octylcarbazole (11.0g,25.0mmol) and 120ml of dry tetrahydrofuran were charged into a 250ml flask, purged with air, protected with argon, and a dry ice acetone bath. 28ml of n-butyllithium (2.5M,70mmol) were placed in a constant pressure dropping funnel and slowly added dropwise to the stirred reaction mixture, after completion of the addition. After the reaction was kept at low temperature for 1 hour, the isopropoxyboronic acid pinacol ester (18ml,88mmol) was poured into the reaction mixture, and the reaction mixture was allowed to return to room temperature naturally overnight. The reaction solution was poured into 200ml of water, extracted twice with 100ml of diethyl ether, the organic phase was collected, washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation. Recrystallization from ethanol gave 8.2g of a white solidBulk, yield 61%. Mass spectrometry of 531.3 (M)+)。
(3) Preparation of 3, 6-dibromo-9- (4- (4',6' -di-tert-butyl-1, 3, 5-triazine)) phenylcarbazole
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000162
the method comprises the following specific steps: 9- (4- (4',6' -di-tert-butyl-1, 3, 5-triazine)) phenylcarbazole (2.17g,5.0mmol) and N-bromosuccinimide (1.78g,10.0mmol) were stirred in 50ml of tetrahydrofuran at room temperature in the dark for 10 hours. The reaction solution was poured into 100ml of water, extracted twice with ethyl acetate, washed twice with water, the organic phase was collected, dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation, and recrystallized from ethanol to give 2.6g of a white solid with a yield of 90%. Mass Spectrometry test was 592.0 (M)+)。
(4) Preparation of Polymer I-1
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000171
the method comprises the following specific steps: bis (4-bromophenyl) diphenylsilicon (0.198g, 0.4mmol), 3, 6-dibromo-9- (4- (4',6' -di-tert-butyl-1, 3, 5-triazine)) phenylcarbazole (0.059g, 0.1mmol), 3, 6-pinacol ester diboron diboronate-9-octylcarbazole (0.329g, 0.5mmol), tris (dibenzylideneacetone) dipalladium (4mg, 0.05mmol) and 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (8mg,0.2mmol) were weighed into a flask, and gas was purged and argon gas was used for protection. Then, deoxygenated tetrahydrofuran (8ml) and potassium phosphate solution (2M,1.5ml) were added to the flask, and the mixture was stirred under reflux at 80 ℃ for 24h under an atmosphere of argon under suction gas. Phenylboronic acid (0.015g,0.1mmol) dissolved in 2ml of tetrahydrofuran was injected into the reaction solution for reaction for 5 hours, and bromobenzene (0.1ml) dissolved in 2ml of toluene was injected into the reaction solution for reaction for 5 hours; sodium diethylaminothioate (1g) dissolved in 20ml of water is added into the reaction solution, and stirring is continued for 24 hours; cooling to room temperature, extracting with dichloromethane and water for three times, collecting an organic phase, performing rotary evaporation and concentration to about 2ml, dripping the organic phase into methanol to separate out a polymer, filtering, washing with water, extracting with acetone for 24 hours, and collecting residues to obtain 0.33g of white solid with the yield of 80%. The polymer thus obtained was examined, and the number average molecular weight Mn was 12000 and the molecular weight distribution index PDI was 2.2 as measured by GPC.
Example 2: synthesis of Polymer I-2
(1) Preparation of 3, 6-dibromo-9- (4- (4',6' -phenyl-1, 3, 5-triazine)) phenylcarbazole
Figure GDA0001648750100000181
The method comprises the following specific steps: 3, 6-dibromocarbazole (1.30g,4.0mmol), 2- (4-fluorophenyl) -4, 6-diphenyl-1, 3, 5-triazine (1.14g,3.5mmol) and cesium carbonate (2.60g,8.0mmol) were placed in 30ml of N, N-dimethylformamide and stirred under argon atmosphere at 150 ℃ for 20 h. Cooling to room temperature, pouring the reaction solution into 200ml of water, precipitating a large amount of solid, performing suction filtration, washing with water, collecting a filter cake, dispersing the filter cake in 30ml of ethanol, performing ultrasonic treatment for 5min, heating and stirring at 70 ℃ for 10min, performing suction filtration, repeating the steps twice, and drying to obtain 2.0g of light yellow solid with the yield of 90%. Mass Spectrometry test was 630.0 (M)+)。
(2) Synthesis of Polymer I-2
Figure GDA0001648750100000182
In a specific procedure, in the same manner as in the case of the polymer I-1, the monomer 3, 6-dibromo-9- (4- (4',6' -di-t-butyl-1, 3, 5-triazine)) phenylcarbazole was replaced with 3, 6-dibromo-9- (4- (4',6' -phenyl-1, 3, 5-triazine)) phenylcarbazole. 0.34g of a pale yellow solid was obtained in 80% yield. The polymer thus obtained was examined, and the number average molecular weight Mn was 12000 and the molecular weight distribution index PDI was 2.3 as measured by GPC.
Example 3: synthesis of Polymer I-3
(1)3, 6-dibromo-9- (4-benzoylphenyl) carbazole
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000183
the specific procedure was the same as in (3) in example 1.
(2) Synthesis of Polymer I-3
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000191
the specific procedure was the same as for polymer I-1, replacing the monomer 3, 6-dibromo-9- (4- (4',6' -di-tert-butyl-1, 3, 5-triazine)) phenylcarbazole with 3, 6-dibromo-9- (4-benzoylphenyl) carbazole. 0.32g of a pale yellow solid was obtained in 80% yield. The polymer thus obtained was examined, and the number average molecular weight Mn was 11000 and the molecular weight distribution index PDI was 2.1 as measured by GPC.
Example 4: synthesis of Polymer I-4
(1)3, 6-dibromo-9- (4- (4' -picolinoyl) phenyl) carbazole
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000192
the specific procedure was the same as in (3) in example 1.
(2) Synthesis of Polymer I-3
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000193
in a specific procedure, in the same manner as for the polymer I-1, the monomer 3, 6-dibromo-9- (4- (4',6' -di-tert-butyl-1, 3, 5-triazine)) phenylcarbazole was replaced with 3, 6-dibromo-9- (4- (4' -picolinoyl) phenyl) carbazole. 0.32g of a yellow solid is obtained in 82% yield. The polymer thus obtained was examined, and the number average molecular weight Mn was 11000 and the molecular weight distribution index PDI was 2.1 as measured by GPC.
Example 5: synthesis of Polymer I-5
(1) Preparation of 3, 6-dibromo-9- (4- (4' -trifluoromethylbenzoyl) phenyl) carbazole
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000201
the specific procedure was the same as in (3) in example 1.
(2) Synthesis of Polymer I-5
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000202
in a specific procedure, in the same manner as for the polymer I-1, the monomer 3, 6-dibromo-9- (4- (4',6' -di-tert-butyl-1, 3, 5-triazine)) phenylcarbazole was replaced with 3, 6-dibromo-9- (4- (4' -trifluoromethylbenzoyl) phenyl) carbazole. 0.32g of a yellow solid is obtained in 83% yield. The polymer thus obtained was examined, and the number average molecular weight Mn was 12000 and the molecular weight distribution index PDI was 2.3 as measured by GPC.
Example 6: synthesis of Polymer I-6
(1) Synthesis of 2- (3, 6-dibromocarbazole) -10, 10-dioxythioxanthone
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000211
the specific procedure was the same as in (3) in example 1.
(2) Synthesis of Polymer I-6
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000212
in a specific procedure, in the same manner as for the polymer I-1, the monomer 3, 6-dibromo-9- (4- (4',6' -di-tert-butyl-1, 3, 5-triazine)) phenylcarbazole was replaced with 2- (3, 6-dibromocarbazole) -10, 10-dioxothioxanthone. 0.33g of a yellow solid is obtained in 82% yield. The polymer thus obtained was examined, and the number average molecular weight Mn was 11000 and the molecular weight distribution index PDI was 2.3 as measured by GPC.
Example 7: synthesis of Polymer I-7
(1) Synthesis of N- (4-tert-butylphenyl) -4- (3, 6-dibromocarbazole) phthalimide
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000213
the specific procedure was the same as in (3) in example 1.
(2) Synthesis of Polymer I-7
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000221
in a specific step, in the same manner as in the case of the polymer I-1, the monomer 3, 6-dibromo-9- (4- (4',6' -di-tert-butyl-1, 3, 5-triazine)) phenylcarbazole is replaced with N- (4-tert-butylphenyl) -4- (3, 6-dibromocarbazole) phthalimide. 0.33g of an orange-yellow solid is obtained in 80% yield. The polymer thus obtained was examined, and the number average molecular weight Mn was 12000 and the molecular weight distribution index PDI was 2.1 as measured by GPC.
Example 8: synthesis of Polymer I-8
(1) Synthesis of 2, 7-dibromo-9, 9-dimethyl-10- (6- (4',6' -di-tert-butyl-1, 3, 5-triazine)) phenyl-9, 10-dihydroacridine
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000222
the specific procedure was the same as in (3) in example 1.
(2) Synthesis of Polymer I-8
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000223
in a specific procedure, in the same manner as for the polymer I-1, the monomer 3, 6-dibromo-9- (4- (4',6' -di-t-butyl-1, 3, 5-triazine)) phenylcarbazole was replaced with 2, 7-dibromo-9, 9-dimethyl-10- (6- (4',6' -di-t-butyl-1, 3, 5-triazine)) phenyl-9, 10-dihydroacridine. 0.33g of a yellow solid is obtained in 83% yield. The polymer thus obtained was examined, and by GPC, the number average molecular weight Mn was 13000 and the molecular weight distribution index PDI was 2.2.
Example 9: synthesis of Polymer I-9
(1) Synthesis of 2, 7-dibromo-9, 9-dimethyl-10- (4-benzoylphenyl) -9, 10-dihydroacridine
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000231
the specific procedure was the same as in (3) in example 1.
(2) Synthesis of Polymer I-9
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000232
in a specific procedure, in the same manner as for the polymer I-1, the monomer 3, 6-dibromo-9- (4- (4',6' -di-t-butyl-1, 3, 5-triazine)) phenylcarbazole was replaced with 2, 7-dibromo-9, 9-dimethyl-10- (4-benzoyl) phenyl-9, 10-dihydroacridine. 0.32g of a yellow solid is obtained in 82% yield. The polymer thus obtained was examined, and the number average molecular weight Mn was 12000 and the molecular weight distribution index PDI was 2.3 as measured by GPC.
Example 10: synthesis of Polymer I-10
(1) Synthesis of 2, 7-dibromo-9, 9-dimethyl-10- (4- (10 ', 10' -dioxothioxanthone) phenyl) -9, 10-dihydroacridine
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000241
the specific procedure was the same as in (3) in example 1.
(2) Synthesis of Polymer I-10
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000242
in a specific procedure, in the same manner as for the polymer I-1, the monomer 3, 6-dibromo-9- (4- (4',6' -di-t-butyl-1, 3, 5-triazine)) phenylcarbazole was replaced with 2, 7-dibromo-9, 9-dimethyl-10- (4- (10 ', 10' -dioxothioxanthone) phenyl) -9, 10-dihydroacridine. 0.33g of an orange-yellow solid is obtained in 80% yield. The polymer thus obtained was examined, and the number average molecular weight Mn was 11000 and the molecular weight distribution index PDI was 2.2 as measured by GPC.
Example 11: synthesis of Polymer I-11
(1) Synthesis of 2, 7-dibromo-9, 9-dimethyl-10- (4- (N-tert-butylphenyl phthalimide) phenyl) -9, 10-dihydroacridine
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000243
the specific procedure was the same as in (3) in example 1.
(2) Synthesis of Polymer I-11
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000251
in the specific procedure, in the same manner as in the case of the polymer I-1, the monomer 3, 6-dibromo-9- (4- (4',6' -di-t-butyl-1, 3, 5-triazine)) phenylcarbazole was replaced with 2, 7-dibromo-9, 9-dimethyl-10- (4- (N-t-butylphenyl phthalimide) phenyl) -9, 10-dihydroacridine. 0.33g of an orange-yellow solid is obtained in 80% yield. The polymer thus obtained was examined, and the number average molecular weight Mn was 11000 and the molecular weight distribution index PDI was 2.1 as measured by GPC.
Example 12: synthesis of Polymer I-12
(1) Synthesis of 4- (2, 7-dibromo-9, 9-diphenyl-9, 10-dihydroacridine) -N-tert-butylphenyl-1, 8-naphthylimine
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000252
the specific procedure was the same as in (3) in example 1.
(2) Synthesis of Polymer I-12
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000261
in a specific procedure, in the same manner as for the polymer I-1, the monomer 3, 6-dibromo-9- (4- (4',6' -di-t-butyl-1, 3, 5-triazine)) phenylcarbazole was replaced with 4- (2, 7-dibromo-9, 9-diphenyl-9, 10-dihydroacridine) -N-t-butylphenyl-1, 8-naphthylimine. 0.34g of a red solid was obtained in 81% yield. The polymer thus obtained was examined, and the number average molecular weight Mn was 12000 and the molecular weight distribution index PDI was 2.3 as measured by GPC.
Example 13: synthesis of Polymer I-13
(1) Synthesis of 3- (4-di-p-bromophenylamine) phenyl-xanthone
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000262
the specific procedure was the same as in (3) in example 1.
(2) Synthesis of Polymer I-13
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000263
the specific procedure was the same as for polymer I-1, replacing the monomer 3, 6-dibromo-9- (4- (4',6' -di-tert-butyl-1, 3, 5-triazine)) phenylcarbazole with 3- (4-di-p-bromophenylamine) phenyl-xanthone. 0.33g of a yellow solid is obtained in 83% yield. The polymer thus obtained was examined, and by GPC, the number average molecular weight Mn was 13000 and the molecular weight distribution index PDI was 2.4.
Example 14: synthesis of Polymer I-14
(1) Synthesis of 2- (4-di-p-bromophenylamine) phenyl-10, 10-dioxythioxanthone
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000271
the specific procedure was the same as in (3) in example 1.
(2) Synthesis of Polymer I-14
The preparation process is shown in the following reaction equation:
Figure GDA0001648750100000272
the specific procedure was the same as for polymer I-1, replacing the monomer 3, 6-dibromo-9- (4- (4',6' -di-tert-butyl-1, 3, 5-triazine)) phenylcarbazole with 2- (4-di-p-bromophenylamine) phenyl-10, 10-dioxothioxanthone. 0.33g of a red solid was obtained in 83% yield. The polymer thus obtained was examined, and the number average molecular weight Mn was 12000 and the molecular weight distribution index PDI was 2.3 as measured by GPC.
Comparative example 1: synthesis of polymer PCTPSi
Figure GDA0001648750100000273
Bis (4-bromophenyl) diphenylsilicon (0.248g, 0.5mmol), 3, 6-diboronic acid pinacol ester-9-octylcarbazole (0.329g, 0.5mmol), tris (dibenzylideneacetone) dipalladium (4mg, 0.05mmol) and 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (8mg,0.2mmol) were weighed into a flask, and gas was purged and argon-blanketed. Then, deoxygenated tetrahydrofuran (8ml) and potassium phosphate solution (2M,1.5ml) were added to the flask, and the mixture was stirred under reflux at 80 ℃ for 24h under an atmosphere of argon under suction gas. Phenylboronic acid (0.015g,0.1mmol) dissolved in 2ml of tetrahydrofuran was injected into the reaction solution for reaction for 5 hours, and bromobenzene (0.1ml) dissolved in 2ml of toluene was injected into the reaction solution for reaction for 5 hours; sodium diethylaminothioate (1g) dissolved in 20ml of water is added into the reaction solution, and stirring is continued for 24 hours; cooling to room temperature, extracting with dichloromethane and water for three times, collecting an organic phase, performing rotary evaporation and concentration to about 2ml, dripping the organic phase into methanol to separate out a polymer, filtering, washing with water, extracting with acetone for 24 hours, and collecting residues to obtain 0.35g of white solid with the yield of 85%. The polymer thus obtained was examined, and the number average molecular weight Mn was 15000 and the molecular weight distribution index PDI was 2.3 as measured by GPC.
Example 15
The results of the luminescence property test on the polymers obtained in examples 1 to 14 of the present invention are shown in fig. 1 to 2, wherein fig. 1 is the film state emission spectrum of the polymers of examples 1 to 7, and fig. 2 is the film state emission spectrum of the polymers of examples 8 to 14.
The results of the polymer tests obtained in examples 1 to 14 are shown in Table 1. Wherein λmaxIs a film state fluorescence emission peak value; the HOMO level is determined by cyclic voltammetry, while the LUMO level is determined by E (LUMO) ═ E (HOMO) -EoptIs calculated to obtain wherein EoptIs an optical bandgap; delta ESTObtained by fluorescence and phosphorescence spectrum test; PLQY is the luminescence quantum efficiency in its film argon atmosphere. As can be seen from the test results, the fluorescence emission from 460 to 620nm can be realized by selecting a proper dye unit and a proper dosage ratio, and the polymers have small delta E on the basis of keeping the PLQY highSTSufficient to achieve efficient thermally induced delayed fluorescence. T of the fluorescent units of the respective polymers at the same time1The energy levels are shown in Table 1 (E)T)。
TABLE 1 electroluminescent properties of the polymer films described in inventive examples 1-14
Figure GDA0001648750100000291
The polymer of comparative example 1 (i.e., the polymer PCTPSi) was subjected to a luminescence spectrum test, and the absorption, fluorescence and low-temperature phosphorescence spectra of the toluene solution were as shown in the following reaction equation 3; from the phosphorescence spectrum, T of the polymer can be calculated1The energy level was 2.68eV (463 nm). And T of the light emitting unit1The energy levels are shown in Table 1, and are all less than 2.68eV, so that the backbone structure is sufficient to suppress quenching between the fluorescent units chemically doped therein in the present invention.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (8)

1. A thermally induced delayed fluorescence polymer with a main chain containing diphenyl silicon and carbazole units has a structure shown in a formula (I),
Figure FDA0002440484560000011
wherein R is1Selected from C1-C20 alkyl, C6-C30 aryl or pyridine;
R2selected from C1-C20 alkyl or C6-C30 aryl;
a is a formula (II-1-a), a formula (II-1-b), a formula (II-1-c), a formula (II-1-d), a formula (II-1-e), a formula (II-1-f), a formula (II-1-g), a formula (II-1-h), a formula (II-1-i), a formula (II-1-j), a formula (II-1-k), a formula (II-1-l), a formula (II-1-m), a formula (II-1-n), a formula (II-1-o), a formula (II-2-a), a formula (II-2-b), a formula (II-2-c), a formula (II-2-d), a 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),
Figure FDA0002440484560000021
Figure FDA0002440484560000031
wherein R is3、R5Independently selected from C1-C20 alkyl or C6-C30 aryl; m is 0 or 1; y is an oxygen atom or a sulfur atom;
x is more than 0 and less than or equal to 0.6;
n is 2 to 200.
2. The polymer of claim 1, wherein R is1Is selected from C1-C15 alkyl, C6-C30 aryl without substituent or aryl with C1-C20 alkyl and/or C1-C20 alkoxy.
3. The polymer of claim 1, wherein R is1Selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, phenyl, p-tolyl or pyridine.
4. The polymer of claim 1, wherein R is2Is selected from C1-C20 alkyl, C6-C30 aryl without substituent or aryl with C1-C20 alkyl and/or C1-C20 alkoxy.
5. The polymer of claim 1, wherein R is2Selected from hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, butylphenyl, hexylphenyl, octylphenyl, decylphenyl, undecylphenyl, tridecylphenyl, heptadecylphenyl, hexyloxyphenyl, octyloxyphenyl, decylphenylUndecoxyphenyl, tridecyloxyphenyl, heptadecyloxyphenyl.
6. The polymer of claim 1, wherein x is 0.002 ≦ x ≦ 0.5.
7. The polymer according to claim 1, wherein the compound of formula (I) is in particular of 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),
Figure FDA0002440484560000041
Figure FDA0002440484560000051
Figure FDA0002440484560000061
8. a method for preparing the thermally induced delayed fluorescence polymer containing diphenyl silicon and carbazole units in the main chain according to claim 1, comprising:
copolymerizing monomers with structures of a formula (III), a formula (IV) and a formula (V) to obtain a polymer shown in a formula (I),
Figure FDA0002440484560000062
Figure FDA0002440484560000071
wherein R is1Selected from C1-C20 alkyl, C6-C30 aryl or pyridine;
R2selected from C1-C20 alkyl or C6-C30 aryl;
a is a formula (II-1-a), a formula (II-1-b), a formula (II-1-c), a formula (II-1-d), a formula (II-1-e), a formula (II-1-f), a formula (II-1-g), a formula (II-1-h), a formula (II-1-i), a formula (II-1-j), a formula (II-1-k), a formula (II-1-l), a formula (II-1-m), a formula (II-1-n), a formula (II-1-o), a formula (II-2-a), a formula (II-2-b), a formula (II-2-c), a formula (II-2-d), a 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),
Figure FDA0002440484560000072
Figure FDA0002440484560000081
Figure FDA0002440484560000091
wherein R is3、R5Independently selected from C1-C20 alkyl or C6-C30 aryl; m is 0 or 1; y is an oxygen atom or a sulfur atom;
x is more than 0 and less than or equal to 0.6;
n is 2 to 200.
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CN109810097B (en) * 2019-01-18 2021-05-28 中国科学院长春应用化学研究所 Thermally induced delayed fluorescence compound and preparation method and application thereof
KR20220117199A (en) 2019-12-16 2022-08-23 미쯔비시 케미컬 주식회사 A polymer, a composition for an organic electroluminescent device, a composition for forming a hole transport layer or a hole injection layer, an organic electroluminescent device, an organic EL display device, and an organic EL lighting device
CN111312928A (en) * 2020-03-12 2020-06-19 昆明理工大学 Semiconductor device for changing band gap through thermal induction

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106117524A (en) * 2016-07-28 2016-11-16 华南理工大学 A kind of side chain thermal activation delayed fluorescence conjugated polymer luminescent material containing sulfuryl group and preparation method and application
CN106589324A (en) * 2016-11-30 2017-04-26 武汉大学 Thermal activation delayed fluorescence high-molecular compound and preparation method and application thereof
CN107142103A (en) * 2017-04-21 2017-09-08 中节能万润股份有限公司 A kind of conjugated polymer electroluminescent organic material and its application and device comprising TADF monomers by skeleton of acridine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106117524A (en) * 2016-07-28 2016-11-16 华南理工大学 A kind of side chain thermal activation delayed fluorescence conjugated polymer luminescent material containing sulfuryl group and preparation method and application
CN106589324A (en) * 2016-11-30 2017-04-26 武汉大学 Thermal activation delayed fluorescence high-molecular compound and preparation method and application thereof
CN107142103A (en) * 2017-04-21 2017-09-08 中节能万润股份有限公司 A kind of conjugated polymer electroluminescent organic material and its application and device comprising TADF monomers by skeleton of acridine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Iridium Complex Grafted to 3，6-Carbazole-alt-tetraphenylsilane Copolymers for Blue Electrophosphorescence;TENG FEI et al;《Journal of Polymer Science: Part A: Polymer Chemistry》;20101231;第48卷;第1859-1865页 *

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