CN114805741B - Polymer luminescent material based on polyurethane main chain, and preparation method and application thereof - Google Patents
Polymer luminescent material based on polyurethane main chain, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a polymer luminescent material based on a polyurethane main chain, a preparation method and application thereof, and relates to the technical field of organic electroluminescent materials. The invention adopts the non-conjugated main chain of polyurethane, which can reduce the interaction under the aggregation state, effectively reduce the aggregation quenching effect caused by pi-pi stacking of the long chain of polymer molecules and improve the photoluminescence quantum yield; and the polyurethane main chain can conveniently adjust the proportion between the soft segment and the hard segment, thereby remarkably improving the solubility and the film forming property of the polymer and being beneficial to improving the performance of the polymer in electroluminescent devices. The invention adopts the polyurethane main chain to facilitate the polymerization, can reach very high polymerization degree, introduces TADF to the receptor unit as a side chain into the polymer, and can realize the regulation and control of the luminous color.
Description
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a polymer luminescent material based on a polyurethane main chain, and a preparation method and application thereof.
Background
Organic Light Emitting Diodes (OLEDs) are becoming increasingly widely used due to their incomparable advantages in lighting, wearable, flexible displays and large-size displays as compared to conventional Liquid Crystal Displays (LCDs). The OLED device prepared based on wet processes such as spin coating and ink-jet printing has incomparable advantages in the aspects of flexible display and large-size display compared with a vacuum evaporation method, and is quite beneficial to industrialized mass production. Among them, the polymer light emitting unit is the most important one in the wet process device, and the preparation of high performance Polymer Light Emitting Diode (PLED) is a current research hot spot.
The existing polymer luminescent materials can be divided into the following three types according to the luminescence mechanism: fluorescent polymers, phosphorescent polymers, and Thermally Activated Delayed Fluorescence (TADF) polymer molecules. The TADF originated in 2012, and professor Chihaya Adachi, university of ninety, japan published in journal of nature under the heading of "efficient organic light emitting diodes derived from delayed fluorescence" (Uoyama, h., goushi, k., shizu, k.et al. Nature 492,234-238 (2012)), which illustrates the concept of TADF, improved the theoretical internal quantum efficiency of fluorescent materials to 100%, with great commercial potential, and was considered as a key technology for next generation OLED display. TADF polymer light emitting materials have high exciton utilization and high efficiency compared to conventional fluorescent or phosphorescent polymer light emitting materials, and thus have received increasing attention.
The main structure of the polymer material based on TADF at present is to take conjugated units as main chains, side chains as TADF donor-acceptor structures (Yun Yang, lei Zhao, shim Wang, junqiao Ding, and Lixiang Wang et al. Macromolecules 2018 51 (23), 9933-9942), and the structures are convenient for adjusting the combination between donor-acceptor, thereby realizing the regulation of luminescent color. However, such a conjugated backbone has a strong interaction in the aggregated state, which results in a sharp drop in photoluminescence quantum yield (PLQY) of the polymer in the thin film state, resulting in an aggregation quenching effect. And the conjugated main chain has poor film forming property, is difficult to reach high polymerization degree, and limits the application of the conjugated main chain to electroluminescent devices.
Disclosure of Invention
The invention aims to provide a polymer luminescent material based on a polyurethane main chain, a preparation method and application thereof, and the polymer luminescent material provided by the invention can improve photoluminescence quantum yield, has better solubility and film forming property, and is beneficial to improving the performance of the polymer luminescent material in electroluminescent devices.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polymer luminescent material based on a polyurethane main chain, which has a structure shown in a formula I:
in the formula I, R 1 Is quinoxalinyl or 2, 3-dicyanoquinoxalinyl; r is R 2 Is carbazolyl, triphenylamine or 9, 9-dimethyl-9, 10-dihydroacridinyl; x+z ranges from 0.05 to 0.5, and y ranges from 0.5 to 0.95.
Preferably, the polyurethane backbone-based polymer light emitting material comprises
The invention provides a preparation method of the polymer luminescent material, which comprises the following steps:
when R is 2 When carbazolyl or triphenylamine, X-R is selected in a protective atmosphere 1 -X、Mixing an alkaline reagent I, a palladium catalyst I and a solvent I, and performing a first coupling reaction to obtain R 2 -R 1 -X；
When R is 2 In the case of 9, 9-dimethyl-9, 10-dihydroacridinyl, X-R is treated under a protective atmosphere 1 Mixing the-X, 9-dimethyl-9, 10-dihydroacridine, an alkaline reagent II, a palladium catalyst II, a catalyst ligand and a solvent II, and performing C-N coupling reaction to obtain R 2 -R 1 -X；
The X-R 1 -X and R 2 -R 1 -X in X is bromo or iodo;
subjecting the R to 2 -R 1 Mixing X, 3, 5-dihydroxyphenylboronic acid, an alkaline reagent III, a palladium catalyst III and a solvent III, and performing a second coupling reaction to obtain a compound with a structure shown in a formula II;
mixing the compound with the structure shown in the formula II with 1, 6-hexamethylene diisocyanate and 2, 2-dimethylolpropionic acid, and performing chain extension reaction to obtain a polymer luminescent material with the structure shown in the formula I;
preferably, the solvent I and solvent III are independently toluene and water.
Preferably, the temperature of the first coupling reaction is 80-110 ℃; the heat preservation time of the first coupling reaction is 10-14 h.
Preferably, the solvent II is toluene.
Preferably, the temperature of the second coupling reaction is 80-110 ℃; the heat preservation time of the second coupling reaction is 10-14 h.
Preferably, the protective atmosphere is a nitrogen atmosphere.
Preferably, the temperature of the chain extension reaction is 85-90 ℃.
The invention provides an application of the polymer luminescent material in the technical scheme or the polymer luminescent material prepared by the preparation method in the technical scheme as an organic electroluminescent material.
The invention provides a polymer luminescent material based on a polyurethane main chain, which adopts a non-conjugated main chain of polyurethane to reduce interaction in an aggregation state, effectively reduce aggregation quenching effect caused by pi-pi stacking of long chains of polymer molecules and improve photoluminescence quantum yield; and the polyurethane main chain can conveniently adjust the proportion between the soft segment and the hard segment, thereby remarkably improving the solubility and the film forming property of the polymer and being beneficial to improving the performance of the polymer in electroluminescent devices. The invention adopts the polyurethane main chain to facilitate the polymerization, can reach very high polymerization degree, introduces TADF to the receptor unit as a side chain into the polymer, and can realize the regulation and control of the luminous color.
Drawings
FIG. 1 is a fluorescence spectrum of the polymer luminescent material prepared in example 1 in toluene;
FIG. 2 is a graph showing fluorescence spectra of the polymer light emitting material prepared in example 2 in toluene;
FIG. 3 is a fluorescence spectrum of the polymer luminescent material prepared in example 3 in toluene.
Detailed Description
The invention provides a polymer luminescent material based on a polyurethane main chain, which has a structure shown in a formula I:
in the formula I, R 1 Is quinoxalinyl or 2, 3-dicyanoquinoxalinyl; r is R 2 Is carbazolyl, triphenylamine or 9, 9-dimethyl-9, 10-dihydroacridinyl; x+z ranges from 0.05 to 0.5, and y ranges from 0.5 to 0.95.
In the present invention, when R 1 In the case of quinoxalinyl, R 2 Is carbazolyl, triphenylamine or 9, 9-dimethyl-9, 10-dihydroacridinyl; when R is 1 R in the case of 2, 3-dicyanoquinoxalinyl 2 Is carbazolyl, triphenylamine or 9, 9-dimethyl-9, 10-dihydroacridinyl.
In the present invention, the quinoxalinyl group has the structure ofThe structure of the 2, 3-dicyanoquinoxalinyl is thatThe carbazolyl group has the structure +.>The triphenylamine group has the structure of +.>The structure of the 9, 9-dimethyl-9, 10-dihydroacridine group is +.>
In the present invention, x+y+z=1. In a specific embodiment of the present invention, x=0.1 to 0.2, z=0.4 to 0.3, and y=0.5.
In the present invention, the number average molecular weight of the polyurethane backbone-based polymer light emitting material is preferably 4699 to 5497Da; the weight average molecular weight is preferably 7330-8190 Da; the dispersity is preferably 1.49 to 1.56.
In the present invention, the polyurethane backbone-based polymer light emitting material preferably includes
The invention provides a preparation method of the polymer luminescent material, which comprises the following steps:
when R is 2 When carbazolyl or triphenylamine, X-R is selected in a protective atmosphere 1 -X、Mixing an alkaline reagent I, a palladium catalyst I and a solvent I, and performing a first coupling reaction to obtain R 2 -R 1 -X；
When R is 2 In the case of 9, 9-dimethyl-9, 10-dihydroacridinyl, X-R is treated under a protective atmosphere 1 Mixing the-X, 9-dimethyl-9, 10-dihydroacridine, an alkaline reagent II, a palladium catalyst II, a catalyst ligand and a solvent II, and performing C-N coupling reaction to obtain R 2 -R 1 -X；
The X-R 1 -X and R 2 -R 1 -X in X is bromo or iodo;
subjecting the R to 2 -R 1 Mixing X, 3, 5-dihydroxyphenylboronic acid, an alkaline reagent III, a palladium catalyst III and a solvent III, and performing a second coupling reaction to obtain a compound with a structure shown in a formula II;
mixing the compound with the structure shown in the formula II with 1, 6-hexamethylene diisocyanate and 2, 2-dimethylolpropionic acid, and performing chain extension reaction to obtain a polymer luminescent material with the structure shown in the formula I;
when R is 2 When carbazolyl or triphenylamine, the invention uses X-R in protective atmosphere 1 -X、Mixing an alkaline reagent I, a palladium catalyst I and a solvent I, and performing a first coupling reaction to obtain R 2 -R 1 -X. In the present invention, the protective atmosphere is preferably a nitrogen atmosphere. In the present invention, the X-R 1 -X and R 2 -R 1 X in X is bromo or iodo, preferably Br.
In the present invention, the X-R 1 -X andthe molar ratio of (2) is preferably 1 to 1.5:1, more preferably 1.1 to 1.4:1. In the present invention, the alkaline agent I preferably includes sodium carbonate, sodium acetate or potassium carbonate; the X-R 1 The molar ratio of X to alkaline agent I is preferably from 10 to 15:20 to 25. In the present invention, the palladium catalyst I preferably comprises tetrakis (triphenylphosphine) palladium, palladium acetate or tris (dibenzylideneacetone) dipalladium; the X-R 1 The molar ratio of X to palladium catalyst I is preferably from 10 to 15:0.5 to 0.75. In the present invention, the solvent I is preferably toluene and water; the volume ratio of toluene to water is preferably 40-60:10-15. In the present invention, the X-R 1 The ratio of X to solvent I is preferably between 10 and 15mmol: 50-75 mL.
In the present invention, the temperature of the first coupling reaction is preferably 80 to 110 ℃, more preferably 90 to 100 ℃; the incubation time for the first coupling reaction is preferably 10 to 14 hours, more preferably 12 to 13 hours.
The present invention preferably further comprises a post-treatment after said first coupling reaction; the post-treatment preferably includes filtration, extraction, spin-drying and column chromatography performed sequentially. In the present invention, the extraction reagent is preferably ethyl acetate or methylene chloride; the reagent for column chromatography is preferably one or more of n-hexane, ethyl acetate and dichloromethane.
When R is 2 In the case of 9, 9-dimethyl-9, 10-dihydroacridinyl, the invention uses X-R under the protection atmosphere 1 Mixing the-X, 9-dimethyl-9, 10-dihydroacridine, an alkaline reagent II, a palladium catalyst II, a catalyst ligand and a solvent II, and performing C-N coupling reaction to obtain R 2 -R 1 -X; the X-R 1 -X and R 2 -R 1 X in X is bromo or iodo, preferably Br.
In the present invention, the X-R 1 The molar ratio of X to 9, 9-dimethyl-9, 10-dihydroacridine is preferably 1 to 1.5:1, more preferably 1.1 to 1.4:1. In the present invention, the alkaline agent II is preferably sodium tert-butoxide; the X-R 1 The molar ratio of X to alkaline reagent II is preferably from 10 to 15:20 to 25. In the present invention, the palladium catalyst II preferably comprises tetrakis (triphenylphosphine) palladium, palladium acetate, or tris (dibenzylideneacetone) dipalladium; the X-R 1 The molar ratio of X to palladium catalyst II is preferably from 10 to 15:0.5 to 0.75. In the present invention, the catalyst ligand is preferably (tri-t-butyl) phosphine tetrafluoroborate; the molar ratio of palladium catalyst II to catalyst ligand is preferably 0.5:1. In the present invention, the solvent II is preferably toluene. In the present invention, the X-R 1 The ratio of X to solvent II is preferably between 10 and 15mmol: 40-75 mL.
In the present invention, the temperature of the C-N coupling reaction is preferably 80 to 110 ℃, more preferably 90 to 100 ℃; the incubation time for the C-N coupling reaction is preferably 10 to 14 hours, more preferably 12 to 13 hours.
The invention preferably further comprises a post-treatment after the C-N coupling reaction; the post-treatment preferably includes filtration, extraction, spin-drying and column chromatography performed sequentially. In the present invention, the extraction reagent is preferably ethyl acetate or methylene chloride; the reagent for column chromatography is preferably one or more of n-hexane, ethyl acetate and dichloromethane.
Obtaining R 2 -R 1 After X, the invention provides the R 2 -R 1 Mixing X, 3, 5-dihydroxyphenylboronic acid, an alkaline reagent III, a palladium catalyst III and a solvent III, and performing a second coupling reaction to obtain a compound with a structure shown in a formula II. In the invention, the structural formula of the 3, 5-dihydroxyphenylboronic acid isIn the present invention, the R 2 -R 1 The molar ratio of X to 3, 5-dihydroxyphenylboronic acid is preferably from 1:1 to 1.5. In the present invention, the alkaline agent III preferably includes sodium carbonate, sodium acetate or potassium carbonate; the R is 2 -R 1 The molar ratio of X to alkaline reagent III is preferably from 10 to 15:20 to 25. In the present invention, the palladium catalyst III preferably comprises tetrakis (triphenylphosphine) palladium, palladium acetate or tris (dibenzylideneacetone) dipalladium; the R is 2 -R 1 The molar ratio of X to palladium catalyst III is preferably from 10 to 15:0.5 to 0.75. In the present invention, the solvent III is preferably toluene and water; the volume ratio of toluene to water is preferably 4-6:1; the R is 2 -R 1 The ratio of X to solvent III is preferably between 10 and 15mmol: 40-60 mL.
In the present invention, the second coupling reaction is preferably performed in a protective atmosphere, more preferably in a nitrogen atmosphere. In the present invention, the temperature of the second coupling reaction is preferably 80 to 110 ℃, more preferably 90 to 100 ℃; the holding time of the second coupling reaction is preferably 10 to 14 hours, more preferably 12 to 13 hours.
The present invention preferably further comprises a post-treatment after said second coupling reaction; the post-treatment comprises sequentially performing filtration, extraction, spin drying and column chromatography. In the present invention, the extraction reagent is preferably ethyl acetate or methylene chloride; the reagent for column chromatography is preferably one or more of n-hexane, ethyl acetate and dichloromethane.
In the present invention, the compound having the structure shown in formula II is
After obtaining the compound with the structure shown in the formula II, the invention mixes the compound with the structure shown in the formula II, 1, 6-hexamethylene diisocyanate and 2, 2-dimethylolpropionic acid, and carries out chain extension reaction to obtain the polymer luminescent material with the structure shown in the formula I. In the invention, the proportion of the compound with the structure shown in the formula II, 1, 6-hexamethylene diisocyanate and 2, 2-dimethylolpropionic acid is based on the structure shown in the formula I. In the present invention, the mixing preferably includes: mixing the compound with the structure shown in the formula II with 1, 6-hexamethylene diisocyanate, heating to 75-80 ℃ and stirring for 2 hours, and then adding 2, 2-dimethylolpropionic acid for mixing.
In the present invention, the temperature of the chain extension reaction is preferably 85 to 90 ℃. The invention preferably adopts TLC to monitor the reaction progress, and particularly preferably comprises the following steps: the system was warmed to 85-90 ℃ for chain extension, the HDI concentration was observed at 2 hour intervals, and when the HDI concentration was minimized, acetone was added to reduce the viscosity and triethylamine was used to quench the HDI.
The invention preferably further comprises post-treatment after the chain extension reaction; the post-processing includes: pouring the obtained reaction solution into methanol to separate out precipitate, and filtering to obtain solid; adding the solid into hydrochloric acid solution, stirring for dissolution, extracting with chloroform, separating and collecting organic phase; adding water into the organic phase, extracting and separating, repeating for 3 times, and collecting the residual organic phase; concentrating the organic phase by vacuum rotary evaporation, pouring the concentrated solution into methanol to separate out precipitate, filtering to obtain solid, placing the solid in a Soxhlet purifier, purifying with acetone, and drying to obtain the polymer luminescent material with the structure shown in formula I. In the specific embodiment of the invention, the reaction solution obtained by the chain extension reaction is poured into methanol, stirred for 25 to 30 minutes to precipitate out and filtered to obtain solid; adding the solid into a hydrochloric acid solution with the concentration of 2mol/L, stirring and dissolving, extracting with chloroform, separating and collecting an organic phase; adding deionized water into the organic phase, stirring for 5-25 min, extracting and separating, repeating for 3 times, and collecting the residual organic phase; the organic phase is concentrated by vacuum rotary evaporation, the concentrated solution is poured into methanol and stirred for 25 to 30min to separate out precipitate, the solid is obtained by filtration, then the solid is placed in a Soxhlet purifier, after being purified by acetone for 24 to 48h, the solid is dried for 4 to 8h in a vacuum drying oven at 50 to 75 ℃ to obtain the polymer luminescent material with the structure shown in the formula I.
In the invention, the yield of the polymer luminescent material with the structure shown in the formula I is preferably 30-60%; the purity is preferably >99%.
The invention also provides an application of the polymer luminescent material prepared by the technical scheme or the preparation method of the technical scheme as an organic electroluminescent material. The polymer luminescent material provided by the invention is used for preparing an organic electroluminescent device with the structure of ITO/poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate (PEDOT: PSS)/polymer luminescent material with the structure shown in formula I/1, 3, 5-tri (m-pyridin-3-yl phenyl) benzene (TmPyPB)/LiF/Al, the electroluminescent color range is yellow light to red light, and the electroluminescent spectrum range is wider. In the invention, the thickness of PEDOT: PSS is preferably 40nm; the thickness of the polymer luminescent material with the structure shown in the formula I is preferably 40-50 nm; the thickness of the TmPyPB is preferably 40-50 nm; the thickness of LiF is preferably 1nm; the Al thickness is preferably 150nm.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Synthesis of polymeric luminescent materials with triphenylamine and quinoxaline as donor-acceptor combinations
(1) Synthesis of 4- (8-bromo-quinoxaline-5-phenyl) -N, N-diphenylamine
To a dry and clean three-necked flask, 11mmol of triphenylamine 4-borate, 10mmol of 1, 4-dibromoquinoxaline and 20mmol of anhydrous sodium carbonate were added, 40mL of anhydrous toluene and 10mL of water were added, then the three-necked flask was evacuated and nitrogen was introduced, 0.5mmol of tetrakis (triphenylphosphine) palladium was added under the protection of nitrogen, then the evacuation and nitrogen introduction were continued for three times, then the reaction was carried out at 100℃for 12 hours, then the reaction was carried out, filtration, extraction and spin-drying were carried out, and then column chromatography was carried out to obtain the product 4- (8-bromo-quinoxaline-5-phenyl) -N, N-diphenylamine.
1 H NMR(500MHz,DMSO-d 6 )δ8.76–8.68(m,1H),7.99–7.91(m,1H),7.66–7.60(m,1H),7.33–7.27(m,2H),7.27–7.22(m,1H),7.14–7.08(m,2H),7.07(tt,J＝7.4,1.4Hz,1H)。
(2) Synthesis of (4- (8-bromo-quinoxalin-5-phenyl) -N, N-dianilino) -1, 3-dihydroxyphenol
To a dry and clean three-necked flask, 11mmol of 3, 5-dihydroxyphenylboronic acid and 10mmol of 4- (8-bromo-quinoxaline-5-phenyl) -N, N-diphenylamine, and 20mmol of anhydrous sodium carbonate were added, and 40mL of anhydrous toluene and 10mL of water were added, followed by vacuum-pumping the three-necked flask, nitrogen gas was introduced, and 0.5mmol of tetrakis (triphenylphosphine) palladium was added under nitrogen protection, followed by continuing vacuum-pumping the nitrogen gas three times, then reacting at 100℃for 12 hours, followed by filtration, extraction, spin-drying, and then column chromatography was performed to obtain the product (4- (8-bromo-quinoxaline-5-phenyl) -N, N-diphenylamino) -1, 3-dihydroxyphenol.
1 H NMR(500MHz,DMSO-d 6 )δ8.71(d,J＝7.5Hz,1H),8.67(d,J＝7.5Hz,1H),7.90(d,J＝7.5Hz,1H),7.85(d,J＝7.5Hz,1H),7.63–7.57(m,2H),7.30–7.23(m,4H),7.21–7.16(m,2H),7.13–7.04(m,6H),7.02(d,J＝1.5Hz,2H),6.25(t,J＝1.4Hz,1H)。
(3) Synthesis of polymeric luminescent materials
Where x=0.1, z=0.4, and y=0.5.
2mmol (4- (8-bromo-quinoxaline-5-phenyl) -N, N-diphenylamino) -1, 3-dihydroxyphenol and 10mmol 1, 6-Hexamethylene Diisocyanate (HDI) are added into a dry and clean three-neck flask, the temperature is raised to 75 ℃ and stirred for two hours, then 8mmol 2, 2-dimethylolpropionic acid (DMPA) is added for chain extension, the temperature is raised to 85 ℃ for reaction, then the HDI concentration is observed at intervals of 2 hours, when the HDI concentration is reduced to the minimum, acetone is added to reduce the viscosity and triethylamine is used for quenching the HDI, the obtained reaction solution is poured into methanol and stirred for 25 minutes to separate out precipitate, and the yellow solid is obtained by filtration; adding the yellow solid into 2mol/L hydrochloric acid solution, stirring and dissolving, extracting with chloroform, separating and collecting an organic phase; adding deionized water into the organic phase, stirring for 30min, extracting and separating, repeating for 3 times, and collecting the residual organic phase; the organic phase is concentrated by vacuum rotary evaporation, the concentrated solution is poured into methanol and stirred for 30min to precipitate, yellow solid is obtained by filtration, then the solid is placed in a Soxhlet purifier, acetone is used for purifying for 40h, and then the solid is dried for 6h in a vacuum drying oven at 70 ℃ to obtain the polymer luminescent material taking triphenylamine and quinoxaline as donor-acceptor combination.
The polymer light emitting material obtained in this example had a number average molecular weight of 5026, a weight average molecular weight of 7690 and a dispersity of 1.53.
FIG. 1 is a graph showing fluorescence spectra of the polymer luminescent material prepared in example 1 in toluene, and as can be seen from FIG. 1, the polymer luminescent material emits green light in toluene solution, and the luminescence peak is at 528nm.
Example 2
Synthesis of polymeric luminescent materials with triphenylamine and dicyanoquinoxaline as donor-acceptor combinations
(1) Synthesis of 6-bromo-7- (4-diphenylamino) -2, 3-dicyanoquinoxaline
To a dry and clean three-necked flask, 11mmol of triphenylamine 4-borate and 10mmol of 6, 7-dibromo-2, 3-dicyanoquinoxaline, and 20mmol of anhydrous sodium carbonate were added, and 40mL of anhydrous toluene and 10mL of water were added, followed by vacuum-pumping the three-necked flask, nitrogen gas was introduced, and 0.5mmol of tetrakis (triphenylphosphine) palladium was added under nitrogen protection, followed by continuing vacuum-pumping and nitrogen gas introduction three times, then reaction was carried out at 100℃for 12 hours, followed by filtration, extraction, spin-drying and then column chromatography to obtain the product 6-bromo-7- (4-diphenylamino) -2, 3-dicyanoquinoxaline.
1 H NMR(500MHz,DMSO-d 6 )δ8.63(s,1H),8.44(s,1H),7.61–7.55(m,2H),7.30–7.22(m,6H),7.13–7.07(m,4H),7.06(tt,J＝7.4,1.5Hz,2H)。
(2) Synthesis of 6- (3, 5-dihydroxybenzene) -7- (4-diphenylamino) -2, 3-dicyanoquinoxaline
To a dry and clean three-necked flask were added 11mmol of 3, 5-dihydroxyphenylboronic acid and 10mmol of 6-bromo-7- (4-diphenylamino) -2, 3-dicyanoquinoxaline, and 20mmol of anhydrous sodium carbonate, and 40mL of anhydrous toluene and 10mL of water, followed by vacuum-pumping of nitrogen, addition of 0.5mmol of tetrakis (triphenylphosphine) palladium under nitrogen protection, followed by continuing vacuum-pumping of nitrogen three times, then reaction at 100℃for 12 hours, filtration, extraction, spin-drying, and column chromatography to obtain the product 6- (3, 5-dihydroxybenzene) -7- (4-diphenylamino) -2, 3-dicyanoquinoxaline.
1 H NMR(500MHz,DMSO-d 6 )δ8.59(s,1H),8.54(s,1H),7.68–7.62(m,2H),7.31–7.24(m,4H),7.27–7.18(m,2H),7.13–7.03(m,6H),6.90(d,J＝1.5Hz,2H),6.27(t,J＝1.4Hz,1H)。
(3) Synthesis of polymeric luminescent materials
Where x=0.1, z=0.4, and y=0.5.
2mmol of 6- (3, 5-dihydroxybenzene) -7- (4-diphenylamino) -2, 3-dicyanoquinoxaline and 10mmol of 1, 6-Hexamethylene Diisocyanate (HDI) are added into a dry and clean three-neck flask, the temperature is raised to 75 ℃ and stirred for two hours, then 8mmol of 2, 2-dimethylolpropionic acid (DMPA) is added for chain extension, the temperature is raised to 85 ℃ for reaction, then the HDI concentration is observed at intervals of 2 hours, when the HDI concentration is reduced to the minimum, acetone is added to reduce the viscosity and the HDI is quenched by triethylamine, the obtained reaction solution is poured into methanol and stirred for 25 minutes to precipitate, and red solid is obtained by filtration; adding the red solid into a hydrochloric acid solution with the concentration of 2mol/L, stirring and dissolving, extracting with chloroform, separating and collecting an organic phase; adding deionized water into the organic phase, stirring for 20min, extracting and separating, repeating for 3 times, and collecting the residual organic phase; the organic phase is concentrated by vacuum rotary evaporation, the concentrated solution is poured into methanol and stirred for 30min to precipitate, the red solid is obtained by filtration, then the solid is placed in a Soxhlet purifier, acetone is used for purifying for 40h, and then the solid is dried for 6h in a vacuum drying oven at 70 ℃ to obtain the polymer luminescent material taking triphenylamine and dicyanoquinoxaline as donor-acceptor combination.
The polymer light-emitting material obtained in this example had a number average molecular weight of 5497, a weight average molecular weight of 8190, and a dispersity of 1.49.
FIG. 2 is a graph showing fluorescence spectra of the polymer luminescent material prepared in example 2 in toluene, and it can be seen from FIG. 2 that the polymer luminescent material emits red light in toluene solution, and the luminescence peak is at 635nm.
Example 3
Synthesis of polymeric luminescent materials with 9, 9-dimethyl-9, 10-dihydroacridine and quinoxaline as donor-acceptor combinations
(1) Synthesis of 10- (8-bromo-quinoxalinyl-5) -9, 9-dimethyl-9, 10-dihydroacridine
To a dry and clean three-necked flask, 11mmol of 9, 9-dimethyl-9, 10-dihydroacridine and 10mmol of 1, 4-dibromoquinoxaline, and 20mmol of anhydrous sodium t-butoxide were added, and 40mL of anhydrous toluene was added, followed by vacuum-pumping the three-necked flask, nitrogen gas was introduced under nitrogen protection, and then 0.5mmol of palladium acetate and 1mmol of (tri-t-butyl) phosphine tetrafluoroborate were added, followed by continuing vacuum-pumping the nitrogen gas three times, then reacting at 110℃for 12 hours, followed by filtration, extraction, spin-drying, and then column chromatography was performed to obtain the product 10- (8-bromo-quinoxaline-5) -9, 9-dimethyl-9, 10-dihydroacridine.
1 H NMR(500MHz,DMSO-d 6 )δ8.64(d,J＝7.5Hz,1H),8.59(d,J＝7.5Hz,1H),7.93(d,J＝7.5Hz,1H),7.45(d,J＝7.5Hz,1H),7.19(ddd,J＝7.9,6.6,2.0Hz,2H),7.17–7.08(m,6H),1.57(s,4H)。
(2) Synthesis of 5- (8- (9, 9-dimethyl-9, 10-dihydroacridine) -quinoxalinyl-5) -1, 3-dihydroxyphenol
To a dry and clean three-necked flask, 11mmol of 3, 5-dihydroxyphenylboronic acid and 10mmol of 10- (8-bromo-quinoxaline-5) -9, 9-dimethyl-9, 10-dihydroacridine, and 20mmol of anhydrous sodium carbonate were added, and 40mL of anhydrous toluene and 10mL of water were added, followed by vacuum-pumping the three-necked flask, followed by adding 0.5mmol of tetrakis (triphenylphosphine) palladium under nitrogen protection, followed by continuing vacuum-pumping the nitrogen for three times, then reacting at 100℃for 12 hours, followed by filtration, extraction, spin-drying, and then column chromatography to obtain the product 5- (8- (9, 9-dimethyl-9, 10-dihydroacridine) -quinoxalinyl-5) -1, 3-dihydroxyphenol.
1 H NMR(500MHz,DMSO-d 6 )δ8.62(d,J＝7.5Hz,1H),8.55(d,J＝7.5Hz,1H),7.86(d,J＝7.5Hz,1H),7.49(d,J＝7.5Hz,1H),7.22–7.17(m,2H),7.17–7.09(m,4H),7.08(ddd,J＝7.1,5.4,3.7Hz,2H),6.95(d,J＝1.4Hz,2H),6.26(t,J＝1.5Hz,1H),1.57(s,4H)。
(3) Synthesis of polymeric luminescent materials
Where x=0.2, z=0.3, and y=0.5.
4mmol of 5- (8- (9, 9-dimethyl-9, 10-dihydroacridine) -quinoxalinyl-5) -1, 3-dihydroxyphenol and 10mmol of 1, 6-Hexamethylene Diisocyanate (HDI) are added into a dry and clean three-neck flask, the temperature is raised to 75 ℃ and stirred for two hours, then 6mmol of 2, 2-dimethylolpropionic acid (DMPA) is added for chain extension, the temperature is raised to 85 ℃ for reaction, then the HDI concentration is observed at intervals of 2 hours, when the HDI concentration is reduced to the minimum, acetone is added to reduce the viscosity and the HDI is quenched by triethylamine, the obtained reaction solution is poured into methanol and stirred for 25 minutes to precipitate, and orange solid is obtained by filtration; adding the orange solid into 2mol/L hydrochloric acid solution, stirring for dissolution, extracting with chloroform, separating and collecting an organic phase; adding deionized water into the organic phase, stirring for 20min, extracting and separating, repeating for 3 times, and collecting the residual organic phase; the organic phase is concentrated by vacuum rotary evaporation, the concentrated solution is poured into methanol and stirred for 25min to precipitate, orange solid is obtained by filtration, then the solid is placed in a Soxhlet purifier, after being purified by acetone for 40h, the solid is dried in a vacuum drying oven at 70 ℃ for 6h, and the polymer luminescent material taking 9, 9-dimethyl-9, 10-dihydroacridine and quinoxaline as donor-acceptor combination is obtained.
The polymer light-emitting material obtained in this example had a number average molecular weight of 4699, a weight average molecular weight of 7330 and a dispersity of 1.56.
FIG. 3 is a graph showing fluorescence spectra of the polymer luminescent material prepared in example 3 in toluene, and as can be seen from FIG. 3, the polymer luminescent material emits orange light in toluene solution, and the luminescence peak is at 604nm.
Application example
The polymer light emitting material prepared in example 1 was prepared into an OLED device by wet process in the structure of ITO/PEDOT: PSS (40 nm in thickness)/polymer light emitting material prepared in example 1 (40 nm in thickness)/TmPyPB (50 nm in thickness)/LiF (1 nm in thickness)/Al (150 nm in thickness), which had an emission color of orange light, an emission spectrum range of 500 to 600nm, a photoluminescence quantum yield of 85%, and a maximum external quantum efficiency of 15%.
The polymer light emitting material prepared in example 2 was prepared into an OLED device by wet process in the structure of ITO/PEDOT: PSS (40 nm in thickness)/polymer light emitting material prepared in example 2 (40 nm in thickness)/TmPyPB (50 nm in thickness)/LiF (1 nm in thickness)/Al (150 nm in thickness), which had a light emitting color of red light, a light emitting spectrum range of 600 to 700nm, a photoluminescence quantum yield of 81%, and a maximum external quantum efficiency of 12%.
The polymer light-emitting material prepared in example 3 was prepared into an OLED device by wet method in the structure of ITO/PEDOT: PSS (40 nm in thickness)/polymer light-emitting material prepared in example 3 (40 nm in thickness)/TmPyPB (50 nm in thickness)/LiF (1 nm in thickness)/Al (150 nm in thickness), which had a light emission color of red light, a light emission spectrum range of 550 to 700nm, a photoluminescence quantum yield of 79%, and a maximum external quantum efficiency of 13%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A polyurethane backbone-based polymer light emitting material having a structure according to formula I:
in the formula I, R 1 Is quinoxalinyl or 2, 3-dicyanoquinoxalinyl; r is R 2 Is carbazolyl, triphenylamine or 9, 9-dimethyl-9, 10-dihydroacridinyl; x+z ranges from 0.05 to 0.5, and y ranges from 0.5 to 0.95;
the preparation method of the polymer luminescent material comprises the following steps:
when R is 2 When carbazolyl or triphenylamine, X-R is selected in a protective atmosphere 1 -X、Mixing an alkaline reagent I, a palladium catalyst I and a solvent I, and performing a first coupling reaction to obtain R 2 -R 1 -X；
When R is 2 In the case of 9, 9-dimethyl-9, 10-dihydroacridinyl, X-R is treated under a protective atmosphere 1 Mixing the-X, 9-dimethyl-9, 10-dihydroacridine, an alkaline reagent II, a palladium catalyst II, a catalyst ligand and a solvent II, and performing C-N coupling reaction to obtain R 2 -R 1 -X；
The X-R 1 -X and R 2 -R 1 -X in X is bromo or iodo;
subjecting the R to 2 -R 1 Mixing X, 3, 5-dihydroxyphenylboronic acid, an alkaline reagent III, a palladium catalyst III and a solvent III, and performing a second coupling reaction to obtain a compound with a structure shown in a formula II;
mixing the compound with the structure shown in the formula II with 1, 6-hexamethylene diisocyanate and 2, 2-dimethylolpropionic acid, and performing chain extension reaction to obtain a polymer luminescent material with the structure shown in the formula I;
2. the polymer light emitting material according to claim 1, wherein the polyurethane backbone-based polymer light emitting material comprises
3. A method of preparing the polymeric luminescent material according to claim 1 or 2, comprising the steps of:
when R is 2 When carbazolyl or triphenylamine, X-R is selected in a protective atmosphere 1 -X、Mixing an alkaline reagent I, a palladium catalyst I and a solvent I, and performing a first coupling reaction to obtain R 2 -R 1 -X；
When R is 2 In the case of 9, 9-dimethyl-9, 10-dihydroacridinyl, X-R is treated under a protective atmosphere 1 Mixing the-X, 9-dimethyl-9, 10-dihydroacridine, an alkaline reagent II, a palladium catalyst II, a catalyst ligand and a solvent II, and performing C-N coupling reaction to obtain R 2 -R 1 -X；
The X-R 1 -X and R 2 -R 1 -X in X is bromo or iodo;
subjecting the R to 2 -R 1 Mixing X, 3, 5-dihydroxyphenylboronic acid, an alkaline reagent III, a palladium catalyst III and a solvent III, and performing a second coupling reaction to obtain a compound with a structure shown in a formula II;
mixing the compound with the structure shown in the formula II with 1, 6-hexamethylene diisocyanate and 2, 2-dimethylolpropionic acid, and performing chain extension reaction to obtain a polymer luminescent material with the structure shown in the formula I;
4. a process according to claim 3, wherein the solvents I and III are independently toluene and water.
5. The method according to claim 3, wherein the temperature of the first coupling reaction is 80 to 110 ℃; the heat preservation time of the first coupling reaction is 10-14 h.
6. A process according to claim 3, wherein the solvent II is toluene.
7. The method of claim 3, wherein the second coupling reaction is at a temperature of 80 to 110 ℃; the heat preservation time of the second coupling reaction is 10-14 h.
8. A method of preparing according to claim 3, wherein the protective atmosphere is a nitrogen atmosphere.
9. The process according to claim 3, wherein the chain extension reaction is carried out at a temperature of 85 to 90 ℃.
10. Use of a polymer light-emitting material according to any one of claims 1 to 2 or a polymer light-emitting material prepared by a preparation method according to any one of claims 3 to 9 as an organic electroluminescent material.
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| KR101704090B1 (en) * | 2009-09-30 | 2017-02-07 | 스미또모 가가꾸 가부시키가이샤 | Laminated structure, polymer, electroluminescent element, and photoelectric conversion element |
| JP5501526B2 (en) * | 2010-05-24 | 2014-05-21 | ▲海▼洋王照明科技股▲ふん▼有限公司 | Quinoxaline conjugated polymer containing fused-ring thiophene units, method for producing the conjugated polymer and application thereof |
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| DE19719925A1 (en) * | 1997-05-13 | 1998-11-19 | Basf Ag | Production of low viscosity amino-polyurethane dispersion |
| CN102093232A (en) * | 2011-01-27 | 2011-06-15 | 华南理工大学 | Trifluoreneamine compound, trifluoreneamine polymer luminescent material and preparation methods and application thereof |
| CN106832175A (en) * | 2017-02-17 | 2017-06-13 | 华南理工大学 | A kind of double hydroxyl fluorescence chain extenders and its preparation and application based on carbazole derivates |
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