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CN111690203A - Preparation method of quantum dot-polymer composite - Google Patents

Preparation method of quantum dot-polymer composite Download PDF

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Publication number
CN111690203A
CN111690203A CN201910191530.1A CN201910191530A CN111690203A CN 111690203 A CN111690203 A CN 111690203A CN 201910191530 A CN201910191530 A CN 201910191530A CN 111690203 A CN111690203 A CN 111690203A
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polymer
quantum dot
polymer composite
preparing
temperature
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马卜
王允军
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Suzhou Xingshuo Nanotech Co Ltd
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Suzhou Xingshuo Nanotech Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2491/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • C08K2003/3036—Sulfides of zinc
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Led Device Packages (AREA)
  • Luminescent Compositions (AREA)

Abstract

The application discloses a preparation method of a quantum dot-polymer complex, which comprises the following steps: providing a precursor comprising quantum dots, an antioxidant, and a polymer; the precursors are mixed at a first temperature at or above the melting point of the polymer and cooled to provide a mixture. The quantum dot-polymer complex prepared by the method has good optical stability, and the preparation method is simple and suitable for large-scale production.

Description

Preparation method of quantum dot-polymer composite
Technical Field
The application relates to the field of fluorescent nano materials, in particular to a preparation method of a quantum dot-polymer complex.
Background
The quantum dots have the characteristics that some rare earth fluorescent materials do not have, such as easy adjustment of emission peak, narrow half-peak width and the like, so that the quantum dots become hot spots for research in the display industry.
The quantum dots are generally dispersed in a polymer and prepared into a quantum dot-polymer composite of a predetermined shape for use, but the quantum dots are extremely vulnerable to oxygen, moisture, and other factors in the external environment, and thus cannot meet the requirements of the display and lighting fields on the light emitting stability. Therefore, the research on the preparation method of the quantum dot-polymer complex is of great significance.
Disclosure of Invention
It is an object of the present application to provide a novel method of preparing quantum dot-polymer composites.
According to one aspect of the present application, there is disclosed a method of preparing a quantum dot-polymer composite, comprising: providing a precursor comprising quantum dots, an antioxidant, and a polymer; the precursors are mixed at a first temperature at or above the melting point of the polymer and cooled to provide a mixture.
Alternatively, the antioxidant comprises at least one of 4-hydroxydodecanoic acid anilide, N' -hexamethylenebis-3 (3, 5-di-t-butyl-4-hydroxyphenyl) propionamide, 4-di-t-octyldiphenylamine, 2, 6-di-t-butyl-p-cresol, octadecyl beta (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-t-butylphenyl ] phosphite, bis (2, 4-di-t-butylphenol) pentaerythritol diphosphite, and dioctadecyl pentaerythritol diphosphite.
Optionally, the antioxidant is present in the quantum dot-polymer composite in an amount of 0.1 wt% to 5 wt%, in terms of weight fraction.
Optionally, the polymer has a crystallinity of greater than 5%.
Optionally, the first temperature is between 90 ℃ and 310 ℃.
Optionally, the polymer includes at least one component, and the first temperature is greater than or equal to the melting point of the highest melting component of the polymer.
Optionally, the polymer includes at least one of an ethylene-based polymer, a propylene-based polymer, a thiolene polymer, an acrylate polymer, a urethane polymer, a carbonate polymer, an epoxy polymer, and a silicone polymer.
Optionally, the precursor further comprises a hydrocarbon additive, at least one component of which has a boiling point above the first temperature at atmospheric pressure.
Optionally, the quantum dot-polymer composite is a quantum dot film.
The application has the following beneficial effects:
(1) the quantum dot-polymer complex is prepared by mixing the quantum dot and the polymer in a molten state, and the preparation method is simple and suitable for large-scale production;
(2) the quantum dot-polymer composite has good optical stability.
Detailed Description
The technical solutions in the examples of the present application will be described in detail below with reference to the embodiments of the present application. It should be noted that the described embodiments are only some embodiments of the present application, and not all embodiments.
According to some exemplary embodiments of the present application, a method of preparing a quantum dot-polymer composite includes: providing a precursor comprising quantum dots, an antioxidant, and a polymer; the precursors are mixed at a first temperature at or above the melting point of the polymer and cooled to provide a mixture.
In the present application, quantum dots refer to nanoparticles having three-dimensional dimensions all within 100 nm. The shape of the nanoparticles includes, but is not limited to, spherical, ellipsoidal, polyhedral, and the like.
In the application, the size of the quantum dots is preferably 1-15 nm. The quantum dots may be group IIB-VIA quantum dots, group IIIA-VA quantum dots, group IVA-VIA quantum dots, group IVA quantum dots, group IB-IIIA-VIA quantum dots, group VIII-VIA quantum dots, or perovskite quantum dots, but are not limited thereto.
In the application, the IIB-VIA quantum dots are not limited to a binary element structure composed of IIB elements and VIA elements, but may be a ternary element structure, such as two IIB elements and one VIA element or one IIB element and two VIA elements; or a four-element structure, such as two IIB elements and two VIA elements. The IIB-VIA group quantum dots can be of a single-shell or multi-shell structure, for example, when the single-shell is ZnS, the IIB-VIA group quantum dots can be CdSe/ZnS, CdSeS/ZnS and the like; for example, when the multi-shell layer is ZnSe/ZnS, the IIB-VIA group quantum dots can be CdSe/ZnSe/ZnS, CdSeS/ZnSe/ZnS and the like. Similar to the IIB-VIA group quantum dots, the IIIA-VA group quantum dots, the IVA-VIA group quantum dots, the IVA group quantum dots, the IB-IIIA-VIA group quantum dots and the VIII-VIA group quantum dots are not limited to be composed of one element or two or three elements.
In an illustrative embodiment, the quantum dots include, but are not limited to, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, PbS, HgSe, HgTe, MgSe, MgS, PbS, CdSeS, CdSeTe, CdSeS, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, MgZnSe, MgZnSTeS, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CgZnSnInAs, HgInAs, HgZnSeTe, GaGaN, GaGaGaGaGaGaGaGaGaGaSb, AlAs, AlNSAlN, InNAs, AlNSNAP, AlGanNAP, AlNSNAP, AlnAs, AlnNAP, AlnAs, AlnNAP, AlnNAs, AlnNAP, AlnAs, AlnNAP, AlnNAs, AlnNAP, AlnAs, AlnNAP, AlnNAs, AlnNAP2C, Si, and SiC, but are not limited thereto.
"perovskite" refers to a compound having a perovskite crystal structure. The perovskite crystal structure refers to a three-dimensional crystal structure corresponding to the crystal structure of CaTiO 3.
Different from organic phosphorus photo molecules or fluorescent molecules, quantum dots have large specific surface area, so that the stability of the quantum dots to other environmental factors such as light, heat and the like is poor. In the prior art, the quantum dots are generally avoided from being processed at high temperature, because the optical properties and stability of the quantum dots are poor. When preparing the quantum dot-polymer composite, the most common way is to directly disperse the quantum dots in a polymer resin solution, and obtain the quantum dot-polymer composite through ultraviolet curing or thermal curing. However, the inventor finds out in experiments that for the most commonly used polymers such as polyacrylic resin, polyepoxy resin and the like, the optical stability of the prepared quantum dot-polymer composite prepared in the mode is still poor, and the water oxygen protection capability of the polymer on the quantum dot is poor.
In the preparation of the quantum dot-polymer composite, another method, which is most common, is to coat the quantum dots in the polymer by using a swelling method, for example, the polymer is dissolved by a solvent, and then the solvent is pumped out after the polymer is mixed with the quantum dots. In the application, the inventor unexpectedly finds that the method is greatly different from the swelling method, and when the quantum dots and the melted polymer are fully and uniformly mixed and then cooled, the service life of the quantum dots in the quantum dot-polymer composite prepared by the method is remarkably prolonged. In addition, in the process of the method, the mixture of the quantum dots and the polymer is irradiated by blue light, the obtained quantum dots have good luminous stability, and the intensity and the emission peak position can be kept stable for a long time.
In the application, the quantum dot-polymer composite is prepared by mixing the quantum dot and the molten polymer, and the antioxidant is further included in the precursor, so that the quantum dot can be further prevented from being damaged by oxygen, and the luminous stability of the quantum dot-polymer composite is improved.
In one illustrative embodiment, the antioxidant comprises at least one of 4-hydroxydodecanoic acid anilide, N' -hexamethylenebis-3 (3, 5-di-t-butyl-4-hydroxyphenyl) propionamide, 4-di-t-octyldiphenylamine, 2, 6-di-t-butyl-p-cresol, octadecyl beta (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-t-butylphenyl ] phosphite, bis (2, 4-di-t-butylphenol) pentaerythritol diphosphite, and dioctadecyl pentaerythritol diphosphite. The content of the antioxidant in the quantum dot-polymer composite is preferably 0.1 to 5 wt%, more preferably 0.2 to 2 wt%.
In an exemplary embodiment of the present application, the quantum dot is present in the quantum dot-polymer composite in an amount of 0.01 wt% to 50 wt%, preferably 0.1 wt% to 1 wt%.
As used herein, the term "melting point" refers to the highest temperature of the melting range of a polymer. Because polymers are not composed of exactly the same crystals, exactly the same degree of polymerization, and exactly the same polymeric segments, and during the heating and melting process, the amorphous domains of the polymer will preferentially melt, while the crystalline domains will also require a higher melting temperature, the "melting point" is generally representative of the temperature at which the crystalline structure of the crystalline domains of the polymer is destroyed. In this application, the first temperature is higher than the melting point of the polymer, and means the highest temperature higher than the melting range of the polymer.
Generally, a polymer comprises crystalline domains with regularly arranged polymer chains and amorphous domains with irregularly arranged polymer chains, it is not common that the polymer is completely formed by the crystalline domains or the amorphous domains, and usually, the crystalline domains and the amorphous domains coexist, so that the polymer generally causes the generation of the crystalline domains during cooling. In this case, the proportion (percentage) of the crystalline domains based on the entire polymer can be expressed in terms of the crystallinity of the polymer. In some exemplary embodiments of the present application, the crystallinity of the polymer used is greater than 5%, and the inventors have found that when the polymer crystallinity is greater, the photo-stability of the resulting quantum dot-polymer composite prepared may be better. Preferably, the crystallinity of the polymer may be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%. For example, the crystallinity of the palm wax is lower than that of polypropylene or polyethylene, and when the latter is used as a polymer for dispersing the quantum dots, the stability of the quantum dots is more favorably improved.
In some exemplary embodiments of the present application, the polymer may include at least one component. When the polymer contains a plurality of components, the first temperature is greater than or equal to the melting point of the highest melting component of the polymers, such that all of the polymers are in a molten state at the first temperature.
In some exemplary embodiments of the present application, the first temperature is preferably 90 to 310 ℃. Specifically, the first temperature may be 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃ and 310 ℃. The first temperature is preferably 90-220 ℃, so that the possible adverse effect on the quantum dots when the first temperature is too high can be further avoided.
For example, the polymer may include at least one of an ethylene-based polymer, a propylene-based polymer, a thiolene-based polymer, an acrylate polymer, a urethane polymer, a carbonate polymer, an epoxy polymer, and a silicone polymer, but is not limited thereto. Specifically, the polymer may be polyethylene, polyvinylidene fluoride, polyvinyl butyral, polyvinyl alcohol, polystyrene, polypropylene, polymethyl acrylate, polymethyl methacrylate (organic glass), polydecylene formamide, polyhexamethylene sebacamide, polyethylene terephthalate glycol-modified polyethylene terephthalate, polyethylene naphthalate, polycarbonate, cellulose acetate butyrate, carnauba wax, polymethylphenyl silicone, polydimethylsiloxane, or the like. For selecting polymers with higher crystallinity, polymers with good symmetry, few or no branches, or small pendant groups are preferred.
In order to increase the mixing uniformity of the quantum dots and the polymer, and further prepare a quantum dot-polymer complex with better dispersion performance. In some exemplary embodiments of the present application, the precursor further comprises a solvent selected from C6-C22Amine compound, nitrogen-containing heterocyclic compound, and C6-C40Aliphatic hydrocarbons, C6-C30Aromatic hydrocarbons, C6-C22Phosphine oxide compound and C12-C22At least one aromatic ether. Specifically, C6-C22Primary alkylamines, e.g. hexadecylamine, C6-C22Secondary alkylamines, e.g. dioctylamine, C6-C40Tertiary alkyl amines, e.g. trioctylamine, nitrogen-containing heterocycles, e.g. pyridine, C6-C40Alkenes, e.g. octadecene, C6-C40Aliphatic hydrocarbons, e.g. hexadecane, octadecane, or squalane, with C6-C30Alkyl-substituted aromatic hydrocarbons, e.g. toluene, phenyldodecane, phenyltetradecane, or phenylhexadecane, substituted by C6-C22Alkyl-substituted phosphines, e.g. trioctylphosphineQuilt C6-C22Alkyl-substituted phosphine oxides, e.g. trioctylphosphine oxide, C12-C22An aromatic ether such as phenyl ether, or benzyl ether, or a combination thereof. The solvent is removed at atmospheric or reduced pressure during the first temperature treatment.
The cooling of the molten polymer can be accomplished in a variety of ways, and in one exemplary embodiment, the cooling is accomplished by water cooling or direct air cooling.
In an exemplary embodiment, the precursor further includes a hydrocarbon additive. At normal pressure, at least one component of the hydrocarbon additive has a boiling point above the first temperature. Thus, at least one component of the hydrocarbon additive will remain in the quantum dot-polymer composite. The hydrocarbon additive is preferably a saturated or unsaturated hydrocarbon, such as white oil. White oil is also known as paraffin oil or white oil or mineral oil and is obtained by subjecting a mixture of refined liquid hydrocarbons obtained from petroleum, mainly a mixture of saturated naphthenes and paraffins, and crude oil to atmospheric and vacuum fractionation, solvent extraction and dewaxing, and hydrorefining. In the application, the function of the hydrocarbon additive is very important, and for the surface modified with a ligand such as alkylamine, alkyl acid, thiol and the like, the quantum dot has strong hydrophobicity, and the compatibility of the quantum dot and a polymer is very poor, namely the quantum dot may not be effectively dispersed in the polymer. The addition of the hydrocarbon additive can ensure that the quantum dots are well compatible with the polymer, so that the quantum dots do not need to be further coated on the surface and the like. In addition, special dispersion means such as ultrasound can be avoided in the melting process. In the application, the inventor finds that the dispersibility of the quantum dots in a polymer can be effectively improved by adding a hydrocarbon additive with a proper content, so that the quantum dots are not greatly agglomerated, and the stable luminescence performance is ensured.
After the quantum dot-polymer composite is prepared, the content of the white oil in the quantum dot-polymer composite is preferably 0.1% to 5%, more preferably 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% by weight.
In some exemplary embodiments of the present application, the emission peak wavelength of the quantum dot-polymer composite may be 515 to 535nm, i.e., in the green range, under excitation by blue light; the emission peak wavelength of the quantum dot-polymer composite can also be 620-760 nm, namely in the red light range. The emission peak of the quantum dot-polymer composite may have a plurality of, for example, two, and one emission peak at 530nm and 630nm, in which case the quantum dot used in the quantum dot-polymer composite includes both a red quantum dot and a green quantum dot.
In some exemplary embodiments of the present application, the quantum dot-polymer composite is a quantum dot film. The quantum dot-polymer composite may also be in other shapes, such as particles, rods, and the like. The above shape can be obtained by preparing the quantum dots into a predetermined shape by lamination, tape casting, cold press molding, transfer molding, low pressure molding, extrusion molding, pultrusion molding, injection molding, blow molding, etc. after the quantum dots and the melted polymer are sufficiently mixed and before the polymer is cooled to be completely hardened.
Perovskite quantum dot-polymer composites according to some exemplary embodiments of the present application will be described in more detail below with reference to the following examples; however, the exemplary embodiments of the present application are not limited thereto.
Preparation examples: preparation of green light CdZnSe/ZnS quantum dot
Basic zinc carbonate (0.33g, 0.6mmol), oleic acid (2.1g, 0.75mmol)10mL _ LODE were weighed into a 100mL three-necked flask, and after 10 minutes of degassing with inert gas, the temperature was raised to 280 ℃ to give a clear solution. The clear solution was cooled to 180 ℃ and 1mL of a 0.5mmol/mL Se-ODE suspension was poured into the solution and reacted for 10 minutes. And then, injecting 2mL of 0.2mmol/mL cadmium oleate solution into the solution, reacting for 10min, then continuously adding 1mL of 2mmol/mL S-TBP, raising the temperature to 310 ℃, and continuing to react for 60min to obtain the CdZnSe/ZnS quantum dot. The reaction solution was purified with methanol and hexane, acetone precipitated, and then the precipitate was dissolved in toluene.
The fluorescence emission spectrum (excitation light wavelength: 447nm) was measured by Hitachi F-7000 spectrometer and the emission peak was 530nm and the half-value width was about 20 nm.
Preparation examples: preparation of red light CdZnSe/ZnS quantum dot
Basic zinc carbonate (0.33g, 0.6mmol), oleic acid (2.1g, 0.75mmol)10mL _ LODE were weighed into a 100mL three-necked flask, and after 10 minutes of degassing with inert gas, the temperature was raised to 280 ℃ to give a clear solution. The clear solution was cooled to 180 ℃ and 2mL of a 0.5mmol/mL Se-ODE suspension was injected and reacted for 10 minutes. And then, injecting 2mL of 0.4mmol/mL cadmium oleate solution into the solution, reacting for 10min, then continuously adding 1mL of 2mmol/mL S-TBP, raising the temperature to 310 ℃, and continuing to react for 60min to obtain the CdZnSe/ZnS quantum dot. The reaction solution was purified with methanol and hexane, acetone precipitated, and then the precipitate was dissolved in toluene.
The fluorescence emission spectrum (excitation light wavelength: 447nm) was measured by using a Hitachi F-7000 spectrometer, and the emission peak was 630nm and the half-value width was about 21 nm.
Example 1
The preparation process of the quantum dot film in example 1 is as follows:
taking a proper amount of the toluene solution of the green light CdZnSe/ZnS quantum dots (the green light CdZnSe/ZnS is about 1.5g), the toluene solution of the red light CdZnSe/ZnS quantum dots (the red light CdZnSe/ZnS is about 0.5g), 1g of white oil, 2g of 2, 6-di-tert-butyl-p-cresol and 500g of polypropylene (the melting point is about 230 ℃) in a glass ware, stirring and mixing at 240 ℃, removing the toluene in the stirring process, uniformly dispersing the green light CdZnSe/ZnS quantum dots and the red light CdZnSe/ZnS quantum dots in the molten polypropylene, and preparing the quantum dot film with the thickness of about 200 microns by tape casting in the air.
Example 2
The procedure for the preparation of quantum dot film in example 2 was substantially the same as in example 1 except that the antioxidant was 10g of dioctadecyl pentaerythritol diphosphite.
Comparative example
The procedure for preparing the quantum dot film in the comparative example was substantially the same as that in example 1, except that an antioxidant was not included in the precursor.
The quantum dot films of example 1, example 2 and comparative example were tested for stability in use. The test conditions were: the quantum dot film was irradiated with blue LEDs having a wavelength of 447nm, the intensity of which was 500nits, and the intensity of white light was measured after 0h, 5h, 10h, and 20h, respectively, in a white light backlight of a liquid crystal display device.
Example 1 (Strength/nits) Example 2 (Strength/nits) COMPARATIVE EXAMPLE (Strength/nits)
0 1530 1530 1530
5h 1503 1517 1467
10h 1489 1504 1402
20h 1485 1497 1365
As can be seen from the above table, in examples 1 and 2, the luminous intensity of the quantum dot film is stable, and the luminance can still be maintained at about 97.1% and 97.8% of the initial luminance after the blue light is irradiated for 20 hours; in contrast, in the comparative example, the luminance was maintained only at about 89.2% of the initial luminance after 20 hours of blue light irradiation. The above results fully indicate that the quantum dot-polymer composite prepared in the embodiments of the present application has excellent optical stability.
Although the present disclosure has been described and illustrated in greater detail by the inventors, it should be understood that modifications and/or alterations to the above-described embodiments, or equivalent substitutions, will be apparent to those skilled in the art without departing from the spirit of the disclosure, and that no limitations to the present disclosure are intended or should be inferred therefrom.

Claims (9)

1. A method of making a quantum dot-polymer composite, comprising:
providing a precursor comprising quantum dots, an antioxidant, and a polymer;
the precursors are mixed at a first temperature at or above the melting point of the polymer and cooled to provide a mixture.
2. The method for preparing a quantum dot-polymer composite according to claim 1, the antioxidant includes at least one of 4-hydroxydodecanoic acid anilide, N' -hexamethylenebis-3 (3, 5-di-t-butyl-4-hydroxyphenyl) propionamide, 4-di-t-octyldiphenylamine, 2, 6-di-t-butyl-p-cresol, octadecyl beta (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-t-butylphenyl ] phosphite, bis (2, 4-di-t-butylphenol) pentaerythritol diphosphite, and dioctadecyl pentaerythritol diphosphite.
3. The method of preparing a quantum dot-polymer composite according to claim 1, wherein the antioxidant is contained in the quantum dot-polymer composite in an amount of 0.1 to 5 wt% in terms of weight fraction.
4. The method of preparing a quantum dot-polymer composite according to claim 1, wherein the polymer has a crystallinity of more than 5%.
5. The method of preparing a quantum dot-polymer composite according to claim 1, wherein the first temperature is between 90 ℃ and 310 ℃.
6. The method of preparing a quantum dot-polymer composite according to claim 1, wherein the polymer comprises at least one component, and the first temperature is greater than or equal to a melting point of a component having a highest melting point among the polymers.
7. The method of preparing a quantum dot-polymer composite according to claim 1, wherein the polymer comprises at least one of an ethylene-based polymer, a propylene-based polymer, a thiol-ene polymer, an acrylate polymer, a urethane polymer, a carbonate polymer, an epoxy polymer, and a silicone polymer.
8. The method of claim 1, wherein the precursor further comprises a hydrocarbon additive, wherein at least one component of the hydrocarbon additive has a boiling point above the first temperature at atmospheric pressure.
9. The method of preparing a quantum dot-polymer composite according to claim 1, wherein the quantum dot-polymer composite is a quantum dot film.
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