CN-121975046-A - Polymerization-induced phase-separated total internal reflection structural color microsphere and preparation method and application thereof

CN121975046ACN 121975046 ACN121975046 ACN 121975046ACN-121975046-A

Abstract

The invention relates to the field of structural color materials, and discloses a polymerization-induced phase-separated total internal reflection structural color microsphere, and a preparation method and application thereof. The method comprises the steps of mixing epoxy vinyl monomers, fluorocarbon incapable of undergoing polymerization reaction and a photoinitiator to obtain an oil phase mixture, enabling the epoxy vinyl monomers and the fluorocarbon to be mutually soluble, enabling the fluorocarbon not to participate in polymerization, adding a first surfactant and a second surfactant into water to be mixed to obtain an aqueous phase mixture, mixing the oil phase mixture and the aqueous phase mixture to form homogeneous emulsion liquid drops, and irradiating under ultraviolet light to obtain the total internal reflection structural color microsphere. According to the invention, through optimizing the two-phase composition of Janus liquid drops and introducing ultraviolet light to initiate monomer polymerization, the ultraviolet light is driven to generate phase separation from emulsion liquid drops, so that the total internal reflection structural color microsphere is prepared, the preparation process is simplified, cosolvent dissolution is not needed, and the requirement of large-scale industrial production can be met.

Inventors

XU JIANGPING
WANG XINRUI
ZHU JINTAO
Xu Yinhan

Assignees

华中科技大学

Dates

Publication Date: 20260505
Application Date: 20260305

Claims (10)

1. The preparation method of the polymerization-induced phase-separated total internal reflection structural color microsphere is characterized by comprising the following steps of: s1, mixing a liquid epoxy vinyl monomer, a liquid fluorocarbon and a photoinitiator to obtain an oil phase mixture, wherein the density of the epoxy vinyl monomer is smaller than that of the fluorocarbon, the refractive index of the epoxy vinyl monomer is larger than that of the fluorocarbon, the epoxy vinyl monomer and the fluorocarbon are mutually soluble, and the fluorocarbon does not participate in polymerization; S2, adding a first surfactant and a second surfactant into water, and mixing to obtain a water phase mixture, wherein the first surfactant is a surfactant capable of reducing interfacial tension between the epoxy vinyl monomer and the water, and the second surfactant is a surfactant capable of reducing interfacial tension between the fluorocarbon and the water; And S3, mixing the oil phase mixture and the water phase mixture to form homogeneous emulsion liquid drops, and placing the homogeneous emulsion liquid drops under ultraviolet light to irradiate so as to polymerize the epoxy vinyl monomer, and gradually separating the epoxy vinyl monomer from the fluorocarbon phase when the conversion rate of the epoxy vinyl monomer is not less than 50 percent, thereby obtaining the total internal reflection structural color microsphere.
2. The method for preparing the polymerization-induced phase-separated total internal reflection structural color microsphere according to claim 1, wherein the method comprises the steps of, The epoxy vinyl monomer comprises at least one of glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether and 3, 4-epoxy cyclohexyl methacrylic acid; the fluorocarbon comprises at least one of methyl nonafluorobutyl ether, perfluorobutyl methyl ether, perfluorohexyl methyl ether and ethyl nonafluorobutyl ether; The photoinitiator comprises at least one of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-isopropyl thioxanthone, 2,4, 6-trimethylbenzoyl ethyl phosphonate, 4-chlorobenzophenone and benzoin dimethyl ether.
3. The method for preparing the polymerization-induced phase-separated total internal reflection structural color microsphere according to claim 1, wherein the method comprises the steps of, The first surfactant comprises at least one of SDS, PVA, TWEEN, tween 40, CTAB, PEG; The second surfactant comprises at least one of a Capstone FS-30, a Capstone 62MA, a FC-4430, and a FC 301.
4. The method for preparing the polymerization-induced phase-separated total internal reflection structural color microsphere according to claim 1, wherein the method comprises the steps of, The concentration of the first surfactant in the water phase mixture is 1-30 mg/mL; the concentration of the second surfactant in the water phase mixture is 1-30 mg/mL; the mass ratio of the first surfactant to the second surfactant is (1:4) - (3:2).
5. The method for preparing the polymerization-induced phase-separated total internal reflection structural color microsphere according to claim 1, wherein the volume ratio of the epoxy vinyl monomer to the fluorocarbon is (1:9) - (7:3), and the addition amount of the photoinitiator is 0.3% -4% of the sum of the epoxy vinyl monomer and the fluorocarbon.
6. The method for preparing the polymerization-induced phase-separated total internal reflection structural color microsphere according to claim 1, wherein the oil phase mixture and the water phase mixture are introduced into a microfluidic chip for mixing to form homogeneous emulsion droplets; The microfluidic chip comprises an outer pipeline, a first inner pipeline and a second inner pipeline, wherein one end of the outer pipeline is communicated with an aqueous phase mixture feeding pipe, the first inner pipeline and the second inner pipeline are arranged on two sides of the outer pipeline and are positioned on one side far away from the aqueous phase mixture feeding pipe, ports, close to each other, of the first inner pipeline and the second inner pipeline are positioned in a cavity of the inner pipeline, the ports, close to each other, of the first inner pipeline and the second inner pipeline penetrate through the outer pipeline, a gap is reserved between the ports, close to each other, of the first inner pipeline and the second inner pipeline, so that the aqueous phase mixture is injected into the outer pipeline through the aqueous phase mixture feeding pipe, the oil phase mixture is sheared by flow of the aqueous phase mixture at the gap and flows out through the second inner pipeline, and homogeneous emulsion drops are formed.
7. The method for preparing the polymerization-induced phase-separated total internal reflection structural color microsphere according to claim 1, wherein the irradiation condition under ultraviolet light is that the power is 1-36W during ultraviolet irradiation, the irradiation time is 30-300 s, and the irradiation distance of ultraviolet light from the homogeneous emulsion liquid drops is 5-30 cm.
8. The method for preparing polymerization-induced phase-separated total internal reflection structural color microspheres according to claim 1, wherein an amine compound is added to the total internal reflection structural color microspheres after step S3 to adjust the structural color of the total internal reflection structural color microspheres; the amine compound comprises at least one of ethylenediamine, ethylamine, n-propylamine, hexamethylenediamine and ammonia water with the mass fraction of 25-35%, and the addition amount of the amine compound is 0.2-2% of the molar mass of the epoxy vinyl monomer.
9. Total internal reflection structural color microspheres produced according to the production method of any one of claims 1-8.
10. Use of the total internal reflection structural color microsphere according to claim 9 in anti-counterfeiting material and detection.

Description

Polymerization-induced phase-separated total internal reflection structural color microsphere and preparation method and application thereof Technical Field The invention belongs to the technical field of structural color materials, and particularly relates to a polymerization-induced phase-separation total internal reflection structural color microsphere, and a preparation method and application thereof. Background Colors are ubiquitous in life, and can be divided into two types of chemical colors and structural colors according to color development causes. The chemical color realizes color development by means of selective absorption of substance molecules to light, but the mode has a plurality of defects, so that not only is the photobleaching phenomenon easy to occur, but also serious environmental pollution is caused, and meanwhile, the imaging resolution is low, and finally, the imaging resolution is limited in practical application. The color development logic of the structural color is completely different, and is formed by the optical interaction of natural light and a micro-nano scale structure, and the physical processes such as light interference, diffraction, photonic crystal effect, total internal reflection and the like are all important mechanisms for color development. Compared with chemical colors, the color of the structural color is bright and full, the saturation is higher, the color-fading-resistant color-changing material has the characteristic of good color-fading resistance, and the whole system is more environment-friendly, so that the color-changing material is widely applied to the fields of display devices, anti-counterfeiting marks, material detection and the like. In recent years, total internal reflection structural colors are further developed, and the total internal reflection structural colors are a novel structural color system which relies on the synergistic effect of total internal reflection and optical interference. At present, most of the microspheres with total internal reflection structure colors are prepared by using micro-flow control, wherein a cosolvent is used for dissolving two phases, and the two phases are induced to be subjected to phase separation by solvent volatilization to form the Jauns microspheres with total internal reflection structure colors. This process is time consuming, typically requiring 2-5 days of volatilization time. At the same time, the co-solvents are costly and environmentally polluting, and practical applications are limited, in view of which improvements are necessary. Disclosure of Invention Aiming at the defects or improvement demands of the prior art, the invention provides a polymerization-induced phase-separation total internal reflection structural color microsphere, a preparation method and application thereof, and aims to introduce ultraviolet light to initiate polymerization of epoxy vinyl monomers to drive the polymerization-induced phase-separation of the epoxy vinyl monomers from emulsion liquid drops to prepare the total internal reflection structural color microsphere by optimizing the composition of Janus liquid drops, thereby providing a brand-new and efficient preparation method of the polymerization-induced phase-separation total internal reflection structural color microsphere. In order to achieve the above object, in one aspect of the present invention, there is provided a method for preparing polymerization-induced phase-separated total internal reflection structural color microspheres, comprising the steps of: s1, mixing a liquid epoxy vinyl monomer, a liquid fluorocarbon and a photoinitiator to obtain an oil phase mixture, wherein the density of the epoxy vinyl monomer is smaller than that of the fluorocarbon, the refractive index of the epoxy vinyl monomer is larger than that of the fluorocarbon, the epoxy vinyl monomer and the fluorocarbon are mutually soluble, and the fluorocarbon does not participate in polymerization; S2, adding a first surfactant and a second surfactant into water, and mixing to obtain a water phase mixture, wherein the first surfactant is a surfactant capable of reducing interfacial tension between the epoxy vinyl monomer and the water, and the second surfactant is a surfactant capable of reducing interfacial tension between the fluorocarbon and the water; And S3, mixing the oil phase mixture and the water phase mixture to form homogeneous emulsion liquid drops, and placing the homogeneous emulsion liquid drops under ultraviolet light to irradiate so as to polymerize the epoxy vinyl monomer, wherein when the conversion rate of the epoxy vinyl monomer is not less than 50%, the epoxy vinyl monomer is gradually separated from a fluorocarbon phase, and thus the total internal reflection structural color microsphere is obtained. Preferably, the epoxy vinyl monomer comprises at least one of glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3, 4-epoxycyclohexyl methacrylic acid;