CN114989808A - Synthetic method of high-stability quantum dot powder - Google Patents
Synthetic method of high-stability quantum dot powder Download PDFInfo
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- CN114989808A CN114989808A CN202210377805.2A CN202210377805A CN114989808A CN 114989808 A CN114989808 A CN 114989808A CN 202210377805 A CN202210377805 A CN 202210377805A CN 114989808 A CN114989808 A CN 114989808A
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- 239000000843 powder Substances 0.000 title claims abstract description 40
- 238000010189 synthetic method Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000004611 light stabiliser Substances 0.000 claims abstract description 27
- 238000004132 cross linking Methods 0.000 claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
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- 238000001035 drying Methods 0.000 claims abstract description 5
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- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 3
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- -1 2,2,6, 6-tetramethyl-4-piperidyl Chemical group 0.000 claims description 22
- 150000002466 imines Chemical class 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
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- 150000001412 amines Chemical class 0.000 claims description 4
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 claims description 4
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- FDAKZQLBIFPGSV-UHFFFAOYSA-N n-butyl-2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CCCCNC1CC(C)(C)NC(C)(C)C1 FDAKZQLBIFPGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
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- DNVYYPUFESRXNT-UHFFFAOYSA-N 2,2,6,6-tetramethyl-4-piperidin-1-yloctadecanoic acid Chemical compound CCCCCCCCCCCCC(C)(C)CC(CC(C)(C)C(O)=O)N1CCCCC1 DNVYYPUFESRXNT-UHFFFAOYSA-N 0.000 claims description 2
- PJCGHPRUNQYHRJ-UHFFFAOYSA-N 2,2,6,6-tetramethyl-4-prop-2-enoxypiperidine Chemical compound CC1(C)CC(OCC=C)CC(C)(C)N1 PJCGHPRUNQYHRJ-UHFFFAOYSA-N 0.000 claims description 2
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 claims description 2
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 150000001502 aryl halides Chemical class 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
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- 239000012454 non-polar solvent Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- OYNOCRWQLLIRON-UHFFFAOYSA-N 1-n,3-n-bis(2,2,6,6-tetramethylpiperidin-4-yl)benzene-1,3-dicarboxamide Chemical compound C1C(C)(C)NC(C)(C)CC1NC(=O)C1=CC=CC(C(=O)NC2CC(C)(C)NC(C)(C)C2)=C1 OYNOCRWQLLIRON-UHFFFAOYSA-N 0.000 claims 1
- FLPKSBDJMLUTEX-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLPKSBDJMLUTEX-UHFFFAOYSA-N 0.000 claims 1
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- YXHRTMJUSBVGMX-UHFFFAOYSA-N 4-n-butyl-2-n,4-n-bis(2,2,6,6-tetramethylpiperidin-4-yl)-2-n-[6-[(2,2,6,6-tetramethylpiperidin-4-yl)amino]hexyl]-1,3,5-triazine-2,4-diamine Chemical compound N=1C=NC(N(CCCCCCNC2CC(C)(C)NC(C)(C)C2)C2CC(C)(C)NC(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)NC(C)(C)C1 YXHRTMJUSBVGMX-UHFFFAOYSA-N 0.000 description 2
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- IJKSQVGRFHBZJV-UHFFFAOYSA-N 1-o-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl] 3-o-(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butylpropanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(CCCC)C(=O)OCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 IJKSQVGRFHBZJV-UHFFFAOYSA-N 0.000 description 1
- YDEVFQUYKOWOLQ-UHFFFAOYSA-N 2-(2,2,6,6-tetramethylpiperidin-4-yl)benzene-1,3-dicarboxamide Chemical compound C1C(C)(C)NC(C)(C)CC1C1=C(C(N)=O)C=CC=C1C(N)=O YDEVFQUYKOWOLQ-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention provides a method for synthesizing high-stability quantum dot powder, which comprises the steps of dissolving a light stabilizer and a quantum dot concentrated solution in a solvent, introducing inert gas for protection, and continuously stirring until the mixture is uniform; then adding a curing crosslinking agent, stirring again, heating to the curing temperature for crosslinking reaction, and keeping the crosslinking reaction until the crosslinking reaction is finished; and drying the obtained product into a solid, and grinding the solid to obtain the high-stability quantum dot powder. The invention firmly coats the light stabilizer on the surface of the quantum dot through a crosslinking reaction to form a protective layer, thereby effectively cutting off the direct contact between external free radicals and internal quantum dots and achieving the purpose of improving the stability of the quantum dots.
Description
Technical Field
The invention belongs to the technical field of quantum dot synthesis, and particularly relates to a method for synthesizing high-stability quantum dot powder.
Background
The quantum dots are easy to be damaged by oxygen and water vapor in the using process, and especially in the field of photoluminescence, oxygen free radicals and hydroxyl free radicals can be formed around the quantum dots due to the irradiation of high-energy blue light, so that the service life of the quantum dots is greatly shortened. There are two common practices at present: 1. the encapsulation is made with a high barrier material, such as a high barrier film. 2. And increasing the shell thickness of the quantum dots. The former is very expensive and the latter is also of limited effectiveness. Therefore, it is necessary to develop new quantum dots with stable performance, so that the quantum dots can maintain stable luminescence characteristics when in use and are not damaged by oxygen and water vapor.
Disclosure of Invention
The invention aims to solve the problem of providing a method for synthesizing high-stability quantum dot powder, wherein a light stabilizer is firmly coated on the surface of a quantum dot through a crosslinking reaction to form a protective layer, so that the direct contact between an external free radical and an internal quantum dot is effectively cut off, and the aim of improving the stability of the quantum dot is fulfilled.
When the quantum dots are applied, the quantum dots are mainly dispersed in materials such as polyacrylic resin, polystyrene, polymethyl methacrylate and the like. The light stabilizer hardly absorbs ultraviolet rays and cannot quench excited chromophore, but can capture free radicals generated by polymer photolysis after absorbing light energy in an aerobic state, so that the oxidation of the free radicals to quantum dots is prevented, and meanwhile, the effective group of the light stabilizer also has a cyclic regeneration function in the light stabilization process, so that the light stabilizer plays a better protection role on the quantum dot powder. In the conventional scheme, the light stabilizer is generally uniformly dispersed in the polymer resin, but free radicals generated by illumination can hide the light stabilizer from being captured to the surface of the quantum dot with a certain probability, so that the quantum dot is damaged.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for synthesizing high-stability quantum dot powder comprises dissolving a light stabilizer and a quantum dot concentrated solution in a solvent, introducing inert gas for protection, and continuously stirring until uniform; then adding a curing crosslinking agent, stirring again, heating to the curing temperature for crosslinking reaction, and keeping the crosslinking reaction till the crosslinking reaction is finished; and drying the obtained product into a solid, and grinding the solid to obtain the high-stability quantum dot powder.
The technical scheme of the invention is that the light stabilizer is firmly coated on the surface of the quantum dot through a crosslinking reaction to form a protective layer, thereby effectively cutting off the direct contact between external free radicals and internal quantum dots and achieving the purpose of improving the stability of the quantum dot. In addition, the quantum dot powder coated by the light stabilizer prepared by the technical scheme of the invention can be added into any resin or plastic, such as UV glue, PMMA, PS, MS, PC and other media, and does not need special water and oxygen blocking protection, thereby greatly reducing the cost.
Further, the light stabilizer, the quantum dot concentrated solution and the solvent are added according to the mass ratio of 10-30:1-10: 50-100.
Further, the light stabilizer is a hindered amine light stabilizer containing-NH or-OH; specifically, a polymer of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 6-hexanediamine with a reaction product of 2,4, 6-trichloro-1, 3, 5-triazine and N-butyl-1-butylamine with N-butyl-2, 2,6, 6-tetramethyl-4-piperidylamine, poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperidyl) imine ] -1, 6-diadipy l [ (2,2,6, 6-tetramethyl-4-piperidyl) imine ] ], 1,5,8, 12-tetrakis [4, 6-bis (N-butyl-N-1, 2,2,6, 6-pentamethyl-4-piperidinylamino) -1,3, 5-triazin-2-yl ] -1,5,8, 12-tetraazadodecane, bis (2,2,6, 6-tetramethyl-4-piperidinyl) sebacate, 2,2,6, 6-tetramethyl-4-piperidinostearate, polysuccinic acid (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol), poly { (6-morpholinyl-5-triazine-2, 4-diyl) (2,2,6, 6-tetramethylpiperidinyl) iminohexamethylene [ (2,2,6, 6-tetramethylpiperidyl) -imino ] }, N, N '-bis (2,2,6, 6-tetramethyl-4-piperidyl) -N, N' -dialdehydehexamethylenediamine, poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperidyl) imine ] -1, 6-diadipy l [ (2,2,6, 6-tetramethyl-4-piperidyl) imine ] ] ] polysuccinic acid (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidylethanol) ester (built up), poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] -1, 6-diadipyl [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] ] ] bis (2,2,6, 6-tetramethyl-4-piperidinyl) sebacate (built), [ [3, 5-di-tert-butyl-4-hydroxyphenyl ] methyl ] butylmalonate (1,2,2,6, 6-pentamethyl-4-piperidinyl) ester; n, N ' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, the product of the polymerization of a-olefin of C20-24 with maleic anhydride and the reaction with 2,2,6, 6-tetramethyl-4-piperidylamine, 4-allyloxy-2, 2,6, 6-tetramethylpiperidine, 1,3, 5-triazine-2, 4, 6-triamine, N2, N2' ' -1, 2-tetraacetylethylenediamine [ N2- [3- [ [4, 6-bis [ butyl (1,2,2,6, 6-p-pentamethyl-4-piperidyl) amine ] -1,3, 5-triazine-2-yl ] amino ] propane ] -N ', N ' ' -dibutyl-N ', n '' -di (1,2,2,6, 6-benzyl-4-piperidyl) -polysuccinic acid (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol) ester, and one of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl.
Further, the solvent is a low-polarity or non-polar solvent, preferably toluene, xylene, chloroform, dichloromethane, dichloroethane, cyclohexane, n-hexane or n-octane.
Further, the curing crosslinking agent is isocyanate, epoxy, isothiocyanate, acyl azide, sulfonyl chloride, aldehyde, aryl halide, imide ester, carbodiimide, anhydride or fluorophenyl ester.
Further, the addition amount of the curing crosslinking agent is 10-30% of the using amount of the light stabilizer.
Further, the curing temperature is 25 ℃ to 180 ℃, preferably 50 ℃ to 150 ℃, more preferably 80 ℃ to 120 ℃ when the crosslinking reaction is carried out; when the cross-linking reaction is carried out, the viscosity of the reactant is detected, and when the reaction is carried out until the viscosity does not change any more, the reaction is ended, and the cross-linking is completed.
Furthermore, the quantum dot concentrated solution is formed by dispersing a quantum dot nano material in an acrylic monomer, wherein the mass concentration percentage of the quantum dot nano material is 5-30%.
Further, the drying is carried out in a vacuum drying oven, and the pulverized powder has a particle size of 1 to 100 μm, preferably 10 to 50 μm.
The invention has the advantages and positive effects that:
1. according to the invention, the light stability of the quantum dots is improved and the service life of the quantum dots is prolonged while the fluorescence efficiency of the quantum dots is not influenced by the coating protection effect of the light stabilizer on the quantum dots and the cyclic regeneration function of the effective groups; the quantum dot powder prepared by the method can be directly added into any resin or plastic, so that the use cost is greatly reduced.
2. The synthesis method is simple to operate and convenient for realizing industrial production.
Drawings
FIG. 1 is a graph showing the luminous efficiency of the anti-water-oxygen performance of the quantum dot PS plate prepared in example 1 and comparative example of the present invention;
FIG. 2 is a graph of the luminous efficiency of the quantum dot PS plates prepared in example 1 and comparative example of the present invention with respect to their resistance to strong blue light irradiation.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Example 1:
taking a polymer (such as Chimassorb 2020) of 10g N, N '-bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 6-hexanediamine and a reaction product of 2,4, 6-trichloro-1, 3, 5-triazine, N-butyl-1-butylamine and N-butyl-2, 2,6, 6-tetramethyl-4-piperidylamine into a 250mL four-mouth bottle, adding 100g of dichloromethane and 1g of 30% quantum dot concentrated solution, stirring at room temperature, adding 1g of 4, 4', 4'' -triphenylmethane triisocyanate after the liquid is completely transparent, continuously stirring, heating to 80 ℃ for crosslinking reaction, wherein the viscosity of the solution gradually rises until the viscosity of the reaction liquid does not change any more, stopping stirring, pouring out the reactant, putting the reactant into a vacuum oven, and carrying out vacuum drying for 1h at the temperature of 60 ℃; and putting the dried solid into a ball mill, setting the ball milling rotation speed to 200 r/min, and taking out the powder after ball milling for 20min to obtain 12g of quantum dot powder.
Example 2-preparation of example the same as example 1, the component ratios are specifically shown in table 1:
TABLE 1 composition ratio of example 1-example
Quantum dot plates were prepared from the prepared quantum dot powders of examples 1 to 11, respectively, wherein the quantum dot powder was added based on the same ratio of the quantum dot concentrate in the plate, so that the prepared plates had equivalent quantum dots. The preparation method comprises the following steps:
and adding Ng quantum dot powder into 1000g of PS particles, stirring and dispersing uniformly, and then granulating by using an extruder to obtain the PS quantum dot master batch. And (3) putting the quantum dot master batch into an extruder, controlling the thickness of a die head to be 1.5mm, and extruding to obtain the quantum dot PS plate with the thickness of 1.5 mm.
In examples 1 to 11, the addition amount N of the quantum dot powder when preparing the quantum dot PS plate is shown in table 2:
table 2 quantum dot powder addition amounts for examples 1-11
| Item | Equivalent content of quantum dots (g) | Proportion of quantum dots in quantum dot powder (%) | Amount of Quantum dot powder added N (g) |
| Example 1 | 10g | 8.33% | 120g |
| Example 2 | 10g | 7.69% | 130g |
| Example 3 | 10g | 27.78% | 36g |
| Example 4 | 10g | 45.45% | 22g |
| Example 5 | 10g | 3.125% | 320g |
| Example 6 | 10g | 13.51% | 74g |
| Example 7 | 10g | 23.25% | 43g |
| Example 8 | 10g | 14.28% | 70g |
| Example 9 | 10g | 7.69% | 130g |
| Example 10 | 10g | 20% | 50g |
| Example 11 | 10g | 17.86% | 56g |
The equivalent content of the quantum dots is specifically the mass of a 30% quantum dot concentrated solution; in each embodiment, when the corresponding quantum dot PS plate is prepared, the 30% quantum dot concentrated solution with the quantum dot content of 10g is ensured, and the content of the quantum dot powder required to be added in each embodiment, namely N, can be directly obtained according to the proportion of the quantum dots in different quantum dot powders.
The proportion of quantum dots in the quantum dot powder in each embodiment is calculated by the following formula: the mass of the 30% quantum dot concentrate/(the mass of the 30% quantum dot concentrate + the mass of the curing crosslinking agent + the mass of the light stabilizer) × 100%.
Comparative example:
10g of 30% quantum dot concentrated solution and 300g of a polymer (for example: Chimassorb 2020) of a reaction product of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 6-hexanediamine and 2,4, 6-trichloro-1, 3, 5-triazine, N-butyl-1-butylamine and N-butyl-2, 2,6, 6-tetramethyl-4-piperidylamine are added to 1000g of PS particles, and the PS particles are stirred, dispersed uniformly and granulated by an extruder to obtain the PS quantum dot master batch. And putting the quantum dot master batch into an extruder, controlling the thickness of a die head to be 1.5mm, and basically obtaining the quantum dot PS plate with the thickness of 1.5 mm.
Test example 1:
in the test example, the quantum dot PS plates prepared in example 1 and the comparative example were used to test the water and oxygen resistance of the quantum dot plates, so as to determine whether the luminescence of the quantum dots is corroded by water and oxygen;
the specific method comprises the following steps: placing the quantum dot PS plates prepared in the embodiment 1 and the comparative example in a 38W/square meter blue backlight module, placing the backlight module in a high-temperature high-humidity box with the temperature of 60 ℃ and the humidity of 90%, and taking out the quantum dot PS plates at different time to detect the luminous efficiency of the quantum dot plates by using an integrating sphere; the luminous efficiency graph shown in fig. 1 was prepared with time as abscissa and relative efficiency as ordinate.
As can be seen from fig. 1, the quantum dot PS plate prepared by the preparation method of example 1 has a decrease in luminous efficiency with an increase in test time, but it is maintained at 80% or more after 30 days, whereas the quantum dot PS plate of the comparative example has a rapid decrease in luminous efficiency with an increase in test time, and it is decreased to about 10% after about 20 days, and is relatively corroded by water and oxygen. Therefore, the quantum dot powder prepared by the synthesis method has stable luminescent property, and the light stabilizer firmly coats the quantum dots, so that the protection purpose is achieved; has good water and oxygen resistance and stable performance.
In addition, the above-described experiments were also performed on the quantum dot PS plates manufactured in examples 2 to 11 of the present invention, and the obtained results were similar to those of example 1.
Test example 2:
in the test example, the quantum dot PS plates prepared in example 1 and the comparative example were used to test the strong blue light irradiation resistance of the quantum dot plate, thereby determining whether the luminescence of the quantum dot is affected by blue light;
the specific method comprises the following steps: the quantum dot PS plates prepared in example 1 and comparative example were placed at 380W/m 2 The light emitting efficiency of the quantum dot plate is detected by taking out the light at different time and using an integrating sphere; the luminous efficiency graph shown in fig. 2 was prepared with time as the abscissa and the relative efficiency as the ordinate.
As can be seen from fig. 2, the light emitting efficiency of the quantum dot PS plate of example 1 is slightly decreased with the increase of the irradiation time under the irradiation of the strong blue light, but the light emitting efficiency is still maintained at 90% or more under the irradiation of the strong blue light for 30 days, so that the quantum dot powder prepared by the synthesis method of the present invention has good blue light irradiation resistance, and the light stabilizer is firmly coated on the surface of the quantum dot by the cross-linking reaction in the synthesis process to form a protective layer, thereby effectively cutting off the direct contact between the external free radical and the internal quantum dot, achieving the purpose of improving the stability of the quantum dot, and having excellent blue light resistance; the quantum dot PS plate of the comparative example rapidly decreases the luminous efficiency with the irradiation of strong blue light for a long time and finally keeps stable at about 24%, so that the phenomenon that the quantum dot is damaged with the increase of time is known in the prior art although the quantum dot can be protected from the damage of free radicals to a certain extent by adding the light stabilizer. The quantum dot powder prepared by the synthesis method has the advantages that the quantum dot is coated and protected in an all-around manner by the light stabilizer, so that the quantum dot is protected from being damaged to the maximum extent, the protection efficiency is improved, and the probability of contact with free radicals is reduced.
In addition, the above-described experiment was also performed on the quantum dot PS plates manufactured in examples 2 to 11 of the present invention, and the obtained results were similar to example 1.
Test example 3:
this test example was used to examine the effect of different curing temperatures on the reaction time during the crosslinking reaction: examples 12 to 18 quantum dot powders were prepared according to the formulation and preparation method of example 1, except that different curing temperatures were used during the crosslinking reaction, and the curing time required for completion of curing was judged according to the change in viscosity, and the curing temperatures and curing times of examples 12 to 18 are shown in table 2:
table 2 curing temperatures and curing times for examples 12-18
| Item | Curing temperature | Curing time |
| Example 1 | 80℃ | 1h |
| Example 12 | 25℃ | 3h |
| Example 13 | 50℃ | 2.5h |
| Example 14 | 70℃ | 1.5h |
| Example 15 | 100℃ | 50min |
| Example 16 | 120℃ | 40min |
| Example 17 | 150℃ | 30min |
| Example 18 | 180℃ | 20min |
As can be seen from the data in Table 2, when the crosslinking reaction is carried out, the higher the curing temperature is, the faster the curing speed is, in order to save time and improve efficiency, the crosslinking reaction is preferably carried out at 80-120 ℃, and at the same time, the external heating cost is appropriate, and the moderate curing reaction rate is also convenient for the complete reaction of the materials.
While specific embodiments of the present invention have been described in detail, the description is merely illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (10)
1. A method for synthesizing high-stability quantum dot powder is characterized in that a light stabilizer and a quantum dot concentrated solution are dissolved in a solvent, inert gas is introduced for protection, and the mixture is continuously stirred until the mixture is uniform; then adding a curing crosslinking agent, stirring again, heating to the curing temperature for crosslinking reaction, and keeping the crosslinking reaction until the crosslinking reaction is finished; and drying the obtained product into a solid, and grinding the solid to obtain the high-stability quantum dot powder.
2. The method for synthesizing high-stability quantum dot powder according to claim 1, wherein the method comprises the following steps: the light stabilizer, the quantum dot concentrated solution and the solvent are added according to the mass ratio of 10-30:1-10: 50-100.
3. The method for synthesizing high-stability quantum dot powder according to claim 1, wherein the method comprises the following steps: the light stabilizer is a hindered amine light stabilizer containing-NH or-OH.
4. The method for synthesizing high-stability quantum dot powder according to claim 3, wherein the method comprises the following steps: the light stabilizer is a polymer of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 6-hexanediamine and a reaction product of 2,4, 6-trichloro-1, 3, 5-triazine, N-butyl-1-butylamine and N-butyl-2, 2,6, 6-tetramethyl-4-piperidylamine, poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperidyl) imine ] -1, 6-diadipy l [ (2,2,6, 6-tetramethyl-4-piperidyl) imine ] ], 1,5,8, 12-tetrakis [4, 6-bis (N-butyl-N-1, 2,2,6, 6-pentamethyl-4-piperidinylamino) -1,3, 5-triazin-2-yl ] -1,5,8, 12-tetraazadodecane, bis (2,2,6, 6-tetramethyl-4-piperidinyl) sebacate, 2,2,6, 6-tetramethyl-4-piperidinostearate, polysuccinic acid (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol), poly { (6-morpholinyl-5-triazine-2, 4-diyl) (2,2,6, 6-tetramethylpiperidinyl) iminohexamethylene [ (2,2,6, 6-tetramethylpiperidyl) -imino ] }, N, N '-bis (2,2,6, 6-tetramethyl-4-piperidyl) -N, N' -dialdehydehexamethylenediamine, poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperidyl) imine ] -1, 6-diadipy l [ (2,2,6, 6-tetramethyl-4-piperidyl) imine ] ] ] polysuccinic acid (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidylethanol) ester (built up), poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperid-ine) imine ] -1, 6-diadipyl [ (2,2,6, 6-tetramethyl-4-piperid-ine) imine ] ] bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate (built up), [ [3, 5-di-tert-butyl-4-hydroxyphenyl ] methyl ] butylmalonic acid bis (1,2,2,6, 6-pentamethyl-4-piperidyl) ester, N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, alpha-olefin of C20-24 polymerized with maleic anhydride and then reacted with 2,2,6, 6-tetramethyl-4-piperidinamine, 4-allyloxy-2, 2,6, 6-tetramethylpiperidine, 1,3, 5-triazine-2, 4, 6-triamine, N2, N2 "-1, 2-tetraacetylethylenediamine [ N2- [3- [ [4, 6-bis [ butyl (1,2,2,6, 6-p-pentamethyl-4-piperidinyl) amine ] -1,3, 5-triazine-2-yl ] amino ] propane ] -N ', N" -dibutyl-N', N "-bis (1,2,2,6, 6-benzyl-4-piperidinyl) -polysuccinic acid (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol), 4-hydroxy-2, 2,6, 6-tetramethyl piperidine-1-oxyl.
5. The method for synthesizing high-stability quantum dot powder according to claim 1, wherein the method comprises the following steps: the solvent is low-polarity or non-polar solvent, preferably toluene, xylene, chloroform, dichloromethane, dichloroethane, cyclohexane, n-hexane or n-octane.
6. The method for synthesizing high-stability quantum dot powder according to claim 1, wherein the method comprises the following steps: the curing crosslinking agent is isocyanate, epoxy, isothiocyanate, acyl azide, sulfonyl chloride, aldehyde, aryl halide, imide ester, carbodiimide, anhydride or fluorophenyl ester.
7. The method for synthesizing high-stability quantum dot powder according to claim 1, wherein the method comprises the following steps: the addition amount of the curing crosslinking agent is 10-30% of the using amount of the light stabilizer.
8. The method for synthesizing high-stability quantum dot powder according to claim 1, wherein the method comprises the following steps: the curing temperature is 25-180 ℃, preferably 50-150 ℃ and more preferably 80-120 ℃ when the crosslinking reaction is carried out; when the crosslinking reaction is carried out, the viscosity of the reactant is detected, and when the reaction is carried out until the viscosity does not change any more, the reaction is ended, and the crosslinking is completed.
9. The method for synthesizing high-stability quantum dot powder according to claim 1, wherein the method comprises the following steps: the quantum dot concentrated solution is formed by dispersing a quantum dot nano material in an acrylic monomer, wherein the mass concentration percentage of the quantum dot nano material is 5-30%.
10. The method for synthesizing high-stability quantum dot powder according to claim 1, wherein the method comprises the following steps: the drying is carried out in a vacuum oven, and the milled powder has a particle size of 1-100 μm, preferably 10-50 μm.
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