Self-healing stretchable electroluminescent elastomer material as well as preparation method and application thereof
By introducing a self-healing polymer network with dynamically reversible bonds and boron ester bonds, a self-healing stretchable electroluminescent elastomer material was prepared, which solved the problem that OLEDs materials cannot be rebuilt after being broken, achieved the self-healing and excellent mechanical properties of the material, and broadened its application range.
Patent Information
- Application Number
- CN202510774174.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-11
- Publication Date
- 2025-09-16
AI Technical Summary
Existing OLEDs materials cannot rebuild covalent bonds after breaking, resulting in material waste and hindering the application of self-healing materials in flexible display devices.
By using a self-healing polymer network with dynamic reversible bonds, introducing a polymer luminescent material with fluorescent effect and a boron ester bond with dynamic network self-healing properties, a self-healing stretchable electroluminescent elastomer material is prepared, achieving self-healing and excellent mechanical properties of the material.
The material achieves self-healing and excellent mechanical properties, broadens its application range in optical and display devices, has high stretchability and charge mobility, and can be recycled and reprocessed.
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Figure CN120647834A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of optoelectronic materials, and in particular relates to a self-healing stretchable electroluminescent elastomer material and a preparation method and application thereof. Background Art
[0002] Flexible and stretchable electronic devices include flexible displays, organic photovoltaics, deformable optoelectronics, stretchable circuits, and flexible energy storage devices. Organic light-emitting diodes (OLEDs) are an ideal choice for stretchable displays. They have properties such as low driving voltage, high brightness, fast response time, long-term durability, and solution processability. In pursuit of high strength and toughness, OLED materials are generally constructed using irreversible covalent bonds, which cannot be rebuilt after breaking, resulting in a large amount of material waste.
[0003] Self-healing materials are materials that possess the ability to repair physical damage and restore function. In biological systems, self-healing is a complex, cascading, multistep process involving three steps: immediate biochemical reactions (e.g., inflammation), wound healing, and then partial or full functional restoration. Self-healing in synthetic systems also involves a sealing phase (intermolecular diffusion) and some chemical / physical repair (bond rearrangement). However, our understanding of the mechanisms of self-healing in synthetic systems remains limited, hindering the development of simple design principles for materials with desirable self-healing properties. In 2010, a self-healing polymer based on aromatic π-π stacking and hydrogen bonding was reported. The synergistic effects of the π-π stacking interactions of chain-folding polyamides and the hydrogen bonding interactions of telerotatory polyurethanes facilitated the self-healing polymer, which, upon healing at 100°C, recovered 95%, 91%, and 77% of its tensile modulus, elongation at break, and tensile toughness, respectively. While this concept of a self-healing polymer incorporating multiple dynamic bonds is currently widely adopted, self-healing materials based on all of these mechanisms remain under development, and their integration into OLED light-emitting materials presents numerous challenges.
[0004] However, in our opinion, the intrinsic self-healing mechanism based on various types of dynamic reversible bonds is the most promising approach to prepare self-healing OLEDs luminescent materials due to its relative simplicity and multi-cycle repair ability.
[0005] Multifunctional luminescent materials with fast self-healing and excellent mechanical properties can greatly broaden their wide range of applications in optical and display devices, but it remains a daunting task.
[0006] The present invention proposes to form a self-healing polymer network with dynamic reversible bonds by introducing reversible covalent and non-covalent bonds. Self-healing polymer networks with dynamic reversible bonds can provide unique viscoelastic properties and can be easily customized due to the compatibility and adaptability of polymer design, where functional groups can be inserted into specific positions of the polymer backbone. Dynamic reversible bonds include hydrogen and ionic bonds, π-π stacking, dynamic covalent bonds, guest-host bonds, and more. All of these bonds can be switched multiple times, thereby achieving multiple healing processes. Summary of the Invention
[0007] In order to provide a material with rapid self-healing and excellent mechanical properties, the present invention provides a self-healing stretchable electroluminescent elastomer material and its preparation method and application. The present invention adopts a polymer luminescent material with a fluorescent effect and a boron ester bond with dynamic network self-healing properties to prepare a material with high stretchability and charge mobility and self-healing properties. The material has strong room temperature self-healing properties and can be reprocessed after recovery and dissolution.
[0008] In a first aspect, the present invention provides a self-healing stretchable electroluminescent elastomer material, the general structure of which is as follows:
[0009] Among them, a, b, and c represent the corresponding repeating units in The molar percentage content in , and a+b+c=1, a, b, c are not 0, and the dotted line represents the bond connected to *; Ar represents a luminescent group; * represents , where the dotted lines represent the bonds to the structures at the corresponding positions.
[0010] Furthermore, the luminescent group Ar is one of the following structures: .
[0011] The dotted line represents the bond between the luminescent group Ar and *.
[0012] Furthermore, the self-healing stretchable electroluminescent elastomer material is one of the following structures:
[0013] .
[0014] In a second aspect, the present invention provides a method for preparing a self-healing, stretchable, electroluminescent elastomer material. The self-healing, stretchable, electroluminescent elastomer material is prepared from styrene-butadiene rubber (SBR), 3-mercapto-1,2-propanediol (3-Mercapto-1,2-propanediol), and a luminescent monomer containing two boric acid groups and one luminescent group (Ar). The SBR is recyclable.
[0015] Furthermore, the preparation method of the self-healing stretchable electroluminescent elastomer material specifically comprises the following steps: Step (1), placing an initiator into a reaction bottle, sealing the reaction bottle with a rubber stopper and a sealing film, pumping out nitrogen, injecting styrene, 1,3-butadiene, and ultra-dry tetrahydrofuran, and reacting at 50°C to 80°C to obtain styrene-butadiene rubber; Step (2), placing a luminescent monomer containing two boronic acid groups and one luminescent group Ar, 3-mercapto-1,2-propanediol, and magnesium sulfate into a two-necked reaction flask, adding an organic solvent under inert protection, and stirring the reaction at room temperature to obtain an intermediate product A; Step (3): adding the intermediate product A, styrene-butadiene rubber, and an initiator into a reaction vessel, adding an organic solvent to dissolve the mixture under inert protection, and stirring and refluxing the mixture at 100° C. to 150° C. to obtain a self-healing stretchable electroluminescent elastomer material.
[0016] Furthermore, the mass ratio of intermediate A to styrene-butadiene rubber is (0.01~0.1):1. As the amount of intermediate A increases, the luminescence and self-healing properties of the elastomer will increase. However, more intermediate A will also lead to a decrease in the self-healing and tensile properties of the elastomer, so the preferred ratio is 0.05:1.
[0017] Furthermore, the initiator in step (1) and step (3) is selected from one of azobisisobutyronitrile, azobisisoheptanenitrile, dibenzoyl peroxide, diacyl peroxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, potassium persulfate, cumene hydroperoxide, and cyclohexyl peroxydicarbonate.
[0018] Furthermore, the organic solvent in step (2) and step (3) is selected from one of toluene, hexane, cyclohexane, dioxane, tetrahydrofuran, diethyl ether, and acetonitrile.
[0019] Furthermore, the structural formula of the styrene-butadiene rubber is as follows:
[0020] Wherein, a, b, and c represent the molar percentage content of each corresponding repeating unit in styrene-butadiene rubber, a+b+c=1, and a, b, and c are not 0.
[0021] Furthermore, the structural formula of 3-mercapto-1,2-propanediol is as follows: .
[0022] Furthermore, the luminescent monomer containing two boric acid groups and one luminescent group Ar is selected from one of the following structures:
[0023] .
[0024] Furthermore, the intermediate product A is one of the following structures:
[0025] .
[0026] In a third aspect, the present invention provides the self-healing stretchable electroluminescent elastomer material which can be used in the field of stretchable electroluminescent devices.
[0027] Beneficial effects: 1) This invention introduces a luminescent monomer containing diboric acid and a luminescent group, 3-mercapto-1,2-propylene glycol, 1,3-butadiene, and styrene into a traditional elastomeric material through chemical crosslinking. This not only maintains the elastomer's stretchability but also achieves a self-healing effect, exhibiting excellent optoelectronic properties. This type of elastomeric material has a novel structure and a unique design strategy, achieving both high stretchability and high optoelectronic performance. Furthermore, using this type of elastomeric material as a light-emitting layer material can produce highly stable, stretchable, and efficient organic electroluminescent devices.
[0028] 2) The stretchable luminescent elastomer described in the present invention can be prepared by a one-pot heat-induced cross-linking reaction synthesis method.
[0029] The present invention introduces a dithiol boronic acid unit into a stretchable luminescent material for the first time. Intermediate A is synthesized by cross-linking a luminescent material having a diboric acid group with 3-mercapto-1,2-propanediol. After the reaction, the product is extracted and purified and cross-linked with styrene-butadiene rubber. Finally, the boronic acid ester with a dynamic network is cross-linked with the main chain ethylene bond to prepare a self-healing stretchable electroluminescent elastomer material.
[0030] 3) The elastomer material prepared by the present invention The structure imparts a dynamic self-healing network to the prepared material, enabling it to self-heal and repair its optoelectronic functions after tensile damage. Intermediate A is a luminescent unit with a dynamic network, i.e., a self-healing luminescent unit. By regulating the luminescent group and its dithiol boronic acid unit (Intermediate A), Intermediate A and styrene-butadiene rubber provide the elastomeric material with luminescent self-healing properties and stretchability, respectively.
[0031] The present invention achieves coordinated regulation of the material's luminescence properties, mechanical stretchability, electrical properties and self-healing properties through the polymerization and cross-linking of intermediate A and styrene-butadiene rubber, which can improve the flexibility, photoelectric properties and self-healing properties of the electroluminescent elastomer film; the material has a novel structure and a unique synthesis mechanism.
[0032] 4) The self-healing stretchable electroluminescent elastomer material can be applied in flexible electronics, smart wearables, luminous displays, smart sensors, biomedicine and other fields. BRIEF DESCRIPTION OF THE DRAWINGS
[0033] Figure 1 Schematic diagram of the stretching effect of a film made of the elastomer P1 of the present invention under ultraviolet light irradiation; Figure 2 Schematic diagram of the self-healing effect of the film prepared from the elastomer P1 of the present invention.
[0034] Figure 3 1 is a tensile test curve of films prepared from elastomers P1-P8 of the present invention; Figure 4 is the UV-Vis spectra of the films prepared from the elastomers P1-P8 of the present invention; Figure 5 PL spectra of films prepared from elastomers P1-P8 of the present invention; Figure 6 This is a diagram of an electroluminescent device prepared using the elastomer P1 of the present invention. DETAILED DESCRIPTION
[0035] The present invention will be further described below with reference to the accompanying drawings and specific embodiments.
[0036] The preparation method of styrene-butadiene rubber (SBR) in the following embodiment is as follows:
[0037] 2,2-Azobisisobutyronitrile (AIBN) (40 mg, 2 wt%) was placed in a 100 mL two-necked reaction flask that had been oven-dried for at least five hours. The flask was sealed with a rubber stopper and sealing film, and the atmosphere was purged with nitrogen. Styrene (0.61 mL, 0.0052 mmol), 2 mol / L 1,3-butadiene (13.5 mL, 0.027 mmol), and ultra-dry tetrahydrofuran (10 mL) were then added. The reaction was allowed to proceed at 65°C for 24 hours. After completion of the reaction, the reaction solution was concentrated, dissolved in dichloromethane, and added to a large amount of methanol for precipitation. The product, SBR (860 mg), was obtained by filtration and drying in a 43% yield.
[0038] Example 1 1) Preparation of intermediate product A1:
[0039] Ar1 (100 mg, 0.345 mmol), 3-mercapto-1,2-propanediol (82 mg, 0.76 mmol), and magnesium sulfate (200 mg, 1.67 mmol) were placed in a 100 mL two-necked flask that had been oven-dried for 12 hours. The flask was sealed with a rubber stopper and parafilm, and the atmosphere was purged and replaced with nitrogen three times. Tetrahydrofuran (15 mL) was quickly added under nitrogen, and the mixture was stirred at room temperature for 24 hours. The raw material was filtered using dichloromethane and ethyl acetate to remove the magnesium sulfate. The reaction mixture was then extracted three times with dichloromethane and saturated brine. The organic phase separated from the lower layer was dried over anhydrous sodium sulfate, filtered, and the solution was concentrated to obtain the crude product. The product was then azeotropically evaporated in n-hexane to dryness. After adding n-hexane and refrigerating for 12 hours, it was filtered and dried in a vacuum oven. A solid, A1 (161 mg), was obtained with a yield of 75%.
[0040] 2) Preparation of elastomer P1:
[0041] A1 (25 mg), SBR (500 mg), and 2,2-azobisisobutyronitrile (AIBN) (10 mg, 2 wt%) were added to a reaction vessel. The nitrogen atmosphere was purged 3–4 times, and toluene (20 mL) was added for dissolution. The mixture was then stirred under reflux at 130°C for 48 h. After the reaction, the mixture was cooled to room temperature, the excess solvent was distilled off under reduced pressure, and the mixture was purified by precipitation in a large amount of n-hexane. After filtration under reduced pressure, the mixture was dried under vacuum at room temperature to obtain elastomer P1 (341 mg) in a 65% yield.
[0042] Example 2 1) Preparation of intermediate product A2:
[0043] Ar2 (100 mg, 0.376 mmol), 3-mercapto-1,2-propanediol-3-ol (89.5 mg, 0.827 mmol), and magnesium sulfate (200 mg, 1.67 mmol) were placed in a 100 mL two-necked flask that had been oven-dried for 12 h. The flask was sealed with a rubber stopper and parafilm, and the atmosphere was purged and replaced with nitrogen three times. Tetrahydrofuran (15 mL) was quickly added under nitrogen, and the mixture was stirred at room temperature for 24 h. The raw material was filtered using dichloromethane and ethyl acetate to remove the magnesium sulfate. The mixture was then extracted three times with dichloromethane and saturated brine. The organic phase separated from the lower layer was dried over anhydrous sodium sulfate, filtered, and the solution was concentrated to obtain the crude product. The product was then azeotropically evaporated in n-hexane to dryness. After adding n-hexane directly and refrigerating for 12 h, it was filtered and dried in a vacuum oven. A2 (138.5 mg) was obtained as a solid with a yield of 73%.
[0044] 2) Preparation of elastomer P2:
[0045] A2 (25 mg), SBR (500 mg), and 2,2-azobisisobutyronitrile (AIBN) (10 mg, 2 wt%) were added to a reaction vessel. The nitrogen atmosphere was purged 3–4 times, and toluene (20 mL) was added for dissolution. The mixture was then stirred under reflux at 130°C for 24 h. After the reaction, the mixture was cooled to room temperature, the excess solvent was distilled off under reduced pressure, and the mixture was purified by precipitation in a large amount of n-hexane. After filtration under reduced pressure, the mixture was dried under vacuum at room temperature to obtain elastomer P2 (315 mg) with a yield of 60%.
[0046] Example 3 1) Preparation of intermediate product A3:
[0047] Ar3 (100 mg, 0.248 mmol), 3-mercapto-1,2-propanediol (58.89 mg, 0.545 mmol), and magnesium sulfate (200 mg, 1.67 mmol) were placed in a 100 mL two-necked flask that had been oven-dried for 12 hours. The flask was sealed with a rubber stopper and parafilm, and the atmosphere was purged and replaced with nitrogen three times. Tetrahydrofuran (15 mL) was quickly added under nitrogen, and the mixture was stirred at room temperature for 24 hours. The raw material was filtered using dichloromethane and ethyl acetate to remove the magnesium sulfate. The mixture was then extracted three times with dichloromethane and saturated brine. The organic phase separated from the lower layer was dried over anhydrous sodium sulfate, filtered, and the solution was concentrated to obtain the crude product. The product was then azeotropically evaporated in n-hexane to dryness. After adding n-hexane directly and refrigerating for 12 hours, it was filtered and dried in a vacuum oven. A3 (111 mg) was obtained as a solid with a yield of 70%.
[0048] 2) Preparation of elastomer P3:
[0049] A3 (25 mg), SBR (500 mg), and 2,2-azobisisobutyronitrile (AIBN) (10 mg, 2 wt%) were added to a reaction vessel. The nitrogen atmosphere was purged 3–4 times, and toluene (20 mL) was added for dissolution. The mixture was stirred under reflux at 130°C for 24 h. After the reaction, the mixture was cooled to room temperature, the excess solvent was distilled off under reduced pressure, and the mixture was purified by precipitation in a large amount of n-hexane. After filtration under reduced pressure, the mixture was dried under vacuum at room temperature to obtain elastomer P3 (336 mg) with a yield of 64%.
[0050] Example 4 1) Preparation of intermediate product A4:
[0051] Ar4 (100 mg, 0.37 mmol), 3-mercapto-1,2-propanediol (87.5 mg, 0.81 mmol), and magnesium sulfate (200 mg, 1.67 mmol) were placed in a 100 mL two-necked flask that had been oven-dried for 12 hours. The flask was sealed with a rubber stopper and parafilm, and the atmosphere was purged and replaced with nitrogen three times. Tetrahydrofuran (15 mL) was quickly added under nitrogen, and the mixture was stirred at room temperature for 24 hours. The raw material was filtered using dichloromethane and ethyl acetate to remove the magnesium sulfate. The reaction mixture was then extracted three times with dichloromethane and saturated brine. The organic phase separated from the lower layer was dried over anhydrous sodium sulfate, filtered, and the solution was concentrated to obtain the crude product. The product was then azeotropically evaporated in n-hexane to dryness. After adding n-hexane and refrigerating for 12 hours, it was filtered and dried in a vacuum oven. A4 (131.2 mg) was obtained as a solid with a yield of 70%.
[0052] 2) Preparation of elastomer P4:
[0053] A4 (25 mg), SBR (500 mg), and 2,2-azobisisobutyronitrile (AIBN) (10 mg, 2 wt%) were added to a reaction vessel. The nitrogen atmosphere was purged 3–4 times, and toluene (20 mL) was added for dissolution. The mixture was stirred under reflux at 130°C for 48 h. After the reaction, the mixture was cooled to room temperature, the excess solvent was distilled off under reduced pressure, and the mixture was purified by precipitation in a large amount of n-hexane. After filtration under reduced pressure, the mixture was dried under vacuum at room temperature to obtain elastomer P4 (288 mg) with a yield of 55%.
[0054] Example 5 1) Preparation of intermediate product A5:
[0055] Ar5 (100 mg, 0.355 mmol), 3-mercapto-1,2-propanediol (84.4 mg, 0.78 mmol), and magnesium sulfate (200 mg, 1.67 mmol) were placed in a 100 mL two-necked flask that had been oven-dried for 12 hours. The flask was sealed with a rubber stopper and parafilm, and the atmosphere was purged and replaced with nitrogen three times. Tetrahydrofuran (15 mL) was quickly added under nitrogen, and the mixture was stirred at room temperature for 24 hours. The raw material was filtered using dichloromethane and ethyl acetate to remove the magnesium sulfate. The mixture was then extracted three times with dichloromethane and saturated brine. The organic phase separated from the lower layer was dried over anhydrous sodium sulfate, filtered, and the solution was concentrated to obtain the crude product. The product was then azeotropically evaporated in n-hexane to dryness. After adding n-hexane directly and refrigerating for 12 hours, it was filtered and dried in a vacuum oven. A3 (147.5 mg) was obtained as a solid with a yield of 80%.
[0056] 2) Preparation of elastomer P5:
[0057] A5 (25 mg), SBR (500 mg), and 2,2-azobisisobutyronitrile (AIBN) (10 mg, 2 wt%) were added to a reaction vessel. The nitrogen atmosphere was purged 3–4 times, and toluene (20 mL) was added for dissolution. The mixture was then stirred under reflux at 130°C for 24 h. After the reaction, the mixture was cooled to room temperature, the excess solvent was distilled off under reduced pressure, and the mixture was purified by precipitation in a large amount of n-hexane. After filtration under reduced pressure, the elastomer P5 (330 mg) was obtained in a 63% yield.
[0058] Example 6 1) Preparation of intermediate product A6:
[0059] Ar6 (100 mg, 0.413 mmol), 3-mercapto-1,2-propanediol (98.39 mg, 0.91 mmol), and magnesium sulfate (200 mg, 1.67 mmol) were placed in a 100 mL two-necked flask that had been oven-dried for 12 hours. The flask was sealed with a rubber stopper and parafilm, and the atmosphere was purged and replaced with nitrogen three times. Tetrahydrofuran (15 mL) was quickly added under nitrogen, and the mixture was stirred at room temperature for 24 hours. The raw material was filtered using dichloromethane and ethyl acetate to remove the magnesium sulfate. The mixture was then extracted three times with dichloromethane and saturated brine. The organic phase separated from the lower layer was dried over anhydrous sodium sulfate, filtered, and the solution was concentrated to obtain the crude product. The product was then azeotropically evaporated in n-hexane to dryness. After adding n-hexane and refrigerating for 12 hours, it was filtered and dried in a vacuum oven. A3 (178.5 mg) was obtained as a solid with a yield of 90%.
[0060] 2) Preparation of elastomer P6:
[0061] A6 (25 mg), SBR (500 mg), and 2,2-azobisisobutyronitrile (AIBN) (10 mg, 2 wt%) were added to a reaction vessel. The nitrogen atmosphere was purged 3–4 times, and toluene (20 mL) was added for dissolution. The mixture was then stirred under reflux at 130°C for 24 h. After the reaction, the mixture was cooled to room temperature, the excess solvent was distilled off under reduced pressure, and the mixture was purified by precipitation in a large amount of n-hexane. After filtration under reduced pressure, the elastomer P6 (274 mg) was obtained in a 52% yield.
[0062] Example 7 1) Preparation of intermediate product A7:
[0063] Ar7 (100 mg, 0.355 mmol), 3-mercapto-1,2-propanediol (84.4 mg, 0.78 mmol), and magnesium sulfate (200 mg, 1.67 mmol) were placed in a 100 mL two-necked flask that had been oven-dried for 12 hours. The flask was sealed with a rubber stopper and parafilm, and the atmosphere was purged and replaced with nitrogen three times. Tetrahydrofuran (15 mL) was quickly added under nitrogen, and the mixture was stirred at room temperature for 24 hours. The raw material was filtered using dichloromethane and ethyl acetate to remove the magnesium sulfate. The mixture was then extracted three times with dichloromethane and saturated brine. The organic phase separated from the lower layer was dried over anhydrous sodium sulfate, filtered, and the solution was concentrated to obtain the crude product. The product was then azeotropically evaporated in n-hexane to dryness. After adding n-hexane and refrigerating for 12 hours, it was filtered and dried in a vacuum oven. A7 (147.5 mg) was obtained as a solid with an 80% yield.
[0064] 2) Preparation of elastomer P7:
[0065] A7 (25 mg), SBR (500 mg), and 2,2-azobisisobutyronitrile (AIBN) (10 mg, 2 wt%) were added to a reaction vessel. The nitrogen atmosphere was purged 3–4 times, and toluene (20 mL) was added for dissolution. The mixture was then stirred under reflux at 130°C for 24 h. After the reaction, the mixture was cooled to room temperature, the excess solvent was distilled off under reduced pressure, and the mixture was purified by precipitation in a large amount of n-hexane. After filtration under reduced pressure, the elastomer P7 (305 mg) was obtained in a 58% yield.
[0066] Example 8 1) Preparation of intermediate product A8:
[0067] Ar8 (100 mg, 0.25 mmol), 3-mercapto-1,2-propanediol (54.22 mg, 0.5 mmol), and magnesium sulfate (200 mg, 1.67 mmol) were placed in a 100 mL two-necked flask that had been oven-dried for 12 hours. The flask was sealed with a rubber stopper and parafilm, and the atmosphere was purged and replaced with nitrogen three times. Tetrahydrofuran (15 mL) was quickly added under nitrogen, and the mixture was stirred at room temperature for 24 hours. The raw material was filtered using dichloromethane and ethyl acetate to remove the magnesium sulfate. The reaction mixture was then extracted three times with dichloromethane and saturated brine. The organic phase separated from the lower layer was dried over anhydrous sodium sulfate, filtered, and the solution was concentrated to obtain the crude product. The product was then azeotropically evaporated in n-hexane to dryness. After adding n-hexane directly and refrigerating for 12 hours, it was filtered and dried in a vacuum oven. A8 (109.5 mg) was obtained as a solid with a yield of 70%.
[0068] 2) Preparation of elastomer P8:
[0069] A8 (25 mg), SBR (500 mg), and 2,2-azobisisobutyronitrile (AIBN) (10 mg, 2 wt%) were added to a reaction vessel. The nitrogen atmosphere was purged 3–4 times, and toluene (20 mL) was added for dissolution. The mixture was then stirred under reflux at 130°C for 24 h. After the reaction, the mixture was cooled to room temperature, the excess solvent was distilled off under reduced pressure, and the mixture was purified by precipitation in a large amount of n-hexane. After filtration under reduced pressure, the elastomer P8 (304 mg) was obtained in a 58% yield.
[0070] Example 9 The film made of the self-healing stretchable electroluminescent elastomer material was subjected to tensile testing, UV-Vis ultraviolet spectrum testing, and PL fluorescence spectrum testing. The elastomer P1 was used to prepare a structured OLED device. The tensile testing method is as follows: 1) Dissolve an appropriate amount of elastomer P1 in a small amount of toluene to prepare a solution. Drop the solution onto a polytetrafluoroethylene film and air-dry it for 4 hours. Remove the film.
[0071] 2) Cut it with scissors and it will heal itself after 1 hour. After 24 hours, the film can be stretched and folded. The film will become slightly longer, but the rest will be intact.
[0072] 3) Cut the stretched film again and place it flat for 24 hours. The film will heal part of the cut, but the cut marks on the surface are still clear. However, it will not break when gently pulled.
[0073] Here are the results: 1) Figure 1 The figure shows the stretching effect of the film made of the elastomer P1 of the present invention under UV light. Figure 2 As shown in FIG. 2 , after 24 hours, the surface of the elastomer film has basically completed the self-healing process, with only some small dents remaining, and the original cuts are almost undetectable to the naked eye.
[0074] 2) If Figure 3 As shown in the figure, the elongation rates of the films prepared from elastomers P1-P8 were 890%, 1200%, 1020%, 900%, 1000%, 760%, 780%, and 750% respectively before being cut, and the elongation rates after the first cut and self-healing for 24 h were 790%, 280%, 390%, 740%, 550%, 700, 600%, and 590% respectively.
[0075] 3) If Figure 4 As shown, the films prepared from elastomers P1-P8 were subjected to UV-Vis spectroscopy tests. The absorption peaks of styrene and polybutadiene were around 260 nm, and the luminescent group had an obvious absorption peak in the range of 300 nm to 350 nm.
[0076] 4) If Figure 5 As shown, the PL fluorescence spectrum of the films prepared from elastomers P1-P8 was tested, and emission peaks appeared between 400 nm and 500 nm, and all had strong fluorescence characteristics.
[0077] 5) If Figure 6 As shown, an OLEDs device with a structure of ITO / PEDOT:PSS(AI 4083) / P1 / LiF / Al was prepared using elastomer P1. The device made of this material emits light blue-green light.
[0078] Finally, it should be noted that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any form. Any non-innovative changes and modifications made to the technical solution of the present invention using the above description, without departing from the scope of the technical solution of the present invention, such as changes to the ratio of raw material and reagent addition, reaction time, and operating procedures, shall be included within the scope of protection of the present invention.
Claims
1. A self-healing stretchable electroluminescent elastomer material, characterized in that: The general structural formula of the self-healing stretchable electroluminescent elastomer material is as follows: ； Among them, a, b, and c represent the corresponding repeating units in The molar percentage content in , and a + b + c = 1, a, b, c are not 0; Ar represents a luminescent group; * represents .
2. The self-healing stretchable electroluminescent elastomer material according to claim 1, characterized in that: The luminescent group Ar is one of the following structures: ； 。 3. The self-healing stretchable electroluminescent elastomer material according to claim 1, characterized in that The self-healing stretchable electroluminescent elastomer material is one of the following structures: 。 4. The method for preparing the self-healing stretchable electroluminescent elastomer material according to claim 1, characterized in that: The self-healing stretchable electroluminescent elastomer material is prepared from styrene-butadiene rubber, 3-mercapto-1,2-propylene glycol, and a luminescent monomer containing two boric acid groups and a luminescent group Ar.
5. The preparation method according to claim 4, characterized in that The structural formula of the styrene-butadiene rubber is as follows: ； Wherein, a, b, and c represent the molar percentage content of each corresponding repeating unit in styrene-butadiene rubber, a+b+c=1, and a, b, and c are not 0.
6. The preparation method according to claim 4, characterized in that A luminescent monomer containing two boric acid groups and a luminescent group Ar, selected from one of the following structures: ； ； ； ； ； 。 7. The preparation method according to claim 4, characterized in that The specific steps include: Step 1) Place the initiator into a reaction bottle, seal the reaction bottle with a rubber stopper and a sealing film, replace the nitrogen, inject styrene, 1,3-butadiene, and ultra-dry tetrahydrofuran, and react at 50°C to 80°C to obtain styrene-butadiene rubber; Step 2) Place a luminescent monomer containing two boronic acid groups and one luminescent group Ar, 3-mercapto-1,2-propanediol, and magnesium sulfate into a two-necked reaction flask, add an organic solvent under inert protection, and stir the reaction at room temperature to obtain an intermediate product A; Step 3) Add the intermediate product A, styrene-butadiene rubber, and initiator into a reaction vessel, add an organic solvent to dissolve under inert protection conditions, reflux and stir the reaction at 100° C. to 150° C. to obtain a self-healing stretchable electroluminescent elastomer material.
8. Use of the self-healing stretchable electroluminescent elastomer material according to claim 1 in the preparation of OLEDs devices.