WO2022179456A1 - Preparation method and application of perovskite quantum dot polymer microsphere having core-shell structure - Google Patents
Preparation method and application of perovskite quantum dot polymer microsphere having core-shell structure Download PDFInfo
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- WO2022179456A1 WO2022179456A1 PCT/CN2022/076984 CN2022076984W WO2022179456A1 WO 2022179456 A1 WO2022179456 A1 WO 2022179456A1 CN 2022076984 W CN2022076984 W CN 2022076984W WO 2022179456 A1 WO2022179456 A1 WO 2022179456A1
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- perovskite quantum
- quantum dot
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- 239000004005 microsphere Substances 0.000 title claims abstract description 93
- 239000002096 quantum dot Substances 0.000 title claims abstract description 80
- 229920000642 polymer Polymers 0.000 title claims abstract description 67
- 239000011258 core-shell material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000010410 layer Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000012792 core layer Substances 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 60
- 239000003960 organic solvent Substances 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 25
- 239000002033 PVDF binder Substances 0.000 claims description 22
- 239000013538 functional additive Substances 0.000 claims description 22
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 17
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- DNJJMLZMBBNATC-UHFFFAOYSA-N [4-(benzotriazol-2-yl)-3-hydroxyphenyl] 2-methylprop-2-enoate Chemical compound OC1=CC(OC(=O)C(=C)C)=CC=C1N1N=C2C=CC=CC2=N1 DNJJMLZMBBNATC-UHFFFAOYSA-N 0.000 claims description 10
- 239000004925 Acrylic resin Substances 0.000 claims description 9
- 229920000178 Acrylic resin Polymers 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000132 electrospray ionisation Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002892 organic cations Chemical class 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003292 glue Substances 0.000 abstract description 4
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000007590 electrostatic spraying Methods 0.000 abstract description 2
- 238000000016 photochemical curing Methods 0.000 abstract 1
- 229920001187 thermosetting polymer Polymers 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QAIHWMZHLIBAFX-QZOPMXJLSA-N (z)-octadec-9-en-1-amine;(z)-octadec-9-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCN.CCCCCCCC\C=C/CCCCCCCC(O)=O QAIHWMZHLIBAFX-QZOPMXJLSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VWSUVZVPDQDVRT-UHFFFAOYSA-N phenylperoxybenzene Chemical compound C=1C=CC=CC=1OOC1=CC=CC=C1 VWSUVZVPDQDVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/122—Pulverisation by spraying
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
-
- 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
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- 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
- 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
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
-
- 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
- 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
- C08J2327/22—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 modified by chemical after-treatment
Definitions
- the invention relates to the technical field of perovskite quantum dots, in particular to a preparation method and application of a core-shell structure perovskite quantum dot polymer microsphere.
- perovskite quantum dots Due to its ionic characteristics, perovskite quantum dots are extremely sensitive to water and oxygen. Usually, perovskite quantum dots are coated with polymer materials and prepared into perovskite quantum dot films, which are used in the backlight of wide color gamut liquid crystal displays. in the module.
- Perovskite quantum dot polymer material is the key material for making perovskite quantum dot film. At present, in the existing process, perovskite quantum dots are generally synthesized first, and the purified perovskite quantum dots are then combined with polymer or polymer The perovskite quantum dot polymer material is prepared by mixing the monomers and heating or illuminating.
- perovskite quantum dots In the synthesis process of perovskite quantum dots, the nucleation and growth of perovskite quantum dots need to be controlled by ligands such as oleylamine oleate, so as to obtain perovskite quantum dots with uniform particle size.
- ligands such as oleylamine oleate
- perovskite quantum dots are synthesized first, and then the preparation of perovskite quantum dot polymer microspheres is performed. It also has the problems of cumbersome steps and complicated processes; in addition, the optical properties and stability of the perovskite quantum dot polymer microspheres prepared by them are also relatively poor.
- the purpose of the present invention is to provide a preparation method and application of perovskite quantum dot polymer microspheres with a core-shell structure.
- the perovskite is formed in situ in the core layer of the polymer microspheres, and different types of polymer materials are used as the core-shell layer to block water and oxygen, thereby improving the aging stability of the perovskite quantum dots; the synthesized
- the core-shell structure of perovskite quantum dot polymer microspheres can be dispersed into conventional light-curing or thermal-curing glue to prepare perovskite quantum dot film, which can be applied to the backlight module of wide color gamut liquid crystal display.
- a preparation method of perovskite quantum dot polymer microspheres with core-shell structure comprising the following steps:
- the molar ratio of AX and BX 2 is 1:1-3, the weight percentage of the total weight of AX and BX 2 to polyvinylidene fluoride is 0.2-10%, and the solid content of the obtained solution is 10-30%;
- B is a metal cation, one or a mixture of Pb 2+ , Sn 2+ , Sb 2+ , Zn 2+ , Mn 2+ , and Cu 2+ ;
- X is a halogen element, which is one or a mixture of Cl - , Br - and I - ;
- Dissolve the fluorocarbon resin in the second organic solvent stir at a constant speed of 250 to 300 r/min for 10 to 15 hours at room temperature, and then stir at a high speed of 1800 to 2000 r/min for 30 to 40 minutes; after filtering it, A colorless and transparent first shell electrospray liquid is obtained, and the solid content of the obtained solution is controlled at 10-50%;
- the fluorocarbon resin is a copolymer of tetrafluoroethylene, vinyl ether and other functional monomers containing hydroxyl and carboxyl groups;
- ethylene-vinyl alcohol copolymer, 2-hydroxy-4-methoxy benzophenone and functional additives into the third organic solvent; wherein, ethylene-vinyl alcohol copolymer, 2-hydroxy-4-methoxy benzophenone
- the weight ratio of benzophenone, functional additives and the third solvent is 2:0.02-0.06:0.08-0.12:8; at room temperature, the obtained mixture is pre-stirred at a constant speed for 10-15h at a rate of 280-320r/min, Then stir at a high speed of 1800-2000r/min for 20-30min, and then filter it; the obtained liquid is the second shell layer electrospray liquid;
- the three electrospray liquids obtained above are respectively added to the liquid storage tank, supplied to the ternary coaxial nozzle at a stable rate, and a high voltage power supply is used to add a rated polarity to the solution, and a high potential is applied between the nozzle and the collector,
- the liquid jet is emitted from the nozzle and accelerated by the high potential, and the prepared polymer microspheres move toward the collector; during this process, the first organic solvent, the second organic solvent and the third organic solvent are volatilized to obtain a three-layer core-shell Structured polymer microspheres; the thickness of each layer of the prepared three-layer structure polymer microspheres can be controlled by controlling the flow rate and voltage of the three electrospray liquids; then the obtained three-layer core-shell structure polymer microspheres
- the ball is vacuum-dried at 35-45 °C, and with the further volatilization of the first organic solvent, the second organic solvent, and the third organic solvent, the perovskite quantum dots are formed in situ in
- the first organic solvent used is any one of N,N-dimethylformamide, N,N-dimethylacetamide, acetone, and butanone. species or a mixture of several.
- the second organic solvent used is N,N-dimethylformamide, N,N-dimethylacetamide, acetone, methyl ethyl ketone, acetic acid Any one or a mixture of ethyl ester and butyl acetate.
- the third organic solvent used is a mixture of N,N-dimethylacetamide and isopropanol, N,N-dimethylacetamide and The weight ratio of isopropanol is 7:1.
- preparation method of the functional additive comprises the following steps:
- cerium oxide porous microspheres obtained above are immersed in an ethanol solution with a concentration of 50-65%, and a silane coupling agent with a mass of 15-25% of the ethanol solution is added to it; then ultrasonically disperse at a frequency of 28-35 kHz 5 to 15 minutes, then the temperature of the obtained mixed components was raised to 50 to 60 ° C, and the reaction was carried out at this temperature for 4 to 6 hours; after the reaction was completed, the mixed components were separated from solid and liquid, and the obtained solid powder was placed in vacuum drying. Drying in the box;
- the obtained solid powder After grinding the obtained solid powder, according to the solid-liquid ratio of 0.1 ⁇ 0.2g/mL, the solid powder is put into the hydroxyacrylic resin solution, and ultrasonically dispersed at a frequency of 25 ⁇ 30kHz for 20 ⁇ 30min, the obtained dispersion is Functional additive finished products.
- the heating rate during calcination is 2 ⁇ 5°C/min.
- the silane coupling agent used is any one of ⁇ -aminopropyltriethoxysilane and ⁇ -(2,3-glycidoxy)propyltrimethoxysilane .
- the solvent in the hydroxy acrylic resin solution used is ethyl acetate, and the solute is hydroxy acrylic resin; and the hydroxyl value of the hydroxy acrylic resin is 80-200 mgKOH/g, and the solid content of the acrylic resin solution is 80-200 mgKOH/g. 40 to 65%.
- the core-shell structure perovskite quantum dot polymer microsphere is used as a backlight module for TVs, mobile phones, notebooks, iPads and vehicle-mounted display screens
- the raw material of perovskite quantum dot optical composite film is used as a backlight module for TVs, mobile phones, notebooks, iPads and vehicle-mounted display screens.
- polyvinylidene fluoride is pretreated by using triethylamine, and then the polyvinylidene fluoride is pretreated by 2-(2-hydroxy-4-methacryloyloxyphenyl)benzotriazole and dibenzoyl peroxide.
- the irradiation intensity of blue light can be weakened to a certain extent to ensure that the blue light intensity tends to be normal, thereby reducing the damage of blue light to human vision.
- the stability of perovskite is significantly improved by the selection of polymer materials for each layer; the core layer of polyvinylidene fluoride can provide water vapor barrier properties, and the intermediate fluorocarbon resin layer increases water vapor barrier, and at the same time, it is connected with the core layer.
- the polyvinylidene fluoride and the ethylene-vinyl alcohol copolymer (EVOH) of the outer layer play a good role in bonding, and the ethylene-vinyl alcohol copolymer (EVOH) of the outer layer plays a good role in blocking oxygen.
- the stability of perovskite quantum dots is significantly improved; the use of functional additives can effectively reduce the hygroscopic properties of ethylene-vinyl alcohol copolymer (EVOH), ensuring the stability of perovskite quantum dots.
- EVOH ethylene-vinyl alcohol copolymer
- the perovskite quantum dots are generated in situ in the three-layered polymer microspheres, and there is no need to synthesize the perovskite quantum dots in advance, the process is simple, the production cost is saved, and it is suitable for industrial production.
- the present invention uses functional additives as raw materials when preparing the shell electrospray liquid, wherein the functional additives use cerium nitrate and polyvinylpyrrolidone as raw materials, and the surface of the prepared cerium oxide has abundant micropores, which makes the prepared Cerium oxide microspheres have large porosity and specific surface area. Then, the surface of the prepared cerium oxide porous microspheres is modified by a silane coupling agent, which not only makes the cerium oxide porous microspheres change from hydrophilic to hydrophobic, but also enables them to be more uniformly dispersed in the second shell layer. In the liquid spray, the uniformity of the quality of the prepared second shell electrospray liquid is ensured. Moreover, the prepared cerium oxide microspheres make the prepared second shell electrospray liquid have a good ability of absorbing ultraviolet rays;
- Fig. 1 is the preparation principle schematic diagram of the core-shell structure polymer microsphere prepared by ternary coaxial electrostatic spraying process in the present invention
- a preparation method of perovskite quantum dot polymer microspheres with core-shell structure comprising the following steps:
- the polyvinylidene fluoride and the first organic solvent were mixed uniformly, and then triethylamine with a mass of 1.2% of the first organic solvent was added thereto; the temperature of the obtained mixed solution was raised to 50° C., and the temperature was kept for 30 min. ; After the treatment is completed, put into the 2-(2-hydroxy-4-methacryloyloxyphenyl) benzotriazole and 1.5% diphenyl peroxide with a mass of 15% polyvinylidene fluoride respectively.
- the molar ratio of FABr and PbBr 2 is 1:1, the weight percentage of the total weight of FABr and PbBr 2 to the polyvinylidene fluoride is 0.2%, and the solid content of the obtained solution is 10%;
- the fluorocarbon resin is a copolymer of tetrafluoroethylene and vinyl ether and other functional monomers containing hydroxyl and carboxyl groups;
- ethylene-vinyl alcohol copolymer, 2-hydroxy-4-methoxy benzophenone and functional additives into the third organic solvent; wherein, ethylene-vinyl alcohol copolymer, 2-hydroxy-4-methoxy benzophenone
- the weight ratio of benzophenone, functional additives, and the third organic solvent is 2:0.02:0.08:8; at room temperature, the obtained mixture is pre-stirred at a constant speed of 280r/min for 10h, and then at a speed of 1800r/min. Stir at high speed for 20min, then filter it; the obtained liquid is the second shell electrospray liquid;
- the three electrospray liquids obtained above are respectively added to the liquid storage tank, supplied to the ternary coaxial nozzle at a stable rate, and a high voltage power supply is used to add a rated polarity to the solution, and a high potential is applied between the nozzle and the collector,
- the liquid jet is emitted from the nozzle and accelerated by the high potential, and the prepared polymer microspheres move toward the collector; during this process, the first organic solvent, the second organic solvent and the third organic solvent are volatilized to obtain a three-layer core-shell Structured polymer microspheres; the thickness of each layer of the prepared three-layer structure polymer microspheres can be controlled by controlling the flow rate and voltage of the three electrospray liquids; then the obtained three-layer core-shell structure polymer microspheres
- the spheres are vacuum-dried at 35°C, and with the further volatilization of the first organic solvent, the second organic solvent, and the third organic solvent, the perovskite quantum dots are formed in situ in the
- the first organic solvent used is N,N-dimethylformamide.
- the second organic solvent used is N,N-dimethylacetamide.
- the third organic solvent used is the mixture of N,N-dimethylacetamide and isopropanol, the weight ratio of N,N-dimethylacetamide and isopropanol 7:1.
- the preparation method of the functional additive comprises the following steps:
- cerium oxide porous microspheres obtained above were immersed in an ethanol solution with a concentration of 50%, and a silane coupling agent with a mass of 15% of the ethanol solution was added to it; then ultrasonically dispersed at a frequency of 28 kHz for 5 min, and then the resulting mixture was mixed.
- the temperature of the components was raised to 50°C, and the reaction was carried out at this temperature for 4 hours; after the reaction was completed, the mixed components were subjected to solid-liquid separation, and the obtained solid powder was placed in a vacuum drying box for drying treatment;
- the solid powder After grinding the obtained solid powder, according to the solid-liquid ratio of 0.1g/mL, the solid powder is put into the hydroxyacrylic resin solution, and ultrasonically dispersed at a frequency of 25kHz for 20min, and the obtained dispersion is the finished product of the functional additive.
- step I the heating rate during calcination is 2°C/min.
- step II the silane coupling agent used is ⁇ -aminopropyltriethoxysilane.
- step III the solvent in the hydroxyacrylic resin solution used is ethyl acetate, and the solute is hydroxyacrylic resin; and the hydroxyl value of the hydroxyacrylic resin is 80 mgKOH/g, and the solid content of the acrylic resin solution is 40%.
- Perovskite quantum dot polymer microspheres with core-shell structure are used as raw materials for perovskite quantum dot optical composite films in backlight modules of TVs, mobile phones, notebooks, iPads and automotive display screens.
- a preparation method of a perovskite quantum dot polymer microsphere with a core-shell structure and its application are roughly the same as those in Example 1, except that:
- the polyvinylidene fluoride and the first organic solvent are mixed evenly, 2-(2-hydroxy-4-methacryloyloxyphenyl) benzotriazole and dibenzoyl peroxide are mixed uniformly.
- the dosage of acyl is respectively 20% and 3.0% of the polyvinylidene fluoride; the compounds added to it are CsBr and PbBr 2 , and pre-stirred at a constant speed of 240r/min for 12h at room temperature, and then at a high speed of 1900r/min Stir for 35min; after stirring evenly, filter it to obtain a clear and transparent nuclear layer electrospray liquid; wherein, the molar ratio of CsBr and PbBr 2 is 1:2, and the total weight of CsBr and PbBr 2 is the same as that of polyvinylidene fluoride. The weight percent is 0.2%, and the solid content of the obtained solution is 10%;
- cerium oxide porous microspheres obtained above are immersed in an ethanol solution with a concentration of 60%, and a silane coupling agent with a mass of 20% of the ethanol solution is added to it; then ultrasonically dispersed at a frequency of 30 kHz for 10 min, and then the resulting mixture is mixed.
- the temperature of the components was raised to 55°C, and the reaction was carried out at this temperature for 5 hours; after the reaction was completed, the mixed components were subjected to solid-liquid separation, and the obtained solid powder was placed in a vacuum drying box for drying treatment;
- the obtained solid powder After grinding the obtained solid powder, according to the solid-to-liquid ratio of 0.15g/mL, the solid powder is put into the hydroxyacrylic resin solution, and ultrasonically dispersed at a frequency of 28kHz for 25min, the obtained dispersion is the finished product of the functional additive.
- a preparation method of a perovskite quantum dot polymer microsphere with a core-shell structure and its application are roughly the same as those in Example 1, except that:
- a preparation method of perovskite quantum dot polymer microspheres with core-shell structure comprising the following steps:
- the polyvinylidene fluoride is mixed with the first organic solvent, and the consumption of 2-(2-hydroxy-4-methacryloyloxyphenyl) benzotriazole and dibenzoyl peroxide is respectively the amount of polyvinylidene fluoride. 30% and 3.6%; add compounds FABr, OABr, PbBr 2 to it, and pre-stir at a constant speed of 300r/min for 15h at room temperature, and then stir at a high speed of 2000r/min for 40min; After filtering, a clear and transparent nuclear layer electrospray liquid is obtained;
- the molar ratio of FABr, OABr and PbBr 2 is 1:0.5:3, the weight percentage of the total weight of FABr, OABr and PbBr 2 to that of polyvinylidene fluoride is 0.2%, and the solid content of the obtained solution is 10%;
- cerium oxide porous microspheres obtained above are immersed in an ethanol solution with a concentration of 65%, and a silane coupling agent with a mass of 25% of the ethanol solution is added to it; then ultrasonically dispersed at a frequency of 35kHz for 15min, and then the resulting mixture is mixed.
- the temperature of the components was raised to 60°C, and the reaction was carried out at this temperature for 6 hours; after the reaction was completed, the mixed components were subjected to solid-liquid separation, and the obtained solid powder was placed in a vacuum drying box for drying treatment;
- the solid powder After grinding the obtained solid powder, according to the solid-liquid ratio of 0.2g/mL, the solid powder is put into the hydroxyacrylic resin solution, and ultrasonically dispersed at a frequency of 30kHz for 30min, and the obtained dispersion is the finished product of the functional additive.
- a preparation method of perovskite quantum dot polymer microspheres with a core-shell structure and its application are roughly the same as those in Example 1, except that 2-hydroxy- 4-methoxybenzophenone;
- a preparation method of perovskite quantum dot polymer microspheres with a core-shell structure and its application are roughly the same as those in Example 1, with the difference that: in the preparation process of the second shell electrospray liquid, the oxidation agent used in the functional additive is used.
- Cerium is common cerium oxide;
- a preparation method of perovskite quantum dot polymer microspheres with a core-shell structure and its application are roughly the same as those in Example 1, except that 2-hydroxy- 4-Methoxybenzophenone and functional additives;
- a preparation method and application of perovskite quantum dot polymer microspheres with a core-shell structure are roughly the same as those in Example 1, except that triethylamine, 2- (2-hydroxy-4-methacryloyloxyphenyl) benzotriazole and dibenzoyl peroxide modify polyvinylidene fluoride;
- the core-shell structure perovskite quantum dot polymer microsphere samples prepared from Examples 1-3 and Comparative Examples 1-3 were aged for 1000 hours at 60°C, 90%, 3mw/cm2 light intensity of 450nm, and then at 450nm. Under the excitation wavelength, the PLQY of each sample was measured; after 6 samples were tested in parallel in each example, the test results were averaged.
- the high-temperature and high-humidity light aging test data of the samples of each embodiment are recorded in Table 1;
- the core-shell structure perovskite quantum dot polymer microsphere samples prepared from Examples 1-3 and Comparative Examples 1-3 were dispersed in UV glue, coated between two layers of 50um barrier films, and light-cured to obtain perovskite
- the perovskite quantum dot film was used to test the NTSC color gamut of the liquid crystal display assembled with each perovskite quantum dot film. After 6 samples were tested in parallel for each example, the test results were averaged.
- the NTSC color gamut test data of each embodiment sample is recorded in Table 1;
- the perovskite quantum dot polymer microspheres with three-layer core-shell structure prepared by the present invention not only have small particle size, excellent anti-aging performance, strong stability and certain anti-blue light effect. Etc. Moreover, the perovskite quantum dot film prepared by it also has excellent optical properties and aging stability.
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Abstract
The present invention relates to the technical field of perovskite quantum dots, and in particular, to a preparation method and application of a perovskite quantum dot polymer microsphere having a core-shell structure. According to the present invention, a polymer microsphere having a three-layer core-shell structure is prepared by a ternary coaxial electrostatic spraying method, perovskite is generated in situ on a core layer of the polymer microsphere after a solvent is dried, and different types of polymer materials are selected as core-shell layers to block water and oxygen, so as to improve the aging stability of perovskite quantum dots. The synthesized perovskite quantum dot polymer microsphere having a core-shell structure can be dispersed into conventional photocuring or thermosetting glue to prepare a perovskite quantum dot film, which is applied to a backlight module for wide-color-gamut liquid crystal display.
Description
本发明涉及钙钛矿量子点技术领域，具体涉及一种核壳结构的钙钛矿量子点聚合物微球的制备方法及其应用。The invention relates to the technical field of perovskite quantum dots, in particular to a preparation method and application of a core-shell structure perovskite quantum dot polymer microsphere.
钙钛矿量子点由于其离子性特征，其对水氧极其敏感，通常将钙钛矿量子点通过聚合物材料包覆并制备成钙钛矿量子点膜，应用在广色域液晶显示器的背光模组中。钙钛矿量子点聚合物材料是制作钙钛矿量子点膜的关键材料，目前，现有工艺中，一般先合成钙钛矿量子点，纯化后的钙钛矿量子点再与聚合物或者聚合物单体进行混合，通过加热或光照的方式制备得到钙钛矿量子点聚合物材料。钙钛矿量子点在合成过程中需要通过油酸油胺等配体来控制钙钛矿量子点的成核与生长，以得到粒径均一的钙钛矿量子点。Due to its ionic characteristics, perovskite quantum dots are extremely sensitive to water and oxygen. Usually, perovskite quantum dots are coated with polymer materials and prepared into perovskite quantum dot films, which are used in the backlight of wide color gamut liquid crystal displays. in the module. Perovskite quantum dot polymer material is the key material for making perovskite quantum dot film. At present, in the existing process, perovskite quantum dots are generally synthesized first, and the purified perovskite quantum dots are then combined with polymer or polymer The perovskite quantum dot polymer material is prepared by mixing the monomers and heating or illuminating. In the synthesis process of perovskite quantum dots, the nucleation and growth of perovskite quantum dots need to be controlled by ligands such as oleylamine oleate, so as to obtain perovskite quantum dots with uniform particle size.
然而，过量的配体及反应原料需要通过高速离心分离去除，大大降低了钙钛矿量子点的合成效率。将钙钛矿分散到聚合物微球中，也是提升钙钛矿量子点稳定性的方法之一，通常也是先合成钙钛矿量子点，再进行钙钛矿量子点聚合物微球的制备，同样具有步骤繁琐、工艺复杂的问题；再者，其所制备的钙钛矿量子点聚合物微球本身的光学性能和稳定性也相对较差。However, excess ligands and reaction materials need to be removed by high-speed centrifugation, which greatly reduces the synthesis efficiency of perovskite quantum dots. Dispersing perovskite into polymer microspheres is also one of the methods to improve the stability of perovskite quantum dots. Usually, perovskite quantum dots are synthesized first, and then the preparation of perovskite quantum dot polymer microspheres is performed. It also has the problems of cumbersome steps and complicated processes; in addition, the optical properties and stability of the perovskite quantum dot polymer microspheres prepared by them are also relatively poor.
发明内容SUMMARY OF THE INVENTION
本发明的目的是提供一种核壳结构的钙钛矿量子点聚合物微球的制备方法及其应用，本发明通过三元同轴静电喷雾法制备三层核壳结构的聚合物微球，溶剂干燥后，钙钛矿在聚合物微球核层原位生成，通过选用不同类型的聚合物材料作为核壳层对水氧进行阻隔，从而提升钙钛矿量子点的老化稳定性；所合成的核壳结构的钙钛矿量子点聚合物微球可以分散到常规的光固化或热固化胶水中，制备成钙钛矿量子点薄膜，应用到广色域液晶显示的背光模组中。The purpose of the present invention is to provide a preparation method and application of perovskite quantum dot polymer microspheres with a core-shell structure. After the solvent is dried, the perovskite is formed in situ in the core layer of the polymer microspheres, and different types of polymer materials are used as the core-shell layer to block water and oxygen, thereby improving the aging stability of the perovskite quantum dots; the synthesized The core-shell structure of perovskite quantum dot polymer microspheres can be dispersed into conventional light-curing or thermal-curing glue to prepare perovskite quantum dot film, which can be applied to the backlight module of wide color gamut liquid crystal display.
本发明采用以下技术方案解决上述技术问题的：The present invention adopts the following technical solutions to solve the above-mentioned technical problems:
一种核壳结构的钙钛矿量子点聚合物微球的制备方法，包括以下步骤：A preparation method of perovskite quantum dot polymer microspheres with core-shell structure, comprising the following steps:
一、核层电喷液的制备；1. Preparation of nuclear layer electrospray liquid;
将聚偏氟乙烯及第一有机溶剂混合均匀，然后向其中加入质量为第一有机溶剂1.2～2.5％的三乙胺；所得混合液的温度升至50～60℃，并在此温度下保温静置处理30～40min；待处理完 毕后，分别向其中投入质量为聚偏氟乙烯15～30％的2-(2-羟基-4-甲基丙烯酰氧基苯基)苯并***及1.5～3.6％的过氧化二苯甲酰；将之混合均匀后，在氮气的保护下，以65～85℃的温度保温反应8～15h；待反应完毕后，将其自然冷却至室温，向其中加入化合物AX、BX
2，并以200～300r/min的速率匀速预搅拌10～15h，然后以1800～2000r/min的速率高速搅拌30～40min；然后对其进行过滤处理，得到澄清透明的核层电喷液；
Mixing the polyvinylidene fluoride and the first organic solvent uniformly, then adding triethylamine with a mass of 1.2 to 2.5% of the first organic solvent to it; the temperature of the obtained mixed solution rises to 50 to 60 ° C, and the temperature is maintained at this temperature stand for treatment for 30-40min; after the treatment is completed, put 2-(2-hydroxy-4-methacryloyloxyphenyl)benzotriazole and 2-(2-hydroxy-4-methacryloyloxyphenyl)benzotriazole and 1.5-3.6% dibenzoyl peroxide; after mixing it uniformly, under the protection of nitrogen, keep the reaction temperature at 65-85 ℃ for 8-15 hours; Compounds AX and BX 2 are added therein, and pre-stirred at a constant speed of 200-300 r/min for 10-15 h, and then stirred at a high speed of 1800-2000 r/min for 30-40 min; Nuclear layer electrospray fluid;
其中，AX、BX
2的摩尔比为1：1～3，AX与BX
2总重量与聚偏氟乙烯的重量百分比为0.2～10％，所得溶液的固含量为10～30％；
Wherein, the molar ratio of AX and BX 2 is 1:1-3, the weight percentage of the total weight of AX and BX 2 to polyvinylidene fluoride is 0.2-10%, and the solid content of the obtained solution is 10-30%;
[根据细则91更正 11.08.2022]
所述化合物AX、BX 2中，A为金属阳离子或者带正电荷的有机阳离子，其为Cs +、Rb +、FA +(HN＝CHNH3 +)、OA +(CH3CH2CH2CH2CH2CH2CH2CH2NH3 +)的一种或几种的混合；[Corrected 11.08.2022 under Rule 91]
In the compounds AX and BX 2 , A is a metal cation or a positively charged organic cation, which is Cs + , Rb + , FA + (HN=CHNH 3 + ), OA + (CH 3 CH 2 CH 2 CH 2 One or more mixtures of CH 2 CH 2 CH 2 CH 2 NH 3 + );
所述化合物AX、BX 2中，A为金属阳离子或者带正电荷的有机阳离子，其为Cs +、Rb +、FA +(HN＝CHNH3 +)、OA +(CH3CH2CH2CH2CH2CH2CH2CH2NH3 +)的一种或几种的混合；[Corrected 11.08.2022 under Rule 91]
In the compounds AX and BX 2 , A is a metal cation or a positively charged organic cation, which is Cs + , Rb + , FA + (HN=CHNH 3 + ), OA + (CH 3 CH 2 CH 2 CH 2 One or more mixtures of CH 2 CH 2 CH 2 CH 2 NH 3 + );
B为金属阳离子，Pb
2+、Sn
2+、Sb
2+、Zn
2+、Mn
2+、Cu
2+中的一种或几种的混合；
B is a metal cation, one or a mixture of Pb 2+ , Sn 2+ , Sb 2+ , Zn 2+ , Mn 2+ , and Cu 2+ ;
X为卤族元素，其为Cl
-、Br
-、I
-中的一种或几种的混合；
X is a halogen element, which is one or a mixture of Cl - , Br - and I - ;
二、第一壳层电喷液的制备；2. Preparation of the first shell electrospray liquid;
将氟碳树脂溶解在第二有机溶剂中，常温下以250～300r/min的速率匀速搅拌10～15h，再以1800～2000r/min的速率高速搅拌30～40min；对其进行过滤处理后，得到无色透明的第一壳层电喷液，所得溶液的固含量控制在10～50％；Dissolve the fluorocarbon resin in the second organic solvent, stir at a constant speed of 250 to 300 r/min for 10 to 15 hours at room temperature, and then stir at a high speed of 1800 to 2000 r/min for 30 to 40 minutes; after filtering it, A colorless and transparent first shell electrospray liquid is obtained, and the solid content of the obtained solution is controlled at 10-50%;
其中，所述氟碳树脂为四氟乙烯和乙烯基醚及其他含羟基、羧基功能性官能团单体共聚物；三、第二壳层电喷液的制备；Wherein, the fluorocarbon resin is a copolymer of tetrafluoroethylene, vinyl ether and other functional monomers containing hydroxyl and carboxyl groups; 3. Preparation of the second shell layer electrospray liquid;
将乙烯-乙烯醇共聚物、2-羟基-4-甲氧基二苯甲酮及功能添加剂投入在第三有机溶剂中；其中，乙烯-乙烯醇共聚物、2-羟基-4-甲氧基二苯甲酮、功能添加剂、第三溶剂的重量比为2：0.02～0.06：0.08～0.12：8；在常温下以280～320r/min的速率对上述所得混合物质匀速预搅拌10～15h，再以1800～2000r/min的速率高速搅拌20～30min，然后对其进行过滤处理；所得液体即为第二壳层电喷液；Put ethylene-vinyl alcohol copolymer, 2-hydroxy-4-methoxy benzophenone and functional additives into the third organic solvent; wherein, ethylene-vinyl alcohol copolymer, 2-hydroxy-4-methoxy benzophenone The weight ratio of benzophenone, functional additives and the third solvent is 2:0.02-0.06:0.08-0.12:8; at room temperature, the obtained mixture is pre-stirred at a constant speed for 10-15h at a rate of 280-320r/min, Then stir at a high speed of 1800-2000r/min for 20-30min, and then filter it; the obtained liquid is the second shell layer electrospray liquid;
四、钙钛矿量子点聚合物微球的制备；4. Preparation of perovskite quantum dot polymer microspheres;
将上述所得三种电喷液分别加入到储液罐中，以稳定的速率供应到三元同轴喷嘴，利用高压电源给溶液附加额定的极性，在喷嘴与收集器之间施加高电势，液体射流从喷嘴发出，并被高电势加速，制备的聚合物微球向收集器移动；在此过程中，随第一有机溶剂、第二有机溶剂、第三有机溶剂挥发，获得三层核壳结构的聚合物微球；通过控制三种电喷液的流速、电压的大小可控制所制备三层结构聚合物微球各层的厚度；然后将所获得的三层核壳结构的聚合物微球在35～45℃进行真空干燥，随第一有机溶剂、第二有机溶剂、第三有机溶剂的进一步挥发，钙钛矿量子点在核层聚合物中原位生成，即得到三层核壳结构的钙钛矿量子点聚合物微球成品。The three electrospray liquids obtained above are respectively added to the liquid storage tank, supplied to the ternary coaxial nozzle at a stable rate, and a high voltage power supply is used to add a rated polarity to the solution, and a high potential is applied between the nozzle and the collector, The liquid jet is emitted from the nozzle and accelerated by the high potential, and the prepared polymer microspheres move toward the collector; during this process, the first organic solvent, the second organic solvent and the third organic solvent are volatilized to obtain a three-layer core-shell Structured polymer microspheres; the thickness of each layer of the prepared three-layer structure polymer microspheres can be controlled by controlling the flow rate and voltage of the three electrospray liquids; then the obtained three-layer core-shell structure polymer microspheres The ball is vacuum-dried at 35-45 °C, and with the further volatilization of the first organic solvent, the second organic solvent, and the third organic solvent, the perovskite quantum dots are formed in situ in the core-layer polymer, that is, a three-layer core-shell structure is obtained. finished perovskite quantum dot polymer microspheres.
更进一步地，所述核层电喷液的制备过程中，所用第一有机溶剂为N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、丙酮、丁酮中的任一种或几种的混合。Further, in the preparation process of the nuclear layer electrospray liquid, the first organic solvent used is any one of N,N-dimethylformamide, N,N-dimethylacetamide, acetone, and butanone. species or a mixture of several.
更进一步地，所述第一壳层电喷液的制备过程中，所用第二有机溶剂为N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、丙酮、丁酮、乙酸乙酯、乙酸丁酯中的任一种或几种的混合。Further, in the preparation process of the first shell electrospray liquid, the second organic solvent used is N,N-dimethylformamide, N,N-dimethylacetamide, acetone, methyl ethyl ketone, acetic acid Any one or a mixture of ethyl ester and butyl acetate.
更进一步地，所述第二壳层电喷液的制备过程中，所用第三有机溶剂为N，N-二甲基乙酰胺与异丙醇的混合物，N，N-二甲基乙酰胺与异丙醇的重量比为7：1。Further, in the preparation process of the second shell electrospray liquid, the third organic solvent used is a mixture of N,N-dimethylacetamide and isopropanol, N,N-dimethylacetamide and The weight ratio of isopropanol is 7:1.
更进一步地，所述功能添加剂的制备方法包括以下步骤：Further, the preparation method of the functional additive comprises the following steps:
Ⅰ、按照质量比1：3～5，准确称取适量的硝酸铈和聚乙烯吡咯烷酮；并将所得的混合组分投至质量为其2～4倍的N，N-二甲基甲酰胺中，然后在室温下对所得混合物搅拌20～30h；待搅拌均匀后，采用电喷离子化工艺制备复合微球；所得复合微球置于马弗炉中，并在560～650℃的温度下焙烧4～5h；待焙烧完毕后，将复合微球取出，并在自然条件下冷却至室温，所得即为氧化铈多孔微球成品；1. Accurately weigh an appropriate amount of cerium nitrate and polyvinyl pyrrolidone according to a mass ratio of 1:3 to 5; and cast the resulting mixed component into N,N-dimethylformamide whose mass is 2 to 4 times. , and then the obtained mixture was stirred at room temperature for 20-30 h; after stirring evenly, composite microspheres were prepared by electrospray ionization process; the obtained composite microspheres were placed in a muffle furnace and calcined at a temperature of 560-650 °C 4 to 5 hours; after the calcination is completed, the composite microspheres are taken out and cooled to room temperature under natural conditions, and the obtained cerium oxide porous microspheres are finished products;
Ⅱ、将上述所得的氧化铈多孔微球浸没于浓度为50～65％的乙醇溶液，并向其中加入质量为乙醇溶液15～25％的硅烷偶联剂；然后在28～35kHz的频率超声分散5～15min，然后将所得混合组分的温度升至50～60℃，并在此温度下反应4～6h；待反应完毕后，对混合组分进行固液分离，所得固体粉末置于真空干燥箱内进行干燥处理；II. The cerium oxide porous microspheres obtained above are immersed in an ethanol solution with a concentration of 50-65%, and a silane coupling agent with a mass of 15-25% of the ethanol solution is added to it; then ultrasonically disperse at a frequency of 28-35 kHz 5 to 15 minutes, then the temperature of the obtained mixed components was raised to 50 to 60 ° C, and the reaction was carried out at this temperature for 4 to 6 hours; after the reaction was completed, the mixed components were separated from solid and liquid, and the obtained solid powder was placed in vacuum drying. Drying in the box;
Ⅲ、将所得固体粉末研磨后，按照固液比0.1～0.2g/mL，将固体粉末投至羟基丙烯酸树脂溶液中，并以25～30kHz的频率，超声分散20～30min，所得分散液即为功能添加剂成品。III. After grinding the obtained solid powder, according to the solid-liquid ratio of 0.1～0.2g/mL, the solid powder is put into the hydroxyacrylic resin solution, and ultrasonically dispersed at a frequency of 25～30kHz for 20～30min, the obtained dispersion is Functional additive finished products.
更进一步地，所述步骤Ⅰ中，焙烧时的升温速率为2～5℃/min。Further, in the step I, the heating rate during calcination is 2～5°C/min.
更进一步地，所述步骤Ⅱ中，所用硅烷偶联剂为γ-氨丙基三乙氧基硅烷、γ-(2，3-环氧丙氧)丙基三甲氧基硅烷中的任意一种。Further, in the step II, the silane coupling agent used is any one of γ-aminopropyltriethoxysilane and γ-(2,3-glycidoxy)propyltrimethoxysilane .
更进一步地，所述步骤Ⅲ中，所用羟基丙烯酸树脂溶液中的溶剂为醋酸乙酯、溶质为羟基丙烯酸树脂；且所述羟基丙烯酸树脂的羟值为80～200mgKOH/g，丙烯酸树脂溶液固含量为40～65％。Further, in the step III, the solvent in the hydroxy acrylic resin solution used is ethyl acetate, and the solute is hydroxy acrylic resin; and the hydroxyl value of the hydroxy acrylic resin is 80-200 mgKOH/g, and the solid content of the acrylic resin solution is 80-200 mgKOH/g. 40 to 65%.
一种核壳结构的钙钛矿量子点聚合物微球的应用，所述核壳结构的钙钛矿量子点聚合物微球用作电视、手机、笔记本、iPad及车载显示屏的背光模组中钙钛矿量子点光学复合膜的原料。Application of a core-shell structure perovskite quantum dot polymer microsphere, the core-shell structure perovskite quantum dot polymer microsphere is used as a backlight module for TVs, mobile phones, notebooks, iPads and vehicle-mounted display screens The raw material of perovskite quantum dot optical composite film.
本发明的优点在于：The advantages of the present invention are:
1、本发明通过使用三乙胺对聚偏氟乙烯进行预处理，然后通过2-(2-羟基-4-甲基丙烯酰氧基苯基)苯并***及过氧化二苯甲酰之间的协同配合，对聚偏氟乙烯进行化学改性；使得2-(2-羟基-4-甲基丙烯酰氧基苯基)苯并***与聚偏氟乙烯之间发生接枝反应，最终成功地将在聚 偏氟乙烯分子的表面引入具有吸收蓝光功能的基团；改性后的聚偏氟乙烯不仅能对不同卤化物进行有效地“固定”，有效抑制了不同卤化物间的离子交换反应维持量子点的效率，使其具有非常好的稳定性。而且其与功能添加剂中的氧化铈多孔微球的微孔结构之间相互协同，能起到一定的吸收蓝光的作用；1. In the present invention, polyvinylidene fluoride is pretreated by using triethylamine, and then the polyvinylidene fluoride is pretreated by 2-(2-hydroxy-4-methacryloyloxyphenyl)benzotriazole and dibenzoyl peroxide. The synergistic cooperation between polyvinylidene fluoride is chemically modified; the grafting reaction between 2-(2-hydroxy-4-methacryloyloxyphenyl)benzotriazole and polyvinylidene fluoride occurs, Finally, the group with the function of absorbing blue light was successfully introduced on the surface of the polyvinylidene fluoride molecule; the modified polyvinylidene fluoride can not only effectively "fix" different halides, but also effectively inhibit the interaction between different halides. The ion exchange reaction maintains the efficiency of the quantum dots, making them very stable. Moreover, it cooperates with the microporous structure of the cerium oxide porous microspheres in the functional additive, and can play a certain role in absorbing blue light;
当蓝光过量时，通过两者的协同配合，能对蓝光的照射强度起到一定地削弱作用，保证蓝光强度趋于正常值；从而减小蓝光对人体视力的伤害。When the blue light is excessive, through the synergy of the two, the irradiation intensity of blue light can be weakened to a certain extent to ensure that the blue light intensity tends to be normal, thereby reducing the damage of blue light to human vision.
2、本发明中通过各层聚合物材料的选择对钙钛矿的稳定性进行了显著提升；芯层聚偏氟乙烯可以提供水汽阻隔性能，中间氟碳树脂层增加水汽阻隔，同时与芯层聚偏氟乙烯与外层的乙烯-乙烯醇共聚物(EVOH)都起到很好的粘接作用，同时外层的乙烯-乙烯醇共聚物(EVOH)起到了很好的阻隔氧气的作用。通过三层结构的设计，显著提升了钙钛矿量子点的稳定性；而功能添加剂的使用能有效地减小乙烯-乙烯醇共聚物(EVOH)的吸湿性能，保证了钙钛矿量子点的光学性能和稳定性。2. In the present invention, the stability of perovskite is significantly improved by the selection of polymer materials for each layer; the core layer of polyvinylidene fluoride can provide water vapor barrier properties, and the intermediate fluorocarbon resin layer increases water vapor barrier, and at the same time, it is connected with the core layer. Both the polyvinylidene fluoride and the ethylene-vinyl alcohol copolymer (EVOH) of the outer layer play a good role in bonding, and the ethylene-vinyl alcohol copolymer (EVOH) of the outer layer plays a good role in blocking oxygen. Through the design of the three-layer structure, the stability of perovskite quantum dots is significantly improved; the use of functional additives can effectively reduce the hygroscopic properties of ethylene-vinyl alcohol copolymer (EVOH), ensuring the stability of perovskite quantum dots. Optical performance and stability.
再者，钙钛矿量子点在三层结构的聚合物微球中原位生成，无需提前进行钙钛矿量子点的合成，工艺简单，节约了生产成本，适宜工业化生产。Furthermore, the perovskite quantum dots are generated in situ in the three-layered polymer microspheres, and there is no need to synthesize the perovskite quantum dots in advance, the process is simple, the production cost is saved, and it is suitable for industrial production.
3、本发明在制备壳层电喷液时，采用功能性添加剂作为原料，其中功能添加剂以硝酸铈及聚乙烯吡咯烷酮为原料，所制备出的氧化铈表面具有丰富的微孔，使得所制备的氧化铈微球具有较大的孔隙率及比表面积。然后通过硅烷偶联剂对所制备的氧化铈多孔微球进行表面改性处理，不仅使得氧化铈多孔微球由亲水性变为疏水性，使其能更加均匀地分散在第二壳层电喷液中，保证了所制备的第二壳层电喷液质量的均一性。而且所制备的氧化铈微球使得所制备的第二壳层电喷液具有很好的吸收紫外线的能力；3. The present invention uses functional additives as raw materials when preparing the shell electrospray liquid, wherein the functional additives use cerium nitrate and polyvinylpyrrolidone as raw materials, and the surface of the prepared cerium oxide has abundant micropores, which makes the prepared Cerium oxide microspheres have large porosity and specific surface area. Then, the surface of the prepared cerium oxide porous microspheres is modified by a silane coupling agent, which not only makes the cerium oxide porous microspheres change from hydrophilic to hydrophobic, but also enables them to be more uniformly dispersed in the second shell layer. In the liquid spray, the uniformity of the quality of the prepared second shell electrospray liquid is ensured. Moreover, the prepared cerium oxide microspheres make the prepared second shell electrospray liquid have a good ability of absorbing ultraviolet rays;
再者，以2-羟基-4-甲氧基二苯甲酮作为制备第二壳层电喷液的原料，不仅能起到很好的吸收紫外线的功效；其与功能添加剂之间协同配合，使得所制备的钙钛矿量子点聚合物微球具有很好的抗紫外性能，有效地减缓了其老化的速率，在一定程度上延长了其使用寿命。Furthermore, using 2-hydroxy-4-methoxybenzophenone as the raw material for preparing the second shell electrospray liquid can not only play a good role in absorbing ultraviolet rays; The prepared perovskite quantum dot polymer microspheres have good anti-ultraviolet performance, effectively slowing down their aging rate, and prolonging their service life to a certain extent.
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained according to these drawings without creative efforts.
图1为本发明中通过三元同轴静电喷雾工艺制备的核壳结构聚合物微球的制备原理示意图；Fig. 1 is the preparation principle schematic diagram of the core-shell structure polymer microsphere prepared by ternary coaxial electrostatic spraying process in the present invention;
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purposes, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments These are some embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例1Example 1
一种核壳结构的钙钛矿量子点聚合物微球的制备方法，包括以下步骤：A preparation method of perovskite quantum dot polymer microspheres with core-shell structure, comprising the following steps:
一、核层电喷液的制备；1. Preparation of nuclear layer electrospray liquid;
将聚偏氟乙烯及第一有机溶剂混合均匀，然后向其中加入质量为第一有机溶剂1.2％的三乙胺；所得混合液的温度升至50℃，并在此温度下保温静置处理30min；待处理完毕后，分别向其中投入质量为聚偏氟乙烯15％的2-(2-羟基-4-甲基丙烯酰氧基苯基)苯并***及1.5％的过氧化二苯甲酰；将之混合均匀后，在氮气的保护下，以65℃的温度保温反应8h；待反应完毕后，将其自然冷却至室温，向其中加入FABr、PbBr
2，并以200r/min的速率匀速预搅拌10h，然后以1800r/min的速率高速搅拌30min；然后对其进行过滤处理，得到澄清透明的核层电喷液；
The polyvinylidene fluoride and the first organic solvent were mixed uniformly, and then triethylamine with a mass of 1.2% of the first organic solvent was added thereto; the temperature of the obtained mixed solution was raised to 50° C., and the temperature was kept for 30 min. ; After the treatment is completed, put into the 2-(2-hydroxy-4-methacryloyloxyphenyl) benzotriazole and 1.5% diphenyl peroxide with a mass of 15% polyvinylidene fluoride respectively. acyl; after mixing it evenly, under the protection of nitrogen, the reaction was kept at 65°C for 8h; after the reaction was completed, it was naturally cooled to room temperature, FABr and PbBr 2 were added to it, and the reaction rate was 200r/min. Pre-stir at a constant speed for 10h, then stir at a high speed of 1800r/min for 30min; then filter it to obtain a clear and transparent nuclear layer electrospray liquid;
其中FABr、PbBr
2的摩尔比为1：1，FABr与PbBr
2总重量与聚偏氟乙烯的重量百分比为0.2％，所得溶液的固含量为10％；
The molar ratio of FABr and PbBr 2 is 1:1, the weight percentage of the total weight of FABr and PbBr 2 to the polyvinylidene fluoride is 0.2%, and the solid content of the obtained solution is 10%;
二、第一壳层电喷液的制备；2. Preparation of the first shell electrospray liquid;
将氟碳树脂溶解在第二有机溶剂中，常温下以250r/min的速率匀速搅拌10h，再以1800r/min的速率高速搅拌30min；对其进行过滤处理后，得到无色透明的第一壳层电喷液，所得溶液的固含量控制在10％；Dissolve the fluorocarbon resin in the second organic solvent, stir at a constant speed of 250r/min for 10h at room temperature, and then stir at a high speed of 1800r/min for 30min; after filtering it, a colorless and transparent first shell is obtained Layer electrospray liquid, the solid content of the obtained solution is controlled at 10%;
其中，氟碳树脂为四氟乙烯和乙烯基醚及其他含羟基、羧基功能性官能团单体共聚物；Among them, the fluorocarbon resin is a copolymer of tetrafluoroethylene and vinyl ether and other functional monomers containing hydroxyl and carboxyl groups;
三、第二壳层电喷液的制备；3. Preparation of the second shell electrospray liquid;
将乙烯-乙烯醇共聚物、2-羟基-4-甲氧基二苯甲酮及功能添加剂投入在第三有机溶剂中；其中，乙烯-乙烯醇共聚物、2-羟基-4-甲氧基二苯甲酮、功能添加剂、第三有机溶剂的重量比为2：0.02：0.08：8；在常温下以280r/min的速率对上述所得混合物质匀速预搅拌10h，再以1800r/min的速率高速搅拌20min，然后对其进行过滤处理；所得液体即为第二壳层电喷液；Put ethylene-vinyl alcohol copolymer, 2-hydroxy-4-methoxy benzophenone and functional additives into the third organic solvent; wherein, ethylene-vinyl alcohol copolymer, 2-hydroxy-4-methoxy benzophenone The weight ratio of benzophenone, functional additives, and the third organic solvent is 2:0.02:0.08:8; at room temperature, the obtained mixture is pre-stirred at a constant speed of 280r/min for 10h, and then at a speed of 1800r/min. Stir at high speed for 20min, then filter it; the obtained liquid is the second shell electrospray liquid;
四、钙钛矿量子点聚合物微球的制备；4. Preparation of perovskite quantum dot polymer microspheres;
将上述所得三种电喷液分别加入到储液罐中，以稳定的速率供应到三元同轴喷嘴，利用高压电源给溶液附加额定的极性，在喷嘴与收集器之间施加高电势，液体射流从喷嘴发出，并被高电势加速，制备的聚合物微球向收集器移动；在此过程中，随第一有机溶剂、第二有机溶剂、第三有机溶剂挥发，获得三层核壳结构的聚合物微球；通过控制三种电喷液的流速、电 压的大小可控制所制备三层结构聚合物微球各层的厚度；然后将所获得的三层核壳结构的聚合物微球在35℃进行真空干燥，随第一有机溶剂、第二有机溶剂、第三有机溶剂的进一步挥发，钙钛矿量子点在核层聚合物中原位生成，即得到三层核壳结构的钙钛矿量子点聚合物微球成品。The three electrospray liquids obtained above are respectively added to the liquid storage tank, supplied to the ternary coaxial nozzle at a stable rate, and a high voltage power supply is used to add a rated polarity to the solution, and a high potential is applied between the nozzle and the collector, The liquid jet is emitted from the nozzle and accelerated by the high potential, and the prepared polymer microspheres move toward the collector; during this process, the first organic solvent, the second organic solvent and the third organic solvent are volatilized to obtain a three-layer core-shell Structured polymer microspheres; the thickness of each layer of the prepared three-layer structure polymer microspheres can be controlled by controlling the flow rate and voltage of the three electrospray liquids; then the obtained three-layer core-shell structure polymer microspheres The spheres are vacuum-dried at 35°C, and with the further volatilization of the first organic solvent, the second organic solvent, and the third organic solvent, the perovskite quantum dots are formed in situ in the core-layer polymer, that is, calcium with a three-layer core-shell structure is obtained. Finished product of titanium ore quantum dot polymer microspheres.
核层电喷液的制备过程中，所用第一有机溶剂为N，N-二甲基甲酰胺。In the preparation process of the nuclear layer electrospray liquid, the first organic solvent used is N,N-dimethylformamide.
第一壳层电喷液的制备过程中，所用第二有机溶剂为N，N-二甲基乙酰胺、。In the preparation process of the first shell electrospray liquid, the second organic solvent used is N,N-dimethylacetamide.
第二壳层电喷液的制备过程中，所用第三有机溶剂为N，N-二甲基乙酰胺与异丙醇的混合物，N，N-二甲基乙酰胺与异丙醇的重量比为7：1。In the preparation process of the second shell electrospray liquid, the third organic solvent used is the mixture of N,N-dimethylacetamide and isopropanol, the weight ratio of N,N-dimethylacetamide and isopropanol 7:1.
功能添加剂的制备方法包括以下步骤：The preparation method of the functional additive comprises the following steps:
Ⅰ、按照质量比1：3，准确称取适量的硝酸铈和聚乙烯吡咯烷酮；并将所得的混合组分投至质量为其2倍的N，N-二甲基甲酰胺中，然后在室温下对所得混合物搅拌20h；待搅拌均匀后，采用电喷离子化工艺制备复合微球；所得复合微球置于马弗炉中，并在560℃的温度下焙烧4h；待焙烧完毕后，将复合微球取出，并在自然条件下冷却至室温，所得即为氧化铈多孔微球成品；1. Accurately weigh an appropriate amount of cerium nitrate and polyvinylpyrrolidone according to the mass ratio of 1:3; and the obtained mixed component is put into N,N-dimethylformamide whose mass is twice as high, and then at room temperature The obtained mixture was stirred for 20 hours; after stirring evenly, composite microspheres were prepared by electrospray ionization process; the obtained composite microspheres were placed in a muffle furnace and calcined at a temperature of 560 ° C for 4 h; after the calcination was completed, the composite microspheres were The composite microspheres are taken out and cooled to room temperature under natural conditions to obtain the finished cerium oxide porous microspheres;
Ⅱ、将上述所得的氧化铈多孔微球浸没于浓度为50％的乙醇溶液，并向其中加入质量为乙醇溶液15％的硅烷偶联剂；然后在28kHz的频率超声分散5min，然后将所得混合组分的温度升至50℃，并在此温度下反应4h；待反应完毕后，对混合组分进行固液分离，所得固体粉末置于真空干燥箱内进行干燥处理；II. The cerium oxide porous microspheres obtained above were immersed in an ethanol solution with a concentration of 50%, and a silane coupling agent with a mass of 15% of the ethanol solution was added to it; then ultrasonically dispersed at a frequency of 28 kHz for 5 min, and then the resulting mixture was mixed. The temperature of the components was raised to 50°C, and the reaction was carried out at this temperature for 4 hours; after the reaction was completed, the mixed components were subjected to solid-liquid separation, and the obtained solid powder was placed in a vacuum drying box for drying treatment;
Ⅲ、将所得固体粉末研磨后，按照固液比0.1g/mL，将固体粉末投至羟基丙烯酸树脂溶液中，并以25kHz的频率，超声分散20min，所得分散液即为功能添加剂成品。Ⅲ. After grinding the obtained solid powder, according to the solid-liquid ratio of 0.1g/mL, the solid powder is put into the hydroxyacrylic resin solution, and ultrasonically dispersed at a frequency of 25kHz for 20min, and the obtained dispersion is the finished product of the functional additive.
步骤Ⅰ中，焙烧时的升温速率为2℃/min。In step I, the heating rate during calcination is 2°C/min.
步骤Ⅱ中，所用硅烷偶联剂为γ-氨丙基三乙氧基硅烷。In step II, the silane coupling agent used is γ-aminopropyltriethoxysilane.
步骤Ⅲ中，所用羟基丙烯酸树脂溶液中的溶剂为醋酸乙酯、溶质为羟基丙烯酸树脂；且羟基丙烯酸树脂的羟值为80mgKOH/g，丙烯酸树脂溶液固含量为40％。In step III, the solvent in the hydroxyacrylic resin solution used is ethyl acetate, and the solute is hydroxyacrylic resin; and the hydroxyl value of the hydroxyacrylic resin is 80 mgKOH/g, and the solid content of the acrylic resin solution is 40%.
核壳结构的钙钛矿量子点聚合物微球用作电视、手机、笔记本、iPad及车载显示屏的背光模组中钙钛矿量子点光学复合膜的原料。Perovskite quantum dot polymer microspheres with core-shell structure are used as raw materials for perovskite quantum dot optical composite films in backlight modules of TVs, mobile phones, notebooks, iPads and automotive display screens.
实施例2Example 2
一种核壳结构的钙钛矿量子点聚合物微球的制备方法及其应用与实施例1大致相同，不同之处在于：A preparation method of a perovskite quantum dot polymer microsphere with a core-shell structure and its application are roughly the same as those in Example 1, except that:
核层电喷液的制备过程中，聚偏氟乙烯与第一有机溶剂混合均匀，2-(2-羟基-4-甲基丙烯酰氧基苯基)苯并***及过氧化二苯甲酰的用量分别为聚偏氟乙烯的20％及3.0％；向其中所加 入化合物为CsBr、PbBr
2，并在常温下以240r/min的速率匀速预搅拌12h，然后以1900r/min的速率高速搅拌35min；待搅拌均匀后，对其进行过滤处理后，得到澄清透明的核层电喷液；其中，CsBr、PbBr
2的摩尔比为1：2，CsBr与PbBr
2总重量与聚偏氟乙烯的重量百分比为0.2％，所得溶液的固含量为10％；
In the preparation process of the nuclear layer electrospray liquid, the polyvinylidene fluoride and the first organic solvent are mixed evenly, 2-(2-hydroxy-4-methacryloyloxyphenyl) benzotriazole and dibenzoyl peroxide are mixed uniformly. The dosage of acyl is respectively 20% and 3.0% of the polyvinylidene fluoride; the compounds added to it are CsBr and PbBr 2 , and pre-stirred at a constant speed of 240r/min for 12h at room temperature, and then at a high speed of 1900r/min Stir for 35min; after stirring evenly, filter it to obtain a clear and transparent nuclear layer electrospray liquid; wherein, the molar ratio of CsBr and PbBr 2 is 1:2, and the total weight of CsBr and PbBr 2 is the same as that of polyvinylidene fluoride. The weight percent is 0.2%, and the solid content of the obtained solution is 10%;
功能添加剂的制备方法不同，其制备方法具体如下：The preparation methods of functional additives are different, and the preparation methods are as follows:
Ⅰ、按照质量比1：4，准确称取适量的硝酸铈和聚乙烯吡咯烷酮；并将所得的混合组分投至质量为其3倍的N，N-二甲基甲酰胺中，然后在室温下对所得混合物搅拌25h；待搅拌均匀后，采用电喷离子化工艺制备复合微球；所得复合微球置于马弗炉中，并在600℃的温度下焙烧4.5h；待焙烧完毕后，将复合微球取出，并在自然条件下冷却至室温，所得即为氧化铈多孔微球成品；1. Accurately weigh an appropriate amount of cerium nitrate and polyvinylpyrrolidone according to the mass ratio of 1:4; and the obtained mixed components are put into N,N-dimethylformamide whose mass is 3 times of their mass, and then at room temperature The obtained mixture was stirred for 25 h; after stirring uniformly, composite microspheres were prepared by electrospray ionization process; the obtained composite microspheres were placed in a muffle furnace, and calcined at a temperature of 600 ° C for 4.5 h; after calcination was completed, The composite microspheres are taken out and cooled to room temperature under natural conditions, and the obtained product is the cerium oxide porous microspheres;
Ⅱ、将上述所得的氧化铈多孔微球浸没于浓度为60％的乙醇溶液，并向其中加入质量为乙醇溶液20％的硅烷偶联剂；然后在30kHz的频率超声分散10min，然后将所得混合组分的温度升至55℃，并在此温度下反应5h；待反应完毕后，对混合组分进行固液分离，所得固体粉末置于真空干燥箱内进行干燥处理；II. The cerium oxide porous microspheres obtained above are immersed in an ethanol solution with a concentration of 60%, and a silane coupling agent with a mass of 20% of the ethanol solution is added to it; then ultrasonically dispersed at a frequency of 30 kHz for 10 min, and then the resulting mixture is mixed. The temperature of the components was raised to 55°C, and the reaction was carried out at this temperature for 5 hours; after the reaction was completed, the mixed components were subjected to solid-liquid separation, and the obtained solid powder was placed in a vacuum drying box for drying treatment;
Ⅲ、将所得固体粉末研磨后，按照固液比0.15g/mL，将固体粉末投至羟基丙烯酸树脂溶液中，并以28kHz的频率，超声分散25min，所得分散液即为功能添加剂成品。III. After grinding the obtained solid powder, according to the solid-to-liquid ratio of 0.15g/mL, the solid powder is put into the hydroxyacrylic resin solution, and ultrasonically dispersed at a frequency of 28kHz for 25min, the obtained dispersion is the finished product of the functional additive.
实施例3Example 3
一种核壳结构的钙钛矿量子点聚合物微球的制备方法及其应用与实施例1大致相同，不同之处在于：A preparation method of a perovskite quantum dot polymer microsphere with a core-shell structure and its application are roughly the same as those in Example 1, except that:
一种核壳结构的钙钛矿量子点聚合物微球的制备方法，包括以下步骤：A preparation method of perovskite quantum dot polymer microspheres with core-shell structure, comprising the following steps:
一、核层电喷液的制备；1. Preparation of nuclear layer electrospray liquid;
将聚偏氟乙烯与第一有机溶剂混合，2-(2-羟基-4-甲基丙烯酰氧基苯基)苯并***及过氧化二苯甲酰的用量分别为聚偏氟乙烯的30％及3.6％；向其中加入化合物FABr、OABr、PbBr
2，并在常温下以300r/min的速率匀速预搅拌15h，然后以2000r/min的速率高速搅拌40min；待搅拌均匀后，对其进行过滤处理后，得到澄清透明的核层电喷液；
The polyvinylidene fluoride is mixed with the first organic solvent, and the consumption of 2-(2-hydroxy-4-methacryloyloxyphenyl) benzotriazole and dibenzoyl peroxide is respectively the amount of polyvinylidene fluoride. 30% and 3.6%; add compounds FABr, OABr, PbBr 2 to it, and pre-stir at a constant speed of 300r/min for 15h at room temperature, and then stir at a high speed of 2000r/min for 40min; After filtering, a clear and transparent nuclear layer electrospray liquid is obtained;
其中，FABr、OABr、PbBr
2的摩尔比为1：0.5：3，FABr、OABr与PbBr
2总重量与聚偏氟乙烯的重量百分比为0.2％，所得溶液的固含量为10％；
Wherein, the molar ratio of FABr, OABr and PbBr 2 is 1:0.5:3, the weight percentage of the total weight of FABr, OABr and PbBr 2 to that of polyvinylidene fluoride is 0.2%, and the solid content of the obtained solution is 10%;
功能添加剂的制备方法不同，其制备方法具体如下：The preparation methods of functional additives are different, and the preparation methods are as follows:
Ⅰ、按照质量比1：5，准确称取适量的硝酸铈和聚乙烯吡咯烷酮；并将所得的混合组分投至质量为其4倍的N，N-二甲基甲酰胺中，然后在室温下对所得混合物搅拌30h；待搅拌均匀后，采用电喷离子化工艺制备复合微球；所得复合微球置于马弗炉中，并在650℃的温度下 焙烧5h；待焙烧完毕后，将复合微球取出，并在自然条件下冷却至室温，所得即为氧化铈多孔微球成品；1. Accurately weigh an appropriate amount of cerium nitrate and polyvinylpyrrolidone according to the mass ratio of 1:5; and the obtained mixed component is put into N,N-dimethylformamide whose mass is 4 times of its mass, and then at room temperature The obtained mixture was stirred for 30 h; after stirring evenly, composite microspheres were prepared by electrospray ionization; the obtained composite microspheres were placed in a muffle furnace and calcined at a temperature of 650 ° C for 5 h; after calcination was completed, the The composite microspheres are taken out and cooled to room temperature under natural conditions to obtain the finished cerium oxide porous microspheres;
Ⅱ、将上述所得的氧化铈多孔微球浸没于浓度为65％的乙醇溶液，并向其中加入质量为乙醇溶液25％的硅烷偶联剂；然后在35kHz的频率超声分散15min，然后将所得混合组分的温度升至60℃，并在此温度下反应6h；待反应完毕后，对混合组分进行固液分离，所得固体粉末置于真空干燥箱内进行干燥处理；II. The cerium oxide porous microspheres obtained above are immersed in an ethanol solution with a concentration of 65%, and a silane coupling agent with a mass of 25% of the ethanol solution is added to it; then ultrasonically dispersed at a frequency of 35kHz for 15min, and then the resulting mixture is mixed. The temperature of the components was raised to 60°C, and the reaction was carried out at this temperature for 6 hours; after the reaction was completed, the mixed components were subjected to solid-liquid separation, and the obtained solid powder was placed in a vacuum drying box for drying treatment;
Ⅲ、将所得固体粉末研磨后，按照固液比0.2g/mL，将固体粉末投至羟基丙烯酸树脂溶液中，并以30kHz的频率，超声分散30min，所得分散液即为功能添加剂成品。Ⅲ. After grinding the obtained solid powder, according to the solid-liquid ratio of 0.2g/mL, the solid powder is put into the hydroxyacrylic resin solution, and ultrasonically dispersed at a frequency of 30kHz for 30min, and the obtained dispersion is the finished product of the functional additive.
对比例1Comparative Example 1
一种核壳结构的钙钛矿量子点聚合物微球的制备方法及其应用与实施例1大致相同，不同之处在于：第二壳层电喷液的制备过程中未使用2-羟基-4-甲氧基二苯甲酮；A preparation method of perovskite quantum dot polymer microspheres with a core-shell structure and its application are roughly the same as those in Example 1, except that 2-hydroxy- 4-methoxybenzophenone;
对比例2Comparative Example 2
一种核壳结构的钙钛矿量子点聚合物微球的制备方法及其应用与实施例1大致相同，不同之处在于：第二壳层电喷液的制备过程中使用功能添加剂中所用氧化铈为普通氧化铈；A preparation method of perovskite quantum dot polymer microspheres with a core-shell structure and its application are roughly the same as those in Example 1, with the difference that: in the preparation process of the second shell electrospray liquid, the oxidation agent used in the functional additive is used. Cerium is common cerium oxide;
对比例3Comparative Example 3
一种核壳结构的钙钛矿量子点聚合物微球的制备方法及其应用与实施例1大致相同，不同之处在于：第二壳层电喷液的制备过程中未使用2-羟基-4-甲氧基二苯甲酮及功能添加剂；A preparation method of perovskite quantum dot polymer microspheres with a core-shell structure and its application are roughly the same as those in Example 1, except that 2-hydroxy- 4-Methoxybenzophenone and functional additives;
对比例4Comparative Example 4
一种核壳结构的钙钛矿量子点聚合物微球的制备方法及其应用与实施例1大致相同，不同之处在于：核层电喷液的制备过程中未使用三乙胺、2-(2-羟基-4-甲基丙烯酰氧基苯基)苯并***及过氧化二苯甲酰对聚偏氟乙烯进行改性处理；A preparation method and application of perovskite quantum dot polymer microspheres with a core-shell structure are roughly the same as those in Example 1, except that triethylamine, 2- (2-hydroxy-4-methacryloyloxyphenyl) benzotriazole and dibenzoyl peroxide modify polyvinylidene fluoride;
性能测试：Performance Testing:
取等量的由实施例1～3及对比例1～3制备的三层核壳结构的钙钛矿量子点聚合物微球样品，将所得微球混合在UV固化胶水中，通过涂布的方式制备成三层钙钛矿量子点膜，第一层为阻隔膜，中间层为量子点聚合物层，第三层为阻隔膜；分别对各组钙钛矿量子点聚合物微球样品及由其制备的钙钛矿量子点膜进行如下性能测试：Take an equal amount of samples of perovskite quantum dot polymer microspheres with three-layer core-shell structure prepared from Examples 1 to 3 and Comparative Examples 1 to 3, mix the obtained microspheres in UV-curable glue, and pass through the coating process. Three-layer perovskite quantum dot films were prepared by the method, the first layer was a barrier film, the middle layer was a quantum dot polymer layer, and the third layer was a barrier film; The perovskite quantum dot films prepared therefrom were tested as follows:
1、粒径测试：1. Particle size test:
通过扫描电子显微镜测试由实施例1～3及对比例1～3制备的核壳结构的钙钛矿量子点聚合物微球样品的平均粒径；所得测试数据记录于表1；The average particle size of the core-shell structure perovskite quantum dot polymer microsphere samples prepared from Examples 1-3 and Comparative Examples 1-3 was tested by scanning electron microscopy; the obtained test data were recorded in Table 1;
2、荧光性能测试：2. Fluorescence performance test:
将由实施例1～3及对比例1～3制备的核壳结构的钙钛矿量子点聚合物微球样品，在450nm 的激发波长下，对各样品的荧光发射峰(PL)、半峰宽(FWHM)、荧光效率(PLQY)进行测试。每个实施例平行测试6个样品后，对测试结果求平均值，各实施例样品的荧光性能测试数据记录于表1；The core-shell structure perovskite quantum dot polymer microsphere samples prepared from Examples 1 to 3 and Comparative Examples 1 to 3, under the excitation wavelength of 450 nm, the fluorescence emission peak (PL), half peak width of each sample. (FWHM), fluorescence efficiency (PLQY) were tested. After 6 samples were tested in parallel for each example, the test results were averaged, and the fluorescence performance test data of the samples of each example were recorded in Table 1;
3、高温高湿光照老化测试：3. High temperature and high humidity light aging test:
将由实施例1～3及对比例1～3制备的核壳结构的钙钛矿量子点聚合物微球样品在60℃、90％、3mw/cm2光强450nm光照老化1000小时后，在450nm的激发波长下，测定各样品的PLQY；每个实施例平行测试6个样品后，对测试结果求平均值。各实施例样品的高温高湿光照老化测试数据记录于表1；The core-shell structure perovskite quantum dot polymer microsphere samples prepared from Examples 1-3 and Comparative Examples 1-3 were aged for 1000 hours at 60°C, 90%, 3mw/cm2 light intensity of 450nm, and then at 450nm. Under the excitation wavelength, the PLQY of each sample was measured; after 6 samples were tested in parallel in each example, the test results were averaged. The high-temperature and high-humidity light aging test data of the samples of each embodiment are recorded in Table 1;
4、NTSC色域测试：4. NTSC color gamut test:
将由实施例1～3及对比例1～3制备的核壳结构的钙钛矿量子点聚合物微球样品分散到UV胶水中，在两层50um阻隔膜间涂布，光固化后得到钙钛矿量子点膜，测试各钙钛矿量子点膜组装的液晶显示器的NTSC色域。每个实施例平行测试6个样品后，对测试结果求平均值。各实施例样品的NTSC色域测试数据记录于表1；The core-shell structure perovskite quantum dot polymer microsphere samples prepared from Examples 1-3 and Comparative Examples 1-3 were dispersed in UV glue, coated between two layers of 50um barrier films, and light-cured to obtain perovskite The perovskite quantum dot film was used to test the NTSC color gamut of the liquid crystal display assembled with each perovskite quantum dot film. After 6 samples were tested in parallel for each example, the test results were averaged. The NTSC color gamut test data of each embodiment sample is recorded in Table 1;
表1Table 1
由上表中的实验结果可知，采用本发明所制备的三层核壳结构的钙钛矿量子点聚合物微球不仅具有粒径小、抗老化性能优、稳定性强及一定的防蓝光效果等优点。而且，通过其所制备的钙钛矿量子点膜也具有优异的光学性能和老化稳定性。It can be seen from the experimental results in the above table that the perovskite quantum dot polymer microspheres with three-layer core-shell structure prepared by the present invention not only have small particle size, excellent anti-aging performance, strong stability and certain anti-blue light effect. Etc. Moreover, the perovskite quantum dot film prepared by it also has excellent optical properties and aging stability.
最后应说明的是：以上实施例仅用以说明本发明而并非限制本发明所描述的技术方案；本领域的普通技术人员应当理解，仍然可以对本发明进行修改或等同替换；而一切不脱离本发明的精神和范围的技术方案及其改进，其均应涵盖在本发明的权利要求范围中。Finally, it should be noted that: the above embodiments are only used to illustrate the present invention and not to limit the technical solutions described in the present invention; those of ordinary skill in the art should understand that the present invention can still be modified or equivalently replaced; The technical solutions and improvements of the spirit and scope of the invention should all be covered by the scope of the claims of the present invention.
Claims (9)
- [根据细则91更正 11.08.2022]
一种核壳结构的钙钛矿量子点聚合物微球的制备方法，其特征在于，包括以下步骤：一、核层电喷液的制备；将聚偏氟乙烯及第一有机溶剂混合均匀，然后向其中加入质量为第一有机溶剂1.2～2.5％的三乙胺；所得混合液的温度升至50～60℃，并在此温度下保温静置处理30～40min；待处理完毕后，分别向其中投入质量为聚偏氟乙烯15～30％的2-(2-羟基-4-甲基丙烯酰氧基苯基)苯并***及1.5～3.6％的过氧化二苯甲酰；将之混合均匀后，在氮气的保护下，以65～85℃的温度保温反应8～15h；待反应完毕后，将其自然冷却至室温，向其中加入化合物AX、BX 2，并以200～300r/min的速率匀速预搅拌10～15h，然后以1800～2000r/min的速率高速搅拌30～40min；然后对其进行过滤处理，得到澄清透明的核层电喷液；其中，AX、BX 2的摩尔比为1：1～3，AX与BX 2总重量与聚偏氟乙烯的重量百分比为0.2～10％，所得溶液的固含量为10～30％；所述化合物AX、BX 2中，A为金属阳离子或者带正电荷的有机阳离子，其为Cs +、Rb +、FA +(HN＝CHNH3 +)、OA +(CH3CH2CH2CH2CH2CH2CH2CH2NH3 +)的一种或几种的混合；B为金属阳离子，Pb 2+、Sn 2+、Sb 2+、Zn 2+、Mn 2+、Cu 2+中的一种或几种的混合；X为卤族元素，其为Cl -、Br -、I -中的一种或几种的混合；二、第一壳层电喷液的制备；将氟碳树脂溶解在第二有机溶剂中，常温下以250～300r/min的速率匀速搅拌10～15h，再以1800～2000r/min的速率高速搅拌30～40min；对其进行过滤处理后，得到无色透明的第一壳层电喷液，所得溶液的固含量控制在10～50％；其中，所述氟碳树脂为四氟乙烯和乙烯基醚及其他含羟基、羧基功能性官能团单体共聚物；三、第二壳层电喷液的制备；将乙烯-乙烯醇共聚物、2-羟基-4-甲氧基二苯甲酮及功能添加剂投入在第三有机溶剂中；其中，乙烯-乙烯醇共聚物、2-羟基-4-甲氧基二苯甲酮、功能添加剂、第三有机溶剂的重量比为2：0.02～0.06：0.08～0.12：8；在常温下以280～320r/min的速率对上述所得混合物质匀速预搅拌10～15h，再以1800～2000r/min的速率高速搅拌20～30min，然后对其进行过滤处理；所得液体即为第二壳层电喷液；四、钙钛矿量子点聚合物微球的制备；将上述所得三种电喷液分别加入到储液罐中，以稳定的速率供应到三元同轴喷嘴，利用高压电源给溶液附加额定的极性，在喷嘴与收集器之间施加高电势，液体射流从喷嘴发出，并被高电势加速，制备的聚合物微球向收集器移动；在此过程中，随第一有机溶剂、第二有机溶剂、第三有机溶剂挥发，获得三层核壳结构的聚合物微球；通过控制三种电喷液的流速、电 压的大小可控制所制备三层结构聚合物微球各层的厚度；然后将所获得的三层核壳结构的聚合物微球在35～45℃进行真空干燥，随第一有机溶剂、第二有机溶剂、第三有机溶剂的进一步挥发，钙钛矿量子点在核层聚合物中原位生成，即得到三层核壳结构的钙钛矿量子点聚合物微球成品。[Corrected 11.08.2022 under Rule 91]
A method for preparing perovskite quantum dot polymer microspheres with a core-shell structure is characterized in that, comprising the following steps:1. Preparation of nuclear layer electrospray liquid;Mixing the polyvinylidene fluoride and the first organic solvent uniformly, then adding triethylamine with a mass of 1.2 to 2.5% of the first organic solvent to it; the temperature of the obtained mixed solution rises to 50 to 60 ° C, and the temperature is maintained at this temperature stand for treatment for 30-40min; after the treatment is completed, put 2-(2-hydroxy-4-methacryloyloxyphenyl)benzotriazole and 2-(2-hydroxy-4-methacryloyloxyphenyl)benzotriazole and 1.5-3.6% dibenzoyl peroxide; after mixing it uniformly, under the protection of nitrogen, keep the reaction temperature at 65-85 ℃ for 8-15 hours; Compounds AX and BX 2 are added therein, and pre-stirred at a constant speed of 200-300 r/min for 10-15 h, and then stirred at a high speed of 1800-2000 r/min for 30-40 min; Nuclear layer electrospray fluid;Wherein, the molar ratio of AX and BX 2 is 1:1-3, the weight percentage of the total weight of AX and BX 2 to polyvinylidene fluoride is 0.2-10%, and the solid content of the obtained solution is 10-30%;In the compounds AX and BX 2 , A is a metal cation or a positively charged organic cation, which is Cs + , Rb + , FA + (HN=CHNH 3 + ), OA + (CH 3 CH 2 CH 2 CH 2 One or more mixtures of CH 2 CH 2 CH 2 CH 2 NH 3 + );B is a metal cation, one or a mixture of Pb 2+ , Sn 2+ , Sb 2+ , Zn 2+ , Mn 2+ , and Cu 2+ ;X is a halogen element, which is one or a mixture of Cl - , Br - and I - ;2. Preparation of the first shell electrospray liquid;Dissolve the fluorocarbon resin in the second organic solvent, stir at a constant speed of 250 to 300 r/min for 10 to 15 hours at room temperature, and then stir at a high speed of 1800 to 2000 r/min for 30 to 40 minutes; after filtering it, A colorless and transparent first shell electrospray liquid is obtained, and the solid content of the obtained solution is controlled at 10-50%;Wherein, the fluorocarbon resin is a copolymer of tetrafluoroethylene, vinyl ether and other functional monomers containing hydroxyl and carboxyl groups;3. Preparation of the second shell electrospray liquid;Put ethylene-vinyl alcohol copolymer, 2-hydroxy-4-methoxy benzophenone and functional additives into the third organic solvent; wherein, ethylene-vinyl alcohol copolymer, 2-hydroxy-4-methoxy benzophenone The weight ratio of benzophenone, functional additives, and the third organic solvent is 2:0.02-0.06:0.08-0.12:8; at room temperature, the obtained mixture is pre-stirred at a constant speed for 10-15h at a rate of 280-320r/min , and then stir at a high speed of 1800-2000r/min for 20-30min, and then filter it; the obtained liquid is the second shell electrospray liquid;4. Preparation of perovskite quantum dot polymer microspheres;The three electrospray liquids obtained above are respectively added to the liquid storage tank, supplied to the ternary coaxial nozzle at a stable rate, and a high voltage power supply is used to add a rated polarity to the solution, and a high potential is applied between the nozzle and the collector, The liquid jet is emitted from the nozzle and accelerated by the high potential, and the prepared polymer microspheres move toward the collector; during this process, the first organic solvent, the second organic solvent and the third organic solvent are volatilized to obtain a three-layer core-shell Structured polymer microspheres; the thickness of each layer of the prepared three-layer structure polymer microspheres can be controlled by controlling the flow rate and voltage of the three electrospray liquids; then the obtained three-layer core-shell structure polymer microspheres The ball is vacuum-dried at 35-45 °C, and with the further volatilization of the first organic solvent, the second organic solvent, and the third organic solvent, the perovskite quantum dots are formed in situ in the core-layer polymer, that is, a three-layer core-shell structure is obtained. The finished product of perovskite quantum dot polymer microspheres. - 根据权利要求1所述的一种核壳结构的钙钛矿量子点聚合物微球的制备方法，其特征在于：所述核层电喷液的制备过程中，所用第一有机溶剂为N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、丙酮、丁酮中的任一种或几种的混合。The method for preparing perovskite quantum dot polymer microspheres with a core-shell structure according to claim 1, wherein in the preparation process of the core layer electrospray liquid, the first organic solvent used is N, Any one or a mixture of N-dimethylformamide, N,N-dimethylacetamide, acetone and butanone.
- 根据权利要求1所述的一种核壳结构的钙钛矿量子点聚合物微球的制备方法，其特征在于：所述第一壳层电喷液的制备过程中，所用第二有机溶剂为N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、丙酮、丁酮、乙酸乙酯、乙酸丁酯中的任一种或几种的混合。The method for preparing perovskite quantum dot polymer microspheres with a core-shell structure according to claim 1, wherein in the preparation process of the first shell electrospray liquid, the second organic solvent used is: Any one or a mixture of N,N-dimethylformamide, N,N-dimethylacetamide, acetone, methyl ethyl ketone, ethyl acetate and butyl acetate.
- 根据权利要求1所述的一种核壳结构的钙钛矿量子点聚合物微球的制备方法，其特征在于：所述第二壳层电喷液的制备过程中，所用第三有机溶剂为N，N-二甲基乙酰胺与异丙醇的混合物，N，N-二甲基乙酰胺与异丙醇的重量比为7：1。The method for preparing perovskite quantum dot polymer microspheres with a core-shell structure according to claim 1, wherein in the preparation process of the second shell electrospray liquid, the third organic solvent used is: The mixture of N,N-dimethylacetamide and isopropanol, the weight ratio of N,N-dimethylacetamide and isopropanol is 7:1.
- 根据权利要求1所述的一种核壳结构的钙钛矿量子点聚合物微球的制备方法，其特征在于，所述功能添加剂的制备方法包括以下步骤：The preparation method of a core-shell structure perovskite quantum dot polymer microsphere according to claim 1, wherein the preparation method of the functional additive comprises the following steps:Ⅰ、按照质量比1：3～5，准确称取适量的硝酸铈和聚乙烯吡咯烷酮；并将所得的混合组分投至质量为其2～4倍的N，N-二甲基甲酰胺中，然后在室温下对所得混合物搅拌20～30h；待搅拌均匀后，采用电喷离子化工艺制备复合微球；所得复合微球置于马弗炉中，并在560～650℃的温度下焙烧4～5h；待焙烧完毕后，将复合微球取出，并在自然条件下冷却至室温，所得即为氧化铈多孔微球成品；1. Accurately weigh an appropriate amount of cerium nitrate and polyvinyl pyrrolidone according to a mass ratio of 1:3 to 5; and cast the resulting mixed component into N,N-dimethylformamide whose mass is 2 to 4 times. , and then the obtained mixture was stirred at room temperature for 20-30 h; after stirring evenly, composite microspheres were prepared by electrospray ionization process; the obtained composite microspheres were placed in a muffle furnace and calcined at a temperature of 560-650 °C 4 to 5 hours; after the calcination is completed, the composite microspheres are taken out and cooled to room temperature under natural conditions, and the obtained cerium oxide porous microspheres are finished products;Ⅱ、将上述所得的氧化铈多孔微球浸没于浓度为50～65％的乙醇溶液，并向其中加入质量为乙醇溶液15～25％的硅烷偶联剂；然后在28～35kHz的频率超声分散5～15min，然后将所得混合组分的温度升至50～60℃，并在此温度下反应4～6h；待反应完毕后，对混合组分进行固液分离，所得固体粉末置于真空干燥箱内进行干燥处理；II. The cerium oxide porous microspheres obtained above are immersed in an ethanol solution with a concentration of 50-65%, and a silane coupling agent with a mass of 15-25% of the ethanol solution is added to it; then ultrasonically disperse at a frequency of 28-35 kHz 5 to 15 minutes, then the temperature of the obtained mixed components was raised to 50 to 60 ° C, and the reaction was carried out at this temperature for 4 to 6 hours; after the reaction was completed, the mixed components were separated from solid and liquid, and the obtained solid powder was placed in vacuum drying. Drying in the box;Ⅲ、将所得固体粉末研磨后，按照固液比0.1～0.2g/mL，将固体粉末投至羟基丙烯酸树脂溶液中，并以25～30kHz的频率，超声分散20～30min，所得分散液即为功能添加剂成品。III. After grinding the obtained solid powder, according to the solid-liquid ratio of 0.1～0.2g/mL, the solid powder is put into the hydroxyacrylic resin solution, and ultrasonically dispersed at a frequency of 25～30kHz for 20～30min, the obtained dispersion is Functional additive finished products.
- 根据权利要求5所述的一种核壳结构的钙钛矿量子点聚合物微球的制备方法，其特征在于：所述步骤Ⅰ中，焙烧时的升温速率为2～5℃/min。The method for preparing perovskite quantum dot polymer microspheres with a core-shell structure according to claim 5, characterized in that: in the step I, the heating rate during roasting is 2 to 5°C/min.
- 根据权利要求5所述的一种核壳结构的钙钛矿量子点聚合物微球的制备方法，其特征在于：所述步骤Ⅱ中，所用硅烷偶联剂为γ-氨丙基三乙氧基硅烷、γ-(2，3-环氧丙氧)丙基三甲氧基硅烷中的任意一种。The method for preparing perovskite quantum dot polymer microspheres with a core-shell structure according to claim 5, wherein in the step II, the silane coupling agent used is γ-aminopropyltriethoxy Silane and γ-(2,3-glycidoxy)propyltrimethoxysilane.
- 根据权利要求5所述的一种核壳结构的钙钛矿量子点聚合物微球的制备方法，其特征在于：所述步骤Ⅲ中，所用羟基丙烯酸树脂溶液的溶剂为醋酸乙酯、溶质为羟基丙烯酸树脂；且所述羟基丙烯酸树脂的羟值为80～200mgKOH/g，丙烯酸树脂溶液固含量为40～65％。The method for preparing perovskite quantum dot polymer microspheres with a core-shell structure according to claim 5, wherein in the step III, the solvent of the hydroxy acrylic resin solution used is ethyl acetate, and the solute is Hydroxy acrylic resin; and the hydroxyl value of the hydroxy acrylic resin is 80-200 mgKOH/g, and the solid content of the acrylic resin solution is 40-65%.
- 根据权利要求1～8中任一项所述的一种核壳结构的钙钛矿量子点聚合物微球的应用方法，其特征在于：所述核壳结构的钙钛矿量子点聚合物微球用作电视、手机、笔记本、iPad及车载显示屏的背光模组中钙钛矿量子点光学复合膜的原料。The method for applying perovskite quantum dot polymer microspheres with a core-shell structure according to any one of claims 1 to 8, characterized in that: the core-shell structure perovskite quantum dot polymer microspheres The ball is used as a raw material for perovskite quantum dot optical composite films in backlight modules of TVs, mobile phones, notebooks, iPads and automotive displays.
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