CN113185731A - Luminescent film with self-repairing property and stretchability and preparation method and application thereof - Google Patents
Luminescent film with self-repairing property and stretchability and preparation method and application thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention provides a luminescent film with self-repairing property and stretchability, and a preparation method and application thereof. The preparation method comprises the steps of preparing modified perovskite quantum dots; and stirring and mixing the modified perovskite quantum dots, the high polymer material and the plasticizer to obtain the luminescent film with self-repairing property and stretchability. The luminescent film prepared by the preparation method can be used in lighting equipment, intelligent display equipment and wearable equipment, and has excellent self-repairability and high-efficiency luminescent stability.
Description
Technical Field
The invention relates to a film, in particular to a luminescent film with self-repairing property and stretchability and a preparation method thereof, belonging to the technical field of polymer films.
Background
In order to deal with the damage of organ functions, a living body and a student have a set of repair mechanisms. The chemical and ecological environment of animal and plant self-repair is completely different, but the final results are similar. During the life cycle of animals and plants, DNA damage occurs at any time and leads to possible mutations, canceration and cell death. Human and mammal repair by inflammatory factors and the like; plants are repaired molecularly by oligomeric peptides and oligosaccharides. Self-healing in living beings involves numerous cascade reactions, of which the exact chemical principles are not yet accurately understood. The self-repairing of macromolecules can be realized by a physical or chemical method at a molecular level. Over the past several decades, the controlled synthesis of self-healing polymers and "life-like" programmable polymer materials have grown in length.
The polymer material is cheap, flexible, light, easy to manufacture and excellent in biocompatibility, so that the polymer material can be applied to wearable equipment. But we also need to pay attention to their durability and flexibility as these devices may be damaged or accidentally damaged over time in practical applications due to mechanical breakage during deformation. Therefore, wearable devices that can correct the harmful effects of scratching and/or mechanical damage and restore mechanical/electrical/chemical performance are particularly important for practical applications.
Technically, a self-healing wearable device is a combination of two rapidly developing research areas, namely a self-healing material and a wearable device. Self-healing materials have recently evolved as a branch of smart materials, aiming to self-heal most mechanical injuries without the use of external stimuli. Devices with self-healing properties, such as chemical sensors, electronic skins (important components for medical and environmental control), self-healing supercapacitors, batteries and solar cells, have all been used at the present stage.
At present, no research report about the illumination display material with the self-repairing function still exists, so the research aiming at the problem can make up for the blank of the related industry, and the illumination display material has great military application prospect in the fields of illumination, intelligent display, wearable equipment and the like used in severe environments.
Disclosure of Invention
In order to solve the above-described technical problems, it is an object of the present invention to provide a luminescent film having both self-repairing ability and high photoluminescence quantum efficiency.
Another object of the present invention is to provide a method for preparing a luminescent film having both self-healing ability and high photoluminescence quantum efficiency.
In order to solve the above technical problems, the present invention first provides a method for preparing a light emitting film having self-repairability and stretchability, wherein the method comprises the steps of:
preparing modified perovskite quantum dots;
and stirring and mixing the modified perovskite quantum dots, the high molecular material and the plasticizer to obtain the luminescent film with self-repairing property and stretchability.
In one embodiment of the present invention, the modified perovskite quantum dot is prepared by the following steps:
drying AX, oleic acid and octadecene at 110-130 ℃ for 0.5-1.5 h, and stirring at 150-170 ℃ for 2-2.5 h under the protection of nitrogen to obtain a precursor solution;
b is to mix BX2Mixing with oleylamine, drying at 110-130 ℃ for 1-1.5 h, adding oleic acid and a modified precursor under the protection of nitrogen, heating to 140-150 ℃, adding the precursor solution, and placing in ice water after 5-7 s;
stirring for 1-1.5 h in air at 50-70 ℃ for hydrolysis, forming an organic silicon dioxide matrix through silanization, centrifuging for 10-20 min at 8000 rpm, and washing to obtain a modified perovskite quantum dot solution.
In a more specific embodiment of the invention, the mixing ratio of AX, oleic acid and octadecene is 0.80g to 0.90 g: 2.5mL-2.7 mL: 28mL-32 mL.
In a more specific embodiment of the present invention, AX is such that: a is cesium ion or organic amine ion R-NH3 +X is a halide ion; r is C1-C4 straight-chain alkyl or branched-chain alkyl; the X halide ions include Cl-、Br-Or I-。
In the inventionIn a more specific embodiment, BX2The mixing ratio of oleylamine, oleic acid, modified precursor and precursor solution is as follows: 0.12g-0.16 g: 10mL of: 70 μ L: 1mL of: 1 mL.
In a more specific embodiment of the invention, BX2Wherein B is divalent metal ion, and X is halogen ion; in particular BX2The medium divalent metal ion comprises Pb2+、Sn2+Or Cu2+(ii) a In particular BX2The middle halogen ion includes Cl-、Br-Or I-。
In a more specific embodiment of the present invention, the modification precursor used is 3-aminopropyltriethoxysilane, tetraethyl orthosilicate, or tetraethyl silicate.
In a more specific embodiment of the present invention, the polymer material used is at least one selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyvinyl chloride, polypropylene, polymethyl methacrylate, polycarbonate, acetate fiber, and polystyrene.
In a more specific embodiment of the present invention, the plasticizer used is at least one selected from the group consisting of phthalates, aliphatic dibasic acid esters, fatty acid esters, benzenepolycarboxylic acid esters, polyol esters, epoxy hydrocarbons, and alkylsulfonic acid esters.
In a more specific embodiment of the present invention, the mixing mass ratio of the modified precursor and the polymer material is 1: 20-28.
In a more specific embodiment of the present invention, the precursor solution further comprises an organic solvent; wherein the organic solvent is at least one selected from N-methylpyrrolidone, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide, N-hexane, acetone and absolute ethyl alcohol.
The invention also provides a luminescent film with self-repairing property and stretchability, which is prepared by the preparation method of the luminescent film with self-repairing property and stretchability. The luminescent film can be used for backlight display, and has self-repairability and stretchability.
The light-emitting film with self-repairability and stretchability of the present invention can be used in lighting devices, smart display devices, wearable devices, and the like.
The preparation method of the luminescent film with self-repairing property and stretchability realizes the repair of the self-repairing high-efficiency luminescent film and the high-efficiency luminescent stability through the inorganic/organic modified perovskite.
In the preparation method of the luminescent film with self-repairing property and stretchability, the assembled display can be used in extreme conditions by introducing the composition of the silicon dioxide modified perovskite quantum dots and the self-repairing polymer, and the self-repairing can still be realized after the luminescent film is broken.
Aiming at the problems that the existing flexible luminescent materials are mainly high-molecular polymers, have poor mechanical properties, have risks of damage in the face of high-intensity operation and severe environment and inevitably cause fatal influence on a display screen once the existing flexible luminescent materials have high mechanical properties, the invention develops the self-repairing lighting display material, and the lighting display material can be applied to the fields of lighting, intelligent display, wearable equipment and the like in severe environment.
Drawings
FIG. 1 shows the repair of the self-repairable and stretchable luminescent film of example 1 after piercing and shearing.
Fig. 2 is a photoluminescence quantum yield of the luminescent thin film having self-repairability and stretchability of example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1
This example provides a luminescent film having self-healing and stretchability, which is prepared by the steps of:
0.82g of AX, 2.5mL of oleic acid and 30mL of octadecene are dried at 120 ℃ for 1h, and stirred at 150 ℃ for 2h under the protection of nitrogen;
0.157g of BX2Drying 10mL of oleylamine at 120 ℃ for 1 hour, adding 70 mu L of oleic acid and 1mL of 3-aminopropyltriethoxysilane under the protection of nitrogen, heating to 140 ℃ after the solution is clarified, quickly injecting 1mL of first precursor solution, and placing in ice water after 5 s;
stirring for 1 hour in the air at 60 ℃ for hydrolysis, forming an organic silicon dioxide matrix through silanization, centrifuging 3-aminopropyltriethoxysilane-coated perovskite quantum dots for 10 minutes at 8000 revolutions per minute, and washing twice by normal hexane to obtain a mixture solution;
after centrifugation, the precipitate is re-dispersed in toluene or n-hexane solvent through ultrasonic oscillation, and then the modified perovskite quantum dot APbX is subjected to3Mixing polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP-5545) and a plasticizer (phthalic acid ester), stirring overnight, and obtaining the luminescent film with self-repairing property and stretchability, wherein the mass ratio of the modified perovskite quantum dot to the polyvinylidene fluoride-hexafluoropropylene is 1: 20.
FIG. 1 is an optical photograph of a light-emitting film having self-repairability and stretchability obtained in example 1 after being cut and repaired. It can be seen that the prepared luminescent film has a self-healing function.
Fig. 2 is a graph showing the photoluminescence quantum efficiency of the luminescent film having self-repairability and stretchability of example 1. The photoluminescence quantum efficiency reaches 90.1 percent, and high luminous efficiency is shown.
Comparative example 1
Compared with example 1, the mass ratio of the 3-aminopropyltriethoxysilane coated perovskite quantum dot to the polyvinylidene fluoride hexafluoropropylene in the example is 1:10, except that the proportion of the 3-aminopropyltriethoxysilane coated perovskite quantum dot added in the comparative example is different.
The addition of 3-aminopropyltriethoxysilane coated perovskite quantum dots is adjusted, the self-repairing performance and the tensile performance of the luminescent film are changed, but the photoluminescence quantum efficiency is only 75%.
Comparative example 2
Compared with example 1, most of the materials are the same, except that the proportion of the 3-aminopropyl triethoxysilane coated perovskite quantum dots added in the comparative example is different, and the ratio of the 3-aminopropyl triethoxysilane to the polyvinylidene fluoride hexafluoropropylene in the example is 1: 5.
The addition of the 3-aminopropyltriethoxysilane-coated perovskite quantum dots is adjusted, the self-repairing performance is not realized, and the photoluminescence quantum efficiency is only 55%.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A preparation method of a luminescent thin film with self-repairing property and stretchability, wherein the preparation method comprises the following steps:
preparing modified perovskite quantum dots;
and stirring and mixing the modified perovskite quantum dots, the high molecular material and the plasticizer to obtain the luminescent film with self-repairing property and stretchability.
2. The production method according to claim 1, wherein the modified perovskite quantum dot is produced by:
drying AX, oleic acid and octadecene at 110-130 ℃ for 0.5-1.5 h, and stirring at 150-170 ℃ for 2-2.5 h under the protection of nitrogen to obtain a precursor solution;
b is to mix BX2Mixing with oleylamine, drying at 110-130 ℃ for 1-1.5 h, adding oleic acid and a modified precursor under the protection of nitrogen, heating to 140-150 ℃, adding the precursor solution, and placing in ice water after 5-7 s;
stirring for 1-1.5 h in air at 50-70 ℃ for hydrolysis, forming an organic silicon dioxide matrix through silanization, centrifuging for 10-20 min at 8000 rpm, and washing to obtain a modified perovskite quantum dot solution.
3. The production method according to claim 2, wherein the mixing ratio of AX, oleic acid and octadecene is 0.80g to 0.90 g: 2.5mL-2.7 mL: 28mL-32 mL;
preferably, in said AX: a is cesium ion or organic amine ion R-NH3 +X is a halide ion;
more preferably, R is C1-C4A linear or branched alkyl group of (a);
more preferably, the X halide ions comprise Cl-、Br-Or I-。
4. The method according to claim 2, wherein BX2The mixing ratio of oleylamine, oleic acid, modified precursor and precursor solution is as follows: 0.12g-0.16 g: 10mL of: 70 μ L: 1mL of: 1 mL;
preferably, BX2Wherein B is divalent metal ion, and X is halogen ion;
more preferably, BX2The medium divalent metal ion comprises Pb2+、Sn2+Or Cu2+；
More preferably, BX2The middle halogen ion includes Cl-、Br-Or I-。
5. The production method according to claim 2 or 4, wherein the modification precursor is 3-aminopropyltriethoxysilane, tetraethyl orthosilicate, or tetraethyl silicate.
6. The production method according to claim 1, wherein the polymer material is selected from at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyvinyl chloride, polypropylene, polymethyl methacrylate, polycarbonate, acetate fiber, and polystyrene;
preferably, the plasticizer is selected from at least one of phthalate, aliphatic dibasic acid ester, fatty acid ester, benzene polyacid ester, polyol ester, epoxy hydrocarbon and alkyl sulfonate.
7. The production method according to claim 2, wherein a mixing mass ratio of the modification precursor and the polymer material is 1: 20-28.
8. The method for preparing a light-emitting thin film having self-repairability and stretchability as claimed in claim 1, wherein the precursor solution further includes an organic solvent;
preferably, the organic solvent is at least one selected from the group consisting of N-methylpyrrolidone, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide, N-hexane, acetone, and anhydrous ethanol.
9. A luminescent thin film having self-healing property and stretchability, which is prepared by the method for preparing a luminescent thin film having self-healing property and stretchability according to any one of claims 1 to 8.
10. Use of the self-healing and stretchable light emitting film according to claim 9 in lighting devices, smart display devices, wearable devices.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110943178A (en) * | 2019-11-25 | 2020-03-31 | 北京科技大学 | Self-assembly multi-dimensional quantum well CsPbX3Perovskite nanocrystalline electroluminescent diode |
| CN111057536A (en) * | 2019-11-15 | 2020-04-24 | 华东理工大学 | Silicon-based ligand-modified all-inorganic perovskite quantum dot composite polydimethylsiloxane fluorescent film and preparation method thereof |
| CN111676017A (en) * | 2020-06-23 | 2020-09-18 | 陕西科技大学 | Silicon dioxide modified bismuth halogen perovskite quantum dot photoluminescence material and preparation method thereof |
| US20210071072A1 (en) * | 2019-09-09 | 2021-03-11 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Modified perovskite quantum dot material, fabricating method thereof, and display device |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210071072A1 (en) * | 2019-09-09 | 2021-03-11 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Modified perovskite quantum dot material, fabricating method thereof, and display device |
| CN111057536A (en) * | 2019-11-15 | 2020-04-24 | 华东理工大学 | Silicon-based ligand-modified all-inorganic perovskite quantum dot composite polydimethylsiloxane fluorescent film and preparation method thereof |
| CN110943178A (en) * | 2019-11-25 | 2020-03-31 | 北京科技大学 | Self-assembly multi-dimensional quantum well CsPbX3Perovskite nanocrystalline electroluminescent diode |
| CN111676017A (en) * | 2020-06-23 | 2020-09-18 | 陕西科技大学 | Silicon dioxide modified bismuth halogen perovskite quantum dot photoluminescence material and preparation method thereof |
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