CN116751579A - Photochromic nano composite microsphere and application thereof - Google Patents
Photochromic nano composite microsphere and application thereof Download PDFInfo
- Publication number
- CN116751579A CN116751579A CN202310729632.0A CN202310729632A CN116751579A CN 116751579 A CN116751579 A CN 116751579A CN 202310729632 A CN202310729632 A CN 202310729632A CN 116751579 A CN116751579 A CN 116751579A
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- photochromic
- color
- microsphere
- changing
- titanium oxide
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- 239000004005 microsphere Substances 0.000 title claims abstract description 80
- 239000002114 nanocomposite Substances 0.000 title claims description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000011258 core-shell material Substances 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims description 115
- 238000000576 coating method Methods 0.000 claims description 115
- 239000000243 solution Substances 0.000 claims description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000002077 nanosphere Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 8
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- -1 alkyl glucoside Chemical class 0.000 claims description 7
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- 150000003608 titanium Chemical class 0.000 claims description 6
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
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- 239000003446 ligand Substances 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- AVBJHQDHVYGQLS-AWEZNQCLSA-N (2s)-2-(dodecanoylamino)pentanedioic acid Chemical compound CCCCCCCCCCCC(=O)N[C@H](C(O)=O)CCC(O)=O AVBJHQDHVYGQLS-AWEZNQCLSA-N 0.000 claims description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- SFBLKWGYRDDITM-UHFFFAOYSA-J [Ti+4].[O-]S([O-])=O.[O-]S([O-])=O Chemical compound [Ti+4].[O-]S([O-])=O.[O-]S([O-])=O SFBLKWGYRDDITM-UHFFFAOYSA-J 0.000 claims description 2
- 229930182478 glucoside Natural products 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 claims description 2
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- ZTUKGBOUHWYFGC-UHFFFAOYSA-N 1,3,3-trimethyl-2-methylideneindole Chemical compound C1=CC=C2N(C)C(=C)C(C)(C)C2=C1 ZTUKGBOUHWYFGC-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
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- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
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- 238000002835 absorbance Methods 0.000 description 3
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 3
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 208000017983 photosensitivity disease Diseases 0.000 description 2
- 231100000434 photosensitization Toxicity 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
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- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical compound C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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- 239000000693 micelle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
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- 238000000733 zeta-potential measurement Methods 0.000 description 1
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
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- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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Abstract
The nanometer composite microsphere has nanometer titania crystal particle as the inner core, surfactant as the outer shell, and photochromic compound in the middle layer between the inner core and the outer shell to form the composite multilayer core-shell structure. The photochromic compound is selected from the group consisting of spiropyrans, naphthopyrans and spirooxazines. The prepared color-changing material can change color under ultraviolet radiation and present various reversible color changes through the compounding of various photochromic compounds and the synergistic effect of the compound and titanium oxide nano crystal grains, and can protect harmful strong light or short-wave blue light in different environments. The photochromic process has the advantages of short color forming change time, high response sensitivity, rich color change, good blue light prevention effect and the like.
Description
Technical Field
The invention belongs to the technical field of photochromic materials, and particularly relates to a photochromic nano composite microsphere, and a blue-light-preventing coating and a light filter prepared from the photochromic nano composite microsphere.
Background
Photochromic materials are a class of materials that undergo a color change upon excitation by a light source. Inorganic photochromic materials and organic photochromic materials can be classified into two main classes. The organic photochromic material has good performances in the fields of information storage, optical lenses, textile clothing, anti-counterfeiting printing and the like due to the advantages of various types, various colors and the like, such as: photochromic compounds such as spiropyrans, spirooxazines, naphthopyrans, fulgides, and the like; the inorganic color-changing material has the defects of single color change, difficult surface modification, slow color-changing response time and the like, but the inorganic color-changing material has better fatigue resistance and thermal stability. Therefore, how to combine the advantages of the two materials, namely organic and inorganic, to form an organic/inorganic hybrid composite material is one of the directions of future photochromic technology research. In addition, the color change of the existing color-changing materials is only gradually deepened from colorless, the reversible change is basically from colored to colorless, and the change color is relatively single. For example: the spiropyrans are mostly colorless to red or purple, the naphthopyrans are mostly colorless to green, the spirooxazines are mostly colorless to yellow or blue, the same photochromic material is difficult to realize colorful overall color change or adjust according to a designed color spectrum, the color is single, satisfactory color cannot be achieved, and some of the photochromic material is colored by dye, but due to the influence of the dye, the light transmittance after fading is influenced, and the photochromic material is not very practical.
Photochromic properties are also often affected by polymer molecules, other chemical aids, microstructure, polymerization environment, etc., for example: the color-changing compound is greatly influenced by the ultraviolet absorber in the polymer, and the ultraviolet is absorbed by the light absorber in the polymer, so that the color-changing compound is greatly limited by ultraviolet spectrum excitation color change, and the color-changing efficiency is low; at the same time, the presence of diopters results in an inconsistency in the thickness of the edges and center of the lens, in which case the addition of color-changing compounds, if still done by bulk, can result in color depth differences at different locations of the lens thickness. Therefore, some manufacturers in China use spin-coating to produce color-changing lenses. The spin coating method is to add the prepared color-changing solution into a spin coater after the substrate is manufactured, and to fix the substrate on the spin coater for centrifugal rotation after full mixing, and to solidify the substrate to form the product with color-changing effect. Compared with the substrate method, the spin coating method has the advantages of high technical content, small color difference of the product, and low color changing efficiency due to the relatively reduced color changing coating space, reduced color changing space and change of external environment temperature. Therefore, development of a photochromic coating technology with high color response speed and high color accuracy is an important development direction in the future.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a photochromic nano composite microsphere, wherein the inner core of the nano composite microsphere is titanium oxide nano crystal particles, the outer shell is coated with a surfactant, and a photochromic compound is positioned in the middle layer between the inner core and the outer shell to form a composite multi-layer core-shell structure. The photochromic compound is selected from spiropyrans, naphthopyrans and spirooxazines. The prepared color-changing material can change color under ultraviolet radiation and present various reversible color changes through the compounding of various photochromic compounds and the synergistic effect of the compound and titanium oxide nano crystal grains, and can protect harmful strong light or short-wave blue light in different environments. The photochromic material has the advantages of short color forming change time, high response sensitivity, rich color change, good blue light prevention effect and the like.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a photochromic nano-composite microsphere is of a titanium oxide/color-changing compound/surfactant three-layer composite core-shell structure, wherein the inner core of the microsphere is titanium oxide nanosphere, the middle layer is a photochromic layer formed by color-changing compounds, and the outer shell is an anionic surfactant or a nonionic surfactant; the outer diameter of the composite microsphere is 45-100 nm, wherein the diameter of the titanium oxide nano microsphere is 15-40 nm, the thickness of the intermediate layer is 7-15 nm, and the thickness of the shell is 8-15 nm;
the color-changing compound is selected from at least one of the following compounds:
the photochromic nano-composite microsphere as described above, preferably, the surfactant is at least one of stearic acid, alkyl glucoside, sodium dodecyl benzene sulfonate, fatty glyceride, polysorbate, lauroyl glutamic acid, thioglycolic acid, mercaptopropionic acid and alpha-mercaptoglycerol.
Preferably, the mass ratio of the surfactant to the titanium oxide to the photochromic compound is (0.5-0.9) to 1 to (1-3).
The photochromic nanocomposite microsphere as described above, preferably, the photochromic nanocomposite microsphere is prepared by the following method:
a. preparing titanium oxide hydrosol:
dropwise adding H into soluble titanium salt aqueous solution with concentration of 0.1-1 mol/L 2 SO 4 The aqueous solution is transparent, then NaOH aqueous solution with the concentration of 15-30wt% is dripped, the PH value is 7-11, and precipitation is gradually carried out; heating to 30-70 ℃, adding acid to dissolve the precipitate, and obtaining titanium oxide hydrosol, wherein the PH value is between 4 and 7;
b. preparing a photochromic color former solution:
adding a photochromic compound into an alcohol solvent, wherein the mass ratio of the photochromic compound to the solvent is 1: (50-120) preparing to obtain a photochromic color former solution;
c. preparing core-shell type photochromic nano composite microspheres:
adding the photochromic color former solution prepared in the step b into titanium oxide hydrosol, adding a surfactant, wherein the mass ratio of the photochromic compound to the soluble titanium salt to the surfactant is 1:5-17:0.5-0.9, stirring for 20-40 minutes, cooling to room temperature, layering and precipitating the reaction solution, filtering and collecting the precipitate, washing and drying to obtain the titanium oxide nano microsphere containing the photochromic compound modified by the surfactant ligand.
In the whole reaction process, tiO is obtained by water phase synthesis 2 The crystal nucleus gradually gathers along with the nanometer crystal nucleus to form secondary particles, namely titanium oxide nanospheres; the titanium oxide nanospheres have larger specific surface area and higher surface energy, and the photochromic compound added in the nanospheres is adsorbed on the TiO in the form of nano particles 2 The surface or gap of the sphere realizes photosensitization modification; along with the addition of the surfactant, the surface tension and critical micelle concentration of a solution system are changed, the nucleation of the nanocrystalline is gradually stopped, and the surfactant and the central atom titanium metal are combined by coordination bonds to form complex coordination units to be coated around the nanocrystalline nucleus, so that TiO is formed 2 Core-shell structure of color former/ligand three-layer.
The photochromic nanocomposite microsphere as described above, preferably, the soluble titanium salt is one of titanium dichloride, titanium tetrachloride, titanium sulfite and titanyl sulfate.
The photochromic nano-composite microsphere as described above, preferably, the solvent is at least one of methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, and hexylene glycol.
In another aspect, the present invention provides the use of a photochromic nanocomposite microsphere as described above as a multi-color chromic material comprising at least one of said photochromic nanocomposite microsphere.
In yet another aspect, the present invention provides the use of a photochromic nanocomposite microsphere as described above as a blue-light-resistant multicolor color-changing coating solution comprising at least one of said photochromic nanocomposite microsphere.
In a preferred embodiment of the present invention, the spirooxazine photochromic compound (IV) is synthesized by, but not limited to, the following method:
step one: mixing cyanide aqueous solution with acid orange II alcohol solution, stirring, controlling temperature to 80-90 ℃ for reaction for 15-42 hours, and introducing CO 2 And (3) gas is saturated, precipitated yellow precipitate is filtered and then is collected, a collected crude product is dissolved at room temperature by using a proper amount of ethanol, a small amount of attapulgite adsorbent is added into filtrate, insoluble substances are filtered after full stirring, excessive water is added into ethanol solution, and the intermediate is precipitated from the ethanol solution due to the fact that the intermediate is insoluble in cold water, filtered and dried in vacuum, so that a purer intermediate product is obtained.
The reaction formula is as follows:
step two: adding a certain amount of intermediate, anhydrous calcium sulfate and sodium bicarbonate into toluene solution of 1, 3-trimethyl-2-methylene indoline, adding dimethyl sulfoxide, controlling the reaction temperature to be 70-80 ℃, carrying out light-proof reaction for 15-24 hours, protecting by nitrogen, filtering to remove impurities, heating filtrate to 80-90 ℃, steaming to remove solvent, washing and drying to obtain the colorless cyano spirooxazine photochromic compound.
The specific reaction formula is as follows:
the synthesis of the spirooxazine photochromic compound (IV) as described above is preferably that in the first step, alcohol is mixed with water according to the mass ratio of 1:1-3, and the alcohol is preferably one of methanol, ethanol and propanol.
Preferably, the cyanide is one of potassium cyanide, sodium cyanide and amine cyanide, and the mass ratio of the acid orange II to the cyanide to the alcohol-water mixed solvent is 1:2-3:10-15.
The synthesis of the spirooxazine photochromic compound (IV) as described above, preferably, the mass ratio of the intermediate to 1, 3-trimethyl-2-methyleneindoline is 1:1-1.5.
The synthesis of the spirooxazine photochromic compound (IV) is preferable that the mass ratio of the intermediate, 1, 3-trimethyl-2-methylene indoline and toluene is 1:1-1.5:20-30.
The spirooxazine photochromic compound (IV) is synthesized by preferably mixing dimethyl sulfoxide, sodium bicarbonate, calcium sulfate and an intermediate in a mass ratio of (0.6-1.0) to (0.9-1.2) to (1.5-2.5) to 1.
The invention has the beneficial effects that:
1. the photochromic nano-composite microsphere prepared by the invention generates color change after being irradiated by sunlight/ultraviolet rays, and can be reduced to a colorless state after losing the sunlight/ultraviolet rays. According to the selection and collocation of different types of photochromic compounds, one color change can be realized, and multiple color changes can also be realized. Because the photochromic compounds of different classes have different sensitivity to spectral response, the color change process and the color fading process can show different color changes, the changeable color and visual effect are realized, and the application performance requirements of the photochromic materials such as optical filters, functional clothes, anti-counterfeiting technology and the like can be met.
2. The photochromic nano-composite microsphere has a three-layer composite core-shell structure, wherein the inner core is titanium oxide nanospheres, the middle layer is a photochromic layer formed by a color-changing compound, and the outer shell is an anionic surfactant or a nonionic surfactant.
3. The three-dimensional space of the titanium oxide core in the microsphere is in the nano-scale range, the energy level changes due to the quantum size effect, so that the Van der Waals area of the color-changing molecule is increased, the activity of the color-changing body is enhanced, the conjugated system is increased, the space volume of the molecule is increased, and the gap between the molecule and the molecule is increased, thereby reducing the conversion obstruction between the color-changing open ring body and the colorless closed ring body, shortening the conversion time and accelerating the speed. The existing blue light absorbing materials absorb ultraviolet rays, and the photochromic reaction can be influenced by the ultraviolet rays. The titanium oxide nanospheres in the core-shell structure are positioned at the innermost part, incident light rays excite the color-changing layer at first, and meanwhile, the titanium oxide nanospheres in the core have the characteristics of reflecting and scattering ultraviolet rays, so that the irradiation intensity of ultraviolet rays required by exciting the color-changing compound is not influenced, and the color-changing effect is good.
4. Titanium oxide surface-loaded photochromic compound in microsphere with core-shell structure and TiO 2 The photosensitization modification is realized, the absorption spectrum is red shifted, the light absorption intensity and the wavelength range are changed by the cooperation of the titanium oxide and the color-changing compound, and the blue light and harmful light protection effect is improved. The colorful color-changing filter lens containing the photochromic nano composite microspheres manufactured by the invention not only can change color in sunlight and protect strong light and ultraviolet light, but also can protect blue light below 435nm indoors, and realize the performance of all-weather protection of ultraviolet light and short-wave blue light in different light and shade environments.
Drawings
Fig. 1 is an infrared spectrum of a spirooxazine photochromic compound (IV) prepared in an embodiment.
Fig. 2 is a transmission electron micrograph of the photochromic nanocomposite microsphere prepared in example 1.
Fig. 3 is an XRD diffractogram of the photochromic nanocomposite microsphere prepared in example 1.
Fig. 4 is a graph showing the comparison spectra before and after irradiation of the color-changing blue-light-preventing lens prepared in example 1.
FIG. 5 is a graph showing the absorption spectrum of the photochromic nano-composite microsphere-containing solution prepared in example 14.
FIG. 6 is a photograph showing the discoloration-discoloration process of the photochromic-containing nanocomposite microsphere solution prepared in example 14.
Detailed Description
The invention is further illustrated by the following specific examples, which are not meant to limit the scope of the invention.
Some of the raw materials in the following examples were prepared by the following methods:
1. spirooxazine photochromic compounds (IV)
4400 g of KCN is added into 15000ml of pure water, 2000 g of acid orange II 9000ml of ethanol solution is added into the water solution, the temperature is raised to 85 ℃ under stirring, the heat preservation reaction is carried out for 42 hours, the solution turns from orange red to dark greenish black, and C0 is introduced 2 The gas is saturated, the yellow precipitate is collected by filtration, 1800g of ethanol is added to dissolve the collected crude product at room temperature, 120g of attapulgite adsorbent is added to the filtrate, insoluble substances are filtered after full stirring, excessive water is added to the ethanol solution, after crystals are separated out, the mixture is collected and filtered, and the mixture is dried in vacuum to obtain an intermediate (SO).
180g of SO intermediate, 320g of anhydrous calcium sulfate and 180g of sodium bicarbonate are added into 4650ml of toluene solution of 200g of 1, 3-trimethyl-2-methyleneindoline, 160ml of dimethyl sulfoxide is added, the reaction temperature is controlled at 80 ℃, and the reaction is carried out for 19 hours in a dark place, N 2 Protecting, filtering to remove impurities, heating the filtrate to 80 ℃, steaming to remove the solvent, washing and drying to obtain the cyano spirooxazine photochromic compound (IV).
Infrared spectroscopy (FT-IR) test: drying the spirooxazine powder sample prepared by the above steps in a vacuum oven to constant weight, taking out about 30mg, tabletting with KBr, and measuring infrared spectrogram (figure 1) by Fourier infrared spectrometer, wherein 797cm can be seen -1 Is characterized by bending vibration characteristic peak of benzene ring, 1030cm -1 And 1240cm -1 The vicinity is the characteristic peak of the stretching vibration of C-O on the spiro; a vibration absorption peak of substituent on indoline ring in the range of 1255-1380 cm-1; 1450. 1600, 2210cm -1 The range is the characteristic peak of stretching vibration of naphthalene ring cyano, 3040cm -1 Nearby is the characteristic peak of C-H stretching vibration.
Elemental analysis: calculated values: C78.18,H 5.28,N 11.72, measured value: and C78.10,H 5.35,N 11.74.
2. Polyurethane acrylate prepolymers
450g of Toluene Diisocyanate (TDI) and 9Kg of ethyl acetate solvent are added into 850g of polyethylene glycol adipate, 5g of dibutyltin dilaurate is slowly dripped into the mixture, the mixture is reacted for 85min under the protection of nitrogen at the temperature of 65 ℃, 15g of 1, 4-butanediol and 12g of 3-methyl-1, 5-pentanediol are sequentially added into the mixture to react for 90min, 230g of hydroxyethyl acrylate (HEA) is added into the mixture, the temperature of the mixture is reduced to 50 ℃, and the reaction time is 5 hours and 8 minutes, and 2236cm of reaction time is measured -1 The stretching vibration absorption peak of the-NCO disappears, and the solvent is distilled off, so that the polyurethane acrylic ester prepolymer is obtained.
Example 1: preparation of photochromic nano composite microsphere, colorful color-changing coating liquid and filter lens
Firstly, preparing photochromic nano composite microspheres:
1. preparing titanium oxide hydrosol: 150g TiCl was taken 4 Adding into 1500ml pure water, and dripping diluted H 2 SO 4 And (3) dropwise adding 25wt% of NaOH aqueous solution until the solution is transparent, adjusting the pH value to 9, heating to 50 ℃ after precipitation, adding acid to adjust the pH value to 5, and dissolving the precipitate to obtain the titanium oxide hydrosol.
2. Preparing a photochromic color former solution: 15g of spirooxazine photochromic compound (IV) and 1000g of ethanol are prepared into a photochromic solution.
3. Preparing core-shell type photochromic nano-microspheres: and (3) adding the photochromic color forming body solution prepared in the step (2) into titanium oxide colloid, adding 5.5g of thioglycollic acid and 3.5g of sodium dodecyl benzene sulfonate, stirring for 35min, cooling to room temperature, filtering, collecting precipitate, washing and drying to obtain the core-shell nano titanium oxide photochromic microsphere. The yield was 69%.
FIG. 2 is a TEM image of a titanium oxide modified nanomaterial. The appearance of the material is spherical and is formed by TiO 2 The light-colored outer layer is formed by agglomerating nanocrystals, and is a shell formed by a spirooxazine color-changing compound and a surfactant, and is shown as a white bright ring in a transmission electron microscope photo. The outer diameter of the composite microsphere is 65nm through the Shelle formula (D=K/beta cos theta) and Zeta potential analysis calculation, wherein the diameter of the titanium oxide nanosphere is 28nm, the thickness of the middle layer is 9.5nm, and the thickness of the shell is 9nm.
FIG. 3 shows XRD diffraction patterns of the nano-titania photochromic microspheres and pure nano-titania prepared in example 1, and from the XRD patterns, it is known that the nanocomposite microspheres have strong diffraction peaks at 2. Theta. Of 25.2 °, 37.6 °, 48.0 °, 53.8 °, 62.6 °, 68.6 °, 70.3 ° and 75.3 °, etc., which are similar to TiO 2 The characteristic diffraction of the anatase phase accords with that of the nano TiO, which shows that the organic matters loaded on the surface are not changed 2 Crystalline phase, thereby determining TiO 2 The structure is orthorhombic anatase type.
Preparing colorful color-changing coating liquid:
1. preparing a first colorful color-changing coating liquid: 15g of the photochromic nano-microsphere prepared by the steps, 38g of ethoxyphenol acrylate and 0.6g of D90 defoamer are added into 420g of polyurethane acrylate prepolymer, and stirred for 30 minutes at room temperature to obtain a component A; 10g of 2-hydroxy-2-methyl-1-phenylpropionic acid 1173 is weighed and added into the component A, and the first colorful color-changing coating liquid is obtained after uniform mixing.
2. Preparing a second colorful color-changing coating liquid: 50g of the first colorful color-changing coating liquid prepared in the step is taken, and 1.9g of ethoxyphenol acrylate is added to obtain the second colorful color-changing coating liquid.
(III) preparing a colorful color-changing filter lens:
filtering and degassing the first colorful color-changing coating liquid by a filter membrane, spin-coating the first colorful color-changing coating liquid on the surface of an acrylic optical lens at the speed of 2500 rpm, and then placing the coating sheet on the surface of the acrylic optical lens with the illumination intensity of 200mW/cm 2 Is irradiated under a UV-LED light curing machine for 61S. And then, coating a second colorful color-changing coating liquid on the cured coating by adopting the same coating and curing operation method to obtain the colorful color-changing blue-light-preventing lens.
Example 2: preparation of photochromic nano composite microsphere, colorful color-changing coating liquid and filter lens
Firstly, preparing photochromic nano composite microspheres:
1. preparing titanium oxide hydrosol: 150g TiCl was taken 4 Adding into 1350ml pure water, and dripping diluted H 2 SO 4 And (3) dropwise adding 25wt% of NaOH aqueous solution until the solution is transparent, adjusting the pH value to 9.5, heating to 50 ℃ after precipitation, adding acid to adjust the pH value to 5.5, and dissolving the precipitate to obtain the titanium oxide hydrosol.
2. Preparing a photochromic color former solution: 15g of spiropyran photochromic compound (compound of formula I) and 1200g of ethanol were prepared as a photochromic solution.
3. Preparing core-shell type photochromic nano-microspheres: adding the photochromic solution prepared in the step 1 into titanium oxide colloid, adding 4.5g of thioglycollic acid and 4g of sodium dodecyl benzene sulfonate, stirring for 35min, cooling to room temperature, filtering, collecting precipitate, washing, and drying to obtain the core-shell nano titanium oxide photochromic microsphere.
Preparing colorful color-changing coating liquid:
1. preparing a first colorful color-changing coating liquid: 15g of the photochromic nano-microsphere prepared by the steps, 40g of ethoxyphenol acrylate and 0.6g of D90 defoamer are added into 400g of polyurethane acrylate prepolymer, and stirred for 30 minutes at room temperature to obtain a component A; 11g of 2-hydroxy-2-methyl-1-phenylpropionic acid 1173 is weighed and added into the component A, and the first colorful color-changing coating liquid is obtained after uniform mixing.
2. Preparing a second colorful color-changing coating liquid: 50g of the first colorful color-changing coating liquid prepared in the step is taken, and 1.8g of ethoxyphenol acrylate is added to obtain the second colorful color-changing coating liquid.
(III) preparing a colorful color-changing filter lens:
filtering and degassing the first colorful color-changing coating liquid by a filter membrane, spin-coating the first colorful color-changing coating liquid on the surface of an optical CR39 lens at a speed of 2500 rpm, and then placing the coating sheet on a light with an illumination intensity of 200mW/cm 2 Is irradiated under the UV-LED light curing machine 63S. And then coating the second colorful color-changing coating liquid prepared in the embodiment 1 on the cured coating by adopting the same coating and curing operation method to obtain the colorful color-changing blue-light-preventing lens.
Example 3: preparation of photochromic nano composite microsphere, colorful color-changing coating liquid and filter lens
Firstly, preparing photochromic nano composite microspheres:
1. preparing titanium oxide hydrosol: 150g TiCl was taken 2 Adding into 1800ml of pure water, and dripping dilute H 2 SO 4 And (3) dropwise adding 25wt% of NaOH aqueous solution until the solution is transparent, adjusting the pH value to 9.5, heating to 50 ℃ after precipitation, adding acid to adjust the pH value to 5.5, and dissolving the precipitate to obtain the titanium oxide hydrosol.
2. Preparing a photochromic color former solution: 15g of a spiropyran photochromic compound (compound of formula II) and 950g of ethanol were prepared as a photochromic solution.
3. Preparing core-shell type photochromic nano-microspheres: and (3) adding the photochromic solution prepared in the step (1) into the titanium oxide colloid, adding 6g of thioglycollic acid and 4g of sodium dodecyl benzene sulfonate, stirring for 35min, cooling to room temperature, filtering, collecting precipitate, washing, and drying to obtain the core-shell nano titanium oxide photochromic microsphere.
Preparing colorful color-changing coating liquid:
1. preparing a first colorful color-changing coating liquid: 15g of the photochromic nano-microsphere prepared by the steps, 45g of ethoxyphenol acrylic ester and 0.6g of D90 defoamer are added into 380g of polyurethane acrylic ester prepolymer, and stirred for 30 minutes at room temperature to obtain a component A; 10g of 2-hydroxy-2-methyl-1-phenylpropionic acid 1173 is weighed and added into the component A, and the first colorful color-changing coating liquid is obtained after uniform mixing.
2. Preparing a second colorful color-changing coating liquid: 50g of the first colorful color-changing coating liquid prepared in the step is taken, and 1.8g of ethoxyphenol acrylate is added to obtain the second colorful color-changing coating liquid.
(III) preparing a colorful color-changing filter lens:
filtering and degassing the first colorful color-changing coating liquid by a filter membrane, spin-coating the first colorful color-changing coating liquid on the surface of an optical PC substrate at a speed of 2500 rpm, and then placing the coating sheet on the surface of the optical PC substrate with an illumination intensity of 200mW/cm 2 Is irradiated under the UV-LED light curing machine for 62S. And then coating the second colorful color-changing coating liquid prepared in the embodiment 2 on the cured coating by adopting the same coating and curing operation method to obtain the colorful color-changing blue-light-preventing lens.
Example 4: preparation of photochromic nano composite microsphere, colorful color-changing coating liquid and filter lens
Firstly, preparing photochromic nano composite microspheres:
1. preparing titanium oxide hydrosol: 150g TiCl was taken 4 Adding the mixture into 1650ml of pure water, and dripping dilute H 2 SO 4 And (3) dropwise adding 25wt% of NaOH aqueous solution until the solution is transparent, adjusting the pH value to 9.5, heating to 50 ℃ after precipitation, adding acid to adjust the pH value to 5.5, and dissolving the precipitate to obtain the titanium oxide hydrosol.
2. Preparing a photochromic color former solution: 15g of naphthopyran photochromic compound (compound of formula III) and 1350g of ethanol were prepared as a photochromic solution.
3. Preparing core-shell type photochromic nano-microspheres: and (3) adding the photochromic solution prepared in the step (1) into the titanium oxide colloid, adding 6g of thioglycollic acid and 5g of sodium dodecyl benzene sulfonate, stirring for 35min, cooling to room temperature, filtering, collecting precipitate, washing, and drying to obtain the core-shell nano titanium oxide photochromic microsphere.
Preparing colorful color-changing coating liquid:
1. preparing a first colorful color-changing coating liquid: 15g of the photochromic nano-microsphere prepared by the steps, 50g of ethoxyphenol acrylate and 0.6g of D90 defoamer are added into 440g of polyurethane acrylate prepolymer, and stirred for 30 minutes at room temperature to obtain a component A; 10g of 2-hydroxy-2-methyl-1-phenylpropionic acid 1173 is weighed and added into the component A, and the first colorful color-changing coating liquid is obtained after uniform mixing.
2. Preparing a second colorful color-changing coating liquid: 50g of the first colorful color-changing coating liquid prepared in the step is taken, and 1.9g of ethoxyphenol acrylate is added to obtain the second colorful color-changing coating liquid.
(III) preparing a colorful color-changing filter lens:
filtering and degassing the first colorful color-changing coating liquid by a filter membrane, spin-coating the first colorful color-changing coating liquid on the surface of an optical polyurethane lens at the speed of 2500 rpm, and then placing the coating sheet on the surface of the optical polyurethane lens with the illumination intensity of 200mW/cm 2 Is irradiated under a UV-LED light curing machine for 60S. And then coating the second colorful color-changing coating liquid prepared in the embodiment 3 on the cured coating by adopting the same coating and curing operation method to obtain the colorful color-changing blue-light-preventing lens.
Example 5: preparation of colorful color-changing filter lens
The first colorful color-changing coating solution prepared in example 1 is filtered and degassed by a filter membrane, and then spin-coated on the surface of an optical PC substrate at 2500 rpm, and then the coating sheet is placed at an illumination intensity of 200mW/em 2 Is irradiated under a UV-LED light curing machine for 61S. And (3) coating the second colorful color-changing coating liquid prepared in the embodiment 4 on the coating by adopting the same coating and curing operation method, and obtaining the colorful color-changing blue-light-preventing lens after the coating is completely cured.
Example 6: preparation of colorful color-changing filter lens
The first colorful color-changing coating solution prepared in example 1 was filtered and degassed by a filter membrane, spin-coated on the surface of an optical PC substrate at 2500 rpm, and then the coated sheet was placed under an illumination intensity of 200mW/cm 2 Is irradiated under the UV-LED light curing machine for 62S. And (3) coating the second colorful color-changing coating liquid prepared in the embodiment 3 on the coating by adopting the same coating and curing operation method, and obtaining the colorful color-changing blue-light-preventing lens after the coating is completely cured.
Example 7: preparation of colorful color-changing filter lens
The first colorful color-changing coating solution prepared in example 1 was filtered and degassed by a filter membrane, spin-coated on the surface of an optical PC substrate at 2500 rpm, and then the coated sheet was placed under an illumination intensity of 200mW/cm 2 Is irradiated under a UV-LED light curing machine for 60S. And (3) coating the second colorful color-changing coating liquid prepared in the embodiment 2 on the coating by adopting the same coating and curing operation method, and obtaining the colorful color-changing blue-light-preventing lens after the coating is completely cured.
Example 8: preparation of colorful color-changing filter lens
The first colorful color-changing coating solution prepared in example 4 is filtered and degassed by a filter membrane, and then spin-coated on the surface of an optical PC substrate at 2500 rpm, and then the coating sheet is placed at an illumination intensity of 200mW/em 2 Is irradiated under the UV-LED light curing machine 63S. And (3) coating the second colorful color-changing coating liquid prepared in the embodiment 3 on the coating by adopting the same coating and curing operation method, and obtaining the colorful color-changing blue-light-preventing lens after the coating is completely cured.
Example 9: preparation of colorful color-changing filter lens
The first colorful color-changing coating solution prepared in example 1 was filtered and degassed by a filter membrane, spin-coated on the surface of an optical PC substrate at 2500 rpm, and then the coated sheet was placed under an illumination intensity of 200mW/cm 2 Is irradiated under the UV-LED light curing machine for 62S. The first colorful color-changing coating liquid prepared in the embodiment 3 is coated on the coating by adopting the same coating and curing operation method, the second colorful color-changing coating liquid prepared in the embodiment 4 is coated after curing, and the coating is completely cured to obtain the colorful color-changing blue-light-preventing lens.
Example 10: preparation of colorful color-changing filter lens
The first colorful color-changing coating solution prepared in example 4 is filtered and degassed by a filter membrane, spin-coated on the surface of an optical PC substrate at 2500 rpm, and then the coating sheet is placed at an illumination intensity of 200mW/cm 2 Is irradiated under a UV-LED light curing machine for 61S. And (3) coating the second colorful color-changing coating liquid prepared in the embodiment 2 on the coating by adopting the same coating and curing operation method, and obtaining the colorful color-changing blue-light-preventing lens after the coating is completely cured.
Example 11: preparation of colorful color-changing coating liquid and filter lens
1. Preparing a first colorful color-changing coating liquid: 5g of the photochromic nano-microsphere prepared in the example 1, 10g of the photochromic nano-microsphere prepared in the example 3, 45g of ethoxyphenol acrylate and 0.6g of D90 defoamer are respectively taken and added into 380g of polyurethane acrylate prepolymer, and the mixture is stirred at room temperature for 30 minutes to obtain a component A; 10g of 2-hydroxy-2-methyl-1-phenylpropionic acid 1173 is weighed and added into the component A, and the first colorful color-changing coating liquid is obtained after uniform mixing.
2. Preparing a second colorful color-changing coating liquid: and (2) taking 50g of the first colorful color-changing coating liquid prepared in the step (1), and adding 1.8g of ethoxyphenol acrylate to obtain a second colorful color-changing coating liquid.
3. Preparing a colorful color-changing filter lens: filtering and degassing the first colorful color-changing coating liquid by a filter membrane, spin-coating the first colorful color-changing coating liquid on the surface of an optical PC substrate at a speed of 2500 rpm, and then placing the coating sheet on the surface of the optical PC substrate with an illumination intensity of 200mW/cm 2 Is irradiated under the UV-LED light curing machine for 62S. And (2) coating the second colorful color-changing coating liquid prepared in the step (2) on the coating by adopting the same coating and curing operation method, and obtaining the colorful color-changing blue-light-preventing lens after the coating is completely cured.
Example 12: photochromic response test for colorful color-changing filter lens
Test of photochromic response value
The detection step and method are as follows: light transmittance tV of the sample under test in the discolored state o And light transmittance tV in a state of color change by light irradiation for 15min 1 The ratio between, namely: spectral response value = tV 0 ÷tV 1 To determine the photochromic response value of the sample being tested. The solar simulator was irradiated with an ultraviolet lamp of 365nm as an excitation light source at a distance of 6 cm. The detection results are shown in Table 1.
(II) photochromic Spectroscopy response time detection
The detection step and method are as follows: placing the filter lenses prepared in examples 1-11 and the prepared filter lenses in a test box respectively, turning on a light source of a sunlight simulator, and recording the time required for the lenses to be colorless to colored; after 15 minutes of irradiation, the simulated light source was turned off, the time required for the lens to recover from the colored to colorless state was recorded, and the detection results are shown in table 1.
Table 1 test of photochromic response values for lenses
The detection result shows that: the colorful color-changing filter lens containing the photochromic nano-composite microspheres can realize the color changing and fading of various colors according to the spectral response time and the speed (sensitivity) of different types of photochromic compounds, so that the color changing and fading process shows various color changes in front and back, and the color change and visual effect are ensured.
Example 13: optical performance test of colorful color-changing filter lens
The optical transmittance (T/%) performance of the filter lenses prepared in examples 1-11 was measured, respectively, using a UV-8000 ultraviolet visible photometer of Shanghai Yuan-Jiujia Instrument Co., ltd; the representative wavelengths of different spectral regions were selected for detection, the detection results are shown in table 2, and fig. 4 is a graph of the comparative spectrum of the multicolor color-changing blue-light-proof lens prepared in example 1 before irradiation and after irradiation.
Table 2 sample light transmittance detection case table unit: t%
The detection result shows that: the colorful color-changing filter lens containing the photochromic nano composite microspheres manufactured by the invention not only can change color in sunlight and protect strong light and ultraviolet light, but also can protect blue light below 435nm indoors, and realize the performance of all-weather protection of ultraviolet light and short-wave blue light in different light and shade environments.
Example 14: absorbance and multi-color changing performance test for photochromic nano composite microsphere
Photochromic nano composite microsphere solution absorption spectrum detection
The detection step comprises: the photochromic nano-composite microspheres prepared in examples 1-4 were taken 0.45g each, 5ml of ethanol solvent was added respectively, the mixed liquids were poured into a plurality of glass beakers containing 50ml of methyl methacrylate monomer, IV-1, I-1, II-1 and III-1 were respectively marked on the beakers, the beakers were put into a xenon lamp test box for ultraviolet irradiation detection and visible light irradiation detection, an ultraviolet lamp was used for irradiation for 120S at normal temperature, the distance between the solution and the light source was 12CM, and the difference between the absorption spectrum before irradiation and the absorption spectrum after irradiation was recorded, and the results are shown in table 3. FIG. 5 is an absorbance spectrum of IV-1 solution, showing that the photochromic response effect is obvious from the difference of the absorbance spectra.
TABLE 3 sample solution absorbance and absorbance spectrum difference conditions
(II) spectral response performance test of photochromic nanocomposite microsphere solution
The detection step comprises: the IV-1, II-1 and III-1 solutions prepared in example 14 are respectively taken as 6g, 6g and 5g, the solutions are mixed and then put under a xenon lamp for ultraviolet irradiation, and the color change and the required time of the mixed solution are recorded; the analog light source was turned off and the fade color change and time was recorded. The results are shown in Table 4, and FIG. 6 shows the process of recording color change for mobile phone photographing.
Table 4 example sample solution spectral response conditions table
Conclusion: the invention shows that the prepared photochromic nano-composite microsphere has sensitive photochromic response by detecting the change of absorbance values before and after the discoloration, and the whole discoloration and fading process has rich colors.
Claims (8)
1. The photochromic nano composite microsphere is characterized by being of a three-layer composite core-shell structure formed by titanium oxide, a color-changing compound and a surfactant, wherein the inner core of the photochromic nano composite microsphere is titanium oxide nanosphere, the middle layer is a photochromic layer formed by the color-changing compound, and the outer shell of the photochromic nano composite microsphere is an anionic surfactant or a nonionic surfactant; the outer diameter of the composite microsphere is 45-100 nm, wherein the diameter of the titanium oxide nano microsphere is 15-40 nm, the thickness of the intermediate layer is 7-15 nm, and the thickness of the shell is 8-15 nm;
the color-changing compound is selected from at least one of the following compounds:
2. the photochromic nanocomposite microsphere of claim 1 wherein the surfactant is at least one of stearic acid, alkyl glucoside, sodium dodecyl benzene sulfonate, fatty acid glycerides, polysorbate, lauroyl glutamic acid, thioglycolic acid, mercaptopropionic acid, and α -mercaptoglycerol.
3. The photochromic nanocomposite microsphere according to claim 1 or 2, wherein the mass ratio of the surfactant, the titanium oxide and the photochromic compound is (0.5-0.9) to 1 to (1-3).
4. The photochromic nanocomposite microsphere of claim 1 or 2, wherein the photochromic nanocomposite microsphere is prepared by:
a. preparing titanium oxide hydrosol:
dropwise adding H into soluble titanium salt aqueous solution with concentration of 0.1-1 mol/L 2 SO 4 The aqueous solution is transparent, then NaOH aqueous solution with the concentration of 15-30wt% is dripped, the PH value is 7-11, and precipitation is gradually carried out; heating to 30-70 ℃, adding acid to dissolve the precipitate, and obtaining titanium oxide hydrosol, wherein the PH value is between 4 and 7;
b. preparing a photochromic color former solution:
adding a photochromic compound into an alcohol solvent, and preparing the photochromic compound and the solvent according to the mass ratio of 1: (50-120) to obtain a photochromic color-forming body solution;
c. preparing core-shell type photochromic nano composite microspheres:
adding the photochromic color former solution prepared in the step b into titanium oxide hydrosol, adding a surfactant, wherein the mass ratio of the photochromic compound to the soluble titanium salt to the surfactant is 1:5-17:0.5-0.9, stirring for 20-40 minutes, cooling to room temperature, layering and precipitating the reaction solution, filtering and collecting the precipitate, washing and drying to obtain the titanium oxide nano microsphere containing the photochromic compound modified by the surfactant ligand.
5. The photochromic nanocomposite microsphere of claim 4 wherein the soluble titanium salt is one of titanium dichloride, titanium tetrachloride, titanium sulfite, and titanyl sulfate.
6. The photochromic nanocomposite microsphere of claim 4 wherein the solvent is at least one of methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, hexylene glycol.
7. Use of the photochromic nanocomposite microsphere according to any one of claims 1-6 as a multi-color-changing material, wherein the multi-color-changing material comprises at least one of said photochromic nanocomposite microsphere.
8. Use of the photochromic nanocomposite microsphere according to any one of claims 1-6 as a blue-light-preventing multicolor-changing coating solution, wherein the coating solution comprises at least one of said photochromic nanocomposite microsphere.
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