Dendritic narrow-band blue-light epoxy resin material
By preparing dendritic narrow-band blue light epoxy resin materials, the problems of insufficient efficiency and stability of traditional blue light materials in high color purity display are solved, and high color purity electroluminescence effect is achieved, with good thermal stability and low cost.
Patent Information
- Application Number
- CN202511657917.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-07
- Publication Date
- 2026-02-24
AI Technical Summary
The broad spectral characteristics of traditional fluorescent and phosphorescent materials are insufficient to meet the high color purity requirements of ultra-high-definition displays, while blue light materials have shortcomings in efficiency and stability, as well as high synthesis costs.
A dendritic narrow-band blue light-emitting epoxy resin material is used to prepare the light-emitting layer through a specific synthetic route, including a multi-step reaction of intermediates, to finally form a dendritic blue light-emitting epoxy resin material for use in organic electroluminescent devices.
The material achieves high color purity electroluminescence spectrum, has high glass transition temperature, good thermal stability and luminescence performance, is easy to synthesize and has low cost, and is suitable for high color purity display devices.
Smart Images
Figure CN121554470A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic electroluminescent materials technology, specifically relating to a dendritic narrow-band blue light epoxy resin material. Background Technology
[0002] Organic light-emitting diode (OLED) technology has been widely used in display and lighting fields after decades of development. However, the broad spectral characteristics of traditional fluorescent and phosphorescent materials are difficult to meet the requirements of high color purity, which restricts their application in ultra-high-definition displays. In 2016, Chihaya Adachi's team first reported a narrowband OLED (DABNA-1) based on MR-TADF material, with a blue light emission half-width (FWHM) of only 14 nm and an external quantum efficiency (EQE) of 20.5%, which sparked a research boom in narrowband OLEDs. Subsequently, Ma Yuguang's team achieved blue light emission with an FWHM of 19 nm (EQE = 12.2%) through the thermal exciton mechanism, Kim Jang-Joo's team developed a green narrowband OLED (FWHM = 29 nm, EQE = 25.6%) based on AIE material, and Kido Jiro's team reported a red narrowband OLED (FWHM = 28 nm, EQE = 18.3%). In 2022, the team led by Duan Lian at Tsinghua University further optimized the MR-TADF material, achieving deep blue light emission (FWHM = 21 nm, EQE = 32.1%). Despite the significant progress, blue light materials still face challenges such as insufficient efficiency and stability, and high synthesis costs. Summary of the Invention
[0003] The purpose of this invention is to address the deficiencies of existing technologies by providing a dendritic narrow-band blue-emitting epoxy resin material to solve the problems mentioned in the background section. To achieve the above objective, this invention provides the following technical solution: a narrow-band blue-emitting epoxy resin material, with a structure as shown in formula (1):
[0004]
[0005] A method for synthesizing a narrow-band blue-emitting epoxy resin material, the specific synthetic route of which is as follows:
[0006]
[0007] The specific steps are as follows:
[0008] Step 1: (3-ethoxycyclodane-3-yl)methanol and 1,6-dibromohexane undergo a substitution reaction to obtain intermediate 1, the structure of which is shown in formula (2):
[0009] Step 2: Intermediate 2 is obtained by substitution reaction of intermediate 1 with 4-(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)phenol, the structure of which is shown in formula (3):
[0010]
[0011] Step 3: The multiple resonance narrow band luminescent nucleus and intermediate 2 are connected to the three para sites of the nitrogen atom of the multiple resonance narrow band luminescent nucleus through the Suzuki reaction to obtain a dendritic narrow band blue light epoxy resin material. The structure of the dendritic narrow band blue light epoxy resin material is shown in formula (1).
[0012] As a preferred technical solution of the present invention, the specific synthesis steps of intermediate 1 in step 1 are as follows: In a nitrogen atmosphere, at room temperature, (3-ethoxycyclodane-3-yl)methanol, 1,6-dibromohexane and tetrabutylammonium bromide are added to a hexane solution containing potassium carbonate and a small amount of water. After vigorous stirring for 24 hours, the mixture is cooled to room temperature, and the insoluble solids are removed by filtration. The resulting solution is concentrated under vacuum to obtain a crude product, which is then purified by silica gel column chromatography to obtain a colorless liquid 3-(((6-bromohexyl)oxy)methyl)-3-ethoxycyclobutane.
[0013] As a preferred technical solution of the present invention, the specific synthesis steps of intermediate 2 in step 2 are as follows: Under a nitrogen atmosphere, at room temperature, 3-(((6-bromohexyl)oxy)methyl)-3-ethoxycyclobutane and 4-(4,4,5,5-tetramethyl-1,3,2-dioxoborane-2-yl)phenol are added to an acetone solution containing potassium carbonate. After vigorous stirring for 24 hours, the mixture is cooled to room temperature, and the insoluble solids are removed by filtration. The mixture is washed repeatedly with dichloromethane 2-3 times, and the resulting solution is concentrated under vacuum to obtain a crude product. The crude product is purified by silica gel column chromatography to obtain a yellow liquid 2-(4-((6-(((3-ethoxy)methoxy)hexyl)oxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane).
[0014] As a preferred embodiment of the present invention, the specific synthesis steps of the dendritic narrow-band blue light epoxy resin material in step 3 are as follows: In a nitrogen atmosphere, at room temperature, 2-(4-((6-(((3-ethoxy)methoxy)hexyl)oxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane and 3,7,11-tribromoquinolinyl[3,2,1-de]acridin-5,9-dione are added to a mixture containing potassium carbonate, tetra(tri... In a tetrahydrofuran solution containing phenylphosphine, palladium, and a small amount of water, the mixture was stirred vigorously for 24 hours. After cooling to room temperature, the insoluble solids were removed by filtration. The mixture was washed 2-3 times with dichloromethane. The resulting solution was concentrated under vacuum to obtain a crude product. The product was purified by silica gel column chromatography to obtain a yellow powder, 3,7,11-tris(4-((6-(((3-ethoxy)methoxy)hexyl)oxy)phenyl)quinolinyl[3,2,1-de]acrid-5,9-dione.
[0015] The application of a dendritic narrow-band blue light-emitting epoxy resin material in the manufacture of organic electroluminescent devices, wherein the light-emitting layer of the organic electroluminescent device is prepared by using the dendritic narrow-band blue light-emitting epoxy resin material as the guest material and doping it with the host material.
[0016] As a preferred embodiment of the present invention, the dendritic narrow-band blue light epoxy resin material accounts for 1 to 5 wt% of the mass of the light-emitting layer material.
[0017] As a preferred embodiment of the present invention, the dendritic narrow-band blue light epoxy resin material accounts for 5 wt% of the mass percentage of the light-emitting layer material.
[0018] As a preferred embodiment of the present invention, the organic electroluminescent device comprises an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode.
[0019] An organic light-emitting diode (OLED) made of epoxy resin with narrow-band blue emission has been developed, and the electroluminescence spectrum of the OLED meets the requirements of high color purity displays.
[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: The narrow-band blue emitting epoxy resin of the present invention effectively utilizes the good solubility of alkyl chains, giving it a high glass transition temperature, high thermal stability, excellent luminescence performance, and good film-forming properties; its synthesis method is simple, easy to purify, and has a high yield, and the luminescence performance and thermal properties of the final product can be adjusted by connecting different numbers of alkyl chains; the OLED device using the above-mentioned narrow-band blue emitting epoxy resin has good stability of the light-emitting layer, thereby enabling the electroluminescence spectrum of the OLED device to meet the requirements of high color purity displays.
[0021] This material has advantages such as low synthesis cost, environmental friendliness, simple synthesis, and easy wet fabrication of devices together with small molecule host materials. It is a TADF polymer material with great potential for future wet fabrication of narrowband OLED devices. Detailed Implementation
[0022] The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby providing a clearer and more explicit definition of the scope of protection of the present invention.
[0023] This invention provides a method for synthesizing a narrow-band blue-emitting epoxy resin material, the reaction route of which is shown below:
[0024]
[0025] Step (1): In a nitrogen atmosphere, at room temperature, (3-ethoxycyclodane-3-yl)methanol, 1,6-dibromohexane and tetrabutylammonium bromide were added to a hexane solution containing potassium carbonate and a small amount of water. After stirring vigorously for 24 hours, the mixture was cooled to room temperature. The insoluble solids were removed by filtration, and the resulting solution was concentrated under vacuum to obtain the crude product. The crude product was purified by silica gel column chromatography to obtain the colorless liquid 3-(((6-bromohexyl)oxy)methyl)-3-ethoxycyclobutane.
[0026] Step (2): Under a nitrogen atmosphere, at room temperature, 3-(((6-bromohexyl)oxy)methyl)-3-ethoxycyclobutane and 4-(4,4,5,5-tetramethyl-1,3,2-dioxoborane-2-yl)phenol were added to an acetone solution containing potassium carbonate. After vigorous stirring for 24 hours, the mixture was cooled to room temperature. The insoluble solids were removed by filtration, and the mixture was washed repeatedly with dichloromethane 2-3 times. The resulting solution was concentrated under vacuum to obtain the crude product, which was purified by silica gel column chromatography to obtain the yellow liquid 2-(4-((6-(((3-ethoxy)methoxy)hexyl)oxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane).
[0027] Step (3): Under a nitrogen atmosphere, at room temperature, 2-(4-((6-(((3-ethoxy)methoxy)hexyl)oxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane and 3,7,11-tribromoquinolinyl[3,2,1-de]acridin-5,9-dione were added to a tetrahydrofuran solution containing potassium carbonate, tetra(triphenylphosphine)palladium and a small amount of water. After vigorous stirring for 24 hours, the mixture was cooled to room temperature. The insoluble solids were removed by filtration, and the mixture was washed repeatedly with dichloromethane 2-3 times. The resulting solution was concentrated under vacuum to obtain the crude product, which was purified by silica gel column chromatography to obtain the yellow powder 3,7,11-tris(4-((6-(((3-ethoxy)methoxy)hexyl)oxy)phenyl)quinolinyl[3,2,1-de]acridin-5,9-dione.
[0028] The application of a narrow-band blue-emitting epoxy resin in the manufacture of organic electroluminescent devices, wherein the light-emitting layer of the organic electroluminescent device is prepared by using the narrow-band blue-emitting epoxy resin as a guest material and doping it with a host material; the narrow-band blue-emitting epoxy resin accounts for 1 to 5 wt% of the mass percentage of the light-emitting layer material, preferably 5 wt%.
[0029] An organic light-emitting diode (OLED) made of epoxy resin with narrow-band blue emission has been developed, and the electroluminescence spectrum of the OLED meets the requirements of high color purity displays. Attached Figure Description
[0030] Figure 1 This is the infrared spectrum of the epoxy resin material of the present invention.
[0031] Figure 2 This is the fluorescence spectrum of the epoxy resin material of the present invention.
[0032] Figure 3 This is a device structure diagram of the epoxy resin material of the present invention.
[0033] Figure 4 This is a device current-voltage curve of the epoxy resin material of the present invention.
[0034] Figure 5 This is a device current-brightness curve of the epoxy resin material of the present invention.
[0035] Figure 6 This is a brightness efficiency curve of the epoxy resin material of the present invention.
Claims
1. A dendritic narrow-band blue light epoxy resin material, characterized in that: With carbonyl nitrogen as the core structure and modified with oxobutane epoxy resin, a multiple resonance thermally activated delayed fluorescence (MR-TADF) system with donor-acceptor interaction is formed, and its molecular structure is shown in formula (1):
2. A method for synthesizing the dendritic narrow-band blue light epoxy resin material as described in claim 1, characterized in that: The specific synthetic route is as follows: The specific steps are as follows: Step 1: (3-ethoxycyclodane-3-yl)methanol and 1,6-dibromohexane undergo a substitution reaction to obtain intermediate 1, the structure of which is shown in formula (2): Step 2: Intermediate 2 is obtained by substitution reaction of intermediate 1 with 4-(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)phenol, the structure of which is shown in formula (3): Step 3: The multiple resonance narrow band luminescent nucleus and intermediate 2 are connected to the three para sites of the nitrogen atom of the multiple resonance narrow band luminescent nucleus through the Suzuki reaction to obtain a dendritic narrow band blue light epoxy resin material. The structure of the dendritic narrow band blue light epoxy resin material is shown in formula (1).
3. The method for synthesizing the dendritic narrow-band blue light epoxy resin material according to claim 1, characterized in that: The specific synthesis steps of intermediate 1 in step 1 are as follows: In a nitrogen atmosphere, at room temperature, (3-ethoxycyclodane-3-yl)methanol, 1,6-dibromohexane and tetrabutylammonium bromide are added to a hexane solution containing potassium carbonate and a small amount of water. After vigorous stirring for 24 hours, the mixture is cooled to room temperature. The insoluble solids are removed by filtration, and the resulting solution is concentrated under vacuum to obtain the crude product. The crude product is purified by silica gel column chromatography to obtain the colorless liquid 3-(((6-bromohexyl)oxy)methyl)-3-ethoxycyclobutane.
4. The method for synthesizing the dendritic narrow-band blue light epoxy resin material according to claim 1, characterized in that: The specific synthesis steps of intermediate 2 in step 2 are as follows: Under a nitrogen atmosphere, at room temperature, 3-(((6-bromohexyl)oxy)methyl)-3-ethoxycyclobutane and 4-(4,4,5,5-tetramethyl-1,3,2-dioxoborane-2-yl)phenol are added to an acetone solution containing potassium carbonate. After vigorous stirring for 24 hours, the mixture is cooled to room temperature. The insoluble solids are removed by filtration, and the mixture is washed repeatedly with dichloromethane 2-3 times. The resulting solution is concentrated under vacuum to obtain the crude product, which is purified by silica gel column chromatography to obtain the yellow liquid 2-(4-((6-(((3-ethoxy)methoxy)hexyl)oxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane).
5. The method for synthesizing the dendritic narrow-band blue light epoxy resin material according to claim 1, characterized in that: The specific synthesis steps of the dendritic narrow-band blue light epoxy resin material described in step 3 are as follows: Under a nitrogen atmosphere, at room temperature, 2-(4-((6-(((3-ethoxy)methoxy)hexyl)oxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane and 3,7,11-tribromoquinolinyl[3,2,1-de]acridin-5,9-dione were added to a tetrahydrofuran solution containing potassium carbonate, tetra-triphenylphosphine palladium, and a small amount of water. After vigorous stirring for 24 hours, the mixture was cooled to room temperature. The insoluble solids were removed by filtration, and the mixture was repeatedly washed 2-3 times with dichloromethane. The resulting solution was concentrated under vacuum to obtain a crude product, which was purified by silica gel column chromatography to obtain a yellow powder, 3,7,11-tris(4-((6-(((3-ethoxy)methoxy)hexyl)oxy)phenyl)quinolinyl[3,2,1-de]acridin-5,9-dione.
6. The application of the dendritic narrow-band blue light epoxy resin material as described in claim 1 in the manufacture of organic electroluminescent devices, characterized in that: The light-emitting layer of the organic electroluminescent device is prepared by using dendritic narrow-band blue light epoxy resin as the guest material and doping it with the host material.
7. The application of the dendritic narrow-band blue light epoxy resin material according to claim 6 in the manufacture of organic electroluminescent devices, characterized in that: The dendritic narrow-band blue light epoxy resin material accounts for 1-5 wt% of the mass of the luminescent layer material.
8. The application of the dendritic narrow-band blue light epoxy resin material according to claim 7 in the manufacture of organic electroluminescent devices, characterized in that: The dendritic narrow-band blue light epoxy resin material accounts for 5 wt% of the mass of the light-emitting layer material.
9. The application of the dendritic narrow-band blue light epoxy resin material according to claim 7 in the manufacture of organic electroluminescent devices, characterized in that: The organic electroluminescent device comprises an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode.
10. An organic light-emitting diode made from the dendritic narrow-band blue light epoxy resin material as described in claim 1, characterized in that: The electroluminescence spectrum of organic light-emitting diodes meets the requirements of high color purity displays.