CN114805741A - 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
- Publication number
- CN114805741A CN114805741A CN202210404648.XA CN202210404648A CN114805741A CN 114805741 A CN114805741 A CN 114805741A CN 202210404648 A CN202210404648 A CN 202210404648A CN 114805741 A CN114805741 A CN 114805741A
- Authority
- CN
- China
- Prior art keywords
- polymer
- coupling reaction
- luminescent material
- solvent
- main chain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3848—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing two nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
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 type, which can reduce the interaction in aggregation state, effectively reduce aggregation quenching effect caused by pi-accumulation of long chain of polymer molecule, and improve photoluminescence quantum yield; and the proportion of soft and hard chain segments can be conveniently adjusted by the polyurethane type main chain, so that the solubility and the film-forming property of the polymer can be obviously improved, and the performance of the polymer in an electroluminescent device can be improved. The invention adopts the polyurethane main chain to facilitate the realization of polymerization, can achieve high polymerization degree, and can realize the regulation and control of luminous color by introducing TADF donor-acceptor units as side chains into the polymer.
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 more and more widely used due to their incomparable advantages over conventional Liquid Crystal Displays (LCDs) in lighting, wearable, flexible displays, and large-scale displays. The OLED device prepared based on the wet processes such as spin coating, ink-jet printing and the like has the advantages which cannot be compared with a vacuum evaporation method in the aspects of flexible display and large-size display, and is very beneficial to industrial large-scale production. Among them, the polymer light emitting unit is the most important ring in the wet device, and the preparation of high performance Polymer Light Emitting Diode (PLED) is the current research focus.
Existing polymer light emitting materials can be classified into the following three types according to a light emitting mechanism: fluorescent polymers, phosphorescent polymers, and Thermally Activated Delayed Fluorescence (TADF) polymer molecules. TADF originated from 2012, professor Chihaya Adachi at kyushu university, japan published in nature journal a paper entitled "highly efficient organic light emitting diode derived from delayed fluorescence" (Uoyama, h., Goushi, k., Shizu, k.et al. nature 492, 234-. TADF polymer light emitting materials have received increasing attention because of their high exciton utilization and high efficiency, compared to conventional fluorescent or phosphorescent polymer light emitting materials.
The main structure of the current TADF-based polymer material is a conjugated unit as a main chain, and a side chain is a TADF donor-acceptor structure (Yun Yang, Lei Zhao, Shumeng Wang, junqi Ding, and Lixiang Wang et al macromolecules 201851 (23), 9933-. However, such a conjugated main chain has strong interaction in an aggregation state, so that the photoluminescence quantum yield (PLQY) of the polymer in a thin film state is sharply reduced, and an aggregation quenching effect is formed. 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 in electroluminescent devices.
Disclosure of Invention
The invention aims to provide a polymer luminescent material based on a polyurethane main chain, and a preparation method and application thereof.
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 2 Is a carbazolyl group, a triphenylamine group or a 9, 9-dimethyl-9, 10 dihydroacridinyl group; x + z ranges from 0.05 to 0.5, and y ranges from 0.5 to 0.95.
Preferably, the polymer light emitting material based on the polyurethane backbone comprises
The invention provides a preparation method of the polymer luminescent material in the technical scheme, which comprises the following steps:
when R is 2 In the case of carbazolyl or triphenylamine, reacting X-R in a protective atmosphere 1 -X、
Mixing an alkaline reagent I, a palladium catalyst I and a solvent I, and carrying out a first coupling reaction to obtain R 2 -R 1 -X；
When R is 2 In the case of a 9, 9-dimethyl-9, 10-dihydroacridinyl radical, X-R is reacted under a protective atmosphere 1 mixing-X, 9-dimethyl-9, 10-dihydroacridine, an alkaline reagent II, a palladium catalyst II, a catalyst ligand and a solvent II, and carrying out 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 a bromo or iodo group;
the R is 2 -R 1 Mixing (E) -X and 3, 5-dihydroxybenzeneboronic acid, an alkaline agent III, a palladium catalyst III and a solvent IIICarrying out 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, 1, 6-hexamethylene diisocyanate and 2, 2-dimethylolpropionic acid, and carrying out chain extension reaction to obtain a polymer luminescent material with the structure shown in the formula I;
preferably, the solvent I and the 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 ℃; and 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 the application of the polymer luminescent material 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 polyurethane type non-conjugated main chain to reduce the interaction under an aggregation state, effectively reduces aggregation quenching effect caused by pi-pi accumulation of a long chain of a polymer molecule, and improves the photoluminescence quantum yield; and the proportion of soft and hard chain segments can be conveniently adjusted by the polyurethane type main chain, so that the solubility and the film-forming property of the polymer can be obviously improved, and the performance of the polymer in an electroluminescent device can be improved. The invention adopts the polyurethane main chain to facilitate the realization of polymerization, can achieve high polymerization degree, and can realize the regulation and control of luminous color by introducing TADF donor-acceptor units as side chains into the polymer.
Drawings
FIG. 1 is a graph showing a fluorescence spectrum of a polymer light emitting material prepared in example 1 in toluene;
FIG. 2 is a graph showing a fluorescence spectrum of a polymer light emitting material prepared in example 2 in toluene;
FIG. 3 is a fluorescence spectrum of the polymer light emitting 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 2 Is a carbazolyl group, a triphenylamine group or a 9, 9-dimethyl-9, 10 dihydroacridinyl group; x + z ranges from 0.05 to 0.5, and y ranges from 0.5 to 0.95.
In the present invention, when R is 1 When it is quinoxalinyl, R 2 Is carbazolyl, triphenylamine group or 9, 9-dimethyl-9, 10 dihydroacridinyl; when R is 1 In the case of 2, 3-dicyanoquinoxalinyl, R 2 Is carbazolyl, triphenylamine group or 9, 9-dimethyl-9, 10 dihydroacridine group.
In the present invention, the quinoxalinyl group has the structure
The 2, 3-dicyano quinoxalinyl has the structure
The structure of the carbazolyl is
The triphenylamine group has a structure of
Of said 9, 9-dimethyl-9, 10-dihydroacridinylHas the structure of
In the present invention, x + y + z is 1. In a specific embodiment of the present invention, x is 0.1 to 0.2, z is 0.4 to 0.3, and y is 0.5.
In the invention, the number average molecular weight of the polymer luminescent material based on the polyurethane main chain is preferably 4699-5497 Da; the weight-average molecular weight is preferably 7330-8190 Da; the dispersion degree is preferably 1.49 to 1.56.
In the present invention, the polymer light emitting material based on the polyurethane backbone preferably includes
The invention provides a preparation method of the polymer luminescent material in the technical scheme, which comprises the following steps:
when R is 2 In the case of carbazolyl or triphenylamine, the reaction is carried out under a protective atmosphere 1 -X、
Mixing an alkaline reagent I, a palladium catalyst I and a solvent I, and carrying out a first coupling reaction to obtain R 2 -R 1 -X；
When R is 2 In the case of a 9, 9-dimethyl-9, 10-dihydroacridinyl radical, X-R is reacted under a protective atmosphere 1 mixing-X, 9-dimethyl-9, 10-dihydroacridine, an alkaline reagent II, a palladium catalyst II, a catalyst ligand and a solvent II, and carrying out 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 a bromo or iodo group;
the R is 2 -R 1 Mixing the-X and the 3, 5-dihydroxy benzene boric acid, an alkaline reagent III, a palladium catalyst III and a solvent III, and carrying out 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, 1, 6-hexamethylene diisocyanate and 2, 2-dimethylolpropionic acid, and carrying out chain extension reaction to obtain a polymer luminescent material with the structure shown in the formula I;
when R is 2 When the compound is carbazolyl or triphenylamine, the invention leads X-R to be in protective atmosphere 1 -X、
Mixing an alkaline reagent I, a palladium catalyst I and a solvent I, and carrying out 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 a bromine group or an iodine group, preferably Br.
In the present invention, the X-R 1 -X and
the molar ratio of (A) to (B) 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 mol ratio of the-X to the alkaline reagent I is preferably 10-15: 20-25. 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 the palladium catalyst I is preferably 10-15: 0.5 to 0.75. In the present invention, the solvent I is preferably toluene and water; the volume ratio of the toluene to the water is preferably 40-60: 10-15. In the present invention, the X-R 1 The dosage ratio of-X to the solvent I is preferably 10-15 mmol: 50-75 mL.
In the invention, the temperature of the first coupling reaction is preferably 80-110 ℃, and more preferably 90-100 ℃; the heat preservation time of the first coupling reaction is preferably 10-14 h, and more preferably 12-13 h.
The present invention preferably further comprises a post-treatment after the first coupling reaction; the post-treatment preferably comprises filtration, extraction, spin-drying and column chromatography performed in sequence. In the present invention, the extraction reagent is preferably ethyl acetate or dichloromethane; 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 a 9, 9-dimethyl-9, 10-dihydroacridinyl group, the invention provides for the reaction of X-R under a protective atmosphere 1 mixing-X, 9-dimethyl-9, 10-dihydroacridine, an alkaline reagent II, a palladium catalyst II, a catalyst ligand and a solvent II, and carrying out 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 a bromine group or an iodine group, preferably Br.
In the present invention, the X-R 1 The molar ratio of-X to 9, 9-dimethyl-9, 10-dihydroacridine is preferably 1-1.5: 1, more preferably 1.1-1.4: 1. In the present invention, the alkaline agent II is preferably sodium tert-butoxide; the X-R 1 The mol ratio of the-X to the alkaline reagent II is preferably 10-15: 20-25. 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 the palladium catalyst II is preferably 10-15: 0.5 to 0.75. In the present invention, the catalyst ligand is preferably (tri-tert-butyl) phosphine tetrafluoroborate; the molar ratio of the palladium catalyst II to the 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 dosage ratio of the-X to the solvent II is preferably 10-15 mmol: 40-75 mL.
In the invention, the temperature of the C-N coupling reaction is preferably 80-110 ℃, and more preferably 90-100 ℃; the heat preservation time of the C-N coupling reaction is preferably 10-14 h, and more preferably 12-13 h.
The present invention preferably further comprises a post-treatment after the C-N coupling reaction; the post-treatment preferably comprises filtration, extraction, spin-drying and column chromatography performed in sequence. In the present invention, the extraction reagent is preferably ethyl acetate or dichloromethane; the reagent for column chromatography is preferably one or more of n-hexane, ethyl acetate and dichloromethane.
To obtain R 2 -R 1 After X, the invention relates to said R 2 -R 1 Mixing the-X and the 3, 5-dihydroxy benzene boric acid, an alkaline reagent III, a palladium catalyst III and a solvent III, and carrying out a second coupling reaction to obtain the compound with the structure shown in the formula II. In the invention, the structural formula of the 3, 5-dihydroxy benzene boric acid is shown as
In the present invention, said R 2 -R 1 The molar ratio of-X to 3, 5-dihydroxybenzoic acid is preferably 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 mol ratio of the-X to the alkaline reagent III is preferably 10-15: 20-25. 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 the palladium catalyst III is preferably 10-15: 0.5 to 0.75. In the present invention, the solvent III is preferably toluene and water; the volume ratio of the toluene to the water is preferably 4-6: 1; the R is 2 -R 1 The dosage ratio of-X to the solvent III is preferably 10-15 mmol: 40-60 mL.
In the present invention, the second coupling reaction is preferably carried out in a protective atmosphere, more preferably in a nitrogen atmosphere. In the invention, the temperature of the second coupling reaction is preferably 80-110 ℃, and more preferably 90-100 ℃; the heat preservation time of the second coupling reaction is preferably 10-14 h, and more preferably 12-13 h.
The present invention preferably further comprises a post-treatment after the second coupling reaction; the post-treatment comprises filtering, extraction, spin-drying and column chromatography which are sequentially carried out. In the present invention, the extraction reagent is preferably ethyl acetate or dichloromethane; the reagent for column chromatography is preferably one or more of n-hexane, ethyl acetate and dichloromethane.
In the invention, the compound with the structure shown in the formula II is
After the compound with the structure shown in the formula II is obtained, the compound with the structure shown in the formula II, 1, 6-hexamethylene diisocyanate and 2, 2-dimethylolpropionic acid are mixed for chain extension reaction, and the polymer luminescent material with the structure shown in the formula I is obtained. In the invention, the proportion of the compound with the structure shown in the formula II, the 1, 6-hexamethylene diisocyanate and the 2, 2-dimethylolpropionic acid is based on the condition that the structure shown in the formula I is satisfied. In the present invention, the mixing preferably comprises: and (2) mixing the compound with the structure shown in the formula II and 1, 6-hexamethylene diisocyanate, heating to 75-80 ℃, stirring for 2 hours, and then adding 2, 2-dimethylolpropionic acid for mixing.
In the invention, the temperature of the chain extension reaction is preferably 85-90 ℃. The invention preferably adopts TLC to monitor the reaction progress, and particularly preferably adopts the following steps: and (3) heating the system to 85-90 ℃ for chain extension reaction, observing the HDI concentration by using a time board at intervals of 2 hours, adding acetone to reduce the viscosity and quenching the HDI by using triethylamine when the HDI concentration is reduced to the minimum.
The invention preferably also comprises post-treatment after the chain extension reaction; the post-processing comprises: pouring the obtained reaction solution into methanol to separate out a precipitate, and filtering to obtain a solid; adding the solid into a hydrochloric acid solution, stirring and dissolving, extracting with chloroform, and separating and collecting an organic phase; adding water into the organic phase, extracting and separating, repeating for 3 times, and collecting the residual organic phase; and (2) concentrating the organic phase by vacuum rotary evaporation, pouring the concentrated solution into methanol to separate out a precipitate, filtering to obtain a solid, then putting the solid into a Soxhlet purifier, purifying with acetone, and drying to obtain the polymer luminescent material with the structure shown in the formula I. In the specific embodiment of the invention, the reaction solution obtained by the chain extension reaction is poured into methanol and stirred for 25-30 min to precipitate, and the solid is obtained by filtering; adding the solid into 2mol/L hydrochloric acid solution, stirring and dissolving, then 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; and (2) concentrating the organic phase by vacuum rotary evaporation, pouring the concentrated solution into methanol, stirring for 25-30 min to separate out a precipitate, filtering to obtain a solid, then putting the solid into a Soxhlet purifier, purifying for 24-48 h by using acetone, and drying for 4-8 h in a vacuum drying oven at 50-75 ℃ 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 the 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-pyridine-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 the PEDOT to PSS is preferably 40 nm; 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 the LiF is preferably 1 nm; the thickness of the Al is preferably 150 nm.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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 luminescent material with triphenylamine and quinoxaline as donor-acceptor combination
(1) Synthesis of 4- (8-bromo-quinoxaline-5-phenyl) -N, N-diphenylamine
Adding 11mmol of 4-triphenylamine borate, 10mmol of 1, 4-dibromoquinoxaline and 20mmol of anhydrous sodium carbonate into a dry and clean three-neck flask, adding 40mL of anhydrous toluene and 10mL of water, vacuumizing the three-neck flask, introducing nitrogen, adding 0.5mmol of tetrakis (triphenylphosphine) palladium under the protection of nitrogen, continuing vacuumizing and introducing nitrogen for three times, reacting for 12 hours at 100 ℃, filtering, extracting, spin-drying, and then performing column chromatography 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-quinoxaline-5-phenyl) -N, N-diphenylamino) -1, 3-dihydroxyphenol
11mmol of 3, 5-dihydroxybenzeneboronic acid and 10mmol of 4- (8-bromo-quinoxaline-5-phenyl) -N, N-diphenylamine, as well as 20mmol of anhydrous sodium carbonate, are added in a dry, clean three-neck flask, 40mL of anhydrous toluene and 10mL of water are added, the three-neck flask is then evacuated and flushed with nitrogen, 0.5mmol of tetrakis (triphenylphosphine) palladium is added under nitrogen protection, the evacuation and flushing with nitrogen are then continued three times, the reaction is carried out for 12 hours at 100 ℃, and then filtration, extraction and spin-drying are carried out, and column chromatography is carried out to obtain the product (4- (8-bromo-quinoxaline-5-phenyl) -N, N-dianilino) -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 polymer luminescent material
Wherein x is 0.1, z is 0.4, and y is 0.5.
Adding 2mmol (4- (8-bromo-quinoxaline-5-phenyl) -N, N-diphenylamino) -1, 3-dihydric phenol and 10mmol 1, 6-Hexamethylene Diisocyanate (HDI) into a dry and clean three-neck flask, heating to 75 ℃, stirring for two hours, then adding 8mmol 2, 2-dimethylolpropionic acid (DMPA) for chain extension, heating to 85 ℃, reacting, observing the HDI concentration at intervals of 2 hours, adding acetone to reduce viscosity and quenching HDI with triethylamine when the HDI concentration is reduced to the minimum, pouring the obtained reaction solution into methanol, stirring for 25 minutes to precipitate, and filtering to obtain a yellow solid; adding the yellow solid into 2mol/L hydrochloric acid solution, stirring and dissolving, then 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 rest organic phase; and (2) concentrating the organic phase by vacuum rotary evaporation, pouring the concentrated solution into methanol, stirring for 30min to separate out a precipitate, filtering to obtain a yellow solid, then putting the solid into a Soxhlet purifier, purifying for 40h by using acetone, and drying for 6h in a vacuum drying oven at 70 ℃ to obtain the polymer luminescent material taking triphenylamine and quinoxaline as a donor-acceptor combination.
The number average molecular weight of the polymer luminescent material obtained in this example was 5026, the weight average molecular weight was 7690, and the dispersity was 1.53.
FIG. 1 is a fluorescence spectrum of the polymer light-emitting material prepared in example 1 in toluene, and it can be seen from FIG. 1 that the polymer light-emitting material emits green light in a toluene solution, and the light-emitting peak is at 528 nm.
Example 2
Synthesis of polymer luminescent material with triphenylamine and dicyanoquinoxaline as donor-acceptor combination
(1) Synthesis of 6-bromo-7- (4-diphenylamino) -2, 3-dicyanoquinoxaline
Adding 11mmol of 4-triphenylamine borate and 10mmol of 6, 7-dibromo-2, 3-dicyanoquinoxaline and 20mmol of anhydrous sodium carbonate into a dry and clean three-neck flask, adding 40mL of anhydrous toluene and 10mL of water, vacuumizing the three-neck flask, introducing nitrogen, adding 0.5mmol of tetrakis (triphenylphosphine) palladium under the protection of nitrogen, continuing vacuumizing and introducing nitrogen for three times, reacting for 12 hours at 100 ℃, filtering, extracting, spin-drying, and then performing 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
11mmol of 3, 5-dihydroxybenzeneboronic acid and 10mmol of 6-bromo-7- (4-dianilino) -2, 3-dicyanoquinoxaline, as well as 20mmol of anhydrous sodium carbonate are added in a dry and clean three-neck flask, 40mL of anhydrous toluene and 10mL of water are added, then the three-neck flask is vacuumized and aerated with nitrogen, 0.5mmol of tetrakis (triphenylphosphine) palladium is added under the protection of nitrogen, then the vacuumization and aeration with nitrogen are continued for three times, then the reaction is carried out for 12 hours at 100 ℃, then the filtration, the extraction and the spin drying are carried out, and then the column chromatography is carried out to obtain the product 6- (3, 5-dihydroxybenzene) -7- (4-dianilino) -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 polymer luminescent material
Wherein x is 0.1, z is 0.4, and y is 0.5.
Adding 2mmol of 6- (3, 5-dihydroxybenzene) -7- (4-diphenylamino) -2, 3-dicyanoquinoxaline and 10mmol of 1, 6-Hexamethylene Diisocyanate (HDI) into a dry and clean three-neck flask, heating to 75 ℃, stirring for two hours, then adding 8mmol of 2, 2-dimethylolpropionic acid (DMPA) for chain extension, heating to 85 ℃, reacting, observing the HDI concentration by a time point board at intervals of 2 hours, adding acetone to reduce viscosity and quenching the HDI by triethylamine when the HDI concentration is reduced to the minimum, pouring the obtained reaction solution into methanol, stirring for 25 minutes to precipitate, and filtering to obtain a red solid; adding the red solid into 2mol/L hydrochloric acid solution, stirring and dissolving, then 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 rest organic phase; and (2) concentrating the organic phase by vacuum rotary evaporation, pouring the concentrated solution into methanol, stirring for 30min to separate out a precipitate, filtering to obtain a red solid, then putting the red solid into a Soxhlet purifier, purifying for 40h by using acetone, and drying for 6h in a vacuum drying oven at 70 ℃ to obtain the polymer luminescent material taking triphenylamine and dicyanoquinoxaline as a 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 a fluorescence spectrum of the polymer light emitting material prepared in example 2 in toluene, and it can be seen from FIG. 2 that the polymer light emitting material emits red light in a toluene solution and the light emission peak is located at 635 nm.
Example 3
Synthesis of polymer luminescent material with 9, 9-dimethyl-9, 10-dihydroacridine and quinoxaline as donor-acceptor combination
(1) Synthesis of 10- (8-bromo-quinoxalinyl-5) -9, 9-dimethyl-9, 10-dihydroacridine
Adding 11mmol of 9, 9-dimethyl-9, 10-dihydroacridine and 10mmol of 1, 4-dibromoquinoxaline, and 20mmol of anhydrous sodium tert-butoxide into a dry and clean three-neck flask, adding 40mL of anhydrous toluene, vacuumizing the three-neck flask, introducing nitrogen, adding 0.5mmol of palladium acetate and 1mmol of (tri-tert-butyl) phosphine tetrafluoroborate under the protection of nitrogen, continuing vacuumizing and introducing nitrogen for three times, reacting at 110 ℃ for 12 hours, filtering, extracting, performing column chromatography after spin-drying 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
11mmol of 3, 5-dihydroxybenzeneboronic acid and 10mmol of 10- (8-bromo-quinoxaline-5) -9, 9-dimethyl-9, 10-dihydroacridine, as well as 20mmol of anhydrous sodium carbonate are added to a dry and clean three-neck flask, 40mL of anhydrous toluene and 10mL of water are added, the three-neck flask is evacuated and nitrogen is introduced, 0.5mmol of tetrakis (triphenylphosphine) palladium is added under the protection of nitrogen, the evacuation and nitrogen introduction are continued three times, then the reaction is carried out at 100 ℃ for 12 hours, and then the product, namely 5- (8- (9, 9-dimethyl-9, 10-dihydroacridine) -quinoxalinyl-5) -1, 3-dihydroxyphenol, is obtained after filtration, extraction, spin-drying and column chromatography.
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 polymer luminescent material
Wherein x is 0.2, z is 0.3, and y is 0.5.
Adding 4mmol of 5- (8- (9, 9-dimethyl-9, 10-dihydroacridine) -quinoxalinyl-5) -1, 3-dihydric phenol and 10mmol of 1, 6-Hexamethylene Diisocyanate (HDI) into a dry and clean three-neck flask, heating to 75 ℃, stirring for two hours, then adding 6mmol of 2, 2-dimethylolpropionic acid (DMPA) for chain extension, heating to 85 ℃, reacting, observing the concentration of HDI at intervals of 2 hours, adding acetone to reduce viscosity and quenching HDI with triethylamine when the concentration of HDI is reduced to the minimum, pouring the obtained reaction solution into methanol, stirring for 25 minutes to precipitate, and filtering to obtain an orange solid; adding the orange solid into 2mol/L hydrochloric acid solution, stirring and dissolving, then 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 rest organic phase; and (2) concentrating the organic phase by vacuum rotary evaporation, pouring the concentrated solution into methanol, stirring for 25min to separate out a precipitate, filtering to obtain an orange solid, then putting the solid into a Soxhlet purifier, purifying for 40h by using acetone, and drying for 6h in a vacuum drying oven at 70 ℃ to obtain the polymer luminescent material taking 9, 9-dimethyl-9, 10-dihydroacridine and quinoxaline as a donor-acceptor combination.
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 fluorescence spectrum of the polymer luminescent material prepared in example 3 in toluene, and it can be seen from FIG. 3 that the polymer luminescent material emits orange light in a toluene solution, and the light emission peak is at 604 nm.
Application example
The polymer luminescent material prepared in example 1 is prepared into an OLED device through a wet method by using a structure of ITO/PEDOT: PSS (thickness of 40nm)/TmPyPB (thickness of 50nm)/LiF (thickness of 1nm)/Al (thickness of 150nm) to obtain the polymer luminescent material, wherein the polymer luminescent material is prepared in example 1, the luminescent color is orange, the luminescent spectrum range is 500-600 nm, the photoluminescence quantum yield is 85%, and the maximum external quantum efficiency is 15%.
The polymer luminescent material prepared in example 2 is prepared into an OLED device through a wet method by using a structure of ITO/PEDOT: PSS (thickness of 40nm)/TmPyPB (thickness of 50nm)/LiF (thickness of 1nm)/Al (thickness of 150nm) to obtain the polymer luminescent material, wherein the structure of the polymer luminescent material prepared in example 2 is ITO/PEDOT: PSS (thickness of 40nm)/TmPyPB (thickness of 50nm)/LiF (thickness of 1nm)/Al (thickness of 150nm), the luminescent color of the OLED device is red light, the luminescent spectrum range is 600-700 nm, the photoluminescence quantum yield is 81%, and the maximum external quantum efficiency is 12%.
The polymer luminescent material prepared in example 3 is prepared into an OLED device through a wet method by using a structure of ITO/PEDOT: PSS (thickness of 40nm)/TmPyPB (thickness of 50nm)/LiF (thickness of 1nm)/Al (thickness of 150nm) to obtain the polymer luminescent material, wherein the structure of the polymer luminescent material prepared in example 3 is ITO/PEDOT: PSS (thickness of 40nm)/TmPyPB (thickness of 50nm)/LiF (thickness of 1nm)/Al (thickness of 150nm), the luminescent color of the polymer luminescent material is red light, the luminescent spectrum range is 550-700 nm, the photoluminescence quantum yield is 79%, and the maximum external quantum efficiency is 13%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A polymer luminescent material based on a polyurethane main chain has a structure shown in formula I:
in the formula I, R 1 Is quinoxalinyl or 2, 3-dicyanoquinoxalinyl; r 2 Is a carbazolyl group, a triphenylamine group or a 9, 9-dimethyl-9, 10 dihydroacridinyl group; x + z ranges from 0.05 to 0.5, and y ranges from 0.5 to 0.95.
2. The polymer light emitting material according to claim 1, wherein the polymer light emitting material based on the polyurethane backbone comprises
3. A method for producing the polymer light emitting material according to claim 1 or 2, comprising the steps of:
when R is 2 In the case of carbazolyl or triphenylamine, reacting X-R in a protective atmosphere 1 -X、
Mixing an alkaline reagent I, a palladium catalyst I and a solvent I, and carrying out a first coupling reaction to obtain R 2 -R 1 -X；
When R is 2 In the case of a 9, 9-dimethyl-9, 10-dihydroacridinyl radical, X-R is reacted under a protective atmosphere 1 mixing-X, 9-dimethyl-9, 10-dihydroacridine, an alkaline reagent II, a palladium catalyst II, a catalyst ligand and a solvent II, and carrying out 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 a bromo or iodo group;
the R is 2 -R 1 Mixing the-X and the 3, 5-dihydroxy benzene boric acid, an alkaline reagent III, a palladium catalyst III and a solvent III, and carrying out 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, 1, 6-hexamethylene diisocyanate and 2, 2-dimethylolpropionic acid, and carrying out chain extension reaction to obtain a polymer luminescent material with the structure shown in the formula I;
4. the method according to claim 3, wherein the solvent I and the solvent III are independently toluene and water.
5. The preparation method according to claim 3, wherein the temperature of the first coupling reaction is 80-110 ℃; the heat preservation time of the first coupling reaction is 10-14 h.
6. The method according to claim 3, wherein the solvent II is toluene.
7. The preparation method according to claim 3, wherein the temperature of the second coupling reaction is 80-110 ℃; and the heat preservation time of the second coupling reaction is 10-14 h.
8. The method according to claim 3, wherein the protective atmosphere is a nitrogen atmosphere.
9. The preparation method according to claim 3, wherein the temperature of the chain extension reaction is 85-90 ℃.
10. Use of the polymer light-emitting material according to any one of claims 1 to 2 or the polymer light-emitting material prepared by the preparation method according to any one of claims 3 to 9 as an organic electroluminescent material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210404648.XA CN114805741B (en) | 2022-04-18 | 2022-04-18 | Polymer luminescent material based on polyurethane main chain, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210404648.XA CN114805741B (en) | 2022-04-18 | 2022-04-18 | Polymer luminescent material based on polyurethane main chain, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114805741A true CN114805741A (en) | 2022-07-29 |
| CN114805741B CN114805741B (en) | 2023-10-13 |
Family
ID=82537283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210404648.XA Active CN114805741B (en) | 2022-04-18 | 2022-04-18 | Polymer luminescent material based on polyurethane main chain, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114805741B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20120181529A1 (en) * | 2009-09-30 | 2012-07-19 | Sumitomo Chemical Company, Limited | Layered structure, polymer, electroluminescent device, and photoelectric conversion device |
| US20130072654A1 (en) * | 2010-05-24 | 2013-03-21 | Ocean's King Lighting Science & Technology Co.,Ltd | Quinoxaline conjugated polymer containing fused-ring thiophene unit, preparation method and uses 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 |
| CN112679732A (en) * | 2020-12-28 | 2021-04-20 | 华南理工大学 | Luminescent polymer and metal-free catalyst polymerization method and application thereof |
-
2022
- 2022-04-18 CN CN202210404648.XA patent/CN114805741B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19719925A1 (en) * | 1997-05-13 | 1998-11-19 | Basf Ag | Production of low viscosity amino-polyurethane dispersion |
| US20120181529A1 (en) * | 2009-09-30 | 2012-07-19 | Sumitomo Chemical Company, Limited | Layered structure, polymer, electroluminescent device, and photoelectric conversion device |
| US20130072654A1 (en) * | 2010-05-24 | 2013-03-21 | Ocean's King Lighting Science & Technology Co.,Ltd | Quinoxaline conjugated polymer containing fused-ring thiophene unit, preparation method and uses thereof |
| 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 |
| CN112679732A (en) * | 2020-12-28 | 2021-04-20 | 华南理工大学 | Luminescent polymer and metal-free catalyst polymerization method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 朱敏志;李洁妤;廖亦晨;郑伟涛;韩小瑜;: "铕配合物及改性发光材料研究进展", 工程塑料应用, no. 02 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114805741B (en) | 2023-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100360579C (en) | Conjugated polymers and blends containing carbazole, preparation method and use thereof | |
| CN1780897B (en) | Novel materials for electroluminescence | |
| CN100549060C (en) | Contain the unitary conjugated polymers of arylamine and preparation and purposes | |
| CN112898282B (en) | D-pi-A type AIE-TADF near-infrared luminescent material, preparation method and application thereof | |
| CN106661446B (en) | Hole transport compounds and compositions | |
| CN109792003B (en) | Crosslinkable polymers based on Diels-Alder reactions and their use in organic electronic devices | |
| CN109761879B (en) | Organic blue fluorescent material, preparation method thereof and organic electroluminescent device | |
| CN109790136B (en) | Furan cross-linking group-containing polymer and application thereof | |
| WO2020073527A1 (en) | Macromolecular thermally activated delayed fluorescence material and preparation method therefor | |
| CN107814916B (en) | Polymer, luminescent material, device and display device | |
| CN105968104A (en) | Luminescent material and preparation method thereof and organic light emitting diode using same | |
| Zhao et al. | White light-emitting devices based on star-shape like polymers with diarylmaleimde fluorophores on the side chain of polyfluorene arms | |
| TW201605767A (en) | Compound | |
| Jiang et al. | Triphenyl phosphine oxide and carbazole-based polymer host materials for green phosphorescent organic light-emitting diodes | |
| CN111777542A (en) | Solution-processable thermally-activated delayed fluorescent material and preparation method and application thereof | |
| WO2020098150A1 (en) | Thermally activated delayed fluorescence dark red light macromolecular material and preparation method therefor | |
| CN107759774B (en) | D-A type polymer with main chain containing S, S-dioxo-dibenzothiophene as well as preparation method and application thereof | |
| CN108276562B (en) | Polymer containing S, S-dioxo-naphtho [2,1-b ] benzothiophene derivative unit, preparation method and application | |
| CN111454435B (en) | Phenanthroimidazole unit-based electroluminescent polymer and preparation method and application thereof | |
| CN110951051B (en) | Preparation method and application of thermotropic delayed fluorescence copolymer with side chain containing trifluoromethyl pyrimidine | |
| CN110183620B (en) | Organic porous polymer and preparation and application thereof | |
| CN108503800B (en) | Polymer containing S, S-dioxo-dibenzothiophene macrocyclic unit, preparation method and application thereof | |
| CN114805741B (en) | Polymer luminescent material based on polyurethane main chain, and preparation method and application thereof | |
| CN112679732B (en) | Luminescent polymer and metal-free catalyst polymerization method and application thereof | |
| CN113336694B (en) | Thermally activated sensitized fluorescent dendritic material capable of being processed in solution and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |