CN112159575A - Preparation method of perovskite quantum dot polymer particles - Google Patents

Preparation method of perovskite quantum dot polymer particles Download PDF

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Publication number
CN112159575A
CN112159575A CN202011030318.6A CN202011030318A CN112159575A CN 112159575 A CN112159575 A CN 112159575A CN 202011030318 A CN202011030318 A CN 202011030318A CN 112159575 A CN112159575 A CN 112159575A
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quantum dot
perovskite quantum
polymer particles
dot polymer
thermoplastic elastomer
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CN202011030318.6A
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Inventor
喻四海
童建宇
施法宽
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Kunshan Bye Polymer Material Co ltd
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Kunshan Bye Polymer Material Co ltd
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Priority to CN202011030318.6A priority Critical patent/CN112159575A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/16Halogen-containing compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00Nanooptics, e.g. quantum optics or photonic crystals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/13Phenols; Phenolates
    • C08K5/134Phenols containing ester groups
    • C08K5/1345Carboxylic esters of phenolcarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664Halogenides
    • C09K11/665Halogenides with alkali or alkaline earth metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide

Abstract

The invention discloses a preparation method of perovskite quantum dot polymer particles, which comprises the following steps of: 13, adding the metal halide A, oleic acid and oleylamine into a stirring tank, drying at 120 ℃ in vacuum to remove moisture in raw materials, heating the obtained mixture to 150 ℃ under the protection of nitrogen until the metal halide is completely dissolved, then heating to 160-220 ℃, adding the thermoplastic elastomer, after the mixture is completely melted, rapidly injecting a certain amount of precursor B under vigorous stirring, and keeping the molar ratio of the metal halide A to the precursor B to be 1: and 0.4, then respectively adding the diffusion particles and the antioxidant, fully stirring, adding the uniformly mixed product into a double-screw extruder after vacuum defoamation, and cooling and granulating the extruded product to obtain the required perovskite quantum dot polymer particles. The invention adopts the thermoplastic elastomer as the dispersing agent, and prepares the perovskite quantum dot polymer particles by using a high-temperature hot injection method, thereby ensuring the optical performance and stability of the perovskite quantum dots.

Description

Preparation method of perovskite quantum dot polymer particles
Technical Field
The invention belongs to the technical field of perovskite quantum dots, and particularly relates to a preparation method of perovskite quantum dot polymer particles.
Background
The perovskite quantum dot film can be used as an optical conversion film of a wide-color-gamut Liquid Crystal Display (LCD) backlight module due to the excellent fluorescence property of the perovskite quantum dot film, and has great market potential. The conventional perovskite quantum dot film has low fluorescence efficiency (PLQY) and poor light stability. The perovskite quantum dot polymer particles are core materials of perovskite quantum dot films, and the performance of the perovskite quantum dot films directly influences the performance of the final perovskite quantum dot films, so that a preparation process of the perovskite quantum dot polymer particles is needed, and the perovskite quantum dot polymer particles are ensured to have high-efficiency luminescence and good stability under severe aging conditions, particularly under light aging conditions and high-temperature and high-humidity aging conditions.
Disclosure of Invention
To solve the problems set forth in the background art described above. The invention provides a preparation method of perovskite quantum dot polymer particles, which comprises the following steps of: 13, adding the metal halide A, oleic acid and oleylamine into a stirring tank, drying at 120 ℃ in vacuum to remove moisture in raw materials, heating the obtained mixture to 150 ℃ under the protection of nitrogen until the metal halide is completely dissolved, then heating to 160-220 ℃, adding the thermoplastic elastomer, after the mixture is completely melted, rapidly injecting a certain amount of precursor B under vigorous stirring, and keeping the molar ratio of the metal halide A to the precursor B to be 1: and 0.4, then respectively adding the diffusion particles and the antioxidant, fully stirring, adding the uniformly mixed product into a double-screw extruder after vacuum defoamation, and cooling and granulating the extruded product to obtain the required perovskite quantum dot polymer particles.
Preferably, the vacuum drying time is 30 minutes.
Preferably, the softening temperature of the thermoplastic elastomer is 120-220 ℃, and the thermoplastic elastomer is one or a mixture of SEBS thermoplastic elastomer, EVA thermoplastic elastomer, TPU thermoplastic elastomer and acrylic block copolymer.
Preferably, the metal cation of the metal halide A is Pb2+、Sn2+、Sb2+、Bi2+、Ag+、Zn2+、Mn2+、Cu2+Or Ge+One or more of (a).
Preferably, the halogen element is Cl-、Br-、I-One or more of (a).
Preferably, the precursor B is an oleate of a metal cation or a positively charged organic cation, and the precursor B is Cs+、Rb+、FA+(HN=CH-NH3+) One or more of the oleates of (a).
Compared with the prior art, the invention has the beneficial effects that:
the thermoplastic elastomer is used as a dispersing agent, and the perovskite quantum dot polymer particles are prepared by a high-temperature hot injection method, so that the optical performance and stability of the perovskite quantum dots can be ensured.
Drawings
Fig. 1 is a schematic structural diagram of a perovskite quantum dot film.
FIG. 2 is a graph of the performance test results of perovskite quantum dot films.
In the figure: 1. the quantum dot layer comprises a first water resisting layer, 2, a first oxygen resisting layer, 3, a quantum dot layer, 4, a second oxygen resisting layer, 5 and a second water resisting layer.
Detailed Description
The present invention will be specifically described below with reference to the drawings and specific examples, and for convenience of explanation, the fluorescence emission peak is represented by PL, the fluorescence quantum efficiency is represented by PLQY, and the full width at half maximum is represented by FWHM.
Example 1: a preparation method of perovskite quantum dot polymer particles.
4.0mmol of PbBr2Oleic acid (32mmol) and oleylamine (32mmol) were charged into a 10L stirred tank and dried under vacuum at 120 ℃ for 30min to remove water from the starting material. The resulting mixture was heated to 150 ℃ under nitrogen blanket until PbBr2And completely dissolving. The temperature was then raised to 180 ℃ and 4kg of the thermoplastic elastomer SEBSG1657M was added, after complete melting, 0.16mmol of cesium oleate precursor was injected. Then respectively stirring 0.1kg of titanium dioxide diffusion particles and 0.01kg of antioxidant 1010 fully, adding the uniformly mixed product into a double-screw extruder after vacuum defoamation, and cooling and granulating the extruded product to obtain the required perovskite quantum dot polymer particles;
example 2: a preparation method of perovskite quantum dot polymer particles.
4.0mmol of PbBr2, oleic acid (32mmol) and oleylamine (32mmol) were charged into a 10L stirred tank and vacuum-dried at 120 ℃ for 30min to remove water from the starting material. The resulting mixture was heated to 150 ℃ under nitrogen blanket until PbBr2 was completely dissolved. And then, heating to 180 ℃, adding 4kg of acrylic block copolymer LA2330, and after the acrylic block copolymer LA2330 is completely melted, injecting 0.16mmol of cesium oleate precursor. Then respectively adding 0.1kg of titanium dioxide diffusion particles and 0.01kg of antioxidant 1010, fully stirring, carrying out vacuum defoamation on the uniformly mixed product, adding the product into a double-screw extruder, and cooling and granulating the extruded product to obtain the required perovskite quantum dot polymer particles;
example 3: a preparation method of perovskite quantum dot polymer particles.
Example 1 was repeated except that in the preparation of the perovskite quantum dot polymer particles, the thermoplastic elastomer was EVA, with the designation Levamelt @ 686.
Example 4: a preparation method of perovskite quantum dot polymer particles.
Example 1 was repeated except that the antioxidant 1010 was added in an amount of 0.02Kg only in the preparation of the perovskite quantum dot polymer particles.
Example 5: a preparation method of perovskite quantum dot polymer particles.
Example 2 was repeated except that the amount of the acrylic block copolymer LA2330 added was 8Kg only in the preparation of the perovskite quantum dot polymer particles.
Example 6: a preparation method of perovskite quantum dot polymer particles.
Example 1 was repeated except that the amount of SEBS G1657M added was 3.2Kg only in the preparation of the perovskite quantum dot polymer particles.
Example 7: a preparation method of perovskite quantum dot polymer particles.
Example 2 was repeated except that the amount of the acrylic block copolymer LA2330 added was 3.2Kg only in the preparation of the perovskite quantum dot polymer particles.
Testing visible light transmittance and haze:
the perovskite quantum dot film comprising the first water-blocking PP layer 1, the first oxygen-blocking EVOH layer 2, the quantum dot polymer layer 3, the second oxygen-blocking EVOH layer 4, and the second water-blocking PP layer 5 shown in fig. 1 was prepared by extruding PP particles, EVOH particles, and perovskite quantum dot polymer particles prepared in examples 1, 2, 3, 4, 5, 6, and 7 through a casting machine. And (3) carrying out visible light transmittance and haze test on each perovskite quantum dot film sample. After testing 6 samples in parallel for each example, the results were averaged to obtain visible light transmission and haze. The results of the visible light transmittance and haze measurements for each example sample are shown in detail in fig. 2.
Fluorescence property test:
the perovskite quantum dot polymer particles prepared in examples 1, 2, 3, 4, 5, 6, and 7 were processed into perovskite quantum dot films as shown in fig. 1, and PL, FWHM, and PLQY of each sample were tested at an excitation wavelength of 450 nm. After testing 6 samples in parallel for each example, the results were averaged to obtain the fluorescence efficiency. The results of the fluorescence efficiency test for each example sample are shown in detail in FIG. 2.
High temperature and high humidity aging test:
the perovskite quantum dot polymer particles obtained in examples 1, 2, 3, 4, 5, 6 and 7 were processed into perovskite quantum dot films as shown in fig. 1, and after aging each perovskite quantum dot film sample in an aging oven at 60 ℃ and 90% relative humidity for 1000 hours, PLQY of each sample was measured at a specific wavelength of 450 nm. After testing 6 samples in parallel in each example, the test results were averaged to obtain the fluorescence efficiency of the film after high temperature, high humidity and aging. The results of the high temperature, high humidity aging test of the samples of each example are shown in detail in fig. 2.
And (3) photo aging test:
the perovskite quantum dot polymer particles obtained in examples 1, 2, 3, 4, 5, 6 and 7 were processed into perovskite quantum dot films as shown in fig. 1, and after aging each perovskite quantum dot film sample in a blue light aging oven at 45 ℃ for 1000 hours, PLQY of each sample was measured at a specific wavelength of 450 nm. After testing 6 samples in parallel in each example, the test results were averaged to obtain the fluorescence efficiency of the film after light aging. The results of the light aging test for each example sample are shown in detail in fig. 2.
NTSC color gamut test:
the perovskite quantum dot polymer particles prepared in examples 1, 2, 3, 4, 5, 6, and 7 were processed into perovskite quantum dot films as shown in fig. 1, and assembled into LCD prototypes, and the NTSC color gamut of each LCD prototype was tested. After testing 6 samples in parallel for each example, the results were averaged to obtain the NTSC color gamut. The NTSC color gamut test results for the example samples are shown in particular in fig. 2.
Experimental results show that the optical performance and stability of the perovskite quantum dots can be ensured by adopting the thermoplastic elastomer as the dispersing agent and preparing the perovskite quantum dot polymer particles by using a high-temperature hot injection method.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.

Claims (6)

1. The preparation method of the perovskite quantum dot polymer particles is characterized by comprising the following steps:
mixing the raw materials in a molar ratio of 1:8: 13, adding the metal halide A, oleic acid and oleylamine into a stirring tank, drying at 120 ℃ in vacuum to remove moisture in raw materials, heating the obtained mixture to 150 ℃ under the protection of nitrogen until the metal halide is completely dissolved, then heating to 160-220 ℃, adding the thermoplastic elastomer, after the mixture is completely melted, rapidly injecting a certain amount of precursor B under vigorous stirring, and keeping the molar ratio of the metal halide A to the precursor B to be 1: and 0.4, then respectively adding the diffusion particles and the antioxidant, fully stirring, adding the uniformly mixed product into a double-screw extruder after vacuum defoamation, and cooling and granulating the extruded product to obtain the required perovskite quantum dot polymer particles.
2. The method for producing perovskite quantum dot polymer particles according to claim 1, characterized in that: the vacuum drying time was 30 minutes.
3. The method for producing perovskite quantum dot polymer particles according to claim 1, characterized in that: the softening temperature of the thermoplastic elastomer is 120-220 ℃, and the thermoplastic elastomer is one or a mixture of SEBS thermoplastic elastomer, EVA thermoplastic elastomer, TPU thermoplastic elastomer and acrylic block copolymer.
4. The method for producing perovskite quantum dot polymer particles according to claim 1, characterized in that: the metal cation of the metal halide A is Pb2+、Sn2+、Sb2+、Bi2+、Ag+、Zn2+、Mn2+、Cu2+Or Ge+One or more of (a).
5. The method for producing perovskite quantum dot polymer particles according to claim 1, characterized in that: the halogen element is Cl-、Br-、I-One or more of (a).
6. The method for producing perovskite quantum dot polymer particles according to claim 1, characterized in that: the precursor B is metal cation or oleate of positively charged organic cation, and the precursor B is Cs+、Rb+、FA+(HN=CH-NH3+) One or more of the oleates of (a).
CN202011030318.6A 2020-09-27 2020-09-27 Preparation method of perovskite quantum dot polymer particles Pending CN112159575A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112574438A (en) * 2021-02-25 2021-03-30 昆山博益鑫成高分子材料有限公司 Preparation method and application of perovskite quantum dot polymer microsphere with core-shell structure
CN114262474A (en) * 2021-08-24 2022-04-01 致晶科技(北京)有限公司 Preparation method of quantum dot composite material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112574438A (en) * 2021-02-25 2021-03-30 昆山博益鑫成高分子材料有限公司 Preparation method and application of perovskite quantum dot polymer microsphere with core-shell structure
CN112574438B (en) * 2021-02-25 2021-05-11 昆山博益鑫成高分子材料有限公司 Preparation method and application of perovskite quantum dot polymer microsphere with core-shell structure
CN114262474A (en) * 2021-08-24 2022-04-01 致晶科技(北京)有限公司 Preparation method of quantum dot composite material

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